CN102372541B - Improve the method for yield of light olefins - Google Patents
Improve the method for yield of light olefins Download PDFInfo
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- CN102372541B CN102372541B CN201010262010.4A CN201010262010A CN102372541B CN 102372541 B CN102372541 B CN 102372541B CN 201010262010 A CN201010262010 A CN 201010262010A CN 102372541 B CN102372541 B CN 102372541B
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- contact area
- peclet number
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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 present invention relates to a kind of method improving yield of light olefins, mainly solve the problem that in prior art, yield of light olefins is lower.The present invention is by adopting a kind of method improving yield of light olefins, the raw material comprised containing methyl alcohol enters the pre-terminated contact area that axial Peclet number is less than 15, contact with regenerated catalyst with reclaimable catalyst, the gaseous stream of pre-terminated contact area and catalyzer enter the main reaction region of axial Peclet number than the axial Peclet number large at least 20% of pre-terminated contact area, generate the technical scheme comprising the product of low-carbon alkene and solve the problems referred to above preferably, can be used in the industrial production of low-carbon alkene.
Description
Technical field
The present invention relates to a kind of method improving yield of light olefins.
Technical background
Low-carbon alkene, i.e. ethene and propylene, be two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are produced by petroleum path, but due to the limited supply of petroleum resources and higher price, produce ethene by petroleum resources, the cost of propylene constantly increases.In recent years, people start to greatly develop the technology that alternative materials transforms ethene processed, propylene.Wherein, one class important for low-carbon alkene produce alternative materials be 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, and as methyl alcohol, can be obtained by coal or Sweet natural gas, technique is very ripe, can realize the industrial scale of up to a million tonnes.Due to the popularity in oxygenatedchemicals source, add the economy transforming and generate low-carbon alkene technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), be particularly subject to increasing attention by the technique of preparing olefin by conversion of methanol (MTO).
Be applied to preparing olefin by conversion of methanol technique to silicoaluminophosphamolecular molecular sieve catalyst in US4499327 patent to study in detail, think that SAPO-34 is the first-selected catalyzer of MTO technique.SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, methanol conversion can be made to be less than the degree of 10 seconds in reaction times of low-carbon alkene, more even reach in the reaction time range of riser tube.
Technology and reactor that a kind of methanol conversion is low-carbon alkene is disclosed in US6166282, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, after rising to the fast subregion that internal diameter diminishes rapidly, special gas-solid separation equipment initial gross separation is adopted to go out most entrained catalyst.Due to reaction after product gas and catalyzer sharp separation, effectively prevent the generation of secondary reaction.Through analog calculation, compared with traditional bubbling fluidization bed bioreactor, needed for this fast fluidized bed reactor internal diameter and catalyzer, reserve all greatly reduces.But there is the lower problem of yield of light olefins in the method.
The multiple riser reaction unit disclosed in CN1723262 with central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises multiple riser reactor, gas solid separation district, multiple 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.There is the lower problem of yield of light olefins equally in the method.
CN200680018303 discloses and is a kind ofly converted into the method for alkene with oxygenatedchemicals in the reactor of baffle plate, reactive moieties is divided into three regions in the method, one is initial conduit, one is contact conduit, one is linking conduit, wherein baffle plate is set in contact conduit, and gas phase linear speed is greater than 1.52 meter per seconds, but there is methanol conversion and the lower shortcoming of selectivity of light olefin in the method, methanol conversion is up to 98%, selectivity of light olefin is up to 76.3%, makes yield of light olefins be only 74.8%.
All there is the lower problem of yield of light olefins in prior art, the present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that the yield of light olefins that exists in prior art is lower, provides a kind of method of raising yield of light olefins newly.The method is used for, in the production of low-carbon alkene, having the advantage that yield of light olefins is higher.
For solving the problem, the technical solution used in the present invention is as follows: a kind of method improving yield of light olefins, the raw material comprised containing methyl alcohol enters the pre-terminated contact area that axial Peclet number is less than 15, contact with regenerated catalyst with reclaimable catalyst, the gaseous stream of pre-terminated contact area and catalyzer enter the main reaction region of axial Peclet number than the axial Peclet number large at least 20% of pre-terminated contact area, generate the product comprising low-carbon alkene.
In technique scheme, described catalyzer is selected from SAPO-34; The axial Peclet number of described pre-terminated contact area is less than 6; The axial Peclet number of described main reaction region is than the axial Peclet number large at least 40% of pre-terminated contact area; The temperature of reaction of described pre-terminated contact area is 380 ~ 450 DEG C, and catalyzer average product carbon amounts massfraction is 1.0 ~ 4.0%; The temperature of reaction of described main reaction region is 400 ~ 485 DEG C, and gas phase linear speed is 0.8 ~ 3.0 meter per second.
Axial Peclet number is non-dimensional number, be characterize gas phase piston flow when gas in reactor flows through beds depart from situation, axial Peclet number is larger, gas phase flowing is more close to piston flow, what infinitely-great Peclet number reflected is desirable piston flow situation, and the Peclet number of general less than 4 can think mixing complete mixing flow Gas-particle Flows mode comparatively thoroughly.In the present invention, the method for calculation of Peclet number are:
Peclet number=μ
g× H/D
g, wherein, μ
gfor gas phase linear speed, meter per second; H is reactor beds layer height, rice; D
gfor axial gas spread coefficient, rice
2/ second.Known in the field, axial gas diffusion coefficient D
gtracing method can be adopted to measure.
Adopt method of the present invention, the pre-terminated contact area that back-mixing is larger is set, regenerated catalyst and reclaimable catalyst are mixed, and converting methanol is low-carbon alkene at a lower temperature, then at the production low-carbon alkene of the less main reaction region highly selective of back-mixing, the object improving yield of light olefins is reached.
Adopt technical scheme of the present invention: described catalyzer is selected from SAPO-34; The axial Peclet number of described pre-terminated contact area is less than 6; The axial Peclet number of described main reaction region is than the axial Peclet number large at least 40% of pre-terminated contact area; The temperature of reaction of described pre-terminated contact area is 380 ~ 450 DEG C, and catalyzer average product carbon amounts massfraction is 1.0 ~ 4.0%; The temperature of reaction of described main reaction region is 400 ~ 485 DEG C, gas phase linear speed is 0.8 ~ 3.0 meter per second, low-carbon alkene carbon base absorption rate reaches 83.17% (weight), at least higher by more than 3% than yield of light olefins of the prior art, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is methyl alcohol bottom feed; 2 is main reaction region; 3 is stripping zone; 4 is heat production coil pipe; 5 is gas-solid sharp separation equipment; 6 is gas-solid cyclone separator; 7 is reactor; 8 is products export pipeline; 9 is inclined tube to be generated; 10 is reclaimable catalyst circulation tube; 11 is regenerator sloped tube; 12 is pre-terminated contact area; 13 is reclaimable catalyst circulation tube; 14 is heat collector.
Methyl alcohol enters pre-terminated contact area 12 from feeding line 1, with the catalyst exposure from reclaimable catalyst circulation tube 10 and regenerator sloped tube 11, then gaseous stream and catalyzer enter main reaction region 2, generate the product comprising low-carbon alkene, enter in gas-solid sharp separation equipment 5, isolated gaseous products enters centrifugal station through pipeline 8 after cyclonic separator 6 is separated again, the reclaimable catalyst that cyclonic separator separates, after the stripping of stripping zone 3, a part goes revivifier to regenerate through inclined tube 9 to be generated, a part returns pre-terminated contact area 12 through catalyst recirculation pipe 10, a part returns in main reaction region 2 through catalyst recirculation pipe 13.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
On reaction unit as shown in Figure 1, pure methanol feeding, catalyzer adopts SAPO-34, pre-terminated contact area temperature of reaction is 405 DEG C, catalyzer average product carbon amounts massfraction is 2.8%, axial Peclet number is 10, main reaction region temperature of reaction is 467 DEG C, gas phase linear speed is 1.25 meter per seconds, axial Peclet number is than the axial Peclet number large 150% of pre-terminated contact area, catalyzer 65% after stripping returns pre-terminated contact area by catalyst recirculation pipe, 25% goes revivifier to regenerate, 10% returns to main reaction region by catalyst recirculation pipe, reactor product adopts gas chromatographic analysis, the low-carbon alkene carbon base absorption rate of reactor outlet is 82.49% (weight).
[embodiment 2]
According to the condition described in embodiment 1 and step, changing pre-terminated contact area temperature of reaction is 380 DEG C, catalyzer average product carbon amounts massfraction is 1.1%, axial Peclet number is 15, main reaction region temperature of reaction is 400 DEG C, gas phase linear speed is 0.8 meter per second, axial Peclet number is than the axial Peclet number large 20% of pre-terminated contact area, catalyzer 55% after stripping returns pre-terminated contact area by catalyst recirculation pipe, 35% goes revivifier to regenerate, 10% returns to main reaction region by catalyst recirculation pipe, reactor product adopts gas chromatographic analysis, the low-carbon alkene carbon base absorption rate of reactor outlet is 79.85% (weight).
[embodiment 3]
According to the condition described in embodiment 1 and step, changing pre-terminated contact area temperature of reaction is 450 DEG C, catalyzer average product carbon amounts massfraction is 3.97%, axial Peclet number is 15, main reaction region temperature of reaction is 485 DEG C, gas phase linear speed is 3.0 meter per seconds, axial Peclet number is than the axial Peclet number large 300% of pre-terminated contact area, catalyzer 75% after stripping returns pre-terminated contact area by catalyst recirculation pipe, 25% goes revivifier to regenerate, reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is 81.95% (weight).
[embodiment 4]
According to the condition described in embodiment 1 and step, changing pre-terminated contact area temperature of reaction is 420 DEG C, catalyzer average product carbon amounts massfraction is 2.5%, axial Peclet number is 6, main reaction region temperature of reaction is 470 DEG C, gas phase linear speed is 1.5 meter per seconds, axial Peclet number is than the axial Peclet number large 180% of pre-terminated contact area, catalyzer 55% after stripping returns pre-terminated contact area by catalyst recirculation pipe, 35% goes revivifier to regenerate, 10% returns to main reaction region by catalyst recirculation pipe, reactor product adopts gas chromatographic analysis, the low-carbon alkene carbon base absorption rate of reactor outlet is 83.17% (weight).
[embodiment 5]
According to the condition described in embodiment 3 and step, changing catalyzer average product carbon amounts massfraction is 2.5%, main reaction region gas phase linear speed is 0.9 meter per second, axial Peclet number is than the axial Peclet number large 40% of pre-terminated contact area, and the low-carbon alkene carbon base absorption rate of reactor outlet is 82.88% (weight).
[comparative example 1]
According to the condition described in embodiment 4 and step, do not arrange pre-terminated contact area, the reclaimable catalyst of 75% is back to bottom, main reaction region, and the reclaimable catalyst of 25% goes regeneration, regenerated catalyst is back to bottom, main reaction region, and the diene carbon base absorption rate of reactor outlet is 80.5% (weight).
Obviously, adopt method of the present invention, the object improving yield of light olefins can be reached, there is larger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (3)
1. one kind is improved the method for yield of light olefins, the raw material comprised containing methyl alcohol enters the pre-terminated contact area that axial Peclet number is less than 15, contact with regenerated catalyst with reclaimable catalyst, the gaseous stream of pre-terminated contact area and catalyzer enter the main reaction region of axial Peclet number than the axial Peclet number large at least 20% of pre-terminated contact area, generate the product comprising low-carbon alkene;
Methyl alcohol enters pre-terminated contact area from feeding line, with the catalyst exposure come from reclaimable catalyst circulation tube and regenerator sloped tube, then gaseous stream and catalyzer enter main reaction region, generate the product comprising low-carbon alkene, enter in gas-solid sharp separation equipment, isolated gaseous products enters centrifugal station through pipeline after cyclonic separator is separated again, the reclaimable catalyst that cyclonic separator separates, after the stripping of stripping zone, a part goes revivifier to regenerate through inclined tube to be generated, a part returns pre-terminated contact area through catalyst recirculation pipe, a part returns in main reaction region through catalyst recirculation pipe,
Wherein, described catalyzer is selected from SAPO-34; The temperature of reaction of described pre-terminated contact area is 380 ~ 450 DEG C, and catalyzer average product carbon amounts massfraction is 1.0 ~ 4.0%; The temperature of reaction of main reaction region is 400 ~ 485 DEG C, and gas phase linear speed is 0.8 ~ 3.0 meter per second.
2. improve the method for yield of light olefins according to claim 1, it is characterized in that the axial Peclet number of described pre-terminated contact area is less than 6.
3. improve the method for yield of light olefins according to claim 1, it is characterized in that the axial Peclet number large at least 40% of the axial Peclet number of described main reaction region than pre-terminated contact area.
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| CN201010262010.4A CN102372541B (en) | 2010-08-23 | 2010-08-23 | Improve the method for yield of light olefins |
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| CN201010262010.4A CN102372541B (en) | 2010-08-23 | 2010-08-23 | Improve the method for yield of light olefins |
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| CN102372541A CN102372541A (en) | 2012-03-14 |
| CN102372541B true CN102372541B (en) | 2016-04-13 |
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Citations (3)
| 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 |
| CN101270023A (en) * | 2008-04-11 | 2008-09-24 | 中国石油化工股份有限公司 | Method for improving selectivity of light olefin hydrocarbon |
| 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 CN201010262010.4A patent/CN102372541B/en active Active
Patent Citations (3)
| 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 |
| CN101270023A (en) * | 2008-04-11 | 2008-09-24 | 中国石油化工股份有限公司 | Method for improving selectivity of light olefin hydrocarbon |
| 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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