CN102875280B - Methanol conversion is the reaction unit of low-carbon alkene - Google Patents
Methanol conversion is the reaction unit of low-carbon alkene Download PDFInfo
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- CN102875280B CN102875280B CN201110193417.0A CN201110193417A CN102875280B CN 102875280 B CN102875280 B CN 102875280B CN 201110193417 A CN201110193417 A CN 201110193417A CN 102875280 B CN102875280 B CN 102875280B
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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
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Abstract
The present invention relates to the reaction unit that a kind of methanol conversion is low-carbon alkene, mainly solve the lower problem of yield of light olefins in prior art. the present invention is the reaction unit of low-carbon alkene by adopting a kind of methanol conversion, mainly comprise reaction zone 2, stripping zone 5, decanting zone 9, regenerated catalyst riser 7 and external warmer, stripping zone 5 is positioned at reaction zone 2 tops, decanting zone 9 is positioned at 5 tops, stripping zone, 5 bottoms, stripping zone are provided with catalyst outlet and are connected with reaction zone 2 with regenerator respectively, 9 tops, decanting zone are provided with product gas outlet, regenerated catalyst riser 7 entrance points are positioned at reaction zone 2 bottoms, the port of export is positioned at reaction zone 2 inside, regenerated catalyst riser 7 bottoms are provided with catalyst inlet and are connected with regenerator sloped tube 6, the technical scheme that the part that regenerated catalyst riser 7 is positioned at reaction zone 2 has at least one catalyst outlet 13 has solved 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 the reaction unit that a kind of methanol conversion is low-carbon alkene.
Technical background
Low-carbon alkene, i.e. ethene and propylene, is two kinds of important basic chemical industry raw materials, its demand is in continuous increase. GenerallyGround, ethene, propylene are to produce by petroleum path, but due to the limited supply of petroleum resources and higher price, byThe cost that petroleum resources are produced ethene, propylene constantly increases. In recent years, people start to greatly develop alternative materials conversion second processedThe technology of alkene, propylene. Wherein, the important alternative materials of producing for low-carbon alkene of a class is oxygenatedchemicals, for example alcoholClass (methyl alcohol, ethanol), ethers (dimethyl ether, ethyl methyl ether), ester class (dimethyl carbonate, methyl formate) etc., these close containing oxidationThing can be transformed by coal, natural gas, living beings equal energy source. It is fairly large that some oxygenatedchemicals can reachProduction, as methyl alcohol, can be made by coal or natural gas, technique is very ripe, can realize the production rule of up to a million tonnesMould. Due to the popularity in oxygenatedchemicals source, add and transform the economy that generates low-carbon alkene technique, so by containing oxygenThe technique of compound conversion to produce olefine (OTO), is particularly subject to more and more by the technique of preparing olefin by conversion of methanol (MTO)Pay attention to.
In US4499327 patent, silicoaluminophosphamolecular molecular sieve catalyst being applied to preparing olefin by conversion of methanol technique has carried out in detailResearch, thinks that SAPO-34 is the first-selected catalyst of MTO technique. SAPO-34 catalyst has very high low-carbon alkene choosingSelecting property, and activity is also higher, can make methanol conversion is reaction time of low-carbon alkene to be less than the degree of 10 seconds, moreEven reach in the reaction time range of riser.
In US6166282, announce technology and reactor that a kind of methanol conversion is low-carbon alkene, adopted fast fluidized bed reactionDevice, gas phase, after the lower Mi Xiangfanyingqu of gas speed has reacted, rises to after the fast subregion that internal diameter diminishes rapidly, adopts specialDifferent gas-solid separation equipment initial gross separation goes out most entrained catalyst. Divide fast owing to reacting afterproduct gas and catalystFrom, effectively prevent the generation of secondary response. Through analog computation, compared with traditional bubbling fluidization bed bioreactor, this is fastSpeed fluidized-bed reactor internal diameter and the required reserve of catalyst all greatly reduce. But there is lower the asking of yield of light olefins in the methodTopic.
In CN1723262, announce with the multiple riser reaction unit of central catalyst return and for oxygenate conversion beLow-carbon alkene technique, this covering device comprises multiple riser reactors, gas solid separation district, multiple offset components etc., Mei GetiRiser reactors has the port of injecting catalyst separately, is pooled to the Disengagement zone of setting, and catalyst and gas product are separated.In the method generally between 75～80%, there is the problem that yield of light olefins is lower in low-carbon alkene carbon base absorption rate equally.
All there is the problem that yield of light olefins is 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 lower problem of yield of light olefins existing in prior art, provides a kind ofNew methanol conversion is the reaction unit of low-carbon alkene. This device, for the production of low-carbon alkene, has yield of light olefinsHigher advantage.
For addressing the above problem, the technical solution used in the present invention is as follows: the reaction unit that a kind of methanol conversion is low-carbon alkene,Mainly comprise reaction zone 2, stripping zone 5, decanting zone 9, regenerated catalyst riser 7 and external warmer, 5 of stripping zonesIn reaction zone 2 tops, decanting zone 9 is positioned at 5 tops, stripping zone, 5 bottoms, stripping zone be provided with catalyst outlet respectively with regenerationDevice is connected with reaction zone 2, and 9 tops, decanting zone are provided with product gas outlet, and regenerated catalyst riser 7 entrance points are positioned at reaction2 bottoms, district, the port of export are positioned at reaction zone 2 inside, and it is oblique with regeneration that regenerated catalyst riser 7 bottoms are provided with catalyst inletPipe 6 is connected, and the part that regenerated catalyst riser 7 is positioned at reaction zone 2 has at least one catalyst outlet 13.
In technique scheme, described catalyst is selected from SAPO-34; Described regenerated catalyst riser 7 is positioned at reaction zone 2Interior part has at least four catalyst outlets 13; The portion that described regenerated catalyst riser 7 is positioned at reaction zone 2 separatesThere are at least eight catalyst outlets 13; 5 bottoms, described stripping zone have catalyst outlet, change through external warmer 14 or 17After heat, catalyst is returned to reaction zone 2; 9 inside, described decanting zone are provided with gas-solid cyclone separator 8; Described regenerated catalystRiser 7 is 0.05～0.15: 1 with the diameter ratio of reaction zone 2.
In the present invention, the lifting medium in described regenerated catalyst riser 7 is in steam, the above hydrocarbon of carbon four, etheneAt least one; The interior reaction condition of described reaction zone 2 is: reaction temperature is 400～500 DEG C, and reaction pressure is counted with gauge pressure0.01～0.3MPa, gas phase linear speed is 1.0～3.0 meter per seconds; Described methanol feedstock enters instead after being heated to 150～300 DEG CAnswer district 2; Reclaimable catalyst in stripping zone 5 50～80% returns to reaction zone 2,20～50% and enters regenerator after strippingRegeneration.
In the present invention, stripping zone 5 is connected but does not communicate with reaction zone 2, and decanting zone 9 joins and communicates with stripping zone 5, thenRaw catalyst riser 7 entrance points be positioned at reaction zone 2 belows and be positioned at reaction zone 2 outsides, the port of export is positioned at reaction zone 2Portion.
Traditional fast fluidized bed reactor for gas phase linear speed at 1～3 meter per second, there is catalysis to be generated in reaction zone bottomWhether uniformly problem of the mixing of agent and regenerated catalyst, if all different two kinds of catalyst mix inequalities of temperature and carbon deposition quantityEven, will greatly reduce the productive rate that methanol conversion is low-carbon alkene. Adopt device of the present invention, regenerated catalyst is importedIn regenerated catalyst riser, this leg outlet end is positioned at reaction zone inside, regenerated catalyst can promoted to carrying of mediumUnder rising, on axially spaced multiple positions, be distributed in reaction zone, ensureing under the prerequisite of high-low carbon olefine selective, effectivelyEnsure high methanol conversion, reach the object that improves yield of light olefins. In addition, can in regenerated catalyst riserAdopt the above hydrocarbon of carbon four or ethene as promoting medium, increased low carbon olefine output in promoting regenerated catalyst, effectively improvesYield of light olefins.
Adopt technical scheme of the present invention: described catalyst is selected from SAPO-34; Described regenerated catalyst riser 7 is positioned at insteadAnswer the part in district 2 to have at least four catalyst outlets 13; Described regenerated catalyst riser 7 is positioned at reaction zone 2Part has at least eight catalyst outlets 13; 5 bottoms, described stripping zone have catalyst outlet, through external warmer 14Or 17 return to catalyst to reaction zone 2 after heat exchange; 9 inside, described decanting zone are provided with gas-solid cyclone separator 8; Described regenerationCatalyst riser 7 is 0.05～0.15: 1 with the diameter ratio of reaction zone 2, and low-carbon alkene carbon base absorption rate reaches 85.92% (weight),Low-carbon alkene carbon base absorption rate height than prior art can reach more than 6%, has obtained good technique effect.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of device of the present invention.
Fig. 2 is the A-B cutaway view in Fig. 1.
In Fig. 1,1 is methanol feed line; 2 is reaction zone; 3 is the quick separation equipment of gas-solid; 4 is inclined tube to be generated; 5For stripping zone; 6 is regenerator sloped tube; 7 is regenerated catalyst riser; 8 is gas-solid cyclone separator; 9 is decanting zone; 10For collection chamber; 11 is product gas outlet pipeline; 12 for promoting medium charging; 13 is regenerated catalyst outlet; 14 for getting outwardHot device; 15 is external warmer catalyst lower oblique tube; 16 is the charging of external warmer fluidizing agent; 17 is external warmer; 18 areThe charging of external warmer fluidizing agent; 19 is heat production coil pipe; 20 is external warmer gaseous substance Returning reactor pipeline; 21 areExternal warmer gaseous substance Returning reactor pipeline; 22 is stripping zone fluidizing agent feeding line; 23 is external warmer catalysisAgent lower oblique tube; 24 is heat production coil pipe.
Methyl alcohol enters reaction zone 2 from feeding line 1, contacts with catalyst, generates the product that comprises low-carbon alkene, enters gasGu in quick separation equipment 3, isolated gaseous products enters point through pipeline 11 after cyclone separator 8 separates againFrom workshop section, the reclaimable catalyst that cyclone separator separates, a part is removed regenerator regeneration, a part of warp through inclined tube 4 to be generatedCross external warmer 14 and 17 and return to reaction zone 2, regenerated catalyst enters in regenerated catalyst riser 7 through regenerator sloped tube 6,With the lifting medium contact from pipeline 12, regenerated catalyst is promoted to reaction zone 2 inside.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
On reaction unit as shown in Figure 1, catalyst adopts SAPO-34, pure methanol feeding, and methyl alcohol is through being heated to 180After DEG C, enter reaction zone, gaseous products enters centrifugal station after cyclone separator separates, and it is to be generated that cyclone separator separatesCatalyst, 30% goes regenerator regeneration through inclined tube to be generated, and 70% returns to reaction zone, and regenerated catalyst enters through regenerator sloped tubeIn regenerated catalyst riser, with lifting medium contact, regenerated catalyst is promoted to reaction zone inside, regenerated catalyst is carriedRiser catalyst outlet is four, is positioned at upwards 1/2 reaction zone At The Height of methanol feeding distribution grid, four catalyst outlet sidesPosition arranges as shown in Figure 2, and lifting medium is steam, and reaction zone reaction condition is: reaction temperature is 470 DEG C, reaction pressurePower is counted 0.1MPa with gauge pressure, and gas phase linear speed is 1.25 meter per seconds, and reactor product adopts gas chromatographic analysis, reactor outletLow-carbon alkene carbon base absorption rate be 82.17% (weight).
[embodiment 2]
According to condition and step described in embodiment 1, methyl alcohol enters reaction zone after being heated to 150 DEG C, reclaimable catalyst20% goes regenerator regeneration through inclined tube to be generated, and 80% returns to reaction zone, and regenerated catalyst riser catalyst outlet is two,Be positioned at upwards 1/2 reaction zone At The Height of methanol feeding distribution grid, 180 DEG C of two catalyst outlet horizontal direction angles, promoteMedium is steam, and reaction zone reaction condition is: reaction temperature is 400 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure,Gas phase linear speed is 2.1 meter per seconds, and reactor product adopts gas chromatographic analysis, and the low-carbon alkene carbon base absorption rate of reactor outlet is80.04% (weight).
[embodiment 3]
According to condition and step described in embodiment 1, methyl alcohol enters reaction zone after being heated to 300 DEG C, reclaimable catalyst50% goes regenerator regeneration through inclined tube to be generated, and 50% returns to reaction zone, and regenerated catalyst riser catalyst outlet is eight,Wherein four are positioned at upwards 1/2 reaction zone At The Height of methanol feeding distribution grid, and four are positioned at methanol feeding distribution grid upwards 3/4Reaction zone At The Height, as shown in Figure 2, promoting medium is the above hydrocarbon of carbon four and steam in every four catalyst outlet orientation settings,The mass ratio of steam and carbon four above hydrocarbon is 0.2: 1, and the C 4 olefin mass fraction in the above hydrocarbon of carbon four is 88%, reactionDistrict's reaction condition is: reaction temperature is 500 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 3.0 meter per seconds,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 condition and step described in embodiment 1, methyl alcohol enters reaction zone after being heated to 210 DEG C, reclaimable catalyst50% goes regenerator regeneration through inclined tube to be generated, and 50% returns to reaction zone, and regenerated catalyst riser catalyst outlet is eight,Wherein four are positioned at upwards 1/2 reaction zone At The Height of methanol feeding distribution grid, and four are positioned at methanol feeding distribution grid upwards 3/4Reaction zone At The Height, as shown in Figure 2, promoting medium is the above hydrocarbon of carbon four and ethene in every four catalyst outlet orientation settings,The mass ratio of ethene and carbon four above hydrocarbon is 0.3: 1, and the C 4 olefin mass fraction in the above hydrocarbon of carbon four is 88%, reaction zoneReaction condition is: reaction temperature is 500 DEG C, and reaction pressure is counted 0.3MPa with gauge pressure, and gas phase linear speed is 1.0 meter per seconds, anti-Answer product to adopt gas chromatographic analysis, the low-carbon alkene carbon base absorption rate of reactor outlet is 83.69% (weight).
[embodiment 5]
According to condition and step described in embodiment 1, methyl alcohol enters reaction zone after being heated to 210 DEG C, reclaimable catalyst30% goes regenerator regeneration through inclined tube to be generated, and 70% returns to reaction zone, and regenerated catalyst riser catalyst outlet is nine,Wherein four are positioned at upwards 1/2 reaction zone At The Height of methanol feeding distribution grid, and four are positioned at methanol feeding distribution grid upwards 3/4Reaction zone At The Height, as shown in Figure 2, another one is positioned at riser top center position in every four catalyst outlet orientation settingsPut, promoting medium is ethene and steam, and the mass ratio of ethene and steam is 4: 1, and reaction zone reaction condition is: reactionTemperature is 500 DEG C, and reaction pressure is counted 0.1MPa with gauge pressure, and gas phase linear speed is 1.6 meter per seconds, and reactor product adopts gas phase lookAnalysis of spectrum, the low-carbon alkene carbon base absorption rate of reactor outlet is 84.38% (weight).
[comparative example 1]
According to condition and step described in embodiment 3, just regenerated catalyst directly returns to reaction zone bottom by regenerator sloped tube,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 object that improves yield of light olefins, there is larger technical advantage,Can be used in the industrial production of low-carbon alkene.
Claims (4)
1. the method that methanol conversion is low-carbon alkene, its reaction unit mainly comprises reaction zone (2), stripping zone (5), heavyFall district (9), regenerated catalyst riser (7) and external warmer, stripping zone (5) are positioned at reaction zone (2) top, decanting zone (9) position(5) top in stripping zone, stripping zone (5) bottom is provided with catalyst outlet and is connected with reaction zone (2) with regenerator respectively, decanting zone (9)Top is provided with product gas outlet, and regenerated catalyst riser (7) entrance point is positioned at reaction zone (2) bottom, the port of export is positioned at reactionInside, district (2), regenerated catalyst riser (7) bottom is provided with catalyst inlet and is connected with regenerator sloped tube (6), and regenerated catalyst is carriedThe part that riser (7) is positioned at reaction zone (2) has at least one catalyst outlet (13); Regenerated catalyst riser (7) with reactThe diameter ratio in district (2) is 0.05～0.15:1; Bottom, stripping zone (5) has catalyst outlet, through external warmer (14) or (17)After heat exchange, catalyst is returned to reaction zone (2);
Lifting medium in described regenerated catalyst riser (7) is at least one in steam, the above hydrocarbon of carbon four, ethene;The interior reaction condition of described reaction zone (2) is: reaction temperature is 400～500 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure,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 DEG C; Stripping zone(5) reclaimable catalyst in 50～80% returns to reaction zone (2) after stripping, and 20～50% enter regenerator regeneration.
2. the method that methanol conversion is low-carbon alkene according to claim 1, is characterized in that described catalyst is selected fromSAPO-34。
3. the method that methanol conversion is low-carbon alkene according to claim 1, is characterized in that described regenerated catalyst carriesThe part that riser (7) is positioned at reaction zone (2) has at least eight catalyst outlets (13).
4. the method that methanol conversion is low-carbon alkene according to claim 1, is characterized in that inside, described decanting zone (9)Be provided with gas-solid cyclone separator (8).
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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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