CN102875280A - Reaction unit for converting methanol into low-carbon olefins - Google Patents
Reaction unit for converting methanol into low-carbon olefins Download PDFInfo
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- CN102875280A CN102875280A CN2011101934170A CN201110193417A CN102875280A CN 102875280 A CN102875280 A CN 102875280A CN 2011101934170 A CN2011101934170 A CN 2011101934170A CN 201110193417 A CN201110193417 A CN 201110193417A CN 102875280 A CN102875280 A CN 102875280A
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Abstract
The invention relates to a reaction unit for converting methanol into low-carbon olefins, mainly solving the problem of low yield of low-carbon olefins in the prior art. The reaction unit mainly comprises a reaction zone 2, a stripping zone 5, a depression zone 9, a regeneration catalyst riser 7, and an external cooler, wherein the stripping zone 5 is arranged above the reaction zone 2, the depression zone 9 is arranged above the stripping zone 5, the bottom of the stripping zone 5 is provided with a catalyst outlet which is respectively connected with the regenerator and the reaction zone 2, the top of the depression zone 9 is provided with a product gas outlet, the inlet end of the regeneration catalyst riser 7 is arranged at the lower portion of the reaction zone 2, the outlet end of the regeneration catalyst riser 7 is arranged in the reaction zone 2, the lower portion of the regeneration catalyst riser 7 is provided with a catalyst inlet which is connected with a regeneration inclined pipe 6, and the part of the regeneration catalyst riser 7 and in the reaction zone 2 is provided with at least one catalyst outlet 13. The reaction unit disclosed herein well solves the problems and can be used in the industrial production of low-carbon olefins.
Description
Technical field
The present invention relates to the reaction unit that a kind of methanol conversion is 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 (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, such as methyl alcohol, can be made by coal or Sweet natural gas, and technique is very ripe, can realize up to a million tonnes industrial 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 catalyzer of MTO technique.The SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is reaction times of low-carbon alkene to be less than 10 seconds degree, more even reach in the reaction time range of riser tube.
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 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 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 disengaging zone of setting, catalyzer 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 it is the reaction unit of low-carbon alkene that a kind of new methanol conversion 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 methanol conversion is the reaction unit of low-carbon alkene, mainly comprise reaction zone 2, stripping zone 5, negative area 9, regenerated catalyst riser tube 7 and external warmer, stripping zone 5 is positioned at reaction zone 2 tops, negative area 9 is positioned at stripping zone 5 tops, stripping zone 5 bottoms are provided with catalyst outlet and link to each other with reaction zone 2 with revivifier respectively, 9 tops, negative area are provided with product gas outlet, regenerated catalyst riser tube 7 entrance ends are positioned at reaction zone 2 bottoms, exit end is positioned at reaction zone 2 inside, regenerated catalyst riser tube 7 bottoms are provided with catalyst inlet and link to each other with regenerator sloped tube 6, and the part that regenerated catalyst riser tube 7 is positioned at reaction zone 2 has at least one catalyst outlet 13.
In the technique scheme, described catalyzer is selected from SAPO-34; The part that described regenerated catalyst riser tube 7 is positioned at reaction zone 2 has at least four catalyst outlets 13; The part that described regenerated catalyst riser tube 7 is positioned at reaction zone 2 has at least eight catalyst outlets 13; Described stripping zone 5 bottoms have catalyst outlet, through after external warmer 14 or 17 heat exchange catalyzer being returned reaction zone 2; 9 inside, described negative area are provided with gas-solid cyclone separator 8; Described regenerated catalyst riser tube 7 is 0.05～0.15: 1 with the diameter ratio of reaction zone 2.
Among the present invention, the lifting medium in the described regenerated catalyst riser tube 7 is at least a in water vapour, carbon four above hydrocarbon, the ethene; Described reaction zone 2 internal reaction conditions are: 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; Described methanol feedstock enters reaction zone 2 after being heated to 150～300 ℃; Reclaimable catalyst in the stripping zone 5 50～80% returns reaction zone 2,20～50% and enters revivifier regeneration behind stripping.
Among the present invention, stripping zone 5 links to each other with reaction zone 2 but does not communicate, and negative area 9 joins with stripping zone 5 and communicates, regenerated catalyst riser tube 7 entrance ends be positioned at reaction zone 2 belows and be positioned at reaction zone 2 outsides, exit end is positioned at reaction zone 2 inside.
For the traditional fast fluidized bed reactor of gas phase linear speed at 1～3 meter per second, uniformly whether the mixing that reaction zone bottom exists reclaimable catalyst and regenerated catalyst problem, if temperature and carbon deposition quantity all different two kinds of catalyst mix are inhomogeneous, the productive rate that methanol conversion is low-carbon alkene will be reduced greatly.Adopt device of the present invention, regenerated catalyst is imported in the regenerated catalyst riser tube, this leg outlet end is positioned at reaction zone inside, regenerated catalyst can be distributed in the reaction zone in axially spaced a plurality of positions under the lifting that promotes medium, under the prerequisite that guarantees the high-low carbon olefine selective, 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, Effective Raise yield of light olefins.
Adopt technical scheme of the present invention: described catalyzer is selected from SAPO-34; The part that described regenerated catalyst riser tube 7 is positioned at reaction zone 2 has at least four catalyst outlets 13; The part that described regenerated catalyst riser tube 7 is positioned at reaction zone 2 has at least eight catalyst outlets 13; Described stripping zone 5 bottoms have catalyst outlet, through after external warmer 14 or 17 heat exchange catalyzer being returned reaction zone 2; 9 inside, described negative area are provided with gas-solid cyclone separator 8; Described regenerated catalyst riser tube 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 85.92% (weight), can reach more than 6% than the low-carbon alkene carbon base absorption rate height of prior art, 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 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 enters reaction zone 2 from feeding line 1, contact with catalyzer, generation comprises the product of low-carbon alkene, enter in the gas-solid sharp separation equipment 3, isolated gaseous products enters centrifugal station through cyclonic separator 8 Re-isolations by pipeline 11, the reclaimable catalyst that cyclonic separator is told, 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 enters in the regenerated catalyst riser tube 7 through regenerator sloped tube 6, with the lifting medium contact from pipeline 12, regenerated catalyst is promoted to reaction zone 2 inside.
The invention will be further elaborated below by embodiment, 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 enters reaction zone after being heated to 180 ℃, gaseous products enters centrifugal station after separating through cyclonic separator, the reclaimable catalyst that cyclonic separator is told, 30% process inclined tube to be generated goes revivifier regeneration, 70% returns reaction zone, regenerated catalyst enters in the regenerated catalyst riser tube through regenerator sloped tube, with the lifting medium contact, regenerated catalyst is promoted to reaction zone inside, regenerated catalyst riser tube catalyst outlet is four, be positioned at upwards 1/2 reaction zone At The Height of methanol feeding grid distributor, four catalyst outlet orientation settings as shown in Figure 2, the lifting medium is water vapour, the reaction zone reaction conditions is: temperature of reaction is 470 ℃, reaction pressure is counted 0.1MPa with gauge pressure, the gas phase linear speed is 1.25 meter per seconds, and reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 82.17% (weight).
[embodiment 2]
According to embodiment 1 described condition and step, methyl alcohol enters reaction zone after being heated to 150 ℃, the 20% process inclined tube to be generated of reclaimable catalyst goes revivifier regeneration, 80% returns reaction zone, regenerated catalyst riser tube catalyst outlet is two, be positioned at upwards 1/2 reaction zone At The Height of methanol feeding grid distributor, 180 ℃ of two catalyst outlet horizontal direction angles, the lifting medium is water vapour, the reaction zone reaction conditions is: temperature of reaction is 400 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and the gas phase linear speed is 2.1 meter per seconds, reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 80.04% (weight).
[embodiment 3]
According to embodiment 1 described condition and step, methyl alcohol enters reaction zone after being heated to 300 ℃, the 50% process inclined tube to be generated of reclaimable catalyst goes revivifier regeneration, 50% returns reaction zone, regenerated catalyst riser tube catalyst outlet is eight, wherein four are positioned at upwards 1/2 reaction zone At The Height of methanol feeding grid distributor, four are positioned at upwards 3/4 reaction zone At The Height of methanol feeding grid distributor, per four catalyst outlet orientation settings as shown in Figure 2, promoting medium is carbon four above hydrocarbon and water vapour, 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 ℃, reaction pressure is counted 0.01MPa with gauge pressure, the gas phase linear speed is 3.0 meter per seconds, and reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 85.92% (weight).
[embodiment 4]
According to embodiment 1 described condition and step, methyl alcohol enters reaction zone after being heated to 210 ℃, the 50% process inclined tube to be generated of reclaimable catalyst goes revivifier regeneration, 50% returns reaction zone, regenerated catalyst riser tube catalyst outlet is eight, wherein four are positioned at upwards 1/2 reaction zone At The Height of methanol feeding grid distributor, four are positioned at upwards 3/4 reaction zone At The Height of methanol feeding grid distributor, per four catalyst outlet orientation settings as shown in Figure 2, promoting medium is carbon four above hydrocarbon and ethene, 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 ℃, reaction pressure is counted 0.3MPa with gauge pressure, the gas phase linear speed is 1.0 meter per seconds, and reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 83.69% (weight).
[embodiment 5]
According to embodiment 1 described condition and step, methyl alcohol enters reaction zone after being heated to 210 ℃, the 30% process inclined tube to be generated of reclaimable catalyst goes revivifier regeneration, 70% returns reaction zone, regenerated catalyst riser tube catalyst outlet is nine, wherein four are positioned at upwards 1/2 reaction zone At The Height of methanol feeding grid distributor, four are positioned at upwards 3/4 reaction zone At The Height of methanol feeding grid distributor, per four catalyst outlet orientation settings as shown in Figure 2, another one is positioned at riser tube top center position, promoting medium is ethene and water vapour, the mass ratio of ethene and water vapour is 4: 1, 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 base absorption rate 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 by regenerator sloped tube, and the low-carbon alkene carbon base absorption rate of reactor outlet is 80.52% (weight).
Obviously, adopt device of the present invention, can reach the purpose that improves yield of light olefins, have larger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (7)
1. reaction unit that methanol conversion is low-carbon alkene, mainly comprise reaction zone (2), stripping zone (5), negative area (9), regenerated catalyst riser tube (7) and external warmer, stripping zone (5) is positioned at reaction zone (2) top, negative area (9) is positioned at stripping zone (5) top, stripping zone (5) bottom is provided with catalyst outlet and links to each other with reaction zone (2) with revivifier respectively, top, negative area (9) is provided with product gas outlet, regenerated catalyst riser tube (7) entrance end is positioned at reaction zone (2) bottom, exit end is positioned at reaction zone (2) inside, regenerated catalyst riser tube (7) bottom is provided with catalyst inlet and links to each other with regenerator sloped tube (6), and the part that regenerated catalyst riser tube (7) is positioned at reaction zone (2) has at least one catalyst outlet (13).
2. described methanol conversion is the reaction unit of low-carbon alkene according to claim 1, it is characterized in that described catalyzer is selected from SAPO-34.
3. described methanol conversion is the reaction unit of low-carbon alkene according to claim 1, it is characterized in that the part that described regenerated catalyst riser tube (7) is positioned at reaction zone (2) has at least four catalyst outlets (13).
4. described methanol conversion is the reaction unit of low-carbon alkene according to claim 3, it is characterized in that the part that described regenerated catalyst riser tube (7) is positioned at reaction zone (2) has at least eight catalyst outlets (13).
5. described methanol conversion is the reaction unit of low-carbon alkene according to claim 1, it is characterized in that described stripping zone (5) bottom has catalyst outlet, through after external warmer (14) or (17) heat exchange catalyzer being returned reaction zone (2).
6. described methanol conversion is the reaction unit of low-carbon alkene according to claim 1, it is characterized in that inside, described negative area (9) is provided with gas-solid cyclone separator (8).
7. described methanol conversion is the reaction unit of low-carbon alkene according to claim 1, it is characterized in that described regenerated catalyst riser tube (7) and the diameter ratio of reaction zone (2) are 0.05～0.15: 1.
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| CN201110193417.0A CN102875280B (en) | 2011-07-12 | 2011-07-12 | Methanol conversion is the reaction unit of low-carbon alkene |
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| CN201110193417.0A CN102875280B (en) | 2011-07-12 | 2011-07-12 | Methanol conversion is the reaction unit of low-carbon alkene |
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Citations (5)
| 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 |
| CN101265150A (en) * | 2008-04-24 | 2008-09-17 | 中国石油化工股份有限公司 | Method for producing low-carbon olefins from oxygen-containing compound |
| 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 |
| CN101318870A (en) * | 2008-06-12 | 2008-12-10 | 中国石油化工股份有限公司 | Process for improving yield of ethylene and propylene |
| CN102372540A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for conversing methanol to light olefin |
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Patent Citations (5)
| 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 |
| CN101265150A (en) * | 2008-04-24 | 2008-09-17 | 中国石油化工股份有限公司 | Method for producing low-carbon olefins from oxygen-containing compound |
| CN101318870A (en) * | 2008-06-12 | 2008-12-10 | 中国石油化工股份有限公司 | Process for improving yield of ethylene and propylene |
| CN102372540A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for conversing methanol to light olefin |
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