CN1050109C - Method for refining waste sulfuric acid from alkylation - Google Patents
Method for refining waste sulfuric acid from alkylation Download PDFInfo
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- CN1050109C CN1050109C CN96109707A CN96109707A CN1050109C CN 1050109 C CN1050109 C CN 1050109C CN 96109707 A CN96109707 A CN 96109707A CN 96109707 A CN96109707 A CN 96109707A CN 1050109 C CN1050109 C CN 1050109C
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- acid
- sulfuric acid
- carclazyte
- alkylation
- water
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses a method for refining alkylation waste acid, after the alkylation waste acid is diluted with water, primary oil removal is carried out, and active carbon and white clay are used for carrying out secondary refining operation; a refining agent and the refined acid are separated out by simple filtration, the colorless transparent sulfuric acid of 25% is obtained and can be used for synthesizing FCC catalyst raw material and other chemicals, wherein the refining agent can be repeatedly used after regeneration. The present invention has the advantages of simple technology and no three-waste discharge.
Description
The present invention relates to a kind of process for purification of waste sulfuric acid from alkylation, specifically, the present invention relates to iso-butylene and Trimethylmethane addition and generate in the octane-iso process institute's depleted catalyzer---the process for purification of the vitriol oil.
The normal sulfuric acid that adopts is made catalyzer in the alkylation process, and the sulfuric acid concentration of industrial employing is 86-99%, when recycle sulfuric acid concentration is lower than 86%, needs to change eo-acid.Sulfuric acid consumption in the sulfuric acid process alkylation process accounts for the 5%-15% of alkylate oil substantially, and 60,000 tons/year alkyl plant year acid discharge amount as not dealing carefully with, can cause great harm to environment between 3000～9000 tons.
The difficulty that the alkylation spent acid utilizes, mainly be in the spent acid about 10% macromolecule organic, organic principal monomer is polymer alkene, diolefine, polymkeric substance and alkylsulphonic acid, sulfuric ester etc., these material colors are dark, quality thickness, smell stimulate, and are difficult to thoroughly remove from sulfuric acid.
Existing spent acid utilizes approach to have two substantially, 1. is used to make other chemical, commonly produces single superphosphate fertilizer with spent acid decomposing phosphate rock stone, general earlier spent acid being deoiled by dilution, reaction then, but because the oil removing measure is unfavorable, the chemical residues organism of producing is a lot, second-rate.2. by thermolysis is carried out in sulfur waste acid, reducing/regenerating, sulfuric acid finally are reduced into SO
2, the hydro carbons major part is condensed into coke.This technology investment is bigger, and unit scale will just have an economic benefit in time more than 3000 tons.
The object of the present invention is to provide a kind of organic method in the waste sulfuric acid from alkylation of thoroughly removing, the product water white transparency that obtains, organic content and suitable substantially by the organic content of the new sulfuric acid preparation of industry, can be used for synthetic different chemical, comprise the synthetic FCC catalyzer raw material that impurity is had relatively high expectations.
The treating process of spent acid among the present invention is divided into following several steps: 1. dilution: the water that will be equivalent to 2.2～2.8 times of vitriol oil weight slowly adds in the vitriol oil, and the water yield is fixed by dilution back acid concentration about 25%, and adding speed is not more than 85 ℃ of controls by the dilution temperature; 2. oil removing: after dilution is finished, leave standstill 8～12hr, nature or water-cooled cooling, most of organism floats on the surface in the acid, emits following acid solution, and the oil on surface can put together as fuel; 3. absorbent charcoal fine purification: the gac of 3.5～6.5% (weights) (is benchmark with 25% acid, down with) is added acid solution after the oil removing, stir 0.5～1hr, filter and tell gac and acid solution, gac anhydrates and washes regeneration; 4. clay-filtered: with the acid solution behind the acid particles carclazyte adding absorbent charcoal fine purification of 3～5% (weights), stir 0.5～1hr, temperature remains on 60～80 ℃, filters and tells carclazyte and acid solution, carclazyte anhydrates and washes regeneration, and acid solution is the water white transparency sulfuric acid of concentration about 25%.
Filter the gac and the carclazyte that produce and recycle, its regeneration condition is: the calcination of heating after the washing (the 2.5-5 times of water yield), calcination temperature 350-450 ℃, calcination time 0.5-1.5h.Gac and carclazyte are reusable at least more than five times.
Washing water in the regeneration returns spent acid dilution operation, as the spent acid dilution water.Corresponding to present spent acid treating processes, the present invention has significant advantage, has promptly thoroughly removed the organism in the acid,
Purification condition relaxes, and temperature is moderate, and technology is simple, and three-waste free discharge obtains concentration and be 25% water white transparency POV, with suitable substantially by 25% organic content of new sulfuric acid preparation, can be used for replacing new sulfuric acid to make various chemical.
Fig. 1 is the schema of the inventive method.
The present invention is further described with embodiment below in conjunction with accompanying drawing.
Embodiment:
The spent acid of 100Kg88% is added in the enamel still of 500 liters, and chuck leads to the cooling water circulation heat of removing, and the water of 252Kg is slowly added in the still again and stirs, control temperature in the kettle ≯ 85 ℃.
After adding water and finishing, material is put into 2M in the still
3In the subsider, left standstill 8 hours, sump tank is gone in surperficial oil reservoir overflow, and the acid after the oil removing is introduced in the 500 liter refining kettles (enamel still), meter 299Kg acid solution.
The gac that adds 18.7Kg (account for acid solution 6.25%) filters filter pressure ≯ 0.2Mpa, the acid solution 297kg after the filtration from being pressed into the sheet frame filter after stirring 0.5hr.
Add the granular carclazyte of 14.85kg (account for acid solution 5%), stirs after 0.5 hour and filter from being pressed into the sheet frame filter, filter pressure ≯ 0.2Mpa, filter afterwards liquid is the water white transparency sulfuric acid of 25% concentration.
Gac, carclazyte are used the water washing of 56.1kg (3 times of amounts of activated carbon) and 44.6kg (3 times of carclazyte amounts) respectively, have washed into Plate Filtration, and the sour water that leaches is got back to the dilution operation, the calcination of heating respectively of gac and carclazyte, 450 ℃ of calcination temperatures, calcination time 0.5hr recycles then.
Table 1 specific embodiment
* be regenerated carbon and regeneration carclazyte * * and be the new sulfuric acid preparation back result of industry
| Embodiment | The sulfur waste acid concentration | Outward appearance | Amounts of activated carbon | The granular carclazyte amount | Refining acid concentration | Outward appearance | KMnO 4Coloring reaction |
| 1 *2 *3 *4 **5 *6 *7 *8 | 83％ 86％ 88％ 86％ 99％ 86％ 86％ 88％ | Dark brown pitchy pitchy pitchy water white transparency black black black | 3.9％ 6.2％ 6.0％ 6.2％ / 5.O％ 3.8％ 6.0％ | 3％ 5％ 5％ 5％ / 5％ 5％ 3％ | 25.6％ 26.1％ 25.3％ 24.9％ 25.0％ 24.8％ 25.3％ 25.7％ | Water white transparency water white transparency water white transparency water white transparency water white transparency water white transparency water white transparency water white transparency | Qualified |
Claims (3)
1. the treatment process of a waste sulfuric acid from alkylation, it is characterized in that using activated carbon and granular carclazyte that spent acid is carried out twice makes with extra care, with 25% acid is benchmark, the gac add-on is 3.5～6.5% by weight percentage, extraction temperature normal temperature, 0.5～1 hour time, carclazyte add-on 3～5%, extraction temperature 60-80 ℃, refining 0.5～1 hour time, the sulfuric acid after making with extra care is 25% water white transparency acid.
2. method according to claim 1, it is characterized in that said gac and carclazyte can recycle after regeneration, at least more than 5 times, washing back calcination method is adopted in regeneration, the washing water yield is gac or carclazyte 2.5～5 times, 350～450 ℃ of calcination temperatures, calcination time 0.5～1.5 hour.
3. according to the described method of claim 2, it is characterized in that: the washing water in the regeneration returns spent acid dilution operation, as the spent acid dilution water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109707A CN1050109C (en) | 1996-09-04 | 1996-09-04 | Method for refining waste sulfuric acid from alkylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109707A CN1050109C (en) | 1996-09-04 | 1996-09-04 | Method for refining waste sulfuric acid from alkylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175550A CN1175550A (en) | 1998-03-11 |
| CN1050109C true CN1050109C (en) | 2000-03-08 |
Family
ID=5120539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109707A Expired - Fee Related CN1050109C (en) | 1996-09-04 | 1996-09-04 | Method for refining waste sulfuric acid from alkylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1050109C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425529C (en) * | 2003-12-22 | 2008-10-15 | 济南钢铁集团总公司 | Treating technology for regenerated acid in coking crude benzole refinery process |
| CN1309657C (en) * | 2004-10-10 | 2007-04-11 | 武汉科技大学 | Method for preparing purified acid from waste-acid after benzene refinery |
| DE102005049084A1 (en) * | 2005-10-13 | 2007-04-26 | Wacker Chemie Ag | Process for the regeneration of sulfuric acid |
| CN106477778A (en) * | 2016-11-29 | 2017-03-08 | 中冶华天工程技术有限公司 | Alkylation spent acid is used for the method and system that Fenton oxidation processes waste water |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767008A (en) * | 1980-10-07 | 1982-04-23 | Asahi Chem Ind Co Ltd | Treatment of waste sulfuric acid containing organic sludge |
-
1996
- 1996-09-04 CN CN96109707A patent/CN1050109C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767008A (en) * | 1980-10-07 | 1982-04-23 | Asahi Chem Ind Co Ltd | Treatment of waste sulfuric acid containing organic sludge |
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| Publication number | Publication date |
|---|---|
| CN1175550A (en) | 1998-03-11 |
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