CN1888099A - Harmful impurity eliminating and density increasing roasting process for activated zinc oxide powder and zinc scum - Google Patents
Harmful impurity eliminating and density increasing roasting process for activated zinc oxide powder and zinc scum Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 90
- 239000011701 zinc Substances 0.000 title claims abstract description 90
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical class [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000012535 impurity Substances 0.000 title claims abstract description 37
- 239000000460 chlorine Substances 0.000 claims abstract description 47
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000280 densification Methods 0.000 claims abstract description 26
- 239000012190 activator Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003546 flue gas Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 3
- 230000003213 activating effect Effects 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000003723 Smelting Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 26
- 239000011737 fluorine Substances 0.000 description 26
- 229910052731 fluorine Inorganic materials 0.000 description 26
- 239000005416 organic matter Substances 0.000 description 14
- 229910052787 antimony Inorganic materials 0.000 description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 12
- 229910052785 arsenic Inorganic materials 0.000 description 12
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 12
- 229910052793 cadmium Inorganic materials 0.000 description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 11
- 239000000428 dust Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000009854 hydrometallurgy Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000002386 leaching Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- 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
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明涉及一种活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法，属于铅锌冶炼领域。将氧化锌粉和锌浮渣与活化剂硫酸和水一起加入到混合器中充分混合并反应完全，然后直接送入增密焙烧炉中加热，控制反应温度100～1300℃，并通入空气作为气体介质，使活化剂选择性地与氧化锌粉和锌浮渣中的氯化物和氟化物反应，生成气态HCI和HF与物料分离，并使其他氯化物和易挥发物质发生挥发，与主体金属锌分离进入烟气，直接脱氟氯和有害杂质。具有工艺流程短、易操作、工艺稳定、能耗低、低污染、成本低、金属回收率高、锌与杂质易分离、有价金属集中的优点。The invention relates to a method for removing harmful impurities by densifying and roasting activated zinc oxide powder and zinc scum, belonging to the field of lead-zinc smelting. Put zinc oxide powder and zinc dross together with activator sulfuric acid and water into the mixer, mix well and react completely, then send them directly into the densification roaster for heating, control the reaction temperature at 100-1300°C, and feed air as Gas medium, make the activator selectively react with chloride and fluoride in zinc oxide powder and zinc dross, generate gaseous HCI and HF to separate from the material, and make other chlorides and volatile substances volatilize, and interact with the main metal Zinc is separated into the flue gas, and the chlorine and harmful impurities are directly defluorinated. It has the advantages of short process flow, easy operation, stable process, low energy consumption, low pollution, low cost, high metal recovery rate, easy separation of zinc and impurities, and concentration of valuable metals.
Description
技术领域：本发明涉及一种活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法，属于铅锌冶炼领域，更具体的说，是一种次氧化锌粉和锌浮渣回收锌和脱除有害杂质的预处理方法。Technical field: The present invention relates to a method for removing harmful impurities by densifying and roasting activated zinc oxide powder and zinc scum, belonging to the field of lead-zinc smelting, more specifically, a method for recovering zinc from secondary zinc oxide powder and zinc scum And pretreatment methods to remove harmful impurities.
背景技术：湿法炼锌中，浸出渣处理分为湿法和火法两种，湿法处理多以高酸高温浸出-黄钾铁矾沉铁技术为主，该技术流程较长，对设备要求高，技术复杂且难度较大；但该技术具有污染较少，能耗较低，综合回收较好的优点。Background technology: in zinc hydrometallurgy, leaching slag treatment is divided into wet method and fire method. The wet method is mainly based on high-acid high-temperature leaching-jaosite iron precipitation technology. The requirements are high, the technology is complicated and difficult; but this technology has the advantages of less pollution, lower energy consumption and better comprehensive recovery.
火法处理浸出渣，一般采用威尔兹法，使其中的锌挥发，并以氧化锌粉尘的形态加以回收，然后再返回湿法炼锌系统生产电锌。该氧化锌烟尘富含铟、锗等易挥发元素，除返回湿法炼锌系统回收金属锌外，其更大的意义还在于同时回收铟、锗等有价元素，由于该烟尘含氯、氟、镉、砷、锑、铅和有机物(炭燃烧和汽化时产生的焦油等有机物)高，在烟尘浸出过程中势必将氯、氟、镉、砷、锑、铅和有机物等带入到溶液，使溶液含氯、氟及有机物超过锌电解沉积对溶液含氟、氯及有机物的要求，导致阳极腐蚀严重，电锌质量下降，阴极消耗增加，影响正常生产。在溶液中的镉、砷、锑和有机物等杂质还将在净化中增加锌粉耗量和净化的难度和复杂程度。因此，必须将氧化锌烟尘中氟、氯、镉、砷、锑、铅和有机物在进入湿法炼锌系统或其它炼锌工艺之前脱除。同时，阴极锌片在熔铸时所产出的浮渣主要含锌、氧化锌、氯化锌，其中金属形态的锌是以锌珠的形态残留在锌浮渣中，锌浮渣含锌一般在70-80％，含氯在2-3％。由于锌浮渣中含有一定量的氯，不可能把锌浮渣直接返回湿法锌冶炼系统或其它炼锌工艺。因而，对这部分氧化锌烟尘和锌浮渣在湿法炼锌或其它炼锌工艺中的应用必须设置专门的脱除氟、氯、镉、砷、锑、铅和有机物工序。Pyrochemical treatment of leaching slag generally adopts Wiltz method to volatilize the zinc in it and recover it in the form of zinc oxide dust, and then return to the hydrometallurgy system to produce electric zinc. The zinc oxide dust is rich in volatile elements such as indium and germanium. In addition to returning to the hydrometallurgy system to recover metal zinc, its greater significance lies in the simultaneous recovery of valuable elements such as indium and germanium. Because the dust contains chlorine and fluorine , cadmium, arsenic, antimony, lead and organic matter (organic matter such as tar produced during charcoal combustion and vaporization) are high, and chlorine, fluorine, cadmium, arsenic, antimony, lead and organic matter are bound to be brought into the solution during the smoke leaching process, The solution containing chlorine, fluorine and organic matter exceeds the requirements of zinc electrolytic deposition for solution containing fluorine, chlorine and organic matter, resulting in serious corrosion of the anode, decline in the quality of electrolytic zinc, and increased consumption of the cathode, affecting normal production. Impurities such as cadmium, arsenic, antimony and organic matter in the solution will also increase the consumption of zinc powder and the difficulty and complexity of purification. Therefore, it is necessary to remove fluorine, chlorine, cadmium, arsenic, antimony, lead and organic matter in zinc oxide dust before entering the hydrometallurgy system or other zinc smelting processes. At the same time, the dross produced by the cathode zinc sheet during casting mainly contains zinc, zinc oxide, and zinc chloride, among which zinc in the form of metal remains in the zinc dross in the form of zinc beads, and zinc dross generally contains zinc in the 70-80%, containing 2-3% chlorine. Since the zinc dross contains a certain amount of chlorine, it is impossible to return the zinc dross directly to the wet zinc smelting system or other zinc smelting processes. Therefore, for the application of this part of zinc oxide dust and zinc dross in hydrometallurgy or other zinc smelting processes, special procedures for removing fluorine, chlorine, cadmium, arsenic, antimony, lead and organic matter must be set up.
目前，从含杂氧化锌烟尘和锌浮渣脱杂技术有高温多膛炉脱氟氯，碱洗脱氟氯，硅胶吸附法，电渗析法，离子交换法，金属离子沉淀法等。工业上从次氧化锌中直接脱除氟氯成功的工艺是多堂炉，但氧化锌粉和锌浮渣脱除氟氯在工业中还没有成熟的技术和工艺，其他方法都由于试剂昂贵、再生困难、操作不便，脱氯率等原因未能在工业应用。这些方法普遍存在的不足是技术工艺复杂，金属回收率低，铅、锌难分离，有价金属分散，药剂消耗量大，难以克服矿物的复杂性，使矿物选别困难。At present, the technologies for removing impurities from miscellaneous zinc oxide dust and zinc dross include high-temperature multi-chamber furnace defluorination and chlorine removal, alkali elution of fluorine and chlorine, silica gel adsorption, electrodialysis, ion exchange, metal ion precipitation, etc. Industrially, there are many successful processes for directly removing fluorine and chlorine from secondary zinc oxide, but there is no mature technology and process for removing fluorine and chlorine from zinc oxide powder and zinc scum in the industry. Other methods are due to expensive reagents, Regeneration difficulties, inconvenient operation, dechlorination rate and other reasons have not been applied in industry. The common disadvantages of these methods are that the technical process is complicated, the metal recovery rate is low, the separation of lead and zinc is difficult, the valuable metals are dispersed, the consumption of chemicals is large, it is difficult to overcome the complexity of minerals, and it is difficult to sort minerals.
发明内容：本发明的目的是克服现有技术的不足，提供一种技术工艺流程短、易操作、工艺稳定、能耗低、低污染、成本低、金属回收率高、锌与杂质易分离的活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法。Summary of the invention: The purpose of the present invention is to overcome the deficiencies of the prior art, and provide a short technological process, easy operation, stable process, low energy consumption, low pollution, low cost, high metal recovery rate, and easy separation of zinc and impurities. A method for removing harmful impurities by densifying and roasting activated zinc oxide powder and zinc dross.
实现本发明的方法是：将氧化锌粉和锌浮渣与硫酸和水作活化剂加入到混合器中充分混合并反应完全，活化剂的加入量为物料重量的0.05～5％(活化剂的硫酸浓度为50％~95％)，经充分混合和反应后，直接进入增密焙烧炉中加热，控制反应温度100～1300℃，通入空气作为气体介质，控制气体流速0.01m/s～1.5m/s条件下，10分钟至180分钟，直接脱除有害杂质。The method for realizing the present invention is: zinc oxide powder and zinc scum and sulfuric acid and water are used as activator to join in mixer and fully mix and react completely, and the add-on of activator is 0.05～5% of material weight (the Sulfuric acid concentration is 50%~95%), after fully mixing and reacting, it is directly heated in a densification roaster, the reaction temperature is controlled at 100-1300°C, air is introduced as the gas medium, and the gas flow rate is controlled at 0.01m/s-1.5 Under m/s conditions, 10 minutes to 180 minutes, directly remove harmful impurities.
在上述条件下，添加的活化剂发生化学反应并在增密焙烧过程中，将选择性地与铅、锌的氯化物和氟化物反应生成硫酸盐、氯化氢和氟化氢，并使其他氯化物和易挥发物质发生挥发，进入烟气与主体金属锌分离，直接脱氟氯和有害杂质，而其它脉石成份则不发生变化保留于物料中。Under the above conditions, the added activator undergoes a chemical reaction and during the densification roasting process, it will selectively react with chlorides and fluorides of lead and zinc to form sulfate, hydrogen chloride and hydrogen fluoride, and make other chlorides and easily The volatile matter volatilizes, enters the flue gas and separates from the main metal zinc, and directly removes chlorine and harmful impurities, while other gangue components remain unchanged in the material.
威尔兹法方法所得产品是密度小、粒度细、含杂高的一种次氧化锌粉。经物相分析可知，在氧化锌烟尘中氯主要以ZnCl2，PbCl2和ZnO·Cl2，ZnO·F2，PbO·Cl2，PbO·F2以及碱金属(Na、Mg)的氯化物形态存在。各种氯化物中含氯量占物料的质量分数分别为：以氯化锌和氧化锌吸附形态存在的氯占总氯量的78-80％；以氧化铅及氧化铅吸附形态存在的氯占总氯量的12-15％；以碱金属氯化物形态存在的氯占总氯量的6-8％。锌浮渣是经过重选处理将其中的大颗粒的锌珠回收后的渣，该锌浮渣为湿渣，外观呈灰黑色色。锌浮渣经化学分析，其物相化学成分如下：水分为20-22％，Zn65-78％，Cl2-12％、F0.02-0.1％。因在活化增密焙烧过程中，有微量氯化氢气体产生，由于氯化氢气体具有腐蚀性和对大气污染，因而采用的增密焙烧炉为内衬耐酸耐火砖的加热炉，加热炉中可分为有链式或无链式容器，容积为1～2000米3，生成的氯化氢是氧化锌粉和锌浮渣中铅锌等金属氯化物在活化和增密焙烧中产生的，活化和增密焙烧过程中添加的活化剂的化学成分是硫酸或水。The product obtained by the Wiltz method is a secondary zinc oxide powder with small density, fine particle size and high impurity content. According to the phase analysis, the chlorine in the zinc oxide dust is mainly ZnCl 2 , PbCl 2 and ZnO·Cl 2 , ZnO·F 2 , PbO·Cl 2 , PbO·F 2 and the chlorides of alkali metals (Na, Mg) Morphology exists. The mass fractions of chlorine content in various chlorides in the material are: chlorine in the form of adsorption of zinc chloride and zinc oxide accounts for 78-80% of the total chlorine; chlorine in the form of adsorption of lead oxide and lead oxide accounts for 12-15% of the total chlorine; chlorine in the form of alkali metal chloride accounts for 6-8% of the total chlorine. Zinc scum is the slag after the large particles of zinc beads are recovered through gravity separation. The zinc scum is wet slag and its appearance is gray-black. After chemical analysis, the chemical composition of the zinc scum is as follows: water content is 20-22%, Zn65-78%, Cl2-12%, F0.02-0.1%. During the activation and densification roasting process, a small amount of hydrogen chloride gas is produced, and because hydrogen chloride gas is corrosive and pollutes the air, the densification roaster used is a heating furnace lined with acid-resistant refractory bricks. The heating furnace can be divided into Chain or chainless container with a volume of 1 to 2000 m3 . The hydrogen chloride produced is produced by the activation and densification roasting of zinc oxide powder and zinc dross metal chlorides such as lead and zinc. The activation and densification roasting process The chemical composition of the activator added in is sulfuric acid or water.
本发明在增密焙烧过程中，浓硫酸和水与烟尘和锌浮渣中的氯化物反应，使烟尘和锌浮渣中的氯和氟以HCI和HF气体形态与物料分离，达到脱氯和氟的目的，反应式为：In the densification roasting process of the present invention, the concentrated sulfuric acid and water react with the chloride in the dust and zinc dross, so that the chlorine and fluorine in the dust and zinc dross are separated from the material in the form of HCI and HF gas, so as to achieve dechlorination and The purpose of fluorine, the reaction formula is:
由热力学计算可知，这些氯化物和氟化物与浓硫酸反应的自由函小于零，这表明这些氯化物和氟化物在一定温度下能够与浓硫酸反应，使氯化物和氟化物中的氯氟转化为HCl和HF气体而脱除。有机物CR在高温下与氧气发生燃烧反应，生成二氧化碳和水；易挥发的金属氧化物MeO(其中Me代表镉、砷、锑、铅等金属)则在高温下发生挥发而进入气相。It can be known from thermodynamic calculations that the free function of these chlorides and fluorides reacting with concentrated sulfuric acid is less than zero, which indicates that these chlorides and fluorides can react with concentrated sulfuric acid at a certain temperature to convert chlorine and fluorine in chlorides and fluorides Removed for HCl and HF gas. The organic compound CR reacts with oxygen at high temperature to generate carbon dioxide and water; the volatile metal oxide MeO (where Me represents metals such as cadmium, arsenic, antimony, and lead) volatilizes at high temperature and enters the gas phase.
本发明由于活化增密焙烧过程是在常压状态下，将活化增密焙烧过程温度控制到100～1300℃，通入空气作为气体介质，在活化剂的作用下，对氧化锌粉和锌浮渣中的铅、锌等元素的氯化物进行活化增密焙烧，生成单一的氯化氢和氟化物挥发，将分离工艺中物质性质选定的复杂分离工艺变成在活化增密焙烧过程中使复杂物质组成转变为单一物质的过程，使分离工艺简化，过程强化，实现氧化锌粉和锌浮渣活化增密焙烧脱除有害杂质，是一种强化转化的清洁生产技术。因此，本发明具有技术工艺流程短、易操作、工艺稳定、能耗低、低污染、成本低、金属回收率高、锌与杂质易分离、有价金属集中的优点。In the present invention, since the activation and densification roasting process is under normal pressure, the temperature of the activation and densification roasting process is controlled to 100-1300°C, and air is introduced as the gas medium. The chlorides of lead, zinc and other elements in the slag are activated and densified to roast to generate a single hydrogen chloride and fluoride to volatilize, and the complex separation process of selecting the material properties in the separation process is changed to make complex substances during the activation and densification roasting process. The process of transforming the composition into a single substance simplifies the separation process, strengthens the process, and realizes the activation, densification and roasting of zinc oxide powder and zinc scum to remove harmful impurities. It is a clean production technology that strengthens transformation. Therefore, the present invention has the advantages of short technological process, easy operation, stable process, low energy consumption, low pollution, low cost, high metal recovery rate, easy separation of zinc and impurities, and concentration of valuable metals.
具体实施方式：下面结合实施例对本发明的技术内容作进一步阐述。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS: The technical content of the present invention will be further elaborated below in conjunction with the embodiments.
实例1：将氧化锌粉和锌浮渣与活化剂(硫酸和水，硫酸浓度为50％)混合并反应完全后，用加料器连续加入增密焙烧炉中，控制活化剂的加入量为物料重量的0.05％、炉内温度为100℃，维持炉内空气流速0.01m/s，对氧化锌粉和锌浮渣进行活化增密焙烧10分钟，生成气态HCI和HF，并使其他氯化物和易挥发物质发生挥发，与主体金属锌分离进入烟气，直接脱氟氯和有害杂质。Example 1: After zinc oxide powder and zinc scum are mixed with activator (sulfuric acid and water, sulfuric acid concentration is 50%) and after reacting completely, add in the densification roasting furnace continuously with feeder, the add-on of control activator is material 0.05% by weight, the temperature in the furnace is 100°C, the air flow rate in the furnace is maintained at 0.01m/s, and the zinc oxide powder and zinc dross are activated and densified roasted for 10 minutes to generate gaseous HCI and HF, and make other chlorides and Volatile substances volatilize, separate from the main metal zinc and enter the flue gas, and directly remove fluorine, chlorine and harmful impurities.
本活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法，脱除氟氯和有害杂质效果为：氯脱除率88％，氟脱除率88％，铅脱除率30％，镉脱除率45％，砷脱除率30％，锑脱除率30％，有机物脱除率80％，锌的损失率5％，焙砂含氯0.1％，锌直收率94％。This activated zinc oxide powder and zinc scum densification roasting removes the harmful impurity method, removes the fluorine chlorine and the harmful impurity effect: the chlorine removal rate is 88%, the fluorine removal rate is 88%, the lead removal rate is 30%, the lead removal rate is 30%, The removal rate of cadmium is 45%, the removal rate of arsenic is 30%, the removal rate of antimony is 30%, the removal rate of organic matter is 80%, the loss rate of zinc is 5%, the chlorine content of calcine is 0.1%, and the direct recovery rate of zinc is 94%.
实例2：将氧化锌粉和锌浮渣与活化剂(硫酸和水，硫酸浓度为95％)混合并反应完全后，用加料器连续加入增密焙烧炉中，控制活化剂的加入量为物料重量的5％，炉内温度在1300℃，维持炉内空气流速1.5m/s，对氧化锌粉和锌浮渣进行活化增密焙烧10分钟，生成气态HCI和HF，并使其他氯化物和易挥发物质发生挥发，与主体金属锌分离进入烟气，直接脱氟氯和有害杂质。Example 2: After zinc oxide powder and zinc scum are mixed with activator (sulfuric acid and water, sulfuric acid concentration is 95%) and reacted completely, add in the densification roasting furnace continuously with feeder, the add-on of control activator is material 5% by weight, the temperature in the furnace is 1300°C, the air flow rate in the furnace is maintained at 1.5m/s, and the zinc oxide powder and zinc dross are activated and densified for 10 minutes to generate gaseous HCI and HF, and make other chlorides and Volatile substances volatilize, separate from the main metal zinc and enter the flue gas, and directly remove fluorine, chlorine and harmful impurities.
本活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法，脱除氟氯和有害杂质效果为：氯脱除率95％，氟脱除率95％，铅脱除率35％，镉脱除率55％，砷脱除率35％，锑脱除率35％，有机物脱除率95％，锌的损失率8％，焙砂含氯0.02％，锌直收率76％。This activated zinc oxide powder and zinc scum densification roasting removes the harmful impurity method, removes the fluorine chlorine and the harmful impurity effect: the chlorine removal rate is 95%, the fluorine removal rate is 95%, the lead removal rate is 35%, The removal rate of cadmium is 55%, the removal rate of arsenic is 35%, the removal rate of antimony is 35%, the removal rate of organic matter is 95%, the loss rate of zinc is 8%, the chlorine content of calcine is 0.02%, and the direct recovery rate of zinc is 76%.
实例3：将氧化锌粉和锌浮渣与活化剂(硫酸和水，硫酸浓度为80％)混合并反应完全后，用加料器连续加入增密焙烧炉中，控制活化剂的加入量为物料重量的0.5％，炉内温度在550℃，维持炉内空气流速1.0m/s，对氧化锌粉和锌浮渣进行活化增密焙烧180分钟，生成气态HCI和HF，并使其他氯化物和易挥发物质发生挥发，与主体金属锌分离进入烟气，直接脱氟氯和有害杂质。Example 3: After zinc oxide powder and zinc scum are mixed with activator (sulfuric acid and water, sulfuric acid concentration is 80%) and after reacting completely, add in the densification roasting furnace continuously with feeder, the add-on of control activator is material 0.5% by weight, the temperature in the furnace is 550°C, the air flow rate in the furnace is maintained at 1.0m/s, and the zinc oxide powder and zinc dross are activated and densified for 180 minutes to generate gaseous HCI and HF, and make other chlorides and Volatile substances volatilize, separate from the main metal zinc and enter the flue gas, and directly remove fluorine, chlorine and harmful impurities.
本活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法，脱除氟氯和有害杂质效果为：氯脱除率89％，氟脱除率89％，铅脱除率31％，镉脱除率47％，砷脱除率30％，锑脱除率30％，有机物脱除率82％，锌的损失率5.5％，焙砂含氯0.08％，锌直收率87％。This activated zinc oxide powder and zinc scum densification roasting method for removing harmful impurities has the following effects for removing fluorine, chlorine and harmful impurities: chlorine removal rate is 89%, fluorine removal rate is 89%, lead removal rate is 31%, The removal rate of cadmium is 47%, the removal rate of arsenic is 30%, the removal rate of antimony is 30%, the removal rate of organic matter is 82%, the loss rate of zinc is 5.5%, the chlorine content of calcined sand is 0.08%, and the direct recovery rate of zinc is 87%.
实例4：将氧化锌粉和锌浮渣与活化剂(硫酸和水，硫酸浓度为75％)混合并反应完全后，用加料器连续加入增密焙烧炉中，控制活化剂的加入量为物料重量的0.4％，炉内温度在350℃，维持炉内空气流速0.5m/s，对氧化锌粉和锌浮渣进行活化增密焙烧60分钟，生成气态HCI和HF，并使其他氯化物和易挥发物质发生挥发，与主体金属锌分离进入烟气，直接脱氟氯和有害杂质。Example 4: After zinc oxide powder and zinc scum are mixed with activator (sulfuric acid and water, sulfuric acid concentration is 75%) and after reacting completely, add in the densification roasting furnace continuously with feeder, the add-on of control activator is material 0.4% by weight, the temperature in the furnace is 350°C, the air flow rate in the furnace is maintained at 0.5m/s, and the zinc oxide powder and zinc dross are activated and densified for 60 minutes to generate gaseous HCI and HF, and make other chlorides and Volatile substances volatilize, separate from the main metal zinc and enter the flue gas, and directly remove fluorine, chlorine and harmful impurities.
本活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法，脱除氟氯和有害杂质效果为：氯脱除率88％，氟脱除率88％，铅脱除率30％，镉脱除率45％，砷脱除率30％，锑脱除率30％，有机物脱除率81％，锌的损失率6％，焙砂含氯0.09％，锌直收率86％。This activated zinc oxide powder and zinc scum densification roasting removes the harmful impurity method, removes the fluorine chlorine and the harmful impurity effect: the chlorine removal rate is 88%, the fluorine removal rate is 88%, the lead removal rate is 30%, the lead removal rate is 30%, The removal rate of cadmium is 45%, the removal rate of arsenic is 30%, the removal rate of antimony is 30%, the removal rate of organic matter is 81%, the loss rate of zinc is 6%, the chlorine content of calcine is 0.09%, and the direct recovery rate of zinc is 86%.
实例5：将氧化锌粉和锌浮渣与活化剂(硫酸和水，硫酸浓度为65％)混合并反应完全后，用加料器连续加入增密焙烧炉中，控制活化剂的加入量为物料重量的0.5％，炉内温度在760℃，维持炉内空气流速0.5m/s，对氧化锌粉和锌浮渣进行活化增密焙烧45分钟，生成气态HCI和HF，并使其他氯化物和易挥发物质发生挥发，与主体金属锌分离进入烟气，直接脱氟氯和有害杂质。Example 5: After zinc oxide powder and zinc scum are mixed with activator (sulfuric acid and water, sulfuric acid concentration is 65%) and react completely, add in the densification roasting furnace continuously with feeder, the add-on of control activator is material 0.5% by weight, the temperature in the furnace is 760°C, the air flow rate in the furnace is maintained at 0.5m/s, and the zinc oxide powder and zinc dross are activated and densified for 45 minutes to generate gaseous HCI and HF, and make other chlorides and Volatile substances volatilize, separate from the main metal zinc and enter the flue gas, and directly remove fluorine, chlorine and harmful impurities.
本活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法，脱除氟氯和有害杂质效果为：氯脱除率90％，氟脱除率90％，铅脱除率33％，镉脱除率48％，砷脱除率33％，锑脱除率33％，有机物脱除率90％，锌的损失率6％，焙砂含氯0.04％，锌直收率89％。This activated zinc oxide powder and zinc scum densification roasting method for removing harmful impurities has the following effects of removing fluorine, chlorine and harmful impurities: chlorine removal rate is 90%, fluorine removal rate is 90%, lead removal rate is 33%, The removal rate of cadmium is 48%, the removal rate of arsenic is 33%, the removal rate of antimony is 33%, the removal rate of organic matter is 90%, the loss rate of zinc is 6%, the chlorine content of calcine is 0.04%, and the direct recovery rate of zinc is 89%.
实例6：将氧化锌粉和锌浮渣与活化剂(硫酸和水，硫酸浓度为85％)混合并反应完全后，用加料器连续加入增密焙烧炉中，控制活化剂的加入量为物料重量的0.3％，炉内温度在950℃，维持炉内空气流速0.25m/s，对氧化锌粉和锌浮渣进行活化增密焙烧50分钟，生成气态HCI和HF，并使其他氯化物和易挥发物质发生挥发，与主体金属锌分离进入烟气，直接脱氟氯和有害杂质。Example 6: After zinc oxide powder and zinc scum are mixed with activator (sulfuric acid and water, sulfuric acid concentration is 85%) and reacted completely, add in the densification roasting furnace continuously with feeder, the add-on of control activator is material 0.3% by weight, the temperature in the furnace is 950°C, the air flow rate in the furnace is maintained at 0.25m/s, and the zinc oxide powder and zinc dross are activated and densified for 50 minutes to generate gaseous HCI and HF, and make other chlorides and Volatile substances volatilize, separate from the main metal zinc and enter the flue gas, and directly remove fluorine, chlorine and harmful impurities.
本活化氧化锌粉和锌浮渣增密焙烧脱除有害杂质的方法，脱除氟氯和有害杂质效果为：氯脱除率93％，氟脱除率93％，铅脱除率34.5％，镉脱除率54.5％，砷脱除率34.5％，锑脱除率34.5％，有机物脱除率93％，锌的损失率6.5％，焙砂含氯0.025％，锌直收率93％。This activated zinc oxide powder and zinc scum densification roasting removes the harmful impurity method, removes the fluorine chlorine and the harmful impurity effect: the chlorine removal rate is 93%, the fluorine removal rate is 93%, the lead removal rate is 34.5%, The removal rate of cadmium is 54.5%, the removal rate of arsenic is 34.5%, the removal rate of antimony is 34.5%, the removal rate of organic matter is 93%, the loss rate of zinc is 6.5%, the chlorine content of calcine is 0.025%, and the direct recovery rate of zinc is 93%.
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| CN102939397A (en) * | 2010-01-22 | 2013-02-20 | 莫利康普矿物有限责任公司 | Hydrometallurgical process and method for recovering metals |
| CN103343237A (en) * | 2013-07-08 | 2013-10-09 | 昆明理工大学 | Method for removing fluorine and chlorine from zinc oxide fume by adopting sulfuric acid activating/microwave roasting |
| CN104773751A (en) * | 2015-04-22 | 2015-07-15 | 衢州市业胜金属材料有限公司 | Method for removing fluorine, chlorine and valuable metals in secondary zinc oxide |
| CN109001007A (en) * | 2018-08-22 | 2018-12-14 | 汉能新材料科技有限公司 | A kind of processing method of material |
| CN110144454A (en) * | 2019-07-04 | 2019-08-20 | 石家庄学院 | A process for removing impurities in zinc dust |
| CN110983032A (en) * | 2019-11-22 | 2020-04-10 | 西北矿冶研究院 | Method for treating high fluorine chlorine zinc-containing oxidation material |
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| JPS53141121A (en) * | 1977-05-14 | 1978-12-08 | Nippon Kinzoku Co Ltd | Method of making zinc sulfate from zinc slag |
| CN1120592A (en) * | 1994-10-08 | 1996-04-17 | 包智香 | Method for extracting zinc and manganese dioxide from waste dry cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102939397A (en) * | 2010-01-22 | 2013-02-20 | 莫利康普矿物有限责任公司 | Hydrometallurgical process and method for recovering metals |
| US8936770B2 (en) | 2010-01-22 | 2015-01-20 | Molycorp Minerals, Llc | Hydrometallurgical process and method for recovering metals |
| US10179942B2 (en) | 2010-01-22 | 2019-01-15 | Secure Natural Resources Llc | Hydrometallurgical process and method for recovering metals |
| CN103343237A (en) * | 2013-07-08 | 2013-10-09 | 昆明理工大学 | Method for removing fluorine and chlorine from zinc oxide fume by adopting sulfuric acid activating/microwave roasting |
| CN104773751A (en) * | 2015-04-22 | 2015-07-15 | 衢州市业胜金属材料有限公司 | Method for removing fluorine, chlorine and valuable metals in secondary zinc oxide |
| CN109001007A (en) * | 2018-08-22 | 2018-12-14 | 汉能新材料科技有限公司 | A kind of processing method of material |
| CN110144454A (en) * | 2019-07-04 | 2019-08-20 | 石家庄学院 | A process for removing impurities in zinc dust |
| CN110983032A (en) * | 2019-11-22 | 2020-04-10 | 西北矿冶研究院 | Method for treating high fluorine chlorine zinc-containing oxidation material |
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