CN101165026B - Method for producing ethylene and propylene from methanol and dimethyl ether - Google Patents
Method for producing ethylene and propylene from methanol and dimethyl ether Download PDFInfo
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- CN101165026B CN101165026B CN2006101173520A CN200610117352A CN101165026B CN 101165026 B CN101165026 B CN 101165026B CN 2006101173520 A CN2006101173520 A CN 2006101173520A CN 200610117352 A CN200610117352 A CN 200610117352A CN 101165026 B CN101165026 B CN 101165026B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 92
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 61
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 36
- 239000005977 Ethylene Substances 0.000 title claims abstract description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 3
- 239000011949 solid catalyst Substances 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002808 molecular sieve Substances 0.000 claims description 18
- 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 18
- 239000002994 raw material Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 5
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- -1 ethylene, propylene Chemical group 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical class OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective 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 present invention relates to one kind of ethylene and propylene producing process with methanol and/or dimethyl ether as material and in high selectivity and high yield. The production process includes the following steps: 1. reaction of the material in a fluidized bed reactor through contacting with catalyst I to produce effluent I containing ethylene, propylene, C4 and C4+ hydrocarbons, andcatalyst; 2. separating the effluent I in the fast separator to deposit most solid catalyst particle, further separating in a cyclonic separator, separating the gaseous product in a post unit to obtain effluent II of C4 and C4+ hydrocarbons, ethylene product and propylene product; 3. contacting the effluent II with catalyst II in a riser reactor to produce effluent III containing ethylene, propylene, C4 and C4+ hydrocarbons, and catalyst; and 4. separating the effluent III with a cyclonic separator in a setter, and separating the gaseous product in a post unit. The production process may be applied in industrial production.
Description
Technical field
The present invention relates to a kind of method of producing ethene and propylene, particularly about adopting at least two fluidized-bed reactors, the method for ethene and propene yield in realization raising methyl alcohol or the dimethyl ether catalysis reaction by methyl alcohol or dme.
Background technology
Petrochemical complex is a mainstay industry important in the national economy, for industry, agricultural, departments such as traffic and national defence provide a large amount of industrial chemicals, is one of related and branch of industry that drive property is stronger in the national economy.Propylene and ethene then are to constitute modern petrochemical complex of paramount importance two big basic materials.
Large derived product of ethene mainly contains polyethylene, oxyethane, ethylene glycol, polyvinyl chloride, vinylbenzene, vinyl acetate between to for plastic etc.The size of ethylene yield is to weigh the sign of a national petrochemical industry and even national economy development degree.Propylene is mainly used in produces polypropylene, isopropyl benzene, oxo-alcohols, vinyl cyanide, propylene oxide, vinylformic acid, Virahol etc., and wherein polypropylene accounts for the over half of world's propylene demand.At present, 67% propylene is produced the byproduct of ethene from steam cracking in the world, and 30% produces the byproduct of vapour, diesel oil from refinery catalytic cracking (FCC), and a small amount of (about 3%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.Estimate that following ethene and propylene demand growth speed are faster than supply.
Higher in view of the growth rate of demand of ethene and propylene, and traditional production model presents the pressure of " supply falls short of demand ", so make-up ethylene and propylene demand need be by means of other various increasing output of ethylene propylene technology.
Oxygenatedchemicals is the promising feedstock candidate that is used to prepare alkene.Promising especially oxygen-containing compound material is alcohols such as methyl alcohol, dme, methyl ethyl ether, diethyl ether, dimethyl carbonate and methyl formate.These oxygenatedchemicalss are many can to comprise coal, recycled plastic, municipal wastes or any suitable organic materials production by fermentation or by Sweet natural gas deutero-synthetic gas, petroleum liquid, carbonaceous material.Because the source is varied, oxygenatedchemicals will become the source of finance that is used for olefin production.
All the time; coal or Sweet natural gas preparing synthetic gas, synthesising gas systeming carbinol and alkene isolation technique have had the mass-producing mature experience; but the process by methanol to olefins is breakpoint and the difficult point of synthetic gas to this industrial chain of alkene, and this solution of key technology can be for providing a new raw material route by non-oil resource production basic organic ethene, propylene.Especially in the last few years, it is high that the demand of ethene and propylene continues, and under the deficient day by day situation of petroleum resources.How to hew out a non-oil resource and produce ethene, the Coal Chemical Industry variation route of propylene, for greatly alleviating China's oil situation in short supply, promote the great-leap-forward development of the heavy chemical industry of China and the structural adjustment of raw material route, have important strategic meaning and society, economic benefit.
Document CN1356299A discloses a kind of processing method and system thereof that produces low-carbon alkene by methyl alcohol or dme.This process using silicoaluminophosphamolecular molecular sieves (SAPO-34) is as catalyzer, utilize the ultrashort contact reactor of gas-solid cocurrent flow descending formula fluidized-bed, catalyzer contacts in the ultrashort contact reactor of gas-solid cocurrent flow descending formula fluidized-bed with raw material, the reactant flow direction is descending; Catalyzer and reaction product go out to enter the gas-solid quick disconnector that is arranged on this reactor lower part behind the reactor and carry out sharp separation; Isolated catalyzer enters charcoal regeneration in the revivifier, and catalyzer is cyclic regeneration in system, and reaction cycle is carried out.This technology dme or conversion of methanol are greater than 98%.
Document CN1356299A discloses a kind of processing method and system thereof that produces low-carbon alkene by methyl alcohol or dme.This process using silicoaluminophosphamolecular molecular sieves (SAPO-34) is as catalyzer, utilize the ultrashort contact reactor of gas-solid cocurrent flow descending formula fluidized-bed, catalyzer contacts in the ultrashort contact reactor of gas-solid cocurrent flow descending formula fluidized-bed with raw material, the reactant flow direction is descending; Catalyzer and reaction product go out to enter the gas-solid quick disconnector that is arranged on this reactor lower part behind the reactor and carry out sharp separation; Isolated catalyzer enters charcoal regeneration in the revivifier, and catalyzer is cyclic regeneration in system, and reaction cycle is carried out.This technology dme or conversion of methanol are greater than 98%.But this method exists ethene and the low technical disadvantages of propene yield.
Summary of the invention
Technical problem to be solved by this invention is to have the low and low problem of selectivity of purpose product ethylene, propylene yield in the technical literature in the past, and a kind of new method by methyl alcohol or dme production ethene and propylene is provided.This method has purpose product ethene, propene yield height, the advantage that selectivity is good.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing ethene and propylene by methyl alcohol or dme, may further comprise the steps successively: a) raw material contacts through the interior catalyst I of fast fluidized bed reactor and reactor, formation contains the effluent I of ethene, propylene, carbon four and above hydrocarbon and catalyzer, and up along fast fluidized bed reactor; B) the effluent I from step a) enters the fast separation device separation, most of solid catalyst particle falls into the settling vessel lower region, the gas phase mixture that contains dust enters cyclonic separator I further to be separated, catalyst dust after the separation returns settling vessel by the dipleg of cyclonic separator I, gas products enters the later separation unit, obtains carbon four and above hydro carbons effluent II, ethylene product and propylene product after separating; C) enter riser reactor from the effluent II of step b) and contact, form the effluent III that contains ethene, propylene, carbon four and above hydrocarbon and catalyzer with catalyst I I; D) the effluent III from step c) enters settling vessel, and separates by cyclonic separator I, and gas products enters the later separation unit.
Shared identical settling vessel of fast fluidized bed reactor and riser reactor and revivifier in the technique scheme.Catalyst I and catalyst I I all are selected from silicon phosphorus aluminium type or ZSM type molecular sieve; Preferred version is selected from SAPO-34 molecular sieve or ZSM-5 molecular sieve; The temperature of reaction of first fast fluidized bed reactor is 200～580 ℃, and reaction pressure is 0.01～1.5MPa, and be 0.1～30 second duration of contact; The temperature of reaction of second riser reactor is 300～650 ℃, and reaction pressure is 0.01～1.0MPa, and be 0.1～50 second duration of contact.The temperature of reaction preferable range of first fast fluidized bed reactor is 300～550 ℃, and the reaction pressure preferable range is 0.05～1.0MPa, and duration of contact, preferable range was 1～20 second; The temperature of reaction preferable range of second riser reactor is 400～600 ℃, and the reaction pressure preferable range is 0.05～0.8MPa, and duration of contact, preferable range was 0.5～20 second.
When oxygenatedchemicals such as methyl alcohol or dimethyl ether catalysis reaction generate ethene and propylene, unavoidably to generate carbon four and above hydro carbons thereof, influence the selectivity and the yield of ethylene, propylene; The method that improves the ethylene, propylene yield or regulate the propylene and ethylene ratio is except that the selectivity of catalyst type, and the reasonable arrangement of Selection of technological conditions or technical process also is an effective means.At least a portion carbon four that will obtain after separating by the resultant by methyl alcohol or dimethyl ether catalysis reaction generation ethene and propylene that fast fluidized bed is realized among the present invention and above hydro carbons by product enter at least the second riser reactor and react, generate ethene and propylene, reach the purpose that improves ethene and propene yield.Adopt technical scheme of the present invention, adopt device as shown in Figure 1, all adopt the SAPO-34 molecular sieve catalyst at first fast fluidized bed reactor and second riser reactor, the temperature of reaction of first fast fluidized bed reactor is 300～550 ℃, reaction pressure is 0.05～1.0MPa, and be 1～20 second duration of contact; The temperature of reaction of second riser reactor is 400～600 ℃, and reaction pressure is 0.05～0.8MPa, and duration of contact, scope was that ethene and propylene diene yield can reach more than 80%, have obtained better technical effect under 0.5～20 second the condition.
Description of drawings
Fig. 1 produces the device synoptic diagram of the method for ethene and propylene by methyl alcohol or dme.
1 is material inlet among Fig. 1, the 2nd, and gas distributor or grid distributor, the 3rd, fast fluidized bed reactor, the 4th, undergauge line of pipes or riser reactor, the 5th, divide device soon, the 6th, settling vessel, the 7th, cyclonic separator, the 8th, reactor product gas; The 9th, stripper, the 10th, revivifier, the 11st, regenerator sloped tube, the 12nd, external warmer, the 13rd, the riser reactor regenerator sloped tube, the 14th, promote medium, the 15th, pre-lifter, the 16th, the riser tube opening for feed, the 17th, riser reactor, the 18th, carbon four and above hydro carbons line of pipes, the 19th, carbon four and above hydrocarbon product, the 20th, propylene, the 21st, ethene, the 22nd, separating unit.
Fig. 1 Raw is entered by the charging aperture 1 of fast fluidized bed reactor 3, after distributor or distribution grid 2 distributes and from the catalyst haptoreaction of regenerator sloped tube 11, the reaction gas solid mixture is up along fast fluidized bed reactor 3, after separating, fast separating device 5 enters settler 6, the reactor product gas that the gas-solid mixture of following a small amount of dust obtains after further separating by cyclone reactor 7 enters separative element 22 to be separated and obtains ethene 21, propylene 20 and carbon four and above hydrocarbon product 19; Carbon four and above hydrocarbon product 19 return riser reactor 17 and regenerated catalyst haptoreaction from pre-riser 15, and the reaction gas solid mixture enters cyclone separator 7 separation that are positioned at settler 6. Catalyst in the pre-riser 15 is from regenerator 10 bottoms, and passed through external warmer 12 heat exchange, and whole process is carried out continuously.
The invention will be further elaborated below by embodiment, but should be by any way as restriction of the present invention.
Embodiment
[embodiment 1]
Adopting device as shown in Figure 1, is raw material with methyl alcohol, is catalyzer with the SAPO-34 molecular sieve, first reactor adopts fast fluidized bed reactor, and second reactor adopts riser reactor, and the first reactor reaction temperature is 460 ℃, be 5 seconds duration of contact, and reaction pressure is 0.1MPa; The second reactor reaction temperature is 480 ℃, and be 3 seconds duration of contact, and reaction pressure is 0.1MPa.In the experiment, the reactor reaction product is after separating, and its carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: methanol conversion 100%, yield of ethene can reach 47.1%, propene yield 36.9%.
[embodiment 2]
Adopting device as shown in Figure 1, is raw material with the dme, is catalyzer with the SAPO-34 molecular sieve, first reactor adopts fast fluidized bed reactor, and second reactor adopts riser reactor, and the first reactor reaction temperature is 560 ℃, be 8 seconds duration of contact, and reaction pressure is 0.05MPa; The second reactor reaction temperature is 570 ℃, and be 4 seconds duration of contact, and reaction pressure is 0.05MPa.In the experiment, the reactor reaction product is after separating, and its carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: dimethyl ether conversion rate 99%, yield of ethene 50.2%, propene yield 34.3%.
[embodiment 3]
Adopt device as shown in Figure 1, with the dme is raw material, water is thinner, and the mass ratio of dme and water is 1: 2, and first reactor adopts riser reactor, with the SAPO-34 molecular sieve is catalyzer, second reactor adopts riser reactor, is catalyzer with the SAPO-34 molecular sieve, 510 ℃ of the first reactor reaction temperature, be 15 seconds duration of contact, and reaction pressure is 1.2MPa; 600 ℃ of the second reactor reaction temperature, be 8 duration of contact, reaction pressure is 1.2MPa.In the experiment, the reactor reaction product is after separating, and its carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: dimethyl ether conversion rate 100%, yield of ethene 43.2%, propene yield 32.1%.
[embodiment 4]
Adopt device as shown in Figure 1, with dme and methyl alcohol is raw material, dme is 1: 1 with the methanol quality ratio, first reactor adopts riser reactor, is catalyzer with the SAPO-34 molecular sieve, and second reactor adopts riser reactor, with the SAPO-34 molecular sieve is catalyzer, the first reactor reaction temperature is 500 ℃, and be 10 seconds duration of contact, and reaction pressure is 0.1MPa; The second reactor reaction temperature is 530 ℃, and be 6 seconds duration of contact, and reaction pressure is 0.1MPa.In the experiment, the first reactor reaction product is after separating, and all the other carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: methyl alcohol and dme total conversion rate 100%, yield of ethene 45.9%, propene yield 41.5%.
[embodiment 5]
Adopting device as shown in Figure 1, is raw material with the dme, is catalyzer with the ZSM-5 molecular sieve, first reactor adopts riser reactor, and second reactor adopts riser reactor, and the first reactor reaction temperature is 480 ℃, be 6 seconds duration of contact, and reaction pressure is 0.05MPa; The second reactor reaction temperature is 530 ℃, and be 4 seconds duration of contact, and reaction pressure is 0.05MPa.In the experiment, the first reactor reaction product is after separating, and all the other carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: dimethyl ether conversion rate 100%, yield of ethene 20.5%, propene yield 53.9%.
[embodiment 6]
Adopt device as shown in Figure 1, with the dme is raw material, first reactor adopts fast fluidized bed reactor, with the SAPO-11 molecular sieve is catalyzer, second reactor adopts riser reactor, is catalyzer with the SAPO-11 molecular sieve, and the first reactor reaction temperature is 530 ℃, be 8 seconds duration of contact, and reaction pressure is 0.04MPa; The second reactor reaction temperature is 560 ℃, and be 10 seconds duration of contact, and reaction pressure is 0.04MPa.In the experiment, the first reactor reaction product is after separating, and all the other carbon four and above hydro carbons enter second reactor reaction, and the total reaction result is: dimethyl ether conversion rate 100%, yield of ethene 18.5%, propene yield 47.3%.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just adopt the first independent fast fluidized bed reactor to react, reaction result is: methanol conversion 97%, ethene 42.2 yield %, propene yield 31.6%.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 4, just adopt the first independent fast fluidized bed reactor to react, reaction result is: methyl alcohol and dme total conversion rate 99%, yield of ethene 40.7%, propene yield 37.4%.
Claims (6)
1. a method of producing ethene and propylene by methyl alcohol or dme is a raw material with methyl alcohol or dme, may further comprise the steps successively:
A) raw material contacts through the interior catalyst I of fast fluidized bed reactor and reactor, forms the effluent I that contains ethene, propylene, carbon four and above hydrocarbon and catalyzer, and up along fast fluidized bed reactor;
B) the effluent I from step a) enters the fast separation device separation, most of solid catalyst particle falls into the settling vessel lower region, the gas phase mixture that contains dust enters cyclonic separator I further to be separated, catalyst dust after the separation returns settling vessel by the dipleg of cyclonic separator I, gas products enters the later separation unit, obtains carbon four and above hydro carbons effluent II, ethylene product and propylene product after separating;
C) enter riser reactor from the effluent II of step b) and contact, form the effluent III that contains ethene, propylene, carbon four and above hydrocarbon and catalyzer with catalyst I I;
D) the effluent III from step c) enters settling vessel, and separates by cyclonic separator I, and gas products enters the later separation unit.
2. according to the described method of producing ethene and propylene of claim 1, it is characterized in that shared identical settling vessel of fast fluidized bed reactor and riser reactor and revivifier by methyl alcohol or dme.
3. according to the described method of producing ethene and propylene of claim 1, it is characterized in that catalyst I or catalyst I I all are selected from silicon phosphorus aluminium type or ZSM type molecular sieve by methyl alcohol or dme.
4. according to the described method of producing ethene and propylene of claim 3, it is characterized in that described catalyst I or catalyst I I all are selected from SAPO-34 molecular sieve or ZSM-5 molecular sieve by methyl alcohol or dme.
5. according to the described method of producing ethene and propylene by methyl alcohol or dme of claim 1, the temperature of reaction that it is characterized in that first fast fluidized bed reactor is 200～580 ℃, and reaction pressure is 0.01～1.5MPa, and be 0.1～30 second duration of contact; The temperature of reaction of second riser reactor is 300～650 ℃, and reaction pressure is 0.01～1.0MPa, and be 0.1～50 second duration of contact.
6. according to the described method of producing ethene and propylene by methyl alcohol or dme of claim 5, the temperature of reaction that it is characterized in that first fast fluidized bed reactor is 300～550 ℃, and reaction pressure is 0.05～1.0MPa, and be 1～20 second duration of contact; The temperature of reaction of second riser reactor is 400～600 ℃, and reaction pressure is 0.05～0.SMPa, and be 0.5～20 second duration of contact.
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| CN102875293A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Reaction unit for catalytic conversion of methanol to low-carbon olefins |
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