CN102228841A - 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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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 comes off when particularly temperature is higher under reaction condition easily, 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, resin catalyst is active to be reduced with causing so sulfonic acid group comes off.The group that absorbs electronics can reduce and takes off sulphur speed.Therefore, generally on phenyl ring, introduce electron withdraw group,, increase the heat endurance of sulfonic acid group in the catalytic resin to prevent and to reduce coming off of sulfonic acid group.
The eighties in last century, rom Haars Co., Ltd introduces Cl first on the resin phenyl ring
-, 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 under the situation that does not have 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, carry out bromination and sulfonation then, after the high temperature deionized water handle, 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 " high temperature resistant 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 polyethylene benzene 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 hear 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 extensive use of at the n-butylene hydration reaction unit, respond well.
But the domestic and international high-temperature cation-exchange resin catalyst of producing, more than 150 ℃ during pyroreaction, resin catalyst has 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, influenced recycling of recirculated water.The recirculated water electrical conductivity is low more, and it is more little to illustrate that the sulfonic group of resin catalyst comes off, and the heat resistance of resin catalyst is good more.
Summary of the invention
The objective of the invention is to: at 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 is that polymerization Archon with resin catalyst is a 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, after the sulfonating agent sulfonation introduce sulfonic acid group and get.
The polymerization Archon of described resin catalyst can be selected from any one in the polymerization Archon of 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 a 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 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
Lewis acid and the good polymerization Archon of step 1) swelling are added in the solvent, add acylating agent again 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
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, be incubated 5h down at 110 ℃ at last, insulation finishes the back and washes with low-concentration sulfuric acid, washing promptly obtains the described high temperature resistant resin catalyst of fluoridizing.
This product has following beneficial effect:
(1) is applicable to that reaction temperature is higher than 150 ℃ course of reaction, can using for a long time below 200 ℃.
(2) be used for the butylene hydration reaction, it is extremely low that recirculated water goes out water conductivity, 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 it is very low to go out water conductivity, and far below similar products at home and abroad, it is low more to go out water conductivity, and it is more little to illustrate that the sulfonic group of resin catalyst comes off, and the heat resistance of resin catalyst is good more.
The specific embodiment
Following example 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 changes)
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 for use, with the abundant swelling of dichloroethanes solvent;
2). acylation reaction
With the dichloroethanes is solvent, adds aluminium chloride and the good polymerization Archon one of step 1) swelling and reacts, and the polymerization Archon adds o-fluoro-benzoyl chloride and carries out acidylate, 60 ℃ of temperature, 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
It is 100% sulfuric acid that the halide reactant product that step 3) is obtained adds excessive concentration, and macroporous cation catalytic resin standard technology ladder-elevating temperature routinely is at last at 110 ℃ of insulation 5h down, insulation finishes the back washes washing, blowing with low-concentration sulfuric acid, 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;
Other is with embodiment 1, and 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;
Other is with embodiment 1, and products obtained therefrom is numbered KRB-3.
Embodiment 4
The temperature that adding chlorine carries out halogenation is 30 ℃;
Other is with embodiment 1, and products obtained therefrom is numbered KRB-4.
Embodiment 5
The temperature that adding chlorine carries out halogenation is 20 ℃;
Other is with embodiment 1, and 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;
Other is with embodiment 1, and 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;
Other is with embodiment 1, and products obtained therefrom is numbered KRB-7.
Embodiment 8
During sulfonation, sulfuric acid concentration is 105%;
Other is with embodiment 1, and products obtained therefrom is numbered KRB-8.
Embodiment 9
During sulfonation, sulfuric acid concentration is 102%;
Other is with embodiment 1, and 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 ℃;
Other is with embodiment 1, and 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 ℃;
Other is with embodiment 1, and 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 ℃;
Other is with embodiment 1, and 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 ℃;
Other is with embodiment 1, and 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;
Other is with embodiment 1, and 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;
Other is with embodiment 1, and 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;
Other is with embodiment 1, and 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;
Other is with embodiment 1, and 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%;
Other is with embodiment 1, and 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%;
Other is with embodiment 1, and 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%;
Other is with embodiment 1, and 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%;
Other is with embodiment 1, and products obtained therefrom is numbered KRB-21.
Embodiment 22: butylene hydration reaction evaluation experiment
This experiment is a laboratory sample with the prepared resin catalyst of embodiment of the invention 1-21, 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 is from passing through four sections beds down, fresh water (FW) enters for four sections from the bed lower part of every section catalyst, 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 running 100h under above-mentioned reaction condition calculates the butylene conversion per pass and also 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 (10)
1. high temperature resistant resin catalyst of fluoridizing; it is that polymerization Archon with resin catalyst is a 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, after the sulfonating agent sulfonation introduce sulfonic acid group and get.
2. the described high temperature resistant resin catalyst of fluoridizing of claim 1 is characterized in that: the polymerization Archon of described resin catalyst is selected from any one in the polymerization Archon of catalytic resins such as commercially available D006, D008, NKC-9 or A45.
3. the described high temperature resistant resin catalyst of fluoridizing of claim 1 is characterized in that: 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.
4. the described high temperature resistant resin catalyst of fluoridizing of claim 1, it is characterized in that: described acylating agent is an o-fluoro-benzoyl chloride.
5. the described high temperature resistant resin catalyst of fluoridizing of claim 1, it is characterized in that: described halogen is selected from any one in fluorine, chlorine, the bromine or iodine.
6. the described high temperature resistant resin catalyst of fluoridizing of claim 1, it is characterized in that: described sulfonating agent is that concentration is the sulfuric acid of 100-105%.
7. the described high temperature resistant preparation method who fluoridizes resin catalyst of 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, add acylating agent again 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;
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, be incubated 5h down at 110 ℃ at last, insulation finishes the back and washes with low-concentration sulfuric acid, washing promptly obtains the described high temperature resistant resin catalyst of fluoridizing.
8. the described preparation method of claim 7 is characterized in that: the described solvent of step 1) 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.
9. the described preparation method of claim 7 is characterized in that: step 2) described lewis acid is selected from any one in aluminium chloride or the iron chloride.
10. the described preparation method of claim 7, it is characterized in that: the described halogen family molecule of step 3) comprises fluorine gas, chlorine, bromine or iodine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110120672 CN102228841B (en) | 2011-05-11 | 2011-05-11 | High-temperature-resistant fluorine-containing resin catalyst and preparation method thereof |
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|---|---|---|---|
| CN 201110120672 CN102228841B (en) | 2011-05-11 | 2011-05-11 | High-temperature-resistant fluorine-containing resin catalyst and preparation method thereof |
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| CN102228841B CN102228841B (en) | 2013-04-10 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102688774A (en) * | 2012-05-30 | 2012-09-26 | 凯瑞化工股份有限公司 | Resin catalyst for light gasoline etherification and preparation method thereof |
| CN102698819A (en) * | 2012-05-31 | 2012-10-03 | 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 |
| CN103447089A (en) * | 2013-09-18 | 2013-12-18 | 凯瑞化工股份有限公司 | Low-carbon olefine oligomerization catalyst and preparation method thereof |
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| 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 |
| WO2000044495A1 (en) * | 1999-01-29 | 2000-08-03 | E.I. Du Pont De Nemours And Company | Porous highly fluorinated acidic polymer catalyst and process for its preparation |
| 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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| US5220087A (en) * | 1991-12-13 | 1993-06-15 | Allied-Signal Inc. | Preparation of strong and super acid catalysts using elemental fluorine |
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| CN1167011A (en) * | 1996-05-31 | 1997-12-10 | 浦昭伦 | Method for preparing high thermal stability sulfonic acid type cation exchange resin catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102688774A (en) * | 2012-05-30 | 2012-09-26 | 凯瑞化工股份有限公司 | Resin catalyst for light gasoline etherification and preparation method thereof |
| 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 |
| CN102698819A (en) * | 2012-05-31 | 2012-10-03 | 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 |
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| CN103447089A (en) * | 2013-09-18 | 2013-12-18 | 凯瑞化工股份有限公司 | Low-carbon olefine oligomerization catalyst and preparation method thereof |
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|---|---|
| CN102228841B (en) | 2013-04-10 |
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