CN113929549A - Selective superposition method for mixed C4 - Google Patents
Selective superposition method for mixed C4 Download PDFInfo
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- CN113929549A CN113929549A CN202010609758.0A CN202010609758A CN113929549A CN 113929549 A CN113929549 A CN 113929549A CN 202010609758 A CN202010609758 A CN 202010609758A CN 113929549 A CN113929549 A CN 113929549A
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- 238000000034 method Methods 0.000 title claims abstract description 35
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 128
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 239000002808 molecular sieve Substances 0.000 claims abstract description 31
- 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 31
- 239000000376 reactant Substances 0.000 claims abstract description 23
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 17
- 229940023913 cation exchange resins Drugs 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052680 mordenite Inorganic materials 0.000 claims description 4
- 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 3
- 238000005336 cracking Methods 0.000 claims description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 24
- 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 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000006471 dimerization reaction 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
- 239000001282 iso-butane Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 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
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002954 polymerization reaction product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 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
- 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
- 239000002551 biofuel Substances 0.000 description 1
- 238000009835 boiling Methods 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
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006266 etherification reaction Methods 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
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009466 transformation Effects 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
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- 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)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a selective superposition method of mixed C4, which comprises the following steps: s1, carrying out a first polymerization reaction on the mixed C4 in the presence of a first catalyst to obtain a first polymerization reactant; s2, carrying out a second polymerization reaction on the first polymerization reactant of 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 cation exchange resins in the hydrogen form and the second catalyst is selected from one or more of molecular sieve catalysts. The method can ensure that the 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 by using the compatibility of the two catalysts, thereby realizing the separation of isobutene and 1-butene and obtaining the residual C4 which meets the requirements 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 selective superposition method and device for mixed carbon four.
Background
1-butene is an important chemical raw material, is alpha-olefin with active chemical properties, and is mainly used as a comonomer for producing Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE) and polybutene-1 (PB) plastics. The 1-butene is generally prepared by reacting the raffinate C4 from the butadiene extraction unit with commercially available methanol to produce MTBE and chemically reacting the isobutylene. The remaining ether post C4 was used to purify polymer grade butene-1 and the product was used in downstream polyethylene units for comonomer or export. With the vigorous popularization and implementation of the embodiment on expanding the production of biofuel ethanol and popularizing and using the ethanol gasoline for vehicles, the MTBE synthesis device faces production stop and transfer, and how to realize the separation of 1-butene and isobutene is a difficult problem for enterprises.
Since the difference between the boiling points of 1-butene and isobutene is only 0.6 ℃, the method is difficult to obtain by a common rectification method. The selective polymerization of mixed C4 is a main way for realizing the separation of isobutene and 1-butene, isobutene is reacted through isobutene polymerization 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 generally adopted as a catalyst for the polymerization of the mixed C4, but in the polymerization reaction process, double bond isomerization and polymerization of 1-butene easily occur, the loss is large, and the loss amount reaches 50-70%. In order to control the conversion rate of 1-butene, the prior art mainly adopts adding an inhibitor to control the conversion degree of the polymerization reaction.
CN209237905 provides a combined production method, in which a system device for obtaining a raw material with high content of 1-butene from C4 is combined with isobutene polymerization reaction to realize deep removal of isobutene in C4 and reduce 1-butene loss, but the 1-butene loss rate still reaches 20% -40%, and simultaneously the addition of water makes the reaction more complicated and the product more complex.
Disclosure of Invention
At present, the selective carbon four polymerization has the defects that on one hand, the loss of 1-butene in the reaction process is too high and cannot be combined with a downstream 1-butene separation device, and on the other hand, the selectivity of carbon eight in the polymerization reaction product is low and the quality of polymerization oil is low. Therefore, there is a need for improvement and research on the selective polymerization process to exploit its potential, so as to achieve the purpose of reducing 1-butene loss and improving economic benefits. The invention provides a mixed carbon four-selective polymerization method, which adopts compatible combination of a resin catalyst and a molecular sieve catalyst, strictly controls the reaction temperature, realizes the conversion rate of isobutene of more than 98 percent and the conversion rate of 1-butene of less than 10 percent in the absence of inhibitors and other additives, and simultaneously can ensure that the selectivity of carbon eight in a polymerization reaction product is more than 80 percent. In a second aspect, the invention provides the use of a mixed C.sub.C.sub.D. selective process for the separation of mixed C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.C.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.C.C.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.C.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.sub.selectively process in a.
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 the mixed C4 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 of 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 cation exchange resins in the hydrogen form 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, eight of the carbons in the dimerization and oligomerization product of isobutene constitutes 80% to 90% and more than twelve carbons constitutes 10% to 20%.
According to some embodiments of the invention, the cation exchange resin in hydrogen form is selected from one or more of the group consisting of strong acid cation exchange resins.
According to some embodiments of the invention, the hydrogen cation exchange resin is selected from one or more of styrenic cation exchange resins, acrylic cation exchange resins, epoxy cation exchange resins and phenolic cation exchange resins.
According to some embodiments of the invention, the cation exchange resin in the hydrogen form 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 method of preparing the molecular sieve comprises: mixing the molecular sieve powder with adhesive and acid in certain proportion, kneading, extruding, drying and roasting.
According to some embodiments of the invention, the binder is pseudoboehmite.
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 present invention, the drying temperature is 100-120 ℃, and the drying time is 2-6 h.
According to some embodiments of the present invention, the calcination temperature is 400-600 ℃, and the calcination time is 4-10 h.
According to some embodiments of the invention, the first stacking reaction has a mixed C4 feed space velocity of 2.0h-1-10h-1E.g. 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-1And any value in between.
According to some embodiments of the invention, the first stacking reaction has a mixed C4 feed space velocity of 2.0h-1-10h-1The conversion degree of isobutene in the first polymerization reactor can be controlled within the range, the space velocity is too high, the isobutene conversion rate is low, the content of isobutene in the residual carbon four is too high, and isobutene reacts in the second polymerization reactor more, so that more isobutene oligomerization products are generated, and the property of polymerization oil is influenced; the space velocity is too low, the carbon four stays in the catalyst bed for a long time, which increases the conversion rate of 1-butene and causes the loss of 1-butene.
In some preferred embodiments of the present invention, the air velocity of the feeding of the mixed C4 in the first polymerization reaction is 3.0h-1-7.0h-1。
According to some embodiments of the invention, the space velocity of the first polymerization reaction is 1h in the second polymerization reaction-1-5.0h-1E.g. 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-1And any value in between.
According to some embodiments of the invention, the space velocity of the first polymerization reaction is 1.0h in the second polymerization reaction-1-5h-1This range can be controlledThe alkene conversion has too high space velocity, which causes that isobutene cannot be completely converted, the residual carbon four cannot meet the separation requirement of 1-butene, and the space velocity is too low, which causes that isobutene polymeric products are increased and the property of the laminated oil is influenced.
In some preferred embodiments of the present invention, the space velocity of the first polymerization reaction is 0.5h in the second polymerization reaction-1-3.0h-1。
According to some embodiments of the invention, the feed space velocity of the first stacking reaction is higher than the feed space velocity of the second stacking reaction.
According to some embodiments of the present invention, the feeding space velocity of the first stacking reaction is higher than that of the second stacking reaction, so that the mixed C4 can be partially converted in the resin catalyst, and the conversion of 1-butene can be controlled, and the mixed C4 with low isobutene content can be converted at a low space velocity in the molecular sieve catalyst, so that the complete conversion of isobutene can be realized, and the requirements of a 1-butene separation device on raw materials can be met.
In some preferred embodiments of the present invention, the ratio of the feed space velocity of the first folding reaction to the feed space velocity of the second folding 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 in between.
In some preferred embodiments of the present 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 polymerization reaction is 15-70 ℃, such as 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 between 25 and 50 ℃.
According to some embodiments of the invention, the pressure of the first folding reaction is between 0.4 and 1.5MPa, such as 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 between 0.5 and 1.0 MPa.
According to some embodiments of the invention, the conversion of isobutylene in the first polymerization reaction is 70-95%, such as 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 isobutylene in the first polymerization reaction is 80-90%.
The invention can ensure a certain conversion of isobutene, reduce the conversion of 1-butylene and improve the selectivity of carbon eight components in the polymerization process 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 polymerization reaction is 30-150 ℃, such as 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 between 0.4 and 1.5MPa, such as 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 between 0.5 and 0.8 MPa.
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 present invention, the temperature of the second polymerization reaction is 20 ℃ to 60 ℃ higher than that of the first polymerization reaction.
According to some embodiments of the invention, the first polymerization reaction and the second polymerization reaction are carried out in different reactors, respectively.
According to some embodiments of the present invention, the apparatus employed in the method of mixed carbon four selective stacking comprises a first stacking reactor and a second stacking 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 used to subject 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 adapted to separate the first reaction product into a gaseous feed comprising isobutene and a liquid feed comprising the reaction oil.
According to some embodiments of the present invention, the second polymerization reactor is used for subjecting the first polymerization product or the gas phase feed comprising isobutylene 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 blended carbon four is selected from one or more of cracked carbon four, refinery carbon four, and FCC light carbon four.
In some preferred embodiments of the invention, the mixed C.sub.four is selected from any of the isobutene-containing C.sub.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 isobutylene content of the mixed C4 is 5-70% by mass.
According to some embodiments of the invention, the isobutene content of the mixed C4 is 10-50% by mass.
According to some embodiments of the invention, the carbon four blend is selected from the group consisting of cracking carbon four and/or refinery carbon four.
According to some embodiments of the invention, the mixed C.sub.D comprises 1 to 20 wt% alkanes and 20 to 90 wt% butenes.
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 present invention, the method further comprises, before step S2, subjecting the first polymerization reactant of step S1 to a separation treatment to obtain a vapor phase material containing isobutylene and a liquid phase material containing polymerization oil, and subjecting the vapor phase material containing isobutylene to a second polymerization reaction in the presence of a second catalyst to obtain a second polymerization reactant.
According to some embodiments of the invention, the method further comprises a step S3 of subjecting the second polymerization reactant of the step S2 to a separation treatment to obtain a second gas-phase material containing crude 1-butene and a second liquid-phase material containing polymerization oil.
According to some embodiments of the invention, the gas phase feed comprising crude 1-butene is used as a feed to a 1-butene separation unit.
According to some embodiments of the present invention, the liquid phase material comprising the folded oil obtained by separating the first folded reactant and the second liquid phase material comprising the folded oil obtained by separating the second folded reactant are mixed and output as gasoline components.
The inventor finds in research that during the reaction of the resin catalyst, the temperature is higher for obtaining higher isobutene conversion rate, but the 1-butene is converted at high temperature; in the reaction process of the molecular sieve catalyst, 1-butene basically does not react, but isobutene polymers are generated more, and the content of C8 in a superposed product is lower. By adopting the compatibility of the resin catalyst and the molecular sieve catalyst and combining the characteristics of the resin catalyst and the molecular sieve catalyst, 80-90% of isobutene is superposed on the low-temperature resin catalyst, and about 10% of isobutene is superposed on the high-temperature molecular sieve, so that the dimerization selectivity of isobutene is ensured to be more than 80%, the conversion rate of 1-butene is ensured to be less than 10%, and the selectivity of carbon eight components in the superposing process can be improved.
In some preferred embodiments of the invention, the method specifically comprises the steps of:
And 2, feeding the first reaction product into a first separation tower, separating at a certain temperature and under a certain pressure, obtaining superposed oil at the tower bottom, and obtaining mixed C4 containing a small amount of isobutene at the tower top.
And 3, feeding the mixed C4 from the top of the first separation tower into a second reactor, and continuing to perform a polymerization reaction under the action of a second catalyst to obtain a second polymerization product.
And 4, allowing the second superposed product to enter a second separation tower, obtaining superposed oil at the tower bottom, mixing the superposed oil with the superposed oil at the tower bottom of the first separation tower, and obtaining residual C4 at the tower top as a raw material of the 1-butene separation device.
According to a second aspect, the present invention provides the use of the process of the first aspect in mixed C-C separations.
According to some embodiments of the present invention, there is provided the use of the process of the first aspect in the separation of 1-butene from isobutene.
In some preferred embodiments of the present invention, the process of the first aspect may be used for the separation of 1-butene in the etherification of C4 in the MTBE synthesis reaction.
The invention has the beneficial effects that: the invention can not only ensure that the conversion rate of isobutene in the mixed C4 is more than 98 percent, but also control the conversion rate of 1-butene and the conversion rate is less than 10 percent, and simultaneously can improve the selectivity of carbon eight components in the overlapping process, thereby realizing the separation of isobutene and 1-butene and obtaining the residual C4 which meets the requirement of raw materials of a 1-butene separation device.
Drawings
FIG. 1 is a process flow diagram of the mixed carbon four selective stacking reaction of the present invention,
description of reference numerals: 1-mixed C-C raw material, 2-first superimposed reactor, 3-first separation tower, 4-second superimposed reactor, 5-second separation tower, 6-residual C-C and 7-tower bottom superimposed product.
Detailed Description
The invention provides a selective superposition method of mixed carbon four, as shown in figure 1, mixed carbon four 1(5.51 percent of isobutane, 11.66 percent of n-butane, 7.53 percent of trans-2-butene, 29.6 percent of 1-butene, 41.33 percent of isobutene and 3.84 percent of cis-2-butene) enters a first superposition 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 space velocity is 3.0h-1-7.0h-1And carrying out a polymerization reaction under the condition, wherein the conversion rate of isobutene is controlled to be 85-90%. The product enters a first separation tower 3, and residual carbon four and a superimposed product with low isobutene content are separated. The separated residual carbon four enters a second reactor 4 which 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-1In the second reactor, the isobutene is deeply converted, the total conversion rate of the isobutene is more than 98 percent, and the total conversion rate of the 1-butene is less than 10 percent. 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 and the product at the bottom of the first separation tower are mixed 7 and sent out of the device as a gasoline component.
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the invention in any way.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1:
mixed C-IV (5.51% of isobutane, 11.66% of n-butane, 7.53% of trans-2-butene, 29.6% of 1-butene, 41.33% of isobutene and 3.84% of cis-2-butene) enters a first polymerization reactor through a metering pump, 15g of NKC-9 resin catalyst is filled in the reactor, the temperature is 30 ℃, the pressure is 0.5MPa, and the feeding airspeed is 3.0h-1Under the condition, the polymerization reaction occurs, and the conversion rate of isobutene is controlled to be 90%. The product enters a first separation tower, and residual carbon four and a superimposed product with low isobutene content are separated. 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-1In the second reactor, the isobutene is deeply converted, with little conversion of 1-butene. And (3) separating a product from the second reactor by using a second separation tower, removing the residual carbon four at the top of the tower to a 1-butene separation device, mixing a superposed product at the bottom of the tower and a product at the bottom of the first separation tower, and sending the mixed product out of the device as a gasoline component.
After the two catalysts are used in a compatible manner, 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 effectively removes isobutene in the cracking carbon four, but also retains 1-butene as much as possible, so that a gas-phase reaction product can be used as a raw material of a 1-butene separation device, and the combination with the 1-butene device is realized, and specific results and conditions are listed in Table 1.
Example 2:
the difference from example 1 is that the space velocity of the feed to the second reactor was adjusted to 1.0h-1. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 99.1%, the conversion rate of 1-butene is 7.5%, and the selectivity of carbon eight is 85.4%, and specific results and conditions are listed in table 1.
Example 3:
the difference from example 1 is that the space velocity of the feed to the second reactor was adjusted to 2.0h-1. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 98.5%, the conversion rate of 1-butene is 6.4%, and the selectivity of carbon to eight is 87.4%, and specific results and conditions are listed in table 1.
Example 4:
the same as example 1, except that the catalyst used in the first reactor was Amberlyst-35 catalyst and the polymerization catalyst used in the second reactor was MCM-22 molecular sieve catalyst. After the two catalysts are matched for reaction, the total conversion rate of isobutene is 99.8%, the conversion rate of 1-butene is 9.0%, and the carbon selectivity is 81.2%, and specific results and conditions are shown in table 1.
Example 5:
the difference from example 4 is that the space velocity of the feed to the second reactor was adjusted to 1.5h-1. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 99.1%, the conversion rate of 1-butene is 8.4%, and the carbon selectivity is 83.7%, and specific results and conditions are listed in table 1.
Example 6:
the difference from example 4 is that the space velocity of the feed to the second reactor was adjusted to 2.5h-1. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 98.7%, the conversion rate of 1-butene is 7.4%, and the selectivity of carbon eight is 85.6%, and specific results and conditions are listed in table 1.
Example 7:
the difference from example 4 is that the space velocity of the first reactor feed was adjusted to 5.0h-1The feeding space velocity of the second reactor is adjusted to be 1.0h-1. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 98.2%, the conversion rate of 1-butene is 5.4%, and the selectivity of carbon eight is 84.3%, and specific results and conditions are listed in table 1.
Example 8:
the difference from example 4 is that the space velocity of the first reactor feed was adjusted to 3.0h-1The feeding space velocity of the second reactor is adjusted to be 3.0h-1. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 96.2%, the conversion rate of 1-butene is 7.3%, and the selectivity of carbon eight is 76.3%, and specific results and conditions are listed in table 1.
Example 9:
the difference from example 4 is that the space velocity of the feed to the first reactor was adjusted to 1.0h-1Second reactor feed airThe speed is adjusted to 5.0h-1. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 97.3%, the conversion rate of 1-butene is 16.2%, and the selectivity of carbon eight is 86.1%, and specific results and conditions are listed in table 1.
Comparative example 1
The same as example 1, except that the first polymerization reactor was charged with 15g of NKC-9 resin catalyst and the second reactor was charged with 30g of NKC-9 resin catalyst, the total conversion of isobutylene 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 are shown in Table 1.
Comparative example 2
The same as example 1, except that 15g of MCM-22 molecular sieve catalyst was packed in the first polymerization reactor and 30g of MCM-22 molecular sieve catalyst was packed in the second polymerization reactor, the total conversion of isobutene was 99.3%, the conversion of 1-butene was 3.0%, and the selectivity to carbon eight was 65.2% after the reaction, and the specific results and conditions are shown in Table 1.
TABLE 1
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A hybrid carbon four selective lamination process comprising the steps of:
s1, carrying out a first polymerization reaction on the mixed C4 in the presence of a first catalyst to obtain a first polymerization reactant;
s2, carrying out a second polymerization reaction on the first polymerization reactant of 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 cation exchange resins in the hydrogen form and the second catalyst is selected from one or more of molecular sieve catalysts.
2. The method according to claim 1, wherein the cation exchange resin in hydrogen form is selected from one or more of strong acid cation exchange resins, preferably from one or more of styrenic cation exchange resins, acrylic cation exchange resins, epoxy cation exchange resins and phenolic cation exchange resins, more preferably from one or more of D006 resin, D002 resin, Amberlyst-15 resin, Amberlyst-35 resin, Amberlyst-45 resin and NKC-9 resin.
3. The process according to claim 1 or 2, characterized in that the molecular sieve catalyst is selected from one or more of mordenite, Y-series molecular sieves, ZSM-series molecular sieves, MCM-series molecular sieves, beta-series molecular sieves and SAPO-series molecular sieves, preferably from one or more of ZSM-5, MCM-22, mordenite, MCM-41, SAPO-11 and SAPO-41.
4. The method as claimed in any one of claims 1 to 3, wherein the first polymerization reaction has a mixed C4 feed space velocity of 2.0h-1-10h-1Preferably 3.0h-1-7.0h-1；
And/or the feeding space velocity of the first polymerization reactant in the second polymerization reaction is 1h-1-5.0h-1Preferably 0.5h-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 (1-10):1, preferably (2-6): 1.
5. The process according to any one of claims 1 to 4, wherein the temperature of the first polymerization reaction is 15 to 70 ℃, preferably 25 to 50 ℃;
and/or the pressure of the first polymerization reaction is 0.4-1.5MPa, preferably 0.5-1.0 MPa;
and/or the conversion of isobutene in the first polymerization reaction is from 70 to 95%, preferably from 80 to 90%.
6. The process according to any one of claims 1 to 5, wherein the temperature of the second polymerization reaction is between 30 and 150 ℃, preferably between 60 and 120 ℃;
and/or the pressure of the second polymerization reaction is 0.4-1.5MPa, preferably 0.5-0.8 MPa;
preferably, the temperature of the second polymerization reaction is higher than that of the first polymerization reaction, and preferably, the temperature of the second polymerization reaction is 20-60 ℃ higher than that of the first polymerization reaction.
7. The process according to any one of claims 1 to 6, wherein the first polymerization reaction and the second polymerization reaction are carried out in separate reactors.
8. The process according to any one of claims 1 to 7, wherein the mixed carbon four is selected from one or more of cracking carbon four, refinery carbon four and FCC light carbon four, preferably, the mixed carbon four has an isobutene content of 5 to 70% by mass, more preferably 10 to 50% by mass.
9. The method of any one of claims 1-8, further comprising, before step S2, subjecting the first polymerization reactant of step S1 to a separation treatment to obtain a gas-phase material containing isobutylene and a liquid-phase material containing polymerization oil, and subjecting the gas-phase material containing isobutylene to a second polymerization reaction in the presence of a second catalyst to obtain a second polymerization reactant.
10. Use of the process according to any one of claims 1 to 9 for mixed carbon four separation, in particular for separating 1-butene from isobutene.
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