EP0344376A1 - Verfahren zur Umwandlung von schweren Kohlenwasserstoffen zu leichteren Kohlenwasserstoffen - Google Patents
Verfahren zur Umwandlung von schweren Kohlenwasserstoffen zu leichteren Kohlenwasserstoffen Download PDFInfo
- Publication number
- EP0344376A1 EP0344376A1 EP88306021A EP88306021A EP0344376A1 EP 0344376 A1 EP0344376 A1 EP 0344376A1 EP 88306021 A EP88306021 A EP 88306021A EP 88306021 A EP88306021 A EP 88306021A EP 0344376 A1 EP0344376 A1 EP 0344376A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- feed
- process according
- range
- catalyst
- coke
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
-
- 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
- C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
- C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
- C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal cracking steps
-
- 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
- C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
- C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
- C10G51/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only including only thermal and catalytic cracking steps
-
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
Definitions
- FCC fluidized catalytic cracking
- the concentrations of the various materials in the feed should be limited to the following: sulfur, from about 0.15 weight & ("wt %") to about 1.5 wt %; for heavy metals, from about 0.1 ppm to about 100 ppm of nickel and/or its equivalents; sodium, from 1 to about 8ppm; conradson carbon content, from about 1 wt % to about 12 wt %.
- the atmospheric residues contain high concentrations of the above-mentioned contaminants and, in general, cannot be directly used as feed for FCC.
- the art has developed some processes such as visbreaking, delayed coking, deasphalting, hydrotreating, and hydrocracking for reduced contaminants. These processes, however, further increase the capital investment and operating cost.
- the present invention in its broadest context encompasses a process and catalyst for converting heavy crude oils and/or solid hydrocarbons to gasoline and other light fraction products in a liquid phase reactor or in a fluidized catalytic cracking converter comprising the steps of:
- the process of the present invention for converting heavy crude oils and/or solid hydrocarbons to gasoline and other lighter fraction products comprises the steps of:
- the process of the present invention can use various heavy crude oils as feed, whether they are of petroleum origin or not.
- the various heavy crude oils include widely diverse material, such as crude oils as removed from the well, atmospheric residues containing distillates above about 340°C from a crude oil distillation column.
- the feed is composed of fairly high molecualr weight materials of very complex chemical character. Crude oils and atmospheric residues usually contain a high proportion of total nitrogen, sulfur and metals.
- feeds include heavy crude from vacuum residues, extracts from solvent deasphalting, aromatic extracts from lube refining, tar bottoms, heavy cycle oil and other refinery waste strams, as well as naturally occurring extra heavy oils, shale oils, tar sand extracts, oil from coal liquefactions, bitumen crude oil and mixtures of the foregoing.
- the feed can be directly converted to light hydrocarbons without pre-treating such as demetalation, desulfurization, and decarbonization or the passivation of heavy metals in a fluidized catalytic cracking unit.
- the process of the present invention is also applicable to various solid hydrocarbons.
- the solid hydrocarbons include widely diverse materials; synthetic polymers, such as polyethylenes, polyvinyls, polystyrenes, polyamides and polyesters; elastomers, including SBR, butyl rubber, natural rubbers and polychloroprene; coals, including bituminous coal and sub bituminous coal; and waste streams from waste plastic, waste cable, scrap tires and the like. Mixtures of the foregoing may also be used as feeds.
- These solid hydrocarbon feeds may have a sulfur content, high chloride content, high nitrogen content and high metals content. But additional purification to remove the contaminants prior to conversion is not required.
- the particle size of the solid hydrocarbons is preferably about 1 mm.
- the solid hydrocarbons is admixed with the catalyst and liquid hydrocarbons to from a paste or slurry.
- the liquid hydrocarbons can be recycled oils formed in the conversion or any heavy oils such as Virgin Gas Oil, Light cyclie Oil, atmospheric residues and crude oils.
- the catalysts suitable for the process of the invention is a particulate catalyst comprising metal alkoxides and/or phenoxides as the active ingredient.
- the organometallic compound is represented by the formula: M(OR) n wherein M represents a metal selected from the group consisting of groups IA, IIA, IIIA, IVA, IB, IIB, and IVB of the Periodic Table; OR is a alkoxy functional group derived from Grignard reagents, phenols, ethers or from primary, secondary, or tertiary alcohols; n is 1, 2, 3, or 4; and R represents alkyl, cycloalkyl, phenyl, or allyl with 1 to 10 carbon atoms.
- the selected catalyst is soluble in the feed or in a hydrocarbon solvent miscible with the feed.
- Suitable solvents are Virgin Gas Oil, Light Cycle Oils, Heavy Gas Oil, naphtha, alcohols, aromatic and organic solvents.
- the amount of the catalyst effective to convert said feed to light fraction hydrocarbons is about 0.001 wt % to about 1 wt % based on the total weight of the heavy crude oil and/or solid hydrocarbons.
- the catalyst may be introduced in any suitable fashions. For instance, they may be admixed with crude oils before the atmospheric distallation column or admixed with atmospheric residues from the bottom of the distillation column.
- the catalyst may, if desired, be admixed with atmospheric residues before or after the furnace for delayed coking and visbreaking. Alternatively, the catalyst may be admixed with the feed prior to being contacted with carrier particles later into the cracking zone, or be deposited with carrier particles prior to being contacted with the feed later into the cracking zone.
- the catalyst when used in accordance with this invention in a gas solid system such as in fluidized catalytic cracking, is continuously contacted with the feed and carrier particles in the cracking zone.
- the composition of the solid carrier particles useful in this invention is not critical, provided that such carrier particles are capable of promoting the desired final hydrocarbon conversion.
- Carrier particles having widely varying compositions conventionally used as carriers in hydrocarbon conversion can be used.
- suitable materials include natural clay such as montmorillonite, kaolin and bentonite clays, natural or synthetic amorphous materials, such as amorphous silica/alumina, silica/magnesia and silica/zirconia composites; and an alternative of coke and carbon.
- the carrier particles can be solid particles or discrete entities. This is not critical to the present invention. It may depend on the type of fluidized reactor-regenerator system employed. Such carrier particles may be formed into any desired shapes, such as pills, cakes, powders, granules and the like using conventional methods.
- the catalyst with a particle size of 0.25 mm to about 6 mm may be used.
- the catalyst particles have a diameter in range of about 10 microns to about 650 microns.
- the cracking reaction of the present invention is carried out at a temperature of from about 250°C to about 500°C, preferably from about 350°C to about 450°C, and a pressure of from about 1 to about 20 atms.
- a residence time of from about 1 minute to 30 minutes is required.
- the residence times for liquid feeds can be lower, from about 1 sec to about 5 minutes.
- the resultant products, including light fraction hydrocarbons and coke, are further contacted with superheated steam at a temperatures of about 300°C to about 500°C and a pressure of about 1 to about 10 atms for a residence time of about 0.1 sec to about 5 minutes.
- the preferred liquid phase reactor may be a tank, a tubular reactor of a tower, and are described in "Perry's Chemical Engineers' Handbook".
- the tank, or tubular reactor, or tower or furnace, or the bottom of the distillation column is maintained at a temperature of from about 350°C to about 450°C and a pressure of about 1 to about 20 atms.
- the preferred gas solid converter of this invention is a conventional fluidized catalytic cracking unit.
- the catalyst is admixed with feed prior to being contacted with carrier particles from the regenerator later into the cracking zone.
- the cracking reaction is carried out both in liquid phase and gas solid phase at a temperature of from about 350°C to about 500°C for a residence time of about 1 sec to about 5 minutes.
- the spent, coke and catalyst laden carrier particles are separated from the stream of the resultant cracked products, and regenerated in regeneration beds by burning the coke on the spent catalyst particles with oxygen.
- the regenerated hot carrier particles is recycled to the cracking zone to be contacted with feed and catalyst mixtures.
- any separation operation which can effectively separate the light hydrocarbons and coke from the other cracked products, such as described in "Perry's Chemical Engineers' Handbook", is contemplated to be useful in the present invention.
- the product mixture of light hydrocarbons and coke is admixed with superheated steam and is sprayed into a spray drying unit, or a cyclone separator, or a delayed coking unit.
- a conventional fluidized catalytic cracking unit is used.
- Any conventional reactor regenerator system may also be applied, e.g., a fixed bed catalyst conversion regenerator and separator system in a ebullition catalyst conversion and separation system, or a system which continuously circulates carrier particles between the reaction zone and the regeneration zone, or the like.
- the atomizing fluid for the foregoing separation is superheated steam or hot carrier particles at a temperature of about 350°C to about 500°C.
- a liquid hydrocarbon for example heavy crude oils
- a tubular reactor 4 which is operated at a temperature of about 350°C to about 450°C and maintained at a pressure for about 1 to about 7 atms via 5.
- the residence time in the tubular reactor is about 1 sec to about 5 minutes.
- the resultant light hydrocarbons and coke are withdrawn from 7 and contacted with superheated steam via 8 at 350°C to 450°C and fed into separator 9.
- the vaporized light hydrocarbons mixed with steam is withdrawn from 10 to a fractionator.
- the coke is withdrawn from 11.
- Fig. 1 pertaining to foregoing system can be modified to be applicable to any existing integrated refinery operation in a suitable fashion.
- the atmospheric residues 1 are admixed with the catalyst from 12 and fed into the furance 14 where the temperature is allowed to rise to a preset point for a preset residence time in a tubular reactor 15 for hydrocarbon conversion.
- the resulting cracked products are contacted with superheated steam 16 and fed into the delayed coking unit 17.
- the vaporized light hydrocarbons mixed with steam is withdrawn from 19 and fed to distallation column 20, and coke is withdrawn from 18.
- crushed polymers for example, such as waste tires, waste cables, waste plastic and coals together with heavy crude oils or recycle oils from a conversion process and catalyst via 21, 22, 23, is introduced into a tubular reactor 24 under cracking conditions at a temperature range of about 350°C to about 450°C for a residence time about 1 to about 30 minutes.
- the pressure in the tubular reactor is maintained via 25 in a range of about 1 to about 7 atms.
- Any waste steel and copper wires are withdrawn from 26.
- the waste steel and copper wires are withdrawn from 26.
- the cracked light fraction products and coke are fed via 27 and contacted with superheated steam via 28 at 350°C to 450°C and brought into separator 29.
- the light fractions mixed with superheated steam are withdrawn from 30 for fractionating.
- the coke is withdrawn from 31.
- a conventional fluidized catalytic cracking unit can be improved by introducing feed via 41 together with catalyst via 32 into tubular reactor 3 at a temperature from about 350°C to about 450°C and a pressure from about 1 to about 7 atms for a residence time from about 1 sec to about 5 minutes.
- the mixture of feeds is further contacted with carrier particles via 38 into the cracking zone 35.
- the cracked light hydrocarbons and spent coke is separated in the reactor.
- the coke laden particles are withdrawn via 36 and fed into regenerator 37 for removing the coke by burning with oxygen.
- the vaporized light fractions is withdrawn from 50 for further fractionating.
- the temperature of the carrier particles is maintained in a range from about 350°C to about 500°C.
- the catalyst may, if desired, by mixed with the carrier particles prior to being contacted with feed later into the cracking zone such as via the dotted line from 32.
- the catalyst used for the foregoing described hydrocarbon conversion process is in an amount of about 0.001 to about 1 weight percent of feed, preferably about 0.001 to about 0.1 weight percent of feed.
- Asphaltene and tar as feed is tested. 300 grams of feed with catalyst is placed into a one liter tubular reactor at a preset temperature and pressure. After the desired residence time is reached, nitrogen is introduced into the tubular reactor in an amount sufficient to separate the light fraction hydrocarbons from coke. The cracking conditions, characteristics of the feeds and the cracked products are presented in Table 2. Table 2 Test No. 4 5 6 Feed Asphaltene Asphaltene Tar MC-150 MC-180 - Conradson carbon % wt 22.8 7.1 21.2 Catalyst A A C Catalyst, wt % 0.04 0.04 0.04 Cracking temperature, C 400 400 400 Pressure, atm 3.5 3.5 1.
- waste cables, waste tires, and coal are prepared as feed.
- the waste cables and waste tires are crushed to a size of less than 25 mm and coal is ground to a size of less than 1 mm.
- the feed and catalyst a combined with atmospheric residues from test No. 2 or gas oil are placed in a one liter tubular reactor in a tubular furnace. Heat is applied and the reactor pressurized to preset temperature and pressure. After a preset residence time is reached, nitrogen is introduced into the tubular reactor in an amount sufficient to separate the light fractions from coke and metal wire.
- a portion of a catalyst is mixed with atmospheric residues from test No. 2 and heavy gas oil, and another portion of a catalyst is deposited on the coke particle from test 7.
- a tubular reactor in a tube furnace is filled with catalyst deposited coke particles.
- the reactor is attached to a condenser and a nitrogen purger. Heat is applied to a preset temperature and the feed is introduced by a syringe pump to be contacted with the catalyst particles.
- the resultant cracked products are continuously withdrawn from the condenser.
- nitrogen gas is introduced to further separate light fractions from coke. The results are shown in Table 4. Table 4 Test No.
- a commercial fuel oil was used as the feed in the cracking operations in the following tests and had the following characteristics: API gravity 21; sulfur 2.5 st %; conradson carbon number 6.33; nickel equivalent metals 120 ppm.
- 300 grams of the feed and 0.2 cc of catalyst A is placed in a one liter tubular reactor in a tube furnace and heat and pressure were applied to a preset temperature and pressure. After a preset residence time is reached, the resultant products of Test No. 12 is contacted with superheated steam at 350°C; and the resultant products of Test No. 13 is contacted with nitrogen at 350°C.
- the data are shown in Table 6 below. Treatment with superheated steam reduced the amount of coke formed by about 50%.
- Table 6 Test No. 12 13 Cracking temperature, °C 395 395 Cracking pressure, atm 3.0 4.0 Residence time, sec. 3.0 3.0 Coke, wt % 3.24 7.14
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US20205488A | 1988-06-03 | 1988-06-03 | |
US202054 | 1988-06-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0344376A1 true EP0344376A1 (de) | 1989-12-06 |
Family
ID=22748347
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88306021A Withdrawn EP0344376A1 (de) | 1988-06-03 | 1988-07-01 | Verfahren zur Umwandlung von schweren Kohlenwasserstoffen zu leichteren Kohlenwasserstoffen |
Country Status (1)
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EP (1) | EP0344376A1 (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0745659A2 (de) * | 1995-06-01 | 1996-12-04 | ENIRICERCHE S.p.A. | Verfahren zur vollständigen Umwandlung von Kohlenwasserstoff-Werkstoffen mit hohem Molekulargewicht |
EP0814143A2 (de) * | 1996-06-06 | 1997-12-29 | Mitsubishi Heavy Industries, Ltd. | Verfahren und Apparat zur Konvertierung von Kunststoffabfällen in Öl |
US6504068B1 (en) | 1996-06-06 | 2003-01-07 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for converting a plastic waste into oil in a stainless steel reactor |
CN114436735A (zh) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | 原油裂解的装置及方法 |
CN114437768A (zh) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | 原油裂解的方法 |
CN115353904A (zh) * | 2022-08-02 | 2022-11-18 | 中国矿业大学 | 一种过热蒸汽体系高效液化塑料垃圾制油的方法及其装置 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3862898A (en) * | 1973-07-30 | 1975-01-28 | Pullman Inc | Process for the production of olefinically unsaturated hydrocarbons |
US4244839A (en) * | 1978-10-30 | 1981-01-13 | Exxon Research & Engineering Co. | High surface area catalysts |
WO1981001576A1 (en) * | 1979-12-04 | 1981-06-11 | K Schmid | Process for producing lower-molecular-weight hydrocarbons from higher molecular-weight hydrocarbons and auxiliary agents therefor |
US4743357A (en) * | 1983-12-27 | 1988-05-10 | Allied Corporation | Catalytic process for production of light hydrocarbons by treatment of heavy hydrocarbons with water |
-
1988
- 1988-07-01 EP EP88306021A patent/EP0344376A1/de not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3862898A (en) * | 1973-07-30 | 1975-01-28 | Pullman Inc | Process for the production of olefinically unsaturated hydrocarbons |
US4244839A (en) * | 1978-10-30 | 1981-01-13 | Exxon Research & Engineering Co. | High surface area catalysts |
WO1981001576A1 (en) * | 1979-12-04 | 1981-06-11 | K Schmid | Process for producing lower-molecular-weight hydrocarbons from higher molecular-weight hydrocarbons and auxiliary agents therefor |
US4743357A (en) * | 1983-12-27 | 1988-05-10 | Allied Corporation | Catalytic process for production of light hydrocarbons by treatment of heavy hydrocarbons with water |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5788724A (en) * | 1995-06-01 | 1998-08-04 | Eniricerche S.P.A. | Process for the conversion of hydrocarbon materials having a high molecular weight |
EP0745659A3 (de) * | 1995-06-01 | 1997-03-05 | Eniricerche Spa | Verfahren zur vollständigen Umwandlung von Kohlenwasserstoff-Werkstoffen mit hohem Molekulargewicht |
EP0745659A2 (de) * | 1995-06-01 | 1996-12-04 | ENIRICERCHE S.p.A. | Verfahren zur vollständigen Umwandlung von Kohlenwasserstoff-Werkstoffen mit hohem Molekulargewicht |
CN1097608C (zh) * | 1996-06-06 | 2003-01-01 | 三菱重工业株式会社 | 将废塑料转化为油的方法和装置 |
EP0814143A3 (de) * | 1996-06-06 | 1998-04-01 | Mitsubishi Heavy Industries, Ltd. | Verfahren und Apparat zur Konvertierung von Kunststoffabfällen in Öl |
US6352674B2 (en) | 1996-06-06 | 2002-03-05 | Mitsubishi Heavy Industries, Ltd. | Apparatus for converting a plastic waste into oil |
EP0814143A2 (de) * | 1996-06-06 | 1997-12-29 | Mitsubishi Heavy Industries, Ltd. | Verfahren und Apparat zur Konvertierung von Kunststoffabfällen in Öl |
US6504068B1 (en) | 1996-06-06 | 2003-01-07 | Mitsubishi Jukogyo Kabushiki Kaisha | Method for converting a plastic waste into oil in a stainless steel reactor |
CN114436735A (zh) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | 原油裂解的装置及方法 |
CN114437768A (zh) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | 原油裂解的方法 |
CN114437768B (zh) * | 2020-10-30 | 2023-05-12 | 中国石油化工股份有限公司 | 原油裂解的方法 |
CN115353904A (zh) * | 2022-08-02 | 2022-11-18 | 中国矿业大学 | 一种过热蒸汽体系高效液化塑料垃圾制油的方法及其装置 |
CN115353904B (zh) * | 2022-08-02 | 2024-02-23 | 中国矿业大学 | 一种过热蒸汽体系高效液化塑料垃圾制油的方法及其装置 |
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