CN120900522A - Polylactic acid-based waste plastic catalytic hydrogenolysis system and catalytic hydrogenolysis method - Google Patents

Polylactic acid-based waste plastic catalytic hydrogenolysis system and catalytic hydrogenolysis method

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Publication number
CN120900522A
CN120900522A CN202511434907.3A CN202511434907A CN120900522A CN 120900522 A CN120900522 A CN 120900522A CN 202511434907 A CN202511434907 A CN 202511434907A CN 120900522 A CN120900522 A CN 120900522A
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hydrogenolysis
based waste
waste plastics
gas
polylactic acid
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CN120900522B (en
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段培高
侯潇珂
穆冠中
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Xian Jiaotong University
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Xian Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • 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
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • 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
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/001—Controlling catalytic processes
    • 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
    • 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
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

The invention discloses a polylactic acid-based waste plastic catalytic hydrogenolysis system and a method, and belongs to the technical field of waste plastic treatment. According to the hydrogenolysis method, firstly, polylactic acid-based waste plastics are heated, melted and liquefied in a hydrogenolysis reaction kettle, the liquefied polylactic acid macromolecules undergo a cracking reaction under the action of a hydrogenolysis catalyst to generate a large amount of unsaturated lactic acid and active C 3 intermediates, and then chemical products such as butyl propionate, hexyl propionate and the like are generated through catalytic hydrogenation and reconstruction reaction. Solves the problems of low product yield and complex components existing in the prior pyrolysis process.

Description

Polylactic acid-based waste plastic catalytic hydrogenolysis system and catalytic hydrogenolysis method
Technical Field
The invention belongs to the technical field of waste plastic treatment, and particularly relates to a polylactic acid-based waste plastic catalytic hydrogenolysis system and method.
Background
Polylactic acid (Polylactic Acid, PLA) is a renewable biological plastic, but the overall recovery rate of the PLA-based waste plastic is still low at present, and a large amount of PLA-based waste plastic cannot be recycled, so that serious environmental pollution and great resource waste are caused.
At present, waste plastics are mainly recovered in a physical or chemical mode, and mainly comprise landfill technology, incineration technology, recovery and regeneration technology and the like. However, both incineration and landfill technologies can cause serious environmental damage. Although the recycling technology has environmental protection potential, due to the wide variety of plastics, different types of plastics often need to undergo complex classification and treatment processes, resulting in low efficiency. In addition, the problems of molecular chain fracture, degradation, impurity residue and the like are easy to occur in the regeneration process, so that the mechanical property and durability of the regenerated plastic are obviously reduced, and the regenerated product is poor in general performance. Therefore, the recycling technology cannot realize the efficient utilization of the resources of the waste plastics.
PLA-based waste plastics can also be treated by means of biodegradation, i.e. the PLA is degraded by the presence of degradable microorganisms and enzymes in the environment, but PLA products are difficult to be completely degraded by microorganisms in the short term under natural conditions. Therefore, finding a technology for recycling PLA-based waste plastics in green is increasingly urgent.
The pyrolysis process is a chemical conversion process of waste plastics. The pyrolysis process is to convert waste plastics into pyrolysis gas and pyrolysis oil under the condition of high temperature and no oxygen, and the pyrolysis oil is cooled into liquid oil by a cooling system. The pyrolysis is used for treating waste plastics in an anaerobic thermal cracking mode, a harmless and efficient plastic recycling mode is provided, and the method has good cost performance and conversion rate. However, despite the significant advantages of pyrolysis processes, problems of low pyrolysis oil yield and poor oil quality remain in practical use. These disadvantages are mainly due to limitations of the existing processes on raw material adaptability, non-uniformity of temperature and residence time control during pyrolysis, and difficulty in completely suppressing side reactions such as secondary cracking, thus resulting in reduced yield of liquid products, complex components and poor stability. For PLA-based waste plastics, the pyrolysis process is still a main way for degrading the PLA-based waste plastics, and can convert PLA into a value-added product with low energy input, so that the efficient upgrading of the PLA-based waste plastics is realized, but a pyrolysis process with a high-selectivity resource utilization mode has not been developed at present.
Disclosure of Invention
The invention provides a polylactic acid-based waste plastic catalytic hydrogenolysis system and a method, which are used for solving the problems of low pyrolysis product yield and complex components in the existing pyrolysis process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
In a first aspect, the invention provides a polylactic acid-based waste plastic catalytic hydrogenolysis system, which comprises a pulverizer, a hydrogenolysis reaction kettle, a pressure reducer, a liquid phase delivery pump, a hydrogen separation system and a rectifying tower;
the outlet of the pulverizer is connected with a solid-phase feed inlet of the hydrogenolysis reaction kettle;
The hydrogenolysis reaction kettle comprises a kettle body, a stirring device, a catalyst fixed bed, a temperature and pressure control device and a heating sleeve, wherein stirring blades of the catalyst fixed bed and the stirring device are positioned in the kettle body, the heating sleeve is coated outside the kettle body, and the temperature and pressure control device is electrically connected with the heating sleeve;
the kettle body is provided with a solid phase feed inlet, a gas phase discharge outlet and a liquid phase discharge outlet;
the gas phase discharging port is connected with the inlet of the pressure reducer, the outlet of the pressure reducer is connected with the inlet of the hydrogen separation system, and the outlet of the hydrogen separation system is connected with the gas phase feeding port;
The liquid phase discharge port is connected with the inlet of the rectifying tower.
The hydrogen separation system further comprises a drying tank, a cold box, a hydrogen storage tank and a compressor, wherein the inlet of the drying tank is connected with the outlet of the pressure reducer, the outlet of the drying tank is connected with the inlet of the cold box, the outlet of the cold box is connected with the inlet of the hydrogen storage tank, the outlet of the hydrogen storage tank is connected with the inlet of the compressor, and the outlet of the compressor is connected with the gas-phase feed inlet.
Further, the rotation track of the stirring blade of the stirring device is tangential to the inner surface of the catalyst fixed bed.
In a second aspect, the present invention provides a catalytic hydrogenolysis method for polylactic acid-based waste plastics, which is based on the above-mentioned catalytic hydrogenolysis system for polylactic acid-based waste plastics, comprising the steps of:
The method comprises the steps of 1, crushing and screening polylactic acid-based waste plastics through a crusher, then sending the crushed and screened polylactic acid-based waste plastics into a hydrogenolysis reaction kettle, and introducing H 2 into the hydrogenolysis reaction kettle, heating, melting and liquefying the polylactic acid-based waste plastics in the hydrogenolysis reaction kettle, carrying out hydrogenolysis reaction on the melted and liquefied polylactic acid macromolecules under the action of a hydrogenolysis catalyst and H 2 to break ester bonds of unsaturated polylactic acid macromolecules and generate saturated micromolecular lactic acid and an active C 3 intermediate, and then carrying out catalytic hydrogenation and reconstruction reaction on the saturated micromolecular lactic acid and the active C 3 intermediate to generate hydrogenolysis oil, hydrogenolysis gas and H 2 O, wherein the hydrogenolysis catalyst is a Pt-loaded catalyst, and the carrier is Nb 2O5;
step2, decompressing and drying the hydrogen gas and the residual H 2 in the hydrogenolysis reaction, and then sending the hydrogen gas and the residual H 2 into a cold box, and separating the hydrogen gas and the H 2 by a cryogenic separation method;
and (3) separating components of the hydrogenolysis oil and water mixture to obtain water, hexyl propionate and butyl propionate.
Further, in the step 1, the mass ratio of the polylactic acid-based waste plastic to the hydrogenolysis catalyst is 1.
In the step 1, the mass percentage of Pt in the hydrogenolysis catalyst is 1% -10%.
In the step 1, the conditions of the hydrogenolysis reaction comprise that the temperature of the hydrogenolysis reaction is 250-300 ℃, the pressure of the hydrogenolysis reaction is 1-6 MPa, and the time of the hydrogenolysis reaction is 2-12 hours.
In the step 1, during the hydrogenolysis reaction, the stirring speed of the stirring device is 1000 r/min-3000 r/min.
In step 2, after the hydrogen gas and the H 2 are separated, the separated H 2 is sent to a hydrogen storage tank for storage, and the stored H 2 is compressed by a compressor and then used as a reaction gas for the hydrogenolysis reaction.
In the step 2, the mixture of hydrogenolysis oil and water is subjected to component separation by adopting a rectification mode, wherein the boiling point of a light component is less than or equal to 75 ℃ and the boiling point of a heavy component is more than 140 ℃ during rectification.
Compared with the prior art, the invention has at least the following beneficial technical effects:
The polylactic acid-based waste plastic catalytic hydrogenolysis system provided by the invention has the advantages of remarkably reducing equipment investment by relying on a rectifying tower and a catalyst fixed bed arranged in a reaction kettle, being convenient to operate and maintain, being capable of monitoring and adjusting process parameters in real time by a temperature and pressure control device, being convenient to fill and replace hydrogenolysis catalyst, being reasonable in gas-liquid phase outlet layout and reducing manual intervention and daily maintenance workload while realizing high-efficiency resource regeneration by reasonable unit integration.
Meanwhile, the hydrogenolysis catalyst is fixed in the hydrogenolysis reaction kettle through the catalyst fixed bed, so that the hydrogenolysis catalyst is easy to fill and separate and can be recycled, the traditional energy-consuming operations such as centrifugal separation and the like are avoided, the hydrogenation reaction is carried out under relatively mild conditions, and the overall energy consumption is low.
Furthermore, the combination of cryogenic separation and a compressor realizes the efficient recovery and cyclic utilization of hydrogen, greatly reduces the consumption of external energy and raw materials, and the hydrogen can be returned to the catalytic hydrogenolysis system for repeated use after being purified and compressed in the reaction process, so that the resource recycling property is strong, the economy is effectively improved, and the environmental benefit and sustainable operation capability of the catalytic hydrogenolysis system are highlighted.
According to the catalytic hydrogenolysis method for polylactic acid-based waste plastics, polylactic acid-based waste plastics are melted and liquefied, the liquefied polylactic acid macromolecules undergo a cracking reaction under the action of a hydrogenolysis catalyst to generate a large amount of unsaturated lactic acid and active C 3 intermediates, and then butyl propionate, hexyl propionate, hydrogenolysis gas and water are generated through catalytic hydrogenation and reconstruction reaction. In the reaction process, the hydrogen gas and the H 2 are separated and stored by using a cryogenic separation method, and the stored H 2 can be recycled to be used as the reaction gas of the hydrogenolysis reaction, so that H 2 resources are saved, and the double advantages of economic benefit and environmental benefit are achieved.
Further, the mass ratio of the polylactic acid-based waste plastics to the hydrogenolysis catalyst is (1-10): 1, so as to ensure efficient catalytic hydrogenolysis activity.
Further, the mass percentage of Pt in the hydrogenolysis catalyst is 1% -10%, so that the cost is effectively controlled while the catalytic performance is ensured, and the economic requirement in industrial application is met.
Furthermore, the invention realizes effective guidance of the reaction path and the product distribution under the relatively mild reaction condition by the coordinated regulation and control of the hydrogenolysis catalyst, hydrogenolysis temperature, pressure and reaction time, not only remarkably improves the selectivity and yield of high added value products such as butyl propionate, but also inhibits side reactions such as excessive cracking and coking, thereby improving the economy of the whole process while guaranteeing the product quality.
Further, during hydrogenolysis reaction, the stirring speed of the stirring device is 1000 r/min-3000 r/min, so that the reactants are fully mixed, the contact efficiency of hydrogen and a substrate is improved, and the reaction process is accelerated.
Further, after the hydrogen gas and the H 2 are separated, the separated H 2 is sent into a hydrogen storage tank for storage, and the stored H 2 is compressed by a compressor and then used as reaction gas for hydrogenolysis reaction, so that the recycling of the H 2 is realized, and the utilization rate of the H 2 is improved.
Further, the mixture of hydrogenolysis oil and water is subjected to component separation by adopting a rectification mode, wherein the boiling point of a light component is less than or equal to 75 ℃ and the boiling point of a heavy component is more than 140 ℃ during rectification, so that the light component, water and the heavy component are efficiently and thoroughly separated, and the purity and quality of tower top and tower bottom products are ensured.
Drawings
Fig. 1 is a schematic diagram of a system for hydrogenolysis of polylactic acid-based waste plastics.
In the drawing, a 1-pulverizer, a 21-solid phase feed inlet, a 22-gas phase feed inlet, a 23-gas phase discharge outlet, a 24-stirring device, a 25-catalyst fixed bed, a 26-temperature pressure control device, a 27-heating jacket, a 28-liquid phase discharge outlet, a 3-pressure reducer, a 4-drying tank, a 5-cold box, a 6-hydrogen storage tank, a 7-compressor, an 8-liquid phase conveying pump, a 9-rectifying tower, a 10-exhaust valve and an 11-air inlet valve are arranged.
Detailed Description
For the purpose of making the technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail by way of specific embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Referring to fig. 1, a catalytic hydrogenolysis system for polylactic acid-based waste plastics comprises a pulverizer 1, a hydrogenolysis reaction kettle, a pressure reducer 3, a drying tank 4, a cold box 5, a hydrogen storage tank 6, a compressor 7, a liquid phase transfer pump 8 and a rectifying tower 9.
The hydrogenolysis reaction kettle comprises a kettle body, a stirring device 24, a catalyst fixed bed 25, a temperature and pressure control device 26 and a heating sleeve 27, wherein a solid-phase feed inlet 21 is arranged at the top of the kettle body, a gas-phase feed inlet 22 and a gas-phase discharge outlet 23 are arranged at the upper part of the kettle body, and a liquid-phase discharge outlet 28 is arranged at the bottom of the kettle body. The liquid phase discharging port 28 is arranged at the bottom of the kettle body, so that liquid phase product discharging is facilitated, a stirring motor in the stirring device 24 is positioned at the outer part of the kettle body, a stirring blade is positioned at the middle lower part of the kettle body and used for stirring substances in the kettle body, uniformity of liquefied plastics in the reaction process is guaranteed, the rotating track of the stirring blade is tangential to the inner surface of the catalyst fixed bed 25, so that hydrogenolysis reaction is facilitated to fully occur, the catalyst fixed bed 25 is fixed on the inner wall of the kettle body and used for filling a hydrogenolysis catalyst, and hydrogenolysis catalyst replacement and separation of liquid phase products are facilitated.
The gas phase discharging hole 23 at the top of the hydrogenolysis reaction kettle is connected with the inlet of the pressure reducer 3 through a gas phase discharging pipe for conveying gas phase products into a hydrogen separation system, the gas phase discharging pipe is provided with an exhaust valve 10, and the hydrogen separation system comprises a drying tank 4, a cold box 5, a hydrogen storage tank 6 and a compressor 7. The export of pressure reducer 3 links to each other with the entry linkage of drying tank 4, and the export of drying tank 4 links to each other with the entry of cold box 5, and the export of cold box 5 links to each other with the air inlet of hydrogen holding vessel 6, and the gas outlet of hydrogen holding vessel 6 links to each other with the entry of compressor 7, and the export of compressor 7 is connected with gaseous phase feed inlet 22 through the gaseous phase inlet pipe, installs admission valve 11 on the gaseous phase inlet pipe.
The heating jacket 27 is covered on the outer side of the kettle body and is electrically connected with the temperature and pressure control device 26 to jointly form a regulation and control unit for the reaction conditions. The pressure sensor signal installed in the kettle body is obtained in real time by the regulation and control unit, and the opening degree of the air inlet valve 11 or the air outlet valve 10 is dynamically regulated by combining the temperature, the pressure and the time of the hydrogenolysis reaction, so that the H 2 feeding or the outflow of gas-phase products is controlled, and the stability and the accuracy control of the pressure of a reaction system are realized. At the same time, the heating jacket 27 adjusts the heating power under the instruction of the temperature and pressure control device 26, and accurately maintains the reaction temperature.
The discharge port of the pulverizer 1 is connected with a solid phase feed port 21 of the hydrogenolysis reaction kettle through a pipeline. The liquid phase discharge port 28 is connected with the inlet of the liquid phase delivery pump 8, the outlet of the liquid phase delivery pump 8 is connected with the feed port of the rectifying tower 9 through a pipeline, and the liquid phase product is sent into the rectifying tower 9 to separate the liquid phase components.
The working flow of the polylactic acid-based waste plastic catalytic hydrogenolysis system is that PLA-based plastic raw materials from a waste plastic storage yard are sent to a pulverizer 1 for pulverization and screening, the pulverized and screened PLA-based waste plastics are used as raw materials for hydrogenolysis reaction, and enter the hydrogenolysis reaction kettle through a solid-phase feed port 21 at the top of the hydrogenolysis reaction kettle for catalytic hydrogenolysis, so that gas mixture and liquid-phase product-hydrogenolysis oil are obtained, wherein the gas mixture comprises gas-phase product hydrogenolysis gas and residual H 2 of catalytic hydrogenolysis. The fixed catalyst bed 25 is filled with hydrogenolysis catalyst and can realize the separation of the hydrogenolysis catalyst and liquid phase products, in the catalytic hydrogenolysis process, a temperature and pressure control device 26 is used for controlling a heating sleeve 27 to control the temperature of a hydrogenolysis reaction kettle through an electric heating method, meanwhile, the internal pressure of the hydrogenolysis reaction kettle is detected and controlled, gas mixture contains a large amount of H 2, a gas phase discharge port 23 at the top of the hydrogenolysis reaction kettle is decompressed by a decompressing device 3 and then is sent into a drying tank 4 to be dried, and the dried gas mixture enters a cold box 5 to be subjected to cryogenic separation, so that the hydrogen chloride and H 2 are obtained. The separated H 2 can be stored in a hydrogen storage tank 6, when the hydrogenolysis reaction is needed, H 2 enters the hydrogenolysis reaction kettle through a gas phase feed port 22 after being compressed by a compressor 7 and is used as hydrogenolysis reaction gas, hydrogenolysis oil is discharged from a liquid phase discharge port 28 at the bottom of the hydrogenolysis reaction kettle, a liquid phase product is sent into a rectifying tower 9 to be rectified by a liquid phase conveying pump 8, and a liquid phase component is separated, so that light components, heavy components and water are finally obtained.
The invention also provides a catalytic hydrogenolysis method of the polylactic acid-based waste plastics, which comprises the following steps:
The method comprises the steps of 1, crushing and screening PLA-based waste plastics, sending the PLA-based waste plastics into a hydrogenolysis reaction kettle through a solid-phase feed port 21, introducing reaction gas H 2 into the hydrogenolysis reaction kettle through a gas-phase feed port 22, heating the hydrogenolysis reaction kettle through an electric heating method by using a temperature and pressure control device 26 to control a heating sleeve 27, simultaneously starting a stirring device 24, melting and liquefying the PLA-based waste plastics in the hydrogenolysis reaction kettle, carrying out hydrogenolysis reaction on the melted and liquefied PLA-based waste plastics under the action of a hydrogenolysis catalyst and H 2 to break ester bonds of macromolecules of the unsaturated PLA-based waste plastics, generating saturated small-molecule lactic acid and active C 3 intermediates similar to lactic acid, and then generating hydrogenolysis oil such as butyl propionate, hexyl propionate and the like, hydrogen gas such as CO and the like through catalytic hydrogenation and reconstruction reaction of the saturated small-molecule lactic acid and the active C 3 intermediates, and H 2 O, and forming gas mixture by the hydrogen gas and the residual hydrogen 2 of the hydrogenolysis reaction;
the hydrogenolysis reaction temperature is 250-300 ℃, the hydrogenolysis reaction pressure is 1 MPa-6 MPa, the hydrogenolysis reaction time is 2-12 hours, and the stirring speed in the hydrogenolysis reaction process is 1000 r-5000 r/min.
In order to improve the yield of the hydrogenolysis reaction and the quality of hydrogenolysis oil, a hydrogenolysis catalyst is selected for hydrogenolysis reaction, the hydrogenolysis catalyst is a metal supported catalyst, a carrier is Nb 2O5, supported metal is Pt, and the Pt load is 1-10%. The hydrogenolysis catalyst is pre-packed in a fixed catalyst bed 25.
In this step, the source of the PLA-based waste plastics is not particularly limited, and may be from industrial production or from daily life.
The step 2 is that the gas mixture is conveyed to a pressure reducer 3 through a gas phase discharge hole 23 and a pipeline for pressure relief, the pressure is reduced to 1-3 MPa, damage to a device caused by excessive pressure is prevented, the gas mixture after pressure relief is conveyed to a drying tank 4 for drying, subsequent separation is prevented from being influenced, the dried gas mixture is conveyed to a cold box 5, the hydrogen gas and H 2 are separated through a cryogenic separation method, the separated H 2 is stored in a hydrogen storage tank 6, the stored H 2 can be continuously used as reaction gas for hydrogenolysis reaction after being compressed by a compressor 7, and the separated hydrogen gas can be used as fuel.
And 3, pumping the hydrogenolysis oil and H 2 O into a rectifying tower 9 through a liquid phase discharge port 28 and a liquid phase conveying pump 8, and separating light components from heavy components based on boiling point difference by controlling the distillation temperature to obtain water, other unknown carbon-containing compounds, light component hexyl propionate and heavy component butyl propionate.
Wherein the boiling point of the light component is less than or equal to 75 ℃, and the boiling point of the heavy component is more than 140 ℃. The invention does not limit the condition of distillation, and can be carried out according to the conventional distillation operation.
In one possible embodiment, the mass percentage of PLA in the PLA-based waste plastic feedstock in step 1 is 90%.
In one possible implementation manner, in step 1, the PLA-based waste plastics are subjected to a crushing treatment, and the particle size of the crushed PLA-based waste plastics is less than 50 mm, so that continuous and stable conveying of the crushed PLA-based waste plastics is ensured.
In one possible embodiment, in step 1, the mass percentage of Pt of the hydrogenolysis catalyst is 1% -10%.
In one possible embodiment, in step 1, the mass ratio of PLA-based waste plastics to the hydrogenolysis catalyst is (1-10): 1.
The method not only enhances the economy of the PLA-based waste plastic recycling process, but also ensures the uniformity and reliability of the quality of the final product due to simple and convenient system operation control and stable working condition.
Example 1
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
the crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 3 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 2
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle through a pipeline and a solid-phase feed inlet 21 from the outlet of the crusher 1 according to the mass ratio of the PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 300 ℃ and H 2 pressure of 3 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 3
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 250 ℃ and H 2 pressure of 3 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 4
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 1 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 5
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 6
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 2H under the conditions of 275 ℃ and H 2 pressure of 3 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 7
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 4 hours under the conditions of 275 ℃ and H 2 pressure of 3 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 8
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 12 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 9
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 5:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 3 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 10
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 1:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 11
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 1 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 12
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 10 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 13
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 1000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 14
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
the crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 5000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 2 MPa through a pressure reducer 3, then the gas mixture with the pressure of 2 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 15
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, and the mass percent of Pt is 5 percent and is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 1 MPa through a pressure reducer 3, then the gas mixture with the pressure of 1 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
Example 16
The PLA-based waste plastics are subjected to a hydrogenolysis reaction in the PLA-based waste plastics hydrogenolysis system shown in fig. 1, the specific process is as follows:
Step 1, crushing PLA-based waste plastics of a certain refuse landfill, wherein the granularity of the crushed PLA-based waste plastics is less than 50 mm, and the mass percentage of PLA is 90%;
The crushed PLA-based waste plastics are conveyed to a hydrogenolysis reaction kettle from the outlet of the crusher 1 through a pipeline and a solid-phase feed inlet 21 according to the mass ratio of the crushed PLA-based waste plastics to the hydrogenolysis catalyst of 10:1. Wherein the hydrogenolysis catalyst is a Pt/Nb 2O5 catalyst, the mass percentage of Pt is 3 percent, and the Pt is pre-filled in a catalyst fixed bed 25 in the hydrogenolysis reaction kettle;
Introducing Ar gas into the hydrogenolysis reaction kettle to purge the hydrogenolysis reaction kettle so as to remove air in the hydrogenolysis reaction kettle, then introducing reaction gas H 2 into the hydrogenolysis reaction kettle, starting a temperature and pressure control device 26, and reacting for 6 hours under the conditions of 275 ℃ and H 2 pressure of 6 MPa and stirring speed of a stirring device 24 of 3000 r/min to finally obtain gas mixture, hydrogenolysis oil and water;
Step 2, the gas mixture is firstly decompressed to 3 MPa through a pressure reducer 3, then the gas mixture with the pressure of 3 MPa is dried through a drying tank 4 and then is sent into a cold box 5 with the temperature of minus 100 ℃ for cryogenic separation, H 2 and hydrogenolysis gas are separated, and the separated H 2 is sent into a hydrogen storage tank 6 for storage for subsequent use;
and 3, delivering the hydrogenolysis oil to a rectifying tower 9 by using a liquid phase delivery pump 8 to rectify to obtain water, hexyl propionate, butyl propionate and other unknown carbon-containing compounds, wherein the hexyl propionate is a light component, and the butyl propionate is a boiling point heavy component.
The liquid mass is obtained by weighing, the gas product mass is obtained by subtraction, and the product yield is calculated according to each product mass. The yields of the hydrogen peroxide gas, hexyl propionate, butyl propionate and water obtained in this example are shown in Table 1.
TABLE 1
The conversion in Table 1 is calculated as follows:
;
after the treatment by the catalytic hydrogenolysis method provided by the invention, the conversion rate of PLA-based waste plastics is up to 100%, the yield of butyl propionate is up to 56.8%, the yield of hexyl propionate is up to 10.5%, and the boiling points of the products are greatly different and are easy to separate by rectification.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not deviate from the essence of the technical solution of the corresponding embodiments of the present invention.

Claims (10)

1. The polylactic acid-based waste plastic catalytic hydrogenolysis system is characterized by comprising a pulverizer (1), a hydrogenolysis reaction kettle, a pressure reducer (3), a liquid phase conveying pump (8), a hydrogen separation system and a rectifying tower (9);
The outlet of the pulverizer (1) is connected with a solid-phase feed inlet (21) of the hydrogenolysis reaction kettle;
The hydrogenolysis reaction kettle comprises a kettle body, a stirring device (24), a catalyst fixed bed (25), a temperature and pressure control device (26) and a heating sleeve (27), wherein stirring blades of the catalyst fixed bed (25) and the stirring device (24) are positioned in the kettle body, the heating sleeve (27) is coated outside the kettle body, and the temperature and pressure control device (26) is electrically connected with the heating sleeve (27);
the kettle body is provided with a solid phase feed inlet (21), a gas phase feed inlet (22), a gas phase discharge outlet (23) and a liquid phase discharge outlet (28);
the gas-phase discharge port (23) is connected with the inlet of the pressure reducer (3), the outlet of the pressure reducer (3) is connected with the inlet of the hydrogen separation system, and the outlet of the hydrogen separation system is connected with the gas-phase feed port (22);
The liquid phase discharge port (28) is connected with the inlet of the rectifying tower (9).
2. The polylactic acid-based waste plastic catalytic hydrogenolysis system according to claim 1 is characterized in that the hydrogen separation system comprises a drying tank (4), a cold box (5), a hydrogen storage tank (6) and a compressor (7), wherein the inlet of the drying tank (4) is connected with the outlet of a pressure reducer (3), the outlet of the drying tank (4) is connected with the inlet of the cold box (5), the outlet of the cold box (5) is connected with the inlet of the hydrogen storage tank (6), the outlet of the hydrogen storage tank (6) is connected with the inlet of the compressor (7), and the outlet of the compressor (7) is connected with a gas phase feed port (22).
3. A polylactic acid-based waste plastics catalytic hydrogenolysis system according to claim 1 characterized in that the rotation trajectory of the stirring blades of the stirring device (24) is tangential to the inner surface of the fixed bed (25) of catalyst.
4. A catalytic hydrogenolysis method of polylactic acid-based waste plastics based on the catalytic hydrogenolysis system of any one of claims 1-3, characterized by comprising the following steps:
The method comprises the steps of 1, crushing and screening polylactic acid-based waste plastics through a crusher (1), then feeding the crushed and screened polylactic acid-based waste plastics into a hydrogenolysis reaction kettle, and introducing H 2 into the hydrogenolysis reaction kettle, heating, melting and liquefying the polylactic acid-based waste plastics in the hydrogenolysis reaction kettle, wherein the melted and liquefied polylactic acid macromolecules are subjected to hydrogenolysis reaction under the action of a hydrogenolysis catalyst and H 2 to break ester bonds of unsaturated polylactic acid macromolecules so as to generate saturated micromolecular lactic acid and an active C 3 intermediate, and then the saturated micromolecular lactic acid and the active C 3 intermediate are subjected to catalytic hydrogenation and reconstruction reaction so as to generate hydrogenolysis oil, hydrogenolysis gas and H 2 O, wherein the hydrogenolysis catalyst is a Pt supported catalyst, and a carrier is Nb 2O5;
Step 2, decompressing and drying the hydrogen gas and the residual H 2 in the hydrogenolysis reaction, and then sending the hydrogen gas and the residual H 2 into a cold box (5), and separating the hydrogen gas and the H 2 by a cryogenic separation method;
and (3) separating components of the hydrogenolysis oil and water mixture to obtain water, hexyl propionate and butyl propionate.
5. The method for catalytic hydrogenolysis of polylactic acid-based waste plastics according to claim 4, wherein in the step 1, the mass ratio of the polylactic acid-based waste plastics to the hydrogenolysis catalyst is (1-10): 1.
6. The method for catalytic hydrogenolysis of polylactic acid-based waste plastics according to claim 4, wherein in the step 1, the mass percentage of Pt in the hydrogenolysis catalyst is 1% -10%.
7. The method for catalytic hydrogenolysis of polylactic acid-based waste plastics according to claim 4, wherein in the step 1, conditions of the hydrogenolysis reaction include a hydrogenolysis reaction temperature of 250 ℃ to 300 ℃, a hydrogenolysis reaction pressure of 1MPa to 6MPa, and a hydrogenolysis reaction time of 2 hours to 12 hours.
8. The method for catalytic hydrogenolysis of polylactic acid-based waste plastics according to claim 4, wherein in the step 1, the stirring speed of the stirring device (24) is 1000 r/min-3000 r/min.
9. The method for catalytic hydrogenolysis of polylactic acid-based waste plastics according to claim 4, wherein in the step 2, after separating the hydrogen gas from H 2, the separated H 2 is sent to a hydrogen storage tank (6) for storage, and the stored H 2 is compressed by a compressor (7) and then used as a reaction gas for the hydrogenolysis reaction.
10. The method for catalytic hydrogenolysis of polylactic acid-based waste plastics according to claim 4, wherein in step 2, the mixture of hydrogenolysis oil and water is subjected to component separation by means of rectification, wherein the boiling point of light components is less than or equal to 75 ℃ and the boiling point of heavy components is >140 ℃.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5136113A (en) * 1991-07-23 1992-08-04 E. I. Du Pont De Nemours And Company Catalytic hydrogenolysis
CN106831677A (en) * 2016-12-28 2017-06-13 浙江正大新材料科技有限公司 A kind of novel preparation method of methyl hexahydrophthalic anhydride
CN109942378A (en) * 2019-01-25 2019-06-28 华东理工大学 A kind of method that wooden vegetable oil prepares alkylphenol and alkyl diphenol
CN110819372A (en) * 2019-10-15 2020-02-21 中国科学院广州能源研究所 A method for preparing aromatic hydrocarbons and hydrogen-rich fuel gas by catalytic thermal conversion of polyolefin waste plastics
CN210559364U (en) * 2019-04-18 2020-05-19 裴栋中 Hydrogen-containing dry gas purification hydrogen production device for refinery plant
US20210031163A1 (en) * 2018-04-11 2021-02-04 W. L. Gore & Associates, Inc. Metal Supported Powder Catalyst Matrix And Processes For Multiphase Chemical Reactions
CN116262217A (en) * 2021-12-13 2023-06-16 中国科学院大连化学物理研究所 A kind of heterogeneous hydrocarbon conversion device and conversion method thereof
CN117000287A (en) * 2022-04-29 2023-11-07 上海科技大学 Catalyst and its preparation method, application and method for catalytic hydrogenolysis

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5136113A (en) * 1991-07-23 1992-08-04 E. I. Du Pont De Nemours And Company Catalytic hydrogenolysis
CN106831677A (en) * 2016-12-28 2017-06-13 浙江正大新材料科技有限公司 A kind of novel preparation method of methyl hexahydrophthalic anhydride
US20210031163A1 (en) * 2018-04-11 2021-02-04 W. L. Gore & Associates, Inc. Metal Supported Powder Catalyst Matrix And Processes For Multiphase Chemical Reactions
CN109942378A (en) * 2019-01-25 2019-06-28 华东理工大学 A kind of method that wooden vegetable oil prepares alkylphenol and alkyl diphenol
CN210559364U (en) * 2019-04-18 2020-05-19 裴栋中 Hydrogen-containing dry gas purification hydrogen production device for refinery plant
CN110819372A (en) * 2019-10-15 2020-02-21 中国科学院广州能源研究所 A method for preparing aromatic hydrocarbons and hydrogen-rich fuel gas by catalytic thermal conversion of polyolefin waste plastics
CN116262217A (en) * 2021-12-13 2023-06-16 中国科学院大连化学物理研究所 A kind of heterogeneous hydrocarbon conversion device and conversion method thereof
CN117000287A (en) * 2022-04-29 2023-11-07 上海科技大学 Catalyst and its preparation method, application and method for catalytic hydrogenolysis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘明;郑典模;胡萍;: "废塑料催化裂解制燃料油的研究", 江西化工, no. 01, 30 March 2006 (2006-03-30), pages 10 - 13 *

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