CN102649088A - Treatment method for catalyst escaping from reactor during preparing low-carbon alkene from methanol or dimethyl ether - Google Patents

Treatment method for catalyst escaping from reactor during preparing low-carbon alkene from methanol or dimethyl ether Download PDF

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Publication number
CN102649088A
CN102649088A CN2011100455215A CN201110045521A CN102649088A CN 102649088 A CN102649088 A CN 102649088A CN 2011100455215 A CN2011100455215 A CN 2011100455215A CN 201110045521 A CN201110045521 A CN 201110045521A CN 102649088 A CN102649088 A CN 102649088A
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catalyst
dimethyl ether
reactor
regenerator
escaping
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CN2011100455215A
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CN102649088B (en
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齐国祯
钟思青
张惠明
杨远飞
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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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective 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
    • 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 treatment method for a catalyst escaping from a reactor during preparing low-carbon alkene from methanol or dimethyl ether, which mainly solves the problem of high consumption of the catalyst in the prior art. By the adoption of the treatment method for the catalyst escaping from the reactor during preparing low-carbon alkene from methanol or dimethyl ether, raw materials mainly comprising methanol or dimethyl ether are contacted with the catalyst containing molecular sieve of aluminosilicophosphate in a fluidized bed reactor to generate products fluid, after a gas-solid separation, the products fluid carrying a few of the catalyst enter into a third cyclone separator arranged out of the reactor, at least 60 percent of the catalyst is extracted, and the catalyst extracted from the third cyclone separator is transmitted to a thin-phase section of a regenerator. According to the technical scheme, the problem is better solved, and the method can be applied in the industrial production of low-carbon alkene.

Description

The processing method that methyl alcohol or dimethyl ether are low carbon olefin hydrocarbon reactor escaping lost catalyst produced
Technical field
The present invention relates to the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of a kind of methyl alcohol or dimethyl ether.
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 through 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, One type of important alternative materials that is used for light olefin production is an oxygenatedchemicals; For example alcohols (methyl alcohol, ethanol), ethers (dimethyl ether, ethyl methyl ether), ester class (dimethyl carbonate, methyl formate) etc., these oxygenatedchemicals can be transformed through coal, natural gas, living beings equal energy source.Some oxygenatedchemicals can reach fairly large production, like methyl alcohol, can be made by coal or natural gas, and technology is very ripe, can realize up to a million tonnes production 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) receives increasing attention.
In the US4499327 patent silicoaluminophosphamolecular molecular sieves catalyst applications is studied in great detail in methanol conversion system olefin process, think that SAPO-34 is the first-selected catalyst of MTO technology.The SAPO-34 catalyst 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 time of light olefin 10 seconds, more even reach in the reaction time range of riser.
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 accomplished; 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 afterproduct gas separates with catalyst fast, has effectively prevented the generation of secondary response.Through analog computation, to compare with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyst 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 offset components etc.; Each riser reactor has the port of injecting catalyst separately; Be pooled to the Disengagement zone of setting, catalyst and product gas are separated.
CN 200810043615 has announced a kind of methyl alcohol or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether; Run the catalyst that decreases in the autoreactor and get into separative element; Through forming the higher slag slurry of catalyst concn after washing, filtering, then this part slag is starched the dilute phase section that is delivered to regenerator, most of catalyst is run out of entering fines collection jar from the regenerator outlet after the regenerator drying; Obtain dry catalyst fines; But because reactor race damage catalytic amount is bigger, the catalytic amount that makes later separation unit quench tower, catalyst detergent and filtration operation to handle is very big, can cause problems such as quench tower tower tray obstruction; In addition; Owing in separative element, usually adopt the method for annotating alkali to go out the acidic materials in the product stream, cause the activity of catalyst fines in the final catalyst slag slurry that obtains to receive big havoc, cause the value of this part catalyst to be had a greatly reduced quality.
Known in the field, fluid catalyst exist to run decreases phenomenon, and the catalyst cost of methyl alcohol or dimethyl ether producing light olefins is higher, and how as much as possible utilization is run and decreased catalyst and become a difficult problem.The present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the catalyst attrition problem of higher that exists in the prior art, and a kind of new methyl alcohol or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether are provided.This method is used for the production of low-carbon alkene, has the lower advantage of catalyst attrition.
For addressing the above problem; The technical scheme that the present invention adopts is following: the processing method that a kind of methyl alcohol or dimethyl ether are low carbon olefin hydrocarbon reactor escaping lost catalyst produced; The raw material that is mainly methyl alcohol or dimethyl ether contacts with the catalyst that comprises silicoaluminophosphamolecular molecular sieve in fluidized-bed reactor; The product stream that generates; After gas solid separation, carry little amount of catalyst and get into the external third level cyclone separator of reactor, isolate at least 60% catalyst, then with the dilute phase section of the isolated catalyst transport of said third level cyclone separator to regenerator.
In the technique scheme, said silicoaluminophosphamolecular molecular sieve is selected from SAPO-34; Said reactor and regenerator are fluid bed; Catalyst content is less than 0.4 gram/rice in the product stream before the said third level cyclone separator of said entering 3The close phase section temperature of regenerator is 600～700 ℃, and regenerator dilute phase Duan Yumi phase section temperature difference is less than 100 ℃.
Known in the field, can there be the less fine powder of part catalyst particle size in fluid catalyst because of the size consist of its broad and more violent wearing and tearing, and these fine powders can not separatedly be run out of reactor with product gas down in conventional gas-solid cyclone separator.For price higher methyl alcohol or dimethyl ether system alkene catalyst, run this part fine powder that decreases and be necessary to recycle, to reduce the cost of catalyst.The inventor is through discovering, running this part catalyst fines that decreases is can be added in the Preparation of Catalyst flow process, utilizes once more, and outlet is run the catalyst fines that decreases and can be transported to the preparation again that catalyst manufacturer carries out catalyst like regenerator.Therefore, scheme of the present invention is exactly to have solved the recycling problem that reactor outlet runs the most of catalyst fines that decreases.Third level cyclone separator is set outside reactor; Recovery is back to few 60% race damage catalyst; Because this part catalyst activity is higher, and contains a certain amount of carbon distribution, so it is delivered in the regenerator dilute phase section; Behind high temperature and rapid drying; Most of catalyst fines directly exports out from regenerator and gets into the catalyst fines collecting tank, comprises regenerator in this catalyst fines collecting tank and runs catalyst fines that decreases and the dry catalyst fine powder that decreases from the reactor outlet race, then the catalyst fines in the catalyst fines collecting tank is transported to catalyst manufacturer and recycles.Adopt technical scheme of the present invention; Except above-mentioned advantage, also effectively utilized energy, after the reactor that temperature is lower runs and decreases catalyst entering regenerator dilute phase section; Can play and reduce regenerator dilute phase section action of temperature; Effectively reduced in the regenerated flue gas CO in " tail combustion " phenomenon of dilute phase section, thereby shortened the temperature difference of close phase section of regenerator and dilute phase section, guaranteed that regenerator device moves under security context.
Adopt technical scheme of the present invention: said silicoaluminophosphamolecular molecular sieve is selected from SAPO-34; Said reactor and regenerator are fluid bed; Catalyst content is less than 0.4 gram/rice in the product stream before the said third level cyclone separator of said entering 3The close phase section temperature of regenerator is 600～700 ℃, and regenerator dilute phase Duan Yumi section temperature difference mutually is added into the catalyst fines that reclaims in the Preparation of Catalyst less than 100 ℃ again; The catalyst reactivity worth that contains catalyst fines that obtains is good; Low-carbon alkene carbon back yield had both reduced the loss of catalyst all more than 82%, had made full use of to run to decrease catalyst fines; Improve low-carbon alkene carbon back yield again, obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
React in the regenerating unit at recirculating fluidized bed, reactor is a fast fluidized bed, and regenerator is the bubbling fluidized bed bed, and catalyst is the SAPO-34 molecular sieve, and the mean temperature of reactor reaction zone is 470 ℃, and the mean temperature of regenerator renewing zone is 650 ℃.The catalyst that has reacted is after gas-solid separation fast, sedimentation, built-in two-stage gas-solid cyclone separate; Most of dipleg through built-in cyclone separator returns stripping zone; The catalyst fines that is not separated gets into external third level cyclone separator from reactor head outlet with product gas, gets into that catalyst content is 0.19 gram/rice in the product stream before the said third level cyclone separator 3, third level cyclone separator is recovered to about 75% catalyst fines, and the residual catalyst fine powder gets into centrifugal station with product stream.The isolated catalyst fines of third level cyclone separator is transported to the dilute phase section of regenerator; About 53 ℃ of the dilute phase Duan Yumi phase section temperature difference of regenerator; This part catalyst fines is after high temperature drying; About 70% catalyst fines gets into the external third level cyclone separator of regenerator with flue gas, gets into the fines collection jar through isolated catalyst fines.Catalyst fines cooling back barrelling is transported catalyst manufacturer back and is prepared.It is good to add the finished catalyst reactivity worth for preparing behind the catalyst fines, and ethene+propylene carbon back yield is 82.47% weight.
[embodiment 2]
According to embodiment 1 described method and step, the mean temperature of regenerator renewing zone changes 602 ℃ into, and regenerator dilute phase Duan Yumi section temperature difference mutually is 98 ℃, and catalyst content is 0.39 gram/rice in the product stream before the entering reactor third level cyclone separator 3, isolate about 61% catalyst fines through third level cyclone separator, catalyst fines is delivered to regenerator dilute phase section.Adding the finished catalyst reactivity worth for preparing behind the catalyst fines is: ethene+propylene carbon back yield is 82.71% weight.
[embodiment 3]
According to embodiment 1 described method and step, the mean temperature of regenerator renewing zone is 700 ℃, and regenerator dilute phase Duan Yumi section temperature difference mutually is 34 ℃, and catalyst content is 0.24 gram/rice in the product stream before the entering reactor third level cyclone separator 3, isolate about 82% catalyst fines through third level cyclone separator, catalyst fines is delivered to regenerator dilute phase section.It is good to add the finished catalyst reactivity worth for preparing behind the catalyst fines, and ethene+propylene carbon back yield is 82.22% weight.
[comparative example 1]
According to embodiment 1 described method and step, reactor third level cyclone separator is not set, reactor runs the catalyst that decreases and directly gets into separative element, through obtaining catalyst slag slurry after washing, the filtration, the slag slurry is delivered to the dilute phase section of regenerator.It is good to add the finished catalyst reactivity worth for preparing behind the catalyst fines, and ethene+propylene carbon back yield is 81.32% weight.
Obviously; Adopt method of the present invention; Not only recycle reactor and run the most of catalyst that decreases, and active higher after the catalyst of the recycling process regenerator drying, obtained higher low-carbon alkene carbon back yield; Have bigger technical advantage, can be used for the commercial production of low-carbon alkene.

Claims (5)

1. methyl alcohol or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether; The raw material that is mainly methyl alcohol or dimethyl ether contacts with the catalyst that comprises silicoaluminophosphamolecular molecular sieve in fluidized-bed reactor; The product stream that generates; After gas solid separation, carry little amount of catalyst and get into the external third level cyclone separator of reactor, isolate at least 60% catalyst, then with the dilute phase section of the isolated catalyst transport of said third level cyclone separator to regenerator.
2. according to said methyl alcohol of claim 1 or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether, it is characterized in that said silicoaluminophosphamolecular molecular sieve is selected from SAPO-34.
3. according to said methyl alcohol of claim 1 or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether, it is characterized in that said reactor and regenerator are fluid bed.
4. according to said methyl alcohol of claim 1 or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether, it is characterized in that catalyst content is less than 0.4 gram/rice in the preceding product stream of the said third level cyclone separator of said entering 3
5. according to said methyl alcohol of claim 1 or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether, it is characterized in that the close phase section temperature of regenerator is 600～700 ℃, regenerator dilute phase Duan Yumi phase section temperature difference is less than 100 ℃.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108840786A (en) * 2018-07-27 2018-11-20 国家能源投资集团有限责任公司 Methanol-to-olefins device

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CN101165018A (en) * 2006-10-20 2008-04-23 中国石油化工股份有限公司 Method for producing ethylene and propylene
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101165018A (en) * 2006-10-20 2008-04-23 中国石油化工股份有限公司 Method for producing ethylene and propylene
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108840786A (en) * 2018-07-27 2018-11-20 国家能源投资集团有限责任公司 Methanol-to-olefins device

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