CN103554330B - A kind of efficient and environment-friendly type chelated dispersants and preparation method thereof - Google Patents
A kind of efficient and environment-friendly type chelated dispersants and preparation method thereof Download PDFInfo
- Publication number
- CN103554330B CN103554330B CN201310539092.6A CN201310539092A CN103554330B CN 103554330 B CN103554330 B CN 103554330B CN 201310539092 A CN201310539092 A CN 201310539092A CN 103554330 B CN103554330 B CN 103554330B
- Authority
- CN
- China
- Prior art keywords
- parts
- environment
- integer
- efficient
- friendly type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- DQVRGSIXUGZCOV-UHFFFAOYSA-N CN(C)CC1CC1 Chemical compound CN(C)CC1CC1 DQVRGSIXUGZCOV-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a kind of efficient and environment-friendly type chelated dispersants and preparation method thereof, its structural formula general formula is:
wherein, R
1, R
2be ethyl or methoxyl group independently, R
3be selected from H, Na,
in any one, R be H or
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of efficient and environment-friendly type chelated dispersants and preparation method thereof.
Background technology
At present, industrial when preparing the product such as polyalcohol acrylate and polyhydroxy alkyl acrylate, the organic by-product waste liquid of high density can be produced in production process, this waste liquid is mainly containing organic compound and suspended substances such as vinylformic acid, tricarbimide, polyvalent alcohol and ester classes thereof, COD content is high, considerably beyond the emission standard of national regulation.And at present the treatment process of this high concentrated organic waste liquid is mainly directly burned, this not only can consume a large amount of fuel, also can produce secondary waste gas simultaneously, contaminate environment.
Now, utilize waste water for raw material as the patent No. patent of invention that is CN102225976B discloses, polyacrylic dispersion agent is prepared by radical polymerization is incompatible, but the performance of the dispersion agent produced is similar to commercially available acrylic dispersants or slightly poor, and it is obviously poor than organic phosphine class dispersion agent, further, the productive rate of the polyacrylic dispersion agent of this patent synthesis is low, low in economic efficiency.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of efficient and environment-friendly type chelated dispersants utilizing waste liquid to prepare of improvement.
Another technical problem to be solved by this invention is to provide a kind of preparation method of above-mentioned efficient and environment-friendly type chelated dispersants.
For solving above technical problem, the present invention adopts following technical scheme:
A kind of efficient and environment-friendly type chelated dispersants, its structural formula general formula is:
Wherein, R
1, R
2be ethyl or methoxyl group independently, R3 be selected from H, Na,
in any one, R be H or
x is the integer of 1 to 4, and m is the integer of 1 to 1000, and n is the integer of 1 to 1000.
The preparation method of above-mentioned efficient and environment-friendly type chelated dispersants, comprises the steps:
(1) with parts by weight, be the basic solution of 28 ~ 32% by 1000 parts of waste liquids after separating and extracting, 10 ~ 30 parts of carbonyl diamines, 100 ~ 260 parts of water, 150 ~ 300 parts of mass percents, be warming up to 85 ± 2 DEG C, carry out saponification, sampling in every 30 minutes is observed once, when seeing that solution becomes homogeneous phase transparent from muddiness, then continue insulation reaction 1.5 ~ 2 hours;
(2) under the temperature condition of 85 DEG C ~ 90 DEG C, in the reaction system after step (1) process, 120 ~ 280 parts of Sunmorl N 60Ss are added, 5 ~ 10 parts of mercaptoethanols, after to be dissolved, dripping 90 ~ 110 parts of mass percents is the initiator of 14% ~ 16%, dropwised in 4 ~ 6 hours, sampling is observed, if clear viscous liquid, viscosity is 50 ~ 90mpa.s, then carry out step (3), if viscosity is less than 50mpa.s, continue to drip initiator, until viscosity is 50 ~ 90mpa.s;
(3) by the reaction system after step (2) process, at 85 DEG C ~ 90 DEG C, insulation reaction 150 ~ 180 minutes, is then down to room temperature;
(4) by mass percent be 18% ~ 22% acidic solution the pH value of reaction system after step (3) process is adjusted to 7 ~ 8, then add 50 ~ 80 parts of ethylenediamine tetraacetic acid (EDTA)s, finally carry out dusting granulation, obtain described chelated dispersants;
Wherein, the described waste liquid after separating and extracting comprises polyvalent alcohol, carboxylic acid and ester class, the solid content of described waste liquid is 5% ~ 50%, and the pH value of described waste liquid is 7 ~ 14, described polyvalent alcohol is by tetramethylolmethane, propylene glycol and trihydroxymethyl propane composition, described organic acid is tricarbimide and vinylformic acid, described ester class is polyalcohol acrylate and polyhydroxy alkyl acrylate, described tetramethylolmethane, described propylene glycol, described trihydroxymethyl propane, described tricarbimide, described vinylformic acid, described polyalcohol acrylate, the weight ratio of described polyhydroxy alkyl acrylate is 1:1:1:1:7 ~ 15:2 ~ 5:2 ~ 5.
Preferably, described initiator is persulphate or superoxide.
It is more preferably ammonium persulphate.
Preferably, described basic solution is sodium hydroxide solution or potassium hydroxide solution.
Be more preferably sodium hydroxide.
Preferably, described acidic solution is any one in citric acid, tartrate, Glacial acetic acid.
It is more preferably citric acid.
Beneficial effect of the present invention is:
The by-product waste liquid produced when the present invention is to prepare polyhydroxy alkyl acrylate and polyalcohol acrylate is main raw material, prepare efficient and environment-friendly type chelated dispersants, waste resource when not only solving liquid waste disposal, produce the new problem polluted, also achieve the recycle of waste liquid, create new industrial value, reduce the production cost of enterprise, improve economic benefit.
Efficient and environment-friendly type chelated dispersants of the present invention is mainly used in the water quality treatment agent in weave dyeing and finishing technique.Feature is Environmentally-friephosphorus-free phosphorus-free, biodegradable, and can be issued to good chelating dispersion effect at cold neutral water condition.Can run and non-scaling under alkalescence or neutral cycles of concentration condition, the crystallite of the salt such as calcium carbonate, calcium sulfate or silt can be scattered in water and not precipitate, can be applicable to paper industry and do slurry dispersion agent, calcium carbonate dispersant is done for ceramic industry, do pigment dispersing agent for coating industry, in washing composition as washing auxiliary detergent.
Commercially available acrylic dispersants is only applicable in high temperature, alkaline medium.
The method of efficient and environment-friendly type chelated dispersants is simple, raw material is cheap, easy handling to utilize waste liquid to prepare, and the excellent performance of the efficient and environment-friendly type chelated dispersants produced, adaptability is extensive.
Accompanying drawing explanation
Accompanying drawing 1 is the infrared spectrum of efficient and environment-friendly type chelated dispersants.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.
Embodiment 1:
The component target of the waste liquid raw material after separating and extracting:
Composition: the mass ratio of tetramethylolmethane, propylene glycol, trihydroxymethyl propane, tricarbimide, vinylformic acid, polyalcohol acrylate, polyhydroxy alkyl acrylate is 1:1:1:1:7:2:2;
Solid content: 20%;
pH：7；
Preparation method:
Be the sodium hydroxide solution of 30% by the waste liquid of 1000kg after separating and extracting, 12kg carbonyl diamine, 100kg water, 150kg mass percent, be warming up to 85 ± 2 DEG C, carry out saponification, sampling in every 30 minutes is observed once, when seeing that solution becomes homogeneous phase transparent from muddiness, then continue insulation reaction 2 hours.After insulation terminates, under the temperature condition of 85 DEG C ~ 90 DEG C, 260kg Sunmorl N 60S is added in reaction system, 5kg mercaptoethanol, stirring and dissolving is even, and dripping 95kg mass percent is the ammonium persulphate of 15%, dropwised in 4 hours, liquid in still is observed in sampling, and be clear viscous liquid, viscosity is 60mpa.s.Continue insulation reaction 150 minutes at 85 DEG C ~ 90 DEG C, be then down to room temperature.The pH value of reaction system is regulated to be 7 ~ 8 with the citric acid solution that mass percent is 20%, add 50kg ethylenediamine tetraacetic acid (EDTA) (EDTA) again, send drying tower to carry out dusting granulation after stirring, obtain described efficient and environment-friendly type chelated dispersants 560kg, solid content is 95%.
Because composition in waste liquid is comparatively complicated, the efficient and environment-friendly type chelated dispersants therefore prepared is mixture, but its structural formula general formula is:
Wherein, R
1, R
2be ethyl or methoxyl group independently, R
3be selected from H, Na,
in any one, R be H or
x is the integer of 1 to 4, and m is the integer of 400 to 500, and n is the integer of 350 to 450.
Its infrared spectrum as shown in Figure 1.
Embodiment 2
The component target of the waste liquid raw material after separating and extracting:
Composition: the mass ratio of tetramethylolmethane, propylene glycol, trihydroxymethyl propane, tricarbimide, vinylformic acid, polyalcohol acrylate, polyhydroxy alkyl acrylate is 1:1:1:1:10:3:4;
Solid content: 25%;
pH：10；
Preparation method:
Be the sodium hydroxide solution of 30% by the waste liquid of 1000kg after separating and extracting, 20kg carbonyl diamine, 180kg water, 200kg mass percent, be warming up to 85 ± 2 DEG C, carry out saponification, sampling in every 30 minutes is observed once, when seeing that solution becomes homogeneous phase transparent from muddiness, then continue insulation reaction 2 hours.After insulation terminates, under 85 DEG C ~ 90 DEG C conditions, 180kg Sunmorl N 60S is added in reaction system, 5kg mercaptoethanol, stirring and dissolving is even, and dripping 100kg mass percent is the ammonium persulphate of 15%, dropwised in 4 hours, liquid in still is observed in sampling, and be clear viscous liquid, viscosity is 78mpa.s.Continue insulation reaction 150 minutes at 85 DEG C ~ 90 DEG C, be then down to room temperature.The pH value of reaction system is regulated to be 7 ~ 8 with the citric acid solution that mass percent is 20%, add 65kg ethylenediamine tetraacetic acid (EDTA) (EDTA) again, send drying tower to carry out dusting granulation after stirring, obtain described efficient and environment-friendly type chelated dispersants 570kg, solid content is 96%.
Because the composition in waste liquid is comparatively complicated, the efficient and environment-friendly type chelated dispersants therefore prepared is mixture, and its structural formula general formula is:
Wherein, R1, R2 are ethyl or methoxyl group independently, and R3 is selected from
in any one, R is
x is the integer of 1 to 4, and m is the integer of 500 ~ 600, and n is the integer of 550 ~ 650, and its infrared spectrum as shown in Figure 1.
Embodiment 3
The component target of the waste liquid raw material after separating and extracting:
Composition: the mass ratio of tetramethylolmethane, propylene glycol, trihydroxymethyl propane, tricarbimide, vinylformic acid, polyalcohol acrylate, polyhydroxy alkyl acrylate is 1:1:1:1:15:5:5;
Solid content: 35%;
pH：12；
Preparation method:
Be the sodium hydroxide solution of 30% by the waste liquid of 1000kg after separating and extracting, 25kg carbonyl diamine, 240kg water, 260kg mass percent, be warming up to 85 ± 2 DEG C, carry out saponification, sampling in every 30 minutes is observed once, when seeing that solution becomes homogeneous phase transparent from muddiness, then continue insulation reaction 2 hours.After insulation terminates, under 85 DEG C ~ 90 DEG C conditions, 150kg Sunmorl N 60S is added in reaction system, 5kg mercaptoethanol, stirring and dissolving is even, and dripping 110kg mass percent is the ammonium persulphate of 15%, dropwised in 4 hours, liquid in still is observed in sampling, and be clear viscous liquid, viscosity is 89mpa.s.Continue insulation reaction 150 minutes at 85 DEG C ~ 90 DEG C, be then down to room temperature.The pH value of reaction system is regulated to be 7 ~ 8 with the citric acid solution that mass percent is 20%, add 75kg ethylenediamine tetraacetic acid (EDTA) (EDTA) again, send drying tower to carry out dusting granulation after stirring, obtain described efficient and environment-friendly type chelated dispersants 670kg, solid content is 97%.
Because the composition in waste liquid is comparatively complicated, the efficient and environment-friendly type chelated dispersants therefore prepared is mixture, and its structural formula general formula is:
Wherein, R1, R2 are ethyl or methoxyl group independently, and R3 is selected from
in any one, R is
x is the integer of 1 to 4, and m is the integer of 300 ~ 400, and n is the integer of 800 ~ 900, and its infrared spectrum as shown in Figure 1
Embodiment 4
Contrasted by other like products on the sequestering power of the chelated dispersants of embodiment 1,2,3 gained and dispersive ability and market, the physical and chemical performance of each product is listed in table 1, and the comparing result of each product is listed in table 2.
The measuring method of chelating value and dispersion value is as follows:
Ca
2+chelating value: by the sequestrant of 1.0g test diluted sample in the deionized water of 80ml, add sodium hydroxide (80g/l) solution, pH value is adjusted between 10 to 11.Add the sodium carbonate solution of 10ml2%.Dropwise add the calcium acetate solution of 0.25mol/l, until precipitation no longer increases.In the process dripped, add sodium hydroxide solution, pH value is between 10 ~ 11 all the time.Record consumption.Calculate sequestering power: Ca
2+the milliliter number * 20.2 of milligram number/gram product=calcium chloride solution.
Fe
3+chelating value: take 5g sample, by water dissolution in 500ml volumetric flask, draws 5ml, adds 50ml distilled water, add 10mlNH
4fe(SO
4)
212H
2the indicator of O solution and 2 sulphosalicylic acids, being titrated to solution with EDTA reference liquid, to become glassy yellow from red-purple be terminal, does blank test simultaneously.
Dispersion value: get 5g sample in 250ml volumetric flask, add deionized water to scale marks, turns upside down evenly, draws 25ml in 250ml Erlenmeyer flask, adds the sodium carbonate solution 10ml of 10%, dropwise add the Ca (CH of 0.1mol/l
3cOO)
2solution, until occur obviously muddy; Replace sample to make blank assay with 25ml deionized water simultaneously.Calculate dispersive ability: Ca
2+milligram number/gram product=Ca (CH
3cOO)
2(the milliliter number-blank solution number of solution) * 20.2.
Table 1
| Numbering | Type | Outward appearance | pH | Solid content |
| 1 | The product of embodiment 1 | Grey powder | 6.5 | 95% |
| 2 | The product of embodiment 2 | Grey powder | 6.2 | 96% |
| 3 | The product of embodiment 3 | Grey powder | 6.9 | 97% |
| 4 | Amino Trimethylene Phosphonic Acid (ATMP) | White crystal particle | 1 | 97% |
| 5 | Acrylic dispersants | Micro-yellow transparent liquid | 7.2 | 40% |
| 6 | Acid-co-maleic acid dispersion agent | White powdery solids | 7.5 | 95% |
Table 2
| Numbering | Ca 2+Chelating value | Fe 3+Chelating value | Dispersion value |
| 1 | 200 | 100 | 900 |
| 2 | 230 | 120 | 930 |
| 3 | 250 | 110 | 920 |
| 4 | 300 | 111 | 950 |
| 5 | 120 | 70 | 800 |
| 6 | 140 | 64 | 500 |
From table 2, the chelated dispersants of gained of the present invention is similar to the performance of ATMP dispersion agent, and is obviously better than acrylic dispersants and acid-co-maleic acid dispersion agent.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (5)
1. an efficient and environment-friendly type chelated dispersants, is characterized in that: its structural formula general formula is:
Wherein, R
1, R
2be ethyl or methoxyl group independently, R
3be selected from H, Na,
in any one, R be H or
x is the integer of 1 to 4, and m is the integer of 1 to 1000, and n is the integer of 1 to 1000.
2. the preparation method of efficient and environment-friendly type chelated dispersants as claimed in claim 1, is characterized in that: comprise the steps:
(1) with parts by weight, be the basic solution of 28 ~ 32% by 1000 parts of waste liquids after separating and extracting, 10 ~ 30 parts of carbonyl diamines, 100 ~ 260 parts of water, 150 ~ 300 parts of mass percents, be warming up to 85 ± 2 DEG C, carry out saponification, sampling in every 30 minutes is observed once, when seeing that solution becomes homogeneous phase transparent from muddiness, then continue insulation reaction 1.5 ~ 2 hours;
(2) under the temperature condition of 85 DEG C ~ 90 DEG C, to in the reaction system after step (1) process, add 120 ~ 280 parts of Sunmorl N 60Ss, 5 ~ 10 parts of mercaptoethanols, after to be dissolved, dripping 90 ~ 110 parts of mass percents is the initiator of 14% ~ 16%, dropwised in 4 ~ 6 hours, sampling is observed, if clear viscous liquid, viscosity is 50 ~ 90mpa.s, then carry out step (3), if viscosity is less than 50mpa.s, continue to drip initiator, until viscosity is 50 ~ 90mpa.s;
(3) by the reaction system after step (2) process, at 85 DEG C ~ 90 DEG C, insulation reaction 150 ~ 180 minutes, is then down to room temperature;
(4) by mass percent be 18% ~ 22% acidic solution the pH value of reaction system after step (3) process is adjusted to 7 ~ 8, add 50 ~ 80 parts of ethylenediamine tetraacetic acid (EDTA)s again, finally carry out dusting granulation, obtain described chelated dispersants;
Wherein, the described waste liquid after separating and extracting comprises polyvalent alcohol, organic acid and ester deter-mation class, the solid content of described waste liquid is 5% ~ 50%, and the pH value of described waste liquid is 7 ~ 14, described polyvalent alcohol is by tetramethylolmethane, propylene glycol and trihydroxymethyl propane composition, described organic acid is tricarbimide and vinylformic acid, described ester class is polyalcohol acrylate and polyhydroxy alkyl acrylate, described tetramethylolmethane, described propylene glycol, described trihydroxymethyl propane, described tricarbimide, described vinylformic acid, described polyalcohol acrylate, the weight ratio of described polyhydroxy alkyl acrylate is 1:1:1:1:7 ~ 15:2 ~ 5:2 ~ 5.
3. preparation method according to claim 2, is characterized in that: described initiator is persulphate or superoxide.
4. preparation method according to claim 2, is characterized in that: described basic solution is sodium hydroxide solution or potassium hydroxide solution.
5. preparation method according to claim 2, is characterized in that: described acidic solution is any one in citric acid, tartrate, Glacial acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310539092.6A CN103554330B (en) | 2013-11-04 | 2013-11-04 | A kind of efficient and environment-friendly type chelated dispersants and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310539092.6A CN103554330B (en) | 2013-11-04 | 2013-11-04 | A kind of efficient and environment-friendly type chelated dispersants and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103554330A CN103554330A (en) | 2014-02-05 |
| CN103554330B true CN103554330B (en) | 2015-09-30 |
Family
ID=50008712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310539092.6A Active CN103554330B (en) | 2013-11-04 | 2013-11-04 | A kind of efficient and environment-friendly type chelated dispersants and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103554330B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105064087A (en) * | 2015-07-07 | 2015-11-18 | 宜兴市华联化工有限公司 | Efficient and environment-friendly chelating dispersant |
| CN115262247B (en) * | 2022-08-24 | 2023-10-31 | 张家港市德宝化工有限公司 | Polyester cotton tooling fabric and one-step dyeing process thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5149441A (en) * | 1991-10-18 | 1992-09-22 | Loctite Corporation | Method of treating wastewater containing heat-curable (meth) acrylic monomer compositions |
| CN101786742B (en) * | 2010-02-09 | 2011-10-05 | 广东工业大学 | Treatment method of methacrylate or acrylate industrial wastewater |
| CN102225976B (en) * | 2011-04-29 | 2012-10-10 | 张家港市德宝化工有限公司 | Method for preparing polyacrylic acid dispersing agents by adopting acrylic acid waste water as raw material |
-
2013
- 2013-11-04 CN CN201310539092.6A patent/CN103554330B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103554330A (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467670B (en) | Preparation method of anti-mud polycarboxylic water reducer | |
| CN104774293B (en) | A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof | |
| CN104192918A (en) | Sewage treatment agent, as well as preparation method and application thereof | |
| CN108751770B (en) | Cement grinding aid and preparation method thereof | |
| CN101921365B (en) | Preparation method for instant cationic polyacrylamide | |
| CN103554330B (en) | A kind of efficient and environment-friendly type chelated dispersants and preparation method thereof | |
| CN103555460B (en) | Reactive dye anti-staining soaping agent and preparation method thereof | |
| CN108103839B (en) | Preparation method of modified calcium sulfate whisker papermaking filler | |
| CN102976659A (en) | Chemical-waste compounded cement grinding aid | |
| CN101676201A (en) | Technology for removing arsenic in polyphosphoric acid | |
| CN102295355B (en) | Identifiable environmentally-friendly scale and corrosion inhibitor | |
| CN105669069A (en) | Additive for silicate cement and method for preparing additive | |
| CN101709169A (en) | Water-based inner wall environmentally-friendly sealing compound using circulating resources and method for preparing same | |
| CN113072084A (en) | Method for preparing modified magnesium hydroxide flame retardant by using light-burned active magnesium oxide produced in salt lake | |
| CN103772748B (en) | A kind of silicon oxide compound micro encapsulation rare earth metal hypophosphite and preparation method thereof | |
| CN105152565B (en) | Polyphosphonic acid type water reducing agents and synthesis method thereof | |
| CN113651436B (en) | Non-phosphorus non-nitrogen scale inhibition and dispersion agent and preparation method and application thereof | |
| CN102391383A (en) | Modification method for ZG gum for production in oil field and application thereof | |
| CN113200701B (en) | Grinding aid for improving cement durability and preparation method thereof | |
| CN106277376B (en) | A kind of five isothiourea group succinic acid pentitol ester of environment-friendly type corrosion inhibiter and preparation method thereof for deionized water | |
| CN109020300A (en) | A kind of cement grinding aid and preparation method thereof | |
| CN104528959B (en) | A kind of environmental protection dirt dispersion agent and preparation method thereof | |
| CN103755207B (en) | A kind of phosphine carboxylic acid water reducer and preparation method thereof | |
| CN113999603A (en) | Method for preparing organic resin aggregate for elastic polyurethane static millstone terrace | |
| CN102049211A (en) | Organic-inorganic composite dispersing agent as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |