CN102190548A - Method for enhancing yield of light olefins in MTO technology - Google Patents

Method for enhancing yield of light olefins in MTO technology Download PDF

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CN102190548A
CN102190548A CN2010101163934A CN201010116393A CN102190548A CN 102190548 A CN102190548 A CN 102190548A CN 2010101163934 A CN2010101163934 A CN 2010101163934A CN 201010116393 A CN201010116393 A CN 201010116393A CN 102190548 A CN102190548 A CN 102190548A
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reaction zone
catalyzer
light olefins
reaction
sapo
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CN102190548B (en
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齐国祯
钟思青
杨远飞
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

Abstract

The invention relates to a method for enhancing yield of light olefins in MTO technology. The method mainly solves the problem of low yield of light olefins in the prior art, and comprises the following steps that: (1) raw materials containing methanol enter into a first rapid fluidized bed reaction zone and contact with a catalyst containing a silicoaluminophosphate molecular sieve to produce a product flow I containing light olefins and to make the catalyst inactivating; (2) the inactivating catalyst enters into a reactivator for regeneration, the regenerated catalyst enters into a riser reaction zone and contacts with raw materials containing fractions with four or more carbon atoms, the product and catalyst enter into a second rapid fluidized bed reaction zone and contact with raw materials containing fractions with four or more carbon atoms and with a second catalyst coming from the reactivator so as to produce a product flow II containing light olefins and a pre-coked catalyst; (3) after gas-solid separation, the product flow II is mixed with the product flow I, and the mixture is subjected to separation. The technique scheme that pre-coked catalyst returns to the first rapid fluidized bed reaction zone enables effective solving of problems in the prior art and can be used for industrial production of light olefins.

Description

Improve the method for yield of light olefins in the methanol-to-olefins technology
Technical field
The present invention relates to improve in a kind of methanol-to-olefins technology the method for yield of light olefins.
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.
In Chinese invention patent 200810043971.9, announced a kind of method that improves yield of light olefins, it is that the first reaction zone top of low-carbon alkene is provided with one second reaction zone that this method adopts in methanol conversion, and this second reaction zone diameter is greater than first reaction zone, to increase the residence time of product gas in second reaction zone of first reaction zone outlet, make unreacted methanol, dme that generates and carbon four above hydrocarbon continue reaction, reach the purpose that improves yield of light olefins, this method comprises that also the charging of second reaction zone can be through isolating freshening carbon four above hydrocarbon.Though this method can improve the yield of low-carbon alkene to a certain extent, but because the catalyzer that first reaction zone comes out has had more carbon distribution, and the carbon four above hydrocarbon pyrolysiss need higher catalyst activity, so the carbon four above hydrocarbon changing effects in second reaction zone are still on the low side in this method.
Therefore, need a kind of novel method, make the carbon four above hydrocarbon purpose that is converted into low-carbon alkene as much as possible, finally reach the purpose that improves yield of light olefins and process economy to reach.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 the method that improves yield of light olefins in a kind of new methanol-to-olefins technology is 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 solution used in the present invention is as follows: the method that improves yield of light olefins in a kind of methanol-to-olefins technology, mainly may further comprise the steps: (1) comprises that the raw material of methyl alcohol enters the first fast fluidized bed reaction zone, contact with comprising the silicoaluminophosphamolecular molecular sieves catalyzer, generation comprises the product stream I of low-carbon alkene, forms the catalyzer of inactivation simultaneously; (2) catalyzer of described inactivation enters revivifier regeneration, the catalyzer that regeneration is finished enters riser reaction zone, contact with the raw material that comprises carbon four above hydrocarbon, the product and the catalyzer that generate enter the second fast fluidized bed reaction zone, contact with the raw material that comprises carbon four above hydrocarbon and from second strand of next catalyzer of revivifier, generation comprises the product stream II of low-carbon alkene, forms the catalyzer of pre-carbon deposit simultaneously; (3) described product stream II is mixed into centrifugal station with product stream I after gas solid separation, and the catalyzer of described pre-carbon deposit returns the first fast bed reaction zone.
In the technique scheme, described silicoaluminophosphamolecular molecular sieves is selected from least a among SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, the SAPO-56, and preferred version is SAPO-34; Temperature of reaction in the described first fast bed reaction zone is 400~500 ℃, preferred version is 430~480 ℃, and reaction pressure is counted 0.01~0.3MPa with gauge pressure, and preferred version is 0.1~0.2MPa, linear gas velocity is 0.8~2.5 meter per second, and preferred version is 1.0~1.5 meter per seconds; Temperature of reaction in the riser reaction zone is 510~650 ℃, preferred version is 550~600 ℃, and reaction pressure is counted 0.01~0.3MPa with gauge pressure, and preferred version is 0.1~0.2MPa, linear gas velocity is 3.0~10.0 meter per seconds, and preferred version is 5.0~7.0 meter per seconds; Temperature of reaction in the second fast bed reaction zone is 500~630 ℃, preferred version is 530~580 ℃, and reaction pressure is counted 0.01~0.3MPa with gauge pressure, and preferred version is 0.1~0.2MPa, linear gas velocity is 0.8~2.0 meter per second, and preferred version is 1.0~1.5 meter per seconds; The carbon deposition quantity of the catalyzer of described pre-carbon deposit is 0.1~1.8% weight, and preferred version is 0.5~1.2% weight.
The preparation method of silicoaluminophosphamolecular molecular sieve of the present invention is: at first preparing the molecular sieve presoma, is 0.03-0.6R with the mole proportioning: (Si 0.01-0.98: Al 0.01-0.6: P 0.01-0.6): 2~500 H 2O, wherein R represents template, and the constitutive material mixed solution obtains through after the crystallization of certain hour at a certain temperature; Once more, with molecular sieve presoma, phosphorus source, silicon source, aluminium source, organic formwork agent, water etc. according to after at least 0.1 hour, finally obtaining the SAPO molecular sieve at 110~260 ℃ of following hydrothermal crystallizings after certain mixed.
The molecular sieve of preparation is mixed with a certain proportion of binding agent, and through obtaining final SAPO catalyzer after the operation stepss such as spraying drying, roasting, the weight percentage of binding agent in molecular sieve is generally between 10~90%.
Be provided with three reaction zones in the method for the invention, the first fast bed reaction zone is relatively independent, be used for methanol conversion system alkene, the series connection of riser reaction zone and the second fast bed reaction zone is used to transform carbon four above hydrocarbon and is the methyl alcohol of reaction or dme etc., reaches the purpose of raising feed stock conversion and yield of light olefins.Wherein, the second fast bed reaction zone linear speed significantly reduces, guaranteed the enough reaction times, and contact with one high activated catalyst after regeneration is finished, maximized conversion carbon four above hydrocarbon are low-carbon alkene, and parameters such as its material level, temperature of reaction can independently control, and the catalyzer in the riser reaction zone is directly from revivifier, the activity of temperature of carrying and catalyzer self is all higher, helps the conversion of carbon four above hydrocarbon to low-carbon alkene.In addition, regenerated catalyst by the riser reaction zone and the second fast bed reaction zone after, can accumulate a certain amount of carbon deposit after the reaction, the inventor is by discovering, carbon four above hydrocarbon are converted into a certain amount of carbon distribution that is accumulated in the low carbon olefin hydrocarbon on the catalyzer and help improving the selectivity that methanol conversion is a low-carbon alkene, so after this part catalyzer that has an a certain amount of carbon distribution returns the first fast bed reaction zone, can obviously improve the selectivity of light olefin in the first fast bed reaction zone.Simultaneously, because the carbon four above hydrocarbon pyrolysiss are that low-carbon alkene is a strong endothermic reaction, therefore the heat of the catalyst entrainment after riser reaction zone and the reaction of the second fast bed reaction zone are finished descends, after returning the first fast bed reaction zone, alleviate the heat-obtaining load of the first fast bed reaction zone, effectively utilized heat.Therefore, adopt described method of the present invention, both effectively improved the yield of purpose product low-carbon alkene, optimized energy distribution and utilization again.
Adopt technical scheme of the present invention: described silicoaluminophosphamolecular molecular sieves is selected from least a among SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, the SAPO-56; Temperature of reaction in the described first fast bed reaction zone is 400~500 ℃, and reaction pressure is counted 0.01~0.3MPa with gauge pressure, and linear gas velocity is 0.8~2.5 meter per second; Temperature of reaction in the riser reaction zone is 510~650 ℃, and reaction pressure is counted 0.01~0.3MPa with gauge pressure, and linear gas velocity is 3.0~10.0 meter per seconds; Temperature of reaction in the second fast bed reaction zone is 500~630 ℃, and reaction pressure is counted 0.01~0.3MPa with gauge pressure, and linear gas velocity is 0.8~2.0 meter per second; The carbon deposition quantity of the catalyzer of described pre-carbon deposit is 0.1~1.8% weight, and selectivity of light olefin can reach 90.33% 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 first fast bed reaction zone bottom feed; 2 is the first fast bed reaction zone; 3 are gas-solid sharp separation equipment; 4 is stripping stage; 5 return the line of pipes of the first fast bed reaction zone for the stripping stage catalyzer; 6 is the reclaimable catalyst inclined tube; 7 is the first fast bed reaction zone external warmer; 8 is gas-solid cyclone separator; 9 is reactor gas solid separation district; 10 is collection chamber; 11 is the reactor product outlet line; 12 is revivifier gas solid separation district; 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 the regenerated catalyst inclined tube; 19 is the riser reaction zone charging; 20 is buffering mixing zone, riser reaction zone bottom; 21 is riser reaction zone; 22 is second fast bed reaction zone outlet gas-solid separation equipment; 23 is the second fast bed reaction zone feeds; 24 is second strand of regenerated catalyst line; 25 is the second fast bed reaction zone.
Raw material enters in the first fast bed reaction zone 2 through feeding line 1, contact with molecular sieve catalyst, reaction generates the product stream I that contains low-carbon alkene, and through entering gas solid separation district 9 behind the quick separation equipment 3 of gas-solid, decaying catalyst enters regenerator regeneration from reclaimable catalyst inclined tube 6. Catalyst after regeneration is finished enters the catalyst buffering area 20 of riser reaction zone 21 bottoms from regenerated catalyst inclined tube 18, with enter riser reaction zone 21 after raw material from pipeline 19 contacts, product and the catalyst of riser reaction zone 21 outlets enter in the second fast bed reaction zone 25, again contact with second strand of regenerated catalyst that the raw material that comprises carbon four above hydrocarbon reaches from pipeline 24, generate low-carbon alkene product stream II, after gas-solid separator 22 separates, in the product introduction reactor Disengagement zone 9, enter centrifugal station from outlet line 11 after mixing with product stream I. Reacted catalyst returns the first fast bed reaction zone 2 from pipeline 5 in the second fast bed reaction zone 25.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In reaction unit as shown in Figure 1, the first fast bed reaction zone medial temperature is 480 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, and linear gas velocity is 1.5 meter per seconds; The riser reaction zone medial temperature is 550 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, and linear gas velocity is 5.0 meter per seconds; The second fast bed reaction zone medial temperature is 500 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, and linear gas velocity is 0.8 meter per second.The carbon deposition quantity of pre-carbon deposition catalyst is 0.5% weight.The first fast bed reaction zone bottom feed is pure methyl alcohol, and charging is 2 kilograms/hour, and catalyzer is SAPO-34, wherein SiO in the molecular sieve 2: Al 2O 3: P 2O 5=0.1: 1: 1, the binding agent massfraction was 60% in the catalyzer.The riser reaction zone bottom feed is a mixed c 4, C 4 olefin content 87%, the second fast bed reaction zone bottom feed is identical with the riser reaction zone bottom feed, the stability that keeps catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 87.64% weight.
[embodiment 2]
According to embodiment 1 described condition, the first fast bed reaction zone medial temperature is 500 ℃, and reaction pressure is counted 0.2MPa with gauge pressure, and linear gas velocity is 2.5 meter per seconds; The riser reaction zone medial temperature is 650 ℃, and reaction pressure is counted 0.2MPa with gauge pressure, and linear gas velocity is 10.0 meter per seconds; The second fast bed reaction zone medial temperature is 630 ℃, and reaction pressure is counted 0.2MPa with gauge pressure, and linear gas velocity is 2.0 meter per seconds.The carbon deposition quantity of pre-carbon deposition catalyst is 1.8% weight.The riser reaction zone bottom feed is a mixed c 4, C 4 olefin content 58%, and the stability of maintenance catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 85.55% weight.
[embodiment 3]
According to embodiment 1 described condition, the first fast bed reaction zone medial temperature is 400 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and linear gas velocity is 0.8 meter per second; The riser reaction zone medial temperature is 600 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and linear gas velocity is 3.0 meter per seconds; The second fast bed reaction zone medial temperature is 530 ℃, and reaction pressure is counted 0.01MPa with gauge pressure, and linear gas velocity is 1.0 meter per seconds.The carbon deposition quantity of pre-carbon deposition catalyst is 0.1% weight.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 85.80% weight.
[embodiment 4]
According to embodiment 1 described condition, the first fast bed reaction zone medial temperature is 430 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and linear gas velocity is 1.0 meter per seconds; The riser reaction zone medial temperature is 510 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and linear gas velocity is 7.0 meter per seconds; The second fast bed reaction zone medial temperature is 500 ℃, and reaction pressure is counted 0.3MPa with gauge pressure, and linear gas velocity is 1.5 meter per seconds.The carbon deposition quantity of pre-carbon deposition catalyst is 1.2% weight.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 86.97% weight.
[embodiment 5]
According to embodiment 1 described condition, the first fast bed reaction zone linear gas velocity is 1.2 meter per seconds; The riser reaction zone medial temperature is 600 ℃; The second fast bed reaction zone medial temperature is 580 ℃.The carbon deposition quantity of pre-carbon deposition catalyst is 0.8% weight.The riser reaction zone bottom feed is a mixed c 4, C 4 olefin content 95%, and the stability of maintenance catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 88.95% weight.
[embodiment 6]
According to embodiment 5 described conditions, the riser reaction zone bottom feed is a mixed c 4, C 4 olefin content 75%, the second fast bed reaction zone bottom feed is a mixed c 4, C 4 olefin content 95%, keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 88.84% weight.
[embodiment 7]
According to embodiment 5 described conditions, the second fast bed reaction zone bottom feed is mixed c 4 and methyl alcohol, and the olefin(e) centent in the mixed c 4 is 95%, and the weight ratio of mixed c 4 and methyl alcohol is 5: 1.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 90.33% weight.
[embodiment 8~11]
According to embodiment 1 described condition, just change the type of molecular sieve in the catalyzer, experimental result sees Table 1.
Table 1
Parameter Molecular sieve type Yield of light olefins, % (weight)
Embodiment 8 SAPO-20 80.11
Embodiment 9 SAPO-18 86.96
Embodiment 10 SAPO-56 69.37
Embodiment 11 SAPO-34+SAPO-18 (weight ratio is 2: 1) 88.22
[embodiment 12]
According to embodiment 1 described condition, SiO in the molecular sieve 2: Al 2O 3: P 2O 5=0.2: 1: 1, the binding agent massfraction was 70% in the catalyzer, and light olefin carbon back yield is 85.18% (weight).
[comparative example 1]
According to embodiment 1 described condition, do not establish the riser reaction zone and the second fast bed reaction zone, regenerated catalyst directly turns back to the bottom of the first fast bed reaction zone, and low-carbon alkene carbon back yield is 79.5% 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 (7)

1. improve the method for yield of light olefins in the methanol-to-olefins technology, mainly may further comprise the steps:
(1) raw material that comprises methyl alcohol enters the first fast fluidized bed reaction zone, contacts with comprising the silicoaluminophosphamolecular molecular sieves catalyzer, generates the product stream I that comprises low-carbon alkene, forms the catalyzer of inactivation simultaneously;
(2) catalyzer of described inactivation enters revivifier regeneration, the catalyzer that regeneration is finished enters riser reaction zone, contact with the raw material that comprises carbon four above hydrocarbon, the product and the catalyzer that generate enter the second fast fluidized bed reaction zone, contact with the raw material that comprises carbon four above hydrocarbon and from second strand of next catalyzer of revivifier, generation comprises the product stream II of low-carbon alkene, forms the catalyzer of pre-carbon deposit simultaneously;
(3) described product stream II is mixed into centrifugal station with product stream I after gas solid separation, and the catalyzer of described pre-carbon deposit returns the first fast bed reaction zone.
2. according to the method that improves yield of light olefins in the described methanol-to-olefins technology of claim 1, it is characterized in that described silicoaluminophosphamolecular molecular sieves is selected from least a among SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, the SAPO-56.
3. according to the method that improves yield of light olefins in the described methanol-to-olefins technology of claim 2, it is characterized in that described silicoaluminophosphamolecular molecular sieves is selected from SAPO-34.
4. according to the method that improves yield of light olefins in the described methanol-to-olefins technology of claim 1, it is characterized in that the temperature of reaction in the described first fast bed reaction zone is 400~500 ℃, reaction pressure is counted 0.01~0.3MPa with gauge pressure, and linear gas velocity is 0.8~2.5 meter per second; Temperature of reaction in the riser reaction zone is 510~650 ℃, and reaction pressure is counted 0.01~0.3MPa with gauge pressure, and linear gas velocity is 3.0~10.0 meter per seconds; Temperature of reaction in the second fast bed reaction zone is 500~630 ℃, and reaction pressure is counted 0.01~0.3MPa with gauge pressure, and linear gas velocity is 0.8~2.0 meter per second.
5. according to the method that improves yield of light olefins in the described methanol-to-olefins technology of claim 4, it is characterized in that the temperature of reaction in the described first fast bed reaction zone is 430~480 ℃, reaction pressure is counted 0.1~0.2MPa with gauge pressure, and linear gas velocity is 1.0~1.5 meter per seconds; Temperature of reaction in the riser reaction zone is 550~600 ℃, and reaction pressure is counted 0.1~0.2MPa with gauge pressure, and linear gas velocity is 5.0~7.0 meter per seconds; Temperature of reaction in the second fast bed reaction zone is 530~580 ℃, and reaction pressure is counted 0.1~0.2MPa with gauge pressure, and linear gas velocity is 1.0~1.5 meter per seconds.
6. according to the method that improves yield of light olefins in the described methanol-to-olefins technology of claim 1, the carbon deposition quantity that it is characterized in that the catalyzer of described pre-carbon deposit is 0.1~1.8% weight.
7. according to the method that improves yield of light olefins in the described methanol-to-olefins technology of claim 6, the carbon deposition quantity that it is characterized in that the catalyzer of described pre-carbon deposit is 0.5~1.2% weight.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539608A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Method for producing low-carbon olefine from methanol
CN103664438A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method for preparing low-carbon olefine from methanol
CN103664441A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method for preparing low-carbon olefin from methanol
CN103739418A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Method of increasing the yield of low-carbon olefins in process of preparing the low-carbon olefins from methanol
CN105828937A (en) * 2013-12-20 2016-08-03 巴斯夫欧洲公司 Catalyst and process for the conversion of oxygenates to olefins
CN111423302A (en) * 2019-01-09 2020-07-17 国家能源投资集团有限责任公司 Method and device for preparing olefin from methanol
CN114377624A (en) * 2020-10-16 2022-04-22 中国科学院大连化学物理研究所 Coke regulation reactor, device for preparing low-carbon olefin from oxygen-containing compound and application
CN115304442A (en) * 2021-05-08 2022-11-08 国家能源投资集团有限责任公司 Preparation of C from methanol 2 -C 3 Process and apparatus for olefins
CN114377624B (en) * 2020-10-16 2024-03-19 中国科学院大连化学物理研究所 Coke regulation reactor, device for preparing low-carbon olefin from oxygen-containing compound and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4499327A (en) * 1982-10-04 1985-02-12 Union Carbide Corporation Production of light olefins
US6166282A (en) * 1999-08-20 2000-12-26 Uop Llc Fast-fluidized bed reactor for MTO process
CN101195554A (en) * 2006-12-07 2008-06-11 中国石油化工股份有限公司 Method for producing low carbon olefin hydrocarbon with C4 hydrocarbon
CN101333141A (en) * 2008-07-08 2008-12-31 中国石油化工股份有限公司 Reaction device for conversing methanol or dimethyl ether to be low carbon olefin

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4499327A (en) * 1982-10-04 1985-02-12 Union Carbide Corporation Production of light olefins
US6166282A (en) * 1999-08-20 2000-12-26 Uop Llc Fast-fluidized bed reactor for MTO process
CN101195554A (en) * 2006-12-07 2008-06-11 中国石油化工股份有限公司 Method for producing low carbon olefin hydrocarbon with C4 hydrocarbon
CN101333141A (en) * 2008-07-08 2008-12-31 中国石油化工股份有限公司 Reaction device for conversing methanol or dimethyl ether to be low carbon olefin

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103539608A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Method for producing low-carbon olefine from methanol
CN103539608B (en) * 2012-07-12 2016-08-03 中国石油化工股份有限公司 The method of preparing low carbon olefin hydrocarbon with methanol
CN103664438A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method for preparing low-carbon olefine from methanol
CN103664441A (en) * 2012-09-05 2014-03-26 中国石油化工股份有限公司 Method for preparing low-carbon olefin from methanol
CN103664441B (en) * 2012-09-05 2015-09-09 中国石油化工股份有限公司 By the method for preparing low-carbon olefin by using methanol
CN103664438B (en) * 2012-09-05 2015-12-09 中国石油化工股份有限公司 The method of preparing light olefins from methanol
CN103739418B (en) * 2012-10-17 2016-07-13 中国石油化工股份有限公司 Improve the method for yield of light olefins in preparing light olefins from methanol technique
CN103739418A (en) * 2012-10-17 2014-04-23 中国石油化工股份有限公司 Method of increasing the yield of low-carbon olefins in process of preparing the low-carbon olefins from methanol
CN105828937A (en) * 2013-12-20 2016-08-03 巴斯夫欧洲公司 Catalyst and process for the conversion of oxygenates to olefins
CN105828937B (en) * 2013-12-20 2019-10-29 巴斯夫欧洲公司 For the Catalyst And Method by oxygenate conversion at alkene
CN111423302A (en) * 2019-01-09 2020-07-17 国家能源投资集团有限责任公司 Method and device for preparing olefin from methanol
CN111423302B (en) * 2019-01-09 2023-09-19 国家能源投资集团有限责任公司 Method and device for preparing olefin from methanol
CN114377624A (en) * 2020-10-16 2022-04-22 中国科学院大连化学物理研究所 Coke regulation reactor, device for preparing low-carbon olefin from oxygen-containing compound and application
CN114377624B (en) * 2020-10-16 2024-03-19 中国科学院大连化学物理研究所 Coke regulation reactor, device for preparing low-carbon olefin from oxygen-containing compound and application
CN115304442A (en) * 2021-05-08 2022-11-08 国家能源投资集团有限责任公司 Preparation of C from methanol 2 -C 3 Process and apparatus for olefins

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