CN1541955A - Recovery and utilization method for copper bearing spent acid solution from sodium saccharin production process - Google Patents
Recovery and utilization method for copper bearing spent acid solution from sodium saccharin production process Download PDFInfo
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- CN1541955A CN1541955A CNA2003101084557A CN200310108455A CN1541955A CN 1541955 A CN1541955 A CN 1541955A CN A2003101084557 A CNA2003101084557 A CN A2003101084557A CN 200310108455 A CN200310108455 A CN 200310108455A CN 1541955 A CN1541955 A CN 1541955A
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Abstract
The present invention provides one waste copper containing acid solution recovering and utilizing process in saccharin sodium production. The waste copper containing acid solution recovering and utilizing process includes filtering to eliminate suspended organic matter, oxidizing the filtrate with mixed oxidant of sodium hypochlorite and potassium hypermanganate to eliminate low boiling point organic matter, decompression distilling the solution in vacuum to obtain dilute hydrochloric acid solution, further extraction and concentrating distillation to obtain hydrochloric acid solution of 30 % concentration, burning residue after decompression distilling to eliminate organic matter and obtain high purity copper sulfate and powder of other inorganic salts. The said process can recover the useful matter from waste acid solution and avoid environmental pollution effectively.
Description
Technical field:
The present invention relates to the recoverying and utilizing method of copper-containing waste acid liquid in a kind of soluble saccharin production, concentrate distillation, reclaim the useful matter in the spent acid solution, eliminate the pollution of refuse environment by oxidation, underpressure distillation and extraction.
Background technology:
When displacement, chloride process, need to make catalyzer during soluble saccharin is produced, produce the mixing sour water that contains mantoquita, sodium-chlor, sodium pyrosulfate, sulfuric acid, hydrochloric acid through reaction with copper sulfate.The massfraction of cupric ion is about 1% in this sour water, and hydrochloric acid is about 5%, and sulfuric acid is about 9%.To the processing of this waste water, what adopt mostly at present is the iron substitution method.In the copper waste liquid, add iron, copper reduction is reclaimed.But contain ferrous sulfate in the remaining acid solution, still will cause new pollution as discharging of waste liquid.Simultaneously, the acid-respons in iron and the waste liquid produces a large amount of hydrogen, and is dangerous big, explosive, and a large amount of acid consumed.Other has a kind of electrolytic process, by electrolytic recovery copper, and from waste liquid recovered acid.This method current consumption is big, the cost height, and have chlorine to produce, and cause secondary pollution, produce hydrogen simultaneously, consume a large amount of acid.Another kind of adoptable method is the diffusion dialysis embrane method.Though this method can be separated acid and mantoquita, process only depends on concentration difference to separate, and separates not exclusively, and treatment capacity is little, and acid has 20% loss, and cupric ion has 10% loss, and the cost of equipment costliness.Present reverse osmosis technology and mineral membrane technology can't be handled the waste liquid of high acid content like this, handle such spent acid solution big meaning is arranged so this is studied to obtain suitable method.
Distillation under vacuum is the method that another kind can be used for handling this spent acid solution, though the more normal-temperature distilled energy consumption of having saved greatly, but the low-boiling-point organic compound during owing to straight run distillation in the spent acid solution will be separated out in prolong, stop up prolong, have a strong impact on the heat exchange efficiency of condenser simultaneously, limited the application of this method greatly.For the Treatment of Copper spent acid solution, have not yet to see the report of industrial application.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, the recoverying and utilizing method of copper-containing waste acid liquid in a kind of soluble saccharin production is provided, technology is simple, and recyclable useful matter is utilized effectively spent acid solution, thoroughly eliminates the pollution of refuse to environment simultaneously.
For realizing such purpose, the present invention at first filters to remove suspended organic matter wherein copper-containing waste acid liquid, adopt clorox and potassium permanganate blending oxidizing agent that filtrate is carried out oxide treatment then, low-boiling-point organic compound in the former spent acid solution is oxidized away, afterwards with solution underpressure distillation under vacuum, the dilute hydrochloric acid solution that recovery obtains continues extraction and concentrates distillation, can get the hydrochloric acid of concentration 30%, and the residue after the underpressure distillation is removed organism through calcination, promptly obtains the mixed powder of high purity copper sulfate and other inorganic salt.
The method that copper-containing waste acid liquid is recycled in the soluble saccharin production provided by the invention is specially: at first copper-containing waste acid liquid is filtered, to remove the suspended organic matter in the stoste, adopt clorox and potassium permanganate blending oxidizing agent that filtrate was carried out oxide treatment 20 minutes then, wherein clorox concentration is 0.6 ‰-1%, potassium permanganate concentration is 0.1 ‰-0.3 ‰, solution after this oxidation of underpressure distillation under the vacuum tightness of 0.07-0.08Mpa afterwards, boiling point is 80-90 ℃, reclaims the dilute hydrochloric acid solution that obtains about 13%.CaCl with above-mentioned gained dilute hydrochloric acid adding 5%
2Extract and concentrate distillation, vacuum tightness is 0.07Mpa, and boiling temperature is 92 ℃, obtains 30% hydrochloric acid.With the 600 ℃ of following calcinations 2 hours in retort furnace of underpressure distillation residue, obtain the powder of copper sulfate (content 20%) and other inorganic salt.
Core content of the present invention is that spent acid solution has been carried out oxide treatment, and distillation residue is carried out calcination handle.Above-mentioned processing makes the present invention can carry out industrialization, and obtains 30% hydrochloric acid and highly purified copper sulphate powder, and spent acid solution is utilized effectively, and thoroughly eliminates the pollution of refuse to environment simultaneously.
Spent acid solution is carried out oxide treatment, and purpose is low-boiling-point organic compound such as the adjacent SULPHURYL CHLORIDE methyl benzoate of removing wherein, in case this low boilers is separated out in prolong during follow-up underpressure distillation, stops up prolong and influences heat exchange.Former spent acid solution is steamed to the nearly situation that the prolong obstruction also can not occur of doing simultaneously, improve the salt acid recovering rate, the dilute hydrochloric acid volume of recovery can reach the 85-90% of former spent acid solution.Simultaneously, when former spent acid solution was closely dried, sulfuric acid that is concentrated and chlorion reaction generated hydrogenchloride and enter in the dilute hydrochloric acid distillate, are about to sulfuric acid conversion and become the form of hydrochloric acid to be reclaimed, and spent acid reclaims fully.
The present invention selects for use clorox and potassium permanganate blending oxidizing agent to carry out the oxidation of low-boiling-point organic compound in the spent acid solution, and cost is low, and oxidation effectiveness is good, in the whole process of underpressure distillation, do not have cotton-shaped organism and stop up prolong, do not influence heat exchange, can steam the dilute hydrochloric acid of former spent acid solution volume 85-90%.If do not take oxide treatment, the dilute hydrochloric acid that goes out when underpressure distillation be former spent acid solution volume 60% the time, promptly occur cotton-shaped organism in the prolong and stop up prolong, also influence heat exchange efficiency greatly simultaneously, make still-process be difficult to go on.
Used clorox and potassium permanganate mixed oxidization agent concentration should be in above-mentioned scopes, and during excessive concentration, the agent of reaction rear oxidation has residue, and the acid solution color is changed; Concentration is low excessively, can not the complete oxidation organism.
The dilute hydrochloric acid (concentration is about 13%) that underpressure distillation is obtained carries out CaCl
2Extractive distillation, concentration is 30% hydrochloric acid, thereby can directly carry out industrial application.
Underpressure distillation is carried out under vacuum tightness 0.07-0.08Mpa.If vacuum tightness is too big, the liquid foam enters distillate in the time of will causing seething with excitement, and influences the dilute hydrochloric acid quality; If vacuum tightness is too little, energy consumption will be increased.
When residue is carried out calcination, carried out under 600 ℃ 2 hours, fall non-environmental-pollution with wherein remaining a small amount of organism calcination charing this moment.The powder that obtains is copper sulfate and other inorganic salt mixts, and sulfur acid copper is 20%.Experiment shows that if temperature is crossed low as in the time of 500 ℃, inorganics is not divisible, recording copper sulfate content is 10% during calcination; If temperature is too high as in the time of 800 ℃, copper sulfate has loss, recording copper sulfate content is 4%.
The recoverying and utilizing method of contained waste liquid during soluble saccharin provided by the invention is produced can effectively separate the acid in the waste liquid and utilize, and the quality product height, but 30% hydrochloric acid industrial application of acquisition.The copper sulphate powder purity height that obtains, and can further carry copper, also can be again as the catalyzer utilization, contained inorganic salt are produced harmless to soluble saccharin in the powder.Method technology of the present invention is simple, can handle spent acid solution 100-500 ton every day, and handling spent acid solution cost per ton is 100-120 unit, reclaims hydrochloric acid copper sulfate and is worth 250-300 unit, and economic benefit is very considerable.
Embodiment:
Further specify technical scheme of the present invention below by specific embodiment.
Embodiment 1
The spent acid solution of getting after 500ml filters places the 1000ml beaker, adds 0.1g potassium permanganate and 3ml clorox, stirring reaction 20 minutes, and spent acid solution darkens during beginning, becomes green afterwards again again.After having reacted, the cup end, do not have
FlossGenerate, floating on the acid solution face have a small amount of brown suspended substance.This suspended substance of elimination carries out underpressure distillation in the matrass of 1000ml under the 0.08Mpa vacuum tightness.Initial boiling temperature is 80 ℃, and terminal temperature is 87 ℃.Obtain the dilute hydrochloric acid of stoste volume 85%, concentration of hydrochloric acid is 12.6%, does not almost have floss in the prolong and occurs.This shows that potassium permanganate and clorox composite oxidant oxidize away low-boiling-point organic compound, and effect is better.
Embodiment 2
Get the 2000L spent acid solution and in enamel still, carry out pilot scale, add 450g potassium permanganate and 12L clorox, carried out oxidizing reaction 20 minutes under stirring, 0.07Mpa following underpressure distillation, the still kettle mean average boiling point is 90 ℃, obtain the dilute hydrochloric acid of stoste volume 85%, concentration of hydrochloric acid is 13.5%, does not almost have floss in the prolong and occurs.This shows that this oxidizing process can oxidize away low-boiling-point organic compound in the technical scale spent acid solution, satisfies industrial underpressure distillation requirement fully.
Embodiment 3
Get above-mentioned 13% dilute hydrochloric acid 500ml and place the 1000ml matrass, add 5% CaCl
2Carry out extractive distillation, vacuum tightness is 0.07Mpa, and boiling temperature is 92 ℃, obtains 30% hydrochloric acid 400ml.This shows that extraction of the present invention concentrates distillation method and concentration of hydrochloric acid can be brought up to 30% from 13%.
Embodiment 4
Get the 20g distillation residue, under 600 ℃ of temperature, placed the retort furnace calcination 2 hours respectively, obtain the blue solid powder.With EDTA is developer, and (750nm place) carries out the copper sulfate content analysis with spectrophotometer, and the result is 20% for copper sulfate content.With compare under other temperature in the specification sheets, 600 ℃ is suitable calcination temperature, has both removed organic matters impurity, purifying copper sulfate, copper sulfate is lost.
Claims (3)
1, the recoverying and utilizing method of copper-containing waste acid liquid during a kind of soluble saccharin is produced, it is characterized in that at first copper-containing waste acid liquid being filtered, adopt clorox and potassium permanganate blending oxidizing agent that filtrate was carried out oxide treatment 20 minutes then, wherein clorox concentration is 0.6 ‰-1%, potassium permanganate concentration is 0.1 ‰-0.3 ‰, solution after this oxidation of underpressure distillation under the vacuum tightness of 0.07-0.08Mpa afterwards, boiling point is 80-90 ℃, reclaims to obtain 13% dilute hydrochloric acid solution.
2, the recoverying and utilizing method of copper-containing waste acid liquid during soluble saccharin as claimed in claim 1 is produced is characterized in that the CaCl with above-mentioned gained dilute hydrochloric acid adding 5%
2Extract and concentrate distillation, vacuum tightness is 0.07Mpa, and boiling temperature is 92 ℃, obtains 30% hydrochloric acid.
3, the recoverying and utilizing method of copper-containing waste acid liquid during soluble saccharin as claimed in claim 1 is produced is characterized in that residue obtained 600 ℃ of following calcinations 2 hours in retort furnace after the underpressure distillation are obtained the copper sulfate of content 20%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310108455 CN1218890C (en) | 2003-11-06 | 2003-11-06 | Recovery and utilization method for copper bearing spent acid solution from sodium saccharin production process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310108455 CN1218890C (en) | 2003-11-06 | 2003-11-06 | Recovery and utilization method for copper bearing spent acid solution from sodium saccharin production process |
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| CN1541955A true CN1541955A (en) | 2004-11-03 |
| CN1218890C CN1218890C (en) | 2005-09-14 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102745791A (en) * | 2011-04-21 | 2012-10-24 | 攀钢集团有限公司 | Method for treating industrial wastewater |
| CN106868495A (en) * | 2017-01-23 | 2017-06-20 | 江苏理工学院 | A kind of recycling method of cobalt salt chemical oxidation waste liquid |
| CN109626329A (en) * | 2018-12-18 | 2019-04-16 | 江苏永葆环保科技有限公司 | A method of vacuum distillation recycling aluminum products surface acid-washing waste liquid |
| CN111302474A (en) * | 2019-12-12 | 2020-06-19 | 山东理工大学 | Method and device for treating organic wastewater by normal-pressure continuous wet oxidation |
| CN112591831A (en) * | 2020-12-04 | 2021-04-02 | 兰州有色冶金设计研究院有限公司 | Harmless treatment method for strongly acidic mine tailings |
-
2003
- 2003-11-06 CN CN 200310108455 patent/CN1218890C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102745791A (en) * | 2011-04-21 | 2012-10-24 | 攀钢集团有限公司 | Method for treating industrial wastewater |
| CN102745791B (en) * | 2011-04-21 | 2014-05-07 | 攀钢集团有限公司 | Method for treating industrial wastewater |
| CN106868495A (en) * | 2017-01-23 | 2017-06-20 | 江苏理工学院 | A kind of recycling method of cobalt salt chemical oxidation waste liquid |
| CN106868495B (en) * | 2017-01-23 | 2019-06-11 | 江苏理工学院 | A kind of recycling and reusing method of cobalt salt chemical oxidation waste liquid |
| CN109626329A (en) * | 2018-12-18 | 2019-04-16 | 江苏永葆环保科技有限公司 | A method of vacuum distillation recycling aluminum products surface acid-washing waste liquid |
| CN109626329B (en) * | 2018-12-18 | 2022-07-05 | 江苏永葆环保科技有限公司 | Method for recovering pickling waste liquid on surface of aluminum product through reduced pressure distillation |
| CN111302474A (en) * | 2019-12-12 | 2020-06-19 | 山东理工大学 | Method and device for treating organic wastewater by normal-pressure continuous wet oxidation |
| CN111302474B (en) * | 2019-12-12 | 2022-06-10 | 山东理工大学 | Method and device for treating organic wastewater through normal-pressure continuous wet oxidation |
| CN112591831A (en) * | 2020-12-04 | 2021-04-02 | 兰州有色冶金设计研究院有限公司 | Harmless treatment method for strongly acidic mine tailings |
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| Publication number | Publication date |
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| CN1218890C (en) | 2005-09-14 |
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