CN102372552A - Catalytic pyrolysis method for producing ethene and propylene - Google Patents
Catalytic pyrolysis method for producing ethene and propylene Download PDFInfo
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Abstract
The invention relates to a catalytic pyrolysis method for producing ethene and propylene, and aims to solve technical problems of low raw material conversion rate and low yield of ethene and propylene when an existing fluidized bed catalyst is applied to naphtha catalytic pyrolysis for producing ethene and propylene. According to the invention, raw materials of naphtha and water contact with a fluidized bed catalyst to obtain the ethene and propylene, under a reaction temperature of 600-750 DEG C, an air speed of 0.1-2 h <-1> and a weight ratio of water to oil of 0.2-8:1. The fluidized bed catalyst includes the following ingredients, by weight: 0.5-15.0 parts of at least one selected from phosphor, rare earth or alkaline earth element oxide, 85-99.5 parts of microballoon with a particle size of 10-200 mum, from in situ synthesis and containing ZSM-5 molecular sieve. The above technical scheme well solves the problems and can be applied to industrial production of producing ethene and propylene by naphtha catalytic pyrolysis.
Description
Technical field
The present invention relates to a kind of catalytic pyrolysis and produce the method for ethene and propylene, is raw material about adopting petroleum naphtha specifically, with the fluid catalyst of the in-situ crystallization technology preparation method through catalytic pyrolysis process production ethylene, propylene.
Background technology
Ethene, propylene are very important two kinds of petrochemical materials, and present global ethene and propylene mainly are to be produced by the steam cracking process.Because prior steam scission reaction temperature is up to 820～1000 ℃, the process energy consumption is very high, accounts for 50% of whole ethylene industry energy consumption.This process is non-catalytic radical thermally splitting mechanism, ethylene/propene lower (0.5～0.7) in its product.Current, face country petrochemical industry is proposed during the 11th Five-Year energy-saving and cost-reducing 20% requirement and the propylene demand that increases day by day, the prior steam cracking process is just standing acid test.Catalytic pyrolysis is to utilize catalyzer petroleum naphtha to be carried out the process of producing low-carbon olefins by cracking.Compare with steam cracking, catalytic pyrolysis has temperature of reaction low (600～780 ℃), and energy consumption significantly reduces and the reaction product propylene/ethylene compares the advantage of high (0.6～1.3).This technology occurs, and the innovation of producing the ethylene, propylene process for the prior steam cracking has brought hope.
Russia organic synthesis research institute and catalytic cracking catalyst active ingredient mainly are variable valency metal compounds such as manganese, vanadium, niobium, tin, iron, and wherein catalytic performance is optimum is to be potassium vanadate (or sodium) fluid catalyst of carrier with ceramic (andaluzite-corundum).Though this catalyzer has good heat resistance, the advantage of low coking rate and high stability, its cracking reaction temperature are during still up to 770 ℃.[Picciotti?M.[J].Oil?Gas?J，1997，95(25)：53～56.]
Japan Toyo Engineering Corporation is from the THR-RC fluid catalyst, and typical chemistry consists of CaO: Al
2O
3: SiO
2: Fe
2O
3MgO=51.46: 47.74: 0.06: 0.185: 0.25.This catalyzer is raw material with the petroleum naphtha, and the cracked temperature of reaction is still up to 750 ℃.[Zhang Jian, etc. [J]. petrochemical complex is dynamic, and 1995; (11): 24～30; 34.] MS4087350 disclosed that the fluidized-bed Mg of normal pressure and vacuum residuum catalysis raising the output alkene is catalyst based, this catalyst reaction temperatures is up to 745 ℃, and the ethylene, propylene yield also has only 28.6%.
Patent CN02152479 has reported that the aperture that Li, alkaline earth, phosphorus and REE are modified is the sieve catalyst of 0.45～0.75nm, and this catalyzer mainly is applicable to the technology of fixed bed hydrocarbon catalytic cracking system alkene.Also use intensity and abrasion that the material of aluminum oxide, aluminum oxide and amorphous aluminum silicide class is used to improve catalyzer in its catalyzer inevitably.
Patent MS6566693B1 has reported the catalyzer of a kind of ZSM-5 of the phosphorous modification that is used for petroleum hydrocarbon catalytic pyrolysis system alkene; The ZSM-5 molecular sieve content has only 40% at the most in this fluid catalyst, and all the other are the component such as amorphous alumina and silicon oxide that is used for sticker.
At present; The molecular sieve type fluid catalyst that is used for naphtha cracking system alkene is formed; Mostly to introduce silicon-aluminum oxide materials such as aluminum oxide, silicon-dioxide and amorphous aluminum silicide as sticker, make the fluidized catalyst of spray shaping have physical strength and shape preferably.In addition, the FCC catalyzer also will add some clays, like some materials such as kaolin, polynite, carclazytes, is used to increase the wear resistance of fluidized catalyst.More than this traditional method prepare fluid catalyst and be called as the preformed catalyst that narrows.Introduce sticker and wear resistant components in the fluidized catalyst, not only can reduce the content of catalytic active component-molecular sieve, cause the adsorptive capacity of catalyzer to descend, effective surface area reduces.And because sticker and wear-resisting possibility part component can get into zeolite cavity or blocking portion zeolite aperture; Therefore introduced diffusional limitation; Cause adsorptive power to weaken, the adsorption selectivity variation, absorption and desorption rate descend; In catalytic cracking reaction, then cause cracking activity to reduce, the ethylene, propylene yield reduces.Like sticker or all or part of zeolite that is converted into of wear resistant components that the traditional spray moulding is introduced; Can effectively improve the content of the active ingredient-zeolite in the fluidized catalyst; Improve its effective active specific surface; Alleviate the stopping state in reaction duct, may improve the activity and stability of fluid catalyst.The method of this synthetic fluidized-bed is called as in-situ synthesis, and catalyzer is called as the synthetic fluid catalyst of original position.
In sum, prior art is applied to fluid catalytic cracking when producing ethene with the propylene process, has the low and ethene of feed stock conversion, technical problem that propene yield is low.
Summary of the invention
Technical problem to be solved by this invention be prior art exist feed stock conversion low with ethene, technical problem that propene yield is low; The method that provides a kind of new catalytic pyrolysis to produce ethene and propylene; Be applied to the naphtha catalytic pyrolysis preparing ethylene propylene process, this method have feed stock conversion high with ethene, advantage that propene yield is high.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of catalytic pyrolysis is produced the method for ethene and propylene, is raw material with petroleum naphtha and water, and 600～750 ℃ of temperature of reaction, weight space velocity is 0.1～4.0h
-1Water weight of oil ratio is under 0.2～8.0: 1 the processing condition; The raw material reaction that contacts with fluid catalyst obtains ethene and propylene, and wherein fluid catalyst comprises following component in parts by weight: a) 0.5～15 part is selected from least a in phosphorus, rare earth or the alkaline earth element oxide compound; B) 85～99.5 parts are selected from the microballoon that the original position synthetic contains 10～200 μ m of ZSM-5 molecular sieve.
Such scheme middle-weight rare earths element oxide preferred version is selected from the oxide compound of La or Ce element at least a, and its consumption preferred range is counted 0.1～8.0 part with parts by weight; Alkaline earth element oxide compound preferred version is selected from least a in Mg or the Ca element oxide, and its consumption preferred range is counted 0.1～5.0 part with parts by weight; The consumption preferred range of phosphoric oxide compound is counted 0.1～5.0 part with parts by weight; The relative crystallinity of ZSM-5 molecular sieve is 30～60% in the catalyzer.
Wherein the presoma of metallic element oxide compound can be nitrate salt, vitriol, muriate or acetate.Can originate at least a in the mixture of phosphoric acid, ammonium di-hydrogen phosphate, DAP, ammonium phosphate or phosphoric acid and ammoniacal liquor of the presoma of phosphoric oxide compound.The method of load can adopt the mode of dipping or IX.
Preparing method of the present invention is following: at least a and water in kaolin or other the silica-based raw materials is mixed; Spray-dried moulding obtains the microballoon of 10～200 μ m; Through 500～1200 ℃ of roastings after 1～12 hour; Mix the back with aluminium source, water and alkali and in changing airtight crystallizing kettle over to, take out after 24～120 hours, through washing, 4～12 hours dry and after 500～650 ℃ of roastings were deviate from template in 2～12 hours, obtain sodium type microballoons that contain the ZSM-5 molecular sieve of 100～120 ℃ of dryings 120～180 ℃ of crystallization.Wherein raw silicon oxide material can be at least a in WHITE CARBON BLACK, silicon sol, water glass, zeyssatite, silicic acid or the water glass.The aluminium source can be aluminium salt or meta-aluminate.In the crystallization mixture, can select not add or add template, template can be a kind of in quadrol, Tri N-Propyl Amine, n-Butyl Amine 99, triethylamine, 4-propyl bromide or the TPAOH.Microballoon and ammonium salt, nitric acid or the hydrochloric acid of sodium type are carried out IX, 100～120 ℃ of dryings 4～12 hours, obtained the Hydrogen microballoon in 2～12 hours then 500～650 ℃ of roastings.Mode through dipping or IX; At least a in 0.5～15 part the oxide compound that is selected from phosphorus, rare earth or alkaline earth element counted in load with parts by weight on the Hydrogen microballoon; 120 ℃ of dryings of warp 4～12 hours, 500～700 ℃ of roastings obtained the catalytic cracking catalyst of in-situ preparing in 4～12 hours.
Compare with fluid catalyst in the prior art; The present invention adopts the catalyzer that contains the ZSM-5 molecular sieve through the in-situ techniques preparation; Sticker in the moulding presoma and anti-wear agent (kaolin, carclazyte, polynite etc.) part are converted into active molecular sieve component, thereby have effectively improved the relative content of molecular sieve, alleviated the stopping state in reaction duct; And formed the meso-hole structure of rich, these all help improving activity, the diene yield and stability of fluid catalyst.Simultaneously; Through the introducing of rare earth, phosphorus or earth alkali metal, can modify the acid sites of catalyzer, regulate the density and the strength of acid of the acid sites of catalyzer; Take place thereby reach side reactions such as suppressing hydrogen transference and carbon distribution, improve the stability and the diene yield of catalyzer.
The present invention is through being raw material with petroleum naphtha and water, and 600～750 ℃ of temperature of reaction, weight space velocity is 0.1～2.0h
-1, water and weight of oil ratio are that raw material contacts with fluid catalyst and obtains ethene and propylene product under 0.2～8.0: 1 the processing condition.Use the present invention to adopt the fluid catalyst that phosphorus, alkaline earth or rare earth oxide are modified that contains of in-situ method preparation, at 650 ℃, weight space velocity=1.0 hour
-1, the water weight of oil is than=4: 1, under the non-pressurized reaction conditions; With the petroleum naphtha is raw material, and the transformation efficiency of petroleum naphtha can reach 42.5～490%, is higher than the catalyzer 5～12% of prior art for preparing; The diene yield is 22.1～25.7%; Higher by 4～9% than the catalyzer of prior art for preparing, have conversion of raw material high with ethene, advantage that propylene diene yield is high, obtained better technical effect.
Through embodiment the present invention is done further elaboration below.
Embodiment
Diffraction angle 2 θ of the commercial ZSM-5 (the sial atomic molar is than 25) that produces with Catalyst Factory, Nankai Univ=7～10 °; The total area of the diffraction peak between 22～25 ° is benchmark (100%), and the relative crystallinity of sample is area and the ratio of standard model diffraction peak area of the diffraction peak of its response.
[embodiment 1]
With the original kaolin of 40 grams, 150 gram silicon sol and 310 gram water mix and obtain slurries, obtain the bead of 20～200 μ m through spray shaping, obtain atomized microball a in 4 hours 1000 ℃ of roastings.
Get 50 gram atomized microball a, 16.0 gram sodium hydroxide, 15.0 gram aluminum nitrates; 6.2 gram quadrol and 300 gram water mix the back (in this mixture composition; Do not comprise kaolin, the sial atomic molar ratio of all the other raw materials is 25.0), change in the closed reactor 170 ℃ of crystallization 48 hours.Product was through washing, 120 ℃ of dryings 4 hours after the crystallization, and 550 ℃ of roastings obtained sodium type original position molecular sieve microballoon in 8 hours.Sodium type microballoon is exchanged through washing, 120 ℃ of dryings 8 hours with 1 mole ammonium nitrate solution, and 600 ℃ of roastings roasting in 3 hours obtains the molecular sieve microballoon b of Hydrogen.
Get 50 gram atomized microball a, with 8.0 gram sodium hydroxide, 1.37 gram sodium aluminates; 7.0 gram quadrol and 300 gram water mix the back (in this mixture composition; Do not comprise kaolin, the mol ratio of the sial atom of all the other raw materials is 60), change in the closed reactor 140 ℃ of crystallization 24 hours.Product was through washing, 120 ℃ of dryings 12 hours after the crystallization, and 550 ℃ of roastings roasting in 4 hours obtains sodium type molecular sieve microballoon.The ammonium nitrate solution of sodium type bead with 1 mole exchanged, and through washing, 120 ℃ of dryings 8 hours, 600 ℃ of roastings roasting in 3 hours obtained the original position molecular sieve microballoon c of Hydrogen.
Get 50 gram atomized microball a; With 8.0 gram sodium hydroxide; 3.13 gram aluminum nitrate, 6.5 gram 4-propyl bromides and 300 gram water mix the back and (in this mixture composition, do not comprise kaolin; The mol ratio of the sial atom of all the other raw materials is 120), change in the closed reactor 140 ℃ of crystallization 10 hours.120 ℃ of dryings of product warp are 12 hours after the crystallization, and 550 ℃ of roastings roasting in 4 hours obtains sodium type molecular sieve microballoon.The ammonium nitrate solution of sodium type bead with 1 mole exchanged, and through washing, 120 ℃ of dryings 8 hours, 600 ℃ of roastings roasting in 3 hours obtained the molecular sieve microballoon of Hydrogen.Obtain the original position molecular sieve microballoon d of Hydrogen.
Synthetic Hydrogen microballoon b goes up load and counts 1.5 parts of P with parts by weight in position
2O
5, 0.5 part of BaO, 0.5 part of BeO, 20 parts of SrO, through 120 ℃ of dryings 4 hours, 500 ℃ of roastings obtained catalyzer e after 4 hours, the relative crystallinity of ZSM-5 zeolite is 60% in the catalyzer.
[embodiment 2]
The b load is counted 2.0 parts of P with parts by weight on the synthetic Hydrogen microballoon in position
2O
5, 8.0 parts of La
2O
3And 5.0 parts of MgO, 120 ℃ of dryings of warp 4 hours, 500 ℃ of roastings obtain catalyzer f after 4 hours, and the relative crystallinity of ZSM-5 zeolite is 52% in the catalyzer.
[embodiment 3]
Synthetic Hydrogen microballoon c load is counted 5.0 parts of P with parts by weight in position
2O
5, 4.0 parts of CeO
2And 2.5 parts of CaO, 120 ℃ of dryings of warp 4 hours, 500 ℃ of roastings obtain catalyzer g after 4 hours, and the relative crystallinity of ZSM-5 zeolite is 38% in the catalyzer.
[embodiment 4]
Synthetic Hydrogen microballoon c goes up load and counts 1.5 parts of P with parts by weight in position
2O
5, 2.5 parts of CeO
2And 1.5 parts of MgO, 120 ℃ of dryings of warp 4 hours, 500 ℃ of roastings obtain catalyzer h after 4 hours, and the relative crystallinity of ZSM-5 zeolite is 39% in the catalyzer.
[embodiment 5]
Synthetic in position Hydrogen ZSM-5 microballoon c, load is counted 2.5 parts of P with parts by weight
2O
5, 3.5 parts of Y
2O
3And 3.0 parts of Ag
2O, 120 ℃ of dryings of warp 4 hours, 500 ℃ of roastings obtain catalyzer i after 4 hours, and the relative crystallinity of ZSM-5 zeolite is 38% in the catalyzer.
[embodiment 6]
Synthetic in position Hydrogen ZSM-5 microballoon c goes up load and counts 2.0 parts of P with parts by weight
2O
5, 0.1 part of La
2O
3And 0.1 part of SrO, 120 ℃ of dryings of warp 4 hours, 500 ℃ of roastings obtain catalyzer j after 4 hours, and the relative crystallinity of ZSM-5 zeolite is 39% in the catalyzer.
[embodiment 7]
Synthetic in position Hydrogen ZSM-5 microballoon c goes up load and counts 0.5 part of P with parts by weight
2O
5, 8.0 parts of La
2O
3And 5.0 parts of MgO, 120 ℃ of dryings of warp 4 hours, 500 ℃ of roastings obtain catalyzer k after 4 hours, and the relative crystallinity of ZSM-5 zeolite is 38% in the catalyzer.
[embodiment 8]
It is 0.3 part of P in parts by weight that synthetic in position Hydrogen ZSM-5 microballoon c goes up load
2O
5With 0.1 part of La
2O
3, 120 ℃ of dryings of 02 part of MgO warp 4 hours, 500 ℃ of roastings obtain catalyzer l after 4 hours, and the relative crystallinity of ZSM-5 zeolite is 40.0% in the catalyzer.
[embodiment 9]
It is 2.0 parts of P in parts by weight that synthetic in position Hydrogen ZSM-5 microballoon d goes up load
2O
5With 5.0 parts of Y
2O
3, 120 ℃ of dryings of 5.0 parts of BaO warps 4 hours, 500 ℃ of roastings obtain catalyzer m after 4 hours, and the relative crystallinity of ZSM-5 zeolite is 30.0% in the catalyzer.
[comparative example 1]
Get 40 gram kaolin, 50 gram silicon sol (content of silicon-dioxide is 40% with weight percent), the ZSM-5 (sial atomic molar ratio is 60) of 40 gram Nankai University catalyzer with mix after, spray shaping obtains the catalyzer of 20～200 μ m.Post-treating method according to embodiment 3 obtains counting 5.0 parts of P with parts by weight
2O
5, 4.0 parts of CeO
2And the catalyzer of 2.5 parts of CaO, the relative crystallinity of ZSM-5 zeolite is 39% in the catalyzer.
[comparative example 2]
Get 40 the gram kaolin, 50 the gram silicon sol (content of silicon-dioxide is 40% with weight percent), 40 the gram Catalyst Factory, Nankai Univs ZSM-5 (sial atomic molar ratio is 120) with mix after, spray shaping obtains the catalyzer of 20～200 μ m.Post-treating method according to embodiment 9 obtains counting 2.0 parts of P with parts by weight
2O
5With 5.0 parts of Y
2O
3, the catalyzer of 5.0 parts of BaO, the relative crystallinity of ZSM-5 zeolite is 35.0% in the catalyzer.
Catalyzer adopts the fluidized-bed evaluation, and appreciation condition: 650 ℃, weight space velocity is 1.0 hours
-1, water and weight of oil ratio=1, normal pressure, the visible table 1 of raw material oil composition.
Table 1 high bridge petrochemical industry steam cracking is specialized in the rerum natura of petroleum naphtha
| Physical parameter | Representative data |
| Over point ℃ | 40 |
| Final boiling point ℃ | 162 |
| Sulphur content (m/m) | 0.0097 |
| Arsenic content (μ g/Kg) | 1.07 |
| Alkane content/% | 65.18 |
| Normal paraffin/% | 32.54 |
| Alkene/% | 0.17 |
| Naphthenic hydrocarbon/% | 28.44 |
| Aromatic hydrocarbons/% | 6.21 |
| Color (Saybolt number) | 30 |
The performance of the producing ethene, propylene through catalytic cracking of 2 different catalysts
| Catalyzer | Transformation efficiency/% | Ethylene yield (weight)/% | Productivity of propylene (weight)/% | Second+third productive rate (weight)/% |
| e | 48.8 | 12.4 | 12.1 | 24.5 |
| f | 48.7 | 13.2 | 12.4 | 25.7 |
| g | 49.0 | 12.9 | 12.3 | 25.2 |
| h | 48.6 | 12.1 | 12.7 | 24.8 |
| i | 48.2 | 11.7 | 12.9 | 24.6 |
| j | 46.5 | 12.5 | 11.3 | 23.8 |
| k | 44.2 | 12.0 | 11.2 | 23.2 |
| l | 43.2 | 11.2 | 11.6 | 22.8 |
| m | 42.5 | 10.9 | 11.2 | 22.1 |
| Comparative example 1 | 37.6 | 9.4 | 8.6 | 18.0 |
| Comparative example 2 | 36.2 | 8.5 | 8.0 | 16.5 |
The influence of 10～13 pairs of processing condition of embodiment further specifies, the catalyzer h of employing, and reaction result is seen table 3.
Catalytic cracking reaction result under table 3 different technology conditions
| Embodiment | Temperature/℃ | Weight space velocity/h -1 | Water weight of oil ratio | Transformation efficiency/% | Ethene+propylene weight yield/% |
| 13 | 600 | 0.1 | 0.2 | 20.0 | 15.4 |
| 14 | 650 | 1.0 | 1.0 | 48.6 | 24.8 |
| 15 | 680 | 1.0 | 4.0 | 70.0 | 38.0 |
| 16 | 750 | 2.0 | 8.0 | 96.0 | 54.3 |
The present invention is through being raw material with petroleum naphtha and water, and 600～750 ℃ of temperature of reaction, weight space velocity is 0.1～2.0h
-1, water and weight of oil ratio are that raw material contacts with fluid catalyst and obtains ethene and propylene product under 0.2～8.0: 1 the processing condition.Can find out that by table 2 the present invention adopts synthetic micro-ball load phosphorus, alkaline earth or the rare earth component that contains ZSM-5 of original position as fluid catalyst, at 650 ℃, weight space velocity=1.0 hour
-1, water and weight of oil ratio=4: 1 are under the non-pressurized reaction conditions; With petroleum naphtha and water is raw material, and the transformation efficiency of petroleum naphtha can reach 42.5～49.0%, is higher than the catalyzer 5～12% of prior art for preparing; The diene yield is 22.1～25.7%; Higher by 4～9% than the catalyzer of prior art for preparing, have feed stock conversion high with ethene, advantage that propylene diene yield is high, obtained better technical effect.
Claims (5)
1. the method that catalytic pyrolysis is produced ethene and propylene is a raw material with petroleum naphtha and water, and 600～750 ℃ of temperature of reaction, weight space velocity is 0.1～2.0h
-1Water weight of oil ratio is under 0.2～8.0: 1 the processing condition; Raw material contacts with fluid catalyst and obtains ethene and propylene, and wherein fluid catalyst comprises following component in parts by weight: a) at least a in 0.5～15 part of oxide compound that is selected from phosphorus, rare earth or alkaline earth element; B) 85～99.5 parts are selected from the microballoon that the original position synthetic contains 10～200 μ m of ZSM-5 molecular sieve.
2. a kind of catalytic pyrolysis according to claim 1 is produced the method for ethene and propylene, it is characterized in that rare earth oxide is selected from least a in the oxide compound of La or Ce element, and its content is counted 0.1～8.0 part with parts by weight.
3. catalytic pyrolysis according to claim 1 is produced the method for ethene and propylene, and the oxide compound that it is characterized in that alkaline earth element is selected from least a in Mg or the Ca element oxide, and its content is counted 0.2～5.0 part with parts by weight.
4. catalytic pyrolysis according to claim 1 is produced the method for ethene and propylene, it is characterized in that the content of phosphoric oxide compound is counted 0.3～5.0 part with parts by weight.
5. catalytic pyrolysis according to claim 1 is produced the method for ethene and propylene, and the relative crystallinity that it is characterized in that ZSM-5 molecular sieve in the catalyzer is 30～60%.
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| CN106607089A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for coupling catalytic pyrolysis of methanol and naphtha, preparation method and application |
| CN111939971A (en) * | 2020-07-01 | 2020-11-17 | 湖南聚力催化剂股份有限公司 | Preparation method of catalytic cracking auxiliary agent for increasing yield of propylene |
| CN112745899A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Catalytic conversion method and catalytic conversion device for producing low-carbon olefins |
| CN113943008A (en) * | 2021-12-01 | 2022-01-18 | 南宁师范大学 | Preparation method of ZSM-5 molecular sieve |
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| CN101279287A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Catalyst for producing olefin hydrocarbon by catalytic pyrolysis |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106607089A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst for coupling catalytic pyrolysis of methanol and naphtha, preparation method and application |
| CN112745899A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Catalytic conversion method and catalytic conversion device for producing low-carbon olefins |
| CN112745899B (en) * | 2019-10-30 | 2023-01-13 | 中国石油化工股份有限公司 | Catalytic conversion method and catalytic conversion device for producing low-carbon olefins |
| CN111939971A (en) * | 2020-07-01 | 2020-11-17 | 湖南聚力催化剂股份有限公司 | Preparation method of catalytic cracking auxiliary agent for increasing yield of propylene |
| CN113943008A (en) * | 2021-12-01 | 2022-01-18 | 南宁师范大学 | Preparation method of ZSM-5 molecular sieve |
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Application publication date: 20120314 |