CN1063407C - Method for treatment of waste acid liquid containing copper production of gluside and sodium saccharin - Google Patents

Method for treatment of waste acid liquid containing copper production of gluside and sodium saccharin Download PDF

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CN1063407C
CN1063407C CN 96104509 CN96104509A CN1063407C CN 1063407 C CN1063407 C CN 1063407C CN 96104509 CN96104509 CN 96104509 CN 96104509 A CN96104509 A CN 96104509A CN 1063407 C CN1063407 C CN 1063407C
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water
liquid
liquor
filtrate
waste acid
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CN1141888A (en
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刘立华
杨瑞凤
李馥
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Abstract

The present invention relates to a method for treating waste acid water with copper in saccharine or saccharin sodium production. Waste acid water is distilled and condensed to recover hydrochloric acid; residues are dissolved with water, and the pH value is regulated to liquor A which reacts with prepared solution B; after filtration, cuprous chloride and filter liquor C are obtained; sodium sulfide is added to liquor C to obtain filter liquor D through filtration; active carbon is added to the filter liquor D to obtain liquor E through filtration; the liquor E is concentrated, crystallized and dried to obtain sodium sulphate decahydrate. The present invention avoids environmental pollution, recovers useful chemical substances and effectively treats waste acid water; the present invention has obvious social and economic benefits.

Description

Handle the method for copper-containing waste acid water in asccharin, the soluble saccharin production
The present invention relates to produce a kind of treatment process smart or soluble saccharin sun copper-containing waste acid water.
In the production process of asccharin, soluble saccharin, when displacement, chlorination reaction. produce a large amount of copper-containing waste acid water, contain a large amount of bivalent cupric ions, monovalence chlorion in the copper-containing waste acid water.The divalent sulfur acid group, the monovalence hydrogen ion, monovalence sodium ion etc., this solution directly discharges, and can pollute environment.Handle this waste acid water at present and adopt the substitution method and the precipitator method usually.The precipitator method mainly are to add sodium sulfide solution in copper-containing waste acid water, make the reaction of cupric and sulphur root; The CuS that generates can sell after precipitation, filtration, the drying, but still contain a large amount of H in the filtrate of being discharged +, Cl -, SO 4 2-, Na +, S 2-, do not reach emission standard, and in generative process, also produce certain toxic gas H 2S causes new source of pollution.Substitution method is that iron filings are dropped in the cupric sour water, replaces copper with fe, and after filtration, drying, obtaining copper powder can sell, and the deficiencies in the prior art part mainly is: contain a large amount of Cl in the filtrate equally -, SO 4 2-, H +, Fe 2+, Fe 3+, Na +And Cu 2+, do not reach emission standard, in reaction process because of heating, produce the hydrogen chloride gas contaminate environment, and because , dangerous big, easily blast, and energy consumption is big.
The objective of the invention is to avoid weak point of the prior art, and the decontamination of a kind of energy is provided, effectively handle the improvement method of copper-containing waste acid water in asccharin, the soluble saccharin production.
Can take following technical scheme to realize purpose.The method of copper-containing waste acid water mainly was that copper-containing waste acid water is distilled during this processing asccharin, soluble saccharin were produced. make H +, Cl -With HCl form and water azeotropic. hydrochloric acid is reclaimed in condensation: the residuum in the water dissolution vessel, regulate PH=2-3, obtain A liquid. be mixed into B liquid with S-WAT or sulfurous acid oxygen sodium and sodium hydroxide, water; SO in the B liquid 3 2-With A liquid Cu 2+Redox reaction takes place at Cl -Exist to generate the cuprous chloride precipitation down, its reaction formula is: , after filtering, obtain cuprous chloride and liquor C.Add sodium sulphite, gac in C liquid, filter, concentrating filter liquor, crystallization, separation after drying obtain sal glauberi.
In conjunction with the accompanying drawings, embodiment is described in further detail the content of the technical program.
Accompanying drawing is a process flow sheet.
Present method, by weight:
A/ is 1 part in copper-containing waste acid water, distills in 105 ℃～130 ℃ in distil container, makes H +, Cl -With HCl form and water azeotropic, just can obtain hydrochloric acid through cooling.Fore-running is divided into 4-8% (volume percent) hydrochloric acid, and collecting amount is former sour water 8-10% (volume ratio); It is 14-21% (volume percent) hydrochloric acid that second section is collected liquid, and collecting amount is former sour water 70-75% (volume ratio), adds water several times and distill in distil container, and purpose is with unnecessary H +, Cl -, steam so that carry out following reaction, collecting liquid for the third time is 2-5% (volume percent), the hydrochloric acid collecting amount is former sour water 40-60% (volume ratio).Obtain 2-5% in the still-process, the hydrochloric acid of 4-8% (volume percent) can be used as pickling agent and sells, and also can be used for the absorption liquid of the ammonia absorber of the amidation operation that asccharin produces; 14-21% hydrochloric acid can be used for asccharin production.Notice that temperature is not above 130 ℃.
B/ with respect to the volume of former sour water, calculates by the former sour water chloride ion-containing amount and the difference of the chloride ion-containing amount that steams hydrochloric acid when the residuum chlorinity is .0.01g/ml in the container.Stop heating, close water coolant; With the residuum in 0.5-0.7 part water dissolution container, and, obtain A liquid with 40-50% caustic lye of soda adjusting PH=2-3;
C/ 0.012-0.017 part Na 2SO 3With 0.008-0.015 part sodium hydroxide, 0.08 part of water obtain solution B.Be warming up to 60-70 ℃.
When d/A solution is warming up to 60-70 ℃, B liquid is slowly added in the A liquid, stir and control PH=2-4.In the time of 60 ℃-70 ℃, stirred 15-30 minute, filter when being cooled to 40 ℃, obtain cuprous chloride and liquor C;
The c/ cuprous chloride is used 0.025-0.04 part 95% washing with alcohol, filtration again, and 50 ℃ of-70 ℃ of dryings, is obtained cuprous chloride after washing with 0.03-0.05 part 1% acid solution.Measure conformance with standard, can sell.Washings is all recyclable.
When c liquid is warming up to 60 ℃-70 ℃, after adding 0.004-0.009 part sodium sulphite reacts half an hour, filters and obtain filter cake and filtrate D.Filter cake is FeS, Fe 2S 3, CuS, CU 2S, but central selling after the drying, they are raw materials of smelting steel, iron.
Filtrate D 5%H 2SO 4Regulate PH=3-4, be warming up to 60 ℃-70 ℃, add 0.003-0.007 part gac, stir 15 minutes after-filtration, obtain charcoal and filtrate E.Carbon can regeneration.
Filtrate E concentrates, crystallization, obtains sal glauberi and mother liquor after the centrifugation drying, can sell after the sal glauberi analysis is qualified.Mother liquor can recycled.
Treatment effect the best both can be avoided contaminate environment as stated above, and recyclable again useful chemical substance is effectively administered the copper-containing waste acid water that produces in asccharin, the soluble saccharin production process, achieves many things at one stroke.
The specification of each raw material and consumption are as follows in the above-mentioned technological process:
Operation Material name Specification Weight part Remarks
Still-process Water 0.3-0.65
The dissolving residuum is regulated PH Water sodium hydroxide ≥98％ 0.5-0.7 0.06-0.14 Preparation 40-50% solution
B liquid S-WAT or sodium bisulfite sodium hydroxide water ≥93％ ≥98％ 0.012-0.017 0.008-0.015 0.006-0.008 0.08 Redox reaction consumes B liquid 0.1Kg/Kg sour water
The washing cuprous chloride Nitric acid (hydrochloric acid) ethanol 1％ 95％ 0.03-0.05 0.025-0.04
Precipitin reaction removes Cu 2+,Fe 3+ Sodium sulphite ≥60％ 0.004-0.009
Decolouring Gac 0.003-0.007
Transfer PH Sulfuric acid 5％ In right amount
Close the copper waste acid water 1 d=1.200-1.2300
Example 1,
A/ copper-containing waste acid water 500ml in the 1000ml matrass, with the electric mantle heating, comes to life in the time of 105 ℃, and phlegma distillates in the time of 106 ℃; Collecting its content of 50ml salt acidity test is 5.2% (volume percent), change receiving flask and proceed distillation, it is 16% (volume percent) that 350ml salt acidity test content is reclaimed in condensation, this moment matrass in residuum near evaporate to dryness, add 25ml water, continue the distillation controlled temperature and be no more than 130 ℃, steam the 25ml phlegma after, add 25ml water again, steam the 25ml phlegma again.Add entry altogether 8 times, each 25ml collects condensation hydrochloric acid 200ml altogether and measures content 2.5% (volume percent).
B/ calculates by above-mentioned b method, when residuum chloride ion-containing amount is 0.01g/ml in the matrass, stop distillation, with the residuum in the 350ml water dissolution matrass, heating up makes the residuum dissolving, and regulates PH=2 with 50% sodium hydroxide, add alkali number 85ml, filter, have with the less water washing leaching cake to leach thing on a small quantity, obtain filtrate A liquid;
C/ takes by weighing the 8.5g S-WAT, and 4.5g sodium hydroxide is dissolved in 50ml water, and heating for dissolving obtains B liquid, is warming up to 60 ℃;
When d/A liquid is warming up to 65 ℃, keep A liquid between 60-65 ℃, B liquid is slowly added in the A liquid, stirs and control PH=3; After all adding finished with B liquid, at 60 ℃, PH=3 stirred 20 minutes, filtered when being cooled to 40 ℃, obtained filter cake cuprous chloride and liquor C;
E/ filter cake cuprous chloride washs with 1% nitric acid, uses sour 40ml, drains, and collects the pickle solution recycled; Draining collection filtrate with the 20ml95% washing with alcohol again applies mechanically.Cuprous chloride is dry in 55 ℃ of thermostat containers, obtains cuprous chloride 7g, content 97.5%.The rate of recovery 80%; Annotate in the 500ml sour water and contain bivalent cupric ion 5.5g after measured.
When c liquid is warming up to 70 ℃, add sodium sulphite 2g, be incubated and stir after 15 minutes and be cooled to 60 ℃, filter and obtain filter cake and filtrate D;
Filtrate D 5%H 2SO 4Regulate PH=4, be warming up to 60 ℃-70 ℃, add the 2g gac, stir 15 minutes after-filtration, obtain charcoal and filtrate E; Filtrate E is 450ml.
Filtrate E is concentrated into 330ml on electric furnace, be cooled to 20 ℃, filter with cold water, and drying obtains sal glauberi and mother liquor.Sal glauberi output 249g.
Example 2,
A/ copper-containing waste acid water 1000ml, in the 2000ml matrass, heat with electric mantle, in the time of 105 ℃, come to life, phlegma distillates and collects 110ml phlegma mensuration content of hydrochloric acid 5.1% (volume percent) in the time of 105 ℃, change the hydrochloric acid that receiving flask is proceeded to distill, 700ml is reclaimed in condensation, content is 16% (volume percent).Change a receiving flask again, this moment, the matrass residuum was added 50ml water near evaporate to dryness, continued distillation, controlled temperature is no more than 130 ℃, and residuum is added 50ml water during near evaporate to dryness again, adds water altogether 9 times, each 50ml collects 450ml hydrochloric acid altogether, and content is 2.3% (volume percent).
B/ calculates by above-mentioned b/ method, when residuum chloride ion-containing amount is 0.01g/ml in the matrass, stops distillation, with the residuum in the 720ml water dissolution matrass, heating up makes the residuum dissolving, and regulates PH=2.5 with 50% caustic lye of soda, hydro-oxidation sodium liquid measure 160ml obtains A liquid.
C/ takes by weighing the 17g S-WAT, and 9g sodium hydroxide is dissolved in heating for dissolving in the 100ml water, obtains B liquid, is warming up to 65 ℃.
When d/A liquid is warming up to 70 ℃, B liquid is slowly added in the A liquid, stir and control PH=3, after all adding finishes with B liquid, stirred 20 minutes at 63 ℃-65 ℃, PH=3 when being cooled to 40 ℃, filters, and obtains filter cake cuprous chloride and liquor C.
E/ filter cake cuprous chloride washs with 1% nitric acid, drains with sour 70ml, and filtrate collection is applied mechanically, and with 95% ethanol 40ml washing, filtrate collection is applied mechanically again, and dry in 55 ℃ of thermostat containers, obtains cuprous chloride 13.6g, content 97%, the rate of recovery 78%.Annotate in the 1000ml sour water and contain bivalent cupric ion 11g.
C liquid is heated up 70 ℃ the time, add sodium sulphite 4g, stir insulation after 15 minutes, be cooled to 60 ℃, filter and obtain filter cake and filtrate D.
Filtrate D 5%H 2SO 4Regulate PH=4, be warming up to 60 ℃, add gac 4g, stir insulation after 15 minutes, filter, obtain filter cake charcoal and filtrate E.Filtrate E volume is 910ml.
Filtrate E is concentrated to 655ml on electric furnace, be cooled to 23 ℃ with cold water, filters, and drying obtains sal glauberi and mother liquor.Sal glauberi output is 500g.
Example 3,
A/ copper-containing waste acid water 2000L, in 3000L enamel retort, heating comes to life in the time of 105 ℃, and phlegma distillates in the time of 106 ℃, and the hydrochloric acid solution content of collecting 200L is 5% (volume percent).Phlegma imported in the concentrated hydrochloric acid holding tank to collect the 1480L content of hydrochloric acid be the basic evaporate to dryness of residuum in 16.2% (volume percent) retort this moment, controlled temperature can not surpass 130 ℃, adds the distillation of 100L water.After steaming nearly 100L phlegma, add 100L water again, steam nearly 100L phlegma, add water 100L and amount to 10 times, steaming the 1000L content of hydrochloric acid is 2.2% (volume percent).
B/ calculates by above-mentioned b/ method, when residuum chloride ion-containing amount is 0.01g/ml in the retort, stop distillation, with the residuum in the 1400L water dissolution retort, intensification makes the residuum dissolving, and regulates PH=2 with 50% caustic lye of soda, and adding alkali number is 298L, with solution suction filtration in Φ=1000mm suction filtration groove, obtain liquid A in the filtrate suction 3000L retort.
C/ takes by weighing the 34Kg S-WAT, and 18Kg sodium hydroxide and 200L water mix at the 400L heating tank, and rising temperature for dissolving obtains B liquid, is warming up to 66 ℃.
When d/A liquid is warming up to 66 ℃, B liquid is slowly added in the A liquid, stir also control PH=3, stirred 20 minutes at 60 ℃, when being cooled to 40 ℃, Φ obtains filter cake cuprous chloride and liquor C at=1000mm cuprous chloride suction filtration groove inner filtration; Filtrate is put into the 2000L retort.
E/ filter cake cuprous chloride washs, drains with 1% nitric acid 160L in cuprous chloride suction filtration groove, in the filtrate suction 1% sour holding tank, wash with 95% ethanol 80L again, in the filtrate suction alcohol holding tank, cuprous chloride is dry in 55 ℃ of thermostat containers, obtains cuprous chloride 28Kg, content 97%, the rate of recovery 80%, the copper ions amount is 22Kg in the notes 2000L cupric sour water.
C liquid when the precipitin reaction jar is warming up to 60 ℃, is added sodium sulphite 8Kg, stir insulation after 15 minutes, filter, obtain filter cake and filtrate D at metallic sulfide suction filtration groove; In the filtrate D suction 2000L bleacher.Filter cake is collected and is sold.
Filtrate D 5%H 2SO 4Regulate PH=4, be warming up to 65 ℃, add gac 8Kg, stir insulation and filter in decolouring suction filtration groove after 15 minutes, obtain charcoal and filtrate E, filtrate E puts into the 2000L crystallizer.
Filtrate E is concentrated to 1000L in crystallizer, be cooled to 22 ℃ with cold water, dries in Φ=1000mm whizzer, obtains sal glauberi and mother liquor, and dry back sal glauberi output is 1100Kg.Recycling Mother Solution is used.
The relative prior art of the technical program has following advantage and effect.
1, this method is a kind of the copper-containing waste acid water that produces in asccharin, the saccharin sodium production process thoroughly to be separated into hydrochloric acid, stannous chloride, and the improvement method of sal glauberi does not have the atmosphere pollutions such as acid gas, hydrogen sulfide gas in the processing procedure, do not have waste residue yet; Isolated product can be used as industrial chemicals, is used for Chemical Manufacture and other industry and applies mechanically rear solution discharge capacity and only be Treatment of Copper waste acid water volume 1/5, and PH=7 reaches discharge standard substantially after measured.
2, for the enterprise that produces 1000 tons of asccharin per year, with this method Treatment of Copper waste acid water, by present industrial chemicals calculation of price, its comprehensive benefit can reach 1,000,000 yuan; Social and economic benefits is obvious.

Claims (2)

1, a kind of method of handling copper-containing waste acid water in asccharin, the soluble saccharin production is characterized in that:
A, hydrochloric acid is reclaimed in cupric sour water distillation, condensation;
Residuum in b, the water dissolution vessel is regulated PH=2-3 with alkali, obtains A liquid;
C, receive, be mixed into solution B with sodium hydroxide and water with S-WAT or bisulfite;
D, B liquid and A liquid carry out redox reaction, after the filtration, obtain cuprous chloride and liquor C;
E, add sodium sulphite, gac, filtration in C liquid, concentrating filter liquor, crystallization, separation after drying obtain sal glauberi.
2, the method for copper-containing waste acid water during processing asccharin as claimed in claim 1, soluble saccharin are produced is characterized in that by weight:
A, copper-containing waste acid water are 1 part, and distillation temperature is 105-130 ℃, and hydrochloric acid is reclaimed in condensation;
Before b, the residuum in the water dissolution vessel, earlier residuum chlorine ion concentration in the container is distilled to 0.01g/ml, described alkali is 40-50% sodium hydroxide;
The umber of c, described S-WAT, sodium hydroxide and water is respectively: 0.012-0.017,0.008-0.015, and 0.08, and rising temperature for dissolving;
D, when A liquid is warming up to 60-70 ℃, B liquid is slowly added A liquid, stirring and control PH=2-4; Stirred 15 minutes-30 minutes at 60-70 ℃, filter when being cooled to 40 ℃, obtain filter cake cuprous chloride and liquor C;
E, filter cake cuprous chloride with the washing of 0.03-0.05 part 1% acid solution after, use 0.025-0.04 part 95% washing with alcohol, filtration again and 50-70 ℃ of drying, obtaining is cuprous;
When C liquid is warming up to 60-70 ℃, add 0.004-0.009 part sodium sulphite, filter and obtain filter cake and filtrate D;
Filtrate D 5%H 2SO 4Regulate PH=3-4, be warming up to 60-70 ℃, add 0.003-0.007 part gac, stir 15 minutes after-filtration, obtain charcoal and filtrate E;
Filtrate E concentrates, crystallization, centrifugation obtain sal glauberi and mother liquor.
CN 96104509 1996-04-11 1996-04-11 Method for treatment of waste acid liquid containing copper production of gluside and sodium saccharin Expired - Fee Related CN1063407C (en)

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CN1063407C true CN1063407C (en) 2001-03-21

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2235495T3 (en) * 1998-06-23 2005-07-01 Shell Internationale Research Maatschappij B.V. PROCESOPARA TREATMENT OF RESIDUAL WATER.
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
CN101916890B (en) * 2010-08-16 2012-09-05 长春劲能锂电池科技有限公司 Method for recovering current collector from waste lithium ion battery
CN103420935B (en) * 2012-05-15 2015-04-29 张卫民 Method of processing sodium saccharin crystallized mother liquid
CN106277514B (en) * 2015-06-05 2019-02-15 西南大学 The method for being recycled saccharin sodium wastewater

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