CN105601012A - Method for treating acid-containing waste liquid by condensation and distillation purification - Google Patents
Method for treating acid-containing waste liquid by condensation and distillation purification Download PDFInfo
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- CN105601012A CN105601012A CN201510979942.3A CN201510979942A CN105601012A CN 105601012 A CN105601012 A CN 105601012A CN 201510979942 A CN201510979942 A CN 201510979942A CN 105601012 A CN105601012 A CN 105601012A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/12—Methods and means for introducing reactants
- B01D2259/124—Liquid reactants
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
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- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
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Abstract
The invention provides a method for treating acid-containing waste liquid by condensation and distillation purification. The method comprises the following steps sequentially: A, condensation, wherein the acid-containing waste liquid is condensed in a condensation device with a heating evaporation and/or reverse osmosis method, acidity in the waste liquid is gradually increased till the hydrogen-ion-containing concentration is 10-20g/L, and heating evaporation is in a manner of heating film or tower distillation; B, distillation purification, wherein the high-acid waste liquid obtained from condensation in the step A is subjected to distillation treatment at a temperature of 100-120 DEG C by a distillation column, so that chloride ions and fluorine ions contained in the waste liquid are volatilized into steam, and a pure acid solution is obtained. According to the method, the condensation and distillation purification manners are adopted to treat the acid-containing waste liquid, the chloride ions and the fluorine ions in the waste liquid form volatile hydrogen chloride and hydrogen fluoride gas, and the gas is volatilized from the solution; however, a sulfuric acid solution with high concentration has a relatively high volatile point and is less volatile, therefore, the acid-containing waste liquid is purified.
Description
Technical field
The invention belongs to the technical field of industry containing acid waste liquid processing, be specifically related to a kind of by concentrated and distillationPurified treatment is containing the method for acid waste liquid.
Background technology
Produce in metal smelt, electrolytic etching of metal, in the industries such as flue gas acid preparing, produces a large amount of acid waste liquids that contains,If without processing, be discharged in water body, will produce severe contamination to water body. What produce is useless containing acidLiquid acidity is high, generally contains sulfate radical, chlorion, fluorine ion etc., more difficult. At present, the most frequently usedProcessing method be to add the nertralizers such as lime, gypsum, the acid in consumable liquid, and add chemical agent,Make chlorine and fluorine change sediment into and separate, this processing method need to consume a large amount of nertralizers, locatesReason cost is high, cannot reclaim containing acid waste liquid, causes the wasting of resources. Also have by the method for distillation and concentration nextDispose waste liquid, but after concentrated, the chlorine containing in waste liquid and fluorine are difficult to remove, and can cause serious corruption to equipmentErosion. General use electrodialysis in prior art, counter-infiltration, the modes such as ion-exchange remove in waste liquidChlorine and fluorine, but need to expend a large amount of electric energy, processing speed is slow, and cost is higher, is difficult to adapt to industrialization largeThe needs of producing. Contain the processing of acid waste liquid and recycle, be puzzlement technical staff's a difficult problem always.
Based on above technical problem, the invention provides a kind of processing purifying containing acid waste liquid distillation and concentrationMethod, it develops simple process, and organic efficiency is high, contains acid waste liquid by concentrated distil(l),Remove chlorion and fluorine ion in waste liquid, recycle the processing method of waste liquid. Evidence, applicationRespond well, the present invention adopts concentrated distil(l) mode, to processing containing acid waste liquid, by concentratedAfter obtain the liquid that contains high-concentration sulfuric acid, chlorion, fluorine ion, under vapo(u)rizing temperature, high concentrationPreferential and the water of sulfuric acid is combined into sulfuric acid solution, makes chlorion and fluorine ion in solution, form unstable shapeState, forms volatile hydrogen chloride and hydrogen fluoride gas, from solution, evaporates, and the sulphur of high concentrationAcid solution volatilization point is higher, not volatile, thereby purifies containing acid waste liquid. The steam volatilizing passes through alkali lyeDrip washing, reclaims contained hydrogen chloride and hydrogen fluoride. In the regenerated acid obtaining after processing, the present invention does not produceWaste water, regenerated acid reusable edible after treatment, the clearance of chlorion and fluorine ion reaches more than 95%,The advantages such as it is simple that the present invention has technique, and organic efficiency is high, and cost is lower.
Summary of the invention
The object of this invention is to provide a kind of structure and use simply, rationally, precision is high, stable performanceA kind of processing method purifying containing acid waste liquid distillation and concentration.
For achieving the above object, the present invention adopts following technical scheme: a kind of clean containing acid waste liquid distillation and concentrationThe processing method of changing, is characterized in that, it comprises concentrated, distil(l) and caustic wash process successively, eachThe concrete steps of operation are:
A, concentrated: will concentrate in enrichment facility containing acid waste liquid, described method for concentration is heating steamingSend out and/or counter-infiltration, it is 10-20g/L that the acidity in waste liquid is increased to containing hydrogen ion concentration gradually, Qi ZhongjiaThermal evaporation is to adopt the mode of heating film or column distillation to evaporate;
B, distil(l): the concentrated steps A high acid waste liquid obtaining, by distillation column equipment, is distilledProcess, vapo(u)rizing temperature is 100～120 DEG C, and the chlorion and the fluorine ion that in waste liquid, contain are evaporated in steam,Obtain pure acid solution;
C, alkali cleaning: steam after treatment step B is carried out to drip washing processing, use alkali lye spray, reclaim chlorineIon and fluorine ion.
Further, as preferably, in described A step, method for concentration is steam Multi-effect concentration, and addsHeat, containing acid waste liquid to 100～130 DEG C, makes water change steam into and overflows.
Further, as preferably, in described A step, method for concentration for heating containing acid waste liquid extremely90～100 DEG C, send hydrophobic membrane device to filter, film filter passes through water vapour, holds back down other molecules.
Further, as preferably, in described B step, adopt fountain destilling tower, high acid waste liquid fromTower top spray and under, with the hot-air counter current contacting that tower bottom enters, reach fast required distillation temperatureDegree, the hot air temperature entering is 150～200 DEG C.
Further, as preferably, in described C step, the suspension that described alkali lye is calcium hydroxide,Chlorion in steam is absorbed and is transformed into calcium chloride solution, and fluorine ion is absorbed and changes calcirm-fluoride solid into.
Further, as preferably, while adopting reverse osmosis concentration, permeable membrane forefront pressure is 1～5Mpa, filmFlux 5～20L/m2.h, 30～55 DEG C of thickening temperatures,
Further, as preferably, in described steps A concentration process, require to be contained after concentratedThere is the liquid of high-concentration sulfuric acid, chlorion, fluorine ion, and require under vapo(u)rizing temperature the sulphur of high concentrationPreferentially sour and water is combined into sulfuric acid solution, makes chlorion and fluorine ion in solution, form labile state,Form volatile hydrogen chloride and hydrogen fluoride gas, from solution, evaporate, and ensure temperature controlMaking, the sulfuric acid solution of high concentration is non-volatile, thereby purifies containing acid waste liquid.
Further, as preferably, the pH value of described alkali lye is 8-10.
Further, as preferably, in described A step, method for concentration adopts mechanical compress evaporimeter to enterRow is concentrated.
Beneficial effect of the present invention is:
A kind of processing method purifying containing acid waste liquid distillation and concentration provided by the invention, its development is gone to workSkill is easy, and organic efficiency is high, by concentrated distil(l) containing acid waste liquid, remove chlorion in waste liquid andFluorine ion, recycles the processing method of waste liquid. Evidence, effect is good, and the present invention adoptsConcentrated distil(l) mode, to processing containing acid waste liquid, by after concentrated, obtain containing high-concentration sulfuric acid,The liquid of chlorion, fluorine ion, under vapo(u)rizing temperature, the preferential and water of the sulfuric acid of high concentration is combined into sulfuric acidSolution, makes chlorion and fluorine ion in solution, form labile state, forms volatile hydrogen chlorideAnd hydrogen fluoride gas, from solution, evaporate, and the sulfuric acid solution volatilization point of high concentration is higher, be difficult forVolatilization, thus purify containing acid waste liquid. The steam volatilizing, by alkali lye drip washing, reclaims contained hydrogen chlorideAnd hydrogen fluoride. In the regenerated acid obtaining after processing, the present invention does not produce waste water, and regenerated acid after treatment canRecycle, the clearance of chlorion and fluorine ion reaches more than 95%, and it is simple that the present invention has technique, returnsThe advantages such as the rate of producing effects is high, and cost is lower. The present invention adopts concentrated distil(l) mode, to entering containing acid waste liquidRow is processed, and the chlorion in waste liquid and fluorine ion form volatile hydrogen chloride and hydrogen fluoride gas, from moltenIn liquid, evaporate, and the sulfuric acid solution volatilization point of high concentration is higher, not volatile, thus purify containing acidWaste liquid. It is simple that the present invention has technique, and organic efficiency is high, and cost is lower.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of a kind of processing method purifying containing acid waste liquid distillation and concentration of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried outDescribe clearly and completely, obviously, described embodiment is only the present invention's part embodiment, andNot whole embodiment. Based on the embodiment in the present invention, those of ordinary skill in the art are not doingGo out the every other embodiment obtaining under creative work prerequisite, all belong to the scope of protection of the invention.
As shown in Figure 1, the invention provides a kind of processing method purifying containing acid waste liquid distillation and concentration, it is complied withInferior concentrated, distil(l) and the caustic wash process of comprising, the concrete steps of each operation are:
A, concentrated: will concentrate in enrichment facility containing acid waste liquid, described method for concentration is heating steamingSend out and/or counter-infiltration, it is 10-20g/L that the acidity in waste liquid is increased to containing hydrogen ion concentration gradually, Qi ZhongjiaThermal evaporation is to adopt the mode of heating film or column distillation to evaporate;
B, distil(l): the concentrated steps A high acid waste liquid obtaining, by distillation column equipment, is distilledProcess, vapo(u)rizing temperature is 100～120 DEG C, and the chlorion and the fluorine ion that in waste liquid, contain are evaporated in steam,Obtain pure acid solution;
C, alkali cleaning: steam after treatment step B is carried out to drip washing processing, use alkali lye spray, reclaim chlorineIon and fluorine ion.
In the present embodiment, in described A step, method for concentration is steam Multi-effect concentration, and heating containsAcid waste liquid to 100～130 DEG C, make water change steam into and overflow. As another embodiment, described A stepIn, method for concentration, for heating is containing acid waste liquid to 90～100 DEG C, send hydrophobic membrane device to filter, film filterWater vapour is passed through, hold back down other molecules.
In described B step, adopt fountain destilling tower, high acid waste liquid from tower top spray and, withThe hot-air counter current contacting that tower bottom enters, reaches required vapo(u)rizing temperature fast, the hot-air temperature enteringDegree is 150～200 DEG C. In described C step, the suspension that described alkali lye is calcium hydroxide, in steamChlorion be absorbed and be transformed into calcium chloride solution, fluorine ion is absorbed and changes calcirm-fluoride solid into. AsA kind of embodiment, in the time adopting reverse osmosis concentration, permeable membrane forefront pressure is 1～5Mpa, membrane flux 5～20L/m2.h, 30～55 DEG C of thickening temperatures.
In described steps A concentration process, require by after concentrated, obtain containing high-concentration sulfuric acid, chlorine fromThe liquid of son, fluorine ion, and requiring under vapo(u)rizing temperature, the preferential and water of the sulfuric acid of high concentration is combined into sulphurAcid solution, makes chlorion and fluorine ion in solution, form labile state, forms volatile chlorinationHydrogen and hydrogen fluoride gas evaporate from solution, and ensure that temperature is controlled at the sulfuric acid that makes high concentrationSolution is non-volatile, thereby purifies containing acid waste liquid. The pH value of described alkali lye is 8-10. Described A stepIn, method for concentration adopts mechanical compress evaporimeter to concentrate.
Simple process of the present invention, organic efficiency is high, containing acid waste liquid, removes waste liquid by concentrated distil(l)In chlorion and fluorine ion, recycle the processing method of waste liquid. Evidence, effect is good,The present invention adopts concentrated distil(l) mode, to processing containing acid waste liquid, after concentrated, is containedThe liquid of high-concentration sulfuric acid, chlorion, fluorine ion, under vapo(u)rizing temperature, the sulfuric acid of high concentration preferential andWater is combined into sulfuric acid solution, makes chlorion and fluorine ion in solution, form labile state, forms easilyHydrogen chloride and the hydrogen fluoride gas of volatilization evaporate from solution, and the volatilization of the sulfuric acid solution of high concentrationPoint is higher, not volatile, thereby purifies containing acid waste liquid. The steam volatilizing, by alkali lye drip washing, reclaimsContained hydrogen chloride and hydrogen fluoride. In the regenerated acid obtaining after processing, the present invention does not produce waste water, processesAfter regenerated acid reusable edible, the clearance of chlorion and fluorine ion reaches more than 95%, the present invention hasThe advantages such as technique is simple, and organic efficiency is high, and cost is lower. The present invention adopts concentrated distil(l) mode,To processing containing acid waste liquid, the chlorion in waste liquid and fluorine ion form volatile hydrogen chloride and fluoridizeHydrogen evaporates from solution, and the sulfuric acid solution volatilization point of high concentration is higher, not volatile,Thereby purify containing acid waste liquid. It is simple that the present invention has technique, and organic efficiency is high, and cost is lower.
Although illustrated and described embodiments of the invention, for those of ordinary skill in the art andSpeech, is appreciated that without departing from the principles and spirit of the present invention and can carries out these embodimentMultiple variation, amendment, replacement and modification, scope of the present invention is limit by claims and equivalent thereofFixed.
Claims (9)
1. the processing method purifying containing acid waste liquid distillation and concentration, is characterized in that, it comprises dense successivelyContracting, distil(l) and caustic wash process, the concrete steps of each operation are:
A, concentrated: will concentrate in enrichment facility containing acid waste liquid, described method for concentration is heating steamingSend out and/or counter-infiltration, it is 10-20g/L that the acidity in waste liquid is increased to containing hydrogen ion concentration gradually, Qi ZhongjiaThermal evaporation is to adopt the mode of heating film or column distillation to evaporate;
B, distil(l): the concentrated steps A high acid waste liquid obtaining, by distillation column equipment, is distilledProcess, vapo(u)rizing temperature is 100～120 DEG C, and the chlorion and the fluorine ion that in waste liquid, contain are evaporated in steam,Obtain pure acid solution;
C, alkali cleaning: steam after treatment step B is carried out to drip washing processing, use alkali lye spray, reclaim chlorineIon and fluorine ion.
2. a kind of processing method purifying containing acid waste liquid distillation and concentration according to claim 1, its featureBe, in described A step, method for concentration is steam Multi-effect concentration, and heating containing acid waste liquid extremely100～130 DEG C, make water change steam into and overflow.
3. a kind of processing method purifying containing acid waste liquid distillation and concentration according to claim 1, its featureBe, in described A step, method for concentration, for heating is containing acid waste liquid to 90～100 DEG C, send hydrophobic membrane dressPut filtration, film filter passes through water vapour, holds back down other molecules.
4. a kind of processing method purifying containing acid waste liquid distillation and concentration according to claim 1, its featureBe, in described B step, adopt fountain destilling tower, high acid waste liquid from tower top spray and,Hot-air counter current contacting with tower bottom enters, reaches required vapo(u)rizing temperature fast, the hot-air enteringTemperature is 150～200 DEG C.
5. a kind of processing method purifying containing acid waste liquid distillation and concentration according to claim 1, its featureBe, in described C step, the suspension that described alkali lye is calcium hydroxide, the chlorion in steamBe absorbed and be transformed into calcium chloride solution, fluorine ion is absorbed and changes calcirm-fluoride solid into.
6. a kind of processing method purifying containing acid waste liquid distillation and concentration according to claim 1, its featureBe, while adopting reverse osmosis concentration, permeable membrane forefront pressure is 1～5Mpa, membrane flux 5～20L/m2.h,30～55 DEG C of thickening temperatures.
7. a kind of processing method purifying containing acid waste liquid distillation and concentration according to claim 1, its featureBe, in described steps A concentration process, require to obtain containing high-concentration sulfuric acid, chlorine after concentratedThe liquid of ion, fluorine ion, and requiring under vapo(u)rizing temperature, the preferential and water of the sulfuric acid of high concentration is combined intoSulfuric acid solution, makes chlorion and fluorine ion in solution, form labile state, forms volatile chlorineChange hydrogen and hydrogen fluoride gas, from solution, evaporate, and ensure that temperature is controlled at the sulphur that makes high concentrationAcid solution is non-volatile, thereby purifies containing acid waste liquid.
8. a kind of processing method purifying containing acid waste liquid distillation and concentration according to claim 5, its featureBe, the pH value of described alkali lye is 8-10.
9. a kind of processing method purifying containing acid waste liquid distillation and concentration according to claim 1, its featureBe, in described A step, method for concentration adopts mechanical compress evaporimeter to concentrate.
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| CN107673539A (en) * | 2017-11-17 | 2018-02-09 | 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) | A kind of acid waste water processing equipment and processing method |
| CN108033433A (en) * | 2017-10-26 | 2018-05-15 | 青岛海湾集团有限公司 | A kind of industrial waste acid processing system |
| CN109795991A (en) * | 2019-04-11 | 2019-05-24 | 常州安海化工工程技术有限公司 | Safe and energy-saving purification treatment process for fluorosulfuric acid |
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| CN109795991A (en) * | 2019-04-11 | 2019-05-24 | 常州安海化工工程技术有限公司 | Safe and energy-saving purification treatment process for fluorosulfuric acid |
| CN109795991B (en) * | 2019-04-11 | 2020-12-29 | 常州安海化工工程技术有限公司 | Safe and energy-saving purification treatment process for fluorosulfuric acid |
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Application publication date: 20160525 |