CN102276400A - Low carbon olefin reaction-regeneration device by using methanol - Google Patents
Low carbon olefin reaction-regeneration device by using methanol Download PDFInfo
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- CN102276400A CN102276400A CN2010101999772A CN201010199977A CN102276400A CN 102276400 A CN102276400 A CN 102276400A CN 2010101999772 A CN2010101999772 A CN 2010101999772A CN 201010199977 A CN201010199977 A CN 201010199977A CN 102276400 A CN102276400 A CN 102276400A
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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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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective 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
- 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 low carbon olefin reaction-regeneration device by using methanol, which mainly solves the problem of low yield of low carbon olefin in the reaction-regeneration device in the prior art. The low carbon olefin reaction-regeneration device by using methanol comprises a methanol conveying reactor 3, a by-product conveying reactor 11, a regenerator 18, an overflow pipe 12 and a lifting pipe 10, the upper part of the by-product conveying reactor 11 is connected with the regenerator 18, the lower part of the by-product conveying reactor 11 is connected with the methanol conveying reactor 3, a degassing zone 20 is provided in the regenerator 18, a catalyst in the degassing zone 20 is entered into the by-product conveying reactor 11 through the overflow pipe 12, a catalyst outlet is opened at the lower part of the by-product conveying reactor 11 and is connected with the methanol conveying reactor 3 through the catalyst conveying tube 5, a stripping zone 6 is provided in the methanol conveying reactor 3, a catalyst in the stripping zone 6 is entered into the regenerator 18 through the lifting pipe 10, a product outlet is opened at the upper part of the methanol conveying reactor 3 and the by-product conveying reactor 11, the problem is better solved by the present invention by the technical scheme that the fume outlet is opened at the top of the regenerator 18. The present invention can be used for the industrial production of low carbon olefin.
Description
Technical field
The present invention relates to a kind of reaction for preparing light olefins from methanol-regenerating unit.
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 by 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, the alternative materials that is used for light olefin production that one class is important 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 by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, as 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 light olefin technology, so by the technology of oxygen-containing compound conversion to produce olefine (OTO), particularly the technology by methanol conversion system alkene (MTO) is subjected to increasing attention.
In the US4499327 patent silicoaluminophosphamolecular molecular sieves catalyzer is applied to methanol conversion system olefin process and studies in great detail, think that SAPO-34 is the first-selected catalyzer of MTO technology.The SAPO-34 catalyzer has very high light olefin selectivity, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of light olefin 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US6166282 that a kind of oxygenate conversion is the technology and the reactor of low-carbon alkene, 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 significantly reduce.
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.
Known in the field, guarantee high selectivity of light olefin, need the carbon distribution of some amount on the catalyzer, and methanol conversion is very responsive to processing parameters such as temperature of reaction in the process of low-carbon alkene.All there is the lower problem of yield of light olefins that causes greatly owing to reaction zone inner catalyst carbon deposit skewness, temperature of reaction fluctuation in prior art.In addition, prepare in the process of low-carbon alkene, inevitably can produce some by product,,, will improve the yield and the process economy of low-carbon alkene if these by products further are converted into the purpose product as carbon four above hydrocarbon etc. at methyl alcohol.The present invention has solved the problems referred to above targetedly.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of yield of light olefins that exists in the prior art, and a kind of new reaction for preparing light olefins from methanol-regenerating unit is provided.This device 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 solution used in the present invention is as follows: a kind of reaction for preparing light olefins from methanol-regenerating unit, mainly comprise methanol conversion 3, by product conversion reactor 11, revivifier 18, upflow tube 12, riser tube 10, by product conversion reactor 11 tops link to each other with revivifier 18, the bottom links to each other with methanol conversion 3, revivifier 18 inside are provided with degas zone 20, degas zone 20 inner catalysts enter by product conversion reactor 11 by upflow tube 12, by product conversion reactor 11 bottoms have catalyst outlet, link to each other with methanol conversion 3 by catalyst transport 5, methanol conversion 3 inside are provided with stripping zone 6, stripping zone 6 inner catalysts enter revivifier 18 by riser tube 10, methanol conversion 3 and by product conversion reactor 11 tops have products export, and revivifier 18 tops have exhanst gas outlet.
In the technique scheme, described catalyzer comprises the SAPO-34 molecular sieve; Gas-solid cyclone separator all is set before described products export and the exhanst gas outlet; Described degas zone 20 degassing media are selected from water vapour, and stripping zone 6 stripping media are selected from water vapour, and riser tube 10 promotes medium and is selected from water vapour; Described revivifier 18 is by built-in heat collector control regeneration temperature; Described methanol conversion 3 can be provided with external or built-in heat collector control reaction temperature; Described degas zone 20 and stripping zone 6 side wall upper part have at least one catalyst inlet; The shared cover separation process of described by product conversion reactor 11 products and methanol conversion 3 products; Described by product is carbon four～carbon six hydrocarbon mixtures; Carbon four hydrocarbon mass content are greater than 80% in the described hydrocarbon mixture, and the alkene mass content is greater than 60%.
Inevitably can produce by products such as carbon four above hydrocarbon in the reaction for preparing light olefins from methanol process, this part by-product yields height and olefin(e) centent height, by discovering, the carbon four above hydrocarbon mixtures that this part olefin(e) centent is very high are raw materials of good production low-carbon alkene.Adopt method of the present invention, a by product convertor is set, be mainly used in and transform the carbon four～carbon six hydrocarbon by products that form in the preparing low carbon olefin hydrocarbon by methanol, be used for increased low carbon olefine output.The catalyzer of by product convertor helps guaranteeing that directly from revivifier carbon four above hydrocarbon transform required temperature of reaction and catalyst activity.The inventor is by discovering, carbon four above hydrocarbon conversion meetings generate carbon distribution on catalyzer, and the carbon distribution that generates has significantly improved selectivity of catalyst, helps the production low-carbon alkene of methyl alcohol highly selective.Simultaneously, high-temperature regenerated catalyst is by behind the by product convertor, and temperature decreases, the corresponding heat-obtaining load that has reduced methanol conversion.In addition, prior art generally all adopts reactor, revivifier to be arranged in juxtaposition, and the occupation of land space is big, the catalyst transport pipeline is longer.Adopt revivifier, by product convertor, methanol conversion coaxial arrangement among the present invention, significantly reduced the occupation of land space of traditional reaction-regenerative device, the catalyst transport pipeline shortens greatly simultaneously.
Adopt technical scheme of the present invention: described catalyzer comprises the SAPO-34 molecular sieve; Gas-solid cyclone separator all is set before described products export and the exhanst gas outlet; Described degas zone 20 degassing media are selected from water vapour, and stripping zone 6 stripping media are selected from water vapour, and riser tube 10 promotes medium and is selected from water vapour; Described revivifier 18 is by built-in heat collector control regeneration temperature; Described methanol conversion 3 can be provided with external or built-in heat collector control reaction temperature; Described degas zone 20 and stripping zone 6 side wall upper part have at least one catalyst inlet; The shared cover separation process of described by product conversion reactor 11 products and methanol conversion 3 products; Described by product is carbon four～carbon six hydrocarbon mixtures; Carbon four hydrocarbon mass content are greater than 80% in the described hydrocarbon mixture, the alkene mass content is greater than 60%, low-carbon alkene carbon back yield reaches 80.67% (weight) in the methanol conversion exported product, yield of light olefins reaches 35.47% (weight) in the by product conversion reactor exported product, has obtained better technical effect.
Description of drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
Among Fig. 1,1 is the charging of riser tube lifting medium; 2 is the charging of stripping medium; 3 is methanol conversion; 4 is the methanol feedstock charging; 5 is catalyst transport; 6 is stripping zone; 7 is stripping zone sidewall catalyst inlet; 8 is the reactor external warmer; 9 is gas-solid cyclone separator; 10 is riser tube; 11 is the by product conversion reactor; 12 is upflow tube; 13 is gas-solid cyclone separator; 14 is the by product charging; 15 is products export; 16 is collection chamber; 17 is the regenerating medium charging; 18 is revivifier; 19 are the charging of degassing medium; 20 is degas zone; 21 is the revivifier heat collector; 22 is gas-solid cyclone separator; 23 is exhanst gas outlet.
Raw material enters in the methanol conversion 3 through feeding line 4, contact with molecular sieve catalyst, reaction generates the product that contains low-carbon alkene, through entering collection chamber 16 after 9 separation of gas-solid sharp separation equipment, enter revivifier 18 regeneration by riser tube 10 behind decaying catalyst process stripping zone 6 strippings, regenerated catalyst enters in the by product conversion reactor 11 by upflow tube 12, contact with by products such as carbon four above hydrocarbon, the product that generates enters collection chamber after separating through gas-solid cyclone separator 13, catalyzer in the by product conversion reactor enters in the methanol conversion 3 by catalyst transport 5, continues and the methyl alcohol reaction.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In reaction-regenerative device as shown in Figure 1, collection chamber just is not set, methanol conversion product and by product conversion reactor product separate on-line analysis.The medial temperature of methanol conversion is 450 ℃, and bed density is 170 kilograms per cubic meter, and the medial temperature of by product conversion reactor is 552 ℃, and bed density is 220 kilograms per cubic meter.Reaction-regeneration system pressure is normal pressure, methanol conversion is 99.5% methanol feeding with purity, charging is 1 kilogram/hour, catalyzer is SAPO-34, stripping zone stripping medium, degas zone degassing medium, riser tube promote medium and are water vapour, heat production coil pipe control regeneration temperature in revivifier is provided with, regeneration temperature is 674 ℃.The charging of by product conversion reactor is carbon four above hydrocarbon mixtures, wherein carbon four hydrocarbon mass content are 91%, the alkene mass content is 87%, the regenerated catalyst carbon deposition quantity is 0.47%, the carbon deposition quantity of catalyst that comes out from the by product conversion reactor is 1.6%, the stability that keeps catalyst flow control, the reactor outlet product all adopts online gas chromatographic analysis, low-carbon alkene carbon back yield is 80.67% (weight) in the methanol conversion exported product, and yield of light olefins is 35.47% (weight) in the by product conversion reactor exported product.
[embodiment 2]
According to embodiment 1 described condition, the charging of by product conversion reactor is carbon four above hydrocarbon mixtures, wherein carbon four hydrocarbon mass content are 80%, the alkene mass content is 60%, the regenerated catalyst carbon deposition quantity is 0.27%, the carbon deposition quantity of catalyst that comes out from the by product conversion reactor is 1.18%, the stability that keeps catalyst flow control, the reactor outlet product all adopts online gas chromatographic analysis, low-carbon alkene carbon back yield is 80.48% (weight) in the methanol conversion exported product, and yield of light olefins is 30.61% (weight) in the by product conversion reactor exported product.
[comparative example 1]
According to embodiment 1 described condition, do not establish the by product conversion reactor, regenerated catalyst directly turns back to the methanol conversion bottom, and low-carbon alkene carbon back yield is 79.63% 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 (10)
1. reaction for preparing light olefins from methanol-regenerating unit, mainly comprise methanol conversion (3), by product conversion reactor (11), revivifier (18), upflow tube (12), riser tube (10), by product conversion reactor (11) top links to each other with revivifier (18), the bottom links to each other with methanol conversion (3), revivifier (18) inside is provided with degas zone (20), degas zone (20) inner catalyst enters by product conversion reactor (11) by upflow tube (12), by product conversion reactor (11) bottom has catalyst outlet, link to each other with methanol conversion (3) by catalyst transport (5), methanol conversion (3) inside is provided with stripping zone (6), stripping zone (6) inner catalyst enters revivifier (18) by riser tube (10), methanol conversion (3) and by product conversion reactor (11) top have products export, and revivifier (18) top has exhanst gas outlet.
2. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 1, it is characterized in that described catalyzer comprises the SAPO-34 molecular sieve.
3. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 1, it is characterized in that before described products export and the exhanst gas outlet gas-solid cyclone separator being set all.
4. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 1, it is characterized in that described degas zone (20) degassing medium is selected from water vapour, stripping zone (6) stripping medium is selected from water vapour, and riser tube (10) promotes medium and is selected from water vapour.
5. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 1, it is characterized in that described revivifier (18) is by built-in heat collector control regeneration temperature.
6. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 1, it is characterized in that described methanol conversion (3) can be provided with external or built-in heat collector control reaction temperature.
7. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 1, it is characterized in that described degas zone (20) and stripping zone (6) side wall upper part have at least one catalyst inlet.
8. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 1, it is characterized in that the shared cover separation process of described by product conversion reactor (11) product and methanol conversion (3) product.
9. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 1, it is characterized in that described by product is carbon four～carbon six hydrocarbon mixtures.
10. according to the described reaction for preparing light olefins from methanol-regenerating unit of claim 9, it is characterized in that carbon four hydrocarbon mass content are greater than 80% in the described hydrocarbon mixture, the alkene mass content is greater than 60%.
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| CN201010199977.2A CN102276400B (en) | 2010-06-11 | 2010-06-11 | Low carbon olefin reaction-regeneration device by using methanol |
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| CN201010199977.2A CN102276400B (en) | 2010-06-11 | 2010-06-11 | Low carbon olefin reaction-regeneration device by using methanol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872770A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Reaction unit for preparing low-carbon olefins |
| CN103537235A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Reaction device for preparing low-carbon olefin by using oxy-compounds |
| CN111871343A (en) * | 2020-07-10 | 2020-11-03 | 中石化洛阳工程有限公司 | Device for producing low-carbon olefin by using oxygen-containing compound |
Citations (3)
| 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 |
| CN1962573A (en) * | 2006-12-01 | 2007-05-16 | 中国化学工程集团公司 | Method and reactor for catalytic cracking for producing propylene using fluid bed |
| 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
- 2010-06-11 CN CN201010199977.2A patent/CN102276400B/en active Active
Patent Citations (3)
| 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 |
| CN1962573A (en) * | 2006-12-01 | 2007-05-16 | 中国化学工程集团公司 | Method and reactor for catalytic cracking for producing propylene using fluid bed |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872770A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Reaction unit for preparing low-carbon olefins |
| CN102872770B (en) * | 2011-07-12 | 2015-04-08 | 中国石油化工股份有限公司 | Reaction unit for preparing low-carbon olefins |
| CN103537235A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Reaction device for preparing low-carbon olefin by using oxy-compounds |
| CN103537235B (en) * | 2012-07-12 | 2016-04-13 | 中国石油化工股份有限公司 | The reaction unit of preparing low-carbon olefin from oxygen-containing compounds |
| CN111871343A (en) * | 2020-07-10 | 2020-11-03 | 中石化洛阳工程有限公司 | Device for producing low-carbon olefin by using oxygen-containing compound |
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| CN102276400B (en) | 2014-05-28 |
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