CN111375447A - Modified cation exchange resin and preparation method and application thereof - Google Patents
Modified cation exchange resin and preparation method and application thereof Download PDFInfo
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- CN111375447A CN111375447A CN201811614738.1A CN201811614738A CN111375447A CN 111375447 A CN111375447 A CN 111375447A CN 201811614738 A CN201811614738 A CN 201811614738A CN 111375447 A CN111375447 A CN 111375447A
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- cation exchange
- exchange resin
- organic amine
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- cyclic
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 71
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 38
- 150000001412 amines Chemical class 0.000 claims abstract description 36
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000012986 modification Methods 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 235000019441 ethanol Nutrition 0.000 description 18
- 229940023913 cation exchange resins Drugs 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 dimerization Chemical compound 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QIJIUJYANDSEKG-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N QIJIUJYANDSEKG-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- INLZPWGDAXIEAT-UHFFFAOYSA-N cyclohexanamine;ethanol Chemical compound CCO.NC1CCCCC1 INLZPWGDAXIEAT-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- RQVGZVZFVNMBGS-UHFFFAOYSA-N n-octyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCCCCCC)C1=CC=CC=C1 RQVGZVZFVNMBGS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
- C07C2531/10—Ion-exchange resins sulfonated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a modified cation exchange resin, which is prepared by modifying the cation exchange resin with cyclic organic amine. The acidic active sites on the surface of the cation exchange resin are modified by using the cyclic organic amine, so that the isobutene dimerization selectivity of the modified cation exchange resin reaches over 90 percent.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a modified cation exchange resin and a preparation method and application thereof.
Background
With the popularization and use of ethanol gasoline, methyl tert-butyl ether (MTBE) as a gasoline high-octane blending component will exit the historical arena. Meanwhile, isobutene is one of the main raw materials for preparing MTBE, and thus isobutene also faces the problem of excess capacity. Therefore, the effective utilization of isobutene has become one of the main problems facing the chemical industry in recent years.
One of the ways in which isobutene can be effectively utilized is by utilizing the isobutene dimerization technique to prepare diisobutylene (isooctene). Isooctane can be produced by hydrotreating diisobutylene. Isooctane, which can replace MTBE as an additional component in high octane gasoline, has an octane number of 100. In addition, diisobutylene is also used for synthetic rubber tackifiers, various surfactants, modifiers for phenol resins and epoxy resins, ultraviolet absorbers, polymerization inhibitors, polyvinyl chloride stabilizers, plasticizers, and the like; also used for producing fine chemicals such as p-octylphenol, resin, isononanol, octyldiphenylamine, versatic acid, t-octylamine, etc.
The cation exchange resin has the advantages of strong acidity, uniform acid content, large pore diameter and the like, and is suitable for serving as a catalyst for isobutene dimerization reaction. However, during the dimerization of isobutylene in which the cation exchange resin participates, copolymerization products such as trimerization and tetramerization are generated, thereby decreasing the selectivity of the dimerization reaction.
In order to increase the selectivity of the dimerization product as much as possible while maintaining the activity of the cation exchange resin, many researchers have employed the addition of alcohols, ethers, etc. to the isobutylene-containing raw material to increase the dimerization selectivity of isobutylene. However, the presence of these alcohols, ethers, etc. not only makes the system more complicated, but also increases the difficulty of the post-treatment of the isobutylene dimerization product, resulting in unnecessary energy and material consumption.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a modified cation exchange resin, a preparation method and an application thereof, wherein cyclic organic amine is used to modify acidic active sites on the surface of the cation exchange resin, so that the modified cation exchange resin is endowed with high isobutylene dimerization selectivity.
The invention provides a modified cation exchange resin, which is prepared by modifying the cation exchange resin with cyclic organic amine.
Acidic active sites (sulfonic acid group, -SO) on the surface of cation exchange resin3H) Can promote the polymerization reaction of isobutene, including dimerization, trimerization, tetramerization and the like, and thus the production of diisobutylene as a target product cannot obtain good yield. The inventor of the present application has found through research that the cyclic organic amine can exert a desirable modification effect on the acidic active sites on the surface of the cation exchange resin to improve the selectivity of the dimerization reaction. The inventors speculate that the reason is that the N atom in the cyclic organic amine has a lone pair electron and the cyclic organic amine is basic and can react with — SO3H is reacted. In addition, the cyclic organic amine has larger steric hindrance and can prevent isobutene from contacting with an acidic active site to a certain extent. Therefore, excessive contact between isobutene and excessive acid sites can be avoided, so that high-selectivity dimerization reaction of isobutene can be ensured, and undesirable copolymerization reactions such as trimerization, tetramerization and the like of isobutene can be effectively reduced and avoided.
In a preferred embodiment of the present invention, the cyclic organic amine is used in an amount of 0.5 to 20.0%, preferably 1.0 to 15.0%, and more preferably 2.0 to 10.0%, based on the total weight of the modified cation exchange resin.
According to the present invention, by controlling the amount of the cyclic organic amine in the modified cation exchange resin within the above-specified range, the surface of the cation exchange resin can be provided with an appropriate number of acidic active sites, thereby ensuring that the isobutylene is dimerized with high selectivity.
According to the invention, the exchange of the cyclic organic amine is referred to as-SO3The mass of the H-reacted cyclic organic amine is the percentage of the total weight of the modified cation exchange resin.
In another aspect, the present invention provides a method for preparing a modified cation exchange resin, comprising the steps of:
providing an alcoholic solution of cyclic organic amine dissolved in an alcohol organic solvent;
and modifying the cation exchange resin by using the alcoholic solution of the cyclic organic amine.
According to the invention, the cyclic organic amine is dissolved in the alcohol organic solvent, so that the alcohol solution of the cyclic organic amine with proper concentration and excellent dispersibility can be obtained, and the cyclic organic amine can be ensured to uniformly and fully modify the surface acidic active sites of the cation exchange resin, so that the modified cation exchange resin has proper activity and isobutene dimerization selectivity.
According to the present invention, the method for preparing the modified cation exchange resin further comprises:
the cation exchange resin is pretreated before the modification treatment.
According to the invention, the pre-treatment comprises: the cation exchange resin is subjected to a first washing treatment and a first drying treatment. The solvent of the first washing treatment is low-alcohol, such as absolute ethyl alcohol, and the washing is carried out until the water content in the eluate is lower than 3%; the temperature of the first drying treatment is room temperature-100 ℃, and the time is 4h-10 h.
According to the present invention, by subjecting the cation exchange resin to the first washing treatment and the first drying treatment, the removal of moisture from the cation exchange resin is facilitated.
According to the present invention, the method for preparing the modified cation exchange resin further comprises:
after the modification treatment, the modified cation exchange resin is subjected to a post-treatment.
According to the invention, the post-treatment comprises a second washing treatment and a second drying treatment of the modified cation exchange resin. The solvent of the second washing treatment is deionized water, and the solvent is washed until the solvent is neutral; the temperature of the second drying treatment is 35-70 ℃, and the time is 6-12 h.
According to the invention, the second washing treatment and the second drying treatment are carried out on the cation exchange resin, so that the alcohol solution of the cyclic organic amine remained in the cation exchange resin is favorably removed.
In another preferred embodiment of the present invention, the cyclic organic amine is selected from aliphatic cyclic amines and/or aromatic cyclic amines, preferably aliphatic cyclic amines and/or aromatic cyclic amines having 2 to 6 carbon atoms, and most preferably at least one of cyclohexylamine, aniline, cyclic ethyleneimine and nitroaniline. .
According to the invention, the cyclic organic amine with the specific carbon number has proper steric hindrance, and is favorable for further improving the isobutene dimerization selectivity of the modified cation exchange resin.
According to the present invention, the number of carbon atoms in the "aliphatic cyclic amine and/or aromatic cyclic amine having 2 to 6 carbon atoms" means the number of carbon atoms constituting the aliphatic ring and/or aromatic ring.
In another preferred embodiment of the present invention, the alcoholic organic solvent is selected from C1-C5At least one of the alcohols is preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, iso-butanol and n-pentanol.
In another preferred embodiment of the present invention, the concentration of the cyclic organic amine in the alcohol solution of the cyclic organic amine is 10 wt% to 60 wt%, preferably 20 wt% to 40 wt%, based on 100 wt% of the alcohol solution of the cyclic organic amine.
According to the present invention, by controlling the concentration of the cyclic organic amine within the above range, uniform and sufficient modification of the surface acidic active sites of the cation exchange resin is facilitated.
In another preferred embodiment of the present invention, the cation exchange resin is a cation exchange resin in the hydrogen form, preferably a sulfonic acid resin in the hydrogen form, more preferably D006, D002, Amberlyst-15, Amberlyst-35, Amberlyst-45 or nkc-9.
According to the present invention, D006, D002, Amberlyst-15, Amberlyst-35, Amberlyst-45 and nkc-9 were all purchased from resin works at southern university.
In another preferred embodiment of the present invention, the mass-to-volume ratio of the cation exchange resin to the alcohol solution of the cyclic organic amine is 1:1 to 1: 5; the temperature of the modification treatment is between room temperature and 50 ℃, and the time is 4 to 12 hours, preferably 5 to 8 hours.
According to the present invention, by controlling the volume ratio of the cation exchange resin to the alcohol solution of the cyclic organic amine within the above range, uniform and sufficient modification of the surface acidic active sites of the cation exchange resin is facilitated.
In a further aspect, the present invention provides a modified cation exchange resin as described above or a modified cation exchange resin prepared by the above preparation method for use in isobutylene dimerization, particularly as a catalyst.
In another preferred embodiment of the present invention, the reaction temperature of the isobutylene dimerization reaction is 30 ℃ to 100 ℃; the reaction pressure is 0.5MPa to 1.2 MPa; the space velocity of isobutene is 0.5h-1～4.0h-1。
When the modified cation exchange resin provided by the invention is applied to the dimerization reaction of isobutene, the dimerization selectivity of the isobutene can reach more than 90%.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
For the product of test example 1, its composition was analyzed as follows:
the product was separated into liquid and gas phases by a gas-liquid separator, and the compositions of the gas and liquid phases were analyzed by chromatography, respectively.
The isobutene conversion was calculated by the formula (2):
c8 selectivity is calculated by equation (3):
example 1
A. Pretreatment of cation exchange resins
50g of cation exchange resin Nkc-9 is put into a conical flask and washed by absolute ethyl alcohol, and when the water content in the washing liquid is lower than 3 percent, the washing is finished. Subsequently, the resin was dried at 80 ℃ for 6 hours to complete the pretreatment of the cation exchange resin.
B. Modification treatment of cation exchange resin
And (3) placing the pretreated cation exchange resin into a three-neck flask, adding 100ml of ethanol solution of 10% cyclohexylamine, and reacting at room temperature for 5h to complete modification treatment on the cation exchange resin.
C. Post-treatment of modified cation exchange resins
Washing the modified cation exchange resin by deionized water, performing suction filtration, and drying at 50 ℃ for 12h to complete post-treatment of the cation exchange resin, thereby obtaining the modified cation exchange resin C-1.
Example 2
A. Pretreatment of cation exchange resins
Pretreatment of the cation exchange resin was carried out in the same manner as in example 1.
B. Modification treatment of cation exchange resin
And (3) placing the pretreated cation exchange resin into a three-neck flask, adding 100ml of 20% cyclohexylamine ethanol solution, and reacting at room temperature for 5h to complete modification treatment on the cation exchange resin.
C. Post-treatment of modified cation exchange resins
After-treatment of the cation exchange resin was carried out in the same manner as in example 1 to obtain a modified cation exchange resin C-2.
Example 3
A. Pretreatment of cation exchange resins
Pretreatment of the cation exchange resin was carried out in the same manner as in example 1.
B. Modification treatment of cation exchange resin
And (3) placing the pretreated cation exchange resin into a three-neck flask, adding 100ml of 40% ethanol solution of cyclohexylamine, and reacting at room temperature for 5h to complete modification treatment on the cation exchange resin.
C. Post-treatment of modified cation exchange resins
After-treatment of the cation exchange resin was carried out in the same manner as in example 1 to obtain a modified cation exchange resin C-3.
Example 4
A. Pretreatment of cation exchange resins
Pretreatment of the cation exchange resin was carried out in the same manner as in example 1.
B. Modification treatment of cation exchange resin
And (3) placing the pretreated cation exchange resin into a three-neck flask, adding 100ml of ethanol solution of cyclic ethyleneimine with the concentration of 10%, and reacting at room temperature for 5 hours to complete modification treatment on the cation exchange resin.
C. Post-treatment of modified cation exchange resins
After-treatment of the cation exchange resin was carried out in the same manner as in example 1 to obtain a modified cation exchange resin C-4.
Example 5
50g of cation exchange resin Nkc-9 was placed in a three-necked flask, and then 100ml of a 10% ethanol solution of cyclohexylamine was added thereto and reacted at room temperature for 5 hours to complete the modification treatment of the cation exchange resin.
Then drying for 12h at 50 ℃ to prepare the modified cation exchange resin C-5.
Comparative example 1
Cation exchange resin D-1 was obtained by carrying out the pretreatment of the cation exchange resin without carrying out the modification treatment and the post-treatment in the same manner as in example 1.
Comparative example 2
A. Pretreatment of cation exchange resins
Pretreatment of the cation exchange resin was carried out in the same manner as in example 1.
B. Modification treatment of cation exchange resin
And (3) placing the pretreated cation exchange resin into a three-neck flask, adding 100ml of ethanol solution of 10% ethylenediamine, and reacting at room temperature for 5 hours to complete modification treatment on the cation exchange resin.
C. Post-treatment of modified cation exchange resins
After-treatment of the cation exchange resin was carried out in the same manner as in example 1 to obtain a modified cation exchange resin D-2.
Test example 1
Feeding the raw material containing isobutene into fixed bed reactors respectively filled with (modified) cation exchange resins C-1, C-2, C-3, C-4, C-5, D-1 and D-2, controlling the reaction temperature to be 55 ℃, the reaction pressure to be 0.75MPa and the space velocity of the raw material containing isobutene to be 1h-1. The results of the evaluation while maintaining the equivalent conversion of isobutylene are shown in the following table.
As can be seen from the above table, although the cation exchange resin of comparative example 1, which was not subjected to the modification treatment, had a conversion higher than that of examples 1 to 4 of the present application, the selectivity was much lower than that of the present application, and the amounts of by-products C12 and C16 were much greater than that of the present application. The modified cation exchange resin of comparative example 2, which employed linear amine, had lower conversion and selectivity than the present application and higher amounts of by-products C12 and C16 than the present application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation 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 modified cation exchange resin is characterized by being prepared by modifying a cation exchange resin with cyclic organic amine.
2. The modified cation exchange resin of claim 1, wherein the cyclic organic amine is used in an amount of 0.5 to 20.0%, preferably 1.0 to 15.0%, and more preferably 2.0 to 10.0%, based on the total weight of the modified cation exchange resin.
3. A method for preparing a modified cation exchange resin, comprising the steps of:
providing an alcoholic solution of cyclic organic amine dissolved in an alcohol organic solvent;
and modifying the cation exchange resin by using the alcoholic solution of the cyclic organic amine.
4. The method according to claim 3, wherein the cyclic organic amine is selected from aliphatic cyclic amines and/or aromatic cyclic amines, preferably aliphatic cyclic amines and/or aromatic cyclic amines having 2 to 6 carbon atoms, and most preferably at least one of cyclohexylamine, aniline, cyclic ethyleneimine and nitroaniline.
5. The process according to claim 3 or 4, wherein the alcoholic organic solvent is selected from C1-C5At least one of the alcohols is preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, iso-butanol and n-pentanol.
6. The method according to any one of claims 3 to 5, wherein the concentration of the cyclic organic amine in the alcohol solution of the cyclic organic amine is 10 to 60 wt%, preferably 20 to 40 wt%, based on 100 wt% of the alcohol solution of the cyclic organic amine.
7. The process according to any one of claims 3 to 6, wherein the cation exchange resin is a cation exchange resin in hydrogen form, preferably a sulfonic acid resin in hydrogen form, more preferably D006, D002, Amberlyst-15, Amberlyst-35, Amberlyst-45 or nkc-9.
8. The preparation method according to any one of claims 3 to 7, wherein the mass-to-volume ratio of the cation exchange resin to the alcohol solution of the cyclic organic amine is 1:1 to 1: 5; the temperature of the modification treatment is between room temperature and 50 ℃, and the time is 4 to 12 hours, preferably 5 to 8 hours.
9. Use of the modified cation exchange resin according to claim 1 or 2 or the modified cation exchange resin prepared according to the preparation process of any one of claims 3 to 8 in the dimerization of isobutene, in particular as a catalyst.
10. Use according to claim 9, characterized in that the reaction temperature of the isobutene dimerization reaction is between 30 ℃ and 100 ℃; the reaction pressure is 0.5MPa to 1.2 MPa; the space velocity of isobutene is 0.5h-1～4.0h-1。
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| CN113501742A (en) * | 2021-05-28 | 2021-10-15 | 中国石油化工股份有限公司 | Utilization method of ethylene cracking C4 |
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| WO2015137422A1 (en) * | 2014-03-13 | 2015-09-17 | 出光興産株式会社 | Olefin oligomerization catalyst, and method for manufacturing olefin dimer |
| CN106552668A (en) * | 2015-09-25 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method of modifying of cation exchange resin catalyst and its application |
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| WO2015137422A1 (en) * | 2014-03-13 | 2015-09-17 | 出光興産株式会社 | Olefin oligomerization catalyst, and method for manufacturing olefin dimer |
| TW201601834A (en) * | 2014-03-13 | 2016-01-16 | Idemitsu Kosan Co | Olefin oligomerization catalyst, and method for manufacturing olefin dimer |
| CN106552668A (en) * | 2015-09-25 | 2017-04-05 | 中国石油化工股份有限公司 | A kind of method of modifying of cation exchange resin catalyst and its application |
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