CN102276388A - Reaction device for preparing light olefin from oxygen-containing compound - Google Patents
Reaction device for preparing light olefin from oxygen-containing compound Download PDFInfo
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- CN102276388A CN102276388A CN2010101997993A CN201010199799A CN102276388A CN 102276388 A CN102276388 A CN 102276388A CN 2010101997993 A CN2010101997993 A CN 2010101997993A CN 201010199799 A CN201010199799 A CN 201010199799A CN 102276388 A CN102276388 A CN 102276388A
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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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- 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 device for preparing a light olefin from an oxygen-containing compound. The reaction device mainly solves a problem that a yield of a light olefin is low during production of the light olefin. The reaction device for preparing a light olefin from an oxygen-containing compound mainly comprises a main reactor 4, an auxiliary reactor 3, a catalystrunner pipe 12, a heat exchange pipe 5 and a gas-solidcyclone separator 8. The upper part of the main reactor 4 is connected to a settling section 9. The lower part of the main reactor 4 is connected to the auxiliary reactor 3. The gas-solidcyclone separator 8 is arranged in the settling section 9. The top of the settling section 9 is provided with a product gas outlet 10. The catalystrunner pipe 12 is arranged in a connection part of the main reactor 4 and the auxiliary reactor 3. The heat exchange pipe is arranged in the auxiliary reactor 3. The lower part of the auxiliary reactor 3 is provided with a catalyst outlet. The catalyst outlet is connected with a regenerator through a waitinginclined pipe 7. The lower part of the main reactor 4 is provided with a catalyst inlet. The catalyst inlet is connected with the regenerator through a waitinginclined pipe 11. Through the technical schemeof the reaction device, the problem is solved well. The reaction device for preparing a light olefin from an oxygen-containing compound can be utilized for industrial production of light olefins.
Description
Technical field
The present invention relates to a kind of reaction unit of producing low-carbon olefins from oxygen-containing compound.
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 low-carbon alkene 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 low-carbon alkene 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 selectivity of light olefin, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US6166282 that a kind of methanol 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.
The method that relates to catalyzer coke content in a kind of MTO of control reactor reaction zone in US 20060025646 patents is the catalyzer part of inactivation to be sent into the breeding blanket make charcoal, and another part decaying catalyst turns back to reaction zone and continues reaction.
CN200910087868 has announced a kind of producing ethylene from dehydration of ethanol catalyzer, this catalyzer is the SAPO-34 molecular sieve of metal M n ion modification, be Mn/SAPO-34, with the morphine quinoline is that template is introduced the modified metal ion by direct synthesis technique and is prepared from before the molecular sieve crystallization, the gained molecular sieve is big crystal grain monocrystalline, can be directly used in fluidized-bed, the ethanol conversion height, selectivity of ethylene and purity are all very high.
Though producing ethylene with ethyl alcohol (ETO) technology has higher ethylene selectivity, and lower raw material dividing potential drop helps the raising of ethylene selectivity equally, but there are problems such as raw material production small scale, process economy in ETO technology at present, if ETO technology is relied on MTO technology, saved the construction cost of ETO process unit, had area development ethene, the propylene industry particularly suitable of a large amount of methyl alcohol and small amount of ethanol for some.
Though prior art can be carried out producing low-carbon olefins from oxygen-containing compound such as methyl alcohol or ethanol, but prior art is all less than the coupled problem that well solves MTO and ETO, also do not have the lower problem of fine solution yield of light olefins, 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 producing low-carbon olefins from oxygen-containing compound 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 unit of producing low-carbon olefins from oxygen-containing compound, mainly comprise main reactor 4, auxiliary reactor 3, catalyst stream siphunculus 12, heat transfer tube 5, gas-solid cyclone separator 8, main reactor 4 tops link to each other with settling section 9, the bottom links to each other with auxiliary reactor 3, settling section 9 inside are provided with gas-solid cyclone separator 8, the top has product gas outlet 10, in main reactor 4 and auxiliary reactor 3 connection portions catalyst stream siphunculus 12 is arranged, auxiliary reactor 3 inside are provided with heat transfer tube, the bottom has catalyst outlet, link to each other with revivifier by inclined tube 7 to be generated, main reactor 4 bottoms have catalyst inlet, link to each other with revivifier by regenerator sloped tube 11.
In the technique scheme, described silicoaluminophosphamolecular molecular sieve comprises SAPO-34; Described main reactor and auxiliary reactor are fluidized-bed; Described oxygenatedchemicals comprises methyl alcohol or ethanol, and the main reactor charging comprises methyl alcohol, and the auxiliary reactor charging comprises ethanol; The described main reactor charging that comprises methyl alcohol at first enters heat transfer tube and the catalyst heat exchange in the auxiliary reactor, enters main reactor then; Described auxiliary reactor top links to each other with main reactor, and auxiliary reactor gas phase and carbon deposition catalyst are counter-current flow in catalyst stream is threaded a pipe; Described inclined tube inner catalyst carbon deposition quantity massfraction to be generated is between 2.0～6.0%; Described auxiliary reactor interior reaction temperature is between 300～420 ℃.
The inventor is by discovering, the carbon deposition catalyst that forms in the methanol-to-olefins reaction process still keeps higher activity and selectivity, possesses the ability that transforms some low-carbon alcohol (as ethanol).Adopt device of the present invention, adopting the carbon deposition catalyst that forms in the MTO reaction to transform ethanol is ethene, and ethene enters the MTO reactor simultaneously, further propylene enhancing, not only solved the coupled problem of MTO and ETO technology, improved low-carbon alkene simultaneously, especially the yield of propylene.Simultaneously, after the product that auxiliary reactor generates enters main reactor, also reduce the dividing potential drop of methyl alcohol, helped the raising of selectivity of light olefin.Because producing ethylene with ethyl alcohol is temperature required lower, adopt the mode of methanol feeding among the present invention in auxiliary reactor and carbon deposition catalyst heat exchange, not only heat methanol feedstock, and reduced the temperature of auxiliary reactor, guaranteed the carrying out of producing ethylene with ethyl alcohol reaction.Adopt reaction unit of the present invention, can guarantee that alcoholic acid 100% transforms, and has improved the yield of low-carbon alkene.
Adopt technical scheme of the present invention: described silicoaluminophosphamolecular molecular sieve comprises SAPO-34; Described main reactor and auxiliary reactor are fluidized-bed; Described oxygenatedchemicals comprises methyl alcohol or ethanol, and the main reactor charging comprises methyl alcohol, and the auxiliary reactor charging comprises ethanol; The described main reactor charging that comprises methyl alcohol at first enters heat transfer tube and the catalyst heat exchange in the auxiliary reactor, enters main reactor then; Described auxiliary reactor top links to each other with main reactor, and auxiliary reactor gas phase and carbon deposition catalyst are counter-current flow in catalyst stream is threaded a pipe; Described inclined tube inner catalyst carbon deposition quantity massfraction to be generated is between 2.0～6.0%; Described auxiliary reactor interior reaction temperature is between 300～420 ℃, methanol conversion reaches 99.82% (weight), and ethanol conversion reaches 100% (weight), and yield of ethene reaches 18.27% (weight), propene yield reaches 17.81% (weight), 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 for comprising the charging of alcoholic acid raw material; 2 is the raw material hot feed that comprises methyl alcohol; 3 is auxiliary reactor; 4 is main reactor; 5 is heat transfer tube; 6 is the raw material cold feed pipeline that comprises methyl alcohol; 7 is inclined tube to be generated; 8 is gas-solid cyclone separator; 9 is the main reactor settling section; 10 is the products export pipeline; 11 is regenerator sloped tube; 12 is the catalyst stream siphunculus.
The raw material that comprises methyl alcohol is gone into main reactor 4 with the carbon deposition catalyst heat exchange is laggard in auxiliary reactor 3, contact with the silicoaluminophosphamolecular molecular sieve catalyzer, generation comprises the product of low-carbon alkene, form carbon deposition catalyst simultaneously, carbon deposition catalyst enters auxiliary reactor 3 from main reactor 4 bottoms by catalyst stream siphunculus 12, contact with comprising the alcoholic acid raw material, generation comprises the product of ethene, enter main reactor 4, form reclaimable catalyst simultaneously, reclaimable catalyst enters revivifier regeneration by inclined tube 7 to be generated, and the catalyzer that regeneration is finished returns main reactor 4 by regenerator sloped tube 11.
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, main reactor and auxiliary reactor adopt fluidized-bed, main reactor employing purity is 99.5% methanol feeding, feeding temperature is 210 ℃, grid distributor is set enters reaction zone, the main reactor reaction conditions is: temperature of reaction is that 450 ℃, reaction pressure are counted 0.01MPa with gauge pressure, and gaseous line speed is 0.7 meter per second in the reactor; Auxiliary reactor adopts the straight alcohol charging, and the liquid-phase nozzle feeding manner is adopted in charging, and auxiliary reactor internal reaction condition: the mass ratio of ethanol charging and methanol feeding is 0.2, and temperature of reaction is 350 ℃, and gaseous line speed is 0.5 meter per second.The carbon deposition catalyst carbon deposition quantity is 2.5%, the reclaimable catalyst carbon deposition quantity is 2.97%, the main reactor outlet adopts the gas chromatographic analysis product to form, experimental result is: methanol conversion is 99.5% (weight), ethanol conversion is 100% (weight), yield of ethene is 17.38% (weight), and propene yield is 17.69% (weight).
[embodiment 2]
According to embodiment 1 described condition, main reactor employing purity is 99.5% methanol feeding, feeding temperature is 180 ℃, and the main reactor reaction conditions is: temperature of reaction is that 400 ℃, reaction pressure are counted 0.1MPa with gauge pressure, and gaseous line speed is 0.67 meter per second in the reactor; Auxiliary reactor adopts ethanol and methanol mixed charging, the liquid-phase nozzle feeding manner is adopted in charging, the mass ratio of ethanol and methanol feeding is 5.2 in the auxiliary reactor charging, the mass ratio of ethanol and methyl alcohol is 0.6 in the combined feed total feed, auxiliary reactor internal reaction condition: temperature of reaction is 420 ℃, and gaseous line speed is 0.8 meter per second.The carbon deposition catalyst carbon deposition quantity is 3.17%, the reclaimable catalyst carbon deposition quantity is 3.51%, and experimental result is: methanol conversion is 98.31% (weight), and ethanol conversion is 100% (weight), yield of ethene is 14.08% (weight), and propene yield is 16.92% (weight).
[embodiment 3]
According to embodiment 1 described condition, main reactor employing purity is 99.5% methanol feeding, feeding temperature is 300 ℃, and the main reactor reaction conditions is: temperature of reaction is that 500 ℃, reaction pressure are counted 0.3MPa with gauge pressure, and gaseous line speed is 0.5 meter per second in the reactor; Auxiliary reactor internal reaction condition: the mass ratio of ethanol charging and methanol feeding is 0.1, and temperature of reaction is 300 ℃, and gaseous line speed is 0.3 meter per second.The carbon deposition catalyst carbon deposition quantity is 4.98%, the reclaimable catalyst carbon deposition quantity is 5.94%, and experimental result is: methanol conversion is 99.76% (weight), and ethanol conversion is 100% (weight), yield of ethene is 15.23% (weight), and propene yield is 15.61% (weight).
[embodiment 4]
According to embodiment 1 described condition, main reactor employing purity is 99.5% methanol feeding, feeding temperature is 180 ℃, and the main reactor reaction conditions is: temperature of reaction is that 470 ℃, reaction pressure are counted 0.01MPa with gauge pressure, and gaseous line speed is 1.0 meter per seconds in the reactor; Auxiliary reactor internal reaction condition: the mass ratio of ethanol charging and methanol feeding is 0.4, and temperature of reaction is 367 ℃, and gaseous line speed is 0.59 meter per second.The carbon deposition catalyst carbon deposition quantity is 3.08%, the reclaimable catalyst carbon deposition quantity is 4.57%, and experimental result is: methanol conversion is 99.82% (weight), and ethanol conversion is 100% (weight), yield of ethene is 18.27% (weight), and propene yield is 17.81% (weight).
[comparative example 1]
According to embodiment 4 described conditions, auxiliary reactor is not set, methyl alcohol is laggardly gone into main reactor through being heated to 180 ℃, gaseous line speed is 0.86 meter per second in the main reactor, the reclaimable catalyst carbon deposition quantity is 3.23%, experimental result is: methanol conversion is 99.77% (weight), and yield of ethene is 16.86% (weight), and propene yield is 16.28% (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 (8)
1. the reaction unit of a producing low-carbon olefins from oxygen-containing compound, mainly comprise main reactor (4), auxiliary reactor (3), catalyst stream siphunculus (12), heat transfer tube (5), gas-solid cyclone separator (8), main reactor (4) top links to each other with settling section (9), the bottom links to each other with auxiliary reactor (3), settling section (9) inside is provided with gas-solid cyclone separator (8), the top has product gas outlet (10), in main reactor (4) and auxiliary reactor (3) connection portion catalyst stream siphunculus (12) is arranged, auxiliary reactor (3) inside is provided with heat transfer tube (5), the bottom has catalyst outlet, link to each other with revivifier by inclined tube to be generated (7), main reactor (4) bottom has catalyst inlet, links to each other with revivifier by regenerator sloped tube (11).
2. according to the reaction unit of the described producing low-carbon olefins from oxygen-containing compound of claim 1, it is characterized in that described silicoaluminophosphamolecular molecular sieve comprises SAPO-34.
3. according to the reaction unit of the described producing low-carbon olefins from oxygen-containing compound of claim 1, it is characterized in that described main reactor and auxiliary reactor are fluidized-bed.
4. according to the reaction unit of the described producing low-carbon olefins from oxygen-containing compound of claim 1, it is characterized in that described oxygenatedchemicals comprises methyl alcohol or ethanol, the main reactor charging comprises methyl alcohol, and the auxiliary reactor charging comprises ethanol.
5. according to the reaction unit of the described producing low-carbon olefins from oxygen-containing compound of claim 1, it is characterized in that the described main reactor charging that comprises methyl alcohol at first enters heat transfer tube and the catalyst heat exchange in the auxiliary reactor, enters main reactor then.
6. according to the reaction unit of the described producing low-carbon olefins from oxygen-containing compound of claim 1, it is characterized in that described auxiliary reactor top links to each other with main reactor, auxiliary reactor gas phase and carbon deposition catalyst are counter-current flow in catalyst stream is threaded a pipe.
7. according to the reaction unit of the described producing low-carbon olefins from oxygen-containing compound of claim 1, it is characterized in that described inclined tube inner catalyst carbon deposition quantity massfraction to be generated is between 2.0～6.0%.
8. according to the reaction unit of the described producing low-carbon olefins from oxygen-containing compound of claim 1, it is characterized in that described auxiliary reactor interior reaction temperature is between 300～420 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239874A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Reaction device for converting oxygen-containing compound to low-carbon olefins |
| CN101279876A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing ethylene and propone with oxocompound |
| CN101306969A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Reaction device for preparing low-carbon olefin from oxygen-containing compounds |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239874A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Reaction device for converting oxygen-containing compound to low-carbon olefins |
| CN101279876A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing ethylene and propone with oxocompound |
| CN101306969A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Reaction device for preparing low-carbon olefin from oxygen-containing compounds |
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