CN108126750A - Strong acid type cationic resin catalyst and its ethyl tert-butyl ether (ETBE) catalysis application and preparation - Google Patents
Strong acid type cationic resin catalyst and its ethyl tert-butyl ether (ETBE) catalysis application and preparation Download PDFInfo
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- CN108126750A CN108126750A CN201810073614.0A CN201810073614A CN108126750A CN 108126750 A CN108126750 A CN 108126750A CN 201810073614 A CN201810073614 A CN 201810073614A CN 108126750 A CN108126750 A CN 108126750A
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- Prior art keywords
- etbe
- catalyst
- archon
- cationic resin
- strong acid
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- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 22
- 239000011347 resin Substances 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 7
- 241001566735 Archon Species 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- -1 sorbitan ester Chemical class 0.000 claims abstract description 37
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000746 purification Methods 0.000 claims abstract description 19
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 19
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 12
- JYTNGEWJAZCVAN-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O JYTNGEWJAZCVAN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004088 foaming agent Substances 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000012071 phase Substances 0.000 claims description 33
- 238000010792 warming Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 229910001220 stainless steel Inorganic materials 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000006266 etherification reaction Methods 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 210000003298 dental enamel Anatomy 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000003643 water by type Substances 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ZMOIYZMATKKAST-UHFFFAOYSA-N [S].C(CCCCCCCCCCCCCCC)C1=CC=CC=C1 Chemical compound [S].C(CCCCCCCCCCCCCCC)C1=CC=CC=C1 ZMOIYZMATKKAST-UHFFFAOYSA-N 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- CTIFKKWVNGEOBU-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O CTIFKKWVNGEOBU-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 235000015424 sodium Nutrition 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 241000220324 Pyrus Species 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000021017 pears Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/16—Homopolymers or copolymers of alkyl-substituted styrenes
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- Polymers & Plastics (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application provides a kind of strong acid type cationic resin catalyst and its ethyl tert-butyl ether (ETBE) catalysis application and preparations, strong acid type cationic resin catalyst therein, by p-tert-butylstyrene and divinylbenzene monomers, copolymer Archon is copolymerized to obtain in pore-foaming agent and the Action of Surfactant low suspension formed with cetyl benzenesulfonic acid sodium of being received including sorbitan ester, alkyl phenol polyoxyethylene ether, secondary alkyl sulfonic acid, is obtained by hole purification and sulfonation.Ethyl tert-butyl ether (ETBE) the present invention also provides the strong acid type cationic resin catalyst is catalyzed application and preparation.The preparation method of the technical program catalyst is safe and simple, practice also confirms, this catalyst is applied to embody higher activity and stability in ethyl tert-butyl ether (ETBE) catalyst etherifying technique, alfin molar ratio is reduced, isobutene conversion reaches more than 95%, ethyl tert-butyl ether (ETBE) and is selectively more than 99%.
Description
Technical field
Present patent application is related to strong acid type cationic resin catalyst more particularly to the catalyst in ethyl tert-butyl ether (ETBE) ether
Change the catalytic applications prepared.
Background technology
Environmentally friendly laws and regulations propose unleaded gasoline for vehicle new application specification, MTBE as produce it is unleaded, oxygen-containing and
The excellent blending component of high-knock rating gasoline is extensively using for many years, since the U.S. finds micro MTBE in underground water,
MTBE environmental issues have made MTBE the ruling of carcinogenicity by public concern, Environmental Protection Agency.Ethyl tert-butyl ether (ETBE) with
MTBE has similar physics and chemical property, is the general trend of events by ethyl tert-butyl ether (ETBE) substitution MTBE with excellent tune oiliness energy
Become.But ethyl tert-butyl ether (ETBE) production is prepared there is still a need for the research and development of technological innovation support, wherein, existing ethyl tert-butyl ether (ETBE) ether
Change to prepare and there is big alfin ratio, conversion ratio and selectivity, therefore aggravated ethyl tert-butyl ether (ETBE) preparation
Material consumption and energy consumption, increase the ethanol content of carbon four after ether, aggravate subsequent processing burden, and therefore affect ethyl uncle
The product purity of butyl ether.
Invention content
The goal of the invention of present patent application is to provide a kind of novel strong acid type cationic resin catalyst and its ethyl
Tertbutyl ether is catalyzed application and preparation, and the strong acid type cationic resin catalyst is not only in ethyl tert-butyl ether (ETBE) preparation process
Special-purpose catalyst, and coordinate ethyl tert-butyl ether (ETBE) preparation process, realize efficient etherification reaction, reach improve conversion ratio, choosing
Selecting property, the technical purpose for reducing alfin ratio.
The strong acid type cationic resin catalyst technology scheme that present patent application provides, main technical content are：It is a kind of
Strong acid type cationic resin catalyst, by p-tert-butylstyrene and divinylbenzene monomers, in pore-foaming agent and surfactant
Effect low suspension is copolymerized to obtain copolymer Archon, is obtained by hole purification and sulfonation, therein to be polymerized to：It is being configured with reflux condensation mode
In the stainless steel stirred tank of device, water and surfactant are added in, heats with stirring, acquisition water phase is completely dissolved, stainless
Steel stirred tank kettle temperature adds in the oil phase of mixing organic phase when being warming up to 60 DEG C -70 DEG C, under 80 DEG C -90 DEG C of temperature condition, stir
Mix rotating speed is 60-120r/min polymerisations 8-10 hours, obtains copolymer Archon；The surfactant includes dehydration mountain
Pears alcohol ester, alkyl phenol polyoxyethylene ether, secondary alkyl sulfonic acid receives and cetyl benzenesulfonic acid sodium, and by weight, water phase composition is：
2000-2500 parts of water
20-50 parts of sorbitan ester
20-50 parts of alkyl phenol polyoxyethylene ether
Secondary alkyl sulfonic acid receives 10-30 parts
10-30 parts of cetyl benzenesulfonic acid sodium；
The oil phase forms：
500-600 parts of p-tert-butylstyrene
400-500 parts of divinylbenzene
It is 20-50 parts one of arbitrary in pentane or acetone
10-30 parts of benzoyl peroxide
The weight part ratio of the water phase and oil phase：2060-2660:930-1180.
A kind of ethyl tert-butyl ether (ETBE) the present patent application also provide strong acid type cationic resin catalyst is catalyzed system
Standby application, the strong acid type cationic resin catalyst are loaded into fixed bed reactors with modularization or bale packingization, contained
The mixing carbon four and ethyl alcohol of isobutene press alfin molar ratio（1.1~1.3）:1 enters fixed bed reactors, the reaction item of reactor
Part is：Pressure 1.0-1.5MPa, air speed 0.5-2h-1, temperature are 40 DEG C of -60 DEG C of etherification reactions.
The ethyl tert-butyl ether (ETBE) catalysis application and preparation of the strong acid type cationic resin catalyst, it is preferably solid
The reaction pressure of fixed bed reactor is 1.0~1.2MPa.
Strong acid type cationic resin catalyst disclosed in present patent application and its ethyl tert-butyl ether (ETBE) catalysis application and preparation skill
Art scheme, strong acid type cationic resin catalyst prepare reaction special designs, catalyst for ethyl tert-butyl ether (ETBE) catalyst etherifying
Preparation method it is safe and simple, practice also confirms, this catalyst be applied to ethyl tert-butyl ether (ETBE) catalyst etherifying technique in embody
Higher activity and stability reduces alfin molar ratio, and isobutene conversion reaches the choosing of more than 95%, ethyl tert-butyl ether (ETBE)
Selecting property is more than 99%, is etherified preparation process material consumption and energy consumption substantially reduces, and therefore, the ethanol content of carbon four is reduced after ether, is alleviated
The burden of subsequent processing, and substantially increase ethyl tert-butyl ether (ETBE) product purity.
Specific embodiment
The technology contents that present patent application will be described in detail by each embodiment below, but the protection domain of present patent application
It is not only restricted to embodiment contents.This strong acid type cationic resin catalyst, by p-tert-butylstyrene and divinylbenzene
Monomer is copolymerized to obtain copolymer Archon in pore-foaming agent and Action of Surfactant low suspension, is obtained by hole purification and sulfonation.
Embodiment 1:
Catalyst C-1
In the stainless steel stirred tank for being configured with reflux condensate device, water 2000g and surfactant are added in, heating is adjoint to stir
It mixes, is completely dissolved acquisition water phase, the oil phase of mixing organic phase is added in when stainless steel stirred tank kettle temperature is warming up to 60 DEG C, in temperature
It is 60r/min polymerisations 8 hours for 80 DEG C, speed of agitator, obtains copolymer Archon；The surfactant loses for 20g
Water sorbitol ester, 20g alkyl phenol polyoxyethylene ether, 10g secondary alkyl sulfonic acid are received and 10g cetyl benzenesulfonic acid sodiums, the oil
Phase composition is 500g p-tert-butylstyrenes, 400g divinylbenzenes, 20g pentanes and 10g benzoyl peroxides；
The finished catalyst that the copolymer Archon is obtained through hole purification and sulfonation, hole purification therein：What is be obtained by filtration is total to
Polymers Archon is placed in 70 DEG C of deionized waters, is depressurized and is boiled 8 hours, then be washed with deionized 3 under the pressure of -0.090MPa
Secondary, room temperature is dried, and obtains Archon；Sulfonation：The purified Archon in hole is moved into enamel stirred tank, oleum, control are added in stirring
Temperature in the kettle processed is less than 65 DEG C, until not having Archon just；It is warming up to 80 DEG C later, reacts 2 hours, is warming up to 100 again thereafter
DEG C, reaction 2 hours, be finally warming up to 120 DEG C, reaction 2 hours, cooling；Hereafter in stirring, temperature is less than 40 DEG C of condition
Under, deionized water is added dropwise into kettle and releases simultaneously, so repeatedly until the liquid shows neutral released, the physical property of this catalyst
Index is shown in Table 1.
Above-mentioned fresh catalyst C-1 400ml is taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, are contained
The mixing carbon four and ethyl alcohol of isobutene press alfin molar ratio 1.1:1 is pumped into fixed bed reactors, the reaction in fixed bed reactors
Condition is：Pressure 1.0MPa, air speed 0.5h-1, reaction temperature be 40 DEG C of etherification reactions, reaction product through actual measurement：Isobutene turns
Rate is 95.1%, and ethyl tert-butyl ether (ETBE) is selectively 99.3%.
Embodiment 2:
Catalyst C-2
In the stainless steel stirred tank for being configured with reflux condensate device, water 2500g and surfactant are added in, heating is adjoint to stir
It mixes, is completely dissolved acquisition water phase, the oil phase of mixing organic phase is added in when stainless steel stirred tank kettle temperature is warming up to 70 DEG C, in temperature
85 DEG C, speed of agitator 80r/min, polymerisation 10 hours obtain copolymer Archon：The surfactant loses for 30g
Water sorbitol ester, 50g alkyl phenol polyoxyethylene ether, 20g secondary alkyl sulfonic acid are received and 20g cetyl benzenesulfonic acid sodiums, the oil
Phase component is respectively 600g p-tert-butylstyrenes, 500g divinylbenzenes, 50g acetone and 30g benzoyl peroxides；
The finished catalyst that the copolymer Archon is obtained through hole purification and sulfonation, hole purification therein：What is be obtained by filtration is total to
Polymers Archon is placed in 80 DEG C of deionized waters, is depressurized and is boiled 10 hours, then be washed with deionized under the pressure of -0.095MPa
3 times, room temperature is dried, and obtains Archon；Sulfonation：The purified Archon in hole is moved into enamel stirred tank, oleum, control are added in stirring
Temperature in the kettle processed is less than 65 DEG C, until not having Archon just；It is warming up to 90 DEG C later, reacts 3 hours, is warming up to 100 again thereafter
DEG C, reaction 4 hours, be finally warming up to 120 DEG C, reaction 2 hours, cooling；Hereafter in stirring, temperature is less than 40 DEG C of condition
Under, deionized water is added dropwise into kettle and releases simultaneously, so repeatedly until the liquid shows neutral released, the physical property of this catalyst
Index is shown in Table 1.
Above-mentioned fresh catalyst C-2 400ml is taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, contain isobutyl
The mixing carbon four and ethyl alcohol of alkene press alfin molar ratio 1.3:1 is pumped into fixed bed reactors, the reaction condition in fixed bed reactors
For：Pressure 1.2MPa, air speed 1.5h-1, reaction temperature are 60 DEG C of etherification reactions, and reaction product is through actual measurement：：The conversion of isobutene
Rate is 95.7%, and ethyl tert-butyl ether (ETBE) is selectively 99.1%.
Embodiment 3:
Catalyst C-3：
In the stainless steel stirred tank for being configured with reflux condensate device, water 2200g and surfactant are added in, heating is adjoint to stir
It mixes, is completely dissolved acquisition water phase, the oil phase of mixing organic phase is added in when stainless steel stirred tank kettle temperature is warming up to 70 DEG C, in temperature
It is polymerisation 8 hours in 100r/min for 90 DEG C, speed of agitator, obtains copolymer Archon；The surfactant is 40g
Sorbitan ester, 40g alkyl phenol polyoxyethylene ether, 20g secondary alkyl sulfonic acid receive with 20g cetyl benzenesulfonic acid sodiums, it is described
Oil phase forms：550g p-tert-butylstyrenes, 450g divinylbenzenes, 20g pentanes and 20 benzoyl peroxides；
The finished catalyst that the copolymer Archon is obtained through hole purification and sulfonation, hole purification therein：What is be obtained by filtration is total to
Polymers Archon is placed in 80 DEG C of deionized waters, is depressurized and is boiled 8 hours, then be washed with deionized 3 under the pressure of -0.090MPa
Secondary, room temperature is dried, and obtains Archon；Sulfonation：The purified Archon in hole is moved into enamel stirred tank, oleum, control are added in stirring
Temperature in the kettle processed is less than 65 DEG C, until not having Archon just；It is warming up to 90 DEG C later, reacts 3 hours, is warming up to 100 again thereafter
DEG C, reaction 2 hours, be finally warming up to 120 DEG C, reaction 4 hours, cooling；Hereafter in stirring, temperature is less than 40 DEG C of condition
Under, deionized water is added dropwise into kettle and releases simultaneously, so repeatedly until the liquid shows neutral released, the physical property of this catalyst
Index is shown in Table 1.
Above-mentioned fresh catalyst C-3 400ml is taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, are contained
The mixing carbon four and ethyl alcohol of isobutene press alfin molar ratio 1.2:1 is pumped into fixed bed reactors, the reaction in fixed bed reactors
Condition is：Pressure 1.5MPa, air speed 1.0h-1, reaction temperature be 50 DEG C of etherification reactions, reaction product through actual measurement：Isobutene turns
Rate is 95.9%, and ethyl tert-butyl ether (ETBE) is selectively 99.5%.
Embodiment 4:
Catalyst C-4：
In the stainless steel stirred tank for being configured with reflux condensate device, water 2500g and surfactant are added in, heating is adjoint to stir
It mixes, is completely dissolved acquisition water phase, the oil phase of mixing organic phase is added in when stainless steel stirred tank kettle temperature is warming up to 70 DEG C, in temperature
It is polymerisation 9 hours in 120r/min for 80 DEG C, speed of agitator, obtains copolymer Archon；The surfactant is 50g
Sorbitan ester, 50g alkyl phenol polyoxyethylene ether, 10g secondary alkyl sulfonic acid receive with 10g cetyl benzenesulfonic acid sodiums, it is described
Oil phase forms：550g p-tert-butylstyrenes, 400g divinylbenzenes, 20g acetone and 20 benzoyl peroxides；
The finished catalyst that the copolymer Archon is obtained through hole purification and sulfonation, hole purification therein：What is be obtained by filtration is total to
Polymers Archon is placed in 70 DEG C of deionized waters, is depressurized and is boiled 8 hours, then be washed with deionized 3 under the pressure of -0.095MPa
Secondary, room temperature is dried, and obtains Archon；Sulfonation：The purified Archon in hole is moved into enamel stirred tank, oleum, control are added in stirring
Temperature in the kettle processed is less than 65 DEG C, until not having Archon just；It is warming up to 90 DEG C later, reacts 2 hours, is warming up to 100 again thereafter
DEG C, reaction 2 hours, be finally warming up to 120 DEG C, reaction 3 hours, cooling；Hereafter in stirring, temperature is less than 40 DEG C of condition
Under, deionized water is added dropwise into kettle and releases simultaneously, so repeatedly until the liquid shows neutral released, the physical property of this catalyst
Index is shown in Table 1.
Above-mentioned fresh catalyst C-4 400ml is taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, are contained
The mixing carbon four and ethyl alcohol of isobutene press alfin molar ratio 1.2:1 is pumped into fixed bed reactors, the reaction in fixed bed reactors
Condition is：Pressure 1.0MPa, air speed 2.0h-1, reaction temperature be 50 DEG C of etherification reactions, reaction product through actual measurement：Isobutene turns
Rate is 96.1%, and ethyl tert-butyl ether (ETBE) is selectively 99.4%.
Embodiment 5:
Catalyst C-5：
In the stainless steel stirred tank for being configured with reflux condensate device, water 2000g and surfactant are added in, heating is adjoint to stir
It mixes, is completely dissolved acquisition water phase, the oil phase of mixing organic phase is added in when stainless steel stirred tank kettle temperature is warming up to 65 DEG C, in temperature
90 DEG C, speed of agitator be polymerisation in 80r/min 10 hours, obtain copolymer Archon；The surfactant loses for 40g
Water sorbitol ester, 40g alkyl phenol polyoxyethylene ether, 30g secondary alkyl sulfonic acid are received and 20g cetyl benzenesulfonic acid sodiums；The oil
Phase composition is：600g p-tert-butylstyrenes, 400g divinylbenzenes, 30g acetone and 20 benzoyl peroxides；
The finished catalyst that the copolymer Archon is obtained through hole purification and sulfonation, hole purification therein：What is be obtained by filtration is total to
Polymers Archon is placed in 80 DEG C of deionized waters, is depressurized and is boiled 9 hours, then be washed with deionized 3 under the pressure of -0.095MPa
Secondary, room temperature is dried, and obtains Archon；Sulfonation：The purified Archon in hole is moved into enamel stirred tank, oleum, control are added in stirring
Temperature in the kettle processed is less than 65 DEG C, until not having Archon just；It is warming up to 90 DEG C later, reacts 2 hours, is warming up to 100 again thereafter
DEG C, reaction 3 hours, be finally warming up to 120 DEG C, reaction 4 hours, cooling；Hereafter in stirring, temperature is less than 40 DEG C of condition
Under, deionized water is added dropwise into kettle and releases simultaneously, so repeatedly until the liquid shows neutral released, the physical property of this catalyst
Index is shown in Table 1.
Above-mentioned fresh catalyst C-5 400ml is taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, are contained
The mixing carbon four and ethyl alcohol of isobutene press alfin molar ratio 1.2:1 is pumped into fixed bed reactors, the reaction in fixed bed reactors
Condition is：Pressure 1.0MPa, air speed 1.0h-1, reaction temperature be 55 DEG C of etherification reactions, reaction product through actual measurement：Isobutene turns
Rate is 96.2%, and ethyl tert-butyl ether (ETBE) is selectively 99.3%.
Embodiment 6:
Catalyst C-6：
In the stainless steel stirred tank for being configured with reflux condensate device, water 2300g and surfactant are added in, heating is adjoint to stir
It mixes, is completely dissolved acquisition water phase, the oil phase of mixing organic phase is added in when stainless steel stirred tank kettle temperature is warming up to 60 DEG C, in temperature
80 DEG C, polymerisation 8 hours in speed of agitator 60r/min, obtain copolymer Archon；The surfactant is 30g dehydrations
Sorbitol ester, 30g alkyl phenol polyoxyethylene ether, 20g secondary alkyl sulfonic acid are received and 10g cetyl benzenesulfonic acid sodiums；The oil phase
It forms as 500g p-tert-butylstyrenes, 450g divinylbenzenes, 20g pentanes and 10 benzoyl peroxides；
The finished catalyst that the copolymer Archon is obtained through hole purification and sulfonation, hole purification therein：What is be obtained by filtration is total to
Polymers Archon is placed in 70 DEG C of deionized waters, is depressurized and is boiled 8 hours, then be washed with deionized 3 under the pressure of -0.090MPa
Secondary, room temperature is dried, and obtains Archon；Sulfonation：The purified Archon in hole is moved into enamel stirred tank, oleum, control are added in stirring
Temperature in the kettle processed is less than 65 DEG C, until not having Archon just；It is warming up to 80 DEG C later, reacts 2 hours, is warming up to 100 again thereafter
DEG C, reaction 4 hours, be finally warming up to 120 DEG C, reaction 2 hours, cooling；Hereafter in stirring, temperature is less than 40 DEG C of condition
Under, deionized water is added dropwise into kettle and releases simultaneously, so repeatedly until the liquid shows neutral released, the physical property of this catalyst
Index is shown in Table 1.
Above-mentioned fresh catalyst C-6 400ml is taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, are contained
The mixing carbon four and ethyl alcohol of isobutene press alfin molar ratio 1.1:1 is pumped into fixed bed reactors, the reaction in fixed bed reactors
Condition is：Pressure 1.5MPa, air speed 0.5h-1, reaction temperature be 45 DEG C of etherification reactions, reaction product through actual measurement：Isobutene turns
Rate is 95.3%, and ethyl tert-butyl ether (ETBE) is selectively 99.3%.
Embodiment 7:
Catalyst C-7：
In the stainless steel stirred tank for being configured with reflux condensate device, water 2400g and surfactant are added in, heating is adjoint to stir
It mixes, is completely dissolved acquisition water phase, the oil phase of mixing organic phase, temperature 80 are added in when stainless steel stirred tank kettle temperature is warming up to 70 DEG C
DEG C, polymerisation 8 hours in speed of agitator 120r/min, obtain copolymer Archon；The surfactant is 20g dehydrations mountain
Pears alcohol ester, 20g alkyl phenol polyoxyethylene ether, 20g secondary alkyl sulfonic acid are received and 10g cetyl benzenesulfonic acid sodiums；The oil phase group
As 550g p-tert-butylstyrenes, 450g divinylbenzenes, 20g acetone and 20 benzoyl peroxides；
The finished catalyst that the copolymer Archon is obtained through hole purification and sulfonation, hole purification therein：What is be obtained by filtration is total to
Polymers Archon is placed in 80 DEG C of deionized waters, is depressurized and is boiled 8 hours, then be washed with deionized 3 under the pressure of -0.095MPa
Secondary, room temperature is dried, and obtains Archon；Sulfonation：The purified Archon in hole is moved into enamel stirred tank, oleum, control are added in stirring
Temperature in the kettle processed is less than 65 DEG C, until not having Archon just；It is warming up to 80 DEG C later, reacts 4 hours, is warming up to 100 again thereafter
DEG C, reaction 2 hours, be finally warming up to 120 DEG C, reaction 4 hours, cooling；Hereafter in stirring, temperature is less than 40 DEG C of condition
Under, deionized water is added dropwise into kettle and releases simultaneously, so repeatedly until the liquid shows neutral released, the physical property of this catalyst
Index is shown in Table 1.
Above-mentioned fresh catalyst C-6 400ml is taken to be fitted into the fixed bed reactors of internal diameter 50mm, long 1000mm, are contained
The mixing carbon four and ethyl alcohol of isobutene press alfin molar ratio 1.3:1 is pumped into fixed bed reactors, the reaction in fixed bed reactors
Condition is：Pressure 1.5MPa, air speed 1.0h-1, reaction temperature be 55 DEG C of etherification reactions, reaction product through actual measurement：Isobutene turns
Rate is 95.8%, and ethyl tert-butyl ether (ETBE) is selectively 99.5%.
1 each embodiment catalyst physical index of table
| Number | Catalyst | Average pore radius（nm） | Specific surface area（m2/g） | Specific pore volume ml/g |
| 1 | C-1 | 26.1 | 82.2 | 0.46 |
| 2 | C-2 | 25.3 | 84.5 | 0.47 |
| 3 | C-3 | 22.8 | 85.7 | 0.50 |
| 4 | C-4 | 25.3 | 74.8 | 0.46 |
| 5 | C-5 | 24.5 | 78.9 | 0.46 |
| 6 | C-6 | 25.7 | 74.8 | 0.48 |
| 7 | C-7 | 26.9 | 75.4 | 0.49 |
Claims (5)
1. a kind of strong acid type cationic resin catalyst, it is characterised in that this catalyst is by p-tert-butylstyrene and divinyl
Benzene monomer is copolymerized to obtain copolymer Archon in pore-foaming agent and Action of Surfactant low suspension, is obtained by hole purification and sulfonation,
In be polymerized to：In the stainless steel stirred tank for being configured with reflux condensate device, water and surfactant are added in, heating is adjoint to stir
It mixes, is completely dissolved acquisition water phase, the oil phase of mixing organic phase is added in when stainless steel stirred tank kettle temperature is warming up to 60 DEG C -70 DEG C,
Under 80 DEG C -90 DEG C of temperature condition, speed of agitator is 60-120r/min polymerisations 8-10 hours, obtains copolymer Archon；
The surfactant includes sorbitan ester, alkyl phenol polyoxyethylene ether, secondary alkyl sulfonic acid and receives and cetyl benzene sulphur
Sour sodium, by weight, water phase composition is：
2000-2500 parts of water
20-50 parts of sorbitan ester
20-50 parts of alkyl phenol polyoxyethylene ether
Secondary alkyl sulfonic acid receives 10-30 parts
10-30 parts of cetyl benzenesulfonic acid sodium；
The oil phase forms：
500-600 parts of p-tert-butylstyrene
400-500 parts of divinylbenzene
It is 20-50 parts one of arbitrary in pentane or acetone
10-30 parts of benzoyl peroxide
The weight part ratio of the water phase and oil phase：2060-2660:930-1180.
2. strong acid type cationic resin catalyst according to claim 1, it is characterised in that the hole purification：It will copolymerization
Object Archon is placed in 70 DEG C of -90 DEG C of deionized waters, is depressurized and is boiled 8-10 hours, then use under the pressure of -0.090--0.095MPa
Deionized water is washed 3 times, and room temperature is dried, and obtains catalyst Archon.
3. strong acid type cationic resin catalyst according to claim 1, it is characterised in that the sulfonation：Hole is purified
Archon is moved into enamel stirred tank, and oleum is added in stirring, and control temperature in the kettle is less than 65 DEG C, until do not had Archon just,
Then heat to 80 DEG C -90 DEG C, reaction 2-4 hour, then be warming up to 100 DEG C, reaction 2-4 hours, be finally warming up to 120 DEG C, instead
It answers 2-4 hours, postcooling, stirs and temperature is less than under conditions of 40 DEG C, deionized water is added dropwise into kettle and releases simultaneously, such as
This is repeatedly until liquid shows neutral is released.
4. a kind of ethyl tert-butyl ether (ETBE) catalysis of the strong acid type cationic resin catalyst described in claims 1 to 3 is one of arbitrary
Application and preparation, the strong acid type cationic resin catalyst are loaded with modularization or bale packingization into fixed bed reactors,
It is characterized in that the mixing carbon four containing isobutene and ethyl alcohol by alfin molar ratio（1.1~1.3）:1 enters fixed bed reactors, instead
Answering the reaction condition of device is：Pressure 1.0-1.5MPa, air speed 0.5-2h-1, temperature be 40 DEG C of -60 DEG C of etherification reactions.
5. the ethyl tert-butyl ether (ETBE) catalysis application and preparation of strong acid type cationic resin catalyst according to claim 4,
The reaction pressure for being characterized in that fixed bed reactors is 1.0-1.2MPa.
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