CN104016851A - Method for recovering cation exchange resin - Google Patents
Method for recovering cation exchange resin Download PDFInfo
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- CN104016851A CN104016851A CN201310064763.8A CN201310064763A CN104016851A CN 104016851 A CN104016851 A CN 104016851A CN 201310064763 A CN201310064763 A CN 201310064763A CN 104016851 A CN104016851 A CN 104016851A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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Abstract
The invention relates to a method for recovering cation exchange resin, belonging to the field of chemical material recycling. The method comprises the steps of carrying out pyrolysis on the cation exchange resin or waste thereof by using a medium as a carrier, and separating and purifying a pyrolysis product, thereby obtaining acrylic acid and derivatives thereof, divinylbenzene and other products. By adding a proper catalyst, the pyrolysis process can be promoted. The method has the advantages that the disadvantages of low decomposition efficiency, large decomposition medium usage amount and high operating cost of the general chemical recovery methods are overcome; after treating with the recovery technology, no new waste is generated, so that the requirements for circular economy and low-carbon economy are met.
Description
Technical field:
That the present invention relates to produce in a kind of Zeo-karb production process and use after the recovery method of waste, belong to chemical materials and recycle field.
Background technology:
In thermosetting resin, Zeo-karb is a kind of typical material, be to produce polyreaction by vinylformic acid and derivative thereof and linking agent divinylbenzene, by polyreaction, generate the skeleton with three-dimensional space dimensional network structure, then on skeleton, import acidic-group and make.Zeo-karb is a kind of thermosetting resin, when it is under the effect of heat or initiator, curablely becomes a kind of insoluble polymer network polymer not melting.After being mixed with linking agent Vinylstyrene by vinylformic acid and derivative thereof, under heating or the effect at catalyzer, form the build macromole with three-dimensional net structure, i.e. thermoset.Zeo-karb has good ion-exchange capacity, and tool has been widely used, and aspect water treatment, decolouring, purification, is having multiple use.But Zeo-karb is thermosetting resin, after using, its waste can not be as thermoplastic resin as polyethylene, and melting regeneration moulding, can not recycle by the method for dissolution with solvents again.
The traditional treatment process of thermoset cationic exchange waste is to bury and burn, and buries the shortcoming that takies a large amount of soils and polluted underground water, burns and has the shortcoming that produces obnoxious flavour contaminate environment.Other treatment process comprises to be pulverized thermosetting resin waste as blast furnace ironmaking reductive agent or as the filler of light cement plate, concrete, finishing material and simple glass product made from steel and uses, and chemical recycling, high temperature pyrolytic cracking etc.The advantage of general chemistry absorption method is to utilize general synthetic resins equipment to carry out waste decomposition, do not need to increase facility investment, but the decomposition efficiency of existing technique is lower, and decomposition media usage quantity is large, causes running cost high, and economic feasibility is poor.Although high temperature pyrolysis technological process is simple, easily produce the safety problem such as leaks, catch fire, in while treating processes, also can produce carbon distribution, cause thermo-efficiency low, service life of equipment is low.Therefore, develop the advantage of the comprehensive above-mentioned the whole bag of tricks of a kind of energy, simultaneously can avoid shortcoming separately again, not only the cationic exchange waste recovery method of economy but also environmental protection in the urgent need to.
1. the waste of this patent for waste material in current Zeo-karb production of articles process and after using, utilizes medium and catalyzer to carry out thermo-cracking to waste, obtains vinylformic acid and derivative thereof, divinylbenzene and other its products.
2. summary of the invention:
The object of this invention is to provide a kind of Zeo-karb aborning with use after the recovery novel method of the waste that produces.The present invention can overcome the shortcoming of the main cationic exchange waste recovery method using at present, takes into account the advantage of each method, has again the feature of economy and environmental protection simultaneously.
Described recovery method is:
Zeo-karb in the present invention, it is characterized in that comprising by vinylformic acid and derivative and linking agent divinylbenzene generation polyreaction, by polyreaction, generate the skeleton with three-dimensional space dimensional network structure, then on skeleton, import acidic-group and make.
The recovery method of a kind of Zeo-karb in the present invention, is positioned over Zeo-karb in reactor and carries out, and utilizes medium and catalyzer to carry out thermo-cracking to Zeo-karb, obtains thermal cracking products, then split product is carried out to separating-purifying.One end of reactor is the entrance of raw material, medium and catalyzer, normally from the side of reactor.The other end of reactor connects refrigerating unit, normally from the upper end of reactor, connects.The product cooling down is carried out to separating-purifying to obtaining containing vinylformic acid and derivative, divinylbenzene and other its products.Oil phase part also can directly be used as oil fuel.Undecomposed Zeo-karb can participate in the cracking process of next batch, realizes and continues cracking.
First Zeo-karb, medium and catalyzer are packed in reactor, keep the temperature of reactor between 120～750 ℃, can heat to carry out to reactor.There is degraded and cracking in Zeo-karb, the decomposition of the mixture of formation is cooled by refrigerating unit under medium and catalyst action.Collection, through overcooled liquid, utilizes purification technique to be separated into micromolecular polymer raw and oil fuel.
The medium that adds reactor, can be water, organic bases, mineral oil, synthetic oil, vegetable and animals oils, silicone oil, dibasic alcohol, polyvalent alcohol, can be also the mixture of their arbitrary proportion.Under the acting in conjunction of medium, catalyzer and heat, there is cracking in Zeo-karb, obtains containing vinylformic acid and derivative thereof, divinylbenzene and other its products, and and the mixture of used medium and the condensed liquid of medium cracking.
Adding the organic bases in reactor, can be the mixture of a kind of or their arbitrary proportions of the organic basess such as ammoniacal liquor, urea, diethylamine, diethanolamine, trolamine, triethylamine, three propylene diamine, hexanediamine.
Adding reactor medium can be mineral oil.Mineral oil is the base oil extracting from oil by physics distillating method.
Adding reactor medium can be synthetic oil.Synthetic oil is the formed base oil of compound by polyalkenes or ester class, and the method for processing by chemosynthesis or refining obtains.
Adding the vegetable and animals oils in reactor, can be the mixture of a kind of or their arbitrary proportions of lard, butter, sheep oil, soybean oil, peanut oil, Oleum Gossypii semen, rapeseed oil, sweet oil, sewer oil, paraffin wet goods vegetable and animals oils.
Adding the silicone oil in reactor, can be methyl-silicone oil, ethyl silicon oil, phenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, methyl phenyl silicone oil, methyl chloride phenyl silicone oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methyl hydroxy silicon oil, ethyl containing hydrogen silicone oil, hydroxyl hydrogen silicone oil, containing the mixture of a kind of or their arbitrary proportions of the silicone oil such as nitrile silicone.
Adding the dibasic alcohol in reactor, can be ethylene glycol, 1,2-PD, 1,3-PD, BDO, the mixture of a kind of or their arbitrary proportions of the dibasic alcohol such as hexylene glycol.For example, the medium adding is ethylene glycol, can be also propylene glycol, the mixture of ethylene glycol and propylene glycol.
Adding the polyvalent alcohol in reactor, can be the mixture of a kind of or their arbitrary proportions of the polyvalent alcohols such as glycerol, sorbyl alcohol, N.F,USP MANNITOL, tetramethylolmethane.
In this Zeo-karb recovery method, heat scission reaction can carry out under catalyzer exists, and catalyzer is basic compound catalysis agent, 0.1～5% of consumption Zeo-karb weight.The catalyzer using is the mixture of one or more materials in sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydrated barta, sodium oxide, calcium oxide, magnesium oxide or barium oxide.The existence of catalyzer can be accelerated the cracking of Zeo-karb.
The thermal cracking products of Zeo-karb, obtains containing vinylformic acid and derivative thereof, divinylbenzene and other its products, and and the mixture of used medium and the condensed liquid of medium cracking.To resulting product after separating-purifying, the vinylformic acid obtaining and derivative thereof, divinylbenzene and other its products, again synthesizing cationic exchange or other products.Other oil phases of split product, can be directly as oil fuel, use, and unnecessary continuations are separated, and the cost of generation while having avoided further purification can obviously improve the economic benefit of this recovery method.
Embodiment:
Following embodiment will describe the present invention in more detail, but the present invention should not be limited only within these specific embodiments.
Embodiment 1
100 grams of Zeo-karbs and 30ml ethylene glycol are packed in reactor, be heated to 120 ℃, react 6 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 70.2 grams, and rate of decomposition is 29.8%.Undecomposed Zeo-karb can participate in the cracking process of next batch.The decomposition of the mixture forming is cooled by refrigerating unit, obtains vinylformic acid and derivative thereof, divinylbenzene and other its products after separating-purifying.
Embodiment 2
By 100 grams of Zeo-karbs, 70g glycerol, 3g calcium oxide packs in reactor, is heated to 750 ℃, reacts 6 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 12.2 grams, and rate of decomposition is 87.8%.Undecomposed Zeo-karb can participate in the cracking process of next batch.The decomposition of the mixture forming is cooled by refrigerating unit, obtains vinylformic acid and derivative thereof, divinylbenzene and other its products after separating-purifying.
Embodiment 3
By 100 grams of Zeo-karbs, 50g mineral oil, 1g magnesium hydroxide packs in reactor, is heated to 350 ℃, reacts 4 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 13.6 grams, and rate of decomposition is 86.4%.Undecomposed Zeo-karb can participate in the cracking process of next batch.The decomposition of the mixture forming is cooled by refrigerating unit, obtains vinylformic acid and derivative thereof, divinylbenzene and other its products after separating-purifying.
Embodiment 4
By 100 grams of Zeo-karbs, 40 stearic acid, 30g soybean oil, 1g sodium hydroxide, 1g potassium hydroxide packs in reactor, is heated to 300 ℃, reacts 3 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 16.1 grams, and rate of decomposition is 83.9%.Undecomposed Zeo-karb can participate in the cracking process of next batch.The decomposition of the mixture forming is cooled by refrigerating unit, obtains vinylformic acid and derivative thereof, divinylbenzene and other its products after separating-purifying.
Embodiment 5
By 100 grams of Zeo-karbs, 50g synthetic oil, 1g magnesium oxide packs in reactor, is heated to 500 ℃, reacts 4 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 15.9 grams, and rate of decomposition is 84.1%.Undecomposed Zeo-karb can participate in the cracking process of next batch.The decomposition of the mixture forming is cooled by refrigerating unit, obtains vinylformic acid and derivative thereof, divinylbenzene and other its products after separating-purifying.
Embodiment 6
By 100 grams of Zeo-karb resins, 40g trolamine packs in reactor, is heated to 250 ℃, reacts 5 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 16.3 grams, and rate of decomposition is 83.7%.Undecomposed Zeo-karb can participate in the cracking process of next batch.The decomposition of the mixture forming is cooled by refrigerating unit, obtains vinylformic acid and derivative thereof, divinylbenzene and other its products after separating-purifying.
Embodiment 7
By 100 grams of Zeo-karb resins, 10g trolamine and 40g mineral oil pack in reactor, are heated to 650 ℃, react 2 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 12.3 grams, and rate of decomposition is 87.7%.Undecomposed Zeo-karb can participate in the cracking process of next batch.The decomposition of the mixture forming is cooled by refrigerating unit, obtains vinylformic acid and derivative thereof, divinylbenzene and other its products after separating-purifying.
Embodiment 8
100 grams of Zeo-karb resins are packed in reactor, add calcium oxide 3.5g, adding 80g kinematic viscosity is the dimethyl silicone oil of 350 centipoises, and 350 ℃ of temperature of reactor react 5 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 15.0 grams, and minute rate is 85.0%.Undecomposed Zeo-karb can participate in the cracking process of next batch.Form decomposition of the mixture and be cooled by refrigerating unit, after separating-purifying, obtain vinylformic acid and derivative thereof, divinylbenzene and other its products.
Embodiment 9
By 100 grams of Zeo-karbs, 50g ammoniacal liquor and 1g magnesium oxide pack in reactor, and 150 ℃ of temperature of reactor react 5 hours.Stopped reaction, remaining solid drying in reactor, weighs, and weighs 43.2 grams, and minute rate is 56.8%.Undecomposed Zeo-karb can participate in the cracking process of next batch.Form decomposition of the mixture and be cooled by refrigerating unit, after separating-purifying, obtain vinylformic acid and derivative thereof, divinylbenzene and other its products.
Claims (8)
1. a recovery method for Zeo-karb, is characterized in that utilizing medium and catalyzer to carry out thermo-cracking to Zeo-karb, obtains thermal cracking products.
2. the recovery method of a kind of Zeo-karb according to claim 1, is characterized in that Zeo-karb is by vinylformic acid and derivative and linking agent divinylbenzene generation polyreaction, is generated and is had by polyreaction
three-dimensional spacethe skeleton of dimensional network structure, then on skeleton, import acidic-group and make.
3. the recovery method of a kind of Zeo-karb according to claim 1, it is characterized in that used medium is organic acid, organic acid anhydride, organic bases, mineral oil, synthetic oil, vegetable and animals oils, silicone oil, dibasic alcohol, polyvalent alcohol, can be also the mixture of their arbitrary proportion.
4. the recovery method of a kind of Zeo-karb according to claim 3, is characterized in that dibasic alcohol used is ethylene glycol, 1,2-PD, 1,3-PD, BDO or hexylene glycol.
5. the recovery method of a kind of Zeo-karb according to claim 1, is characterized in that used thermo-cracking temperature is 120～750 ℃.
6. the recovery method of a kind of Zeo-karb according to claim 1, it is characterized in that utilizing medium Zeo-karb to be carried out in the process of thermo-cracking, can add basic compound catalysis agent, the consumption of catalyzer is 0.1～5% of Zeo-karb weight.
7. the recovery method of a kind of Zeo-karb according to claim 6, is characterized in that basic compound catalysis agent used is the mixture of one or more materials in sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydrated barta, sodium oxide, calcium oxide, magnesium oxide or barium oxide.
8. the recovery method of a kind of Zeo-karb according to claim 1, is characterized in that reclaiming the thermal cracking products of resulting Zeo-karb, can vinylformic acid and derivative, divinylbenzene and other its products after separating-purifying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310064763.8A CN104016851A (en) | 2013-03-01 | 2013-03-01 | Method for recovering cation exchange resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310064763.8A CN104016851A (en) | 2013-03-01 | 2013-03-01 | Method for recovering cation exchange resin |
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| CN104016851A true CN104016851A (en) | 2014-09-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021088123A1 (en) * | 2019-11-04 | 2021-05-14 | 中国商用飞机有限责任公司北京民用飞机技术研究中心 | Catalyst for thermal degradation of carbon-fiber-and-resin-based composite material and application method therefor |
Citations (3)
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|---|---|---|---|---|
| CN101148535A (en) * | 2007-11-01 | 2008-03-26 | 哈尔滨工业大学 | Water-phase decomposition method for thermosetting epoxy resin or composite material thereof |
| CN102464806A (en) * | 2010-11-16 | 2012-05-23 | 湖州瑞赛科碳化学有限公司 | Recycling method of unsaturated polyester button resin material |
| CN102464805A (en) * | 2010-11-16 | 2012-05-23 | 湖州瑞赛科碳化学有限公司 | Recycling method of unsaturated polyester material |
-
2013
- 2013-03-01 CN CN201310064763.8A patent/CN104016851A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148535A (en) * | 2007-11-01 | 2008-03-26 | 哈尔滨工业大学 | Water-phase decomposition method for thermosetting epoxy resin or composite material thereof |
| CN102464806A (en) * | 2010-11-16 | 2012-05-23 | 湖州瑞赛科碳化学有限公司 | Recycling method of unsaturated polyester button resin material |
| CN102464805A (en) * | 2010-11-16 | 2012-05-23 | 湖州瑞赛科碳化学有限公司 | Recycling method of unsaturated polyester material |
Non-Patent Citations (1)
| Title |
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| 杜昭辉: "废旧不饱和聚酯树脂裂解工艺", 《辽宁石油化工大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021088123A1 (en) * | 2019-11-04 | 2021-05-14 | 中国商用飞机有限责任公司北京民用飞机技术研究中心 | Catalyst for thermal degradation of carbon-fiber-and-resin-based composite material and application method therefor |
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Application publication date: 20140903 |