WO2022002091A1 - 废塑料处理方法和系统 - Google Patents

废塑料处理方法和系统 Download PDF

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Publication number
WO2022002091A1
WO2022002091A1 PCT/CN2021/103336 CN2021103336W WO2022002091A1 WO 2022002091 A1 WO2022002091 A1 WO 2022002091A1 CN 2021103336 W CN2021103336 W CN 2021103336W WO 2022002091 A1 WO2022002091 A1 WO 2022002091A1
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Prior art keywords
unit
plastic
waste plastic
waste
inlet
Prior art date
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Ceased
Application number
PCT/CN2021/103336
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English (en)
French (fr)
Inventor
李明丰
邹亮
王志强
李红伟
魏晓丽
夏国富
徐润
王树青
侯吉礼
王鹏飞
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Publication date
Priority claimed from CN202010617815.XA external-priority patent/CN113862018B/zh
Priority claimed from CN202011171603.XA external-priority patent/CN114479901B/zh
Application filed by Sinopec Research Institute of Petroleum Processing , China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to EP21831987.9A priority Critical patent/EP4174122A4/en
Priority to US18/004,041 priority patent/US12384972B2/en
Priority to JP2022581514A priority patent/JP7791848B2/ja
Publication of WO2022002091A1 publication Critical patent/WO2022002091A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/40—Extractive distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0293—Dissolving the materials in gases or liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B2017/0424—Specific disintegrating techniques; devices therefor
    • B29B2017/0496—Pyrolysing the materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present application relates to the technical field of solid waste plastic treatment, in particular to a waste plastic treatment method and system.
  • the existing waste plastic treatment technologies mainly include landfill and incineration.
  • landfill can easily cause secondary pollution and cannot solve the problem in essence.
  • garbage that can process waste plastics in China.
  • the physical recycling process of waste plastics has high cost, low economic value, insufficient corporate profits and secondary pollution during the recycling process, which all lead to the slow development of waste plastic resource recycling.
  • thermoplastic waste plastics can obtain oil and gas through the pyrolysis process. Therefore, the pyrolysis process is currently one of the main process paths for the chemical conversion of waste plastics.
  • Chinese patent CN106635115B discloses a method and a hydrothermal reaction system for efficiently cleaning oil by using mixed waste plastic waste.
  • the method includes using an alkaline aqueous solution to The mixed waste plastic waste is subjected to thermal hydrolysis treatment; the mixed waste plastic waste contains one or more of polyethylene (PE), polypropylene (PP), polystyrene (PS), and PET, optionally the
  • the mixed waste plastic waste can also include polyvinyl chloride (PVC); the water phase and the solid phase in the material after hydrothermal treatment are separated, and the separated solid phase is used to make oil.
  • PVC polyvinyl chloride
  • Chinese patent application CN108456328A discloses a method for treating waste plastics, which includes: adding waste plastics, modified catalysts and reaction solvents into a catalytic cracking reactor to mix evenly, and then performing a catalytic cracking reaction, characterized in that: the modified catalyst is characterized in that: The catalyst is HZSM-5 and HY composite molecular sieve catalyst modified by modifier oxide, the modifier is selected from one or more of Sn, Fe, Ti and Zn, and the reaction solvent is tetralin and the mixture of n-hexadecane, the catalytic cracking reaction conditions are as follows: the reaction temperature is 150-300 ° C, the reaction time is 120-240 minutes, the reaction is carried out under stirring, and the stirring rate is 600-1000 rev/min, and the reaction Pass in hydrogen, and the partial pressure of hydrogen is 4-7MPa.
  • Chinese patent CN102786980B discloses a waste plastic oil refining production method and its production line.
  • the method includes the following steps: 1) waste plastic pretreatment; 2) cracking reaction; 3) catalytic reaction; 4) condensation;
  • waste plastics are treated with oil, and the oil yield is high and the slag yield is low;
  • the production line includes a feeding device, a high-frequency electric heating reactor, a catalytic tower, a cooling filter tank, a cooling liquefaction tower and an oil storage tank,
  • the feeding device is connected with the high-frequency electric heating reaction kettle, the high-frequency electric heating reaction kettle and the catalytic tower are connected by pipelines, the catalytic tower and the cooling filter tank are connected by pipelines, the cooling filter tank and the cooling liquefaction tower are connected by pipelines, and the cooling and liquefaction tower is connected with the pipeline.
  • the oil storage tanks are connected by pipes.
  • waste plastics Due to the complex composition of waste plastics, it contains a large number of heteroatoms; a large number of organic or inorganic additives are also added in the plastic production process to improve the performance of plastics; plastics are easy to adhere to a large number of impurities in the process of discarding, etc.
  • the main problem of the pyrolysis process is that the quality of the pyrolysis oil is not up to standard, especially the high content of Cl and Si impurities.
  • the Cl in pyrolysis oil mainly comes from the decomposition of PVC in waste plastics, mostly small molecular organic chlorine, which is easily decomposed to form HCl in the subsequent oil processing process, causing serious corrosion.
  • Si in pyrolysis oil mainly comes from the decomposition of polymer additives such as silicone oil, silicone resin, and silicone rubber powder, and inorganic additives such as SiO 2 , mainly alkyl epoxy silanes, which are poisons of catalysts in subsequent processing processes, and will lead to permanent catalysts. Sexual inactivation.
  • the purpose of this application is to provide a novel waste plastic processing method and system, which can solve one or more of the above-mentioned problems in the prior art.
  • the present application provides a method for pretreatment of waste plastics, comprising the following steps:
  • the pretreatment agent is selected from humus, red mud, spent catalysts of oil refineries, kaolin, semi-coke, activated carbon, gasification ash, or their combination;
  • step 2) Carry out solid-liquid separation on the effluent of step 1) to obtain insoluble matter and de-impurity-containing plastic solution.
  • the waste plastic used in step 1) is subjected to dechlorination treatment, and the dechlorination treatment includes the following steps:
  • step ii) performing solid-liquid separation on the mixture obtained in step i) to obtain a chlorine-containing solution and dechlorinated waste plastics.
  • the present application provides a waste plastic pretreatment system for implementing the waste plastic pretreatment method according to the present application, comprising a waste plastic pretreatment unit and a solid-liquid separation unit, wherein the waste plastic pretreatment unit is provided with The waste plastic inlet, the optional dechlorination waste plastic inlet, the pretreatment agent inlet, the solvent oil inlet and the pretreated material outlet, the solid-liquid separation unit is provided with an inlet, an insoluble matter outlet and an outlet for the decontaminated plastic-containing solution, so The pretreated material outlet of the waste plastic pretreatment unit is communicated with the inlet of the solid-liquid separation unit.
  • the waste plastic pretreatment system further includes a waste plastic dissolution and dechlorination unit and a dechlorination separation unit
  • the waste plastic dissolution and dechlorination unit is provided with a waste plastic inlet, a first organic solvent inlet and a dissolved material outlet
  • the dechlorination separation unit is provided with an inlet, an outlet for a chlorine-containing solution and an outlet for dechlorination waste plastics, and the dissolved material outlet of the waste plastic dissolution dechlorination unit is communicated with the inlet of the dechlorination separation unit, and the dechlorination separation unit
  • the dechlorination waste plastic outlet of the unit communicates with the dechlorination waste plastic inlet of the waste plastic pretreatment unit.
  • the application provides a method for producing vehicle fuel from waste plastics, comprising the following steps:
  • step III Separation of the reaction product of step II) to obtain a gasoline fraction and/or a diesel fraction.
  • the present application provides a system for implementing the method for producing vehicle fuel from waste plastics of the present application, comprising a waste plastics pretreatment system and a catalytic cracking unit according to the present application; A plastic solution inlet, an optional catalytic cracking raw material inlet and at least one outlet, the decontamination plastic solution outlet of the solid-liquid separation unit of the waste plastic pretreatment system is communicated with the decontamination plastic solution inlet of the catalytic cracking unit.
  • the waste plastic pretreatment method and system of the present application can effectively remove metal impurities, chlorine impurities and silicon impurities in waste plastics, avoiding the influence of metal impurities and chlorine impurities on subsequent processing units; wherein, silicon impurities are The original form of the silicone polymer added in the plastic processing process is removed, which effectively avoids the problem of deactivation of the catalyst in the subsequent processing unit.
  • the waste plastic pretreatment method and system of the present application have little pollution during operation, are environmentally friendly, and can reduce carbon emissions.
  • the method and system for producing vehicle fuel from waste plastics of the present application can prepare vehicle fuels from waste plastics, which helps to solve "white pollution” and has good environmental, social and economic benefits.
  • Figure 1 shows a schematic diagram of a preferred embodiment of the waste plastic pretreatment method and system according to the present application.
  • FIG. 2 shows a schematic diagram of a preferred embodiment of a method and system for producing vehicle fuel from waste plastics according to the present application.
  • any specific numerical value disclosed herein, including the endpoints of a numerical range, is not limited to the precise value of the numerical value, but is to be understood to encompass values approximating the precise value, such as within ⁇ 5% of the precise value. all possible values. And, for the disclosed numerical range, between the endpoint values of the range, between the endpoint values and the specific point values in the range, and between the specific point values, one or more new values can be obtained in any combination. Numerical ranges, these new numerical ranges should also be considered to be specifically disclosed herein.
  • humus refers to a mixture of plant matter and various types of organic wastes entrained in waste plastics excavated from landfills after decomposing.
  • si-coke refers to the solid product generated by the pyrolysis of carbonaceous materials such as coal, biomass, waste plastics, etc. at 350-600°C.
  • gasification ash refers to the reaction of carbonaceous materials such as coal, semi-coke, coke, biomass, petroleum coke, waste plastics, etc. with gasification agent at a temperature higher than 600°C, normal pressure or pressure solid product remaining.
  • red mud is also referred to as “red mud”, which refers to the industrial solid waste discharged after refining alumina from bauxite.
  • the term “mineral oil” has its art-recognized meaning, which is generally a complex mixture of hydrocarbons.
  • the "solvent oil” is an aromatic-rich distillate oil
  • the aromatic-rich distillate oil can be a petroleum processing process, a coal pyrolysis process, a direct coal liquefaction process, a biomass and/or waste plastic pyrolysis process One of the obtained liquid distillates, or a mixture of many of them.
  • step, unit, component or component is optional, but not required, that is, the step, unit, component or component may or may not be present.
  • reaction pressures and process pressures are given as gauge pressures.
  • any matter or matter not mentioned is directly applicable to those known in the art without any change.
  • any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of the present invention, and should not be It is considered to be new content not disclosed or anticipated herein, unless a person skilled in the art considers that the combination is obviously unreasonable.
  • the present application provides a method for pretreatment of waste plastics, comprising the following steps:
  • the pretreatment agent is selected from humus, red mud, spent catalysts of oil refineries, kaolin, semi-coke, activated carbon, gasification ash, or combinations thereof, and optionally including alkaline oxides;
  • step 2) Carry out solid-liquid separation on the effluent of step 1) to obtain insoluble matter and de-impurity-containing plastic solution.
  • step 1) is carried out at a temperature of 200-450°C; further preferably, the treatment conditions of step 1) include: a temperature of 250-410°C, a pressure of 0.1-5MPa, a time (ie, waste plastics) The residence time) is 10-60min.
  • the processing conditions of step 1) include: a temperature of 320-390° C., a pressure of 0.5-4.0 MPa, and a time of 15-45 min.
  • the processing conditions of step 1) include: the temperature is 280-390° C., the pressure is 0.1-5MPa, and the time is 10-30min.
  • the solvent oil used in step 1) has a distillation range of 80-550° C., and the solvent oil has a content of total aromatic hydrocarbons higher than 50% by mass and a content of monocyclic aromatic hydrocarbons higher than 20% by mass. Further preferably, the mineral spirits have a monocyclic aromatic hydrocarbon content higher than 40% by mass.
  • the solvent oil may be vacuum gas oil (VGO), hydrogenated light cycle oil (HLCO), straight-run diesel (straight diesel), coal tar, and the like.
  • the weight ratio of solvent oil to waste plastics in step 1) is 1:10 to 10:1, more preferably 1:1 to 7:1.
  • the pretreatment agent used in step 1) can be one of humus, red mud, waste catalyst of oil refinery, kaolin, semi-coke, activated carbon, gasification ash, or a mixture of multiple compositions thereof. and optionally contain basic oxides.
  • the pretreatment agent used in step 1) is selected from spent catalytic cracking catalyst, humus, activated carbon, or a combination thereof, and optionally comprises basic oxides.
  • the particle size range of the pretreatment agent used in step 1) is 75-150 ⁇ m; further preferably, the weight ratio of the pretreatment agent to waste plastic in step 1) is 1:10 to 2: 1, more preferably 1:7 to 1:5.
  • the weight fraction of the pretreatment agent is 1-10%.
  • the waste plastics used in step 1) are cleaned, dried and crushed in advance, and the particle size of the crushed waste plastics is 1-200 mm, preferably 1-50 mm.
  • the operating temperature of the solid-liquid separation in step 2) is 250-410°C.
  • the impurity content in the obtained decontaminated plastic-containing solution can be controlled within a desired range, so as to facilitate Subsequent further processing and treatment, such as catalytic cracking.
  • the decontaminated plastic-containing solution has a metal content of less than 5 ⁇ g/g, a chlorine content of less than 20 ⁇ g/g and a silicon content of less than 3 ⁇ g/g; further preferably, the decontaminated plastic-containing solution has a metal content of less than 5 ⁇ g/g, a chlorine content of less than 3 ⁇ g/g and a silicon content of less than 3 ⁇ g/g; particularly preferably, the decontamination plastic-containing solution has a metal content of less than 3 ⁇ g/g, a metal content of less than 1 ⁇ g/g Chlorine content and silicon content less than 1 ⁇ g/g.
  • step 1) is subjected to dechlorination treatment, and the dechlorination treatment includes the following steps:
  • step ii) performing solid-liquid separation on the mixture obtained in step i) to obtain a chlorine-containing solution and dechlorinated waste plastics.
  • the first organic solvent is used to selectively dissolve the waste plastics, and the chlorine-containing plastics in the waste plastics are dissolved into the solution.
  • the waste plastic contains polystyrene
  • the chlorine-containing plastic and the polystyrene are dissolved together in the first organic solvent.
  • the chlorine-containing plastic may be selected from one or more of polyvinyl chloride, polyvinylidene chloride and copolymers thereof.
  • a first organic solvent with good dissolving effect on chlorine-containing plastics and high dissolving efficiency is preferably used.
  • the first organic solvent used in step i) is a mixed solvent composed of tetrahydrofuran and a ketone solvent in any weight ratio, further preferably, the first organic solvent is tetrahydrofuran and a ketone solvent with 1 : 3 to 3: 1, more preferably a mixed solvent of 1: 2 to 2: 1 by weight, wherein the ketone solvent is selected from methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, Or their combination, preferably selected from methyl ethyl ketone, cyclohexanone or their combination, more preferably methyl ethyl ketone.
  • the waste plastic is dissolved in the first organic solvent for 30-60 min at a temperature of 50-100° C. in step i).
  • the weight ratio of the first organic solvent to waste plastic used in step i) is 1:10 to 10:1.
  • the first organic solvent used in step i) is preheated, and the preheating temperature is 40-60°C.
  • the operating temperature of the solid-liquid separation in step ii) is 50-100°C.
  • the chlorine content in the obtained dechlorinated waste plastics is less than 20 ⁇ g/g.
  • the dechlorination treatment further comprises the steps of:
  • step iii) carry out precipitation treatment and separation to the chlorine-containing solution obtained in step ii) to obtain plastic (such as PVC and/or PS) particles and the recovered first organic solvent, wherein the precipitation treatment is selected from back extraction, simple distillation, flash evaporation , rectification, or a combination thereof.
  • plastic such as PVC and/or PS
  • the precipitation treatment in step iii) adopts the method of back-extraction coupled distillation
  • the back-extraction agent is water
  • the back-extraction temperature is 70-100°C
  • the distillation temperature is 80-100°C.
  • the dissolved plastic such as PVC and/or PS
  • the liquid part is Water-containing first organic solvent
  • the material after back-extraction is separated by means of filtration to obtain plastic (eg PVC and/or PS) particles and organic solvent-containing wastewater.
  • the waste plastic pretreatment method according to the present application further comprises the following steps:
  • step 2) The insoluble matter obtained in step 2) is contacted with a second organic solvent for solvent extraction, and the obtained product is subjected to solid-liquid separation to obtain a solid-phase material and a liquid-phase material, and the second organic solvent is selected from benzene, toluene, trichloride Methane, cyclohexanone, ethyl acetate, butyl acetate, carbon disulfide, tetrahydrofuran, gasoline, or a combination thereof;
  • step 4) Process the solid phase material obtained in step 3) to recover the pretreatment agent, and recycle at least a portion of the recovered pretreatment agent to step 1), the treatment being selected from screening, regeneration, or the like combination;
  • step 5 precipitation treatment and separation are carried out to the liquid phase material obtained in step 3) to obtain solid plastic particles and the recovered second organic solvent, and the precipitation treatment is selected from back-extraction, simple distillation, flash distillation, rectification, or their combination.
  • the waste plastics suitable for this application can be any common waste plastic materials, such as waste plastics in fresh domestic waste, waste plastics in industrial and agricultural production, waste plastics in aged wastes, preferably those of quality that cannot be physically recycled Poor waste plastic.
  • the form of the waste plastic can be selected from waste plastic rods, waste plastic pellets, waste plastic sheets formed by preliminary processing of the above waste plastics, or a combination thereof.
  • the waste plastics may contain any one or more of PE, PP, PS and PVC plastics.
  • the waste plastic pretreatment method of the present application includes the following steps:
  • the waste plastic pretreatment unit the waste plastic is contacted with a pretreatment agent and solvent oil for decontamination treatment;
  • step 2) In the solid-liquid separation unit, the effluent of step 1) is separated to obtain insoluble matter and a de-impurity-containing plastic-containing solution, and the de-impurity-containing plastic solution has a metal content of less than 5 ⁇ g/g and a metal content of less than 20 ⁇ g/g. Chlorine content and silicon content less than 3 ⁇ g/g.
  • the waste plastic pretreatment method further comprises the following steps:
  • step 2) in the extraction unit, the insoluble matter obtained in step 2) is contacted with the second organic solvent to carry out solvent extraction, and the obtained product is subjected to solid-liquid separation to obtain solid-phase material and liquid-phase material;
  • step 4) The solid phase material obtained in step 3) is processed in the pretreatment agent recovery unit to recover the pretreatment agent, and at least a part of the recovered pretreatment agent is returned to the waste plastic pretreatment agent in step 1) as a recycled pretreatment agent. processing unit;
  • step 5 In the second solvent recovery unit, the liquid phase material obtained in step 3) is subjected to precipitation treatment and separation to obtain solid plastic particles and the recovered second organic solvent.
  • the waste plastic pretreatment method of the present application comprises the following steps:
  • step b) in the dechlorination separation unit, the material dissolved in step a) is subjected to solid-liquid separation to obtain a chlorine-containing solution and dechlorinated waste plastic;
  • step b) in the waste plastic pretreatment unit, contacting the dechlorinated waste plastic and optional additional waste plastic obtained in step b) with a pretreatment agent and solvent oil for decontamination treatment;
  • step c) in the solid-liquid separation unit, the effluent of step c) is separated to obtain insoluble matter and a decontaminated plastic-containing solution, the decontaminated plastic-containing solution has a metal content of less than 5 ⁇ g/g and a metal content of less than 20 ⁇ g/g. Chlorine content and silicon content less than 3 ⁇ g/g.
  • step a) the waste plastic is fully dissolved in the first organic solvent at a temperature of 50-100° C. in the waste plastic dissolving and dechlorination unit, and the residence time of the waste plastic is 30-60min;
  • the dissolved material is subjected to solid-liquid separation with a dechlorination separation unit in step b), and the operating temperature of the dechlorination separation unit is 50-100°C.
  • the chlorine-containing solution obtained by the dechlorination separation unit in the step b) is subjected to precipitation treatment and separation in the first solvent recovery unit to obtain plastic (such as PVC and/or PS) particles and recycled
  • plastic such as PVC and/or PS
  • the waste plastic pretreatment method further comprises the following steps:
  • step d) in the extraction unit, the insoluble matter obtained in step d) is contacted with the second organic solvent to carry out solvent extraction, and the obtained product is subjected to solid-liquid separation to obtain solid-phase material and liquid-phase material;
  • step f) The solid phase material obtained in step e) is processed in the pretreatment agent recovery unit to recover the pretreatment agent, and at least a part of the recovered pretreatment agent is returned to the waste plastic pretreatment agent in step c) as a recycled pretreatment agent. processing unit;
  • step e) Precipitating and separating the liquid-phase material obtained in step e) in the second solvent recovery unit to obtain solid plastic particles and the recovered second organic solvent.
  • the specific operating conditions of the extraction unit in step 3) or step e) are matched with the selected second organic solvent, and the purpose of extraction is to remove the solvent adhering to the excluded solid phase material Oil, reduce the total amount of solid materials discharged, and ultimately achieve the goal of reducing emissions.
  • the precipitation treatment described in step 5) or step g) is preferably selected from stripping, simple distillation, flash distillation, rectification, or a combination thereof, and the specific operating temperature can be selected according to the selected solvent. Types and ratios are flexibly regulated.
  • the waste plastic pretreatment method of the present application can effectively remove the metal impurities, chlorine impurities and silicon impurities in the waste plastic, and the obtained de-impurity-containing plastic solution can be used as a hydrocarbon raw material for subsequent processing to produce olefins, Aromatics and other chemical raw materials, or the production of vehicle fuels and other products.
  • the silicon impurities are removed in the original form of the organic silicon polymer added in the plastic processing process, which effectively avoids the influence of silicon impurities on the catalyst of the subsequent processing unit.
  • the influence of chlorine impurities on subsequent processing units is effectively avoided.
  • the present application provides a waste plastic pretreatment system for implementing the waste plastic pretreatment method of the present application, including a waste plastic pretreatment unit and a solid-liquid separation unit, wherein the waste plastic pretreatment unit is provided with a waste plastic inlet , Optional dechlorination waste plastic inlet, pretreatment agent inlet, solvent oil inlet and pretreated material outlet, the solid-liquid separation unit is provided with an inlet, an insoluble matter outlet and an outlet for decontaminated plastic-containing solution, the waste plastic The pretreated material outlet of the pretreatment unit is communicated with the inlet of the solid-liquid separation unit.
  • the waste plastic pretreatment unit can effectively remove metal impurities, chlorine impurities and silicon impurities in the waste plastics, and the obtained decontaminated plastic-containing solution preferably has a content of less than 5 ⁇ g/g Metal content, chlorine content of less than 20 ⁇ g/g and silicon content of less than 3 ⁇ g/g; further preferably metal content of less than 5 ⁇ g/g, chlorine content of less than 3 ⁇ g/g and silicon content of less than 3 ⁇ g/g; particularly preferred Metal content of 3 ⁇ g/g, chlorine content of less than 1 ⁇ g/g and silicon content of less than 1 ⁇ g/g.
  • the silicon impurities are removed in the original form of the organic silicon polymer added in the plastic processing process, which effectively avoids the influence of silicon impurities on the catalyst of the subsequent processing unit.
  • the influence of chlorine impurities on subsequent processing units is effectively avoided.
  • the waste plastic pretreatment unit can be a one-stage or multi-stage series or parallel tank-type dissolving device, or a special-shaped dissolving device with dissolving function, or a device with the same function such as a continuous spiral Extractor.
  • a stirring device and a heating device are provided in the waste plastic pretreatment unit, and the stirring device can be electric drive or magnetic drive, and can be a paddle type, an anchor type, a frame type, or a screw type.
  • the stirring rate of the stirring device can be 1-300r/min, preferably 60-100r/min;
  • the heating device can be an internal heating type and/or an external heating type heating device.
  • the external heating type heating device can be one or more of jacket type or semi-circular coil tube, the internal heating type heating device can be various built-in coil tubes;
  • the heat source can be electricity, heat transfer oil, steam, open flame heating. one or more.
  • the waste plastic pretreatment system of the present application has no special requirements on the specific form of the solid-liquid separation unit, which can be various forms of filters, centrifuges, or combinations thereof.
  • the solid-liquid separation unit can be a series of various forms of oil-resistant and organic-solvent-resistant continuous automatic solid-liquid separation equipment with heat preservation function in one or more stages, or various types of equipment.
  • One or more of the filter, filter press with scraper, cross-flow filter, decanter centrifuge, and screw extrusion desolvation equipment can be automatically replaced.
  • the solid-liquid separation unit can be provided with a heating and heat preservation device, the heating device can be one or more of an external heating type or an internal heating type heating device, and the external heating type heating device can be a jacket type. Or one or more of semi-circular coils, the internal heating device can be various built-in coils; the heat source can be one or more of electricity, heat transfer oil, steam, and open flame heating.
  • the operating temperature of the solid-liquid separation unit may be, for example, 250-410°C.
  • the pore size of the filter screen can be 0.1-1 mm, preferably 0.1-10 ⁇ m.
  • the waste plastic pretreatment system further includes a waste plastic dissolution and dechlorination unit and a dechlorination separation unit, and the waste plastic dissolution and dechlorination unit is provided with a waste plastic inlet, a first organic solvent inlet and a post-dissolving unit.
  • the dechlorination separation unit is provided with an inlet, an outlet for a chlorine-containing solution and an outlet for dechlorination waste plastics, and the dissolved material outlet of the waste plastic dissolution dechlorination unit is communicated with the inlet of the dechlorination separation unit, and the The dechlorination waste plastic outlet of the dechlorination separation unit is communicated with the dechlorination waste plastic inlet of the waste plastic pretreatment unit.
  • the waste plastics can be fully dissolved in the first organic solvent at a temperature of, for example, 50-100°C in the waste plastics dissolving and dechlorination unit, and the residence time of the waste plastics can be, for example, 30-60min .
  • the treated material is subjected to solid-liquid separation in a dechlorination plastic separation unit to obtain a chlorine-containing solution and dechlorinated waste plastic, and the operating temperature of the dechlorination separation unit may be, for example, 50-100°C.
  • the waste plastics pass through the waste plastics dissolving and dechlorination unit to remove most of the chlorine-containing waste plastics in the waste plastics, and the chlorine content in the dechlorinated waste plastics separated by the dechlorination separation unit can be less than 20 ⁇ g/g.
  • the waste plastics dissolving and dechlorination unit can be a one-stage or multi-stage series or parallel tank-type dissolving device, or a special-shaped dissolving device with dissolving function, or a device with the same function such as Continuous Spiral Extractor.
  • a stirring device and a heating device are provided in the waste plastic dissolving and dechlorination unit.
  • the stirring rate of the stirring device can be 1-300r/min, preferably 60-100r/min
  • the heating device can be an internal heating type and/or an external heating type heating device one or more of.
  • the external heating type heating device can be one or more of jacket type or semi-circular coil tube, the internal heating type heating device can be various built-in coil tubes;
  • the heat source can be electricity, heat transfer oil, steam, open flame heating. one or more.
  • the dechlorination separation unit can be a series of various forms of oil-resistant, organic solvent-resistant continuous automatic solid-liquid separation equipment with heat preservation function, or various models One or more of the filter with automatic filter screen replacement, filter press with scraper, cross-flow filter, decanter centrifuge, and screw extrusion desolvation equipment.
  • the dechlorination separation unit can be provided with a heating and heat preservation device, and the heating device can be one or more of an external heating type or an internal heating type heating device; the external heating type heating device can be a jacket type Or one or more of semi-circular coils, the internal heating device can be various built-in coils; the heat source can be one or more of electricity, heat transfer oil, steam, and open flame heating.
  • the pore size of the filter screen used can be 0.1-10 mm, more preferably 0.1-1 mm.
  • the waste plastic pretreatment system further includes a first solvent recovery unit, the first solvent recovery unit is provided with a chlorine-containing solution inlet, a plastic particle outlet, and a recovered first organic solvent outlet, The chlorine-containing solution outlet of the waste plastic dissolving and dechlorination unit is communicated with the chlorine-containing solution inlet of the first solvent recovery unit.
  • the chlorine-containing solution obtained by the dechlorination separation unit is subjected to precipitation treatment and separation in the first solvent recovery unit to obtain plastic (such as PVC and/or PS) particles and the recovered first organic solvent.
  • the precipitation treatment is selected from stripping, simple distillation, flash distillation, rectification, or a combination thereof, and correspondingly, the precipitation treatment equipment used can be selected from stripping kettles, stripping towers, fractionation towers, flashing towers, Rectification column, or a combination thereof.
  • the precipitation treatment adopts a method of back extraction coupled with distillation, and the back extraction agent is water.
  • the dissolved plastic such as PVC and/or PS
  • the liquid part is Water-containing first organic solvent
  • the back-extracted material is separated by filtration to obtain plastic (PVC and/or PS) particles and organic solvent-containing wastewater
  • the filtration device used is selected from one or more stages Series or parallel filter presses, plate and frame, centrifuges, screw extrusion desolventizers, or a combination thereof.
  • the waste plastic pretreatment system further comprises an extraction unit, a pretreatment agent recovery unit and a second solvent recovery unit;
  • the extraction unit is provided with an insoluble matter inlet, a second organic solvent inlet, a solid-phase material outlet, and a liquid-phase material outlet, and the insoluble matter outlet of the solid-liquid separation unit is communicated with the insoluble matter inlet of the extraction unit;
  • the pretreatment agent recovery unit is provided with a solid phase material inlet, a circulating pretreatment agent outlet, the solid phase material outlet of the extraction unit is connected with the solid phase material inlet of the pretreatment agent recovery unit, and the circulating pretreatment agent outlet of the pretreatment agent recovery unit Connected with the pretreatment agent inlet of the waste plastic pretreatment unit;
  • the second solvent recovery unit is provided with a liquid-phase material inlet, a solid plastic particle outlet and a recovered second organic solvent outlet, and the liquid-phase material outlet of the extraction unit communicates with the liquid-phase material inlet of the second solvent recovery unit.
  • one or more of a solvent extraction column or a static mixing extractor can be set in the extraction unit, and the specific operating conditions of the extraction unit are matched with the selected second organic solvent,
  • the purpose of extraction is to remove the solvent oil adhering to the discharged solid phase material, reduce the total amount of discharged solid material, and finally achieve the purpose of emission reduction.
  • the solid phase material obtained by the extraction unit is processed in the pretreatment agent recovery unit, and part or all of it is returned to the waste plastics pretreatment unit as a circulating pretreatment agent.
  • the processing method of the pretreatment agent recovery unit Can be selected from screening, regeneration, or a combination thereof.
  • the pretreatment agent recovery unit can be in the form of an oscillating screen, a trommel screen, a single-stage or multi-stage fluidized bed regeneration furnace, a rotary kiln-type regeneration furnace, an infrared heating furnace, and the like.
  • the liquid phase material obtained by the extraction unit is subjected to precipitation treatment and separation in the second solvent recovery unit to obtain solid plastic particles and the recovered second organic solvent, and the precipitation treatment can be selected from back-extraction, Simple distillation, flash distillation, rectification, or their combination, the specific operating temperature is flexibly adjusted according to the selected solvent type and ratio.
  • the types of equipment that can be used in the second solvent recovery unit are the same as those described above for the first solvent recovery unit, and will not be repeated here.
  • FIG. 1 is a schematic diagram of a preferred embodiment of the waste plastic pretreatment method and system according to the present application.
  • the dried and crushed waste plastics 25 enter the waste plastics dissolving and dechlorination unit 1, and are fully dissolved in the first organic solvent 8.
  • the dissolved materials are separated from solid and liquid in the dechlorination separation unit to obtain Chlorine-containing solution 10 and dechlorinated waste plastic 9.
  • the obtained chlorine-containing solution 10 enters the first solvent recovery unit 2, and after precipitation treatment and separation, the plastic (such as PVC and/or PS) particles 12 and the recovered first organic solvent 11 are obtained, and the recovered first organic solvent 11 is recycled for use .
  • the plastic such as PVC and/or PS
  • the dried and crushed waste plastics 13 and optional dechlorinated waste plastics 9 enter the waste plastics pretreatment unit 3, and are contacted with solvent oil 14 and pretreatment agent 15 for decontamination treatment.
  • the treated effluent 16 is solidified.
  • the liquid separation unit 4 separates the insoluble matter 17 and the decontamination-containing plastic solution 24 .
  • the obtained insoluble matter 17 enters the extraction unit 5, contacts with the second organic solvent 18 for solvent extraction, and the obtained product is subjected to solid-liquid separation to obtain a solid-phase material 21 and a liquid-phase material 19.
  • the obtained solid phase material 21 is processed in the pretreatment agent recovery unit 7, at least part of it is returned to the waste plastics pretreatment unit 3 as a circulating pretreatment agent 22, and the remaining part of the solid phase material 23 is discharged from the device.
  • the obtained liquid-phase material 19 is subjected to precipitation treatment and separation in the second solvent recovery unit 6 to obtain solid plastic particles 26 and a recovered second organic solvent 20, and the recovered second organic solvent 20 is recycled.
  • the application provides a method for producing vehicle fuel from waste plastics, comprising the following steps:
  • step III Separation of the reaction product of step II) to obtain a gasoline fraction and/or a diesel fraction.
  • the optional catalytic cracking feedstock may be any conventional catalytic cracking feedstock such as VGO, atmospheric residue (AR), deasphalted oil (DAO), etc.
  • the catalytic cracking catalyst used in step II) can be any conventional catalytic cracking catalyst.
  • the catalytic cracking catalyst comprises a zeolite, an inorganic oxide binder and optionally a clay; The content of oxides is 5-90% by weight and the content of clay is 0-70% by weight.
  • the zeolite is selected from Y-type or HY-type zeolite with or without rare earth, ultra-stable Y-type zeolite with or without rare earth, zeolite with MFI structure, or a combination thereof.
  • the catalytic cracking reaction conditions used in step II) include: a reaction temperature of 460-530° C., a reaction pressure of 0.1-0.4MPa, an agent-oil ratio of 3-10, and a reaction time of 2-4s.
  • the catalyst oil ratio refers to the weight ratio of the catalyst circulating amount to the total feed amount
  • the reaction time refers to the average residence time of the material from the riser feed to the cyclone inlet .
  • the catalytic cracking reaction product obtained in step II) is separated in step III) to obtain at least gas, gasoline fraction and diesel fraction.
  • the obtained gasoline fractions and diesel fractions are high-quality vehicle fuel components.
  • gasoline fractions can be obtained by S-Zorb technology of Sinopec and RSDS technology of Sinopec Academy of Sciences. Or national VI standard clean gasoline.
  • Diesel fractions and straight-run diesel fractions can be combined with RTS technology and diesel hydrogenation ultra-deep desulfurization technology of China Petrochemical Academy to obtain clean diesel that meets the national V standard or national VI standard.
  • the method for producing vehicle fuel from waste plastics of the present application comprises the following steps:
  • the waste plastic dissolving and dechlorination unit also referred to as the waste plastic first decontamination unit in this application
  • the waste plastic is mixed with the first organic solvent (also referred to as solvent I in this application), at 25-120 Fully dissolved at °C temperature;
  • step A) in the dechlorination separation unit (also referred to as solid-liquid separation device 1 or separation unit 1 in this application), perform solid-liquid separation on the dissolved material in step A) to obtain a chlorine-containing solution (also referred to in this application as a chlorine-containing solution).
  • a chlorine-containing solution also referred to in this application as a chlorine-containing solution
  • the first solution and the dechlorinated waste plastic (also referred to in this application as the first solid mixture);
  • waste plastic pretreatment unit also referred to as the second decontamination unit of waste plastic in this application
  • step B optional additional waste plastic and pretreatment agent
  • solvent oil also referred to as solvent II in this application
  • step C) In the solid-liquid separation unit (also referred to as separation unit II in this application), the effluent of step C) is separated to obtain insoluble matter (also referred to in this application as the second solid mixture) and decontamination containing plastic a solution (also referred to herein as a second solution), the decontaminated plastic-containing solution having a chlorine content of less than 3 ⁇ g/g and a silicon content of less than 3 ⁇ g/g;
  • step E) in a catalytic cracking unit, contacting and reacting the decontaminated plastic-containing solution and optional catalytic cracking feedstock obtained in step D) with a catalytic cracking catalyst;
  • step F Separating the reaction product of step E) to obtain gas, gasoline fractions and diesel fractions.
  • a system for implementing the method for producing vehicle fuel from waste plastics of the present application including a waste plastics pretreatment system and a catalytic cracking unit according to the present application; the catalytic cracking unit is provided with a decontamination plastic-containing solution An inlet, an optional catalytic cracking feedstock inlet and at least one outlet, the outlet of the decontaminated plastic-containing solution of the solid-liquid separation unit of the waste plastics pretreatment system is communicated with the inlet of the decontaminated plastic-containing solution of the catalytic cracking unit.
  • the catalytic cracking unit may be in the form of various reaction units suitable for implementing catalytic cracking reaction, for example, may be selected from fixed bed catalytic cracking reaction unit, moving bed catalytic cracking reaction unit A reaction unit, a fluid catalytic cracking reaction unit, a riser catalytic cracking reaction unit, or a combination thereof.
  • the catalytic cracking unit can be selected from TSRFCC, MIP, MIP-CGP, FDF-CC, MGG, MIO, ARGG catalytic cracking reaction units, or a combination thereof, which can be flexibly selected according to the existing equipment of the refinery.
  • the system for producing vehicle fuel from waste plastics comprises a waste plastics dissolving and dechlorination unit, a dechlorination separation unit, a waste plastics pretreatment unit, a solid-liquid separation unit and a catalytic cracking unit;
  • the waste plastic dissolving and dechlorination unit is provided with a waste plastic inlet, a first organic solvent inlet, a stirring device, a heating device and an outlet for the dissolved material;
  • the dechlorination separation unit is provided with an inlet, an outlet for chlorine-containing solution and an outlet for dechlorination waste plastics;
  • the waste plastic pretreatment unit is provided with a waste plastic inlet, a dechlorinated waste plastic inlet, a pretreatment agent inlet, a solvent oil inlet, a stirring device, a heating device and a pretreated material outlet;
  • the solid-liquid separation unit is provided with an inlet, an outlet for insoluble matter and an outlet for removing impurities and plastic-containing solution;
  • the catalytic cracking unit is provided with an inlet for removing impurities and a plastic-containing solution, an optional catalytic cracking raw material inlet, a gas outlet, a gasoline fraction outlet and a diesel fraction outlet;
  • the dissolved material outlet of the waste plastic dissolving and dechlorination unit is communicated with the inlet of the dechlorination and separation unit, and the dechlorination waste plastic outlet of the dechlorination and separation unit is connected to the dechlorination waste plastic inlet of the waste plastic pretreatment unit.
  • the outlet of the pretreated material of the waste plastic pretreatment unit is communicated with the inlet of the solid-liquid separation unit, and the outlet of the decontaminated plastic-containing solution of the solid-liquid separation unit is connected to the decontaminated plastic-containing solution of the catalytic cracking unit.
  • the solution inlet is connected.
  • the waste plastic production vehicle fuel system further includes a first solvent recovery unit, and the first solvent recovery unit is provided with a chlorine-containing solution inlet and a plastic particle outlet (which may also be referred to in this application as chlorine-containing plastic particle outlet), and the recovered first organic solvent outlet, the chlorine-containing solution outlet of the dechlorination separation unit is communicated with the chlorine-containing solution inlet of the first solvent recovery unit, optionally, the first The recovered first organic solvent outlet of the solvent recovery unit is communicated with the first organic solvent inlet of the waste plastic dissolving and dechlorination unit.
  • FIG. 2 shows a schematic diagram of a preferred embodiment of the method and system for preparing vehicle fuel from waste plastics according to the present application.
  • the waste plastics enter the drying unit 201 and the crushing unit 202 for processing in turn, and the dried and crushed waste plastic particles and the first organic solvent enter the waste plastics dissolving and dechlorination unit 203 to be fully mixed and dissolved.
  • the latter material is separated into chlorine-containing solution and dechlorinated waste plastic by dechlorination separation unit 204 .
  • the obtained chlorine-containing solution enters the first solvent recovery unit 209 and is processed to obtain the recovered first organic solvent and plastic particles (such as PVC and/or PS).
  • the obtained dechlorinated waste plastic enters the waste plastic pretreatment unit 205, and is subjected to decontamination treatment under the action of solvent oil and pretreatment agent.
  • the obtained decontaminated plastic-containing solution enters the catalytic cracking unit 208 through the fluid conveying unit 207, and is contacted with the catalytic cracking catalyst together with the optional catalytic cracking raw materials to carry out catalytic cracking reaction.
  • gas, gasoline fraction, diesel fraction, heavy cycle oil are obtained Distillates and oil slurries, and the obtained gasoline fractions and diesel fractions are used as vehicle fuels.
  • the obtained insoluble matter is mixed with the second organic solvent and enters the extraction unit 210 and is separated into solid-phase materials and liquid-phase materials, and the obtained solid-phase materials enter the pretreatment agent recovery unit 211. Part of the recovered pretreatment agent is recycled and used, and the rest is used as waste. The pretreatment agent is discharged out, and the obtained liquid phase material enters the second solvent recovery unit 212 for processing to obtain the recovered second organic solvent and solid plastic particles.
  • the application provides the following technical solutions:
  • a pretreatment method for waste plastics comprising the following steps:
  • the waste plastic enters the waste plastic dissolving and dechlorination unit, and is fully dissolved in the first organic solvent. After the dissolving material is separated from solid and liquid, a chlorine-containing solution and dechlorination waste plastic are obtained.
  • the first organic solvent is selected from tetrahydrofuran, ketone solvents, chlorinated aliphatic hydrocarbons, or their combination;
  • Waste plastics and optional steps (1) Dechlorination waste plastics, enter the waste plastics pretreatment unit, contact with pretreatment agent and solvent oil for decontamination treatment, and the effluent is separated into insolubles through the solid-liquid separation unit and a decontaminated plastic-containing solution, the decontaminated plastic-containing solution has a metal content of less than 5 ⁇ g/g, a chlorine content of less than 20 ⁇ g/g and a silicon content of less than 3 ⁇ g/g; the pretreatment agent is humus, red One or more of mud, spent refinery catalyst, kaolin, semi-coke, activated carbon, gasification ash, and optionally basic oxides.
  • waste plastics are selected from waste plastics in fresh household waste, waste plastics in industrial and agricultural production, waste plastics in aged wastes, or a combination thereof, waste plastics
  • the type of plastic is any one or more of PE, PP, PS and PVC.
  • waste plastics are cleaned, dried and crushed before entering the optional waste plastics dissolving and dechlorination unit and waste plastics pretreatment unit, and the particle size of the crushed waste plastics is 1- 200mm, preferably 1-50mm.
  • the first organic solvent is a mixed solvent composed of tetrahydrofuran and a ketone solvent in any weight ratio
  • the ketone solvent is selected from methyl ethyl ketone, methyl isobutyl ketone , cyclohexanone, isophorone, or a combination thereof;
  • the weight ratio of the first organic solvent to the waste plastic is 1:10 to 10:1.
  • ketone solvent is selected from one or more of methyl ethyl ketone and cyclohexanone; preferably methyl ethyl ketone;
  • the first organic solvent is a mixed solvent composed of tetrahydrofuran and a ketone solvent in a weight ratio of 1:3-3:1;
  • the first organic solvent is a mixed solvent composed of tetrahydrofuran and a ketone solvent in a weight ratio of 1:2-2:1.
  • step (1) The method according to item A1, characterized in that in step (1), the waste plastics are dissolved in the waste plastics dechlorination unit at a temperature of 50-100°C, fully dissolved in the first organic solvent, and the waste plastics stay The time is 30-60min.
  • A7 according to the method described in item A1, it is characterized in that, the first solvent recovery unit is set, the chlorine-containing solution obtained in step (1) enters the first solvent recovery unit, and after precipitation treatment and separation, PVC and/or PS particles are obtained and the recovered first organic solvent;
  • the precipitation treatment is selected from stripping, simple distillation, flash distillation, rectification, or a combination thereof.
  • the method according to item A7 is characterized in that, in the first solvent recovery unit, the precipitation treatment adopts the mode of back extraction coupled distillation, the back extraction agent is water, the temperature of back extraction is 70-100 °C, and the distillation temperature is 80-100°C.
  • the method according to item A1 characterized in that the processing conditions of the waste plastic pretreatment unit are as follows: the temperature is 250-410°C, the pressure is 0.1-5MPa, and the residence time of the waste plastic is 10-60min.
  • the method according to item A9 characterized in that the processing conditions of the waste plastic pretreatment unit are: the temperature is 320-390°C, the pressure is 0.5-4.0MPa, and the residence time of the waste plastic is 15-45min.
  • the weight ratio of solvent oil to waste plastic is 1:10 to 10:1.
  • the weight ratio of solvent oil to waste plastic is 1:1 to 7:1.
  • A13 The method according to item A1, characterized in that the particle size of the pretreatment agent is in the range of 75-150 ⁇ m; the weight ratio of the pretreatment agent to the waste plastic is 1:10 to 2:1, preferably 1:7 to 1:5.
  • A14 The method according to item A1 or A13, wherein the pretreatment agent is one or more of spent catalytic cracking catalyst, humus, activated carbon, and optional alkaline oxides.
  • the decontaminated plastic-containing solution has a metal content of less than 3 ⁇ g/g, a chlorine content of less than 1 ⁇ g/g, and a silicon content of less than 1 ⁇ g/g.
  • step (3) the insoluble matter obtained in step (2) enters the extraction unit, and is contacted with the second organic solvent to carry out solvent extraction, and the obtained product is subjected to solid-liquid separation to obtain solid-phase material and liquid-phase material,
  • the obtained liquid phase material is subjected to precipitation treatment and separation in the second solvent recovery unit to obtain solid plastic particles and the recovered second organic solvent;
  • the second organic solvent is selected from benzene, toluene, chloroform, cyclohexanone, ethyl acetate, butyl acetate, carbon disulfide, tetrahydrofuran, gasoline, or a combination thereof.
  • pretreatment agent recovery unit includes one or more of screening and regeneration treatment methods.
  • the precipitation treatment is selected from stripping, simple distillation, flash distillation, rectification, or a combination thereof.
  • a system for any method of items A1 to A18 including optional waste plastic dissolution and dechlorination unit, waste plastic pretreatment unit, and solid-liquid separation unit;
  • the waste plastic dissolving and dechlorination unit is provided with a waste plastic inlet, a first organic solvent inlet, a chlorine-containing solution outlet and a dechlorination waste plastic outlet;
  • the waste plastic pretreatment unit is provided with a waste plastic inlet, an optional dechlorination waste plastic inlet, a pretreatment agent inlet, a solvent oil inlet and a pretreated material outlet, and the pretreated material outlet is communicated with the inlet of the solid-liquid separation unit,
  • the solid-liquid separation unit is provided with an outlet for insoluble matter and an outlet for removing impurities and plastic-containing solution.
  • A20 The system according to item A19, characterized in that a first solvent recovery unit is further provided, and the first solvent recovery unit is provided with an inlet for a chlorine-containing solution, an outlet for PVC and/or PS particles, and an outlet for the recovered first organic solvent ;
  • the chlorine-containing solution outlet of the waste plastic dissolving and dechlorination unit is communicated with the chlorine-containing solution inlet of the first solvent recovery unit.
  • system according to item A19, characterized in that the system further comprises an extraction unit, a pretreatment agent recovery unit, and a second solvent recovery unit;
  • the extraction unit is provided with an insoluble matter inlet, a second organic solvent inlet, a solid-phase material outlet, and a liquid-phase material outlet, and the insoluble matter outlet of the solid-liquid separation unit is communicated with the insoluble matter inlet of the extraction unit;
  • the pretreatment agent recovery unit is provided with a solid phase material inlet and a circulating pretreatment agent outlet.
  • the solid phase material outlet of the extraction unit is connected to the solid phase material inlet of the pretreatment agent recovery unit, and the circulating pretreatment agent outlet of the pretreatment agent recovery unit is connected to The pretreatment agent inlet of the waste plastic pretreatment unit is connected;
  • the second solvent recovery unit is provided with a liquid-phase material inlet, a solid plastic particle outlet and a recovered second organic solvent outlet, and the liquid-phase material outlet of the extraction unit communicates with the liquid-phase material inlet of the second solvent recovery unit.
  • a method for producing vehicle fuel from waste plastics comprising the following steps:
  • the waste plastic and the first organic solvent enter the waste plastic dissolving and dechlorination unit, and are fully mixed and dissolved at a temperature of 25-120 ° C. After the dissolution, the material is separated into chlorine-containing solution and dechlorination waste plastic by the dechlorination separation unit.
  • the first organic solvent is selected from tetrahydrofuran, ketone solvents, chlorinated aliphatic hydrocarbons, or their combination;
  • dechlorinated waste plastic enters the waste plastic pretreatment unit, and under the action of solvent oil and pretreatment agent, decontamination treatment is carried out at a temperature of 200-450 °C.
  • Plastic solution and insoluble matter, in the decontamination-containing plastic solution the chlorine content is less than 3 ⁇ g/g, and the silicon content is less than 3 ⁇ g/g;
  • the first organic solvent is a mixed solvent composed of tetrahydrofuran and a ketone solvent in any weight ratio
  • the ketone solvent is selected from methyl ethyl ketone, methyl isobutyl ketone , cyclohexanone, isophorone, or a combination thereof;
  • the weight ratio of the first organic solvent to the waste plastic is 1:10 to 10:1.
  • ketone solvent is selected from one or more of methyl ethyl ketone and cyclohexanone; preferably methyl ethyl ketone
  • the first organic solvent is a mixed solvent composed of tetrahydrofuran and a ketone solvent in a weight ratio of 1:3-3:1.
  • step (1) in the waste plastic dissolving and dechlorination unit, at a temperature of 50-100° C., the waste plastic is fully mixed and dissolved in the first organic solvent;
  • the residence time is 30-60min.
  • step (2) the solvent oil is a distillate rich in aromatic hydrocarbons, and the distillation range is 80-540° C.; the solvent oil has a total aromatic hydrocarbon content higher than 50% by mass and monocyclic aromatic hydrocarbon content higher than 20% by mass;
  • the content of monocyclic aromatic hydrocarbons in the mineral spirits is higher than 40% by mass.
  • step (2) the pretreatment agent is selected from one of humus, red mud, waste catalysts of oil refining units, kaolin, activated carbon, semi-coke, and gasification ash. one or more; the particle size range of the pretreatment agent is 75-150 ⁇ m.
  • step (2) characterized in that, in step (2), the pretreatment agent is selected from one or more of the spent catalytic cracking catalyst of the catalytic cracking unit, humus, and activated carbon.
  • step (2) The method according to item B1, characterized in that, in step (2), the weight ratio of solvent oil to waste plastic is 1:10 to 10:1;
  • the weight fraction of the pretreatment agent is 1% to 10%.
  • step (2) The method according to item B1, characterized in that, in step (2), the conditions for removing impurities are as follows: the temperature is 280-390°C, the pressure is 0.1-5MPa, and the residence time of the chlorine-containing solution is 10-30min .
  • step (3) the catalytic cracking catalyst comprises zeolite, inorganic oxide binder and optional clay;
  • the content of the zeolite is 5-50% by weight, the content of the inorganic oxide is 5-90% by weight, and the content of the clay is 0-70% by weight;
  • the zeolite is selected from Y-type or HY-type zeolite with or without rare earth, ultrastable Y-type zeolite with or without rare earth, zeolite with MFI structure, or a combination thereof.
  • step (3) The method according to item 1B1, characterized in that, in step (3), the catalytic cracking reaction conditions are: reaction temperature 460-530° C., agent-oil ratio 5-10, and residence time 2-4s.
  • waste plastics are selected from waste plastics in fresh household waste, waste plastics in industrial and agricultural production, waste plastics in aged wastes, or a combination thereof.
  • the type of plastic is any one or more of PE, PP, PS and PVC.
  • step (1) solvent recovery unit adopts the mode of back-extraction coupled distillation, back-extraction agent is water, the temperature of back-extraction is 70-100 °C, and the distillation temperature is 80- 100°C.
  • waste plastic production vehicle fuel system used in any of the projects B1 to B15, including: waste plastic dissolution and dechlorination unit, waste plastic pretreatment unit and catalytic cracking unit;
  • the waste plastic dissolving and dechlorination unit is provided with a waste plastic inlet, a first organic solvent inlet, a material outlet, a stirring device, and a heating device, and the material outlet of the waste plastic dissolving and dechlorination unit is communicated with the dechlorination separation unit, and the dechlorination
  • the separation unit is provided with chlorine solution outlet and dechlorination waste plastic outlet;
  • the waste plastic pretreatment unit is provided with a dechlorination waste plastic inlet, a solvent oil inlet, a pretreatment agent inlet, a material outlet, a stirring device, and a heating device.
  • the dechlorination waste plastic outlet of the dechlorination separation unit and the waste plastic pretreatment unit are provided.
  • the inlet of the dechlorination waste plastic is connected;
  • the material outlet of the waste plastic pretreatment unit is connected with the solid-liquid separation unit, and the solid-liquid separation unit is provided with an outlet for removing impurities and plastic-containing solution and an outlet for insoluble matter;
  • the catalytic cracking unit is provided with an inlet for removing impurities and plastic-containing solution, an optional catalytic cracking raw material inlet, a gas outlet, an outlet for gasoline fractions, and an outlet for diesel fractions, and the solid-liquid separation unit is provided with an outlet for removing impurities and plastic-containing solution and a catalytic cracking unit.
  • the inlet of the decontamination-containing plastic solution is connected.
  • waste plastic production vehicle fuel system used in the method of item B16, including: waste plastic dissolution and dechlorination unit, solvent recovery unit, waste plastic pretreatment unit, catalytic cracking unit;
  • the waste plastic dissolving and dechlorination unit is provided with a waste plastic inlet, a first organic solvent inlet, a material outlet, a stirring device, and a heating device, and the material outlet of the waste plastic dissolving and dechlorination unit is communicated with the dechlorination separation unit, and the dechlorination
  • the separation unit is provided with chlorine solution outlet and dechlorination waste plastic outlet;
  • the solvent recovery unit is provided with a chlorine-containing solution inlet, a recovery first organic solvent outlet, and a chlorine-containing plastic particle outlet.
  • the chlorine-containing solution outlet of the dechlorination separation unit is communicated with the chlorine-containing solution inlet of the solvent recovery unit.
  • An organic solvent outlet is communicated with the first organic solvent inlet of the waste plastic dissolving and dechlorination unit;
  • the waste plastic pretreatment unit is provided with a dechlorination waste plastic inlet, a solvent oil inlet, a pretreatment agent inlet, a material outlet, a stirring device, and a heating device.
  • the dechlorination waste plastic outlet of the dechlorination separation unit and the waste plastic pretreatment unit are provided.
  • the inlet of the dechlorination waste plastic is connected;
  • the material outlet of the waste plastic pretreatment unit is connected with the solid-liquid separation unit, and the solid-liquid separation unit is provided with an outlet for removing impurities and plastic-containing solution and an outlet for insoluble matter;
  • the catalytic cracking unit is provided with an inlet for removing impurities and plastic-containing solution, an optional catalytic cracking raw material inlet, a gas outlet, an outlet for gasoline fractions, and an outlet for diesel fractions, and the solid-liquid separation unit is provided with an outlet for removing impurities and plastic-containing solution and a catalytic cracking unit.
  • the inlet of the decontamination-containing plastic solution is connected.
  • the chlorine content in the solid material is measured by the Coulomb method, and the specific method can be with reference to the standard method of RIPP 64-90 (referring to "Petrochemical Analysis Method” (RIPP Test Method) edited by Yang Cuiding et al, Science Press, Published in 1990, pp. 164-167, "The Coulometric Determination of Total Chlorine in Crude Oil”).
  • the instrument used is a Thermo Fisher ECS300 microcoulometric analyzer, and the sample is a frozen and crushed waste plastic powder sample.
  • the chlorine content in the liquid material is also measured by the method of RIPP 64-90, the difference is that the sample is a liquid mixture.
  • the silicon content and metal content in the liquid material were determined according to GB17476-1998, Determination of Additive Elements, Wear Metals and Contaminants in Used Lubricating Oils and Certain Elements in Base Oil (Inductively Coupled Plasma Emission Spectroscopy)" to measure.
  • the waste plastics were crushed by a shearing crusher, and the aperture of the filter screen was 50 mm.
  • Waste plastic A1 is the greenhouse film, mulch film, etc. in a certain area of Shandong province. After cleaning and drying, it is broken. The ash content of the obtained waste plastic A1 is 4.3% and the moisture content is 0.5%.
  • the main plastic components are PE and a small amount of EVA, and also contain Traces of other materials such as PP and PS that cannot be separated, the average total chlorine content is about 850ppm;
  • Waste plastic B1 is a waste plastic sorted from the waste of a paper mill in Jiangsu province. After cleaning and deep drying, it is broken. The ash content of the obtained waste plastic B1 is 9.5%, and the moisture is 0. The main components of waste plastic are PE, PP, and Contains a small amount of PVC, PET, PS, etc., with an average chlorine content of 2.2%;
  • Waste plastic C is the waste plastic in the aged garbage excavated from a landfill in Guangdong. After cleaning and deep drying, it is broken. The ash content of the obtained waste plastic C is 7.3% and the moisture is 0.
  • the waste plastic contains PE, Mixed waste plastics including PP, PS, PET and PVC with a chlorine content of 1.9%; and
  • Waste plastic D is the waste plastic excavated from a landfill in Ganzhou, Jiangxi province. After cleaning and deep drying, it is broken. The ash content of the obtained waste plastic D is 11.9%, the moisture content is 0.5%, and the chlorine content is 2.2%.
  • the main components of waste plastics It is mixed waste plastic including PE, PP, PS, PET and PVC.
  • the crushed waste plastic A1 is sent to the waste plastic pretreatment unit through the screw feeder.
  • the waste plastic pretreatment unit adopts an external heat dissolving kettle. Removal of impurities, the residence time of waste plastic A1 is 30min.
  • the material is separated into insoluble matter and de-impurity-containing plastic solution by solid-liquid separation unit.
  • the plastic components in the obtained de-impurity-containing plastic solution are mainly PE and PP (EVA decomposes and enters solvent oil), and the concentration is 14.4%. Its silicon content is ⁇ 1 ⁇ g/g, its chlorine content is 6 ⁇ g/g, and its total metal content is 5.5 ⁇ g/g.
  • the insolubles are sent to the extraction unit, contacted with tetrahydrofuran for solvent extraction, and the obtained products are separated to obtain solid-phase materials and liquid-phase materials.
  • the treatment agent is returned to the waste plastic pretreatment unit.
  • the liquid-phase material is contacted with the stripping agent for stripping treatment, the solid-liquid mixture obtained is filtered to obtain solid plastic particles and a mixed solution, and the obtained mixed solution is rectified to recover tetrahydrofuran and stripping agent respectively. recycle.
  • the solvent oil used is catalytic cracking light cycle oil with a distillation range of 195-355° C., the content of total aromatic hydrocarbons is 73% by mass, and the content of monocyclic aromatic hydrocarbons is 52% by mass; the weight ratio of solvent oil to waste plastics is 5:1 .
  • the used pretreatment agent is the waste FCC balancer provided by the refinery, the particle size is 75-150 ⁇ m, the SiO 2 content is 38.1%, and the main metal components are as follows: Al 2 O 3 50.5%; Fe 2 O 3 1.31% ; NiO 1.8%; La 2 O 3 3.3%; CeO 2 1.4%; the weight ratio of pretreatment agent to waste plastic is 1:9.
  • the back-extraction agent used is water, and the dosage is 3 times that of the liquid-phase material, and the back-extraction temperature is normal temperature.
  • the crushed waste plastic B1 is sent to the waste plastic pretreatment unit through the screw feeder.
  • the waste plastic pretreatment unit adopts an external heat dissolving kettle. Removal of impurities, the residence time of waste plastic B1 is 40min.
  • the material is separated into insoluble matter and de-impurity-containing plastic solution by a solid-liquid separation unit.
  • the plastic components in the obtained de-impurity-containing plastic solution are PE and PP, the concentration is 14.2%, the silicon content is ⁇ 1 ⁇ g/g, and the chlorine content is less than 1 ⁇ g/g. The content was 18 ⁇ g/g, and the total metal content was 7.9 ⁇ g/g.
  • the insolubles are sent to the extraction unit, contacted with tetrahydrofuran for solvent extraction, and the obtained products are separated to obtain solid-phase materials and liquid-phase materials.
  • the treatment agent is returned to the waste plastic pretreatment unit.
  • the liquid-phase material is in the solvent recovery unit, and is contacted with the stripping agent water for stripping treatment.
  • the obtained solid-liquid mixture is filtered to obtain solid plastic particles and a mixed solution.
  • the obtained mixed solution is rectified to recover tetrahydrofuran and stripping agent respectively for recycling. use.
  • the solvent oil used is catalytic cracking light cycle oil with a distillation range of 195-355° C., the content of total aromatic hydrocarbons is 73% by mass, and the content of monocyclic aromatic hydrocarbons is 52% by mass; the weight ratio of solvent oil to waste plastics is 5:1 .
  • the pretreatment agent used is a mixture of sieved humus and CaO, wherein the humus is sieved to remove the organic matter, and the part with a particle size of 75-150 ⁇ m is taken as the pretreatment agent;
  • the samples of the same particle size were mixed with the humus soil in proportion, and the mass ratio of the two was 8:2; the weight ratio of the pretreatment agent to the waste plastic was 1:7.
  • the crushed waste plastic B1 is sent to the waste plastic pretreatment unit through the screw feeder.
  • the waste plastic pretreatment unit adopts an external heat dissolving kettle, mixed with the pretreatment agent and solvent oil, and the process is carried out at 350 ° C and 1.8 MPa. Removal of impurities, the residence time of waste plastic B1 is 45min.
  • the material is separated into insoluble matter and a de-impurity-containing plastic solution by a solid-liquid separation unit.
  • the plastic components in the obtained de-impurity-containing plastic solution are PE and PP, the concentration is 14.2%, the silicon content is less than 1 ⁇ g/g, chlorine The content was 10 ⁇ g/g, and the total metal content was 3.8 ⁇ g/g.
  • the solvent oil used is refinery VGO, its distillation range is 275-581°C, the total aromatic hydrocarbon content is 45.1 mass %, and the monocyclic aromatic hydrocarbon content is 21 mass %; the weight ratio of solvent oil and waste plastics is 5:1.
  • the used pretreatment agent is a mixture of coal-based activated carbon and Fe 2 O 3 , the mass ratio of the two is 9:1, and the particle size is 75-150 ⁇ m.
  • the weight ratio of pretreatment agent to waste plastic is 1:8.
  • the crushed waste plastic B1 is sent to the waste plastic pretreatment unit through the screw feeder.
  • the waste plastic pretreatment unit adopts an external heat dissolving kettle, mixed with the pretreatment agent and solvent oil, and the process is carried out at 350 ° C and 1.8 MPa. Removal of impurities, the residence time of waste plastic B1 is 30min.
  • the material is separated into insoluble matter and a de-impurity-containing plastic solution by a solid-liquid separation unit.
  • the plastic components in the obtained de-impurity-containing plastic solution are PE and PP, the concentration is 14.2%, the silicon content is less than 1 ⁇ g/g, chlorine The content was 11 ⁇ g/g, and the total metal content was 4.1 ⁇ g/g.
  • the solvent oil used is catalytic cracking light cycle oil, its distillation range is 156-338°C, the total aromatic hydrocarbon content is 76.8 mass %, and the monocyclic aromatic hydrocarbon content is 63.8 mass %; the weight ratio of solvent oil and waste plastics is 5:1 .
  • the used pretreatment agent is a mixture of coal-based activated carbon and Fe 2 O 3 , the mass ratio of the two is 9:1, and the particle size is 75-150 ⁇ m.
  • the weight ratio of pretreatment agent to waste plastic is 1:8.
  • This comparative example is the same as the waste plastic raw material, solvent oil, and decontamination treatment conditions of Example I-4, the difference is that no pretreatment agent is used in this comparative example.
  • the material is separated into insoluble matter and a de-impurity-containing plastic solution by a solid-liquid separation unit.
  • the plastic components in the obtained de-impurity-containing plastic solution are PE and PP, the concentration is 14.2%, the silicon content is 42 ⁇ g/g, and the chlorine content is 42 ⁇ g/g. was 207 ⁇ g/g, and the total metal content was 13 ⁇ g/g.
  • the impurity content of the de-impurity-containing plastic solution obtained in this comparative example is too high and cannot be directly used as the feed of the subsequent processing unit.
  • the crushed waste plastic C is preheated to 60°C, and sent to the waste plastics dissolving and dechlorination unit of the waste plastics dissolving and dechlorination unit.
  • the residence time in the dissolving and dechlorination device is 30min.
  • the material is separated into chlorine-containing solution and dechlorination waste plastic through screw extrusion desolvation equipment.
  • the dechlorination waste plastic is further at a temperature slightly higher than the boiling point of the first organic solvent. After drying, the solvent was recovered.
  • the first organic solvent used in Example 1-5 was tetrahydrofuran, and the weight ratio of the organic solvent to the waste plastic C was 10:1; the chlorine content in the gained dechlorination waste plastic was 23 ⁇ g/g.
  • the first organic solvent used in Example I-6 was methyl ethyl ketone, and the weight ratio of the organic solvent to the waste plastic C was 10:1; the chlorine content in the obtained dechlorinated waste plastic was 20 ⁇ g/g.
  • the first organic solvent used in Example 1-7 was cyclohexanone, and the weight ratio of the organic solvent to the waste plastic C was 10:1; the chlorine content in the gained dechlorination waste plastic was 25 ⁇ g/g.
  • the first organic solvent used in embodiment 1-8 is the mixture that the weight ratio of tetrahydrofuran and methyl ethyl ketone is 1: 1, and the weight ratio of organic solvent and waste plastic C is 10: 1; the chlorine content in the gained dechlorination waste plastic is 17 ⁇ g/g .
  • the first organic solvent used in embodiment 1-9 is the mixture that the weight ratio of tetrahydrofuran and methyl ethyl ketone is 1: 2, and the weight ratio of organic solvent and waste plastic C is 10: 1; chlorine content in the gained dechlorination waste plastic is 19 ⁇ g/g .
  • Example I-5 The experiment was carried out with reference to Example I-5, the differences were: the first organic solvent used was chlorobenzene, the dissolving temperature was 80°C, and the drying temperature of the dechlorinated waste plastic was 140°C.
  • the chlorine content in the obtained dechlorinated waste plastics was 32 ⁇ g/g.
  • the flow rate is sent to the continuous waste plastic dissolving and dechlorination device, and the speed of the propeller in the waste plastic dissolving and dechlorination device is adjusted to make the residence time 60min.
  • the mixed liquid is sent to the screw extrusion desolventizing equipment, and is separated into dechlorinated waste plastics and chlorine-containing solution at 60 °C.
  • the chlorine-containing solution is sent to a stripping device at 80°C for stripping with hot water, the mixture is sent to a plate and frame filter press to separate PVC and PS, and the solvent is sent to a fractionation system for fractionation recovery of the first organic solvent and water for recycling.
  • Dechlorinated waste plastics are sent to a stirred tank-type waste plastics pretreatment unit through a screw feeder.
  • 80kg/h of catalytic cracking light cycle oil preheated to 350°C is used as solvent oil
  • 2kg/h of FCC balancer is used as solvent oil.
  • the pretreatment agent is sent to the waste plastic pretreatment unit for 35 minutes at 350°C and 1.5MPa, and then sent to the screw extrusion desolvation device to obtain oil-containing insoluble matter and de-impurity-containing plastic solution.
  • the plastic components in the obtained decontaminated plastic-containing solution are mainly PE and PP, the concentration of which is 9.7%, the silicon content is 2.3 ⁇ g/g, the chlorine content is 2.8 ⁇ g/g, and the total metal content is 1.8 ⁇ g/g.
  • the obtained oil-containing insolubles are sent to the extraction unit, contacted with toluene for solvent extraction, and the obtained products are separated to obtain solid-phase materials and liquid-phase materials, and the obtained solid-phase materials are processed in the pretreatment agent recovery unit. It is returned to the waste plastic pretreatment device as a circulating pretreatment agent.
  • the liquid phase material is subjected to rectification treatment in the solvent recovery unit to obtain solid plastic particles (PS), recovered toluene and a small amount of adherent solvent oil, respectively.
  • Waste plastic B2 is the waste plastic sorted from the aged garbage excavated from a landfill in Guangdong province. It is a mixed waste plastic containing PE, PP, and a small amount of PS, PET and PVC. The sorted waste plastic is basically free. Moisture was present, the ash content was approximately 9.9% by weight, and the total chlorine content was 1.18%.
  • the first organic solvent used in Example II-1 was tetrahydrofuran, and the weight ratio of the first organic solvent to the waste plastic A2 was 10:1; the chlorine content in the obtained dechlorinated waste plastic was 23 ⁇ g/g.
  • the first organic solvent used in Example II-2 was methyl ethyl ketone, and the weight ratio of the first organic solvent to the waste plastic A2 was 10:1; the chlorine content in the obtained dechlorinated waste plastic was 25 ⁇ g/g.
  • the first organic solvent used in Example II-3 is a mixture whose weight ratio of tetrahydrofuran and cyclohexanone is 1: 1, and the weight ratio of the first organic solvent and waste plastic A2 is 5: 1; the chlorine content in the gained dechlorination waste plastic is 22 ⁇ g/g.
  • the first organic solvent used in Example II-4 is a mixture whose weight ratio of tetrahydrofuran and methyl ethyl ketone is 1: 1, and the weight ratio of the first organic solvent and waste plastic A2 is 10: 1; the chlorine content in the gained dechlorination waste plastic is 13 ⁇ g/ g.
  • the organic solvent used in Example II-5 is a mixture of tetrahydrofuran and methyl ethyl ketone in a weight ratio of 1: 2, and the weight ratio of the first organic solvent and waste plastic A2 is 10: 1; the chlorine content in the gained dechlorination waste plastic is 19 ⁇ g/g.
  • the dechlorinated waste plastic obtained in Example II-5 was sent to the waste plastic pretreatment unit, and under the action of solvent oil and pretreatment agent, it was dissolved at 350 ° C and 1.5 MPa for 30 min to carry out decontamination treatment, and the treated material was filtered at high temperature. It is separated into a de-impurity-containing plastic solution and an insoluble matter.
  • the plastic components in the obtained de-impurity-containing plastic solution are PE and PP, the concentration of which is 16.1%, the chlorine content is 2.7 ⁇ g/g, and the silicon content is 3.0 ⁇ g/g , the total metal content was 2.1 ⁇ g/g.
  • the solvent oil used is a distillate oil rich in aromatic hydrocarbons, which is a mixed oil of wax oil fractions obtained in the petroleum processing process. %; the weight ratio of solvent oil and dechlorinated waste plastic is 5:1.
  • the pretreatment agent used is semi-coke, and the particle size is 75-100 ⁇ m. Based on the total weight of the mixed materials in the waste plastic pretreatment unit, the weight fraction of the pretreatment agent is 2.5%.
  • the dechlorinated waste plastic obtained in Example II-5 was sent to the waste plastic pretreatment unit, and under the action of solvent oil and pretreatment agent, it was dissolved at 350 ° C and 1.5 MPa for 30 min to carry out decontamination treatment, and the treated material was filtered at high temperature. It is separated into a de-impurity-containing plastic solution and an insoluble matter.
  • the plastic components in the obtained de-impurity-containing plastic solution are PE and PP, the concentration of which is 16.1%, the chlorine content is 2.5 ⁇ g/g, and the silicon content is 2.2 ⁇ g/g , the total metal content was 1.2 ⁇ g/g.
  • the solvent oil used is catalytic cracking distillate oil, its distillation range is 150-338 ° C, the content of total aromatic hydrocarbons is 76.8% by mass, and the content of monocyclic aromatic hydrocarbons is 63.8% by mass; the weight ratio of solvent oil and dechlorinated waste plastics is 5: 1.
  • the used pretreatment agent is humus soil with a particle size of 75-100 ⁇ m. Based on the total weight of the mixed materials in the waste plastic pretreatment unit, the weight fraction of the pretreatment agent is 2.5%.
  • the dechlorinated waste plastic obtained in Example II-5 was sent to the waste plastic pretreatment unit, and under the action of solvent oil and pretreatment agent, it was dissolved at 350 ° C and 1.5 MPa for 30 min to carry out decontamination treatment, and the treated material was filtered at high temperature. It is separated into the de-impurity-containing plastic solution and the insoluble matter, the plastic components in the obtained de-impurity-containing plastic solution are PE and PP, the concentration of which is 15.9%, the chlorine content is 2.5 ⁇ g/g, and the silicon content is 2.5 ⁇ g/g , the total metal content was 1.3 ⁇ g/g.
  • the solvent oil used is a distillate rich in aromatic hydrocarbons, with a distillation range of 138-362° C., the content of total aromatic hydrocarbons is 90.9% by mass, and the content of monocyclic aromatic hydrocarbons is 26.8% by mass; the weight ratio of solvent oil to dechlorinated waste plastics is 5 : 1.
  • the used pretreatment agent is a mixture of gasification ash and FCC balancer in a weight ratio of 1:1, and the particle size is 75-100 ⁇ m. Based on the total weight of the mixed materials in the waste plastic pretreatment unit, the weight fraction of the pretreatment agent is 2.5%.
  • the dechlorinated waste plastic obtained in Example II-5 was sent to the waste plastic pretreatment unit, and under the action of solvent oil and pretreatment agent, it was dissolved at 350 ° C and 1.5 MPa for 30 min to carry out decontamination treatment, and the treated material was filtered at high temperature. It is separated into a decontamination-containing plastic solution and an insoluble matter.
  • the plastic components in the decontaminated plastic-containing solution are PE and PP, the concentration of which is 16.1%, the chlorine content is 2.5 ⁇ g/g, and the silicon content is 2.8 ⁇ g/g/g g, the total metal content was 1.9 ⁇ g/g.
  • the solvent oil used is a distillate rich in aromatic hydrocarbons, with a distillation range of 138-362° C., the content of total aromatic hydrocarbons is 90.9% by mass, and the content of monocyclic aromatic hydrocarbons is 26.8% by mass; the weight ratio of solvent oil to dechlorinated waste plastics is 5 : 1.
  • the pretreatment agent used is FCC balancer, and the particle size is 75-100 ⁇ m. Based on the total weight of the mixed materials in the waste plastic pretreatment unit, the weight fraction of the pretreatment agent is 2.5%.
  • the de-impurity-containing plastic solution obtained in Example II-6 was sent to the riser catalytic cracking unit, contacted with the catalytic cracking catalyst, and carried out catalytic cracking reaction, and separated to obtain gas, gasoline fraction, diesel fraction, heavy circulating oil, and oil slurry.
  • the obtained Heavy cycle oil is circulated within the catalytic cracking unit.
  • the catalytic cracking catalyst grade is GOR-Q, which is produced by Sinopec Catalyst Branch.
  • the properties of the catalyst balancer are as follows: specific surface area: ⁇ 240m 2 /g; bulk density: >0.68g/ml; pore volume: >0.34ml/g; abrasion resistance: ⁇ 2.8%/h; 800°C, 4h
  • the catalytic cracking reaction conditions include a temperature of 500° C., a pressure of 0.15MPa, an agent-oil ratio of 4, and a reaction time of 2.02s.
  • the product yields obtained are shown in Table 1. Since the decomposition products of organosilicon are mainly octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, which are mainly concentrated in gasoline fractions, the impurity content in gasoline fractions is mainly analyzed.
  • the decontaminated plastic-containing solution obtained in Example II-7 and the catalytic cracking raw material VGO are sent to the riser catalytic cracking unit together, and the weight ratio of the decontaminated plastic-containing solution to VGO is 1:1, and the solution is contacted with the catalytic cracking catalyst to carry out catalytic cracking.
  • gas, gasoline fraction, diesel fraction, heavy circulating oil and oil slurry are obtained after separation, and the obtained heavy circulating oil is circulated in the catalytic cracking unit.
  • the catalytic cracking catalyst grade is GOR-Q, and the catalytic cracking reaction conditions include a temperature of 500 °C, a pressure of 0.15 MPa, an agent-oil ratio of 4, and a reaction time of 2.02 s.
  • the waste plastic B2 is sent to the intermittent heat exchange dryer through the conveyor belt.
  • the heat source used is low-order steam.
  • the temperature of the dryer is 105 ° C.
  • the residence time of the waste plastic in the dryer is 30min; the dried waste plastic is sent to the dryer through the conveyor belt.
  • Shearing crusher, the mesh aperture is 10mm.
  • the ratio of: 5 is sent to the externally heated still-type dissolving kettle.
  • the dissolving temperature of the dissolving kettle is 65°C
  • the operating pressure is normal pressure
  • the rotational speed of the stirring paddle is 60 r/min
  • the waste plastic B2 is dissolved in the dissolving kettle for 30 minutes. Then replace the fresh solvent to dissolve once, and dissolve three times in total, for a total of 90min.
  • the dissolving kettle is connected in parallel; the mixture is sent to a high temperature filter through the discharge port at the bottom of the dissolution kettle, and the mixture is separated into dechlorinated waste plastics and chlorine-containing solution at 65°C.
  • the chlorine-containing solution is flashed to recover the first organic solvent and chlorine-containing waste plastics.
  • the dechlorinated waste plastic is dried at 80°C to further recover the first organic solvent, and then transported to the externally heated kettle-type dissolving kettle of the waste plastic pretreatment unit through a screw feeder, and the solvent oil is converted to the weight of waste plastic/solvent oil through a metering pump.
  • the ratio of 1:10 is sent to the external heating type kettle type dissolving kettle, and the waste FCC balancer is sent to the external heating type kettle type dissolution kettle in the ratio of pretreatment agent/waste plastic weight ratio 1:10 through a metering pump.
  • the temperature of impurity removal treatment is 390°C
  • the operating pressure is 0.5MPa
  • the rotational speed of the stirring paddle is 60r/min
  • the residence time of the dechlorinated waste plastics in the dissolving tank is 30min
  • the dissolving tank adopts the mode of two tanks in parallel; the mixture obtained after treatment It is sent to a high temperature filter through the discharge port at the bottom of the dissolving kettle, and the insoluble impurities are removed by filtration at 350°C to obtain a de-impurity-containing plastic solution.
  • the plastic components in the decontamination-containing plastic solution are mainly PE and PP, with a concentration of about 8.7%, wherein the chlorine content is 2.2 ⁇ g/g, the silicon content is 1.7 ⁇ g/g, and the total metal content is 3.6 ⁇ g/g. g.
  • a single screw pump is used to send the decontaminated plastic-containing solution to the riser catalytic cracking unit, and contact with the catalytic cracking catalyst to carry out catalytic cracking reaction. After separation, gas, gasoline fraction, diesel fraction, oil slurry and semi-coke are obtained.
  • the solvent oil is a catalytic cracking distillate oil with a distillation range of 150-338° C., a total aromatic hydrocarbon content of 76.8 mass %, and a monocyclic aromatic hydrocarbon content of 63.8 mass %.
  • the catalytic cracking catalyst grade is GOR-Q, and the catalytic cracking reaction conditions include a temperature of 500 °C, a pressure of 0.15 MPa, an agent-oil ratio of 4, and a reaction time of 2.02 s.
  • the used waste plastic B2 raw material, the first organic solvent and treatment conditions of the waste plastic dissolving and dechlorination unit, the solvent oil, pretreatment agent and treatment conditions of the waste plastic pretreatment unit, and the catalyst and reaction conditions of the catalytic cracking unit are all the same as those in Example II. -12 is the same, the difference is: the feed into the catalytic cracking unit is a mixed raw material with a weight ratio of the de-impurity-containing plastic solution and the catalytic cracking raw material Shengli VGO of 1:1, and the catalytic cracking unit used is a conventional circulating fluidized bed device.
  • the deactivated catalyst is regenerated in the regeneration device, and the catalyst replacement amount required to process 1 t of feedstock oil when maintaining the stable operation of the device is used as an index.
  • the catalytic cracking catalyst replacement amount is 1.2 kg/t.
  • the used waste plastic B2 raw material, the first organic solvent and processing conditions of the waste plastic dissolving and dechlorination unit, the solvent oil and processing conditions of the waste plastic pretreatment unit, the feed, catalyst and reaction conditions of the catalytic cracking unit are all the same as those in Example II. -13 is the same, the difference is: the waste plastic pretreatment unit does not use pretreatment agent.
  • the replacement amount of the catalytic cracking catalyst is 1.22 kg/t.

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Abstract

一种废塑料的预处理方法和系统以及由废塑料生产车用燃料的方法和系统，所述废塑料预处理方法包括：1)使废塑料与预处理剂和溶剂油接触进行脱杂质处理；以及2)对步骤1)的流出物进行固液分离，得到不溶物和脱杂质含塑溶液。所述脱杂质含塑溶液中金属含量、氯含量和硅含量均很低，有效减少了对后续处理单元的影响。

Description

废塑料处理方法和系统
相关申请的交叉引用
本申请要求2020年6月30日递交的、发明名称为“一种废塑料生产车用燃料的方法及系统”的中国专利申请No.202010617815.X号，和2020年10月28日递交的、发明名称为“一种废塑料预处理的方法和系统”的中国专利申请No.202011171603.X号的优先权，它们的内容经此引用全文并入本文。
技术领域
本申请涉及固体废塑料处理的技术领域，具体涉及一种废塑料处理方法和系统。
背景技术
塑料工业的发展给社会发展做出了巨大的贡献，目前我国的年塑料生产量已经高达1.2亿吨左右，其中绝大多数经过一次使用后即丢弃到环境中。据统计，我国的废塑料产量约为240-480万吨/年；到2035年全球约有80亿吨废塑料存在于自然环境中，由于塑料完全降解需要200-500年，因此废塑料的不断累积不仅造成了严重的环境污染，甚至影响了自然环境中的生态平衡。
现有的废塑料处理技术主要有填埋和焚烧两种方式，填埋除了占用大量土地外，极易造成二次污染，并不能从本质上解决问题；而目前国内有能够处理废塑料的垃圾焚烧发电厂仅约400个，如将所有废塑料采用垃圾焚烧发电的方式解决，预计仍需建设1000个以上，这明显是不可行的。此外，废塑料物理回收工艺成本高，经济价值低，企业获利不足且回收过程中易造成二次污染，均导致废旧塑料资源回收发展较慢。
废塑料化学转化是实现废塑料快速回收和转化的有效手段，特别是热塑性废塑料通过热解工艺能得到油品和气体，因此，热解工艺是目前废塑料化学转化的主要工艺路径之一。
中国专利CN106635115B公开了一种利用混合废塑料垃圾高效清洁制油的方法及水热反应系统，所述方法包括在温度为160～300℃及 压力为20～220bar的条件下，使用碱性水溶液对混合废塑料垃圾进行热水解处理；所述混合废塑料垃圾含聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)中的一种或多种，及PET，选择性的该混合废塑料垃圾还可包括聚氯乙烯(PVC)；将水热处理后的物料中的水相与固相进行分离，将分离得到的固相进行制油。本申请不仅避免了混合废塑料中的PET、PVC对油品质的不利影响，能高效清洁制油，还可产生高附加值的产品，例如TA粉末或颗粒，PS再生塑料。
中国专利申请CN108456328A公开了一种废塑料的处理方法，包括：将废塑料、改性催化剂、反应溶剂加入到催化裂解反应器中混合均匀，然后进行催化裂解反应，其特征在于：所述的改性催化剂为改性剂氧化物改性的HZSM-5和HY复合型分子筛催化剂，改性剂选自Sn、Fe、Ti和Zn中的一种或多种，所述的反应溶剂为四氢化萘和正十六烷的混合物，所述的催化裂解反应条件如下：反应温度为150-300℃，反应时间为120-240分钟，反应在搅拌下进行，搅拌速率为600-1000转/分钟，反应中通入氢气，氢分压为4-7MPa。
中国专利CN102786980B公开了一种废塑料炼油生产方法及其生产线，所述方法包括以下步骤：1)废塑料预处理；2)裂解反应；3)催化反应；4)冷凝；5)过滤脱水，通过本方法对废旧塑料进行油化处理，出油率高，出渣率低；所述生产线包括上料装置、高频电加热反应釜、催化塔、冷却过滤罐、冷却液化塔和储油罐，上料装置与高频电加热反应釜连接，高频电加热反应釜与催化塔通过管道连接，催化塔与冷却过滤罐通过管道连接，冷却过滤罐与冷却液化塔通过管道连接，冷却液化塔与储油罐通过管道连接。
由于废塑料组成复杂，本身含有大量的杂原子；在塑料生产过程中也会添加大量有机或无机的各类添加剂以提高塑料性能；塑料在丢弃过程中易粘连大量的杂质等原因，现有技术的热解工艺主要存在的问题是热解油品质不达标，特别是其中Cl、Si杂质含量高。热解油中的Cl主要来自于废塑料中的PVC分解，多为小分子有机氯，在后续的油品加工过程中易分解形成HCl而造成严重的腐蚀。现有技术中针对热解油脱氯主要采用碱性物质中和，但这一方面产生了大量的固废，另一方面使PVC最终转化成NaCl、CaCl 2等无机盐，本质上降低了其价值。热解油中的Si主要来自于硅油、硅树脂、硅橡胶粉末等高分子 添加剂的分解以及SiO 2等无机添加剂，主要为烷基环氧硅烷，是后续加工工艺催化剂的毒物，会导致催化剂永久性失活。
因此，仍然迫切需要一种新的废塑料处理技术，用以解决现有技术中废塑料热解油中有害元素Cl、Si杂质含量高，致使后续工艺过程管线和设备易腐蚀、催化剂易失活的问题。
发明内容
本申请的目的是提供一种新颖的废塑料处理方法和系统，其可以解决一个或多个上述现有技术中存在的问题。
为了实现上述目的，一方面，本申请提供了一种废塑料的预处理方法，包括以下步骤：
1)使废塑料与预处理剂和溶剂油接触进行脱杂质处理，所述预处理剂选自腐殖土、赤泥、炼油装置废催化剂、高岭土、半焦、活性炭、气化灰渣，或者它们的组合；以及
2)对步骤1)的流出物进行固液分离，得到不溶物和脱杂质含塑溶液。
优选地，步骤1)中所用的废塑料的至少一部分经过脱氯处理，所述脱氯处理包括如下步骤：
i)用第一有机溶剂对废塑料进行溶解，所述第一有机溶剂选自四氢呋喃、酮类溶剂、氯化脂肪烃，或者它们的组合；以及
ii)对步骤i)所得的混合物进行固液分离，得到含氯溶液和脱氯废塑料。
另一方面，本申请提供了一种用于实施根据本申请的废塑料预处理方法的废塑料预处理系统，包括废塑料预处理单元和固液分离单元，所述废塑料预处理单元设置有废塑料入口、任选的脱氯废塑料入口、预处理剂入口、溶剂油入口和预处理后物料出口，所述固液分离单元设置有入口、不溶物出口和脱杂质含塑溶液出口，所述废塑料预处理单元的预处理后物料出口与所述固液分离单元的入口连通。
优选地，所述废塑料预处理系统还包括废塑料溶解脱氯单元和脱氯分离单元，所述废塑料溶解脱氯单元设置有废塑料入口、第一有机溶剂入口和溶解后物料出口，所述脱氯分离单元设置有入口、含氯溶液出口和脱氯废塑料出口，所述废塑料溶解脱氯单元的溶解后物料出 口与所述脱氯分离单元的入口连通，且所述脱氯分离单元的脱氯废塑料出口与所述废塑料预处理单元的脱氯废塑料入口连通。
再一方面，本申请提供了一种废塑料生产车用燃料的方法，包括以下步骤：
I)采用本申请的废塑料预处理方法或者本申请的废塑料预处理系统对所述废塑料进行预处理，得到脱杂质含塑溶液；
II)使所述脱杂质含塑溶液和任选的催化裂化原料与催化裂化催化剂接触反应；以及
III)分离步骤II)的反应产物，得到汽油馏分和/或柴油馏分。
又一方面，本申请提供了用于实施本申请的废塑料生产车用燃料的方法的系统，包括根据本申请的废塑料预处理系统和催化裂化单元；所述催化裂化单元设置有脱杂质含塑溶液入口、任选的催化裂化原料入口和至少一个出口，所述废塑料预处理系统的固液分离单元的脱杂质含塑溶液出口与所述催化裂化单元的脱杂质含塑溶液入口连通。
本申请的废塑料预处理方法和系统，可以将废塑料中的金属杂质、氯杂质和硅杂质进行有效脱除，避免了金属杂质、氯杂质对后续加工单元的影响作用；其中，硅杂质以塑料加工过程中添加的有机硅高分子的原始形态脱除，有效避免了后续加工单元的催化剂的失活问题。此外，本申请的废塑料预处理方法和系统在运行过程中排污小，环保性好，可降低碳排放。
本申请的废塑料生产车用燃料的方法和系统可以由废塑料制备车用燃料，有助于解决“白色污染”，具有良好的环境效益、社会效益和经济效益。
本申请的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本申请的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本申请，但并不构成对本申请的限制。在附图中：
图1显示了根据本申请的废塑料预处理方法和系统的一种优选实施方式的示意图；以及
图2显示了根据本申请的废塑料生产车用燃料的方法和系统的一种优选实施方式的示意图。
具体实施方式
以下结合附图对本申请的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值，而应当理解为还涵盖了接近该精确值的值，例如在该精确值±5％范围内的所有可能的数值。并且，对于所披露的数值范围而言，在该范围的端点值之间、端点值与范围内的具体点值之间，以及各具体点值之间可以任意组合而得到一个或多个新的数值范围，这些新的数值范围也应被视为在本文中具体公开。
除非另有说明，本文所用的术语具有与本领域技术人员通常所理解的相同的含义，如果术语在本文中有定义，且其定义与本领域的通常理解不同，则以本文的定义为准。
在本申请中，术语“腐殖土”指垃圾填埋场挖掘出的废塑料夹带的由植物物质及各类有机垃圾腐烂后形成的混合物。
在本申请中，术语“半焦”指煤、生物质、废塑料等含碳物质在350-600℃条件下热解生成的固体产物。
在本申请中，术语“气化灰渣”指煤、半焦、焦炭、生物质、石油焦、废塑料等含碳物质在高于600℃、常压或加压条件下与气化剂反应后剩余的固体产物。
在本申请中，术语“赤泥”也称“红泥”，指从铝土矿中提炼氧化铝后排出的工业固体废物。
在本申请中，术语“溶剂油”具有本领域公知的含义，其通常为烃类的复杂混合物。优选地，所述“溶剂油”为富含芳烃的馏分油，所述富含芳烃馏分油可以是石油加工过程、煤热解过程、煤直接液化过程、生物质和/或废塑料热解过程所得的液体馏分油中的一种，或者其中多种的混合物。
在本申请中，术语“任选”意思是指相应的步骤、单元、组件或者成分是可选择的，而非必需的，亦即该步骤、单元、组件或者成分可以 存在也可以不存在。
在本申请中，如无相反表示，所给反应压力和处理压力均为表压。
本申请中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
在本文中提及的所有专利和非专利文献，包括但不限于教科书和期刊文章等，均通过引用方式全文并入本文。
第一方面，本申请提供了一种废塑料的预处理方法，包括以下步骤：
1)使废塑料与预处理剂和溶剂油接触进行脱杂质处理，所述预处理剂选自腐殖土、赤泥、炼油装置废催化剂、高岭土、半焦、活性炭、气化灰渣，或者它们的组合，并且任选包含碱性氧化物；以及
2)对步骤1)的流出物进行固液分离，得到不溶物和脱杂质含塑溶液。
在优选的实施方式中，步骤1)在200-450℃的温度下进行；进一步优选地，步骤1)的处理条件包括：温度为250-410℃，压力为0.1-5MPa，时间(即废塑料的停留时间)为10-60min。在某些更进一步优选的实施方式中，步骤1)的处理条件包括：温度为320-390℃，压力为0.5-4.0MPa，时间为15-45min。在另一些更进一步优选的实施方式中，步骤1)的处理条件包括：温度为280-390℃，压力为0.1-5MPa，时间为10-30min。
在优选的实施方式中，步骤1)所用溶剂油的馏程范围为80-550℃，所述溶剂油具有高于50质量％的总芳烃含量和高于20质量％的单环芳烃含量。进一步优选地，所述溶剂油具有高于40质量％的单环芳烃含量。例如，所述溶剂油可以为减压瓦斯油(VGO)、加氢轻循环油(HLCO)、直馏柴油(直柴)、煤焦油等。
在优选的实施方式中，步骤1)中所述溶剂油与废塑料的重量比例为1∶10至10∶1，更优选为1∶1至7∶1。
根据本申请，步骤1)中所用的预处理剂可以是腐植土、赤泥、炼 油装置废催化剂、高岭土、半焦、活性炭、气化灰渣中的一种，或者其中多种组成的混配物，并且任选包含碱性氧化物。在优选的实施方式中，步骤1)中所用的预处理剂选自废催化裂化催化剂、腐殖土、活性炭，或者它们的组合，并且任选包含碱性氧化物。
在优选的实施方式中，步骤1)中所用预处理剂的粒径范围为75-150μm；进一步优选地，步骤1)中所述预处理剂与废塑料的重量比例为1∶10至2∶1，更优选为1∶7至1∶5。例如，在某些特别优选的实施方式中，以步骤1)中所得混合物料的总重量为基准，所述预处理剂的重量分数为1-10％。
在优选的实施方式中，步骤1)所用的废塑料预先经过清洗、干燥和破碎，破碎后的废塑料粒度为1-200mm，优选为1-50mm。
在优选的实施方式中，步骤2)的固液分离的操作温度为250-410℃。
在本申请的方法中，通过采用所述经过精心选择的预处理剂和溶剂油类型、以及处理条件，能够将所得脱杂质含塑溶液中的杂质含量控制在所期望的范围内，以有利于后续的进一步加工和处理，例如催化裂化。在优选的实施方式中，所述脱杂质含塑溶液具有小于5μg/g的金属含量、小于20μg/g的氯含量和小于3μg/g的硅含量；进一步优选地，所述脱杂质含塑溶液具有小于5μg/g的金属含量、小于3μg/g的氯含量和小于3μg/g的硅含量；特别优选地，所述脱杂质含塑溶液具有小于3μg/g的金属含量、小于1μg/g的氯含量和小于1μg/g的硅含量。
在优选的实施方式中，步骤1)中所用的废塑料的至少一部分经过脱氯处理，所述脱氯处理包括如下步骤：
i)用第一有机溶剂对废塑料进行溶解，所述第一有机溶剂选自四氢呋喃、酮类溶剂、氯化脂肪烃，或者它们的组合；以及
ii)对步骤i)所得的混合物进行固液分离，得到含氯溶液和脱氯废塑料。
根据该优选实施方式，步骤i)中采用第一有机溶剂对废塑料进行选择性溶解，将废塑料中的含氯塑料溶解到溶液中。当废塑料中含有聚苯乙烯时，在步骤i)中，含氯塑料和聚苯乙烯会一起溶解在第一有机溶剂中。根据本申请，所述含氯塑料可以选自聚氯乙烯、聚偏二氯乙烯及其共聚物中的一种或多种。
根据该优选实施方式，在步骤i)中优选使用对含氯塑料的溶解效果好，溶解效率高的第一有机溶剂。在进一步优选的实施方式中，步骤i)中所用的第一有机溶剂为四氢呋喃与酮类溶剂以任意重量比例组成的混合溶剂，进一步优选地所述第一有机溶剂为四氢呋喃与酮类溶剂以1∶3至3∶1、更优选1∶2至2∶1的重量比例组成的混合溶剂，其中所述酮类溶剂选自甲乙酮、甲基异丁基酮、环己酮、异佛尔酮，或者它们的组合，优选选自甲乙酮、环己酮或者它们的组合，更优选为甲乙酮。
在进一步优选的实施方式中，步骤i)中在50-100℃温度下使废塑料在第一有机溶剂中溶解30-60min。
在进一步优选的实施方式中，步骤i)中所用所述第一有机溶剂与废塑料的重量比例为1∶10至10∶1。
在某些进一步优选的实施方式中，步骤i)中所用的第一有机溶剂经过预热处理，预热温度为40-60℃。
在进一步优选的实施方式中，步骤ii)的固液分离的操作温度为50-100℃。优选地，所得脱氯废塑料中氯含量为小于20μg/g。
在进一步优选的实施方式中，所述脱氯处理还包括如下步骤：
iii)对步骤ii)所得的含氯溶液进行析出处理和分离，得到塑料(如PVC和/或PS)颗粒以及回收的第一有机溶剂，所述析出处理选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合。
在更进一步优选的实施方式中，步骤iii)的所述析出处理采用反萃取耦合蒸馏的方式，反萃取剂为水，反萃取的温度为70-100℃，蒸馏温度为80-100℃。在某些特别优选的实施方式中，在步骤iii)中所述含氯溶液与反萃取剂水接触后，溶解的塑料(如PVC和/或PS)以固体颗粒的形式析出，液体部分则是含水的第一有机溶剂；含水的第一有机溶剂经蒸馏处理后，得到水和回收的第一有机溶剂，所得回收的第一有机溶剂可重复使用。在某些具体实施方式中，反萃取后物料采用过滤的方式进行分离，得到塑料(如PVC和/或PS)颗粒和含有机溶剂废水。
在优选的实施方式中，根据本申请的废塑料预处理方法还包括如下步骤：
3)使步骤2)所得的不溶物与第二有机溶剂接触进行溶剂抽提， 所得产物经固液分离得到固相物料和液相物料，所述第二有机溶剂选自苯、甲苯、三氯甲烷、环己酮、乙酸乙酯、乙酸丁酯、二硫化碳、四氢呋喃、汽油，或者它们的组合；
4)对步骤3)所得的固相物料进行处理以回收预处理剂，并将所回收的预处理剂的至少一部分再循环到步骤1)中，所述处理选自筛分、再生，或者它们的组合；以及
5)对步骤3)所得的液相物料进行析出处理和分离，得到固体塑料颗粒和回收的第二有机溶剂，所述析出处理选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合。
适用于本申请的废塑料可以为任何常见的废弃塑料材料，例如为新鲜生活垃圾中的废塑料、工农业生产中的废塑料、陈化垃圾中的废塑料，优选为无法物理回收再生的品质较差的废塑料。所述废塑料的形式可以选自上述废塑料经初步加工形成的废塑料棒、废塑料粒、废塑料片，或者它们的组合。所述废塑料可以包含PE、PP、PS和PVC塑料中的任意一种或多种。
在某些优选实施方式中，本申请的废塑料预处理方法包括以下步骤：
1)在废塑料预处理单元中，使废塑料与预处理剂和溶剂油接触进行脱杂质处理；以及
2)在固液分离单元中，对步骤1)的流出物进行分离，得到不溶物和脱杂质含塑溶液，所述脱杂质含塑溶液具有小于5μg/g的金属含量、小于20μg/g的氯含量和小于3μg/g的硅含量。
在某些进一步优选的实施方式中，所述废塑料预处理方法还包括以下步骤：
3)在抽提单元中，使步骤2)所得的不溶物与第二有机溶剂接触进行溶剂抽提，所得产物经固液分离后，得到固相物料和液相物料；
4)在预处理剂回收单元中对步骤3)所得的固相物料进行处理以回收预处理剂，并将所回收的预处理剂的至少一部分作为循环预处理剂返回步骤1)的废塑料预处理单元；以及
5)在第二溶剂回收单元中对步骤3)所得的液相物料进行析出处理和分离，得到固体塑料颗粒和回收的第二有机溶剂。
在另一些优选实施方式中，本申请的废塑料预处理方法包括以下 步骤：
a)在废塑料溶解脱氯单元中，使废塑料在第一有机溶剂中充分溶解；
b)在脱氯分离单元中，对步骤a)溶解后的物料进行固液分离，得到含氯溶液和脱氯废塑料；
c)在废塑料预处理单元中，使步骤b)得到的脱氯废塑料和任选的附加废塑料与预处理剂和溶剂油接触进行脱杂质处理；以及
d)在固液分离单元中，对步骤c)的流出物进行分离，得到不溶物和脱杂质含塑溶液，所述脱杂质含塑溶液具有小于5μg/g的金属含量、小于20μg/g的氯含量和小于3μg/g的硅含量。
在进一步优选的实施方式中，步骤a)中废塑料在废塑料溶解脱氯单元中，在50-100℃温度下，在第一有机溶剂中充分溶解，废塑料的停留时间为30-60min；溶解后物料在步骤b)中用脱氯分离单元进行固液分离，所述脱氯分离单元的操作温度为50-100℃。
在更进一步优选的实施方式中，所述步骤b)中脱氯分离单元所得含氯溶液在第一溶剂回收单元中进行析出处理和分离，得到塑料(如PVC和/或PS)颗粒和回收的第一有机溶剂，所述析出处理的操作和条件如前所述，在此不再赘述。
在某些进一步优选的实施方式中，所述废塑料预处理方法还包括以下步骤：
e)在抽提单元中，使步骤d)所得的不溶物与第二有机溶剂接触进行溶剂抽提，所得产物经固液分离后，得到固相物料和液相物料；
f)在预处理剂回收单元中对步骤e)所得的固相物料进行处理以回收预处理剂，并将所回收的预处理剂的至少一部分作为循环预处理剂返回步骤c)的废塑料预处理单元；以及
g)在第二溶剂回收单元中对步骤e)所得的液相物料进行析出处理和分离，得到固体塑料颗粒和回收的第二有机溶剂。
在上述进一步优选的实施方式中，步骤3)或步骤e)中抽提单元的具体操作条件与所选第二有机溶剂相匹配，抽提的目的是脱除外排固相物料上粘附的溶剂油，降低外排固体物料总量，最终达到减排的目的。
在上述进一步优选的实施方式中，步骤5)或步骤g)中所述的析 出处理优选选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合，具体操作温度可根据所选溶剂种类及配比灵活调控。
本申请的废塑料预处理方法可以将废塑料中的金属杂质、氯杂质和硅杂质进行有效脱除，所得的脱杂质含塑溶液可以作为烃类原料，继续进行后续加工处理，以生产烯烃、芳烃等化工原料，或者生产车用燃料等产品。其中硅杂质以塑料加工过程中添加的有机硅高分子的原始形态脱除，有效避免了硅杂质对后续加工单元催化剂的影响作用。同时通过降低废塑料中的氯含量，有效避免了氯杂质对后续加工单元的影响作用。
第二方面，本申请提供了用于实施本申请的废塑料预处理方法的废塑料预处理系统，包括废塑料预处理单元和固液分离单元，所述废塑料预处理单元设置有废塑料入口、任选的脱氯废塑料入口、预处理剂入口、溶剂油入口和预处理后物料出口，所述固液分离单元设置有入口、不溶物出口和脱杂质含塑溶液出口，所述废塑料预处理单元的预处理后物料出口与所述固液分离单元的入口连通。
在本申请的废塑料预处理系统中，在所述废塑料预处理单元内，大多数塑料溶解于溶剂油并在预处理剂的作用下进行脱硅和脱金属处理，废塑料中的PVC充分分解为HCl并被预处理剂捕获，起到了脱氯的作用。脱杂质后的流出物进入固液分离单元，分离为不溶物和脱杂质含塑溶液。
在本申请的废塑料预处理系统中，所述废塑料预处理单元可以将废塑料中金属杂质、氯杂质和硅杂质进行有效脱除，所得的脱杂质含塑溶液优选具有小于5μg/g的金属含量、小于20μg/g的氯含量和小于3μg/g的硅含量；进一步优选具有小于5μg/g的金属含量、小于3μg/g的氯含量和小于3μg/g的硅含量；特别优选具有小于3μg/g的金属含量、小于1μg/g的氯含量和小于1μg/g的硅含量。其中硅杂质以塑料加工过程中添加的有机硅高分子的原始形态脱除，有效避免了硅杂质对后续加工单元催化剂的影响作用。同时通过降低废塑料中的氯含量，有效避免了氯杂质对后续加工单元的影响作用。
在优选的实施方式中，所述废塑料预处理单元可以是一级或多级串联或并联的釜式溶解装置，或者是具有溶解作用的异形溶解装置，或者是具有相同功能的设备如连续螺旋浸取器。进一步优选地，所述 废塑料预处理单元内设置有搅拌装置及加热装置，所述搅拌装置可以是电力驱动，或者是磁力驱动，并且可以是桨式、锚式、框式、螺条式中的一种或多种，所述搅拌装置的搅拌速率可以为1-300r/min，优选为60-100r/min；所述加热装置可以是内加热式和/或外加热式加热装置中的一种或多种。例如，外热式加热装置可以是夹套式或半圆盘管中的一种或多种，内热式加热装置可以是各类内置盘管；热源可以是电、导热油、蒸汽、明火加热中的一种或多种。
本申请的废塑料预处理系统对所述固液分离单元的具体形式没有特别要求，可以是各种形式的过滤器、离心机，或者它们的组合。在优选的实施方式中，所述固液分离单元可以是一级或多级串联的各种形式的带保温功能的耐油、耐有机溶剂的连续式自动固液分离设备，或者是各种型号的可自动更换滤网的过滤器、带刮板的压滤机、错流过滤器、卧螺离心机、螺旋挤压脱溶剂设备中的一种或多种。进一步优选地，所述固液分离单元可以设置有加热及保温装置，所述加热装置可以为外热式或内热式加热装置中的一种或多种，外热式加热装置可以是夹套式或半圆盘管中的一种或多种，内热式加热装置可以是各类内置盘管；热源可以是电、导热油、蒸汽、明火加热中的一种或多种。优选地，所述固液分离单元的操作温度可以为例如250-410℃。所述的固液分离单元为过滤器时，滤网孔径可以为0.1-1mm，优选为0.1-10μm。
在优选的实施方式中，所述废塑料预处理系统还包括废塑料溶解脱氯单元和脱氯分离单元，所述废塑料溶解脱氯单元设置有废塑料入口、第一有机溶剂入口和溶解后物料出口，所述脱氯分离单元设置有入口、含氯溶液出口和脱氯废塑料出口，所述废塑料溶解脱氯单元的溶解后物料出口与所述脱氯分离单元的入口连通，且所述脱氯分离单元的脱氯废塑料出口与所述废塑料预处理单元的脱氯废塑料入口连通。
在该优选实施方式中，废塑料可以在废塑料溶解脱氯单元中，在例如50-100℃的温度下，在第一有机溶剂中充分溶解处理，废塑料的停留时间可为例如30-60min。处理后物料在脱氯塑料分离单元中进行固液分离得到含氯溶液和脱氯废塑料，所述脱氯分离单元的操作温度可为例如50-100℃。
在该优选实施方式中，废塑料经过废塑料溶解脱氯单元，脱除了 废塑料中大部分含氯废塑料，经脱氯分离单元分离所得的脱氯废塑料中氯含量可以小于20μg/g。
在进一步优选的实施方式中，所述废塑料溶解脱氯单元可以是一级或多级串联或并联的釜式溶解装置，或者是具有溶解作用的异形溶解装置，或者是具有相同功能的设备如连续螺旋浸取器。进一步优选地，所述废塑料溶解脱氯单元内设置有搅拌装置及加热装置，所述的搅拌装置可以是电力驱动，或者是磁力驱动，并且可以是桨式、锚式、框式、螺条式中的一种或多种，所述搅拌装置的搅拌速率可以为1-300r/min，优选为60-100r/min；所述的加热装置可以是内加热式和/或外加热式加热装置中的一种或多种。例如，外热式加热装置可以是夹套式或半圆盘管中的一种或多种，内热式加热装置可以是各类内置盘管；热源可以是电、导热油、蒸汽、明火加热中的一种或多种。
在进一步优选的实施方式中，所述脱氯分离单元可以是一级或多级串联的各种形式的带保温功能的耐油、耐有机溶剂的连续式自动固液分离设备，或者是各种型号的可自动更换滤网的过滤器、带刮板的压滤机、错流过滤器、卧螺离心机、螺旋挤压脱溶剂设备中的一种或多种。进一步优选地，所述脱氯分离单元可以设置有加热及保温装置，所述加热装置可以是外热式或内热式加热装置中的一种或多种；外热式加热装置可以是夹套式或半圆盘管中的一种或多种，内热式加热装置可以是各类内置盘管；热源可以是电、导热油、蒸汽、明火加热中的一种或多种。所述的脱氯分离单元为过滤器时，所用的滤网孔径可以为0.1-10mm，进一步优选为0.1-1mm。
在进一步优选的实施方式中，所述废塑料预处理系统还包括第一溶剂回收单元，所述第一溶剂回收单元设置有含氯溶液入口，塑料颗粒出口，和回收的第一有机溶剂出口，所述废塑料溶解脱氯单元的含氯溶液出口与第一溶剂回收单元的含氯溶液入口连通。
在该进一步优选的实施方式中，所述脱氯分离单元所得的含氯溶液在第一溶剂回收单元中进行析出处理和分离，得到塑料(如PVC和/或PS)颗粒和回收的第一有机溶剂。优选地，所述析出处理选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合，相应地所用析出处理设备可选自反萃取釜、反萃取塔、分馏塔、闪蒸塔、精馏塔，或者它们的组合。进一步优选地，所述析出处理采用反萃取耦合蒸馏的方式， 反萃取剂为水。例如，在某些具体实施方式中，含氯溶液进入第一溶剂回收单元中与反萃取剂水接触后，溶解的塑料(如PVC和/或PS)以固体颗粒的形式析出，液体部分则是含水的第一有机溶剂；含水的第一有机溶剂经蒸馏处理后，得到水和回收的第一有机溶剂，所得回收的第一有机溶剂可重复使用。
在某些更进一步优选的实施方式中，反萃取后的物料采用过滤的方式进行分离，得到塑料(PVC和/或PS)颗粒和含有机溶剂废水，所用的过滤装置选自一级或多级串联或并联的压滤机、板框、离心机、螺旋挤压脱溶剂设备，或者它们的组合。
在优选的实施方式中，所述废塑料预处理系统还包括抽提单元、预处理剂回收单元和第二溶剂回收单元；
所述抽提单元设置有不溶物入口、第二有机溶剂入口、固相物料出口、液相物料出口，所述固液分离单元的不溶物出口与抽提单元的不溶物入口连通；
预处理剂回收单元设置有固相物料入口，循环预处理剂出口，抽提单元的固相物料出口与预处理剂回收单元的固相物料入口连通，预处理剂回收单元的循环预处理剂出口与废塑料预处理单元的预处理剂入口连通；
第二溶剂回收单元设置有液相物料入口，固体塑料颗粒出口和回收的第二有机溶剂出口，抽提单元的液相物料出口与第二溶剂回收单元的液相物料入口连通。
在该优选实施方式中，所述抽提单元中可以设置溶剂抽提塔或静态混合抽提器中的一种或多种，抽提单元的具体操作条件与所选第二有机溶剂相匹配，抽提的目的是脱除外排固相物料上粘附的溶剂油，降低外排固体物料总量，最终达到减排的目的。
在该优选实施方式中，抽提单元所得的固相物料在预处理剂回收单元进行处理，部分或全部作为循环预处理剂返回废塑料预处理单元中，所述预处理剂回收单元的处理方式可以选自筛分、再生，或者它们的组合。所述预处理剂回收单元可以为振荡筛、滚筒筛、单段或多段流化床再生炉、回转窑式再生炉、红外线加热炉等的形式。
在该优选实施方式中，抽提单元所得的液相物料在第二溶剂回收单元中进行析出处理和分离，得到固体塑料颗粒和回收的第二有机溶 剂，所述析出处理可以选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合，具体操作温度根据所选溶剂种类及配比灵活调控。可用于所述第二溶剂回收单元的设备的类型与上文针对第一溶剂回收单元所述的相同，在此不再赘述。
图1为根据本申请的废塑料预处理方法和系统的一种优选实施方式的示意图。如图1所示，经过干燥、破碎处理的废塑料25进入废塑料溶解脱氯单元1，在第一有机溶剂8中充分溶解，溶解后物料在脱氯分离单元中经固液分离后，得到含氯溶液10和脱氯废塑料9。所得含氯溶液10进入第一溶剂回收单元2，经析出处理和分离后，得到塑料(如PVC和/或PS)颗粒12和回收的第一有机溶剂11，回收的第一有机溶剂11循环使用。
经过干燥、破碎处理的废塑料13和任选的脱氯废塑料9，进入废塑料预处理单元3，与溶剂油14、预处理剂15接触进行脱杂质处理，处理后的流出物16经固液分离单元4，分离为不溶物17和脱杂质含塑溶液24。
所得不溶物17进入抽提单元5，与第二有机溶剂18接触进行溶剂抽提，所得产物经固液分离后，得到固相物料21和液相物料19。所得固相物料21在预处理剂回收单元7经处理后，至少部分作为循环预处理剂22返回废塑料预处理单元3，剩余部分固相物料23排出装置。所得液相物料19在第二溶剂回收单元6中进行析出处理和分离，得到固体塑料颗粒26和回收的第二有机溶剂20，回收的第二有机溶剂20循环使用。
第三方面，本申请提供了一种废塑料生产车用燃料的方法，包括以下步骤：
I)采用本申请的废塑料预处理方法或本申请的废塑料预处理系统对所述废塑料进行预处理，得到脱杂质含塑溶液；
II)使所述脱杂质含塑溶液和任选的催化裂化原料与催化裂化催化剂接触反应；以及
III)分离步骤II)的反应产物，得到汽油馏分和/或柴油馏分。
根据本申请，所述任选的催化裂化原料可以是任何常规的催化裂化原料，例如VGO、常压渣油(AR)、脱沥青油(DAO)等
根据本申请，步骤II)中所用的催化裂化催化剂可以是任何常规 的催化裂化催化剂。在优选的实施方式中，所述催化裂化催化剂包括沸石、无机氧化物粘结剂和任选的粘土；优选地，以催化剂的总重量计，所述沸石的含量为5-50重量％，无机氧化物的含量为5-90重量％，粘土的含量为0-70重量％。进一步优选地，所述沸石选自含或不含稀土的Y型或HY型沸石、含或不含稀土的超稳Y型沸石、具有MFI结构的沸石，或者它们的组合。
在优选的实施方式中，步骤II)中所用的催化裂化反应条件包括：反应温度460-530℃，反应压力为0.1-0.4MPa，剂油比3-10，反应时间2-4s。在使用提升管反应器进行该催化裂化反应的情况下，剂油比指催化剂循环量与总进料量的重量比，而反应时间指物料在提升管进料至旋风分离器入口的平均停留时间。
在优选的实施方式中，步骤II)所得的催化裂化反应产物在步骤III)中经分离至少得到气体、汽油馏分和柴油馏分。所得的汽油馏分、柴油馏分均是优质的车用燃料组分，分别经过后续处理后，如汽油馏分经中国石化S-Zorb技术、中国石化石科院的RSDS技术等，能得到符合国V标准或者国VI标准的清洁汽油。柴油馏分与直馏柴油馏分一起经中国石化石科院的RTS技术、柴油加氢超深度脱硫技术等，能得到符合国V标准或者国VI标准的清洁柴油。
在某些优选实施方式中，本申请的废塑料生产车用燃料的方法，包括以下步骤：
A)在废塑料溶解脱氯单元(本申请中也称为废塑料第一脱杂单元)中，使废塑料与第一有机溶剂(本申请中也称为溶剂I)混合，在25-120℃温度下充分溶解；
B)在脱氯分离单元(本申请中也称为固液分离装置I或分离单元I)中，对步骤A)溶解后的物料进行固液分离，得到含氯溶液(本申请中也称为第一溶液)和脱氯废塑料(本申请中也称为第一固体混合物)；
C)在废塑料预处理单元(本申请中也称为废塑料第二脱杂单元)中，使步骤B)得到的脱氯废塑料和任选的附加废塑料与预处理剂(本申请中也称为脱杂助剂)和溶剂油(本申请中也称为溶剂II)接触，在200-450℃温度下进行脱杂质处理；
D)在固液分离单元(本申请中也称为分离单元II)中，对步骤C) 的流出物进行分离，得到不溶物(本申请中也称为第二固体混合物)和脱杂质含塑溶液(本申请中也称为第二溶液)，所述脱杂质含塑溶液具有小于3μg/g的氯含量和小于3μg/g的硅含量；
E)在催化裂化单元中，使步骤D)所得的脱杂质含塑溶液和任选的催化裂化原料与催化裂化催化剂接触反应；以及
F)分离步骤E)的反应产物，得到气体、汽油馏分和柴油馏分。
第四方面，提供了用于实施本申请的废塑料生产车用燃料的方法的系统，包括根据本申请的废塑料预处理系统和催化裂化单元；所述催化裂化单元设置有脱杂质含塑溶液入口、任选的催化裂化原料入口和至少一个出口，所述废塑料预处理系统的固液分离单元的脱杂质含塑溶液出口与所述催化裂化单元的脱杂质含塑溶液入口连通。
在本申请的废塑料生产车用燃料的系统中，所述催化裂化单元可以是各种适用于实施催化裂化反应的反应单元的形式，例如可以选自固定床催化裂化反应单元、移动床催化裂化反应单元、流化床催化裂化反应单元、提升管催化裂化反应单元，或者它们的组合。特别地，所述催化裂化单元可以选自TSRFCC、MIP、MIP-CGP、FDF-CC、MGG、MIO、ARGG催化裂化反应单元，或者它们的组合，具体可根据炼厂现有装置进行灵活选择。
在某些优选实施方式中，所述废塑料生产车用燃料的系统包括废塑料溶解脱氯单元、脱氯分离单元、废塑料预处理单元、固液分离单元和催化裂化单元；
所述废塑料溶解脱氯单元设置有废塑料入口、第一有机溶剂入口、搅拌装置、加热装置和溶解后物料出口；
所述脱氯分离单元设置有入口、含氯溶液出口和脱氯废塑料出口；
所述废塑料预处理单元设置有废塑料入口、脱氯废塑料入口、预处理剂入口、溶剂油入口、搅拌装置、加热装置和预处理后物料出口；
所述固液分离单元设置有入口、不溶物出口和脱杂质含塑溶液出口；
所述催化裂化单元设置脱杂质含塑溶液入口、任选的催化裂化原料入口、气体出口、汽油馏分出口和柴油馏分出口；
所述废塑料溶解脱氯单元的溶解后物料出口与所述脱氯分离单元的入口连通，所述脱氯分离单元的脱氯废塑料出口与所述废塑料预处 理单元的脱氯废塑料入口连通，所述废塑料预处理单元的预处理后物料出口与所述固液分离单元的入口连通，所述固液分离单元的脱杂质含塑溶液出口与所述催化裂化单元的脱杂质含塑溶液入口连通。
在进一步优选的实施方式中，所述废塑料生产车用燃料系统还包括第一溶剂回收单元，所述第一溶剂回收单元设置有含氯溶液入口、塑料颗粒出口(本申请中也可称为含氯塑料颗粒出口)，和回收的第一有机溶剂出口，所述脱氯分离单元的含氯溶液出口与所述第一溶剂回收单元的含氯溶液入口连通，任选地，所述第一溶剂回收单元的回收第一有机溶剂出口与所述废塑料溶解脱氯单元的第一有机溶剂入口连通。
图2显示了根据本申请的废塑料制备车用燃料的方法和系统的一种优选实施方式的示意图。如图2所示，废塑料依次进入干燥单元201和破碎单元202进行处理，干燥和破碎后的废塑料颗粒和第一有机溶剂进入废塑料溶解脱氯单元203中，进行充分的混合溶解，溶解后物料经脱氯分离单元204分离为含氯溶液和脱氯废塑料。所得含氯溶液进入第一溶剂回收单元209经处理后，得到回收第一有机溶剂和塑料颗粒(如PVC和/或PS)。所得脱氯废塑料进入废塑料预处理单元205，在溶剂油和预处理剂的作用下进行脱杂质处理，处理后物料经固液分离单元206，分离为脱杂质含塑溶液和不溶物。所得脱杂质含塑溶液经流体输送单元207进入催化裂化单元208，与任选的催化裂化原料一同与催化裂化催化剂接触，进行催化裂化反应，经分离得到气体、汽油馏分、柴油馏分、重循环油馏分和油浆，所得汽油馏分和柴油馏分为车用燃料。所得不溶物与第二有机溶剂混合进入抽提单元210并分离为固相物料和液相物料，所得固相物料进入预处理剂回收单元211，部分回收的预处理剂回收使用，其余部分作为废预处理剂外排，所得液相物料进入第二溶剂回收单元212经处理后得到回收第二有机溶剂和固体塑料颗粒。
在特别优选的实施方式中，本申请提供了如下的技术方案：
A1、一种废塑料的预处理方法，包括以下步骤：
(1)任选的废塑料溶解脱氯单元，废塑料进入废塑料溶解脱氯单元，在第一有机溶剂中充分溶解，溶解后物料经固液分离后，得到含氯溶液和脱氯废塑料，所述第一有机溶剂选自四氢呋喃、酮类溶剂、 氯化脂肪烃，或者它们的组合；
(2)废塑料和任选的步骤(1)脱氯废塑料，进入废塑料预处理单元，与预处理剂、溶剂油接触进行脱杂质处理，流出物经固液分离单元，分离为不溶物和脱杂质含塑溶液，所述脱杂质含塑溶液具有小于5μg/g的金属含量、小于20μg/g的氯含量和小于3μg/g的硅含量；所述预处理剂为腐殖土、赤泥、炼油装置废催化剂、高岭土、半焦、活性炭、气化灰渣中的一种或多种，以及任选的碱性氧化物。
A2、根据项目A1所述的方法，其特征在于，所述废塑料选自新鲜生活垃圾中的废塑料、工农业生产中的废塑料、陈化垃圾中的废塑料，或者它们的组合，废塑料的种类为PE、PP、PS和PVC中的任意一种或多种。
A3、根据项目A1所述的方法，其特征在于，废塑料在进入任选的废塑料溶解脱氯单元、废塑料预处理单元前进行清洗、干燥和破碎，破碎后的废塑料粒度为1-200mm，优选为1-50mm。
A4、根据项目A1所述的方法，其特征在于，所述第一有机溶剂为四氢呋喃与酮类溶剂以任意重量比例组成的混合溶剂，所述酮类溶剂选自甲乙酮、甲基异丁基酮、环己酮、异佛尔酮，或者它们的组合；
第一有机溶剂与废塑料的重量比例为1∶10至10∶1。
A5、根据项目A1或A4所述的方法，其特征在于，所述酮类溶剂选自甲乙酮、环己酮中一种或多种；优选为甲乙酮；
所述第一有机溶剂为四氢呋喃与酮类溶剂以1∶3-3∶1重量比例组成的混合溶剂；
优选所述第一有机溶剂为四氢呋喃与酮类溶剂以1∶2-2∶1重量比例组成的混合溶剂。
A6、根据项目A1所述的方法，其特征在于，步骤(1)中废塑料在废塑料溶解脱氯单元，在50-100℃温度下，在第一有机溶剂中充分溶解，废塑料的停留时间为30-60min。
A7、根据项目A1所述的方法，其特征在于，设置第一溶剂回收单元，步骤(1)所得含氯溶液进入第一溶剂回收单元，经析出处理和分离后，得到PVC和/或PS颗粒和回收的第一有机溶剂；
所述析出处理选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合。
A8、根据项目A7所述的方法，其特征在于，第一溶剂回收单元中，析出处理采用反萃取耦合蒸馏的方式，反萃取剂为水，反萃取的温度为70-100℃，蒸馏温度为80-100℃。
A9、根据项目A1所述的方法，其特征在于，废塑料预处理单元的处理条件为：温度为250-410℃，压力为0.1-5MPa，废塑料的停留时间为10-60min。
A10、根据项目A9所述的方法，其特征在于，废塑料预处理单元的处理条件为：温度为320-390℃，压力为0.5-4.0MPa，废塑料的停留时间为15-45min。
A11、根据项目A1所述的方法，其特征在于，溶剂油的馏程范围为80-550℃，溶剂油具有高于50质量％的总芳烃含量和高于20质量％的单环芳烃含量；溶剂油与废塑料的重量比例为1∶10至10∶1。
A12、根据项目A11所述的方法，其特征在于，溶剂油中单环芳烃含量高于40质量％；
溶剂油与废塑料的重量比例为1∶1至7∶1。
A13、根据项目A1所述的方法，其特征在于，预处理剂的粒径范围为75-150μm；预处理剂与废塑料的重量比例为1∶10至2∶1，优选为1∶7至1∶5。
A14、根据项目A1或A13所述的方法，其特征在于，所述预处理剂为废催化裂化催化剂、腐殖土、活性炭中的一种或多种，以及任选的碱性氧化物。
A15、根据项目A1所述的方法，其特征在于，固液分离单元的操作温度为250-410℃；
所述脱杂质含塑溶液具有小于3μg/g的金属含量、小于1μg/g的氯含量和小于1μg/g的硅含量。
A16、根据项目A1所述的方法，其特征在于，还包括步骤(3)：
(3)步骤(2)所得不溶物进入抽提单元，与第二有机溶剂接触进行溶剂抽提，所得产物经固液分离后，得到固相物料和液相物料，
所得固相物料在预处理剂回收单元经处理后，至少部分作为循环预处理剂返回步骤(2)的废塑料预处理单元；
所得液相物料在第二溶剂回收单元，进行析出处理和分离，得到固体塑料颗粒和回收的第二有机溶剂；
所述第二有机溶剂选自苯、甲苯、三氯甲烷、环己酮、乙酸乙酯、乙酸丁酯、二硫化碳、四氢呋喃、汽油，或者它们的组合。
A17、根据项目A16所述的方法，其特征在于，预处理剂回收单元包括筛分、再生处理方式中的一种或多种。
A18、根据项目A16所述的方法，其特征在于，在第二溶剂回收单元中，所述析出处理选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合。
A19、用于项目A1至A18任一方法的系统，包括，任选的废塑料溶解脱氯单元、废塑料预处理单元、固液分离单元；
所述废塑料溶解脱氯单元设置废塑料入口、第一有机溶剂入口、含氯溶液出口和脱氯废塑料出口；
所述废塑料预处理单元设置废塑料入口、任选的脱氯废塑料入口、预处理剂入口、溶剂油入口和预处理后物料出口，预处理后物料出口与固液分离单元的入口连通，固液分离单元设置不溶物出口和脱杂质含塑溶液出口。
A20、根据项目A19所述的系统，其特征在于，还设置第一溶剂回收单元，所述第一溶剂回收单元设置含氯溶液入口，PVC和/或PS颗粒出口、回收的第一有机溶剂出口；废塑料溶解脱氯单元的含氯溶液出口与第一溶剂回收单元的含氯溶液入口连通。
A21、根据项目A19所述的系统，其特征在于，所述系统还包括抽提单元、预处理剂回收单元、第二溶剂回收单元；
所述抽提单元设置不溶物入口、第二有机溶剂入口、固相物料出口、液相物料出口，固液分离单元的不溶物出口与抽提单元的不溶物入口连通；
预处理剂回收单元设置固相物料入口，循环预处理剂出口，抽提单元的固相物料出口与预处理剂回收单元的固相物料入口连通，预处理剂回收单元的循环预处理剂出口与废塑料预处理单元的预处理剂入口连通；
第二溶剂回收单元设置液相物料入口，固体塑料颗粒出口和回收的第二有机溶剂出口，抽提单元的液相物料出口与第二溶剂回收单元的液相物料入口连通。
B1、一种废塑料生产车用燃料的方法，包括以下步骤：
(1)废塑料和第一有机溶剂进入废塑料溶解脱氯单元中，在25-120℃温度下，进行充分混合溶解，溶解后物料经脱氯分离单元分离为含氯溶液和脱氯废塑料，所述第一有机溶剂选自四氢呋喃、酮类溶剂、氯化脂肪烃，或者它们的组合；
(2)脱氯废塑料进入废塑料预处理单元，在溶剂油、预处理剂的作用下，在200-450℃温度下进行脱杂质处理，处理后物料经固液分离单元分离为脱杂质含塑溶液和不溶物，所述脱杂质含塑溶液中，氯含量为小于3μg/g，硅含量为小于3μg/g；
(3)脱杂质含塑溶液和任选的催化裂化原料进入催化裂化单元，与催化裂化催化剂接触，进行催化裂化反应，经分离至少得到气体、汽油馏分、柴油馏分。
B2、根据项目B1所述的方法，其特征在于，所述第一有机溶剂为四氢呋喃与酮类溶剂以任意重量比例组成的混合溶剂，所述酮类溶剂选自甲乙酮、甲基异丁基酮、环己酮、异佛尔酮，或者它们的组合；
第一有机溶剂与废塑料的重量比例为1∶10至10∶1。
B3、根据项目B2所述的方法，其特征在于，所述酮类溶剂选自甲乙酮、环己酮中一种或多种；优选为甲乙酮
所述第一有机溶剂为四氢呋喃与酮类溶剂以1∶3-3∶1重量比例组成的混合溶剂。
B4、根据项目B1至B3任一所述的方法，其特征在于，所述第一有机溶剂为四氢呋喃与酮类溶剂以1∶2-2∶1重量比例组成的混合溶剂。
B5、根据项目B1所述的方法，其特征在于，步骤(1)废塑料溶解脱氯单元中，在50-100℃温度下，废塑料在第一有机溶剂中充分混合溶解；优选废塑料的停留时间为30-60min。
B6、根据项目B1所述的方法，其特征在于，所得脱氯废塑料中氯含量为小于20μg/g。
B7、根据项目B1所述的方法，其特征在于，步骤(2)中，溶剂油为富含芳烃馏分油，馏程范围为80-540℃；溶剂油具有高于50质量％的总芳烃含量和高于20质量％的单环芳烃含量；
优选溶剂油中单环芳烃含量高于40质量％。
B8、根据项目B1所述的方法，其特征在于，步骤(2)中，预处理剂选自腐植土、赤泥、炼油装置废催化剂、高岭土、活性炭、半焦、 气化灰渣中的一种或多种；预处理剂的粒径范围为75-150μm。
B9、根据项目B8所述的方法，其特征在于，步骤(2)中，预处理剂选自催化裂化单元废催化裂化催化剂、腐殖土、活性炭中的一种或多种。
B10、根据项目B1所述的方法，其特征在于，步骤(2)中，溶剂油与废塑料的重量比例为1∶10至10∶1；
以废塑料预处理单元内混合物料总重量为基准，所述的预处理剂的重量分数为1％-10％。
B11、根据项目B1所述的方法，其特征在于，步骤(2)中，脱杂质处理的条件为：温度为280-390℃，压力为0.1-5MPa，含氯溶液的停留时间为10-30min。
B12、根据项目B1所述的方法，其特征在于，步骤(3)中，催化裂化催化剂包括沸石、无机氧化物粘结剂和任选的粘土；
以催化剂的总重量计，所述沸石的含量为5-50重量％，无机氧化物的含量为5-90重量％，粘土的含量为0-70重量％；
所述沸石选自含或不含稀土的Y型或HY型沸石、含或不含稀土的超稳Y型沸石、具有MFI结构的沸石，或者它们的组合。
B13、根据项目1B1所述的方法，其特征在于，步骤(3)中，催化裂化反应条件为：反应温度460-530℃，剂油比5-10，停留时间2-4s。
B14、根据项目B1所述的方法，其特征在于，所述废塑料选自新鲜生活垃圾中的废塑料、工农业生产中的废塑料、陈化垃圾中的废塑料，或者它们的组合，废塑料的种类为PE、PP、PS和PVC中的任意一种或多种。
B15、根据项目B1所述的方法，其特征在于，废塑料在进入废塑料溶解脱氯单元前进行清洗、干燥和破碎，破碎后的废塑料粒度为1-200mm，优选为1-50mm。
B16、根据项目B1至B15任一所述的方法，其特征在于，步骤(1)中设置溶剂回收单元，含氯溶液进入溶剂回收单元，经选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合后，得到回收的第一有机溶剂和含氯塑料颗粒。
B17、根据项目B16所述的方法，其特征在于，步骤(1)溶剂回收单元采用反萃取耦合蒸馏的方式，反萃取剂为水，反萃取的温度为 70-100℃，蒸馏温度为80-100℃。
B18、用于项目B1至B15任一方法的废塑料生产车用燃料系统，包括：废塑料溶解脱氯单元、废塑料预处理单元和催化裂化单元；
所述废塑料溶解脱氯单元设置废塑料入口、第一有机溶剂入口、物料出口、搅拌装置、加热装置，所述废塑料溶解脱氯单元的物料出口与脱氯分离单元连通，所述脱氯分离单元设置含氯溶液出口和脱氯废塑料出口；
所述废塑料预处理单元设置脱氯废塑料入口、溶剂油入口、预处理剂入口、物料出口、搅拌装置、加热装置，所述脱氯分离单元的脱氯废塑料出口与废塑料预处理单元的脱氯废塑料入口连通；所述废塑料预处理单元的物料出口与固液分离单元连通，所述固液分离单元设置脱杂质含塑溶液出口和不溶物出口；
所述催化裂化单元设置脱杂质含塑溶液入口、任选的催化裂化原料入口、气体出口、汽油馏分出口、柴油馏分出口，所述固液分离单元设置脱杂质含塑溶液出口与催化裂化单元设置脱杂质含塑溶液入口连通。
B19、用于项目B16方法的废塑料生产车用燃料系统，包括：废塑料溶解脱氯单元、溶剂回收单元、废塑料预处理单元、催化裂化单元；
所述废塑料溶解脱氯单元设置废塑料入口、第一有机溶剂入口、物料出口、搅拌装置、加热装置，所述废塑料溶解脱氯单元的物料出口与脱氯分离单元连通，所述脱氯分离单元设置含氯溶液出口和脱氯废塑料出口；
所述溶剂回收单元设置含氯溶液入口、回收第一有机溶剂出口、含氯塑料颗粒出口，脱氯分离单元的含氯溶液出口与溶剂回收单元的含氯溶液入口连通，溶剂回收单元的回收第一有机溶剂出口与废塑料溶解脱氯单元的第一有机溶剂入口连通；
所述废塑料预处理单元设置脱氯废塑料入口、溶剂油入口、预处理剂入口、物料出口、搅拌装置、加热装置，所述脱氯分离单元的脱氯废塑料出口与废塑料预处理单元的脱氯废塑料入口连通；所述废塑料预处理单元的物料出口与固液分离单元连通，所述固液分离单元设置脱杂质含塑溶液出口和不溶物出口；
所述催化裂化单元设置脱杂质含塑溶液入口、任选的催化裂化原 料入口、气体出口、汽油馏分出口、柴油馏分出口，所述固液分离单元设置脱杂质含塑溶液出口与催化裂化单元设置脱杂质含塑溶液入口连通。
实施例
下面结合实施例对本申请作进一步的说明，但并不因此而使本申请受到任何限制。
在以下实施例中，固体物料中的氯含量采用库仑法进行测定，具体方法可参照RIPP 64-90的标准方法(参见《石油化工分析方法》(RIPP试验方法)杨翠定等编，科学出版社，1990年出版，164-167页，“电量法测定原油中总氯含量”)。所用仪器为Thermo Fisher ECS300型微库仑分析仪，试样为冷冻粉碎后的废塑料粉末样品。
在以下实施例中，液体物料中的氯含量同样采用RIPP 64-90的方法进行测定，所不同的是试样为液体混合物。
在以下实施例中，液体物料中的硅含量及金属含量根据GB17476-1998，《使用过的润滑油中添加剂元素、磨损金属和污染物以及基础油中某些元素测定法(电感耦合等离子体发射光谱法)》，进行测定。
在以下实施例中，如无明确说明，废塑料的破碎采用剪切式破碎机进行，滤网孔径为50mm。
实施例I和对比例I系列中所用的废塑料原料如下：
废塑料A1为山东省某地区温室大棚棚膜、地膜等，经清洗、干燥后破碎，所得废塑料A1中灰分为4.3％，水分为0.5％，主要塑料组分为PE和少量EVA，还含有微量其它无法分离的PP、PS等材料，平均总氯含量约为850ppm；
废塑料B1为江苏省某造纸厂垃圾中分选出的废塑料，经清洗、深度干燥后破碎，所得废塑料B1中灰分为9.5％，水分为0，废塑料主要成分为PE、PP，还含有少量的PVC、PET、PS等，平均氯含量为2.2％；
废塑料C为广东某垃圾填埋场挖掘出的陈化垃圾中的废塑料，经清洗、深度干燥后破碎，所得废塑料C中灰分为7.3％，水分为0，该废塑料为包含PE、PP、PS、PET及PVC在内的混合废塑料，氯含量 为1.9％；以及
废塑料D为江西赣州某垃圾填埋场挖掘出的废塑料，经清洗、深度干燥后破碎，所得废塑料D中灰分为11.9％，水分为0.5％，氯含量为2.2％，废塑料主要成分为包含PE、PP、PS、PET及PVC在内的混合废塑料。
实施例I-1
将破碎后的废塑料A1通过螺旋进料器送往废塑料预处理单元，废塑预处理单元采用外热式溶解釜，与预处理剂、溶剂油混合后，在350℃、1.5MPa下进行脱杂质处理，废塑料A1的停留时间为30min。处理后物料经固液分离单元分离为不溶物和脱杂质含塑溶液，所得脱杂质含塑溶液中的塑料组分主要为PE、PP(EVA发生分解，进入溶剂油)，浓度为14.4％，其硅含量为＜1μg/g，氯含量为6μg/g，总金属含量为5.5μg/g。将不溶物送至抽提单元，与四氢呋喃接触进行溶剂抽提，所得产物经分离后，得到固相物料和液相物料，所得固相物料在预处理剂回收单元经处理后，部分作为循环预处理剂返回废塑料预处理单元。液相物料在第二溶剂回收单元，与反萃取剂接触进行反萃取处理，所得固液混合物经过过滤，得到固体塑料颗粒和混合液，所得的混合液经精馏分别回收四氢呋喃和反萃取剂以循环使用。
采用的溶剂油为催化裂化轻循环油，其馏程范围为195-355℃，总芳烃含量为73质量％，单环芳烃含量为52质量％；溶剂油与废塑料的重量比例为5∶1。
采用的预处理剂为炼厂提供的废FCC平衡剂，粒径为75-150μm，其SiO 2含量为38.1％，主要金属组分含量如下：Al 2O 3 50.5％；Fe 2O 3 1.31％；NiO 1.8％；La 2O 3 3.3％；CeO 2 1.4％；预处理剂与废塑料的重量比例为1∶9。
采用的反萃取剂为水，用量为液相物料的3倍，反萃取温度为常温。
实施例I-2
将破碎后的废塑料B1通过螺旋进料器送往废塑料预处理单元，废塑预处理单元采用外热式溶解釜，与预处理剂、溶剂油混合后，在300 ℃、1.2MPa下进行脱杂质处理，废塑料B1的停留时间为40min。处理后物料经固液分离单元分离为不溶物和脱杂质含塑溶液，所得脱杂质含塑溶液中的塑料组分为PE和PP，浓度为14.2％，其硅含量为＜1μg/g，氯含量为18μg/g，总金属含量为7.9μg/g。将不溶物送至抽提单元，与四氢呋喃接触进行溶剂抽提，所得产物经分离后，得到固相物料和液相物料，所得固相物料在预处理剂回收单元经处理后，部分作为循环预处理剂返回废塑料预处理单元。液相物料在溶剂回收单元，与反萃取剂水接触进行反萃取处理，所得固液混合物经过过滤，得到固体塑料颗粒和混合液，所得的混合液经精馏分别回收四氢呋喃和反萃取剂以循环使用。
采用的溶剂油为催化裂化轻循环油，其馏程范围为195-355℃，总芳烃含量为73质量％，单环芳烃含量为52质量％；溶剂油与废塑料的重量比例为5∶1。
采用的预处理剂为筛分后的腐殖土与CaO的混合物，其中腐殖土经过筛分，除去其中有机质，取粒径75-150μm的部分作为预处理剂；块状氧化钙破碎后筛分，取相同粒度样品与腐殖土按比例混配，两者的质量比为8∶2；预处理剂与废塑料的重量比例为1∶7。
实施例I-3
将破碎后的废塑料B1通过螺旋进料器送往废塑料预处理单元，废塑预处理单元采用外热式溶解釜，与预处理剂、溶剂油混合后，在350℃、1.8MPa下进行脱杂质处理，废塑料B1的停留时间为45min。处理后物料经固液分离单元分离为不溶物和脱杂质含塑溶液，所得脱杂质含塑溶液中的塑料组分为PE和PP，浓度为14.2％，其硅含量为小于1μg/g，氯含量为10μg/g，总金属含量为3.8μg/g。
采用的溶剂油为炼厂VGO，其馏程范围为275-581℃，总芳烃含量为45.1质量％，单环芳烃含量为21质量％；溶剂油与废塑料的重量比例为5∶1。
采用的预处理剂为煤基活性炭与Fe 2O 3的混合物，两者的质量比为9∶1，粒径为75-150μm。预处理剂与废塑料的重量比例为1∶8。
实施例I-4
将破碎后的废塑料B1通过螺旋进料器送往废塑料预处理单元，废塑预处理单元采用外热式溶解釜，与预处理剂、溶剂油混合后，在350℃、1.8MPa下进行脱杂质处理，废塑料B1的停留时间为30min。处理后物料经固液分离单元分离为不溶物和脱杂质含塑溶液，所得脱杂质含塑溶液中的塑料组分为PE和PP，浓度为14.2％，其硅含量为小于1μg/g，氯含量为11μg/g，总金属含量为4.1μg/g。
采用的溶剂油为催化裂化轻循环油，其馏程范围为156-338℃，总芳烃含量为76.8质量％，单环芳烃含量为63.8质量％；溶剂油与废塑料的重量比例为5∶1。
采用的预处理剂为煤基活性炭与Fe 2O 3的混合物，两者的质量比为9∶1，粒径为75-150μm。预处理剂与废塑料的重量比例为1∶8。
对比例I-1
本对比例与实施例I-4的废塑料原料、溶剂油、脱杂质处理条件都相同，不同的是本对比例中不采用任何预处理剂。处理后物料经固液分离单元分离为不溶物和脱杂质含塑溶液，所得脱杂质含塑溶液中的塑料组分为PE和PP，浓度为14.2％，其硅含量为42μg/g，氯含量为207μg/g，总金属含量为13μg/g。
本对比例所得脱杂质含塑溶液中杂质含量过高，不能直接作为后续加工单元的进料。
实施例I-5至I-9
将破碎后的废塑料C预热至60℃，送入废塑料溶解脱氯单元的废塑料溶解脱氯装置中，在60℃温度下，在第一有机溶剂中溶解，废塑料C在废塑料溶解脱氯装置内的停留时间为30min，溶解后物料经螺旋挤压脱溶剂设备，分离为含氯溶液和脱氯废塑料，脱氯废塑料进一步在略高于第一有机溶剂沸点的温度下进行干燥，回收溶剂。
实施例I-5所用第一有机溶剂为四氢呋喃，有机溶剂与废塑料C的重量比例为10∶1；所得脱氯废塑料中氯含量为23μg/g。
实施例I-6所用第一有机溶剂为甲乙酮，有机溶剂与废塑料C的重量比例为10∶1；所得脱氯废塑料中氯含量为20μg/g。
实施例I-7所用第一有机溶剂为环己酮，有机溶剂与废塑料C的重 量比例为10∶1；所得脱氯废塑料中氯含量为25μg/g。
实施例I-8所用第一有机溶剂为四氢呋喃与甲乙酮的重量比为1∶1的混合物，有机溶剂与废塑料C的重量比例为10∶1；所得脱氯废塑料中氯含量为17μg/g。
实施例I-9所用第一有机溶剂为四氢呋喃与甲乙酮的重量比为1∶2的混合物，有机溶剂与废塑料C的重量比例为10∶1；所得脱氯废塑料中氯含量为19μg/g。
实施例I-10
参照实施例I-5进行试验，不同之处在于：所用第一有机溶剂为氯苯，溶解温度为80℃，且脱氯废塑料的干燥温度为140℃。所得脱氯废塑料中氯含量为32μg/g。
实施例I-11
破碎后的废塑料D以10kg/h的流量送往废塑料溶解脱氯单元的连续废塑料溶解脱氯装置；预热至60℃的THF∶MEK＝1∶1第一有机溶剂以100kg/h的流量送往连续废塑料溶解脱氯装置，调整废塑料溶解脱氯装置中螺旋桨转速，使停留时间为60min。混合液送往螺旋挤压脱溶剂设备，在60℃下分离为脱氯废塑料和含氯溶液。
含氯溶液送往80℃的反萃取装置中用热水进行反萃取，混合物送往板框压滤机分离出PVC和PS，溶剂则送往分馏系统分馏回收第一有机溶剂和水循环使用。
脱氯废塑料通过螺旋进料器送往带搅拌的釜式废塑料预处理单元，以80kg/h的预热至350℃的催化裂化轻循环油为溶剂油、2kg/h的FCC平衡剂为预处理剂一并送往废塑料预处理单元在350℃、1.5MPa下处理35分钟后，后送往螺旋挤压脱溶剂装置，得到含油的不溶物和脱杂质含塑溶液。所得脱杂质含塑溶液中的塑料组分主要为PE和PP，其浓度为9.7％，硅含量为2.3μg/g，氯含量为2.8μg/g，总金属含量为1.8μg/g。
将所得含油的不溶物送至抽提单元，与甲苯接触进行溶剂抽提，所得产物经分离后，得到固相物料和液相物料，所得固相物料在预处理剂回收单元经处理后，部分作为循环预处理剂返回废塑料预处理装置。液相物料在溶剂回收单元，进行精馏处理，分别得到固体塑料颗 粒(PS)和回收的甲苯和少量粘附的溶剂油。
实施例II和对比例II系列中所用的废塑料原料如下：
废塑料A2为按重量比PE∶PP∶PS∶PVC＝10∶5∶1∶1.5比例混配的混合物，氯含量0.88％，其中PE、PP、PVC为薄膜状，PS为泡沫状。
废塑料B2为广东省某垃圾填埋场挖出陈化垃圾中分选出的废塑料，为包含PE、PP，以及少量PS、PET和PVC的混合废塑料，分选后的废塑料基本无水分存在，灰分含量约为9.9重量％，总氯含量为1.18％。
实施例II-1至II-5
破碎后的废塑料A2颗粒和预热至65℃的第一有机溶剂进入废塑料溶解脱氯单元中，在65℃下溶解60min，溶解后物料经高温过滤器，并在65℃下分离为含氯溶液和脱氯废塑料，脱氯废塑料进一步干燥回收溶剂后分析脱氯废塑料中的氯含量。
实施例II-1所用第一有机溶剂为四氢呋喃，第一有机溶剂与废塑料A2的重量比例为10∶1；所得脱氯废塑料中氯含量为23μg/g。
实施例II-2所用第一有机溶剂为甲乙酮，第一有机溶剂与废塑料A2的重量比例为10∶1；所得脱氯废塑料中氯含量为25μg/g。
实施例II-3所用第一有机溶剂为四氢呋喃和环己酮重量比为1∶1的混合物，第一有机溶剂与废塑料A2的重量比例为5∶1；所得脱氯废塑料中氯含量为22μg/g。
实施例II-4所用第一有机溶剂为四氢呋喃与甲乙酮重量比为1∶1的混合物，第一有机溶剂与废塑料A2的重量比例为10∶1；所得脱氯废塑料中氯含量为13μg/g。
实施例II-5所用有机溶剂为四氢呋喃与甲乙酮重量比为1∶2的混合物，第一有机溶剂与废塑料A2的重量比例为10∶1；所得脱氯废塑料中氯含量为19μg/g。
实施例II-6
将实施例II-5所得脱氯废塑料送至废塑料预处理单元，在溶剂油、预处理剂的作用下，在350℃、1.5MPa下溶解30min进行脱杂质处理，处理后物料经高温过滤器，分离为脱杂质含塑溶液和不溶物，所得脱 杂质含塑溶液中的塑料组分为PE和PP，其浓度为16.1％，氯含量为2.7μg/g，硅含量为3.0μg/g，总金属含量为2.1μg/g。
采用的溶剂油为富含芳烃的馏分油，是石油加工过程中所得蜡油馏分的混合油，其馏程范围为220-540℃，总芳烃含量为59.6质量％，单环芳烃含量为21质量％；溶剂油与脱氯废塑料的重量比例为5∶1。
采用的预处理剂为半焦，粒径为75-100μm。以废塑料预处理单元内混合物料总重量为基准，所述的预处理剂的重量分数为2.5％。
实施例II-7
将实施例II-5所得脱氯废塑料送至废塑料预处理单元，在溶剂油、预处理剂的作用下，在350℃、1.5MPa下溶解30min进行脱杂质处理，处理后物料经高温过滤器，分离为脱杂质含塑溶液和不溶物，所得脱杂质含塑溶液中的塑料组分为PE和PP，其浓度为16.1％，氯含量为2.5μg/g，硅含量为2.2μg/g，总金属含量为1.2μg/g。
采用的溶剂油为催化裂化馏分油，其馏程范围为150-338℃，总芳烃含量为76.8质量％，单环芳烃含量为63.8质量％；溶剂油与脱氯废塑料的重量比例为5∶1。
采用的预处理剂为腐殖土，粒径为75-100μm。以废塑料预处理单元内混合物料总重量为基准，所述的预处理剂的重量分数为2.5％。
实施例II-8
将实施例II-5所得脱氯废塑料送至废塑料预处理单元，在溶剂油、预处理剂的作用下，在350℃、1.5MPa下溶解30min进行脱杂质处理，处理后物料经高温过滤器，分离为脱杂质含塑溶液和不溶物，所得脱杂质含塑溶液中的塑料组分为PE和PP，其浓度为15.9％，氯含量为2.5μg/g，硅含量为2.5μg/g，总金属含量为1.3μg/g。
采用的溶剂油为富含芳烃馏分油，其馏程范围为138-362℃，总芳烃含量为90.9质量％，单环芳烃含量为26.8质量％；溶剂油与脱氯废塑料的重量比例为5∶1。
采用的预处理剂为气化灰渣与FCC平衡剂以重量比为1∶1混合的混合物，粒径为75-100μm。以废塑料预处理单元内混合物料总重量为基准，所述的预处理剂的重量分数为2.5％。
实施例II-9
将实施例II-5所得脱氯废塑料送至废塑料预处理单元，在溶剂油、预处理剂的作用下，在350℃、1.5MPa下溶解30min进行脱杂质处理，处理后物料经高温过滤器，分离为脱杂质含塑溶液和不溶物，所述脱杂质含塑溶液中的塑料组分为PE和PP，其浓度为16.1％，氯含量为2.5μg/g，硅含量为2.8μg/g，总金属含量为1.9μg/g。
采用的溶剂油为富含芳烃馏分油，其馏程范围为138-362℃，总芳烃含量为90.9质量％，单环芳烃含量为26.8质量％；溶剂油与脱氯废塑料的重量比例为5∶1。
采用的预处理剂为FCC平衡剂，粒径为75-100μm。以废塑料预处理单元内混合物料总重量为基准，所述的预处理剂的重量分数为2.5％。
实施例II-10
将实施例II-6所得脱杂质含塑溶液送至提升管催化裂化单元，与催化裂化催化剂接触，进行催化裂化反应，经分离得到气体、汽油馏分、柴油馏分、重循环油、油浆，所得重循环油在催化裂化单元内进行循环。
催化裂化催化剂牌号为GOR-Q，是中国石化催化剂分公司生产。该催化剂剂平衡剂的性质如下：比表面积：≥240m 2/g；堆密度：＞0.68g/ml；孔体积：＞0.34ml/g；耐磨强度：≤2.8％/h；800℃，4h的微反活性≥76％；平均粒径70-75μm；Al 2O 3≥46％；Re 2O 3≥3％
催化裂化反应条件包括温度为500℃，压力为0.15MPa，剂油比为4，反应时间为2.02s。
所得产品产率如表1所示。由于有机硅分解产物主要为八甲基环四硅氧烷和十甲基环五硅氧烷，主要集中在汽油馏分中，因此重点分析汽油馏分中的杂质含量。
实施例II-11
将实施例II-7所得脱杂质含塑溶液和催化裂化原料VGO一起送至提升管催化裂化单元，脱杂质含塑溶液与VGO的重量比为1∶1，与催化裂化催化剂接触，进行催化裂化反应，经分离得到气体、汽油馏分、 柴油馏分、重循环油和油浆，所得重循环油在催化裂化单元内进行循环。
催化裂化催化剂牌号为GOR-Q，催化裂化反应条件包括温度为500℃，压力为0.15MPa，剂油比为4，反应时间为2.02s。
所得产品产率如表1所示。
表1实施例的反应结果
Figure PCTCN2021103336-appb-000001
实施例II-12
废塑料B2通过传送带送入间歇换热式干燥器中，所用热源为低阶蒸汽，干燥器温度为105℃，废塑料在干燥器中的停留时间为30min；干燥后的废塑料通过传送带送往剪切式破碎机，滤网孔径为10mm。通过螺旋进料器将破碎的废塑料送至废塑料溶解脱氯单元的外热式釜式溶解釜中，通过计量泵将甲乙酮∶四氢呋喃＝2∶1的混合溶剂以废塑料/溶剂重量比1∶5的比例，一并送往所述外热式釜式溶解釜，溶解釜溶解温度为65℃，操作压力为常压，搅拌桨转速为60r/min，废塑料B2在溶解釜内溶解30min后更换新鲜溶剂溶解一次，合计溶解三次，共计90min。溶解釜采用两釜并联的方式；混合物通过溶解釜底部的卸料口送往高温过滤器，在65℃下将混合物分离为脱氯废塑料及含氯溶液。含氯溶液通过闪蒸回收第一有机溶剂和含氯废塑料。
脱氯废塑料在80℃下干燥进一步回收第一有机溶剂后通过螺旋进料器输送至废塑料预处理单元的外热式釜式溶解釜，通过计量泵将溶剂油以废塑料/溶剂油重量比1∶10的比例送往所述外热式釜式溶解釜，通过计量泵将废FCC平衡剂按预处理剂/废塑料重量比1∶10的比例送往所述外热式釜式溶解釜，脱杂质处理温度为390℃，操作压力为0.5MPa，搅拌桨转速为60r/min，脱氯废塑料在溶解釜内停留时间为30min，溶解釜采用两釜并联的方式；处理后所得混合物通过溶解釜底部的卸料口送往高温过滤器，在350℃下过滤脱除其中不溶杂质得到脱杂质含塑溶液。所述脱杂质含塑溶液中的塑料组分主要为PE和PP两类，浓度约为8.7％，其中氯含量为2.2μg/g，硅含量为1.7μg/g，总金属含量为3.6μg/g。
利用单螺杆泵将脱杂质含塑溶液送往提升管催化裂化单元，与催化裂化催化剂接触，进行催化裂化反应，经分离得到气体、汽油馏分、柴油馏分、油浆和半焦。
溶剂油为催化裂化馏分油，其馏程范围为150-338℃，总芳烃含量为76.8质量％，单环芳烃含量为63.8质量％。
催化裂化催化剂牌号为GOR-Q，催化裂化反应条件包括温度为500℃，压力为0.15MPa，剂油比为4，反应时间为2.02s。
所得产品产率及部分杂质含量如表2所示。
实施例II-13
所用废塑料B2原料，废塑料溶解脱氯单元的第一有机溶剂和处理条件，废塑料预处理单元的溶剂油、预处理剂和处理条件，催化裂化单元的催化剂与反应条件均与实施例II-12相同，所不同的是：进入催化裂化单元的进料是脱杂质含塑溶液与催化裂化原料胜利VGO重量比为1∶1的混合原料，所用催化裂化单元为常规循环流化床装置。
本实施例中，失活的催化剂在再生装置中再生，并且以维持装置稳定运转时处理1t原料油所需的催化剂置换量为指标，本实施例中催化裂化催化剂置换量为1.2kg/t。
所得产品产率及部分杂质含量如表2所示。
对比例II-1
采用胜利VGO在催化裂化单元进行反应，催化裂化单元的催化剂与反应条件均与实施例II-12相同。所得产品产率及部分杂质含量如表2所示。
对比例II-2
所用的废塑料B2原料，废塑料溶解脱氯单元的第一有机溶剂和处理条件，废塑料预处理单元的溶剂油和处理条件，催化裂化单元的进料、催化剂与反应条件均与实施例II-13相同，所不同的是：废塑料预处理单元未使用预处理剂。
本对比例中催化裂化催化剂置换量为1.22kg/t。
所得产品产率及部分杂质含量如表2所示。
表2实施例和对比例的反应结果
Figure PCTCN2021103336-appb-000002
由表2所示的结果可以发现，本申请的方法和系统可以大幅降低所得油品中有害元素的相对含量，获得合格的成品油。需说明的是，由于VGO中添加了部分塑料，导致FCC单元的干气、液化气和焦炭产率略有增加，而汽、柴油收率略有降低。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (16)

  1. 一种废塑料的预处理方法，包括以下步骤：
    1)使废塑料与预处理剂和溶剂油接触进行脱杂质处理，所述预处理剂选自腐殖土、赤泥、炼油装置废催化剂、高岭土、半焦、活性炭、气化灰渣，或者它们的组合，优选选自废催化裂化催化剂、腐殖土、活性炭，或者它们的组合，并且任选包含碱性氧化物；以及
    2)对步骤1)的流出物进行固液分离，得到不溶物和脱杂质含塑溶液，优选地所述脱杂质含塑溶液具有小于5μg/g的金属含量、小于20μg/g的氯含量和小于3μg/g的硅含量。
  2. 根据权利要求1所述的方法，具有以下特征中的一个或多个：
    步骤1)的处理条件包括：处理温度为250-410℃，优选320-390℃；压力为0.1-5MPa，优选0.5-4.0MPa；处理时间为10-60min，优选15-45min；
    步骤1)所用溶剂油的馏程范围为80-550℃，所述溶剂油具有高于50质量％的总芳烃含量和高于20质量％、优选高于40质量％的单环芳烃含量；
    步骤1)中所述溶剂油与废塑料的重量比例为1∶10至10∶1，优选为1∶1至7∶1；
    步骤1)中所用预处理剂的粒径范围为75-150μm；
    步骤1)中所述预处理剂与废塑料的重量比例为1∶10至2∶1，优选为1∶7至1∶5；以及
    步骤1)所用的废塑料预先经过清洗、干燥和破碎，破碎后的废塑料粒度为1-200mm，优选为1-50mm。
  3. 根据在先权利要求中任一项所述的方法，其中步骤2)的固液分离的操作温度为250-410℃；所述脱杂质含塑溶液具有小于3μg/g的金属含量、小于1μg/g的氯含量和小于1μg/g的硅含量。
  4. 根据在先权利要求中任一项所述的方法，其中步骤1)中所用的废塑料的至少一部分经过脱氯处理，所述脱氯处理包括如下步骤：
    i)用第一有机溶剂对废塑料进行溶解，所述第一有机溶剂选自四氢呋喃、酮类溶剂、氯化脂肪烃，或者它们的组合；以及
    ii)对步骤i)所得的混合物进行固液分离，得到含氯溶液和脱氯 废塑料。
  5. 根据权利要求4所述的方法，具有以下特征中的一个或多个：
    步骤i)中在50-100℃温度下使废塑料在第一有机溶剂中溶解30-60min；
    步骤i)中所用第一有机溶剂为四氢呋喃与酮类溶剂以任意重量比例组成的混合溶剂，优选地所述第一有机溶剂为四氢呋喃与酮类溶剂以1∶3至3∶1、更优选1∶2至2∶1的重量比例组成的混合溶剂，其中所述酮类溶剂选自甲乙酮、甲基异丁基酮、环己酮、异佛尔酮，或者它们的组合，优选选自甲乙酮、环己酮或者它们的组合，更优选为甲乙酮；以及
    步骤i)中所用第一有机溶剂与废塑料的重量比例为1∶10至10∶1。
  6. 根据权利要求4或5所述的方法，其中所述脱氯处理还包括如下步骤：
    iii)对步骤ii)所得的含氯溶液进行析出处理和分离，得到塑料颗粒以及回收的第一有机溶剂，所述析出处理选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合；
    优选地，所述析出处理采用反萃取耦合蒸馏的方式，反萃取剂为水，反萃取的温度为70-100℃，蒸馏温度为80-100℃。
  7. 根据在先权利要求中任一项所述的方法，还包括如下步骤：
    3)使步骤2)所得的不溶物与第二有机溶剂接触进行溶剂抽提，所得产物经固液分离得到固相物料和液相物料，所述第二有机溶剂选自苯、甲苯、三氯甲烷、环己酮、乙酸乙酯、乙酸丁酯、二硫化碳、四氢呋喃、汽油，或者它们的组合；
    4)对步骤3)所得的固相物料进行处理以回收预处理剂，并将所回收的预处理剂的至少一部分再循环到步骤1)中，所述处理选自筛分、再生，或者它们的组合；以及
    5)对步骤3)所得的液相物料进行析出处理和分离，得到固体塑料颗粒和回收的第二有机溶剂，所述析出处理选自反萃取、简单蒸馏、闪蒸、精馏，或者它们的组合。
  8. 根据在先权利要求中任一项所述的方法，其中所述废塑料选自新鲜生活垃圾中的废塑料、工农业生产中的废塑料、陈化垃圾中的废塑料，或者它们的组合，所述废塑料包含聚乙烯(PE)、聚丙烯(PP)、 聚苯乙烯(PS)和聚氯乙烯(PVC)塑料中的一种或多种。
  9. 用于实施权利要求1-8中任一项所述的废塑料预处理方法的废塑料预处理系统，包括废塑料预处理单元和固液分离单元，
    所述废塑料预处理单元设置有废塑料入口、任选的脱氯废塑料入口、预处理剂入口、溶剂油入口和预处理后物料出口，
    所述固液分离单元设置有入口、不溶物出口和脱杂质含塑溶液出口，
    所述废塑料预处理单元的预处理后物料出口与所述固液分离单元的入口连通。
  10. 根据权利要求9所述的系统，还包括废塑料溶解脱氯单元和脱氯分离单元，
    所述废塑料溶解脱氯单元设置有废塑料入口、第一有机溶剂入口和溶解后物料出口，
    所述脱氯分离单元设置有入口、含氯溶液出口和脱氯废塑料出口，
    所述废塑料溶解脱氯单元的溶解后物料出口与所述脱氯分离单元的入口连通，且所述脱氯分离单元的脱氯废塑料出口与所述废塑料预处理单元的脱氯废塑料入口连通。
  11. 根据权利要求10所述的系统，还包括第一溶剂回收单元，所述第一溶剂回收单元设置有含氯溶液入口，塑料颗粒出口、回收的第一有机溶剂出口，所述脱氯分离单元的含氯溶液出口与第一溶剂回收单元的含氯溶液入口连通。
  12. 根据权利要求9-11中任一项所述的系统，还包括抽提单元、预处理剂回收单元和第二溶剂回收单元；
    所述抽提单元设置有不溶物入口、第二有机溶剂入口、固相物料出口、液相物料出口，所述固液分离单元的不溶物出口与抽提单元的不溶物入口连通；
    预处理剂回收单元设置有固相物料入口，循环预处理剂出口，抽提单元的固相物料出口与预处理剂回收单元的固相物料入口连通，预处理剂回收单元的循环预处理剂出口与废塑料预处理单元的预处理剂入口连通；
    第二溶剂回收单元设置有液相物料入口，固体塑料颗粒出口和回收的第二有机溶剂出口，抽提单元的液相物料出口与第二溶剂回收单 元的液相物料入口连通。
  13. 一种废塑料生产车用燃料的方法，包括以下步骤：
    I)采用权利要求1-8中任一项所述的方法或者权利要求9-12中任一项所述的废塑料预处理系统对所述废塑料进行预处理，得到脱杂质含塑溶液；
    II)使所述脱杂质含塑溶液和任选的催化裂化原料与催化裂化催化剂接触反应；以及
    III)分离步骤II)的反应产物，得到汽油馏分和/或柴油馏分。
  14. 根据权利要求13所述的方法，其中步骤II)中所用的催化裂化催化剂包括沸石、无机氧化物粘结剂和任选的粘土；
    以催化剂的总重量计，所述催化裂化催化剂中沸石的含量为5-50重量％，无机氧化物的含量为5-90重量％，粘土的含量为0-70重量％；
    所述沸石选自含或不含稀土的Y型或HY型沸石、含或不含稀土的超稳Y型沸石、具有MFI结构的沸石，或者它们的组合。
  15. 根据权利要求13或14所述的方法，其中步骤II)中所用的反应条件包括：反应温度460-530℃，反应压力0.1-0.4MPa，剂油比5-10，反应时间2-4s。
  16. 用于实施权利要求13-15中任一项所述的废塑料生产车用燃料的方法的系统，包括权利要求9-12中任一项所述的废塑料预处理系统和催化裂化单元；
    所述催化裂化单元设置有脱杂质含塑溶液入口、任选的催化裂化原料入口和至少一个出口，所述废塑料预处理系统的固液分离单元的脱杂质含塑溶液出口与所述催化裂化单元的脱杂质含塑溶液入口连通。
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