CN102746873B - Method for preparing ethylene and propylene through catalytic cracking of light hydrocarbons - Google Patents
Method for preparing ethylene and propylene through catalytic cracking of light hydrocarbons Download PDFInfo
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for preparing ethylene and propylene through the catalytic cracking of light hydrocarbons to mainly solve problems of difficult realization of the light hydrocarbon high temperature cracking, and low ethylene and propylene yields in the light carbon catalytic cracking process in the prior art. The method which allows the light hydrocarbon catalytic cracking to be carried out through a parallel type or coaxial type internal riser cycle reaction-regeneration device mainly comprises the following steps: 1, allowing a preheated light hydrocarbon raw material to enter an internal riser reactor, and reacting through contacting with a catalyst at 570-720DEG C to generate low carbon olefin-containing products and simultaneously form a carbon deposition catalyst; and 2, regenerating the carbon deposition catalyst through allowing it to enter a regenerator, and returning the regenerated catalyst to the riser reactor, wherein the active component of the catalyst is selected from at least one of a silicon-aluminum molecular sieve, an aluminum-phosphorous molecular sieve, a silicon-phosphorous-aluminum molecular sieve or a composite molecular sieve thereof, and the molecular sieve has a bore diameter of 0.4-0.65nm. The method well solves the problems through above technical scheme, and can be applied to the industrial production of ethylene and propylene.
Description
Technical field
The present invention relates to a kind of method of lighter hydrocarbons catalytic pyrolysis preparing ethylene, propylene.
Background technology
Ethene, propylene are important basic organic synthesis raw materials, in recent years, by the driving of downstream derivative thing demand, and the market requirement sustainable growth of global ethene, propylene.At present, the production of ethene, propylene mainly relies on steam heat cracking.The ethene of about 90 % by weight and the propylene of 61 % by weight are from steam heat cracking process, although this technique is used widely in the world, but still there is unsatisfactory part, especially reaction needed high temperature (800 ~ 1000 DEG C), energy consumption is large, and low value-added dry gas yield is high.If introducing catalyzer, adopt the method for catalytic pyrolysis, then temperature of reaction can be made to reduce by 50 ~ 200 DEG C, reduce the generation of energy consumption and dry gas, and improve Propylene Selectivity, so many investigators are devoted to catalytic pyrolysis preparing ethylene, propylene research at present.
Because true boiling point boiling range is lower than the light hydrocarbon feedstocks of 350 DEG C, as hybrid C 4, liquefied gas, catalytically cracked gasoline, solar oil, diesel oil, petroleum naphtha, hydrogenation tail oil etc., hydrogen richness higher, when carrying out catalytic pyrolysis, ethene, Propylene Selectivity are high, and thus the research of lighter hydrocarbons catalytic pyrolysis preparing ethylene, propylene causes and pays close attention to more and more widely.
For adopting the lighter hydrocarbons deep catalytic cracking technology of circulating fluid bed reactor generally to use for reference the fluidized catalyst cracking technology pattern of conventional heavy oils, namely reaction-regeneration system comprises riser reactor, revivifier, a settling vessel; Revivifier and riser reactor separate, in laid out in parallel; Raw material enters riser reactor, with regenerated catalyst contact reacts, generates all kinds of product, forms reclaimable catalyst simultaneously; Reclaimable catalyst enters coke-burning regeneration in revivifier, and the catalyzer regenerated returns riser tube and participates in reaction.
But compare with heavy oil, the hydrogen richness of lighter hydrocarbons is high, even if pyroreaction, green coke amount is still little, and coking yield is less than 1 % by weight.React institute's heat requirement in Circulating Fluidized Bed Process to be provided by the coke generated during revivifier burning-off catalyst reaction, for heavy oil fluid catalytic cracking, the heat produced when the coking yield of 5.1 % by weight regenerates can provide the heat needed for the reaction of 500 DEG C, heavy oil, infers that the green coke amount of lighter hydrocarbons catalytic pyrolysis is difficult to ensure the high temperature needed for cracking thus.Therefore, the Circulating Fluidized Bed Process of lighter hydrocarbons catalytic pyrolysis preparing ethylene, propylene is in needs pyroreaction with green coke amount is few, there is more scabrous contradiction in heat undersupply.
For addressing this problem, application number be 200780029774.5 Chinese patent in lighter hydrocarbons charging, add a small amount of coke precursors, namely the one in the acetylene of coking, the acetylene of replacement, diolefine and combination thereof is easy to, riser temperature can reach 600 ~ 720 DEG C, and diene yield reaches 35.84 % by weight.Although the method improves light hydrocarbon cracking temperature, the coke precursors added can affect reaction process, and diene yield is low.
Also lighter hydrocarbons catalytic pyrolysis and heavy oil fluid catalytic cracking are coupled by some method.Application number be 01808100.2 with 01808224.6 Chinese patent propose light catalytic naphtha, catalytic cycle oil are injected heavy oil fluid catalytic cracking riser reactor top together with water vapour, react at 620 ~ 775 DEG C, propylene and butylene total recovery bring up to 10.4 % by weight.
Patent ZL200510089849.1 and ZL200510093782.9 adopts two riser reactors, main riser tube carries out heavy oil catalytic cracking reaction, isolate liquefied gas cracking propylene enhancing in subsidiary riser of propylene, subsidiary riser has two reaction zones, carries out building-up reactions and catalytic cracking and dehydrating alkanes successively and reacts.Temperature of reaction in main riser tube is 450 ~ 650 DEG C, and the temperature of subsidiary riser first reaction zone is 150 ~ 450 DEG C, and the temperature of second reaction zone is 450 ~ 650 DEG C, and propylene can reach 19.03 % by weight.
The method can make the temperature of lighter hydrocarbons catalytic pyrolysis higher than 600 DEG C, and compare can improve propene yield to a certain extent with heavy oil fluid catalytic cracking, but owing to lighter hydrocarbons catalytic pyrolysis and heavy oil fluid catalytic cracking being coupling in a circulating reaction device, lighter hydrocarbons catalytic pyrolysis has to be limited by heavy oil catalytic cracking process in reaction conditions and catalyst performance, lighter hydrocarbons can not catalytic pyrolysis be ethene, propylene to greatest extent, thus the yield of ethene, propylene is still lower, can not realize the object of lighter hydrocarbons High-efficient Production ethene, propylene.The present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention exists in prior art lighter hydrocarbons catalytic pyrolysis process to be difficult to realize lighter hydrocarbons Pintsch process, and the problem that ethene, propene yield are low, provides a kind of method of new lighter hydrocarbons catalytic pyrolysis preparing ethylene, propylene.It is high that the method has temperature of reaction, the advantage that ethene, propene yield are high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of lighter hydrocarbons catalytic pyrolysis preparing ethylene, propylene, block form or the embedded riser tube circulating reaction-regenerating unit of coaxial-type is adopted to carry out lighter hydrocarbons catalytic pyrolysis, mainly comprise the following steps: the light hydrocarbon feedstocks after (1) preheating enters in embedded riser reactor, with catalyst I contact reacts at 570 ~ 720 DEG C, generate the product containing low-carbon alkene, form carbon deposition catalyst II simultaneously; (2) carbon deposition catalyst II enters revivifier regeneration, and the catalyzer after regeneration returns riser reactor; Wherein the active ingredient of catalyzer is selected from sial, aluminium phosphorus, aluminium silicophosphate molecular sieve or its composite molecular screen that at least one aperture is 0.4 ~ 0.65 nanometer.
In technique scheme, the main reaction region of embedded riser reactor is positioned at internal regenerator.Multiple feed nozzles set by embedded riser tube can enter different light hydrocarbon feedstocks respectively.
In technique scheme, the average reaction temperature of each embedded riser reactor is 570 ~ 720 DEG C, and reaction pressure counts 0.1 ~ 0.35 MPa with gauge pressure, and catalystoil ratio is 6 ~ 40: 1, and catalyst in reactor density is 50 ~ 400 kgs/m
3, it is carry out lighter hydrocarbons catalytic pyrolysis preparing ethylene, propylene under the condition of 1 ~ 8 meter per second that oil gas enters reactor place linear velocity.
In technique scheme, light hydrocarbon feedstocks is boiling range lower than the hydrocarbon mixture of 350 DEG C, preferred mixed C
4, liquefied gas, petroleum naphtha, catalytically cracked gasoline, light FCC gasoline, solar oil, diesel oil, hydrogenation tail oil or these lighter hydrocarbons press the mixture of different ratios mixing.The preheating temperature of light hydrocarbon feedstocks is 150 ~ 300 DEG C.
In technique scheme, the active ingredient of used catalyst I comprises the composite molecular screen mutually formed between ZSM-5, ZSM-23, ZSM-11, Y/USY, β, SAPO-34, MOR or four, preferred ZSM-5 molecular sieve.The carrier of catalyst I is porous matrix material mixture, and porous matrix material comprises kaolin, aluminum oxide, silicon oxide, magnesium oxide, preferred kaolin, aluminum oxide, silicon oxide.
In technique scheme, the carbon deposition quantity of carbon deposition catalyst II is 0.3 ~ 8 % by weight.
Product yield of the present invention is defined as the total raw material amount of product amount divided by the unit time of unit time generation.Transformation efficiency is defined as (total raw material amount (ton/hour)-unconverted material quantity (ton/hour))/total raw material amount (ton/hour) × 100%.Catalystoil ratio (C/O) is the ratio of catalyst recirculation amount (ton/hour) and total raw material amount (ton/hour).Oil gas refers to the mixture of various hydrocarbon in riser reactor.Carbon deposition quantity on carbon deposition catalyst is defined as the mass percentage of carbon on unit mass coked catalyst.
The present inventor is found by research, and the ethene of lighter hydrocarbons catalytic pyrolysis and propene yield are subject to the impact of temperature of reaction obvious, and high temperature is favourable.For FCC petroleum naphtha, adopt ZSM-5 catalyzer, when temperature of reaction is elevated to 680 DEG C from 600 DEG C, ethene and propylene gross weight yield add more than 10 percentage points.
Coke burning on spent agent in revivifier, in device, temperature is between 600 DEG C ~ 750 DEG C, if riser reactor is placed in internal regenerator, both the hot environment of internal regenerator had been utilized to provide reaction institute heat requirement, reduce again the calorific loss of riser reactor, lighter hydrocarbons catalytic pyrolysis under high temperature more than 600 DEG C can be realized easily, thus solve the problem of the circulating fluidized bed heat undersupply of the independent catalytic pyrolysis of lighter hydrocarbons.
In riser tube, average reaction temperature reaches 570 ~ 720 DEG C to adopt technical scheme of the present invention to ensure.With FCC petroleum naphtha for raw material, adopt ZSM-5 molecular sieve catalyzer, temperature of reaction is 670 DEG C, pressure 0.12 MPa, and when catalystoil ratio is 30: 1, yield of ethene is 17.68 % by weight, and propene yield is 23.03 % by weight, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embedded riser tube circulating reaction-regenerating unit of block form of the present invention.
In Fig. 1,1 is embedded riser reactor; 2 is revivifier; 3 is settling vessel; 4 is stripping stage; 5 is regenerator sloped tube; 6 is regeneration guiding valve; 7 is plug valve to be generated; 8 is settling vessel internal cyclone separators; 9 is air-distributor; 10 is nozzle; 11 is lighter hydrocarbons, light oil raw material; 12 is splitting gas; 13 for promoting medium; 14 is regeneration air; 15 is fuel oil gas nozzle; 16 is exhanst gas outlet; 18 is reclaimable catalyst transfer lime; 19 is revivifier internal cyclone separators; 20 is gas-solid quick disconnector.
Light hydrocarbon feedstocks 11 enters in embedded riser reactor 2 through feed nozzle 10, contacts with regenerated catalyst, and reaction generates the product containing low-carbon alkene, carries reclaimable catalyst and enters settling vessel 3 through gas-solid quick disconnector 20; Most of catalyzer that cyclonic separator 8 is separated enters settling vessel 3, and gaseous products and part are not entered next stage cyclonic separator by the catalyzer that cyclonic separator 8 is separated and be again separated, gaseous products 12 enters follow-up centrifugal station through outlet line; In settling vessel 3 reclaimable catalyst after stripping stage 4 stripping through reclaimable catalyst transfer lime 18 and plug valve to be generated 7, enter coke-burning regeneration in revivifier 2, the flue gas that coke burning generates, through revivifier internal cyclone separators 19, enters follow-up energy-recuperation system from exhanst gas outlet 16; The catalyzer regenerated enters in embedded riser tube 1 by regenerated catalyst circulation inclined tube 5; Promoting medium 13 makes the regenerated catalyst in embedded riser reactor 1 move upward, and raw material 11 contact reacts.
Fig. 2 is the structural representation of the embedded riser tube circulating reaction-regenerating unit of coaxial-type of the present invention.
In Fig. 2,21 is embedded riser reactor, and 22 is revivifier, and 23 is settling vessel, 24 is stripping stage, and 25 is regenerator sloped tube, and 26 is regeneration guiding valve, and 28 is settling vessel internal cyclone separators, 29 is air-distributor, and 30 is nozzle, and 31 is lighter hydrocarbons, light oil raw material, 32 is splitting gas, and 33 for promoting medium, and 34 is regeneration air, 35 is fuel oil gas nozzle, and 36 is exhanst gas outlet, and 37 is guiding valve to be generated, 38 is inclined tube to be generated, and 39 is revivifier internal cyclone separators, and 40 is gas-solid quick disconnector.
Light hydrocarbon feedstocks 31 enters in embedded riser reactor 22 through feed nozzle 30, contacts with regenerated catalyst, and reaction generates the product containing low-carbon alkene, carries reclaimable catalyst and enters settling vessel 23 through gas-solid quick disconnector 40; Most of catalyzer that cyclonic separator 28 is separated enters settling vessel 23, and gaseous products and part are not entered next stage cyclonic separator by the catalyzer that cyclonic separator 28 is separated and be again separated, gaseous products 32 enters follow-up centrifugal station through outlet line; In settling vessel 23 reclaimable catalyst after stripping stage 24 stripping through inclined tube 38 to be generated and guiding valve to be generated 37, enter coke-burning regeneration in revivifier 22, the flue gas that coke burning generates, through revivifier internal cyclone separators 39, enters follow-up energy-recuperation system from exhanst gas outlet 36; The catalyzer regenerated enters in embedded riser tube 21 by regenerated catalyst circulation inclined tube 25; Promoting medium 33 makes the regenerated catalyst in embedded riser reactor 21 move upward, and raw material 31 contact reacts.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
On the device shown in Fig. 1, carried out 4 groups of experiments, reaction raw materials, catalyzer, reaction conditions and result are as shown in table 1.
In hybrid C 4, the content of butylene is 73.8 % by weight, and normal butane content is 26.2 % by weight; Petroleum naphtha is mainly C
5~ C
8alkane, content is respectively 12.62 % by weight, 25.54 % by weight, 25.25 % by weight, 17.86 % by weight; Light FCC gasoline (FCC petroleum naphtha) is mainly amylene, hexene, and content is respectively 36.4 % by weight and 34.1 % by weight.
Testing catalyzer used adopts semi-synthesis method to be prepared from, and namely first by molecular sieve, carrier and binding agent mechanically mixing, adds suitable quantity of water, HCl and H
3pO
4when SAPO-34 catalyzer (preparation do not add), controls pH value and is not less than 3, slurry agitation evenly after at 500 DEG C spray shaping.In ZSM-5 catalyzer used, the mass ratio of HZSM-5 molecular sieve and matrix is 3: 6.8, P
2o
5content is 2 % by weight; The silica alumina ratio of HZSM-5 molecular sieve is 38; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 2: 8.In ZSM-5+ beta catalyst used, the mass ratio of ZSM-5+ beta-molecular sieve and matrix is 3: 7; The silica alumina ratio of ZSM-5 molecular sieve is 25; The silica alumina ratio of beta-molecular sieve is 20; The mass ratio of ZSM-5 and beta-molecular sieve is 7: 3; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 1: 9.In SAPO-34 catalyzer used, the mass ratio of HSAPO-34 molecular sieve and matrix is 3.5: 6.5; The phosphorus al mole ratio of HSAPO-34 molecular sieve is 0.9, and silica alumina ratio is 1.2; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 1: 9.
Table 1
[comparative example 1]
Do not use the embedded riser tube in Fig. 1, utilize the external riser tube of the traditional fluid catalytic cracking unit of same size to carry out 3 groups of contrast experiments.Reaction raw materials, catalyzer, reaction conditions and result are as shown in table 2.Raw materials used composition and catalyst preparation process are shown in embodiment 1.
Table 2
[embodiment 2]
Adopt embedded riser arrangement substantially the same manner as Example 1, but embedded riser tube is arranged two feed nozzles, two nozzles are at a distance of 0.3 meter, and enter hybrid C 4 and FCC petroleum naphtha from bottom to top respectively, reaction raw materials, reaction conditions, catalyzer and reaction result are as shown in table 3.Raw materials used composition and catalyst preparation process are shown in embodiment 1.
Table 3
[embodiment 3 ~ 7]
Device shown in Fig. 2 has carried out 5 groups of experiments, and reaction raw materials, reaction conditions, catalyzer and reaction result are as shown in table 4.Raw materials used composition and catalyst preparation process are shown in embodiment 1.
In liquefied gas, propane content is 7.5 % by weight, and propylene content is 2.5 % by weight, and butene content is 33.8 % by weight, and butane content is 56.2 % by weight.The density of solar oil is 0.72 gram per centimeter
3, H content is 15.2 % by weight, and the content of saturated point is 91.37 % by weight, and the content that fragrance divides is 8.63 % by weight.The density of diesel oil is 0.78 gram per centimeter
3, H content is 14.7 % by weight, and saturated point of content is 89.29 % by weight, and fragrance point content is 10.71 % by weight.Catalytically cracked gasoline (FCC gasoline) is mainly C
5~ C
10hydro carbons, alkene, alkane, naphthenic hydrocarbon, aromaticity content are 36.4 % by weight, 34.1 % by weight.
The preparation method of catalyzer is with embodiment 1.With the catalyzer that the mixture of MOR molecular sieve is active ingredient, the mass ratio of its molecular sieve and matrix is 3: 7; The silicoaluminophosphate molecular ratio of MOR molecular sieve is 10; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 8: 2.With the catalyzer that the mixture of beta-molecular sieve is active ingredient, the mass ratio of its molecular sieve and matrix is 3.5: 6.5; The silicoaluminophosphate molecular ratio of beta-molecular sieve is 20; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 7: 3.With the catalyzer that the mixture of Y molecular sieve is active ingredient, the mass ratio of its molecular sieve and matrix is 2.5: 7.5; The silicoaluminophosphate molecular ratio of Y molecular sieve is 6; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 7: 3.With the catalyzer that the mixture of ZSM-23 molecular screen is active ingredient, the mass ratio of its molecular sieve and matrix is 3: 7; The silicoaluminophosphate molecular ratio of ZSM-23 molecular screen is 60; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 7: 3.With the catalyzer that the mixture of ZSM-11 molecular sieve is active ingredient, the mass ratio of its molecular sieve and matrix is the silicoaluminophosphate molecular ratio of 3.2: 68, ZSM-11 molecular sieve is 50; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 7: 3.
Table 4
Claims (4)
1. the method for a lighter hydrocarbons catalytic pyrolysis preparing ethylene, propylene, the embedded riser tube circulating reaction-regenerating unit of coaxial-type is adopted to carry out lighter hydrocarbons catalytic pyrolysis, mainly comprise the following steps: the light hydrocarbon feedstocks after (1) preheating enters in embedded riser reactor, with catalyst I contact reacts at 570 ~ 720 DEG C, generate the product containing low-carbon alkene, form carbon deposition catalyst II simultaneously; (2) carbon deposition catalyst II enters revivifier regeneration, and the catalyzer after regeneration returns riser reactor; Wherein the active ingredient of catalyst I is selected from sial, aluminium phosphorus, aluminium silicophosphate molecular sieve or its composite molecular screen that at least one aperture is 0.4 ~ 0.65 nanometer;
Wherein, light hydrocarbon feedstocks is boiling range lower than the hydrocarbon mixture of 350 DEG C, and hydrocarbon mixture is selected from mixed C
4, liquefied gas, petroleum naphtha, catalytically cracked gasoline, diesel oil or these lighter hydrocarbons mixture;
The preheating temperature of light hydrocarbon feedstocks is 150 ~ 300 DEG C;
The composite molecular screen that catalyst I active ingredient used comprises ZSM-23, ZSM-11, Y/USY, β, SAPO-34, MOR or formed each other;
The carrier of catalyst I is porous matrix material mixture, and porous matrix material comprises kaolin, aluminum oxide, silicon oxide, magnesium oxide;
The carbon deposition quantity of carbon deposition catalyst II is 0.3 ~ 8 % by weight.
2. the method for lighter hydrocarbons catalytic pyrolysis preparing ethylene according to claim 1, propylene, is characterized in that the main reaction region of embedded riser reactor is positioned at internal regenerator.
3. the method for lighter hydrocarbons catalytic pyrolysis preparing ethylene according to claim 1, propylene, is characterized in that the multiple feed nozzles set by embedded riser tube can enter different light hydrocarbon feedstocks respectively.
4. the method for lighter hydrocarbons catalytic pyrolysis preparing ethylene according to claim 1, propylene, it is characterized in that the average reaction temperature of each embedded riser reactor is 570 ~ 720 DEG C, reaction pressure counts 0.1 ~ 0.35 MPa with gauge pressure, the mass ratio of agent/oil is 6 ~ 40: 1, and catalyst in reactor density is 50 ~ 400 kgs/m
3, it is 1 ~ 8 meter per second that oil gas enters reactor place linear velocity.
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| CN104418685B (en) * | 2013-08-30 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of catalysis conversion method for producing ethene and propylene |
| CN107879876B (en) * | 2016-09-30 | 2020-07-24 | 中国石油化工股份有限公司 | Method and device for producing ethylene and propylene from light hydrocarbon raw material |
| CN115624987A (en) * | 2022-09-07 | 2023-01-20 | 山东京博石油化工有限公司 | Preparation method and application of catalyst for preparing low-carbon olefin by catalytic cracking of straight-run diesel oil |
| CN115888797A (en) * | 2022-11-08 | 2023-04-04 | 洛阳市科创石化科技开发有限公司 | Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof |
| CN116371454A (en) * | 2023-04-07 | 2023-07-04 | 山东京博石油化工有限公司 | Preparation method and application of light hydrocarbon cracking catalyst |
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| CN101992046A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Parallel combined riser circular reaction-regeneration device |
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| KR20010043239A (en) * | 1998-05-05 | 2001-05-25 | 나체만 제시카 알 | Two stage fluid catalytic cracking process for selectively producing c2 to c4 olefins |
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