CN114621381A - Preparation method of anion exchange resin for purifying sulfolane with high colloid content - Google Patents
Preparation method of anion exchange resin for purifying sulfolane with high colloid content Download PDFInfo
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- CN114621381A CN114621381A CN202210258466.6A CN202210258466A CN114621381A CN 114621381 A CN114621381 A CN 114621381A CN 202210258466 A CN202210258466 A CN 202210258466A CN 114621381 A CN114621381 A CN 114621381A
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- sulfolane
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000084 colloidal system Substances 0.000 title claims abstract description 66
- 239000003957 anion exchange resin Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 96
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 71
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 71
- 238000005406 washing Methods 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 52
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001816 cooling Methods 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000004793 Polystyrene Substances 0.000 claims abstract description 32
- 229920002223 polystyrene Polymers 0.000 claims abstract description 32
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 28
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 26
- 239000011592 zinc chloride Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 61
- 238000010438 heat treatment Methods 0.000 claims description 32
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 27
- 238000005576 amination reaction Methods 0.000 claims description 27
- 238000007265 chloromethylation reaction Methods 0.000 claims description 27
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- -1 isobutanol peroxide Chemical class 0.000 claims description 19
- 229940057995 liquid paraffin Drugs 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- KWHDXJHBFYQOTK-UHFFFAOYSA-N heptane;toluene Chemical compound CCCCCCC.CC1=CC=CC=C1 KWHDXJHBFYQOTK-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 claims description 8
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Substances CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000001993 wax Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000895 extractive distillation Methods 0.000 claims description 6
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 6
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000003361 porogen Substances 0.000 claims 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 abstract 2
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 33
- 150000001450 anions Chemical class 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 21
- 238000005303 weighing Methods 0.000 description 21
- 239000002904 solvent Substances 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 14
- 238000011069 regeneration method Methods 0.000 description 14
- 239000004088 foaming agent Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 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 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C08F212/08—Styrene
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of anion exchange resin for purifying sulfolane with high colloid content, which comprises the steps of adding styrene monomers, a cross-linking agent, an initiator, a pore-forming agent, a dispersing agent and deionized water into a polymerization kettle, and mixing and stirring to obtain small polystyrene particles; placing the polystyrene small particles and chloromethyl ether into a reaction kettle for chlorination at the temperature of 30-50 DEG CPerforming a reaction for 1-3 h, adding zinc chloride, reacting at 40-60 ℃ for 10-12 h, cooling to room temperature, washing and drying to obtain chloromethylated polystyrene resin, mixing the chloromethylated polystyrene resin with a trimethylamine aqueous solution, reacting at 50-120 ℃ for 10-20 h, cooling, washing and drying to obtain the anion exchange resin for adsorbing and purifying the high-colloid sulfolane. The anion exchange resin has a specific surface area of 300-500 m2The exchange capacity and the capacity of adsorbing colloid of the resin are improved, and the removal rate of the colloid and chloride ions is higher.
Description
Technical Field
The invention relates to a preparation method of anion exchange resin for purifying sulfolane with high colloid content, belonging to the field of polymer chemistry.
Background
The aromatic hydrocarbon extraction system is a unit of an aromatic hydrocarbon combination unit, and C extracted from the top of a deheptanizer of the aromatic hydrocarbon combination unit6～C7The components are used as extraction raw materials, and are processed and treated by an extraction system to be separated into aromatic hydrocarbons and non-aromatic hydrocarbons.
The aromatics extraction system comprises an extraction tower, a raffinate oil washing tower, an extraction stripping tower, a recovery tower, a solvent decompression regeneration tower, a water stripping tower and related pumps, heat exchangers, a middle tank, instruments and connecting pipelines. The extraction raw material enters from the lower part of the aromatic extraction tower and is in countercurrent contact with sulfolane entering from the upper part of the extraction tower, and the extraction raw material is divided into two phases: the upper raffinate oil phase enters a water washing tower to recover a small amount of solvent, the raffinate oil phase enters from the bottom of the water washing tower and is in countercurrent contact with water washing water entering from the top, raffinate oil exits from the top of the tower, water containing a small amount of sulfolane solvent circulates to a water stripping tower from the bottom of the water washing tower to generate steam, and the generated steam enters a recovery tower to strip C6 and C7 aromatic hydrocarbons or enters a pressure reduction regeneration tower to reduce the partial pressure of the solvent and then enters the recovery tower along with the tower top solvent, the tower top steam of the water stripping tower contains a certain amount of non-aromatic hydrocarbons and is introduced into a tower top pipeline of an extraction stripping tower; the sulfolane rich solvent with the arene dissolved in the lower layer of the arene extracting tower enters the extracting and stripping tower from the tower bottom. A large amount of light non-aromatic hydrocarbon is evaporated from the top of the extraction stripping tower, the light non-aromatic hydrocarbon passes through the phase splitting of a tower top tank of the extraction stripping tower, a hydrocarbon phase in the tower top tank is used as a backwash liquid and returns to the bottom of the extraction tower to replace the heavy non-aromatic hydrocarbon dissolved in the solvent, the purity of an extract is improved, and a water phase in the tower top tank and water at the bottom of a water washing tower enter the water stripping tower together to generate steam; a tower bottom heat exchanger of a tower bottom dehydration stripping tower of the extraction stripping tower supplies heat for a water stripping tower, then the heat is supplied to a recovery tower, and C is separated from the top of the recovery tower through steam stripping6～C7Aromatic hydrocarbon enters a downstream B.T unit, and most of the poor solvent at the bottom of the recovery tower passes through the circulating solventThe cooler and the lean/rich solvent heat exchanger return to the top of the extraction tower, and a small part of the mixture enters a solvent regeneration tower for decompression and regeneration, so that colloid and degraded products are removed.
The sulfolane extraction process comprises a liquid-liquid extraction process and an extraction distillation process. The extraction raw material contains olefin, colloid is generated by oligomerization in the extraction process, the extraction temperature of the liquid-liquid extraction process is 93 ℃, the generated colloid is less, but the extraction temperature of the extraction distillation process is 174 ℃, and the generated colloid is more. The gum in the sulfolane can cause the reduction of the sulfolane solvent extraction efficiency, can be accumulated at the bottom of a solvent regeneration tower, is hung on the wall of the solvent regeneration tower, and can influence the operation of the regeneration tower when the gum is accumulated in the solvent regeneration tower or is hung on the wall seriously, the regeneration tower needs to be cut out from a system for cleaning the regeneration tower, the cleaning frequency is 3-4 times per year, the cleaning operation influences the stable operation of a device, the cleaned tower bottom with the gum can not only cause the sulfolane loss, but also bring the problem of post-treatment or environmental protection.
Removing the colloid in the sulfolane in the extraction distillation process can improve the extraction efficiency, reduce the agent/oil ratio of the extraction operation, reduce the tower cleaning times of the regeneration tower, reduce the solvent consumption and relieve the environmental protection pressure.
Reported in research on sulfolane purification method with high colloid content in extractive distillation unit in modern chemical engineering in 6 months in 2013, the extraction temperature of aromatic hydrocarbon extractive distillation process is high, the colloid content in sulfolane reaches 179.4mg/100mL, and Cl is contained-The content is 9.28 mg/L. Anion exchange resin is filled in an ion exchange column for purifying, extracting and distilling sulfolane with high gum content, and compared with the sulfolane effect in an anion exchange resin purifying liquid-liquid extracting process, and simultaneously compared with a purifying scheme of serially connecting activated clay or activated carbon degumming units in front of the resin, the activated carbon has high chloride ion content, but degumming of the activated carbon easily causes sulfolane and activated carbon fine powder to frequently block a discharging filter, thereby bringing adverse effects to operation and purification; the carclazyte has certain adsorption effect on chloride ions and colloid, but because the acidic carclazyte contains acidic impurities, the activated carclazyte is connected in series before the resin, so that the times of purifying sulfolane by the resin are reduced; purification of crude oil with anion exchange resinGum content sulfolane is the best solution, but gum reduces the single cycle cleaning effect of the resin on sulfolane.
In the 'influence of colloid on sulfolane poor solvent in aromatic hydrocarbon extraction purification by ion exchange resin method' reported in 'petroleum refining and chemical engineering' in 4 months in 2013, the colloid has obvious influence on sulfolane solvent purification by ion exchange resin method, the sulfolane colloid content in liquid-liquid extraction unit is low, the colloid removal rate is 85.5%, and Cl is-The removal rate is 79.94 percent, but the sulfolane colloid content of the extractive distillation unit is high, the colloid removal rate is 32.6 percent, and Cl is added-The removal rate was 54.98%.
Although the macroporous weakly-alkaline anion exchange resin effectively solves the problems of equipment corrosion and colloid removal of a liquid-liquid sulfolane extraction system, the sulfolane colloid content of an aromatic extraction distillation system is high, anion exchange resin with a larger specific surface area needs to be found to improve the colloid removal rate and reduce the influence of the colloid on resin dechlorination, and the purification problem of sulfolane with high colloid content in an extraction distillation unit can be effectively solved.
Disclosure of Invention
The invention provides a preparation method of anion exchange resin for purifying sulfolane with high colloid content, which adjusts the mechanical strength and the specific surface area of the resin through a cross-linking agent, a pore-forming agent and an initiator, improves the exchange capacity and the colloid adsorption capacity of the resin, effectively solves the problem of purifying sulfolane with high colloid content in an aromatic extraction distillation process, prolongs the service life of the resin and reduces the purifying cost of the sulfolane.
A preparation method of anion exchange resin for purifying sulfolane with high colloid content comprises polymerization, chloromethylation and amination reaction; the method is characterized by comprising the following steps:
(1) polymerization reaction: adding styrene monomer, a cross-linking agent, an initiator, a pore-forming agent, a dispersing agent and deionized water into a polymerization kettle, mixing and stirring, starting heating when an oil phase is dispersed into small droplets, raising the temperature to 50-60 ℃, reacting for 2-4 hours, raising the temperature to 80-90 ℃ at the speed of 1-1.5 ℃/2min, reacting for 2-4 hours, raising the temperature to 100-110 ℃, keeping for 4-8 hours, cooling to room temperature, filtering, washing and drying in vacuum to obtain the polystyrene resin particles.
(2) Chloromethylation reaction: adding the small polystyrene particles and chloromethyl ether into a reaction kettle, stirring, reacting for 1-3 hours at 30-50 ℃, adding zinc chloride, reacting for 10-12 hours at 40-60 ℃, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
(3) Amination reaction: adding chloromethylated polystyrene resin and hydrazine hydrate into a reaction kettle, stirring, reacting at 50-120 ℃ for 12-20 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin for removing acid anions such as chloride ions and colloid in sulfolane.
The crosslinking agent is one of o-divinylbenzene, p-divinylbenzene and m-divinylbenzene.
The pore-foaming agent is one of toluene-n-heptane and toluene-liquid paraffin, and the mass ratio of toluene/n-heptane or toluene/liquid paraffin is 1: 1-2: 1.
the initiator is one of isobutanol peroxide, cumene peroxide and azodiisobutyronitrile.
The dispersing agent is one of polyethylene glycol, polypropylene glycol, polyethylene wax and oxidized polyethylene wax.
In the polymerization reaction, the ratio of raw materials including styrene, a cross-linking agent, a pore-forming agent, an initiator, a dispersing agent and deionized water is 100: (1.0-2.0): (2.0-10): (0.5-1.0): (10-100): (100-1000).
In the polymerization reaction, more than 95 percent of polystyrene particles have the diameter of 0.315-1.25 mm and the specific surface area of 300-500 m2The porosity is 40-50 percent.
Polystyrene particles in the chloromethylation reaction: chloromethyl ether: zinc chloride (mass ratio) 100: (200-500): (10-50).
The mass ratio of chloromethyl polystyrene particles with the mass fraction of hydrazine hydrate aqueous solution being 10-30% to hydrazine hydrate in the amination reaction is 100: (100-1000).
Purification of sulfolane using anion exchange resins prepared according to claim 1, characterized in that after filtrationThe sulfolane is prepared at the temperature of 38-45 ℃ and the airspeed of 3-9 h-The waste water flows through a bed layer filled with anion exchange resin, colloid and chloride ions in the sulfolane are adsorbed, and the purified sulfolane is obtained. After the resin in the bed layer is adsorbed and saturated, the resin bed layer is washed by 4 percent sodium hydroxide solution, so that the adsorption capacity of the anion exchange resin is recovered.
Detailed Description
The starting materials and equipment used in the present invention are commercially available unless otherwise specified.
The methods in the examples of the present invention are conventional in the art unless otherwise specified.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, as defined in the claims.
Example 1
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.0g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 2.0g of 1 toluene-liquid paraffin (pore-foaming agent), 0.5g of isobutanol peroxide as an initiator, 10g of polyethylene glycol as a dispersant and 100g of deionized water are stirred for 1h in a polymerization kettle, the temperature is raised to 50-60 ℃ for 2h, then the temperature is raised to 80-90 ℃ at the rate of 1 ℃/2min for reaction for 2h, then the temperature is raised to 100-110 ℃ for 8 h, then the reaction product is cooled to room temperature, filtered, washed and dried in vacuum, and the polystyrene resin particles are obtained.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 100g of chloromethyl ether into a reaction kettle, stirring, reacting at 30 ℃ for 1 hour, adding 50g of zinc chloride, reacting at 40 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: adding 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 100g of hydrazine hydrate with the mass fraction of 30% into a reaction kettle, stirring, reacting at 50 ℃ for 20 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin DJ-1 for removing acid anions such as chloride ions and the like and colloid in sulfolane.
Example 2
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.5g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 4.0g of 1 toluene-liquid paraffin (pore-foaming agent), 0.5g of initiator cumyl peroxide, 50g of dispersant polyethylene glycol and 100g of deionized water in a polymerization kettle are stirred for 1h, the temperature is raised to 50-60 ℃ for 2h, then the temperature is raised to 80-90 ℃ at 1.5 ℃/2min for reaction for 4h, the temperature is raised to 100-110 ℃ for 6 h, then the mixture is cooled to room temperature, filtered, washed and dried in vacuum, and the polystyrene resin particles are obtained.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 200g of chloromethyl ether into a reaction kettle, stirring, reacting at 30 ℃ for 2 hours, adding 10g of zinc chloride, reacting at 50 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 200g of hydrazine hydrate with the mass fraction of 30% are added into a reaction kettle and stirred, the mixture reacts at 60 ℃ for 19 hours, the temperature is reduced to room temperature, and the anion exchange resin DJ-2 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 3
Polymerization reaction: weighing 100g of polymerization monomer styrene and 2.0g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 6.0g of 1 toluene-liquid paraffin (pore-foaming agent), 0.5g of initiator azodiisobutyronitrile, 100g of dispersant polyethylene glycol and 300g of deionized water in a polymerization kettle, stirring for 1h, heating to 50-60 ℃ for 3h, heating to 80-90 ℃ at the speed of 1.2 ℃/2min for reaction for 3h, heating to 100-110 ℃ for 5h, cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 300g of chloromethyl ether into a reaction kettle, stirring, reacting at 30 ℃ for 2.5 hours, adding 20g of zinc chloride, reacting at 60 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: adding 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 300g of hydrazine hydrate with the mass fraction of 30% into a reaction kettle, stirring, reacting at 70 ℃ for 18 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin DJ-3 for removing acidic anions such as chloride ions and the like and colloid in sulfolane.
Example 4
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.0g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 8.0g of 1 toluene-liquid paraffin (pore-foaming agent), 0.8g of isobutanol peroxide as an initiator, 100g of polyvinyl alcohol as a dispersant and 500g of deionized water in a polymerization kettle are stirred for 1h, the temperature is raised to 50-60 ℃ for 4h, then the temperature is raised to 80-90 ℃ at the rate of 1.3 ℃/2min for reaction for 4h, then the temperature is raised to 100-110 ℃ for 6 h, then the mixture is cooled to room temperature, filtered, washed and dried in vacuum, and the polystyrene resin particles are obtained.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 400g of chloromethyl ether into a reaction kettle, stirring, reacting at 30 ℃ for 3 hours, adding 30g of zinc chloride, reacting at 40 ℃ for 12 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 400g of hydrazine hydrate with the mass fraction of 30% are added into a reaction kettle and stirred, the mixture reacts for 17 hours at the temperature of 80 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-4 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 5
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.5g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 10.0g of 1 toluene-liquid paraffin (pore-foaming agent), 0.8g of initiator cumyl oxide, 50g of dispersant polypropylene alcohol and 700g of deionized water in a polymerization kettle, stirring for 1h, heating to 50-60 ℃, keeping for 2.5h, heating to 80-90 ℃ at 1 ℃/2min, reacting for 2.5h, heating to 100-110 ℃ for 7 h, cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 500g of chloromethyl ether into a reaction kettle, stirring, reacting at 40 ℃ for 1 hour, adding 40g of zinc chloride, reacting at 50 ℃ for 12 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 500g of hydrazine hydrate with the mass fraction of 20% are added into a reaction kettle and stirred, the mixture reacts for 16 hours at 90 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-5 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 6
Polymerization reaction: weighing 100g of polymerization monomer styrene and 2.0g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 2.0g of 1 toluene-n-heptane (pore-forming agent), 0.8g of initiator azodiisobutyronitrile, 100g of dispersant polypropylene alcohol and 900g of deionized water, stirring for 1h, heating to 50-60 ℃, keeping for 3.5h, heating to 80-90 ℃ at the speed of 1.5 ℃/2min, reacting for 3.5h, heating to 100-110 ℃, keeping for 8 h, cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 250g of chloromethyl ether into a reaction kettle, stirring, reacting at 40 ℃ for 2 hours, adding 50g of zinc chloride, reacting at 60 ℃ for 12 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: adding 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 600g of hydrazine hydrate with the mass fraction of 20% into a reaction kettle, stirring, reacting at 100 ℃ for 15 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin DJ-6 for removing acid anions such as chloride ions and the like and colloid in sulfolane.
Example 7
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.0g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 5.0g of 1 toluene-n-heptane (pore-forming agent), 1.0g of initiator namely peroxyisobutyronitrile, 10g of polyethylene wax serving as dispersant and 1000g of deionized water are stirred for 1 hour in a polymerization kettle, the temperature is raised to 50-60 ℃ for 2.5 hours, then the temperature is raised to 80-90 ℃ at the rate of 1.3 ℃/2min for reaction for 3.5 hours, the temperature is raised to 100-110 ℃ for 4.5 hours, then the temperature is cooled to room temperature, and the polystyrene resin particles are obtained through filtration, washing and vacuum drying.
Chloromethylation reaction: 100g of polystyrene small particles with the particle size of 0.315-1.25 mm and 350g of chloromethyl ether are added into a reaction kettle to be stirred, the mixture reacts for 3 hours at the temperature of 40 ℃, 25g of zinc chloride is added, the mixture reacts for 11 hours at the temperature of 40 ℃, the temperature is reduced to the room temperature, and the chloromethylated polystyrene resin is obtained by filtering, washing and vacuum drying.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 700g of hydrazine hydrate with the mass fraction of 20% are added into a reaction kettle and stirred, the mixture reacts for 13 hours at the temperature of 110 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-7 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 8
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.5g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 7.0g of 1 toluene-n-heptane (pore-forming agent), 1.0g of initiator cumyl peroxide, 50g of dispersant polyethylene wax and 200g of deionized water in a polymerization kettle are stirred for 1h, the temperature is raised to 50-60 ℃ for 2.5h, then the temperature is raised to 80-90 ℃ at the rate of 1 ℃/2min for reaction for 3.0h, then the temperature is raised to 100-110 ℃ for 6.5 h, then the reaction product is cooled to room temperature, filtered, washed and dried in vacuum, and the polystyrene resin particles are obtained.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 450g of chloromethyl ether into a reaction kettle, stirring, reacting at 50 ℃ for 1 hour, adding 35g of zinc chloride, reacting at 50 ℃ for 11 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 800g of hydrazine hydrate with the mass fraction of 10% are added into a reaction kettle and stirred, the mixture reacts for 12 hours at 120 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-8 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 9
Polymerization reaction: weighing 100g of polymerization monomer styrene and 2.0g of cross-linking agent o-divinylbenzene, wherein the mass ratio is 1: 10.0g of 1 toluene-n-heptane (pore-forming agent), 1.0g of azodiisobutyronitrile as an initiator, 100g of polyethylene wax as a dispersant and 400g of deionized water in a polymerization kettle, stirring for 1h, heating to 50-60 ℃, keeping for 4.0h, heating to 80-90 ℃ at the speed of 1 ℃/2min, reacting for 4.0h, heating to 100-110 ℃, keeping for 8.0 h, cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 200g of chloromethyl ether into a reaction kettle, stirring, reacting at 50 ℃ for 2 hours, adding 45g of zinc chloride, reacting at 60 ℃ for 11 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 1000g of hydrazine hydrate with the mass fraction of 10% are added into a reaction kettle and stirred, the mixture reacts for 12 hours at 75 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-9 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 10
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.2g of cross-linking agent p-divinylbenzene, wherein the mass ratio is 1: 8.5g of 1 toluene-n-heptane (pore-forming agent), 0.6g of initiator cumyl peroxide, 10g of dispersant oxidized polyethylene wax and 600g of deionized water in a polymerization kettle are stirred for 2 hours, the temperature is raised to 50-60 ℃ for 4.0 hours, then the temperature is raised to 80-90 ℃ at the speed of 1.4 ℃/2min for reaction for 2.0 hours, the temperature is raised to 100-110 ℃ for 4.0 hours, then the temperature is cooled to room temperature, and the polystyrene resin particles are obtained by filtering, washing and vacuum drying.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 250g of chloromethyl ether into a reaction kettle, stirring, reacting at 50 ℃ for 3 hours, adding 10g of zinc chloride, reacting at 40 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: adding 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 100g of hydrazine hydrate with the mass fraction of 30% into a reaction kettle, stirring, reacting at 50 ℃ for 20 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin DJ-10 for removing acid anions such as chloride ions and the like and colloid in sulfolane.
Example 11
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.5g of cross-linking agent p-divinylbenzene, wherein the mass ratio is 1: 6.5g of 1 toluene-liquid paraffin (pore-foaming agent), 0.6g of initiator peroxyazobisisobutyronitrile, 50g of dispersant oxidized polyethylene wax and 800g of deionized water, stirring for 2h, heating to 50-60 ℃, keeping for 4.0h, then heating to 80-90 ℃ at 1 ℃/2min, reacting for 4.0h, then heating to 100-110 ℃ and keeping for 8.0 h, then cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 300g of chloromethyl ether into a reaction kettle, stirring, reacting at 30 ℃ for 2.5 hours, adding 20g of zinc chloride, reacting at 50 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: adding 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 300g of hydrazine hydrate with the mass fraction of 30% into a reaction kettle, stirring, reacting at 120 ℃ for 12 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin DJ-11 for removing acid anions such as chloride ions and the like and colloid in sulfolane.
Example 12
Polymerization reaction: weighing 100g of polymerization monomer styrene and 2.0g of cross-linking agent p-divinylbenzene according to the mass ratio of 1: 4.5g of 1 toluene-n-heptane (pore-forming agent), 0.6g of isobutanol peroxide as an initiator, 100g of polyethylene wax oxide as a dispersant and 1000g of deionized water in a polymerization kettle are stirred for 2 hours, the temperature is raised to 50-60 ℃ for 3.0 hours, then the temperature is raised to 80-90 ℃ at the rate of 1 ℃/2min for reaction for 3.0 hours, then the temperature is raised to 100-110 ℃ for 7.0 hours, then the mixture is cooled to room temperature, filtered, washed and dried in vacuum, and the polystyrene resin particles are obtained.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 350g of chloromethyl ether into a reaction kettle, stirring, reacting at 40 ℃ for 2.5 hours, adding 30g of zinc chloride, reacting at 60 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 500g of hydrazine hydrate with the mass fraction of 20% are added into a reaction kettle and stirred, the mixture reacts for 12 hours at the temperature of 50 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-12 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 13
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.2g of cross-linking agent p-divinylbenzene according to the mass ratio of 1: 10.0g of 1 toluene-liquid paraffin (pore-foaming agent), 0.7g of initiator cumyl peroxide, 60g of dispersant oxidized polyethylene glycol and 100g of deionized water in a polymerization kettle, stirring for 2h, heating to 50-60 ℃, keeping for 2.5h, then heating to 80-90 ℃ at 1.1 ℃/2min, reacting for 3.5h, heating to 100-110 ℃ and keeping for 6.0 h, then cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 400g of chloromethyl ether into a reaction kettle, stirring, reacting at 50 ℃ for 2.5 hours, adding 40g of zinc chloride, reacting at 40 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 700g of hydrazine hydrate with the mass fraction of 20% are added into a reaction kettle and stirred, the mixture reacts for 20 hours at 120 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-13 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 14
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.5g of cross-linking agent p-divinylbenzene, wherein the mass ratio is 1: 2.0g of 1 toluene-n-heptane (pore-forming agent), 0.7g of initiator azodiisobutyronitrile, 60g of dispersant oxidized polypropylene alcohol and 250g of deionized water in a polymerization kettle, stirring for 2h, heating to 50-60 ℃, keeping for 3.5h, heating to 80-90 ℃ at the speed of 1.3 ℃/2min, reacting for 2.5h, heating to 100-110 ℃ for 5.5 h, cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: 100g of polystyrene small particles with the particle size of 0.315-1.25 mm and 450g of chloromethyl ether are added into a reaction kettle to be stirred, the mixture is reacted for 2.5 hours at the temperature of 30 ℃, 50g of zinc chloride is added, the reaction is carried out for 10 hours at the temperature of 50 ℃, the temperature is reduced to the room temperature, and the chloromethylated polystyrene resin is obtained by filtering, washing and vacuum drying.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 900g of hydrazine hydrate with the mass fraction of 10% are added into a reaction kettle and stirred, the mixture reacts for 20 hours at 80 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-14 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 15
Polymerization reaction: weighing 100g of polymerization monomer styrene and 2.0g of cross-linking agent p-divinylbenzene according to the mass ratio of 1: 10.0g of 1 toluene-liquid paraffin (pore-foaming agent), 0.7g of isobutanol peroxide as an initiator, 60g of polyethylene wax oxide as a dispersant and 550g of deionized water are stirred in a polymerization kettle for 2 hours, the temperature is raised to 50-60 ℃ for 2.0 hours, then the temperature is raised to 80-90 ℃ at the rate of 1 ℃/2min for reaction for 4.0 hours, then the temperature is raised to 100-110 ℃ for 7.5 hours, then the mixture is cooled to room temperature, filtered, washed and dried in vacuum, and the polystyrene resin particles are obtained.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 500g of chloromethyl ether into a reaction kettle, stirring, reacting at 40 ℃ for 1.5 hours, adding 35g of zinc chloride, reacting at 60 ℃ for 11 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: adding 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 1000g of hydrazine hydrate with the mass fraction of 10% into a reaction kettle, stirring, reacting at 100 ℃ for 16 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin DJ-15 for removing acid anions such as chloride ions and the like and colloid in sulfolane.
Example 16
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.0g of cross-linking agent m-divinylbenzene, wherein the mass ratio is 1: 2.0g of 1 toluene-n-heptane (pore-forming agent), 0.5g of initiator cumyl peroxide, 60g of dispersant oxidized polyethylene wax and 850g of deionized water in a polymerization kettle, stirring for 2h, heating to 50-60 ℃, keeping for 2.0h, heating to 80-90 ℃ at 1 ℃/2min, reacting for 4.0h, heating to 100-110 ℃, keeping for 4.0h, cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 200g of chloromethyl ether into a reaction kettle, stirring, reacting at 50 ℃ for 1.5 hours, adding 10g of zinc chloride, reacting at 40 ℃ for 11 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: adding 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 100g of hydrazine hydrate with the mass fraction of 30% into a reaction kettle, stirring, reacting at 50 ℃ for 20 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin DJ-16 for removing acid anions such as chloride ions and the like and colloid in sulfolane.
Example 17
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.5g of cross-linking agent m-divinylbenzene, wherein the mass ratio is 1: 2.0g of 1 toluene-liquid paraffin (pore-foaming agent), 0.5g of initiator azodiisobutyronitrile, 80g of dispersant oxidized polyvinyl alcohol and 950g of deionized water in a polymerization kettle, stirring for 2h, heating to 50-60 ℃, keeping for 4.0h, heating to 80-90 ℃ at 1 ℃/2min, reacting for 2.0h, heating to 100-110 ℃, keeping for 5.0 h, cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 250g of chloromethyl ether into a reaction kettle, stirring, reacting at 45 ℃ for 1.0 hour, adding 20g of zinc chloride, reacting at 50 ℃ for 11 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 200g of hydrazine hydrate with the mass fraction of 30% are added into a reaction kettle and stirred, the mixture reacts for 20 hours at the temperature of 120 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-17 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 18
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.6g of cross-linking agent m-divinylbenzene, wherein the mass ratio is 1: 10.0g of 1 toluene-n-heptane (pore-foaming agent), 0.5g of isobutanol peroxide serving as an initiator, 80g of polypropylene oxide serving as a dispersant and 350g of deionized water in a polymerization kettle are stirred for 2 hours, the temperature is raised to 50-60 ℃ for 3.0 hours, then the temperature is raised to 80-90 ℃ at the speed of 1 ℃/2min for reaction for 3.0 hours, the temperature is raised to 100-110 ℃ for 6.0 hours, then the temperature is cooled to room temperature, and the polystyrene resin particles are obtained through filtering, washing and vacuum drying.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 300g of chloromethyl ether into a reaction kettle, stirring, reacting at 45 ℃ for 1.5 hours, adding 30g of zinc chloride, reacting at 60 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 400g of hydrazine hydrate with the mass fraction of 30% are added into a reaction kettle and stirred, the mixture reacts at 50 ℃ for 12 hours, the temperature is reduced to room temperature, and the anion exchange resin DJ-18 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 19
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.8g of cross-linking agent m-divinylbenzene, wherein the mass ratio is 1: 10.0g of 1 toluene-liquid paraffin (pore-foaming agent), 1.0g of initiator cumyl peroxide, 80g of dispersant polyethylene wax and 650g of deionized water in a polymerization kettle are stirred for 2 hours, the temperature is raised to 50-60 ℃ for 2.5 hours, then the temperature is raised to 80-90 ℃ at 1 ℃/2min for reaction for 3.5 hours, the temperature is raised to 100-110 ℃ for 7.0 hours, then the reaction product is cooled to room temperature, filtered, washed and dried in vacuum, and the polystyrene resin particles are obtained.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 350g of chloromethyl ether into a reaction kettle, stirring, reacting at 45 ℃ for 2.0 hours, adding 40g of zinc chloride, reacting at 40 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 600g of hydrazine hydrate with the mass fraction of 25% are added into a reaction kettle and stirred, the mixture reacts for 20 hours at 120 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-19 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 20
Polymerization reaction: weighing 100g of polymerization monomer styrene and 1.9g of cross-linking agent m-divinylbenzene, wherein the mass ratio is 1: 8.0g of 1 toluene-n-heptane (pore-forming agent), 1.0g of initiator azodiisobutyronitrile, 80g of dispersant oxidized polyethylene wax and 750g of deionized water in a polymerization kettle, stirring for 2h, heating to 50-60 ℃, keeping for 3.5h, heating to 80-90 ℃ at the speed of 1 ℃/2min, reacting for 2.5h, heating to 100-110 ℃, keeping for 8.0 h, cooling to room temperature, filtering, washing and vacuum drying to obtain the polystyrene resin particles.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 400g of chloromethyl ether into a reaction kettle, stirring, reacting at 45 ℃ for 2.0 hours, adding 50g of zinc chloride, reacting at 50 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 800g of hydrazine hydrate with the mass fraction of 15% are added into a reaction kettle and stirred, the mixture reacts for 15 hours at 80 ℃, the temperature is reduced to room temperature, and the anion exchange resin DJ-20 for removing acid anions such as chloride ions and the like and colloid in sulfolane is obtained after filtration and washing.
Example 21
Polymerization reaction: weighing 100g of polymerization monomer styrene and 2.0g of cross-linking agent m-divinylbenzene, wherein the mass ratio is 1: 8.0g of 1 toluene-liquid paraffin (pore-foaming agent), 1.0g of isobutanol peroxide as an initiator, 90g of polyethylene glycol as a dispersant and 1000g of deionized water in a polymerization kettle are stirred for 2 hours, the temperature is raised to 50-60 ℃ for 3.5 hours, then the temperature is raised to 80-90 ℃ at the rate of 1 ℃/2min for reaction for 3.5 hours, then the temperature is raised to 100-110 ℃ for 6.5 hours, then the mixture is cooled to room temperature, filtered, washed and dried in vacuum, and the polystyrene resin particles are obtained.
Chloromethylation reaction: adding 100g of small polystyrene particles with the particle size of 0.315-1.25 mm and 500g of chloromethyl ether into a reaction kettle, stirring, reacting at 45 ℃ for 3.0 hours, adding 35g of zinc chloride, reacting at 60 ℃ for 10 hours, cooling to room temperature, filtering, washing, and drying in vacuum to obtain the chloromethylated polystyrene resin.
Amination reaction: adding 100g of chloromethylated polystyrene resin with the particle size of 0.315-1.25 mm and 1000g of hydrazine hydrate with the mass fraction of 15% into a reaction kettle, stirring, reacting at 100 ℃ for 20 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin DJ-21 for removing acid anions such as chloride ions and the like and colloid in sulfolane.
Example 22
And (3) evaluating the performance of removing colloid, chloride ion and other anions in the sulfolane by the resin.
20ml of the resins DJ-1 to DJ-21 prepared in examples 1 to 21 and commercially available two styrene series macroporous weak base resins D301 and D392 were loaded on an ion exchange column having a diameter of 12mm, respectively, the resins were converted from the-Cl form to the-OH form with 100ml of 4% NaOH solution, and then washed with 8000ml of deionized water, and then the extractive distillation unit was charged with high-colloid-content sulfolane (colloid content 182.4mg/100ml, Cl)-The content is 9.6mg/L), and the filtrate is filtered at the temperature of 38-45 ℃ and the volume space velocity of 3-9 h-Flowing down the bed layer filled with anion exchange resin, adsorbing colloid and chloride ions in the sulfolane to obtain purified sulfolane, and measuring the colloid content and Cl in the purified sulfolane when the purifying amount of the sulfolane is 2000ml-Content, calculation of gum and Cl-And (4) removing rate. The removal rate of the resins DJ-1 to DJ-21 prepared in the embodiments 1 to 21 is 38.5 to 58.4 percent of colloid, the removal rate of chloride ions is 71.7 to 85.2 percent, and the removal rates are higher than that of two kinds of commercial styrene28.8 to 32.5 percent and 54.0 to 59.9 percent of series macroporous weak base resin DB-1 and DB-2. The evaluation results are shown in Table 1.
TABLE 1 effect of purifying, extracting and distilling high gum content sulfolane with anion exchange resin
Example 23
And (4) evaluating the regeneration performance of the resin.
The resins DJ-1 to DJ-21 evaluated in the ion exchange column of example 23 and two commercially available styrenic macroporous weakly basic resins D301 and D392 were converted from the-Cl form to the-OH form with 100ml of a 4% NaOH solution, washed with 8000ml of deionized water, and then subjected to an extractive distillation unit to obtain sulfolane having a high gum content (gum content 182.4mg/100ml, Cl content: M)-The content is 9.6mg/L), and the filtrate is filtered at the temperature of 38-45 ℃ and the volume space velocity of 3-9 h-Flowing down the bed layer filled with anion exchange resin, adsorbing colloid and chloride ions in the sulfolane to obtain purified sulfolane, and measuring the colloid content and Cl in the purified sulfolane when the purifying amount of the sulfolane is 2000ml-Content, calculation of gum and Cl-And (4) removing rate. The colloid removal rate of the resins DJ-1 to DJ-21 prepared in examples 1 to 21 is reduced from 38.5 to 58.4 percent to 37.9 to 58.1 percent, the removal rate of chloride ions is reduced from 71.7 to 85.2 percent to 70.3 to 84.0 percent, the colloid removal rate of the commercially available polystyrene macroporous weak base resins DB-1 and DB-2 is reduced from 28.8 to 32.5 percent to 27.5 to 31.4 percent, and the removal rate of chloride ions is reduced from 54.0 to 59.9 percent to 52.3 to 58.6 percent. The regeneration performance of DJ-1 to DJ-21 resins was slightly better than that of commercially available DB-1 and DB-2. The evaluation results are shown in Table 2.
TABLE 2 purification, extraction and distillation of high gum content sulfolane after anion exchange resin regeneration
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and modifications of the methods and techniques described herein may be practiced without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A preparation method of anion exchange resin for purifying sulfolane with high colloid content comprises polymerization, chloromethylation and amination reaction; the method is characterized by comprising the following steps:
(1) polymerization reaction: adding styrene monomers, a cross-linking agent, an initiator, a pore-forming agent, a dispersing agent and deionized water as raw materials into a polymerization kettle, mixing and stirring, starting heating when an oil phase is dispersed into small droplets, raising the temperature to 50-60 ℃, reacting for 2-4 hours, raising the temperature to 80-90 ℃ at the speed of 1-1.5 ℃/2min, reacting for 2-4 hours, raising the temperature to 100-110 ℃, keeping for 4-8 hours, cooling to room temperature, filtering, washing and drying in vacuum to obtain polystyrene resin particles;
(2) chloromethylation reaction: adding the small polystyrene particles and chloromethyl ether into a reaction kettle, stirring, reacting for 1-3 hours at 30-50 ℃, adding zinc chloride, reacting for 10-12 hours at 40-60 ℃, cooling to room temperature, filtering, washing, and drying in vacuum to obtain chloromethylated polystyrene resin;
(3) amination reaction: adding chloromethylated polystyrene resin and hydrazine hydrate into a reaction kettle, stirring, reacting at 50-120 ℃ for 12-20 hours, cooling to room temperature, filtering, and washing to obtain the anion exchange resin.
2. The process of claim 1, wherein the crosslinking agent is one of ortho-divinylbenzene, para-divinylbenzene or meta-divinylbenzene.
3. The method as set forth in claim 1, wherein the porogen is one of toluene-n-heptane or toluene-liquid paraffin, and the mass ratio of toluene/n-heptane or toluene/liquid paraffin in the porogen is 1: 1-2: 1.
4. the method of claim 1, wherein the initiator is one of isobutanol peroxide, cumene peroxide or azobisisobutyronitrile.
5. The method of claim 1, wherein the dispersing agent is one of polyethylene glycol, polypropylene glycol, polyethylene wax or oxidized polyethylene wax.
6. The method as set forth in claim 1, characterized in that the ratio of raw materials of styrene, cross-linking agent, pore-forming agent, initiator, dispersant and deionized water in the polymerization reaction is 100: (1.0-2.0): (2.0-10): (0.5-1.0): (10-100): (100-1000).
7. The method according to claim 1, wherein the polystyrene has 95% or more of particles having a diameter of 0.315 to 1.25mm and a specific surface area of 300 to 500m2The porosity is 40-50 percent.
8. The process as claimed in claim 1, wherein the weight ratio of polystyrene particles in the chloromethylation reaction: chloromethyl ether: the mass ratio of zinc chloride is 100: (200-500): (10-50).
9. The method as set forth in claim 1, characterized in that the mass fraction of the aqueous solution of hydrazine hydrate in the amination is 10% -30% of the mass ratio of chloromethyl polystyrene particles to hydrazine hydrate is 100: (100-1000).
10. The method for purifying sulfolane by using the anion exchange resin prepared by the method of claim 1, which is characterized in that the filtered sulfolane with high colloid content in the extractive distillation unit is purified at the temperature of 38-45 ℃ and the space velocity of 3-9 h-Downflow fillingIn the bed layer of anion exchange resin, colloid and chloride ions in the sulfolane are adsorbed to obtain the purified sulfolane, wherein the colloid removal rate and the chloride ion removal rate in the sulfolane are respectively 38.5-58.4% and 71.7-85.2%; after the resin in the bed layer is adsorbed and saturated, the resin bed layer is washed by 4 percent sodium hydroxide solution, so that the adsorption capacity of the anion exchange resin is recovered.
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| US4694044A (en) * | 1984-03-09 | 1987-09-15 | Research Development Corp. Of Japan | Adsorbent |
| CN105254783A (en) * | 2015-11-05 | 2016-01-20 | 上海树脂厂有限公司 | Strongly alkaline anion exchange resin and preparation method thereof |
| CN107216415A (en) * | 2017-06-14 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of preparation method for adsorbing the resin of anion in the steady salt of heat in amine liquid |
| CN109365009A (en) * | 2018-11-20 | 2019-02-22 | 杭州多能环保科技有限公司 | A kind of preparation method of the ion exchange resin for sulfolane purification |
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2022
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|---|---|---|---|---|
| US4694044A (en) * | 1984-03-09 | 1987-09-15 | Research Development Corp. Of Japan | Adsorbent |
| CN105254783A (en) * | 2015-11-05 | 2016-01-20 | 上海树脂厂有限公司 | Strongly alkaline anion exchange resin and preparation method thereof |
| CN107216415A (en) * | 2017-06-14 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of preparation method for adsorbing the resin of anion in the steady salt of heat in amine liquid |
| CN109365009A (en) * | 2018-11-20 | 2019-02-22 | 杭州多能环保科技有限公司 | A kind of preparation method of the ion exchange resin for sulfolane purification |
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