CN112387096A - Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium - Google Patents
Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium Download PDFInfo
- Publication number
- CN112387096A CN112387096A CN202011106886.XA CN202011106886A CN112387096A CN 112387096 A CN112387096 A CN 112387096A CN 202011106886 A CN202011106886 A CN 202011106886A CN 112387096 A CN112387096 A CN 112387096A
- Authority
- CN
- China
- Prior art keywords
- flue gas
- acid
- washing
- purifying
- liquid medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003546 flue gas Substances 0.000 title claims abstract description 121
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000007788 liquid Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 45
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 43
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000005406 washing Methods 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 29
- 239000011737 fluorine Substances 0.000 claims abstract description 28
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000460 chlorine Substances 0.000 claims abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 27
- 238000000746 purification Methods 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000000779 smoke Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 64
- 239000000428 dust Substances 0.000 abstract description 25
- 238000003723 Smelting Methods 0.000 abstract description 21
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 9
- 230000005484 gravity Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 abstract description 2
- -1 and meanwhile Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 21
- 238000011084 recovery Methods 0.000 description 15
- 239000002699 waste material Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000008235 industrial water Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000013028 medium composition Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010440 gypsum Chemical group 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical group S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
-
- 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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
-
- 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
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
- F27D17/008—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases cleaning gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biomedical Technology (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Sustainable Development (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a novel method for purifying and recycling arsenic-containing flue gas by using an acidic liquid medium, belonging to the technical field of heavy metal pollution treatment. The invention replaces water washing in the acid preparation process with acid washing, can effectively enrich heavy metal ions and realizeThe recycling of acid is suitable for the purification of heavy non-ferrous smelting flue gas and the treatment of arsenic pollution. After heavy non-ferrous smelting flue gas is subjected to gravity dust collection and electric dust collection, before the heavy non-ferrous smelting flue gas enters an acid making link, a part of auxiliary additives are added into an acid medium solution containing sulfuric acid to prepare a proper washing solution, the flue gas is sprayed or sprayed for washing, the washed mixed liquid is concentrated for recovering sulfuric acid and heavy metals, and meanwhile, fluorine and chlorine are removed by adding a fluorine and chlorine remover. The invention utilizes the acidic liquid medium to replace water washing for purifying SO2Flue gas can avoid the generation of contaminated acid, effectively recovers arsenic and heavy metal elements, fully utilizes and recovers SO2Soluble sulfur oxides in the flue gas have important significance for arsenic pollution treatment in the heavy non-ferrous metal smelting industry.
Description
Technical Field
The invention relates to a novel method for purifying and recycling arsenic-containing flue gas by using an acidic liquid medium, belonging to the technical field of heavy metal pollution treatment.
Background
Arsenic is a commonly encountered element in heavy metal smelting. The arsenic compound has strong toxicity, so a great amount of arsenic-containing smoke dust and furnace produced in the smelting processSlag, wastewater and arsenic-containing intermediate products cause serious pollution to the environment and directly affect the physical health of operators and people. As arsenic and compounds thereof have limited use in national economy, the timely treatment of various arsenic-containing materials in a smelting plant is limited, so that the vicious cycle of arsenic in a production system is caused, or the stockpiling and overstocking of a large amount of arsenic-containing materials are caused, the comprehensive recovery of valuable metals in the arsenic-containing materials is influenced, and the pollution of the arsenic to the environment is aggravated. The non-ferrous metal industry is one of industries with serious environmental pollution, and a plurality of enterprises actively begin to eliminate old processes and improve the technology mainly for treating environmental pollution while increasing the treatment intensity of the existing pollution sources. The smelting flue gas produced by the nonferrous metallurgy kiln has SO2The concentration is lower, the fluctuation range is big, contain heavy metal and various harmful impurity, the processing degree of difficulty is big characteristics, in order to satisfy the system acid demand, still need further purification after the smelting flue gas removes dust. SO-containing industrial flue gas acid making and utilizing2The smelting flue gas generates SO under the action of a catalyst3And reacting with water to produce sulfuric acid. Because the flue gas contains various impurities, the flue gas is firstly purified before the acid making process. And the flue gas purification and pollution control are also the focus of the current research.
At present, the types of the non-ferrous smelting flue gas purification processes are very many, and the methods of gravity dust collection, electrostatic dust removal and water washing purification are mainly adopted. The gravity dust collection is suitable for collecting dust particles larger than 50 μm, the dust collection efficiency is low, and the dust collection rate is only 40-50%. The electrostatic dust collection is suitable for treating fine dust and smoke dust with the particle size of less than 1 micron, and the initial dust collection efficiency can reach 99 percent. However, electrostatic dust collection has certain requirements on dust specific resistance, so that the electrostatic dust collection has certain selectivity on dust, and high purification efficiency cannot be obtained for all dust. Even if the electrostatic dust collection is carried out, some particles with poor volatility or charging effect still exist in the smoke and are not removed. Thus, the flue gas needs to be deeply purified and washed by water washing. Except the particle size of the flue gas, SO in the flue gas2The concentration also has a great influence on the acid making. Generally by reacting SO2The flue gas with the content of more than 3.5 percent becomes high-concentration SO2. When SO is contained in flue gas2When the concentration is too low, the production cost of acid making is high, the smoke gas treatment amount is large, and the product yield is low; when SO is contained in oxygen2When the concentration is too high, the temperature in the acid preparation reaction process is too high, the vanadium-containing catalyst can be damaged, and a large amount of concentrated sulfuric acid needs to be consumed to absorb SO2. Thus converting SO in flue gas2The concentration of (A) is not more than 10%. Currently, flue gas purification processes are mainly classified into these three categories: the first is a water washing purification process. By spraying a large amount of clear water to enrich SO2The volatile heavy metal smoke dust and other harmful impurities in the smoke enter the washing wastewater to reach the aim of enriching SO2The purpose of flue gas purification provides conditions for the flue gas to produce acid. The second is the common dilute sulfuric acid purification process. The common dilute sulfuric acid process is mainly characterized in that heat in the flue gas is taken away by circulating acid through a cooler, and the generated amount of sewage is very small at this time; the recovery of the sludge has certain economic value after the recovery, and the defect is that the capital investment of the whole process is large. The third is the adiabatic humidifying acid purification process. The adiabatic humidifying acid purification process mainly uses the washing liquid circularly in the circulating process, and the washing liquid absorbs part of sulfur trioxide to finally become dilute sulfuric acid. The cooler is not provided in the first and second scrubber acid circulation systems. And (4) carrying out heat insulation, evaporation and temperature reduction on the flue gas. The main flow of adiabatic evaporation is to introduce flue gas into the heat-insulating environment, keep the temperature of circulating acid at a higher temperature all the time, and the gas-liquid 'double-membrane theory', continuously transfer mass and heat, and adiabatic evaporation: the saturated vapor pressure of the acid liquor at the temperature of the section is larger than the partial pressure of the water vapor in the furnace gas, when the water is evaporated in the acid, part of sensible heat parts in the flue gas can be converted into the latent heat of the water vapor, so that the temperature in the furnace gas is reduced, the latent heat is increased, and the heat is removed in the subsequent operation.
According to the above description, the amount of the washing water is large, and a large amount of heavy metals are brought into the washing water after the flue gas is washed by the water, so that dirty acid is generated. But the treatment of the waste acid and the waste water still faces three problems of large slag quantity, high cost and high fluorine and chlorine ion concentration. Because the waste acid water has high acidity, most enterprises adopt the prior 'sulfuration' or 'neutralization' process to treat the waste acid, which can generate a large amount of waste residues such as arsenic sulfide residue, gypsum residue and the like containing toxic heavy metals, thereby bringing secondary pollution and environmental risk.
The prior art for removing (recovering) arsenic in flue gas is divided into a dry method and a wet method, wherein the dry method is used for separating and collecting arsenic from the flue gas in a cooling mode, and a quenching mode is adopted in a quenching arsenic-collecting technology to enable the temperature of the flue gas to rapidly pass through a glass arsenic temperature range, so that the problem of glass arsenic bonding caused by slow cooling of a traditional cooling flue is solved. Wet process, such As electric heating rotary kiln distillation method, and Sumitomo method, for treating arsenic-containing soot or arsenic-containing waste acid sewage to extract high-purity As2O3But the investment is far larger than that of the quenching arsenic-collecting technology. The early quenching arsenic-collecting technology is used for treating arsenic-containing flue gas in gold smelting project, and is currently applied to treating arsenic-containing flue gas in copper and lead smelting, wherein As in the flue gas is As2O3The smoke form is recovered, the load of a waste acid treatment system can be reduced, and the reduction of hazardous waste residues can be realized to a certain extent.
In recent years, the nonferrous smelting flue gas purification process becomes a research hotspot. Xichengyuan' carbon calcining rotary kiln and cooling kiln SO2Discussion of flue gas purification in the text, it is mentioned that wet absorption method of HGLW type desulfurizing tower purifies SO in flue gas2. The method is to use SO2The characteristic relation between the equilibrium degree of the atomized alkaline absorption liquid and the liquid-liquid interface in the purification tower and the solubility of the alkaline absorption liquid in the liquid phase, especially the SO in the gas phase2Mass transfer rate of (3), SO in liquid phase2Mass transfer rate, physical absorption gas phase mass transfer component coefficient, physical absorption liquid phase mass transfer component coefficient, SO2Partial pressure in the gas phase, SO2Concentration in the liquid phase, by diffusion of gas in the liquid, on SO2Absorption is carried out. Chinese patent CN105126587A reports a method for dedusting and purifying 2 flue gas by using supergravity flue gas, but the gravity dedusting effect is not ideal, so that the overall treatment effect of the process is reduced. Chinese patent CN102079511B reports an acid making system suitable for flue gas containing high-concentration sulfur dioxide, but the SO is not determined2Limit of concentration ofThe value, the guiding meaning to the gas cleaning is limited.
Disclosure of Invention
The invention provides a new method for purifying arsenic-containing flue gas by using an acidic liquid medium and recycling the arsenic-containing flue gas, aiming at the problems in the prior art. The invention can save more than 50% of industrial water by replacing water washing with acid washing medium purification, and simultaneously generates little or no waste acid, thereby greatly relieving the environmental and enterprise pressure. The invention better solves the problems existing in the prior art, has low energy consumption and has wider market prospect.
In order to realize the purpose, the invention is realized by the following technical scheme:
the novel method for purifying and recycling the arsenic-containing flue gas by using the acidic liquid medium comprises the following specific steps:
(1) preparing an acidic liquid medium by using sulfuric acid as a main component, and controlling the concentration of the sulfuric acid to be 50-100% of the total concentration of the acidic liquid medium;
(2) adding 0.1-1% of auxiliary additive by mass into an acidic liquid medium to enhance the purification effect on impurity components in the flue gas and obtain a washing solution
(3) Spraying the washing solution cold solution prepared in the step (2) on flue gas (flue gas to be deeply purified before entering flue gas acid making), and washing and purifying the flue gas in a countercurrent gas-liquid contact mode;
(4) concentrating the acidic liquid and the flue gas mixture after the flue gas is washed by a concentration method, evaporating to remove hydrogen fluoride and hydrogen chloride to obtain a concentrated solution, and collecting and recovering sulfuric acid;
(5) adding a fluorine-chlorine removing agent into the concentrated solution to treat residual fluorine and chlorine in the water, and recovering the heavy metals after removing fluorine and chlorine.
Further, in the step (2), the added auxiliary additive comprises one or more of activated carbon, ceramic porous particles and graphite particles.
Further, in the step (3), the temperature for purifying and washing the flue gas is 25-359 ℃.
Further, in the step (4), the concentration temperature range is controlled to be 110-125 ℃.
Further, in the step (5), the fluorine and chlorine removing agent comprises one or more of bismuth nitrate, aluminum nitrate and sodium silicate, and the mass ratio of the fluorine and chlorine in the concentrated solution to the fluorine and chlorine removing agent is (10-45): 1.
The invention has the beneficial effects that:
the invention replaces water washing in the acid making process with acid washing, can effectively enrich heavy metal ions and realize the recycling of acid, and is suitable for the purification of heavy non-ferrous smelting flue gas and the treatment of arsenic pollution. After heavy non-ferrous smelting flue gas is subjected to gravity dust collection and electric dust collection, a part of auxiliary additive is added into an acid medium solution containing sulfuric acid to prepare a washing solution suitable for washing the flue gas before the acid medium solution enters an acid making link, and the washing solution containing heavy metal and SO are mixed in a spraying or atomizing mode2The flue gas is fully contacted, the flue gas is washed, and dust particles and SO in the flue gas are removed3And trapping the volatile heavy metal in an acidic medium; after washing, the content of impurity components in the flue gas is obviously reduced, the flue gas acid preparation quality requirement is met, the flue gas acid preparation quality requirement is sent to an acid preparation link, and the contents of sulfuric acid and heavy metals in an acid medium obtained after washing are improved; the acid liquid medium after washing is subjected to further concentration and dechlorination to recover sulfuric acid and heavy metals. The invention utilizes the acidic liquid medium to replace water washing for purifying SO2The flue gas can save more than 50 percent of industrial water, can avoid the generation of contaminated acid, effectively recover arsenic and heavy metal elements, fully utilize and recover SO2Soluble sulfur oxides in the flue gas have important significance for arsenic pollution treatment in the heavy non-ferrous metal smelting industry.
The invention uses the concentrated sulfuric acid to wash the nonferrous smelting arsenic-containing flue gas, can greatly save water resources, simultaneously reduce the generation of waste acid, can also play a role in enriching heavy metals, and can also recycle sulfuric acid by adopting evaporation concentration. The invention better improves the problems existing in the prior art, fundamentally solves the technical problems of less heavy metal enrichment, serious water resource consumption and large production amount of waste acid in the process of washing the flue gas, and has wider market prospect.
Drawings
FIG. 1 is a flow chart of the acidic liquid medium for purifying arsenic-containing flue gas.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1:
the washing solutions formulated in this example are shown in table 1.
TABLE 1 cleaning solution Components
A new method for purifying and recycling arsenic-containing flue gas by using an acidic liquid medium comprises the following specific steps:
(1) sulfuric acid is added into the flue gas washing water to prepare an acidic medium solution, so that the concentration of the sulfuric acid accounts for 50% of the total concentration of the washing solution.
(2) Adding 0.1% of auxiliary additive in the washing solution to enhance the washing effect; wherein the added auxiliary additive is activated carbon.
(3) Spraying flue gas (flue gas to be deeply purified before entering flue gas acid making) by using the prepared cold solution of the washing solution, wherein the reaction temperature is room temperature, and washing and purifying the flue gas in a countercurrent gas-liquid contact mode; wherein the temperature for cleaning and washing the flue gas is 359 ℃.
(4) Concentrating the acidic liquid and the flue gas mixture after the flue gas is washed by a concentration method, evaporating to remove hydrogen fluoride and hydrogen chloride, and collecting and recovering sulfuric acid; wherein the concentration temperature range is controlled at 110 ℃.
(5) Adding a fluorine-chlorine removing agent into the concentrated solution to treat residual fluorine and chlorine in the water, removing fluorine and chlorine, and then recovering the enriched heavy metals in a large scale; wherein the fluorine-chlorine remover is bismuth nitrate, and the mass ratio of the fluorine-chlorine in the concentrated solution to the fluorine-chlorine remover is 10: 1.
The main components of the heavy metals recovered from the arsenic-containing flue gas purified by the acidic medium are shown in table 2, the recovery amount of sulfuric acid is shown in table 3, and the components of the flue gas before and after purification are shown in table 4;
TABLE 2 recovery of the main constituents of heavy metals
TABLE 3 comparison of sulfuric acid recovery (copper smelter producing more than 30 million tons of acid produced in a year)
TABLE 4 comparison of smoke constituents before and after cleaning
The results obtained in example 1 are: sulfuric acid is added into the flue gas washing water to prepare an acidic medium solution, so that the concentration of the sulfuric acid accounts for 50% of the total concentration of the washing solution, and 0.1% of activated carbon is added to prepare acidic liquid medium washing water for treating the flue gas containing acid sulfur dioxide. The total smoke trapping efficiency after treatment was 95%. The fluorine removal rate in the concentration process is 88 percent, and the chlorine removal rate is 90 percent. After the fluorine and chlorine removing agent is added, the fluorine removal rate is 95 percent, and the chlorine removal rate is 97 percent. Taking a copper smelting plant producing more than 30 ten thousand tons of acid in one year in Yunnan as an example, the washed SO2The smoke is about 15000m3And the recovery rate of sulfuric acid after acid washing and concentration is increased by 82 percent. As can be seen from table 4, the base material before and after the flue gas scrubbing is in equilibrium. The production of waste acid is reduced by acid washing, and 50% of industrial water is saved.
Example 2:
the washing solutions formulated in this example are shown in table 5.
TABLE 5 acidic liquid Medium composition
A new method for purifying and recycling arsenic-containing flue gas by using an acidic liquid medium comprises the following specific steps:
(1) sulfuric acid is added into the flue gas washing water to prepare an acidic medium solution, so that the concentration of the sulfuric acid accounts for 100% of the total concentration of the washing solution.
(2) Adding 1% of auxiliary additive by mass into the washing solution to enhance the washing effect; wherein the added auxiliary additive is ceramic porous particles.
(3) Spraying flue gas (flue gas to be deeply purified before entering flue gas acid making) by using the prepared acidic liquid medium cold solution, wherein the reaction temperature is 350 ℃, and washing and purifying the flue gas in a countercurrent gas-liquid contact mode; wherein the temperature for cleaning and washing the flue gas is room temperature.
(4) Concentrating the acidic liquid and the flue gas mixture after the flue gas is washed by a concentration method, evaporating to remove hydrogen fluoride and hydrogen chloride, and collecting and recovering sulfuric acid; wherein the concentration temperature range is controlled at 125 ℃.
(5) Adding a fluorine-chlorine removing agent into the concentrated solution to treat residual fluorine and chlorine in the water, removing fluorine and chlorine, and then recovering the enriched heavy metals in a large scale; wherein the fluorine-chlorine removing agent is aluminum nitrate, and the mass ratio of the fluorine-chlorine to the fluorine-chlorine removing agent in the mixed solution is 45: 1.
The main components of the heavy metals recovered from the arsenic-containing flue gas purified by the acidic medium are shown in Table 8, the recovery amount of sulfuric acid is shown in Table 9, and the components of the flue gas before and after purification are shown in Table 10;
TABLE 6 recovery of the main constituents of heavy metals
TABLE 7 comparison of sulfuric acid recovery (copper smelter producing more than 30 million tons of acid produced in a year)
TABLE 8 comparison of smoke constituents before and after cleaning
The results obtained in example 2 are: sulfuric acid is added into the flue gas washing water to prepare an acidic medium solution, so that the concentration of the sulfuric acid accounts for 100% of the total concentration of the washing solution, and simultaneously 1% of activated carbon is added to prepare the acidic liquid medium washing water for treating the flue gas containing acid sulfur dioxide. The total smoke trapping efficiency after treatment is 98%. The fluorine removal rate in the concentration process is 92%, and the chlorine removal rate is 93%. After the fluorine and chlorine removing agent is added, the fluorine removal rate is 97 percent, and the chlorine removal rate is 99 percent. Taking a copper smelting plant producing more than 30 ten thousand tons of acid in one year in Yunnan as an example, the washed SO2The smoke is about 15000m3The recovery rate of sulfuric acid after acid washing and concentration is increased by 66%. As can be seen from table 8, the base material before and after the flue gas scrubbing was in equilibrium. The production of waste acid is reduced by acid washing, and 100% of industrial water is saved.
Example 3:
the sulfuric acid concentrations formulated in this example are shown in table 9.
TABLE 9 acidic liquid Medium composition
A new method for purifying and recycling arsenic-containing flue gas by using an acidic liquid medium comprises the following specific steps:
(1) sulfuric acid is added into the flue gas washing water to prepare an acidic medium solution, so that the concentration of the sulfuric acid accounts for 75% of the total concentration of the washing solution.
(2) Adding 0.5% of auxiliary additive in the washing solution to enhance the washing effect; wherein the added auxiliary additive is graphite particles.
(3) Spraying flue gas (flue gas to be deeply purified before entering flue gas acid making) by using the prepared acidic liquid medium cold solution, wherein the reaction temperature is 150 ℃, and washing and purifying the flue gas in a countercurrent gas-liquid contact mode; wherein the temperature for cleaning and washing the flue gas is 155 ℃.
(4) Concentrating the acidic liquid and the flue gas mixture after the flue gas is washed by a concentration method, evaporating to remove hydrogen fluoride and hydrogen chloride, and collecting and recovering sulfuric acid; wherein the concentration temperature range is controlled at 120 ℃.
(5) Adding a fluorine-chlorine removing agent into the concentrated solution to treat residual fluorine and chlorine in the water, removing fluorine and chlorine, and then recovering the enriched heavy metals in a large scale; wherein the fluorine-chlorine removing agent is sodium silicate, and the mass ratio of the fluorine-chlorine to the fluorine-chlorine removing agent in the mixed solution is 27: 1.
The main components of the heavy metals recovered from the arsenic-containing flue gas purified by the acidic medium are shown in table 10, the recovery amount of sulfuric acid is shown in table 11, and the components of the flue gas before and after purification are shown in table 12;
TABLE 10 recovery of the main constituents of heavy metals
TABLE 11 comparison of sulfuric acid recovery (copper smelter producing more than 30 million tons of acid produced in a year)
TABLE 12 comparison of smoke constituents before and after cleaning
The results obtained in example 3 are: sulfuric acid is added into the flue gas washing water to prepare an acidic medium solution, so that the concentration of the sulfuric acid accounts for 100% of the total concentration of the washing solution, and simultaneously 1% of activated carbon is added to prepare the acidic liquid medium washing water for treating the flue gas containing acid sulfur dioxide. Total smoke dust collecting efficiency after treatmentThe content was 93%. The fluorine removal rate in the concentration process is 89%, and the chlorine removal rate is 91%. After the fluorine and chlorine removing agent is added, the fluorine removal rate is 95 percent, and the chlorine removal rate is 97 percent. Taking a copper smelting plant producing more than 30 ten thousand tons of acid in one year in Yunnan as an example, the washed SO2The smoke amount is about 15000m3The recovery rate of sulfuric acid after acid washing and concentration is increased by 62%. As can be seen from table 12, the base material before and after the flue gas scrubbing was in equilibrium. The production of waste acid is reduced by acid washing, and 75% of industrial water is saved.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (5)
1. A new method for purifying and recycling arsenic-containing flue gas by using an acidic liquid medium is characterized in that: the method comprises the following specific steps:
(1) preparing an acidic liquid medium by using sulfuric acid as a main component, and controlling the concentration of the sulfuric acid to be 50-100% of the total concentration of the acidic liquid medium;
(2) adding 0.1-1% of auxiliary additive by mass into an acidic liquid medium to enhance the purification effect on impurity components in the smoke, thereby obtaining a washing solution
(3) Spraying the cold solution of the washing solution prepared in the step (2) on the flue gas, and washing and purifying the flue gas in a countercurrent gas-liquid contact mode;
(4) concentrating the acidic liquid and the flue gas mixture after the flue gas is washed by a concentration method, evaporating to remove hydrogen fluoride and hydrogen chloride to obtain a concentrated solution, and collecting and recovering sulfuric acid;
(5) adding a fluorine-chlorine removing agent into the concentrated solution to treat residual fluorine and chlorine in the water, and recovering the heavy metals after removing fluorine and chlorine.
2. The method of claim 1, wherein the acidic liquid medium is used for purifying and recycling arsenic-containing flue gas, and the method comprises the following steps: in the step (2), the added auxiliary additive comprises one or more of activated carbon, ceramic porous particles and graphite particles.
3. The method of claim 1 or 2, wherein the acidic liquid medium is used for purifying and recycling arsenic-containing flue gas, and the method comprises the following steps: in the step (3), the temperature for purifying and washing the flue gas is 25-359 ℃.
4. The method of any one of claims 1 to 3, wherein the acidic liquid medium is used for purifying and recycling arsenic-containing flue gas, and the method comprises the following steps: in the step (4), the concentration temperature range is controlled to be 110-125 ℃.
5. The method of any one of claims 1 to 4, wherein the acidic liquid medium is used for purifying and recycling arsenic-containing flue gas, and the method comprises the following steps: in the step (5), the fluorine and chlorine removing agent comprises one or more of bismuth nitrate, aluminum nitrate and sodium silicate, and the mass ratio of the fluorine and chlorine in the concentrated solution to the fluorine and chlorine removing agent is (10-45): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011106886.XA CN112387096A (en) | 2020-10-16 | 2020-10-16 | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011106886.XA CN112387096A (en) | 2020-10-16 | 2020-10-16 | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112387096A true CN112387096A (en) | 2021-02-23 |
Family
ID=74596874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011106886.XA Pending CN112387096A (en) | 2020-10-16 | 2020-10-16 | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112387096A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113289473A (en) * | 2021-06-11 | 2021-08-24 | 封云 | Method for treating heavy metal before smelting flue gas desulfurization |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258714A (en) * | 2014-10-22 | 2015-01-07 | 宝钢金属有限公司 | Method for flue gas purification and dust harmless treatment of refuse incineration power plant |
| CN105461138A (en) * | 2015-12-28 | 2016-04-06 | 中南大学 | Method for recycling sulfuric acid and hydrochloric acid from smelting wastewater and realizing fluorine open circuit |
| CN105502307A (en) * | 2015-12-24 | 2016-04-20 | 南通三圣石墨设备科技股份有限公司 | Method for removing fluorine and chlorine from waste acid through concentration and special device |
| CN105776703A (en) * | 2016-04-08 | 2016-07-20 | 南通三圣石墨设备科技股份有限公司 | Method for processing smelting waste acid |
| CN106268179A (en) * | 2016-08-25 | 2017-01-04 | 长沙有色冶金设计研究院有限公司 | The energy saving technique of a kind of synthetical recovery sulfuric acid purification spent acid and system |
| CN109019530A (en) * | 2018-10-31 | 2018-12-18 | 河南菲迪泰环境科技有限公司 | A kind of waste acid processing recovery system and its processing recovery method |
| CN109055748A (en) * | 2018-08-30 | 2018-12-21 | 西北矿冶研究院 | Defluorination chlorine agent and preparation method thereof and method for defluorination chlorine using same |
| CN109078351A (en) * | 2018-09-17 | 2018-12-25 | 杭州东日节能技术有限公司 | A kind of defluorinate chlorine tower and technique and device using fluorine chlorine in tower removing sulfuric acid |
| CN110155956A (en) * | 2019-04-18 | 2019-08-23 | 南京汇仁化工设备有限公司 | Fluoride Waste acid treating device and its processing method |
| CN111018221A (en) * | 2019-12-25 | 2020-04-17 | 长沙华时捷环保科技发展股份有限公司 | Method for recycling smelting waste acid wastewater |
-
2020
- 2020-10-16 CN CN202011106886.XA patent/CN112387096A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258714A (en) * | 2014-10-22 | 2015-01-07 | 宝钢金属有限公司 | Method for flue gas purification and dust harmless treatment of refuse incineration power plant |
| CN105502307A (en) * | 2015-12-24 | 2016-04-20 | 南通三圣石墨设备科技股份有限公司 | Method for removing fluorine and chlorine from waste acid through concentration and special device |
| CN105461138A (en) * | 2015-12-28 | 2016-04-06 | 中南大学 | Method for recycling sulfuric acid and hydrochloric acid from smelting wastewater and realizing fluorine open circuit |
| CN105776703A (en) * | 2016-04-08 | 2016-07-20 | 南通三圣石墨设备科技股份有限公司 | Method for processing smelting waste acid |
| CN106268179A (en) * | 2016-08-25 | 2017-01-04 | 长沙有色冶金设计研究院有限公司 | The energy saving technique of a kind of synthetical recovery sulfuric acid purification spent acid and system |
| CN109055748A (en) * | 2018-08-30 | 2018-12-21 | 西北矿冶研究院 | Defluorination chlorine agent and preparation method thereof and method for defluorination chlorine using same |
| CN109078351A (en) * | 2018-09-17 | 2018-12-25 | 杭州东日节能技术有限公司 | A kind of defluorinate chlorine tower and technique and device using fluorine chlorine in tower removing sulfuric acid |
| CN109019530A (en) * | 2018-10-31 | 2018-12-18 | 河南菲迪泰环境科技有限公司 | A kind of waste acid processing recovery system and its processing recovery method |
| CN110155956A (en) * | 2019-04-18 | 2019-08-23 | 南京汇仁化工设备有限公司 | Fluoride Waste acid treating device and its processing method |
| CN111018221A (en) * | 2019-12-25 | 2020-04-17 | 长沙华时捷环保科技发展股份有限公司 | Method for recycling smelting waste acid wastewater |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113289473A (en) * | 2021-06-11 | 2021-08-24 | 封云 | Method for treating heavy metal before smelting flue gas desulfurization |
| CN113289473B (en) * | 2021-06-11 | 2022-11-29 | 封云 | Method for treating heavy metal before smelting flue gas desulfurization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100355485C (en) | Waste gas desulfurizing method with composite absorbant comprising pyrolusite and pH buffering agent | |
| CN110124507B (en) | Method and device for cleaning and treating multi-pollutant flue gas | |
| WO2020024350A1 (en) | System and method for recovering sulfur during copper smelting process | |
| CN110280125B (en) | Containing arsenic and SO3Dry purification method of smelting flue gas | |
| CN102949926B (en) | Method for recycling sulfur dioxide (SO2) and heavy metal in metallurgical gas | |
| CN110127918B (en) | Zero-discharge treatment method and device for acidic flue gas washing wastewater | |
| CN103303877A (en) | Comprehensive multi-gas source low-concentration SO2 fume recycling acid-making technological process | |
| CN109052335A (en) | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid | |
| CN110090548B (en) | Method for wet desulphurization and zinc sulfate recovery of copper slag tailings and zinc smelting fly ash | |
| CN101696062B (en) | Treatment process for waster water from preparation of ammonium paratungstate | |
| US4133650A (en) | Removing sulfur dioxide from exhaust air | |
| CN101597070A (en) | Sintering, pelletizing and stove purifying device of ammonium sulphate solution produced by flue gas desulfurization by ammonia process and method | |
| CN110116991A (en) | A kind of recovery process of metallurgical off-gas acid-making purification waste acid | |
| CN1994868A (en) | Method for producing vitriol and iron ore concentrate using ferrous sulfate | |
| CN201658945U (en) | Sintering smoke purifying system based on heat pipe afterheat recovery technology | |
| CN104383801A (en) | Method and system for treating electronic scrap smoke | |
| CN101979130B (en) | Method for removing hydrogen sulfide from industrial gas in recycling way | |
| CN109244582B (en) | Process for harmless treatment and resource utilization of waste lead storage battery | |
| CN112387096A (en) | Novel method for purifying and recycling arsenic-containing flue gas by using acidic liquid medium | |
| CN111115587A (en) | Method and system for preparing analytically pure sulfuric acid from smelting flue gas | |
| CN109351150B (en) | Device and method for gradient utilization of energy in carbon thermal reduction process | |
| CN209161488U (en) | A kind of system of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid | |
| CN108793089B (en) | Process for producing refined sulfuric acid in sulfuric acid plant | |
| CN204261551U (en) | The system of process electronic waste flue gas | |
| CN113213433B (en) | Method for directly preparing sulfuric acid for storage battery by using secondary lead smelting flue gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |