CN103965003A - Production method of butadiene - Google Patents
Production method of butadiene Download PDFInfo
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- CN103965003A CN103965003A CN201310034421.1A CN201310034421A CN103965003A CN 103965003 A CN103965003 A CN 103965003A CN 201310034421 A CN201310034421 A CN 201310034421A CN 103965003 A CN103965003 A CN 103965003A
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- divinyl
- butylene
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 117
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- -1 ethylene, propylene Chemical group 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 45
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002808 molecular sieve Substances 0.000 claims description 22
- 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 22
- 239000011777 magnesium Substances 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 230000003247 decreasing effect Effects 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052596 spinel Inorganic materials 0.000 claims description 9
- 239000011029 spinel Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 44
- 229910052799 carbon Inorganic materials 0.000 abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 28
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 abstract description 24
- 150000001336 alkenes Chemical class 0.000 abstract description 23
- 239000006227 byproduct Substances 0.000 abstract description 13
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000001282 iso-butane Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 15
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 10
- 239000000284 extract Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical group [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 6
- 230000002779 inactivation Effects 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 210000000952 spleen Anatomy 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001273 butane Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006701 autoxidation reaction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing 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
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production method of butadiene, and mainly solves the technical problems of low utilization rate of carbon base, low utilization value of C4 hydrocarbon and low technical economic performance of olefin preparation from methanol in the prior art. A technical scheme provided by the invention includes the following steps: a) converting raw materials including methanol into a product flow including ethylene, propylene, C4 olefin and C4 above olefin under effective conditions, passing the product flow through a separation system to obtain ethylene, propylene, mixed C4 and above hydrocarbons, and other by-products; and b) separating isobutane, isobutene and n-butane component from the mixed C4, so as to obtain a product flow containing butylene; contacting the product flow containing butylene, and oxygen-containing gas and water vapor with a catalyst in a reactor to generate an oxidation dehydrogenation reaction, so as to obtain a product flow rich in butadiene. The technical scheme well solves the above problems and can be used for industrial production of butadiene.
Description
Technical field
The present invention relates to a kind of production method of divinyl.
Background technology
Ethene and propylene are two kinds of important basic chemical industry raw materials, and its demand is in continuous increase.Usually, ethene, propylene are to produce by petroleum path, but due to the limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people start to greatly develop the technology that alternative materials transforms ethene processed, propylene.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.Popularity due to oxygenatedchemicals source, add and transform the economy that generates light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), particularly the technique by preparing olefin by conversion of methanol (MTO) is subject to increasing attention.
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, have been 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 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 greatly reduce.
The multiple riser reaction unit of having announced in CN1723262 with central catalyst return is low-carbon alkene technique 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 gas product are separated.
Technique by preparing olefin by conversion of methanol (MTO), in product except ethene, propylene, also have more than 10% carbon four components, wherein butylene accounts for 90% left and right, if can this part butylene be used, improve its added value, will effectively improve the comprehensive economy of preparing olefin by conversion of methanol (MTO) technique, and Oxidative Dehydrogenation of Butene into Butadiene technique is a kind of extraordinary approach.
At present the mode of production of divinyl mainly contains two kinds of the separated and synthesis methods (comprising butane dehydrogenation, butylene dehydrogenation, butylene oxidation-dehydrogenation etc.) of C-4-fraction.At present except the U.S., the by-product C-4-fraction (again can be written as C-4-fraction) of countries in the world divinyl during almost all directly from hydrocarbon cracking ethene processed.The source of U.S.'s divinyl, only about half of from butane, butylene dehydrogenation, half is directly from cracking c_4 cut.
Take petroleum naphtha or diesel oil when cracking stock is produced ethene, the C-4-fraction of by-product is generally 8%～10%(quality of material quantity), wherein butadiene content is up to 40%～50%(quality), so separation of butadiene is economic production method from cracking c_4 cut.The industrial method that all adopts extracting rectifying adds acetonitrile, methylformamide equal solvent to increase the relative volatility of divinyl and other carbon four hydrocarbon in cut, by rectifying separation (seeing that C-4-fraction is separated), obtains divinyl.
Along with the development of China's Rubber Industry, the output of divinyl can not meet the demand of domestic rubber production in recent years.Development along with China's chemical industry, national economy will become increasingly conspicuous to the demand contradictory of divinyl, the amount that the amount that petroleum naphtha produces carbon four and divinyl during as cracking stock generates when using carbon two, carbon three and carbon fourth class light constituent as cracking stock, so the cracking technology that light constituent is made raw material does not have butadiene extraction unit supporting conventionally.Meanwhile, the technology of this olefin hydrocarbon making by coal of methanol-to-olefins (MTO) does not have divinyl by-product.Therefore developing Oxidative Dehydrogenation of Butene into Butadiene method has important practical significance.As patent CN100494130C, its flow process is the reactor that raw material normal butane enters non-oxidizable catalytic dehydrogenation, obtains the mixture flow that contains normal butane, butylene, divinyl, hydrogen, lower boiling secondary component and steam.This mixture flow and oxygen-containing gas are mixed into oxydehydrogenation region, obtain the product gas flow that contains divinyl, normal butane, butylene, hydrogen, lower boiling secondary component and steam, next from this product gas flow, isolate divinyl.Similarly also has patent CN100447117C, different from patent CN100494130C is, after removing hydrogen, lower boiling secondary species and steam, the product gas in autoxidation dehydrogenation region is divided into two portions by extracting rectifying, the logistics that a part mainly comprises normal butane and butylene loops back non-oxide dehydrogenation region, and another part mainly comprises butadiene stream.
Similar with the first two patent described in patent CN100387557C, after the product gas in different is autoxidation dehydrogenation region is removed hydrogen, lower boiling secondary species and steam, by extracting rectifying, be divided into two portions, the logistics that mainly comprises normal butane and butylene is divided into three parts by rectifying region: other purposes are made in the logistics that is rich in 1-butylene.The logistics that is rich in 2-butylene changes into 1-butylene by isomerization and loops back rectifying region.The logistics that is rich in 2-butylene and normal butane loops back non-oxide dehydrogenation region.
Summary of the invention
Technical problem to be solved by this invention is that in prior art, the carbon back utilization ratio in methanol-to-olefins process is low, and the utility value of carbon four hydrocarbon is low, the technical problem that MTO technology economy is low; The invention provides a kind of production method of new divinyl, the method is for the production of low-carbon alkene, there is the carbon back utilization ratio in effective raising methanol-to-olefins process, improve the utility value of carbon four hydrocarbon, thereby reach the advantage that improves MTO technology economy.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production method of divinyl, comprises the following steps:
A) comprise that the raw material of methyl alcohol contacts in reactor with molecular sieve catalyst, reaction generates the product stream that comprises ethene, propylene, C 4 olefin, after separation system separation, obtains ethene, propylene, mixed c 4 and above hydrocarbon;
B) mixed c 4, after isolating Trimethylmethane, iso-butylene component, obtains containing 1-butylene cis-2-butene, the butylene logistics I of Trans-2-butene;
C) there is to contact with catalyzer in certain proportion reactor the logistics II that oxidative dehydrogenation obtains being rich in divinyl with oxygen-containing gas, water vapor in butylene logistics I; Wherein, the mol ratio that enters butylene, oxygen and the water vapor of oxidative dehydrogenation reactor is 1:0.40～1.5:2～18;
D) the logistics II that is rich in divinyl is after separating unit is isolated divinyl, and unreacted butylene returns to step c).
In technique scheme, preferably technical scheme is, the raw material of methyl alcohol contacts in reactor with molecular sieve catalyst, and reaction conditions comprises: temperature of reaction is 400～600 ℃, and reaction pressure is counted 0～2MPa with gauge pressure, and methyl alcohol weight space velocity is 0.1 ~ 20h
-1, reactor is fast fluidized bed, catalyzer is the microsphere particle that comprises SAPO-34 molecular sieve.Preferably technical scheme is, the isolated mixed c 4 of step a) is by a pre-separation tower, and pre-separation tower number of theoretical plate is 60～100, and tower top service temperature is 40～80 ℃, and pressure is 0.5～1.3MPaG.Preferred technical scheme is that in step b), Trimethylmethane, iso-butylene decreasing ratio reach more than 95%.Preferred technical scheme is that the mol ratio that enters butylene, oxygen and the water vapor of oxidative dehydrogenation reactor is 1:0.45～0.9:2～18.Oxidative dehydrogenation reactor is at least 2 grades, and the temperature of reaction of each stage reactor is 300～480 ℃, and pressure is 0.05～0.5MPaG.
Preferred technical scheme is, in step c), oxidative dehydrogenation is thermal insulation or isothermal reaction technique, reactor be respectively insulation fix bed axially or radial reactor or shell and tube remove hot isothermal reactor outward.Preferred technical scheme is that oxygen-containing gas is air or pure oxygen, or the mixture of air and oxygen.Preferably technical scheme is, the required catalyzer of oxidative dehydrogenation is Fe-series catalyst, and chief component comprises iron, zinc, and magnesium component, molar ratio is: Fe:Zn:Mg=10:1 ~ 5:2 ~ 6, adopt coprecipitation method preparation, main crystalline phase is ZnFe
2o
4spinel.Preferred technical scheme is, separating unit described in step d) adopts same solvent, by the method for extracting rectifying, extract divinyl, solvent is at least one of acetonitrile (ACN) or dimethyl formamide (DMF) or N--methyl-2-pyrrolidone (NMP).
Preferred technical scheme is, the raw material of methyl alcohol contacts in reactor with molecular sieve catalyst, and reaction conditions comprises: temperature of reaction is 450～550 ℃, and reaction pressure is counted 0.1～2MPa with gauge pressure, and methyl alcohol weight space velocity is 0.5 ~ 10h
-1, reactor is fast fluidized bed, catalyzer is the microsphere particle that comprises SAPO-34 molecular sieve; The isolated mixed c 4 of step a) is by a pre-separation tower, and pre-separation tower number of theoretical plate is 70～90, and tower top service temperature is 50～70 ℃, and pressure is 0.6～1.2MPaG; In step b), Trimethylmethane, iso-butylene decreasing ratio reach more than 96%; The mol ratio that enters butylene, oxygen and the water vapor of oxidative dehydrogenation reactor is 1:0.5～0.8:6～14; Oxidative dehydrogenation reactor is at least 3 grades, and the temperature of reaction of each stage reactor is 350～450 ℃, and pressure is 0.1～0.4MPaG; In step c), oxidative dehydrogenation is thermal insulation or isothermal reaction technique, reactor be respectively insulation fix bed axially or radial reactor or shell and tube remove hot isothermal reactor outward; Oxygen-containing gas is air or pure oxygen, or the mixture of air and oxygen; The required catalyzer of oxidative dehydrogenation is Fe-series catalyst, and chief component comprises iron, zinc, and magnesium component, molar ratio is: Fe:Zn:Mg=10:2 ~ 5:2 ~ 5, adopt coprecipitation method preparation, main crystalline phase is ZnFe2O4 spinel; Separating unit described in step d) adopts different solvents, by the method for extracting rectifying, extracts divinyl, and solvent is at least two kinds in acetonitrile, dimethyl formamide (DMF) or N----methyl-2-pyrrolidone (NMP).
The preparation method of SAPO-34 molecular sieve of the present invention is: first preparing molecular sieve presoma, is 0.03～0.6R by mole proportioning: (Si 0.01～0.98: Al 0.01～0.6: P 0.01～0.6): 2～500 H
2o, wherein R represents template, constitutive material mixed solution obtains at a certain temperature after the crystallization of certain hour; Again, molecular sieve presoma, phosphorus source, silicon source, aluminium source, organic formwork agent, water etc. are mixed according to certain ratio after at 110～260 ℃ hydrothermal crystallizing after at least 0.1 hour, finally obtain SAPO-34 molecular sieve.The molecular sieve of preparation is mixed with a certain proportion of binding agent, after the operation stepss such as, roasting dry through spraying, obtain final SAPO-34 catalyzer, the weight percentage of binding agent in molecular sieve is generally between 10～90%.
In methanol-to-olefins reaction process, inevitably can produce the by products such as carbon four above hydrocarbon.Because the butene content in described carbon four hydrocarbon is higher, by adopting method of the present invention, by Oxidative Dehydrogenation of Butene Into Butadiene, simultaneously except oxide compounds such as the methyl alcohol of carrying secretly in carbon elimination four hydrocarbon, dme.Method of the present invention can effectively improve the carbon back utilization ratio in methanol-to-olefins process, improves the utility value of carbon four hydrocarbon, thereby reaches the object that improves MTO technology economy.
Adopt technical scheme of the present invention, in temperature of reaction, it is 400～500 ℃, reaction pressure is counted 0～0.3MPa with gauge pressure, reactor is fast fluidized bed, catalyzer is to comprise under the microsphere particle condition of SAPO-34 molecular sieve, comprise that the feedstock conversion of methyl alcohol is for comprising ethene, propylene, the product stream of C 4 olefin, after separation system, obtain ethene, propylene, mixed c 4 and above hydrocarbon and other by product, wherein first mixed c 4 enters pre-separation tower, method by conventional distillation removes Trimethylmethane and iso-butylene wherein, pretreated butylene purity reaches more than 90%, enter oxydehydrogenation unit, in butylene oxidation-dehydrogenation unit, under the condition that butylene and oxygen exist at water vapor, there is oxidative dehydrogenation, generate divinyl and aldehyde, acid, CO
2, the by product such as CO, by washing, the water-soluble materials such as acid, aldehyde are separated from hydrocarbon, then by oily absorption portion by carbon four hydrocarbon from nitrogen, CO
2, separate in the impurity such as CO, enter follow-up Butadiene Extraction unit, Butadiene Extraction unit is divided into butadiene extraction rectifying part and divinyl FF, and object is butane, butylene, alkynes to separate from divinyl, finally obtains polymerization-grade product butadiene.
By above method, effectively improved the carbon back utilization ratio in methanol-to-olefins process, improved the utility value of carbon four hydrocarbon, obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the production method schematic diagram of a kind of divinyl of the present invention.
In Fig. 1,101 is the raw material that comprises methyl alcohol, 102 is ethene, propylene and the above hydrocarbon of carbon four, 103 mixed c 4 hydrocarbon, and 104 is Trimethylmethane and isobutene mixture, 105 is the mixture of normal butane and butylene, 106 is oxygen-containing gas, and 107 is water vapor, and 108 is oxidative dehydrogenation product, 109 is circulation butylene, and 110 is product divinyl.1 is methanol-to-olefins unit, and 2 is carbon four pre-separation unit, and 3 is oxydehydrogenation unit, and 4 is divinyl refined unit.
In Fig. 1, the raw material 101 that comprises methyl alcohol is converted into and comprises ethene in methanol-to-olefins unit 1, propylene, the product stream of C 4 olefin, after separation, obtain ethene, the above hydrocarbon 102 of propylene and carbon four and mixed c 4 103, first mixed c 4 103 enters pre-separation unit 2, by the method for conventional distillation, remove the mixture 104 of Trimethylmethane and iso-butylene, normal butane and butene mixture 105 enter oxydehydrogenation unit 3, under water vapor 107 existence conditions, there is oxidative dehydrogenation in 105 logistics and oxygen-containing gas 106, obtain the oxidative dehydrogenation product 108 containing divinyl, at the refining product divinyl 110 that obtains of divinyl refined unit 4.
Below by embodiment, invention is further elaborated.
Embodiment
[embodiment 1]
Certain 1,000,000 tons/year of methanol-to-olefins device, adopt the Technology of Fig. 1, at methanol to olefins reaction unitary reactor, it is fast fluidized bed, revivifier is turbulent fluidized bed, catalyzer is SAPO-34, the methanol feedstock of 99.9% (weight) contacts with catalyzer, generates the product that comprises ethene, propylene, carbon four and above hydrocarbon, and the catalyzer of inactivation recycles after entering revivifier regeneration.Temperature of reaction is 460 ℃, reaction pressure is counted 0.15MPaG with gauge pressure, the ratio of molecular sieve in catalyzer is 35% (weight), methyl alcohol weight hourly space velocity is 9.0 hours-1, product weight distribution is: ethene 42%, propylene 40%, butylene 10%, iso-butylene 2%, normal butane 0.5%, Trimethylmethane 0.5%, other by product (hydrogen, methane, ethane, propane etc.) 5%, after separation, obtain mixed c 4, consist of: butylene 77%, iso-butylene 15%, normal butane 4%, Trimethylmethane 4%, this mixed c 4 enters pre-separation tower, pre-separation tower number of theoretical plate is 80, tower top service temperature is 45 ℃, pressure is 0.55MPaG, tower top is Trimethylmethane and iso-butylene, its decreasing ratio is 99%, tower reactor cymogene alkene enters oxydehydrogenation unit and air reaction, oxydehydrogenation unit adopts two-stage radial fixed-bed reactor technique, Fe-series catalyst, chief component comprises iron, zinc, magnesium component, ratio (mole) be: Fe:Zn:Mg=10:3:5, the preparation of employing coprecipitation method, main crystalline phase is ZnFe
2o
4spinel, total mol ratio of butylene, oxygen, water is 1:0.65:12, and temperature of reaction is 320 ℃, and pressure 0.12MPaG works off one's feeling vent one's spleen and enters divinyl refined unit containing the oxidative dehydrogenation of divinyl, with acetonitrile, is that extraction agent extracts product divinyl.
This device oxydehydrogenation unit butene conversion 75%, divinyl selectivity 92%, product divinyl purity is greater than 99.6%, produces 80000 tons of divinyl per year.
[embodiment 2]
Certain 1,000,000 tons/year of methanol-to-olefins device, adopt the Technology of Fig. 1, at methanol to olefins reaction unitary reactor, it is fast fluidized bed, revivifier is turbulent fluidized bed, catalyzer is SAPO-34, the methanol feedstock of 99.9% (weight) contacts with catalyzer, generates the product that comprises ethene, propylene, carbon four and above hydrocarbon, and the catalyzer of inactivation recycles after entering revivifier regeneration.Temperature of reaction is 500 ℃, reaction pressure is counted normal pressure with gauge pressure, the ratio of molecular sieve in catalyzer is 30% (weight), methyl alcohol weight hourly space velocity is 12.0 hours-1, product weight distribution is: ethene 48%, propylene 32%, butylene 9.5%, iso-butylene 1.5%, normal butane 0.5%, Trimethylmethane 0.5%, other by product (hydrogen, methane, ethane, propane etc.) 8%, after separation, obtain mixed c 4, consist of: butylene 79%, iso-butylene 12.5%, normal butane 4%, Trimethylmethane 4%, this mixed c 4 enters pre-separation tower, pre-separation tower number of theoretical plate is 90, tower top service temperature is 45 ℃, pressure is 0.55MPaG, tower top is Trimethylmethane and iso-butylene, its decreasing ratio is 99%, tower reactor cymogene alkene enters oxydehydrogenation unit and air reaction, oxydehydrogenation unit adopts two-stage radial fixed-bed reactor technique, Fe-series catalyst, chief component comprises iron, zinc, magnesium component, ratio (mole) be: Fe:Zn:Mg=10:3:5, the preparation of employing coprecipitation method, main crystalline phase is ZnFe2O4 spinel, butylene, oxygen, total mol ratio of water is 1:0.65:12, temperature of reaction is 320 ℃, pressure 0.12MPaG, containing the oxidative dehydrogenation of divinyl, work off one's feeling vent one's spleen and enter divinyl refined unit, with acetonitrile, be that extraction agent extracts product divinyl.
This device oxydehydrogenation unit butene conversion 75%, divinyl selectivity 92%, this device product divinyl purity is greater than 99.6%, produces 7.5 ten thousand tons of divinyl per year.
[embodiment 3]
Certain 1,000,000 tons/year of methanol-to-olefins device, adopt the Technology of Fig. 1, at methanol to olefins reaction unitary reactor, it is fast fluidized bed, revivifier is turbulent fluidized bed, catalyzer is SAPO-34, the methanol feedstock of 99.9% (weight) contacts with catalyzer, generates the product that comprises ethene, propylene, carbon four and above hydrocarbon, and the catalyzer of inactivation recycles after entering revivifier regeneration.Temperature of reaction is 460 ℃, reaction pressure is counted 0.15MPa with gauge pressure, the ratio of molecular sieve in catalyzer is 35% (weight), methyl alcohol weight hourly space velocity is 9.0 hours-1, product weight distribution is: ethene 42%, propylene 40%, butylene 10%, iso-butylene 2%, normal butane 0.5%, Trimethylmethane 0.5%, other by product (hydrogen, methane, ethane, propane etc.) 5%, after separation, obtain mixed c 4, consist of: butylene 77%, iso-butylene 15%, normal butane 4%, Trimethylmethane 4%, this mixed c 4 enters pre-separation tower, pre-separation tower number of theoretical plate is 80, tower top service temperature is 45 ℃, pressure is 0.55MPaG, tower top is Trimethylmethane and iso-butylene, its decreasing ratio is 99%, tower reactor cymogene alkene enters oxydehydrogenation unit and air reaction, oxydehydrogenation unit adopts three grades of radial fixed-bed reactor techniques, Fe-series catalyst, chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:M(Mg)=10:3:5, the preparation of employing coprecipitation method, main crystalline phase is ZnFe2O4 spinel, butylene, oxygen, total mol ratio of water is 1:0.65:8.5, temperature of reaction is 320 ℃, pressure 0.12MPaG, containing the oxidative dehydrogenation of divinyl, work off one's feeling vent one's spleen and enter divinyl refined unit, with acetonitrile, be that extraction agent extracts product divinyl.
This device oxydehydrogenation unit butene conversion 76%, divinyl selectivity 91.8%, this device product divinyl purity is greater than 99.6%, produces 7.9 ten thousand tons of divinyl per year.
[embodiment 4]
Certain 1,000,000 tons/year of methanol-to-olefins device, adopt the Technology of Fig. 1, at methanol to olefins reaction unitary reactor, it is fast fluidized bed, revivifier is turbulent fluidized bed, catalyzer is SAPO-34, the methanol feedstock of 99.9% (weight) contacts with catalyzer, generates the product that comprises ethene, propylene, carbon four and above hydrocarbon, and the catalyzer of inactivation recycles after entering revivifier regeneration.Temperature of reaction is 460 ℃, reaction pressure is counted 0.15MPa with gauge pressure, the ratio of molecular sieve in catalyzer is 35% (weight), methyl alcohol weight hourly space velocity is 9.0 hours-1, product weight distribution is: ethene 42%, propylene 40%, butylene 10%, iso-butylene 2%, normal butane 0.5%, Trimethylmethane 0.5%, other by product (hydrogen, methane, ethane, propane etc.) 5%, after separation, obtain mixed c 4, consist of: butylene 77%, iso-butylene 15%, normal butane 4%, Trimethylmethane 4%, this mixed c 4 enters pre-separation tower, pre-separation tower number of theoretical plate is 80, tower top service temperature is 45 ℃, pressure is 0.55MPaG, tower top is Trimethylmethane and iso-butylene, its decreasing ratio is 99%, tower reactor cymogene alkene enters oxydehydrogenation unit and air reaction, oxydehydrogenation unit adopts the axially-located bed reactor process of two-stage, adopt Fe-series catalyst, chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:M(Mg)=10:2:6, the preparation of employing coprecipitation method, main crystalline phase is ZnFe2O4 spinel, butylene, oxygen, total mol ratio of water is 1:0.70:14, temperature of reaction is 330 ℃, pressure 0.15MPaG, containing the oxidative dehydrogenation of divinyl, work off one's feeling vent one's spleen and enter divinyl refined unit, with acetonitrile, be that extraction agent extracts product divinyl.
This device oxydehydrogenation unit butene conversion 70%, divinyl selectivity 90%, this device product divinyl purity is greater than 99.5%, produces 7.5 ten thousand tons of divinyl per year.
[embodiment 5]
Certain 1,000,000 tons/year of methanol-to-olefins device, adopt the Technology of Fig. 1, at methanol to olefins reaction unitary reactor, it is fast fluidized bed, revivifier is turbulent fluidized bed, catalyzer is SAPO-34, the methanol feedstock of 99.9% (weight) contacts with catalyzer, generates the product that comprises ethene, propylene, carbon four and above hydrocarbon, and the catalyzer of inactivation recycles after entering revivifier regeneration.Temperature of reaction is 460 ℃, reaction pressure is counted 0.15MPa with gauge pressure, the ratio of molecular sieve in catalyzer is 35% (weight), methyl alcohol weight hourly space velocity is 9.0 hours-1, product weight distribution is: ethene 42%, propylene 40%, butylene 10%, iso-butylene 2%, normal butane 0.5%, Trimethylmethane 0.5%, other by product (hydrogen, methane, ethane, propane etc.) 5%, after separation, obtain mixed c 4, consist of: butylene 77%, iso-butylene 15%, normal butane 4%, Trimethylmethane 4%, this mixed c 4 enters pre-separation tower, pre-separation tower number of theoretical plate is 80, tower top service temperature is 45 ℃, pressure is 0.55MPaG, tower top is Trimethylmethane and iso-butylene, its decreasing ratio is 99%, tower reactor cymogene alkene enters oxydehydrogenation unit and pure oxygen reaction, oxydehydrogenation unit adopts two-stage radial fixed-bed reactor technique, Fe-series catalyst, chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:M(Mg)=10:3:5, the preparation of employing coprecipitation method, main crystalline phase is ZnFe2O4 spinel, butylene, oxygen, total mol ratio of water is 1:0.62:11.5, temperature of reaction is 320 ℃, pressure 0.12MPaG, containing the oxidative dehydrogenation of divinyl, work off one's feeling vent one's spleen and enter divinyl refined unit, with acetonitrile, be that extraction agent extracts product divinyl.
This device oxydehydrogenation unit butene conversion 70%, divinyl selectivity 90%, this device product divinyl purity is greater than 99.5%, produces 7.7 ten thousand tons of divinyl per year.
[embodiment 6]
Certain 1,000,000 tons/year of methanol-to-olefins device, adopt the Technology of Fig. 1, at methanol to olefins reaction unitary reactor, it is fast fluidized bed, revivifier is turbulent fluidized bed, catalyzer is SAPO-34, the methanol feedstock of 99.9% (weight) contacts with catalyzer, generates the product that comprises ethene, propylene, carbon four and above hydrocarbon, and the catalyzer of inactivation recycles after entering revivifier regeneration.Temperature of reaction is 460 ℃, reaction pressure is counted 0.15MPa with gauge pressure, the ratio of molecular sieve in catalyzer is 35% (weight), methyl alcohol weight hourly space velocity is 9.0 hours-1, product weight distribution is: ethene 42%, propylene 40%, butylene 10%, iso-butylene 2%, normal butane 0.5%, Trimethylmethane 0.5%, other by product (hydrogen, methane, ethane, propane etc.) 5%, after separation, obtain mixed c 4, consist of: butylene 77%, iso-butylene 15%, normal butane 4%, Trimethylmethane 4%, this mixed c 4 enters pre-separation tower, pre-separation tower number of theoretical plate is 80, tower top service temperature is 45 ℃, pressure is 0.55MPaG, tower top is Trimethylmethane and iso-butylene, its decreasing ratio is 99%, tower reactor cymogene alkene enters oxydehydrogenation unit and air reaction, oxydehydrogenation unit adopts two-stage radial fixed-bed reactor technique, Fe-series catalyst, chief component comprises iron, zinc, the compositions such as magnesium, molar ratio is: Fe:Zn:M(Mg)=10:3:5, the preparation of employing coprecipitation method, main crystalline phase is ZnFe2O4 spinel, butylene, oxygen, total mol ratio of water is 1:0.65:12, temperature of reaction is 320 ℃, pressure 0.12MPaG, containing the oxidative dehydrogenation of divinyl, work off one's feeling vent one's spleen and enter divinyl refined unit, with dimethyl formamide (DMF), extract product divinyl for extraction agent.
This device oxydehydrogenation unit butene conversion 80%, divinyl selectivity 93%, this device product divinyl purity is greater than 99.7%, produces 8.2 ten thousand tons of divinyl per year.
Claims (10)
1. a production method for divinyl, comprises the following steps:
The raw material that comprises methyl alcohol contacts in reactor with the catalyzer containing molecular sieve, and reaction generates the product stream that comprises ethene, propylene, C 4 olefin, after separation system separation, obtains ethene, propylene, mixed c 4 and above hydrocarbon;
Mixed c 4, after isolating Trimethylmethane, iso-butylene component, obtains containing 1-butylene cis-2-butene, the butylene logistics I of Trans-2-butene;
Butylene logistics I contacts with catalyzer with certain proportion with oxygen-containing gas, water vapor in reactor, and the logistics II that oxidative dehydrogenation obtains being rich in divinyl occurs; Wherein, the mol ratio that enters butylene, oxygen and the water vapor of oxidative dehydrogenation reactor is 1:0.40～1.5:2～18;
Be rich in the logistics II of divinyl after separating unit is isolated divinyl, unreacted butylene returns to step c).
2. the production method of divinyl according to claim 1, the raw material that it is characterized in that methyl alcohol contacts in reactor with the catalyzer containing molecular sieve, reaction conditions comprises: temperature of reaction is 400～600 ℃, reaction pressure is counted 0～2MPa with gauge pressure, reactor is fast fluidized bed, and methyl alcohol weight space velocity is 0.1 ~ 20h
-1, catalyzer is the microsphere particle that contains SAPO-34 molecular sieve.
3. the production method of divinyl according to claim 1, is characterized in that the isolated mixed c 4 of step a) is by a pre-separation tower, and pre-separation tower number of theoretical plate is 60～100, and tower top service temperature is 40～80 ℃, and pressure is 0.5～1.3MPaG.
4. the production method of divinyl according to claim 1, its feature is more than in step b), Trimethylmethane, iso-butylene decreasing ratio reach 95wt%.
5. the production method of divinyl according to claim 1, the mol ratio that it is characterized in that entering butylene, oxygen and the water vapor of oxidative dehydrogenation reactor is 1:0.45～0.9:2～18.
6. the production method of divinyl according to claim 1, is characterized in that oxidative dehydrogenation reactor is at least 2 grades, and the temperature of reaction of each stage reactor is 300～520 ℃, and pressure is 0.05～0.5MPaG.
7. the production method of divinyl according to claim 1, is characterized in that in step c), oxidative dehydrogenation is thermal insulation or isothermal reaction technique, reactor be respectively insulation fix bed axially or radial reactor or shell and tube remove hot isothermal reactor outward.
8. the production method of divinyl according to claim 1, is characterized in that oxygen-containing gas is air or pure oxygen, or the mixture of air and oxygen.
9. the production method of divinyl according to claim 1, is characterized in that the required catalyzer of oxidative dehydrogenation is Fe-series catalyst, and chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:1 ~ 5:2 ~ 6, the preparation of employing coprecipitation method, main crystalline phase is ZnFe
2o
4spinel.
10. the production method of divinyl according to claim 1, it is characterized in that the separating unit described in step d) adopts the method for extracting rectifying to extract divinyl, solvent is at least one of acetonitrile (ACN) or dimethyl formamide (DMF) or N--methyl-2-pyrrolidone (NMP).
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| CN110568085B (en) * | 2018-06-05 | 2021-10-29 | 中国石油化工股份有限公司 | Method for determining acetonitrile content in sample |
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| CN111302885B (en) * | 2020-03-02 | 2022-11-04 | 齐鲁工业大学 | One-pot high-efficiency synthesis of ethylene and 1,3-butadiene from bioethanol |
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