CN102732396B - Method for comprehensive utilization of dominant bath type continuous sulfonation waste acid - Google Patents
Method for comprehensive utilization of dominant bath type continuous sulfonation waste acid Download PDFInfo
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- CN102732396B CN102732396B CN 201210206624 CN201210206624A CN102732396B CN 102732396 B CN102732396 B CN 102732396B CN 201210206624 CN201210206624 CN 201210206624 CN 201210206624 A CN201210206624 A CN 201210206624A CN 102732396 B CN102732396 B CN 102732396B
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Abstract
The invention which discloses a method for the comprehensive utilization of a dominant bath type continuous sulfonation waste acid relates to the technical fields of sulfonation and the comprehensive utilization of waste liquids. A technology for producing alkyl benzene sulfonic acid through adopting alkyl benzene sulfonic acid allows a large amount of the waste acid to be generated, the waste acid has a low concentration, a brownish yellow color, and is difficult to recycle, the cost for separating acids in the waste acid one by one is very high, and the cost of an alkaline solution consumed for neutralizing the waste acid for later discharge is very high. The invention which aims at above problems existing in the prior art provides a method for producing a sanitary ware cleaning agent through the comprehensive utilization of the dominant bath type waste acid. The method comprises the following steps: adding sodium hypochlorite to the waste acid to decolor; and adding thiourea, citric acid, aluminum sulfate, a pigment and water to prepare the sanitary ware cleaning agent with the oil removal and scaling effects. The method allows the sulfonation waste acid to be comprehensively utilized, has a simple and economic process, and has good economic and social benefits.
Description
Technical field
The present invention relates to sulfonation, spent acid comprehensive utilization and clean-out system technical field.
Technical background
Sodium alkyl benzene sulfonate has good surfactivity and anti-hard water, is widely used in the industry such as textile printing and dyeing and washing composition.The production method of sodium alkyl benzene sulfonate is: alkylbenzene generates alkyl benzene sulphonate (ABS) through sulfonation, then makes with the sodium hydroxide neutralization.
the continuous sulfonation method of dominant bath is with oleum, alkylbenzene is the sulfonation reaction that raw material carries out in the sulfonation pump, mainly that in oleum, the absorption sulphur trioxide reacts with alkylbenzene, the trans-utilization rate of sulfuric acid is low, sulfuric acid excessive in the alkyl benzene sulphonate (ABS) that generates after reaction and reaction forms homogeneous mixture, be difficult to separate, add a certain amount of water in mixture, after making sulfuric acid concentration be reduced to weight percent 65%～70%, be divided into gradually two-phase, the upper strata is alkyl benzene sulphonate (ABS), lower floor is 65%～70% sulfuric acid for containing weight percent, the mixing spent acid of 4%～5% alkyl benzene sulphonate (ABS) 25%～31% water.The concentration of mixing spent acid is low, and color presents brown color, is difficult to utilize will use in alkali and rear discharging.
The exploitation of sulphur trioxide film sulfonation reactor and use have solved and have produced the problem of spent acid in the sulfonation process.Sulphur trioxide membrane-type sulfonation method is to react in film sulfonation reactor take sulphur trioxide, alkylbenzene as raw material, the transformation efficiency of this reaction sulphur trioxide is high, without discharging of waste liquid, but facility investment is large, sulphur trioxide film sulfonation reactor and support equipment gross investment 6,000,000 yuan of left and right.Though the continuous sulfonation method of dominant bath has a large amount of spent acid dischargings, equipment is simple, and less investment, a complete set of equipment are counted roughly 7～80,000 yuan, and most enterprises still adopt the continuous sulfonation method of dominant bath to produce alkyl benzene sulphonate (ABS).
The spent acid solution concentration that produces in the continuous sulfonation method of dominant bath is produced is low, and look presents pale brown, can't utilize for a long time always, the processing before discharging spent acid by the method that adds the alkali neutralization.So far yet there are no the open source information that described spent acid is effectively processed or fully utilized.
Other for the treatment process that contains other composition spent acid are: Chinese patent application number is in 86101738.2, for the disclosed method of utilizing of the spent acid of sulfuric acid alkylation be: with acid sludge direct heating, filtration, the concentrated vitriol oil of producing, and first acid sludge is hydrolyzed, static layering obtains dilute sulphuric acid, dilute sulphuric acid can be used the attached absorption method of gac or phenol extraction process decolouring and deodorizing, then the dilute sulphuric acid heating is concentrated or produces the vitriol oil with hot carrier gas direct heating.The method that heating is concentrated be that the gasification of the moisture in waste liquid is concentrated, so energy consumption is large, and operating process is after concentration reaches more than 80 ℃, and the large a large amount of bubbles of liquid viscosity have little time release and can cause excessively, want therefore that stopped heating is repeated multiple times to carry out.
Number be in 200410077926.7 by the spent acid treatment process in Chinese patent application, make Waste Sulfuric Acid cracking under 1000～1100 ℃ of high temperature, transform and twice absorption through acid-scrubbing cleaning, twice contact process, produce qualified sulfuric acid product, the raw material that technological process is used is single 85～90% waste sulfuric acid from alkylation, and the Waste Sulfuric Acid rate of recovery can reach 90%.There is the large problem of energy consumption equally in this technique.
The method of alkylation sulphuric acid refine in being 96109707.8 Chinese patent, application number is disclosed, after alkylation spent acid dilute with water, and preliminary oil removing, then adopt gac and carclazyte to carry out secondary refining; By simple filtration, the acid after telling finishing agent and making with extra care obtains 25% water white transparency sulfuric acid.As everyone knows, the sulfuric acid of high density has strong oxidizing property, forms fine and close oxide film with the iron reaction, thus stoped the corrosion of sulfuric acid for iron, therefore available tank car transportation, large-scale iron flask stores, thereby the storage transportation cost is low.And 25% sulfuric acid will be packed with plastic tank usually to the seriously corroded of iron, and the sulphur acid meter with 100% needs the plastic tank packing charge, at least also want 600 yuan of left and right, and 98% sulfuric acid price is 550～620 yuan/tons.
Summary of the invention
The objective of the invention is to overcome and produce a large amount of spent acid in the continuous sulfonation process of prior art dominant bath, investment improvement in addition, and a kind of simple and economic method of comprehensive utilization that proposes.
thinking of the present invention is, spent acid described in background technology is to contain weight percent to consist of 65%～70% sulfuric acid, the mixing spent acid of 4%～5% alkyl benzene sulphonate (ABS) 25%～31% water, alkyl benzene sulphonate (ABS) and alkyl benzene sulphonate (ABS) sodium salt have equally surfactivity and anti-hard water is strong, can be used in the alternative alkylbenzene sulfonate of sour environment and make clean-out system, sulfuric acid has very strong scale removal effect, can be used as scale remover, by adding the clorox decolouring, improve the spent acid outward appearance, and clorox has the sterilization and disinfection effect, add again the inhibiter thiocarbamide, citric acid, buffer reagent Tai-Ace S 150 can be mixed with the higher sanitary ware clean-out system of added value with cleaning and descaling effect, urinal toilet tailored version clean-out system specifically, thereby each component of described spent acid all is fully utilized.(with reference to QB/T 21241-2007 sanitary ware clean-out system current standards)
Technical scheme of the present invention is characterized in that, adds clorox, thiocarbamide, citric acid, Tai-Ace S 150, pigment, water to be mixed with the sanitary ware clean-out system in the spent acid of the continuous sulfonation of dominant bath.Described pigment is preferentially selected light blue.
In the sanitary ware clean-out system, the weight percent of each material forms table
Beneficial effect of the present invention
1, solved the sulfonation liquid waste disposal problem that people for a long time thirst for solving, saved spent acid and process spending;
2, utilize the alkyl benzene sulphonate (ABS) in spent acid to save production sanitary ware clean-out system dosage of surfactant, reduce sanitary ware clean-out system production cost;
3, technique simple device less investment only increases the acidproof tank that a band stirs;
4, produce part material spending and the spending of saving waste acid treatment that sanitary ware clean, economic benefit and social benefit are remarkable;
5, along with the differentiation of village urbanization, residence building, the demand of sanitary ware clean-out system constantly increases, and the sanitary ware clean-out system that method of the present invention is produced has the stronger market competitiveness with its low production cost.
In the spent acid per ton table of reducing expenses
To produce sanitary ware clean-out system raw materials cost per ton and product indication pricing schedule
Market sanitary ware clean-out system price contrast table
Description of drawings
Accompanying drawing is the continuous sulfonation of dominant bath and spent acid comprehensive utilization process figure.
In accompanying drawing: 1 spinner-type flowmeter, 2 alkylbenzene pipes, 3 oleum acid tubes, 4 sulfonation pumps, 5 nitration mixture pipe I, 6 acidproof condensers, 7 digestors, 8 nitration mixture pipe II, 9 water inlet pipes, 10 minutes sour pumps, 11 acid distributing tubes, 12 graphite condensers, 13 nitration mixture pipe III, 14 minutes sour tanks, 15 sulfonic acid pipes, 16 spent acid pipes, 17 retort, 18 impurity vent pipes, 19 finished product vent pipes.
Embodiment
The present invention will be further described with reference to accompanying drawing
The method of the spent acid comprehensive utilization that the continuous sulfonation of dominant bath produces is, the spent acid of the generation of the continuous sulfonation of dominant bath, put into retort from the bottom spent acid pipe of minute sour tank, under constantly stirring, after adding successively entry, clorox, thiocarbamide, citric acid, Tai-Ace S 150, pigment and fully dissolving, be mixed with the sanitary ware clean-out system.
Concrete formula " the enforcement formula table that spent acid prepares special-purpose midwifery sanitary equipment clean-out system " the described formula group that sees the following form of implementing all becomes weight percent and forms.
Spent acid prepares the enforcement formula table of special sanitary sanitary equipment clean-out system
Detect quality and QB/T 21241-2007 current standards contrast table
The known technology in field under being except the disclosed technology of specification sheets.
Claims (2)
1. the method for the spent acid comprehensive utilization that produces of the continuous sulfonation of dominant bath, it is characterized in that, the spent acid that produces in the continuous sulfonation process of dominant bath is by the spent acid pipe of minute sour pot bottom, put into retort, under constantly stirring, adding successively entry, clorox, thiocarbamide, citric acid, Tai-Ace S 150, pigment fully dissolves, be mixed with the sanitary ware clean-out system, the weight percent of various raw materials consists of: spent acid 21% ~ 23%, clorox 1% ~ 2%, thiocarbamide 1.5% ~ 2%, citric acid 1% ~ 2%, Tai-Ace S 150 3% ~ 5%, pigment 0.0001% ~ 0.00015%, water surplus.
2. the method for the spent acid comprehensive utilization of the continuous sulfonation generation of dominant bath as claimed in claim 1, is characterized in that the preferred light blue of pigment.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210206624 CN102732396B (en) | 2012-06-18 | 2012-06-18 | Method for comprehensive utilization of dominant bath type continuous sulfonation waste acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201210206624 CN102732396B (en) | 2012-06-18 | 2012-06-18 | Method for comprehensive utilization of dominant bath type continuous sulfonation waste acid |
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| CN102732396A CN102732396A (en) | 2012-10-17 |
| CN102732396B true CN102732396B (en) | 2013-06-05 |
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| CN 201210206624 Expired - Fee Related CN102732396B (en) | 2012-06-18 | 2012-06-18 | Method for comprehensive utilization of dominant bath type continuous sulfonation waste acid |
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| CN114516822B (en) * | 2022-03-07 | 2023-06-02 | 运城学院 | Refining and recycling method for waste sulfonic acid generated by sulfonation of alkylbenzene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311888A (en) * | 2011-08-12 | 2012-01-11 | 湖南丽臣实业股份有限公司 | Washing assistant produced from sulfonation byproduct nigrotic acid and application thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311888A (en) * | 2011-08-12 | 2012-01-11 | 湖南丽臣实业股份有限公司 | Washing assistant produced from sulfonation byproduct nigrotic acid and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘长春等.硫酸法钛白粉副产废酸的综合利用.《焦作大学学报》.2002,(第2期),第12-15页. |
| 硫酸法钛白粉副产废酸的综合利用;刘长春等;《焦作大学学报》;20020630(第2期);第12-15页 * |
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| CN102732396A (en) | 2012-10-17 |
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