CN1594133A - Method for reusing contaminant separated from naphthalenesulfonic acid neutralization wash waste liquor - Google Patents
Method for reusing contaminant separated from naphthalenesulfonic acid neutralization wash waste liquor Download PDFInfo
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Abstract
Disclosed is a method for reusing contaminant separated from naphthalenesulfonic acid neutralization wash waste liquor which consists of, concentrating the isolated polluted material into waste water concentration liquid with the solid material content being 40-70%, charging sulphuric acid into the waste water concentration liquid, adjusting the total acidify to be 24%-32%, charging methylene oxide into the waste water concentration liquid for condensation reaction, charging alkali for neutralization reaction, segregating the solid sulphate, thus obtaining the filter liquor, i.e. naphthalene family water reducing agent.
Description
Technical Field
The invention relates to a method for treating and recycling 'naphthalene sulfonic acid neutralization washing waste liquid' in a 2-naphthol production process. In particular to a method for further utilizing the chemical substances which are separated from the 'naphthalene sulfonic acid neutralization washing waste liquid' and pollute the environment.
Background
2-naphthol is a fine chemical intermediate, is mainly applied to the production of dyes and organic pigments, and is widely applied to the industries of medicines, pesticides and leather. At present, the traditional method for producing 2-naphthol in China is to prepare refined naphthalene as a raw material through processes of sulfonation, hydrolysis, neutralization, alkali fusion, acidification, refining and the like, and each ton of 2-naphthol produced is discharged with nearly 10 tons of filtered mother liquor and washing water, namely naphthalene sulfonic acid neutralization washing waste liquor, in the neutralization process. The 'naphthalene sulfonic acid neutralization washing waste liquid' mainly contains sodium naphthalene sulfonate, sodium methyl naphthalene sulfonate, and indene sodium sulfonate, sodium sulfite, sodium sulfate and other substances, wherein the sodium naphthalene sulfonate comprises 16000-25000mg/l, 34-38g/l, 55-60g/l, and the COD concentration reaches 25000-40000 mg/l. The part of waste water has high salt content, high toxicity and deep color, and is directly discharged without treatment, so that not only is serious environmental pollution caused and human health harmed, but also a large amount of expensive chemical raw materials and intermediates are lost.
In the prior art, the treatment method of the naphthalenesulfonic acid neutralization washing waste liquid mainly comprises a resin adsorption method, a carbonization and incineration method, a membrane separation method, a chemical oxidation method, a biochemical method, an extraction method and the like. Wherein, the extraction method, the resin adsorption method or the evaporation concentration and other conventional treatment methods can separate the chemical substances polluting the environment in the naphthalenesulfonic acid neutralized washing waste liquid from the waste liquid, and the residual waste water can reach the discharge standard after post treatment. The chemical substances which are separated from the naphthalene sulfonic acid neutralization washing waste liquid and pollute the environment are concentrated into waste water concentrated liquid, and the waste water concentrated liquid is treated by adopting a concentrated incineration method. Through analysis, the chemical substances of the waste water concentrated solution are complex in components, and still contain a large amount of useful substances such as naphthalene sulfonate and the like, mainly including 2-sodium naphthalene sulfonate, 1-sodium naphthalene sulfonate, sodium methyl naphthalene sulfonate, sodium oxaindene naphthalene sulfonate, sodium aza indene naphthalene sulfonate, sodium thiaindene sulfonate, sodium naphthalene disulfonate and the like. The prior art has two problems in the treatment method of the chemical substances which are separated from the 'naphthalene sulfonic acid neutralization washing waste liquid' and pollute the environment: firstly, secondary pollution is generated by burning; secondly, the amount of the environment-polluting chemicals separated from the naphthalenesulfonic acid neutralization washing waste liquid is still large, about 1 ton of the environment-polluting chemicals is separated from each ton of 2-naphthol produced, therefore, the energy consumption cost of incineration is high, and the cost of each ton of the environment-polluting chemicals reaches 1600 yuan; thirdly, the effective ingredients of the chemical substances which are separated from the 'naphthalene sulfonic acid neutralization washing waste liquid' and pollute the environment are not utilized, thus causing resource waste.
Disclosure of Invention
The invention aims to provide a method for further utilizing environment-polluting chemical substances separated from naphthalene sulfonic acid neutralized washing waste liquid aiming at the defects of the prior art.
The invention aims to achieve the following technical scheme, and the invention relates to a method for recycling pollutants separated from naphthalenesulfonic acid neutralization washing waste liquid, which is characterized in that the pollutants separated from the naphthalenesulfonic acid neutralization washing waste liquid are concentrated or added with naphthalenesulfonic acid or added with methylnaphthalenesulfonic acid or added with a mixture of the naphthalenesulfonic acid and the methylnaphthalenesulfonic acid until the solid content of the materials is 40-70% by weight concentration, and the recycling method of the waste water concentrate is completed according to the following steps:
(a) adding sulfuric acid into the waste water concentrated solution to adjust the total acidity to 24-32%, adding formaldehyde into the waste water concentrated solution, wherein the amount of the added formaldehyde is 0.6-1.0 time of the molar number of the sulfonate in the material, and carrying out condensation reaction for 2-6 hours at the temperature of 80-150 ℃;
(b) after the condensation reaction is finished, adding alkali to adjust the pH value to 7-9, carrying out neutralization reaction, and separating solid sulfate to obtain filtrate, namely the naphthalene water reducer;
in the neutralization reaction (b), the base is: sodium hydroxide or calcium hydroxide and calcium oxide are used as main and auxiliary materials.
In the technical scheme, the main components of the waste water concentrated solution are naphthalenesulfonic acid sodium salt and a small amount of inorganic salt, the waste water concentrated solution contains a large amount of naphthalenesulfonic acid salts, methylnaphthalenesulfonic acid salts and indene sulfonates, formaldehyde is added under the condition of keeping a certain acidity, condensation reaction is carried out at a certain temperature, acid plays a role of a condensing agent in the condensation reaction, the naphthalenesulfonic acid molecules can be connected after the formaldehyde molecules are activated, alkali is added after the reaction is finished for neutralization reaction, solid sulfate is removed and separated through filtration, and the obtained filtrate is the naphthalene liquid water reducer, and the main components of the naphthalene liquid water reducer are aryl alkane sulfonates, namely a naphthalenesulfonic acid formaldehyde condensate and a polymethacrylic formaldehyde condensate, and belongs to an anionic surfactant. The condensation process of formaldehyde with aromatic compounds can be represented by the following general formula:
the condensing agent used in the reaction is sulfuric acid. The condensing agent functions to convert formaldehyde into a reactive carbonyl ion (a hydroxyformaldehyde cation).
This cation then reacts with the aromatic compound.
The naphthalene water-reducing agent obtained by condensation of formaldehyde and naphthalene sulfonic acid is a mixture of several substances containing two or more naphthalene nuclei which are bonded by-CH2The-radicals (alkyl) are linked.
And
in the invention, as the waste water concentrated solution is a mixture, the main component of the mixture is sodium naphthalenesulfonate, the sodium naphthalenesulfonate reacts with acid to generate naphthalenesulfonic acid under a certain acidity condition, and the naphthalenesulfonic acid is condensed with formaldehyde. The reaction of the main components can be expressed by the following equation:
1. main equation of condensation reaction
2. Main equation of neutralization reaction
a. Main reaction
b. Side reactions
The main components in the naphthol wastewater comprise naphthalenesulfonic acid, methylnaphthalenesulfonic acid, oxaindene, azaindene, thiaindene and the like. They are all high-quality raw materials for synthesizing the water reducing agent, but because they exist in the form of aqueous solution, and are directly synthesized by the traditional process, the qualified high-efficiency water reducing agent is difficult to obtain, so the high-efficiency water reducing agent is required to be obtained by extraction, back extraction, or resin adsorption, back washing, concentration, then acidification by adding sulfuric acid, then concentration to the required concentration, and condensation under the specified conditions.
Compared with the high-efficiency naphthalene water reducing agent produced by using industrial naphthalene, when pure naphthalene is used as a raw material, the rhythm is very slow, so that a plurality of uncondensed mononuclear naphthalenesulfonic acids exist in the product, however, once the rhythm stage is completed, the condensation reaction is rapidly carried out, so that a plurality of high-condensation compounds exist in the product. Compared with the high-efficiency naphthalene water reducing agent produced by pure methylnaphthalene, the situation is just opposite when the pure methylnaphthalene is used as a raw material, and the rhythm stage of the high-efficiency naphthalene water reducing agent is easier to carry out. Therefore, the uncondensed monokaryon molecules in the product are less, but the condensation reaction is only carried out until 3-4 karyons, so that the high condensation compound in the product is less. However, if a mixture of naphthalene and methylnaphthalene is used as the starting material, the product combines the advantages of having fewer uncondensed mononuclear molecules than when pure naphthalene is used as the starting material, and more polynuclear high condensates than when pure methylnaphthalene is used as the starting material. It can be said that pure naphthalene is used as a raw material, the condensation reaction has poor roundness, uncondensed naphthalenesulfonic acid remains, industrial preparation is difficult, and the formation of a pot is easy, while pure methylnaphthalene is used as a raw material, high condensation is difficult to obtain, and the gas-filling property of the product is too high. The mixture of naphthalene and methylnaphthalene in a proper proportion is used as a raw material, so that the defects can be overcome. Because the wastewater is rich in methylnaphthalenesulfonic acid, indene and the like, subsections such as methylnaphthalenesulfonic acid and indene are mixed in the molecular chain of the formaldehyde condensate of the naphthalenesulfonic acid. Due to the synergistic effect of the components, the prepared high-efficiency water reducing agent has better effect than the traditional water reducing agent directly synthesized by industrial naphthalene, and particularly, the early strengthening progress of concrete is obviously accelerated.
The object of the present invention can be further achieved by the following means. The method for utilizing the pollutants is characterized in that sodium hydroxide is added in the neutralization reaction (b) to adjust the pH value to 7-9, after the neutralization reaction is finished, the reaction liquid is cooled to 0-15 ℃, and solid sulfate precipitated by cooling is filtered and separated out to obtain the naphthalene water reducer.
The object of the present invention can be further achieved by the following means. The method for utilizing the pollutants is characterized in that in the neutralization reaction (b), sodium hydroxide is added according to the molar number of the sulfonic acid groups in the material, sodium hydroxide is added according to the molar amount of the sum of the molar number of the naphthalene sulfonic acid groups and the molar number of the methyl naphthalene sulfonic acid groups in the material, calcium hydroxide or calcium oxide is added to adjust the pH value to 7-9, and after the neutralization reaction is carried out for not less than 20 minutes, solid sulfate is separated by filtration to obtain the naphthalene water reducer.
The object of the present invention can be further achieved by the following means. The method for utilizing the pollutants is characterized in that the relative pressure of the condensation reaction (a) is 0-0.4 MPa.
As the naphthalenesulfonic acid in the waste water concentrated solution exists in the form of sodium salt and contains a large amount of impurities, the high-quality product is difficult to obtain by directly adopting the reaction condition of synthesizing the naphthalene water reducing agent, so that the invention aims at the characteristic of the waste water concentrated solution and adopts a pressurizing method to further improve the quality of the product.
Compared with the prior art, the invention has the following advantages: secondary pollution generated by burning is eliminated; the cost and the energy consumption of incineration are saved; the effective components of the chemical substances which are separated from the 'naphthalene sulfonic acid neutralization washing waste liquid' and pollute the environment are further utilized, so that the environmental protection problem that the 'waste water concentrated solution' is difficult to treat is solved, and the test proves that 2.5 to 3 tons of black liquor can produce 1 ton of high-concentration high-efficiency water reducing agent with the effective component content of about 36 percent. The high-efficiency naphthalene water reducing agent produced by the waste water concentrated solution reaches the same index as the high-efficiency naphthalene water reducing agent produced by industrial naphthalene, and the use effect is better. The direct cost is much lower than the production cost of industrial naphthalene, the incineration cost of the waste water concentrated solution is saved, waste is changed into valuable, and higher economic benefit is generated. The quality index of the prepared naphthalene water reducer reaches the performance index requirementof the high-efficiency naphthalene water reducer in the concrete admixture of the standard numbers GB 8076-1997 and GB/T8077-2000.
Drawings
FIG. 1 is a flow chart of the present invention for recycling the pollutants separated from the "neutralization of washing waste liquid with naphthalenesulfonic acid" and using sodium hydroxide for the neutralization reaction.
FIG. 2 is a flow chart of the neutralization reaction of the method for recycling pollutants separated from the naphthalene sulfonic acid neutralization washing waste liquid by using sodium hydroxide as the main component and calcium hydroxide and calcium oxide as the auxiliary component.
Detailed Description
The first embodiment is as follows: the present invention is further described in the following as an embodiment of the present invention, which is a method for recycling pollutants separated from "naphthalene sulfonic acid neutralized washing waste liquid", wherein 2000 g of pollutants separated from "naphthalene sulfonic acid neutralized washing waste liquid" is first heated, evaporated and concentrated to 437 g of "waste water concentrated solution" with a solid content of 59% by weight, the "waste water concentrated solution" is placed in a 2000ml four-neck round bottom flask, heated in an oil bath, 196 g of concentrated sulfuric acid with a weight concentration of 98% is added dropwise to the "waste water concentrated solution", the total acidity is adjusted to 27.5%, formaldehyde is added dropwise in an amount of 45 g which is 0.8 times the molar number of sulfonate in the material, stirring is performed at a reaction temperature of 80 ℃ and a relative pressure of 0 mpa (i.e. normalpressure), condensation reaction is performed for 6 hours, 467 g of sodium hydroxide with a weight concentration of 30% is added to the four-neck round bottom flask after completion of the condensation reaction, and (3) adjusting the pH value to 8, carrying out neutralization reaction, cooling the reaction material liquid to 0 ℃ after the neutralization reaction is finished, filtering and separating sodium sulfate separated out by cooling to obtain 343 g of filtrate with the density of 1.2 g per ml, namely the naphthalene water reducer. The naphthalene series water reducing agent is detected by a national quality inspection mechanism and is higher than the national standards with the standard numbers GB 8076-1997 and GB/T8077-2000.
Example two: the following is a further embodiment of the invention, the summary of the invention continuing. The embodiment is a method for recycling pollutants separated from 'naphthalene sulfonic acid neutralization washing waste liquid', firstly concentrating the pollutants separated from 'naphthalene sulfonic acid neutralization washing waste liquid' to 30 kg of 'waste water concentrated solution' with the material solid content of 40% weight concentration, placing the 'waste water concentrated solution' into a reaction kettle, dropwise adding 15 kg of concentrated sulfuric acid with the weight concentration of 98% into the 'waste water concentrated solution', adjusting the total acidity to 32%, adding 4.2 kg of formaldehyde which is 1.0 times of the molar number of sulfonate groups in the materials, stirring at the reaction temperature of 150 ℃ and the relative pressure of 0.4 MPa, carrying out condensation reaction for 2 hours, cooling to 80 ℃ after the condensation reaction is finished, adding 40 kg of sodium hydroxide with the weight concentration of 30% into the reaction kettle, adjusting the pH to 7, carrying out neutralization reaction, cooling the reaction liquid to 15 ℃ after the neutralization reaction is finished, sodium sulfate precipitated by cooling is separated by filtration, and 32 kg of filtrate with the density of 1.2 g per ml is obtained, namely the naphthalene water reducer. The naphthalene water reducer is detected by a national quality inspection mechanism and is higher than the national standards of GB 8076-1997 and GB/T8077-2000.
Example three: the following is a further embodiment of the invention, the summary of the invention continuing. The embodiment is a method for recycling pollutants separated from 'naphthalene sulfonic acid neutralization washing waste liquid', firstly adding a mixture of naphthalene sulfonic acid and methyl naphthalene sulfonic acid to the pollutants separated from 'naphthalene sulfonic acid neutralization washing waste liquid' to obtain 30 kg of 'waste water concentrated liquid' with the material solid content of 70% by weight, placing the 'waste water concentrated liquid' in a reaction kettle, dropwise adding 10 kg of concentrated sulfuric acid with the weight concentration of 98% into the 'waste water concentrated liquid', adjusting the total acidity to 24%, adding 4.2 kg of formaldehyde in an amount which is 1.0 time of the molar number of sulfonate in the material, stirring at the reaction temperature of 130 ℃ and the relative pressure of 0.2 MPa, carrying out condensation reaction for 3 hours, cooling to 80 ℃, adding 28 kg of sodium hydroxide with the weight concentration of 30% into the reaction kettle, adjusting the pH to 9, carrying out neutralization reaction, after the neutralization reaction is completed, cooling the reaction liquid to 10 ℃, filtering and separating sodium sulfate precipitated by cooling to obtain 36 kg of filtrate with the density of 1.2 g per ml, namely the naphthalene water reducer. The naphthalene series water reducing agent is detected by a national quality inspection mechanism and reaches the national standards of GB 8076-1997 and GB/T8077-2000.
Example four: the following is a further embodiment of the invention, the summary of the invention continuing. The embodiment is a method for recycling pollutants separated from naphthalene sulfonic acid neutralized washing waste liquid, firstly concentrating the pollutants separated from naphthalene sulfonic acid neutralized washing waste liquid and adding naphthalene sulfonic acid to obtain 300 g of waste water concentrated solution with the solid content of 51% by weight, placing the waste water concentrated solution in a 2000ml four-neck round bottom flask, dropwise adding 120 g of concentrated sulfuric acid with the weight concentration of 98% into the waste water concentrated solution, adjusting the total acidity to 28%, adding 25 g of formaldehyde which is 0.6 times of the molar number of sulfonic acid groups in the material, stirring at the reaction temperature of 100 ℃ and the relative pressure of 0 MPa, carrying out condensation reaction for 4 hours, after the condensation reaction is finished, firstly adding 62 g of sodium hydroxide with the weight concentration of 30% into the four-neck round bottom flask according to the molar number of sulfonic acid groups in the material, adding calcium hydroxide to adjust the pH value to 7, and (3) carrying out neutralization reaction for 20 minutes, and filtering to separate out solid sulfate to obtain 280 g of filtrate with the density of 1.2 g per ml, namely the naphthalene water reducer. The naphthalene series water reducing agent is detected by a national quality inspection mechanism and reaches the national standards of GB 8076-1997 and GB/T8077-2000.
Example five: the following is a further embodiment of the invention, the summary of the invention continuing. The embodiment is a method for recycling pollutants separated from naphthalene sulfonic acid neutralized washing waste liquid, firstly adding methyl naphthalene sulfonic acid into pollutants separated from naphthalene sulfonic acid neutralized washing waste liquid to obtain 300 g of waste water concentrated solution with the solid content of 51% by weight, placing the waste water concentrated solution into a 2000ml four-neck round bottom flask, dropwise adding 140 g of concentrated sulfuric acid with the weight concentration of 98% into the waste water concentrated solution, adjusting the total acidity to 30%, adding 30 g of formaldehyde in an amount which is 0.7 times of the molar number of sulfonic acid groups in the materials, stirring at the reaction temperature of 110 ℃ and the relative pressure of 0 MPa, carrying out condensation reaction for 5 hours, cooling to 80 ℃ after the condensation reaction is finished, firstly adding 62 g of sodium hydroxide with the weight concentration of 30% into the four-neck round bottom flask according to the molar number of sulfonic acid groups in the materials, then adding calcium oxide to adjust the pH value to 9, after neutralization reaction is carried out for 40 minutes, solid sulfate is separated out by filtration, and 310 g of filtrate with the density of 1.2 g per ml is obtained, namely the naphthalene water reducer. The naphthalene series water reducing agent is detected by a national quality inspection mechanism and is higher than the national standards with the standard numbers GB 8076-1997 and GB/T8077-2000.
Claims (4)
1. A method for recycling pollutants separated from ' naphthalene sulfonic acid neutralization washing waste liquid ' is characterized in that the pollutants separated from ' naphthalene sulfonic acid neutralization washing waste liquid ' are concentrated or added with naphthalene sulfonic acid or added with methyl naphthalene sulfonic acid or added with a mixture of naphthalene sulfonic acid and methyl naphthalene sulfonic acid until the solid content of materials is 40-70% of a waste water concentrated solution by weight concentration, and the recycling method of the waste water concentrated solution ' is completed according to the following steps:
(a) adding sulfuric acid into the waste water concentrated solution to adjust the total acidity to 24-32%, adding formaldehyde into the waste water concentrated solution, wherein the amount of the added formaldehyde is 0.6-1.0 time of the molar number of the sulfonate in the material, and carrying out condensation reaction for 2-6 hours at the temperature of 80-150 ℃;
(b) after the condensation reaction is finished, adding alkali to adjust the pH value to 7-9, carrying out neutralization reaction, and separating solid sulfate to obtain filtrate, namely the naphthalene water reducer;
in the neutralization reaction (b), the base is: sodium hydroxide or calcium hydroxide and calcium oxide are used as main and auxiliary materials.
2. The method for utilizing pollutants as claimed in claim 1, wherein in the neutralization reaction (b), sodium hydroxide is added to adjust the pH value to 7-9, after the neutralization reaction is completed, the reaction solution is cooled to 0-15 ℃, and solid sulfate precipitated by cooling is separated by filtration to obtain the naphthalene water reducer.
3. The method for utilizing pollutants as claimed in claim 1, wherein in the neutralization reaction (b), sodium hydroxide is added according to the molar number of the sulfonic acid groups in the material, then calcium hydroxide or calcium oxide is added to adjust the pH value to 7-9, and after the neutralization reaction is carried out for not less than 20 minutes, solid sulfate is separated out by filtration to obtain the naphthalene water reducer.
4. The method forutilizing contaminants of claim 1, wherein the condensation reaction (a) is conducted at a relative pressure of 0 to 0.4 mpa.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311125B (en) * | 2007-05-23 | 2011-12-21 | 山东省莱芜市汶河化工有限公司 | Treatment and recovery method of production waste drainage of naphthalene-based water reducer |
| CN102372456A (en) * | 2010-08-26 | 2012-03-14 | 浙江龙盛集团股份有限公司 | Method for preparing naphthalene series additive from low-acidity process waste water |
| CN102584086A (en) * | 2012-01-16 | 2012-07-18 | 天津市飞龙砼外加剂有限公司 | Preparation method for synthetizing high efficiency water reducing agent by 2-naphthol waste water |
| CN102910853A (en) * | 2011-08-03 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for producing naphthalene-based superplasticizer by using H acid wastewater recovered solution |
| CN103723746A (en) * | 2013-11-28 | 2014-04-16 | 枣庄市泰瑞精细化工有限公司 | Preparation method for producing anhydrous sodium sulfate with 2,7-dihydroxy naphthalene mother liquid |
| CN105461252A (en) * | 2015-11-27 | 2016-04-06 | 中蓝连海设计研究院 | Method for preparation of naphthalene dispersing agent by using naphthalenesulfonate recycled waste liquid and use of naphthalene dispersing agent |
| CN107573471A (en) * | 2017-08-31 | 2018-01-12 | 浙江吉盛化学建材有限公司 | A kind of production technology of FDN high efficiency water reducing agents |
| CN110981059A (en) * | 2019-12-09 | 2020-04-10 | 常州中源工程技术有限公司 | System and process for treating waste water containing sodium sulfate salt and sodium sulfite salt dinaphthol |
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2004
- 2004-07-10 CN CN 200410041369 patent/CN1269742C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311125B (en) * | 2007-05-23 | 2011-12-21 | 山东省莱芜市汶河化工有限公司 | Treatment and recovery method of production waste drainage of naphthalene-based water reducer |
| CN102372456A (en) * | 2010-08-26 | 2012-03-14 | 浙江龙盛集团股份有限公司 | Method for preparing naphthalene series additive from low-acidity process waste water |
| CN102372456B (en) * | 2010-08-26 | 2013-06-12 | 浙江龙盛集团股份有限公司 | Method for preparing naphthalene series additive from low-acidity process waste water |
| CN102910853A (en) * | 2011-08-03 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for producing naphthalene-based superplasticizer by using H acid wastewater recovered solution |
| CN102584086A (en) * | 2012-01-16 | 2012-07-18 | 天津市飞龙砼外加剂有限公司 | Preparation method for synthetizing high efficiency water reducing agent by 2-naphthol waste water |
| CN103723746A (en) * | 2013-11-28 | 2014-04-16 | 枣庄市泰瑞精细化工有限公司 | Preparation method for producing anhydrous sodium sulfate with 2,7-dihydroxy naphthalene mother liquid |
| CN103723746B (en) * | 2013-11-28 | 2014-09-03 | 枣庄市泰瑞精细化工有限公司 | Preparation method for producing anhydrous sodium sulfate with 2,7-dihydroxy naphthalene mother liquid |
| CN105461252A (en) * | 2015-11-27 | 2016-04-06 | 中蓝连海设计研究院 | Method for preparation of naphthalene dispersing agent by using naphthalenesulfonate recycled waste liquid and use of naphthalene dispersing agent |
| CN107573471A (en) * | 2017-08-31 | 2018-01-12 | 浙江吉盛化学建材有限公司 | A kind of production technology of FDN high efficiency water reducing agents |
| CN107573471B (en) * | 2017-08-31 | 2019-10-29 | 浙江吉盛化学建材有限公司 | A kind of production technology of FDN high efficiency water reducing agent |
| CN110981059A (en) * | 2019-12-09 | 2020-04-10 | 常州中源工程技术有限公司 | System and process for treating waste water containing sodium sulfate salt and sodium sulfite salt dinaphthol |
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