CN101333141B - Reaction device for conversing methanol or dimethyl ether to be low carbon olefin - Google Patents
Reaction device for conversing methanol or dimethyl ether to be low carbon olefin Download PDFInfo
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- CN101333141B CN101333141B CN2008100436138A CN200810043613A CN101333141B CN 101333141 B CN101333141 B CN 101333141B CN 2008100436138 A CN2008100436138 A CN 2008100436138A CN 200810043613 A CN200810043613 A CN 200810043613A CN 101333141 B CN101333141 B CN 101333141B
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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 invention relates to a reaction device which uses methanol or dimethyl ether to prepare low-carbon olefin, mainly to solve the problem of low low-carbon olefin production rate in the prior art. The reaction device which uses methanol or dimethyl ether to prepare low-carbon olefin mainly comprises a reactor reaction zone 2, a catalyst circulation zone, a stripping zone 4, a reactor separation zone 9, a regenerator regeneration zone 14 and a regenerator separation zone 12; a material inlet 1 is arranged at the lower part of the reactor reaction zone 2; the upper part of the reactor reaction zone is connected with a gas-solid rapid separation equipment 3; a gas-solid cyclone separator 8 is arranged inside the reactor separation zone 9; the upper part of the reactor separation zone 9 is provided with a product outlet 11; the stripping zone 4 is arranged at the upper part of the reactor reaction zone 2; two catalyst outlets are arranged at the lower part of the reactor reaction zone 2, wherein, one catalyst outlet is connected with the reactor reaction zone 2, while the other catalyst outlet is connected with the regenerator regeneration zone 14; a gas-solid cyclone separator 16 is arranged inside the regenerator separation zone 12; a flue gas outlet 17 is arranged at the upper part of the regenerator separation zone 12; a catalyst outlet is arranged at the upper part of the regenerator regeneration zone 14 and connected with a regenerated catalyst standpipe 21; the opening of the regenerated catalyst standpipe 21 is connected with the stripping zone 4. Such a technical proposal solves all the problems and the device can be used for low-carbon olefin industrial production.
Description
Technical field
The present invention relates to the reaction unit that a kind of methyl alcohol or dimethyl ether conversion are low-carbon alkene.
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 through 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, One type of important alternative materials that is used for light olefin production 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 through coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, like 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) receives increasing attention.
In the US4499327 patent silicoaluminophosphamolecular molecular sieves catalyst applications is studied in great detail in methanol conversion system olefin process, 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 drum of low-carbon alkene; Adopt fast fluidized bed reactor; Gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is accomplished; 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 methyl alcohol or dimethyl ether conversion are very responsive to processing parameters such as temperature of reaction in the process of low-carbon alkene.All there are problems such as the fluctuation of reaction zone inner catalyst carbon deposit skewness, temperature of reaction is big 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 not high 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 methyl alcohol or dimethyl ether conversion are provided.This method is used for the production of low-carbon alkene, has that yield of light olefins is higher, the advantage of low-carbon alkene production technique better economy.
For addressing the above problem; The technical scheme that the present invention adopts is following: a kind of methyl alcohol or dimethyl ether conversion are the reaction unit of low-carbon alkene, mainly comprise reactor reaction zone 2, catalyst recirculation district, stripping zone 4, reactor drum disengaging zone 9, revivifier breeding blanket 14, revivifier disengaging zone 12; Reactor reaction zone 2 bottoms have opening for feed 1, and top links to each other with gas-solid sharp separation equipment 3, and 9 inside, reactor drum disengaging zone are provided with gas-solid cyclone separator 8, and top has products export 11; Stripping zone 4 is positioned at reactor reaction zone 2 tops, and the bottom has two catalyst outlets, and one links to each other with reactor reaction zone 2, and another links to each other with revivifier breeding blanket 14; 12 inside, revivifier disengaging zone are provided with gas-solid cyclone separator 16, and top has exhanst gas outlet 17; 14 tops, revivifier breeding blanket have catalyst outlet, link to each other with regenerated catalyst standpipe 21, and regenerated catalyst standpipe 21 outlets link to each other with stripping zone 4.
In the technique scheme, said reactor drum is a fast fluidized bed; The diameter of gas-solid sharp separation equipment 3 and the diameter ratio of reactor reaction zone 2 are 0.1～0.5: 1; Gas-solid cyclone separator 8 in the reactor drum disengaging zone 9 is 1～3 grade; Gas-solid cyclone separator 16 in the revivifier disengaging zone 12 is 1～3 grade; Lifting medium in the regeneration standpipe 21 is water vapour, unreacted methanol or dme, carbon four above hydrocarbon; Catalyzer comprises the SAPO-34 molecular sieve; Revivifier external warmer 15 is the back-mixing formula.
Because oxygenate is in the reaction process of low-carbon alkene, needs to be with on the catalyzer a certain amount of carbon, to improve the selectivity of low-carbon alkene.General, adopt with reclaimable catalyst and regenerated catalyst method of mixing, to reach required coke content requirement.And more importantly be that before mixed catalyst contact raw material, catalyzer requires to mix, and could realize maximized selectivity requirement.Known in the field; In the existing circulating fluidized bed technique; Like FCC (FCC); Be regenerated catalyst directly to be turned back to riser reaction zone contact, but, do not relate to the mixed problem of different carbon-bearing amount catalyzer because prior art generally all requires the mean carbon content of reaction zone catalyzer low more good more with raw material.In addition; Because oxygenate is that the reaction of low-carbon alkene is very responsive for temperature of reaction; The fluctuation of reaction zone temperature of reaction will directly influence reaction effect, if the higher regenerated catalyst of temperature directly turns back to reaction zone, will certainly influence the temperature of reaction of reaction zone.Therefore, generally speaking, be in the process of low-carbon alkene in oxygenate, the solid flow of regenerated catalyst line mainly plays two effects: the one, control suitable flow and mix with reclaimable catalyst, reach the required average coke content of catalyzer; The 2nd, control suitable flow and get into reaction zone, guarantee the stable of heat that reaction zone is required and temperature of reaction.And in the prior art, above-mentioned two effects tend to produce contradiction, as: the regenerated catalyst flow is big; Then the heat of reaction zone acquisition is high; Temperature of reaction raises, but owing to the ratio of regenerated catalyst in the mixed catalyst increases, has then reduced the average coke content of mixed catalyst.Adopt method of the present invention, regenerated catalyst is turned back to stripping zone through the catalyzer standpipe, and, reduced the temperature of regenerated catalyst simultaneously, effectively solved the problems referred to above the mixing region of stripping zone as catalyzer.
Therefore, adopt method of the present invention, regenerated catalyst is risen to the disengaging zone of reactor drum,, can also reach the effect that influences the reaction zone operating parameters that minimizes so that mix with reclaimable catalyst through promoting medium.In addition; Because methyl alcohol or dimethyl ether conversion are in the reaction process of low-carbon alkene; Can there be unreacted methanol or dme, and can produce the above hydrocarbon of the lower C4 of a certain amount of added value, if the above hydrocarbon of C4 in unreacted methanol or dme or the product is contacted with regenerated catalyst as promoting medium; Not only can generate low-carbon alkene; Improved the utilising efficiency of methyl alcohol or dme or the above hydrocarbon of C4, but also regenerated catalyst has been carried out preparatory coking, thereby the carbon that dwindles reclaimable catalyst and regenerated catalyst is poor.When the average coke content of reaction zone mixed catalyst one regularly because the carbon difference of reclaimable catalyst and regenerated catalyst is less, catalyst carbon deposit narrow distribution then, thereby improved the selectivity of low-carbon alkene greatly.In addition, because dwindling of reclaimable catalyst and regenerated catalyst carbon difference can be adopted bigger catalyst recirculation amount operation between reaction and regeneration system rapidly, be easy to control more.
Adopt technical scheme of the present invention: said reactor drum is a fast fluidized bed; The diameter of gas-solid sharp separation equipment 3 and the diameter ratio of reactor reaction zone 2 are 0.1～0.5: 1; Gas-solid cyclone separator 8 in the reactor drum disengaging zone 9 is 1～3 grade; Gas-solid cyclone separator 16 in the revivifier disengaging zone 12 is 1～3 grade; Lifting medium in the regeneration standpipe 21 is water vapour, unreacted methanol or dme, carbon four above hydrocarbon; Catalyzer comprises the SAPO-34 molecular sieve; Revivifier external warmer 15 is the back-mixing formula, and selectivity of light olefin can reach 83.67% 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 is the reactor feedstocks charging; 2 is reactor reaction zone; 3 are gas-solid sharp separation equipment; 4 is stripping zone; 5 is reclaimable catalyst circulation inclined tube; 6 remove the revivifier line of pipes for reclaimable catalyst; 7 is the reactor drum external warmer; 8 is the reactor drum gas-solid cyclone separator; 9 is the reactor drum disengaging zone; 10 is the product collection chamber; 11 is the product gas outlet pipeline; 12 is the revivifier disengaging zone; 13 is the regenerating medium source line; 14 is the revivifier breeding blanket; 15 is the revivifier external warmer; 16 is the revivifier gas-solid cyclone separator; 17 is the regenerated flue gas outlet line; 18 is regenerated catalyst circulation inclined tube; 19 are regenerated catalyst standpipe lifting medium inlet pipeline; 20 is the mixing section of regenerated catalyst standpipe bottom; 21 is regenerated catalyst standpipe; 22 gas-solid cyclone separators for the regenerated catalyst standpipe outlet.
Oxygen-containing compound material gets in the reactor reaction zone 2 through feeding line 1; Contact with sieve catalyst; Reaction generates the product that contains low-carbon alkene, carries reclaimable catalyst and gets into the reactor drum disengaging zone through gas-solid sharp separation equipment 3, wherein; Most of catalyzer that gas-solid sharp separation equipment 3 is separated gets into stripping zone 4; And gaseous products and part are not separated through going into cyclonic separator 8 separation by the catalyzer of gas-solid sharp separation device separates once more, and catalyzer turns back to stripping zone 4 through the dipleg of cyclonic separator 8, and gaseous products gets into collection chamber 10 after outlet line 11 gets into follow-up centrifugal station.Be divided into two portions by gas-solid sharp separation equipment 3 and cyclonic separator 8 isolated reclaimable catalysts through behind the stripping; A part is through turning back to the bottom of reactor reaction zone 2 through catalyst recirculation inclined tube 5 after interchanger 7 heat exchange; A part gets into coke-burning regeneration in the revivifier breeding blanket 14 through catalyst transport pipeline 6 in addition; The flue gas that the coke burning generates gets into follow-up energy-recuperation system through cyclonic separator 16 backs through exhanst gas outlet pipeline 17; The catalyzer that regeneration is accomplished gets in the mixing section 20 of catalyzer standpipe 21 bottoms through regenerated catalyst circulation inclined tube 18, mixes with lifting medium 19, and the regenerated catalyst standpipe outlet is provided with gas-solid cyclone separator 22; Isolated regenerated catalyst gets in the stripping zone 4 and mixes with reclaimable catalyst, and part turns back to through circulation inclined tube 5 and continues to participate in reaction in the reaction zone 2.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In the fast fluidized bed reaction device, the same Fig. 1 of reaction unit pattern.The medial temperature of reactor reaction zone 2 is 470 ℃, and the medial temperature of revivifier breeding blanket 14 is 650 ℃, and reactor drum disengaging zone 9 top pressures are counted 0.14MPa with gauge pressure; Pure methanol feeding; Charging is 2 kilograms/hour, and catalyzer is a modified SAPO-34, and stripping zone 4 stripping media are water vapour; The lifting medium of regenerated catalyst standpipe 21 is unreacted methanol and dme, and the heat transferring medium with reclaimable catalyst in the reactor drum external warmer 7 is a water vapour.The diameter of gas-solid sharp separation equipment 3 and the diameter ratio of reactor reaction zone 2 are 0.2: 1; Gas-solid cyclone separator 8 in the reactor drum disengaging zone 9 is 2 grades; Gas-solid cyclone separator 16 in the revivifier disengaging zone 12 is 2 grades; Revivifier external warmer 15 is the back-mixing formula.Average catalyst coke content in the reactor reaction zone 2 is controlled at about 3% weight, keeps the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 81.04% weight.
[embodiment 2]
According to embodiment 1 described condition; It is the above hydrocarbon of the isolated C4 of product separation workshop section that regenerated catalyst standpipe promotes medium; The medial temperature that changes reactor reaction zone 2 is 500 ℃, and the diameter of gas-solid sharp separation equipment 3 and the diameter ratio of reactor reaction zone 2 are 0.5: 1; Gas-solid cyclone separator 8 in the reactor drum disengaging zone 9 is 3 grades; Gas-solid cyclone separator 16 in the revivifier disengaging zone 12 is 1 grade, and yield of light olefins reaches 83.67% weight.
[embodiment 3]
According to embodiment 1 described condition, it is water vapour that regenerated catalyst standpipe promotes medium, and the medial temperature that changes reactor reaction zone 2 is 450 ℃, and the diameter of gas-solid sharp separation equipment 3 and the diameter ratio of reactor reaction zone 2 are 0.1: 1; Gas-solid cyclone separator 8 in the reactor drum disengaging zone 9 is 1 grade; Gas-solid cyclone separator 16 in the revivifier disengaging zone 12 is 3 grades, and yield of light olefins reaches 80.01% weight.
[comparative example 1]
According to embodiment 1 described condition, regenerated catalyst is directly turned back to the bottom of reactor reaction zone 2 through regenerated catalyst circulation inclined tube 18, yield of light olefins is 78.28% 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 (5)
1. methyl alcohol or dimethyl ether conversion are the reaction unit of low-carbon alkene, mainly comprise reactor reaction zone (2), catalyst recirculation district, stripping zone (4), reactor drum disengaging zone (9), revivifier breeding blanket (14), revivifier disengaging zone (12); Reactor reaction zone (2) bottom has opening for feed (1), and top links to each other with gas-solid sharp separation equipment (3), and inside, reactor drum disengaging zone (9) is provided with gas-solid cyclone separator (8), and top has products export (11); Stripping zone (4) is positioned at reactor reaction zone (2) top, and the bottom has two catalyst outlets, and one links to each other with reactor reaction zone (2), and another links to each other with revivifier breeding blanket (14); Inside, revivifier disengaging zone (12) is provided with gas-solid cyclone separator (16), and top has exhanst gas outlet (17); Top, revivifier breeding blanket (14) has catalyst outlet, links to each other with regenerated catalyst standpipe (21), and regenerated catalyst standpipe (21) outlet links to each other with stripping zone (4); Said low-carbon alkene is ethene and propylene.
2. be the reaction unit of low-carbon alkene according to said methyl alcohol of claim 1 or dimethyl ether conversion, it is characterized in that said reactor drum is a fast fluidized bed; The diameter ratio of the diameter of gas-solid sharp separation equipment (3) and reactor reaction zone (2) is 0.1～0.5: 1.
3. be the reaction unit of low-carbon alkene according to said methyl alcohol of claim 2 or dimethyl ether conversion, it is characterized in that the gas-solid cyclone separator (8) in the said reactor drum disengaging zone (9) is 1～3 grade; Gas-solid cyclone separator (16) in the revivifier disengaging zone (12) is 1～3 grade.
4. be the reaction unit of low-carbon alkene according to said methyl alcohol of claim 1 or dimethyl ether conversion, it is characterized in that the lifting medium in the said regenerated catalyst standpipe (21) is water vapour, unreacted methanol or dme, carbon four above hydrocarbon.
5. be the reaction unit of low-carbon alkene according to said methyl alcohol of claim 1 or dimethyl ether conversion, it is characterized in that said catalyzer is the SAPO-34 molecular sieve.
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| CN2008100436138A CN101333141B (en) | 2008-07-08 | 2008-07-08 | Reaction device for conversing methanol or dimethyl ether to be low carbon olefin |
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| CN2008100436138A CN101333141B (en) | 2008-07-08 | 2008-07-08 | Reaction device for conversing methanol or dimethyl ether to be low carbon olefin |
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| CN101333141B true CN101333141B (en) | 2012-05-30 |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190550B (en) | 2010-03-03 | 2016-02-10 | 中国石油化工股份有限公司 | The production method of low-carbon alkene |
| CN102190540B (en) * | 2010-03-03 | 2013-09-18 | 中国石油化工股份有限公司 | Method for producing propylene |
| CN102190548B (en) * | 2010-03-03 | 2014-07-02 | 中国石油化工股份有限公司 | Method for enhancing yield of light olefins in MTO technology |
| CN102274761B (en) * | 2010-06-11 | 2013-06-05 | 中国石油化工股份有限公司 | Regeneration device of low carbon olefine catalyst by using methanol |
| CN102276381B (en) * | 2010-06-11 | 2014-04-23 | 中国石油化工股份有限公司 | Method for improving selectivity of light olefins prepared from conversion of oxygenated compound |
| CN102276383B (en) * | 2010-06-11 | 2013-12-04 | 中国石油化工股份有限公司 | Method of reducing runoff of catalysts in conversion of oxygen containing compounds to low carbon olefins |
| CN102276406B (en) * | 2010-06-11 | 2014-07-23 | 中国石油化工股份有限公司 | Method for increasing yield of propylene |
| CN102276386B (en) | 2010-06-11 | 2013-12-25 | 中国石油化工股份有限公司 | Production method of light olefins |
| CN102463086B (en) * | 2010-11-17 | 2014-01-22 | 中国石油化工股份有限公司 | Reaction device for co-producing low-carbon olefin and p-xylene |
| CN102464532B (en) | 2010-11-17 | 2014-07-02 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefins |
| CN102463072B (en) * | 2010-11-17 | 2014-07-23 | 中国石油化工股份有限公司 | Reaction device for producing p-xylene |
| CN102872907A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Regenerator for preparing olefins from methanol |
| CN102875290B (en) * | 2011-07-12 | 2014-08-13 | 中国石油化工股份有限公司 | Reaction unit for preparing low-carbon olefins by using methanol and naphtha |
| CN102659499B (en) * | 2012-05-14 | 2014-08-27 | 神华集团有限责任公司 | Device and method for converting methyl alcohol into low-carbon olefin |
| CN115155466B (en) * | 2022-08-05 | 2023-10-13 | 中国石油大学(北京) | Coupling reaction system and method for preparing ethylene by oxidative coupling of methane |
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