CN102872770A - Reaction unit for preparing low-carbon olefins - Google Patents
Reaction unit for preparing low-carbon olefins Download PDFInfo
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- CN102872770A CN102872770A CN2011101934306A CN201110193430A CN102872770A CN 102872770 A CN102872770 A CN 102872770A CN 2011101934306 A CN2011101934306 A CN 2011101934306A CN 201110193430 A CN201110193430 A CN 201110193430A CN 102872770 A CN102872770 A CN 102872770A
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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 reaction unit for preparing low-carbon olefins, mainly solving the problem of low yield of low-carbon olefins in the prior art. The reaction unit disclosed herein mainly comprises a reaction zone 2, a depression zone 9, and a riser 7, wherein the depression zone 9 is arranged above the reaction zone 2, the bottom of the depression zone 9 is provided with a catalyst outlet which is connected with a regenerator and the riser 7, the top of the depression zone 9 is provided with a product gas outlet, the inlet end of the riser 7 is arranged outside the reaction zone 2, the outlet end of the riser 7 is arranged in the reaction zone 2, the lower portion of the riser 7 is provided with a catalyst inlet which is connected with a catalyst circulation pipe 6, the part of the riser 7 arranged in the reaction zone is provided with at least a catalyst outlet 13, the height of the part of the riser 7 in the reaction zone 2 is at least 1/4 the height of the reaction zone 2, the lower portion of the reaction zone 2 is provided with a catalyst inlet which is connected with the regenerator through a regeneration inclined pipe 5. The reaction unit disclosed herein disclosed herein well solves the problem and can be used in the industrial production of low-carbon olefins.
Description
Technical field
The present invention relates to a kind of reaction unit for preparing low-carbon alkene.
Technical background
Low-carbon alkene, namely 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 and the higher price of petroleum resources, 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 ethene processed, propylene.Wherein, the important alternative materials that is used for low-carbon alkene production of one class is oxygenatedchemicals, such as 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, such as methyl alcohol, can be made by coal or natural gas, and technique is very ripe, can realize up to a million tonnes production scale.Because the popularity in oxygenatedchemicals source, add and transform the economy that generates low-carbon alkene technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), particularly the technique by preparing olefin by conversion of methanol (MTO) is subject to increasing attention.
In the US4499327 patent silicoaluminophosphamolecular molecular sieve catalyst is applied to preparing olefin by conversion of methanol technique and studies in great detail, think that SAPO-34 is the first-selected catalyst of MTO technique.The SAPO-34 catalyst has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is reaction time of low-carbon alkene to be less than 10 seconds degree, more even reach in the reaction time range of riser.
Technology and reactor that a kind of methanol conversion is low-carbon alkene have been announced among the US6166282, 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 greatly reduce.But there is the lower problem of yield of light olefins in the method.
The multiple riser reaction unit of having announced among the CN1723262 with central catalyst return is low-carbon alkene technique 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 gas product are separated.Generally between 75～80%, there is the lower problem of yield of light olefins in the low-carbon alkene carbon base absorption rate equally in the 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 a kind of reaction unit of new preparation low-carbon alkene is provided.This device is used for the production of low-carbon alkene, has the higher advantage of yield of light olefins.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of reaction unit for preparing low-carbon alkene, mainly comprise reaction zone 2, decanting zone 9, spent riser 7, decanting zone 9 is positioned at reaction zone 2 tops, 9 bottoms, decanting zone are provided with catalyst outlet respectively by inclined tube 4 to be generated and catalyst circulation pipe 6 and regenerator, riser 7 links to each other, 9 tops, decanting zone are provided with product gas outlet, spent riser 7 entrance points are positioned at reaction zone 2 outsides, the port of export is positioned at reaction zone 2 inside, spent riser 7 bottoms are provided with catalyst inlet and link to each other with catalyst circulation pipe 6, the part that spent riser 7 is positioned at reaction zone 2 has at least one catalyst outlet 13, the height that riser 7 is positioned at reaction zone 2 inside is at least 1/4 of reaction zone 2 height, reaction zone 2 bottoms are provided with catalyst inlet, link to each other with regenerator by regenerator sloped tube 5.
In the technique scheme, described catalyst is selected from SAPO-34; Described reclaimable catalyst enters in the reaction zone 2 at least from two catalyst outlets that riser 7 in axial direction separates; The height that described riser 7 is positioned at reaction zone 2 inside is at least 1/3 of reaction zone 2 height; Described riser 7 top exits arrange seedpod of the lotus shape gas-solid distribution apparatus 3, and percent opening is 0.5～0.8; Described spent riser 7 is 0.05～0.15: 1 with the diameter ratio of reaction zone 2.
Among the present invention, percent opening refers to the effective area of distribution grid, namely refers to the area summation in hole on the distribution grid face and the ratio of the distribution grid face gross area.
Described reaction zone 2 internal reaction conditions are: reaction temperature is 450～580 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 0.5～2.0 meter per second; Described reclaimable catalyst 50～80% returns reaction zone 2,20～50% through riser 7 and enters regenerator regeneration; Described regenerated catalyst coke content mass fraction is 0.02～0.5%; Described riser 7 internal reaction conditions are: reaction temperature is 400～500 ℃, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and the gas phase linear speed is 4～8 meter per seconds
The inventor finds that by research it is low-carbon alkene that the SAPO-34 molecular sieve catalyst both can transform methyl alcohol, can be low-carbon alkene at the conversion C 4 olefin of high conversion under the optimal conditions simultaneously.Adopt device of the present invention, enter the raw material that comprises C 4 olefin in fluidized-bed reactor reaction zone bottom, main high temperature with coming from regenerator, the high activated catalyst contact, under lower linear speed, the generation low-carbon alkene of high conversion, and methyl alcohol enters in the riser that gos deep into reaction zone inside, contact with reclaimable catalyst, because reclaimable catalyst contains a certain amount of coke content, has better Shape-selective, can be with the low-carbon alkene that is converted into of methyl alcohol high selectivity, and unconverted methyl alcohol, the dimethyl ether and some high-carbon hydrocarbon that generate out continue to react in fluidized bed reaction zone from riser afterwards, thereby guarantee higher methyl alcohol total conversion.Riser arranges at least one catalyst outlet, optimal case is that at least two catalyst outlets are set, one of them mixes in fluidized-bed reactor reaction zone bottom with regenerated catalyst, regulate the average activity that C 4 olefin is converted into low-carbon alkene zone catalyst, and the another one outlet enters fluidized bed reaction zone from the seedpod of the lotus shape gas-solid distribution apparatus at riser top, finally finishes the conversion of methyl alcohol.C 4 olefin of the present invention comes from methanol conversion and prepares isolated carbon four above hydrocarbon in the low-carbon alkene separation process.Therefore, by above means, can realize improving the purpose of yield of light olefins.
Adopt technical scheme of the present invention: described catalyst is selected from SAPO-34; Described reclaimable catalyst enters in the reaction zone 2 at least from two catalyst outlets that riser 7 in axial direction separates; The height that described riser 7 is positioned at reaction zone 2 inside is at least 1/3 of reaction zone 2 height; Described riser 7 top exits arrange seedpod of the lotus shape gas-solid distribution apparatus 3, and percent opening is 0.5～0.8; Described spent riser 7 is 0.05～0.15: 1 with the diameter ratio of reaction zone 2, and the low-carbon alkene carbon base absorption rate reaches 89.17% (weight), improves than the low-carbon alkene carbon base absorption rate of prior art to reach 7%, has obtained preferably technique effect.
Description of drawings
Fig. 1 is the schematic flow sheet of device of the present invention.
Fig. 2 is the A-B cutaway view among Fig. 1.
Among Fig. 1,1 is the first material feeding tube line; 2 is fluidized bed reaction zone; 3 is gas-solid separation equipment; 4 is inclined tube to be generated; 5 is regenerator sloped tube; 6 is the catalyst circulation pipe; 7 is spent riser; 8 is gas-solid cyclone separator; 9 is the decanting zone; 10 is collection chamber; 11 is the product gas outlet pipeline; 12 is the second raw material charging; 13 are the reclaimable catalyst outlet; 14 is the first raw material feed distributing plate.
The first raw material enters fluidized-bed reactor reaction zone 2, contact with catalyst, generation comprises the product of low-carbon alkene, form simultaneously reclaimable catalyst, a described reclaimable catalyst part enters regenerator regeneration, form regenerated catalyst, a part enters entrance point through catalyst circulation pipe 6 and is positioned at described reaction zone 2 outsides, the port of export is positioned at the riser 7 of described reaction zone 2 inside, contact with the second raw material, reclaimable catalyst is promoted in the described reaction zone 2, reclaimable catalyst enters in the reaction zone 2 of the first raw material feed distributing plate 14 tops from least one catalyst outlet that described riser 7 in axial direction separates, and described regenerated catalyst returns fluidized-bed reactor reaction zone 2 bottoms.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
The specific embodiment
[embodiment 1]
On reaction unit as shown in Figure 1, catalyst adopts SAPO-34, the C 4 olefin mass fraction is that 88% carbon four hydrocarbon mixtures enter the fluidized-bed reactor reaction zone, contact with catalyst, generation comprises the product of low-carbon alkene, form simultaneously reclaimable catalyst, described reclaimable catalyst 50% enters regenerator regeneration, form regenerated catalyst, 50% enters entrance point through the catalyst circulation pipe is positioned at the reaction zone outside, the port of export is positioned at the riser of reaction zone inside, contact with methanol feedstock, reclaimable catalyst is promoted in the reaction zone, reclaimable catalyst enters from two catalyst outlets that riser in axial direction separates in the reaction zone of the first raw material feed distributing plate top, two catalyst outlets lay respectively at the riser top, the riser middle part, the riser top exit arranges seedpod of the lotus shape gas-solid distribution apparatus, and percent opening is 0.5, the height that riser is positioned at reaction zone inside is 1/3 of described fluidized bed reaction zone height, and riser is 0.15: 1 with the diameter ratio of reaction zone.Reaction zone internal reaction condition is: reaction temperature is 580 ℃, reaction pressure is counted 0.01MPa with gauge pressure, the gas phase linear speed is 2 meter per seconds, regenerated catalyst coke content mass fraction is 0.02%, described riser internal reaction condition is: reaction temperature is 500 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 8 meter per seconds, reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 89.17% (weight).
[embodiment 2]
According to embodiment 1 described condition and step, the C 4 olefin mass fraction is that 88% carbon four hydrocarbon mixtures enter the fluidized-bed reactor reaction zone, contact with catalyst, generation comprises the product of low-carbon alkene, form simultaneously reclaimable catalyst, described reclaimable catalyst 20% enters regenerator regeneration, form regenerated catalyst, 80% enters entrance point through the catalyst circulation pipe is positioned at the reaction zone outside, the port of export is positioned at the riser of reaction zone inside, contact with methanol feedstock, reclaimable catalyst is promoted in the reaction zone, reclaimable catalyst enters from two catalyst outlets that riser in axial direction separates in the reaction zone of the first raw material feed distributing plate top, two catalyst outlets lay respectively at the riser top, the riser middle part, the riser top exit arranges seedpod of the lotus shape gas-solid distribution apparatus, percent opening is 0.8, and the height that riser is positioned at reaction zone inside is 1/4 of described fluidized bed reaction zone height, and riser is 0.05: 1 with the diameter ratio of reaction zone.Reaction zone internal reaction condition is: reaction temperature is 450 ℃, reaction pressure is counted 0.01MPa with gauge pressure, the gas phase linear speed is 0.5 meter per second, regenerated catalyst coke content mass fraction is 0.5%, described riser internal reaction condition is: reaction temperature is 400 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 4 meter per seconds, reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 85.27% (weight).
[embodiment 3]
According to embodiment 1 described condition and step, the C 4 olefin mass fraction is that 88% carbon four hydrocarbon mixtures enter the fluidized-bed reactor reaction zone, contact with catalyst, generation comprises the product of low-carbon alkene, form simultaneously reclaimable catalyst, described reclaimable catalyst 30% enters regenerator regeneration, form regenerated catalyst, 70% enters entrance point through the catalyst circulation pipe is positioned at the reaction zone outside, the port of export is positioned at the riser of reaction zone inside, contact with methanol feedstock, reclaimable catalyst is promoted in the reaction zone, reclaimable catalyst enters from two catalyst outlets that riser in axial direction separates in the reaction zone of the first raw material feed distributing plate top, two catalyst outlets lay respectively at the riser top, the riser middle part, the riser top exit arranges seedpod of the lotus shape gas-solid distribution apparatus, percent opening is 0.8, and the height that riser is positioned at reaction zone inside is 1/2 of described fluidized bed reaction zone height.Reaction zone internal reaction condition is: reaction temperature is 550 ℃, reaction pressure is counted 0.01MPa with gauge pressure, the gas phase linear speed is 0.8 meter per second, regenerated catalyst coke content mass fraction is 0.12%, described riser internal reaction condition is: reaction temperature is 470 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 5 meter per seconds, reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 87.09% (weight).
[embodiment 4]
According to embodiment 1 described condition and step, the C 4 olefin mass fraction is that 94% carbon four hydrocarbon mixtures enter the fluidized-bed reactor reaction zone, contact with catalyst, generation comprises the product of low-carbon alkene, form simultaneously reclaimable catalyst, described reclaimable catalyst 30% enters regenerator regeneration, form regenerated catalyst, 70% enters entrance point through the catalyst circulation pipe is positioned at the reaction zone outside, the port of export is positioned at the riser of reaction zone inside, contact with methanol feedstock, reclaimable catalyst is promoted in the reaction zone, reclaimable catalyst enters from the catalyst outlet of riser top in the reaction zone of the first raw material feed distributing plate top, the riser top exit arranges seedpod of the lotus shape gas-solid distribution apparatus, and percent opening is 0.8, and the height that riser is positioned at reaction zone inside is 2/3 of described fluidized bed reaction zone height.Reaction zone internal reaction condition is: reaction temperature is 570 ℃, reaction pressure is counted 0.3MPa with gauge pressure, the gas phase linear speed is 0.6 meter per second, regenerated catalyst coke content mass fraction is 0.15%, described riser internal reaction condition is: reaction temperature is 480 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and the gas phase linear speed is 4.5 meter per seconds, reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 86.13% (weight).
[comparative example 1]
According to embodiment 1 described condition and step, riser is not set, methyl alcohol and C 4 olefin diameter enter reaction zone from fluidized-bed reactor reaction zone bottom, and the low-carbon alkene carbon base absorption rate of reactor outlet is 82.15% (weight).
Obviously, adopt reaction unit of the present invention, can reach the purpose that improves yield of light olefins, have larger technical advantage, can be used in the industrial production of low-carbon alkene.
Claims (6)
1. reaction unit for preparing low-carbon alkene, mainly comprise reaction zone (2), decanting zone (9), spent riser (7), decanting zone (9) is positioned at reaction zone (2) top, bottom, decanting zone (9) is provided with catalyst outlet respectively by inclined tube to be generated (4) and catalyst circulation pipe (6) and regenerator, riser (7) links to each other, top, decanting zone (9) is provided with product gas outlet, spent riser (7) entrance point is positioned at reaction zone (2) outside, the port of export is positioned at reaction zone (2) inside, spent riser (7) bottom is provided with catalyst inlet and links to each other with catalyst circulation pipe (6), the part that spent riser (7) is positioned at reaction zone (2) has at least one catalyst outlet (13), riser (7) is positioned at the inner height of reaction zone (2) and is at least 1/4 of reaction zone (2) height, reaction zone (2) bottom is provided with catalyst inlet, links to each other with regenerator by regenerator sloped tube (5).
2. the reaction unit of described preparation low-carbon alkene according to claim 1 is characterized in that described catalyst is selected from SAPO-34.
3. the reaction unit of described preparation low-carbon alkene according to claim 1 is characterized in that described reclaimable catalyst enters in the reaction zone (2) at least from two catalyst outlets that riser (7) in axial direction separates.
4. the reaction unit of described preparation low-carbon alkene according to claim 1 is characterized in that described riser (7) is positioned at the inner height of reaction zone (2) and is at least 1/3 of reaction zone (2) height.
5. the reaction unit of described preparation low-carbon alkene according to claim 1 is characterized in that described riser (7) top exit arranges seedpod of the lotus shape gas-solid distribution apparatus (3), and percent opening is 0.5～0.8.
6. the reaction unit of described preparation low-carbon alkene according to claim 1 is characterized in that described spent riser (7) and the diameter ratio of reaction zone (2) are 0.05～0.15: 1.
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