CN102276406B - Method for increasing yield of propylene - Google Patents
Method for increasing yield of propylene Download PDFInfo
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- CN102276406B CN102276406B CN201010199918.5A CN201010199918A CN102276406B CN 102276406 B CN102276406 B CN 102276406B CN 201010199918 A CN201010199918 A CN 201010199918A CN 102276406 B CN102276406 B CN 102276406B
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- 238000000034 method Methods 0.000 title claims abstract description 38
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 146
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims description 54
- 239000002994 raw material Substances 0.000 claims description 38
- 239000004215 Carbon black (E152) Substances 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- -1 C 4 olefin Chemical class 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 230000002779 inactivation Effects 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 25
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001131 transforming effect Effects 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 2
- 239000005977 Ethylene Substances 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 39
- 238000010521 absorption reaction Methods 0.000 description 25
- JGNPSJMNGPUQIW-UHFFFAOYSA-N [C].CC=C Chemical compound [C].CC=C JGNPSJMNGPUQIW-UHFFFAOYSA-N 0.000 description 14
- 238000004587 chromatography analysis Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for increasing the yield of propylene, and mainly solves the problem that the yield of carbon groups of the propylene is low in the prior art. In the invention, the problem is better solved by the technical scheme that three reaction zones are set, the first fast bed reaction zone is used for preparing olefin through methanol transformation, and the riser reaction zone and the second fast bed reaction zone are connected in series and used for transforming ethylene, hydrocarbons above C4 and unreacted methanol or dimethyl ether; and the technical scheme can be used for the industrial production of low-carbon olefin.
Description
Technical field
The present invention relates to a kind of method for increasing yield of propylene.
Technical background
Propylene, is important basic chemical industry raw material, and its demand is in continuous increase.Usually, propylene is to produce by petroleum path, but due to the limited supply of petroleum resources and higher price, the cost of being produced propylene by petroleum resources constantly increases.In recent years, people start to greatly develop the preparing propylene transformed technology of alternative materials.Wherein, the important alternative materials for light olefin production of one class is oxygenatedchemicals, such as 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 technique is very ripe, can realize the industrial scale of up to a million tonnes.Due to the popularity in oxygenatedchemicals source, add and transform the economy that generates light olefin technique, so be subject to increasing attention by the technique of oxygen-containing compound conversion to produce olefine (OTO).
In US4499327 patent, silicoaluminophosphamolecular molecular sieve catalyst is applied to preparing olefin by conversion of methanol technique and studies in detail, think that SAPO-34 is the first-selected catalyzer of MTO technique.SAPO-34 catalyzer has very high light olefin selectivity, and activity is also higher, and can make methanol conversion is reaction times of light olefin to be less than the degree of 10 seconds, more even reaches in the reaction time range of riser tube.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene in US6166282, are announced, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, rise to after the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Due to reaction after product gas and catalyzer sharp separation, effectively prevent the generation of secondary reaction.Through analog calculation, compared with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all greatly reduce.
In CN1723262, having announced with the multiple riser reaction unit of central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises multiple riser reactors, gas solid separation district, multiple offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the disengaging zone of setting, catalyzer and gas product are separated.
In Chinese invention patent 200810043971.9, announce a kind of method that improves yield of light olefins, the first top, reaction zone that it is low-carbon alkene in methanol conversion that the method adopts arranges a second reaction zone, and this second reaction zone diameter is greater than the first reaction zone, the residence time with the gas product that increases by the first reaction zone outlet in second reaction zone, make unreacted methyl alcohol, the above hydrocarbon of the dme generating and carbon four continues reaction, reach the object that improves yield of light olefins, the method also comprises that the charging of second reaction zone can be the above hydrocarbon of freshening carbon four through separating.Although the method can improve the first trip of low-carbon alkene to a certain extent, but because the first reaction zone catalyzer is out with more carbon distribution, and the above hydrocarbon pyrolysis of carbon four needs higher catalyst activity, therefore in the method, the above hydrocarbon changing effect of the carbon four in second reaction zone is still on the low side, thereby causes propene yield on the low side.
A kind of announced methanol production propylene in EP0448000 and EP0882692 method, first methyl alcohol be converted into DME and water, then mixture is transported to First reactor, and adds steam in this reactor.In the first reactor, methyl alcohol and (or) dme or its mixture contact and react with catalyzer, catalyzer adopts the special ZSM-5 catalyzer containing ZnO and CdO, 280～570 DEG C of temperature of reaction, pressure 0.01～0.1MPa, prepares the product taking propylene as main hydro carbons.Heavier product is as C
5 +hydrocarbon continues in second reactor, to react the hydro carbons being converted into taking propylene as master, sends separator after cooling back to.Product is compressed, can obtain purity after further refining is 97% chemical grade propylene.But in this technique, adopt multiple fixed-bed reactor, due to the activity restriction of catalyzer, therefore need frequent blocked operation, and heat-obtaining problem is also very complicated.
Therefore, need a kind of novel method, with producing more propylene as much as possible, improve the economy of production of propylene technique.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 propylene carbon base absorption rate existing in prior art, and a kind of new method for increasing yield of propylene is provided.The method is for the production of low-carbon alkene, has that propylene carbon base absorption rate is higher, the good advantage of production of propylene process economy.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method for increasing yield of propylene, mainly comprise the following steps: the first raw material that (1) is mainly methyl alcohol enters the first fast fluidized bed reaction zone, contact with the catalyzer that comprises molecular sieve, generation comprises the product stream I of ethene, propylene, the above hydrocarbon of C4, forms the catalyzer of inactivation simultaneously; (2) catalyzer of described inactivation enters revivifier regeneration, the regenerated catalyst forming enters riser reaction zone, contact with the second raw material, the product and the catalyzer that generate enter the second fast fluidized bed reaction zone, contact with the catalyzer coming from stripping zone with the 3rd raw material, generation comprises the product stream II of propylene, forms the catalyzer of pre-carbon deposit simultaneously, enters the pre-stripper of whirlwind; (3) product stream II and the product stream I after the pre-stripper of whirlwind separates is mixed into centrifugal station, and the catalyzer of described pre-carbon deposit enters stripping zone, returns to the first fast bed reaction zone after stripping; Wherein, described regenerated catalyst activity index is 0.8～1.0, and described the second raw material is the above hydrocarbon of described C4, and described the 3rd raw material is mainly methyl alcohol and ethene.
In technique scheme, at least one in SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, SAPO-56, ZSM-5, ZSM-34 of described molecular screening, preferred version is selected from least one in SAPO-34 or ZSM-5, and most preferably scheme is selected from SAPO-34; Described regenerated catalyst activity index is 0.9～1.0; In described the second raw material, C 4 olefin mass content is greater than 60%; Temperature of reaction in described the first fast bed reaction zone is 380～480 DEG C, preferred version is 400～440 DEG C, 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 riser reaction zone is 510～650 DEG C, preferred version is 550～600 DEG C, 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 450～630 DEG C, preferred version is 470～550 DEG C, 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 0.3～1.8% weight, and preferred version is 0.5～1.2% weight; The described point pre-stripper that revolves is connected with the second fast bed reaction zone exit end, passes into water vapour carry out stripping at catalyst outlet end.
In the present invention, low-carbon alkene refers to ethene and propylene.
Regenerated catalyst activity index is for embodying the regeneration level of decaying catalyst, taking live catalyst as benchmark, the amount that transforms methyl alcohol with each catalyzer under rigid condition is carried out relatively, and method of calculation are: regenerated catalyst activity index=(quantity of methyl alcohol that under quantity of methyl alcohol/certain condition that under certain condition, regenerated catalyst transforms, live catalyst transforms) × 100%.
The second raw material of the present invention is selected from the above hydrocarbon of the hybrid C 4 generating in preparing olefin by conversion of methanol process, and wherein alkene mass content is greater than 60%; In the 3rd raw material, the mass content of methyl alcohol and ethene is greater than 75%, and the mass ratio of methyl alcohol and ethene is 0.2～0.5: 1, and wherein methyl alcohol is from the unreacted methanol of methanol feedstock or centrifugal station recovery, and ethene is from the ethene producing in methanol-to-olefins process; In the second raw material and the 3rd raw material, can add a certain amount of water vapour as thinner, the mass ratio of water vapour and the second raw material or the 3rd raw material is less than 1: 3; The mass ratio of methyl alcohol and the second raw material is between 1: 0.1～0.3, and the mass ratio of the second raw material and the 3rd raw material is 1.0～1.5: between 1.
In the method for the invention, be provided with three reaction zones, the first fast bed reaction zone is relatively independent, for preparing olefin by conversion of methanol, riser reaction zone and the series connection of the second fast bed reaction zone are used for transforming ethene, the above hydrocarbon of carbon four and unreacted methyl alcohol or dme etc., reach the object that improves feed stock conversion and propene yield.Wherein, the second fast bed reaction zone linear speed significantly reduces, ensure the enough reaction times, maximized conversion ethene, the above hydrocarbon of carbon four and unreacted methyl alcohol or dme are propylene, and catalyzer in riser reaction zone is directly from revivifier, the activity index of the temperature of carrying and catalyzer self is all higher, is conducive to the conversion of the above hydrocarbon of carbon four to low-carbon alkene.In addition, regenerated catalyst by riser reaction zone and the second fast bed reaction zone after, after reaction, can accumulate a certain amount of carbon deposit, the inventor finds by research, a certain amount of carbon distribution is conducive to improve the selectivity that methanol conversion is low-carbon alkene, so return with the catalyzer of a certain amount of carbon distribution behind the first fast bed reaction zone when this part, can obviously improve the selectivity of light olefin in the first fast bed reaction zone.Simultaneously, because the reactions such as the carbon four above hydrocarbon pyrolysiss are thermo-negative reaction, the heat of the catalyst entrainment after therefore having reacted in riser reaction zone and the second fast bed reaction zone declines, return behind the first fast bed reaction zone, the heat-obtaining load that has alleviated the first fast bed reaction zone, has effectively utilized heat.Therefore, adopt described method of the present invention, both effectively improved the yield of object product low-carbon alkene, optimized again energy distribution and utilization.
Adopt technical scheme of the present invention: at least one in SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, SAPO-56, ZSM-5, ZSM-34 of described molecular screening; In described the second raw material, C 4 olefin mass content is greater than 60%; Temperature of reaction in described the first fast bed reaction zone is 380～480 DEG C, 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 riser reaction zone is 510～650 DEG C, 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 450～630 DEG C, 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 0.3～1.8% weight, the described point pre-stripper that revolves is connected with the second fast bed reaction zone exit end, pass into water vapour at catalyst outlet end and carry out stripping, low-carbon alkene carbon base absorption rate reaches 90.01% weight, wherein propylene carbon base absorption rate is 70.52%, has obtained good technique effect.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is the first fast bed reaction zone bottom feed; 2 is the first fast bed reaction zone; 3 is gas-solid sharp separation equipment; 4 is stripping zone; 5 return to the line of pipes of the first fast bed reaction zone for stripping stage catalyzer; 6 is 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 reactor product outlet line; 12 is revivifier gas solid separation district; 13 is regenerating medium source line; 14 is revivifier breeding blanket; 15 is external catalyst cooler for regenerator; 16 is revivifier gas-solid cyclone separator; 17 is regenerated flue gas outlet line; 18 is regenerated catalyst inclined tube; 19 is riser reaction zone charging; 20 is buffering mixing zone, bottom, riser reaction zone; 21 is riser reaction zone; 22 is the pre-stripper of the second fast bed reaction zone outlet whirlwind; 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; 26 is stripped vapor.
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, after gas-solid sharp separation equipment 3, enters gas solid separation district 9, and decaying catalyst enters revivifier regeneration from reclaimable catalyst inclined tube 6.Catalyzer after having regenerated enters the catalyzer buffer zone 20 of 21 bottoms, riser reaction zone from regenerated catalyst inclined tube 18, after contacting with from the second raw material of pipeline 19, enter riser reaction zone 21, the product that riser reaction zone 21 exports and catalyzer enter in the second fast bed reaction zone 25, again contact with the 3rd raw material, generate low-carbon alkene product stream II, after the pre-stripper 22 of whirlwind separates, in product introduction reactor disengaging zone 9, after mixing with product stream I, enter centrifugal station from outlet line 11.In the second fast bed reaction zone 25, reacted catalyzer returns the first fast bed reaction zone 2 from pipeline 5.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
In reaction unit as shown in Figure 1, the first fast bed reaction zone medial temperature is 480 DEG C, and reaction pressure is counted 0.1MPa with gauge pressure, and linear gas velocity is 1.5 meter per seconds; Riser reaction zone medial temperature is 550 DEG C, 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 470 DEG C, 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, charging is 2 kgs/hr, catalyzer is SAPO-34, the second raw material is the above hydrocarbon of carbon four generating in product, wherein C 4 olefin mass content is 88%, the 3rd raw material is methyl alcohol and ethene, and the weight ratio of methyl alcohol and ethene is 0.3: 1, and ethene is from the ethene generating in product.The mass ratio of methyl alcohol and carbon four above hydrocarbon is: 1: 0.2, the mass ratio of the total amount of the above hydrocarbon of carbon four and methyl alcohol and ethene is: 1.0: 1, regenerated catalyst activity index is 0.95, keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, low-carbon alkene carbon base absorption rate reaches 88.57% weight, and wherein propylene carbon base absorption rate is 67.12%.
[embodiment 2]
According to the condition described in embodiment 1, the first fast bed reaction zone medial temperature is 440 DEG C, and reaction pressure is counted 0.2MPa with gauge pressure, and linear gas velocity is 2.5 meter per seconds; Riser reaction zone medial temperature is 650 DEG C, 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 DEG C, 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 second raw material is the above hydrocarbon of carbon four, wherein C 4 olefin mass content is 91%, the 3rd raw material is methyl alcohol and ethene, the weight ratio of methyl alcohol and ethene is 0.5: 1, keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate reaches 89.05% weight, and wherein propylene carbon base absorption rate is 68.22%.
[embodiment 3]
According to the condition described in embodiment 1, the first fast bed reaction zone medial temperature is 380 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and linear gas velocity is 0.8 meter per second; Riser reaction zone medial temperature is 510 DEG C, 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 450 DEG C, 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 1.2% weight.The second raw material is the above hydrocarbon of carbon four, wherein C 4 olefin mass content is 61%, the 3rd raw material is methyl alcohol and ethene, the weight ratio of methyl alcohol and ethene is 0.3: 1, keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate reaches 84.11% weight, and wherein propylene carbon base absorption rate is 60.35%.
[embodiment 4]
According to the condition described in embodiment 1, the first fast bed reaction zone medial temperature is 400 DEG C, and reaction pressure is counted 0.3MPa with gauge pressure, and linear gas velocity is 1.0 meter per seconds; Riser reaction zone medial temperature is 600 DEG C, 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 550 DEG C, and reaction pressure is counted 0.3MPa with gauge pressure, and linear gas velocity is 1.5 meter per seconds.The second raw material is the above hydrocarbon of carbon four, wherein C 4 olefin mass content is 88%, the 3rd raw material is methyl alcohol, dme and ethene, the weight ratio of methyl alcohol, dme and ethene is 0.2: 0.15: 1, keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate reaches 84.76% weight, and wherein propylene carbon base absorption rate is 61.71%.
[embodiment 5]
According to the condition described in embodiment 1, the first fast bed reaction zone medial temperature is 425 DEG C, and reaction pressure is counted 0.15MPa with gauge pressure, and linear gas velocity is 1.5 meter per seconds; Riser reaction zone medial temperature is 600 DEG C, and reaction pressure is counted 0.15MPa with gauge pressure, and linear gas velocity is 6.0 meter per seconds; The second fast bed reaction zone medial temperature is 530 DEG C, and reaction pressure is counted 0.15MPa with gauge pressure, and linear gas velocity is 1.3 meter per seconds.The carbon deposition quantity of pre-carbon deposition catalyst is 1.05% weight.The stability that keeps catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate reaches 88.43% weight, and wherein propylene carbon base absorption rate is 69.57%.
[embodiment 6]
According to the condition described in embodiment 5, just changing regenerated catalyst activity index is 0.8, keeps the stability of catalyst flow control, and reactor outlet product adopts online gas chromatographic analysis, low-carbon alkene carbon base absorption rate reaches 86.27% weight, and wherein propylene carbon base absorption rate is 65.17%.
[embodiment 7]
According to the condition described in embodiment 2, in the second raw material charging, sneak into water vapour, the weight ratio of water vapour and the second raw material is 1: 3, in the 3rd raw material, sneak into water vapour, the weight ratio of water vapour and the 3rd raw material is 1: 3, and pre-carbon deposition catalyst carbon deposition quantity is 0.5% (weight), keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate reaches 87.13% weight, and wherein propylene carbon base absorption rate is 67.48%.
[embodiment 8～14]
According to the condition described in embodiment 1, just change the type of molecular sieve in catalyzer, experimental result is in table 1.
Table 1
| Parameter | Molecular sieve type | Yield of light olefins, % (weight) | Propylene carbon base absorption rate, % (weight) |
| Embodiment 8 | SAPO-20 | 79.63 | 60.12 |
| Embodiment 9 | SAPO-18 | 85.41 | 63.77 |
| Embodiment 10 | SAPO-56 | 66.81 | 47.68 |
| Embodiment 11 | ZSM-5 | 84.91 | 67.52 |
| Embodiment 12 | ZSM-34 | 78.39 | 59.08 |
| Embodiment 13 | SAPO-34+ZSM-5 (weight ratio is 2: 1) | 87.44 | 64.17 |
| Embodiment 14 | SAPO-34+SAPO-18 (weight ratio is 2: 1) | 87.06 | 65.17 |
[embodiment 15]
According to the condition described in embodiment 5, just changing regenerated catalyst activity index is 0.9, keeps the stability of catalyst flow control, and reactor outlet product adopts online gas chromatographic analysis, low-carbon alkene carbon base absorption rate reaches 87.22% weight, and wherein propylene carbon base absorption rate is 67.06%.
[embodiment 16]
According to the condition described in embodiment 5, just changing regenerated catalyst activity index is 0.99, keeps the stability of catalyst flow control, and reactor outlet product adopts online gas chromatographic analysis, low-carbon alkene carbon base absorption rate reaches 90.01% weight, and wherein propylene carbon base absorption rate is 70.52%.
[comparative example 1]
According to the condition described in embodiment 1, do not establish 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 base absorption rate is 79.68% weight, and wherein propylene carbon base absorption rate is 41.96%.
Obviously, adopt method of the present invention, can reach raising yield of light olefins, the especially object of propene yield, has larger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (5)
1. a method for increasing yield of propylene, mainly comprises the following steps:
(1) the first raw material that is mainly methyl alcohol enters the first fast fluidized bed reaction zone, contacts with the catalyzer that comprises molecular sieve, generates the product stream I that comprises ethene, propylene, the above hydrocarbon of C4, forms the catalyzer of inactivation simultaneously;
(2) catalyzer of described inactivation enters revivifier regeneration, the regenerated catalyst forming enters riser reaction zone, contact with the second raw material, the product and the catalyzer that generate enter the second fast fluidized bed reaction zone, contact with the catalyzer coming from stripping zone with the 3rd raw material, generation comprises the product stream II of propylene, forms the catalyzer of pre-carbon deposit simultaneously, enters the pre-stripper of whirlwind;
(3) product stream II and the product stream I after the pre-stripper of whirlwind separates is mixed into centrifugal station, and the catalyzer of described pre-carbon deposit enters stripping zone, returns to the first fast bed reaction zone after stripping;
Wherein, described regenerated catalyst activity index is 0.9～1.0, regenerated catalyst activity index is for embodying the regeneration level of decaying catalyst, taking live catalyst as benchmark, the amount that transforms methyl alcohol with each catalyzer under rigid condition is carried out relatively, and method of calculation are: regenerated catalyst activity index=(quantity of methyl alcohol that under quantity of methyl alcohol/certain condition that under certain condition, regenerated catalyst transforms, live catalyst transforms) × 100%;
Described the second raw material is the above hydrocarbon of described C4, and described the 3rd raw material is mainly methyl alcohol and ethene;
The carbon deposition quantity of the catalyzer of described pre-carbon deposit is 0.5～1.2% weight;
At least one in SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, SAPO-56, ZSM-5, ZSM-34 of described molecular screening; In described the second raw material, C 4 olefin mass content is greater than 60%;
Temperature of reaction in described the first fast fluidized bed reaction zone is 380～480 DEG C, 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 riser reaction zone is 510～650 DEG C, 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 fluidized bed reaction zone is 450～630 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and linear gas velocity is 0.8～2.0 meter per second.
2. method for increasing yield of propylene according to claim 1, is characterized in that at least one in SAPO-34 or ZSM-5 of described molecular screening.
3. method for increasing yield of propylene according to claim 2, is characterized in that described molecular screening is from SAPO-34.
4. method for increasing yield of propylene according to claim 1, is characterized in that the temperature of reaction in described the first fast fluidized bed reaction zone is 400～440 DEG C, and 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 riser reaction zone is 550～600 DEG C, 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 fluidized bed reaction zone is 470～550 DEG C, and reaction pressure is counted 0.1～0.2MPa with gauge pressure, and linear gas velocity is 1.0～1.5 meter per seconds.
5. method for increasing yield of propylene according to claim 1, is characterized in that the pre-stripper of described whirlwind is connected with the second fast fluidized bed reaction zone exit end, passes into water vapour at catalyst outlet end and carries out stripping.
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| US9718743B2 (en) | 2013-12-03 | 2017-08-01 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing a light olefin using an oxygen-containing compound, and device for use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BR112016012613B1 (en) | 2013-12-03 | 2021-08-03 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | REACTION DEVICE TO PREPARE LIGHT OLEFINS FROM METHANOL AND/OR DIMETHYL ETHER |
| KR101847474B1 (en) | 2013-12-03 | 2018-04-10 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Method for preparing a light olefin using an oxygen-containing compound |
| CN107286985B (en) * | 2016-04-12 | 2019-04-12 | 中国石油化工股份有限公司 | The method of C 4 olefin gasoline component coproduction ethylene or propylene |
| CN107961743B (en) * | 2016-10-19 | 2021-12-31 | 中国科学院大连化学物理研究所 | Fast fluidized bed reactor, device and method for preparing propylene and C4 hydrocarbons from oxygen-containing compounds |
| KR102803671B1 (en) | 2020-10-16 | 2025-05-07 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Coke-controlled reactor, apparatus and application for producing low-carbon olefins from oxygen-containing compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172926A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Propylene yield increasing method |
| CN101279875A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for increasing production of ethylene and propone |
| 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 |
-
2010
- 2010-06-11 CN CN201010199918.5A patent/CN102276406B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172926A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Propylene yield increasing method |
| CN101279875A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for increasing production of ethylene and propone |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9718743B2 (en) | 2013-12-03 | 2017-08-01 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing a light olefin using an oxygen-containing compound, and device for use thereof |
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