CN102311893B - Production process for comprehensive cyclic utilization of sulfonation by-product nigrotic acid - Google Patents
Production process for comprehensive cyclic utilization of sulfonation by-product nigrotic acid Download PDFInfo
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- CN102311893B CN102311893B CN2011102320015A CN201110232001A CN102311893B CN 102311893 B CN102311893 B CN 102311893B CN 2011102320015 A CN2011102320015 A CN 2011102320015A CN 201110232001 A CN201110232001 A CN 201110232001A CN 102311893 B CN102311893 B CN 102311893B
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Abstract
The invention discloses a production process for comprehensive cyclic utilization of the sulfonation by-product nigrotic acid. The process comprises the following steps: 1) adding caustic soda into nigrotic acid for a neutralization reaction so as to allow a surfactant in nigrotic acid to turn to a sodium salt of the surfactant and waste sulfuric acid in nigrotic acid to turn to a raw material for a washing agent, i.e., mirabilite; 2) bleaching the resultant of neutralization of nigrotic acid with a sodium hypochlorite solution; 3) adding clear water into the bleached solution and carrying out spray drying; 4) adding soda ash or 4A zeolite into a product obtained after spray drying for granulation. Nigrotic acid treated with the process provided in the invention turns into particles, main components of which are a surfactant, mirabilite and soda ash, and the particles are extensively applied in washing agents, thereby utmostly realizing utilization of the waste, conservation of cost and a good environmental protection effect.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of production technique of sulfonation by product nigrotic acid comprehensive reutilization.
Background technology
Tensio-active agent is a main raw material of producing products such as washing composition, shampoo, makeup, when the sulfonation production of tensio-active agents such as sulfonic acid, AOS, AES, contains organic mist particle, SO in the tail gas
2, SO
3Deng material, adopt electrostatic precipitator can the organic particle in the tail gas be removed effectively.Because organism is by the over-drastic sulfonation; The color of the by product that comes out is very dark; The spent acid of receiving from electrostatic precipitator (0.1%-0.4% that occupies the machine raw material) generally be black and also form unstablely, these by products can not directly utilize basically, are referred to as nigrotic acid.And the sulfonation production of by-products, environmental protection having been produced very big influence, can not directly discharge, so also must handle these by products.
At present at home following several kinds of modes are generally adopted in the processing of nigrotic acid:
1, the acid sludge of professional production factory is discarded: unlikely when the producer that produces waste material has a responsibility for guaranteeing blowdown operator, the public or environment are worked the mischief.This just requires the abandoned areas of allowance, can be competent at and reliable waste disposal contractor, and special tags etc. is arranged.This method does not have very big investment, increases gradually but shortcoming is an expense, and environmental stress, waste material are formed the accident hazard in explanation and the transportation etc.
2, the on-site incineration of AR: acid electrostatic precipitator residue only accounts for a spot of company and requires incineration residue in some specialized company or those waste materials.
The mode that the specialty that the processing of external spent acid residue is also adopted is burned; Still environment is had very big influence but burn the waste gas that is produced, a kind of in addition processing mode is a biochemical processing process, and the occupation of land scope is very big; The used device more complicated, investment and working cost are all very high.
Domestic SO
3The nigrotic acid that xanthator produced has few part doing neutralization, and after the simple bleaching processing, extracts sodium alkyl benzene sulfonate wherein.But few people will pass through the product of neutralization and bleaching processing and directly use; Because it is saltcake and sodium-chlor that nigrotic acid reclaimed materials after treatment contains the inorganic salt of 15-30%; And the content of moisture is also about 30-50%; Add-on is too much in liquid washing agent, and inorganic salt content also increases thereupon, makes detergent product produce layering; And add-on is too much in solid detergent, because moisture content is high, will make the solid phase prod flowability extreme difference that becomes, and has also reduced the aesthetics of product.
Make the application of handling the back product receive great restriction just because of material moisture in the nigrotic acid by product treating processes is higher; The present invention adopts guide's drying plant LPG-9 type centrifugal spray dryer that material is carried out spraying drying; With the extruding type tablets press material is carried out granulation then, expanded the space that utilizes of sulfonation by product greatly.
Through analytical test, contain the tensio-active agent of 40-50%, the sulfuric acid of 20-30% in the composition of sulfonation by product, if can sulfonated products be handled, can be used as the activeconstituents of washing composition and be used; It is a kind of washing auxiliary detergent with many-sided purposes.The staple of this washing auxiliary detergent is tensio-active agent and inorganic additive; Have emulsifying power, detersive power and excellent dispersion of calcium soap preferably; Soluble in water; Biological degradability is good, can be widely used in aspects such as powdered detergent, soap, textile and dyeing industry, petrochemical industry, oil recovery, industry cleaning.
Summary of the invention
The purpose of this invention is to provide a kind of new sulfonation by product and handle the production technique that reclaims; Having become staple after nigrotic acid handled is the particle of tensio-active agent, saltcake and soda ash; And this particle is extensive in the extreme in detergent application, has realized utilization of waste material, cost savings and environmental protection effect preferably largely.
A kind of production technique of sulfonation by product nigrotic acid comprehensive reutilization may further comprise the steps:
1) at first caustic soda is joined and carry out neutralization reaction in the nigrotic acid, make the tensio-active agent in the nigrotic acid become its sodium salt, make the sulfur waste acid in the nigrotic acid become the detergent raw material saltcake;
2) in the nigrotic acid with after product bleach with the chlorine bleach liquor; Nigrotic acid solution after the bleaching is maroon, and it is very shallow that color has become.
3) to carrying out spraying drying behind the adding of the solution after the bleaching clear water.
4) material adding soda ash or the 4A zeolite that obtains after the spraying drying carried out granulation.
The nigrotic acid that described nigrotic acid produces when comprising the sulfonation production of sulfonic acid, AOS or AES.
PH value with after product during step 1) is described is 7-10.The temperature of control neutralization reaction is at 50-80 ℃.
Temperature when step 2) bleaching is no more than 50 ℃.Control chlorine bleach liquor's adding speed does not make reaction too violent, and the PM add-on is the 1-2% of chlorine bleach liquor's total amount.
Add clear water in the step 3); The mass content of the total solid matters of control solution is at 40-60%; Spray-dired temperature remains on 80-95 ℃, and the water cut of dry back material comes out to be the fine particle of particle diameter at the 50-200 micron at 1-10% through centrifugal spraying drying.
With drying plant LPG-9 type centrifugal spray dryer material is carried out spraying drying.With peristaltic pump nigrotic acid solution is slowly joined in the drying machine with centrifugal spray, keep certain flow.
The dried product of the present invention is a buff powder; Density is less; Be not easy to the use of product; Buff powder is added behind the part soda ash with GL4-100 non-slurry pelletizing machine, utilize that contained crystal water carries out the extruding type granulation in the powder, the adding quality of soda ash or 4A zeolite is the 10-20% of the material that obtains after the spraying drying; The particle diameter of granulation is 0.3-2mm.Material density after the granulation is bigger, in air, is difficult for suction.
The present invention is a comprehensive recovery processing technique of being produced washing auxiliary detergent by nigrotic acid through neutralization, bleaching, spraying drying, non-slurry pelletizing.Making full use of the sulfonation by product on the one hand is raw material, the particle that the washing auxiliary detergent that makes mainly is made up of tensio-active agent, saltcake, soda ash, and gross activity thing content is greater than 35%, and moisture content is less than 5%; Be added in the detersive power that can improve washing composition in the washing composition, perhaps can reduce the consumption of detergent surfactant, cost economizes in raw materials; On the other hand, the direct discharged in burning of avoiding nigrotic acid with stack environmental pollution and the processing cost problem that causes such as bury.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1:
1, the solid caustic soda of claiming 1Kg, and caustic soda is made into 30% solution for standby;
2, with the sulfonic acid nigrotic acid with take by weighing 5Kg mixing acid after the AOS nigrotic acid mixed by 4: 6, moulding in the bucket of 25Kg, lentamente caustic soda is added and ceaselessly stirs, controls reaction speed is to prevent temperature too high (about 60 ℃) and to prevent swollen material;
The pH value of back with pH test paper survey liquid material diluted in sampling in moulding bucket, and it is 7-10 that the object in moulding bucket becomes pH neutral, and neutralization reaction stops to add caustic soda when accomplishing; Make the tensio-active agent in the nigrotic acid become its sodium salt, make the sulfur waste acid in the nigrotic acid become the detergent raw material saltcake;
3, place for some time and will mould that material is cooled to 40 ℃ in the bucket; Carry out bleaching action again, can make the effect of bleaching better, do not stopping to add chlorine bleach liquor's (mass concentration 10%) under the condition of stirring lentamente; And the speed of control reaction; To prevent the too high and swollen material of material temperature, probably add the chlorine bleach liquor about 3Kg after, bleaching action is accomplished;
When 4, the material color after the bleaching is not so good, adds a spot of Youxiaolin again and bleach, can place subsequent use during as if good colors;
5, the mass content of the total solid matters of the Material control solution of bleaching processing is at 40-60%; Add colorants such as needed light blue or famille rose if necessary therein; Squeeze into spray-drier with peristaltic pump and dry processing; Spray-dired temperature remains on 80-95 ℃, becomes water cut and be about 5% powder material, and particle diameter is at the 50-200 micron;
6, powder material is added soda ash or the 4A zeolite of 10-20wt%, carry out granulation with LG4-100 non-slurry pelletizing machine, the particulate size is produced the used particulate state washing auxiliary detergent REA of washing composition at 0.3-2mm.
Embodiment 2:
1, the application in washing powder
Because nigrotic acid of the present invention recycling back material contains high actives, can all or part of alternative sulfonic acid and other tensio-active agent in washing powder, can reduce cost like this, improve the scourability of product.Detergency test shows that sodium alkyl benzene sulfonate (LAS) and washing auxiliary detergent REA be both mass ratioes 4 in containing phosphorus powder: all show good synergism between the 1-5, LAS: REA is the most remarkable, as shown in the table 4: 3 o'clock synergies.
| LAS and REA ratio | Do not add REA | 4∶1 | 4∶2 | 4∶3 | 4∶4 | 4∶5 |
| The detersive power contrast | Be 1 relatively | 1.05 | 1.1 | 1.15 | 1.1 | 1.05 |
Be in the non-phosphide detergent of anion active composition with LAS and REA, when the mass ratio that REA accounts for the anion active component was 30-50%, decontamination significantly improved.The decontamination synergy of washing auxiliary detergent REA in non-phosphide detergent is than showing more outstandingly in containing phosphorus powder, and the quality consumption of REA in phosphorous and non-phosphide detergent is 10-20%.
2, the application in soap
Soap generates insoluble soap scum in hard water, influence clean effect.Add the REA washing auxiliary detergent solubleness of soap in water is improved, soap lye wetting power and foam power at low temperatures also improves rapidly thereupon.In the perfumed soap that with the sodium soap is major ingredient, add the washing auxiliary detergent REA of 5-20wt%, the various characteristics of perfumed soap improves, and foaming power strengthens, and resistance to hard water improves, and snappiness strengthens, and is not easy to crack.
Foaming power (mm, the activity concentration: 1g.L of different ratios washing auxiliary detergent REA in different hard water
-1) as follows:
| REA adds per-cent | Do not add REA | 5％ | 10％ | 15％ | 20％ |
| CaCO 3Content 100mg.kg -1 | ?40 | 50 | 55 | 60 | 60 |
| CaCO 3Content 200mg.kg -1 | ?10 | 20 | 30 | 35 | 40 |
3, the application in hard surface cleaner
Washing auxiliary detergent REA product is specially adapted to the cleaning of crust, owing to wherein contain the higher surface activity agent, a large amount of inorganic additives can directly apply to the decontamination of crust, and the content in hard surface cleaner is 10-30wt%.
4, the application in the kitchen surface stain remover
Washing auxiliary detergent REA has the high-efficient washing performance for the decontamination of kitchen surface, earlier with greasy dirt emulsification, under the interaction of tensio-active agent and inorganic assistant agent, easily greasy dirt is cleaned again.Content in the kitchen surface stain remover is 10-30wt%.
Claims (8)
1. the production technique of a sulfonation by product nigrotic acid comprehensive reutilization is characterized in that may further comprise the steps:
1) at first caustic soda is joined and carry out neutralization reaction in the nigrotic acid, make the tensio-active agent in the nigrotic acid become its sodium salt, make the sulfur waste acid in the nigrotic acid become the detergent raw material saltcake;
2) in the nigrotic acid with after product bleach with the chlorine bleach liquor;
3) to carrying out spraying drying behind the adding of the solution after the bleaching clear water;
4) material adding soda ash or the 4A zeolite that obtains after the spraying drying carried out granulation;
Add clear water in the step 3), the mass content of the total solid matters of solution was at 40-60% after the control bleaching was handled;
Spray-dired temperature remains between 80-95 ℃ in the step 3), and the water cut of dry back material comes out to be the fine particle of particle diameter at the 50-200 micron at 1-10% through centrifugal spraying drying.
2. production technique according to claim 1 is characterized in that: the nigrotic acid that described nigrotic acid produces when comprising sulfonic acid, AOS or AES sulfonation production.
3. production technique according to claim 1 is characterized in that: step 1) obtain in and the pH value of after product be between the 7-10.
4. according to claim 1 or 3 described production technique, it is characterized in that: the temperature of control neutralization reaction is at 50-80 ℃.
5. production technique according to claim 1 is characterized in that: step 2) temperature in when bleaching is no more than 50 ℃.
6. according to claim 1 or 5 described production technique, it is characterized in that: control chlorine bleach liquor's adding speed, the PM add-on is the 1-2% of chlorine bleach liquor's total amount.
7. production technique according to claim 1 is characterized in that: the adding quality of step 4) soda ash or 4A zeolite is the 10-20% of the material that obtains after the spraying drying.
8. production technique according to claim 1 is characterized in that: the particle diameter of step 4) granulation is 0.3-2mm.
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| CN2011102320015A CN102311893B (en) | 2011-08-12 | 2011-08-12 | Production process for comprehensive cyclic utilization of sulfonation by-product nigrotic acid |
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| CN2011102320015A CN102311893B (en) | 2011-08-12 | 2011-08-12 | Production process for comprehensive cyclic utilization of sulfonation by-product nigrotic acid |
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| CN102311893A CN102311893A (en) | 2012-01-11 |
| CN102311893B true CN102311893B (en) | 2012-11-07 |
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| CN104451714B (en) * | 2014-12-05 | 2017-02-22 | 浙江赞宇科技股份有限公司 | Production process and production device for preparing industrial additives from electrostatic acid and application thereof |
| CN109750301A (en) * | 2017-11-06 | 2019-05-14 | 南风化工集团股份有限公司 | A method of metal cleaner is produced using sulfonation black sulfonic acid |
| CN109437645B (en) * | 2018-12-17 | 2021-04-13 | 赞宇科技集团股份有限公司 | Method for preparing mortar additive from organic acid serving as sulfonation byproduct |
| CN115612572A (en) * | 2022-07-14 | 2023-01-17 | 南京华狮新材料有限公司 | Application of amino acid surfactant in production of separated water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811993A (en) * | 2010-05-05 | 2010-08-25 | 中国日用化学工业研究院 | Process for preparing fatty acid ester sulfonate |
| US20110147963A1 (en) * | 2009-12-18 | 2011-06-23 | Larry Savio Cardozo | Spray-Drying Process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63309597A (en) * | 1987-06-11 | 1988-12-16 | Lion Corp | Granular detergent composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110147963A1 (en) * | 2009-12-18 | 2011-06-23 | Larry Savio Cardozo | Spray-Drying Process |
| CN101811993A (en) * | 2010-05-05 | 2010-08-25 | 中国日用化学工业研究院 | Process for preparing fatty acid ester sulfonate |
Non-Patent Citations (2)
| Title |
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| JP昭63-309597A 1988.12.16 |
| 刘景明等.高浓度苯磺酸甲酯废水处理方法的研究.《环境科学研究》.1997,第10卷(第6期), * |
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Effective date of registration: 20160825 Address after: 201500 No. 6388 Jinshan Road, Shanghai, Jinshan District Patentee after: Shanghai Aowei Chemical Co. Ltd. Address before: 410003 No. 1 Liuyang Road, Changsha, Hunan Patentee before: Hu'nan Licheng Industrial Co., Ltd. |