CN113929550B - Mixed carbon four superposition reaction method and device - Google Patents
Mixed carbon four superposition reaction method and device Download PDFInfo
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- CN113929550B CN113929550B CN202010609034.6A CN202010609034A CN113929550B CN 113929550 B CN113929550 B CN 113929550B CN 202010609034 A CN202010609034 A CN 202010609034A CN 113929550 B CN113929550 B CN 113929550B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 127
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 31
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 110
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000003054 catalyst Substances 0.000 claims abstract description 94
- 238000000926 separation method Methods 0.000 claims abstract description 78
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 67
- 239000000376 reactant Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims description 42
- 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 41
- 239000011347 resin Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 31
- 239000003729 cation exchange resin Substances 0.000 claims description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229940023913 cation exchange resins Drugs 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 241000269350 Anura Species 0.000 description 3
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- -1 polyethylene units Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/177—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by selective oligomerisation or polymerisation of at least one compound of the mixture
Abstract
The invention relates to a mixed carbon four polymerization reaction method, which comprises the following steps of S1, enabling mixed carbon four to perform a first polymerization reaction in a first reactor to obtain a first polymerization reactant, wherein a first catalyst is arranged in the first reactor; s2, introducing the first superposition reactant obtained in the step S1 into a second reaction separation tower, wherein the second reaction separation tower is provided with a separation section and a reaction section, the reaction section is provided with a second catalyst, the first superposition reactant is subjected to gas-liquid separation in the separation section, and the obtained first gas phase is subjected to a second superposition reaction in the reaction section to obtain the second superposition reactant. The method can ensure that the deep conversion rate of isobutene in the mixed C4 is more than 97 percent and the conversion rate of 1-butene is controlled to be less than 10 percent through the compatible use of the two catalysts, thereby realizing the separation of isobutene and 1-butene, and the obtained residual C4 meets the requirement of raw materials of a 1-butene separation device.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of carbon four, and particularly relates to a mixed carbon four superposition reaction method and device.
Background
1-butene is a chemically active alpha-olefin, an important chemical raw material, and is mainly used as a comonomer for producing Linear Low Density Polyethylene (LLDPE), high Density Polyethylene (HDPE) and polybutene-1 (PB) plastics. In addition, the method can also be used for producing fine chemical products such as sec-butyl alcohol, methyl ethyl ketone and epoxybutane, such as butadiene, 1-octene, dodecene, valeraldehyde, derivatives, higher plasticizer alcohol, special solvent oil and the like by oxidative dehydrogenation.
The preparation of 1-butene is generally carried out by reacting the raffinate C4 from the butadiene extraction unit with outsourced methanol to form MTBE, and reacting the isobutene chemically. The remaining post-ether C4 is used to purify the polymer grade butene-1 and the product is used in downstream polyethylene units for comonomer or export. With the great popularization and implementation of the implementation scheme of expanding the production of the biofuel ethanol and the popularization and the application of the ethanol gasoline for vehicles, the MTBE synthesis device faces production stopping and production transferring, and how to realize the separation of the 1-butene and the isobutene is a difficult problem facing enterprises.
The mixed C4 selective superposition is a main way for separating isobutene from 1-butene, and the isobutene is reacted through isobutene superposition reaction, and the residual C4 is used as a raw material of the 1-butene separation device, so that the transformation of the MTBE synthesis device is realized. Resin is usually used as a catalyst for mixing C4 superposition, but in the superposition reaction process, double bond isomerization and polymerization of 1-butene are easy to occur, the loss is more, and the loss amount reaches 50% -70%. In order to control the conversion rate of 1-butene, the prior art mainly adopts the addition of inhibitors to control the conversion degree of the superposition reaction.
CN101190860a is prepared by feeding C4 raw material and methanol simultaneously, and in the presence of solid acid, performing superposition-etherification reaction, and controlling the weight conversion rate of n-butene to be less than 10% by controlling the reaction conditions, but has the problems of MTBE content in the product to be more than 50%, low conversion rate of isobutylene reaction, etc.
Disclosure of Invention
At present, the carbon four polymerization reaction has the defects that the loss of 1-butene is too high in the reaction process and the 1-butene cannot be combined with a downstream 1-butene separation device. Therefore, the selective lamination process is necessary to be improved and researched, and the potential of the selective lamination process is explored, so that the purposes of reducing the loss of 1-butene and improving the economic benefit are achieved. Therefore, the first aspect of the invention provides a mixed carbon four-superposition reaction method, which realizes the isobutene conversion rate of more than 97 percent and the 1-butene conversion rate of less than 10 percent by the compatible use of a resin catalyst and a molecular sieve catalyst. The second aspect of the invention provides an application of the mixed carbon four superposition reaction method in mixed carbon four separation. In a third aspect, the invention provides an apparatus for use in a hybrid carbon four folding reaction process.
According to a first aspect, the method for the mixed carbon four polymerization reaction provided by the invention comprises the following steps:
s1, carrying out a first polymerization reaction on mixed carbon four in a first reactor to obtain a first polymerization reactant, wherein a first catalyst is arranged in the first reactor;
s2, introducing the first superposition reactant obtained in the step S1 into a second reaction separation tower, wherein the second reaction separation tower is provided with a separation section and a reaction section, the reaction section is provided with a second catalyst, the first superposition reactant is subjected to gas-liquid separation in the separation section, and the obtained first gas phase is subjected to a second superposition reaction in the reaction section to obtain a second superposition reactant;
wherein the first catalyst is selected from one or more of hydrogen type cation exchange resins, and the second catalyst is selected from one or more of molecular sieve catalysts.
According to some embodiments of the invention, the first polymerization reactant comprises dimerization and oligomerization products of isobutylene.
According to some embodiments of the invention, the second polymerization reactant comprises dimerization and oligomerization products of isobutylene.
According to some preferred embodiments of the invention, the dimerization and oligomerization products of isobutene have 80% to 90% carbon eight and 10% to 20% carbon twelve or more.
According to some embodiments of the invention, the reaction section is disposed at an upper portion of the second reaction separation column, and the separation section is disposed at a lower portion of the second reaction separation column.
According to some embodiments of the present invention, the first polymerization reactant is introduced into a separation section of a second reaction separation tower to perform separation treatment, so as to obtain a gas-phase material containing isobutene, and the gas-phase material containing isobutene is introduced into a reaction section to perform a second polymerization reaction, so as to obtain a second polymerization reactant.
According to some embodiments of the invention, the upper part of the second reaction separation tower is a reaction section, and the lower part of the second reaction separation tower is a separation section, so that the equilibrium conversion rate of isobutene is further improved and the investment cost of the device is saved by carrying out the reaction and the separation simultaneously.
According to some embodiments of the invention, the mass ratio of the first catalyst to the second catalyst is 1 (1-10), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, and any value therebetween.
According to some embodiments of the invention, the mass ratio of the first catalyst to the second catalyst is 1 (1-10), the mass ratio is too high, the mixed carbon four stays on the resin catalyst for too long, the 1-butene conversion probability is increased, and more 1-butene loss is caused; the mass ratio is too low, so that the dosage of the molecular sieve catalyst is increased, the cost of the molecular sieve catalyst is increased, and excessive isobutene is polymerized on the molecular sieve to generate excessive oligomer.
According to some embodiments of the invention, the mass ratio of the first catalyst to the second catalyst is 1 (2-7).
According to some embodiments of the invention, the hydrogen form cation exchange resin is selected from one or more of the group consisting of strongly acidic cation exchange resins.
According to some embodiments of the invention, the hydrogen form cation exchange resin is selected from one or more of a styrenic cation exchange resin, an acrylic cation exchange resin, an epoxy cation exchange resin, and a phenolic cation exchange resin.
According to some embodiments of the invention, the hydrogen form cation exchange resin is selected from one or more of the group consisting of D006 resin, D002 resin, amberlyst-15 resin, amberlyst-35 resin, amberlyst-45 resin, and nkc-9 resin.
According to some embodiments of the invention, the molecular sieve catalyst is selected from one or more of mordenite, a Y-series molecular sieve, a ZSM-series molecular sieve, an MCM-series molecular sieve, a beta-series molecular sieve, and a SAPO-series molecular sieve.
According to some embodiments of the invention, the molecular sieve catalyst is selected from one or more of ZSM-5, MCM-22, mordenite, MCM-41, SAPO-11, and SAPO-41.
According to some embodiments of the invention, the molecular sieve catalyst is synthesized using conventional methods, preferably the molecular sieve is prepared by a process comprising: mixing the molecular sieve raw powder, an adhesive and acid according to a certain proportion, kneading, extruding strips, drying and roasting.
According to some embodiments of the invention, the binder is pseudo-boehmite.
According to some embodiments of the invention, the acid is nitric acid.
According to some embodiments of the invention, the molecular sieve to binder weight ratio is from 8:2 to 5:5.
According to some embodiments of the invention, the drying temperature is 100-120 ℃ and the drying time is 2-6 hours.
According to some embodiments of the invention, the firing temperature is 400-600 ℃ and the firing time is 4-10 hours.
According to some embodiments of the invention, the mixed carbon four is selected from one or more of cracked carbon four, refined carbon four, and FCC light carbon four.
In some preferred embodiments of the invention, the mixed carbon four is selected from any isobutylene-containing carbon four, such as steam cracked C4, FCC light C4 or mixed C4, and coal chemical by-product C4.
According to some embodiments of the invention, the mass content of isobutene in the mixed carbon four is 5-90%.
According to some embodiments of the invention, the mass content of isobutene in the mixed carbon number four is 10-80%.
According to some embodiments of the invention, the mixed carbon four is selected from cracking carbon four and/or refining carbon four.
According to some embodiments of the invention, the mixed carbon number four comprises 1-20wt% alkane and 20-90wt% butene.
According to some embodiments of the invention, the butenes include 1-butene, isobutene, trans-2-butene, and cis-2-butene.
According to some embodiments of the invention, the alkane comprises isobutane and/or n-butane.
According to some embodiments of the invention, the temperature of the first folding reaction is 15-70 ℃, e.g. 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ and any value in between.
According to some embodiments of the invention, the temperature of the first polymerization reaction is 25-50 ℃.
According to some embodiments of the invention, the pressure of the first polymerization reaction is 0.4-1.5MPa, e.g. 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa and any value in between.
According to some embodiments of the invention, the pressure of the first polymerization reaction is 0.5-1.0MPa.
According to some embodiments of the invention, in the first polymerization reaction, the space velocity of the mixed carbon four feed is 0.5h -1 -5h -1 For example 0.5h -1 、1.0h -1 、1.5h -1 、2.0h -1 、2.5h -1 、3.0h -1 、3.5h -1 、4.0h -1 、4.5h -1 、5.0h -1 And any value in between.
According to some embodiments of the invention, the mixed carbon four feed space velocity is 1.5-4.0h -1 。
According to some embodiments of the invention, the conversion of isobutene in the first polymerization reaction is 70-95%, e.g. 70%, 72%, 74%, 75%, 76%, 78%, 80%, 82%, 84%, 74%, 85%, 86%, 87%, 88%, 90%, 92%, 94%, 95% and any value in between.
According to some embodiments of the invention, the conversion of isobutene in the first polymerization reaction is 80 to 90%.
The invention can ensure a certain conversion of isobutene and reduce the conversion of 1-butene by controlling the reaction temperature of the first polymerization reaction and the conversion rate of isobutene in the first polymerization reaction.
According to some embodiments of the invention, the temperature of the second folding reaction is 50-150 ℃, e.g. 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 78 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ and any value in between.
According to some embodiments of the invention, the temperature of the second polymerization reaction is 60-120 ℃.
According to some embodiments of the invention, the pressure of the second polymerization reaction is 0.4-1.5MPa, e.g. 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa and any value in between.
According to some embodiments of the invention, the pressure of the second polymerization reaction is 0.6-1.0MPa.
According to some embodiments of the invention, the temperature of the separation treatment is 180-230 ℃, e.g. 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃ and any value in between.
According to some embodiments of the invention, the temperature of the separation treatment is 190-210 ℃.
According to some embodiments of the invention, the pressure of the separation treatment is 0.4-1.5MPa, e.g. 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa and any value in between.
According to some embodiments of the invention, the pressure of the separation treatment is 0.6-1.0MPa.
According to some embodiments of the invention, the temperature of the second polymerization reaction is higher than the temperature of the first polymerization reaction.
In some preferred embodiments of the invention, the temperature of the second polymerization reaction is 20-60 ℃ higher than the temperature of the first polymerization reaction.
In some preferred embodiments of the invention, the method comprises in particular the steps of:
step 1, mixing C4, firstly, carrying out a first polymerization reaction through a fixed bed polymerization reactor filled with a resin catalyst, controlling the reaction temperature and the space velocity, and adjusting the polymerization reaction degree of isobutene to obtain a first polymerization reaction product.
And 2, enabling the first superposition reaction product to enter a separation tower, wherein a molecular sieve solid acid catalyst is arranged at the upper part of the separation tower, and further carrying out superposition reaction on unreacted isobutene under the catalysis of the molecular sieve catalyst, so that residual C4 rich in 1-butene is obtained at the tower top, and a superposition product is obtained at the tower bottom.
The inventor finds that in the process of resin catalyst reaction, the temperature is higher to obtain higher isobutene conversion rate, but the high temperature can convert 1-butene; in the reaction process of the molecular sieve catalyst, 1-butene basically does not react, but isobutene polymers are more formed, and the content of a superposed product C8 is lower. The invention combines the resin catalyst and the molecular sieve catalyst, so that 80-90% of isobutene is overlapped on the low-temperature resin catalyst and about 10% of isobutene is overlapped on the high-temperature molecular sieve, thereby ensuring the selectivity of isobutene dimerization to be more than 80% and the 1-butene conversion rate to be lower than 10%, simultaneously ensuring the upper part of the second reaction separation tower in the molecular sieve catalyst reaction process to be a reaction section and the lower part to be a separation section, and simultaneously carrying out the reaction and the separation, thereby further improving the isobutene equilibrium conversion rate and saving the investment cost of the device.
In a second aspect of the invention, the invention provides the use of the method of the first aspect in a mixed carbon four separation.
According to some embodiments of the present invention there is provided the use of the process of the first aspect for the separation of 1-butene from isobutene.
In some preferred embodiments of the invention, the process described in the first aspect may be used for the separation of 1-butene in etherified C4 in MTBE synthesis reactions.
According to a third aspect, the invention provides a first folding reactor and a second reaction separation tower, the second reaction separation tower is provided with a separation section and a reaction section, and the first folding reactor is connected with the separation section of the second reaction separation tower.
According to some embodiments of the invention, the reaction section is disposed at an upper portion of the second reaction separation column, and the separation section is disposed at a lower portion of the second reaction separation column.
According to some embodiments of the invention, the first polymerization reactor is configured to subject the mixed carbon four to a first polymerization reaction to obtain a first polymerization reactant.
According to some embodiments of the invention, the second reaction separation column is used to subject the first polymerization product to a second polymerization reaction to obtain a second polymerization reactant.
In some preferred embodiments of the present invention, the separation section of the second reaction separation column is used for separating the first polymerization reactant to obtain a gas phase material containing isobutene, and the reaction section of the second reaction separation column is used for performing a second polymerization reaction on the gas phase material containing isobutene to obtain a second polymerization reactant.
The beneficial effects of the invention are as follows: according to the invention, through the compatible use of the two catalysts, the deep conversion rate of isobutene in the mixed C4 can be higher than 97%, the conversion rate of 1-butene can be controlled to be lower than 10%, so that the separation of isobutene and 1-butene is realized, and the obtained residual C4 meets the raw material requirement of a 1-butene separation device.
Drawings
Figure 1 is a process flow diagram of a hybrid carbon four folding reaction of the present invention,
reference numerals illustrate: 1-mixed C4 raw material, 2-first superposition reactor, 3-second reaction separation tower, 4-molecular sieve catalyst, 5-residual C4 and 6-superposition product.
Detailed Description
The invention provides a method for mixing four carbon polymerization, as shown in figure 1, the mixed four carbon (5.51% isobutane, 11.66% n-butane, 7.53% trans-2-butene, 29.6% 1-butene, 41.33% isobutene, 3.84% cis-2-butene) is fed into a first fixed bed polymerization reactor 1 through a metering pump, resin catalyst is filled in the reactor, the temperature is 25-50 ℃, the pressure is 0.5-1.0MPa, and the feeding airspeed is 1.5h -1 ～4.0h -1 Under the condition, the superposition reaction is carried out, and the conversion rate of isobutene is controlled to be 85-90%. The superposed product enters the separating tower from the middle lower part of the separating tower, the molecular sieve catalyst is arranged at the upper part of the separating tower, the reaction temperature is 60-120 ℃, the pressure is 0.6-1.0MPa, and the superposed reaction is continuously carried out on the partial molecular sieve catalyst bed layer at the upper part of the separating tower. The total conversion rate of isobutene is more than 97 percent, and the total conversion rate of 1-butene is less than 10 percent. And obtaining residual C four rich in 1-butene at the top of the separation tower, and obtaining a superposition product at the bottom of the separation tower.
The invention is further illustrated below with reference to the examples, which are merely illustrative of the invention and do not constitute a limitation of the invention in any way.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
the mixed carbon four (5.51% isobutane, 11.66% n-butane, 7.53% trans-2-butene, 29.6% 1-butene, 41.33% isobutene, 3.84% cis-2-butene) is fed into a fixed bed superposition reactor through a metering pump, 15g NKC-9 resin catalyst is filled in the reactor, the temperature is 30 ℃, the pressure is 0.75MPa, and the feeding space velocity is 1.5h -1 Under this condition, the polymerization reaction occurs, and the conversion of isobutene is controlled to 87%. The superposed product enters a separating tower from the middle lower part of the separating tower, and the upper part of the separating tower is filled with 30g of SAPO-11 molecular sieve catalyst (resinThe mass ratio of the catalyst to the molecular sieve catalyst is 1:2), the reaction temperature is 70 ℃, the pressure is 0.6MPa, and the feeding airspeed is 0.5h -1 . The temperature of the tower bottom of the separation tower is 193 ℃ and the pressure is 0.55MPa, and under the condition, the superposed product and unreacted C4 are separated. And separating out the system from the bottom of the separation tower, allowing unreacted C4 to enter the upper part of the separation tower and the catalyst bed of the sub-sieve to continue to perform the superposition reaction, allowing the product of the continuous reaction to enter the lower part of the separation tower for separation, and extracting the residual C4 from the top of the separation tower. Through the combined reaction, the total conversion of isobutene was 97.2% and the total conversion of 1-butene was 6.5%. The top of the separation tower is provided with 1-butene-rich residual C four, the bottom of the separation tower is provided with a superposed product, and specific results and conditions are listed in Table 1.
Example 2:
the difference from example 1 is that Amberlyst-35 catalyst is used as catalyst for the polymerization reactor. After the two catalysts were reacted together, the total conversion of isobutene was 98.1% and the conversion of 1-butene was 7.5%, the specific results and conditions are shown in Table 1.
Example 3:
the difference from example 1 is that the catalyst used in the polymerization reactor is Amberlyst-35 catalyst and the catalyst packed in the upper part of the separation column is MCM-22 molecular sieve catalyst. After the two catalysts were reacted together, the total conversion of isobutene was 98.5% and the conversion of 1-butene was 8.2%, the specific results and conditions are shown in Table 1.
Example 4
The difference from example 1 is that the first polymerization reactor contains 10g Amberlyst-35 resin catalyst and the second reactor contains 60g MCM-22 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst is 1:6. After the two catalysts were reacted together, the total conversion of isobutene was 99.5% and the conversion of 1-butene was 8.5%, the specific results and conditions are shown in Table 1.
Example 5
The difference from example 1 is that the first polymerization reactor is charged with 15g of NKC-9 resin catalyst and the second reactor is charged with 60g of MCM-22 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst being 1:4. After the two catalysts were reacted together, the total conversion of isobutene was 99.0% and the conversion of 1-butene was 8.2%, the specific results and conditions are shown in Table 1.
Example 6
The difference from example 1 is that the first polymerization reactor is charged with 10g of NKC-9 resin catalyst and the second reactor is charged with 50g of MCM-22 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst being 1:5. After the two catalysts were reacted together, the total conversion of isobutene was 99.3% and the conversion of 1-butene was 7.5%, the specific results and conditions are shown in Table 1.
Example 7
The difference from example 1 is that the first polymerization reactor is charged with 10g Amberlyst-35 resin catalyst and the second reactor is charged with 50g SAPO 11 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst being 1:5. After the two catalysts were reacted together, the total conversion of isobutene was 98.6% and the conversion of 1-butene was 8.0%, the specific results and conditions are shown in Table 1.
Example 8
The difference from example 1 is that the first polymerization reactor is charged with 10g of NKC-9 resin catalyst and the second polymerization reactor is charged with 70g of SAPO 11 molecular sieve catalyst, and the mass ratio of resin catalyst to molecular sieve catalyst is 1:7. After the two catalysts were reacted together, the total conversion of isobutene was 99.1% and the conversion of 1-butene was 7.7%, the specific results and conditions are shown in Table 1.
Example 9
The difference from example 1 is that 50g of NKC-9 resin catalyst was charged in the first polymerization reactor, 25g of SAPO 11 molecular sieve catalyst was charged in the second polymerization reactor, and the mass ratio of resin catalyst to molecular sieve catalyst was 1:0.5. After the two catalysts were reacted together, the total conversion of isobutene was 98.2% and the conversion of 1-butene was 14.3%, the specific results and conditions are shown in Table 1.
Comparative example 1
The difference from example 1 was that the first polymerization reactor was charged with 25g of NKC-9 resin catalyst and the second polymerization reactor was charged with 50g of NKC-9 resin catalyst, and after the reaction, the total conversion of isobutene was 92.5% and the conversion of 1-butene was 15.6%, and the specific results and conditions were as shown in Table 1.
Comparative example 2
The difference from example 2 is that the first polymerization reactor is charged with 25g Amberlyst-35 catalyst and the second reactor is charged with 50g Amberlyst-35 catalyst, and after the reaction, the total conversion of isobutene is 95.1% and the conversion of 1-butene is 17.0%, and the specific results and conditions are shown in Table 1.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (12)
1. A hybrid carbon four polymerization reaction process comprising the steps of:
s1, carrying out a first polymerization reaction on mixed carbon four in a first reactor to obtain a first polymerization reactant, wherein a first catalyst is arranged in the first reactor;
s2, introducing the first superposition reactant obtained in the step S1 into a second reaction separation tower, wherein the second reaction separation tower is provided with a separation section and a reaction section, the reaction section is provided with a second catalyst, the first superposition reactant is subjected to gas-liquid separation in the separation section, and the obtained first gas phase is subjected to a second superposition reaction in the reaction section to obtain a second superposition reactant;
wherein the first catalyst is selected from one or more of hydrogen type cation exchange resins, and the second catalyst is selected from one or more of molecular sieve catalysts; the mass ratio of the first catalyst to the second catalyst is 1 (1-10);
the hydrogen type cation exchange resin is selected from Amberlyst-35 resin and nkc-9 resin;
the molecular sieve catalyst is selected from MCM-22 and SAPO-11;
the reaction section is arranged at the upper part of the second reaction separation tower, and the separation section is arranged at the lower part of the second reaction separation tower;
the temperature of the second polymerization reaction is higher than that of the first polymerization reaction; the conversion of isobutene in the first polymerization reaction is 80-90%.
2. The method according to claim 1, wherein the mass ratio of the first catalyst to the second catalyst is 1 (2-7).
3. The method of claim 1 or 2, wherein the mixed carbon four is selected from one or more of cracked carbon four, refined carbon four, and FCC light carbon four.
4. A method according to claim 3, characterized in that the mass content of isobutene in the mixed carbon four is 5-90%.
5. The method according to claim 4, wherein the mass content of isobutene in the mixed carbon four is 10 to 80%.
6. The method according to claim 1 or 2, wherein the temperature of the first folding reaction is 15-70 ℃;
and/or the pressure of the first superposition reaction is 0.4-1.5MPa;
and/or the space velocity of the feed of the mixed carbon four is 0.5 to 5.0h -1 。
7. The method of claim 6, wherein the temperature of the first polymerization reaction is 25-50 ℃;
and/or the pressure of the first superposition reaction is 0.5-1.0MPa;
and/or the space velocity of the feed of the mixed carbon four is 1.5-4.0h -1 。
8. The method according to claim 1 or 2, wherein the temperature of the second folding reaction is 50-150 ℃;
and/or the pressure of the second polymerization reaction is 0.4-1.5MPa;
and/or the temperature of the separation treatment is 180-230 ℃;
and/or the pressure of the separation treatment is 0.4-1.5MPa.
9. The method of claim 8, wherein the temperature of the second polymerization reaction is 60-120 ℃;
and/or the pressure of the second superposition reaction is 0.6-1.0MPa;
and/or the temperature of the separation treatment is 190-210 ℃;
and/or the pressure of the separation treatment is 0.6-1.0MPa.
10. A method according to claim 1 or 2, characterized in that the temperature of the second polymerization reaction is 20-60 ℃ higher than the temperature of the first polymerization reaction.
11. Use of the method according to any one of claims 1-10 in a mixed carbon tetra separation.
12. Use of the process according to any one of claims 1-10 for the separation of 1-butene from isobutene.
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