CN101444752B - Catalytic resin produced by using polystyrene/SBS/waste white ball composite material and preparation method thereof - Google Patents
Catalytic resin produced by using polystyrene/SBS/waste white ball composite material and preparation method thereof Download PDFInfo
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- CN101444752B CN101444752B CN2008101832423A CN200810183242A CN101444752B CN 101444752 B CN101444752 B CN 101444752B CN 2008101832423 A CN2008101832423 A CN 2008101832423A CN 200810183242 A CN200810183242 A CN 200810183242A CN 101444752 B CN101444752 B CN 101444752B
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Abstract
The invention provides a catalytic resin produced by polystyrene/SBS/waste white ball composite material and a preparation method thereof. The catalytic resin is produced according to the following steps: taking unqualified white balls for making a macrocellular resin after wax extraction as raw materials, and crushing the raw materials into powders for standby application; blending and pelletizing a mixed material consisting of polystyrene and SBS for the first time by a double-screw extruder; blending the powder obtained from the blending and palletizing with the powder obtained by crushingthe white balls after wax extraction, wherein, stearic acid is also blended; obtaining disc shape or other specific shapes through injection molding by a plastic injection molding machine; soaking out the stearic acid with acetone or ethanol; cleaning with ethanol and water to obtain a resin having a microcellular structure; sulphonating the resin according to macrocellular cation-exchange resin sulphonation process which is publicly known, and fixing the resin to prepare a highly acid cation catalytic resin having a specific shape. The highly acid cation catalytic resin prepared according tothe method has various specific shapes and is easy for filling; and, by taking the unqualified white balls used for making a macrocellular resin as raw materials, wastes are reused and cost is reduced, therefore, the catalytic resin can be widely applied to the fields such as etherification, esterification and alkylation as a catalyst.
Description
Technical field
The present invention relates to a kind of catalytic resin and preparation method thereof, particularly a kind of catalytic resin of using polystyrene/SBS/ waste product Archon composite production and preparation method thereof.
Technical background
More existing announcements of the technology of the similar production catalytic resin of development both at home and abroad, as patent CN1304917 (a kind of method of preparing tert-butanol from isobutylene by hydration), a kind of bulky grain resin catalyst that Lanzhou petrochemical industry research institute research and development are produced is the cation resin catalyzing agent of wheel shape, corrugated, shape macropore strong acid such as cylindric; And yet there are no report with the making of polystyrene/waste product Archon composite injection molding forming method production catalytic resin, this patent adopts polystyrene to do matrix resin, Powdered waste product Archon is made filler, adopt Plastics Injection Molding Technology, shape by the control mould, obtain difform catalytic resin intermediate, and then carry out process for sulfonation, sulfonic group need be through the high-temperature fusion process of extruder or injection machine like this, can Yin Gaowen and come off, thereby product has higher exchange capacity, has guaranteed catalytic effect preferably.
Summary of the invention
Purpose of the present invention mainly contains 2 points:
1) the macroporous type styrene of our factory production and the copolymer of divinylbenzene, be commonly called as Archon, in the polymerization process as trade mark Archons such as D001, D006, D201, D301, qualified ball rate is 85%, there is 15% not qualified ball to fall as waste disposal, the present invention uses these waste products to be raw material, can improve utilization ratio of raw materials, for enterprise increases new profit growth point.
2) catalytic resin of the present invention's preparation can have difformity, can directly fill in fixed bed and the tower reactor, compare with the spherical particle resin catalyst, having bed resistance falls little, convenient filling, does not need complicated advantages such as reactor internal components, can be used for chemical reactions such as etherificate, hydration, hydrolysis and esterification, be particularly useful for reactive distillation and counter-current reactor field.
To achieve these goals, the defective Archon that the present invention will make macroporous ion-exchange resin is carried behind the wax as raw material, and it is stand-by to be ground into powder earlier; Polystyrene/SBS is pressed 1: the mixed material of weight ratio preparation (0.1-0.3), earlier carry out the blend granulation first time with double screw extruder, again with the powder of defective Archon and stearic acid by 1: (2-3): 0.5 weight ratio is carried out the blend second time, with plastic-injection moulding machine be injection molded into discoid or other can injection molded given shape, soak out stearic acid with acetone or alcohol then, obtain having the resin of microcellular structure, through large hole cation exchanger resin sulfonation manufacturing technique known in those skilled in the art resin is carried out sulfonation again, thereby make highly acidic cation catalytic resin with given shape.
The synthetic of this resin can be realized by following steps:
1). Archon is pulverized
The defective Archon of making macroporous ion-exchange resin is carried wax, use high speed disintegrator to be ground into 100-200 purpose powder, promptly product 1.
2). grain is moulded in polystyrene/SBS blend
Polystyrene/SBS is pressed 1: weight ratio (0.1-0.3), mix by high-speed mixer, then mixed material is carried out the blend granulation first time with double screw extruder earlier, promptly product 2.
3). injection mo(u)lding
With product 2 and product 1 and stearic acid 1: (2-3): 0.5 weight ratio is carried out the blend second time, is injection molded into discoid or other shape with plastic-injection moulding machine, and promptly product 3.
4). soaked in solvent
Product 3 soaked in solvents after the injection moulding are after 20 hours, be washed to solvent-free, thereby obtain having the resin of microcellular structure, it is product 4, described solvent is that one or more of common solvent such as gasoline, methyl alcohol, ethanol, sec-butyl alcohol, toluene, dichloroethanes, nitrobenzene, acetoneand ethyl acetate mix, and is preferably acetone or alcohol.
5). the sulfonation engage a gear
Product 4 is pressed known large hole cation exchanger resin sulfonation manufacturing technique, through sulfonation, and engage a gear, thus make highly acidic cation catalytic resin with given shape, promptly end product 5.
This product has following beneficial effect:
1) the defective Archon of use macroporous ion-exchange resin of the present invention is a raw material, can improve utilization ratio of raw materials, has cost advantage.
2) catalytic resin of the present invention's preparation can have difformity, compare with the spherical particle resin catalyst, having bed resistance falls little, convenient filling, does not need complicated advantages such as reactor internal components, can be used for chemical reactions such as etherificate, hydration, hydrolysis and esterification, be particularly useful for reactive distillation and counter-current reactor field.
The specific embodiment
Following example only is to further specify the present invention, is not the restriction the scope of protection of the invention.
Embodiment 1: the preparation of catalytic resin
1) base stock
Polystyrene, Beijing Yanshan Petrochemical oil limited company, the trade mark: 666D;
SBS, Ba Ling petrochemical industry, the trade mark: 4412 (milky fine strip shape things)
Stearic acid, sky, Lu, Sichuan carburetion fat chemistry limited company
Make the defective Archon KaiRui Chemical Engineering Co., Ltd of macroporous ion-exchange resin
2) instrument and equipment of preparation use
SHJ-36 double screw extruder and auxiliary equipment, Nanjing chemical machinery Co., Ltd of sincere alliance
The GHJ-36 high-speed mixer, Shanghai plastics machinery factory
The SZ-100/80 plastic-injection moulding machine, Shanghai plastics machinery factory
The YSC-701 micronizer, the positive moral plant equipment in the Yanshan Mountain, Beijing Co., Ltd
3) preparation technology
3.1) the Archon pulverizing
Restrain the defective Archon make macroporous ion-exchange resin with 500, carry wax 4 times with gasoline in the time of 60 ℃, oven dry uses the YSC-701 micronizer to be ground into powder, promptly gets product 1.
3.2). grain is moulded in polystyrene/SBS blend
Polystyrene/SBS is reached the mixed material of preparation by a certain percentage, carry out the blend granulation first time with double screw extruder earlier, promptly product 2.
In the extrusion, barrel temperature is 175 ℃ in a district, 183 ℃ in two districts, and 183 ℃ in three districts, 183 ℃ in four districts, 183 ℃ in five districts, 183 ℃ in six districts, 178 ℃ in seven districts, head temperature is 175 ℃,
Proportioning is: (part) (weight portion)
Polystyrene 100
SBS 15
3.3) injection mo(u)lding
Get product 2/ product 1/ stearic acid and carry out the blend second time with high-speed mixer by a certain percentage, it is discoid to be injection molded into φ 1cm with plastic-injection moulding machine, thick 2mm, uniform φ 2mm aperture in the middle of the disk, also be designed to other shape, do not influence result of use, promptly product 3.
Temperature is controlled to be 170 ℃ in a district in the injection moulding process, 185 ℃ in two districts, 188 ℃ in three districts, 185 ℃ at nozzle.
Injection pressure is 35MPa, dwell time 15s, cool time 10s.
Proportioning is: (part) (weight portion)
Product 2 100
Product 1 200
Stearic acid 50
3.4) soak with acetone or alcohol
Product 3 usefulness acetone after the injection moulding soak 48h, clean with ethanol, and washing, thus obtain having the resin of microcellular structure, promptly product 4.
3.5) sulfonation and engage a gear
Get 100 gram products, 4 usefulness dichloroethanes swelling 10h, take out and desolvate, adding the 300g mass percentage concentration is the concentrated sulfuric acid of 90-100%, be warming up to 90 ℃, insulation, the sampling test cross changes capacity, and exchange capacity 〉=4.5 o'clock stop reaction, engage a gear, washing makes that to have a φ 1cm discoid, thick 2mm, the highly acidic cation catalytic resin of uniform φ 2mm aperture in the middle of the disk, promptly end product 5.
The exchange capacity of the highly acidic cation catalytic resin with given shape that present embodiment makes is 4.63mmol/g.
Embodiment 2: the preparation of catalytic resin
Raw material that uses and instrument and equipment are with embodiment 1, wherein:
The injection mo(u)lding step is:
Get product 2/ product 1/ stearic acid and carry out the blend second time with high-speed mixer by a certain percentage, it is discoid to be injection molded into φ 1cm with plastic-injection moulding machine, thick 2mm, uniform φ 2mm aperture in the middle of the disk, also be designed to other shape, do not influence result of use, promptly product 3.
Temperature is controlled to be 170 ℃ in a district in the injection moulding process, 185 ℃ in two districts, 188 ℃ in three districts, 185 ℃ at nozzle.
Injection pressure is 35MPa, dwell time 15s, cool time 10s.
Proportioning is: (part) (weight portion)
Product 2 100
Product 1 300
Stearic acid 50
Other step is with embodiment 1
The exchange capacity of the highly acidic cation catalytic resin with given shape that present embodiment makes is 4.52mmol/g.
Embodiment 3: the preparation of catalytic resin
Raw material that uses and instrument and equipment are with embodiment 1, wherein:
The injection mo(u)lding step is:
Get product 2/ product 1/ stearic acid and carry out the blend second time with high-speed mixer by a certain percentage, it is discoid to be injection molded into φ 1cm with plastic-injection moulding machine, thick 2mm, uniform φ 2mm aperture in the middle of the disk, also be designed to other shape, do not influence result of use, promptly product 3.
Temperature is controlled to be 170 ℃ in a district in the injection moulding process, 185 ℃ in two districts, 188 ℃ in three districts, 185 ℃ at nozzle.Injection pressure is 35MPa, dwell time 15s, cool time 10s.
Proportioning is: (part) (weight portion)
Product 2 100
Product 1 260
Stearic acid 50
Other step is with embodiment 1
The exchange capacity of the highly acidic cation catalytic resin with given shape that present embodiment makes is 4.72mmol/g.
Embodiment 4: the positive butyl ester of catalytic resin product catalysis acrylic acid synthesizing that uses the embodiment of the invention 1
Reaction raw materials and condition: acrylic acid 100g, n-butanol 48g adds benzene: 35%; The catalytic resin that embodiment 1 produces: 10%; Hydroquinones: 0.1% (above percentage is and accounts for the acrylic acid weight ratio); About 6 hours of reaction time.
In the there-necked flask of 1000ml, add the resin catalyst of aforementioned proportion, acrylic acid and n-butanol are measured water liquid benzene then according to the above ratio, mix with reactant liquor, and add several zeolites in flask.Before the reaction, in water knockout drum, add some water.Reactant liquor is behind ebuillition of heated, and the azeotropic mixture of formation enters water knockout drum after condensation, layering.Water is wherein stayed in the water knockout drum, and organic facies is back in the reactor.For preventing current in the water knockout drum bottle that flashes back,, under keeping refluxing, react to the water knockout drum till anhydrous the telling its continuous discharge.After reaction finished, filtering reacting liquid was isolated resin catalyst.Filtrate is transferred to distilling flask, under normal pressure, steam water liquid benzene and n-butanol etc. than low-boiling point material.After the cooling, with alkali lye neutralization reaction liquid, wash with water to neutrality again, add hydroquinone of polymerization retarder then, the following 55 ℃ outflow liquid of 30mmHg pressure is collected in decompression distillation, promptly obtains the n-butyl acrylate product, records n-butyl acrylate content through gas-chromatography.
Catalyst amount is 10%, and the reaction time is 6h.The reactant liquor that obtains is carried out chromatography, and parallel reaction 5 times the results are shown in Table 1
Table 1:
| The reaction sequence number | Conversion ratio % |
| 1 | 91 |
| 2 | 88 |
| 3 | 94 |
| 4 | 92 |
| The reaction sequence number | Conversion ratio % |
| 5 | 94 |
| Average conversion | 92 |
As seen gained catalyst of the present invention has catalytic effect preferably, can be extensive use of aborning.
Claims (8)
1. method of producing catalytic resin with polystyrene/SBS/ waste product Archon composite comprises: the defective Archon of macroporous ion-exchange resin is carried behind the wax as raw material, and it is stand-by to be ground into powder earlier; Mixed material with polystyrene/SBS, earlier carry out the blend granulation first time with double screw extruder, powder and the stearic acid carried after wax is pulverized of the powder that the blend granulation is obtained and Archon before carries out the blend second time again, be injection molded into discoid or other given shape with plastic-injection moulding machine, soak out stearic acid with acetone or alcohol then, ethanol cleans, washing, obtain having the resin of microcellular structure, press the large hole cation exchanger resin production technology again, with above-mentioned resin through sulfonation, engage a gear, thus make highly acidic cation catalytic resin with given shape.
2. the method for producing catalytic resin with polystyrene/SBS/ waste product Archon composite of a claim 1 wherein uses high speed disintegrator will carry the defective Archon of the macroporous ion-exchange resin behind the wax, is ground into 100-200 purpose powder.
3. polystyrene/SBS/ waste product Archon the composite of using of a claim 1 is produced the method for catalytic resin, wherein polystyrene: the SBS weight ratio is 1: (0.1-0.3).
4. the method for producing catalytic resin with polystyrene/SBS/ waste product Archon composite of a claim 1, the wherein powder that obtains of blend granulation: Archon is carried the powder after wax is pulverized: stearic weight ratio is 1: (2-3): 0.5.
5. the method for producing catalytic resin with polystyrene/SBS/ waste product Archon composite of a claim 1, the disk diameter 1cm of injection mo(u)lding wherein, thick 2mm is evenly equipped with the aperture of diameter 2mm on the disk.
6. polystyrene/SBS/ waste product Archon the composite of using of a claim 1 is produced the method for catalytic resin, wherein sulfonation and engage a gear technology comprise: the resin with microcellular structure that will obtain is used dichloroethanes solvent swell 10 hours, take out and desolvate, add the 90-100% concentrated sulfuric acid, be warming up to 90 ℃, insulation, the sampling test cross changes capacity, when exchange capacity 〉=4.5mmol/g, stop reaction, engage a gear, washing.
7. method of producing catalytic resin with polystyrene/SBS/ waste product Archon composite may further comprise the steps:
1). Archon is pulverized
The defective Archon of macroporous ion-exchange resin is carried wax, and be ground into 100-200 purpose powder, promptly product 1;
2). polystyrene/SBS blend granulation
With the mixed material of polystyrene/SBS by 100: 15 weight ratio preparation, carry out the blend granulation first time with double screw extruder earlier, promptly product 2;
3). injection mo(u)lding
With product 2 and product 1 and stearic acid by 100: 200-300: 50 weight ratio is carried out the blend second time, is injection molded into discoid or other given shape with plastic-injection moulding machine, and promptly product 3;
4). soak
Product 3 usefulness acetone or alcohols are soaked out stearic acid, use ethanol, wash, thereby obtain having the resin of microcellular structure, promptly product 4;
5). sulfonation and engage a gear
Product 4 is carried out sulfonation and engage a gear by those skilled in the art's large pores cation exchange resin production technology in common knowledge, comprise: the resin with microcellular structure that will obtain is used dichloroethanes solvent swell 10 hours, takes out and desolvates, and adds the 90-100% concentrated sulfuric acid, be warming up to 90 ℃, insulation, the sampling test cross changes capacity, stops reaction when exchange capacity 〉=4.5mmol/g, engage a gear, washing, thus make highly acidic cation catalytic resin with given shape, and promptly end product 5.
8. highly acidic cation catalytic resin that uses claim 1-7 either party method preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101832423A CN101444752B (en) | 2008-12-17 | 2008-12-17 | Catalytic resin produced by using polystyrene/SBS/waste white ball composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101832423A CN101444752B (en) | 2008-12-17 | 2008-12-17 | Catalytic resin produced by using polystyrene/SBS/waste white ball composite material and preparation method thereof |
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| CN101444752A CN101444752A (en) | 2009-06-03 |
| CN101444752B true CN101444752B (en) | 2010-08-25 |
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| CN103611572B (en) * | 2013-12-10 | 2015-04-08 | 王金明 | Catalyst for tert-butyl alcohol cleavage reaction and preparation method thereof |
| CN103724172B (en) * | 2014-01-17 | 2016-01-20 | 天津市道福化工新技术开发有限公司 | The synthesis technique of diacetone alcohol |
| CN111790442A (en) * | 2020-07-13 | 2020-10-20 | 凯瑞环保科技股份有限公司 | Modified resin catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112580A (en) * | 1994-05-21 | 1995-11-29 | 宋临泽 | Waste ion exchange resin waste white balls pyrolytic cracking and recovery technology |
| US5622997A (en) * | 1994-07-04 | 1997-04-22 | Bp Chemicals Limited | Process for preparing a molded ion exchange resin structure |
| CN1304917A (en) * | 2000-09-28 | 2001-07-25 | 中国石油天然气股份有限公司兰州石化分公司 | Process for preparing tert-butanol from isobutylene by hydration |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112580A (en) * | 1994-05-21 | 1995-11-29 | 宋临泽 | Waste ion exchange resin waste white balls pyrolytic cracking and recovery technology |
| US5622997A (en) * | 1994-07-04 | 1997-04-22 | Bp Chemicals Limited | Process for preparing a molded ion exchange resin structure |
| CN1304917A (en) * | 2000-09-28 | 2001-07-25 | 中国石油天然气股份有限公司兰州石化分公司 | Process for preparing tert-butanol from isobutylene by hydration |
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Granted publication date: 20100825 Termination date: 20191217 |