CN101265150A - Method for producing low-carbon olefins from oxygen-containing compound - Google Patents

Method for producing low-carbon olefins from oxygen-containing compound Download PDF

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CN101265150A
CN101265150A CNA200810043296XA CN200810043296A CN101265150A CN 101265150 A CN101265150 A CN 101265150A CN A200810043296X A CNA200810043296X A CN A200810043296XA CN 200810043296 A CN200810043296 A CN 200810043296A CN 101265150 A CN101265150 A CN 101265150A
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catalyst
reaction zone
sapo
oxygen
containing compound
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齐国祯
钟思青
金永明
王华文
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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 of producing low-carbon alkenes by using oxygenated compounds, mainly solves the problem of not high yield coefficient of the low-carbon alkenes in prior art. The method is that a spent catalyst after steam stripping is divided into two parts, wherein, a first part is put in a regenerator to contact with a regenerating medium to form a regenerated catalyst; a second part is put in a heat interchanger to return to the bottom of a reacting region after the heat exchange with heat-transfer mediums; at least one part of the regenerated catalyst is put in a steam stripping region through a catalyst standpipe to be mixed with the spent catalyst, wherein, the heat-transfer mediums are selected from at least one of the raw material or products, and the ratio between the heat-transfer medium weight flow rate and the raw material weight flow rate is 0.01 to 0.5:1; the technical proposal that the heat-transfer mediums are injected into the reacting region from at least one position which is axially separated along the reacting region after the heat exchange of the catalyst in the second part better solves the problems, and the method can be used in the industrial production of the low-carbon alkenes.

Description

The method of producing low-carbon olefins from oxygen-containing compound
Technical field
The present invention relates to a kind of method 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 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 oxygenate is 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 a kind of method of new producing low-carbon olefins from oxygen-containing compound is provided.This method is used for the production of low-carbon alkene, has that yield of light olefins is higher, low-carbon alkene production technique economy advantage of higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method of producing low-carbon olefins from oxygen-containing compound, said method comprising the steps of: a kind of fluidized-bed reactor (a) is provided, comprise reaction zone, race way, stripping zone, disengaging zone, the raw material that comprises described oxygenatedchemicals is contacted under the condition for validity of described reaction zone with comprising the silicoaluminophosphamolecular molecular sieve catalyzer, form the logistics 1 that comprises low-carbon alkene, catalyzer; (b) catalyzer in the described logistics 1 is separated in the disengaging zone, forms reclaimable catalyst, and described reclaimable catalyst enters stripping zone; (c) will be divided into two portions through steam stripped described reclaimable catalyst, wherein first part enters revivifier by the catalyst transport pipeline and contacts with regenerating medium, form regenerated catalyst, second section enters interchanger by the catalyst transport pipeline, with the bottom that turns back to described reaction zone after the heat transferring medium heat exchange; (d) at least a portion of described regenerated catalyst enters in the catalyst transport standpipe, contact with the lifting medium, the regenerated catalyst of described at least a portion is thus lifted to the disengaging zone of described reactor, after the gas-solid cyclone separator separation, the regenerated catalyst of described at least a portion enters stripping zone, mixes with described reclaimable catalyst; Wherein, described heat transferring medium is selected from least a in raw material or the product, heat transferring medium is 0.01~0.5: 1 with the ratio of the weight flow rate of raw material, behind heat transferring medium and the second section catalyst heat exchange from being injected into reaction zone along axially spaced at least one position of described reaction zone.
In the technique scheme, described oxygen-containing compound material is selected from least a in methyl alcohol, the dme, and preferred version is selected from methyl alcohol; Silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56, preferred version is selected from least a among SAPO-18 or the SAPO-34, and more preferably scheme is selected from SAPO-34; Described reactor is fast fluidized bed or riser tube, and preferred version is selected from fast fluidized bed; Described heat transferring medium is selected from least a in the diolefine in methyl alcohol, dme, carbon four above hydrocarbon, low-carbon alkanes, ethene, propylene or the product, preferred version is selected from least a in the diolefine in methyl alcohol, dme, carbon four above hydrocarbon or the product, more preferably scheme is selected from least a in dme, C 4 olefin or the diolefine of unreacted methanol, generation, and most preferably scheme is selected from least a in the dme of unreacted methanol, generation or the diolefine; Heat transferring medium is 0.05~0.2: 1 with the ratio preferred version of the weight flow rate of raw material, and more preferably scheme is 0.06~0.1: 1; Described distance along axially spaced at least one inlet of reaction zone to reaction zone bottom feed grid distributor is 1/8~1/2 reaction zone height, and preferred version is 1/6~1/4 reaction zone height; Stripping medium in the described stripping zone is a water vapour; Lifting medium in the described catalyzer standpipe is a water vapour; Described condition for validity is: reaction pressure is counted 0~1MPa with gauge pressure, and temperature of reaction is 300~600 ℃, and the raw material weight hourly space velocity is 1~5 hour -1, the average coke content of reaction zone catalyzer is 0.01~7% weight, and the described condition for validity of preferred version is: reaction pressure is counted 0.01~0.3MPa with gauge pressure, and temperature of reaction is 400~500 ℃, and the raw material weight hourly space velocity is 6~25 hours -1, the average coke content of reaction zone catalyzer is 1~4% weight; The reclaimable catalyst that described first part enters revivifier by the catalyst transport pipeline accounts for 5~90% weight of total reclaimable catalyst, and preferred version is 15~40% weight; 10~100% weight of described regenerated catalyst enter in the catalyst transport standpipe, contact with promoting medium, and preferred version is selected from 50~100% weight.
Weight hourly space velocity of the present invention is defined as the raw material inlet amount that comprises in unit time active ingredient (as the molecular sieve) content divided by the reaction zone inner catalyst.
Carbon deposit quality on the catalyzer that coke content method of calculation of the present invention are certain mass is divided by described catalyst quality.Carbon deposit measuring method on the catalyzer is as follows: will mix the catalyst mix that has carbon deposit comparatively uniformly, the accurate carbon-bearing catalyzer of weighing certain mass then, be put in the pyrocarbon analyser and burn, the carbonic acid gas quality that generates by infrared analysis burning, thus carbonaceous amount on the catalyzer obtained.
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 blended method, 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 yield requirement.Known in the field, in the existing circulating fluidized bed technique, as fluid catalytic cracking (FCC), be regenerated catalyst directly to be turned back to riser reaction zone contact with raw material, 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.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 enter 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, the heat height that obtains of reaction zone then, 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 by 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.Method of the present invention has also reduced the height of revivifier to a certain extent.
In addition, with the dme recycle and reuse of unreacted methanol, generation to improve the total conversion rate of oxygenatedchemicals, and with the low value-added material that generates in the product, as carbon four above hydrocarbon, loop back reactor, be converted into low-carbon alkene again, all can improve the total recovery of low-carbon alkene, improve the economy of technology.Owing to materials such as the methyl alcohol that reclaims from centrifugal station, dme, carbon four above hydrocarbon need heating before entering reaction zone, therefore, the present invention passes through above-mentioned substance and the heat exchange of second section reclaimable catalyst, not only can heat above-mentioned substance, but also can reduce the temperature of second section reclaimable catalyst, realize purpose from the reaction zone heat-obtaining.In addition, the present invention also adopts the heat transferring medium after the heat exchange by being injected into reaction zone along axially spaced at least one position of reaction zone, plays and reduces the raw material dividing potential drop, the effect that improves selectivity of light olefin.
Adopt technical scheme of the present invention: described oxygen-containing compound material is selected from least a in methyl alcohol, the dme; Silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56; Described reactor is fast fluidized bed or riser tube; Stripping medium in the described stripping zone is a water vapour; Lifting medium in the described catalyzer standpipe is a water vapour; Described distance along axially spaced at least one inlet of reaction zone to reaction zone bottom feed grid distributor is 1/8~1/2 reaction zone height; Described condition for validity is: reaction pressure is counted 0~1MPa with gauge pressure, and temperature of reaction is 300~600 ℃, and the raw material weight hourly space velocity is 1~50 hour -1, the average coke content of reaction zone catalyzer is 0.01~7% weight; The reclaimable catalyst that described first part enters revivifier by the catalyst transport pipeline accounts for 5~90% weight of total reclaimable catalyst, 10~100% weight of described regenerated catalyst enter in the catalyst transport standpipe, contact with the lifting medium, yield of light olefins can reach 83.03% 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 interchanger; 8 is the reactor gas-solid cyclone separator; 9 is the reactor disengaging zone; 10 is the product collection chamber; 11 is the product gas outlet pipeline; 12 is revivifier; 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 line; 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; 23 is the heat transferring medium source line; 24 is heat transferring medium outlet line or reaction zone axial feed inlet source line.
The logistics that comprises oxygen-containing compound material enters in the reactor reaction zone 2 through feeding line 1, contact with molecular sieve catalyst, reaction generates the product that contains low-carbon alkene, carry reclaimable catalyst and enter the reactor Disengagement zone through the quick separation equipment 3 of gas-solid, wherein, most of catalyst that the quick separation equipment 3 of gas-solid is separated enters stripping zone 4, and gaseous products and part are not carried out Re-isolation by the catalyst that the quick separation equipment of gas-solid separates through entering cyclone separator 8 separation, catalyst turns back to stripping zone 4 through the dipleg of cyclone separator 8, and gaseous products enters collection chamber 10 and enters follow-up centrifugal station by outlet line 11. Be divided into two parts by the quick separation equipment 3 of gas-solid and cyclone separator 8 isolated reclaimable catalysts through behind the stripping, a part is through heat exchanger 7 and the bottom that turns back to reaction zone 2 after the heat transferring medium heat exchange of pipeline 23 by catalyst circulation inclined tube 5, heat transferring medium by pipeline 24 from entering reaction zone along the axially spaced inlet of reaction zone; A part enters coke-burning regeneration in the renewing zone 14 of regenerator 12 through catalyst transport pipeline 6 in addition, the flue gas that the coke burning generates enters follow-up energy-recuperation system through behind the cyclone separator 16 by smoke outlet tube line 17, the catalyst that regeneration is finished enters in the mixing section 20 of catalyst standpipe 21 bottoms by catalyst transport pipeline 18, mix with lifting medium 19, the regeneration catalyzing agent is promoted in the reactor Disengagement zone 9, the regenerated catalyst standpipe outlet is provided with gas-solid cyclone separator 22, isolated regeneration catalyzing agent enters in the stripping zone 4 and mixes with reclaimable catalyst, and part turns back to sustainable participation reaction in the reaction zone 2 through circulation inclined tube 5.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1~4]
In the fast fluidized bed reaction unit, the same Fig. 1 of reactive system.The reaction zone medial temperature is 500 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, pure methanol feeding, and the methyl alcohol weight hourly space velocity is 25 hours -1Catalyst type sees Table 1, stripping zone stripping medium is a water vapour, it is water vapour that regenerated catalyst standpipe promotes medium, heat transferring medium with reclaimable catalyst in the interchanger 7 is a methyl alcohol, and heat transferring medium is 0.05: 1 with the ratio of the weight flow rate of raw material, is 2 along the axially spaced inlet quantity of reaction zone, be 1/6,1/4 reaction zone height apart from reaction zone bottom grid distributor respectively, the heat transferring medium flow in two inlets is 1: 1.The reclaimable catalyst that first part enters revivifier 12 by catalyst transport pipeline 6 accounts for 40% weight of total reclaimable catalyst, 100% weight of described regenerated catalyst enters in the catalyst transport standpipe, contact with promoting medium, the average coke content of the catalyzer in the reaction zone 2 is 2.5% weight.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and experimental result sees Table 1.
Table 1
Parameter Catalyst type Low-carbon alkene carbon back yield, % weight
Embodiment
1 SAPO-11 33.85
Embodiment 2 SAPO-18 79.21
Embodiment 3 SAPO-56 50.46
Embodiment 4 SAPO-34 81.35
[embodiment 5~6]
According to embodiment 4 described conditions, just change temperature of reactor, experimental result sees Table 2.
Table 2
Parameter Temperature of reaction, ℃ Low-carbon alkene carbon back yield, % weight
Embodiment
5 400 76.89
Embodiment 6 450 81.90
[embodiment 7~8]
According to embodiment 4 described conditions, just change type of feed and raw material weight hourly space velocity, experimental result sees Table 3.
Table 3
Parameter Type of feed Raw material weight hourly space velocity hour -1 Low-carbon alkene carbon back yield % weight
Embodiment
7 Dme 15 79.24
Embodiment 8 Methyl alcohol: dme=5: 1 6 80.18
[embodiment 9~11]
According to embodiment 4 described conditions, change reactor pattern, reaction pressure and raw material weight hourly space velocity, experimental result sees Table 4.
Table 4
Parameter The reactor pattern The raw material weight hourly space velocity, hour -1 Reaction pressure is in gauge pressure, MPa Low-carbon alkene carbon back yield, % weight
Embodiment
9 Riser tube 50 0.3 76.70
Embodiment 10 Fast fluidized bed 1.2 0.01 78.99
Embodiment 11 Fast fluidized bed 50 1.0 75.01
[embodiment 12~14]
According to embodiment 4 described conditions, change ratio and average coke content that reclaimable catalyst that first part enters revivifier 12 by catalyst transport pipeline 6 accounts for total reclaimable catalyst, 50% weight of described regenerated catalyst enters in the catalyst transport standpipe, contact with promoting medium, experimental result sees Table 5.
Table 5
Parameter The average coke content of reaction zone catalyzer, % weight The reclaimable catalyst weight that second section enters revivifier accounts for the ratio of total reclaimable catalyst weight, % Low-carbon alkene carbon back yield, % weight
Embodiment
12 1.0 15 74.07
Embodiment 13 4.0 60 76.81
Embodiment 14 7.0 5 74.62
[embodiment 15]
According to embodiment 4 described conditions, heat transferring medium with reclaimable catalyst in the interchanger 7 is a dme, heat transferring medium is 0.06: 1 with the ratio of the weight flow rate of raw material, along the axially spaced inlet quantity of reaction zone is 3, be 1/8,1/6,1/4 reaction zone height apart from reaction zone bottom grid distributor respectively, heat transferring medium flow in three inlets is 1: 1: 1, and yield of light olefins is 81.221% weight.
[embodiment 16]
According to embodiment 4 described conditions, heat transferring medium with reclaimable catalyst in the interchanger 7 is a 1-butylene, heat transferring medium is 0.1: 1 with the ratio of the weight flow rate of raw material, along the axially spaced inlet quantity of reaction zone is 1, apart from reaction zone bottom grid distributor is 1/2 reaction zone height, and yield of light olefins is 82.52% weight.
[embodiment 17]
According to embodiment 4 described conditions, heat transferring medium with reclaimable catalyst in the interchanger 7 is the mixture of methyl alcohol and diolefine, the weight ratio of methyl alcohol and diolefine is 10: 1, and heat transferring medium is 0.2: 1 with the ratio of the weight flow rate of raw material, and yield of light olefins is 81.24% weight.
[embodiment 18]
According to embodiment 4 described conditions, the heat transferring medium with reclaimable catalyst in the interchanger 7 is an ethene, and heat transferring medium is 0.01: 1 with the ratio of the weight flow rate of raw material, and yield of light olefins is 80.81% weight.
[embodiment 19]
According to embodiment 4 described conditions, heat transferring medium with reclaimable catalyst in the interchanger 7 is the mixture of methyl alcohol and ethene, the part by weight of methyl alcohol and ethene is 5: 1, and heat transferring medium is 0.5: 1 with the ratio of the weight flow rate of raw material, and yield of light olefins is 83.03% weight.
[comparative example 1]
According to embodiment 4 described conditions, just regenerated catalyst is directly turned back to reaction zone 2 bottoms, low-carbon alkene carbon back yield is 78.31% weight.
[comparative example 2]
According to embodiment 13 described conditions, regenerated catalyst is directly turned back to reaction zone 2 bottoms, low-carbon alkene carbon back yield is 75.17% weight.
[comparative example 3]
According to embodiment 4 described conditions, just change heat transferring medium into water vapour, the water vapour after the heat exchange does not enter reaction zone, and low-carbon alkene carbon back yield is 80.12% 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, a kind of method of producing low-carbon olefins from oxygen-containing compound said method comprising the steps of:
(a) for a kind of fluidized-bed reactor, comprise reaction zone, race way, stripping zone, disengaging zone, the raw material that comprises described oxygenatedchemicals is contacted under the condition for validity of described reaction zone with comprising the silicoaluminophosphamolecular molecular sieve catalyzer, form the logistics 1 that comprises low-carbon alkene, catalyzer;
(b) catalyzer in the described logistics 1 is separated in the disengaging zone, forms reclaimable catalyst, and described reclaimable catalyst enters stripping zone;
(c) be divided into two portions through steam stripped described reclaimable catalyst, wherein first part enters revivifier by the catalyst transport pipeline and contacts with regenerating medium, form regenerated catalyst, second section enters interchanger by the catalyst transport pipeline, with the bottom that turns back to described reaction zone after the heat transferring medium heat exchange;
(d) at least a portion of described regenerated catalyst enters in the catalyst transport standpipe, contact with the lifting medium, the regenerated catalyst of described at least a portion is thus lifted to the disengaging zone of described reactor, after the gas-solid cyclone separator separation, the regenerated catalyst of described at least a portion enters stripping zone, mixes with described reclaimable catalyst;
Wherein, described heat transferring medium is selected from least a in raw material or the product, heat transferring medium is 0.01~0.5: 1 with the ratio of the weight flow rate of raw material, behind heat transferring medium and the second section catalyst heat exchange from being injected into reaction zone along axially spaced at least one position of described reaction zone.
2,, it is characterized in that described oxygen-containing compound material is selected from least a in methyl alcohol, the dme according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 1; Described silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56; Described reactor is fast fluidized bed or riser tube; Described heat transferring medium is selected from least a in the diolefine in methyl alcohol, dme, carbon four above hydrocarbon, low-carbon alkanes, ethene, propylene or the product, and heat transferring medium is 0.05~0.2: 1 with the ratio of the weight flow rate of raw material; Described distance along axially spaced at least one inlet of reaction zone to reaction zone bottom feed grid distributor is 1/8~1/2 reaction zone height.
3,, it is characterized in that described oxygen-containing compound material is selected from methyl alcohol according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 2; Described silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18 or the SAPO-34; Described reactor is a fast fluidized bed; Described heat transferring medium is selected from least a in the diolefine in methyl alcohol, dme, carbon four above hydrocarbon or the product, and heat transferring medium is 0.06~0.1: 1 with the ratio of the weight flow rate of raw material; Described distance along axially spaced at least one inlet of reaction zone to reaction zone bottom feed grid distributor is 1/6~1/4 reaction zone height.
4,, it is characterized in that described silicoaluminophosphamolecular molecular sieve is SAPO-34 according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 3; Described heat transferring medium is selected from least a in dme, C 4 olefin or the diolefine of unreacted methanol, generation.
5,, it is characterized in that described heat transferring medium is selected from least a in the dme of unreacted methanol, generation or the diolefine according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 4.
6,, it is characterized in that the stripping medium in the described stripping zone is a water vapour according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 1; Lifting medium in the described catalyzer standpipe is a water vapour.
7, according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 1, it is characterized in that described condition for validity is: reaction pressure is counted 0~1MPa with gauge pressure, and temperature of reaction is 300~600 ℃, and the raw material weight hourly space velocity is 1~50 hour -1, the average coke content of reaction zone catalyzer is 0.01~7% weight.
8, according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 7, it is characterized in that described condition for validity is: reaction pressure is counted 0.01~0.3MPa with gauge pressure, and temperature of reaction is 400~500 ℃, and the raw material weight hourly space velocity is 6~25 hours -1, the average coke content of reaction zone catalyzer is 1~4% weight.
9,, it is characterized in that reclaimable catalyst that described first part enters revivifier by the catalyst transport pipeline accounts for 5~90% weight of total reclaimable catalyst according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 1; 10~100% weight of described regenerated catalyst enter in the catalyst transport standpipe, contact with the lifting medium.
10,, it is characterized in that reclaimable catalyst that described first part enters revivifier by the catalyst transport pipeline accounts for 15~40% weight of total reclaimable catalyst according to the method for the described producing low-carbon olefins from oxygen-containing compound of claim 9; 50~100% weight of described regenerated catalyst enter in the catalyst transport standpipe, contact with the lifting medium.
CNA200810043296XA 2008-04-24 2008-04-24 Method for producing low-carbon olefins from oxygen-containing compound Pending CN101265150A (en)

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Cited By (9)

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CN101898927A (en) * 2009-05-27 2010-12-01 中国石油化工股份有限公司 Method for preparing light olefins from alcohols
CN102276383A (en) * 2010-06-11 2011-12-14 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
CN102464525A (en) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 Method for converting methanol into low-carbon olefins
CN102875280A (en) * 2011-07-12 2013-01-16 中国石油化工股份有限公司 Reaction unit for converting methanol into low-carbon olefins
CN103387477A (en) * 2013-08-06 2013-11-13 神华集团有限责任公司 System and process for preparing olefin from organic oxygen-containing compound for reducing catalyst coking
US8692045B2 (en) 2010-11-17 2014-04-08 China Petroleum & Chemical Corporation Processes for producing light olefins
US9212105B2 (en) 2010-03-03 2015-12-15 Shanghai Research Institute Of Petrochemical Technology, Sinopec Processes for producing at least one light olefin
US9221724B2 (en) 2010-06-11 2015-12-29 China Petroleum & Chemical Corporation Processes for producing light olefins
CN105669339A (en) * 2014-11-20 2016-06-15 中国石油化工股份有限公司 Method for preparing low carbon olefins from oxygen-containing compound by conversion

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101898927A (en) * 2009-05-27 2010-12-01 中国石油化工股份有限公司 Method for preparing light olefins from alcohols
US9212105B2 (en) 2010-03-03 2015-12-15 Shanghai Research Institute Of Petrochemical Technology, Sinopec Processes for producing at least one light olefin
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
CN102276383A (en) * 2010-06-11 2011-12-14 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
US9221724B2 (en) 2010-06-11 2015-12-29 China Petroleum & Chemical Corporation Processes for producing light olefins
US9295963B2 (en) 2010-11-17 2016-03-29 China Petroleum & Chemical Corporation Processes for producing light olefins
US8692045B2 (en) 2010-11-17 2014-04-08 China Petroleum & Chemical Corporation Processes for producing light olefins
CN102464525A (en) * 2010-11-17 2012-05-23 中国石油化工股份有限公司 Method for converting methanol into low-carbon olefins
CN102875280A (en) * 2011-07-12 2013-01-16 中国石油化工股份有限公司 Reaction unit for converting methanol into low-carbon olefins
CN102875280B (en) * 2011-07-12 2016-05-18 中国石油化工股份有限公司 Methanol conversion is the reaction unit of low-carbon alkene
CN103387477A (en) * 2013-08-06 2013-11-13 神华集团有限责任公司 System and process for preparing olefin from organic oxygen-containing compound for reducing catalyst coking
CN105669339A (en) * 2014-11-20 2016-06-15 中国石油化工股份有限公司 Method for preparing low carbon olefins from oxygen-containing compound by conversion
CN105669339B (en) * 2014-11-20 2018-05-11 中国石油化工股份有限公司 The production method of converting oxygen-containing compound to low-carbon olefins

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