CN109806980B - A kind of method and application of malachite sulfide product control - Google Patents
A kind of method and application of malachite sulfide product control Download PDFInfo
- Publication number
- CN109806980B CN109806980B CN201910081680.7A CN201910081680A CN109806980B CN 109806980 B CN109806980 B CN 109806980B CN 201910081680 A CN201910081680 A CN 201910081680A CN 109806980 B CN109806980 B CN 109806980B
- Authority
- CN
- China
- Prior art keywords
- malachite
- vulcanization
- flotation
- sulfide
- film
- 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.)
- Active
Links
- 241000907663 Siproeta stelenes Species 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 32
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000005188 flotation Methods 0.000 claims abstract description 28
- 238000004073 vulcanization Methods 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims abstract 2
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 2
- 239000000463 material Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 5
- 238000009837 dry grinding Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical group [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
一种孔雀石硫化产物控制的方法及其应用，使用1：1配比的硫磺：硫脲粉末作为硫化剂，铁粉作为硫化反应助剂，在磨矿过程中利用机械化学作用完成孔雀石硫化，可以在孔雀石表面生成一层CuFeS2为主的硫化物薄膜，该硫化物薄膜化学稳定性和机械稳定性强，在后续浮选过程中不会发生氧化反应，浮选机搅拌转子在160～180rpm的转速下产物薄膜不会机械脱落。用该方法硫化后的孔雀石浮选回收率可以达到75.6％～82.5％，接近硫化矿的浮选指标，具有广阔的推广应用前景。A method for controlling malachite sulfide products and application thereof, using a 1:1 ratio of sulfur: thiourea powder as a vulcanizing agent, iron powder as a vulcanization reaction assistant, and using mechanochemical action in the grinding process to complete the malachite vulcanization , a layer of CuFeS 2 -based sulfide film can be formed on the surface of malachite. The sulfide film has strong chemical and mechanical stability, and no oxidation reaction occurs in the subsequent flotation process. The stirring rotor of the flotation machine is at 160 The product film did not mechanically peel off at ~180 rpm. The flotation recovery rate of malachite sulfided by this method can reach 75.6% to 82.5%, which is close to the flotation index of sulfide ore, and has broad application prospects.
Description
技术领域technical field
本发明属于矿物加工技术领域，涉及孔雀石的硫化浮选，特别涉及一种孔雀石硫化产物控制的方法及其应用。The invention belongs to the technical field of mineral processing, relates to the sulfide flotation of malachite, and particularly relates to a method for controlling the sulfide product of malachite and its application.
背景技术Background technique
随着矿产资源日趋贫细杂，人们对资源的综合回收率、精矿产品的质量及浮选分离效果的要求不断提高，复杂多金属氧化矿的浮选分离也显得日趋重要。孔雀石相对于硫化铜矿来说，溶解度较好而且表面亲水性较高，不易浮选，因此浮选前先硫化是目前应用最为广泛的方法。硫化就是通过添加硫化剂改变矿物表面性质，使矿物表面生成一层硫化矿薄膜，提高疏水性变得易浮，提高回收率。目前普遍使用的硫化剂是硫化钠或者硫氢化钠，该类硫化剂存在硫化反应较慢、过程不易控制、硫化物薄膜稳定性差的问题，且生成的硫化物薄膜在矿浆复杂流场作用下易于疏松脱落，尤其是用量很难把握，硫化钠或者硫氢化钠用量过少不能保障足够的还原性气氛，达不到硫化效果，用量过多又会对后续浮选产生明显的抑制作用。As mineral resources become increasingly depleted and miscellaneous, people's requirements for the comprehensive recovery rate of resources, the quality of concentrate products and the effect of flotation separation continue to increase, and the flotation separation of complex polymetallic oxide ore is becoming more and more important. Compared with copper sulfide ore, malachite has better solubility and higher surface hydrophilicity, and is not easy to flotation. Therefore, vulcanization before flotation is the most widely used method at present. Sulfurization is to change the surface properties of minerals by adding vulcanizing agents, so that a layer of sulfide ore film is formed on the surface of the minerals, which improves the hydrophobicity and becomes easy to float and improves the recovery rate. At present, the commonly used vulcanizing agent is sodium sulfide or sodium hydrosulfide. These vulcanizing agents have the problems of slow vulcanization reaction, difficult process control, and poor stability of sulfide film, and the generated sulfide film is easy to be generated under the action of complex flow field of pulp. Loose and shedding, especially the dosage is difficult to grasp. Too little sodium sulfide or sodium hydrosulfide cannot guarantee a sufficient reducing atmosphere and cannot achieve the vulcanization effect. Too much dosage will have a significant inhibitory effect on the subsequent flotation.
发明内容SUMMARY OF THE INVENTION
为了克服上述孔雀石浮选指标差的缺点，本发明的目的在于提供一种孔雀石硫化产物控制的方法及其应用，该方法能有效控制孔雀石硫化产物，在孔雀石表面生成一层CuFeS2为主的硫化物薄膜，该硫化物薄膜疏水性、机械稳定性和化学稳定性强，在后续浮选过程中不会发生氧化，反应浮选机搅拌转子在50-60rpm的转速下产物薄膜不会机械脱落，采用该方法可有效硫化了孔雀石并能有效控制孔雀石硫化产物，大幅度提高孔雀石的精矿回收率。In order to overcome the shortcoming that the above-mentioned malachite flotation index is poor, the object of the present invention is to provide a method for the control of malachite sulfide products and application thereof, which can effectively control the malachite sulfide products, and generate a layer of CuFeS on the surface of the malachite. The main sulfide film, the sulfide film has strong hydrophobicity, mechanical stability and chemical stability, and will not be oxidized in the subsequent flotation process. The method can effectively sulfide the malachite and effectively control the malachite sulfide product, and greatly improve the recovery rate of the malachite concentrate.
为了实现上述目的，本发明采用的技术方案是：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种孔雀石硫化产物控制的方法，使用硫磺和硫脲粉末作为硫化剂，铁粉作为硫化反应助剂，在磨矿过程中利用机械化学作用完成孔雀石硫化。A method for controlling malachite sulfide products, using sulfur and thiourea powder as vulcanizing agent, iron powder as vulcanization reaction assistant, and utilizing mechanochemical action to complete malachite vulcanization during ore grinding.
所述硫磺和硫脲的质量比为1：1。The mass ratio of the sulfur and thiourea is 1:1.
所述孔雀石为细碎后孔雀石，粒径<8mm。The malachite is finely crushed malachite, and the particle size is less than 8 mm.
所述硫化剂用量为300～1000g/t。The dosage of the vulcanizing agent is 300-1000 g/t.
所述硫化反应助剂用量为100～300g/t。The dosage of the vulcanization reaction assistant is 100-300 g/t.
所述磨矿方式为干式磨矿，磨矿时间为5～15min。The grinding method is dry grinding, and the grinding time is 5-15 minutes.
将硫化后孔雀石进行浮选(采用常规浮选流程)，浮选回收率达到75.6％～82.5％，接近硫化矿的浮选指标，具有广阔的推广应用前景。The flotation of malachite after vulcanization (using a conventional flotation process), the flotation recovery rate reaches 75.6% to 82.5%, which is close to the flotation index of sulfide ore, and has broad application prospects.
所述浮选采用丁基黄药为捕收剂，用量为55-100mg/L，2#油为起泡剂，加入量1～4μL/L。The flotation adopts butyl xanthate as the collector, the dosage is 55-100 mg/L, the 2# oil is the foaming agent, and the addition amount is 1-4 μL/L.
本发明的原理是：The principle of the present invention is:
使用1：1配比的硫磺：硫脲粉末作为硫化剂，铁粉作为硫化反应助剂，在磨矿过程中利用机械化学作用发生离子交换，在孔雀石表面生成一层CuFeS2为主的硫化物薄膜，该硫化物薄膜疏水性、化学稳定性和机械稳定性强，有利用孔雀石浮选回收率的提高。Using 1:1 ratio of sulfur: thiourea powder as vulcanizing agent, iron powder as vulcanization reaction assistant, ion exchange occurs by mechanochemical action during the grinding process, and a layer of CuFeS2-based sulfide is formed on the surface of malachite Thin film, the sulfide thin film has strong hydrophobicity, chemical stability and mechanical stability, and can improve the recovery rate of malachite flotation.
与现有的硫化孔雀石的方法相比，本发明硫化速度快、效率高，操作方便，能够实现对氧化铜资源的最大化利用。Compared with the existing method for vulcanizing malachite, the present invention has the advantages of fast vulcanization speed, high efficiency, convenient operation, and can realize maximum utilization of copper oxide resources.
具体实施方式Detailed ways
下面结合实施例详细说明本发明的实施方式。The embodiments of the present invention will be described in detail below with reference to the examples.
实施例1Example 1
在孔雀石的磨矿过程中，按照质量比为1：1配置硫磺、硫脲粉末作为硫化剂，按300g/t的用量加入到磨机中，再按照100g/t的用量加入助剂铁粉，干磨5min；磨矿后采用常规浮选方法，用量为55mg/L的丁基黄药为捕收剂，作用3min，2#油为起泡剂，加入量1μL/L，作用1min，刮泡4min，孔雀石浮选回收率可以达到75.6％。In the grinding process of malachite, sulfur and thiourea powder were prepared as vulcanizing agent according to the mass ratio of 1:1, added to the mill at the dosage of 300g/t, and then added the auxiliary iron powder according to the dosage of 100g/t , dry grinding for 5min; after grinding, adopt conventional flotation method, use 55mg/L butyl xanthate as collector, act for 3min, 2# oil as foaming agent, add 1μL/L, act for 1min, scrape After soaking for 4min, the recovery rate of malachite flotation can reach 75.6%.
与不加硫化剂的选别方案，该方法提高孔雀石回收率35个百分点。Compared with the option without vulcanizing agent, this method improves the recovery rate of malachite by 35%.
实施例2Example 2
在孔雀石的磨矿过程中，按照质量比为1：1配置硫磺、硫脲粉末作为硫化剂，按500g/t的用量加入到磨机中，再按照200g/t的用量加入助剂铁粉，干磨10min；磨矿后采用常规浮选方法，丁基黄药为捕收剂，用量为85mg/L，作用3min，2#油为起泡剂，加入量2μL/L，作用1min，刮泡4min，孔雀石浮选回收率可以达到80.3％。In the grinding process of malachite, sulfur and thiourea powder were prepared as vulcanizing agent according to the mass ratio of 1:1, added to the mill at the dosage of 500g/t, and then added the auxiliary iron powder according to the dosage of 200g/t , dry grinding for 10min; conventional flotation method is adopted after grinding, butyl xanthate is used as collector, dosage is 85mg/L, and action is 3min. After soaking for 4min, the recovery rate of malachite flotation can reach 80.3%.
与不加硫化剂的选别方案，该方法提高孔雀石回收率39.7个百分点。Compared with the option without vulcanizing agent, the method improves the recovery rate of malachite by 39.7%.
实施例3Example 3
在孔雀石的磨矿过程中，按照质量比为1：1配置硫磺、硫脲粉末作为硫化剂，按1000g/t的用量加入到磨机中，再按照300g/t的用量加入助剂铁粉，干磨15min；磨矿后采用常规浮选方法，丁基黄药为捕收剂，用量为100mg/L，作用3min，2#油为起泡剂，加入量4μL/L，作用1min，刮泡4min，孔雀石浮选回收率可以达到82.5％。In the grinding process of malachite, sulfur and thiourea powder are prepared as vulcanizing agent according to the mass ratio of 1:1, added to the mill in the amount of 1000g/t, and then the auxiliary iron powder is added in the amount of 300g/t , dry grinding for 15min; conventional flotation method is adopted after grinding, butyl xanthate is used as collector, dosage is 100mg/L, action is 3min, 2# oil is foaming agent, adding amount is 4μL/L, action is 1min, scraping After soaking for 4min, the recovery rate of malachite flotation can reach 82.5%.
与不加硫化剂的选别方案，该方法提高孔雀石回收率41.9个百分点。Compared with the option without vulcanizing agent, this method improves the recovery rate of malachite by 41.9%.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910081680.7A CN109806980B (en) | 2019-01-28 | 2019-01-28 | A kind of method and application of malachite sulfide product control |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910081680.7A CN109806980B (en) | 2019-01-28 | 2019-01-28 | A kind of method and application of malachite sulfide product control |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109806980A CN109806980A (en) | 2019-05-28 |
| CN109806980B true CN109806980B (en) | 2020-12-01 |
Family
ID=66605641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910081680.7A Active CN109806980B (en) | 2019-01-28 | 2019-01-28 | A kind of method and application of malachite sulfide product control |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109806980B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113634375A (en) * | 2021-08-13 | 2021-11-12 | 西安建筑科技大学 | A kind of beneficiation method of low-grade mixed copper oxide ore |
| CN115487932B (en) * | 2022-09-26 | 2024-04-09 | 昆明理工大学 | Method for surface pretreatment-xanthate flotation of silicate copper oxide ore |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008048495A2 (en) * | 2006-10-13 | 2008-04-24 | Archer-Daniels-Midland Company | Hydrogenation process and high monoene compositions obtained therefrom |
| CN105363565A (en) * | 2015-11-11 | 2016-03-02 | 湖南有色金属研究院 | Malachite catalytic activating agent and method for flotation of malachite through malachite catalytic activating agent |
| CN108479827A (en) * | 2018-04-03 | 2018-09-04 | 太原理工大学 | Medium temperature hydrolyzation converts carbonyl sulfur and the difunctional coupled catalyst of deoxidation and preparation method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB815088A (en) * | 1954-07-12 | 1959-06-17 | Phillips Petroleum Co | Improvements in a process for the production of halogenated hydrocarbons |
| CN101125311B (en) * | 2007-09-24 | 2010-09-01 | 昆明理工大学 | Vulcanizing-flotation combing method for treating zinc kiln slag |
| KR101572861B1 (en) * | 2014-08-21 | 2015-12-01 | 한국세라믹기술원 | A method of flotation for copper oxide ore using multi-collector |
| CN105363562B (en) * | 2015-12-08 | 2017-10-17 | 中南大学 | A kind of beneficiation method of low-grade cuprite |
-
2019
- 2019-01-28 CN CN201910081680.7A patent/CN109806980B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008048495A2 (en) * | 2006-10-13 | 2008-04-24 | Archer-Daniels-Midland Company | Hydrogenation process and high monoene compositions obtained therefrom |
| CN105363565A (en) * | 2015-11-11 | 2016-03-02 | 湖南有色金属研究院 | Malachite catalytic activating agent and method for flotation of malachite through malachite catalytic activating agent |
| CN108479827A (en) * | 2018-04-03 | 2018-09-04 | 太原理工大学 | Medium temperature hydrolyzation converts carbonyl sulfur and the difunctional coupled catalyst of deoxidation and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109806980A (en) | 2019-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108160313B (en) | A kind of method of cupric oxide ore thickness grading-reinforcing fine fraction sulfide flotation | |
| CN109806980B (en) | A kind of method and application of malachite sulfide product control | |
| CN101831559B (en) | A kind of beneficiation and smelting method of carbonate gangue type oxygen-sulfur mixed copper ore with high binding rate | |
| CN104909507B (en) | Contaminated acid concentrating and recycling method | |
| CN101829635B (en) | Process for reclaiming gold and silver by floatation from acid leaching ore pulp in wet zinc smelting | |
| CN106111350A (en) | A kind of method for floating of zinc oxide ore | |
| CN102513203B (en) | Method for recycling high-phosphorus/sulfur siderite resource | |
| CN111530622A (en) | Method for removing impurities from high-grade sulfur concentrate | |
| CN108456153B (en) | Phenylpropenyl hydroxamic acid and its preparation method and its application in the flotation of tungsten ore | |
| CN109261364A (en) | The solution of pyrite presses down activation method in a kind of shallow crust structures | |
| CN110947523B (en) | A collector for recovering copper, lead and zinc minerals from iron beneficiation tailings | |
| CN113856911A (en) | Beneficiation method for high-sulfur copper gold silver ore | |
| CN109731693B (en) | Method for sulfurizing and floating copper-lead-zinc oxide ore by using cyanuric acid saturated solution | |
| CN108311290B (en) | A method of microwave pretreatment to improve ilmenite flotation efficiency | |
| CN103194618A (en) | Method for sulfurizing zinc oxide ore | |
| CN114749282B (en) | Calcium molybdate vulcanization flotation method | |
| CN105289850A (en) | Independent silver ore flotation method | |
| CN115155820A (en) | A method for strengthening zinc-sulfur separation and flotation | |
| CN115318448A (en) | A kind of high entropy activation flotation method of zinc oxide ore | |
| CN115947323A (en) | Method for extracting lithium from waste lithium iron phosphate and preparing iron phosphate | |
| CN115487932B (en) | Method for surface pretreatment-xanthate flotation of silicate copper oxide ore | |
| CN108048659A (en) | A kind of leaching method of zinc replacement slag | |
| CN106834738A (en) | A kind of compound additive and application that copper is reclaimed for copper smelting slag | |
| CN117816379B (en) | Vulcanization flotation method for refractory zinc oxide ores | |
| CN113731643B (en) | A method for recovering oxidized fine-grained copper sulfide minerals by selective agglomeration flotation |
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 |