WO2024219930A1 - Procédé et système de fabrication d'hydrocarbures raffinés à partir d'huile de pyrolyse de déchets plastiques - Google Patents

Procédé et système de fabrication d'hydrocarbures raffinés à partir d'huile de pyrolyse de déchets plastiques Download PDF

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Publication number
WO2024219930A1
WO2024219930A1 PCT/KR2024/095677 KR2024095677W WO2024219930A1 WO 2024219930 A1 WO2024219930 A1 WO 2024219930A1 KR 2024095677 W KR2024095677 W KR 2024095677W WO 2024219930 A1 WO2024219930 A1 WO 2024219930A1
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Prior art keywords
waste plastic
pyrolysis oil
oil
plastic pyrolysis
mixture
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PCT/KR2024/095677
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English (en)
Korean (ko)
Inventor
김용운
강서영
강수길
박민규
박영무
신민우
이재환
장진성
조상환
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SK Innovation Co Ltd
SK Geo Centric Co Ltd
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SK Innovation Co Ltd
SK Geo Centric Co Ltd
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Priority claimed from KR1020240037564A external-priority patent/KR20240155091A/ko
Application filed by SK Innovation Co Ltd, SK Geo Centric Co Ltd filed Critical SK Innovation Co Ltd
Publication of WO2024219930A1 publication Critical patent/WO2024219930A1/fr
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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
    • 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
    • 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/02—Dewatering or demulsification of hydrocarbon oils with electrical or magnetic means
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen

Definitions

  • the present invention relates to a method and system for producing purified hydrocarbons from waste plastic pyrolysis oil.
  • Waste plastics are manufactured using petroleum as a raw material, and the recycling rate, such as energy recovery and mechanical recycling, is low, and a significant amount is simply incinerated or landfilled. Since these wastes take a long time to decompose in nature, they contaminate the soil and cause serious environmental pollution.
  • As a method for recycling waste plastics there is a method of converting waste plastics into usable oil by pyrolyzing them, and the oil produced by pyrolyzing waste plastics in this way is called waste plastic pyrolysis oil.
  • waste plastic pyrolysis oil has a high content of impurities such as chlorine, nitrogen, and metals compared to the oil produced from crude oil by a general method, so only a limited amount can be blended into high value-added fuels such as gasoline and diesel.
  • impurities contained in a high content in waste plastic pyrolysis oil can act as poison to the catalyst used in the isomerization process, significantly reducing the efficiency of the process. Therefore, waste plastic pyrolysis oil must go through a purification process to remove the impurities.
  • Known methods for removing impurities such as chlorine, nitrogen, oxygen, and metals contained in waste plastic pyrolysis oil include a method of reacting waste plastic pyrolysis oil with hydrogen in the presence of a hydrogenation catalyst to perform dechlorination/denitrogenation/deoxygenation, or a method of adsorbing and removing chlorine contained in waste plastic pyrolysis oil using a chlorine adsorbent.
  • U.S. Patent Publication No. 3,935,295 discloses a technique for removing chloride contaminants from various hydrocarbon oils.
  • the technique is a conventional technique in which oil is hydrogenated in the presence of a hydrogenation catalyst in a first reactor, a fluid containing hydrogen chloride (HCl) produced in the process and purified oil is introduced into a second reactor, and then the chlorine component contained in the fluid is removed by adsorption using an adsorbent.
  • HCl hydrogen chloride
  • the purpose of the present disclosure is to provide a method and a system for producing purified hydrocarbons from waste plastic pyrolysis oil, which minimizes the production of ammonium salts (NH 4 Cl) in the process of refining waste plastic pyrolysis oil containing impurities including chlorine and nitrogen.
  • NH 4 Cl ammonium salts
  • Another object of the present disclosure is to provide a method and system for producing refined hydrocarbons from waste plastic pyrolysis oil, in which the activity of the catalyst is maintained for a long time, the purification efficiency is excellent, and long-term operation is possible.
  • Another object of the present disclosure is to provide a method and system for producing purified hydrocarbons from waste plastic pyrolysis oil, which can prevent the phenomenon of impurity particles becoming fixed within a reactor.
  • Another object of the present disclosure is to provide a method and a system for producing refined hydrocarbons having excellent quality and a very low content of impurities such as chlorine, nitrogen, oxygen, and metals from waste plastic pyrolysis oil.
  • a method for producing refined hydrocarbons from waste plastic pyrolysis oil including the steps of S1) applying voltage to a first mixture comprising waste plastic pyrolysis oil, wash water, and a demulsifier to dehydrate them; S2) hydrogenating the first mixture dehydrated in step S1) and a second mixture comprising a sulfur source to produce refined oil from which impurities have been removed; and S3) catalytic cracking the refined oil from which impurities have been removed in step S2).
  • the waste plastic pyrolysis oil can be mixed in a larger volume than the wash water.
  • the first mixture may be a mixture of waste plastic pyrolysis oil and washing water in a volume ratio of 1:0.001 to 0.5.
  • the first mixture may be a mixture of waste plastic pyrolysis oil and a demulsifier in a volume ratio of 1:0.000001 to 0.001.
  • the voltage according to an example of the present disclosure may be applied as an alternating current or a combination of alternating current and direct current.
  • the voltage may be applied through a vertical electrode.
  • a method for producing refined hydrocarbons from waste plastic pyrolysis oil according to an example of the present disclosure may further include, in the step S1), a step of removing a rag layer from the first mixture after the voltage is applied.
  • the step S1) can be performed at a temperature of 20° C. to 300° C.
  • the ratio of the moisture content of the waste plastic pyrolysis oil and the moisture content of the first mixture dehydrated in step S1) may be 1:0.0001 to 0.9.
  • the step S1) may further dehydrate the dehydrated first mixture by coagulating the moisture.
  • the second mixture may have a weight ratio of nitrogen to chlorine of 1:1 to 10.
  • the sulfur source according to one example of the present disclosure may include a sulfur-containing oil.
  • the sulfur-containing oil may be included in an amount of less than 0.5 parts by weight based on 100 parts by weight of the first mixture dehydrated in step S1).
  • the sulfur source may include one or more sulfur-containing organic compounds selected from a disulfide compound, a sulfide compound, a sulfonate compound, and a sulfate compound.
  • the hydrogenation treatment according to an example of the present disclosure can be performed in the presence of a molybdenum-based hydrogenation catalyst.
  • the molybdenum-based hydrogenation catalyst according to one example of the present disclosure may be a catalyst in which a molybdenum-based metal or a metal including one or more selected from nickel, cobalt, and tungsten and the molybdenum-based metal are supported on a support.
  • the molybdenum-based hydrogenation catalyst according to one example of the present disclosure may include a molybdenum-based sulfide hydrogenation catalyst.
  • the hydrogenation treatment according to an example of the present disclosure can be performed under pressure conditions of 50 bar to 150 bar.
  • a method for producing refined hydrocarbons from waste plastic pyrolysis oil may further include, after step S2), a step of subjecting a stream containing refined oil from which the impurities have been removed to gas-liquid separation and then washing.
  • the step S3) may be to catalytically decompose the purified oil fraction separated by distillation from the purified oil from which impurities have been removed in the step S2).
  • the step S3) may be to catalytically decompose a mixed oil mixture of refined oil from which impurities have been removed in the step S2) and petroleum hydrocarbons.
  • the method and system for producing refined hydrocarbon according to the present disclosure can minimize the production of ammonium salt (NH 4 Cl) in the process of refining waste plastic pyrolysis oil containing impurities including chlorine and nitrogen.
  • the method and system for producing refined hydrocarbons according to the present disclosure have excellent purification efficiency and enable long-term operation of the process since deactivation of the catalyst used in the process is prevented.
  • the method and system for producing refined hydrocarbon according to the present disclosure can provide refined hydrocarbon having a low content of impurities such as chlorine, nitrogen, oxygen, and metals and being hardened from waste plastic pyrolysis oil.
  • the method and system for producing refined hydrocarbons according to the present disclosure can be used in the production of environmentally friendly refined oil and petrochemical products using waste plastics as raw materials.
  • FIG. 1 is a process diagram of a method for producing purified hydrocarbons from waste plastic pyrolysis oil according to one embodiment of the present disclosure.
  • the numerical range used in this specification includes the lower and upper limits and all values within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of a numerical range defined in different shapes. Unless otherwise specifically defined in the specification of the present invention, values outside the numerical range that may arise due to experimental error or rounding of values are also included in the defined numerical range.
  • reactor used in this specification may mean a device that can be used in processes such as production, refining, separation, and mixing of waste plastic pyrolysis oil.
  • reactor may be interpreted to mean devices such as a dehydrator, a coalescer, a hydrotreating reactor, and a separator used in a process of refining waste plastic pyrolysis oil.
  • vertical electrode as used herein may mean an electrode erected vertically with respect to the ground
  • horizontal electrode may mean an electrode laid horizontally with respect to the ground
  • the method and system for producing refined hydrocarbons from waste plastic pyrolysis oil according to the present disclosure include a dehydration step that involves washing, demulsification, and voltage application, etc., to reduce problems such as catalyst deactivation due to moisture dispersed in the waste plastic pyrolysis oil in an emulsion form, corrosion of a reactor due to chlorine contained in the moisture and low pH of the moisture, and the like.
  • the method includes a hydrogenation treatment step that removes impurities contained in the waste plastic pyrolysis oil through a hydrogenation reaction, and a catalytic decomposition step that catalytically decomposes refined oil from which impurities have been removed through the above steps.
  • the method for producing refined hydrocarbons from waste plastic pyrolysis oil according to the present disclosure can stably produce a light refined hydrocarbon with a low impurity content from waste plastic pyrolysis oil by organically combining the above series of sequential steps.
  • the present disclosure provides a method for producing refined hydrocarbons from waste plastic pyrolysis oil, including the steps of S1) applying voltage to a first mixture comprising waste plastic pyrolysis oil, wash water, and a demulsifier to dehydrate them; S2) hydrogenating a second mixture comprising the first mixture dehydrated in step S1) and a sulfur source to produce refined oil from which impurities have been removed; and S3) catalytic cracking the refined oil from which impurities have been removed.
  • step S1) is a dehydration step in which voltage is applied to a first mixture of waste plastic pyrolysis oil flowing from a feed tank, washing water, and a demulsifier.
  • Waste plastic pyrolysis oil contains moisture, and problems such as deactivation of a hydrogenation catalyst and corrosion of a reactor may occur due to moisture in the pyrolysis oil, and water-soluble impurities are contained in the moisture, so it is necessary to remove moisture.
  • moisture existing in the form of an emulsion in the waste plastic pyrolysis oil can be easily removed.
  • the waste plastic pyrolysis oil may be a hydrocarbon oil mixture produced by pyrolyzing waste plastic, wherein the waste plastic may include solid or liquid waste related to synthetic polymer compounds such as waste synthetic resin, waste synthetic fiber, waste synthetic rubber, and waste vinyl.
  • the hydrocarbon oil mixture according to one embodiment of the present disclosure may include impurities such as chlorine compounds, nitrogen compounds, oxygen compounds, metal compounds, char-derived particles, etc., in addition to hydrocarbon oil, and may include impurities in the form of compounds in which chlorine, nitrogen, oxygen, or metals are combined within the hydrocarbon, and may include hydrocarbons in the form of paraffins, olefins, naphthene, or aromatics.
  • the wash water can serve to increase the probability of contact between waste plastic pyrolysis oil and the water in the form of an emulsion.
  • a basic compound can be added to the wash water so as to remove a water-soluble acidic substance contained in the water, and the basic compound can be sodium hydroxide (NaOH), but is not particularly limited.
  • the waste plastic pyrolysis oil can be mixed in a larger volume than the wash water, and specifically, the first mixed solution can be a mixture of waste plastic pyrolysis oil and wash water in a volume ratio of 1:0.001 to 0.5, more specifically in a volume ratio of 1:0.005 to 0.4, and most specifically in a volume ratio of 1:0.01 to 0.3.
  • the first mixed solution can be a mixture of waste plastic pyrolysis oil and wash water in a volume ratio of 1:0.001 to 0.5, more specifically in a volume ratio of 1:0.005 to 0.4, and most specifically in a volume ratio of 1:0.01 to 0.3.
  • the demulsifier may be one or a mixture of two or more selected from the group consisting of polyethylene glycol, tert-butanol, acetone, alkylnaphthalenesulfonate, alkylbenzenesulfonate, nonionic alkoxylated alkyl phenol resin, polyalkylene oxide, and polyoxyethylene sorbitan ester, but is not limited thereto.
  • the first mixture may be a mixture of waste plastic pyrolysis oil and a demulsifier in a volume ratio of 1:0.000001 to 0.001, specifically, a volume ratio of 1:0.000002 to 0.0005, and more specifically, a volume ratio of 1:0.000003 to 0.0001.
  • the emulsion can be decomposed while minimizing the impact on the quality of the pyrolysis oil.
  • the emulsifier may have a weight average molecular weight of 200 to 2,000, specifically, a weight average molecular weight of 300 to 1,000, and more specifically, a weight average molecular weight of 400 to 800.
  • a weight average molecular weight of 200 to 2,000 specifically, a weight average molecular weight of 300 to 1,000, and more specifically, a weight average molecular weight of 400 to 800.
  • the emulsion-type moisture contained in the first mixture containing waste plastic pyrolysis oil, washing water, and a demulsifier is still difficult to remove because it is stable. Therefore, the moisture can be easily removed by applying voltage to the first mixture.
  • the voltage may be applied as an alternating current or a combination of an alternating current and a direct current.
  • Some impurity particles contained in waste plastic pyrolysis oil exhibit polarity, and when a direct current voltage is applied, polar impurity particles may accumulate on a specific electrode, and when the process is performed for a long period of time, a phenomenon in which the impurities are fixed on the electrode may occur.
  • the frequency of the alternating current according to one embodiment of the present disclosure may be a single frequency or a combination of two or more frequencies.
  • an alternating current having a frequency of 60 Hz may be applied, and in the case of a combination of two or more frequencies, an alternating current having frequencies of 50 Hz and 60 Hz may be applied alternately, but is not limited thereto.
  • the voltage may be applied via a vertical electrode. If impurity particles accumulate on the electrode during the process of preparing the mixture or applying the voltage, if they are not artificially washed, the phenomenon of the impurity particles being fixed on the electrode may occur after a long period of time. However, if a vertical electrode is used, the impurity particles fall to the bottom of the reactor without being accumulated on the electrode due to gravity without performing a separate washing operation, so the phenomenon of the impurity particles being fixed can be prevented in advance.
  • the magnitude of the voltage according to one embodiment of the present disclosure may be, but is not limited to, 0.1 to 50 kV, specifically 1 to 30 kV, and more specifically 5 to 20 kV.
  • the dehydration according to one embodiment of the present disclosure may be performed by any method known in the art.
  • the water may be removed by following the separated water layer after voltage application.
  • the water may also be removed in a gas-liquid separator.
  • a rag layer Metal impurities in the waste plastic pyrolysis oil stabilize the emulsion, hindering the oil-water separation, and help form a stable emulsion layer, commonly called a rag layer.
  • This rag layer can be formed between the demineralized oil layer on the upper side of the first mixture and the water layer below, and can gradually thicken during the continuous dehydration process.
  • the excessively thick rag layer can be discharged to the hydrogenation treatment stage equipment together with the demineralized oil. This reduces the demineralization effect of the demineralized oil, thereby reducing the efficiency of the process.
  • the rag layer can be discharged together with the water, causing problems in the wastewater treatment process. Therefore, it is desirable to remove the rag layer formed between the demineralized oil layer and the water layer.
  • the method for producing refined hydrocarbons from waste plastic pyrolysis oil may further include a step of removing a rag layer from the first mixture after applying voltage in step S1).
  • the removal of the rag layer may be performed through a pipe that penetrates the wall of the dehydrator and is connected to the outside after measuring a change in the density of the mixture through a density meter in the dehydrator to determine the formation location and thickness of the rag layer, but is not necessarily limited thereto.
  • the step S1) may be to dehydrate the first mixture, and then further dehydrate the dehydrated first mixture by coagulating the moisture.
  • the additional dehydration may be performed by supplying the dehydrated first mixture to a coalescer.
  • the residual moisture contained in the dehydrated first mixture may be removed by being coagulated by a collection filter in the coalescer, but this is only a specific example and is not necessarily limited thereto.
  • the moisture content in the waste plastic pyrolysis oil is further reduced through the additional dehydration, the deactivation of the catalyst due to moisture is prevented, and the stability of the process and the quality of the refined hydrocarbon can be improved.
  • the ratio of the moisture content of the waste plastic pyrolysis oil and the moisture content of the dehydrated first mixture may be 1:0.0001 to 0.9, specifically 1:0.0005 to 0.5, and more specifically 1:0.001 to 0.1.
  • the risk of trouble occurring in subsequent processes including hydrogenation treatment is significantly reduced, and high-quality refined oil satisfying the specifications as a raw material can be produced, but is not necessarily limited thereto.
  • the step S1) according to one embodiment of the present disclosure can be performed at a pressure of 50 bar or less.
  • a pressure of 50 bar or less moisture in the pyrolysis oil can be easily removed, and process stability can be secured.
  • it can be performed at a pressure of 30 bar or less, more specifically, it can be performed at a pressure of 20 bar or less, and, without limitation, it can be performed at a pressure of 5 bar or more.
  • the step S1) according to one embodiment of the present disclosure may be performed at a temperature of 20° C. to 300° C. When the above range is satisfied, emulsion decomposition and moisture coagulation may occur well, thereby improving dehydration efficiency. Specifically, it may be performed at a temperature of 50° C. to 250° C., and more specifically, 80° C. to 200° C.
  • one or more additional processes selected from the group consisting of centrifugation and distillation may be performed before and/or after dehydration.
  • the above-described additional processes may be performed by methods known in the art and are not particularly limited.
  • step S2) is a step of hydrogenating the first mixture dehydrated in step S1) and the second mixture mixed with a sulfur source to produce refined oil from which impurities have been removed.
  • the second mixture according to one embodiment of the present disclosure may have a concentration of chlorine (Cl) of 10 ppm or more, specifically 100 ppm or more, more specifically 200 ppm or more, and an upper limit may be, but is not limited to, 3000 ppm or less.
  • the second mixture may have a weight ratio of nitrogen to chlorine of 1:0.1 to 10, specifically 1:0.5 to 5, and more specifically 1:1 to 2.
  • the weight ratio is only a specific example that may be included in the waste plastic pyrolysis oil, and the composition of the waste plastic pyrolysis oil is not limited thereto.
  • the hydrogenation treatment according to one embodiment of the present disclosure can be performed under a condition where the ratio of hydrogen to the second mixture is 100 Nm 3 /Sm 3 to 5000 Nm 3 /Sm 3 , specifically 500 Nm 3 /Sm 3 to 3000 Nm 3 /Sm 3 , and more specifically 1000 Nm 3 /Sm 3 to 1500 Nm 3 /Sm 3 .
  • the ratio of hydrogen to the second mixture is 100 Nm 3 /Sm 3 to 5000 Nm 3 /Sm 3 , specifically 500 Nm 3 /Sm 3 to 3000 Nm 3 /Sm 3 , and more specifically 1000 Nm 3 /Sm 3 to 1500 Nm 3 /Sm 3 .
  • the above sulfur source refers to a sulfur source that can continuously supply sulfur components during the refining process.
  • the above step S2) can suppress deactivation of a molybdenum-based hydrogenation catalyst due to insufficient sulfur source and high-temperature operation during the purification process and maintain catalytic activity by producing a second mixture containing the sulfur source.
  • the sulfur supply source may include a sulfur-containing oil fraction.
  • the sulfur-containing oil fraction refers to an oil fraction composed of hydrocarbons containing sulfur obtained using crude oil as a raw material.
  • the sulfur-containing oil fraction may include light gas oil, straight run naphtha, vacuum naphtha, thermal cracking naphtha, straight run kerosene, vacuum kerosene, thermal cracking kerosene, straight run light oil, vacuum kerosene, thermal cracking light oil, sulfur-containing waste tire oil, or any mixture thereof.
  • waste tire oil as the sulfur-containing oil
  • the high content of sulfur contained in the waste tire is converted into oil together with hydrocarbons, so that it can preferably function as a sulfur source for waste plastic pyrolysis oil.
  • waste tire oil as a sulfur source for waste plastic pyrolysis oil, it is advantageous in terms of reducing the environmental load due to recycling of waste tires and maintaining catalytic activity for a long period of time.
  • the sulfur-containing fraction may be light gas oil (LGO) having a specific gravity of 0.7 to 1. When this is used, it can be uniformly mixed with the dehydrated first mixture, and has the advantage of high hydrogenation efficiency. Specifically, the specific gravity may be 0.75 to 0.95, and more specifically, may be 0.8 to 0.9.
  • the sulfur-containing fraction may contain sulfur in an amount of 100 ppm or more. When the sulfur component is contained in an amount of 100 ppm or less, the content of the supplied sulfur component may be small, and the effect of preventing deactivation of the molybdenum-based hydrogenation catalyst may be minimal. Specifically, the sulfur component may be contained in an amount of 800 ppm or more, more specifically, 8,000 ppm or more, and, but not limited to, 200,000 ppm or less.
  • the second mixture according to one embodiment of the present disclosure may contain sulfur in an amount of 100 ppm or more.
  • the sulfur component in the second mixture is contained in an amount of 100 ppm or less, the content of the supplied sulfur component may be small, and thus the effect of preventing deactivation of the molybdenum-based hydrogenation catalyst may be minimal.
  • the sulfur component may be contained in an amount of 800 ppm or more, more specifically, in an amount of 8,000 ppm or more, and, without limitation, in an amount of 200,000 ppm or less.
  • the sulfur-containing oil may be included in an amount of less than 0.5 parts by weight based on 100 parts by weight of the first mixture dehydrated in step S1). Specifically, the sulfur-containing oil may be included in an amount of less than 0.1 parts by weight, more specifically, less than 0.05 parts by weight, and, without limitation, more than 0.01 parts by weight. Since the sulfur-containing oil is included in an amount of less than 0.5 parts by weight, the concentration of chlorine (Cl) or nitrogen (N) included in the waste plastic pyrolysis oil is diluted, thereby controlling the production rate of ammonium salt (NH 4 Cl) and improving process stability.
  • NH 4 Cl ammonium salt
  • the sulfur source may include one or more sulfur-containing organic compounds selected from a disulfide compound, a sulfide compound, a sulfonate compound, and a sulfate compound. Specifically, it may include one or a mixture of two or more selected from dimethyldisulfide, dimethylsulfide, polysulfide, dimethyl sulfoxide (DMSO), methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, propenyl propenesulfonate, propenyl cyanoethansulfonate, ethylene sulfate, bicyclo glyoxal sulfate, and methyl sulfate, which is provided by way of example only and the present disclosure is not limited thereto.
  • DMSO dimethyl sulfoxide
  • the sulfur-containing organic compound may be included in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the first mixture dehydrated in step S1). Specifically, it may be included in an amount of 0.02 to 0.08 parts by weight, and more specifically, it may be included in an amount of 0.03 to 0.06 parts by weight. If it is included in an amount of less than 0.01 parts by weight, the content of the supplied sulfur component may be low, and thus the effect of preventing deactivation of the molybdenum-based hydrogenation catalyst may be minimal.
  • the above hydrogenation treatment means a hydrogenation reaction in which a reaction gas containing hydrogen gas (H 2 ) is added to a first mixture solution dehydrated in the step S1) and a second mixture solution containing a sulfur source under a molybdenum-based hydrogenation catalyst.
  • the hydrogenation treatment may mean a conventionally known hydrogenation treatment including a hydrodesulfurization reaction, a hydrocracking reaction, a hydrodechlorination reaction, a hydrodenitrogenation reaction, a hydrodeoxygenation reaction, and a hydrodemetallation reaction.
  • impurities including chlorine (Cl), nitrogen (N), and oxygen (O) and a portion of olefins are removed, and other metal impurities can also be removed, and by-products containing the above impurities are generated.
  • the above by-product is generated by the reaction of hydrogen gas (H 2 ) with impurities contained in the waste plastic pyrolysis oil, such as chlorine (Cl), nitrogen (N), sulfur (S), or oxygen (O), and specifically, may include hydrogen sulfide gas (H 2 S), hydrogen chloride (HCl), ammonia (NH 3 ) or water vapor (H 2 O), and in addition, may include unreacted hydrogen gas (H 2 ), trace amounts of methane (CH 4 ), ethane (C 2 H 6 ), propane (C 3 H 8 ) or butane (C 4 H 10 ).
  • the molybdenum-based hydrogenation catalyst may be a catalyst in which a molybdenum-based metal, or a metal including one or more selected from nickel, cobalt, and tungsten, and the molybdenum-based metal are supported on a support.
  • the molybdenum-based hydrogenation catalyst has high catalytic activity during hydrogenation treatment, and may be used alone or, if necessary, in the form of a binary system catalyst combined with a metal such as nickel, cobalt, or tungsten.
  • the support may be, but is not limited to, alumina, silica, silica-alumina, titanium oxide, molecular sieve, zirconia, aluminum phosphate, carbon, niobia or a mixture thereof.
  • the molybdenum-based hydrogenation catalyst may include a molybdenum-based sulfide hydrogenation catalyst.
  • a molybdenum-based sulfide hydrogenation catalyst may include molybdenum sulfide (MoS) or molybdenum disulfide (MoS 2 ), but is not limited thereto, and may include a known molybdenum-based sulfide hydrogenation catalyst.
  • the reaction gas according to one embodiment of the present disclosure may further include hydrogen sulfide gas (H 2 S).
  • the hydrogen sulfide gas (H 2 S) included in the reaction gas may act as a sulfur source and regenerate the activity of a molybdenum-based hydrogenation catalyst that has been deactivated during a purification process, such as a sulfur source mixed with waste plastic pyrolysis oil.
  • the hydrogenation treatment according to one embodiment of the present disclosure can be performed at a pressure of 150 bar or less. Specifically, it can be performed at a pressure of 120 bar or less, more specifically, 100 bar or less, and, but not limited to, it can be performed at a pressure of 50 bar or more.
  • a pressure condition exceeding 150 bar since ammonia and hydrogen chloride are generated in excess during the hydrogenation treatment, the ammonium salt formation temperature increases, which can easily cause a differential pressure in the process such as a reactor, and the process stability can be significantly reduced.
  • the increase in the ammonium salt formation temperature can be partially suppressed even under a pressure condition exceeding 150 bar; however, in this case, the waste plastic pyrolysis oil that is the target of the purification process according to the present disclosure can be extremely limited, which is not appropriate.
  • the hydrogenation treatment according to one embodiment of the present disclosure may be performed at a temperature of 150° C. to 500° C. When the above range is satisfied, the hydrogenation treatment efficiency may be improved. Specifically, it may be performed at a temperature of 200° C. to 400° C.
  • the hydrogenation treatment according to one embodiment of the present disclosure may be performed in multiple stages, and as a specific example, may be performed in two stages.
  • the first stage may be performed at a lower temperature than the second stage.
  • the first stage may be performed at a temperature of 150° C. to 300° C., specifically 200° C. to 250° C.
  • the second stage may be performed at a temperature of 300° C. to 500° C., specifically 350° C. to 400° C., but is not limited thereto.
  • a method for producing refined hydrocarbons from waste plastic pyrolysis oil may further include, after step S2), a step of washing a stream containing refined oil from which impurities have been removed after gas-liquid separation.
  • the stream containing the refined oil from which the impurities have been removed may include the refined oil from which the impurities have been removed, discharged from the rear end of the reactor where the step S2) is performed, as well as hydrogen chloride, ammonia, and unreacted hydrogen gas.
  • ammonia and hydrogen chloride generated by hydrogenation can be removed from a stream containing refined oil from which impurities have been removed through the gas-liquid separation, and unreacted hydrogen gas can be recovered.
  • the gas-liquid separation according to one embodiment of the present disclosure can be performed using a separator by a method known in the art and is not particularly limited.
  • the gas-liquid separation may be performed 2 to 4 times, specifically 3 to 4 times, and more specifically 4 times.
  • the above range is satisfied, since the refined oil contains trace amounts of NH 3 and HCl, the generation of ammonium salts may be minimized even under low-temperature conditions for oil-water separation.
  • an oil refining process using this as a raw material may be stably performed.
  • the gas stream generated as a result of the gas-liquid separation may include off-gas including light hydrocarbons, hydrogen sulfide, ammonia, or hydrogen chloride, and unreacted hydrogen gas.
  • the off-gas and unreacted hydrogen gas are separated according to a method known in the art, and the unreacted hydrogen gas is recycled within the process, and the off-gas is treated through the steps described below and can be used as fuel or discharged into the atmosphere.
  • the washing may be performed to dissolve and remove salts contained in the gas stream, or to dissolve gases capable of forming salts, thereby inhibiting salt formation.
  • the washing may be performed by a method known in the art, and is not particularly limited.
  • the washing according to one embodiment of the present disclosure may be performed 2 to 4 times, specifically 2 to 3 times.
  • the salt removal and salt formation inhibition effects are sufficiently exerted, so that high-quality refined oil can be obtained, and the stability of the process can be secured.
  • a method for producing refined hydrocarbons from waste plastic pyrolysis oil may further include, after the step of subjecting a stream containing refined oil from which impurities have been removed to gas-liquid separation and then washing, a step of combusting the separated off-gas; and a step of treating uncombusted off-gas.
  • the waste gas may include light hydrocarbons of C1-C4, hydrogen sulfide (H 2 S), ammonia (NH 3 ), etc. Therefore, in order to use the waste gas as fuel, it is necessary to remove hydrogen sulfide (H 2 S), ammonia (NH 3 ), etc.
  • the exhaust gas containing sulfur dioxide (SO 2 ), nitrogen dioxide (NO 2 ), etc. generated by the combustion of the waste gas may be discharged into the atmosphere after performing caustic scrubbing to meet emission standards.
  • the uncombusted waste gas can be discharged as waste water after being treated by sour water stripping, adsorption, biological treatment, oxidation, amine scrubbing, or caustic scrubbing.
  • step S3) is a step of catalytically decomposing the refined oil from which the impurities have been removed.
  • the hydrocarbons contained in the refined oil can be lightened through a catalytic decomposition process that consumes less energy and minimizes environmental pollution compared to a conventional thermal decomposition process.
  • catalytic cracking may typically mean a process of contact cracking heavy oils such as naphtha with a catalyst to obtain light hydrocarbons such as ethylene and propylene.
  • the catalytic cracking of step S3) may be performed as a fluid catalytic cracking process that cracks heavy oil by the catalytic action of an acid catalyst maintained in a fluidized state, and may be performed in combination with hydrocracking, but is not limited thereto.
  • the step S3) according to one embodiment of the present disclosure may be to catalytically decompose the purified oil fraction separated by distillation of the pyrolysis oil from which impurities have been removed.
  • the distillation may be performed in a fractionator.
  • the purified oil fraction according to one embodiment of the present disclosure may be at least one selected from the group consisting of naphtha, kerosene, light gas oil, heavy gas oil, vacuum gas oil (VGO), and residue, but is not limited thereto.
  • the step S3) may be to catalytically crack a mixed oil mixture in which refined oil from which impurities have been removed in the step S2) and petroleum-based hydrocarbons are mixed.
  • the mixed oil mixture in which the refined oil fraction and petroleum-based hydrocarbons are mixed can be catalytically cracked.
  • the above petroleum hydrocarbons collectively refer to a mixture of hydrocarbons that exist naturally or a fraction separated from the mixture, and specifically, may be any one or a mixture of two or more selected from the group consisting of kerosene, light gas oil, heavy gas oil, and VGO (vacuum gas oil) derived from crude oil, but is not limited thereto.
  • the mixed oil may contain refined oil from which the impurities have been removed in an amount of 5 wt% or more, 10 wt% or more, 20 wt% or more, 40 wt% or more, or 50 wt% or more, and an upper limit of, but not limited to, 95 wt% or less or 90 wt% or less, relative to the total weight of the mixed oil.
  • the present disclosure is not necessarily limited to the above range, generally, the lower the impurity content in the refined oil, the higher the proportion of pyrolysis oil that can be included in the mixed oil.
  • the temperature at which the step S3) according to one embodiment of the present disclosure is performed may be 100° C. or higher, 200° C. or higher, 300° C. or higher, 400° C. or higher, 1000° C. or lower, 900° C. or lower, 800° C. or lower, 700° C. or lower, 600° C. or lower, 500° C. or lower, or a value between the above values, and specifically may be 300° C. to 600° C., and more specifically, 400° C. to 500° C., but is not limited thereto.
  • the pressure performed in step S3) may be 0.5 bar or more, 1 bar or more, 2 bar or more, 3 bar or more, 5 bar or more, 7 bar or more, 9 bar or more, 100 bar or less, 70 bar or less, 50 bar or less, 40 bar or less, 30 bar or less, 20 bar or less, 10 bar or less or a value between the above values, and may be 1 bar to 10 bar, specifically 2 bar to 10 bar, but is not limited thereto.
  • the catalyst used for catalytic decomposition in step S3) may be ZSM-5, USY, REY, or ⁇ -zeolite, which not only allows easy control of acidity through changes in chemical composition but also has shape selectivity, but is not limited thereto.
  • the present disclosure provides a system for producing refined hydrocarbons from waste plastic pyrolysis oil, including a dehydrator for performing dehydration by applying voltage to a first mixture containing waste plastic pyrolysis oil, washing water, and a demulsifier; a hydrogenation reactor into which the first mixture dehydrated in the dehydrator and hydrogen gas are introduced and refined oil from which impurities are removed is generated by hydrogenation treatment under a hydrogenation catalyst; and a catalytic cracking device for catalytically cracking the refined oil from which impurities are removed.
  • the description of the method for producing refined hydrocarbons from waste plastic pyrolysis oil can be equally applied to the description of the system for producing refined hydrocarbons from waste plastic pyrolysis oil within the overlapping scope.
  • the dehydrator according to one embodiment of the present disclosure may be equipped with vertical electrodes.
  • the number of vertical electrodes equipped in the dehydrator according to one embodiment of the present disclosure may be at least 2 or more, specifically 4 or more, more specifically 6 or more, and may be 20 or less as an upper limit, but is not necessarily limited thereto.
  • the dehydrator according to one embodiment of the present disclosure may include a coalescer therein.
  • the coalescer is a device that collects fine droplets to form large droplets, and a device commonly used in the industry can be used, and is not particularly limited.
  • the first mixture dehydrated in the dehydrator may be introduced into the coagulator to produce an additionally dehydrated first mixture.
  • the additionally dehydrated first mixture is of course introduced into the hydrogenation reactor together with hydrogen gas.
  • the system for producing refined hydrocarbons from the waste plastic pyrolysis oil may further include a separator for gas-liquid separation of refined oil from which impurities have been removed, generated from the hydrogenation treatment reactor.
  • the number of the separators according to one embodiment of the present disclosure may be 2 to 4, specifically 3 to 4, and more specifically 4.
  • the above range is satisfied, since the refined oil contains trace amounts of NH 3 and HCl, the generation of ammonium salts can be minimized even under low-temperature conditions for oil-water separation.
  • a process using the refined oil as a raw material can be stably performed without adding a separate salt remover to the refined oil in the future.
  • the system for producing refined hydrocarbons from the waste plastic pyrolysis oil may further include a recycle gas compressor for recovering unreacted hydrogen gas from the gas stream separated from the separator and feeding it into a hydrogenation reactor.
  • waste plastic pyrolysis oil, washing water, and polyethylene glycol having a weight average molecular weight of 500 were introduced into a dehydrator in a volume ratio of 1:0.25:0.0001 and stirred to prepare a first mixture.
  • the first mixture was separated into oil and water by applying an AC voltage of 15 kV through a vertical electrode, and then the water layer was removed to perform dehydration.
  • the waste plastic pyrolysis oil had a moisture content of about 5,000 ppm or more and contained high concentrations of impurities such as nitrogen (N) of 500 ppm or more, chlorine (Cl) of 200 ppm or more, and olefin of 20 volume% or more.
  • impurities such as nitrogen (N) of 500 ppm or more, chlorine (Cl) of 200 ppm or more, and olefin of 20 volume% or more.
  • a second mixture was prepared by mixing 0.04 parts by weight of dimethyl disulfide with 100 parts by weight of the first mixture dehydrated in the above dehydrator, and then hydrogenation was performed under the conditions of 300°C and 70 bar to produce refined oil from which impurities were removed.
  • the refined oil from which the above impurities have been removed was distilled to separate the naphtha and the naphtha derived from crude oil with a boiling point of 150°C or lower were mixed in a weight ratio of 2:8, and the mixed oil was subjected to catalytic cracking at 500°C and 2 bar to obtain refined hydrocarbons.
  • Example 1 the same conditions as in Example 1 were performed, except that waste plastic pyrolysis oil, washing water, and polyethylene glycol were added to the dehydrator in the volume ratios shown in Table 1 below, to obtain purified hydrocarbons.
  • a purified hydrocarbon was obtained by performing the same process as in Example 1 except that a direct current voltage was applied through a horizontal electrode.
  • Example 1 dehydration of the first mixture was performed under the same conditions as in Example 1, except that it was performed at a temperature of 120°C, to obtain a purified hydrocarbon.
  • Example 5 waste plastic pyrolysis oil and polyethylene glycol were introduced in a volume ratio of 1:0.00001, and the hydrogenation process was performed under the same conditions as Example 1, except that the pressure was 180 bar, to obtain a purified hydrocarbon.
  • Example 1 the same conditions as in Example 1 were performed, except that additional dehydration was performed through a coagulant after dehydration of the first mixture, to obtain a purified hydrocarbon.
  • a purified hydrocarbon was obtained by performing the process under the same conditions as in Example 1, except that no washing water was added.
  • a purified hydrocarbon was obtained by performing the same process as in Example 1 except that polyethylene glycol was not added.
  • a purified hydrocarbon was obtained by performing the same process as in Example 1 except that no voltage was applied.
  • a purified hydrocarbon was obtained under the same conditions as in Example 1, except that dimethyl disulfide was not mixed into the dehydrated first mixture in Example 1.
  • the moisture and chlorine contents in the mixture obtained after the dehydration process and the chlorine content in the refined oil from which impurities were removed were measured and displayed using ICP and XRF analysis methods.
  • the hydrogenation catalyst activity retention time was measured in hours based on the point at which the nitrogen content in the refined oil exceeded 10 ppm through Total Nitrogen & Sulfur (TNS element) analysis on refined oil.
  • Particle fixation rate (%) (amount of impurity particles fixed on the electrode/amount of impurity particles in the pyrolysis oil)*100
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 dehydration Washing water (volume ratio) 0.25 0.50 0.25 0.25 0.25 0.25 0.25 0.25 - 0.25 0.25 0.25 Emulsifier (volume ratio) 0.0001 0.0001 0.00001 0.0001 0.00001 0.0001 0.0001 - 0.0001 0.0001 temperature (°C) 150 150 150 150 120 120 150 150 150 150 150 150 enter (bar) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 voltage type Exchange Exchange Exchange direct current Exchange Exchange Exchange Exchange Exchange Exchange - Exchange electrode perpendicular perpendicular perpendicular horizontality perpendicular perpendicular perpendicular perpendicular perpendicular perpendicular perpendicular - perpendicular Whether it is a coagulant or not X X
  • Comparative Examples 1 to 3 showed low moisture and Cl removal effects by the dehydration step because the presence or absence of washing water, the presence or absence of demulsifier, and the presence or absence of voltage application were different from the examples, respectively.
  • the waste plastic pyrolysis oil containing many impurities was hydrogenated, the Cl content in the refined oil was high and the hydrogenation catalyst was deactivated relatively quickly.
  • Comparative Example 4 moisture and some impurities in the waste plastic pyrolysis oil were sufficiently removed in the dehydration step, the hydrogenation catalyst was deactivated in a short period of time due to the insufficient sulfur content, and when the process was maintained for a long period of time, the Cl content in the refined oil was high, as in the other Comparative Examples.
  • Examples 1 to 7 according to the method for producing refined hydrocarbons from waste plastic pyrolysis oil of the present disclosure significantly prolonged the activity of the hydrogenation catalyst by removing a significant amount of moisture contained in the waste plastic pyrolysis oil through the dehydration step and adding a sulfur source.
  • a large amount of refined oil can be input into the catalytic decomposition step without performing additional impurity removal because some water-soluble impurities are preemptively removed in the dehydration step and the content of impurities including Cl in the refined oil is low by hydrogenation treatment.
  • Example 6 the dehydration result was poor compared to other examples, but since the hydrogenation treatment was performed under high pressure conditions, the Cl content of impurities in the refined oil was very low. However, since ammonia and hydrogen chloride are generated in excess due to the high pressure, it was confirmed that a relatively large amount of ammonium salts were generated even at the temperature at which the hydrogenation treatment was performed.
  • Example 7 as additional dehydration was performed using a coagulant, the moisture and chlorine contents after dehydration were lower than in other examples. Therefore, it can be expected that the activation time of the catalyst, process stability, and quality of purified hydrocarbons are relatively better than in other examples.

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Abstract

La présente invention concerne un procédé et un système de fabrication d'hydrocarbures raffinés à partir d'huile de pyrolyse de déchets plastiques. Le procédé et le système de fabrication d'hydrocarbures raffinés à partir d'huile de pyrolyse de déchets plastiques selon la présente invention permettent réduire au maximum la production de sels d'ammonium (NH4Cl) pendant un processus de raffinage d'huile de pyrolyse de déchets plastiques contenant des impuretés telles que du chlore et de l'azote, et peut empêcher des particules d'impuretés de se coincer à l'intérieur d'un réacteur. De plus, le procédé et le système de fabrication d'hydrocarbures raffinés à partir d'huile de pyrolyse de déchets plastiques selon la présente invention empêchent la désactivation d'un catalyseur utilisé dans le procédé, et ont ainsi une excellente efficacité de raffinage, permettent la mise en œuvre à long terme du procédé, et permettent de produire des hydrocarbures affinés durcis ayant une faible teneur en impuretés à partir d'huile de pyrolyse de déchets plastiques.
PCT/KR2024/095677 2023-04-19 2024-04-04 Procédé et système de fabrication d'hydrocarbures raffinés à partir d'huile de pyrolyse de déchets plastiques Ceased WO2024219930A1 (fr)

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Publication number Priority date Publication date Assignee Title
KR20140098953A (ko) * 2013-01-31 2014-08-11 단국대학교 산학협력단 탄화수소 함유 폐기물 열분해유 정제방법
CN114479913A (zh) * 2022-01-10 2022-05-13 北京科安博科技有限公司 一种重、劣质原油预处理工艺
KR20230010198A (ko) * 2020-04-07 2023-01-18 토탈에너지스 원테크 벨지움 에스.에이. 1차 트랩과 1차 수소처리 및 2차 트랩과 2차 수소처리를 통한 폐플라스틱 기반 오일의 정제
JP2023504127A (ja) * 2019-11-29 2023-02-01 ネステ オサケ ユキチュア ユルキネン 液化廃プラスティックをアップグレードするための方法
KR20230021353A (ko) * 2021-08-05 2023-02-14 에스케이이노베이션 주식회사 폐플라스틱 열분해유의 정제 장치 및 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140098953A (ko) * 2013-01-31 2014-08-11 단국대학교 산학협력단 탄화수소 함유 폐기물 열분해유 정제방법
JP2023504127A (ja) * 2019-11-29 2023-02-01 ネステ オサケ ユキチュア ユルキネン 液化廃プラスティックをアップグレードするための方法
KR20230010198A (ko) * 2020-04-07 2023-01-18 토탈에너지스 원테크 벨지움 에스.에이. 1차 트랩과 1차 수소처리 및 2차 트랩과 2차 수소처리를 통한 폐플라스틱 기반 오일의 정제
KR20230021353A (ko) * 2021-08-05 2023-02-14 에스케이이노베이션 주식회사 폐플라스틱 열분해유의 정제 장치 및 방법
CN114479913A (zh) * 2022-01-10 2022-05-13 北京科安博科技有限公司 一种重、劣质原油预处理工艺

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