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WO2020093234A1 - 一种铜冶炼燃料混合物 - Google Patents

一种铜冶炼燃料混合物 Download PDF

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Publication number
WO2020093234A1
WO2020093234A1 PCT/CN2018/114126 CN2018114126W WO2020093234A1 WO 2020093234 A1 WO2020093234 A1 WO 2020093234A1 CN 2018114126 W CN2018114126 W CN 2018114126W WO 2020093234 A1 WO2020093234 A1 WO 2020093234A1
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WO
WIPO (PCT)
Prior art keywords
copper
fuel mixture
smelting
furnace
copper smelting
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Application number
PCT/CN2018/114126
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English (en)
French (fr)
Inventor
朱振祥
李洪彬
王延庆
Original Assignee
东营金玺铜业有限公司
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Application filed by 东营金玺铜业有限公司 filed Critical 东营金玺铜业有限公司
Priority to PCT/CN2018/114126 priority Critical patent/WO2020093234A1/zh
Publication of WO2020093234A1 publication Critical patent/WO2020093234A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • 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

Definitions

  • the invention relates to the technical field of efficient smelting and clean discharge of copper smelting.
  • Copper and copper alloys are one of the most widely used non-ferrous metal materials except ferrous metals. They are widely used in the fields of electronics, communications, defense, aerospace, automobiles, power, machinery, construction, transportation, etc. It has become a typical functional material and structural material. There are many smelting and processing enterprises of copper and copper alloys. At present, there are two ways to obtain copper metal. First, they are originally obtained from copper mines. They are divided into pyrometallurgical copper and hydrometallurgical copper, in which pyrometallurgical copper occupies a large proportion, including matte smelting and copper matte blowing. There are two basic processes of refining; the second is obtained from waste copper scrap through regeneration and recovery, including two basic processes of melting and refining.
  • the purpose of the present invention is to provide a copper smelting fuel mixture, which solves the problems of enhanced mass and heat transfer, improved combustion efficiency, controllable redox atmosphere and adjustable slag pH.
  • the purpose of the present invention is achieved as follows:
  • a copper smelting fuel mixture including: composite carbon powder, oxygen and natural gas, the three are stored in their respective storage tanks, transported into the mixing gun through their respective pipelines and merged, and finally the mixing gun is introduced into the copper together The bottom of the smelting furnace.
  • the composite toner first flows into the composite toner conveying pipeline from the storage tank with a flow rate of 135-165kg / hour, and then is blown into the mixing gun by the air that is dried and pressed into the composite toner conveying pipeline, and the dry air flow rate is 2500 -3800m3 / hour;
  • composite carbon powder includes the following components by weight: petroleum coke powder 70-85 parts, dicyclopentadiene iron 10-20 parts, 2,6-di-tert-butyl-4-methylphenol 5-10 copies; the particle size of the composite toner is ⁇ 10 microns.
  • oxygen is pure oxygen with an oxygen content of 99.99%; the flow rate of oxygen in the oxygen pipeline is 1350-1650m3 / hour.
  • the flow rate of natural gas in the pipeline is 675-825m3 / hour.
  • the copper smelting fuel mixture can be used in different pyrometallurgical copper smelting furnace types such as reverberatory furnace, open hearth furnace, tilting furnace, rotary anode furnace, blast furnace, and flash furnace.
  • the copper smelting fuel mixture can be used for the smelting of blister copper and scrap copper, and can also be used for the initial smelting of copper ore.
  • the obtained copper smelting fuel mixture, composite carbon powder is the main combustion agent and reducing agent, high calorific value, high combustion efficiency, no combustion residue, no harmful gas generation, while participating in the reduction reaction, will Copper oxide is reduced to elemental copper; Oxygen is a combustion aid and an oxidant, which improves the combustion efficiency and participates in the oxidation reaction.
  • the copper and impurity metals are fully oxidized while generating oxidation heat, which helps melting and save energy; natural gas is used to ignite , And balance the heating value of the entire fuel mixture.
  • the petroleum coke powder in the composite carbon powder is the main combustion agent and the reducing agent.
  • the dicyclopentadiene iron compound can first undergo olefinic polymerization to obtain a metal-containing polymer protective film with a carbon chain skeleton, which can protect Introduce the mixing gun and lining at the bottom of the copper smelting furnace to extend the service life of the two. Secondly, it can increase the calorific value, increase the combustion efficiency, reduce emissions, play a role in eliminating smoke and supporting combustion. In addition, it can also promote the conversion of CO to CO2 and adjust Reducing atmosphere; 2,6-di-tert-butyl-4-methylphenol is an antioxidant, to ensure that the carbon powder is not oxidized and has no harmful emissions before production, storage and transportation until use.
  • the copper smelting fuel mixture flows from the bottom of the copper smelting furnace through the mixing gun from the bottom to the top, and has a sufficiently high pressure, while burning, it can also act as a stirrer, thereby enhancing the mass and heat transfer, improving To improve the combustion efficiency in the furnace.
  • petroleum coke powder as a low-end, cheap petroleum by-product, is used as the main combustion agent and reducing agent of the composite carbon powder of the copper smelting fuel mixture in this invention, which makes it obtain the largest application value and economic benefit at present, which is typical Application of turning waste into treasure.
  • the direct economic effects are: saving more than 20% of the furnace time, extending the service life of the furnace (lining) by more than 20%, reducing the amount of slag copper by more than 10%, and saving fuel costs by more than 30% Therefore, the overall economic benefit has increased by more than 20%.
  • the best embodiment of the invention is used for regenerating and smelting a certain waste copper, to obtain anode copper for electrolysis, and the furnace type is a reverberatory furnace.
  • the installed capacity was 140 tons, including 0.7 tons of slag-making agent, and 133.3 tons of waste copper
  • the composition of waste copper was as follows: Fe 0.25%, Ni 0.37%, Sb 0.16%, Bi 0.11 %, Pb is 0.27%, S is 0.36%, the balance is Cu is 98.48%.
  • the ignition and smelting started.
  • the composite carbon powder, oxygen and natural gas in the fuel mixture are stored in their respective storage tanks, are transported into the mixing gun through their respective pipelines, and finally the mixing gun is introduced into the bottom of the copper smelting furnace.
  • the fuel is transported from bottom to top, and at the same time, it achieves the effect of stirring to accelerate heat transfer.
  • the components of the composite carbon powder are: 78 parts of petroleum coke powder, 14 parts of dicyclopentadiene iron, and 8 parts of 2,6-di-tert-butyl-4-methylphenol (below weight).
  • the particle size of the toner is about 8 microns.
  • the flow rate of the dry air is 3000m3 / hour;
  • the flow rate of controlled oxygen in the pipeline is 1550m3 / hour, and the pure oxygen content is 99.99%; the flow rate of controlled oxygen in the pipeline of natural gas is 700m3 / hour.
  • the total furnace time was 12 hours, saving 4 hours, the amount of slag copper was reduced from 15% to only 9%, and the economic benefit was expected to increase by 35%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

一种铜冶炼燃料混合物，包括：复合碳粉，氧气和天然气，三者经各自的输送管道，输送至混合枪内汇合，并最终由混合枪一并导入铜冶炼炉的底部。复合碳粉包括以重量计的以下组分：石油焦粉70-85份、双环戊二烯合铁10-20份、2，6-二叔丁基-4-甲基苯酚5-10份。该铜冶炼燃料混合物可以被用于不同的火法铜冶炼炉型中。该铜冶炼燃料混合物可以被用于粗铜、废铜的再生冶炼，也可以被用于铜矿石的初始冶炼。该铜冶炼燃料混合物可以加强传质传热、提高燃烧效率、控制氧化还原气氛以及调整炉渣酸碱度等，从而，节约炉时，延长炉(衬)龄使用寿命，减少渣铜量，节约燃料成本，提高综合经济效益。

Description

一种铜冶炼燃料混合物 技术领域
本发明涉及铜冶炼的高效熔炼和清洁排放的技术领域。
 背景技术
铜及铜合金是除黑色金属外，人类应用最广泛的一种有色金属材料之一，在电子、通讯、国防、航空航天、汽车、电力、机械、建筑、交通等领域中广泛得到应用，已成为典型的功能材料和结构材料，铜及铜合金的冶炼和加工企业众多。目前，铜金属的获取途径有两个，一是从铜矿中原始获得，分为火法炼铜和湿法炼铜，其中火法炼铜占有绝大比例，包括造锍熔炼和铜锍吹炼两个基本过程；二是从废杂铜中通过再生回收获得，包括熔化、精炼等两个基本过程。除了湿法炼铜，其他途径中的每个基本过程，都需要燃烧熔炼，经过基本的燃烧、熔化、氧化、还原、造渣等步骤。实现高效熔炼和清洁排放，是铜冶炼行业一直寻求突破的技术难点，也是当前新的发展理念和新的经济生产形势下，实现安全、高效、经济、环保生产的必然途径。
 技术问题
在炉内化学反应设计、气氛调控以及温度场分布规律的理论研究之上，进行炉型结构改进、炉料配制以及燃料选择和有效燃烧，是铜冶炼高效熔炼和清洁排放技术的发展方向。在燃料选择和有效燃烧方面，采用氮气搅动加强传质传热，使用热值更高、燃烧效率更高的气体燃料，并借助富氧、甚至完全氧气助燃，是目前实现铜冶炼高效熔炼和清洁排放的重要途径，改变了传统燃烧煤炭、重油等廉价的固、液燃料，采用空气助燃，燃烧效率和生产效率低、污染排放严重的生产现状。但是，在正常的炉体结构上，增加氮气搅动，显然增加了炉体结构的复杂程度，天然气等气体燃料热值仍旧有限，完全氧气助燃，则容易造成炉内熔炼气氛的富氧状态而对还原反应和烟气清洁产生不利影响，且此时产生的炉渣含铜量高，铜损失严重。
 技术解决方案
本发明的目的是要提供一种铜冶炼燃料混合物，解决传质传热加强、燃烧效率提高、氧化还原气氛可控以及炉渣酸碱度可调的问题。本发明的目的是这样实现的：
一种铜冶炼燃料混合物，包括：复合碳粉，氧气和天然气，三者分别储放于各自储罐内，经各自的输送管道，输送至混合枪内汇合，并最终有混合枪一并导入铜冶炼炉的底部。其中，复合碳粉，首先从储罐内流入复合碳粉输送管道，流量为135-165kg/小时，然后被干燥且压入复合碳粉输送管道的空气吹入混合枪，干燥空气的流量为2500-3800m3/小时；复合碳粉包括以重量计的以下组分：石油焦粉70-85份、双环戊二烯合铁10-20份、2,6-二叔丁基-4-甲基苯酚5-10份；复合碳粉的粒径≤10微米。其中氧气，为含氧量为99.99%的纯氧；氧气的输送管道内，氧气的流量为1350-1650m3/小时。其中天然气，其输送管道内，流量为675-825m3/小时。该铜冶炼燃料混合物可以被用于反射炉、平炉、倾动炉、回转式阳极炉、鼓风炉、闪速炉等不同的火法铜冶炼炉型中。该铜冶炼燃料混合物可以被用于粗铜、废铜的再生冶炼，也可以被用于铜矿石的初始冶炼。
 有益效果
由于采用了上述方案，所获得的一种铜冶炼燃料混合物，复合碳粉是主燃剂和还原剂，热值高、燃烧效率高，无燃烧残留，无有害气体产生，同时参与还原反应，将氧化铜还原为单质铜；氧气是助燃剂和氧化剂，提高燃烧效率和参与氧化反应，将铜及杂质金属充分氧化的同时产生氧化放热，有助于熔化，节约能源；天然气的作用是引燃，并均衡整个燃料混合物的热值。复合碳粉中的石油焦粉，是主燃剂和还原剂；双环戊二烯合铁在燃烧过程中，首先能发生烯键聚合，得到碳链骨架的含金属高聚物保护膜，可以保护导入铜冶炼炉底部的混合枪和炉衬，延长两者的使用寿命，其次可以提高热值、增加燃烧效率、减少排放，起到消烟助燃的作用，另外，还可以促使CO转化为CO2，调节还原气氛；2,6-二叔丁基-4-甲基苯酚是抗氧化剂，确保符合碳粉在生产、储运直到使用之前，不被氧化，无有害排放。同时，铜冶炼燃料混合物通过混合枪，从铜冶炼炉底部自下而上通入，且具有足够高的压力，在燃烧的同时，还可以起到搅动作用，从而加强了传质传热，提高了炉内燃烧效率。另外，石油焦粉作为低端、廉价的石油副产品，被用作该发明中，铜冶炼燃料混合物复合碳粉的主燃剂和还原剂，使其获得目前最大的应用价值和经济效益，属于典型的变废为宝的应用。与目前常规的铜冶炼燃料相比，直接的经济效果为：节约炉时20%以上，延长炉（衬）龄使用寿命20%以上，减少渣铜量10%以上，节约燃料成本30%以上，因此，综合的经济效益提高20%以上。
 附图说明
无。
 本发明的最佳实施方式
本发明的最佳实施方式：用于某废杂铜的再生冶炼，获得电解用的阳极铜，炉型为反射炉。
 本发明的实施方式
某次实施应用，装炉量140吨，包括0.7吨造渣剂，及133.3吨废杂铜，废杂铜的成分如下：Fe为0.25%,Ni为0.37%,Sb为0.16%,Bi为0.11%,Pb为0.27%,S为0.36%，余量为Cu为98.48%。投料后开始引燃熔炼。燃料混合物中复合碳粉，氧气和天然气，三者分别储放于各自储罐内，经各自的输送管道，输送至混合枪内汇合，并最终有混合枪一并导入铜冶炼炉的底部，自下而上输送燃料，并同时达到搅拌加速传热的作用。其中，复合碳粉的组分为：石油焦粉78份、双环戊二烯合铁14份、2,6-二叔丁基-4-甲基苯酚8份（以重量计的以下），复合碳粉的粒径约8微米。首先从复合碳粉储罐内流入复合碳粉输送管道，流量为139kg/小时，然后被干燥且压入复合碳粉输送管道的空气吹入混合枪，干燥空气的流量为3000m3/小时；氧气的输送管道内控制氧气的流量为1550m3/小时，含氧量为99.99%的纯氧；天然气的输送管道内控制氧气的流量为700m3/小时。经充分燃烧、熔炼、氧化、还原，并测定熔液成分，含铜量达到阳极板要求，结束冶炼，开始浇注。。
工业实用性
此次应用，总炉时12小时，节约4小时，渣铜量有15%降低至仅有9%，预计经济效益提高35%。
 序列表自由内容
无。

Claims (9)

  1. 一种铜冶炼燃料混合物，其特征在于，该铜冶炼燃料混合物包括：复合碳粉，氧气和天然气。
  2. 根据权利要求1所述的铜冶炼燃料混合物，其特征在于，所述复合碳粉，氧气和天然气分别储放于各自储罐内，经各自的输送管道，输送至混合枪内汇合，并最终有混合枪一并导入铜冶炼炉的底部。
  3. 根据权利要求1和2所述的铜冶炼燃料混合物，其特征在于，所述复合碳粉，首先从储罐内流入复合碳粉输送管道，流量为135-165kg/小时，然后被干燥且压入复合碳粉输送管道的空气吹入混合枪，干燥空气的流量为2500-3800m 3/小时。
  4. 根据权利要求1、2和3所述的铜冶炼燃料混合物，其特征在于，所述复合碳粉，包括以重量计的以下组分：石油焦粉70-85份、双环戊二烯合铁10-20份、2,6-二叔丁基-4-甲基苯酚5-10份。
  5. 根据权利要求1、2、3和4所述的铜冶炼燃料混合物，其特征在于，所述复合碳粉，粒径≤10微米。
  6. 根据权利要求1和2所述的铜冶炼燃料混合物，其特征在于，所述氧气，含氧量为99.99%。
  7. 根据权利要求1、2和6所述的铜冶炼燃料混合物，其特征在于，氧气的输送管道内，氧气的流量为1350-1650m 3/小时，天然气的输送管道内，天然气的流量为675-825m 3/小时。
  8. 根据权利要求1和2所述的铜冶炼燃料混合物，其特征在于，该铜冶炼燃料混合物可以被用于反射炉、平炉、倾动炉、回转式阳极炉、鼓风炉、闪速炉等不同的火法铜冶炼炉型中。
  9. 根据权利要求1和2所述的铜冶炼燃料混合物，其特征在于，该铜冶炼燃料混合物可以被用于粗铜、废铜的再生冶炼，也可以被用于铜矿石的初始冶炼。
PCT/CN2018/114126 2018-11-06 2018-11-06 一种铜冶炼燃料混合物 WO2020093234A1 (zh)

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