CN108704767A - A kind of composite restrainer and its in separation containing the application in molybdenum and other metal sulfides - Google Patents
A kind of composite restrainer and its in separation containing the application in molybdenum and other metal sulfides Download PDFInfo
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- CN108704767A CN108704767A CN201810497050.3A CN201810497050A CN108704767A CN 108704767 A CN108704767 A CN 108704767A CN 201810497050 A CN201810497050 A CN 201810497050A CN 108704767 A CN108704767 A CN 108704767A
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 54
- 239000011733 molybdenum Substances 0.000 title claims abstract description 54
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 41
- 238000000926 separation method Methods 0.000 title claims description 29
- 239000002131 composite material Substances 0.000 title claims 18
- 239000000837 restrainer Substances 0.000 title claims 18
- 238000005188 flotation Methods 0.000 claims abstract description 32
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 20
- 239000011707 mineral Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- 229940074391 gallic acid Drugs 0.000 claims description 21
- 235000004515 gallic acid Nutrition 0.000 claims description 21
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052949 galena Inorganic materials 0.000 claims description 3
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052959 stibnite Inorganic materials 0.000 claims description 3
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical compound S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 235000003283 Pachira macrocarpa Nutrition 0.000 claims 1
- 241001083492 Trapa Species 0.000 claims 1
- 235000014364 Trapa natans Nutrition 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 claims 1
- 229910000072 bismuth hydride Inorganic materials 0.000 claims 1
- BPBOBPIKWGUSQG-UHFFFAOYSA-N bismuthane Chemical compound [BiH3] BPBOBPIKWGUSQG-UHFFFAOYSA-N 0.000 claims 1
- 230000000881 depressing effect Effects 0.000 claims 1
- 229910052973 jamesonite Inorganic materials 0.000 claims 1
- 235000009165 saligot Nutrition 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 abstract description 53
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000012141 concentrate Substances 0.000 abstract description 11
- 230000002401 inhibitory effect Effects 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 6
- 229910052787 antimony Inorganic materials 0.000 abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910052569 sulfide mineral Inorganic materials 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 230000009920 chelation Effects 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 11
- 238000010408 sweeping Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- IZIJITWQULSWFA-UHFFFAOYSA-N [Bi]=S.[Mo] Chemical compound [Bi]=S.[Mo] IZIJITWQULSWFA-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- APJCSJROWXUZJT-UHFFFAOYSA-N [Mo].[Bi].[Cu] Chemical compound [Mo].[Bi].[Cu] APJCSJROWXUZJT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明属于有色金属选矿技术领域，特别涉及一种组合抑制剂及其在分离含钼和其它金属硫化矿中的应用。本发明利用组合药剂的协同效应，提高对矿物吸附、螯合、抑制的作用，有效抑制含铋、铅、锑等硫化矿物。其产生的抑制效果比单一抑制剂产生的效果要更强，可使钼与其它金属硫化矿物选择性的分离，提高钼精矿浮选指标。在浮选过程中，本发明所述组合抑制剂可直接进行添加，方便操作。本发明所开发的组合抑制剂具有使用安全，用量低，毒性低，环保，不影响后续精选作业等优点，对于提高金属资源综合回收利用和矿山的经济效益具有非常重要的意义。
The invention belongs to the technical field of non-ferrous metal beneficiation, in particular to a combined inhibitor and its application in separating molybdenum-containing and other metal sulfide ores. The invention utilizes the synergistic effect of the combined medicament to improve the effects of mineral adsorption, chelation and inhibition, and effectively inhibit the sulfide minerals containing bismuth, lead, antimony and the like. The inhibitory effect produced by it is stronger than that produced by a single inhibitor, which can selectively separate molybdenum from other metal sulfide minerals and improve the flotation index of molybdenum concentrate. During the flotation process, the combined inhibitor of the present invention can be directly added, which is convenient for operation. The combined inhibitor developed by the present invention has the advantages of safe use, low dosage, low toxicity, environmental protection, and does not affect subsequent beneficiation operations, etc., and has very important significance for improving the comprehensive recovery and utilization of metal resources and the economic benefits of mines.
Description
技术领域technical field
本发明属于有色金属选矿技术领域，特别涉及一种组合抑制剂及其在分离含钼和其它金属硫化矿中的应用。The invention belongs to the technical field of non-ferrous metal beneficiation, in particular to a combined inhibitor and its application in separating molybdenum-containing and other metal sulfide ores.
背景技术Background technique
有色金属是重要的工业原料，在电器、轻工、运输、建筑工业、机械制造、国防工业等领域应用十分广泛。近年来随着国民经济的不断发展，对钼、铋、铜、铅、锑等金属资源需求与日俱増，与此同时我国金属资源存在严重的供需不平衡，对外依存度髙、进口渠道单一等特点。提高我国有色金属资源的自给率，对于有色金属产业保持合理快速的发展具有重要的战略意义和经济意义。Non-ferrous metals are important industrial raw materials, widely used in electrical appliances, light industry, transportation, construction industry, machinery manufacturing, national defense industry and other fields. In recent years, with the continuous development of the national economy, the demand for metal resources such as molybdenum, bismuth, copper, lead, and antimony is increasing day by day. At the same time, there is a serious imbalance between supply and demand of metal resources in my country, with high foreign dependence and single import channels. Features. Improving the self-sufficiency rate of non-ferrous metal resources in my country has important strategic and economic significance for the non-ferrous metal industry to maintain a reasonable and rapid development.
目前钼与铜、铅、铋、锑、铁等硫化矿物浮选分离是选矿界一直关注的问题之一，由于硫化矿物的可浮性通常相近，都属于易浮矿物，因此在生产实践中通常难以将各金属硫化矿分开，为实现钼与其它金属硫化矿的有效分离，如何选择具有高效抑制效果的浮选药剂就显得尤为重要。国内传统的选矿工艺是采用硫化钠、氰化物、巯基乙酸、石灰等抑制剂在高碱体系实现对铜、铅、铁、铋、锑等硫化矿物的抑制。但高碱条件(工业生产实际的pH>12)对部分钼矿物的浮选不利，造成钼精矿中钼的回收率降低。尤其是高碱对低品位复杂斑岩型钼铋矿以及伴生有贵金属的钼铋铜多金属硫化矿的综合利用非常不利，大量的金、银、钼等伴生的有价金属元素会被高碱抑制进入硫精矿中而得不到综合回收的效果，造成矿山综合效益的下降和贵金属的流失。并且，高碱条件需要大量硫化钠，不仅增加矿山的直接生产成本，而且有大量的高碱废水需要处理，对环境造成很大的危害。并且氰化物和硫化钠属于有毒抑制剂，对选矿工作者的生命健康具有潜在的危害。At present, the flotation separation of molybdenum and copper, lead, bismuth, antimony, iron and other sulfide minerals is one of the problems that the beneficiation industry has been paying attention to. Since the sulfide minerals are usually similar in floatability, they are all easy-floating minerals, so in production practice usually It is difficult to separate metal sulfide ores. In order to realize the effective separation of molybdenum and other metal sulfide ores, how to choose flotation agents with high-efficiency inhibition effect is particularly important. The traditional domestic beneficiation process is to use inhibitors such as sodium sulfide, cyanide, thioglycolic acid, and lime in a high-alkali system to suppress sulfide minerals such as copper, lead, iron, bismuth, and antimony. However, high alkali conditions (pH>12 in industrial production) are unfavorable to the flotation of some molybdenum minerals, resulting in a decrease in the recovery rate of molybdenum in molybdenum concentrates. In particular, high alkalinity is very unfavorable to the comprehensive utilization of low-grade complex porphyry-type molybdenum-bismuth ores and molybdenum-bismuth-copper polymetallic sulfide ores associated with precious metals. Inhibiting the entry into the sulfur concentrate and not getting the effect of comprehensive recovery, resulting in the decline of the mine's comprehensive benefits and the loss of precious metals. Moreover, high alkali conditions require a large amount of sodium sulfide, which not only increases the direct production cost of the mine, but also requires a large amount of high alkali wastewater to be treated, causing great harm to the environment. And cyanide and sodium sulfide are toxic inhibitors, which are potentially harmful to the life and health of mineral processing workers.
国内外矿山的工程技术人员也已经认识到高碱流程和现有浮选抑制剂的缺陷，并进行了相应的研究工作，希望能在弱碱性或中性条件下找到一种稳定、高效、无毒的抑制剂，实现钼与其它金属硫化矿物的高效分离。目前，在现有相关文献资料中，以过氧化氢和没食子酸为组合抑制剂用于分离钼与其它金属硫化矿的技术鲜有报道。The engineers and technicians of mines at home and abroad have also realized the defects of the high-alkali process and the existing flotation inhibitors, and have carried out corresponding research work, hoping to find a stable, efficient, Non-toxic inhibitors for efficient separation of molybdenum from other metal sulfide minerals. At present, in the existing relevant literature, there are few reports on the technology of using hydrogen peroxide and gallic acid as a combined inhibitor to separate molybdenum from other metal sulfide ores.
发明内容Contents of the invention
本发明的目的在于针对上述问题提出一种能在弱碱性或中性条件下使用、高效环保、来源广、用量小、稳定性好，能高效分离钼和其它金属硫化矿的组合抑制剂。The object of the present invention is to propose a combined inhibitor that can be used under weakly alkaline or neutral conditions, is highly efficient and environmentally friendly, has wide sources, small dosage, good stability, and can efficiently separate molybdenum and other metal sulfide ores.
本发明一种组合抑制剂；所述组合抑制剂包括过氧化氢进和没食子酸。过氧化氢分子式为H2O2，没食子酸分子式为C7H6O5，过氧化氢化学结构式如下：The present invention is a combined inhibitor; the combined inhibitor includes hydroperoxide and gallic acid. The molecular formula of hydrogen peroxide is H 2 O 2 , the molecular formula of gallic acid is C 7 H 6 O 5 , and the chemical structure of hydrogen peroxide is as follows:
没食子酸化学结构式如下：The chemical structural formula of gallic acid is as follows:
本发明一种组合抑制剂；所述组合抑制剂中过氧化氢、没食子酸的质量比为2～6:8～4、优选为5～6:4～5。The present invention is a combined inhibitor; the mass ratio of hydrogen peroxide and gallic acid in the combined inhibitor is 2-6:8-4, preferably 5-6:4-5.
作为优选，本发明一种组合抑制剂；所述组合抑制剂由过氧化氢溶液、没食子酸溶液构成。Preferably, the present invention is a combined inhibitor; the combined inhibitor is composed of hydrogen peroxide solution and gallic acid solution.
作为优选，本发明一种组合抑制剂；所述组合抑制剂中过氧化氢和没食子酸可以以纯固体、纯液体、不同浓度溶液中任一一种形态进行使用。As a preference, the present invention is a combined inhibitor; hydrogen peroxide and gallic acid in the combined inhibitor can be used in any form of pure solid, pure liquid, or solutions with different concentrations.
作为优选，本发明一种组合抑制剂在分离含钼和其它金属硫化矿中的应用；其实施方案为：以同时含有钼的硫化物和其它金属硫化物的矿物为原料，在浮选过程中，控制浮选体系的pH值为1～14，优选为6～10，进一步优选为8～9；以过氧化氢和没食子酸为其它金属硫化物浮选抑制剂，进行浮选分离钼的硫化物和其它金属硫化物。As a preference, the application of a combined inhibitor of the present invention in the separation of molybdenum-containing and other metal sulfide ores; its embodiment is: using minerals containing molybdenum sulfide and other metal sulfides as raw materials, in the flotation process , the pH value of the control flotation system is 1-14, preferably 6-10, more preferably 8-9; hydrogen peroxide and gallic acid are used as other metal sulfide flotation inhibitors to carry out the sulfide separation of molybdenum by flotation compounds and other metal sulfides.
作为优选，本发明一种组合抑制剂在分离含钼和其它金属硫化矿中的应用；；其在浮选过程中抑制其它金属硫化矿的浮选，达到分离钼和其它金属硫化矿的目的。所述其它金属硫化物选自辉铋矿、泡铋矿、菱铋矿、铜铋矿、方铅铋矿、方铅矿、白铅矿、铬铅矿、辉锑矿、深红银矿、辉锑铅矿、脆硫锑铅矿、硫锑铅矿中的至少一种。As a preference, the application of a combined inhibitor of the present invention in the separation of molybdenum-containing and other metal sulfide ores; it inhibits the flotation of other metal sulfide ores during the flotation process to achieve the purpose of separating molybdenum and other metal sulfide ores. The other metal sulfides are selected from the group consisting of bismuthite, bismuthite, bismuthite, copper bismuthite, galena, galena, white lead ore, chromite, stibnite, dark red silver ore, At least one of stibnite, brittle stymbite, and styroite.
作为优选，本发明一种组合抑制剂在分离含钼和其它金属硫化矿中的应用；；所述组合抑制剂可用于粗选作业、精选作业、扫选作业中任一浮选作业。As a preference, the application of a combined inhibitor of the present invention in the separation of molybdenum-containing and other metal sulfide ores; the combined inhibitor can be used for any flotation operation in roughing operations, beneficiation operations, and sweeping operations.
作为优选，本发明一种组合抑制剂在分离含钼和其它金属硫化矿中的应用；；所述组合抑制剂可分开加入浮选矿浆中，亦可混合后加入浮选矿浆中。As a preference, the application of a combined inhibitor in the separation of molybdenum-containing and other metal sulfide ores; the combined inhibitor can be added to the flotation pulp separately, or can be added to the flotation pulp after mixing.
作为优选，本发明一种组合抑制剂在分离含钼和其它金属硫化矿中的应用；所述组合抑制剂在粗选作业中总用量范围为200～1500克/吨给矿、优选为200-800克/吨给矿、进一步优选为200-500克/吨给矿，用量低于范围则可能产生抑制效果不足，矿物无法分离；超出本范围则会破坏矿物的可浮性，导致有价金属回收率降低。As a preference, the application of a combined inhibitor of the present invention in the separation of molybdenum-containing and other metal sulfide ores; the total amount of the combined inhibitor in the roughing operation ranges from 200 to 1500 grams per ton of ore, preferably 200- 800g/ton of ore, and more preferably 200-500g/ton of ore, if the dosage is lower than the range, the inhibitory effect may be insufficient, and the minerals cannot be separated; if the amount exceeds this range, the buoyancy of the minerals will be destroyed, resulting in the loss of valuable metals. The recovery rate is reduced.
作为优选，本发明一种组合抑制剂在分离含钼和其它金属硫化矿中的应用；所述组合抑制剂在精选作业中总用量范围为50～500克/吨给矿，优选为50-300克/吨给矿、进一步优选为50-150克/吨给矿，用量低于范围则可能产生抑制效果不足，矿物无法分离；超出本范围则会破坏矿物的可浮性，导致有价金属回收率降低。As a preference, the application of a combined inhibitor of the present invention in the separation of molybdenum-containing and other metal sulfide ores; the total amount of the combined inhibitor used in the beneficiation operation ranges from 50 to 500 grams per ton of ore, preferably 50- 300g/ton of ore, more preferably 50-150g/ton of ore, if the amount is lower than the range, the inhibitory effect may be insufficient, and the minerals cannot be separated; if the amount exceeds this range, the buoyancy of the minerals will be destroyed, resulting in valuable metals The recovery rate is reduced.
作为优选，本发明一种组合抑制剂在分离含钼和其它金属硫化矿中的应用；所述组合抑制剂在扫选作业中总用量范围为50～300克/吨给矿，优选为50-200克/吨给矿、进一步优选为50-100克/吨给矿，用量低于范围则可能产生抑制效果不足，矿物无法分离；超出本范围则会破坏矿物的可浮性，导致有价金属回收率降低。As a preference, the application of a combined inhibitor of the present invention in the separation of molybdenum-containing and other metal sulfide ores; the total amount of the combined inhibitor in the sweeping operation ranges from 50 to 300 grams per ton of ore, preferably 50- 200 g/t ore feed, more preferably 50-100 g/t ore feed, if the amount is lower than the range, the inhibitory effect may be insufficient, and the minerals cannot be separated; if the amount exceeds this range, the buoyancy of the minerals will be destroyed, resulting in valuable metals The recovery rate is reduced.
选矿过程中，原料的细度、捕收剂、起泡剂的用量制度和现有技术相关参数的控制可以是一致的。During the beneficiation process, the fineness of raw materials, the dosage system of collectors and foaming agents and the control of relevant parameters of the existing technology can be consistent.
本发明所采用的过氧化氢、没食子酸等均属于市售常规试剂。The hydrogen peroxide, gallic acid and the like used in the present invention all belong to commercially available conventional reagents.
相对目前的用于钼与其它金属硫化矿浮选分离的抑制剂，本发明技术方案带来的有益效果：Compared with the current inhibitor used for the flotation separation of molybdenum and other metal sulfide ores, the beneficial effects brought by the technical solution of the present invention are as follows:
⑴本发明的所公开的一种用于分离钼和其它金属硫化矿的组合抑制剂，在pH为8～9的矿浆体系下进行钼与其他金属硫化矿的分离作业，取代高碱体系，提高分选的效率。(1) A disclosed combination inhibitor for separating molybdenum and other metal sulfide ores of the present invention carries out the separation operation of molybdenum and other metal sulfide ores under a pulp system with a pH of 8 to 9, replaces the high-alkali system, and improves Sorting efficiency.
⑵本发明所公开的一种用于分离钼和其它金属硫化矿的组合抑制剂可广泛的应用优先浮选、混合浮选、等可浮等浮选工艺流程，具有选择性强，药剂用量小，药剂制度简单，不影响后续精选作业的优点，能大幅度降低生产成本，提高矿产资源利用率。同时，采用本发明所开发的抑制剂，还能简化工艺流程。(2) A combined depressant for separating molybdenum and other metal sulfide ores disclosed in the present invention can be widely used in flotation processes such as preferential flotation, mixed flotation, and other flotation, and has strong selectivity and small dosage of chemicals , the pharmaceutical system is simple, does not affect the advantages of subsequent beneficiation operations, can greatly reduce production costs, and improve the utilization rate of mineral resources. At the same time, the process flow can be simplified by adopting the inhibitor developed by the invention.
⑶本发明所公开的一种钼铋分离组合抑制剂过氧化氢+没食子酸为稳定、高效、安全、低毒的抑制剂，对环境友好，便于处理，且浮选过程稳定，且易于控制，对于提高金属资源综合回收利用和矿山的经济效益具有非常重要的意义。(3) A molybdenum-bismuth separation combination inhibitor hydrogen peroxide+gallic acid disclosed by the present invention is a stable, efficient, safe, and low-toxic inhibitor, which is environmentally friendly, easy to handle, and the flotation process is stable and easy to control. It is of great significance to improve the comprehensive recycling of metal resources and the economic benefits of mines.
附图说明Description of drawings
图1为本发明一种组合抑制剂应用于钼铋硫化矿的选矿工艺流程图。Fig. 1 is a flow chart of the beneficiation process of a combined inhibitor of the present invention applied to molybdenum-bismuth sulfide ore.
具体实施方式Detailed ways
以下结合实施例子旨在再进一步说明本发明内容，而非限制本发明权利要求的保护范围。The following examples are intended to further illustrate the content of the present invention, rather than limit the protection scope of the claims of the present invention.
实施例1Example 1
1.矿物原料1. Mineral raw materials
选别的某钼铋硫化矿中含钼品位为0.9-1.0％，铋品位为0.4-0.5％，钼主要为辉钼矿，铋主要为辉铋矿。The grade of molybdenum in a certain molybdenum-bismuth sulfide ore is 0.9-1.0%, and the grade of bismuth is 0.4-0.5%. The molybdenum is mainly molybdenite, and the bismuth is mainly bismuthite.
2.操作步骤及技术条件如下：2. The operation steps and technical conditions are as follows:
①粗选作业：称取一定量的钼铋矿，加水调至矿浆浓度为30～35％，将矿浆倒入合适的浮选槽中，调节矿浆pH为8-9，往浮选槽中加入捕收剂乙硫氮300g/t，煤油50g/t，搅拌3～5分钟，加入起泡剂25g/t松醇油，搅拌3分钟后进行钼铋混合粗选作业，得到混合粗精矿和尾矿，尾矿经2次空白扫选后得到最终尾矿；① Rough selection: Weigh a certain amount of molybdenum-bismuth ore, add water to adjust the pulp concentration to 30-35%, pour the pulp into a suitable flotation tank, adjust the pH of the pulp to 8-9, and add 300g/t collector, 50g/t kerosene, stirring for 3 to 5 minutes, adding 25g/t terpineol oil as a foaming agent, stirring for 3 minutes, and then carrying out mixed roughing of molybdenum and bismuth to obtain mixed coarse concentrate and Tailings, the final tailings are obtained after the tailings are swept twice in the blank;
②钼铋分离：在混合粗精矿中加入本发明所述组合抑制剂500g/t(其中过氧化氢、没食子酸的质量比为：5：5)，搅拌2～5分钟后进行钼铋分离作业；②Separation of molybdenum and bismuth: add 500g/t of the combined inhibitor of the present invention to the mixed coarse concentrate (wherein the mass ratio of hydrogen peroxide and gallic acid is: 5:5), stir for 2 to 5 minutes and carry out molybdenum and bismuth separation Operation;
③钼精选一：在钼铋分离作业的精矿中加入150g/t的组合抑制剂(其中过氧化氢、没食子酸的质量比为：5：5),搅拌3～5分钟,接着添加20g/t煤油,搅拌3～5分钟后进行钼精选一作业；③Molybdenum concentration 1: Add 150g/t combined inhibitor (the mass ratio of hydrogen peroxide and gallic acid: 5:5) to the concentrate of molybdenum-bismuth separation operation, stir for 3-5 minutes, then add 20g /t kerosene, after stirring for 3-5 minutes, carry out the operation of molybdenum selection;
④钼精选二：在钼精选一作业的精矿中加入50g/t的组合抑制剂(其中过氧化氢、没食子酸的质量比为：5：5),搅拌2～3分钟,接着添加20g/t的煤油,搅拌2～3分钟后进行钼精选二作业；④Molybdenum concentration 2: Add 50g/t combined inhibitor (the mass ratio of hydrogen peroxide and gallic acid: 5:5) to the concentrate of molybdenum concentration 1 operation, stir for 2-3 minutes, then add 20g/t kerosene, after stirring for 2-3 minutes, carry out the second operation of molybdenum selection;
⑤钼精选三到六：将钼精选二作业的精矿搅拌2～3分钟后进行空白精选作业，精选次数为3次，最终精矿为钼精矿；⑤Molybdenum concentration 3 to 6: Stir the concentrate of molybdenum concentration 2 operation for 2 to 3 minutes and then perform blank concentration operation. The number of separations is 3 times, and the final concentrate is molybdenum concentrate;
⑥钼扫选一：在钼铋分离作业的尾矿中同时加入15g/t煤油,搅拌2～3分钟，接着加入起泡剂15g/t松醇油，搅拌2～3分钟后进行钼扫选一作业；⑥Molybdenum sweeping 1: add 15g/t kerosene to the tailings of molybdenum-bismuth separation operation, stir for 2-3 minutes, then add foaming agent 15g/t terpineol oil, stir for 2-3 minutes and carry out molybdenum sweeping a homework;
⑦钼扫选二到五：在钼扫选一作业的尾矿中加入15g/t煤油,搅拌2～3分钟后进行空白扫选作业，扫选次数为3次，最终尾矿即为铋精矿；⑦Molybdenum sweeping 2 to 5: add 15g/t kerosene to the tailings of molybdenum sweeping operation 1, stir for 2 to 3 minutes and then carry out blank sweeping operation. The sweeping times are 3 times, and the final tailings are bismuth concentrate mine;
⑧钼精选段、铋精选段浮选作业的中矿依次返回上一次浮选作业。⑧ The middlings in the molybdenum concentrating section and bismuth concentrating section flotation operations return to the previous flotation operation in turn.
实验结果如表1所示。The experimental results are shown in Table 1.
实施例2Example 2
其它条件均与实施例1一致，不同之处在于：在步骤②中，加入本发明所述组合抑制剂最大用量1500g/t(其中过氧化氢、没食子酸的质量比为：5：5)，在步骤③、④中加入本发明所述组合抑制剂最大用量500g/t，其结果如表1所示。Other conditions are all consistent with embodiment 1, and difference is: in step 2. in, add the combination inhibitor maximum consumption 1500g/t of the present invention (wherein the mass ratio of hydrogen peroxide, gallic acid is: 5:5), In steps ③ and ④, the combined inhibitor of the present invention is added with a maximum dosage of 500 g/t, and the results are shown in Table 1.
实施例3Example 3
其它条件均与实施例1一致，不同之处在于：在步骤②中，加入本发明所述组合抑制剂最小用量200g/t(其中过氧化氢、没食子酸的质量比为：5：5)，在步骤③、④中加入本发明所述组合抑制剂最小用量50g/t，其结果如表1所示。Other conditions are all consistent with embodiment 1, and difference is: in step 2. in, add combination inhibitor of the present invention minimum dosage 200g/t (wherein the mass ratio of hydrogen peroxide, gallic acid is: 5:5), In steps ③ and ④, the combined inhibitor of the present invention is added with a minimum dosage of 50 g/t, and the results are shown in Table 1.
对比例1Comparative example 1
其它条件均与实施例1一致，不同之处在于：浮选过程中，只以没食子酸为抑制剂(其用量等于实施例1中双氧水+没食子酸的量)，其结果如表1所示。Other conditions are all consistent with Example 1, except that in the flotation process, only gallic acid is used as inhibitor (its consumption is equal to the amount of hydrogen peroxide+gallic acid in Example 1), and the results are shown in Table 1.
对比例2Comparative example 2
其它条件均与实施例1一致，不同之处在于：浮选过程中，组合抑制剂在钼铋分离作业中的药剂用量为3000g/t，其结果如表1所示。Other conditions are the same as those in Example 1, except that during the flotation process, the dosage of the combined inhibitor in the separation of molybdenum and bismuth is 3000 g/t, and the results are shown in Table 1.
对比例3Comparative example 3
其它条件均与实施例1一致，不同之处在于：浮选过程中，组合抑制剂在钼精选段一、二的药剂用量为1000g/t，其结果如表1所示。Other conditions are the same as in Example 1, the difference is that in the flotation process, the dosage of the combination inhibitor in the first and second molybdenum concentration sections is 1000g/t, and the results are shown in Table 1.
对比例4Comparative example 4
其它条件均与实施例1一致，不同之处在于：浮选过程中，以硫化钠等量替代组合抑制剂，其结果如表1所示。Other conditions were consistent with Example 1, except that during the flotation process, the combined inhibitor was replaced by an equivalent amount of sodium sulfide. The results are shown in Table 1.
表1浮选实验结果Table 1 Flotation experiment results
由实施例1实验结果可知，本发明所得抑制剂对铋的硫化矿有很好的抑制作用，适用于含钼硫化矿与其他金属硫化矿的浮选分离。同时，由对比例1-3的实验结果可知，本发明所述组合抑制剂药剂用量范围不在本发明所保护范围内或单一组分药剂均不能实现对铜铅铁铋锑等硫化矿的抑制作用。由对比例4可知，本发明所述抑制剂能实现比现有选矿技术中用于钼与其它金属硫化矿的抑制剂更好的抑制效果。From the experimental results of Example 1, it can be seen that the inhibitor obtained in the present invention has a good inhibitory effect on bismuth sulfide ores, and is suitable for the flotation separation of molybdenum-containing sulfide ores and other metal sulfide ores. Simultaneously, from the experimental results of comparative examples 1-3, it can be seen that the dosage range of the combined inhibitor agent of the present invention is not within the protection scope of the present invention or the single component agent cannot realize the inhibitory effect on sulfide minerals such as copper, lead, iron, bismuth, antimony, etc. . From Comparative Example 4, it can be seen that the inhibitor of the present invention can achieve a better inhibitory effect than the inhibitor used for molybdenum and other metal sulfide ores in the existing mineral processing technology.
需要说明的是，尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。It should be noted that although the embodiments of the present invention have been shown and described, those skilled in the art can understand that these embodiments can be modified in various ways without departing from the principle and spirit of the present invention. Changes, modifications, substitutions and variations, the scope of the present invention is defined by the appended claims and their equivalents.
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