CN110591011B - Process method for preparing color fixing agent by using special acrylate wastewater - Google Patents
Process method for preparing color fixing agent by using special acrylate wastewater Download PDFInfo
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- CN110591011B CN110591011B CN201910846204.XA CN201910846204A CN110591011B CN 110591011 B CN110591011 B CN 110591011B CN 201910846204 A CN201910846204 A CN 201910846204A CN 110591011 B CN110591011 B CN 110591011B
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- fixing agent
- color fixing
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- wastewater
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
Abstract
The invention discloses a process method for preparing a color fixing agent by using special acrylate wastewater, which comprises the steps of taking the wastewater generated by synthesizing specific acrylate as a raw material, recycling monomer acrylic acid and acrylate in the wastewater, mixing the wastewater, dimethyl diallyl ammonium chloride, an initiator and a chain transfer agent to prepare the color fixing agent, in particular to a cationic polymer type color fixing agent, realizing deep resource utilization and near zero emission of the wastewater, creating new industrial output, comparing the prepared color fixing agent with other similar products in the market, and enabling the color fastness of fabrics treated by the color fixing agent to reach over 4 grades of the national standard, wherein the using effect is not transfused in the similar products and even superior to the similar products.
Description
Technical Field
The invention relates to the field of chemical waste liquid treatment, in particular to a process method for preparing a color fixing agent by using special acrylate waste water.
Background
The color fixing agent is one of important auxiliaries in the printing and dyeing industry, and can be used for improving the color fastness of the dye on fabrics to wet treatment. The insoluble color substance can be formed on the fabric with the dye, thereby improving the washing fastness and the perspiration fastness of the color and sometimes also improving the light fastness of the color. The fixing agent can be roughly divided into a cationic polymer type fixing agent, an ester type fixing agent (containing formaldehyde ester type fixing agent and polyamine ester type fixing agent) and a crosslinking reaction type fixing agent.
In the process of preparing the polyol acrylate by using acrylic acid and other alcohol raw materials, waste liquid containing acrylic acid and acrylate thereof is generated, the capacity of the special acrylate reaches 50 ten thousand tons/year by 2018, and the production amount of industrial waste liquid is about 150 ten thousand tons/year. Although the development of related enterprises is increasing year by year, the development of the related enterprises is restricted because of the generation of a large amount of industrial waste liquid with high concentration which is difficult to treat in the production process. The existing methods for treating acrylic acid and ester wastewater mainly comprise an incineration method, a wet catalytic oxidation method, a biological method and the like. The treatment method commonly adopted at home and abroad adopts an incineration method, and because the waste water can not be directly combusted, heavy oil needs to be added for combustion supporting, and the treatment cost per ton is about 7000 yuan; although the catalytic oxidation method can effectively decompose pollutants, the key point is that the catalyst has strong specificity and higher limitation on water inlet conditions, only a few acrylic acid manufacturers adopt the method at present, and in addition, the catalytic wet oxidation method for treating the wastewater needs high-temperature and high-pressure conditions and has potential safety hazards. The anaerobic method, the aerobic method, the Fenton reagent oxidation method, the ion exchange fiber method and the like of the method also treat theoretical research stages, and a great number of technical problems cannot be overcome effectively and cannot be popularized.
Therefore, the reasonable utilization of the waste liquid is beneficial to realizing the resource saving and the reduction of the waste liquid treatment cost. The invention provides a process method for converting waste liquid containing acrylic acid into a color fixing agent, in particular to a cationic polymer type color fixing agent.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a process method for preparing a color fixing agent by using special acrylate wastewater.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows: a process method for preparing a color fixing agent by using special acrylate wastewater comprises the following steps:
mixing the waste liquid containing acrylic ester with dimethyl diallyl ammonium chloride and a chain transfer agent to obtain a mixed liquid;
heating the mixed solution to 75-85 ℃, adding an initiator sodium persulfate, and reacting for 1 hour;
cooling the mixed solution added with the sodium persulfate to 25 ℃ to obtain a macromolecular color fixing agent with the molecular weight of 5000-20000 and the double-construction monomer residue rate of less than 0.5%;
the production process of the waste liquid is as follows:
adding acrylic acid, neopentyl glycol and 2-methyl-1, 3-propanediol into a reaction kettle, and pumping 1, 4-butanediol and refined coconut oil in vacuum;
controlling the temperature of the reaction kettle at 220-240 ℃, and keeping the pressure at normal pressure to-0.1 MPa to perform polycondensation reaction between acid and alcohol;
continuously separating alcohol and water by using a packed tower and an oil-water separator;
cooling the reaction kettle to below 75 ℃;
the high-concentration condensed waste liquid generated by the separation of the oil-water separator is discharged into an organic waste liquid receiving tank and an organic waste liquid storage tank, and is conveyed to an organic waste liquid recovery tank by a waste liquid pump;
cooling the high-concentration condensation waste liquid, adding a sodium carbonate aqueous solution with the concentration of 5%, stirring for 30 minutes, and standing for layering;
separating the ester layer from the waste liquid containing unreacted acrylic monomer.
Preferably, the waste liquid, the dimethyldiallylammonium chloride and the chain transfer agent are respectively in parts by weight: 40-50 parts, 20-50 parts and 1-5 parts.
Preferably, the chain transfer agent is sodium bisulfite.
Preferably, the step of heating the mixed solution to 75-85 ℃, adding an initiator sodium persulfate, and reacting for 1 hour comprises:
and (3) stabilizing the temperature of the reaction liquid of the mixed liquid at 75-85 ℃ all the time, quantitatively and regularly adding 5-10 parts of initiator sodium persulfate aqueous solution into the reactor for many times, and carrying out free radical polymerization.
Preferably, the step of cooling the mixed solution into which the sodium persulfate is added to 25 ℃ to obtain the polymeric color fixing agent comprises:
and cooling the mixed solution added with the sodium persulfate to 25 ℃, adding 30-40 parts of sodium hydroxide aqueous solution and pure water, adjusting the pH value and concentration of the reaction solution, and directly transferring the obtained liquid serving as a finished product to a storage tank to obtain the cationic color fixing agent.
Preferably, the waste liquid contains 20-30% of acrylic acid, 1-2% of organic polyol, 0.5-1% of refined coconut oil and 2-3% of polyol acrylate.
Preferably, the ester layer is repeatedly cleaned for 3 times, dewatered, filtered, barreled and sealed to obtain the polyol acrylate product.
Preferably, the step of continuously separating alcohol and water using a packed tower and a water-oil separator includes: continuously performing alcohol-water separation by using a packed tower and an oil-water separator, condensing, refluxing and recovering evaporated materials in the reaction process by using a primary heat exchanger and a secondary heat exchanger, and returning the materials to the reaction kettle;
due to the application of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the method takes the waste liquid generated by synthesizing the specific acrylate as the raw material, recycles the monomer acrylic acid and the acrylate in the waste liquid, prepares the color fixing agent, particularly the cationic polymer type color fixing agent, has the advantages of complete process flow, simple preparation method, low cost of the raw material and easy operation, directly outputs the final reaction liquid as a product, does not generate any waste liquid, avoids the generation of secondary waste liquid, realizes the recycling of effective substances in the waste liquid, creates new industrial output, and ensures that the color fastness of the fabric treated by the color fixing agent reaches more than the national standard 4 grade after the prepared color fixing agent is compared with other similar products in the market, and the using effect is not output to the similar products and is even superior to the similar products.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples:
an embodiment of the invention provides a process method for preparing a color fixing agent by using special acrylate wastewater, which comprises the following steps:
mixing the waste liquid containing acrylic ester with dimethyl diallyl ammonium chloride and a chain transfer agent to obtain a mixed liquid;
heating the mixed solution to 75-85 ℃, adding an initiator sodium persulfate, reacting for 1 hour, and carrying out free radical polymerization in the reaction;
cooling the mixed solution added with the sodium persulfate to 25 ℃ to obtain a macromolecular color fixing agent with the molecular weight of 5000-20000 ten thousand and the double-construction monomer residue rate of less than 0.5%;
the main technical indexes of the macromolecular color fixing agent are as follows:
the double-built monomer in the waste liquid is basically polymerized into the macromolecular color fixing agent, and the waste liquid can be completely recycled according to the method. If the method is not adopted, the waste liquid is treated by an incineration method generally at home and abroad, the waste water cannot be directly combusted, heavy oil is required to be added for combustion supporting, the treatment cost per ton is about 7000 yuan, if the waste liquid is not treated in time, the waste liquid is automatically exploded to generate a large amount of solid waste, the treatment cost is up to 15000 yuan per ton, the treatment cost is high, and dioxin is released into the atmosphere to cause secondary pollution; the price of the color fixing agent prepared by the method is about 15000 yuan/ton, loss is changed into income, and economic value is realized.
The waste liquid is generated by the following method:
adding acrylic acid, neopentyl glycol and 2-methyl-1, 3-propanediol into a reaction kettle, and pumping 1, 4-butanediol and refined coconut oil in vacuum;
controlling the temperature of the reaction kettle at 220-240 ℃, and keeping the pressure at normal pressure to-0.1 MPa to perform polycondensation reaction between acid and alcohol;
continuously separating alcohol and water by using a packed tower and an oil-water separator;
after the reaction is carried out for a certain period, sampling and analyzing, and when a certain specification requirement is met, finishing the reaction; then further adjustment is carried out;
cooling the reaction kettle to below 75 ℃;
the high-concentration condensed waste liquid generated by the separation of the oil-water separator is discharged into an organic waste liquid receiving tank and an organic waste liquid storage tank, and is conveyed to an organic waste liquid recovery tank by a waste liquid pump;
cooling the high-concentration condensation waste liquid, adding a sodium carbonate aqueous solution with the concentration of 5%, stirring for 30 minutes, and standing for layering;
separating the ester layer from the waste liquid containing unreacted acrylic monomer.
Further, the waste liquid, the dimethyl diallyl ammonium chloride and the chain transfer agent are respectively prepared from the following components in parts by weight: 40-50 parts, 20-50 parts and 1-5 parts.
The above solution was put into a 250ml four-necked flask to carry out a reaction.
Further, sodium bisulfite is used as the chain transfer agent.
Further, the step of heating the mixed solution to 75-85 ℃, adding an initiator sodium persulfate, and reacting for 1 hour comprises the following steps:
and (3) stabilizing the temperature of the reaction liquid of the mixed liquid at 75-85 ℃ all the time, quantitatively and regularly adding 5-10 parts of initiator sodium persulfate aqueous solution into the reactor for many times, and carrying out free radical polymerization.
Further, the step of cooling the mixed solution added with the sodium persulfate to 25 ℃ to obtain the macromolecular color fixing agent comprises the following steps:
and cooling the mixed solution added with the sodium persulfate to 25 ℃, adding 30-40 parts of sodium hydroxide aqueous solution and pure water, adjusting the pH value and concentration of the reaction solution, and directly transferring the obtained liquid serving as a finished product to a storage tank to obtain the cationic color fixing agent.
Further, the waste liquid contains 20-30% of acrylic acid, 1-2% of organic polyol, 0.5-1% of refined coconut oil and 2-3% of polyol acrylate, and trace amounts of antioxidant and polymerization inhibitor are obtained.
And further, the ester layer is repeatedly cleaned for 3 times, then dewatered, filtered, barreled and sealed for storage to obtain a polyol acrylate product, and the wastewater is conveyed to a unified organic waste liquid recovery tank through a waste liquid pump.
Further, the step of continuously separating alcohol and water by using a packed tower and an oil-water separator comprises the following steps: continuously performing alcohol-water separation by using a packed tower and an oil-water separator, condensing, refluxing and recovering evaporated materials in the reaction process by using a primary heat exchanger and a secondary heat exchanger, and returning the materials to the reaction kettle;
compared with other similar products in the market by taking the fixing agent obtained by the scheme as an embodiment, the fixing agent has the following indexes and requirements:
and (3) performance testing:
pure cotton fabric: soaking a pure cotton fabric dyed by reactive dyes (reactive turquoise blue KNG, reactive red 3BS, reactive black 3RS and 6% of dye concentration) in a color fixing agent with the use amount of 2% o.w.f for 20min in 50min, and dehydrating and drying.
The performance measurement method comprises the following steps:
soaping color fastness: according to GB/T2391-2008 textile color fastness test: measuring by a soaping fastness method;
color fastness to rubbing: according to GB/T2390-2008 textile color fastness test: the rubbing fastness is measured by the method;
the results of the comparison for each product are shown in the following table:
as can be seen from the above table, the color fastness of the fabric treated by the color fixing agent on the three-color dyed fabric is above grade 4, which shows that the color fixing agent obtained by the invention can obviously improve the soaping color fastness and the rubbing color fastness of the dyed fabric, and the color fastness of the dyed fabric is better than that of the contrast samples 1, 2 and 3.
Compared with the prior art, the embodiment has the following beneficial effects:
the method takes the waste liquid generated by synthesizing the specific acrylate as the raw material, recycles the monomer acrylic acid and the acrylate in the waste liquid, prepares the color fixing agent, particularly the cationic polymer type color fixing agent, has the advantages of complete process flow, simple preparation method, low cost of the raw material and easy operation, directly outputs the final reaction liquid as a product, realizes the deep resource utilization and near zero emission of the waste water, creates new industrial output, and after the prepared color fixing agent is compared with other similar products in the market, the color fastness of the fabric treated by the color fixing agent reaches more than 4 grades of the national standard, and the using effect is not output to the similar products and is even superior to the similar products.
The above-mentioned embodiments are merely illustrative of the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the scope of the present invention.
Claims (8)
1. A process method for preparing a color fixing agent by using special acrylate wastewater is characterized by comprising the following steps:
mixing the waste liquid containing acrylic ester with dimethyl diallyl ammonium chloride and a chain transfer agent to obtain a mixed liquid;
heating the mixed solution to 75-85 ℃, adding an initiator sodium persulfate, and reacting for 1 hour;
cooling the mixed solution added with the sodium persulfate to 25 ℃ to obtain a macromolecular color fixing agent with the molecular weight of 5000-20000 and the double bond monomer residue rate of less than 0.5%;
the waste liquid generation process is as follows:
adding acrylic acid, neopentyl glycol and 2-methyl-1, 3-propanediol into a reaction kettle, and pumping 1, 4-butanediol and refined coconut oil in vacuum;
controlling the temperature of the reaction kettle at 220-240 ℃, and keeping the pressure at normal pressure to-0.1 MPa to perform polycondensation reaction between acid and alcohol;
continuously separating alcohol and water by using a packed tower and an oil-water separator;
cooling the reaction kettle to below 75 ℃;
the high-concentration condensed waste liquid generated by the separation of the oil-water separator is discharged into an organic waste liquid receiving tank and an organic waste liquid storage tank, and is conveyed to an organic waste liquid recovery tank by a waste liquid pump;
cooling the high-concentration condensation waste liquid, adding a sodium carbonate aqueous solution with the concentration of 5%, stirring for 30 minutes, and standing for layering;
separating the ester layer from the waste liquid containing unreacted acrylic monomer.
2. The process method for preparing the color fixing agent by using special acrylate wastewater as claimed in claim 1, wherein the process method comprises the following steps: the waste liquid, the dimethyl diallyl ammonium chloride, the initiator and the chain transfer agent are respectively prepared from the following components in parts by weight: 40-50 parts, 20-50 parts, 1-5 parts and 1-5 parts.
3. The process method for preparing the color fixing agent by using special acrylate wastewater as claimed in claim 2, wherein the process method comprises the following steps: the step of cooling the mixed solution added with the sodium persulfate to 25 ℃ to obtain the macromolecular color fixing agent comprises the following steps:
and cooling the mixed solution added with the sodium persulfate to 25 ℃, adding 30-40 parts of sodium hydroxide aqueous solution and pure water, and directly transferring the obtained liquid serving as a finished product to a storage tank to obtain the cationic color fixing agent.
4. The process method for preparing the color fixing agent by using special acrylate wastewater as claimed in claim 2, wherein the process method comprises the following steps: the method comprises the following steps of heating the mixed solution to 75-85 ℃, adding an initiator sodium persulfate, and reacting for 1 hour:
and (3) stabilizing the temperature of the reaction liquid of the mixed liquid at 75-85 ℃ all the time, quantitatively and regularly adding 5-10 parts of initiator sodium persulfate aqueous solution into the reactor for many times, and carrying out free radical polymerization.
5. The process method for preparing the color fixing agent by using special acrylate wastewater as claimed in claim 1, wherein the process method comprises the following steps: the chain transfer agent adopts sodium bisulfite.
6. The process method for preparing the color fixing agent by using special acrylate wastewater as claimed in claim 1, wherein the process method comprises the following steps: the waste liquid contains 20-30% of acrylic acid, 1-2% of organic polyol, 0.5-1% of refined coconut oil and 2-3% of polyol acrylate.
7. The process method for preparing the color fixing agent by using special acrylate wastewater as claimed in claim 1, wherein the process method comprises the following steps: and (3) repeatedly cleaning the ester layer for 3 times, dewatering, filtering, filling into a barrel, and sealing for storage to obtain the polyol acrylate product.
8. The process method for preparing the color fixing agent by using special acrylate wastewater as claimed in claim 1, wherein the process method comprises the following steps: the step of continuously separating alcohol and water by using a packed tower and an oil-water separator comprises the following steps: and (3) continuously carrying out alcohol-water separation by using a packed tower and an oil-water separator, condensing, refluxing and recovering materials evaporated in the reaction process by a primary heat exchanger and a secondary heat exchanger, and returning the materials to the reaction kettle.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5951719A (en) * | 1998-06-15 | 1999-09-14 | Callaway Corporation | Process of after-treating dyed cellulose fabrics with a glyoxalated acrylamide polymer |
| CN102206562A (en) * | 2011-04-29 | 2011-10-05 | 张家港市德宝化工有限公司 | Method for preparing polyacrylic acid soaping agent from acrylic acid wastewater serving as raw material |
| CN105175631A (en) * | 2013-12-27 | 2015-12-23 | 石狮市清源精细化工有限公司 | Cationic type formaldehyde-free color fixing agent for reactive dye and preparation method thereof |
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2019
- 2019-09-09 CN CN201910846204.XA patent/CN110591011B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5951719A (en) * | 1998-06-15 | 1999-09-14 | Callaway Corporation | Process of after-treating dyed cellulose fabrics with a glyoxalated acrylamide polymer |
| CN102206562A (en) * | 2011-04-29 | 2011-10-05 | 张家港市德宝化工有限公司 | Method for preparing polyacrylic acid soaping agent from acrylic acid wastewater serving as raw material |
| CN105175631A (en) * | 2013-12-27 | 2015-12-23 | 石狮市清源精细化工有限公司 | Cationic type formaldehyde-free color fixing agent for reactive dye and preparation method thereof |
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