CN102372538A - Method for producing low-carbon olefin through methanol transformation - Google Patents
Method for producing low-carbon olefin through methanol transformation Download PDFInfo
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- CN102372538A CN102372538A CN2010102619215A CN201010261921A CN102372538A CN 102372538 A CN102372538 A CN 102372538A CN 2010102619215 A CN2010102619215 A CN 2010102619215A CN 201010261921 A CN201010261921 A CN 201010261921A CN 102372538 A CN102372538 A CN 102372538A
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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
Abstract
The invention relates to a method for producing low-carbon olefin through methanol transformation, and mainly solves the problem that the yield of the low-carbon olefin is lower in the prior art. The problem is better solved by adopting the technical scheme that the method for producing the low-carbon olefin through methanol transformation comprises the following steps that: a raw material which mainly comprises methanol enters a catalyst mixing tube at the gas-phase linear velocity of between 2.0 and 7.0m/s at the temperature of between 170 and 250 DEG C, and is contacted with a spent catalyst and a regenerated catalyst to form product material flow I; the product material flow I enters a main reaction zone with the axial Peclet number of between 6 and 100 through a distribution plate along with a catalyst and reacts to generate product material flow II at the temperature of between 400 and 500 DEG C; the production material flow II enters a riser reaction zone of which the axial Peclet number is at least 100 percent greater than that of the main reaction zone to obtain a product comprising the low-carbon olefin; and water vapor or ethanol of which the temperature is lower than the reaction temperature of the main reaction zone is sprayed at the bottom of the riser reaction zone. The method can be used for the industrial production of the low-carbon olefin.
Description
Technical field
The present invention relates to a kind of methanol conversion and produce the method for low-carbon alkene.
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 low-carbon alkene production 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 through coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, like 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 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) 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 catalyzer of MTO technology.The SAPO-34 catalyzer 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 times of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US6166282 that a kind of methanol conversion is the technology and the reactor drum 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 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.But in this method, there are the problem of methanolysis in raw material and catalyzer when reactor bottom contacts, cause yield of light olefins lower.
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 disengaging zone of setting, catalyzer and product gas are separated.But there is the lower problem of yield of light olefins in this method.
It is the method for alkene with oxygenate in the reactor drum of baffle plate that CN 200680018303 has announced a kind of, in this method reactive moieties is divided into three zones, and one is initial conduit; One is the contact conduit; One is linking conduit, wherein in the contact conduit, baffle plate is set, and the gas phase linear speed is greater than 1.52 meter per seconds; But this method exists methanol conversion and the lower shortcoming of selectivity of light olefin; Methanol conversion is up to 98%, and selectivity of light olefin is up to 76.3%, makes yield of light olefins be merely 74.8%.
All there is the yield of light olefins problem of lower 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 low problem of yield of light olefins that exists in the prior art, the method that provides a kind of new methanol conversion to produce low-carbon alkene.This method is used for the production of low-carbon alkene, has the yield of light olefins advantage of higher.
For addressing the above problem; The technical scheme that the present invention adopts is following: a kind of methanol conversion is produced the method for low-carbon alkene; Comprise that it is the catalyst mix pipe of 2.0～7.0 meter per seconds that the raw material that is mainly methyl alcohol gets into the gas phase linear speed down at 170～250 ℃; Contact with regenerated catalyst with reclaimable catalyst, forming product stream I and catalyzer, to get into axial Peclet number through grid distributor together be 6～100 main reaction region; React generation product stream II down at 400～500 ℃; Get into the riser reaction zone of axial Peclet number than the accurate number of the axial Peclet of main reaction region big at least 100% together with catalyzer, generate the product that comprises low-carbon alkene, said riser reaction zone bottom sprays into water vapour or the ethanol that temperature is lower than the main reaction region temperature of reaction.
In the technique scheme, said catalyzer is selected from least a among SAPO-18, the SAPO-34, and preferred version is SAPO-34; Said main reaction region is a fluidized-bed, and catalyst mix pipe top links to each other with the main reaction region bottom, and the main reaction region top links to each other with the riser reaction zone bottom; The average carbon deposition quantity massfraction of said main reaction region catalyzer is 1.5～4.5%; It is 100～300 ℃ ethanol that said riser reaction zone bottom sprays into temperature; Said regenerated catalyst temperature is 470～580 ℃, and the carbon deposition quantity massfraction is 0.01～2.5%; The water vapour that said riser reaction zone bottom sprays into or the weight ratio of ethanol and methanol feedstock are 0.05～0.2: 1.
Axially the Peclet number is a non-dimensional number; It is the situation that departs from that characterizes gas phase piston flow when gas stream is crossed beds in the reactor drum; Axially the Peclet number is big more; Gas phase flows and to approach piston flow more, infinitely-great Peclet number reflection be ideal piston flow situation, and general Peclet number 4 below can be thought mixing complete mixing flow gas-solid flow flowing mode comparatively completely.The method of calculation of Peclet number are among the present invention:
Peclet number=μ
g* H/D
g, wherein, μ
gBe gas phase linear speed, meter per second; H is the reactor beds layer height, rice; D
gBe the axial gas spread coefficient, rice
2/ second.Known in the field, the axial gas diffusion coefficient D
gCan adopt tracing method to measure.
Adopt method of the present invention, methanol feedstock gets into the catalyst mix pipe, contacts with regenerated catalyst with reclaimable catalyst.In this catalyst mix pipe, not only reach the purpose of heating methanol, also realize the well blend of reclaimable catalyst and regenerated catalyst simultaneously, reach that carbon distribution and temperature homogeneous are laggard goes into main reaction region and react.Simultaneously, in the catalyst mix pipe, part methyl alcohol can also highly selective under the high linear speed be converted into the low-carbon alkene product, after getting into main reaction region, this part gaseous substance plays the effect that reduces methanol partial pressure, further improves the selectivity of low-carbon alkene.The gaseous products of accomplishing in the main reaction region reaction gets into the more riser reaction zone of high linear speed; Spray into lower water vapour of temperature or ethanol in the riser reaction zone bottom simultaneously; In riser reaction zone; Except transforming unreacted methanol etc., can also realize the sharp separation of gas-solid, reduce the probability of main products generation secondary reaction.Simultaneously, if spray into ethanol, can also be ethene with ethanol conversion in the short period of time, reduce the temperature of product stream simultaneously.Comprehensive above factor adopts method of the present invention, can realize improving the purpose of yield of light olefins.
Adopt technical scheme of the present invention: said catalyzer is selected from least a among SAPO-18, the SAPO-34; Said main reaction region is a fluidized-bed, and catalyst mix pipe top links to each other with the main reaction region bottom, and the main reaction region top links to each other with the riser reaction zone bottom; The average carbon deposition quantity massfraction of said main reaction region catalyzer is 1.5～4.5%; It is 100～300 ℃ ethanol that said riser reaction zone bottom sprays into temperature; Said regenerated catalyst temperature is 470～580 ℃, and the carbon deposition quantity massfraction is 0.01～2.5%; The water vapour that said riser reaction zone bottom sprays into or the weight ratio of ethanol and methanol feedstock are 0.05～0.2: 1; Low-carbon alkene carbon back yield reaches 84.19% (weight); Exceed about 4.5 percentage points than low-carbon alkene carbon back yield of the prior art, 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 methyl alcohol bottom feed; 2 is the products export pipeline; 3 is the catalyst mix pipe; 4 is the catalyst recirculation pipe; 5 is regenerator sloped tube; 6 is main reaction region bottom methanol feeding; 7 is main reaction region; 8 is inclined tube to be generated; 9 is settling section; 10 is riser reaction zone; 11 is gas-solid cyclone separator; 12 is stripping zone; 13 spray into the material pipeline bottom riser reaction zone; 14 is the macropore grid distributor.
Methyl alcohol is from catalyst mix pipe 3 bottom feed pipelines 1 injecting catalyst mixing head 3, contacts with regenerated catalyst with reclaimable catalyst and reacts, and forms the logistics that comprises the low-carbon alkene product; Get into main reaction region 7 together with catalyzer; Continue the reaction generation and comprise that the product of low-carbon alkene and catalyzer get in the riser reaction zone 10 together, generate the product that comprises low-carbon alkene; Form reclaimable catalyst simultaneously; Reclaimable catalyst at least a portion is gone revivifier regeneration through inclined tube 8 to be generated, and at least a portion is through catalyst recirculation pipe 4 return catalizer mixing heads 3, and the catalyzer that regeneration is accomplished is through regenerator sloped tube 5 return catalizer mixing heads 3.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
On reaction unit as shown in Figure 1, catalyzer adopts SAPO-34, and catalyst mix pipe top links to each other with the main reaction region bottom; The main reaction region top links to each other with the riser reaction zone bottom, and main reaction region is a fluidized-bed, and the main reaction region reaction conditions is: temperature of reaction is 470 ℃; The average carbon deposition quantity of catalyzer is 2.8% (weight), and the axial Peclet number of main reaction region is 25, and to be 99.5% methyl alcohol 70% get into the catalyst mix pipe from catalyst mix pipe bottom down at 180 ℃ to purity; 30% from main reaction region bottom entering main reaction region, and linear speed is 3.5 meter per seconds in the catalyst mix pipe, and regenerated catalyst temperature is 549 ℃; The regenerated catalyst carbon deposition quantity is 0.5%; The riser reaction zone bottom sprays into 258 ℃ water vapour, and the weight ratio of water vapour and methanol feeding amount is 0.1: 1, and axial Peclet number is 100 in the riser reaction zone; Product adopts gas chromatographic analysis to form, and low-carbon alkene carbon back yield is 82.32% (weight).
[embodiment 2]
According to embodiment 1 described condition and step, just catalyzer adopts SAPO-18, and low-carbon alkene carbon back yield is 80.11% (weight).
[embodiment 3]
According to embodiment 1 described condition and step, change main reaction region reaction conditions is: temperature of reaction is 400 ℃, and the average carbon deposition quantity of catalyzer is 1.5% (weight); The axial Peclet number of main reaction region is 6, and to be 99.5% methyl alcohol 50% get into the catalyst mix pipe from catalyst mix pipe bottom down at 170 ℃ to purity, and 50% gets into main reaction region from the main reaction region bottom; Linear speed is 2.0 meter per seconds in the catalyst mix pipe; Regenerated catalyst temperature is 471 ℃, and the regenerated catalyst carbon deposition quantity is 0.01%, and the riser reaction zone bottom sprays into 102 ℃ ethanol; The weight ratio of ethanol and methanol feeding amount is 0.1: 1; Axial Peclet number is 57 in the riser reaction zone, and product adopts gas chromatographic analysis to form, and low-carbon alkene carbon back yield is 83.67% (weight).
[embodiment 4]
According to embodiment 1 described condition and step, change main reaction region reaction conditions is: temperature of reaction is 500 ℃, and the average carbon deposition quantity of catalyzer is 4.5% (weight); The axial Peclet number of main reaction region is 100, and to be 99.5% methyl alcohol 50% get into the catalyst mix pipe from catalyst mix pipe bottom down at 250 ℃ to purity, and 50% gets into main reaction region from the main reaction region bottom; Linear speed is 2.0 meter per seconds in the catalyst mix pipe; Regenerated catalyst temperature is 580 ℃, and the regenerated catalyst carbon deposition quantity is 2.5%, and the riser reaction zone bottom sprays into 300 ℃ ethanol; The weight ratio of ethanol and methanol feeding amount is 0.05: 1; Axial Peclet number is 200 in the riser reaction zone, and product adopts gas chromatographic analysis to form, and low-carbon alkene carbon back yield is 82.58% (weight).
[embodiment 5]
According to embodiment 1 described condition and step; Methyl alcohol 100% gets into the catalyst mix pipe from catalyst mix pipe bottom, and linear speed is 7.0 meter per seconds in the catalyst mix pipe, and the riser reaction zone bottom sprays into 210 ℃ ethanol; The weight ratio of ethanol and methanol feeding amount is 0.2: 1; Axial Peclet number is 200 in the riser reaction zone, and product adopts gas chromatographic analysis to form, and low-carbon alkene carbon back yield is 84.19% (weight).
[comparative example 1]
According to embodiment 1 described condition and step; Catalyst mix pipe and riser reaction zone are not set; Methyl alcohol gets into main reaction region through grid distributor; Reclaimable catalyst directly is back to the main reaction region bottom, and regenerated catalyst directly is back to the main reaction region bottom, and low-carbon alkene carbon back yield is 79.69% (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 (8)
1. a methanol conversion is produced the method for low-carbon alkene; Comprise that it is the catalyst mix pipe of 2.0～7.0 meter per seconds that the raw material that is mainly methyl alcohol gets into the gas phase linear speed down at 170～250 ℃; Contact with regenerated catalyst with reclaimable catalyst; Form the product stream I; Getting into axial Peclet number through grid distributor together with catalyzer is 6～100 main reaction region, 400～500 ℃ down reaction generate the product stream II and catalyzer gets into the riser reaction zone of axial Peclet number than the accurate number of the axial Peclet of main reaction region big at least 100% together; Generation comprises the product of low-carbon alkene, and said riser reaction zone bottom sprays into water vapour or the ethanol that temperature is lower than the main reaction region temperature of reaction.
2. produce the method for low-carbon alkene according to the said methanol conversion of claim 1, it is characterized in that said catalyzer is selected from least a among SAPO-18, the SAPO-34.
3. the method for producing low-carbon alkene according to the said methanol conversion of claim 2 is characterized in that said catalyzer is selected from SAPO-34.
4. the method for producing low-carbon alkene according to the said methanol conversion of claim 1 is characterized in that said main reaction region is a fluidized-bed, and catalyst mix pipe top links to each other with the main reaction region bottom, and the main reaction region top links to each other with the riser reaction zone bottom.
5. the method for producing low-carbon alkene according to the said methanol conversion of claim 1 is characterized in that the average carbon deposition quantity massfraction of said main reaction region catalyzer is 1.5～4.5%.
6. produce the method for low-carbon alkene according to the said methanol conversion of claim 1, it is characterized in that it is 100～300 ℃ ethanol that said riser reaction zone bottom sprays into temperature.
7. the method for producing low-carbon alkene according to the said methanol conversion of claim 1 is characterized in that said regenerated catalyst temperature is 470～580 ℃, and the carbon deposition quantity massfraction is 0.01～2.5%.
8. produce the method for low-carbon alkene according to the said methanol conversion of claim 1, it is characterized in that the water vapour that said riser reaction zone bottom sprays into or the weight ratio of ethanol and methanol feedstock are 0.05～0.2: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102619215A CN102372538A (en) | 2010-08-23 | 2010-08-23 | Method for producing low-carbon olefin through methanol transformation |
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| CN2010102619215A CN102372538A (en) | 2010-08-23 | 2010-08-23 | Method for producing low-carbon olefin through methanol transformation |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184709A (en) * | 2005-05-27 | 2008-05-21 | 埃克森美孚化学专利公司 | Oxygenate-to-olefin conversions in a baffled reactor |
| CN101402538A (en) * | 2008-11-21 | 2009-04-08 | 中国石油化工股份有限公司 | Method for improving yield of light olefins |
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- 2010-08-23 CN CN2010102619215A patent/CN102372538A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184709A (en) * | 2005-05-27 | 2008-05-21 | 埃克森美孚化学专利公司 | Oxygenate-to-olefin conversions in a baffled reactor |
| CN101402538A (en) * | 2008-11-21 | 2009-04-08 | 中国石油化工股份有限公司 | Method for improving yield of light olefins |
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Application publication date: 20120314 |