CN105753357A - Method for synthesizing modified sulfamate water reducer by utilizing wastewater generated in tobias acid production process - Google Patents
Method for synthesizing modified sulfamate water reducer by utilizing wastewater generated in tobias acid production process Download PDFInfo
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- CN105753357A CN105753357A CN201610110637.5A CN201610110637A CN105753357A CN 105753357 A CN105753357 A CN 105753357A CN 201610110637 A CN201610110637 A CN 201610110637A CN 105753357 A CN105753357 A CN 105753357A
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- water reducer
- tobias
- waste water
- acid process
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
- C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention relates to a method for synthesizing a modified sulfamate water reducer by utilizing wastewater generated in the tobias acid production process. In the method, the modified sulfamate water reducer is prepared by adopting the wastewater generated in the tobias acid production process, sodium sulfanilate and a compound of phenolic hydroxy. The synthesized modified sulfamic acid has higher water-reducing rate of concrete and excellent slump retaining property and more importantly opens up a new path of comprehensive utilization of dye intermediate wastewater. The method has the beneficial effects that the environmental pressure in the dye intermediate production process is reduced while the raw material cost of the water reducer is reduced; and the method has good economic and environmental protection benefits.
Description
Technical field
The present invention relates to a kind of method of waste water synthesis modification sulfamate water reducer produced by utilization in Tobias-acid process.
Background technology
In the building-up process of dyestuff, usually use more naphthalene series dye intermediate, such as H-acid, K acid, J acid, γ-acid, tobias acid and G salt etc..Generally requiring the unit process through multiple steps such as persulfonic acid-nitrated-reduction-alkali fusion-acid outs in the process preparing naphthalene series dye intermediate, course of reaction complexity is tediously long, and not only the yield of product is relatively low, produces substantial amounts of acid waste water simultaneously.Produced waste water is often that highly acidity, high chroma, high salinity contain substantial amounts of Organic substance simultaneously, biology has stronger toxic, adopts traditional biochemical process very difficult degradation treatment again, bring great pressure to environment.Our country's volume of production of dyestuff and make consumption all occupy No. 1 in the world, it is therefore necessary to find the approach of Appropriate application H-acid waste water just to can help to the stable sound development of dyestuff and relevant Intermediates Industry.
A few days ago, the comprehensive control of environment has all been put into great energy by the whole nation from the leadership to the masses.Around the recovery of dye intermediate wastewater with utilize scientific research institutions at home, colleges and universities and enterprise all to do substantial amounts of specific works.
Publication CN102910853A describes a kind of method utilizing H-acid waste water reclamation liquid to produce naphthalene water reducer.The strip liquor obtained after complexometric extraction or resin absorption technique by H-acid production waste water or resin desorption liquid are added naphthalene water reducer condensation as additive and produce, neutralize reaction link, the prepared naphthalene series high-efficiency water-reducing agent conformed to quality requirements.The present invention opens the new way of H-acid liquid waste processing and comprehensive utilization, it is possible to effectively improve the pollution situation of H-acid industry, has both protected environment, makes again H-acid produce waste water and is comprehensively utilized, has good economic benefit and environmental benefit.
Publication CN102863053A discloses improvement and its recovery method as resource of washing waste water in 2-naphthalene ammonia-3,6,8-trisulfonic acid (K acid) production process.From waste water, overwhelming majority useful resources is separated and recovered, it is achieved the combination of waste water treatment and resource recycling by washing adsorption-desorption-recycling.
The method disclosing J acid wastewater comprehensive treatment and recycling in publication CN103896438A.During J acid is produced, remaining hydrolyzed waste water extracts and back extraction, it is thus achieved that Na2SO4And abstraction waste liquor, abstraction waste liquor is for the hydrolyzing process in J acid production process.
Publication CN105129955A relates to a kind of medicament processing waste water and using method thereof, the pre-treatment medicaments of waste water being specifically related in a kind of naphthalene series dye intermediate γ-acid production process to produce and the method using this chemicals treatment waste water.Use this chemicals treatment acid-bearing wastewater, can effectively reduce COD, BOD content in waste water, cost can also be greatly reduced in addition.
From disclosed patent discloses it can be seen that be directed in naphthalene series dye intermediate production process produced waste acid water and mostly carried out concentration, extraction/back extraction, resin absorption are then recycled.But actual recovered to Organic substance in composition extremely complex, and containing a certain amount of inorganic salts ingredients, it is difficult to be back to use in the dyestuff intermediate of certified products, just by the Organic substance of H-acid waste water reclamation for example, wherein containing the gas chromatographies such as H-acid, T acid, W acid, chromotropic acid, so complicated molecular structure is nearly impossible for the synthesis of dyestuff.And specific to concrete additive, mainly value itself on the dispersive property of cement and the impact on concrete strength, durability, purity requirement to polymer molecular structure is not high especially, add the Organic substance that is recovered in naphthalene series dye Intermediate Wastewater and mainly on naphthalene ring, introduce some characteristic groups, this Organic substance itself have stronger can condensation activity.Therefore, the Organic substance reclaimed in the waste water of naphthalene series dye intermediate is used for the synthesis of water reducer can yet be regarded as a kind of more satisfactory process approach.
Concrete chemical admixture is a kind of construction material emerging in recent years.Through development in recent years, concrete chemical admixture can be divided into diminishing component, setting time to regulate component, strength modified component and rheological characteristic adjustment component.Wherein maximum with diminishing component application quantity, lignin water reducer, naphthalene water reducer, sulfamate water reducer, melamine resin water reducer, aliphatic water reducing agent and polycarboxylate water-reducer can be divided into again.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of method of waste water synthesis modification sulfamate water reducer produced by utilization in Tobias-acid process, the comprehensive utilization principally for the naphthalene series dye Intermediate Wastewater being representative with tobias acid opens new approach.The water reducer prepared has that volume is low, dispersibility is strong, water-reducing rate is high, slump holding capacity is strong, concrete strength is high, and can increase substantially the feature in concrete service life.
In order to realize above-mentioned purpose, present invention employs following technical scheme:
A kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer, the method comprises the following steps:
1) the component C of quality accounting 25 ~ 60% component A, quality accounting 20 ~ 40% component B and quality accounting 15 ~ 55% is put in reaction bulb, described component A is for being evaporated concentration to waste water produced in Tobias-acid process, then utilizing solvent-extracted mode by organic facies therein and aqueous phase separation, isolated organic facies is neutralized back extraction and obtains corresponding Organic substance；Component B is sodium sulfanilate salt；Component C is the compound containing phenolic hydroxyl group；
2) adding water and be configured to the solution of 20 ~ 40% concentration, regulating solution ph by ionic membrane NaOH solution is between 7.5 ~ 9.5, is warming up to 60 ~ 70 DEG C, drips a certain amount of formaldehyde and carry out condensation and modification, and formaldehyde dropwises and is warming up to 95 ~ 100 DEG C of insulation reaction 3 ~ 20 hours；
3) enter molecule reforming phase after insulation, in molecule reforming process, when holding temperature is constant before this, regulates material pH value insulation reaction 1 ~ 10 hour by ionic membrane NaOH solution, namely obtain modified sulfamate water reducer.
As preferably, the compound of described phenolic hydroxyl group is phenol ,/hydroquinone, cresol, naphthols, bisphenol-A, bisphenol S, one or more mixture in high activity lignin.
As preferably, described to Organic substance in inorganic salt content not higher than 20%.
As preferably, described evaporation and concentration adopts MVR vaporizer, neutralizes and back extraction adopts 32% ionic membrane caustic soda.
As preferably, described step 2) in, the thing mass ratio of the amount of formaldehyde and component B is 2.0:1.0 ~ 5.5:1.0.
As preferably, described step 2) in, the insulation reaction time is 6 ~ 12 hours, it is preferable that 8 ~ 10 hours.
As preferably, in described step 3), the pH value regulating material is between 11.0 ~ 11.5.
As preferably, in described step 3), the insulation reaction time is 2 ~ 6 hours, it is preferable that 3 ~ 5 hours.
As preferably, described step 2) and step 3) in, ionic membrane NaOH solution adopts the ionic membrane NaOH solution of 32%.
Present invention also offers the modified sulfamate water reducer adopting above-mentioned any one method to prepare.
The major significance of the present invention is in that to accomplish to combine closely by the integrated disposal processing of waste acid water produced in dyestuff intermediate production process and the synthesis of water reducer, open the new way of dye intermediate wastewater comprehensive utilization, normal production for several dyestuff intermediates has cleared away obstacle, alleviates intermediate manufacturing enterprise and processes economic pressures and the ambient pressure of industrial wastewater.Simultaneously, it will the Organic substance received, for high performance water-reducer, reduces the cost of material of water reducer, promotes the market competitiveness of water reducer enterprise itself.The water reducer prepared has that volume is low, dispersibility is strong, water-reducing rate is high, slump holding capacity is strong, concrete strength is high, and can increase substantially the feature in concrete service life.
Specific embodiment
The present invention enumerates section Example and is intended to illustrate specific embodiment of the invention situation, but the protection domain of invention is not limited to embodiment.
Embodiment 1
The Organic substance 30g(wherein sodium sulphate content that will extract in tobias acid waste water: 13.2%), sodium sulfanilate 18g and phenol 32g puts in four mouthfuls of reaction flasks, add water 185g, warming while stirring, when temperature is increased to 45 DEG C, it is 8.8 that ionic membrane NaOH solution with 32% regulates solution ph, is continuously heating to 70 DEG C, and starts at this temperature to drip 37% formaldehyde 26.5g.Being warming up to 98 DEG C after formaldehyde dropwises, insulation reaction 8 hours, it is 11.2 that insulation reaction regulates material pH value by the ionic membrane NaOH solution of 32% after terminating, and 98 DEG C of insulation reaction 4 hours, reaction terminated.Being cooled to room temperature, namely discharging obtains modified sulfamate water reducer, is numbered ANS-01.
Embodiment 2
The Organic substance 22g(wherein sodium sulphate content that will extract in tobias acid waste water: 9.6%), sodium sulfanilate 15g and cresol 40g puts in four mouthfuls of reaction flasks, add water 175g, warming while stirring, when temperature is increased to 45 DEG C, it is 8.3 that ionic membrane NaOH solution with 32% regulates solution ph, is continuously heating to 70 DEG C, and starts at this temperature to drip 37% formaldehyde 30.5g.Being warming up to 98 DEG C after formaldehyde dropwises, insulation reaction 10 hours, it is 11.5 that insulation reaction regulates material pH value by the ionic membrane NaOH solution of 32% after terminating, and 98 DEG C of insulation reaction 3 hours, reaction terminated.Being cooled to room temperature, namely discharging obtains modified sulfamate water reducer, is numbered ANS-02.
Embodiment 3
The Organic substance 13g(wherein sodium sulphate content that will extract in tobias acid waste water: 5.8%), the Organic substance 16g(wherein potassium sulfate content extracted in G salt waste water: 8.6%), sodium sulfanilate 17g, bisphenol-A 40g and high activity lignin 5g puts in four mouthfuls of reaction flasks, and add water 210g, warming while stirring, when temperature is increased to 45 DEG C, it is 7.7 that ionic membrane NaOH solution with 32% regulates solution ph, is continuously heating to 70 DEG C, and starts at this temperature to drip 37% formaldehyde 34.6g.Being warming up to 100 DEG C after formaldehyde dropwises, insulation reaction 9 hours, it is 11.5 that insulation reaction regulates material pH value by the ionic membrane NaOH solution of 32% after terminating, and 100 DEG C of insulation reaction 5 hours, reaction terminated.Being cooled to room temperature, namely discharging obtains modified sulfamate water reducer, is numbered ANS-03.
Embodiment 4
The Organic substance 26g(wherein sodium sulphate content that will extract in tobias acid waste water: 9.6%), sodium sulfanilate 13g and bisphenol S 47g puts in four mouthfuls of reaction flasks, add water 195g, warming while stirring, when temperature is increased to 45 DEG C, it is 7.5 that ionic membrane NaOH solution with 32% regulates solution ph, is continuously heating to 70 DEG C, and starts at this temperature to drip 37% formaldehyde 30.8g.Being warming up to 100 DEG C after formaldehyde dropwises, insulation reaction 10 hours, it is 11.0 that insulation reaction regulates material pH value by the ionic membrane NaOH solution of 32% after terminating, and 100 DEG C of insulation reaction 4 hours, reaction terminated.Being cooled to room temperature, namely discharging obtains modified sulfamate water reducer, is numbered ANS-04.
Comparative example 1
Being put in four mouthfuls of reaction flasks by sodium sulfanilate 39g and phenol 34g, add water 165g, warming while stirring, when temperature is increased to 45 DEG C, it is 9.2 that ionic membrane NaOH solution with 32% regulates solution ph, is continuously heating to 70 DEG C, and starts at this temperature to drip 37% formaldehyde 48.5g.Being warming up to 100 DEG C after formaldehyde dropwises, insulation reaction 8 hours, reaction terminates.Being cooled to room temperature, namely discharging obtains modified sulfamate water reducer, is numbered BNS-01.
Comparative example 2
Being put in four mouthfuls of reaction flasks by sodium sulfanilate 39g and bisphenol-A 45.6g, add water 195g, warming while stirring, when temperature is increased to 45 DEG C, it is 7.6 that ionic membrane NaOH solution with 32% regulates solution ph, is continuously heating to 70 DEG C, and starts at this temperature to drip 37% formaldehyde 40.5g.Being warming up to 97 DEG C after formaldehyde dropwises, insulation reaction 8 hours, reaction terminates.Being cooled to room temperature, namely discharging obtains modified sulfamate water reducer, is numbered BNS-02.
By water reducer sample obtained with comparative example for modified sulfamate water reducer sample obtained in the various embodiments described above according to GB8077-2000 and GB876-2008 national standard, profit in south is used to reach cement PO.42.5, admixture dosage 0.4%(rolls over powder) carry out paste flowing degree and testing concrete performance, concrete test result is such as shown in table 1, table 2, and wherein test concrete mix is as follows.
Table 1 the property of neat cement grout is tested
Table 2 testing concrete performance
Can be seen that from the test data of table 1 and table 2, the organic synthesis modified sulfamate water reducer utilizing the salinity collected from Tobias-acid waste water relatively low has good cement dispersive property, concrete has the good slump holding capacity during application, and the intensity of concrete each age can be increased substantially.
Claims (10)
1. one kind utilizes the method for produced waste water synthesis modification sulfamate water reducer in Tobias-acid process, it is characterised in that the method comprises the following steps:
1) the component C of quality accounting 25 ~ 60% component A, quality accounting 20 ~ 40% component B and quality accounting 15 ~ 55% is put in reaction bulb, described component A is for being evaporated concentration to waste water produced in Tobias-acid process, then utilizing solvent-extracted mode by organic facies therein and aqueous phase separation, isolated organic facies is neutralized back extraction and obtains corresponding Organic substance；Component B is sodium sulfanilate salt；Component C is the compound containing phenolic hydroxyl group；
2) adding water and be configured to the solution of 20 ~ 40% concentration, regulating solution ph by ionic membrane NaOH solution is between 7.5 ~ 9.5, is warming up to 60 ~ 70 DEG C, drips a certain amount of formaldehyde and carry out condensation and modification, and formaldehyde dropwises and is warming up to 95 ~ 100 DEG C of insulation reaction 3 ~ 20 hours；
3) enter molecule reforming phase after insulation, in molecule reforming process, when holding temperature is constant before this, regulates material pH value insulation reaction 1 ~ 10 hour by ionic membrane NaOH solution, namely obtain modified sulfamate water reducer.
2. a kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer according to claim 1, it is characterized in that the compound of phenolic hydroxyl group is phenol ,/hydroquinone, cresol, naphthols, bisphenol-A, bisphenol S, one or more mixture in high activity lignin.
3. a kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer according to claim 1, it is characterised in that to Organic substance in inorganic salt content not higher than 20%.
4. a kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer according to claim 1, it is characterised in that evaporation and concentration adopts MVR vaporizer, neutralizes and back extraction adopts 32% ionic membrane caustic soda.
5. a kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer according to claim 1, it is characterised in that in step 2) in, the thing mass ratio of the amount of formaldehyde and component B is 2.0:1.0 ~ 5.5:1.0.
6. a kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer according to claim 1, it is characterised in that step 2) in, the insulation reaction time is 6 ~ 12 hours, it is preferable that 8 ~ 10 hours.
7. a kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer according to claim 1, it is characterised in that in step 3), the pH value regulating material is between 11.0 ~ 11.5.
8. a kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer according to claim 1, it is characterised in that in step 3), the insulation reaction time is 2 ~ 6 hours, it is preferable that 3 ~ 5 hours.
9. a kind of method utilizing in Tobias-acid process produced waste water synthesis modification sulfamate water reducer according to claim 1, it is characterised in that in step 2) and step 3) in, the ionic membrane NaOH solution of ionic membrane NaOH solution employing 32%.
10. the modified sulfamate water reducer that the method described in claim 1 ~ 9 any one claim prepares.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610110637.5A CN105753357A (en) | 2016-02-29 | 2016-02-29 | Method for synthesizing modified sulfamate water reducer by utilizing wastewater generated in tobias acid production process |
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| CN201610110637.5A CN105753357A (en) | 2016-02-29 | 2016-02-29 | Method for synthesizing modified sulfamate water reducer by utilizing wastewater generated in tobias acid production process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317357A (en) * | 2016-08-24 | 2017-01-11 | 安徽鑫固环保股份有限公司 | High-efficiency water-reducing agent of modified amino benzene sulfonic acid series of G sulfonic acid producing wastewater |
| CN106349445A (en) * | 2016-08-24 | 2017-01-25 | 安徽鑫固环保股份有限公司 | Modified sulfamic acid high efficiency water reducing agent prepared from 2-aminophenol-4-sulfonic acid production wastewater |
| CN106380558A (en) * | 2016-08-25 | 2017-02-08 | 安徽鑫固环保股份有限公司 | Naphthalene sulfonic acid dye intermediate waste liquid modified superplasticizer |
| CN107602788A (en) * | 2017-08-31 | 2018-01-19 | 浙江吉盛化学建材有限公司 | A kind of production technology of sulfamate water reducer |
-
2016
- 2016-02-29 CN CN201610110637.5A patent/CN105753357A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317357A (en) * | 2016-08-24 | 2017-01-11 | 安徽鑫固环保股份有限公司 | High-efficiency water-reducing agent of modified amino benzene sulfonic acid series of G sulfonic acid producing wastewater |
| CN106349445A (en) * | 2016-08-24 | 2017-01-25 | 安徽鑫固环保股份有限公司 | Modified sulfamic acid high efficiency water reducing agent prepared from 2-aminophenol-4-sulfonic acid production wastewater |
| CN106317357B (en) * | 2016-08-24 | 2018-09-28 | 安徽鑫固环保股份有限公司 | A kind of waste liquid modified aminobenzenesulfonic acid series high-efficiency water-reducing agent of G sulfonic acid production |
| CN106380558A (en) * | 2016-08-25 | 2017-02-08 | 安徽鑫固环保股份有限公司 | Naphthalene sulfonic acid dye intermediate waste liquid modified superplasticizer |
| CN106380558B (en) * | 2016-08-25 | 2019-05-10 | 安徽鑫固环保股份有限公司 | A kind of waste liquid modified high efficiency water reducing agent of naphthalene sulfonic dyestuff intermediate |
| CN107602788A (en) * | 2017-08-31 | 2018-01-19 | 浙江吉盛化学建材有限公司 | A kind of production technology of sulfamate water reducer |
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Application publication date: 20160713 |