CN102274704B - Stripping method of deactivated catalyst in preparation of alkene from methanol - Google Patents
Stripping method of deactivated catalyst in preparation of alkene from methanol Download PDFInfo
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- CN102274704B CN102274704B CN2010101997828A CN201010199782A CN102274704B CN 102274704 B CN102274704 B CN 102274704B CN 2010101997828 A CN2010101997828 A CN 2010101997828A CN 201010199782 A CN201010199782 A CN 201010199782A CN 102274704 B CN102274704 B CN 102274704B
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- decaying catalyst
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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 stripping method of a deactivated catalyst in preparation of alkene from methanol, and mainly solves a problem of low deactivated catalyst stripping efficiency in an alkene preparation technology from methanol. A stripping method of the deactivated catalyst in preparation of alkene from methanol is employed in the invention to well solve the problem. The method comprises the steps that a catalyst contacts with raw materials containing methanol to form a deactivated catalyst with a carbon deposition concentration of 1.5%-5.0% in a reactor; the deactivated catalyst enters into a stripping zone to contact with stripping steam under a condition of a carbon deposition-steam contact coefficient being 0.01-0.1; the deactivated catalyst comes out from the stripping zone and enters into a regenerator for regeneration. In addition, the method can be applied to industrial production of light olefins.
Description
Technical field
The present invention relates to a kind of gas stripping process of methanol-to-olefins decaying catalyst.
Technical background
Low-carbon alkene refers to ethene and propylene, is important basic chemical industry raw material, and its demand is in continuous increase.Usually, ethene and propylene are to produce by petroleum path, but because the limited supply of petroleum resources and higher price, the cost of being produced propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms producing light olefins.Wherein, the important alternative materials that is used for low-carbon alkene production of one class is 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 be subjected to increasing attention by the technology of oxygen-containing compound conversion to produce olefine (OTO).
In the US4499327 patent silicoaluminophosphamolecular molecular sieves catalyst is applied to methanol conversion olefin process processed 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.
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 arranges 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 time of staying of product gas in second reaction zone of first reaction zone outlet, make unreacted methanol, the dimethyl ether 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 the freshening carbon four above hydrocarbon through separating.Though this method can improve the yield of low-carbon alkene to a certain extent, but because the catalyst that first reaction zone comes out has had more carbon distribution, and the carbon four above hydrocarbon pyrolysis 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.
Two sections or multistage short contact stripping process in a kind of catalytic cracking process are disclosed among EP 175301 and the EP171330, to improve displacement efficiency.
Propose the gas stripping process of two stacked stripping sections in the catalytic cracking process among the US 5032252, improve the stripping temperature of hypomere, reduce the hydrogen content in the coke.
In the prior art, the gas stripping process of spent agent generally all adopts the gas stripping process of catalytic cracking catalyst, but adopted the aperture SAPO-34 molecular sieve of three-dimensional open-framework in the methanol-to-olefins reaction process, its carbon distribution character and pore structure all are essentially different with catalytic cracking, prior art does not solve the gas stripping process problem of methanol-to-olefins decaying catalyst, all has the lower problem of decaying catalyst steam stripping efficiency.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 low problem of decaying catalyst steam stripping efficiency in the methanol-to-olefins technology, and a kind of gas stripping process of new methanol-to-olefins decaying catalyst is provided.This method is used for the production of low-carbon alkene, has decaying catalyst steam stripping efficiency advantage of higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of gas stripping process of methanol-to-olefins decaying catalyst, this method comprises that catalyst contacts with the raw material that comprises methyl alcohol and reacts in reactor, and formation carbon deposition quantity mass fraction is 1.5%～5.0% decaying catalyst, it is to contact under 0.01～0.1 the condition at carbon distribution-steam contact coefficient that described decaying catalyst enters stripping zone and stripped vapor, and the decaying catalyst that comes out from stripping zone enters regenerator regeneration.
In the technique scheme, described catalyst comprises SAPO-34; Described reactor and regenerator are fluid bed; Described stripped vapor is steam; Described stripping zone arranges baffle plate, and form is ramp type baffle plate or chevron shaped baffle plate; Described carbon distribution-steam contact coefficient is 0.02～0.05; In the material and stripped vapor Returning reactor that described stripping zone stripping goes out.
Among the present invention:
Wherein, the stripping zone catalyst inventory calculates density of catalyst and the bed height of stripping zone by measuring the pressure reduction on the stripping zone diverse location, can calculate the reserve of catalyst; Carbon deposition quantity of catalyst adopts thermogravimetric analyzer (TGA) to measure.
The product tolerance that decaying catalyst is carried secretly can obtain by the logistics composition that adopts gas chromatography analysis method to analyze the stripping zone outlet.
Steam stripping efficiency is relevant with multiple factors such as stripping zone baffle plate pattern, stripping zone operating condition and stripped vapor consumptions, and the computational methods of steam stripping efficiency are with reference to " " catalytic cracking process and engineering ", second edition; Chen Junwu chief editor, chapter 7, the 1204th page; Sinopec publishing house, 2005 years ".
The gas stripping process of decaying catalyst generally is similar to the gas stripping process of catalytic cracking catalyst, but because the difference of methanol to olefins reaction catalyst physical property and the carbon distribution different in kind of generation make traditional gas stripping process can't satisfy the requirement of methanol-to-olefins technology.Because methanol-to-olefins catalyst activity component is the small pore molecular sieve of three-dimensional open-framework, in the bigger cage in space, very easily carry more product secretly and answer product, and olefin(e) centent is high especially in the methanol to olefins reaction product, easier being adsorbed in the catalyst pores, if the steam stripping efficiency of stripping zone is not high, the product volume that makes decaying catalyst carry secretly increases, and generates waste gas and enter the regenerator burning, has also reduced the yield of low-carbon alkene product to a certain extent.In addition, because the carbon distribution that generates in the methanol to olefins reaction makes molecular sieve pore passage more narrow, thereby increased steam stripped difficulty to a certain extent.So carbon distribution has close relationship on steam stripping efficiency and the catalyst.Adopt method of the present invention, by control carbon distribution-steam contact coefficient, can guarantee that decaying catalyst is carried secretly in the stripping zone product is high efficiency to be removed by stripped vapor.
Adopt technical scheme of the present invention: described catalyst comprises SAPO-34; Described reactor and regenerator are fluid bed; Described stripped vapor is steam; Described stripping zone arranges baffle plate, and form is ramp type baffle plate or chevron shaped baffle plate; Described carbon distribution-steam contact coefficient is 0.02～0.05; In the material and stripped vapor Returning reactor that described stripping zone stripping goes out, steam stripping efficiency reaches 94.7%, has obtained better technical effect.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
In reaction unit as shown in Figure 1, reactor and regenerator are fluid bed, and the reaction zone mean temperature is 465 ℃, reaction pressure is normal pressure, beds density is 210 kilograms per cubic meter, and linear gas velocity is 0.8 meter per second, and the average carbon deposition quantity of catalyst is 3.5%; The regenerator regeneration temperature is 675 ℃, and regeneration pressure is normal pressure.The reaction zone bottom feed is that purity is 99.5% methyl alcohol, catalyst is SAPO-34, skeletal density is about 1600 kilograms per cubic meter, decaying catalyst partly enters the outer stripping zone of reactor in the reaction zone, contact with steam, the stripping zone mean temperature is about 419 ℃, the stripping zone bed density is 476 kilograms per cubic meter, catalyst inventory is about 2 kilograms, carbon distribution-steam contact coefficient is controlled 0.057, the built-in chevron shaped baffle plate of stripping zone, and theoretical height of transfer unit is about 3.2 meters, the stability that keeps catalyst to flow and control, the stripping zone steam stripping efficiency that calculates is 93%.
[embodiment 2]
According to embodiment 1 described condition, the reaction zone mean temperature is 425 ℃, and reaction pressure is normal pressure, and beds density is 300 kilograms per cubic meter, and linear gas velocity is 0.58 meter per second, and the average carbon deposition quantity of catalyst is 4.96%; The regenerator regeneration temperature is 683 ℃.The stripping zone mean temperature is about 398 ℃, the stripping zone bed density is 482 kilograms per cubic meter, catalyst inventory is about 2.3 kilograms, carbon distribution-steam contact coefficient is controlled 0.1, the built-in ramp type baffle plate of stripping zone, theoretical height of transfer unit is about 3.9 meters, the stability that keeps catalyst to flow and control, and the stripping zone steam stripping efficiency that calculates is 89%.
[embodiment 3]
According to embodiment 1 described condition, the average carbon deposition quantity of catalyst is 1.54%; The regenerator regeneration temperature is 655 ℃.The stripping zone mean temperature is about 423 ℃, the stripping zone bed density is 469 kilograms per cubic meter, and catalyst inventory is about 2.0 kilograms, and carbon distribution-steam contact coefficient is controlled 0.08, the stability that keeps catalyst to flow and control, the stripping zone steam stripping efficiency that calculates is 94.7%.
[embodiment 4]
According to embodiment 1 described condition, the average carbon deposition quantity of catalyst is 4.5%, the stripping zone mean temperature is about 415 ℃, the stripping zone bed density is 487 kilograms per cubic meter, catalyst inventory is about 2.1 kilograms, carbon distribution-steam contact coefficient is controlled 0.01, the stability that keeps catalyst to flow and control, and the stripping zone steam stripping efficiency that calculates is 84.6%.
[embodiment 5]
According to embodiment 1 described condition, the average carbon deposition quantity of catalyst is 3.75%, the stripping zone mean temperature is about 417 ℃, the stripping zone bed density is 501 kilograms per cubic meter, catalyst inventory is about 2.5 kilograms, carbon distribution-steam contact coefficient is controlled 0.02, the stability that keeps catalyst to flow and control, and the stripping zone steam stripping efficiency that calculates is 85.9%.
[comparative example 1]
According to embodiment 1 described condition, carbon distribution-steam contact coefficient is controlled 0.005, the stability that keeps catalyst to flow and control, and the stripping zone steam stripping efficiency that calculates is 76.8%.
Obviously, adopt method of the present invention, guaranteed the steam stripping efficiency that stripping zone is higher, thereby 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 gas stripping process of a methanol-to-olefins decaying catalyst, this method comprises that catalyst contacts with the raw material that comprises methyl alcohol and reacts in reactor, and formation carbon deposition quantity mass fraction is 1.5%～5.0% decaying catalyst, it is to contact under 0.01～0.1 the condition at carbon distribution-steam contact coefficient that described decaying catalyst enters stripping zone and stripped vapor, and the decaying catalyst that comes out from stripping zone enters regenerator regeneration; Described catalyst comprises SAPO-34; Described stripped vapor is steam.
2. according to the gas stripping process of the described methanol-to-olefins decaying catalyst of claim 1, it is characterized in that described reactor and regenerator are fluid bed.
3. according to the gas stripping process of the described methanol-to-olefins decaying catalyst of claim 1, it is characterized in that described stripping zone arranges baffle plate, form is ramp type baffle plate or chevron shaped baffle plate.
4. according to the gas stripping process of the described methanol-to-olefins decaying catalyst of claim 1, it is characterized in that described carbon distribution-steam contact coefficient is 0.02～0.05.
5. according to the gas stripping process of the described methanol-to-olefins decaying catalyst of claim 1, it is characterized in that in the material and stripped vapor Returning reactor that described stripping zone stripping goes out.
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| CN2010101997828A CN102274704B (en) | 2010-06-11 | 2010-06-11 | Stripping method of deactivated catalyst in preparation of alkene from methanol |
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| CN2010101997828A CN102274704B (en) | 2010-06-11 | 2010-06-11 | Stripping method of deactivated catalyst in preparation of alkene from methanol |
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| CN102274704B true CN102274704B (en) | 2013-07-17 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244969A (en) * | 2008-03-25 | 2008-08-20 | 清华大学 | Continuous aromatization and catalyst regeneration device and method thereof |
| CN101327440A (en) * | 2008-06-27 | 2008-12-24 | 安徽理工大学 | Composite catalyst for producing hydrogen by methane steam reforming technology |
| CN101633593A (en) * | 2008-07-26 | 2010-01-27 | 中国石化集团洛阳石油化工工程公司 | Conversion method of C4 and heavier components |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2317395A1 (en) * | 1998-02-24 | 1999-09-02 | Cicero A. Bernales | Hydrogen production via the direct cracking of hydrocarbons |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244969A (en) * | 2008-03-25 | 2008-08-20 | 清华大学 | Continuous aromatization and catalyst regeneration device and method thereof |
| CN101327440A (en) * | 2008-06-27 | 2008-12-24 | 安徽理工大学 | Composite catalyst for producing hydrogen by methane steam reforming technology |
| CN101633593A (en) * | 2008-07-26 | 2010-01-27 | 中国石化集团洛阳石油化工工程公司 | Conversion method of C4 and heavier components |
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