CN110170222A - A kind of processing method and system of Tungsten smelting exhaust gas - Google Patents
A kind of processing method and system of Tungsten smelting exhaust gas Download PDFInfo
- Publication number
- CN110170222A CN110170222A CN201910399327.3A CN201910399327A CN110170222A CN 110170222 A CN110170222 A CN 110170222A CN 201910399327 A CN201910399327 A CN 201910399327A CN 110170222 A CN110170222 A CN 110170222A
- Authority
- CN
- China
- Prior art keywords
- waste gas
- eluent
- tungsten smelting
- sulfur
- tower
- 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.)
- Granted
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 59
- 239000010937 tungsten Substances 0.000 title claims abstract description 59
- 238000003723 Smelting Methods 0.000 title claims abstract description 57
- 238000003672 processing method Methods 0.000 title 1
- 239000002912 waste gas Substances 0.000 claims abstract description 130
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 74
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 72
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 56
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 54
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011593 sulfur Substances 0.000 claims abstract description 49
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 48
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 38
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 38
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
- 239000007921 spray Substances 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008399 tap water Substances 0.000 claims abstract description 23
- 235000020679 tap water Nutrition 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000005507 spraying Methods 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000003480 eluent Substances 0.000 claims description 123
- 238000010828 elution Methods 0.000 claims description 43
- 239000007800 oxidant agent Substances 0.000 claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- 230000001590 oxidative effect Effects 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006477 desulfuration reaction Methods 0.000 claims description 16
- 230000023556 desulfurization Effects 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 47
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 16
- 239000007788 liquid Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- AQGDXJQRVOCUQX-UHFFFAOYSA-N N.[S] Chemical compound N.[S] AQGDXJQRVOCUQX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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
- B01D53/002—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 by condensation
-
- 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
- B01D53/14—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 by absorption
-
- 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
- B01D53/14—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 by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- 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
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
-
- 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
- B01D53/75—Multi-step processes
-
- 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
- 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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/022—Preparation of aqueous ammonia solutions, i.e. ammonia water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
Abstract
本发明提供了一种钨冶炼废气的处理方法，将钨冶炼废气分别进行一次换热降温处理、自来水循环喷淋、二次换热降温处理、稀盐酸循环喷淋和稀硫酸循环喷淋，得到净化的废气。本发明还提供了一种钨冶炼废气的处理系统，以上方法和系统通过将冷凝降温后的氨水和废气一同进行自来水循环喷淋，不需要加碱和吹脱即可完成氨的高效回收，且通过多级的喷淋吸收，氨、硫的去除效果好，同时得到具有较高价值的氨水、氯化铵、硫酸铵等产品，喷淋所用溶液均进行循环使用，一方面可以提高得到的产品浓度，另一方面减少试剂消耗，能耗低、成本低，实现了钨冶炼废气的高效吸收和利用。
The invention provides a method for treating waste gas from tungsten smelting. The waste gas from tungsten smelting is respectively subjected to primary heat exchange cooling treatment, tap water circulating spraying, secondary heat exchange cooling treatment, dilute hydrochloric acid circulating spraying and dilute sulfuric acid circulating spraying to obtain Purified exhaust gas. The invention also provides a treatment system for waste gas from tungsten smelting. The above method and system can complete the efficient recovery of ammonia without adding alkali and stripping by performing tap water cycle spraying together with the condensed and cooled ammonia water and waste gas. Through multi-stage spray absorption, the removal effect of ammonia and sulfur is good, and at the same time, high-value ammonia water, ammonium chloride, ammonium sulfate and other products are obtained. On the other hand, it reduces the consumption of reagents, has low energy consumption and low cost, and realizes the efficient absorption and utilization of tungsten smelting waste gas.
Description
技术领域technical field
本发明涉及废气处理技术领域，具体涉及一种钨冶炼废气的处理方法和系统。The invention relates to the technical field of waste gas treatment, in particular to a treatment method and system for waste gas of tungsten smelting.
背景技术Background technique
仲钨酸铵(APT)是制取钨粉末的重要前驱体，生产仲钨酸铵的主要工艺为，首先钨矿通过氢氧化钠分解/碳酸钠分解法制备钨酸钠料液，然后通过传统分解法、溶剂萃取法、离子交换法等将钨酸钠料液转换为钨酸铵料液，然后对钨酸铵料液进行净化除钼，最后采用蒸发结晶法制得仲钨酸铵固体。其中在钨酸铵料液净化除钼的过程中，为达到较好的除钼效果，要先将钨酸铵料液进行硫化，然后再进行除钼操作，经过深度除钼的钨酸铵硫化料液在最后蒸发结晶生产APT的环节，将产生大量的含硫含氨废气，对环境产生污染。Ammonium paratungstate (APT) is an important precursor for the preparation of tungsten powder. The main process for producing ammonium paratungstate is to first prepare sodium tungstate feed solution from tungsten ore by sodium hydroxide decomposition/sodium carbonate decomposition method, and then by traditional decomposition method and solvent extraction method. , ion exchange method, etc., the sodium tungstate feed liquid is converted into ammonium tungstate feed liquid, then the ammonium tungstate feed liquid is purified to remove molybdenum, and finally ammonium paratungstate solid is obtained by evaporation crystallization method. Among them, in the process of purifying and removing molybdenum from the ammonium tungstate feed solution, in order to achieve a better molybdenum removal effect, the ammonium tungstate feed solution should be vulcanized first, and then the molybdenum removal operation should be carried out. In the final process of evaporating and crystallizing the feed liquid to produce APT, a large amount of sulfur-containing and ammonia-containing waste gas will be generated, which will pollute the environment.
中国专利文献CN101816841A公开了一种仲钨酸铵(APT)蒸发结晶过程中产生的含氨水蒸汽中氨氮的回收利用方法，首先利用换热器将含氨水蒸汽冷凝回收为稀氨水，将回收的稀氨水加入双氧水作为脱硫剂搅拌脱硫，然后加入碱使溶液pH≥7，加热至不沸腾，再鼓入压缩空气吹脱氨气，脱出的氨气用中性或酸性溶液循环喷淋吸收提浓，得到的溶液直接返回工艺流程作为解吸剂使用，或进行蒸发结晶，该方法的氨氮脱除率较高，但该方法需要加碱，且为了保持较高的pH值，碱的消耗量大，且需要吹脱氨气，能耗大，吹脱后氨浓度较低的溶液需要采用离子交换树脂进行二次处理，成本高。Chinese patent document CN101816841A discloses a method for recycling ammonia nitrogen in the ammonia-containing water vapor generated in the ammonium paratungstate (APT) evaporation and crystallization process. First, the ammonia-containing water vapor is condensed and recovered into dilute ammonia water by using a heat exchanger, and the recovered dilute ammonia water is added to hydrogen peroxide. Stir and desulfurize as a desulfurizing agent, then add alkali to make the pH of the solution ≥ 7, heat it until it does not boil, and then blow compressed air to remove ammonia gas. Directly returning to the process flow as a desorbent, or performing evaporative crystallization, the ammonia nitrogen removal rate of this method is high, but this method needs to add alkali, and in order to maintain a higher pH value, the consumption of alkali is large, and it needs to be stripped. Ammonia gas has high energy consumption, and the solution with lower ammonia concentration after stripping needs to be treated with ion exchange resin for secondary treatment, and the cost is high.
发明内容SUMMARY OF THE INVENTION
因此，本发明要解决的技术问题在于克服现有技术中钨冶炼含氨含硫废气的处理过程中碱的消耗量大、能耗高、成本高的缺陷，从而提供一种低试剂消耗、低能耗、成本低，氨硫的吸收效果好且可得到高附加值的副产品的一种钨冶炼废气的处理方法和系统。Therefore, the technical problem to be solved by the present invention is to overcome the defects of large consumption of alkali, high energy consumption and high cost in the treatment process of tungsten smelting ammonia-containing and sulfur-containing waste gas in the prior art, thereby providing a low reagent consumption, low energy consumption A method and system for treating waste gas from tungsten smelting, which has the advantages of low consumption, low cost, good absorption effect of ammonia and sulfur, and can obtain high value-added by-products.
为此,本发明提供了一种钨冶炼废气的处理方法，包括，For this reason, the present invention provides a kind of treatment method of tungsten smelting waste gas, comprising,
S1、将钨冶炼废气进行一次换热降温处理，得到一次冷凝氨水和废气；S1, the tungsten smelting waste gas is subjected to a heat exchange and cooling treatment to obtain a condensed ammonia water and waste gas;
S2、将S1得到的一次冷凝氨水和废气进行自来水循环喷淋，得到含硫氨水和废气；S2, carry out tap water cycle spraying with the primary condensed ammonia water and waste gas obtained in S1 to obtain sulfur-containing ammonia water and waste gas;
S3、将S2得到的废气进行二次换热降温处理，得到二次冷凝氨水和废气；S3, the waste gas obtained by S2 is subjected to secondary heat exchange and cooling treatment to obtain secondary condensed ammonia water and waste gas;
S4、将S3得到的二次冷凝氨水和废气进行稀盐酸循环喷淋，得到含硫氯化铵溶液和废气；S4, carry out dilute hydrochloric acid circulating spray with the secondary condensed ammonia water and waste gas obtained in S3, obtain sulfur-containing ammonium chloride solution and waste gas;
S5、将S4得到的废气进行稀硫酸循环喷淋，得到含硫硫酸铵溶液和废气；S5, carrying out dilute sulfuric acid circulating spraying on the waste gas obtained in S4 to obtain sulfur-containing ammonium sulfate solution and waste gas;
S6、将S5得到的废气进行二次自来水循环喷淋，得到净化的废气。S6, the waste gas obtained in S5 is subjected to secondary tap water circulating spray to obtain purified waste gas.
所述的钨冶炼废气的处理方法，还包括向所述含硫氨水、含硫氯化铵溶液、含硫硫酸铵溶液中加入氧化剂脱硫的步骤，得到脱硫后氨水、脱硫后氯化铵溶液和脱硫后硫酸铵溶液。The method for treating waste gas from tungsten smelting further includes the step of adding an oxidant for desulfurization to the sulfur-containing ammonia water, sulfur-containing ammonium chloride solution, and sulfur-containing ammonium sulfate solution, to obtain the desulfurized ammonia water, the desulfurized ammonium chloride solution, and the sulfur-containing ammonium chloride solution. Ammonium sulfate solution after desulfurization.
所述的钨冶炼废气的处理方法，S2步骤中，当含硫氨水中游离氨的浓度≥50g/L时，加入氧化剂，当氨水中S2-浓度为0g/L时，停止加入氧化剂；S4步骤中，当含硫氯化铵溶液中氯化铵浓度≥150g/L时，加入氧化剂，当氯化铵溶液中S2-浓度为0g/L时，停止加入氧化剂；S5步骤中，当含硫硫酸铵溶液中硫酸铵浓度≥150g/L时，加入氧化剂，当硫酸铵溶液中S2-浓度为0g/L时，停止加入氧化剂。In the method for treating waste gas from tungsten smelting, in step S2, when the concentration of free ammonia in the sulfur - containing ammonia water is ≥50 g/L, add an oxidant, and when the concentration of S2- in the ammonia water is 0 g/L, stop adding an oxidant; S4 In the step, when the concentration of ammonium chloride in the sulfur-containing ammonium chloride solution is greater than or equal to 150 g/L, add an oxidizing agent, and when the S 2- concentration in the ammonium chloride solution is 0 g/L, stop adding an oxidizing agent; When the ammonium sulfate concentration in the ammonium sulfate solution is greater than or equal to 150g/L, add the oxidant, and when the S 2- concentration in the ammonium sulfate solution is 0g/L, stop adding the oxidant.
所述的钨冶炼废气的处理方法，所述氧化剂为双氧水。In the method for treating waste gas from tungsten smelting, the oxidant is hydrogen peroxide.
所述的钨冶炼废气的处理方法，S1步骤中，所述一次换热降温处理时，控制换热出水温度为≤45℃。In the method for treating waste gas from tungsten smelting, in step S1, during the primary heat exchange cooling treatment, the temperature of the heat exchange outlet water is controlled to be ≤45°C.
所述的钨冶炼废气的处理方法，S3步骤中，所述二次换热降温处理时，控制换热出水温度为≤35℃。In the method for treating waste gas from tungsten smelting, in step S3, during the secondary heat exchange and cooling treatment, the temperature of the heat exchange outlet water is controlled to be ≤35°C.
所述的钨冶炼废气的处理方法，S4步骤中，所述稀盐酸的质量浓度为5-10％。In the method for treating waste gas from tungsten smelting, in step S4, the mass concentration of the dilute hydrochloric acid is 5-10%.
所述的钨冶炼废气的处理方法，S5步骤中，所述稀硫酸的质量浓度为5-10％。In the method for treating tungsten smelting waste gas, in step S5, the mass concentration of the dilute sulfuric acid is 5-10%.
所述的钨冶炼废气的处理方法，所述得到的脱硫后氨水、脱硫后氯化铵溶液返回仲钨酸铵的生产系统，作为解吸剂使用，脱硫后硫酸铵溶液用于结晶回收硫酸铵。In the method for treating waste gas from tungsten smelting, the obtained desulfurized ammonia water and desulfurized ammonium chloride solution are returned to the production system of ammonium paratungstate to be used as a desorbent, and the desulfurized ammonium sulfate solution is used to crystallize and recover ammonium sulfate.
所述的钨冶炼废气的处理方法，S6步骤中，通过二次自来水循环喷淋，将废气中残余的氨和氯化氢气体淋洗吸附，废气达标后外排，淋洗水进入环保处理系统。In the described method for treating waste gas from tungsten smelting, in step S6, the residual ammonia and hydrogen chloride gas in the waste gas are washed and adsorbed by secondary tap water circulating spray, the waste gas is discharged after reaching the standard, and the washing water enters the environmental protection treatment system.
本发明还提供了一种钨冶炼废气的处理系统，包括，根据所述钨冶炼废气的处理顺序，顺次连接的第一换热器、第一淋洗塔、第二换热器、第二淋洗塔、第三淋洗塔、第四淋洗塔，所述淋洗塔均配置有淋洗液槽和淋洗泵，所述淋洗液槽与所述淋洗塔的淋洗液出口连接，所述淋洗泵与所述淋洗塔的淋洗液入口连接，所述淋洗液槽与淋洗泵连接，所述淋洗液槽还设有氧化剂入口、淋洗液补加口和淋洗液排出口。The present invention also provides a treatment system for tungsten smelting waste gas, comprising, according to the treatment sequence of the tungsten smelting waste gas, a first heat exchanger, a first washing tower, a second heat exchanger, a second heat exchanger, a second The elution tower, the third elution tower and the fourth elution tower are all equipped with an eluent tank and an eluent pump, the eluent tank and the eluent outlet of the eluent tower The eluent pump is connected to the eluent inlet of the elution tower, the eluent tank is connected to the eluent pump, and the eluent tank is also provided with an oxidant inlet and an eluent replenishing port and eluent drain.
所述的钨冶炼废气的处理系统，还包括第一风机、第二风机和第三风机，所述第一风机与所述第一换热器的气体入口连接，所述第二风机连接于所述第二换热器和第二淋洗塔之间，所述第三风机连接于所述第三淋洗塔和第四淋洗塔之间。The tungsten smelting waste gas treatment system further includes a first fan, a second fan and a third fan, the first fan is connected to the gas inlet of the first heat exchanger, and the second fan is connected to the between the second heat exchanger and the second rinsing tower, and the third fan is connected between the third rinsing tower and the fourth rinsing tower.
所述的钨冶炼废气的处理系统，所述换热器为板式换热器，换热面积为100m2。In the treatment system for tungsten smelting waste gas, the heat exchanger is a plate heat exchanger, and the heat exchange area is 100m 2 .
本发明技术方案，具有如下优点：The technical scheme of the present invention has the following advantages:
1.本发明提供的一种钨冶炼废气的处理方法，包括，S1、将钨冶炼废气进行一次换热降温处理，得到一次冷凝氨水和废气；S2、将S1得到的一次冷凝氨水和废气进行自来水循环喷淋，得到含硫氨水和废气；S3、将S2得到的废气进行二次换热降温处理，得到二次冷凝氨水和废气；S4、将S3得到的二次冷凝氨水和废气进行稀盐酸循环喷淋，得到含硫氯化铵溶液和废气；S5、将S4得到的废气进行稀硫酸循环喷淋，得到含硫硫酸铵溶液和废气；S6、将S5得到的废气进行二次自来水循环喷淋，得到净化的废气，该方法通过一次换热降温处理，对废气进行初步冷凝降温，将得到的氨水和含氨废气一同进行自来水循环喷淋，由于喷淋所用的自来水是循环使用的，因此可以对氨水起到提浓作用，不需要加碱和吹脱，即可制得高浓度的氨水，可以作为仲钨酸铵生产流程的解吸剂使用，且氨水与氯化铵、硫酸铵相比市场价值更高，实现了氨的低成本制取和高价值利用。处理后的废气再进行二次换热降温处理，可以进一步对含氨废气进行冷凝降温处理，通过两次冷凝降温，可大幅度减少风量，增加气体与喷淋液的接触时间，提高喷淋效果。之后废气通过稀盐酸循环喷淋，可以在吸收硫和氨气的同时，制得可以用作解吸剂的氯化铵，实现了废气的高效利用，但由于盐酸是挥发性较强的酸，采用盐酸喷淋烟气较大，为了保证对氨的喷淋效果，增加了硫酸喷淋，强化了喷淋效果的同时，制得硫酸铵副产品，也为后续废气达标排放提供保障。最后废气又进行二次自来水循环喷淋，一方面可以吸收经过稀盐酸、稀硫酸喷淋后废气中残余的酸雾，另一方面可以吸收废气中残余的微量氨，同时也可以对废气的异味进行吸收，保证废气的达标排放。该方法通过将冷凝降温后的氨水和废气一同进行自来水循环喷淋，不需要加碱和吹脱即可完成氨的高效回收，又通过多级的喷淋吸收，氨、硫的去除效果好，同时得到具有较高价值的氨水、氯化铵、硫酸铵等产品，且喷淋所用溶液均进行循环使用，一方面可以提高得到的产品浓度，另一方面减少试剂消耗，能耗低、成本低，实现了钨冶炼废气的高效吸收和利用。1. the treatment method of a kind of tungsten smelting waste gas provided by the invention, comprising, S1, carry out a heat exchange and cooling process with tungsten smelting waste gas, obtain a condensed ammoniacal liquor and waste gas; S2, carry out tap water with a condensed ammoniacal liquor and waste gas obtained by S1. Circulating spraying to obtain sulfur-containing ammonia water and waste gas; S3, carrying out secondary heat exchange and cooling treatment on the waste gas obtained in S2, to obtain secondary condensed ammonia water and waste gas; S4, carrying out dilute hydrochloric acid circulation with the secondary condensed ammonia water and waste gas obtained in S3 Spray to obtain sulfur-containing ammonium chloride solution and waste gas; S5, carry out dilute sulfuric acid circulating spraying on the waste gas obtained in S4, to obtain sulfur-containing ammonium sulfate solution and waste gas; S6, carry out secondary tap water circulating spraying on the waste gas obtained in S5 , to obtain purified waste gas, the method performs preliminary condensation and cooling on the waste gas through a heat exchange and cooling treatment, and the obtained ammonia water and ammonia-containing waste gas are subjected to tap water circulating spraying. Since the tap water used for spraying is recycled, it can It can concentrate ammonia water without adding alkali and stripping to obtain high-concentration ammonia water, which can be used as a desorbent in the production process of ammonium paratungstate, and the market value of ammonia water is higher than that of ammonium chloride and ammonium sulfate. , realizing the low-cost production and high-value utilization of ammonia. The treated waste gas is then subjected to secondary heat exchange and cooling treatment, which can further condense and cool the ammonia-containing waste gas. Through two condensation cooling, the air volume can be greatly reduced, the contact time between the gas and the spray liquid can be increased, and the spray effect can be improved. . After that, the waste gas is sprayed through the dilute hydrochloric acid cycle, which can absorb sulfur and ammonia gas and obtain ammonium chloride which can be used as a desorbent, thus realizing the efficient utilization of waste gas. However, since hydrochloric acid is a highly volatile acid, the The hydrochloric acid spraying flue gas is relatively large. In order to ensure the spraying effect of ammonia, sulfuric acid spraying is added, which strengthens the spraying effect, and produces ammonium sulfate by-products, which also provides guarantee for the subsequent discharge of waste gas. Finally, the exhaust gas is sprayed with tap water for a second time. On the one hand, it can absorb the residual acid mist in the exhaust gas after being sprayed with dilute hydrochloric acid and dilute sulfuric acid; Absorb it to ensure that the exhaust gas is discharged up to the standard. In the method, the condensed and cooled ammonia water and waste gas are sprayed together with tap water, and high-efficiency recovery of ammonia can be accomplished without adding alkali and stripping, and through multi-stage spray absorption, the removal effect of ammonia and sulfur is good. At the same time, high-value ammonia water, ammonium chloride, ammonium sulfate and other products are obtained, and the solutions used for spraying are all recycled. On the one hand, the concentration of the obtained products can be increased, on the other hand, the consumption of reagents can be reduced, and the energy consumption and cost are low. , to achieve efficient absorption and utilization of tungsten smelting waste gas.
2.本发明提供的一种钨冶炼废气的处理方法，还包括向所述含硫氨水、含硫氯化铵溶液、含硫硫酸铵溶液中加入氧化剂脱硫的步骤，得到脱硫后氨水、脱硫后氯化铵溶液和脱硫后硫酸铵溶液，通过加入氧化剂，可以将硫氧化，去除溶液中的S2-，得到脱硫后的溶液可以直接用于仲钨酸铵生产流程中的解吸步骤或结晶回收，实现高效利用。2. A method for treating tungsten smelting waste gas provided by the present invention further comprises the step of adding oxidant desulfurization to the sulfur-containing ammonia water, sulfur-containing ammonium chloride solution, and sulfur-containing ammonium sulfate solution to obtain the desulfurized ammonia water and the desulfurized ammonia solution. Ammonium chloride solution and ammonium sulfate solution after desulfurization, by adding an oxidant, can oxidize sulfur to remove S 2- in the solution, and the obtained solution after desulfurization can be directly used in the desorption step or crystallization recovery in the production process of ammonium paratungstate to achieve high efficiency use.
3.本发明提供的一种钨冶炼废气的处理方法，S2步骤中，当含硫氨水中游离氨的浓度≥50g/L时，加入氧化剂，当氨水中S2-浓度为0g/L时，停止加入氧化剂；S4步骤中，当含硫氯化铵溶液中氯化铵浓度≥150g/L时，加入氧化剂，当氯化铵溶液中S2-浓度为0g/L时，停止加入氧化剂；S5步骤中，当含硫硫酸铵溶液中硫酸铵浓度≥150g/L时，加入氧化剂，当硫酸铵溶液中S2-浓度为0g/L时，停止加入氧化剂，通过控制加入氧化剂时游离氨、氯化铵、硫酸铵的浓度，可以保证得到的溶液具有较高的浓度，脱硫后不需要二次处理即可直接作为解吸剂使用或结晶回收；通过控制S2-浓度为0g/L时停止加入氧化剂，保证S2-被充分氧化，使硫脱除彻底。3. A method for treating waste gas from tungsten smelting provided by the present invention, in step S2, when the concentration of free ammonia in the sulfur - containing ammonia water is ≥50 g/L, an oxidant is added, and when the S2- concentration in the ammonia water is 0 g/L, Stop adding oxidant; in step S4, when the concentration of ammonium chloride in the sulfur-containing ammonium chloride solution is greater than or equal to 150 g/L, add oxidizing agent, and when the S 2- concentration in the ammonium chloride solution is 0 g/L, stop adding oxidizing agent; S5 In the step, when the concentration of ammonium sulfate in the sulfur-containing ammonium sulfate solution is greater than or equal to 150 g/L, add an oxidizing agent, when the S 2- concentration in the ammonium sulfate solution is 0 g/L, stop adding an oxidizing agent, and control the free ammonia, chlorine and chlorine when adding an oxidizing agent. The concentration of ammonium chloride and ammonium sulfate can ensure that the obtained solution has a higher concentration, and can be directly used as a desorbent or crystallized without secondary treatment after desulfurization; by controlling the S2- concentration is 0g/L, stop adding Oxidant, to ensure that S 2- is fully oxidized, so that the sulfur removal is complete.
4.本发明提供的一种钨冶炼废气的处理方法，所述氧化剂为双氧水，通过加入双氧水作为氧化剂，可以较好地将硫氧化脱除。4. The present invention provides a method for treating waste gas from tungsten smelting, wherein the oxidant is hydrogen peroxide, and by adding hydrogen peroxide as the oxidant, sulfur can be preferably removed by oxidation.
5.本发明提供的一种钨冶炼废气的处理方法，S1步骤中，所述一次换热降温处理时，控制换热出水温度为≤45℃，通过控制换热出水温度为≤45℃，可以使从仲钨酸铵制备过程中排出的温度较高的废气降低温度，将废气中大部分的氨冷凝下来，制取更多价值更高的氨水，提高对氨的利用效率。5. In a method for treating tungsten smelting waste gas provided by the present invention, in step S1, during the first heat exchange and cooling treatment, the temperature of the heat exchange outlet water is controlled to be ≤45°C, and the temperature of the heat exchange outlet water is controlled to be ≤45°C, which can be The temperature of the waste gas with higher temperature discharged from the preparation process of ammonium paratungstate is lowered, and most of the ammonia in the waste gas is condensed to produce more ammonia water with higher value and improve the utilization efficiency of ammonia.
6.本发明提供的一种钨冶炼废气的处理方法，S3步骤中，所述二次换热降温处理时，控制换热出水温度为≤35℃，由于经过一次冷凝处理，含氨废气温度已经下降，通过控制二次换热出水温度，可以进一步冷凝废气中剩余的氨气，大幅度降低风量，增加气体与喷淋液的接触时间，提高喷淋效果。6. A method for treating tungsten smelting waste gas provided by the present invention, in step S3, during the secondary heat exchange and cooling treatment, the temperature of the heat exchange outlet water is controlled to be ≤35°C. By controlling the effluent temperature of the secondary heat exchange, the remaining ammonia gas in the exhaust gas can be further condensed, the air volume can be greatly reduced, the contact time between the gas and the spray liquid can be increased, and the spray effect can be improved.
7.本发明提供的一种钨冶炼废气的处理方法，S4步骤中，所述稀盐酸的质量浓度为5-10％，通过控制稀盐酸的浓度，可以保证对氨的充分吸收。7. In a method for treating waste gas from tungsten smelting provided by the present invention, in step S4, the mass concentration of the dilute hydrochloric acid is 5-10%, and by controlling the concentration of dilute hydrochloric acid, the sufficient absorption of ammonia can be ensured.
8.本发明提供的一种钨冶炼废气的处理方法，S5步骤中，所述稀硫酸的质量浓度为5-10％，通过控制稀硫酸的浓度，可以保证对氨的充分吸收。8. In a method for treating tungsten smelting waste gas provided by the present invention, in step S5, the mass concentration of the dilute sulfuric acid is 5-10%, and by controlling the concentration of the dilute sulfuric acid, the sufficient absorption of ammonia can be ensured.
9.本发明提供了一种钨冶炼废气的处理系统，包括，根据所述钨冶炼废气的处理顺序，顺次连接的第一换热器、第一淋洗塔、第二换热器、第二淋洗塔、第三淋洗塔、第四淋洗塔，所述淋洗塔均配置有淋洗液槽和淋洗泵，所述淋洗液槽与所述淋洗塔的淋洗液出口连接，所述淋洗泵与所述淋洗塔的淋洗液入口连接，所述淋洗液槽与淋洗泵连接，所述淋洗液槽还设有氧化剂入口、淋洗液补加口和淋洗液排出口，该系统通过将第一换热器与第一淋洗塔相连，可以将通过第一换热器冷凝降温后的氨水和废气一同进入第一淋洗塔进行自来水循环喷淋，不需要加碱和吹脱即可完成氨的高效回收，通过设置多级喷淋塔进行多级的喷淋吸收，氨、硫的去除效果好，同时得到具有较高价值的氨水、氯化铵、硫酸铵等产品，且喷淋塔均配置有淋洗液槽和淋洗泵，淋洗液槽与淋洗塔的淋洗液出口连接，与淋洗液槽相连的淋洗泵与淋洗塔的淋洗液入口连接，淋洗液流入淋洗液槽，淋洗泵又将淋洗液槽中的淋洗液循环泵入淋洗塔，使所用溶液均进行循环使用，一方面可以提高得到的产品浓度，另一方面减少试剂消耗，能耗低、成本低，实现了钨冶炼废气的高效吸收和利用。9. The present invention provides a treatment system for tungsten smelting waste gas, comprising, according to the treatment sequence of the tungsten smelting waste gas, a first heat exchanger, a first washing tower, a second heat exchanger, a first heat exchanger, a first The second elution tower, the third elution tower, and the fourth elution tower are all equipped with an eluent tank and an eluent pump, and the eluent tank and the eluent of the elution tower The outlet is connected, the eluent pump is connected with the eluent inlet of the elution tower, the eluent tank is connected with the eluent pump, and the eluent tank is also provided with an oxidant inlet, and an eluent supplement The system connects the first heat exchanger with the first leaching tower, and the ammonia water and waste gas after condensed and cooled by the first heat exchanger can enter the first leaching tower together for tap water circulation By spraying, high-efficiency recovery of ammonia can be completed without adding alkali and stripping. By setting up a multi-stage spray tower for multi-stage spray absorption, the removal effect of ammonia and sulfur is good, and at the same time, high-value ammonia water, Ammonium chloride, ammonium sulfate and other products, and the spray tower is equipped with an eluent tank and an eluent pump. It is connected to the eluent inlet of the eluent tower, the eluent flows into the eluent tank, and the eluent pump circulates the eluent in the eluent tank into the eluent tower, so that the solution used is recycled. On the one hand, the obtained product concentration can be increased, on the other hand, the consumption of reagents can be reduced, the energy consumption and cost are low, and the efficient absorption and utilization of tungsten smelting waste gas can be realized.
10.本发明提供了一种钨冶炼废气的处理系统，还包括第一风机、第二风机和第三风机，所述第一风机与所述第一换热器的气体入口连接，所述第二风机连接于所述第二换热器和第二淋洗塔之间，所述第三风机连接于所述第三淋洗塔和第四淋洗塔之间，通过设置风机，可以更好地将气体引入各个装置，提高废气处理效率。10. The present invention provides a treatment system for tungsten smelting waste gas, further comprising a first fan, a second fan and a third fan, wherein the first fan is connected to the gas inlet of the first heat exchanger, and the first fan is connected to the gas inlet of the first heat exchanger. The second fan is connected between the second heat exchanger and the second elution tower, and the third fan is connected between the third elution tower and the fourth elution tower. The gas is introduced into each device to improve the efficiency of waste gas treatment.
附图说明Description of drawings
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to illustrate the specific embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the specific embodiments or the prior art. Obviously, the accompanying drawings in the following description The drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative efforts.
图1是本发明实施例2中的一种钨冶炼废气的处理系统示意图；Fig. 1 is a kind of processing system schematic diagram of tungsten smelting waste gas in the embodiment 2 of the present invention;
附图标记：Reference number:
1-第一换热器；2-第一淋洗塔；3-第二换热器；4-第二淋洗塔；5-第三淋洗塔；6-第四淋洗塔；7-淋洗液槽；8-淋洗泵；9-淋洗液槽；10-淋洗泵；11-淋洗液槽；12-淋洗泵；13-淋洗液槽；14-淋洗泵；15-第一风机；16-第二风机；17-第三风机；18-结晶釜。1-first heat exchanger; 2-first elution tower; 3-second heat exchanger; 4-second elution tower; 5-third elution tower; 6-fourth elution tower; 7- Eluent tank; 8-Eluent pump; 9-Eluent tank; 10-Eluent pump; 11-Eluent tank; 12-Eluent pump; 13-Eluent tank; 14-Eluent pump; 15- the first fan; 16- the second fan; 17- the third fan; 18- crystallization kettle.
具体实施方式Detailed ways
以下实施例的含氨含硫废气均来自于钨冶炼厂钨酸铵结晶APT环节。The ammonia- and sulfur-containing waste gases in the following examples all come from the APT link of ammonium tungstate crystallization in a tungsten smelter.
实施例1Example 1
采用纳氏试剂分光光度法(HJ535-2009)测定钨冶炼废气处理前氨的浓度为200mg/m3，采用离子色谱法(HJ549-2009)测定钨冶炼废气处理前硫化氢的浓度为10mg/m3。The concentration of ammonia before the treatment of tungsten smelting waste gas was 200mg/m 3 by Nessler reagent spectrophotometry (HJ535-2009), and the concentration of hydrogen sulfide before the treatment of tungsten smelting waste gas was 10mg/m by ion chromatography (HJ549-2009). 3 .
本实施例提供了一种钨冶炼废气的处理方法，包括，The present embodiment provides a method for treating waste gas from tungsten smelting, including:
S1、将钨冶炼废气进行一次换热降温处理，控制换热出水温度为≤45℃，得到一次冷凝氨水和废气。S1. Perform primary heat exchange and cooling treatment on tungsten smelting waste gas, and control the temperature of the heat exchange outlet water to be ≤45°C to obtain primary condensed ammonia water and waste gas.
S2、将S1得到的一次冷凝氨水和废气进行自来水循环喷淋，得到含硫氨水和废气，当含硫氨水中游离氨(NH3)的浓度达到50g/L时，逐步加入双氧水，取样检测，当氨水中S2-浓度为0g/L时，停止加入双氧水，得到脱硫后氨水，返回仲钨酸铵的生产系统，作为解吸剂使用。S2. The primary condensed ammonia water and waste gas obtained in S1 are subjected to tap water circulating spray to obtain sulfur-containing ammonia water and waste gas. When the concentration of free ammonia (NH 3 ) in the sulfur-containing ammonia water reaches 50 g/L, hydrogen peroxide is gradually added, and sampling is performed to detect, When the S 2- concentration in the ammonia water is 0 g/L, the addition of hydrogen peroxide is stopped to obtain ammonia water after desulfurization, which is returned to the production system of ammonium paratungstate and used as a desorbent.
S3、将S2得到的废气进行二次换热降温处理，控制换热出水温度为≤35℃，得到二次冷凝氨水和废气。S3. The waste gas obtained in S2 is subjected to secondary heat exchange and cooling treatment, and the temperature of the heat exchange outlet water is controlled to be less than or equal to 35°C to obtain secondary condensed ammonia water and waste gas.
S4、将S3得到的二次冷凝氨水和废气进行稀盐酸循环喷淋，所用的稀盐酸的质量浓度为5％。得到含硫氯化铵溶液和废气，当含硫氯化铵溶液中氯化铵浓度达到150g/L时，逐步加入双氧水，取样检测，当氯化铵溶液中S2-浓度为0g/L时，停止加入双氧水，得到脱硫后氯化铵溶液，返回仲钨酸铵的生产系统，作为解吸剂使用。S4, carry out dilute hydrochloric acid circulating spraying with the secondary condensed ammonia water and waste gas obtained in S3, and the mass concentration of used dilute hydrochloric acid is 5%. Obtain sulfur-containing ammonium chloride solution and waste gas, when the concentration of ammonium chloride in the sulfur-containing ammonium chloride solution reaches 150g/L, gradually add hydrogen peroxide, sample and detect, when the S 2- concentration in the ammonium chloride solution is 0g/L , stop adding hydrogen peroxide, obtain ammonium chloride solution after desulfurization, return to the production system of ammonium paratungstate, and use as desorbent.
S5、将S4得到的废气进行稀硫酸循环喷淋，所用的稀硫酸的质量浓度为5％。得到含硫硫酸铵溶液和废气，当含硫硫酸铵溶液中硫酸铵浓度达到150g/L时，逐步加入双氧水，取样检测，当硫酸铵溶液中S2-浓度为0g/L时，停止加入双氧水，得到脱硫后硫酸铵溶液，用于结晶回收硫酸铵。S5. The waste gas obtained in S4 is subjected to dilute sulfuric acid circulating spray, and the mass concentration of the used dilute sulfuric acid is 5%. Obtain sulfur-containing ammonium sulfate solution and waste gas, when the concentration of ammonium sulfate in the sulfur-containing ammonium sulfate solution reaches 150g/L, gradually add hydrogen peroxide, sample and detect, when the S2 - concentration in the ammonium sulfate solution is 0g/L, stop adding hydrogen peroxide , to obtain ammonium sulfate solution after desulfurization, which is used for crystallization and recovery of ammonium sulfate.
S6、将S5得到的废气进行二次自来水循环喷淋，将废气中残余的氨和氯化氢彻底淋洗吸附，得到净化的废气后排放，淋洗水进入环保系统进行处理。S6. The waste gas obtained in S5 is subjected to secondary tap water circulating spray, and the residual ammonia and hydrogen chloride in the waste gas are thoroughly washed and adsorbed, and the purified waste gas is discharged, and the washing water enters the environmental protection system for treatment.
采用纳氏试剂分光光度法(HJ535-2009)测定废气处理后氨的浓度为0.06mg/m3，采用离子色谱法(HJ549-2009)测定废气处理后硫化氢的浓度为0.008mg/m3。The concentration of ammonia after waste gas treatment was determined by Nessler reagent spectrophotometry (HJ535-2009) to be 0.06 mg/m 3 , and the concentration of hydrogen sulfide after waste gas treatment was determined by ion chromatography (HJ549-2009) to be 0.008 mg/m 3 .
实施例2Example 2
采用纳氏试剂分光光度法(HJ535-2009)测定废气处理前氨的浓度为200mg/m3，采用离子色谱法(HJ549-2009)测定废气处理前硫化氢的浓度为10mg/m3。The concentration of ammonia before waste gas treatment was determined by Nessler reagent spectrophotometry (HJ535-2009) to be 200 mg/m 3 , and the concentration of hydrogen sulfide before waste gas treatment was determined by ion chromatography (HJ549-2009) to be 10 mg/m 3 .
本实施例提供了一种钨冶炼废气的处理系统，包括，根据钨冶炼废气的处理顺序，顺次连接的第一换热器1、第一淋洗塔2、第二换热器3、第二淋洗塔4、第三淋洗塔5、第四淋洗塔6，第一风机15与第一换热器1的气体入口连接，第二风机16连接于第二换热器3和第二淋洗塔4之间，第三风机17连接于第三淋洗塔5和第四淋洗塔6之间。其中，淋洗塔均配置有淋洗液槽和淋洗泵，第一淋洗塔2配置有淋洗液槽7和淋洗泵8，淋洗液槽7与第一淋洗塔2的淋洗液出口连接，淋洗泵8与第一淋洗塔2的淋洗液入口连接，淋洗液槽7与淋洗泵8连接，淋洗液槽7还设有氧化剂入口、淋洗液补加口和淋洗液排出口；第二淋洗塔4配置有淋洗液槽9和淋洗泵10，淋洗液槽9与第二淋洗塔4的淋洗液出口连接，淋洗泵10与第二淋洗塔4的淋洗液入口连接，淋洗液槽9与淋洗泵10连接，淋洗液槽9还设有氧化剂入口、淋洗液补加口和淋洗液排出口；第三淋洗塔5配置有淋洗液槽11和淋洗泵12，淋洗液槽11与第三淋洗塔5的淋洗液出口连接，淋洗泵12与第三淋洗塔5的淋洗液入口连接，淋洗液槽11与淋洗泵12连接，淋洗液槽11还设有氧化剂入口、淋洗液补加口和淋洗液排出口；第四淋洗塔6配置有淋洗液槽13和淋洗泵14，淋洗液槽13与第四淋洗塔6的淋洗液出口连接，淋洗泵14与第四淋洗塔6的淋洗液入口连接，淋洗液槽13与淋洗泵14连接，淋洗液槽13还设有氧化剂入口、淋洗液补加口和淋洗液排出口。This embodiment provides a treatment system for tungsten smelting waste gas, including, according to the treatment sequence of tungsten smelting waste gas, a first heat exchanger 1 , a first washing tower 2 , a second heat exchanger 3 , a first heat exchanger 1 , a first washing tower 2 , a second heat exchanger 3 , a The second washing tower 4, the third washing tower 5, the fourth washing tower 6, the first fan 15 is connected to the gas inlet of the first heat exchanger 1, and the second fan 16 is connected to the second heat exchanger 3 and the second fan 16. Between the two rinsing towers 4 , the third fan 17 is connected between the third rinsing tower 5 and the fourth rinsing tower 6 . Among them, the elution towers are equipped with eluent tank and elution pump, the first elution tower 2 is equipped with eluent tank 7 and elution pump 8, the eluent tank 7 and the first elution tower 2 are equipped with The eluent outlet is connected, the eluent pump 8 is connected with the eluent inlet of the first elution tower 2, the eluent tank 7 is connected with the eluent pump 8, and the eluent tank 7 is also provided with an oxidant inlet, an eluent replenisher. The addition port and the eluent discharge port; the second elution tower 4 is equipped with an eluent tank 9 and an eluent pump 10, and the eluent tank 9 is connected with the eluent outlet of the second eluent tower 4, and the eluent pump 10 is connected with the eluent inlet of the second eluent tower 4, the eluent tank 9 is connected with the eluent pump 10, and the eluent tank 9 is also provided with an oxidant inlet, an eluent replenishing port and an eluent discharge port The third eluent tower 5 is equipped with an eluent tank 11 and an eluent pump 12, the eluent tank 11 is connected with the eluent outlet of the third eluent tower 5, and the eluent pump 12 is connected with the third eluent tower 5 The eluent inlet is connected to the eluent, the eluent tank 11 is connected to the eluent pump 12, and the eluent tank 11 is also provided with an oxidant inlet, an eluent replenishing port and an eluent discharge port; the fourth eluent tower 6 is configured with There is an eluent tank 13 and an eluent pump 14, the eluent tank 13 is connected with the eluent outlet of the fourth elution tower 6, the eluent pump 14 is connected with the eluent inlet of the fourth elution tower 6, and the eluent The washing liquid tank 13 is connected with the rinsing pump 14, and the washing liquid tank 13 is also provided with an oxidant inlet, a washing liquid replenishing port and a washing liquid discharging port.
第一换热器1、第二换热器3均为板式换热器，换热面积为100m2。The first heat exchanger 1 and the second heat exchanger 3 are both plate heat exchangers with a heat exchange area of 100m 2 .
第一风机15、第二风机16、第三风机17均为玻璃钢防腐离心风机，功率为2.2kw。The first fan 15, the second fan 16, and the third fan 17 are all FRP anti-corrosion centrifugal fans with a power of 2.2kw.
第一淋洗塔2、第二淋洗塔4、第三淋洗塔5、第四淋洗塔6均为pp材质，规格为φ1.8m×8m。The first elution tower 2, the second elution tower 4, the third elution tower 5, and the fourth elution tower 6 are all made of pp material, with a size of φ1.8m×8m.
淋洗泵8、淋洗泵10、淋洗泵12、淋洗泵14均为循环喷淋反腐离心泵，功率为2.2kw。The rinsing pump 8, the rinsing pump 10, the rinsing pump 12, and the rinsing pump 14 are all circulating spray anti-corruption centrifugal pumps with a power of 2.2kw.
结晶釜18中排出的含氨含硫钨冶炼废气经第一风机15引入第一换热器1中进行一次换热降温处理，控制换热器换热出水温度为≤45℃，得到一次冷凝氨水和废气。The ammonia-containing sulfur-containing tungsten smelting waste gas discharged from the crystallization kettle 18 is introduced into the first heat exchanger 1 through the first fan 15 for primary heat exchange and cooling treatment, and the temperature of the heat exchange outlet water of the heat exchanger is controlled to be ≤ 45 ° C, to obtain primary condensed ammonia water and exhaust gas.
一次冷凝氨水和废气一同进入第一淋洗塔2进行自来水循环喷淋，淋洗液槽7中的自来水通过淋洗泵8泵入第一淋洗塔2，淋洗水通过第一淋洗塔2的淋洗液出口流回淋洗液槽7中，最终在淋洗液槽7中得到含硫氨水，当含硫氨水中游离氨的浓度达到50g/L时，通过淋洗液槽7上的氧化剂入口逐步加入双氧水，取样检测，当氨水中S2-浓度为0g/L时，停止加入双氧水，得到脱硫后氨水，返回仲钨酸铵的生产系统，作为解吸剂使用，淋洗液槽7中重新放入新的自来水，进行下一轮的淋洗。The primary condensed ammonia water and the waste gas enter the first elution tower 2 together to carry out tap water circulating spray, the tap water in the eluent tank 7 is pumped into the first elution tower 2 through the elution pump 8, and the elution water passes through the first elution tower. The eluent outlet of 2 flows back into the eluent tank 7, and finally the sulfur-containing ammonia water is obtained in the eluent tank 7. When the concentration of free ammonia in the sulfur-containing ammonia water reaches 50 g/L, it passes through the eluent tank 7. The oxidant inlet of the oxidant is gradually added with hydrogen peroxide, sampled and detected, when the S2- concentration in the ammonia water is 0g/L, stop adding hydrogen peroxide, obtain the ammonia water after desulfurization, return to the production system of ammonium paratungstate, use as a desorbent, and re-dry in the eluent tank 7. Put in fresh tap water for the next round of rinsing.
经过自来水循环喷淋处理的废气进入第二换热器3进行二次换热降温处理，控制换热出水温度为≤35℃，得到二次冷凝氨水和废气。The waste gas after the tap water circulating spray treatment enters the second heat exchanger 3 for secondary heat exchange and cooling treatment.
二次冷凝氨水和废气通过第二风机16引入第二淋洗塔4，利用质量浓度为10％的稀盐酸进行循环喷淋，淋洗液槽9中的稀盐酸通过淋洗泵10泵入第二淋洗塔4，淋洗后的稀盐酸通过第二淋洗塔4的淋洗液出口流回淋洗液槽9中，最终在淋洗液槽9中得到含硫氯化铵溶液，当含硫氯化铵溶液中氯化铵浓度达到150g/L时，通过淋洗液槽9上的氧化剂入口逐步加入双氧水，取样检测，当氯化铵溶液中S2-浓度为0g/L时，停止加入双氧水，得到脱硫后氯化铵溶液，返回仲钨酸铵的生产系统，作为解吸剂使用，淋洗液槽9中重新放入新的稀盐酸，进行下一轮的淋洗。The secondary condensed ammonia water and waste gas are introduced into the second leaching tower 4 through the second fan 16, and the dilute hydrochloric acid with a mass concentration of 10% is used for circulating spraying. In the second rinsing tower 4, the diluted hydrochloric acid after rinsing flows back to the eluent tank 9 through the eluent outlet of the second rinsing tower 4, and finally a sulfur-containing ammonium chloride solution is obtained in the eluent tank 9. When When the ammonium chloride concentration in the sulfur-containing ammonium chloride solution reaches 150 g/L, hydrogen peroxide is gradually added through the oxidant inlet on the eluent tank 9, and sampling is performed to detect, when the S 2- concentration in the ammonium chloride solution is 0 g/L, Stop adding hydrogen peroxide to obtain ammonium chloride solution after desulfurization, which is returned to the production system of ammonium paratungstate and used as a desorbent, and new dilute hydrochloric acid is put into the eluent tank 9 again to carry out the next round of elution.
经过稀盐酸循环喷淋处理过的废气进入第三淋洗塔5，利用质量浓度为10％的稀硫酸进行循环喷淋，淋洗液槽11中的稀硫酸通过淋洗泵12泵入第三淋洗塔5，淋洗后的稀硫酸通过第三淋洗塔5的淋洗液出口流回淋洗液槽11中，最终在淋洗液槽11中得到含硫硫酸铵溶液，当含硫硫酸铵溶液中硫酸铵浓度达到150g/L时，通过淋洗液槽11上的氧化剂入口逐步加入双氧水，取样检测，当硫酸铵溶液中S2-浓度为0g/L时，停止加入双氧水，得到脱硫后硫酸铵溶液，用于结晶回收硫酸铵，淋洗液槽11中重新放入新的稀硫酸，进行下一轮的淋洗。The waste gas treated by the circulating spray of dilute hydrochloric acid enters the third elution tower 5, and is sprayed with dilute sulfuric acid with a mass concentration of 10%. The dilute sulfuric acid in the eluent tank 11 is pumped into the third elution tower In the eluent tower 5, the diluted sulfuric acid after leaching flows back to the eluent tank 11 through the eluent outlet of the third eluent tower 5, and finally a sulfur-containing ammonium sulfate solution is obtained in the eluent tank 11. When the ammonium sulfate concentration in the ammonium sulfate solution reaches 150g/L, hydrogen peroxide is gradually added through the oxidant inlet on the eluent tank 11, and sampling is performed to detect, when the S2 - concentration in the ammonium sulfate solution is 0g/L, stop adding hydrogen peroxide to obtain The ammonium sulfate solution after desulfurization is used for crystallization and recovery of ammonium sulfate, and new dilute sulfuric acid is put into the eluent tank 11 again for the next round of elution.
经过稀硫酸循环喷淋处理过的废气由第三风机17引入第四淋洗塔6，进行二次自来水循环喷淋，淋洗液槽13中的自来水通过淋洗泵14泵入第四淋洗塔6，淋洗后的水通过第四淋洗塔6的淋洗液出口流回淋洗液槽13中，最终在淋洗液槽13中得到淋洗水，待废气中残余的氨和氯化氢彻底淋洗吸附后，得到净化的废气，通过管道排放，得到的淋洗水引入环保系统进行处理，淋洗液槽13中更换新鲜自来水，进行下一轮的淋洗。The exhaust gas treated by the circulating spray of dilute sulfuric acid is introduced into the fourth rinsing tower 6 by the third fan 17 for secondary tap water circulating spray, and the tap water in the rinsing liquid tank 13 is pumped into the fourth rinsing through the rinsing pump 14 Tower 6, the water after rinsing flows back to the eluent tank 13 through the eluent outlet of the fourth eluent tower 6, and finally obtains eluent water in the eluent tank 13, until the residual ammonia and hydrogen chloride in the exhaust gas After thorough rinsing and adsorption, purified waste gas is obtained, which is discharged through the pipeline, and the obtained rinsing water is introduced into the environmental protection system for treatment, and fresh tap water is replaced in the eluent tank 13 for the next round of rinsing.
采用纳氏试剂分光光度法(HJ535-2009)测定废气处理后氨的浓度为0.03mg/m3，采用离子色谱法(HJ549-2009)测定废气处理前硫化氢的浓度为0.005mg/m3。The concentration of ammonia after waste gas treatment was determined by Nessler reagent spectrophotometry (HJ535-2009) to be 0.03 mg/m 3 , and the concentration of hydrogen sulfide before waste gas treatment was determined by ion chromatography (HJ549-2009) to be 0.005 mg/m 3 .
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above-mentioned embodiments are only examples for clear description, and are not intended to limit the implementation manner. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. And the obvious changes or changes derived from this are still within the protection scope of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910399327.3A CN110170222B (en) | 2019-05-14 | 2019-05-14 | Treatment method and system for tungsten smelting waste gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910399327.3A CN110170222B (en) | 2019-05-14 | 2019-05-14 | Treatment method and system for tungsten smelting waste gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110170222A true CN110170222A (en) | 2019-08-27 |
| CN110170222B CN110170222B (en) | 2022-09-23 |
Family
ID=67691260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910399327.3A Active CN110170222B (en) | 2019-05-14 | 2019-05-14 | Treatment method and system for tungsten smelting waste gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110170222B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705002A (en) * | 2021-01-13 | 2021-04-27 | 厦门钨业股份有限公司 | Tail gas treatment method for tungsten ore decomposition |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816841A (en) * | 2010-05-17 | 2010-09-01 | 赣州华兴钨制品有限公司 | Method for recovering ammonia nitrogen from ammonia-containing steam |
| CN101857245A (en) * | 2010-05-28 | 2010-10-13 | 厦门嘉鹭金属工业有限公司 | Ammonia recovery method in tungsten metallurgy |
| CN103785263A (en) * | 2014-02-14 | 2014-05-14 | 赣州华茂钨材料有限公司 | Ammonia-containing tail gas treatment recycling method |
| CN204841334U (en) * | 2015-07-17 | 2015-12-09 | 许长威 | Crystal system ammonia nitrogen recovery unit |
| CN206901756U (en) * | 2017-04-17 | 2018-01-19 | 河源普益硬质合金厂有限公司 | A kind of three-level dehydration tungsten oxide reduction tail gas predrainage system |
| CN207755952U (en) * | 2017-12-21 | 2018-08-24 | 力冠能源（天津）有限公司 | Tungsten reaction kettle device for recovering tail gas |
| CN109464910A (en) * | 2018-12-07 | 2019-03-15 | 铜陵泰富特种材料有限公司 | Coke oven flue gas low-temp desulfurization method of denitration |
-
2019
- 2019-05-14 CN CN201910399327.3A patent/CN110170222B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816841A (en) * | 2010-05-17 | 2010-09-01 | 赣州华兴钨制品有限公司 | Method for recovering ammonia nitrogen from ammonia-containing steam |
| CN101857245A (en) * | 2010-05-28 | 2010-10-13 | 厦门嘉鹭金属工业有限公司 | Ammonia recovery method in tungsten metallurgy |
| CN103785263A (en) * | 2014-02-14 | 2014-05-14 | 赣州华茂钨材料有限公司 | Ammonia-containing tail gas treatment recycling method |
| CN204841334U (en) * | 2015-07-17 | 2015-12-09 | 许长威 | Crystal system ammonia nitrogen recovery unit |
| CN206901756U (en) * | 2017-04-17 | 2018-01-19 | 河源普益硬质合金厂有限公司 | A kind of three-level dehydration tungsten oxide reduction tail gas predrainage system |
| CN207755952U (en) * | 2017-12-21 | 2018-08-24 | 力冠能源（天津）有限公司 | Tungsten reaction kettle device for recovering tail gas |
| CN109464910A (en) * | 2018-12-07 | 2019-03-15 | 铜陵泰富特种材料有限公司 | Coke oven flue gas low-temp desulfurization method of denitration |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705002A (en) * | 2021-01-13 | 2021-04-27 | 厦门钨业股份有限公司 | Tail gas treatment method for tungsten ore decomposition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110170222B (en) | 2022-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102531222B (en) | Treatment method for vanadium precipitating waste water | |
| CN105461138B (en) | A kind of method that sulfuric acid and hydrochloric acid and fluorine open circuit are reclaimed from smelting wastewater | |
| CN102531221B (en) | Method used for processing waste water after vanadium precipitation | |
| CN106086480B (en) | A kind of processing method of Tungsten smelting molybdenum removal slag | |
| CN108439438A (en) | The method that nickel cobalt mn sulphate and lithium carbonate are prepared by waste and old ternary battery material | |
| CN104355472B (en) | A kind of containing inorganic ammonium salt Waste Water Treatment, process technique and application thereof | |
| CN110170222B (en) | Treatment method and system for tungsten smelting waste gas | |
| WO2016110081A1 (en) | Acid waste gas treatment and resource utilization | |
| CN106381397A (en) | Method for dechlorinating through zinc ash material ammonia-leaching ion exchange combined process | |
| CN105714129B (en) | Comprehensive treatment method for extraction stage in cobalt hydrometallurgy | |
| CN204337983U (en) | The recycling treatment process system of MOCVD waste gas in a kind of LED chip production process | |
| CN109921126B (en) | Method for recovering active material from waste cobalt-containing lithium ion battery positive electrode material | |
| CN109517630B (en) | Process and system for producing ammonium sulfate by deammoniation of coke oven gas using ammonium sulfite | |
| CN220090988U (en) | Production line for recycling lithium hexafluorophosphate fluorine-containing tail gas | |
| CN114853242B (en) | Method for recycling acidic wastewater | |
| CN218146236U (en) | System of getting rid of fluorine chlorine ion in acid waste water | |
| CN114516701A (en) | Method and device for treating ammonia-containing wastewater | |
| CN107042060A (en) | A resource recovery method of acidic gas | |
| CN111893326A (en) | A method for extracting tungsten by two-step acid decomposition method | |
| CN104928501A (en) | Method for recycling arsenic from black copper sludge | |
| CN203244803U (en) | Ammonia-containing vapor gaseous phase distillation equipment used during APT (ammonium tungstate) production | |
| CN218393045U (en) | Tail gas treatment system of desulfurization catalyst apparatus for producing | |
| CN108439432A (en) | A kind of method of lithium sodium separation | |
| CN108588418B (en) | Device and method for recycling negative divalent sulfur in tungstate solution | |
| CN203379792U (en) | Comprehensive silver electrolyte nitrogen oxide and electrolyzed nitric acid tail gas treatment system |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |