CN113929549B - Mixed carbon four selective superposition method - Google Patents
Mixed carbon four selective superposition method Download PDFInfo
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- CN113929549B CN113929549B CN202010609758.0A CN202010609758A CN113929549B CN 113929549 B CN113929549 B CN 113929549B CN 202010609758 A CN202010609758 A CN 202010609758A CN 113929549 B CN113929549 B CN 113929549B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 140
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 119
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 239000000376 reactant Substances 0.000 claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940023913 cation exchange resins Drugs 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 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
- 239000012071 phase Substances 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000010030 laminating Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 23
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 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
- 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
- 239000003112 inhibitor 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
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-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
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 230000008901 benefit Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000009835 boiling Methods 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
- 239000013064 chemical raw material 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006703 hydration reaction Methods 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
- 229910017604 nitric acid Inorganic materials 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
- -1 polyethylene units Polymers 0.000 description 1
- 229920000642 polymer Polymers 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
- 230000009466 transformation Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a mixed carbon four-selective laminating method, which comprises the following steps: s1, carrying out a first superposition reaction on mixed carbon four in the presence of a first catalyst to obtain a first superposition reactant; s2, carrying out a second polymerization reaction on the first polymerization reactant in the step S1 in the presence of a second catalyst to obtain a second polymerization 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 method can ensure that the deep conversion rate of isobutene in the mixed C4 is more than 98 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 method and a device for selective superposition of mixed carbon four.
Background
1-butene is an important chemical raw material, is a relatively active alpha-olefin in chemical nature, and is mainly used as a comonomer for producing Linear Low Density Polyethylene (LLDPE), high Density Polyethylene (HDPE) and polybutene-1 (PB) plastics. 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 polymeric 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 the ethanol production and the popularization and the application of the ethanol gasoline for vehicles of the expanded biofuel, the MTBE synthesis device faces production stopping and production transferring, and how to realize the separation of 1-butene and isobutene is a difficult problem facing enterprises.
Since the boiling point difference between 1-butene and isobutene is only 0.6 ℃, the 1-butene and isobutene are difficult to obtain by a common rectification method. 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 a 1-butene separation device, so that the transformation of an 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.
CN209237905 provides a co-production method, in which a system device for preparing a raw material from high-content 1-butene obtained from C4, and the loss of 1-butene is reduced while deep removal of isobutene in C4 is achieved by combining isobutene hydration reaction with isobutene superposition reaction, but the loss rate of 1-butene still reaches 20% -40%, and meanwhile, the reaction is more complicated due to the addition of water, and the product is also more complicated.
Disclosure of Invention
At present, the selective superposition of the carbon four has the defects that on one hand, the loss of the 1-butene in the reaction process is too high and can not be combined with a downstream 1-butene separation device, and on the other hand, the selectivity of the carbon eight in the superposition reaction product is low and the quality of the superposition oil is low. 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-selective laminating method, which adopts a compatibility combination of a resin catalyst and a molecular sieve catalyst, strictly controls the reaction temperature, realizes the isobutene conversion rate of more than 98 percent and the 1-butene conversion rate of less than 10 percent in the absence of inhibitors and other additives, and simultaneously can ensure that the selectivity of the carbon eight in a laminating reaction product is more than 80 percent. In a second aspect the invention provides the use of a mixed carbon tetraselective process in a mixed carbon tetraseparation.
According to a first aspect, the present invention provides a mixed carbon four-selective process comprising the steps of:
s1, carrying out a first superposition reaction on mixed carbon four in the presence of a first catalyst to obtain a first superposition reactant;
s2, carrying out a second polymerization reaction on the first polymerization reactant in the step S1 in the presence of a second catalyst to obtain a second polymerization 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 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 a D006 resin, a D002 resin, an Amberlyst-15 resin, an Amberlyst-35 resin, an Amberlyst-45 resin, and a 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 2-6h.
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, in the first polymerization reaction, the space velocity of the mixed carbon four feed is 2.0h -1 -10h -1 For example 2.0h -1 、2.5h -1 、3.0h -1 、3.5h -1 、4.0h -1 、4.5h -1 、5.0h -1 、5.5h -1 、6.0h -1 、 6.5h -1 、7.0h -1 、7.5h -1 、8.0h -1 、8.5h -1 、9.0h -1 、9.5h -1 、10h -1 And any value in between.
According to some embodiments of the invention, in the first polymerization reaction, the space velocity of the mixed carbon four feed is 2.0h -1 -10h -1 The conversion degree of isobutene in the first polymerization reactor can be controlled in the range, the airspeed is too high, the isobutene conversion rate is low, the isobutene content in the residual C4 is too high, and more isobutene reacts in the second polymerization reactor to generate more isobutene oligomerization products, so that the property of the polymerization oil is influenced; the space velocity is too low, the residence time of the carbon four in the catalyst bed layer is long, the conversion rate of the 1-butene is increased, and the 1-butene is lost.
In some preferred embodiments of the present invention, the empty rate of the feed of mixed carbon four is 3.0h in the first polymerization reaction -1 -7.0h -1 。
According to some embodiments of the invention, in the second polymerization reaction, the space velocity of the first polymerization reactant is 1h -1 -5.0h -1 For example 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, in the second polymerization reaction, the space velocity of the first polymerization reactant is 1.0h -1 -5h -1 The range can control the conversion of isobutene, the space velocity is too high, so that isobutene cannot be completely converted, the residual carbon number four cannot meet the 1-butene separation requirement, the space velocity is too low, the isobutene multimerization product is increased, and the property of the laminated oil is affected.
In some preferred embodiments of the present invention, the space velocity of the feed of the first polymerization reactant in the second polymerization reaction is 0.5h -1 -3.0h -1 。
According to some embodiments of the invention, the first polymerization reaction has a higher feed space velocity than the second polymerization reaction.
According to some embodiments of the present invention, the space velocity of the first polymerization reaction is higher than the space velocity of the second polymerization reaction, so that the mixed carbon four can be partially converted in the resin catalyst, the conversion of 1-butene is controlled, and the mixed carbon four with low isobutene content can be converted in the molecular sieve catalyst at a low space velocity, so that the complete conversion of isobutene is realized, and the requirement of the 1-butene separation device on the raw material is met.
In some preferred embodiments of the invention, the ratio of the feed space velocity of the first polymerization reaction to the feed space velocity of the second polymerization reaction is (1-10): 1, e.g., 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.
In some preferred embodiments of the invention, the ratio of the feed space velocity of the first polymerization reaction to the feed space velocity of the second polymerization reaction is (2-6): 1.
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, 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, reduce the conversion of 1-butene and improve the selectivity of eight carbon components in the superposition process by controlling the reaction temperature of the first superposition reaction and the conversion rate of isobutene in the first superposition reaction.
According to some embodiments of the invention, the temperature of the second folding reaction is 30-150 ℃, e.g. 30 ℃, 35 ℃, 40 ℃, 45 ℃, 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 0.5-0.8MPa.
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 ℃ to 60 ℃ higher than the temperature of the first polymerization reaction.
According to some embodiments of the invention, the first and second polymerization reactions are performed in separate reactors.
According to some embodiments of the invention, the apparatus employed in the method of mixed carbon four selective polymerization comprises a first polymerization reactor and a second polymerization reactor and optionally a first separation column and a second separation column.
According to some embodiments of the invention, the apparatus comprises a first polymerization reactor, a first separation column, a second polymerization reactor, and a second 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 first separation column is used to separate the first bottoms stream to obtain a vapor phase stream comprising isobutylene and a liquid phase stream comprising bottoms.
According to some embodiments of the invention, the second polymerization reactor is used to subject the first polymerization product or the gas phase material comprising isobutene obtained after the first polymerization reactant to a second polymerization reaction to obtain a second polymerization reactant.
According to some embodiments of the invention, a second separation column is used to separate the second polymerization reactant to obtain crude 1-butene.
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 5-70%.
According to some embodiments of the invention, the mass content of isobutene in the mixed carbon four is 10-50%.
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 method further comprises, before step S2, separating the first polymerization reactant of step S1 to obtain a gas phase material containing isobutene and a liquid phase material containing a polymerization oil, and performing a second polymerization reaction on the gas phase material containing isobutene in the presence of a second catalyst to obtain a second polymerization reactant.
According to some embodiments of the invention, the process further comprises a step S3 of separating the second folding reactant of step S2 to obtain a second gas phase material comprising crude 1-butene and a second liquid phase material comprising folding oil.
According to some embodiments of the invention, the gas phase feed comprising crude 1-butene is used as a 1-butene separation unit feedstock.
According to some embodiments of the present invention, the liquid phase material containing the laminating oil obtained by separating the first laminating reactant and the second liquid phase material containing the laminating oil obtained by separating the second laminating reactant are mixed and output, and can be used as a gasoline component.
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 characteristics of 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 that the selectivity of isobutene dimerization is higher than 80%, ensuring that the 1-butene conversion rate is lower than 10%, and improving the selectivity of the eight carbon components in the overlapping process.
In some preferred embodiments of the invention, the method comprises in particular the steps of:
step 1, heating the mixed C4 by a preheater, and then feeding the mixed C4 into a first reactor, and carrying out superposition reaction under the action of a first catalyst to obtain a first reaction product.
And 2, the first reaction product enters a first separation tower to be separated at a certain temperature and pressure, the bottom of the tower is obtained as the laminated oil, and the top of the tower is obtained as the mixed C4 containing a small amount of isobutene.
And step 3, introducing the mixed C4 from the top of the first separation tower into a second reactor, and continuously carrying out a polymerization reaction under the action of a second catalyst to obtain a second polymerization product.
And 4, enabling the second superposition product to enter a second separation tower, obtaining superposition oil at the bottom of the tower, mixing with superposition oil at the bottom of the first separation tower, and obtaining residual C4 at the top of the tower to serve as a raw material of the 1-butene separation device.
According to a second aspect, the present 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.
The beneficial effects of the invention are as follows: the invention can not only enable the deep conversion rate of isobutene in the mixed C4 to be more than 98 percent, but also control the conversion rate of 1-butene to be less than 10 percent, and can also improve the selectivity of eight carbon components in the stacking process, thereby realizing the separation of isobutene and 1-butene, 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 selective polymerization reaction of the present invention,
reference numerals illustrate: 1-mixed carbon four raw materials, 2-first superposition reactor, 3-first separation tower, 4-second superposition reactor, 5-second separation tower, 6-residual carbon four and 7-tower bottom superposition products.
Detailed Description
The invention provides a method for selectively superposing mixed carbon four, which is shown in figure 1, wherein the mixed carbon four is 1 (5.51 percent of isobutane, 11.66 percent of n-butane and 7.53% of trans-2-butene, 29.6% of 1-butene, 41.33% of isobutene and 3.84% of cis-2-butene) are fed into a first polymerization reactor 2 through a metering pump, a resin catalyst is filled in the reactor, the temperature is 25-50 ℃, the pressure is 0.5-0.8MPa, and the feeding airspeed is 3.0h -1 -7.0h -1 Under the condition, the superposition reaction occurs, and the conversion rate of isobutene is controlled to be 85% -90%. The product enters a first separation tower 3 to separate the residual carbon four and overlapped products with low content of the isobutadiene. The separated residual carbon four enters a second reactor 4, the second reactor is filled with a molecular sieve catalyst, the reaction temperature is 60-120 ℃, the pressure is 0.5-0.8MPa, and the feeding airspeed is 0.5h -1 -3.0h -1 In the second reactor, the deep conversion of isobutene occurs, the total conversion of isobutene is more than 98%, and the total conversion of 1-butene is less than 10%. The product from the second reactor is separated by a second separation tower 5, the residual carbon four 6 at the top of the tower is sent to a 1-butene separation device, and the superposed product at the bottom of the tower is mixed with the product at the bottom of the first separation tower 7 and sent out from the device as a gasoline component.
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 first polymerization reactor through a metering pump, 15g NKC-9 resin catalyst is filled in the reactor, the temperature is 30 ℃, the pressure is 0.5MPa, and the feeding space velocity is 3.0h -1 Under this condition, a polymerization reaction occurs, and the conversion of isobutene is controlled to 90%. The product enters a first separation tower to separate out residual carbon four and overlapped products with low content of the isobutadiene. The separated residual carbon four enters a second reactor, the second reactor is filled with 30g of SAPOP-11 molecular sieve catalyst, the reaction temperature is 70 ℃, the pressure is 0.5MPa, and the feeding airspeed is 0.5h -1 In the second reactor, deep conversion of isobutene takes place with little conversion of 1-butene. Separating the product from the second reactor in the second separating tower, separating the rest carbon four-1-butene in the top of the tower in the 1-butene separating device, and mixing the superposed product at the bottom of the tower with the product at the bottom of the first separating tower to obtain gasoline component.
After the two superposition catalysts are used together, the total conversion rate of isobutene is more than 99.5%, the total conversion rate of 1-butene is 8.1%, and the selectivity of carbon eight is 83.5%. Not only the isobutene in the cracked C4 is effectively removed, but also 1-butene is remained as much as possible, so that the gas phase reaction product can be used as the raw material of the 1-butene separation unit, the combination with the 1-butene unit is realized, and the specific results and conditions are listed in Table 1.
Example 2:
the same as in example 1, except that the space velocity of the second reactor feed was adjusted to 1.0h -1 . After the two catalysts were combined, the total conversion of isobutene was 99.1%, the conversion of 1-butene was 7.5% and the carbon eight selectivity was 85.4%, the specific results and conditions are shown in Table 1.
Example 3:
the same as in example 1, except that the space velocity of the second reactor feed was adjusted to 2.0h -1 . After the two catalysts were combined, the total conversion of isobutene was 98.5%, the conversion of 1-butene was 6.4% and the carbon eight selectivity was 87.4%, and the specific results and conditions are shown in Table 1.
Example 4:
the difference from example 1 is that the catalyst used in the first reactor is Amberlyst-35 catalyst and the catalyst used in the second reactor is MCM-22 molecular sieve catalyst. After the two catalysts were combined, the total conversion of isobutene was 99.8%, the conversion of 1-butene was 9.0% and the carbon eight selectivity was 81.2%, the specific results and conditions are shown in Table 1.
Example 5:
the same as in example 4, except that the space velocity of the second reactor feed was adjusted to 1.5h -1 . After the two catalysts react together, the total conversion rate of isobutene is 99.1 percent, and the 1-butylThe alkene conversion was 8.4% and the carbon octaselectivity was 83.7%, and the specific results and conditions are shown in Table 1.
Example 6:
the same as in example 4, except that the space velocity of the second reactor feed was adjusted to 2.5h -1 . After the two catalysts were combined, the total conversion of isobutene was 98.7%, the conversion of 1-butene was 7.4%, and the carbon eight selectivity was 85.6%, with the specific results and conditions shown in Table 1.
Example 7:
the same as in example 4, except that the space velocity of the feed to the first reactor was adjusted to 5.0h -1 The space velocity of the second reactor feed was adjusted to 1.0h -1 . After the two catalysts were reacted together, the total conversion of isobutene was 98.2%, the conversion of 1-butene was 5.4%, and the carbon octaselectivity was 84.3%, with the specific results and conditions shown in Table 1.
Example 8:
the same as in example 4, except that the space velocity of the feed to the first reactor was adjusted to 3.0h -1 The space velocity of the second reactor feed was adjusted to 3.0h -1 . After the two catalysts were reacted in combination, the total conversion of isobutene was 96.2%, the conversion of 1-butene was 7.3% and the carbon eight selectivity was 76.3%, the specific results and conditions are shown in Table 1.
Example 9:
the same as in example 4, except that the space velocity of the feed to the first reactor was adjusted to 1.0h -1 The space velocity of the second reactor feed was adjusted to 5.0h -1 . After the two catalysts were reacted together, the total conversion of isobutene was 97.3%, the conversion of 1-butene was 16.2%, and the carbon eight selectivity was 86.1%, with the specific results and conditions shown in Table 1.
Comparative example 1
The difference from example 1 was that the first polymerization reactor was charged with 15g of NKC-9 resin catalyst and the second polymerization reactor was charged with 30g of NKC-9 resin catalyst, and after the reaction, the total conversion of isobutene was 93.2%, the conversion of 1-butene was 20.3% and the carbon eight selectivity was 88.1%, and the specific results and conditions were as shown in Table 1.
Comparative example 2
The difference from example 1 was that the first polymerization reactor was charged with 15g of MCM-22 molecular sieve catalyst and the second polymerization reactor was charged with 30g of MCM-22 molecular sieve catalyst, and after the reaction, the total conversion of isobutene was 99.3%, the conversion of 1-butene was 3.0% and the carbon eight selectivity was 65.2%, and the specific results and conditions were as 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 constitute any limitation of the present invention. 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 (14)
1. A method of mixed carbon four selective superimposition comprising the steps of:
s1, carrying out a first superposition reaction on mixed carbon four in the presence of a first catalyst to obtain a first superposition reactant;
s2, carrying out a second polymerization reaction on the first polymerization reactant in the step S1 in the presence of a second catalyst to obtain a second polymerization 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 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 conversion rate of isobutene in the first polymerization reaction is 80-90%;
the method further comprises the steps of separating the first superposition reactant in the step S1 before the step S2 to obtain a gas-phase material containing isobutene and a liquid-phase material containing superposition oil, and carrying out a second superposition reaction on the gas-phase material containing isobutene in the presence of a second catalyst to obtain a second superposition reactant;
in the first polymerization reaction, the space velocity of the mixed carbon four feed is 2.0h -1 -10h -1 ；
In the second polymerization reaction, the feeding airspeed of the first polymerization reactant is 1h -1 -5.0h -1 ；
The temperature of the second polymerization reaction is higher than that of the first polymerization reaction.
2. The process of claim 1 wherein the ratio of the space feed rate of the first polymerization reaction to the space feed rate of the second polymerization reaction is (1-10): 1.
3. The process according to claim 1, wherein in the first polymerization reaction, the space velocity of the mixed carbon four feed is 3.0h -1 -7.0h -1 ；
And/or in the second polymerization reaction, the feeding space velocity of the first polymerization reactant is 1h -1 -3.0h -1 ；
And/or the ratio of the space velocity of the feed of the first polymerization reaction to the space velocity of the feed of the second polymerization reaction is (2-6): 1.
4. A method according to any one of claims 1 to 3, wherein the temperature of the first folding reaction is 15 to 70 ℃;
and/or the pressure of the first polymerization reaction is 0.4-1.5MPa.
5. The method of claim 4, wherein the temperature of the first polymerization reaction is 25-50 ℃;
and/or the pressure of the first polymerization reaction is 0.5-1.0MPa.
6. A method according to any one of claims 1 to 3, wherein the temperature of the second folding reaction is 30 to 150 ℃;
and/or the pressure of the second polymerization reaction is 0.4-1.5MPa.
7. The method of claim 6, wherein the temperature of the second polymerization reaction is 60-120 ℃;
and/or the pressure of the second polymerization reaction is 0.5-0.8MPa.
8. A process according to any one of claims 1 to 3, wherein the temperature of the second polymerisation reaction is 20 ℃ to 60 ℃ higher than the temperature of the first polymerisation reaction.
9. A method according to any one of claims 1-3, characterized in that the first and second polymerization reactions are carried out in separate reactors.
10. A method according to any one of claims 1-3, wherein the mixed carbon four is selected from one or more of cracked carbon four, refinery carbon four and FCC light carbon four.
11. The method according to claim 10, wherein the mass content of isobutene in the mixed carbon four is 5-70%.
12. The method according to claim 11, wherein the mass content of isobutene in the mixed carbon four is 10-50%.
13. Use of a method according to any one of claims 1-12 in a mixed carbon tetra separation.
14. Use of a process according to any one of claims 1 to 12 for the separation of 1-butene from isobutene.
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