RU2316607C1 - Method for removing chlorine and fluorine from dust-like zinc -containing materials of lead-zinc production - Google Patents
Method for removing chlorine and fluorine from dust-like zinc -containing materials of lead-zinc production Download PDFInfo
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- RU2316607C1 RU2316607C1 RU2006124338A RU2006124338A RU2316607C1 RU 2316607 C1 RU2316607 C1 RU 2316607C1 RU 2006124338 A RU2006124338 A RU 2006124338A RU 2006124338 A RU2006124338 A RU 2006124338A RU 2316607 C1 RU2316607 C1 RU 2316607C1
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- Prior art keywords
- fluorine
- zinc
- chlorine
- lead
- sublimates
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 30
- 239000011737 fluorine Substances 0.000 title claims abstract description 30
- 239000000460 chlorine Substances 0.000 title claims abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 15
- 239000011701 zinc Substances 0.000 title claims abstract description 15
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 20
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 17
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 239000002893 slag Substances 0.000 abstract description 3
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 239000000428 dust Substances 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 125000001153 fluoro group Chemical group F* 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000001131 transforming effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 208000024780 Urticaria Diseases 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- NMGSERJNPJZFFC-UHFFFAOYSA-N carbonic acid;sulfuric acid Chemical compound OC(O)=O.OS(O)(=O)=O NMGSERJNPJZFFC-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
Description
Изобретение относится к цветной металлургии и может быть использовано при удалении хлора и фтора из пылевидных материалов свинцово-цинкового производства, например из вельцвозгонов или шлаковозгонов.The invention relates to non-ferrous metallurgy and can be used to remove chlorine and fluorine from pulverized materials of lead-zinc production, for example, from Weltzogon or slag sublimates.
Известен способ удаление хлора и фтора из пылевидных цинксодержащих материалов свинцово-цинкового производства, включающий их прокалку (окислительный обжиг) при температуре 650-700°С и переработку вторичных возгонов (см. книгу Абдеев М.А., Колесников А.В., Ушаков Н.Н. Вельцевание цинк-свинецсодержащих материалов. М.: Металлургия. - 1985. - С.94). Известен способ удаления хлора, фтора и сульфатов из окисленных свинцово-цинковых материалов с использованием водного раствора сульфата натрия и оксида кальция (см. Авт.свид. СССР №1325098, опубл. Б.И. №27, 1987 г. по кл. С22В 3/00).A known method of removing chlorine and fluorine from dusty zinc-containing materials of lead-zinc production, including their calcination (oxidative calcination) at a temperature of 650-700 ° C and the processing of secondary sublimates (see book Abdeev MA, Kolesnikov A.V., Ushakov NN Weltzvanie zinc-lead-containing materials. M: Metallurgy. - 1985. - P.94). A known method of removing chlorine, fluorine and sulfates from oxidized lead-zinc materials using an aqueous solution of sodium sulfate and calcium oxide (see Autosvid. USSR No. 1322598, publ. BI No. 27, 1987, class C22B 3/00).
Недостатком указанных способов является низкая доля удаления фтора и повышенное количество сульфатов в растворах после отмывки.The disadvantage of these methods is the low proportion of fluorine removal and an increased amount of sulfates in solutions after washing.
Наиболее близкий по технической сущности и достигаемому результату является способ удаления хлора и фтора из пылевидных цинксодержащих материалов свинцово-цинкового производства, включающий прокалку вельцвозгонов или шлаковозгонов, улавливание вторичных возгонов и проведение их водно-содовой отмывки на стадии улавливания в 2-е ступени, причем на 1-й ступени поддерживают температуру промывного раствора 70-90°С и рН 8,5-9,0, а на 2-й ступени поддерживают концентрацию соды в промывном растворе 30-55 г/л (см. авт.свид. №1135786 СССР, опубл. Бюл. - 1985. - №3, по кл. С22В 7/02).The closest in technical essence and the achieved result is a method of removing chlorine and fluorine from dusty zinc-containing materials of lead-zinc production, including calcining welts sublimates or slag sublimates, trapping secondary sublimates and conducting their soda-water washing at the recovery stage in the 2nd stage The first stage maintains the temperature of the washing solution 70-90 ° C and pH 8.5-9.0, and at the second stage the concentration of soda in the washing solution is maintained at 30-55 g / l (see Autoswitch No. 1135786 USSR, publ. Bull. - 1985. - No. 3, according to CL C22B 7/02).
Недостатком указанного способа является низкие показатели отмывки вторичных возгонов от фтора.The disadvantage of this method is the low washing rates of secondary sublimates from fluorine.
Техническим результатом данного изобретения является увеличение отмывки от фтора вторичных возгонов. Указанный результат достигается тем, что в способе удаления хлора и фтора из пылевидных цинксодержащих материалов свинцово-цинкового производства, включающем прокалку материалов с получением вторичных хлор- и фторсодержащих возгонов и последующую их двухстадийную водно-содовую отмывку, отмывку хлора и фтора осуществляют водным раствором, содержащим карбонат и сульфат натрия при концентрации их в исходном растворе на каждой стадии, соответственно 67-72 и 8-13 г/л.The technical result of this invention is to increase the washing of fluorine from secondary sublimates. This result is achieved by the fact that in the method of removing chlorine and fluorine from dusty zinc-containing materials of lead-zinc production, including calcining materials to obtain secondary chlorine and fluorine-containing sublimates and their subsequent two-stage water-soda washing, washing of chlorine and fluorine is carried out with an aqueous solution containing sodium carbonate and sodium sulfate at their concentration in the initial solution at each stage, respectively 67-72 and 8-13 g / l.
Способ осуществляется следующим образомThe method is as follows
Пылевидный цинксодержащий материал (вельц-окись) состава, %: цинк 60-67; свинец 3-10; железо 1-5; хлор 0,15-0,55; фтор 0,02-0,15 подвергается прокалке при температуре 650-750°С с получением вторичных возгонов с выходом их от вельц-окиси 3-5% и состава, %: цинк 30-50; свинец 5-20; хлор 3,4-12; фтор 0,42-2,2. Вторичные возгоны отмывают в водном растворе карбоната и сульфата натрия в две стадии при ж:т=7:1 и температуре 75-85°С. На первой и второй стадии концентрация карбоната натрия в исходном растворе составляет 67-72 г/л, а сульфата натрия 8-13 г/л и рН раствора после отмывки возгонов 8,0-8,5 после первой стадии и 8,5-9,0 после второй стадии. Твердый остаток от отмывки вторичных возгонов - карбонатно-сульфатный кек отфильтровывается после каждой стадии отмывки. Цинк, свинец, кадмий практически полностью переходят в карбонатно-сульфатный кек, который поступает на вельцевание. Фильтрат направляется на очистные сооружения на известковую очистку сточных вод.Dusty zinc-containing material (Waelz oxide) composition,%: zinc 60-67; lead 3-10; iron 1-5; chlorine 0.15-0.55; fluorine 0.02-0.15 is calcined at a temperature of 650-750 ° C to obtain secondary sublimates with a yield of Waelz oxide of 3-5% and composition,%: zinc 30-50; lead 5-20; chlorine 3.4-12; fluorine 0.42-2.2. Secondary sublimates are washed in an aqueous solution of sodium carbonate and sodium sulfate in two stages at w: t = 7: 1 and a temperature of 75-85 ° C. In the first and second stages, the concentration of sodium carbonate in the initial solution is 67-72 g / l, and sodium sulfate is 8-13 g / l and the pH of the solution after washing the sublimates is 8.0-8.5 after the first stage and 8.5-9 0 after the second stage. The solid residue from washing the secondary sublimates - carbonate-sulfate cake is filtered out after each stage of washing. Zinc, lead, cadmium almost completely turn into carbonate-sulfate cake, which is supplied to Waelz. The filtrate is sent to treatment plants for lime wastewater treatment.
Предложенный способ испытан в лабораторных условиях.The proposed method is tested in laboratory conditions.
Испытания показали, что удаление хлора и фтора из пылевидных цинксодержащих материалов свинцово-цинкового производства путем прокалки материалов и водно-содой отмывки вторичных возгонов с добавкой сульфата натрия позволит удалить 97-99% хлора и 90-95% фтора из вторичных возгонов, получаемых после прокалки вельц-окиси.Tests have shown that the removal of chlorine and fluorine from dusty zinc-containing materials of lead-zinc production by calcining materials and washing with water-soda to wash secondary sublimates with the addition of sodium sulfate will allow to remove 97-99% chlorine and 90-95% fluorine from secondary sublimates obtained after calcination Waelz oxides.
Пределы изменения концентрации карбоната и сульфата натрия в исходном растворе связаны с получением максимальных результатов отмывки хлора и фтора. Так, при суммарной концентрации карбоната и сульфата натрия составляет 80 г/л при ж: т=7:1 нижний предел содержания сульфата 8 г/л связан с более низкими содержаниями фтора и свинца во вторичных возгонах (фтора 0,42% и свинца 5%). С повышением содержания в возгонах фтора до 2,2% и свинца до 20% концентрация в растворе сульфата натрия возрастает до 13 г/л. Сульфат натрия способствует более эффективному переводу фторидов и хлоридов в растворимые формы в содовом растворе по реакции PbF2(Cl2)+Na2SO4=NaF(Cl)+PbSO4 за счет перевода свинца и других металлов в нерастворимые соединения.The limits of changes in the concentration of sodium carbonate and sodium sulfate in the initial solution are associated with obtaining maximum washing results of chlorine and fluorine. So, at a total concentration of sodium carbonate and sodium sulfate is 80 g / l with w: t = 7: 1, the lower limit of the sulfate content of 8 g / l is associated with lower fluorine and lead contents in secondary sublimates (0.42% fluorine and 5 lead %). With an increase in the content of fluorine in sublimates to 2.2% and lead to 20%, the concentration in the sodium sulfate solution increases to 13 g / l. Sodium sulfate promotes a more efficient conversion of fluorides and chlorides to soluble forms in soda solution by the reaction PbF 2 (Cl 2 ) + Na 2 SO 4 = NaF (Cl) + PbSO 4 due to the conversion of lead and other metals to insoluble compounds.
Проверку способа осуществляли следующим образом.The verification of the method was carried out as follows.
Вельц-окись состава, %: цинк 62,5; свинец 7,5; хлор 0,35; фтор 0,035 подвергали прокалке при температуре 750°С с получением вторичных возгонов состава, %: цинк 45,3; свинец 9,8; хлор 5,9; фтор 0,82. Вторичные возгоны отмывали при температуре 80°С в две стадии в водном растворе карбоната и сульфата натрия с концентрацией указанных солей в исходном растворе, соответственно 68 г/ли 12 г/л на каждой стадии. Суммарный расход карбоната натрия составил 560 кг/т вторичных возгонов. рН на первой стадии отмывки составлял 8,0-8,5 и на второй стадии отмывки 8,5-9,0.Waelz oxide composition,%: zinc 62.5; lead 7.5; chlorine 0.35; fluorine 0.035 was calcined at a temperature of 750 ° C to obtain secondary sublimates of the composition,%: zinc 45.3; lead 9.8; chlorine 5.9; fluorine 0.82. Secondary sublimates were washed at a temperature of 80 ° C in two stages in an aqueous solution of sodium carbonate and sulfate with a concentration of these salts in the initial solution, respectively 68 g / l 12 g / l at each stage. The total consumption of sodium carbonate was 560 kg / t of secondary sublimates. The pH in the first stage of washing was 8.0-8.5 and in the second stage of washing 8.5-9.0.
Известный способ проверяли в соответствии с описанием прототипа, в котором удаление хлора и фтора из пылевидных цинксодержащих материалов свинцово-цинкового производства проводили из вторичных возгонов в 2-е стадии. На первой стадии температуру раствора выдерживали 80°С и рН 8,7, а на 2-й стадии поддерживали концентрацию соды в промывном растворе 50 г/л. Растворы после 1-й и 2-й стадии отфильтровывались.The known method was checked in accordance with the description of the prototype, in which the removal of chlorine and fluorine from dusty zinc-containing materials of lead-zinc production was carried out from secondary sublimates in the 2nd stage. At the first stage, the temperature of the solution was maintained at 80 ° C and pH 8.7, and at the second stage, the concentration of soda in the washing solution was maintained at 50 g / L. Solutions after the 1st and 2nd stages were filtered.
В таблице приведены сравнительные данные проверки известного и предлагаемого способов удаления хлора и фтора из пылевидных цинксодержащих материалов свинцово-цинкового производства. Как видно из полученных данных, использование предлагаемого способа позволяет удалить фтор из вторичных возгонов на 47,5% больше, чем в известном способе.The table shows comparative verification data of the known and proposed methods for the removal of chlorine and fluorine from dusty zinc-containing materials of lead-zinc production. As can be seen from the obtained data, the use of the proposed method allows to remove fluorine from secondary sublimates by 47.5% more than in the known method.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2813068C1 (en) * | 2022-11-29 | 2024-02-06 | Негосударственное частное образовательное учреждение высшего образования "Технический университет УГМК" | Method for removing chlorine and fluorine from dusty zinc-containing materials |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4396424A (en) * | 1980-08-13 | 1983-08-02 | Nippon Kokan Kabushiki Kaisha | Method for recovering useful metals from dust discharged from metal refining metallurgical furnace |
| EP0174641A2 (en) * | 1984-09-11 | 1986-03-19 | Sumitomo Heavy Industries, Ltd | A process for recovering valuable metals from an iron dust containing a higher content of zinc |
| SU1325098A1 (en) * | 1985-11-29 | 1987-07-23 | Северо-Кавказский горно-металлургический институт | Method of washing lead and zinc oxidated materials from sulfate,chloride and fluoride ions |
| US5139567A (en) * | 1990-04-20 | 1992-08-18 | Sumitomo Heavy Industries, Ltd. | Process for recovering valuable metals from a dust containing zinc |
| WO1998004755A1 (en) * | 1996-07-30 | 1998-02-05 | Kcm - S.A. | 'waelz' method for processing of zinc containing materials in pelletized form |
-
2006
- 2006-07-06 RU RU2006124338A patent/RU2316607C1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4396424A (en) * | 1980-08-13 | 1983-08-02 | Nippon Kokan Kabushiki Kaisha | Method for recovering useful metals from dust discharged from metal refining metallurgical furnace |
| EP0174641A2 (en) * | 1984-09-11 | 1986-03-19 | Sumitomo Heavy Industries, Ltd | A process for recovering valuable metals from an iron dust containing a higher content of zinc |
| SU1325098A1 (en) * | 1985-11-29 | 1987-07-23 | Северо-Кавказский горно-металлургический институт | Method of washing lead and zinc oxidated materials from sulfate,chloride and fluoride ions |
| US5139567A (en) * | 1990-04-20 | 1992-08-18 | Sumitomo Heavy Industries, Ltd. | Process for recovering valuable metals from a dust containing zinc |
| WO1998004755A1 (en) * | 1996-07-30 | 1998-02-05 | Kcm - S.A. | 'waelz' method for processing of zinc containing materials in pelletized form |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2813068C1 (en) * | 2022-11-29 | 2024-02-06 | Негосударственное частное образовательное учреждение высшего образования "Технический университет УГМК" | Method for removing chlorine and fluorine from dusty zinc-containing materials |
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