CN101811071A - Control method of coke-burning regeneration of deactivated catalyst in methanol-to-olefins process - Google Patents
Control method of coke-burning regeneration of deactivated catalyst in methanol-to-olefins process Download PDFInfo
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- CN101811071A CN101811071A CN200910056893A CN200910056893A CN101811071A CN 101811071 A CN101811071 A CN 101811071A CN 200910056893 A CN200910056893 A CN 200910056893A CN 200910056893 A CN200910056893 A CN 200910056893A CN 101811071 A CN101811071 A CN 101811071A
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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
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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
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Abstract
The invention relates to a control method of the coke-burning regeneration of deactivated catalyst in methanol-to-olefins process and solves the problem of the prior art that the low-carbon olefin yield is low. The method comprises the following steps: using oxygen-containing regenerating medium in an auxiliary combustion chamber to contact with combustion medium and burn, controlling the concentration of oxygen in the outlet gas of the auxiliary combustion chamber to be 5-20vol%, and after combustion, sending the generated mixed gases and residual regenerating medium into a fluidized bed regenerator to contact with deactivated catalyst and perform coke-burning regeneration. The technical scheme of the invention can be used to effectively solve the problem and can be used in the industrial production of low-carbon olefins.
Description
Technical field
The present invention relates to the control method of decaying catalyst coke-burning regeneration in a kind of methanol-to-olefins process.
Background technology
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 low-carbon alkene production that one class is important 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 by coal, natural gas, living beings equal energy source.Some oxygenatedchemicals can reach fairly large production, as 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 low-carbon alkene 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 catalyst is applied to methanol conversion system olefin process and studies in great detail, think that SAPO-34 is the first-selected catalyst of MTO technology.The SAPO-34 catalyst has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction time of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser.
Announced among the US6166282 that a kind of methanol 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 afterproduct gas separates fast with catalyst, 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.
Known in the field, be in the process of low-carbon alkene in methanol conversion, need to have a certain amount of carbon deposit on the catalyst, to guarantee higher yield of light olefins.And this part required carbon deposit needs the mixing of reclaimable catalyst and regenerated catalyst to realize.There is the bigger problem of difference of reclaimable catalyst and regenerated catalyst coke content in prior art, makes that the coke content on the mixed catalyst is inhomogeneous, makes the yield of low-carbon alkene reduce.
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 the control method of decaying catalyst coke-burning regeneration in a kind of new methanol-to-olefins process 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 technology economy advantage of higher.
For addressing the above problem, the technical solution used in the present invention is: contain the oxygen regenerating medium and enter auxiliary combustion chamber, with the combustion medium catalytic combustion, making the oxygen concentration in the auxiliary combustion chamber exit gas is 5～20% volumes, mist that burning generates and remaining regenerating medium carry heat and enter fluid bed regenerator, contact with decaying catalyst and carry out coke-burning regeneration.
In the technique scheme, described combustion medium comprises at least a in methane, hydrogen, propane, the diesel oil; Comprise nitrogen and oxygen in the regenerating medium, preferred version is a compressed air; Described catalyst comprises the SAPO-34 molecular sieve.
In the technical solutions according to the invention, because the control of the oxygen partial pressure in the regenerator, realize reclaimable catalyst oxygen deprivation regeneration, dwindled " carbon is poor " of reclaimable catalyst and regenerated catalyst, improve the mixed carbon deposit uniformity of reclaimable catalyst and regenerated catalyst, improved the yield of low-carbon alkene.In the technical scheme of the present invention, by adopting the burning of the indoor regenerating medium of auxiliary combustion, when changing oxygen concentration, produce a large amount of heats, this part heat can be brought in the regenerator by the mist that regenerating medium and burning generate, effectively replenished the scarce heat when oxygen deprivation is regenerated in the regenerator, for maintaining heat balance in the regenerator.Combustion medium of the present invention can be selected methane, hydrogen etc., and these gases all can be from the accessory substance that produces in the methanol-to-olefins technical process.Therefore, the indoor regenerating medium of employing auxiliary combustion contacts and burning with combustion medium, both controlled the partial pressure of oxygen that enters regenerator gases, replenished heat for regenerator again, and required combustion medium directly utilizes the accessory substance of reaction generation, thereby has improved the economy of low-carbon alkene production technology.
Adopt technical scheme of the present invention: described combustion medium comprises at least a in methane, hydrogen, propane, the diesel oil; Comprise nitrogen and oxygen in the regenerating medium, preferred version is a compressed air; Described catalyst comprises the SAPO-34 molecular sieve, and yield of light olefins can reach 82.69% 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 regenerating medium inlet; 2 are the combustion medium inlet; 3 are the reclaimable catalyst inlet; 4 is the regenerator emulsion zone; 5 is the regenerator dilute-phase zone; 6 is gas-solid cyclone separator; 7 is exhanst gas outlet; 8 are the regenerated catalyst outlet; 9 is auxiliary combustion chamber.
Regenerating medium enters in the auxiliary combustion chamber 9 from pipeline 1, contact with the combustion medium from pipeline 2, regenerating medium after the burning and the mist of generation enter regenerator emulsion zone 4 from regenerator bottoms, contact with the reclaimable catalyst from pipeline 3, the flue gas that generates is with after regenerated catalyst separates through regeneration dilute-phase zone 5, gas-solid cyclone separator 6, flue gas enters follow-up energy recovery stage from pipeline 7, and regenerated catalyst portion is through pipeline 8 Returning reacting systems.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
On fluidized-bed reaction-regeneration cycle device, catalyst is SAPO-34, regeneration temperature is 650 ℃, regenerating medium is a compressed air, combustion medium is methane and hydrogen, the volume ratio of methane and hydrogen was at 5: 1, oxygen concentration in the auxiliary combustion chamber exit gas is 17.5% volume, the carbon difference of reclaimable catalyst and regenerated catalyst can be stabilized in about 2.2% weight, regeneration temperature changes in controlling value (650 ℃) ± 5 ℃, the difference of regenerator dilute phase temperature and dense phase temperature finds no the generation of CO tail combustion phenomenon about 80 ℃.Contact with methanol feedstock after catalyst after the regeneration enters reactor and reclaimable catalyst mixes, reaction temperature is 450 ℃, and yield of light olefins is 82.69% weight.
[embodiment 2]
On fluidized-bed reaction-regeneration cycle device, catalyst is SAPO-34, regeneration temperature is 650 ℃, regenerating medium is a compressed air, combustion medium is a light diesel fuel, the igniting initiation temperature is 370 ℃, oxygen concentration in the auxiliary combustion chamber exit gas is 5% volume, the carbon difference of reclaimable catalyst and regenerated catalyst can be stabilized in about 0.8% weight, regeneration temperature changes in controlling value (650 ℃) ± 7 ℃, the difference of regenerator dilute phase temperature and dense phase temperature finds no the generation of CO tail combustion phenomenon about 110 ℃.Contact with methanol feedstock after catalyst after the regeneration enters reactor and reclaimable catalyst mixes, reaction temperature is 450 ℃, and yield of light olefins is 80.24% weight.
[embodiment 3]
On fluidized-bed reaction-regeneration cycle device, catalyst is SAPO-34, regeneration temperature is 650 ℃, regenerating medium is the mixture of nitrogen and oxygen, the volume ratio of nitrogen and oxygen is 3: 1, combustion medium is a propane, oxygen concentration in the auxiliary combustion chamber exit gas is 20% volume, the carbon difference of reclaimable catalyst and regenerated catalyst can be stabilized in about 2.5% weight, regeneration temperature changes in controlling value (650 ℃) ± 10 ℃, the difference of regenerator dilute phase temperature and dense phase temperature finds no the generation of CO tail combustion phenomenon about 68 ℃.Contact with methanol feedstock after catalyst after the regeneration enters reactor and reclaimable catalyst mixes, reaction temperature is 450 ℃, and yield of light olefins is 80.03% weight.
Obviously, adopt method of the present invention, can reach the purpose that improves yield of light olefins, have bigger technical advantage, can be used in the industrial production of low-carbon alkene.
Claims (5)
1. the control method of decaying catalyst coke-burning regeneration in the methanol-to-olefins process, contain the oxygen regenerating medium and enter auxiliary combustion chamber, with the combustion medium catalytic combustion, making the oxygen concentration in the auxiliary combustion chamber exit gas is 5～20% volumes, mist that burning generates and remaining regenerating medium carry heat and enter fluid bed regenerator, contact with decaying catalyst and carry out coke-burning regeneration.
2. according to the control method of decaying catalyst coke-burning regeneration in the described methanol-to-olefins process of claim 1, it is characterized in that described combustion medium comprises at least a in methane, hydrogen, propane, the diesel oil.
3. according to the control method of decaying catalyst coke-burning regeneration in the described methanol-to-olefins process of claim 1, it is characterized in that described regenerating medium comprises nitrogen and oxygen.
4. according to the control method of decaying catalyst coke-burning regeneration in the described methanol-to-olefins process of claim 1, it is characterized in that described regenerating medium is a compressed air.
5. according to the control method of decaying catalyst coke-burning regeneration in the described methanol-to-olefins process of claim 1, it is characterized in that described catalyst comprises the SAPO-34 molecular sieve.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100568930A CN101811071B (en) | 2009-02-19 | 2009-02-19 | Control method of coke-burning regeneration of deactivated catalyst in methanol-to-olefins process |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102463154A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for discharging carbonized fluid catalyst |
| CN102963866A (en) * | 2012-11-30 | 2013-03-13 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN103071360A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Operation method of catalytic cracking flue gas adsorbent in catalytic cracking device |
| CN103193574A (en) * | 2012-01-10 | 2013-07-10 | 中国石油化工股份有限公司 | On-stream method of methanol to light olefin reaction-regeneration device |
| CN109456137A (en) * | 2018-11-01 | 2019-03-12 | 国家能源投资集团有限责任公司 | Methanol to olefins reaction-regeneration system stops start-up method |
| CN110183299A (en) * | 2019-05-30 | 2019-08-30 | 中国神华煤制油化工有限公司 | Improve the method and system of methanol-to-olefins product yield |
| CN115055211A (en) * | 2022-06-10 | 2022-09-16 | 中国石油大学(北京) | Methanol-to-olefin regeneration method with carbon dioxide zero emission and carbon monoxide byproduct |
-
2009
- 2009-02-19 CN CN2009100568930A patent/CN101811071B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102463154A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for discharging carbonized fluid catalyst |
| CN102463154B (en) * | 2010-11-17 | 2014-01-22 | 中国石油化工股份有限公司 | Method for discharging carbonized fluid catalyst |
| CN103071360A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Operation method of catalytic cracking flue gas adsorbent in catalytic cracking device |
| CN103071360B (en) * | 2011-10-26 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method that catalytic cracking flue gas adsorbent operates in catalytic cracking unit |
| CN103193574A (en) * | 2012-01-10 | 2013-07-10 | 中国石油化工股份有限公司 | On-stream method of methanol to light olefin reaction-regeneration device |
| CN103193574B (en) * | 2012-01-10 | 2015-01-07 | 中国石油化工股份有限公司 | On-stream method of methanol to light olefin reaction-regeneration device |
| CN102963866A (en) * | 2012-11-30 | 2013-03-13 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN102963866B (en) * | 2012-11-30 | 2015-01-21 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN109456137A (en) * | 2018-11-01 | 2019-03-12 | 国家能源投资集团有限责任公司 | Methanol to olefins reaction-regeneration system stops start-up method |
| CN109456137B (en) * | 2018-11-01 | 2021-03-02 | 国家能源投资集团有限责任公司 | Work stopping and starting method of methanol-to-olefin reaction-regeneration system |
| CN110183299A (en) * | 2019-05-30 | 2019-08-30 | 中国神华煤制油化工有限公司 | Improve the method and system of methanol-to-olefins product yield |
| CN115055211A (en) * | 2022-06-10 | 2022-09-16 | 中国石油大学(北京) | Methanol-to-olefin regeneration method with carbon dioxide zero emission and carbon monoxide byproduct |
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| CN101811071B (en) | 2012-05-09 |
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