CN116005019A - A method based on self-heating of pyrite to promote efficient recovery of antimony-containing hazardous waste materials - Google Patents
A method based on self-heating of pyrite to promote efficient recovery of antimony-containing hazardous waste materials Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000011028 pyrite Substances 0.000 title claims abstract description 30
- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 30
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 29
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 29
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000011084 recovery Methods 0.000 title claims abstract description 14
- 238000010438 heat treatment Methods 0.000 title claims abstract description 12
- 238000003723 Smelting Methods 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 11
- 230000001737 promoting effect Effects 0.000 claims abstract description 8
- 238000007664 blowing Methods 0.000 claims abstract description 6
- 229910001245 Sb alloy Inorganic materials 0.000 claims abstract description 4
- 239000002140 antimony alloy Substances 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims 2
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- 238000000926 separation method Methods 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002452 interceptive effect Effects 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
本发明公开的一种基于硫铁矿自热促进含锑危废物料高效回收的方法，将含锑危废物料和硫铁矿混合配料后，送入底吹熔炼炉中进行熔炼造渣，通入底吹熔炼炉内所需的纯氧量，使混合原料在富氧条件下进行氧化脱离及交互反应，放出反应热，将底吹熔炼渣在还原炉焦碳强还原气氛下进行冶炼，产出铅锑合金。本发明通过添加廉价硫铁矿，利用硫铁矿中的铁为渣型控制提供铁组份，降低生产成本，同时利用硫铁矿中的硫在氧化气氛下，与含铅锑危废物料中的氧元素发生反应，产生反应热量，从而达到冶炼回收的目的。The invention discloses a method for promoting the efficient recovery of antimony-containing hazardous waste materials based on the self-heating of pyrite. After mixing the antimony-containing hazardous waste materials and pyrite ore, they are sent to a bottom blowing smelting furnace for smelting and slagging. The amount of pure oxygen required to enter the bottom-blown smelting furnace enables the mixed raw materials to undergo oxidative detachment and interactive reactions under oxygen-enriched conditions, releasing reaction heat. lead antimony alloy. In the present invention, by adding cheap pyrite, the iron in the pyrite is used to provide iron components for slag type control, reducing production costs, and at the same time, the sulfur in the pyrite is used in an oxidizing atmosphere to combine with lead-containing antimony hazardous waste materials The oxygen element reacts to generate reaction heat, so as to achieve the purpose of smelting and recycling.
Description
技术领域technical field
本发明属于含锑危废物料回收领域，具体涉及一种基于硫铁矿自热促进含锑危废物料高效回收的方法。The invention belongs to the field of recycling hazardous waste materials containing antimony, and in particular relates to a method for promoting efficient recovery of hazardous waste materials containing antimony based on pyrite self-heating.
背景技术Background technique
含锑危废物料传统回收的方法是通过添加铅锑硫化矿冶炼回收，中国专利201410026152.9公开了一种从含锑铅复杂硫化矿中回收锑、铅的方法。但铅锑硫化矿成本高，升值空间小，而硫铁矿成本低廉，如何通过廉价的硫铁矿实现含锑危废物料冶炼高效回收并降低成本成为当前选矿界研究的热点。The traditional method of recycling antimony-containing hazardous waste materials is to smelt and recycle by adding lead and antimony sulfide ores. Chinese patent 201410026152.9 discloses a method for recovering antimony and lead from complex sulfide ores containing antimony and lead. However, the cost of lead-antimony sulfide ore is high and the appreciation space is small, while the cost of pyrite is low. How to achieve efficient recovery of antimony-containing hazardous waste smelting and reduce costs through cheap pyrite has become a hot research topic in the current mineral processing industry.
发明内容Contents of the invention
针对现有技术存在的问题，本发明提供一种基于硫铁矿自热促进含锑危废物料高效回收的方法，通过添加廉价硫铁矿，利用其中的铁为渣型控制提供铁组份，降低生产成本，同时利用硫铁矿中的硫在氧化气氛下，与铅锑危废物料中的氧元素发生反应，产生较大热量，从而达到冶炼回收的目的。Aiming at the problems existing in the prior art, the present invention provides a method based on the self-heating of pyrite to promote the efficient recovery of antimony-containing hazardous waste materials. By adding cheap pyrite, the iron in it is used to provide iron components for slag type control, Reduce production costs, and at the same time, use sulfur in pyrite to react with oxygen in lead and antimony hazardous waste materials in an oxidizing atmosphere to generate greater heat, thereby achieving the purpose of smelting and recycling.
为实现上述目的，本发明的具体方案如下：一种基于硫铁矿自热促进含锑危废物料高效回收的方法，包括如下步骤：In order to achieve the above object, the specific scheme of the present invention is as follows: a method for promoting the efficient recovery of antimony-containing hazardous waste materials based on pyrite self-heating, comprising the steps of:
(1)物料含硫量检测：对含锑危废物料进行分析检测，检测硫及有价金属；(1) Detection of sulfur content in materials: analysis and detection of antimony-containing hazardous waste materials, detection of sulfur and valuable metals;
(2)配硫：根据对含锑危废物料化验分析结果，配入硫铁矿，使混合物料含硫量在12-16％的范围，控制渣型范围Fe/SiO2＝1.1-1.3，CaO/SiO2＝0.4-0.7；(2) Sulfur compounding: according to the analysis results of antimony-containing hazardous waste materials, pyrite is added to make the sulfur content of the mixed material in the range of 12-16%, and the range of slag type is controlled Fe/SiO 2 =1.1-1.3, CaO/ SiO2 = 0.4-0.7;
(3)控制氧硫比：根据步骤(2)的混合物料含硫量计算出氧气需求量，确保入炉混合物料氧硫比800－1200；(3) Control the oxygen-sulfur ratio: calculate the oxygen demand according to the sulfur content of the mixture in step (2), and ensure the oxygen-sulfur ratio of the mixture into the furnace is 800-1200;
(4)熔炼造渣：混合物料入炉后在富氧条件下进行氧化脱离及交互反应，放出反应热，通过对物料及氧气的控制，确保在底吹熔炼温度在950-1100℃内造渣；(4) Smelting and slagging: After the mixed material is put into the furnace, it will be oxidized, detached and interactively reacted under oxygen-enriched conditions to release heat of reaction. Through the control of materials and oxygen, slagging is ensured at the bottom blowing smelting temperature within 950-1100°C ;
(5)还原熔炼：底吹熔炼渣在还原炉焦碳强还原气份下进行冶炼，产出铅锑合金。(5) Reduction smelting: Bottom-blown smelting slag is smelted under the strong reducing gas of coke in the reduction furnace to produce lead-antimony alloy.
步骤(1)所述物料中的硫及有价金属含量为：硫:7％-12％有价金属:30％-40％The content of sulfur and valuable metal in the material described in step (1) is: sulfur: 7%-12% valuable metal: 30%-40%
步骤(2)所述硫铁矿配入量为混合物料的20％-25％The amount of pyrite added in step (2) is 20%-25% of the mixed material
步骤(4)混合物料入炉后在富氧条件下进行氧化脱离及交互反应，放出反应热按下式反应：Step (4) After the mixed material is put into the furnace, it is oxidized and detached and interactively reacted under oxygen-enriched conditions, and the heat of reaction is released to react as follows:
反应式为：2/3FeS+O2＝2/3FeO+2/3SO2ΔG＝-303340-52.68T J。The reaction formula is: 2/3FeS+O 2 =2/3FeO+2/3SO 2 ΔG=-303340-52.68T J.
本发明的优点Advantages of the invention
本发明的一种基于硫铁矿自热促进含锑危废物料高效回收的方法通过添加廉价硫铁矿，利用其中的铁为渣型控制提供铁组份，降低生产成本，同时利用硫铁矿中的硫在氧化气氛下，与铅锑危废物料中的氧元素发生反应，产生较大热量，从而达到冶炼回收的目的，其反应式为：2/3FeS+O2＝2/3FeO+2/3SO2，ΔG＝-303340-52.68T J。该方法采用硫铁矿自热促进含锑危废物料回收的投入成本低，回收效率高。A method of the present invention based on the self-heating of pyrite to promote the efficient recovery of antimony-containing hazardous waste materials adds cheap pyrite, and uses the iron in it to provide iron components for slag type control, reducing production costs, and at the same time using pyrite In an oxidizing atmosphere, the sulfur in the sulfur reacts with the oxygen element in the lead-antimony hazardous waste material to generate a large amount of heat, so as to achieve the purpose of smelting and recycling. The reaction formula is: 2/3FeS+O 2 =2/3FeO+2 /3SO 2 , ΔG=-303340-52.68T J. The method adopts the self-heating of pyrite to promote the recovery of antimony-containing hazardous waste materials, which has low input cost and high recovery efficiency.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步地解释和说明，需要注意的是，本具体实施例不用于限定本发明的权利范围。The present invention will be further explained and described below in conjunction with specific examples. It should be noted that the specific examples are not intended to limit the scope of rights of the present invention.
本具体实施例提供的一种采用添加廉价硫铁矿的含锑危废物料冶炼回收方法，其步骤如下：A method for smelting and recycling antimony-containing hazardous waste materials provided by this specific embodiment by adding cheap pyrite, the steps are as follows:
(1)含硫量检测：对多种含锑危废物料中的有效硫组分和有价金属组分进行化验分析，检测硫及有价金属成分的含量为硫:7％-12％有价金属:30％-40％；(1) Sulfur content detection: carry out laboratory analysis on effective sulfur components and valuable metal components in various antimony-containing hazardous waste materials, and detect the content of sulfur and valuable metal components as sulfur: 7%-12% Valence metal: 30%-40%;
(2)配硫：根据步骤(1)中对多种含锑危废物料化验分析的检测结果，将多种含锑危废物料和廉价的硫铁矿混合配料，硫铁矿配入量为混合物料的20％-25％，使混合配料中的含硫量在12～16％的范围，有价金属成分以生产经营效益最佳为宜进行配比，同时将硫铁矿中的铁作为渣型以控制提供所需要的铁组份，从而降低原料成本，渣型范围Fe/SiO2＝1.1～1.3，CaO/SiO2＝0.4～0.7；(2) Sulfur compounding: according to the detection result of the laboratory analysis of multiple antimony hazardous waste materials in the step (1), multiple antimony hazardous waste materials and cheap pyrite mixed batching, the pyrite input amount is 20%-25% of the mixed material, so that the sulfur content in the mixed material is in the range of 12-16%. Slag type to control and provide the required iron components, thereby reducing the cost of raw materials. The range of slag type is Fe/SiO 2 =1.1~1.3, CaO/SiO 2 =0.4~0.7;
(3)控制氧硫比：根据步骤(2)中混合配料的含硫量，计算出所需要的纯氧量，通过终端控制系统对纯氧量进行精准控制，确保入炉混合物料的氧硫比为800～1200；(3) Control the oxygen-sulfur ratio: Calculate the required pure oxygen amount according to the sulfur content of the mixed ingredients in step (2), and precisely control the pure oxygen amount through the terminal control system to ensure the oxygen-sulfur ratio of the mixed materials into the furnace 800~1200;
(4)熔炼造渣：将步骤(2)的混合配料送入底吹熔炼炉后，通入步骤(3)所需要的纯氧量，使混合配料在富氧条件下进行氧化脱离及交互反应，放出反应热，通过对混合配料及氧气的控制，确保底吹熔炼温度在950～1100℃内造渣；(4) Melting and slagging: After sending the mixed ingredients in step (2) into the bottom blowing smelting furnace, feed the amount of pure oxygen required in step (3), so that the mixed ingredients can be oxidized, detached and interactively reacted under oxygen-enriched conditions , release heat of reaction, and ensure slagging at the bottom blowing smelting temperature within 950-1100°C by controlling the mixing ingredients and oxygen;
(5)还原熔炼：将步骤(4)的底吹熔炼渣在还原炉焦碳强还原气氛下进行冶炼，产出铅锑合金。(5) Reduction smelting: smelting the bottom-blown smelting slag in step (4) in a coke-reducing atmosphere of a reduction furnace to produce a lead-antimony alloy.
下面结合市场，采用价格高的铅锑硫化矿进行冶炼的传统方法与本实施例采用硫铁矿自然冶炼的方法进行冶炼成本的对比，如表1所示：Below in conjunction with the market, the comparison of the smelting cost between the traditional method of smelting the high-priced lead-antimony sulfide ore and the method of natural smelting of pyrite in this embodiment is shown in Table 1:
表1：传统方法与本实施例的冶炼成本对比(单位：元/吨)Table 1: Comparison of smelting costs between the traditional method and the present embodiment (unit: yuan/ton)
从表1的结果可以看出：利用基于硫铁矿自热促进含锑危废物料高效回收工艺路线后,能很好的拓宽冶炼生产工艺模式,有利于对危废资源整合,提高冶炼效益,很好的分担社会环保负担,为进一步推进危废物料综合回收利用开拓了新的方向。From the results in Table 1, it can be seen that using pyrite self-heating to promote the efficient recovery of antimony-containing hazardous waste materials can well broaden the smelting production process model, which is conducive to the integration of hazardous waste resources and improve smelting efficiency. It can share the burden of social environmental protection very well, and has opened up a new direction for further promoting the comprehensive recycling of hazardous waste materials.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0036768A1 (en) * | 1980-03-20 | 1981-09-30 | Asarco Incorporated | Separation of antimony |
| CN103924094A (en) * | 2014-04-16 | 2014-07-16 | 济源市万洋冶炼(集团)有限公司 | Method for treating copper dross |
| CN104278162A (en) * | 2014-11-01 | 2015-01-14 | 中南大学 | Method of selectively smelting antimony-lead-containing complex materials in smelting tank |
| CN115058603A (en) * | 2022-07-26 | 2022-09-16 | 梧州华锡环保科技有限公司 | Anode mud removing device for high-antimony lead anode scrap and using method thereof |
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- 2022-12-15 CN CN202211615229.7A patent/CN116005019A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0036768A1 (en) * | 1980-03-20 | 1981-09-30 | Asarco Incorporated | Separation of antimony |
| CN103924094A (en) * | 2014-04-16 | 2014-07-16 | 济源市万洋冶炼(集团)有限公司 | Method for treating copper dross |
| CN104278162A (en) * | 2014-11-01 | 2015-01-14 | 中南大学 | Method of selectively smelting antimony-lead-containing complex materials in smelting tank |
| CN115058603A (en) * | 2022-07-26 | 2022-09-16 | 梧州华锡环保科技有限公司 | Anode mud removing device for high-antimony lead anode scrap and using method thereof |
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