CN101260015A - Method for preparing low-carbon olefins from oxygen-containing compound - Google Patents

Method for preparing low-carbon olefins from oxygen-containing compound Download PDF

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Publication number
CN101260015A
CN101260015A CNA2008100433017A CN200810043301A CN101260015A CN 101260015 A CN101260015 A CN 101260015A CN A2008100433017 A CNA2008100433017 A CN A2008100433017A CN 200810043301 A CN200810043301 A CN 200810043301A CN 101260015 A CN101260015 A CN 101260015A
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catalyst
sapo
transferring medium
weight
heat transferring
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CN101260015B (en
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齐国祯
钟思青
张惠明
俞志楠
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • 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 used to prepare low carbon alkene by means of oxygen compound, and mainly aims to solve the problem of the prior art that the yield of the low carbon alkene is low. The method adopts the following technical proposal: regenerated catalyst is fed into a heat exchanger through a catalyst conveying pipe, and then is fed into the bottom of a reaction zone after completing heat exchange with heat-exchange medium which is selected from oxygen compound or at least one product; and the heat-exchange medium is fed into the reaction zone after completing heat exchange with the regenerated catalyst. Therefore, the method solves the problem better through adopting the technical proposal and can be used in the industrial production of low carbon alkene.

Description

Method by low carbon olefin preparation by using oxygenated chemical
Technical field
The present invention relates to a kind of method by low carbon olefin preparation by using oxygenated chemical.
Technical background
Low-carbon alkene, 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 low-carbon alkene, 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 low-carbon alkene 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 skew assemblies 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.
Known in the field, guarantee high selectivity of light olefin, need the carbon distribution of some amount on the catalyzer, and oxygenate is very responsive to processing parameters such as temperature of reaction in the process of low-carbon alkene.All there are problems such as the fluctuation of reaction zone inner catalyst carbon deposit skewness, temperature of reaction is big in prior art.The present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of yield of light olefins that exists in the prior art, and a kind of new method by low carbon olefin preparation by using oxygenated chemical is provided.This method is used for the production of low-carbon alkene, has that yield of light olefins is higher, low-carbon alkene production technique economy advantage of higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method by low carbon olefin preparation by using oxygenated chemical, said method comprising the steps of: a kind of fluidized-bed reactor (a) is provided, comprise reaction zone, race way, stripping zone, disengaging zone, the raw material that comprises described oxygenatedchemicals is contacted under the condition for validity of described reaction zone with comprising the silicoaluminophosphamolecular molecular sieve catalyzer, form the logistics 1 that comprises low-carbon alkene, catalyzer; (b) catalyzer in the described logistics 1 is separated in the disengaging zone, forms reclaimable catalyst, and described reclaimable catalyst enters stripping zone; (c) will be divided into two portions through steam stripped described reclaimable catalyst, wherein first part enters revivifier by the catalyst transport pipeline and contacts with regenerating medium, form regenerated catalyst, second section turns back to the bottom of described reaction zone by the catalyst transport pipeline; (d) described regenerated catalyst enters interchanger by the catalyst transport pipeline, and enters described reaction zone bottom after the heat transferring medium heat exchange; Wherein, described heat transferring medium is selected from least a in oxygenatedchemicals or the product, enters reaction zone with heat transferring medium after the regenerated catalyst heat exchange.
In the technique scheme, described oxygen-containing compound material is selected from least a in methyl alcohol, the dme, and preferred version is selected from methyl alcohol; Silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56, preferred version is selected from least a among SAPO-18 or the SAPO-34, and more preferably scheme is selected from SAPO-34; Described reactor is fast fluidized bed or riser tube, and preferred version is selected from fast fluidized bed; Described heat transferring medium is selected from least a in the diolefine in methyl alcohol, dme, carbon four above hydrocarbon, low-carbon alkanes, ethene, propylene or the product, preferred version is selected from least a in the diolefine in methyl alcohol, dme, carbon four above hydrocarbon or the product, more preferably scheme is selected from least a in dme, C 4 olefin or the diolefine of unreacted methanol, generation, and most preferably scheme is selected from least a in the dme of unreacted methanol, generation or the diolefine; Heat transferring medium is 0.01～0.5: 1 with the ratio of the weight flow rate of raw material, and preferred version is 0.05～0.2: 1, and more preferably scheme is 0.06～0.1: 1; Described condition for validity is: reaction pressure is counted 0～1MPa with gauge pressure, and temperature of reaction is 300～600 ℃, and the raw material weight hourly space velocity is 1～50 hour -1, the average coke content of reaction zone catalyzer is 0.01～7% weight, and the described condition for validity of preferred version is: reaction pressure is counted 0.01～0.3MPa with gauge pressure, and temperature of reaction is 400～500 ℃, and the raw material weight hourly space velocity is 6～25 hours -1, the average coke content of reaction zone catalyzer is 1～4% weight; The reclaimable catalyst that described first part enters revivifier by the catalyst transport pipeline accounts for 5～90% weight of total reclaimable catalyst, and preferred version is 15～40% weight.
Weight hourly space velocity of the present invention is defined as the raw material inlet amount that comprises in unit time active ingredient (as the molecular sieve) content divided by the reaction zone inner catalyst.
Carbon deposit quality on the catalyzer that coke content method of calculation of the present invention are certain mass is divided by described catalyst quality.Carbon deposit measuring method on the catalyzer is as follows: will mix the catalyst mix that has carbon deposit comparatively uniformly, the accurate carbon-bearing catalyzer of weighing certain mass then, be put in the pyrocarbon analyser and burn, the carbonic acid gas quality that generates by infrared analysis burning, thus carbonaceous amount on the catalyzer obtained.
Known in the field, in the conversion process of low-carbon alkene, can emit a large amount of heats at methyl alcohol or dme, and the coke-burning regeneration process of decaying catalyst also can be emitted a large amount of heat, and therefore, the process of methyl alcohol or dimethyl ether production low-carbon alkene belongs to reaction and regenerates all processes of strong heat release.And because catalyst regeneration needs higher temperature, therefore the temperature difference between reactor and the revivifier is generally more than 200 ℃, this just makes that the regenerated catalyst that comes out from revivifier brings reactor more heat the process of Returning reactor, must make that the heat surplus in the reactor is even more serious.Therefore, the present invention adopts the method that adds interchanger on the regenerated catalyst line, effectively reduces the heat of regenerated catalyst, thereby has reduced the surplus heat in the reactor.And, the present invention will be used for the unreacted methanol of hot spots raw material, heating cycle utilization or the product (as carbon four hydrocarbon) of dme or hot spots generation from this part heat that regenerated catalyst is got, effectively utilize this part heat, improved the economy of technology.
Adopt technical scheme of the present invention: described oxygen-containing compound material is selected from least a in methyl alcohol, the dme; Silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56; Described reactor is fast fluidized bed or riser tube; Heat transferring medium is 0.01～0.5: 1 with the ratio of the weight flow rate of raw material; Described condition for validity is: reaction pressure is counted 0～1MPa with gauge pressure, and temperature of reaction is 300～600 ℃, and the raw material weight hourly space velocity is 1～50 hour -1, the average coke content of reaction zone catalyzer is 0.01～7% weight; The reclaimable catalyst that described first part enters revivifier by the catalyst transport pipeline accounts for 5～90% weight of total reclaimable catalyst, and yield of light olefins can reach 81.40% 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 reactor feedstocks charging; 2 is reactor reaction zone; 3 are gas-solid sharp separation equipment; 4 is stripping zone; 5 is reclaimable catalyst circulation inclined tube; 6 remove the revivifier line of pipes for reclaimable catalyst; 7 is the revivifier breeding blanket; 8 is the reactor gas-solid cyclone separator; 9 is the reactor disengaging zone; 10 is the product collection chamber; 11 is the product gas outlet pipeline; 12 is revivifier dilute phase section; 13 is the regenerating medium source line; 14 is the regenerated catalyst line; 15 is the revivifier external warmer; 16 is the revivifier gas-solid cyclone separator; 17 is the regenerated flue gas outlet line; 18 is the heat exchanger entrance pipeline; 19 is interchanger; 20 is the heat exchanger exit pipeline; 21 is revivifier; 22 is reactor.
The logistics that comprises oxygen-containing compound material enters in reactor 22 reaction zones 2 through feeding line 1, contact with molecular sieve catalyst, reaction generates the product that contains low-carbon alkene, carry reclaimable catalyst and enter the reactor Disengagement zone through the quick separation equipment 3 of gas-solid, wherein, most of catalyst that the quick separation equipment 3 of gas-solid is separated enters stripping zone 4, and gaseous products and part are not carried out Re-isolation by the catalyst that the quick separation equipment of gas-solid separates through entering cyclone separator 8 separation, catalyst turns back to stripping zone 4 through the dipleg of cyclone separator 8, and gaseous products enters collection chamber 10 and enters follow-up centrifugal station by outlet line 11. Be divided into two parts by the quick separation equipment 3 of gas-solid and cyclone separator 8 isolated reclaimable catalysts through behind the stripping, a part turns back to the bottom of reaction zone 2 by catalyst circulation inclined tube 5; A part enters coke-burning regeneration in the renewing zone 7 of regenerator 21 through catalyst transport pipeline 6 in addition, the flue gas that the coke burning generates enters follow-up energy-recuperation system through behind the cyclone separator 16 by exhanst gas outlet pipeline 17, the catalyst that regeneration is finished enters in the heat exchanger 19 by catalyst transport pipeline 14, with the heat transferring medium heat exchange from pipeline 18, regenerated catalyst after the heat exchange continues reaction by the bottom that the catalyst transport pipeline turns back to reaction zone 2, and heat transferring medium enters reaction zone from pipeline 20.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1～4]
In the fast fluidized bed reaction unit, the same Fig. 1 of reactive system.The reaction zone medial temperature is 500 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, pure methanol feeding, and the methyl alcohol weight hourly space velocity is 25 hours -1, catalyst type sees Table 1, and the heat transferring medium with regenerated catalyst in the interchanger 19 is a methyl alcohol, and heat transferring medium is 0.05: 1 with the ratio of the weight flow rate of raw material.The reclaimable catalyst that first part enters revivifier 21 by catalyst transport pipeline 6 accounts for 40% weight of total reclaimable catalyst, and the average coke content of the catalyzer in the reaction zone 2 is 2.5% weight.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and experimental result sees Table 1.
Table 1
Parameter Catalyst type Low-carbon alkene carbon back yield, % weight
Embodiment 1 SAPO-11 32.97
Embodiment 2 SAPO-18 78.71
Embodiment 3 SAPO-56 49.33
Embodiment 4 SAPO-34 80.19
[embodiment 5～6]
According to embodiment 4 described conditions, just change temperature of reactor, experimental result sees Table 2.
Table 2
Parameter Temperature of reaction, ℃ Low-carbon alkene carbon back yield, % weight
Embodiment 5 400 76.22
Embodiment 6 450 81.29
[embodiment 7～8]
According to embodiment 4 described conditions, just change type of feed and raw material weight hourly space velocity, experimental result sees Table 3.
Table 3
Parameter Type of feed The raw material weight hourly space velocity, hour -1 Low-carbon alkene carbon back yield, % weight
Embodiment 7 Dme 15 79.07
Embodiment 8 Methyl alcohol: dme=5: 1 6 79.68
[embodiment 9～11]
According to embodiment 4 described conditions, change reactor pattern, reaction pressure and raw material weight hourly space velocity, experimental result sees Table 4.
Table 4
Parameter The reactor pattern The raw material weight hourly space velocity, hour -1 Reaction pressure is in gauge pressure, MPa Low-carbon alkene carbon back yield, % weight
Embodiment 9 Riser tube 50 0.3 76.06
Embodiment 10 Fast fluidized bed 1.2 0.01 78.49
Embodiment 11 Fast fluidized bed 50 1.0 74.61
[embodiment 12～14]
According to embodiment 4 described conditions, change ratio and average coke content that reclaimable catalyst that first part enters revivifier 21 by catalyst transport pipeline 6 accounts for total reclaimable catalyst, experimental result sees Table 5.
Table 5
Parameter The average coke content of reaction zone catalyzer, % weight The reclaimable catalyst weight that second section enters revivifier accounts for the ratio of total reclaimable catalyst weight, % Low-carbon alkene carbon back yield, % weight
Embodiment 12 1.0 15 72.69
Embodiment 13 4.0 60 76.24
Embodiment 14 7.0 5 74.22
[embodiment 15]
According to embodiment 4 described conditions, the heat transferring medium with regenerated catalyst in the interchanger 19 is a dme, and heat transferring medium is 0.06: 1 with the ratio of the weight flow rate of raw material, and yield of light olefins is 79.72% weight.
[embodiment 16]
According to embodiment 4 described conditions, the heat transferring medium with regenerated catalyst in the interchanger 19 is a 1-butylene, and heat transferring medium is 0.1: 1 with the ratio of the weight flow rate of raw material, and yield of light olefins is 80.94% weight.
[embodiment 17]
According to embodiment 4 described conditions, heat transferring medium with regenerated catalyst in the interchanger 19 is the mixture of methyl alcohol and diolefine, the weight ratio of methyl alcohol and diolefine is 10: 1, and heat transferring medium is 0.2: 1 with the ratio of the weight flow rate of raw material, and yield of light olefins is 80.15% weight.
[embodiment 18]
According to embodiment 4 described conditions, the heat transferring medium with regenerated catalyst in the interchanger 19 is an ethene, and heat transferring medium is 0.01: 1 with the ratio of the weight flow rate of raw material, and yield of light olefins is 79.85% weight.
[embodiment 19]
According to embodiment 4 described conditions, heat transferring medium with regenerated catalyst in the interchanger 19 is the mixture of methyl alcohol and ethene, the part by weight of methyl alcohol and ethene is 5: 1, and heat transferring medium is 0.5: 1 with the ratio of the weight flow rate of raw material, and yield of light olefins is 81.40% weight.
[comparative example 1]
According to embodiment 4 described conditions, just regenerated catalyst is directly turned back to reaction zone 2 bottoms, low-carbon alkene carbon back yield is 78.03% weight.
[comparative example 2]
According to embodiment 13 described conditions, regenerated catalyst is directly turned back to reaction zone 2 bottoms, low-carbon alkene carbon back yield is 74.28% weight.
[comparative example 3]
According to embodiment 4 described conditions, just change heat transferring medium into water vapour, the water vapour after the heat exchange does not enter in the reaction zone 2, and low-carbon alkene carbon back yield is 78.86% weight.
Obviously, adopt method of the present invention, can reach the purpose that improves yield of light olefins, have bigger technical superiority, can be used in the industrial production of low-carbon alkene.

Claims (9)

1, a kind of method by low carbon olefin preparation by using oxygenated chemical said method comprising the steps of:
(a) provide a kind of fluidized-bed reactor, comprise reaction zone, race way, stripping zone, disengaging zone, the raw material that comprises described oxygenatedchemicals is contacted under the condition for validity of described reaction zone with comprising the silicoaluminophosphamolecular molecular sieve catalyzer, form the logistics 1 that comprises low-carbon alkene, catalyzer;
(b) catalyzer in the described logistics 1 is separated in the disengaging zone, forms reclaimable catalyst, and described reclaimable catalyst enters stripping zone;
(c) will be divided into two portions through steam stripped described reclaimable catalyst, wherein first part enters revivifier by the catalyst transport pipeline and contacts with regenerating medium, form regenerated catalyst, second section turns back to the bottom of described reaction zone by the catalyst transport pipeline;
(d) described regenerated catalyst enters interchanger by the catalyst transport pipeline, and enters described reaction zone bottom after the heat transferring medium heat exchange;
Wherein, described heat transferring medium is selected from least a in oxygenatedchemicals or the product, enters reaction zone with heat transferring medium after the regenerated catalyst heat exchange.
2,, it is characterized in that described oxygen-containing compound material is selected from least a in methyl alcohol, the dme according to the described method of claim 1 by low carbon olefin preparation by using oxygenated chemical; Described silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56; Described reactor is fast fluidized bed or riser tube; Described heat transferring medium is selected from least a in the diolefine in methyl alcohol, dme, carbon four above hydrocarbon, low-carbon alkanes, ethene, propylene or the product, and heat transferring medium is 0.01～0.5: 1 with the ratio of the weight flow rate of raw material.
3,, it is characterized in that described oxygen-containing compound material is selected from methyl alcohol according to the described method of claim 2 by low carbon olefin preparation by using oxygenated chemical; Described silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18 or the SAPO-34; Described reactor is a fast fluidized bed; Described heat transferring medium is selected from least a in the diolefine in methyl alcohol, dme, carbon four above hydrocarbon or the product, and heat transferring medium is 0.05～0.2: 1 with the ratio of the weight flow rate of raw material.
4,, it is characterized in that described silicoaluminophosphamolecular molecular sieve is SAPO-34 according to the described method of claim 3 by low carbon olefin preparation by using oxygenated chemical; Described heat transferring medium is selected from least a in dme, C 4 olefin or the diolefine of unreacted methanol, generation, and heat transferring medium is 0.06～0.1: 1 with the ratio of the weight flow rate of raw material.
5,, it is characterized in that described heat transferring medium is selected from least a in the dme of unreacted methanol, generation or the diolefine according to the described method of claim 4 by low carbon olefin preparation by using oxygenated chemical.
6, according to the described method by low carbon olefin preparation by using oxygenated chemical of claim 1, it is characterized in that described condition for validity is: reaction pressure is counted 0～1MPa with gauge pressure, and temperature of reaction is 300～600 ℃, and the raw material weight hourly space velocity is 1～50 hour -1, the average coke content of reaction zone catalyzer is 0.01～7% weight.
7, according to the described method by low carbon olefin preparation by using oxygenated chemical of claim 6, it is characterized in that described condition for validity is: reaction pressure is counted 0.01～0.3MPa with gauge pressure, and temperature of reaction is 400～500 ℃, and the raw material weight hourly space velocity is 6～25 hours -1, the average coke content of reaction zone catalyzer is 1～4% weight.
8,, it is characterized in that reclaimable catalyst that described first part enters revivifier by the catalyst transport pipeline accounts for 5～90% weight of total reclaimable catalyst according to the described method of claim 1 by low carbon olefin preparation by using oxygenated chemical.
9, the described according to Claim 8 method by low carbon olefin preparation by using oxygenated chemical is characterized in that reclaimable catalyst that described first part enters revivifier by the catalyst transport pipeline accounts for 15～40% weight of total reclaimable catalyst.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102190547A (en) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 Method for improving yield of light olefin products
CN103073377A (en) * 2011-10-25 2013-05-01 中国石油化工股份有限公司 Method for preparation of light olefins through catalytic conversion by oxygen-containing compound
CN103372404A (en) * 2012-04-20 2013-10-30 上海兖矿能源科技研发有限公司 Novel circulating fluidization device for preparing low-carbon olefin from methanol
CN103446959A (en) * 2012-06-04 2013-12-18 中国石油化工股份有限公司 Fluidized bed reactor with feeding heat exchange, reaction regenerating device and applications thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1421044B1 (en) * 2001-07-02 2007-03-07 Exxonmobil Chemical Patents Inc. Inhibiting catalyst coke formation in the manufacture of an olefin

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102190547A (en) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 Method for improving yield of light olefin products
CN102190547B (en) * 2010-03-03 2015-12-09 中国石油化工股份有限公司 Improve the method for yield of light olefin products
CN103073377A (en) * 2011-10-25 2013-05-01 中国石油化工股份有限公司 Method for preparation of light olefins through catalytic conversion by oxygen-containing compound
CN103073377B (en) * 2011-10-25 2015-11-25 中国石油化工股份有限公司 A kind of oxygenatedchemicals catalyzed conversion prepares the method for low-carbon alkene
CN103372404A (en) * 2012-04-20 2013-10-30 上海兖矿能源科技研发有限公司 Novel circulating fluidization device for preparing low-carbon olefin from methanol
CN103446959A (en) * 2012-06-04 2013-12-18 中国石油化工股份有限公司 Fluidized bed reactor with feeding heat exchange, reaction regenerating device and applications thereof
CN103446959B (en) * 2012-06-04 2015-07-29 中国石油化工股份有限公司 A kind of fluidized-bed reactor with charging heat exchange, reaction regeneration device and application thereof

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