CN102228841B - High-temperature-resistant fluorine-containing resin catalyst and preparation method thereof - Google Patents
High-temperature-resistant fluorine-containing resin catalyst and preparation method thereof Download PDFInfo
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- CN102228841B CN102228841B CN 201110120672 CN201110120672A CN102228841B CN 102228841 B CN102228841 B CN 102228841B CN 201110120672 CN201110120672 CN 201110120672 CN 201110120672 A CN201110120672 A CN 201110120672A CN 102228841 B CN102228841 B CN 102228841B
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Abstract
The invention provides a high-temperature-resistant fluorine-containing resin catalyst which is prepared by the steps of: with polymerized white balls of the resin catalyst as raw materials, fully swelling the white balls with a solvent, acylating with an acylating agent, adding a halogen element for halogenating, and finally introducing sulfo groups through sulfonation of a sulfonating agent. The high-temperature-resistant fluorine-containing resin catalyst is suitable for a reaction process with a reaction temperature of higher than 150 DEG C, and can be used for a long time at a temperature of below 200 DEG C. The invention also provides a preparation method of the high-temperature-resistant fluorine-containing resin catalyst.
Description
Technical field
The present invention relates to a kind of resin catalyst, be specifically related to a kind of resistant to elevated temperatures resin catalyst, and preparation method thereof.
Background technology
Sulfonic acid group on the sulfonated cation exchange resin easily comes off when particularly temperature is higher under reaction condition, causes the protonated of cationic ion-exchange resin aromatic ring.Because the catalytic activity of styrene-divinylbenzene azochlorosulfonate acid resin catalyst is directly proportional with the sulfonic concentration of its active group, will cause the resin catalyst activity decreased so sulfonic acid group comes off.The group that absorbs electronics can reduce and takes off sulphur speed.Therefore, generally introduce electron withdraw group at phenyl ring, to prevent and to reduce coming off of sulfonic acid group, increase the heat endurance of sulfonic acid group in the catalytic resin.
The eighties in last century, rom Haars Co., Ltd introduces Cl at the resin phenyl ring first
-, Br
-Deng electron withdraw group, then to the resin sulfonation, thereby obtained the EXCHANGE RESIN CATALYSTS WITHHIGH THERMAL STABILITY cationic ion-exchange resin, and under high-pressure high-temperature environment, had good mechanical stability.Rom and and the patent CN139329A of Haars Co., Ltd in, work out in the situation that there is not organic swelling solvent, the sulfonation by wet cross-linked copolymer has prepared the storng-acid cation exchange resin that has physical stability and do not have the chlorinated solvent pollutant.
Publication number is in the Chinese patent application " high temperature cation exchange resin catalyst preparation method " of CN1076385, raw material styrene-divinylbenzene copolymer microballoon is carried out solvent extraction under high temperature and certain pressure, then carry out bromination and sulfonation, process finally by the high temperature deionized water, obtain catalyst, its specific area, bore dia and pore volume numerical value all are height than the catalyst that conventional method makes.Have high reactivity and resistance to elevated temperatures, obviously improve service life.
Publication number is in the Chinese patent application " Thermostable strong acid cation resin Catalysts and its preparation method " of CN1569334, pressure polymerization and the simple preparation method of hole purification method have been proposed, pressure polymerization has improved the uniformity of polymeric beads body structure, improved the high-temperature machinery stability of resin, when the strong acid cation resin catalyst of preparing had high temperature resistant and good catalytic activity, its high-temperature machinery stability was apparently higher than like product.
The heat resistance of resin catalyst and polystyrene content, electron withdraw group are relevant with sulfonic acid group the position of substitution.What the heatproof strong resin was different from other resin is to have introduced electron-withdrawing group in the contraposition of polystyrene side chain, and the activated centre of resin catalyst is the H on the sulfonic acid group
+, under reaction condition, sulfonic acid group can be by H
+Replace, cause the resin cation aromatic ring protonated, this is an electric replacement process of parent, after introducing electron-withdrawing group on the aromatic ring, can reduce the cloud density on the phenyl ring, cause this electrophilic substitution reaction to be difficult to carry out, thereby reach the purpose that strengthens the thermal stability of sulfonic acid group in the resin catalyst.Therefore this EXCHANGE RESIN CATALYSTS WITHHIGH THERMAL STABILITY storng-acid cation exchange resin is compared with general macropore strong acid cation exchanger resin, has higher heat resistance, the high temperature that the catalyst ability is 140-180 ℃.Adopting publication number is that the D008 resin that the technology in the patent application of CN1569334 is produced is widely used at the n-butylene hydration reaction unit, respond well.
But the high-temperature cation-exchange resin catalyst of producing both at home and abroad, more than 150 ℃ during pyroreaction, resin catalyst is with sulfonic acid group, under the pyroreaction condition, easily come off, the sulfonic group that comes off becomes azochlorosulfonate acid ion in water, make the recirculated water electrical conductivity higher, affected recycling of recirculated water.The recirculated water electrical conductivity is lower, illustrates that the sulfonic group of resin catalyst comes off less, and the heat resistance of resin catalyst is better.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, propose a kind of high temperature resistant resin catalyst and preparation method thereof of fluoridizing, this resin catalyst is particularly useful for the course of reaction that reaction temperature is higher than 150 ℃, can use for a long time below 200 ℃.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of high temperature resistant resin catalyst of fluoridizing is provided; it be polymerization Archon take resin catalyst as raw material, with Archon with the abundant swelling of solvent after, carry out acidylate with acylating agent; and then add halogen and carry out halogenation, introduce sulfonic acid group and get finally by the sulfonating agent sulfonation.
The polymerization Archon of described resin catalyst can be selected from any one in the polymerization Archon of the catalytic resins such as commercially available D006, D008, NKC-9 or A45.
Described solvent can be selected from one or more the mixture in dichloroethanes, gasoline, methyl alcohol, ethanol, sec-butyl alcohol, benzene, toluene, dichloroethanes, nitrobenzene, the ethyl acetate, preferred dichloroethanes.
Described acylating agent is optional from fluorine-containing chlorobenzoyl chloride, preferred o-fluoro-benzoyl chloride.
Described acylation reaction temperature is 30～60 ℃, and the reaction time is 5-10h.
Described halogen can be selected from any one in fluorine, chlorine, the bromine or iodine, preferred chlorine.
The reaction temperature of described halogenation is-5～30 ℃, and the mol ratio between phenyl ring and the halogen is 1: 0.2～0.8 in the control reactant;
Described sulfonating agent preferred concentration is the sulfuric acid of 100-105%.
The present invention also provides the described high temperature resistant preparation method who fluoridizes resin catalyst, may further comprise the steps:
1). swelling
Polymerization Archon with resin catalyst is raw material, fully is swelling to volume and no longer changes in solvent; The polymerization Archon of described resin catalyst can be selected from any one in the polymerization Archon of the catalytic resins such as commercially available D006, D008, NKC-9 or A45; Described solvent can be selected from one or more the mixture in dichloroethanes, gasoline, methyl alcohol, ethanol, sec-butyl alcohol, benzene, toluene, dichloroethanes, nitrobenzene or the ethyl acetate, preferred dichloroethanes.
2). acylation reaction
With lewis acid and step 1) the good polymerization Archon of swelling adds in the solvent, add again acylating agent and carry out acidylate, polymerization Archon wherein: lewis acid: the mol ratio of acylating agent is 1: 1: 0.4～1.5, and the acidylate temperature is 30～60 ℃, and the acylation reaction time is 5～10h; Described solvent can be selected from one or more the mixture in dichloroethanes, gasoline, methyl alcohol, ethanol, sec-butyl alcohol, benzene, toluene, dichloroethanes, nitrobenzene or the ethyl acetate, preferred dichloroethanes; Described lewis acid can be selected from any one in aluminium chloride or the iron chloride; Described acylating agent is optional from fluorine-containing chlorobenzoyl chloride, preferred o-fluoro-benzoyl chloride.
3). halogenation:
In step 2) add the halogen family molecule in the reactant mixture that obtains and carry out halogenation, halogen can be selected from any one in fluorine, chlorine, the bromine or iodine, preferred chlorine; The halogenation temperature is-5～30 ℃, and the mol ratio in the control reactant between phenyl ring and the halogen is 1: 0.2～0.8;
4). sulfonating reaction
With step 3) to add excessive concentration be the sulfuric acid of 100-105% for the halide reactant product that obtains, macroporous cation catalytic resin standard technology ladder-elevating temperature routinely, at last at 110 ℃ of lower insulation 5h, insulation is washed with low-concentration sulfuric acid after finishing, washing namely obtains the described high temperature resistant resin catalyst of fluoridizing.
This product has following beneficial effect:
(1) is applicable to the course of reaction that reaction temperature is higher than 150 ℃, can using for a long time below 200 ℃.
(2) be used for the butylene hydration reaction, the recirculated water water outlet conductivity is extremely low, has reduced cost of water treatment.
The high temperature resistant resin catalyst of fluoridizing of the present invention because of halogen group and fluorine-containing chlorobenzoyl chloride acting in conjunction, makes sulfonic acid group very firm on phenyl ring, difficult drop-off, thus reach resistant to elevated temperatures effect.Product of the present invention is when n-butylene hydration reaction is more than 180 ℃, and water outlet conductivity is very low, and far below similar products at home and abroad, water outlet conductivity is lower, illustrates that the sulfonic group of resin catalyst comes off less, and the heat resistance of resin catalyst is better.
The specific embodiment
Following instance only is to further specify the present invention, is not the restriction the scope of protection of the invention.Device and material that following examples are used are as follows:
1. experimental rig
Thermostat water bath (0～120 ℃)
Adjustable electric mixer (0～2000 turns)
There-necked flask (2000ml)
The plastics stirring arm
Thermometer (0～150 ℃)
Rubber stopper (No. 5)
Beaker (400ml, 1000ml)
Balance (0～1000g)
2. primary raw material
Test medicine:
Divinylbenzene, technical grade;
Benzoyl peroxide (BPO), technical grade;
Styrene, technical grade;
Gelatin, photographic-grade;
The blue solution 1 ‰ of methine;
Liquid wax, technical grade;
Iron chloride, technical grade;
Aluminium chloride, technical grade;
98% sulfuric acid, technical grade;
Dichloroethanes, technical grade;
Water, deionized water;
O-fluoro-benzoyl chloride, technical grade.
Embodiment 1:
1). swelling
Select the polymerization Archon 200g of the D008 resin catalyst of commercially available KaiRui Chemical Engineering Co., Ltd's production, with the abundant swelling of dichloroethanes solvent;
2). acylation reaction
Take dichloroethanes as solvent, adding aluminium chloride and step 1) polymerization Archon one that swelling is good reacts, and the polymerization Archon adds o-fluoro-benzoyl chloride and carries out acidylate, temperature 60 C, reaction time 10h;
Polymerization Archon: aluminium chloride: o-fluoro-benzoyl chloride (mol ratio)=1: 1: 0.4;
3). halogenation
In step 2) add chlorine in the product after the acidylate and carry out halogenation, temperature-5 ℃, the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.2.
4) sulfonating reaction
With step 3) to add excessive concentration be 100% sulfuric acid for the halide reactant product that obtains, macroporous cation catalytic resin standard technology ladder-elevating temperature routinely is at last at 110 ℃ of lower insulation 5h, insulation is washed with low-concentration sulfuric acid after finishing, washing, blowing, obtain product, be numbered KRB-1.
Embodiment 2
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1.5;
The other the same as in Example 1, products obtained therefrom is numbered KRB-2.
Embodiment 3
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1;
The other the same as in Example 1, products obtained therefrom is numbered KRB-3.
Embodiment 4
The temperature that adding chlorine carries out halogenation is 30 ℃;
The other the same as in Example 1, products obtained therefrom is numbered KRB-4.
Embodiment 5
The temperature that adding chlorine carries out halogenation is 20 ℃;
The other the same as in Example 1, products obtained therefrom is numbered KRB-5.
Embodiment 6
Add chlorine and carry out in the halogenation, the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.8;
The other the same as in Example 1, products obtained therefrom is numbered KRB-6.
Embodiment 7
Add chlorine and carry out in the halogenation, the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.4;
The other the same as in Example 1, products obtained therefrom is numbered KRB-7.
Embodiment 8
During sulfonation, sulfuric acid concentration is 105%;
The other the same as in Example 1, products obtained therefrom is numbered KRB-8.
Embodiment 9
During sulfonation, sulfuric acid concentration is 102%;
The other the same as in Example 1, products obtained therefrom is numbered KRB-9.
Embodiment 10
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1.5;
The temperature that adding chlorine carries out chlorination reaction is 30 ℃;
The other the same as in Example 1, products obtained therefrom is numbered KRB-10.
Embodiment 11
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1.5;
The temperature that adding chlorine carries out chlorination reaction is 20 ℃;
The other the same as in Example 1, products obtained therefrom is numbered KRB-11.
Embodiment 12
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1;
The temperature that adding chlorine carries out chlorination reaction is 30 ℃;
The other the same as in Example 1, products obtained therefrom is numbered KRB-12.
Embodiment 13
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1;
The temperature that adding chlorine carries out chlorination reaction is 20 ℃;
The other the same as in Example 1, products obtained therefrom is numbered KRB-13.
Embodiment 14
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1.5;
The temperature that adding chlorine carries out chlorination reaction is 30 ℃, and the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.8;
The other the same as in Example 1, products obtained therefrom is numbered KRB-14.
Embodiment 15
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1.5;
The temperature that adding chlorine carries out chlorination reaction is 20 ℃, and the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.4;
The other the same as in Example 1, products obtained therefrom is numbered KRB-15.
Embodiment 16
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1;
The temperature that adding chlorine carries out chlorination reaction is 30 ℃, and the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.8;
The other the same as in Example 1, products obtained therefrom is numbered KRB-16.
Embodiment 17
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1;
The temperature that adding chlorine carries out chlorination reaction is 20 ℃, and the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.4;
The other the same as in Example 1, products obtained therefrom is numbered KRB-17.
Embodiment 18
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1.5;
The temperature that adding chlorine carries out chlorination reaction is 30 ℃, and the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.8;
During sulfonation, sulfuric acid concentration is 102%;
The other the same as in Example 1, products obtained therefrom is numbered KRB-18.
Embodiment 19
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1.5;
The temperature that adding chlorine carries out chlorination reaction is 20 ℃, and the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.4;
During sulfonation, sulfuric acid concentration is 105%;
The other the same as in Example 1, products obtained therefrom is numbered KRB-19.
Embodiment 20
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1;
The temperature that adding chlorine carries out chlorination reaction is 30 ℃, and the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.8;
During sulfonation, sulfuric acid concentration is 102%;
The other the same as in Example 1, products obtained therefrom is numbered KRB-20.
Embodiment 21
Acidylate proportioning: polymerization Archon: aluminium chloride: the mol ratio of o-fluoro-benzoyl chloride=1: 1: 1;
The temperature that adding chlorine carries out chlorination reaction is 20 ℃, and the mol ratio in the control reactant between phenyl ring and the chlorine element is 1: 0.4;
During sulfonation, sulfuric acid concentration is 105%;
The other the same as in Example 1, products obtained therefrom is numbered KRB-21.
Embodiment 22: butylene hydration reaction evaluation experiment
This experiment is take the prepared resin catalyst of embodiment of the invention 1-21 as laboratory sample, the D007-1 resin catalyst of producing with commercially available KaiRui Chemical Engineering Co., Ltd as a comparison case 1, carry out the grouping comparison experiment, every group of butylene hydration reaction evaluation experiment 10L reactor is divided into four sections, every section filling sample resins catalyst 1L, the n-butene raw material passes through four sections beds from below to up, fresh water (FW) four sections of parts under the bed of every section catalyst enter, and reaction generates sec-butyl alcohol under the effect of catalyst.The SBA that reaction generates flows out from reactor head, and reacted fresh water (FW) flows out from each downflow weir bottom, bed top, through after the water treatment, recycles.180 ℃ of reaction temperatures, butylene air speed 1.7/h, reaction pressure 6.0MPa, water alkene mol ratio 1.1.Continuous operation 100h under above-mentioned reaction condition calculates the butylene conversion per pass and uses conductivity meter to measure water conductivity, and comparing result sees Table 1.
The comparison of table 1. different formulations sample butylene conversion per pass and electrical conductivity
| Numbering | Butylene conversion per pass % | Electrical conductivity μ s/cm |
| KRB-1 | 7.6 | 152 |
| KRB-2 | 7.2 | 144 |
| KRB-3 | 7.4 | 156 |
| KRB-4 | 7.4 | 169 |
| KRB-5 | 6.8 | 121 |
| KRB-6 | 7.2 | 130 |
| KRB-7 | 7.4 | 154 |
| KRB-8 | 7.1 | 180 |
| KRB-9 | 7.4 | 120 |
| KRB-10 | 7.2 | 184 |
| KRB-11 | 7.5 | 101 |
| KRB-12 | 7.0 | 195 |
| KRB-13 | 7.5 | 125 |
| KRB-14 | 7.2 | 130 |
| KRB-15 | 7.8 | 171 |
| KRB-16 | 7.6 | 125 |
| KRB-17 | 7.2 | 133 |
| KRB-18 | 7.7 | 130 |
| KRB-19 | 7.2 | 148 |
| KRB-20 | 7.0 | 171 |
| KRB-21 | 7.4 | 184 |
| Comparative Examples 1 | 6.8 | 1311 |
Claims (8)
1. high temperature resistant resin catalyst of fluoridizing, it be polymerization Archon take resin catalyst as raw material, with Archon with the abundant swelling of solvent after, carry out acidylate with acylating agent, and then add halogen and carry out halogenation, introduce sulfonic acid group and get finally by the sulfonating agent sulfonation; Described solvent is selected from one or more the mixture in dichloroethanes, gasoline, methyl alcohol, ethanol, sec-butyl alcohol, benzene, toluene, dichloroethanes, nitrobenzene or the ethyl acetate; Described acylating agent is fluorine-containing chlorobenzoyl chloride; The described high temperature resistant resin catalyst of fluoridizing prepares by the following method:
1). swelling
The polymerization Archon of resin catalyst fully is swelling to volume in solvent no longer change;
2). acylation reaction
Lewis acid and the good polymerization Archon of step 1) swelling are added in the solvent, and add acylating agent again and carry out acidylate, wherein the polymerization Archon: lewis acid: the mol ratio of acylating agent is 1:1:0.4 ~ 1.5, and the acidylate temperature is 30 ~ 60 ℃, and the acylation reaction time is 5 ~ 10h;
3). halogenation
In step 2) add the halogen family molecule in the reactant mixture that obtains and carry out halogenation, the halogenation temperature be-5 ~ 30 ℃, controls that the mol ratio between the phenyl ring and halogen is 1:0.2 ~ 0.8 in the reactant;
4). sulfonating reaction
The excessive concentration of halide reactant product adding that step 3) is obtained is the sulfuric acid of 100-105%, macroporous cation catalytic resin standard technology ladder-elevating temperature routinely, at last at 110 ℃ of lower insulation 5h, insulation is washed with low-concentration sulfuric acid after finishing, washing namely obtains the described high temperature resistant resin catalyst of fluoridizing.
2. the high temperature resistant resin catalyst of fluoridizing claimed in claim 1 is characterized in that: the polymerization Archon of described resin catalyst is selected from any one in the polymerization Archon of commercially available D006, D008, NKC-9 or A45 catalytic resin.
3. the high temperature resistant resin catalyst of fluoridizing claimed in claim 1, it is characterized in that: described acylating agent is o-fluoro-benzoyl chloride.
4. the high temperature resistant resin catalyst of fluoridizing claimed in claim 1, it is characterized in that: described halogen is selected from any one in fluorine, chlorine, the bromine or iodine.
5. the high temperature resistant resin catalyst of fluoridizing claimed in claim 1, it is characterized in that: described sulfonating agent is that concentration is the sulfuric acid of 100-105%.
6. the high temperature resistant preparation method who fluoridizes resin catalyst claimed in claim 1 may further comprise the steps:
1). swelling
The polymerization Archon of resin catalyst fully is swelling to volume in solvent no longer change;
2). acylation reaction
Lewis acid and the good polymerization Archon of step 1) swelling are added in the solvent, and add acylating agent again and carry out acidylate, wherein the polymerization Archon: lewis acid: the mol ratio of acylating agent is 1:1:0.4 ~ 1.5, and the acidylate temperature is 30 ~ 60 ℃, and the acylation reaction time is 5 ~ 10h;
3). halogenation
In step 2) add the halogen family molecule in the reactant mixture that obtains and carry out halogenation, the halogenation temperature be-5 ~ 30 ℃, controls that the mol ratio between the phenyl ring and halogen is 1:0.2 ~ 0.8 in the reactant;
4). sulfonating reaction
The excessive concentration of halide reactant product adding that step 3) is obtained is the sulfuric acid of 100-105%, macroporous cation catalytic resin standard technology ladder-elevating temperature routinely, at last at 110 ℃ of lower insulation 5h, insulation is washed with low-concentration sulfuric acid after finishing, washing namely obtains the described high temperature resistant resin catalyst of fluoridizing.
7. preparation method claimed in claim 6 is characterized in that: step 2) described lewis acid is selected from any one in aluminium chloride or the iron chloride.
8. preparation method claimed in claim 6, it is characterized in that: the described halogen family molecule of step 3) is selected from fluorine gas, chlorine, bromine or iodine.
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| CN102688774B (en) * | 2012-05-30 | 2014-04-02 | 凯瑞化工股份有限公司 | Resin catalyst for light gasoline etherification and preparation method thereof |
| CN102698819B (en) * | 2012-05-31 | 2014-02-19 | 凯瑞化工股份有限公司 | Deacidification agent applied to methyl tert-butyl ether (MTBE) production device and preparation method for deacidification agent |
| CN103447089B (en) * | 2013-09-18 | 2015-06-10 | 凯瑞环保科技股份有限公司 | Low-carbon olefine oligomerization catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5220087A (en) * | 1991-12-13 | 1993-06-15 | Allied-Signal Inc. | Preparation of strong and super acid catalysts using elemental fluorine |
| CN1076385A (en) * | 1992-03-13 | 1993-09-22 | 中国石油化工总公司抚顺石油化工研究院 | Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst |
| CN1167011A (en) * | 1996-05-31 | 1997-12-10 | 浦昭伦 | Method for preparing high thermal stability sulfonic acid type cation exchange resin catalyst |
| CN1765505A (en) * | 2004-10-28 | 2006-05-03 | 中国石油化工股份有限公司 | Method for preparing fluorin-containing composite strong acid ion exchange resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200924B1 (en) * | 1999-01-29 | 2001-03-13 | E. I. Du Pont De Nemours And Company | Porous highly fluorinated acidic polymer catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5220087A (en) * | 1991-12-13 | 1993-06-15 | Allied-Signal Inc. | Preparation of strong and super acid catalysts using elemental fluorine |
| CN1076385A (en) * | 1992-03-13 | 1993-09-22 | 中国石油化工总公司抚顺石油化工研究院 | Method for preparing high-temp-resistant strong acid type cation exchange resin catalyst |
| CN1167011A (en) * | 1996-05-31 | 1997-12-10 | 浦昭伦 | Method for preparing high thermal stability sulfonic acid type cation exchange resin catalyst |
| CN1765505A (en) * | 2004-10-28 | 2006-05-03 | 中国石油化工股份有限公司 | Method for preparing fluorin-containing composite strong acid ion exchange resin |
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