CN102190547A - Method for improving yield of light olefin products - Google Patents
Method for improving yield of light olefin products Download PDFInfo
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- CN102190547A CN102190547A CN2010101163807A CN201010116380A CN102190547A CN 102190547 A CN102190547 A CN 102190547A CN 2010101163807 A CN2010101163807 A CN 2010101163807A CN 201010116380 A CN201010116380 A CN 201010116380A CN 102190547 A CN102190547 A CN 102190547A
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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
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- 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
- Y02P20/52—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
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention relates to a method for improving yield of light olefin products, which mainly solves the problem of low yield of light olefins in the prior art. The method for improving the yield of the light olefin products mainly comprises the following steps of: (1) making a methanol-containing raw material enter a first reaction area to contact a silicoaluminophosphate molecular sieve-containing catalyst so as to generate an olefin product I and form an inactivated catalyst; (2) making at least one part of the inactivated catalyst enter a regenerator for regeneration, and returning the regenerated catalyst to the first reaction area; (3) performing three stage cyclone recovery on fine catalyst powder lost in the regenerator, introducing into a fine powder collecting tank, introducing into a degassing tank for degassing, mixing with a newly added catalyst, introducing into a second reaction area, contacting a raw material containing olefins with more than 4 carbon atoms to generate an olefin product II, mixing with the olefin product I, and introducing into a separation section; and (4) introducing the inactivated catalyst in the second reaction area into the regenerator for regeneration. The technical scheme better solves the problem; and the method can be applied to industrial production of the light olefins.
Description
Technical field
The present invention relates to a kind of method that improves the light olefin product yield.
Technical background
Light olefin, promptly ethene and propylene are two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are to produce by petroleum path, but because limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms system ethene, propylene.Wherein, the alternative materials that is used for light olefin production that one class is important is an oxygenatedchemicals, for example alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, as methyl alcohol, can be made by coal or Sweet natural gas, and technology is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source is added and is transformed the economy that generates light olefin technology, so by the technology of oxygen-containing compound conversion to produce olefine (OTO), particularly the technology by methanol conversion system alkene (MTO) is subjected to increasing attention.
In the US4499327 patent silicoaluminophosphamolecular molecular sieves catalyzer is applied to methanol conversion system olefin process and studies in great detail, think that SAPO-34 is the first-selected catalyzer of MTO technology.The SAPO-34 catalyzer has very high light olefin selectivity, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of light olefin 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US6166282 that a kind of oxygenate conversion is the technology and the reactor of light olefin, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is finished, after rising to the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction after product gas and catalyzer sharp separation have effectively prevented the generation of secondary reaction.Through analog calculation, to compare with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all significantly reduce.
Announced among the CN1723262 that it is light olefin technology that the multiple riser reaction unit that has central catalyst return is used for oxygenate conversion, this covering device comprises a plurality of riser reactors, gas solid separation district, a plurality of offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the disengaging zone of setting, catalyzer and product gas are separated.
In Chinese invention patent 200810043971.9, announced a kind of method that improves yield of light olefins, it is that the first reaction zone top of low-carbon alkene is provided with one second reaction zone that this method adopts in methanol conversion, and this second reaction zone diameter is greater than first reaction zone, to increase the residence time of product gas in second reaction zone of first reaction zone outlet, make unreacted methanol, dme that generates and carbon four above hydrocarbon continue reaction, reach the purpose that improves yield of light olefins, this method comprises that also the charging of second reaction zone can be through isolating freshening carbon four above hydrocarbon.Though this method can improve the head trip of low-carbon alkene to a certain extent, but because the catalyzer that first reaction zone comes out has had more carbon distribution, and the carbon four above hydrocarbon pyrolysiss need higher catalyst activity, so the carbon four above hydrocarbon changing effects in second reaction zone are still on the low side in this method.
Therefore, need a kind of novel method, make the carbon four above hydrocarbon purpose that is converted into low-carbon alkene as much as possible, finally reach the purpose that improves yield of light olefins and process economy to reach.The present invention has solved the problems referred to above targetedly.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of selectivity of light olefin hydrocarbon that exists in the prior art, and a kind of method of new raising light olefin product yield is provided.This method is used for the production of light olefin, has that selectivity of light olefin hydrocarbon is higher, a light olefin production process economy advantage preferably.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method that improves the light olefin product yield, mainly may further comprise the steps: (1) comprises that the raw material of methyl alcohol enters first reaction zone, contact with comprising the silicoaluminophosphamolecular molecular sieves catalyzer, generate olefin product I and form decaying catalyst; (2) at least a portion of decaying catalyst enters revivifier regeneration, and the catalyzer that regeneration is finished returns first reaction zone; (3) run the catalyst fines that decreases in the revivifier and after three cycles are received, enter the fines collection jar, enter the degassing vessel degassing then, and with enter second reaction zone after the live catalyst that adds mixes, contact with the raw material that comprises carbon four above hydrocarbon, generate olefin product II, enter centrifugal station after merging with olefin product I; The decaying catalyst of (4) second reaction zones enters revivifier regeneration.
In the technique scheme, first reaction zone, second reaction zone and revivifier are fluidized-bed, and preferred version is: first reaction zone is a fast fluidized bed, and second reaction zone is a dense phase fluidized bed, and revivifier is a dense phase fluidized bed; Described silicoaluminophosphamolecular molecular sieves is selected from least a among SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, the SAPO-56, and preferred version is SAPO-34; Temperature of reaction in described first reaction zone is 400～500 ℃, and preferred version is 430～480 ℃, and linear gas velocity is 0.8～2.5 meter per second, and preferred version is 1.0～1.5 meter per seconds; Temperature of reaction in second reaction zone is 450～600 ℃, and preferred version is 500～550 ℃, and linear gas velocity is 0.4～0.9 meter per second, and preferred version is 0.6～0.8 meter per second; Described fine powder is a median size less than 30 microns granules of catalyst, and the median size of described live catalyst is 50～100 microns; By add live catalyst in degassing vessel, keeping the catalyzer median size in second reaction zone is 40～80 microns; Described three are threaded to the second reaction zone scope inner catalyst handling equipment all needs insulation; Decaying catalyst in described second reaction zone enters revivifier regeneration after through the water vapour stripping; Described second reaction zone top gas outlet is provided with three cycles and receives catalyst fines, delivers to the fines collection jar.
The preparation method of silicoaluminophosphamolecular molecular sieve of the present invention is: at first preparing the molecular sieve presoma, is 0.03～0.6R with the mole proportioning: (Si 0.01～0.98: Al 0.01～0.6: P 0.01～0.6): 2～500 H
2O, wherein R represents template, and the constitutive material mixed solution obtains through after the crystallization of certain hour at a certain temperature; Once more, with molecular sieve presoma, phosphorus source, silicon source, aluminium source, organic formwork agent, water etc. according to after at least 0.1 hour, finally obtaining the SAPO molecular sieve at 110～260 ℃ of following hydrothermal crystallizings after certain mixed.
The molecular sieve of preparation is mixed with a certain proportion of binding agent, and through obtaining final SAPO catalyzer after the operation stepss such as spraying drying, roasting, the weight percentage of binding agent in molecular sieve is generally between 10～90%.
Be provided with two reaction zones in the method for the invention, first reaction zone is relatively independent, be used for methanol conversion system alkene, second reaction zone is used to transform carbon four above hydrocarbon or transforms unreacted methanol or dme etc., reaches the purpose that improves feed stock conversion and yield of light olefins.Wherein, second reaction zone is a dense phase fluidized bed, guarantees the enough reaction times, and maximized conversion carbon four above hydrocarbon are low-carbon alkene, and parameter such as its material level, temperature of reaction can independently be controlled.And the inventor is through discovering, the revivifier outlet is run the catalyst fines that decreases and had advantages of high catalytic activity, if mix a certain proportion of live catalyst, adjusts the size distribution of mixed catalyst, can high efficiency conversion carbon four above high-carbon hydrocarbons.After the catalyst fines in the system runs up to a certain degree, can draw off a part in the holding tank from segmentation and recycle.The catalyzer of inactivation returns revivifier regeneration in second reaction zone, so just with first reaction zone shared a revivifier.Therefore, adopt method of the present invention, can reach the purpose that improves selectivity of light olefin hydrocarbon.
Adopt technical scheme of the present invention: first reaction zone, second reaction zone and revivifier are fluidized-bed; Described silicoaluminophosphamolecular molecular sieves is selected from least a among SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, the SAPO-56; Temperature of reaction in described first reaction zone is 400～500 ℃, and linear gas velocity is 0.8～2.5 meter per second; Temperature of reaction in second reaction zone is 450～600 ℃, and linear gas velocity is 0.4～0.9 meter per second; Described fine powder is a median size less than 30 microns granules of catalyst, and the median size of described live catalyst is 50～100 microns; By add live catalyst in degassing vessel, keeping the catalyzer median size in second reaction zone is 40～80 microns; Described three are threaded to the second reaction zone scope inner catalyst handling equipment all needs insulation; Decaying catalyst in described second reaction zone enters revivifier regeneration after through the water vapour stripping; Described second reaction zone top gas outlet is provided with three cycles and receives catalyst fines, delivers to the fines collection jar, and yield of light olefins can reach 92.43% weight, has obtained better technical effect.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
Among Fig. 1,1 is the first reaction zone bottom feed; 2 is first reaction zone; 3 is the first reaction zone products export pipeline; 4 is the line of pipes that decaying catalyst enters revivifier in first reaction zone; 5 is the regenerating medium source line; 6 is revivifier; 7 is flue gas and catalyst fines outlet line; 8 is three to revolve; 9 is the fines collection jar; 10 is fines collection pot bottom discharging pipeline; 11 is three to revolve the exhanst gas outlet pipeline; 12 is degassing vessel; 13 is second reaction zone; 14 is the second reaction zone bottom feed; 15 is the line of pipes that the second reaction zone decaying catalyst enters revivifier; 16 is the second reaction zone top gas outlet line; 17 enter the catalyst transport pipeline of second reaction zone for degassing vessel; 18 enter the catalyst transport pipeline of first reaction zone for the revivifier regenerated catalyst; 19 enter the line of pipes of the degassing for fines collection jar catalyzer; 20 is the pipeline that fine powder that three cycles of the second reaction zone top exit are received enters the fines collection jar; 21 is the pipeline that adds live catalyst to degassing vessel.
Raw material enters in first reaction zone 2 through feeding line 1, contacts with molecular sieve catalyst, and reaction generates the product stream I that contains light olefin, and decaying catalyst enters revivifier regeneration from reclaimable catalyst inclined tube 4.Catalyzer after regeneration is finished returns first reaction zone from regenerated catalyst inclined tube 18.The catalyst fines that run to decrease in the revivifier revolves 8 through three and enters fines collection jar 9 after reclaiming, enter degassing vessel 12 degassings then, and with enter second reaction zone 13 after the live catalyst that adds mixes, contact with the raw material that comprises carbon four above hydrocarbon, generate olefin product II, enter centrifugal station after merging with olefin product I; The decaying catalyst of second reaction zone 13 enters revivifier regeneration from pipeline 15.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In reaction unit as shown in Figure 1, first reaction zone is a fast fluidized bed, and medial temperature is 480 ℃, and linear gas velocity is 1.5 meter per seconds; Second reaction zone is a dense phase fluidized bed, and medial temperature is 550 ℃, and linear gas velocity is 0.8 meter per second; Revivifier is a dense phase fluidized bed, and medial temperature is 660 ℃.The first reaction zone bottom feed is pure methyl alcohol, and charging is 2 kilograms/hour, and catalyzer is SAPO-34, wherein SiO in the molecular sieve
2: Al
2O
3: P
2O
5=0.1: 1: 1, the binding agent massfraction was 60% in the catalyzer.The second reaction zone bottom feed is a mixed c 4, and the fine powder that C 4 olefin content 87%, three revolves collection median size after measured is 20 microns, and the median size of live catalyst is 80 microns; By in degassing vessel, adding live catalyst, keeping the catalyzer median size in second reaction zone is 60 microns, three are threaded to the second reaction zone scope inner catalyst handling equipment all is incubated, decaying catalyst in second reaction zone enters revivifier regeneration after through the water vapour stripping, the outlet of the second reaction zone top gas is provided with three cycles and receives catalyst fines, after deliver to the fines collection jar, the second reaction zone products export and the first reaction zone products export merge and enter separate part.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 90.46% weight.
[embodiment 2]
According to embodiment 1 described condition, the first reaction zone medial temperature is 500 ℃, and linear gas velocity is 2.5 meter per seconds; The second reaction zone medial temperature is 600 ℃, and linear gas velocity is 0.9 meter per second.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 89.47% weight.
[embodiment 3]
According to embodiment 1 described condition, the first reaction zone medial temperature is 400 ℃, and linear gas velocity is 0.8 meter per second; The second reaction zone medial temperature is 450 ℃, and linear gas velocity is 0.4 meter per second.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 84.26% weight.
[embodiment 4]
According to embodiment 1 described condition, the first reaction zone medial temperature is 430 ℃, and linear gas velocity is 1.0 meter per seconds; The second reaction zone medial temperature is 500 ℃, and linear gas velocity is 0.6 meter per second.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 87.87% weight.
[embodiment 5]
According to embodiment 1 described condition, three fine powders that revolve collection median size after measured are 18 microns, the median size of live catalyst is 50 microns, keeping the catalyzer median size in second reaction zone is 40 microns, the stability that keeps catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 88.72% weight.
[embodiment 6]
According to embodiment 1 described condition, three fine powders that revolve collection median size after measured are 28 microns, the median size of live catalyst is 100 microns, keeping the catalyzer median size in second reaction zone is 80 microns, the stability that keeps catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 91.46% weight.
[embodiment 7]
According to embodiment 1 described condition, just change the type of molecular sieve in the catalyzer, experimental result sees Table 1.
Table 1
| Parameter | Molecular sieve type | Yield of light olefins, % (weight) |
| Embodiment 9 | SAPO-20 | 81.54 |
| |
SAPO-18 | 88.11 |
| Embodiment 11 | SAPO-56 | 70.34 |
| |
SAPO-34+SAPO-18 (weight ratio is 2: 1) | 89.04 |
[embodiment 8]
According to embodiment 1 described condition, the second reaction zone bottom feed is the mixture of mixed c 4 and unreacted methanol and dme, wherein the olefin(e) centent in the mixed c 4 is 87%, the weight ratio of mixed c 4 and methyl alcohol and dme is 4: 1, the stability that keeps catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 92.43% weight.
[embodiment 9]
According to embodiment 1 described condition, SiO in the molecular sieve
2: Al
2O
3: P
2O
5=0.2: 1: 1, the binding agent massfraction was 70% in the catalyzer., light olefin carbon back yield is 88.02% (weight).
[comparative example 1]
According to embodiment 1 described condition, do not establish second reaction zone, race damage catalyst fines only reclaims and is not used, and low-carbon alkene carbon back yield is 79.5% weight.
Obviously, adopt method of the present invention, can reach the purpose that improves selectivity of light olefin hydrocarbon, have bigger technical superiority, can be used in the industrial production of light olefin.
Claims (10)
1. method that improves the light olefin product yield mainly may further comprise the steps:
(1) raw material that comprises methyl alcohol enters first reaction zone, contacts with comprising the silicoaluminophosphamolecular molecular sieves catalyzer, generates olefin product I and forms decaying catalyst;
(2) at least a portion of decaying catalyst enters revivifier regeneration, and the catalyzer that regeneration is finished returns first reaction zone;
(3) run the catalyst fines that decreases in the revivifier and after three cycles are received, enter the fines collection jar, enter the degassing vessel degassing then, and with enter second reaction zone after the live catalyst that adds mixes, contact with the raw material that comprises carbon four above hydrocarbon, generate olefin product II, enter centrifugal station after merging with olefin product I;
The decaying catalyst of (4) second reaction zones enters revivifier regeneration.
2. according to the method for the described raising light olefin product of claim 1 yield, it is characterized in that described first reaction zone, second reaction zone and revivifier are fluidized-bed; Described silicoaluminophosphamolecular molecular sieves is selected from least a among SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, the SAPO-56.
3. according to the method for the described raising light olefin product of claim 2 yield, it is characterized in that described first reaction zone is a fast fluidized bed, second reaction zone is a dense phase fluidized bed, and revivifier is a dense phase fluidized bed; Described molecular screening is from SAPO-34.
4. according to the method for the described raising light olefin product of claim 1 yield, it is characterized in that the temperature of reaction in described first reaction zone is 400～500 ℃, linear gas velocity is 0.8～2.5 meter per second; Temperature of reaction in second reaction zone is 450～600 ℃, and linear gas velocity is 0.4～0.9 meter per second.
5. according to the method for the described raising light olefin product of claim 4 yield, it is characterized in that the temperature of reaction in described first reaction zone is 430～480 ℃, linear gas velocity is 1.0～1.5 meter per seconds; Temperature of reaction in second reaction zone is 500～550 ℃, and linear gas velocity is 0.6～0.8 meter per second.
6. according to the method for the described raising light olefin product of claim 1 yield, it is characterized in that described fine powder is a median size less than 30 microns granules of catalyst, the median size of described live catalyst is 50～100 microns.
7. according to the method for the described raising light olefin product of claim 1 yield, it is characterized in that keeping the catalyzer median size in second reaction zone is 40～80 microns by in degassing vessel, adding live catalyst.
8. according to the method for the described raising light olefin product of claim 1 yield, it is characterized in that described three are threaded to the second reaction zone scope inner catalyst handling equipment and all need insulation.
9. according to the method for the described raising light olefin product of claim 1 yield, it is characterized in that the decaying catalyst in described second reaction zone enters revivifier regeneration after through the water vapour stripping.
10. according to the method for the described raising light olefin product of claim 1 yield, it is characterized in that described second reaction zone top gas outlet is provided with three cycles and receives catalyst fines, deliver to the fines collection jar.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135801A (en) * | 2017-06-16 | 2019-01-04 | 中国石油化工股份有限公司 | Catalyst cracking method and device |
| CN111321000A (en) * | 2018-12-14 | 2020-06-23 | 中国石油化工股份有限公司 | Catalytic cracking method and device |
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| CN1345361A (en) * | 1999-02-17 | 2002-04-17 | 埃克森化学专利公司 | Catalytic conversion of oxygenates to olefins |
| CN101260015A (en) * | 2008-04-24 | 2008-09-10 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefins from oxygen-containing compound |
| CN101270023A (en) * | 2008-04-11 | 2008-09-24 | 中国石油化工股份有限公司 | Method for improving selectivity of light olefin hydrocarbon |
| CN101332434A (en) * | 2008-07-08 | 2008-12-31 | 中国石油化工股份有限公司 | Processing method of low carbon olefin hydrocarbon reactor escaping lost catalyst produced by methanol or dimethyl ether |
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| CN1345361A (en) * | 1999-02-17 | 2002-04-17 | 埃克森化学专利公司 | Catalytic conversion of oxygenates to olefins |
| CN101270023A (en) * | 2008-04-11 | 2008-09-24 | 中国石油化工股份有限公司 | Method for improving selectivity of light olefin hydrocarbon |
| CN101260015A (en) * | 2008-04-24 | 2008-09-10 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefins from oxygen-containing compound |
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| CN109135801A (en) * | 2017-06-16 | 2019-01-04 | 中国石油化工股份有限公司 | Catalyst cracking method and device |
| CN109135801B (en) * | 2017-06-16 | 2020-11-13 | 中国石油化工股份有限公司 | Catalytic cracking process and apparatus |
| CN111321000A (en) * | 2018-12-14 | 2020-06-23 | 中国石油化工股份有限公司 | Catalytic cracking method and device |
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