CN1158320A - Method for reclaiming waste keto-acid liquid in prodn. of soluble gluside - Google Patents
Method for reclaiming waste keto-acid liquid in prodn. of soluble gluside Download PDFInfo
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- CN1158320A CN1158320A CN 96115122 CN96115122A CN1158320A CN 1158320 A CN1158320 A CN 1158320A CN 96115122 CN96115122 CN 96115122 CN 96115122 A CN96115122 A CN 96115122A CN 1158320 A CN1158320 A CN 1158320A
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- waste liquid
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Abstract
A process for reclaiming the copper-contained waste acidic liquid generated during production of sodium saccharide includes filtering, vacuum distillation, condensing distilled gas to recover hydrochloric acid and cooling residual distilled liquid to recover copper sulfate crystal and sulfuric acid, and features effective separation, reuse of recovered materials in production of sodium saccharide and eliminating environmental pollution.
Description
The present invention relates to processing method of industrial waste water, particularly the method that the waste liquid that contains copper, sulfuric acid and hydrochloric acid that discharges in the soluble saccharin production is recycled.
At present, industrial production soluble saccharin generally adopts phthalic anhydride method production technique.This technology is to get adjacent formamide benzene sodium formiate (abbreviation acid amides) with benzene feedstock dicarboxylic acid anhydride and ammoniacal liquor, sodium hydroxide effect, hypochlorous sodium and methyl alcohol are degraded and esterification, generate diazonium salt with the Sodium Nitrite effect again, under mantoquita catalysis, get adjacent SULPHURYL CHLORIDE methyl benzoate then, through making finished product with the ammoniacal liquor reaction of sodium bicarbonate with sulfurous gas, chlorine effect.Wherein after diazotization, generate adjacent diazobenzene methyl-formiate, under the katalysis at copper sulfate in the sulfuric acid of certain acidity and hydrochloric acid mixed solution, generate adjacent-sulfinic acid methyl benzoate with the sulfurous gas reaction that feeds, produce the spent acid solution that cupric ion is arranged in this process, 1 ton of soluble saccharin of every production produces 4 tons of this keto-acid containing waste liquids approximately.Contain the copper of 1-1.3%, the hydrochloric acid of 10-13% and the sulfuric acid of 7-10% in the waste liquid.A soluble saccharin factory that produces 1700 tons per year, annual about 6800 tons of the keto-acid containing waste liquid that produces, wherein cupric is about 80 tons, and 800 tons in hydrogenchloride is amounted to 2600 tons of technical hydrochloric acids, about 600 tons of sulfuric acid.Producer does not directly discharge this waste liquid owing to there is practicable recovery and treatment method at present, both environment has been caused severe contamination, and a large amount of resources is wasted.Therefore, the recovery and treatment method of inquiring into this class waste liquid has very big economy and social effect.
Up to now, the method of the above-mentioned keto-acid containing waste liquid of the processing of public use once has two kinds: a kind of is electrolytic process, by electrolysis the form of the copper in the waste liquid with simple substance reclaimed, sour then reclaim with the form of nitration mixture, this method is because of complex process, and current consumption is big, and cost recovery is high and have chlorine to produce, cause secondary pollution, thereby limited it and applied; Another kind method is the iron reduction method, with copper reduction, makes copper obtain reclaiming with the simple substance form with iron, and remaining acid solution is ferrous because of sulfur acid, can't utilize, still will be as discharging of waste liquid, and contaminate environment, so though this method is simple, but still inadvisable.
The objective of the invention is to avoid above-mentioned the deficiencies in the prior art part and provide a kind of soluble saccharin produce in the recovery and treatment method of keto-acid containing waste liquid, with this method recycling keto-acid containing waste liquid, technology is simple, useful composition in the waste liquid all can be recycled, do not reproduced into secondary environmental pollution.
The recovery and treatment method of keto-acid containing waste liquid is made up of following steps in the soluble saccharin production provided by the invention:
(1) the keto-acid containing waste liquid is filtered, remove insoluble impurities;
(2) above-mentioned solution is distilled;
(3) gas that distills out is carried out condensation, obtain hydrochloric acid soln;
(4) vinasse is carried out crystallisation by cooling, obtain copper sulfate crystal, remainder obtains sulfuric acid.
The distillation of above-mentioned keto-acid containing waste liquid is as adopting air distillation, and its azeotropic point is 104 degrees centigrade, distillation concentrate 5 times (be raffinate be former waste liquid 20%) time terminal temperature be 113 degrees centigrade, obviously, heat energy consumption is higher.Experiment showed, that its azeotropic point and terminal temperature can reduce along with the raising of vacuum tightness, consider the reduction energy consumption, are advisable with underpressure distillation as adopting underpressure distillation.
In order to remove the hydrochloric acid in the vinasse as far as possible, it is entered in the distillate, improve the concentration that distillates hydrochloric acid, during underpressure distillation, can adopt vinasse is concentrated near doing, at this moment sulfuric acid is concentrated gradually, reacts with chlorion in the raffinate, generates hydrogenchloride and overflows and enter in the distillate, the water that in raffinate, adds 20% (by the volume ratio of former keto-acid containing waste liquid) after near the doing again, little heating for dissolving crystalline solid, and crystallisation by cooling in the impouring container while hot, reclaim(ed) sulfuric acid copper and sulfuric acid.
The recovery and treatment method of keto-acid containing waste liquid during soluble saccharin provided by the invention is produced, hydrochloric acid in the waste liquid, copper sulfate and sulfuric acid can be separated effectively, wherein the hydrochloric acid mean concns of Huo Deing is about 13%, and foreign matter content is few, can be directly used in the former asccharin process for producing sodium; The copper sulfate that obtains makes copper recovery reach 100%, though contain small amount of impurities in its crystalline solid, these impurity are harmless substantially to former soluble saccharin production, therefore also can be directly used in the former asccharin process for producing sodium; The sulfuric acid that obtains can be used for former asccharin process for producing sodium too.This method does not have the waste water and gas discharging except that a small amount of insoluble solid impurities that leaches, waste liquid substantially all obtains recycling, and has realized the closed cycle on the production technique, has thoroughly eliminated environmental pollution.This method technology is very simple, 6500 tons of the hydrochloric acid of annual recyclable concentration 13%, and about 350 tons of Salzburg vitriol, 360 tons in sulfuric acid is removed cost, can make a profit more than 390 ten thousand yuan, and economic benefit is very remarkable.
Embodiment 1
Experimental procedure: (1) removes insoluble impurities with filter paper filtering keto-acid containing waste liquid; (2) get 100 milliliters of filtrates and add in the matrass, matrass is connected vacuum pump system; (3) do not open vacuum pump, adopt normal pressure to add thermal distillation, measure its azeotropic point; Measure terminal temperature when (4) vinasse reaches 20 milliliters; (5) make the gas that distills out become hydrochloric acid soln simultaneously at distillatory, through taking over through condenser condenses
Be collected into receiving bottle;
(6), the filtrate crystallisation by cooling is separated out copper sulfate crystal to the vinasse heat filtering;
(7) the copper sulfate content of measurement distilled concentration of hydrochloric acid and crystalline solid, water insoluble matter content,
Chloride ion content and free sulfuric acid content.
Experimental result:
104 degrees centigrade of keto-acid containing waste liquid air distillation azeotropic points, 113 degrees centigrade of terminal temperatures distillate concentration of hydrochloric acid 12.6%, copper sulfate content 15.3% in the crystalline solid, water-insoluble 0.14%, chlorion 2.16%, free sulfuric acid 18.3%.
Conclusion: air distillation azeotropic point temperature is higher, and it is higher to consume energy; When the vinasse amount was big, the distilled concentration of hydrochloric acid was relatively low, and chloride ion content is higher in the crystalline solid, and the salt acid recovering rate is corresponding lower.
Embodiment 2
Experimental procedure is except that becoming air distillation the underpressure distillation, and all the other are identical with embodiment 1.Open vacuum pump when promptly distilling, open water coolant, vacuum tightness is transferred to 4.0 * 10
4Handkerchief.
Experimental result: azeotropic point is reduced to 94 degrees centigrade, and terminal temperature is reduced to 97 degrees centigrade, distillates concentration of hydrochloric acid 12.8%, copper sulfate content 15.2% in the crystalline solid, water insoluble matter content 0.18%, free sulfuric acid 17.8%, chlorion 1.56%.
Conclusion: adopt underpressure distillation, because azeotropic point and terminal temperature reduce, the corresponding reduction of energy consumption, the distilled concentration of hydrochloric acid did not have big variation when the vinasse amount was 20% former waste liquid, adopted that chloride ion content reduces in the underpressure distillation crystalline solid.
Embodiment 3
Experimental procedure is identical with embodiment 2, just vacuum tightness is risen to 8.7 * 10
4Handkerchief.
Experimental result: azeotropic point is reduced to 74 degrees centigrade, and terminal temperature is reduced to 81 degrees centigrade, distillates concentration of hydrochloric acid 12.7%, copper sulfate content 15.8% in the crystalline solid, water insoluble matter content 0.19%, free sulfuric acid 18.1%, chlorion 0.78%.
Conclusion: underpressure distillation is along with vacuum tightness improves, and energy consumption further reduces, and vacuum tightness is 8.7 * 10
4Energy consumption can be saved more than 30% during handkerchief.When the vinasse amount was constant, distillating concentration of hydrochloric acid and vacuum tightness did not have big relation, and chloride ion content improves and further reduces with vacuum tightness in the crystalline solid.
Embodiment 4
Experimental procedure is removed vinasse and is done near, and is adding the water of 20% (by former waste liquid volume ratio) thereafter, heating for dissolving crystalline solid, and while hot in the impouring container crystallisation by cooling outer all the other with implement
Example 3 is identical.
Experimental result: distillate concentration of hydrochloric acid 13.7%, copper sulfate content 15.6% in the crystalline solid, water insoluble matter content 0.03%, free sulfuric acid 18.6%, chlorion 0.58%.
Conclusion: adopt this embodiment method, the distilled concentration of hydrochloric acid improves, and copper sulfate content is constant substantially in the crystalline solid, but water-insoluble and chloride ion content reduce the raising of crystallisate quality.
Claims (4)
1, the recovery and treatment method of keto-acid containing waste liquid during a kind of soluble saccharin is produced is characterized in that this method is made up of following steps:
(1) the keto-acid containing waste liquid is filtered, remove insoluble impurities;
(2) above-mentioned filtrate is distilled;
(3) gas that distills out is carried out condensation, obtain hydrochloric acid soln;
(4) vinasse is carried out crystallisation by cooling, obtain copper sulfate crystal, remaining
To sulfuric acid.
2, give birth to the recovery and treatment method of tight middle keto-acid containing waste liquid as the said soluble saccharin of claim 1, it is characterized in that the distillation in the described step (2) is underpressure distillation.
3, produce as the said soluble saccharin of claim 2 in the treatment process of keto-acid containing waste liquid, it is characterized in that said underpressure distillation is to be 8.7 * 10 in vacuum tightness
4Carry out under the handkerchief condition.
4, produce as the said soluble saccharin of claim 3 in the recovery and treatment method of keto-acid containing waste liquid, it is characterized in that, said underpressure distillation takes vinasse to do near, the water that in raffinate, adds 20% (by former keto-acid containing waste liquid volume ratio) then, little heating for dissolving crystalline solid enters raffinate crystallisation by cooling step while hot in the impouring container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96115122 CN1158320A (en) | 1996-02-29 | 1996-02-29 | Method for reclaiming waste keto-acid liquid in prodn. of soluble gluside |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96115122 CN1158320A (en) | 1996-02-29 | 1996-02-29 | Method for reclaiming waste keto-acid liquid in prodn. of soluble gluside |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1158320A true CN1158320A (en) | 1997-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96115122 Pending CN1158320A (en) | 1996-02-29 | 1996-02-29 | Method for reclaiming waste keto-acid liquid in prodn. of soluble gluside |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321910C (en) * | 2004-10-25 | 2007-06-20 | 郭胜 | Method for treating copper-containing waste acid water |
| CN100439257C (en) * | 2006-07-10 | 2008-12-03 | 天津北方食品有限公司 | Method for treating acid-extracted waste liquid used for production of saccharin sodium |
| CN102173522A (en) * | 2011-01-05 | 2011-09-07 | 甘肃农业大学 | Treatment and recycling process for initiator CH335 wastewater |
| CN102849883A (en) * | 2011-06-30 | 2013-01-02 | 山东科技职业学院 | Technology for treating SIPM waste water recovered material |
| CN106277514A (en) * | 2015-06-05 | 2017-01-04 | 西南大学 | The method of recycling saccharin sodium wastewater |
| CN107986576A (en) * | 2017-12-27 | 2018-05-04 | 上海衡洁环保科技有限公司 | A kind of processing system and processing method of saccharin production waste water |
| CN110746052A (en) * | 2019-11-19 | 2020-02-04 | 河南省高新技术实业有限公司 | Method for treating saccharin production wastewater |
| CN114177638A (en) * | 2021-12-28 | 2022-03-15 | 东莞市恒建环保科技有限公司 | Single-steaming treatment process for copper sulfate mother liquor |
-
1996
- 1996-02-29 CN CN 96115122 patent/CN1158320A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321910C (en) * | 2004-10-25 | 2007-06-20 | 郭胜 | Method for treating copper-containing waste acid water |
| CN100439257C (en) * | 2006-07-10 | 2008-12-03 | 天津北方食品有限公司 | Method for treating acid-extracted waste liquid used for production of saccharin sodium |
| CN102173522A (en) * | 2011-01-05 | 2011-09-07 | 甘肃农业大学 | Treatment and recycling process for initiator CH335 wastewater |
| CN102849883A (en) * | 2011-06-30 | 2013-01-02 | 山东科技职业学院 | Technology for treating SIPM waste water recovered material |
| CN106277514A (en) * | 2015-06-05 | 2017-01-04 | 西南大学 | The method of recycling saccharin sodium wastewater |
| CN106277514B (en) * | 2015-06-05 | 2019-02-15 | 西南大学 | The method for being recycled saccharin sodium wastewater |
| CN107986576A (en) * | 2017-12-27 | 2018-05-04 | 上海衡洁环保科技有限公司 | A kind of processing system and processing method of saccharin production waste water |
| CN110746052A (en) * | 2019-11-19 | 2020-02-04 | 河南省高新技术实业有限公司 | Method for treating saccharin production wastewater |
| CN110746052B (en) * | 2019-11-19 | 2021-11-02 | 河南省高新技术实业有限公司 | Method for treating saccharin production wastewater |
| CN114177638A (en) * | 2021-12-28 | 2022-03-15 | 东莞市恒建环保科技有限公司 | Single-steaming treatment process for copper sulfate mother liquor |
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