CN102372540A - Method for conversing methanol to light olefin - Google Patents
Method for conversing methanol to light olefin Download PDFInfo
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- CN102372540A CN102372540A CN2010102620087A CN201010262008A CN102372540A CN 102372540 A CN102372540 A CN 102372540A CN 2010102620087 A CN2010102620087 A CN 2010102620087A CN 201010262008 A CN201010262008 A CN 201010262008A CN 102372540 A CN102372540 A CN 102372540A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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 method for conversing methanol to light olefin, which mainly solves the problem of low yield of light olefin in the prior art. The method of the invention comprises the following steps: (1) methanol as a main raw material enters in a reaction zone and contacted with a catalyst to generate a product comprising light olefin and form a catalyst to be regenerated simultaneously; (2) the catalyst to be regenerated is stripped, one part of the catalyst to be regenerated returns to the reaction zone, another part of the catalyst to be regenerated enters into a regenerator for regeneration to form a regenerated catalyst; (3) the regenerated catalyst enters in a regenerated catalyst lift pipe which is characterized in that an inlet end is positioned at the lower part of the reaction zone and an outlet end is positioned in the reaction zone, the regenerated catalyst is lifted to the reaction zone, the regenerated catalyst enters to the reaction zone which is over a raw material charging distribution plate from at least two isolated catalyst outlets on the lift pipe along an axial direction. The technical scheme better solves the problem, and can be used in the industrial production of light olefin.
Description
Technical field
The present invention relates to the method that a kind of methanol conversion is a 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 there is the lower problem of yield of light olefins in this method.
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.Generally between 75～80%, there is the lower problem of yield of light olefins in low-carbon alkene carbon back yield equally in this method.
All there is the lower problem of yield of light olefins in prior art, and the present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of yield of light olefins that exists in the prior art, and it is the method for low-carbon alkene that a kind of new methanol conversion is provided.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 the method for low-carbon alkene; Mainly may further comprise the steps: the raw material that (1) is mainly methyl alcohol gets into the fluidized-bed reactor reaction zone; Contact with catalyzer, generate the product that comprises low-carbon alkene, form reclaimable catalyst simultaneously; (2) said reclaimable catalyst part behind stripping is returned reaction zone, and a part gets into revivifier regeneration, forms regenerated catalyst; (3) said regenerated catalyst gets into through regenerator sloped tube that entrance end is positioned at the reaction zone bottom, exit end is positioned at the inner regenerated catalyst riser tube of reaction zone; Contact with the lifting medium; Regenerated catalyst is promoted in the reaction zone, in the reaction zone of regenerated catalyst incoming stock feed distributing plate top from least two catalyst outlets that said riser tube in axial direction separates.
In the technique scheme, said catalyzer is selected from SAPO-34; In the reaction zone of said regenerated catalyst incoming stock feed distributing plate top from least four catalyst outlets that said riser tube in axial direction separates, preferred version is eight catalyst outlets; Said lifting medium is at least a in water vapour, carbon four above hydrocarbon, the ethene; Said reaction zone internal reaction condition is: temperature of reaction is 400～500 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 10～3.0 meter per seconds; Said methyl alcohol gets into the charging range of distribution after being heated to 150～300 ℃; Said reclaimable catalyst 50～80% returns reaction zone behind stripping, 20～50% get into revivifiers regeneration.
For the traditional fast fluidized bed reactor of gas phase linear speed at 1～3 meter per second; Whether the mixing that reaction zone bottom exists reclaimable catalyst and regenerated catalyst uniform problem; If two kinds of catalyst mix that temperature is all different with carbon deposition quantity are inhomogeneous, with reducing the productive rate that methanol conversion is a low-carbon alkene greatly.Adopt method of the present invention; Regenerated catalyst is imported in the regenerated catalyst riser tube; This riser tube exit end is positioned at reaction zone inside, can regenerated catalyst be distributed in the reaction zone on axially spaced a plurality of positions under the lifting that promotes medium, is guaranteeing that high low-carbon alkene is optionally under the prerequisite; Effectively guarantee high methanol conversion, reach the purpose that improves yield of light olefins.In addition, in the regenerated catalyst riser tube, can adopt carbon four above hydrocarbon or ethene as promoting medium, increased low carbon olefine output when promoting regenerated catalyst has effectively improved yield of light olefins.
Adopt technical scheme of the present invention: said catalyzer is selected from SAPO-34; In the reaction zone of said regenerated catalyst incoming stock feed distributing plate top from least four catalyst outlets that said riser tube in axial direction separates; Said lifting medium is at least a in water vapour, carbon four above hydrocarbon, the ethene; Said reaction zone internal reaction condition is: temperature of reaction is 400～500 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 1.0～3.0 meter per seconds; Said methyl alcohol gets into the charging range of distribution after being heated to 150～300 ℃; Said reclaimable catalyst 50～80% returns reaction zone behind stripping; 20～50% get into revivifier regeneration; Low-carbon alkene carbon back yield reaches 85.92% (weight), and is higher at least more than 6% than the low-carbon alkene carbon back yield of prior art, obtained better technical effect.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention;
Fig. 2 is the A-B sectional view among Fig. 1.
Among Fig. 1,1 is methanol feed line; 2 is reaction zone; 3 are gas-solid sharp separation equipment; 4 is inclined tube to be generated; 5 is stripping zone; 6 is regenerator sloped tube; 7 is the regenerated catalyst riser tube; 8 is gas-solid cyclone separator; 9 is the negative area; 10 is collection chamber; 11 is the product gas outlet pipeline; 12 for promoting the medium charging; 13 are the regenerated catalyst outlet; 14 is external warmer; 15 is external warmer catalyzer lower oblique tube; 16 is the charging of external warmer fluidizing medium; 17 is external warmer; 18 is the charging of external warmer fluidizing medium; 19 is heat production coil pipe; 20 is external warmer gaseous substance Returning reactor pipeline; 21 is external warmer gaseous substance Returning reactor pipeline; 22 is stripping zone fluidizing medium feeding line; 23 is external warmer catalyzer lower oblique tube; 24 is heat production coil pipe.
Methyl alcohol gets into reaction zone 2 from feeding line 1, contacts with catalyzer, generates the product that comprises low-carbon alkene; Get in the gas-solid sharp separation equipment 3; Isolated gaseous products is separated through cyclonic separator 8 once more after pipeline 11 gets into centrifugal station, the reclaimable catalyst that cyclonic separator is told, and a part is gone revivifier regeneration through inclined tube 4 to be generated; A part is returned reaction zone 2 through external warmer 14 and 17; Regenerated catalyst gets in the regenerated catalyst riser tubes 7 through regenerator sloped tube 6, contacts with lifting medium from pipeline 12, and regenerated catalyst is promoted to reaction zone 2 inside.
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, pure methanol feeding; Methyl alcohol gets into reaction zone after being heated to 180 ℃, gaseous products is separated the back through cyclonic separator and got into centrifugal station, the reclaimable catalyst that cyclonic separator is told; 30% process inclined tube to be generated goes revivifier regeneration, and 70% returns reaction zone, and regenerated catalyst gets in the regenerated catalyst riser tube through regenerator sloped tube; Contact with promoting medium, regenerated catalyst is promoted to reaction zone inside, regenerated catalyst riser tube catalyst outlet is four; Be positioned at upwards 1/2 reaction zone height place of methanol feeding grid distributor, it is as shown in Figure 2 that four catalyst outlet orientation are provided with, and the lifting medium is a water vapour; The reaction zone reaction conditions is: temperature of reaction is 470 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, and the gas phase linear speed is 1.25 meter per seconds; Reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 82.17% (weight).
[embodiment 2]
According to embodiment 1 described condition and step, methyl alcohol gets into reaction zone after being heated to 150 ℃, and the 20% process inclined tube to be generated of reclaimable catalyst goes revivifier regeneration; 80% returns reaction zone, and regenerated catalyst riser tube catalyst outlet is two, is positioned at upwards 1/2 reaction zone height place of methanol feeding grid distributor; 180 ℃ of two catalyst outlet horizontal direction angles, the lifting medium is a water vapour, the reaction zone reaction conditions is: temperature of reaction is 400 ℃; Reaction pressure is counted 0.01MPa with gauge pressure; The gas phase linear speed is 2.1 meter per seconds, and reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 80.04% (weight).
[embodiment 3]
According to embodiment 1 described condition and step, methyl alcohol gets into reaction zone after being heated to 300 ℃, and the 50% process inclined tube to be generated of reclaimable catalyst goes revivifier regeneration; 50% returns reaction zone, and regenerated catalyst riser tube catalyst outlet is eight, and wherein four are positioned at upwards 1/2 reaction zone height place of methanol feeding grid distributor; Four are positioned at upwards 3/4 reaction zone height place of methanol feeding grid distributor; Per four catalyst outlet orientation are provided with as shown in Figure 2, and promoting medium is carbon four above hydrocarbon and water vapour, and the mass ratio of water vapour and carbon four above hydrocarbon is 0.2: 1; C 4 olefin massfraction in the carbon four above hydrocarbon is 88%; The reaction zone reaction conditions is: temperature of reaction is 500 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 3.0 meter per seconds; Reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 85.92% (weight).
[embodiment 4]
According to embodiment 1 described condition and step, methyl alcohol gets into reaction zone after being heated to 210 ℃, and the 50% process inclined tube to be generated of reclaimable catalyst goes revivifier regeneration; 50% returns reaction zone, and regenerated catalyst riser tube catalyst outlet is eight, and wherein four are positioned at upwards 1/2 reaction zone height place of methanol feeding grid distributor; Four are positioned at upwards 3/4 reaction zone height place of methanol feeding grid distributor; Per four catalyst outlet orientation are provided with as shown in Figure 2, and promoting medium is carbon four above hydrocarbon and ethene, and the mass ratio of ethene and carbon four above hydrocarbon is 0.3: 1; C 4 olefin massfraction in the carbon four above hydrocarbon is 88%; The reaction zone reaction conditions is: temperature of reaction is 500 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 1.0 meter per seconds; Reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 83.69% (weight).
[embodiment 5]
According to embodiment 1 described condition and step, methyl alcohol gets into reaction zone after being heated to 210 ℃, and the 30% process inclined tube to be generated of reclaimable catalyst goes revivifier regeneration; 70% returns reaction zone, and regenerated catalyst riser tube catalyst outlet is nine, and wherein four are positioned at upwards 1/2 reaction zone height place of methanol feeding grid distributor; Four are positioned at upwards 3/4 reaction zone height place of methanol feeding grid distributor, and per four catalyst outlet orientation are provided with as shown in Figure 2, and another one is positioned at riser tube top center position; Promoting medium is ethene and water vapour, and the mass ratio of ethene and water vapour is 4: 1, and the reaction zone reaction conditions is: temperature of reaction is 500 ℃; Reaction pressure is counted 0.1MPa with gauge pressure; The gas phase linear speed is 1.6 meter per seconds, and reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon back yield of reactor outlet is 84.38% (weight).
[comparative example 1]
According to embodiment 3 described condition and steps, just regenerated catalyst directly returns the reaction zone bottom through regenerator sloped tube, and the low-carbon alkene carbon back yield of reactor outlet is 80.52% (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. method that methanol conversion is a low-carbon alkene mainly may further comprise the steps:
(1) raw material that is mainly methyl alcohol gets into the fluidized-bed reactor reaction zone, contact with catalyzer, and generation comprises the product of low-carbon alkene, forms reclaimable catalyst simultaneously;
(2) said reclaimable catalyst part behind stripping is returned reaction zone, and a part gets into revivifier regeneration, forms regenerated catalyst;
(3) said regenerated catalyst gets into through regenerator sloped tube that entrance end is positioned at the reaction zone bottom, exit end is positioned at the inner regenerated catalyst riser tube of reaction zone; Contact with the lifting medium; Regenerated catalyst is promoted in the reaction zone, in the reaction zone of regenerated catalyst incoming stock feed distributing plate top from least two catalyst outlets that said riser tube in axial direction separates.
2. be 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 SAPO-34.
3. be the method for low-carbon alkene according to the said methanol conversion of claim 1, it is characterized in that in the reaction zone of said regenerated catalyst incoming stock feed distributing plate top from least four catalyst outlets that said riser tube in axial direction separates.
4. be the method for low-carbon alkene according to the said methanol conversion of claim 3, it is characterized in that in the reaction zone of said regenerated catalyst incoming stock feed distributing plate top from least eight catalyst outlets that said riser tube in axial direction separates.
5. be the method for low-carbon alkene according to the said methanol conversion of claim 1, it is characterized in that said lifting medium is at least a in water vapour, carbon four above hydrocarbon, the ethene.
6. be the method for low-carbon alkene according to the said methanol conversion of claim 1, it is characterized in that said reaction zone internal reaction condition is: temperature of reaction is 400～500 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 1.0～3.0 meter per seconds.
7. be the method for low-carbon alkene according to the said methanol conversion of claim 1, it is characterized in that said methyl alcohol gets into the charging range of distribution after being heated to 150～300 ℃.
8. be the method for low-carbon alkene according to the said methanol conversion of claim 1, it is characterized in that said reclaimable catalyst 50～80% returns reaction zone behind stripping, 20～50% get into revivifiers regeneration.
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| CN2010102620087A CN102372540A (en) | 2010-08-23 | 2010-08-23 | Method for conversing methanol to light olefin |
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| CN2010102620087A CN102372540A (en) | 2010-08-23 | 2010-08-23 | Method for conversing methanol to light olefin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875280A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Reaction unit for converting methanol into low-carbon olefins |
| CN103739425A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Reaction device used for increasing the yields of ethylene and propylene in process of preparing olefins from methanol |
| CN103772092A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Reaction device for converting methanol into light olefin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101274871A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Fluidizer and fluidization method for preparing ethylene by ethanol dehydration |
-
2010
- 2010-08-23 CN CN2010102620087A patent/CN102372540A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101274871A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Fluidizer and fluidization method for preparing ethylene by ethanol dehydration |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875280A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Reaction unit for converting methanol into low-carbon olefins |
| CN102875280B (en) * | 2011-07-12 | 2016-05-18 | 中国石油化工股份有限公司 | Methanol conversion is the reaction unit of low-carbon alkene |
| CN103739425A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Reaction device used for increasing the yields of ethylene and propylene in process of preparing olefins from methanol |
| CN103739425B (en) * | 2012-10-17 | 2015-09-09 | 中国石油化工股份有限公司 | For improving the reaction unit of ethene, propene yield in methanol-to-olefins reaction process |
| CN103772092A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Reaction device for converting methanol into light olefin |
| CN103772092B (en) * | 2012-10-25 | 2016-04-13 | 中国石油化工股份有限公司 | Methanol conversion is the reaction unit of low-carbon alkene |
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Application publication date: 20120314 |