WO2019071793A1

WO2019071793A1 - Method for recovering valuable component from slag containing copper

Info

Publication number: WO2019071793A1
Application number: PCT/CN2017/115648
Authority: WO
Inventors: 张力; 张武
Original assignee: 东北大学
Priority date: 2017-10-10
Filing date: 2017-12-12
Publication date: 2019-04-18
Also published as: CN107699702A

Abstract

A method for recovering a valuable component from slag containing copper, comprising: S1. mixing furnace slag: adding copper slag into a smelting reaction device, adding a calcium-series mineral and an additive, forming mixed slag, heating the mixed slag to a molten state to act as reaction slag, mixing well, monitoring the reaction slag in real time, and obtaining slag after a reaction by means of adjusting the mixed reaction slag to simultaneously satisfy conditions a and b; S2. separation and recovery. Hot slag may be processed by means of the method, fully using the physical thermal resources and hot metallurgical flux of smelting copper slag, while cold furnace slag may also be processed; by means of adjusting the physical and chemical properties of slag, and by using the mature physical and chemical properties of slag containing copper, a metallurgical process for slag containing copper is implemented.

Description

一种由含铜熔渣回收有价组分的方法Method for recovering valuable components from copper-containing slag

技术领域Technical field

本发明属于熔渣冶金技术领域，具体涉及一种由含铜熔渣回收有价组分的方法。The invention belongs to the technical field of slag metallurgy, and in particular relates to a method for recovering valuable components from copper-containing slag.

背景技术Background technique

铜的火法冶炼过程中，产生大量铜渣，铜渣包括含铜熔炼渣、含铜吹炼渣、铜火法贫化渣、铜渣浮选尾矿。During the pyrometallurgical process of copper, a large amount of copper slag is produced. The copper slag includes copper-containing smelting slag, copper-containing blowing slag, copper-fired depleted slag, and copper slag flotation tailings.

含铜熔炼渣产生于铜的火法冶炼工艺的“造锍熔炼”过程中，每年排放出2000万吨以上，目前累计堆存达2亿多吨。随着“造锍熔炼”技术的不断发展，如闪速熔炼炉、诺兰达炉、瓦纽科夫炉、艾萨炉、奥斯麦特炉、三菱炉、金峰炉、底吹炉等，铜熔炼渣中Cu、Fe等金属含量提高，渣中铜含量达到20％，铁含量高达55％，铜熔炼渣是一种重要的二次资源。由“造锍熔炼”工艺的造锍熔炼炉放出的熔融铜熔炼渣温度高于1100℃，熔融铜熔炼渣也是重要的物理热资源。铜熔炼渣主要的利用方法是火法贫化与浮选回收铜组分。The copper-containing smelting slag is produced in the process of “smelting and smelting” of the pyrometallurgical process of copper. It emits more than 20 million tons per year, and currently accumulates more than 200 million tons. With the continuous development of "smelting smelting" technology, such as flash smelting furnace, Noranda furnace, Vanukov furnace, Isa furnace, Osmet furnace, Mitsubishi furnace, Jinfeng furnace, bottom blowing furnace, etc. The content of Cu, Fe and other metals in the copper smelting slag is increased, the copper content in the slag reaches 20%, and the iron content is as high as 55%. Copper smelting slag is an important secondary resource. The molten copper smelting slag discharged from the smelting smelting furnace of the "smelting smelting" process is higher than 1100 ° C, and the molten copper smelting slag is also an important physical heat resource. The main utilization method of copper smelting slag is fire depletion and flotation recovery of copper components.

含铜吹炼渣产生于铜的火法冶炼工艺的“铜锍吹炼”过程中，如转炉吹炼渣、闪速吹炼渣、顶吹炉吹炼渣、底吹炉吹炼渣等，渣中铜含量达到35％，铁含量高达55％。熔融含铜吹炼渣也是重要的物理热资源。主要采用返回熔炼炉或电炉贫化或选矿方法进行回收铜组分。The copper-containing blowing slag is produced in the "copper smelting" process of the fire smelting process of copper, such as converter blowing slag, flash blowing slag, top blowing furnace blowing slag, bottom blowing furnace blowing slag, etc. The copper content in the slag reaches 35% and the iron content is as high as 55%. Molten copper-containing blowing slag is also an important physical thermal resource. The copper component is mainly recovered by a return smelting furnace or an electric furnace depletion or beneficiation method.

铜渣不仅是重要的二次资源，而且含有大量SiO₂、CaO、MgO、Al₂O₃等冶金熔剂，化学反应活性强，是物理化学性质优良的熔渣体系，是热态冶金熟料，是成熟的冶金渣系。但含铜熔炼渣与含铜吹炼渣采用返回熔炼炉或电炉贫化或选矿方法，仅考虑铜组分的回收，贫化或选矿效果不好，而且浮选带来严重的环境污染。贫化或选矿后，渣含铜>0.3％以上，高于铜的可采品位0.2％。而一般铁矿石允许含铜质量分数不超过0.2％。较高的渣含铜，不利于后续的直接还原提铁或熔融还原炼铁，原因在于：在还原过程中，铜易还原并进入生铁。当超过0.3％时会降低钢材的焊接性，并引起钢的“热脆”现象，使轧制时产生裂纹。Copper slag is not only an important secondary resource, but also contains a large amount of metallurgical fluxes such as SiO ₂ , CaO, MgO, Al ₂ O _{3 ,} etc., which has strong chemical reaction activity and is a slag system with excellent physical and chemical properties, and is a thermal metallurgical clinker. It is a mature metallurgical slag system. However, the copper-containing smelting slag and the copper-containing blowing slag are returned to the smelting furnace or the electric furnace depletion or beneficiation method, and only the recovery of the copper component is considered, the depletion or beneficiation effect is not good, and the flotation brings serious environmental pollution. After depletion or beneficiation, the slag contains more than 0.3% copper, which is 0.2% higher than the recoverable grade of copper. In general, iron ore is allowed to contain no more than 0.2% copper. The higher slag contains copper, which is not conducive to the subsequent direct reduction of iron or smelting reduction of iron. The reason is that during the reduction process, copper is easily reduced and enters pig iron. When it exceeds 0.3%, the weldability of the steel is lowered, and the "hot brittleness" phenomenon of the steel is caused, causing cracks during rolling.

发明内容Summary of the invention

(一)要解决的技术问题(1) Technical problems to be solved

为了解决现有技术的上述问题，本发明提供一种利用含铜熔渣回收有价组分的方法。本发明方法是一种新的熔渣冶金工艺，不仅降低渣含铜,，使渣含铜<0.1wt％，而且实现铜、铁、金银、铅、锌等组分的高效回收，获得低铜含铁物料如铁精矿与生铁，并解决目前炉渣大量堆积，环境污染及重金属元素污染等问题。In order to solve the above problems of the prior art, the present invention provides a method of recovering valuable components using copper-containing slag. The method of the invention is a new slag metallurgy process, which not only reduces the copper content of the slag, but also makes the slag contain copper <0.1 wt%, and realizes efficient recovery of components such as copper, iron, gold, silver, lead and zinc, and obtains low efficiency. Copper-containing iron materials such as iron concentrates and pig iron, and solve the problems of large accumulation of slag, environmental pollution and heavy metal elements.

(二)技术方案(2) Technical plan

为了达到上述目的，本发明采用的主要技术方案包括：In order to achieve the above object, the main technical solutions adopted by the present invention include:

一种由含铜熔渣回收有价组分的方法，其包括如下步骤：A method for recovering valuable components from copper-containing slag, comprising the steps of:

S1、炉渣混合：将铜渣加入熔炼反应装置中，并加入钙系矿物与添加剂，形成混合熔渣，将混合熔渣加热至熔融状态作为反应熔渣，混合均匀，实时监测该反应熔渣，通过调控使混合后的反应熔渣同时满足条件a和条件b，获得反应后的熔渣，或将反应后的熔渣倒入保温装置；S1, slag mixing: adding copper slag to the smelting reaction device, adding calcium minerals and additives to form mixed slag, heating the mixed slag to a molten state as reaction slag, mixing uniformly, and monitoring the reaction slag in real time, The slag after the reaction is obtained by adjusting the mixed reaction slag to satisfy the condition a and the condition b, or the slag after the reaction is poured into the heat preservation device;

其中，所述条件a为反应熔渣的温度为1100～1450℃；Wherein the condition a is that the temperature of the reaction slag is from 1100 to 1450 ° C;

所述条件b为反应熔渣的碱度CaO/SiO₂比值＝0.15～1.5；The condition b is the alkalinity CaO / SiO ₂ ratio of the reaction slag = 0.15 ~ 1.5;

S2、分离回收：所述步骤S1反应后的熔渣，保温5～50min，沉降分离获得底部富铜相层、中部富铁相与上部含铁硅酸盐矿物相，同时生成含锌组分与含铅组分的烟烟尘，金组分、银组分进入富铜相；对各相进行回收处理。S2, separation and recovery: the slag after the reaction in the step S1 is kept for 5 to 50 minutes, and the bottom copper-rich phase layer, the middle iron-rich phase and the upper iron-containing silicate mineral phase are obtained by sedimentation separation, and the zinc-containing component is formed at the same time. Lead-containing component Smoke, dust, gold and silver components enter the copper-rich phase; the phases are recycled.

如上所述的方法，优选地，在所述步骤S1中，对于所述条件a调控的方法为：In the method as described above, preferably, in the step S1, the method for regulating the condition a is:

当所述反应熔渣的温度＜1100℃时，利用反应装置自身的加热功能，或向熔渣中加入燃料与预热的氧化性空气，使反应熔渣的温度达到1100～1450℃；When the temperature of the reaction slag is <1100 ° C, using the heating function of the reaction device itself, or adding fuel and preheated oxidizing air to the slag, so that the temperature of the reaction slag reaches 1100 ~ 1450 ° C;

当所述反应熔渣的温度＞1450℃时，向反应熔渣中加入含铜物料、冶金熔剂、含铁物料或含氟物料中的一种或几种，混合均匀，使混合熔渣的温度达到1100～1450℃；When the temperature of the reaction slag is >1450 ° C, one or more of the copper-containing material, the metallurgical flux, the iron-containing material or the fluorine-containing material is added to the reaction slag, and the mixture is uniformly mixed to make the temperature of the mixed slag Up to 1100 ~ 1450 ° C;

对于所述条件b调控的方法为：The method for regulating the condition b is:

当所述反应熔渣中碱度CaO/SiO₂比值<0.15时，向反应熔渣中加入碱性物料和/或碱性含铁物料；When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is <0.15, an alkaline material and/or an alkaline iron-containing material is added to the reaction slag;

当所述反应熔渣中碱度CaO/SiO₂比值>1.5时，向反应熔渣中加入酸性物料和/或酸性含铁物料。如上所述的方法，优选地，所述反应装置为保温装置或可转动的熔炼反应装置或带有渣口或铁口熔渣可流出的熔炼反应装置；其中，所述保温装置为可倾倒的熔炼反应渣灌或保温地坑；When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >1.5, an acidic material and/or an acidic iron-containing material is added to the reaction slag. In the method as described above, preferably, the reaction device is a heat preservation device or a rotatable smelting reaction device or a smelting reaction device with slag or iron slag flowing out; wherein the heat preservation device is pourable Smelting reaction slag irrigation or insulation pit;

所述可转动的熔炼反应装置为转炉、熔炼反应渣罐；The rotatable smelting reaction device is a converter and a smelting reaction slag tank;

所述带有渣口或铁口熔渣可流出的熔炼反应装置为等离子炉、直流电弧炉、交流电弧炉、矿热炉、鼓风炉、高炉、感应炉、冲天炉、侧吹熔池熔炼炉、底吹熔池熔炼炉、顶吹熔池熔炼炉、反射炉、奥斯麦特炉、艾萨炉、瓦钮可夫熔池熔炼炉、侧吹回转炉、底吹回转炉、顶吹回转炉、铜熔炼炉的电热前床。The smelting reaction device with slag or iron slag can flow out is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola furnace, a side blowing molten pool smelting furnace, Bottom-blow pool smelting furnace, top-blow pool smelting furnace, reverberatory furnace, Osmet furnace, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing rotary furnace The electric heating bed of the copper melting furnace.

如上所述的方法，优选地，在所述步骤S1中，满足所述条件a和b的同时，应同时满足，控制所述熔渣保持熔渣中铜氧化物和铁氧化物还原为金属铜和FeO，熔渣中金属铁含量<3％。可通过加入还原剂、含碳的含铁物料中的一种或两种，其中，所述还原剂和/或含碳的含铁物料的的用量为熔渣中铜和铁氧化物还原为金属铜和FeO的理论量110～140％；所述含碳的含铁物料为钢铁尘泥与烟灰、铁精矿含碳预还原球团、铁精矿含碳金属化球团、湿法炼锌挥发窑渣或焦炭炉尘泥与烟灰。In the method as described above, preferably, in the step S1, while satisfying the conditions a and b, it should be simultaneously satisfied to control the reduction of copper oxide and iron oxide in the slag holding slag to metallic copper. And FeO, the metal iron content in the slag is <3%. By adding one or both of a reducing agent, a carbon-containing iron-containing material, wherein the reducing agent and/or the carbon-containing iron-containing material is used in an amount such that copper and iron oxides in the slag are reduced to metal The theoretical amount of copper and FeO is 110-140%; the carbon-containing iron-containing material is steel dust and soot, iron concentrate carbon-containing pre-reduction pellet, iron concentrate carbon-containing metallized pellet, wet zinc smelting Volatile kiln residue or coke oven dust and soot.

如上所述的方法，优选地，所述铜渣是含铜熔炼渣、含铜吹炼渣、铜火法贫化弃渣、浮选尾渣、湿法炼铜渣中一种或几种，其中，所述含铜熔炼渣产生于铜的火法冶炼工艺的“造锍熔炼”过程，所述含铜吹炼渣产生于铜的火法冶炼工艺的“铜锍吹炼”过程，所述铜火法贫化弃渣为含铜熔炼渣与含铜吹炼渣贫化后弃渣，所述浮选尾渣为含铜熔炼渣与含铜吹炼渣选矿后尾渣；其中，所述含铜熔炼渣、含铜吹炼渣与贫化弃渣为熔融态或冷态，其中：所述熔融态的铜熔炼渣由“造锍熔炼”过程的含铜熔炼炉出渣口获得，或将含铜熔炼渣加热至熔融状态，所述熔融铜态的吹炼渣由“铜锍吹炼”过程的铜吹炼炉出渣口获得，或将铜吹炼渣加热至熔融状态，贫化弃渣由贫化炉出渣口获得，获将贫化渣加热至熔融状态；In the method as described above, preferably, the copper slag is one or more of a copper-containing smelting slag, a copper-containing blowing slag, a copper-fired depleted slag, a flotation tailings, and a wet copper slag. Wherein, the copper-containing smelting slag is produced in a "smelting smelting" process of a copper pyrometallurgical smelting process, and the copper-containing smelting slag is produced in a "copper smelting" process of a copper pyrometallurgical process, The copper fire method depleted waste slag is a copper smelting slag and a copper-containing smelting slag, and the slag is depleted, and the flotation tailing slag is a copper smelting slag and a copper-containing smelting slag, and a tailing slag after beneficiation; wherein The copper-containing smelting slag, the copper-containing smelting slag and the depleted slag are in a molten state or a cold state, wherein: the molten copper smelting slag is obtained from a slag-containing smelting furnace slag opening process of the smelting smelting process, or The copper-containing smelting slag is heated to a molten state, and the molten copper slag is obtained from a copper smelting furnace slag tapping port of the "copper smelting" process, or the copper smelting slag is heated to a molten state, and is depleted The waste slag is obtained from the slag outlet of the depleted furnace, and the depleted slag is heated to a molten state;

所述钙系矿物为石灰、石灰石、白云石、电石渣、赤泥或脱钠后高钙赤泥中的一种或几种；所述添加剂为SiO₂、MgO、FeO、Fe₂O₃、MnO₂、Al₂O₃、TiO₂、Fe或Na₂O中的一种或几种。The calcium-based mineral is one or more of lime, limestone, dolomite, calcium carbide slag, red mud or high-calcium red mud after de-sodium; the additive is SiO ₂ , MgO, FeO, Fe ₂ O ₃ , One or more of MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O.

如上所述的方法，优选地，所述含铜物料为铜渣、选铜尾矿、粗铜火法精炼渣、锌冶炼渣、锌冶炼烟灰与尘泥、铅冶炼炉渣、铅锌尾矿、镍冶炼渣、铅冰铜、砷冰铜、粗铅火法精炼渣、含铅烟化炉渣、铅冶炼烟尘与烟灰、铅酸电池、铜冶炼烟灰与尘泥、杂铜、含铜垃圾、含铜电路板、锡冶炼渣、锡尾矿中的一种或几种混合；其中，所述铜渣包括“造锍熔炼”产生的炉渣与“铜鋶吹炼”产生的炉渣、火法贫化炉渣、铜渣浮选尾渣；含铅炉渣为烟化炉炉渣与含铅熔炼渣，“ISP铅锌鼓风炉还原”或“烧结矿鼓风炉还原”或“固态高铅渣还原”或“液态高铅渣还原工艺”还原工艺产生含铅熔炼渣，含铅熔炼渣通过烟化炉冶炼产生含铅烟化炉渣；镍冶炼渣是“造锍熔炼”工艺产生的镍熔炼渣、“铜冰镍吹炼”工艺吹炼后的贫化炉渣、顶吹熔炼产生的镍沉降炉渣中一种或多种；锌冶炼炉渣包括湿法炼锌产生的炉渣与湿法炼锌产生的炉渣，其中湿法炼锌产生的炉渣是锌浸出渣、挥发窑渣、铁矾渣、酸洗后铁矾渣、针铁矿渣、赤铁矿渣一种或多种，竖罐炼锌是竖罐炼锌炉渣、旋涡熔炼炉渣、鼓风炉炉渣、电炉渣中的一种或多种；Preferably, the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead smelting slag, lead-zinc tailings, Nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag, lead-containing smelting furnace slag, lead smelting soot and soot, lead-acid battery, copper smelting soot and dust, copper, copper-containing garbage, containing One or more kinds of copper circuit board, tin smelting slag, tin tailings; wherein the copper slag includes slag produced by "smelting smelting" and slag generated by "copper smelting", depletion by fire method Slag and copper slag flotation tailings; lead-containing slag is smelting furnace slag and lead smelting slag, “ISP lead-zinc blast furnace reduction” or “sinter blast furnace reduction” or “solid high-lead slag reduction” or “liquid high lead” Slag reduction process" reduction process produces lead-containing melting The slag and the lead smelting slag are smelted by the smelting furnace to produce lead-containing smelting furnace slag; the nickel smelting slag is the nickel smelting slag produced by the "smelting smelting" process, and the depleted slag after the "copper ice nickel blowing" process is blown One or more of the nickel settling slag produced by top-blown smelting; the zinc smelting slag includes slag produced by wet zinc smelting and slag produced by wet zinc smelting, wherein the slag produced by the wet zinc smelting is zinc leaching residue and volatilized One or more kinds of kiln slag, iron slag, pickled iron slag, goethite slag, hematite slag, vertical tank zinc smelting is vertical tank zinc slag, vortex smelting slag, blast furnace slag, electric furnace slag One or more

所述冶金熔剂为含CaO或SiO₂的矿物，具体为石英砂、含金银石英砂、赤泥、脱钠后高钙赤泥、电石渣、白云石或石灰石中的一种或几种；The metallurgical flux is a mineral containing CaO or SiO ₂ , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone;

所述含铁物料是普通铁精矿、普通铁精矿直接还原铁，普通铁精矿烧结矿、普通铁精矿球团矿、普通铁精矿金属化球团、普通铁精矿含碳预还原球团、钢渣、锌冶炼渣、焦炭冶炼烟尘与尘泥、钢铁烟尘与尘泥、含镍冶炼渣、铜渣、铅冶炼渣、铜渣、锡冶炼渣、赤泥、脱钠后高钙赤泥、煤粉灰、硫酸烧渣中的一种或几种；所述钢铁烟尘与尘泥包括高炉瓦斯泥、转炉尘泥、电炉尘泥、热或冷轧污泥、烧结粉尘、球团粉尘、出铁厂集尘、高炉瓦斯灰、电炉除尘灰、轧钢氧化铁皮；The iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon-bearing pre- Reducing pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag, copper slag, lead smelting slag, copper slag, tin smelting slag, red mud, high calcium after desodium One or more of red mud, coal dust ash, sulfuric acid slag; the steel dust and dust including blast furnace gas mud, converter dust mud, electric furnace dust, hot or cold rolling sludge, sintering dust, pellets Dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale;

所述含氟物料是萤石、CaF₂或含氟高炉渣中的一种或几种；The fluorine-containing material is one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag;

所述含铜物料、含铁物料和含氟物料均为球团或粉状物料或制粒；其中，粉状物料的粒度≤150μm，粒状物料粒度为5～25mm，粉状物料以喷吹的方式喷入，粒状物料以喷吹或投料的方式加入，载入气体为0～1200℃的氩气、氮气、还原性气体、氧化性气体中的一种或多种；所述的喷吹方式为采用耐火喷枪***熔渣或置于反应熔渣上部或侧面或底部吹入中的一种或几种。如上所述的方法，优选地，所述碱性物料为石灰粉、赤泥、脱钠后高钙赤泥、电石渣、白云石粉或生石灰粉中的一种或几种；所述的碱性含铁物料为CaO/SiO₂>1的含铁物料、碱性烧结矿、碱性铁精矿、铁合金炉渣、钢渣、碱性预还原球团、碱性金属化球团、钢渣或高炉渣中的一种或几种；The copper-containing material, the iron-containing material and the fluorine-containing material are all pellets or powdery materials or granulation; wherein, the granular material has a particle size of ≤150 μm, the granular material has a particle size of 5 to 25 mm, and the powdery material is sprayed. Injecting in a manner, the granular material is added by spraying or feeding, and the gas is loaded into one or more of argon gas, nitrogen gas, reducing gas and oxidizing gas at 0 to 1200 ° C; One or more of the slag inserted into the slag or placed in the upper or side or bottom of the reaction slag. Preferably, the alkaline material is one or more of lime powder, red mud, decalcified high calcium red mud, calcium carbide slag, dolomite powder or quicklime powder; The iron-containing material is CaO/SiO ₂ >1 iron-containing material, alkaline sintered ore, alkaline iron concentrate, iron alloy slag, steel slag, alkaline pre-reduction pellet, alkaline metallized pellet, steel slag or blast furnace slag One or several

所述氧化性气体为0～1200℃的空气、氧气、富氧空气、氩气-空气、氩气-氧气、氮气-空气、氮气-氧气中的一种；The oxidizing gas is one of air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen at 0 to 1200 °C;

所述酸性物料为硅石、粉煤灰、煤矸石中的一种或多种；所述酸性含铁物料为CaO/SiO₂≤1的含铁物料、酸性烧结矿、酸性铁精矿、酸性预还原球团、酸性金属化球团、铜渣、含铅炉渣、锌冶炼渣、镍冶炼渣、锡冶炼渣、铁合金渣、高炉渣中的一种或几种。The acidic material is one or more of silica, fly ash and coal gangue; the acidic iron-containing material is iron-containing material with CaO/SiO ₂ ≤ 1, acid sinter, acid iron concentrate, acid pre- One or more of reducing pellets, acid metallized pellets, copper slag, lead-containing slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, and blast furnace slag.

如上所述的方法，优选地，在所述步骤S2中分离回收中，对所述富铜相、富铁相与含铁硅酸盐矿物相分别进行处理，或将任两相结合处理。In the above-described method, preferably, in the separation and recovery in the step S2, the copper-rich phase, the iron-rich phase, and the iron-containing silicate mineral phase are separately treated, or any two phases are combined.

具体地，所述步骤S2中的分离回收，采用如下方法一到方法五中任一方法处理：Specifically, the separation and recovery in the step S2 is performed by any one of the following methods 1 to 5:

方法一、采用熔渣可流出熔炼反应装置时，反应完成后的熔渣分离后进行如下步骤：Method 1: When the slag can be used to flow out of the smelting reaction device, after the slag separation after the reaction is completed, the following steps are performed:

S2-1-01、所述含铁硅酸盐矿物相，进行如下方法A-G中的任一种处理；S2-1-01, the iron-containing silicate mineral phase, is subjected to any one of the following methods A-G;

方法A：水淬或空冷后直接用作水泥原料；Method A: directly used as a cement raw material after water quenching or air cooling;

方法B：部分或全部所述含铁硅酸盐矿物相返回到所述反应熔渣中作为热态冶金熔剂；Method B: part or all of the iron-containing silicate mineral phase is returned to the reaction slag as a hot metallurgical flux;

方法C：用于浇筑微晶玻璃或作为矿渣棉；方法D：所述含铁硅酸盐矿物相的熔渣氧化后空冷或水淬，方法包括：熔渣保留在熔炼反应装置内或将熔渣倒入保温装置，向含铁硅酸盐的熔渣中，吹入温度为0～1200℃的预热氧化性气体，并保证硅酸盐的熔渣温度>1450℃；当熔渣氧化亚铁的重量百分含量<1％，获得氧化后的熔渣；所述氧化后的熔渣直接空冷或水淬，用作矿渣水泥、水泥调整剂、水泥生产中的添加剂或水泥熟料；Method C: for pouring glass ceramics or as slag wool; Method D: slag containing iron silicate mineral phase is oxidized after air cooling or water quenching, the method comprises: slag remaining in the smelting reaction device or melting The slag is poured into the heat preservation device, and the preheated oxidizing gas having a temperature of 0 to 1200 ° C is blown into the slag containing iron silicate, and the slag temperature of the silicate is ensured to be >1450 ° C; The weight percentage of iron is <1%, and the slag after oxidation is obtained; the slag after oxidation is directly air-cooled or water-quenched, and is used as a slag cement, a cement conditioner, and a cement production. Additive or cement clinker;

进一步地，当含铁硅酸盐熔渣温度<1450℃，喷入预热燃料与预热的氧化性气体，燃烧放热、补充热量，或装置自身加热，使含铁硅酸盐熔渣温度>1450℃；Further, when the temperature of the iron-containing silicate slag is <1450 ° C, the preheated fuel and the preheated oxidizing gas are injected, the heat is burned, the heat is supplemented, or the device itself is heated to make the temperature of the iron-containing silicate slag >1450 ° C;

方法E：所述含铁硅酸盐矿物相用于生产高附加值的水泥熟料，包括如下步骤：Method E: The iron-containing silicate mineral phase is used to produce high value-added cement clinker, including the following steps:

E-1、含铁硅酸盐矿物相保留在熔炼反应装置内或将熔渣倒入保温装置，向含铁硅酸盐矿物相的熔渣中，加入熔融钢渣、石灰、石灰石、铁合金炉渣、粉煤灰、碱性铁贫矿、铝土矿、熔融高炉渣、赤泥、脱钠后赤泥或电石渣中的一种或几种，充分混合，获得熔渣混合物料；E-1. The iron-containing silicate mineral phase is retained in the smelting reaction device or the slag is poured into the heat preservation device, and molten slag, lime, limestone, iron alloy slag, and molten slag are added to the slag containing the iron silicate mineral phase. One or more of fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, red mud after desoda or calcium carbide slag, thoroughly mixed to obtain a slag mixture;

E-2、向上熔渣混合物料中吹入预热温度为0～1190℃的氧化性气体，并保证熔渣混合物料温度>1450℃；当氧化亚铁重量百分比含量<1％，获得氧化后的熔渣；E-2, the slag mixture is blown into the oxidizing gas with a preheating temperature of 0 to 1190 ° C, and the temperature of the slag mixture is >1450 ° C; when the weight percentage of ferrous oxide is <1%, the oxidation is obtained. Slag

E-3、所述氧化后的熔渣，进行空冷或水淬，制得高附加值的水泥熟料；E-3, the oxidized slag is subjected to air cooling or water quenching to obtain a high value-added cement clinker;

方法F：所述含铁硅酸盐矿物相的熔渣作为高炉炼铁原料或直接还原炼铁原料：将含铁硅酸盐熔渣空冷、水淬或缓冷后，用作高炉炼铁或直接还原炼铁原料，直接还原后，采用磁选分离或电炉熔分，磁选产物为金属铁与尾矿，电炉熔分，产物为铁水与熔渣；Method F: the slag containing the iron silicate mineral phase as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: after the iron-containing silicate slag is air-cooled, water-quenched or slowly cooled, used as blast furnace ironmaking or Direct reduction of ironmaking raw materials, after direct reduction, magnetic separation or electric furnace melting, magnetic separation products are metal iron and tailings, electric furnace melting, the product is molten iron and slag;

或将熔渣倒入保温装置后，采用熔渣改性后磁选分离，包括：向保温装置中的熔渣，吹入0～1200℃的预热的氧化性气体，并保证其熔渣温度>1250℃；After the slag is poured into the heat preservation device, the slag is modified and magnetically separated, including: preheating the oxidizing gas at 0 to 1200 ° C into the slag in the heat preservation device, and ensuring the slag temperature thereof. >1250 ° C;

进一步地，当熔渣温度<1250℃，喷入预热燃料与预热的氧化性气体，燃烧放热、补充热量，或装置自身加热，使熔渣温度>1250℃；Further, when the slag temperature is <1250 ° C, the preheated fuel and the preheated oxidizing gas are injected, the heat is burned, the heat is supplemented, or the device itself is heated to make the slag temperature >1250 ° C;

将上述氧化后的熔渣缓冷至室温，破碎、磁选，产物为磁铁矿精矿与尾矿，尾矿作为建筑材料；The oxidized slag is slowly cooled to room temperature, crushed and magnetically selected, and the product is magnetite concentrate and tailings, and tailings are used as building materials;

方法G：所述含铁硅酸盐矿物相进行还原炼铁，包括如下步骤：Method G: The iron-containing silicate mineral phase is subjected to reduction ironmaking, comprising the following steps:

G-1、含铁硅酸盐矿物相保留在熔炼反应装置内或将该熔渣倒入保温装置，或加入含铁物料，同时加入还原剂，进行熔融还原，实时监测反应熔渣，通过调控同时满足条件：反应熔渣的温度为1350～1670℃和反应熔渣的碱度CaO/SiO₂比值＝0.6～2.4，获得反应完成后的熔渣；G-1, the iron-containing silicate mineral phase is retained in the smelting reaction device or the slag is poured into the heat preservation device, or the iron-containing material is added, and the reducing agent is added at the same time to perform smelting reduction, and the reaction slag is monitored in real time, and the slag is controlled. At the same time, the conditions are satisfied: the temperature of the reaction slag is 1350～1670° C. and the alkalinity of the reaction slag is CaO/SiO ₂ ratio=0.6-2.4, and the slag after the completion of the reaction is obtained;

其中，控制反应熔渣的温度的方法为：Among them, the method of controlling the temperature of the reaction slag is:

当反应熔渣的温度＜1350℃，通过反应装置自身的加热，或向熔渣中加入燃料与预热的氧化性气体，使反应熔渣的温度达到1350～1670℃；When the temperature of the reaction slag is <1350 ° C, the heating of the reaction device itself, or the addition of fuel and preheated oxidizing gas to the slag, so that the temperature of the reaction slag reaches 1350 ~ 1670 ° C;

当反应熔渣的温度＞1670℃，向反应熔渣中加入冶金熔剂、含铁物料或含氟物料中的一种或几种，使反应熔渣的温度达到1350～1670℃，其中，所述冶金熔剂为含CaO或SiO₂的矿物，具体为石英砂、含金银石英砂、赤泥、脱钠后高钙赤泥、电石渣、白云石或石灰石中的一种或几种；When the temperature of the reaction slag is >1670 ° C, one or more of a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag, so that the temperature of the reaction slag reaches 1350 to 1670 ° C, wherein The metallurgical flux is a mineral containing CaO or SiO ₂ , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desodiumification, calcium carbide slag, dolomite or limestone;

控制反应熔渣的碱度的方法为：The method of controlling the alkalinity of the reaction slag is:

当反应熔渣中碱度CaO/SiO₂比值<0.6时，向熔渣中加入碱性物料和/或碱性含铁物料；When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is less than 0.6, an alkaline material and/or an alkaline iron-containing material is added to the slag;

当反应熔渣中碱度CaO/SiO₂比值>2.4时，向熔渣中加入酸性物料和/或酸性含铁物料；When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >2.4, an acidic material and/or an acidic iron-containing material is added to the slag;

G-2、所述G-1中熔融还原时还需向熔渣中喷吹0～1200℃预热后的氧化性气体进行熔融还原，形成还原后的熔渣；G-2, in the G-1, in the smelting reduction, the oxidizing gas preheated by 0 to 1200 ° C is sprayed into the slag to be smelted and reduced to form a reduced slag;

G-3、分离回收：采用以下两种方法中的一种进行：G-3, separation and recovery: using one of the following two methods:

方法Ⅰ：将还原后的混合熔渣倒入保温渣罐，缓慢冷却至室温，获得缓冷渣；其中，金属铁沉降到反应装置的底部，形成铁坨，将剩余缓冷渣中含金属铁层，破碎至粒度20～400μm，磨矿，磁选分离出剩余金属铁与尾矿； Method I: Pour the mixed slag after reduction into a heat preservation slag tank, and slowly cool to room temperature to obtain slow cooling slag; wherein, the metal iron settles to the bottom of the reaction device to form iron slag, and the remaining slow slag contains metal iron Layer, broken to a particle size of 20 ~ 400μm, grinding, magnetic separation to separate the remaining metal iron and tailings;

方法Ⅱ：还原后的混合熔渣，沉降，渣-金分离，获得铁水与还原后的熔渣；所述还原后的熔渣，按照方法A～E中的一种或几种方法进行熔渣处理；所述铁水，送往转炉或电炉炼钢；Method II: mixed slag after reduction, sedimentation, slag-gold separation, obtaining molten iron and reduced slag; and the reduced slag is slag according to one or several methods of methods A to E Processing; the molten iron is sent to a converter or an electric furnace for steel making;

S2-1-02、所述富铜相，送往转炉或吹炼炉炼铜或缓冷破碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜；S2-1-02, the copper-rich phase, sent to a converter or a blowing furnace for copper smelting or slow cooling and magnetic separation to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting, or magnetic separation of metal iron or After the metal iron is separated by magnetic separation, the reduction product is directly separated, and the reduced product is separated by magnetic separation, and then sent to a converter or a blowing furnace for copper smelting;

S2-1-03、部分所述含锌组分与含铅组分挥发，以氧化物形式进入烟尘回收；S2-1-03, part of the zinc-containing component and the lead-containing component volatilize, and enter the soot recovery in the form of oxide;

S2-1-04、部分含金组分与含银组分进入富铜相；S2-1-04, part of the gold-containing component and the silver-containing component enter the copper-rich phase;

S2-1-05、所述富铁相层进行水淬或空冷或倒入保温装置缓冷后或经人工分拣与重选结合获得，作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料或浮选提铜原料或磁选分离金属铁后作为炼铜或直接还原炼铁的原料；直接还原过程中，还原产物磁选分离后，获得金属铁与尾矿，尾矿返回炼铜***；浮选过程中，浮选产物为含铜精矿与铁精矿，铜精矿返回炼铜***，铁精矿作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料；其中，所述直接还原过程采用转底炉、隧道窑、车底路、竖炉、回转窑或感应炉作为还原设备，利用气基或煤基还原技术，气基还原为天然气和/或煤气，煤基还原为无烟煤、烟煤、褐煤、焦煤、焦粉或焦炭中的一种或几种，还原温度为900～1400℃，碱度CaO/SiO₂比值＝0.8～1.5；还原产生的煤气在熔渣表面二次燃烧，提供了热量，而且由炉内流出的煤气可以作为烘干炉料与保温装置的热源；S2-1-05, the iron-rich phase layer is obtained by water quenching or air cooling or pouring into a heat preservation device, or after being manually sorted and re-selected, as a raw material for blast furnace ironmaking or directly reducing ironmaking raw materials or smelting reduction Ironmaking raw materials or flotation copper extraction raw materials or magnetic separation of metal iron as a raw material for copper smelting or direct reduction ironmaking; in the direct reduction process, after reduction and magnetic separation of the reduction products, metal iron and tailings are obtained, and tailings are returned to the refining Copper system; during the flotation process, the flotation product is a copper-bearing concentrate and iron concentrate, the copper concentrate is returned to the copper-smelting system, and the iron concentrate is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material or a smelting reduction ironmaking raw material; Wherein, the direct reduction process uses a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary kiln or an induction furnace as a reduction device, and the gas-based or coal-based reduction technology is used to reduce the gas base to natural gas and/or gas. The coal base is reduced to one or more of anthracite, bituminous coal, lignite, coking coal, coke powder or coke, the reduction temperature is 900-1400 ° C, the alkalinity CaO / SiO ₂ ratio = 0.8 ~ 1.5; the gas produced by reduction is melting Secondary combustion of slag surface, provided Heat, and the gas flowing out of the furnace as a heat source can heat and dry the charge device;

此外，因赤泥中含有钾、钠，尘泥与钢铁烟灰中含有铅、锌、铋、铟银，所以添加这些原料时，部分铟组分、铋组分、含钾组分、含钠组分挥发，以氧化物形式进入烟尘。In addition, since the red mud contains potassium, sodium, dust, and steel soot containing lead, zinc, antimony, and indium silver, when these materials are added, some indium, antimony, potassium, and sodium groups are added. It is volatilized and enters the soot as an oxide.

方法二、采用熔渣可流出的熔炼反应装置时，获得的所述熔融态富铁相和含铁硅酸盐矿物相处理方法用方法一中所述方法A～G中一种或几种进行处理，或倒入保温装置缓冷后的富铜相，送往转炉或吹炼炉炼铜，或碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜。Method 2: When the smelting reaction device through which the slag can flow out is used, the obtained molten iron-rich phase and the iron-containing silicate mineral phase treatment method are performed by one or more of the methods A to G described in the first method. Treat, or pour into the copper-rich phase after the slow cooling of the heat preservation device, send it to the converter or the converter to smelt copper, or separate the metal iron by crushing and then send it to the converter or the converter to smelt the copper, or separate the metal by magnetic separation. After the iron or the metal iron is separated by magnetic separation, it is directly reduced, and the reduced product is magnetically separated to separate the metal iron, and then sent to a converter or a blowing furnace for copper smelting.

方法三、采用熔渣可转动的转炉与反应渣罐时，获得含铁硅酸盐矿物相，处理方法用方法一中所述方法A～G中一种或几种进行处理；或含有所述富铁相采用方法一中步骤S2-1-05进行处理；所述熔融态或倒入保温装置缓冷后的富铜相，送往转炉或吹炼炉炼铜，或碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜。Method 3, using a slag rotatable converter and a reaction slag tank, obtaining an iron-containing silicate mineral phase, and the treatment method is treated by one or more of the methods A to G described in the first method; or The iron-rich phase is treated by the step S2-1-05 in the first method; the molten state is poured into the copper-rich phase after the slow cooling of the heat preservation device, sent to the converter or the blowing furnace for copper smelting, or the magnetic separation is used to separate the metallic iron. After being sent to converter or blowing furnace for copper smelting, or magnetic separation to separate metal iron or without magnetic separation, the metal is directly reduced, and the reduced product is separated by magnetic separation and then sent to a converter or a converting furnace. Copper smelting.

方法四、采用熔渣可转动的转炉与反应渣罐时，获得的所述熔融态含铁硅酸盐矿物相与富铁相，处理方法用方法一中所述方法A～G中一种或几种进行处理；所述熔融态富铜相或倒入保温装置缓冷后，送往转炉或吹炼炉炼铜，或缓冷后碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜。Method 4: When the slag rotatable converter and the reaction slag tank are used, the molten iron-containing silicate mineral phase and the iron-rich phase are obtained, and the treatment method is one of the methods A to G described in the first method or Several kinds of processing; the molten copper-rich phase or poured into the heat preservation device after slow cooling, sent to a converter or a blowing furnace for copper smelting, or slow cooling, then magnetic separation to separate the metal iron and then sent to the converter or the converting furnace Copper is smelted, or metal iron is separated by magnetic separation or metal iron is separated by magnetic separation, and the reduction product is subjected to magnetic separation to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting.

方法五：采用保温装置时，或采用熔渣可流出的熔炼反应装置，将熔渣倒入保温装置时，进行如下步骤：Method 5: When using a heat preservation device, or using a smelting reaction device through which slag can flow out, when pouring the slag into the heat preservation device, perform the following steps:

S201、沉降冷却：熔渣缓冷却至室温，获得缓冷渣；所述富铜相沉降到反应装置的底部，形成富铜坨；所述含铁硅酸盐矿物相上浮；中间为缓冷渣为富铁相，同时生成含锌组分与含铅组分；其中，镍、钴、金、银组分迁移到富铜相；S201, sedimentation cooling: the slag is slowly cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to the bottom of the reaction device to form a copper-rich strontium; the iron-containing silicate mineral phase floats; the middle is slow cooling slag For the iron-rich phase, a zinc-containing component and a lead-containing component are simultaneously formed; wherein the nickel, cobalt, gold, and silver components migrate to the copper-rich phase;

S202、分离：人工取出沉降在底部的富铜坨，或富铜坨破碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜；所述富铁相与含铁硅酸盐相作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料或熔融还原炼铁原料或浮选提铜原料或磁选分离金属铁后作为炼铜或直接还原炼铁的原料；直接还原过程中，还原产物磁选分离后，获得金属铁与尾矿，尾矿返回炼铜***；浮选产物为含铜精矿与铁精矿，铜精矿返回炼铜***，铁精矿作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料；S202. Separation: manually taking out copper-rich bismuth deposited at the bottom, or copper-filled ruthenium after magnetic separation to separate metal iron Then send it to converter or blowing furnace for copper smelting, or magnetic separation to separate metal iron or without magnetic separation to separate metal iron, directly reduce, the reduction product is magnetically separated to separate metal iron, and then sent to converter or blowing furnace Copper; the iron-rich phase and the iron-containing silicate phase as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material or a smelting reduction ironmaking raw material or a smelting reduction ironmaking raw material or a flotation copper extraction raw material or magnetic separation of metal iron As a raw material for copper smelting or direct reduction ironmaking; in the direct reduction process, after the magnetic separation of the reduction product, metal iron and tailings are obtained, and the tailings are returned to the copper smelting system; the flotation product is a copper-bearing concentrate and iron concentrate. The copper concentrate is returned to the copper smelting system, and the iron concentrate is used as a raw material for blast furnace ironmaking or directly reducing ironmaking raw materials or smelting reduction ironmaking raw materials;

S203、人工取出上部的含铁硅酸盐矿物相，获得硅酸盐相作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料或水泥原料；S203, manually taking out the upper iron-containing silicate mineral phase, obtaining a silicate phase as a blast furnace ironmaking raw material or directly reducing ironmaking raw materials or smelting reduction ironmaking raw materials or cement raw materials;

S204、部分锌组分与铅组分挥发，以氧化物形式进入烟尘回收；S204, part of the zinc component and the lead component are volatilized, and enter the soot recovery in the form of oxide;

S205、添加有赤泥中或尘泥与钢铁烟灰这些原料时，部分铟组分、铋组分、含钾组分、含钠组分挥发，进入烟尘回收。S205. When adding raw materials such as red mud or dust mud and steel soot, part of the indium component, the strontium component, the potassium component and the sodium component are volatilized and enter the soot recovery.

如上所述方法，优选地，所述氧化性气体为预热的空气、氧气、富氧空气、氮气-空气、氩气-空气、氧气-氮气、氧气-氩气中的一种Preferably, the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, nitrogen-air, argon-air, oxygen-nitrogen, oxygen-argon.

所述还原剂与燃料为固体、液体或气体燃料中的一种或多种，以喷吹或投料的方式喷入，所述喷吹载入气体为预热的氧化性气体、氮气或氩气中的一种或多种，所述预热的温度为0～1200℃；所述固体燃料与还原剂为煤粉、焦粉、焦炭、粉煤灰、烟煤或无烟煤中的一种或多种，形状为粒状或粉状，粒状物料粒度为5～25mm，粉状物料粒度为≤150μm，所述液体燃料与还原剂为重油，气体燃料与还原剂为煤气和/或天然气。The reducing agent and the fuel are one or more of a solid, liquid or gaseous fuel, which is sprayed or fed, and the injected gas is a preheated oxidizing gas, nitrogen or argon. One or more of the preheating temperature is 0 to 1200 ° C; the solid fuel and the reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite The shape is granular or powdery, the granular material has a particle size of 5 to 25 mm, the powdery material has a particle size of ≤150 μm, the liquid fuel and the reducing agent are heavy oil, and the gaseous fuel and the reducing agent are gas and/or natural gas.

如上所述方法，优选地，在所述步骤S1中，所述混合均匀为自然混合或搅拌混合，所述搅拌混合的方式为氩气搅拌、氮气搅拌、氮气-氩气混合气搅拌、还原性气体搅拌、氧化性气体搅拌、电磁搅拌或机械搅拌中的一种或几种；In the above method, preferably, in the step S1, the mixing is uniformly a natural mixing or a stirring mixing, and the stirring mixing is performed by argon stirring, nitrogen stirring, nitrogen-argon gas mixture stirring, reducing property. One or more of gas agitation, oxidative gas agitation, electromagnetic agitation or mechanical agitation;

在所述步骤S2中，所述沉降为自然沉降或旋转沉降或离心沉降；进行冷却沉降时的冷却方式为自然冷却或旋转冷却或离心冷却，所述分离时，用重力分选法是摇床分选、溜槽分选或者二者相结合。In the step S2, the sedimentation is natural sedimentation or spin sedimentation or centrifugal sedimentation; the cooling mode when cooling sedimentation is natural cooling or rotary cooling or centrifugal cooling, and the gravity sorting method is a shaker. Sorting, chute sorting or a combination of the two.

与现有技术相比，本发明的特点是：Compared with the prior art, the features of the invention are:

(1)本发明的由含铜熔渣回收有价组分的方法，既可以处理热态熔渣，充分利用熔融铜渣物理热资源和热态冶金熔剂，又可以处理冷态炉渣，通过调整熔渣物理化学性质，利用含铜熔渣成熟的物理化学性质，实现了含铜熔渣冶金工艺；(1) The method for recovering valuable components from copper-containing slag of the present invention can treat hot slag, make full use of molten copper slag physical heat resources and hot metallurgical flux, and can treat cold slag by adjusting The physical and chemical properties of the slag, using the physical and chemical properties of the copper-containing slag to achieve the metallurgical process of containing copper slag;

(2)熔渣中的熔渣冶金反应，加入有钙系矿物，使铁橄榄石解体，铁氧化物充分释放出来，形成游离态的铁氧化物，实现富铁相长大与沉降，熔渣中的含铁组分聚集、长大与沉降；同时钙系矿物有效改造粘度，使粘度降低，有助于含铜组分沉降；(2) The slag metallurgical reaction in the slag is added with calcium minerals to disintegrate the olivine, and the iron oxide is fully released to form free iron oxide, which realizes the growth and settlement of the iron-rich phase, and the slag The iron-containing components aggregate, grow up and settle; at the same time, the calcium-based minerals effectively modify the viscosity to lower the viscosity and contribute to the sedimentation of the copper-containing component;

(3)熔渣中的铜组分、金银组分分别迁移、富集于富铜相，并实现长大与沉降，富铜相送往转炉或吹炼炉炼铜；其中，富铜相包括有铜、白冰铜、冰铜相、含铁组分中的多种，或部分铜组分进入富铁相，富铁相包括金属铁、FeO相、铁橄榄石相中的多种，作为高炉炼铁或直接还原或熔融还原炼铁的原料；(3) The copper component and the gold and silver components in the slag are separately migrated and enriched in the copper-rich phase, and the growth and sedimentation are realized, and the copper-rich phase is sent to the converter or the smelting furnace for copper smelting; wherein, the copper-rich phase Including copper, white copper, matte phase, a variety of iron-containing components, or part of the copper component into the iron-rich phase, the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phase, as a blast furnace Iron or steel or direct reduction or smelting reduction of ironmaking raw materials;

(4)混合熔渣中的锌组分、铅组分分别迁移、富集于烟灰中，并实现回收；(4) The zinc component and the lead component in the mixed slag are separately migrated, enriched in the soot, and recovered;

(5)部分含铟组分、铋组分、含钾组分、含钠组分挥发进入烟尘进行回收；(5) part of the indium-containing component, the antimony component, the potassium-containing component, and the sodium-containing component are volatilized into the soot for recycling;

(6)采用人工分拣、磁选、重选、渣金分离的方法，分离沉降在底部的富铜相、中部的富铁相与上部的含铁硅酸盐相，实现熔渣中铜组分、铁组分的高效回收；可以处理固态含铜物料，达到资源高效综合利用；(6) Separating the copper-rich phase at the bottom, the iron-rich phase in the middle, and the iron-containing silicate phase in the upper part by manual sorting, magnetic separation, re-election, and slag-gold separation to realize the copper group in the slag Efficient recovery of fractions and iron components; can process solid copper-containing materials to achieve efficient and comprehensive utilization of resources;

(7)本发明方法中加入添加剂，一是用于减小粘度，二是用于降低熔点，在一定温度(1100-1450℃)下有助于富铜相沉降，使沉降分离后获得为低铜富铁相与含铁硅酸盐相，其中富铁相与含铁硅酸盐相的含铜量小于0.1％，可以通过直接还原或熔融还原炼铁，获得金属铁与铁水；(7) Adding an additive to the method of the present invention, one is for reducing the viscosity, the other is for lowering the melting point, and at a certain temperature (1100-1450 ° C), the copper-rich phase is precipitated, and the sedimentation is separated and obtained low. Copper rich iron phase and iron a silicate phase, wherein the iron-rich phase and the iron-containing silicate phase have a copper content of less than 0.1%, and the iron can be obtained by direct reduction or smelting reduction to obtain metallic iron and molten iron;

(9)本发明方法可连续或间断的进行，满足了工业生产的需要。(9) The method of the present invention can be carried out continuously or intermittently to meet the needs of industrial production.

(三)有益效果(3) Beneficial effects

本发明的有益效果是：The beneficial effects of the invention are:

(1)本发明的原料可以是冷态炉渣，冷态炉渣处理，不仅可以实现炉渣中铜组分、金组分、银组分、铁组分、锌组分、铅组分、铟组分、铋组分、钠组分、钾组分、有价组分的综合利用，有效解决目前炉渣大量堆积，环境污染问题，重金属污染等问题。(1) The raw material of the present invention may be cold slag, cold slag treatment, not only can realize copper component, gold component, silver component, iron component, zinc component, lead component, indium component in slag The comprehensive utilization of strontium components, sodium components, potassium components and valuable components can effectively solve the problems of large accumulation of slag, environmental pollution problems and heavy metal pollution.

(2)本发明的原料可以是出渣口中流出的液态熔融铜渣(≥1100℃)，蕴含着丰富的热能资源，具有高温度、高热量的特点，充分利用了熔渣物理热资源，高效节约能源；液态熔融铜渣含有大量的热态冶金熔剂，是物理化学性质优良的熔渣体系，实现了熔渣冶金。(2) The raw material of the present invention may be liquid molten copper slag (≥1100 ° C) flowing out from the slag outlet, which contains abundant thermal energy resources, has the characteristics of high temperature and high heat, and fully utilizes the slag physical heat resource and is highly efficient. Energy saving; liquid molten copper slag contains a large amount of hot metallurgical flux, which is a slag system with excellent physical and chemical properties, which realizes slag metallurgy.

(3)本发明通过调整熔渣物理化学性质，喷吹气体，控制氧势，使熔渣中铜组分、金银组分迁移、富集到富铜相，实现聚集、长大与沉降。(3) The invention adjusts the physical and chemical properties of the slag, injects a gas, controls the oxygen potential, and causes the copper component and the gold and silver component in the slag to migrate and enrich to the copper-rich phase to achieve aggregation, growth and sedimentation.

(4)本发明方法中，加入冷态物料与熔融铜渣避免了熔渣温度过高，提高保温装置的寿命；加入冷态物料与熔融铜渣提高了原料处理量，不仅可以处理液态熔渣，而且可以处理少量冷态物料，原料适应性强；加入冷态物料实现了反应释放的化学热与熔渣物理热的高效利用。(4) In the method of the invention, the cold material and the molten copper slag are added to avoid the slag temperature being too high, and the life of the heat preservation device is increased; adding the cold material and the molten copper slag improves the processing amount of the raw material, and can not only treat the liquid slag Moreover, it can process a small amount of cold materials, and the raw materials have strong adaptability; the addition of cold materials realizes the efficient use of the chemical heat released by the reaction and the physical heat of the slag.

(5)本发明调整熔渣物理化学性质，控制氧势，同时加入钙系矿物，使橄榄石相中铁氧化物释放出来，富集于富铁相，实现聚集、长大与沉降；熔渣中锌组分、铅组分、铟组分、铋组分、钠组分、钾组分挥发，进入烟尘加以回收。(5) The invention adjusts the physical and chemical properties of the slag, controls the oxygen potential, and simultaneously adds the calcium-based minerals to release the iron oxides in the olivine phase, enriched in the iron-rich phase, and realizes aggregation, growth and sedimentation; The zinc component, the lead component, the indium component, the bismuth component, the sodium component, and the potassium component are volatilized, and are collected into the soot to be recovered.

(6)本发明方法自然沉降过程中，熔渣中铜组分、金银组分富集于富铜相，并实现聚集、长大与沉降，熔渣中铁组分富集于富铁相，并实现聚集、长大与沉降，装有熔渣的保温装置置于旋转平台上旋转，加速富铜相、富铁相的聚集、长大与沉降；含氟物料的加入，加速富铜相、富铁相的长大与沉降，缩短沉降时间；富铜相送往转炉或吹炼炉炼铜，低铜富铁相作为高炉炼铁或直接还原或熔融还原炼铁的原料。(6) During the natural sedimentation process of the method of the invention, the copper component and the gold and silver components in the slag are enriched in the copper-rich phase, and the aggregation, growth and sedimentation are realized, and the iron component in the slag is enriched in the iron-rich phase. And to achieve aggregation, growth and settlement, the slag-containing insulation device is placed on the rotating platform to rotate, accelerate the accumulation of copper-rich phase, iron-rich phase, growth and sedimentation; the addition of fluorine-containing materials accelerates the copper-rich phase, The growth and precipitation of the iron-rich phase shortens the settling time; the copper-rich phase is sent to the converter or the converter to smelt copper, and the low-copper iron-rich phase is used as the raw material for blast furnace ironmaking or direct reduction or smelting reduction ironmaking.

(7)本发明方法熔渣矿物可磨性增加，熔渣实现调质。(7) The method of the present invention increases the grindability of the slag mineral, and the slag achieves quenching and tempering.

(8)本发明方法采用人工分拣、磁选、重选结合的方法，分别对分布在上部、中部与底部的硅酸盐矿物相、富铁相、富铜相进行分离，实现熔渣中铜组分、金银组分、铁组分、锌组分、铟组分、铋组分、铅组分、钠组分、钾组分的高效回收；由于富铜相、富铁相沉降在中、下部，其中，富铜相包含铜相、白冰铜、冰铜相、含铁组分中的多种，富铁相包括金属铁、FeO相、铁橄榄石相中的多种，因此，需分选炉渣量小，磨矿、磁选与重选成本低；后续的分离过程采用磁选或重选，分离过程中不会产生环境污染，熔渣处理工艺具有流程短、操作简单、回收率高，具有高效、清洁、环保的特点；尾矿作为水泥原料、建筑材料、代替碎石作骨料、路材使用。(8) The method of the invention separates the silicate mineral phase, the iron-rich phase and the copper-rich phase distributed in the upper part, the middle part and the bottom part by manual sorting, magnetic separation and re-election, respectively, to realize the slag High-efficiency recovery of copper component, gold-silver component, iron component, zinc component, indium component, antimony component, lead component, sodium component and potassium component; due to copper-rich phase and iron-rich phase sedimentation Middle and lower parts, wherein the copper-rich phase comprises a plurality of copper phases, white ice copper, amber phase, and iron-containing components, and the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phases, and therefore, The amount of slag is small, the cost of grinding, magnetic separation and re-election is low; the subsequent separation process uses magnetic separation or re-election, and there is no environmental pollution during the separation process. The slag treatment process has short process, simple operation and recovery rate. High, high-efficiency, clean and environmentally friendly; tailings are used as cement raw materials, building materials, instead of crushed stone for aggregates and road materials.

(9)含铁硅酸盐相与富铁组分的含铜量小于0.1％，可以作为高炉炼铁或直接还原或熔融还原炼铁的原料,获得金属铁与铁水。(9) The iron-containing silicate phase and the iron-rich component have a copper content of less than 0.1%, and can be used as a raw material for blast furnace ironmaking or direct reduction or smelting reduction of ironmaking to obtain metallic iron and molten iron.

(10)本发明既充分利用熔融铜渣物理热资源和热态冶金熔剂，又可以处理冷态炉渣，实现了熔渣冶金，熔渣中铜组分、金银组分富集于富铜相，并实现聚集、长大与沉降，铁组分富集于富铁相，实现聚集、长大与沉降，采用人工分拣、磁选与重选结合的方法，分离沉降在不同部位的富铜相、富铁相与含铁硅酸盐相，实现熔渣中铜组分、铁组分的高效回收；可以处理固态含铜物料，该方法工艺流程短、金属回收率高、生产成本低、原料适应性强、处理量大、环境友好、经济收益高、可解决冶金资源与热能高效回收利用问题。(10) The invention fully utilizes the molten copper slag physical heat resource and the hot metallurgical flux, and can also treat the cold slag, realizes slag metallurgy, and the copper component and the gold and silver component in the slag are enriched in the copper-rich phase. And achieve aggregation, growth and settlement, iron components are enriched in the iron-rich phase, to achieve aggregation, growth and sedimentation, using manual sorting, magnetic separation and re-election methods to separate and deposit copper in different parts Phase, iron-rich phase and iron-containing silicate phase to achieve efficient recovery of copper and iron components in slag; can process solid copper-containing materials, the process is short, metal High recovery rate, low production cost, strong adaptability of raw materials, large processing capacity, environmental friendliness and high economic returns can solve the problem of efficient recycling of metallurgical resources and thermal energy.

具体实施方式Detailed ways

一种含铜熔渣回收有价组分的方法，具体包括以下步骤：A method for recovering valuable components containing copper slag, comprising the following steps:

步骤1，炉渣混合：Step 1, slag mixing:

将铜渣(含铜熔炼渣、含铜吹炼渣、铜火法贫化弃渣、浮选尾渣、湿法炼铜渣中一种或几种)，加入保温装置或熔渣可流出的熔炼反应装置中并加入钙系矿物与添加剂，形成混合熔渣；Adding copper slag (containing one or more of copper smelting slag, copper-containing blowing slag, copper fire depleted slag, flotation tailings, and wet copper slag) to the heat preservation device or slag Calcining the reaction device and adding calcium minerals and additives to form a mixed slag;

将混合熔渣加热至熔融状态，形成含铜反应熔渣；混合均匀，实时监测含铜反应熔渣，通过调控同时保证如下(a)和(b)两个参数，获得反应完成后的熔渣，或将反应后的熔渣倒入保温装置；The mixed slag is heated to a molten state to form a copper-containing reaction slag; the mixture is uniformly mixed, and the copper-containing reaction slag is monitored in real time, and the following parameters (a) and (b) are simultaneously controlled to obtain the slag after completion of the reaction. , or pour the slag after the reaction into the heat preservation device;

(a)含铜反应熔渣的温度为1100～1450℃；(a) the temperature of the copper-containing reaction slag is 1100 ~ 1450 ° C;

(b)含铜反应熔渣的碱度CaO/SiO₂比值＝0.15～1.5；(b) alkalinity CaO / SiO ₂ ratio of copper-containing reaction slag = 0.15 ~ 1.5;

调控方法为：The control method is:

对应(a)：Corresponding to (a):

控制反应熔渣的温度在设定温度范围的方法为：The method for controlling the temperature of the reaction slag in the set temperature range is:

当含铜反应熔渣的温度＜设定温度范围下限时，通过反应装置自身的加热功能，或向含铜反应熔渣中加入燃料，使反应熔渣的温度达到设定温度范围内；喷入燃料时，同时喷入预热的氧化性气体；When the temperature of the copper-containing reaction slag is lower than the lower limit of the set temperature range, the heating function of the reaction device itself or the addition of fuel to the copper-containing reaction slag causes the temperature of the reaction slag to reach a set temperature range; When fuel is injected, a preheated oxidizing gas is simultaneously injected;

当含铜反应熔渣的温度＞设定温度范围上限时，向含铜反应熔渣中加入含铜物料、冶金熔剂、含铁物料或含氟物料中的一种或几种，使混合熔渣的温度达到设定温度范围内；When the temperature of the copper-containing reaction slag is lower than the upper limit of the set temperature range, one or more of the copper-containing material, the metallurgical flux, the iron-containing material or the fluorine-containing material is added to the copper-containing reaction slag to make the mixed slag The temperature reaches the set temperature range;

对应(b)：Corresponding to (b):

当含铜反应熔渣中碱度CaO/SiO₂比值<0.15时，向反应熔渣中加入碱性物料或碱性含铁物料中的一种或几种；When the ratio of alkalinity CaO/SiO ₂ in the copper-containing reaction slag is less than or equal to 0.15, one or more of an alkaline material or an alkaline iron-containing material is added to the reaction slag;

当含铜反应熔渣中碱度CaO/SiO₂比值>1.5时，向反应熔渣中加入酸性物料或酸性含铁物料中的一种或几种；When the ratio of alkalinity CaO/SiO ₂ in the copper-containing reaction slag is >1.5, one or more of an acidic material or an acidic iron-containing material is added to the reaction slag;

步骤2，分离回收：Step 2, separate and recycle:

反应完成后的熔渣，保温5～50min，沉降分离，获得底部熔融态富铜相层、中部熔融态富铁相与上部的熔融态含铁硅酸盐矿物相，同时生成含锌组分与含铅组分的烟尘，金银组分迁移到富铜相，对各项进行如下处理；After the reaction is completed, the slag is kept for 5 to 50 minutes, and the sedimentation is separated to obtain a bottom molten copper-rich phase layer, a central molten iron-rich phase and an upper molten iron-containing silicate mineral phase, and simultaneously form a zinc-containing component and The soot containing lead component, the gold and silver components migrate to the copper-rich phase, and the items are treated as follows;

采用以下方法中的一种：Use one of the following methods:

方法一：采用熔渣可流出熔炼反应装置时，反应完成后的熔渣进行如下步骤：Method 1: When the slag can flow out of the smelting reaction device, the slag after the completion of the reaction is subjected to the following steps:

(1)熔融态含铁硅酸盐矿物相，进行熔渣处理；(1) a molten iron-containing silicate mineral phase, which is subjected to slag treatment;

(2)熔融态富铜相，送往转炉或吹炼炉炼铜或碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜；(2) molten copper-rich phase, sent to converter or blowing furnace for copper smelting or crushing magnetic separation of metal iron and then sent to converter or blowing furnace for copper smelting, or magnetic separation to separate metal iron or without magnetic separation After the metal iron is directly reduced, the reduced product is separated by magnetic separation and then sent to a converter or a blowing furnace for copper smelting;

(3)部分铅组分、锌组分、铟组分、铋组分、钠组分、钾组分挥发，以氧化物形式进入烟尘回收；(3) part of the lead component, the zinc component, the indium component, the strontium component, the sodium component, and the potassium component are volatilized, and are collected into the dust as an oxide;

(4)富铁相进行水淬或空冷或倒入保温装置缓冷或经人工分拣与重选结合获得，作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料或浮选提铜原料或磁选分离金属铁后作为炼铜或直接还原炼铁的原料；浮选产物为含铜精矿与铁精矿，铜精矿返回炼铜***，铁精矿作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料；其中，在直接还原过程中，还原产物磁选分离后，获得金属铁与尾矿，尾矿返回炼铜***；所述直接还原过程采用转底炉、隧道窑、车底路、竖炉、回转窑或感应炉作为还原设备，利用气基或煤基还原技术，气基还原采用天然气和/或煤气，煤基还原采用无烟煤、烟煤、褐煤、焦煤、焦粉或焦炭中的一种或几种，控制还原温度为900～1400℃，控制碱度CaO/SiO₂比值＝0.8～1.5。(4) The iron-rich phase is obtained by water quenching or air cooling or pouring into a heat preservation device, or by manual sorting and re-election, as a raw material for blast furnace ironmaking or direct reduction of ironmaking raw materials or smelting reduction of ironmaking raw materials or flotation Copper raw material or magnetic separation to separate metal iron as raw material for copper smelting or direct reduction ironmaking; flotation products are copper-containing concentrates and iron concentrates, copper concentrates are returned to copper smelting system, iron concentrates are used as blast furnace ironmaking materials or Directly reducing the ironmaking raw material or the smelting reduction ironmaking raw material; wherein, in the direct reduction process, the reduction product is magnetically separated and separated, the metal iron and the tailings are obtained, and the tailings are returned to the copper smelting system; the direct reduction process adopts a rotary hearth furnace , tunnel kiln, vehicle bottom road, shaft furnace, rotary kiln or induction furnace as reducing equipment, using gas-based or coal-based reduction technology, gas-based reduction using natural gas and / or gas, coal-based reduction using anthracite, bituminous coal, lignite, coking coal One or more of coke powder or coke, the controlled reduction temperature is 900-1400 ° C, and the control alkalinity CaO / SiO ₂ ratio = 0.8 ~ 1.5.

其中，步骤(1)中的含铁硅酸盐矿物相，进行熔渣处理，采用方法A～G中的一种：Wherein, the iron-containing silicate mineral phase in the step (1) is subjected to slag treatment, and one of the methods A to G is adopted:

方法A：含铁硅酸盐矿物相作为水泥原料：Method A: Iron-containing silicate mineral phase as cement raw material:

含铁硅酸盐矿物相水淬或空冷直接作为水泥原料或进一步处理成高附加值的水泥原料。The iron-containing silicate mineral phase is directly quenched or air-cooled as a cement raw material or further processed into a high value-added cement raw material.

方法B：部分或全部含铁硅酸盐矿物相返回到所述含铜反应熔渣：Method B: Part or all of the iron-containing silicate mineral phase is returned to the copper-containing reaction slag:

部分或全部含铁硅酸盐矿物相返回到含铜反应熔渣，作为热态冶金熔剂，调整含铜反应熔渣成分，控制含铜反应熔渣温度。Some or all of the iron-containing silicate mineral phase is returned to the copper-containing reaction slag, and as a hot metallurgical flux, the copper-containing reaction slag component is adjusted to control the copper-containing reaction slag temperature.

方法C：含铁硅酸盐矿物相浇筑微晶玻璃或作为矿渣棉。Method C: pouring a glass-ceramic with a ferrite-containing mineral phase or as a slag wool.

方法D：含铁硅酸盐熔渣氧化后空冷或水淬：Method D: Air-cooling or water quenching after oxidation of iron-containing silicate slag:

(1)向熔炼反应装置内的含铁硅酸盐熔渣中，吹入预热的氧化性气体，当熔渣氧化亚铁重量百分比含量<1％，完成熔渣的氧化，获得氧化后的熔渣，其中，氧化性气体的预热温度为0～1200℃；并在整个过程中，保证(c)硅酸盐熔渣温度>1450℃；(1) blowing a preheated oxidizing gas into the iron-containing silicate slag in the smelting reaction device, and when the slag oxidized ferrous oxide content is less than 1%, the slag is oxidized to obtain an oxidized Slag, wherein the preheating temperature of the oxidizing gas is 0 to 1200 ° C; and throughout the process, to ensure (c) silicate slag temperature > 1450 ° C;

对应(c)采用的控制方法：Corresponding to (c) the control method adopted:

当含铁硅酸盐熔渣温度<1450℃，喷入预热燃料与预热的氧化性气体，燃烧放热、补充热量，或装置自身加热，使硅酸盐熔渣温度>1450℃；When the temperature of the iron-containing silicate slag is <1450 ° C, the preheated fuel and the preheated oxidizing gas are injected, the heat is burned, the heat is supplemented, or the device is heated by itself, so that the silicate slag temperature is >1450 ° C;

(2)氧化后的熔渣直接空冷或水淬，用作矿渣水泥、水泥调整剂、水泥生产中的添加剂或水泥熟料。(2) The slag after oxidation is directly air-cooled or water-quenched, and used as slag cement, cement conditioner, additive in cement production or cement clinker.

方法E：含铁硅酸盐熔渣处理生产高附加值的水泥熟料：Method E: Treatment of high value-added cement clinker by treatment with iron silicate slag:

(1)向熔炼反应装置内的含铁硅酸盐熔渣中，加入熔融钢渣、石灰、石灰石、铁合金炉渣、粉煤灰、碱性铁贫矿、铝土矿、熔融高炉渣、赤泥、脱钠后赤泥或电石渣中的一种或几种，充分混合，获得熔渣混合物料；(1) adding molten steel slag, lime, limestone, iron alloy slag, fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, to the iron-containing silicate slag in the smelting reaction device. One or more of red mud or calcium carbide slag after de-sodium removal, thoroughly mixed to obtain a slag mixture;

(2)向熔渣混合物料中吹入预热的氧化性气体，当氧化亚铁重量百分比含量<1％，完成熔渣的氧化，获得氧化后的熔渣，其中，氧化性气体的预热温度为0～1190℃；并在整个过程中，保证(d)熔渣混合物料温度>1440℃；温度控制方法同方法D步骤(1)中的硅酸盐熔渣温度控制方法；(2) blowing a preheated oxidizing gas into the slag mixture, and when the weight percentage of the ferrous oxide is <1%, the oxidation of the slag is completed to obtain the oxidized slag, wherein the oxidizing gas is preheated. The temperature is 0～1190°C; and during the whole process, the (d) slag mixture temperature is >1440° C.; the temperature control method is the same as the silicate slag temperature control method in the method D step (1);

(3)氧化后的熔渣，进行空冷或水淬，制得高附加值的水泥熟料。(3) The slag after oxidation is subjected to air cooling or water quenching to obtain a high value-added cement clinker.

方法F：所述含铁硅酸盐矿物相熔渣作为高炉炼铁原料或直接还原炼铁原料：将含铁硅酸盐矿物相的熔渣空冷、水淬或缓冷后，用作高炉炼铁或直接还原炼铁原料，直接还原后，采用磁选分离或电炉熔分，磁选产物为金属铁与尾矿，电炉熔分，产物为铁水与熔渣；Method F: the iron-containing silicate mineral phase slag is used as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: the slag containing the iron silicate mineral phase is air-cooled, water quenched or slowly cooled, and used as a blast furnace Iron or direct reduction of ironmaking raw materials, after direct reduction, magnetic separation or electric furnace melting, magnetic separation products are metal iron and tailings, electric furnace melting, the product is molten iron and slag;

或将所述含铁硅酸盐矿物相的熔渣倒入保温装置后，采用以下方法进行分离：熔渣改性后磁选分离：向保温装置中的熔渣，吹入0～1200℃的预热的氧化性气体，并保证其熔渣温度>1250℃，完成熔渣中磁铁矿的转化；将上述氧化后的熔渣缓冷至室温，破碎、磁选，产物为磁铁矿精矿与尾矿，尾矿作为建筑材料。Or after pouring the slag containing the iron silicate mineral phase into the heat preservation device, the separation is performed by the following method: magnetic separation after slag modification: slag flowing into the heat preservation device, blowing 0-1200 ° C Preheating the oxidizing gas, and ensuring that the slag temperature is >1250 ° C, completing the transformation of magnetite in the slag; slowly cooling the oxidized slag to room temperature, crushing, magnetic separation, and the product is magnetite Mines and tailings, tailings as building materials.

方法G：含铁硅酸盐熔渣熔融还原炼铁：Method G: Iron-containing silicate slag smelting reduction ironmaking:

(1)将含铁硅酸盐熔渣保留在熔炼反应装置内或将熔渣倒入保温装置，向熔融态熔渣加入含铁物料，还原剂，进行熔融还原，实时监测反应熔渣，通过调控同时保证如下(a)和(b)两个参数，获得反应完成后的熔渣；(1) Retaining the iron-containing silicate slag in the smelting reaction device or pouring the slag into the heat preservation device, adding the iron-containing material to the molten slag, reducing the agent, performing the smelting reduction, and monitoring the reaction slag in real time. The control simultaneously ensures the following two parameters (a) and (b), and obtains the slag after the completion of the reaction;

(a)反应熔渣的温度为1350～1650℃；(a) the temperature of the reaction slag is 1350 ~ 1650 ° C;

(b)反应熔渣的碱度CaO/SiO₂比值＝0.6～2.4； (b) the alkalinity of the reaction slag CaO / SiO ₂ ratio = 0.6 ~ 2.4;

调控方法为：The control method is:

对应(a)：Corresponding to (a):

当反应熔渣的温度＜设定温度范围下限1350℃时，通过反应装置自身的加热功能，或向熔渣中加入燃料与预热的氧化性气体，使反应熔渣的温度达到设定温度范围1350～1650℃内；When the temperature of the reaction slag < lower limit of the set temperature range is 1350 ° C, the temperature of the reaction slag reaches the set temperature range by the heating function of the reaction device itself or by adding the fuel and the preheated oxidizing gas to the slag. Within 1350 ~ 1650 ° C;

当反应熔渣的温度＞设定温度范围上限1650℃时，向反应熔渣中加入冶金熔剂、含铁物料或含氟物料中的一种或几种，使反应熔渣的温度达到设定温度范围1350～1650℃内；When the temperature of the reaction slag > the upper limit of the set temperature range is 1650 ° C, one or more of a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag to bring the temperature of the reaction slag to a set temperature. The range is from 1350 to 1650 ° C;

对应(b)：Corresponding to (b):

(2)向熔渣中喷吹预热后的氧化性气体进行熔融还原，形成还原后的熔渣，其中：氧化性气体的预热温度为0～1200℃，并在喷吹过程中，通过调控同时保证(a)和(b)两个参数：(2) smelting and reducing the oxidizing gas after preheating into the slag to form a reduced slag, wherein: the oxidizing gas is preheated at a temperature of 0 to 1200 ° C, and is passed during the blowing process. Regulation also guarantees two parameters (a) and (b):

(a)反应完成后的熔渣的温度为1350～1650℃；(a) the temperature of the slag after completion of the reaction is 1350 ~ 1650 ° C;

(b)反应完成后的熔渣的碱度CaO/SiO₂比值＝0.6～2.4；(b) the alkalinity of the slag after the completion of the reaction CaO / SiO ₂ ratio = 0.6 ~ 2.4;

其中，设定温度范围和碱度调控方法同方法G步骤(1)；Wherein, the temperature range and the alkalinity control method are the same as the method G step (1);

(3)分离回收：(3) Separation and recovery:

采用以下方法中的一种：Use one of the following methods:

方法Ⅰ：进行如下步骤：Method I: Perform the following steps:

(a)冷却：将还原后的混合熔渣倒入保温渣罐，冷却至室温，获得缓冷渣；(a) cooling: the reduced mixed slag is poured into a holding slag pot, and cooled to room temperature to obtain a slow cooling slag;

(b)分离：金属铁沉降到反应装置的底部，形成铁坨，人工取出铁坨；将剩余缓冷渣中含金属铁层，破碎至粒度20～400μm，磨矿，磁选分离出剩余金属铁与尾矿；(b) Separation: metal iron is settled to the bottom of the reaction device to form iron shovel, and the iron shovel is manually taken out; the metal ferrous layer in the remaining slow slag is crushed to a particle size of 20 to 400 μm, and the remaining metal is separated by magnetic separation. Iron and tailings;

(c)尾矿的回收利用，作为水泥原料、建筑材料、代替碎石作骨料、路材使用；(c) recycling of tailings, used as cement raw materials, building materials, instead of crushed stone as aggregates and road materials;

方法Ⅱ：进行如下步骤：Method II: Perform the following steps:

(a)还原后的混合熔渣，冷却沉降，渣-金分离，获得铁水与还原后的熔渣；(a) the mixed slag after reduction, cooling and sedimentation, separation of slag-gold, obtaining molten iron and reduced slag;

(b)还原后的熔渣，进行炉外熔渣处理，具体方式为：采用步骤2的分离回收方法一中的方法A～E中的一种或几种，进行熔渣处理；(b) the slag after the reduction, the slag treatment outside the furnace, the specific method is: using one or more of the methods A to E in the separation and recovery method 1 of the step 2, the slag treatment;

(c)铁水，送往转炉或电炉炼钢；(c) molten iron, sent to converter or electric furnace steelmaking;

(d)含锌组分与含铅组分挥发，以氧化物形式进入烟尘回收；(d) the zinc-containing component and the lead-containing component are volatilized, and are collected into the dust as an oxide;

(e)部分铟组分、铋组分、钠组分、钾组分挥发进入烟尘；(e) part of the indium component, the bismuth component, the sodium component, and the potassium component are volatilized into the soot;

(f)还原产生的煤气在熔渣表面二次燃烧，提供了热量，而且由炉内流出的煤气可以作为烘干炉料与保温装置的热源；(f) The gas produced by the reduction is secondarily burned on the surface of the slag to provide heat, and the gas flowing out of the furnace can be used as a heat source for the drying furnace material and the heat preservation device;

方法二：采用熔渣可流出的熔炼反应装置时，反应完成后的熔渣进行如下步骤：Method 2: When the smelting reaction device through which the slag can flow out is used, the slag after the completion of the reaction is subjected to the following steps:

(1)熔融态富铜相，送往转炉炼铜或吹炼炉炼铜，或碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜；(1) molten copper-rich phase, sent to converter copper or bake furnace for copper smelting, or crushed magnetic separation of metal iron and then sent to converter or blowing furnace for copper smelting, or magnetic separation of metal iron or not After magnetic separation of metal iron, direct reduction, the reduction product is magnetically separated to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting;

(2)熔融态富铁相层与含铁硅酸盐矿物相采用处理方法用方法一中所述方法A～G中一种或几种进行处理；(2) The molten iron-rich phase layer and the iron-containing silicate mineral phase are treated by one or more of the methods A to G described in the first method;

(3)部分含锌组分与含铅组分挥发，以氧化物形式进入烟尘回收；(3) part of the zinc-containing component and the lead-containing component volatilize, and enter the soot recovery in the form of oxide;

(4)部分铟组分、铋组分、钠组分、钾组分挥发进入烟尘。 (4) Some of the indium, antimony, sodium and potassium components are volatilized into the soot.

方法三：采用熔渣可转动的转炉与反应渣罐时，反应完成后的熔渣进行如下步骤：Method 3: When the slag rotatable converter and the reaction slag tank are used, the slag after the reaction is completed is carried out as follows:

(1)熔融态含铁硅酸盐矿物相，进行熔渣处理，具体处理方式为：采用步骤2的分离回收方法一中的方法A～G中的一种或几种进行熔渣处理；含有所述富铁相采用方法一中的步骤(4)进行处理；(1) The molten iron-containing silicate mineral phase is subjected to slag treatment, and the specific treatment method is: one or more of the methods A to G in the separation and recovery method 1 of the step 2 is used for slag treatment; The iron-rich phase is treated by the step (4) in the first method;

(2)熔融态富铜相或倒入保温装置缓冷后，送往转炉或吹炼炉炼铜，或碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜；(2) After the molten copper-rich phase is poured into the heat preservation device and slowly cooled, it is sent to a converter or a blowing furnace for copper smelting, or the metal iron is separated by crushing and magnetic separation, and then sent to a converter or a blowing furnace for copper smelting, or magnetic separation. Separating metal iron or separating metal iron without magnetic separation, directly reducing, reducing product by magnetic separation to separate metal iron, and then sending it to converter or blowing furnace for copper smelting;

(3)部分铟组分、铋组分、钠组分、钾组分挥发进入烟尘回收；(3) Part of the indium, antimony, sodium and potassium components are volatilized into the soot recovery;

方法四：采用熔渣可转动的转炉与反应渣罐时，反应完成后的熔渣进行如下步骤：Method 4: When the slag rotatable converter and the reaction slag tank are used, the slag after the reaction is completed is as follows:

(1)熔融态含铁硅酸盐矿物相与富铁相，进行熔渣处理，具体方式为：采用步骤2的分离回收方法一中的方法A～G中的一种或几种进行处理；(1) The molten iron-containing silicate mineral phase and the iron-rich phase are subjected to slag treatment in a specific manner: one or more of the methods A to G in the separation and recovery method 1 of the step 2 are used;

(2)熔融态富铜相，送往转炉或吹炼炉炼铜，或缓冷后碎磁选分离金属铁后再送往转炉或吹炼炉炼铜或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜；(2) molten copper-rich phase, sent to converter or blowing furnace for copper smelting, or slow cooling, crushed magnetic separation of metal iron and then sent to converter or blowing furnace for copper smelting or magnetic separation to separate metal iron or not After magnetic separation of metal iron, direct reduction, the reduction product is magnetically separated to separate metal iron, and then sent to a converter or a blowing furnace for copper smelting;

(3)部分铟组分、铋组分、钠组分、钾组分挥发进入烟尘氧化物进入烟尘；(3) part of the indium, antimony, sodium and potassium components volatilize into the soot oxide into the soot;

方法五：采用保温装置时，或采用熔渣可流出的熔炼反应装置，将熔渣倒入保温装置时，反应完成后的熔渣进行如下步骤：Method 5: When using a heat preservation device, or using a smelting reaction device through which slag can flow out, when the slag is poured into the heat preservation device, the slag after the reaction is completed is as follows:

(1)沉降冷却：反应完成后的熔渣冷却至室温，获得缓冷渣；富铜相沉降到反应装置的底部，形成富铜坨；含铁硅酸盐矿物相上浮；富铜相和含铁硅酸盐矿物中间的缓冷渣为富铁相，同时生成含锌组分与含铅组分；金银组分迁移到富铜相；(1) Settling cooling: the slag after the completion of the reaction is cooled to room temperature to obtain slow cooling slag; the copper-rich phase is settled to the bottom of the reaction device to form a copper-rich bismuth; the iron-containing silicate mineral phase is floated; the copper-rich phase and the The slow cooling slag in the middle of the iron silicate mineral is an iron-rich phase, and simultaneously forms a zinc-containing component and a lead-containing component; the gold-silver component migrates to the copper-rich phase;

(2)分离：人工取出沉降在底部的富铜坨，磁选分离金属铁后再送往转炉或吹炼炉炼铜，或碎磁选分离金属铁后再送往转炉或吹炼炉炼铜，或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜；中部的富铁相层作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料或浮选提铜原料或磁选分离金属铁后作为炼铜或直接还原的原料；在浮选过程中，浮选产物为含铜精矿与铁精矿，铜精矿返回炼铜***，铁精矿作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料；其中，在直接还原过程中，还原产物磁选分离后，获得金属铁与尾矿，尾矿返回炼铜***；所述直接还原过程采用转底炉、隧道窑、车底路、竖炉、回转窑或感应炉作为还原设备，利用气基或煤基还原技术，气基还原采用天然气和/或煤气，煤基还原采用无烟煤、烟煤、褐煤、焦煤、焦粉或焦炭中的一种或几种，控制还原温度为900～1400℃，控制碱度CaO/SiO₂比值＝0.8～1.5；(2) Separation: manually take out the copper-rich bismuth deposited at the bottom, magnetically separate the metal iron and then send it to the converter or the smelting furnace for copper smelting, or separate the metal iron by crushing and then send it to the converter or the smelting furnace for copper smelting. , or magnetic separation of metal iron or magnetic separation without metal separation, direct reduction, reduction products after magnetic separation of metal iron, and then sent to converter or blowing furnace copper; the iron-rich phase layer in the middle as a blast furnace The ironmaking raw material or the direct reduction ironmaking raw material or the smelting reduction ironmaking raw material or the flotation copper extraction raw material or the magnetic separation and separation of the metallic iron is used as a raw material for copper smelting or direct reduction; in the flotation process, the flotation product is copper-containing fine Mine and iron concentrate, copper concentrate returned to copper smelting system, iron concentrate as blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material; wherein, in the direct reduction process, after the reduction product is magnetically separated, Obtaining metal iron and tailings, and tailings returning to the copper smelting system; the direct reduction process adopts a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary kiln or an induction furnace as a reduction device, and uses a gas-based or coal-based reduction Technology, gas-based reduction using days Gas and / or gas, coal-based reduced using one or more of anthracite, bituminous coal, lignite, coke, coke breeze or coke, controlled reduction temperature is 900 ~ 1400 ℃, controlling basicity CaO / SiO ₂ ratio = 0.8 1.5;

(3)人工取出上部的含铁硅酸盐矿物相，作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料或作为水泥原料、建筑材料、代替碎石作骨料、路材使用；(3) Manually take out the upper iron-containing silicate mineral phase as a blast furnace ironmaking raw material or directly reduce ironmaking raw materials or smelting reduction ironmaking raw materials or as cement raw materials, building materials, instead of crushed stone as aggregates and road materials. ;

(4)部分铅组分、锌组分、铟组分、铋组分、钠组分、钾组分挥发进入烟尘氧化物进入烟尘。(4) Some lead components, zinc components, indium components, antimony components, sodium components, and potassium components volatilize into soot oxides and enter the soot.

如上所述的方法，优选地，所述的步骤1与2中，所述铜渣是含铜熔炼渣、含铜吹炼渣、铜火法贫化弃渣、浮选尾渣、湿法炼铜渣中一种或几种，其中，所述含铜熔炼渣产生于铜的火法冶炼工艺的“造锍熔炼”过程，所述含铜吹炼渣产生于铜的火法冶炼工艺的“铜锍吹炼”过程，所述贫化弃渣为含铜熔炼渣与含铜吹炼渣贫化后弃渣，所述浮选尾渣为含铜熔炼渣与含铜吹炼渣选矿后尾渣，所述湿法炼铜渣产生于湿法炼铜工艺； In the method as described above, preferably, in the steps 1 and 2, the copper slag is a copper-containing smelting slag, a copper-containing blowing slag, a copper fire-depleted slag, a flotation tailings, a wet process One or more of copper slag, wherein the copper-containing smelting slag is produced in a "smelting smelting" process of copper pyrometallurgical smelting process, and the copper-containing blowing slag is produced in a copper smelting process" In the process of copper blasting, the depleted waste slag is a copper smelting slag and a copper smelting slag, and the slag is depleted, and the flotation tailing slag is a copper smelting slag and a copper smelting slag. The slag, the wet copper slag is produced in a wet copper smelting process;

所述的步骤1与2中，铜熔炼渣、铜吹炼渣与贫化弃渣为熔融态或冷态，其中：熔融铜熔炼渣由“造锍熔炼”过程的含铜熔炼炉出渣口获得，或将含铜熔炼渣加热至熔融状态，熔融铜吹炼渣由“铜锍吹炼”过程的铜吹炼炉出渣口获得，或将铜吹炼渣加热至熔融状态，贫化弃渣由贫化炉出渣口获得，获将贫化渣加热至熔融状态。In the steps 1 and 2, the copper smelting slag, the copper smelting slag and the depleted slag are in a molten state or a cold state, wherein: the molten copper smelting slag is from the smelting smelting furnace of the smelting smelting process Obtaining, or heating the copper-containing smelting slag to a molten state, the molten copper blowing slag is obtained from the copper smelting furnace slag opening of the "copper smelting" process, or heating the copper smelting slag to a molten state, depleted and discarded The slag is obtained from the slag outlet of the depleted furnace, and the depleted slag is heated to a molten state.

所述的步骤1与2中，可采用熔渣可流出的熔炼反应装置为可转动的熔炼反应装置或带有渣口或铁口的熔炼反应装置；其中：In the steps 1 and 2, the smelting reaction device through which the slag can flow out can be a smelting reaction device or a smelting reaction device with a slag port or an iron port; wherein:

所述保温装置为可倾倒的熔炼反应渣灌、保温地坑；The heat preservation device is a pourable smelting reaction slag irrigation and insulation pit;

如上所述的方法，优选地，所述的步骤1中，钙系矿物具体为石灰、石灰石、白云石、电石渣、赤泥或脱钠后高钙赤泥中的一种或几种；添加剂为SiO₂、MgO、FeO、Fe₂O₃、MnO₂、Al₂O₃、TiO₂、Fe或Na₂O中的一种或几种；In the method as described above, preferably, in the step 1, the calcium-based mineral is specifically one or more of lime, limestone, dolomite, calcium carbide slag, red mud or post-sodium high calcium red mud; Is one or more of SiO ₂ , MgO, FeO, Fe ₂ O ₃ , MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O;

所述的步骤1中，通过调控同时保证如下(a)和(b)两个参数，同时保证熔渣中铜氧化物和铁氧化物还原为金属铜和FeO，熔渣中金属铁含量<3％。可通过加入还原剂、含碳的含铁物料中的一种或两种，其中，熔渣中还原剂和/或含碳的含铁物料的的用量为熔渣中铜和铁氧化物还原为金属铜和FeO的理论量110～140％；所述含碳的含铁物料为钢铁尘泥与烟灰、铁精矿含碳预还原球团、铁精矿含碳金属化球团、湿法炼锌挥发窑渣或焦炭炉尘泥与烟灰。In the step 1, the two parameters (a) and (b) are ensured at the same time, and at the same time, the copper oxide and the iron oxide in the slag are reduced to metal copper and FeO, and the metal iron content in the slag is <3. %. By adding one or both of a reducing agent and a carbon-containing iron-containing material, wherein the amount of the reducing agent and/or the carbon-containing iron-containing material in the slag is reduced to copper and iron oxide in the slag The theoretical amount of metallic copper and FeO is 110-140%; the carbon-containing iron-containing material is steel dust and soot, iron concentrate carbon-containing pre-reduction pellet, iron concentrate carbon-containing metallized pellet, wet process Zinc volatilization slag or coke oven dust and soot.

所述的步骤1与2中，所述的燃料与还原剂为固体、液体或气体燃料中的一种或多种，以喷吹或投料的方式喷入，载入气体为预热的氧化性气体、氮气、氩气中的一种或几种，预热温度0～1200℃；固体燃料与还原剂为煤粉、焦粉、焦炭、粉煤灰、烟煤或无烟煤中的一种或多种，形状为粒状或粉状，粒状物料粒度为5～25mm，粉状物料粒度为≤150μm，液体燃料与还原剂为重油，气体燃料与还原剂为煤气和/或天然气；In the steps 1 and 2, the fuel and the reducing agent are one or more of a solid, liquid or gaseous fuel, which is sprayed or charged, and the loaded gas is preheated and oxidized. One or more of gas, nitrogen and argon, preheating temperature 0～1200°C; solid fuel and reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite The shape is granular or powdery, the granular material has a particle size of 5 to 25 mm, the powdery material has a particle size of ≤150 μm, the liquid fuel and the reducing agent are heavy oil, and the gaseous fuel and the reducing agent are gas and/or natural gas;

所述的步骤1与2中含铜物料是铜渣、选铜尾矿、粗铜火法精炼渣、锌冶炼渣、含铅炉渣、镍冶炼渣、铅冰铜、砷冰铜、粗铅火法精炼渣含铅烟化炉渣、含铅烟灰、铅酸电池、含铜烟灰、杂铜、含铜垃圾或含铜电路板中的一种或几种；所述铜渣是含铜熔炼渣、含铜吹炼渣、铜火法贫化弃渣、浮选尾渣、湿法炼铜渣中一种或几种；含铅炉渣为烟化炉炉渣与含铅熔炼渣、“ISP铅锌鼓风炉还原”或“烧结矿鼓风炉还原”或“固态高铅渣还原”或“液态高铅渣还原工艺”还原工艺产生的含铅熔炼渣，含铅熔炼渣通过烟化炉冶炼产生含铅烟化炉渣；镍冶炼渣是“造锍熔炼”工艺产生的镍熔炼渣、“铜冰镍吹炼”工艺吹炼后的贫化炉渣、顶吹熔炼产生的镍沉降炉渣中一种或多种；锌冶炼炉渣包括湿法炼锌产生的炉渣与湿法炼锌产生的炉渣，其中湿法炼锌产生的炉渣是锌浸出渣、挥发窑渣、铁矾渣、酸洗后铁矾渣、针铁矿渣、赤铁矿渣一种或多种，竖罐炼锌是竖罐炼锌炉渣、旋涡熔炼炉渣、鼓风炉炉渣，电炉渣一种或多种；The copper-containing materials in steps 1 and 2 are copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, lead-containing slag, nickel smelting slag, lead ice copper, arsenic matte, and crude lead fire. Method for refining slag containing lead slag slag, lead-containing soot, lead-acid battery, copper-containing soot, copper-containing, copper-containing garbage or copper-containing circuit board; the copper slag is copper-containing smelting slag, One or more of copper-containing blowing slag, copper fire depleted slag, flotation tailings, and wet copper slag; lead-containing slag as smelting furnace slag and lead-containing smelting slag, "ISP lead-zinc blast furnace Lead-containing smelting slag produced by reduction or "sinter blast furnace reduction" or "solid high-lead slag reduction" or "liquid high-lead slag reduction process" reduction process, lead-containing smelting slag is smelted by a smelting furnace to produce lead-containing smelting furnace slag Nickel smelting slag is one or more of nickel smelting slag produced by "smelting smelting" process, depleted slag after blowing by "copper ice nickel blowing" process, and nickel slag slag produced by top blowing smelting; zinc smelting The slag includes slag produced by wet zinc smelting and slag produced by wet zinc smelting, wherein the furnace produced by wet zinc smelting It is zinc leaching residue, volatile kiln residue, iron slag residue, pickled iron slag, goethite slag, hematite slag one or more, vertical tank zinc smelting is vertical tank zinc slag, vortex melting furnace slag, One or more of blast furnace slag and electric furnace slag;

所述的步骤1与2中冶金熔剂为含CaO或SiO₂的矿物，具体为石英砂、含金银石英砂、赤泥、脱钠后高钙赤泥、电石渣、白云石或石灰石中的一种或几种。The metallurgical flux in the steps 1 and 2 is a mineral containing CaO or SiO ₂ , specifically quartz sand, gold-silver-sand quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone. One or several.

如上所述的方法，优选地，所述的1与2中含铁物料是普通铁精矿、普通铁精矿直接还原铁，普通铁精矿烧结矿、普通铁精矿球团矿、普通铁精矿金属化球团、普通铁精矿含碳预还原球团、钢渣、锌冶炼渣、焦炭冶炼烟尘与尘泥、钢铁烟尘与尘泥、含镍冶炼渣、铅冶炼渣、铜渣、锡冶炼渣、赤泥、脱钠后高钙赤泥、煤粉灰、硫酸烧渣中的一种或几种；所述钢铁烟尘与尘泥包括高炉瓦斯泥、转炉尘泥、电炉尘泥、热(冷)轧污泥、烧结粉尘、球团粉尘、出铁厂集尘、高炉瓦斯灰、电炉除尘灰、轧钢氧化铁皮；所述含铜物料与含铁物料为热态或冷态，其中热态物料由冶金炉出料口或出渣口直接获得。In the method as described above, preferably, the iron-containing materials in the 1 and 2 are ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron. Concentrate metallized pellets, ordinary iron concentrates, carbon pre-reduction pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel-containing smelting slag, lead smelting slag, copper slag, tin Smelting slag, red mud, high calcium red mud after desodiumification, coal dust ash, One or more of sulfuric acid slag; the steel dust and dust including blast furnace gas mud, converter dust mud, electric furnace dust mud, hot (cold) rolling sludge, sintering dust, pellet dust, iron pipe factory Dust, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale; the copper-containing material and the iron-containing material are hot or cold, wherein the hot material is directly obtained from the metallurgical furnace discharge port or the slag outlet.

所述湿法炼锌渣与尘泥需经脱水、干燥。The wet zinc slag and dust are subjected to dehydration and drying.

在上述的原料中，锌冶炼渣与烟灰、铅冶炼渣与烟灰含有铟与铋、铅、银、锌、铋；赤泥中含有钠与钾，钢铁烟尘与尘泥含有铟、铋、银、钠与钾，以上物料都有铁，铅冶炼渣与锌冶炼渣都含有铜，铜烟灰与尘泥含有铟与铋，因此在发明的方法中，铟、铋、钠、钾、锌、铅会以氧化物的形式进入烟尘，从而进行回收。Among the above raw materials, zinc smelting slag and soot, lead smelting slag and soot contain indium and antimony, lead, silver, zinc and antimony; red mud contains sodium and potassium, and steel soot and dust contain indium, antimony and silver. Sodium and potassium, the above materials all have iron, lead smelting slag and zinc smelting slag contain copper, copper soot and dust contain indium and antimony, so in the method of the invention, indium, antimony, sodium, potassium, zinc, lead will The fumes are entered in the form of oxides for recycling.

所述的1与2中含氟物料是萤石、CaF₂或含氟高炉渣中的一种或几种；The fluorine-containing materials in 1 and 2 are one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag;

所述的步骤1与2中，含铜物料、含铁物料和含氟物料均为球团或粉状物料或制粒；其中，粉状物料的粒度≤150μm，粒状物料粒度为5～25mm，粉状物料以喷吹的方式喷入，粒状物料以喷吹或投料的方式加入,载入气体为预热的氩气、氮气、还原性气体(煤气和/或天然气)、氧化性气体中的一种或多种，预热温度0～1200℃；所述的喷吹方式为采用耐火喷枪***熔渣或置于反应熔渣上部或侧面或底部吹入中的一种或几种。In the steps 1 and 2, the copper-containing material, the iron-containing material and the fluorine-containing material are pellets or powdery materials or granulation; wherein, the granular material has a particle size of ≤150 μm, and the granular material has a particle size of 5 to 25 mm. The powdery material is sprayed by spraying, and the granular material is added by spraying or feeding, and the loading gas is preheated argon gas, nitrogen gas, reducing gas (gas and/or natural gas), oxidizing gas. One or more preheating temperatures of 0 to 1200 ° C; the blowing method is one or more of inserting slag into a slag by using a refractory lance or placing it in an upper portion or a side or bottom of the reaction slag.

所述的步骤1与2中，熔渣反应过程中，熔渣中铜组分、金银组分富集于富铜相，并实现聚集、长大与沉降，铁组分富集于富铁相，实现聚集、长大与沉降，熔渣中锌组分、铅组分分别进入烟尘，其中烟灰中以氧化锌与氧化铅形式回收，其中，富铜相包括有铜、白冰铜、冰铜相、含铁组分中的多种，或部分铜组分进入富铁相，富铁相包括金属铁、FeO相、铁橄榄石相中的多种，作为高炉炼铁或直接还原或熔融还原炼铁的原料；In the steps 1 and 2, during the slag reaction, the copper component and the gold and silver components in the slag are enriched in the copper-rich phase, and aggregation, growth and sedimentation are achieved, and the iron component is concentrated in the iron-rich phase. The phase, the aggregation, the growth and the sedimentation, the zinc component and the lead component in the slag respectively enter the soot, wherein the soot is recovered in the form of zinc oxide and lead oxide, wherein the copper-rich phase includes copper, white ice copper, ice. a plurality of copper phases, iron-containing components, or part of the copper component enters the iron-rich phase, and the iron-rich phase includes a plurality of metal iron, FeO phase, and fayalite phase, as blast furnace ironmaking or direct reduction or smelting reduction Iron raw material;

所述的步骤1中控制混合熔渣的温度在设定温度范围的方法中：In the step 1 described above, the method of controlling the temperature of the mixed slag in the set temperature range is as follows:

当混合熔渣的温度＞设定温度上限时，加入含铜物料、冶金熔剂、含铁物料或含氟物料中的一种或几种，目的是避免温度过高，保护耐火材料；加入含氟物料的另一个作用是降低粘度，加速熔渣中富铜相、富冰铜相、富铁相的聚集、长大与沉降。When the temperature of the mixed slag is > the upper limit of the set temperature, one or more of the copper-containing material, the metallurgical flux, the iron-containing material or the fluorine-containing material is added, in order to avoid the excessive temperature and protect the refractory material; Another function of the material is to reduce the viscosity and accelerate the accumulation, growth and sedimentation of the copper-rich phase, the ice-rich copper phase, and the iron-rich phase in the slag.

所述步骤1与2中，调整碱度时，所述的碱性物料为石灰粉、赤泥、脱钠后高钙赤泥、电石渣、白云石粉或生石灰粉中的一种或几种；所述的碱性含铁物料为CaO/SiO₂>1的含铁物料、碱性烧结矿、碱性铁精矿、铁合金炉渣、钢渣、碱性预还原球团、碱性金属化球团、钢渣或高炉渣中的一种或几种。In the steps 1 and 2, when the alkalinity is adjusted, the alkaline material is one or more of lime powder, red mud, high calcium red mud after desoda, calcium carbide slag, dolomite powder or quicklime powder; The alkaline iron-containing material is a CaO/SiO ₂ >1 iron-containing material, an alkaline sintered ore, an alkaline iron concentrate, a ferroalloy slag, a steel slag, an alkaline pre-reduction pellet, an alkali metallized pellet, One or more of steel slag or blast furnace slag.

所述步骤1与2中，调整碱度时，所述的酸性物料为硅石、粉煤灰、煤矸石中的一种或多种；所述的酸性含铁物料为CaO/SiO₂≤1的含铁物料，酸性烧结矿、酸性铁精矿、酸性预还原球团、酸性金属化球团、铜渣、含铅炉渣、锌冶炼渣、镍冶炼渣、锡冶炼渣、铁合金渣、高炉渣中的一种或几种；In the steps 1 and 2, when the alkalinity is adjusted, the acidic material is one or more of silica, fly ash and coal gangue; the acidic iron-containing material is CaO/SiO ₂ ≤1. Iron-containing materials, acid sinter, acid iron concentrate, acid pre-reduction pellets, acid metallized pellets, copper slag, lead-containing slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, blast furnace slag One or several

所述的步骤1与2中，保证(a)和(b)两个参数的同时，使熔渣充分混合，混合方式为自然混合或搅拌混合，搅拌方式为氩气搅拌、氮气搅拌、氮气-氩气混合气搅拌、还原性气体搅拌、氧化性气体、电磁搅拌、机械搅拌中的一种或多种；In the steps 1 and 2, the two parameters of (a) and (b) are ensured, and the slag is thoroughly mixed, and the mixing mode is natural mixing or stirring mixing, and the stirring mode is argon stirring, nitrogen stirring, nitrogen- One or more of argon gas mixture agitation, reducing gas agitation, oxidizing gas, electromagnetic stirring, and mechanical agitation;

所述的步骤1与2中，熔渣中富铜相、富铁相聚集、长大与沉降，有利于硅酸盐上浮；In the steps 1 and 2, the copper-rich phase and the iron-rich phase in the slag are aggregated, grown and settled, which is favorable for the silicate to float;

所述的步骤1与2中，氧化性气体为预热的空气、氧气、富氧空气、氩气-空气、氩气-氧气、氮气-空气、氮气-氧气中的一种，预热温度0～1200℃，喷吹方式为采用耐火喷枪***熔渣或置于反应熔渣上部或侧面或底部吹入中的一种或几种。In the steps 1 and 2, the oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, argon-air, argon-oxygen, nitrogen-air, nitrogen-oxygen, and the preheating temperature is 0. ～1200°C, the blowing method is one or several types in which a refractory spray gun is inserted into the slag or placed in the upper part or the side or bottom of the reaction slag.

如上所述的方法，优选地，所述步骤2中，直接还原过程采用转底炉、隧道窑、车底路、竖炉、回转窑或感应炉作为还原设备，利用气基或煤基还原技术，气基还原为天然气和/或煤气，煤基还原为无烟煤、烟煤、褐煤、焦煤、焦粉或焦炭中的一种或几种，还原温度为900～1400℃，碱度CaO/SiO₂比值＝0.8～1.5；In the method as described above, preferably, in the step 2, the direct reduction process uses a rotary hearth furnace, a tunnel kiln, a vehicle bottom road, a shaft furnace, a rotary kiln or an induction furnace as a reduction device, using a gas-based or coal-based reduction technique. The gas base is reduced to natural gas and/or gas, and the coal base is reduced to one or more of anthracite, bituminous coal, lignite, coking coal, coke breeze or coke, the reduction temperature is 900-1400 ° C, and the alkalinity CaO/SiO ₂ ratio =0.8~1.5;

所述步骤2中，冷却方式为自然冷却或旋转冷却或离心冷却，沉降方式为自然沉降或旋转沉降或离心沉降；In the step 2, the cooling mode is natural cooling or rotary cooling or centrifugal cooling, and the sedimentation mode is natural sedimentation or rotary sedimentation or centrifugal sedimentation;

所述步骤2中，旋转与离心的具体操作为：装有反应完成后的熔渣的装置置于旋转平台上，按照一定速度进行旋转，旋转速度依熔渣质量与保温装置高度或深度而定，旋转时间依熔渣质量与熔渣凝固情况而定；将装有反应完成后的熔渣的装置置于旋转平台上旋转，目的是加速富铜相、富铁相聚集、长大与沉降，有利于硅酸盐上浮，缩短沉降时间，改善沉降效果，提高生产效率。In the step 2, the specific operation of the rotation and the centrifugation is: the device containing the slag after the reaction is completed is placed on the rotating platform and rotated according to a certain speed, and the rotation speed depends on the quality of the slag and the height or depth of the heat preservation device. The rotation time depends on the quality of the slag and the solidification of the slag; the device containing the slag after the completion of the reaction is placed on the rotating platform for the purpose of accelerating the accumulation of the copper-rich phase, the iron-rich phase, growth and sedimentation, It is beneficial to silicate floating, shortening settlement time, improving sedimentation effect and improving production efficiency.

所述步骤2中，反应完成后的熔渣冷却过程中，由于密度不同与矿物大小不同，大部分富铜相、富铁相沉降于中下部。In the step 2, during the slag cooling process after the completion of the reaction, most of the copper-rich phase and the iron-rich phase settle in the middle and lower portions due to the difference in density and the size of the mineral.

所述步骤2中，反应完成后的熔渣中铜组分、金银组分继续迁移、富集于富铜相，实现长大与沉降，或部分富集于富铁相；混合熔渣中铁组分继续迁移、富集于富铁相，并实现长大与沉降。In the step 2, the copper component and the gold and silver component in the slag after the reaction is completed to migrate, enriched in the copper-rich phase, to achieve growth and sedimentation, or partially enriched in the iron-rich phase; iron in the mixed slag The components continue to migrate, enrich in the iron-rich phase, and achieve growth and sedimentation.

所述步骤2中，重力分选法是摇床分选、溜槽分选或者二者相结合。In the step 2, the gravity sorting method is a shaker sorting, a chute sorting, or a combination of the two.

采用本发明的方法，最后获得的渣含铜≤0.1％，铁的回收率为≥91％，锌的回收率为≥92％，铅的回收率为≥92％，金的富集率为≥94％，银的富集率为≥94％。By adopting the method of the invention, the finally obtained slag contains copper ≤0.1%, the iron recovery rate is ≥91%, the zinc recovery rate is ≥92%, the lead recovery rate is ≥92%, and the gold enrichment rate is ≥ 94%, the silver enrichment rate is ≥94%.

为了更好的解释本发明，以便于理解，通过具体实施方式，对本发明作详细描述。其中，以下实施例中所用检测方法与原料未明确指出的，均可采用本领域常规技术，除非另有说明，本发明中所用的百分数均为重量百分数。The invention will be described in detail by way of specific embodiments in order to explain the invention. Wherein, the detection methods and raw materials used in the following examples are not specifically indicated, and the conventional techniques in the art can be employed. Unless otherwise stated, the percentages used in the present invention are all by weight.

以下实施例1～10中的步骤(1)熔渣混合时，通过调控保证的(a)和(b)两个参数具体为：In the following steps (1) in the following examples 1 to 10, when the slag is mixed, the two parameters (a) and (b) which are guaranteed by the regulation are specifically:

(a)含铜与铁的反应熔渣的温度为1100～1450℃；(a) The temperature of the reaction slag containing copper and iron is 1100 ~ 1450 ° C;

(b)含铜与铁的反应熔渣碱度CaO/SiO₂比值＝0.15～1.5。(b) Reaction slag basicity CaO/SiO ₂ ratio of copper and iron = 0.15 to 1.5.

实施例1Example 1

一种由含铜熔渣回收有价组分的方法，包括以下步骤：A method for recovering valuable components from copper-containing slag, comprising the steps of:

步骤1，炉渣混合：Step 1, slag mixing:

将由“造锍熔炼”工艺熔炼炉出渣口获得的含铜熔炼渣、“铜鋶吹炼”工艺吹炼炉出渣口获得的含铜吹炼渣加入直流电弧炉，同时加入石灰，以及SiO₂、MgO、Al₂O₃，形成混合熔渣；将混合熔渣加热至熔融状态，形成含铜反应熔渣，并使反应熔渣实现自然混合；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得反应完成后的熔渣；对应(a)：含铜反应熔渣的温度为1660℃，采用耐火喷枪***反应熔渣中，以氮气为载入气，喷入常温粉状粒度≤150μm的铜渣、含铜烟灰、杂铜和含铜垃圾和含铜电路板，同时加入高炉瓦斯泥、电炉尘泥、转炉尘泥、普通铁精矿直接还原铁和高炉瓦斯灰，使温度降至1380℃；(b)：含铜反应熔渣的碱度CaO/SiO₂比值＝2.6，向反应熔渣中加入硅石、粉煤灰和煤矸石混合物，使含铜反应熔渣碱度比值降至1.1；熔渣中金属铁含量为1％；The copper-containing smelting slag obtained from the slag smelting of the smelting process of the smelting process and the copper-containing slag obtained by the slag slag of the "copper smelting" process blowing furnace are added to the DC arc furnace, and lime and SiO are simultaneously added. ₂ , MgO, Al ₂ O ₃ , forming mixed slag; heating the mixed slag to a molten state, forming a copper-containing reaction slag, and allowing the reaction slag to achieve natural mixing; monitoring the reaction slag in real time, and ensuring by regulation ( a) and (b) two parameters, obtain the slag after the completion of the reaction; corresponding (a): the temperature of the copper-containing reaction slag is 1660 ° C, using a refractory spray gun inserted into the reaction slag, with nitrogen as the loading gas, Spraying copper slag, copper-containing soot, copper-containing and copper-containing garbage and copper-containing circuit boards with powder particle size ≤150μm at normal temperature, and adding blast furnace gas mud, electric furnace dust, converter dust, ordinary iron concentrate direct reduced iron and Blast furnace gas ash, the temperature is lowered to 1380 ° C; (b): alkalinity CaO / SiO ₂ ratio of copper-containing reaction slag = 2.6, silica, fly ash and coal gangue mixture is added to the reaction slag to make copper The reaction slag basicity ratio is reduced to 1.1; the slag contains metallic iron 1%;

步骤2，分离回收采用方法一：Step 2, separation and recovery method 1:

保温10min，反应完成后的熔渣自然沉降，渣-金分离，获得熔融态富铜相层、富铁相与含铁硅酸盐矿物相，同时生成锌组分与铅组分，进入烟尘，以氧化物形式回收，进行如下步骤：(1)熔融态含铁硅酸盐矿物相，进行炉外熔渣处理，采用方法F，含铁硅酸盐熔渣空冷后，用作直接还原炼铁原料，直接还原过程中，采用回转窑作为还原设备，利用气基还原技术，气基还原剂为天然气和煤气，还原温度为900℃，碱度CaO/SiO₂比值为0.8，还原后采用电炉熔分温度为1550℃，产物为金属铁水与熔渣；(2)熔融态富铜相，送往连续吹炼炉炼铜；(3)熔融态富铁相倒入保温渣罐，空冷后作为高炉炼铁原料；(4)锌组分、铟组分、铅组分、铋组分、钾组分、钠组分挥发，以氧化物形式进入烟尘回收；最后获得的渣含铜<0.1％，锌回收率为92％，铅回收率为93％；铁回收率为92％，铟回收率为92％，铋回收率为94％，钠回收率为95％，钾回收率为96％，金的富集率为≥96％，银的富集率为≥94％。其中，在本发明的所有实施例中，渣含铜是指富铜相分离后的渣相，具体为富铁相与硅酸盐矿物相中的含铜量，金、银的富集率是指富铜相中金、银的含量占原料中金、银总量的百分比。After 10 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase layer, an iron-rich phase and an iron-containing silicate mineral phase, and at the same time, a zinc component and a lead component are formed, and the smoke is entered. Recycling in the form of oxides, the following steps are carried out: (1) molten iron-containing silicate mineral phase, for external slag treatment, method F, iron silicate slag air cooling, used as direct reduction ironmaking In the direct reduction process, the rotary kiln is used as the reduction equipment, and the gas-based reduction technology is used. The gas-based reducing agent is natural gas and gas, the reduction temperature is 900 ° C, the alkalinity CaO / SiO ₂ ratio is 0.8, and the electric furnace is melted after reduction. The temperature is 1550 ° C, the product is metal molten iron and slag; (2) the molten copper-rich phase is sent to the continuous blowing furnace for copper smelting; (3) the molten iron-rich phase is poured into the insulating slag tank, and the air is cooled as a blast furnace Ironmaking raw materials; (4) zinc component, indium component, lead component, antimony component, potassium component, sodium component volatilization, and enter the soot recovery in the form of oxide; the final obtained slag contains copper <0.1%, The zinc recovery rate was 92%, the lead recovery rate was 93%, and the iron recovery rate was 92%. The indium recovery rate was 92%, the ruthenium recovery rate was 94%, the sodium recovery rate was 95%, the potassium recovery rate was 96%, the gold enrichment rate was ≥96%, and the silver enrichment rate was ≥94%. In all the embodiments of the present invention, the slag-containing copper refers to the slag phase after the copper-rich phase separation, specifically the copper content in the iron-rich phase and the silicate mineral phase, and the gold and silver enrichment ratio is Refers to the content of gold and silver in the copper-rich phase as a percentage of the total amount of gold and silver in the raw material.

实施例2Example 2

步骤1，炉渣混合：Step 1, slag mixing:

将由由“造锍熔炼”工艺熔炼炉出渣口获得的熔融含铜熔炼渣与贫化炉出渣口获得的熔融贫化弃渣加入可倾倒的熔炼反应渣灌，同时加入石灰石、白云石、赤泥以及FeO和Fe₂O₃，形成混合熔渣；用预热温度为800℃的富氧空气，喷吹粒度为20mm无烟煤与焦粒，同时喷入天然气，将混合熔渣加热至熔融状态，形成含铜反应熔渣；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得反应完成后的熔渣；The molten copper-containing smelting slag obtained from the smelting port of the smelting process of the smelting process and the molten depleted slag obtained from the slag outlet of the depleted furnace are added to the pourable smelting reaction slag, and limestone, dolomite, and the like are added simultaneously. Red mud and FeO and Fe ₂ O ₃ form mixed slag; use oxygen-enriched air with a preheating temperature of 800 °C to spray anthracite and coke with a particle size of 20 mm, while injecting natural gas to heat the mixed slag to a molten state. Forming a copper-containing reaction slag; monitoring the reaction slag in real time, and simultaneously controlling the two parameters (a) and (b) to obtain the slag after completion of the reaction;

对应(a)含铜反应熔渣温度为1660℃，采用耐火喷枪***反应熔渣中，以氩气为载气，喷入常温粉状粒度≤150μm铜渣、含铜烟灰、杂铜钢铁烧结粉尘、烧结球团粉尘、出铁厂粉尘、普通铁精矿直接还原铁，使温度降至1350℃；(b)含铜反应熔渣碱度CaO/SiO₂比值为2.4，向反应熔渣中加入酸性铁精矿、酸性预还原球团、含铅熔炼渣、含铅烟化炉渣的混合物，使含铜反应熔渣碱度比值降至1.6；熔渣中金属铁含量为1.5％；Corresponding to (a) copper-containing reaction slag temperature is 1660 ° C, using a refractory spray gun to insert into the reaction slag, using argon as carrier gas, spraying normal temperature powder particle size ≤150μm copper slag, copper-containing soot, copper-copper steel sintered dust , sintering pellet dust, iron plant dust, ordinary iron concentrate direct reduced iron, the temperature is reduced to 1350 ° C; (b) copper containing reaction slag basicity CaO / SiO ₂ ratio of 2.4, added to the reaction slag a mixture of acidic iron concentrate, acidic pre-reduction pellets, lead-containing smelting slag, and lead-containing smelting furnace slag, so that the alkalinity ratio of the copper-containing reaction slag is reduced to 1.6; the metal iron content in the slag is 1.5%;

步骤2，分离回收采用方法二：Step 2, separation and recovery method 2:

保温5min,反应完成后的熔渣自然沉降，渣-金分离，获得熔融态富铜相层、富铁相与含铁硅酸盐矿物相，同时生成锌组分、铅组分与铟组分，进入烟尘，以氧化物形式加以回收，进行如下步骤：After 5 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold separation, the molten copper-rich phase layer, the iron-rich phase and the iron-containing silicate mineral phase are obtained, and the zinc component, the lead component and the indium component are simultaneously formed. To enter the soot and recycle it in the form of oxides, proceed as follows:

(1)熔融态含铁硅酸盐矿物与富铁相，采用方法G进行熔渣处理，熔渣熔融还原炼铁，具体步骤如下：(1) The molten iron-containing silicate mineral and the iron-rich phase are treated by the method G, and the slag is smelted to reduce the iron-making. The specific steps are as follows:

(1-1)熔渣倒入可转动的转炉，用预热温度为600℃的富氧空气，向熔渣中加入粒度为20mm无烟煤与烟煤，进行熔融还原，实时监测反应熔渣，通过调控同时保证如下(a)反应熔渣的温度为1350～1650℃，和(b)反应熔渣的碱度CaO/SiO₂比值＝0.6～2.4两个参数，获得反应后的熔渣；(1-1) The slag is poured into a rotatable converter, and an oxygen-enriched air with a preheating temperature of 600 ° C is used to add anthracite and bituminous coal with a particle size of 20 mm to the slag for smelting reduction, and the reaction slag is monitored in real time. At the same time, it is ensured that the temperature of the reaction slag is 1350~1650 ° C, and (b) the ratio of alkalinity CaO / SiO _{2 of the} reaction slag is 0.6-2.4, and the slag after the reaction is obtained;

对应(a)：反应熔渣的温度为1480℃，在温度范围内；Corresponding to (a): the temperature of the reaction slag is 1480 ° C, in the temperature range;

对应(b)：反应熔渣中碱度CaO/SiO₂比值为0.8时，在碱度范围内；Corresponding to (b): when the ratio of alkalinity CaO/SiO ₂ in the reaction slag is 0.8, in the range of alkalinity;

(1-2)向熔渣中喷吹预热200℃的氧化性气体(富氧空气)进行熔融还原，形成还原后的混合熔渣，并在喷吹过程中，通过调控同时保证(a)反应熔渣的温度为1350～1650℃，和(b)反应熔渣的碱度CaO/SiO₂比值＝0.6～2.4两个参数，(1-2) Spraying an oxidizing gas (oxygen-enriched air) preheated at 200 ° C into the slag to perform smelting reduction to form a mixed slag after reduction, and ensuring (a) during the blowing process The temperature of the reaction slag is 1350 ~ 1650 ° C, and (b) the ratio of alkalinity CaO / SiO ₂ ratio of the reaction slag = 0.6 ~ 2.4,

(1-3)分离回收：(1-3) Separation and recovery:

(a)还原后的混合熔渣，自然沉降，渣-金分离，获得铁水与还原后的熔渣；(a) the mixed slag after reduction, natural sedimentation, slag-gold separation, obtaining molten iron and reduced slag;

(b)还原后的熔渣，采用步骤2方法一中方法A处理做成高附加值水泥原料；(b) The slag after reduction is processed into a high value-added cement raw material by the method A in the method of the second step;

(d)含锌组分、含铅组分、铋组分与铟组分挥发，以氧化物形式进入烟尘回收；(d) the zinc-containing component, the lead-containing component, the antimony component and the indium component are volatilized, and are collected into the soot as an oxide;

(e)含钠组分、含钾组分挥发，进入烟尘回收；(e) The sodium-containing component and the potassium-containing component are volatilized and enter the soot recovery;

(2)熔融态富铜相，送往转炉炼铜； (2) molten copper-rich phase, sent to converter copper smelting;

(3)锌组分与铅组分挥发，以氧化物形式进入烟尘回收；锌回收率为94％，渣含铜<0.1％，铅回收率为92％；铁回收率为93％，铟回收率为96％，铋回收率为96％，钠回收率为97％，钾回收率为98％，金的富集率为≥94％，银的富集率为≥95％。(3) The zinc component and the lead component volatilize and enter the soot recovery in the form of oxide; the zinc recovery rate is 94%, the slag contains copper <0.1%, the lead recovery rate is 92%; the iron recovery rate is 93%, indium recovery The rate was 96%, the recovery rate of cesium was 96%, the recovery rate of sodium was 97%, the recovery rate of potassium was 98%, the enrichment rate of gold was ≥94%, and the enrichment rate of silver was ≥95%.

实施例3Example 3

步骤1，炉渣混合：将由“造锍熔炼”工艺熔炼炉出渣口获得的含铜熔炼渣、“铜鋶吹炼”工艺吹炼炉出渣口获得的含铜吹炼渣、铜渣浮选尾渣加入感应炉，同时加入石灰石与脱钠后高钙赤泥，形成混合熔渣；用预热温度为400℃的氧气，喷吹粒度为20mm无烟煤、焦粒与煤粉，将混合熔渣加热至熔融状态，形成含铜反应熔渣，机械搅拌混合；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得反应完成后的熔渣；Step 1, slag mixing: copper-containing smelting slag obtained from the slag smelting slag of the smelting process, and copper-containing blowing slag and copper slag flotation obtained from the slag outlet of the "copper smelting" process blowing furnace The tailings are added to the induction furnace, and limestone and high-calcium red mud after de-sodium are added to form mixed slag; the slag is sprayed with 20 g of anthracite, coke and pulverized coal with a preheating temperature of 400 ° C. Heating to a molten state, forming a copper-containing reaction slag, mechanically stirring and mixing; monitoring the reaction slag in real time, and simultaneously controlling the two parameters (a) and (b) to obtain the slag after completion of the reaction;

对应(a)：含铜反应熔渣的温度为1685℃，向反应熔渣中加入酸性金属化球团、铜冶炼渣和含铜吹炼渣，同时加入含铜烟灰、含铅烟化炉渣、轧钢氧化铁鳞、普通铁精矿金属化球团和普通铁精矿含碳预还原球团，使温度降至1220℃；(b)：含铜反应熔渣的碱度CaO/SiO₂比值＝2.3，向反应熔渣中加入石英砂、赤泥、湿法炼锌大窑渣的混合物，使含铜反应熔渣的碱度比值降至0.6；熔渣为弱还原气氛，熔渣中金属铁含量为1.2％；Corresponding to (a): the temperature of the copper-containing reaction slag is 1685 ° C, adding acid metallized pellets, copper smelting slag and copper-containing blowing slag to the reaction slag, and adding copper-containing soot, lead-containing smelting furnace slag, Rolled iron oxide scale, ordinary iron concentrate metallized pellets and ordinary iron concentrate carbon-bearing pre-reduction pellets, the temperature is lowered to 1220 ° C; (b): alkalinity CaO / SiO ₂ ratio of copper-containing reaction slag = 2.3. Adding a mixture of quartz sand, red mud and wet zinc smelting slag to the reaction slag to reduce the alkalinity ratio of the copper-containing reaction slag to 0.6; the slag is a weak reducing atmosphere, and the metallic iron in the slag The content is 1.2%;

保温45min，反应完成后的熔渣，自然沉降，渣-金分离，获得熔融态富铜相、富铁相与含铁硅酸盐矿物相，同时生成含锌组分与含铅组分，进入烟尘，以氧化物形式加以回收，进行如下步骤：After heat preservation for 45 min, the slag after the completion of the reaction, natural sedimentation, separation of slag-gold, obtaining a molten copper-rich phase, an iron-rich phase and an iron-containing silicate mineral phase, and simultaneously forming a zinc-containing component and a lead-containing component, enter The soot is recovered as an oxide and the following steps are carried out:

(1)熔融态富铜相，送往转炉炼铜；(1) molten copper-rich phase, sent to converter copper smelting;

(2)熔融态富铁相层与硅酸盐矿物相作为直接还原炼铁原料，；还原过程中，锌组分、铅组分、铋组分与铟组分挥发，进入烟尘；直接还原过程中，采用转底炉，还原温度为1200℃，碱度CaO/SiO₂比值＝1.0，粒度为≤150μm的无烟煤与煤粉；(2) The molten iron-rich phase layer and the silicate mineral phase act as direct reduction ironmaking raw materials; during the reduction process, the zinc component, the lead component, the antimony component and the indium component volatilize and enter the soot; the direct reduction process In the middle, using a rotary hearth furnace, the reduction temperature is 1200 ° C, the alkalinity CaO / SiO ₂ ratio = 1.0, the particle size is ≤ 150 μm anthracite and coal powder;

(3)含锌组分、铟组分、铋组分与含铅组分挥发，以氧化物形式进入烟尘回收，获得氧化锌与氧化铅。渣含铜<0.05％，铁的回收率为91％，锌的回收率为93％，铅的回收率为92％，铟回收率为93％，铋回收率为94％，金的富集率为95％，银的富集率为96％。(3) The zinc-containing component, the indium component, the antimony component and the lead-containing component volatilize, and enter the soot recovery in the form of an oxide to obtain zinc oxide and lead oxide. The slag contains copper <0.05%, the iron recovery rate is 91%, the zinc recovery rate is 93%, the lead recovery rate is 92%, the indium recovery rate is 93%, the ruthenium recovery rate is 94%, and the gold enrichment rate is At 95%, the silver enrichment rate is 96%.

实施例4Example 4

步骤1，炉渣混合：将冷态由“造锍熔炼”工艺熔炼炉出渣口获得的含铜熔炼渣加入等离子炉，同时加入白云石、MgO、Al₂O₃、以及Fe，形成混合熔渣；将混合熔渣加热至熔融状态，形成含铜反应熔渣，并使反应熔渣电磁搅拌，实现混合；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得反应完成后的熔渣；Step 1. Slag mixing: adding the copper-containing smelting slag obtained in the cold state from the smelting port of the smelting process to the plasma furnace, adding dolomite, MgO, Al ₂ O ₃ , and Fe to form mixed slag. The mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is electromagnetically stirred to achieve mixing; the reaction slag is monitored in real time, and two parameters (a) and (b) are obtained through regulation and control. The slag after the reaction is completed;

对应(a)含铜反应熔渣的温度为1670℃，向反应熔渣中加入赤泥、煤粉灰、硫酸烧渣、萤石、铅冰铜、含铅烟灰、含锌烟灰、砷冰铜和湿法炼锌渣，使温度降至1440℃；(b)含铜反应熔渣的碱度CaO/SiO₂比值为2.0，向反应熔渣中加入含铜吹炼渣，使含铜反应熔渣碱度比值降至1.2；用温度为800℃的空气，喷吹天然气、粒度为20mm的焦粒，熔渣中金属铁含量为2％；Corresponding to (a) the temperature of the copper-containing reaction slag is 1670 ° C, and red mud, coal dust ash, sulfuric acid slag, fluorite, lead ice copper, lead-containing soot, zinc-containing soot, arsenic matte copper are added to the reaction slag. And the wet zinc slag, the temperature is lowered to 1440 ° C; (b) the copper-containing reaction slag has a basicity CaO / SiO ₂ ratio of 2.0, and the copper-containing blowing slag is added to the reaction slag to melt the copper-containing reaction The slag alkalinity ratio is reduced to 1.2; the air is sprayed with natural gas, the coke grain having a particle size of 20 mm, and the metal iron content in the slag is 2%;

步骤2，分离回收采用方法三：Step 2, separation and recovery method 3:

保温30min，反应完成后的熔渣自然冷却沉降，渣-金分离，获得熔融态富铜相、富铁相与含铁硅酸盐矿物相，同时生成含锌组分与含铅组分，进入烟尘，以氧化物形式加以回收，进行如下步骤： After 30 minutes of heat preservation, the slag after the completion of the reaction is naturally cooled and settled, and the slag-gold is separated to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and at the same time, a zinc-containing component and a lead-containing component are formed. The soot is recovered as an oxide and the following steps are carried out:

(1)熔融态含铁硅酸盐矿物相，采用步骤2的分离回收方法一种的方法I熔渣改性磁选分离：①用喷枪向熔渣中喷入预热温度为600℃的富氧空气，实现磁铁矿转化，②缓冷至室温，磁选获得铁精矿与尾矿；(1) molten iron-containing silicate mineral phase, using the separation and recovery method of step 2; a method of slag-modified magnetic separation: 1 using a spray gun to spray molten slag into a preheating temperature of 600 ° C Oxygen air, to achieve magnetite transformation, 2 slow cooling to room temperature, magnetic separation to obtain iron concentrate and tailings;

(2)熔融态富铁相与熔融态富铜相直接送往转炉炼铜；(2) The molten iron-rich phase and the molten copper-rich phase are sent directly to the converter for copper smelting;

(3)部分含锌组分铋组分、铟组分与含铅组分挥发，以氧化物形式进入烟尘回收；渣含铜<0.1％，铁的回收率为94％，锌的回收率为93％，铅的回收率为92％，铟回收率为93％，铋回收率为94％，金的富集率为95％，银的富集率为97％。(3) Part of the zinc-containing component bismuth component, indium component and lead-containing component volatilize, and enter the soot recovery in the form of oxide; slag contains copper <0.1%, iron recovery rate is 94%, and zinc recovery rate 93%, the lead recovery rate was 92%, the indium recovery rate was 93%, the ruthenium recovery rate was 94%, the gold enrichment rate was 95%, and the silver enrichment rate was 97%.

实施例5Example 5

步骤1，炉渣混合：将由“造锍熔炼”工艺熔炼炉出渣口获得的含铜熔炼渣、“铜鋶吹炼”工艺吹炼炉出渣口获得的含铜吹炼渣加入保温渣罐，同时加入石灰石以及Fe，形成混合熔渣；用温度为100℃的富氧空气，喷吹粒度≤150μm烟煤，将混合熔渣加热至熔融状态，形成含铜反应熔渣，并使反应熔渣实现混合；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得反应完成后的熔渣；Step 1, slag mixing: the copper-containing smelting slag obtained from the slag smelting port of the smelting process of the smelting process, and the copper-containing smelting slag obtained by the slag discharging port of the "copper smelting" process blowing furnace are added to the slag pot. At the same time, limestone and Fe are added to form mixed slag; the oxygen-enriched air at a temperature of 100 ° C is used to spray the bituminous coal with a particle size of ≤150 μm, and the mixed slag is heated to a molten state to form a copper-containing reaction slag, and the reaction slag is realized. Mixing; monitoring the reaction slag in real time, and simultaneously controlling the two parameters (a) and (b) to obtain the slag after completion of the reaction;

对应(a)：含铜反应熔渣的温度为1330℃；(b)：含铜反应熔渣的碱度CaO/SiO₂比值为1.4，均在要求范围内；熔渣中金属铁含量为2.8％；Corresponding to (a): the temperature of the copper-containing reaction slag is 1330 ° C; (b): the alkalinity CaO / SiO ₂ ratio of the copper-containing reaction slag is 1.4, both within the required range; the metal iron content in the slag is 2.8 %;

步骤2，分离回收采用方法五：Step 2, separation and recovery method 5:

保温49min，将反应完成后的熔渣旋转冷却，进行如下步骤：After the temperature was kept for 49 minutes, the slag after the completion of the reaction was spin-cooled, and the following steps were performed:

(1)沉降冷却：反应完成后的熔渣旋转冷却至室温，获得缓冷渣；富铜相沉降到反应装置的底部，形成富铜坨；含铁硅酸盐矿物相上浮；富铜相和含铁硅酸盐矿物中间缓冷渣为富铁相，同时生成含锌组分与含铅组分；(1) Settling cooling: After the completion of the reaction, the slag is rotated and cooled to room temperature to obtain slow cooling slag; the copper-rich phase is settled to the bottom of the reaction device to form a copper-rich bismuth; the iron-containing silicate mineral phase is floated; the copper-rich phase and The iron-containing silicate mineral intermediate slow cooling slag is an iron-rich phase, and at the same time, a zinc-containing component and a lead-containing component are formed;

(2)分离：人工取出沉降在底部的富铜坨，直接还原，磁选分离铁后，产物送往转炉；中部的富铁相磁选分离金属铁后，送往转炉炼铁；(2) Separation: manually extracting the copper-rich bismuth settled at the bottom, directly reducing, magnetically separating the iron, and then sending the product to the converter; the iron-rich phase in the middle is magnetically separated to separate the metal iron, and then sent to the converter for iron making;

(3)人工取出上部的含铁硅酸盐矿物相，获得含铁硅酸盐尾矿，作为水泥原料使用；(3) manually taking out the upper iron-containing silicate mineral phase to obtain iron-containing silicate tailings, which is used as a cement raw material;

(4)部分锌组分与铅组分挥发，以氧化物形式进入烟尘回收；渣含铜<0.15％，铁的回收率为91％，锌的回收率为92％，铅的回收率为95％，金的富集率为94％，银的富集率为96％。(4) Some zinc components and lead components volatilize and enter the soot recovery as oxides; the slag contains copper <0.15%, the iron recovery rate is 91%, the zinc recovery rate is 92%, and the lead recovery rate is 95. %, the gold enrichment rate is 94%, and the silver enrichment rate is 96%.

实施例6Example 6

步骤1，炉渣混合：将由由“造锍熔炼”工艺熔炼炉出渣口获得的含铜熔炼渣、“铜鋶吹炼”工艺吹炼炉出渣口获得的含铜吹炼渣加入交流电弧炉，同时加入石灰、MgO、Al₂O₃、Fe₂O₃，形成混合熔渣；将混合熔渣加热至熔融状态，形成含铜反应熔渣，喷入温度为1100℃的氩气，并使反应熔渣实现混合；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得反应完成后的熔渣；Step 1, slag mixing: the copper-containing smelting slag obtained from the slag-containing slag obtained from the smelting smelting furnace of the smelting process, and the copper-containing blowing slag obtained from the slag discharging port of the "copper smelting" process blowing furnace is added to the alternating current arc furnace At the same time, adding lime, MgO, Al ₂ O ₃ , Fe ₂ O ₃ to form a mixed slag; heating the mixed slag to a molten state to form a copper-containing reaction slag, spraying argon gas at a temperature of 1100 ° C, and The reaction slag is mixed; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling both parameters (a) and (b);

对应(a)：含铜反应熔渣的温度为1080℃，电弧炉加热，使温度升至1350℃；(b)：含铜反应熔渣的碱度CaO/SiO₂比值为0.1，向反应熔渣中加入碱性铁精矿、高炉瓦斯泥、碱性预还原球团、转炉钢渣，使含铜反应熔渣的碱度比值升至0.4；喷吹天然气，熔渣中金属铁含量为2.2％；Corresponding to (a): the temperature of the copper-containing reaction slag is 1080 ° C, the electric arc furnace is heated to raise the temperature to 1350 ° C; (b): the alkalinity CaO / SiO ₂ ratio of the copper-containing reaction slag is 0.1, to the reaction melt Alkaline iron concentrate, blast furnace gas mud, alkaline pre-reduction pellets, converter steel slag are added to the slag to increase the alkalinity ratio of the copper-containing reaction slag to 0.4; natural gas is sprayed, and the metal iron content in the slag is 2.2%. ;

保温38min，将反应完成后的熔渣自然沉降，渣-金分离，获得熔融态富铜相、熔融态富铁相和熔融态含铁硅酸盐矿物相，同时生成含锌组分与含铅组分，进入烟尘，以氧化物形式回收，进行如下步骤：After 38 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-rich phase, a molten iron-rich phase and a molten iron-containing silicate mineral phase, and at the same time, a zinc-containing component and lead are formed. The components, which enter the soot and are recovered as oxides, are subjected to the following steps:

(1)含铁硅酸盐矿物相采用步骤2分离回收方法一中方法A，水淬直接作为水泥原料；(1) The iron-containing silicate mineral phase is separated and recovered in the second method, Method A, and water quenched directly as cement. raw material;

(2)熔融态富铜相，送往转炉炼铜；(2) molten copper-rich phase, sent to converter copper smelting;

(3)富铁相倒入保温装置冷却后直接还原炼铁；(3) The iron-rich phase is poured into the heat preservation device to directly reduce the iron-making after cooling;

(4)含锌组分与含铅组分挥发，以氧化物形式进入烟尘回收；渣含铜<0.1％，铁的回收率为91％，锌的回收率为92％，铅的回收率为94％，金的富集率为94％，银的富集率为96％。(4) The zinc-containing component and the lead-containing component volatilize and enter the soot recovery as an oxide; the slag contains copper <0.1%, the iron recovery rate is 91%, the zinc recovery rate is 92%, and the lead recovery rate is 94%, the gold enrichment rate is 94%, and the silver enrichment rate is 96%.

实施例7Example 7

步骤1，炉渣混合：将由“造锍熔炼”工艺的冷态含铜熔炼渣、“铜鋶吹炼”工艺的冷态含铜吹炼渣及湿法炼铜渣加入矿热炉，同时加入石灰石、SiO₂、FeO以及MgO，形成混合熔渣；将混合熔渣加热至熔融状态，形成含铜熔渣，喷吹温度为200℃的氩气-氮气混合气，并使熔渣实现混合；实时监测反应熔渣，通过调控保证(a)和(b)两个参数，获得完成后的熔渣；Step 1. Slag mixing: adding the cold copper-containing smelting slag of the "smelting smelting" process, the cold copper-containing blowing slag of the "copper smelting" process, and the wet copper slag to the ore furnace, and adding limestone at the same time. , SiO ₂ , FeO and MgO form a mixed slag; the mixed slag is heated to a molten state to form a copper-containing slag, and an argon-nitrogen mixed gas having a temperature of 200 ° C is sprayed, and the slag is mixed; Monitoring the reaction slag, and ensuring the two parameters of (a) and (b) by regulation to obtain the completed slag;

对应(a)：含铜反应熔渣的温度为1320℃；(b)：含铜反应熔渣的碱度CaO/SiO₂比值为0.8，均在要求范围内；加入粒度≤150μm煤粉与天然气，熔渣中金属铁含量为2.4％；Corresponding to (a): the temperature of the copper-containing reaction slag is 1320 ° C; (b): the ratio of alkalinity CaO / SiO _{2 of the} copper-containing reaction slag is 0.8, both within the required range; adding pulverized coal with a particle size of ≤ 150 μm , the metal iron content in the slag is 2.4%;

步骤2，分离回收采用方法四：Step 2, separation and recovery method 4:

保温39min，将反应完成后的熔渣倒入保温渣罐，旋转沉降，渣-金分离，获得熔融态富铜相、富铁相与含铁硅酸盐矿物相，同时生成锌组分与铅组分，进入烟尘，以氧化物形式加以回收，进行如下步骤：After holding for 39 minutes, the molten slag after the completion of the reaction was poured into the thermal insulation slag tank, and the sediment was sedimented and separated by slag-gold to obtain a molten copper-rich phase, an iron-rich phase and a ferrosilicate-containing mineral phase, and a zinc component and lead were simultaneously formed. The components, which enter the soot and are recovered as oxides, are subjected to the following steps:

(2)熔融态富铁相与含铁硅酸盐矿物采用步骤2分离回收方法一中方法C，熔渣浇铸微晶玻璃；(2) The molten iron-rich phase and the iron-containing silicate mineral are separated and recovered in the second method, Method C, and the molten slag is cast into the glass ceramics;

(3)部分含锌组分与含铅组分挥发，以氧化物形式进入烟尘回收；渣含铜<0.1％，铁的回收率为91％，锌的回收率为93％，铅的回收率为93％，金的富集率为95％，银的富集率为97％。(3) Part of the zinc-containing component and the lead-containing component volatilize, and enter the soot recovery in the form of oxide; the slag contains copper <0.1%, the iron recovery rate is 91%, the zinc recovery rate is 93%, and the lead recovery rate At 93%, the gold enrichment rate is 95% and the silver enrichment rate is 97%.

实施例8Example 8

步骤1，炉渣混合：将由“造锍熔炼”工艺的冷态含铜熔炼渣、“铜鋶吹炼”工艺的冷态含铜吹炼渣、贫化弃渣加入鼓风炉，同时加入白云石、赤泥、MgO，采用600℃的氧气，喷入煤气与粒度≤150μm的焦粉，将混合熔渣加热至熔融状态，形成含铜反应熔渣，并使反应熔渣实现混合；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得完成后的熔渣；Step 1. Slag mixing: adding cold copper-containing smelting slag from the “smelting smelting” process, cold copper-containing blowing slag of the “copper smelting” process, and depleted slag to the blast furnace, and adding dolomite and red Mud, MgO, using 600 ° C oxygen, sprayed into the gas and coke powder with particle size ≤ 150μm, the mixed slag is heated to a molten state, forming a copper-containing reaction slag, and the reaction slag is mixed; real-time monitoring of the reaction slag After the two parameters of (a) and (b) are simultaneously controlled, the completed slag is obtained;

对应(a)：含铜反应熔渣的温度为1330℃；(b)：含铜反应熔渣的碱度CaO/SiO₂比值为1.0，均在要求范围内；熔渣中金属铁含量为2.7％；Corresponding to (a): the temperature of the copper-containing reaction slag is 1330 ° C; (b): the alkalinity CaO / SiO ₂ ratio of the copper-containing reaction slag is 1.0, both within the required range; the metal iron content in the slag is 2.7 %;

保温33min，将反应完成后的熔渣自然沉降，渣-金分离，获得富铜相与中上部的熔融态含铁硅酸盐矿物相，同时生成含锌组分与含铅组分，进入烟尘，以氧化物形式回收，进行如下步骤：After 33 min of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a molten copper-containing silicate mineral phase in the copper-rich phase and the middle-upper portion, and at the same time, a zinc-containing component and a lead-containing component are formed, and the dust is introduced into the dust. To recover as oxide, proceed as follows:

(1)含铁硅酸盐矿物相，具体采用步骤2的分离回收方法一中的方法B，将中上部的熔渣全部返回到含铜反应熔渣，作为热态冶金熔剂，调整熔渣成分，控制熔渣温度；(1) The iron-containing silicate mineral phase, specifically adopting the method B in the separation and recovery method of the second step, and returning the middle and upper slag to the copper-containing reaction slag as a hot metallurgical flux to adjust the slag composition. , controlling the slag temperature;

(2)熔融态富铜相，送往转炉或吹炼炉炼铜；(2) molten copper-rich phase, sent to converter or blowing furnace for copper smelting;

(3)部分含锌组分与含铅组分挥发，以氧化物形式进入烟尘回收，渣含铜<0.1％，铁的回收率为95％，锌的回收率为93％，铅的回收率为94％，金的富集率为98％，银的富集率为96％。(3) Some of the zinc-containing components and the lead-containing components are volatilized, and are collected into the dust as oxides, and the slag contains copper <0.1%. The recovery of iron was 95%, the recovery of zinc was 93%, the recovery of lead was 94%, the enrichment rate of gold was 98%, and the enrichment rate of silver was 96%.

实施例9Example 9

步骤1，炉渣混合：将热由“造锍熔炼”工艺熔炼炉出渣口获得的含铜熔炼渣、“铜鋶吹炼”工艺吹炼炉出渣口获得的含铜吹炼渣、铜渣浮选尾矿加入侧吹炉，同时加入石灰石，形成混合熔渣；采用温度为1100℃的预热空气喷入≤150μm焦粉，将混合熔渣加热至熔融状态，形成含铜反应熔渣，并使反应熔渣实现混合；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得反应完成后的熔渣；Step 1, slag mixing: copper-containing smelting slag and copper slag obtained from the slag-containing slag obtained by the smelting smelting process of the smelting smelting process and the slag vent of the "copper smelting" process blowing furnace The flotation tailings is added to the side blowing furnace, and limestone is added at the same time to form mixed slag; the preheated air with a temperature of 1100 ° C is sprayed with ≤150 μm coke powder, and the mixed slag is heated to a molten state to form a copper-containing reaction slag. And the reaction slag is mixed; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling and simultaneously ensuring two parameters (a) and (b);

对应(a)：含铜反应熔渣的温度为1340℃；(b)：含铜反应熔渣的碱度CaO/SiO₂比值为1.2，均在要求范围内，熔渣中金属铁含量为1.7％；Corresponding to (a): the temperature of the copper-containing reaction slag is 1340 ° C; (b): the alkalinity CaO / SiO ₂ ratio of the copper-containing reaction slag is 1.2, both within the required range, the metal iron content in the slag is 1.7 %;

保温19min，将反应完成后的熔渣自然沉降，渣-金分离，获得富铜相与中上部的含铁硅酸盐矿物相，同时生成含锌组分与含铅组分，进入烟尘，以氧化物形式回收，进行如下步骤：After 19 minutes of heat preservation, the slag after the completion of the reaction is naturally settled, and the slag-gold is separated to obtain a copper-rich phase and a medium-upper iron-containing silicate mineral phase, and at the same time, a zinc-containing component and a lead-containing component are formed, and the smoke is entered into the dust. To recover the oxide form, proceed as follows:

(1)中上部的熔渣倒入熔炼装置，采用步骤2的分离回收方法一中的方法C，将中上部熔渣浇筑微晶玻璃；(1) The middle and upper slag is poured into the smelting device, and the medium and upper slag is poured into the glass ceramics by the method C in the separation and recovery method 1 of the step 2;

(2)下部的熔融态富铜相，送往转炉；(2) the lower molten copper-rich phase is sent to the converter;

(3)部分含锌组分与含铅组分，以氧化物形式进入烟尘；渣含铜<0.1％，铁的回收率为93％，锌的回收率为94％，铅的回收率为95％，金的富集率为94％，银的富集率为96％。(3) Part of the zinc-containing component and lead-containing component enter the soot as oxide; the slag contains copper <0.1%, the iron recovery rate is 93%, the zinc recovery rate is 94%, and the lead recovery rate is 95. %, the gold enrichment rate is 94%, and the silver enrichment rate is 96%.

实施例10Example 10

步骤1，炉渣混合：将由“造锍熔炼”工艺熔炼炉出渣口获得的含铜熔炼渣、“铜鋶吹炼”工艺吹炼炉出渣口获得的含铜吹炼渣加入保温地坑，同时加入石灰石以及Fe，形成混合熔渣；用预热温度为600℃的富氧空气，喷吹粒度≤150μm烟煤，将混合熔渣加热至熔融状态，形成含铜反应熔渣，并使反应熔渣实现混合；实时监测反应熔渣，通过调控同时保证(a)和(b)两个参数，获得反应完成后的熔渣；Step 1, slag mixing: the copper-containing smelting slag obtained from the slag smelting port of the smelting process of the smelting process, and the copper-containing smelting slag obtained by the slag discharging port of the "copper smelting" process blowing furnace are added to the heat preservation pit. At the same time, adding limestone and Fe to form mixed slag; using oxygen-enriched air with a preheating temperature of 600 ° C, blowing bituminous coal with a particle size of ≤150 μm, heating the mixed slag to a molten state, forming a copper-containing reaction slag, and melting the reaction The slag is mixed; the reaction slag is monitored in real time, and the slag after the completion of the reaction is obtained by controlling and simultaneously ensuring two parameters (a) and (b);

对应(a)：含铜反应熔渣的温度为1430℃；(b)：含铜反应熔渣的碱度CaO/SiO₂比值为1.5，均在要求范围内；熔渣中金属铁含量为2.2％；Corresponding to (a): the temperature of the copper-containing reaction slag is 1430 ° C; (b): the alkalinity CaO / SiO ₂ ratio of the copper-containing reaction slag is 1.5, both within the required range; the metal iron content in the slag is 2.2 %;

将反应完成后的熔渣进行如下步骤：The slag after the completion of the reaction is subjected to the following steps:

(1)沉降冷却：保温20min,反应完成后的熔渣缓慢冷却至室温，获得缓冷渣；富铜相沉降到反应装置的底部，形成富铜坨；硅酸盐矿物相上浮；富铜相和含铁硅酸盐矿物相硅酸盐矿物中间缓冷渣为富铁相，同时生成含锌组分与含铅组分的烟尘；(1) Settling cooling: holding for 20 min, the slag after the reaction is slowly cooled to room temperature to obtain slow cooling slag; the copper-rich phase settles to the bottom of the reaction device to form copper-rich strontium; the silicate mineral phase floats; the copper-rich phase And the iron-silicate silicate mineral phase silicate mineral intermediate slow-cooling slag is iron-rich phase, and at the same time, the zinc-containing component and the lead-containing component are generated;

(2)分离：人工取出沉降在底部的富铜坨；中部的富铁相直接还原后，磁选分离金属铁，尾矿返回铜***；(2) Separation: manually extracting the copper-rich strontium deposited at the bottom; after the direct reduction of the iron-rich phase in the middle, the metal iron is separated by magnetic separation, and the tailings are returned to the copper system;

(3)人工取出上部的含铁硅酸盐矿物相，获得硅酸盐尾矿，作为水泥原料使用；(3) manually taking out the upper iron-containing silicate mineral phase to obtain silicate tailings, which are used as cement raw materials;

(4)部分锌组分与铅组分挥发，以氧化物形式进入烟尘回收；渣含铜<0.15％，铁的回收率为98％，锌的回收率为95％，铅的回收率为93％金的富集率为95％，银的富集率为96％。 (4) Part of the zinc component and the lead component volatilize, and enter the soot recovery as an oxide; the slag contains copper <0.15%, the iron recovery rate is 98%, the zinc recovery rate is 95%, and the lead recovery rate is 93. The enrichment rate of % gold is 95%, and the enrichment rate of silver is 96%.

Claims

一种由含铜熔渣回收有价组分的方法，其特征在于，其包括如下步骤：A method for recovering valuable components from copper-containing slag, characterized in that it comprises the following steps:

S1、炉渣混合：将铜渣加入熔炼反应装置中，并加入钙系矿物与添加剂，形成混合熔渣，将混合熔渣加热至熔融状态作为反应熔渣，混合均匀，实时监测该反应熔渣，通过调控使混合后的反应熔渣同时满足条件a和条件b，获得反应后的熔渣，或将反应后的熔渣倒入保温装置；S1, slag mixing: adding copper slag to the smelting reaction device, adding calcium minerals and additives to form mixed slag, heating the mixed slag to a molten state as reaction slag, mixing uniformly, and monitoring the reaction slag in real time, The slag after the reaction is obtained by adjusting the mixed reaction slag to satisfy the condition a and the condition b, or the slag after the reaction is poured into the heat preservation device;

其中，所述条件a为控制熔渣温度为1100～1450℃；Wherein the condition a is controlling the slag temperature to be 1100 to 1450 ° C;

所述条件b为控制熔渣的碱度CaO/SiO₂比值＝0.15～1.5；The condition b is a control alkalinity CaO / SiO ₂ ratio of the slag = 0.15 ~ 1.5;

S2、分离回收：所述步骤S1反应后的熔渣，保温5～50min，沉降分离获得底部富铜相、中部富铁相与上部含铁硅酸盐矿物相，同时生成含锌组分与含铅组分的烟烟尘，金银组分迁移、富集进入富铜相；对各相进行回收处理。S2, separation and recovery: the slag after the reaction in the step S1 is kept for 5 to 50 minutes, and the bottom copper-rich phase, the middle iron-rich phase and the upper iron-containing silicate mineral phase are obtained by sedimentation and separation, and the zinc-containing component and the The smoke and dust of the lead component migrate and enrich the gold and silver components into the copper-rich phase; the phases are recovered.
如权利要求1所述的方法，其特征在于，在所述步骤S1中，所述条件a调控的方法为：The method according to claim 1, wherein in said step S1, said condition a is regulated by:

当所述反应熔渣的温度＜1100℃，利用反应装置自身的加热，或向熔渣中加入燃料与预热的氧化性空气，使反应熔渣的温度达到1100～1450℃；When the temperature of the reaction slag is <1100 ° C, using the heating of the reaction device itself, or adding fuel and preheated oxidizing air to the slag, so that the temperature of the reaction slag reaches 1100 ~ 1450 ° C;

当所述反应熔渣的温度＞1450℃，向反应熔渣中加入含铜物料、冶金熔剂、含铁物料或含氟物料中的一种或几种，混合均匀，使混合的反应熔渣的温度达到1100～1450℃；When the temperature of the reaction slag is >1450 ° C, one or more of a copper-containing material, a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag, and the mixture is uniformly mixed to make the mixed reaction slag The temperature reaches 1100 ~ 1450 ° C;

所述条件b调控的方法为：The method for regulating the condition b is:

当所述反应熔渣中碱度CaO/SiO₂比值<0.15时，向反应熔渣中加入碱性物料和/或碱性含铁物料；When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is <0.15, an alkaline material and/or an alkaline iron-containing material is added to the reaction slag;

当所述反应熔渣中碱度CaO/SiO₂比值>1.5时，向反应熔渣中加入酸性物料和/或酸性含铁物料。When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >1.5, an acidic material and/or an acidic iron-containing material is added to the reaction slag.
如权利要求1所述的方法，其特征在于，所述反应装置为保温装置或可转动的熔炼反应装置或带有渣口或铁口熔渣可流出的熔炼反应装置；其中，所述保温装置为可倾倒的熔炼反应渣灌或保温地坑；The method according to claim 1, wherein said reaction device is a heat retention device or a rotatable smelting reaction device or a smelting reaction device with slag or iron slag flowing out; wherein said heat retention device Pit filling or insulation pit for pourable smelting reaction;

所述可转动的熔炼反应装置为转炉、熔炼反应渣罐；The rotatable smelting reaction device is a converter and a smelting reaction slag tank;

所述带有渣口或铁口熔渣可流出的熔炼反应装置为等离子炉、直流电弧炉、交流电弧炉、矿热炉、鼓风炉、高炉、感应炉、冲天炉、侧吹熔池熔炼炉、底吹熔池熔炼炉、顶吹熔池熔炼炉、反射炉、奥斯麦特炉、艾萨炉、瓦钮可夫熔池熔炼炉、侧吹回转炉、底吹回转炉、顶吹回转炉、铜熔炼炉的电热前床。The smelting reaction device with slag or iron slag can flow out is a plasma furnace, a direct current arc furnace, an alternating current arc furnace, a submerged arc furnace, a blast furnace, a blast furnace, an induction furnace, a cupola furnace, a side blowing molten pool smelting furnace, Bottom-blow pool smelting furnace, top-blow pool smelting furnace, reverberatory furnace, Osmet furnace, Aisa furnace, Waten Kraft melting pool melting furnace, side blowing rotary furnace, bottom blowing rotary furnace, top blowing rotary furnace The electric heating bed of the copper melting furnace.
如权利要求1所述的方法，其特征在于，在所述步骤S1中，满足所述条件a和b的同时，应同时满足控制所述反应熔渣中铜氧化物和铁氧化物还原为金属铜和FeO，反应熔渣中金属铁含量<3％。The method according to claim 1, wherein in said step S1, while satisfying said conditions a and b, simultaneous control of reduction of copper oxide and iron oxide in said reaction slag to metal is satisfied. Copper and FeO, the metal iron content in the reaction slag is <3%.
如权利要求1所述的方法，其特征在于，所述铜渣是含铜熔炼渣、含铜吹炼渣、铜火法贫化弃渣、浮选尾渣、湿法炼铜渣中一种或几种，其中，所述含铜熔炼渣产生于铜的火法冶炼工艺的“造锍熔炼”过程，所述含铜吹炼渣产生于铜的火法冶炼工艺的“铜锍吹炼”过程，所述铜火法贫化弃渣为含铜熔炼渣与含铜吹炼渣贫化后弃渣，所述浮选尾渣为含铜熔炼渣与含铜吹炼渣选矿后尾渣，所述湿法炼铜渣为湿法炼铜后弃渣；所述含铜熔炼渣、含铜吹炼渣与贫化弃渣为熔融态或冷态，其中：所述熔融态的铜熔炼渣由“造锍熔炼”过程的含铜熔炼炉出渣口获得，或将含铜熔炼渣加热至熔融状态，所述熔融铜态的吹炼渣由“铜锍吹炼”过程的铜吹炼炉出渣口获得，或将铜吹炼渣加热至熔融状态，贫化弃渣由贫化炉出渣口获得，获将贫化渣加热至熔融状态； The method according to claim 1, wherein the copper slag is one of copper-containing smelting slag, copper-containing blowing slag, copper-fired depleted slag, flotation tailings, and wet copper slag. Or several, wherein the copper-containing smelting slag is produced in a "smelting smelting" process of a copper pyrometallurgical slag, which is produced in a copper smelting process of "copper smelting" a process, the copper fire method depleted waste slag is a copper smelting slag and a copper-containing smelting slag, and the waste slag is a tail slag after the copper-containing smelting slag and the copper-containing smelting slag. The wet copper slag is a waste slag after the wet copper smelting; the copper smelting slag, the copper containing slag and the depleted slag are in a molten state or a cold state, wherein: the molten copper smelting slag Obtained from the slag-out of the copper-containing smelting furnace in the process of "smelting and smelting", or heating the smelting slag containing copper to a molten state, the copper smelting furnace in the molten copper state is blown by the "copper smelting" process Obtaining the slag outlet, or heating the copper blowing slag to a molten state, and obtaining the depleted slag from the slag outlet of the depleted furnace, and heating the depleted slag to a molten state;

所述钙系矿物为石灰、石灰石、白云石、电石渣、赤泥或脱钠后高钙赤泥中的一种或几种；The calcium-based mineral is one or more of lime, limestone, dolomite, calcium carbide slag, red mud or high-calcium red mud after de-sodium removal;

所述添加剂为SiO₂、MgO、FeO、Fe₂O₃、MnO₂、Al₂O₃、TiO₂、Fe或Na₂O中的一种或几种。The additive is one or more of SiO ₂ , MgO, FeO, Fe ₂ O ₃ , MnO ₂ , Al ₂ O ₃ , TiO ₂ , Fe or Na ₂ O.
如权利要求2所述的方法，其特征在于，所述含铜物料为铜渣、选铜尾矿、粗铜火法精炼渣、锌冶炼渣、锌冶炼烟灰与尘泥、铅冶炼炉渣、铅锌尾矿、镍冶炼渣、铅冰铜、砷冰铜、粗铅火法精炼渣、含铅烟化炉渣、铅冶炼烟尘与烟灰、铅酸电池、铜冶炼烟灰与尘泥、杂铜、含铜垃圾、含铜电路板、锡冶炼渣、锡尾矿中的一种或几种混合；其中，所述铜渣是含铜熔炼渣、含铜吹炼渣、铜火法贫化弃渣、浮选尾渣、湿法炼铜渣中一种或几种；含铅炉渣为烟化炉炉渣与含铅熔炼渣，“ISP铅锌鼓风炉还原”或“烧结矿鼓风炉还原”或“固态高铅渣还原”或“液态高铅渣还原工艺”还原工艺产生含铅熔炼渣，含铅熔炼渣通过烟化炉冶炼产生含铅烟化炉渣；镍冶炼渣是“造锍熔炼”工艺产生的镍熔炼渣、“铜冰镍吹炼”工艺吹炼后的贫化炉渣、顶吹熔炼产生的镍沉降炉渣中一种或多种；锌冶炼炉渣包括湿法炼锌产生的炉渣与湿法炼锌产生的炉渣，其中湿法炼锌产生的炉渣是锌浸出渣、挥发窑渣、铁矾渣、酸洗后铁矾渣、针铁矿渣、赤铁矿渣一种或多种，竖罐炼锌是竖罐炼锌炉渣、旋涡熔炼炉渣、鼓风炉炉渣、电炉渣中的一种或多种；The method according to claim 2, wherein the copper-containing material is copper slag, copper tailings, crude copper fire refining slag, zinc smelting slag, zinc smelting soot and dust, lead smelting slag, lead Zinc tailings, nickel smelting slag, lead ice copper, arsenic matte copper, crude lead fire refining slag, lead-containing smelting furnace slag, lead smelting soot and soot, lead-acid battery, copper smelting soot and dust, copper, containing One or more kinds of copper garbage, copper-containing circuit board, tin smelting slag, tin tailings; wherein the copper slag is copper-containing smelting slag, copper-containing blowing slag, copper fire-depleted slag, One or more of flotation tailings and wet copper slag; lead-containing slag is smelting furnace slag and lead smelting slag, “ISP lead-zinc blast furnace reduction” or “sinter blast furnace reduction” or “solid lead” The slag reduction or the liquid high lead slag reduction process produces a lead-containing smelting slag, and the lead smelting slag is smelted by a smelting furnace to produce a lead-containing smelting furnace slag; the nickel smelting slag is a smelting smelting process produced by the smelting smelting process Depleted slag after slag, "copper ice nickel blowing" process, nickel produced by top blowing smelting One or more of the settled slag; the zinc smelting furnace slag includes slag produced by wet zinc smelting and slag produced by wet zinc smelting, wherein the slag produced by the wet zinc smelting is zinc leaching slag, volatile kiln slag, iron slag, After pickling, iron ore slag, goethite slag, hematite slag one or more, vertical tank zinc smelting is one or more of vertical tank zinc slag, vortex smelting slag, blast furnace slag, electric furnace slag;

所述冶金熔剂为含CaO或SiO₂的矿物，具体为石英砂、含金银石英砂、赤泥、脱钠后高钙赤泥、电石渣、白云石或石灰石中的一种或几种；The metallurgical flux is a mineral containing CaO or SiO ₂ , specifically one or more of quartz sand, gold-silver quartz sand, red mud, high-calcium red mud after desoda, calcium carbide slag, dolomite or limestone;

所述含铁物料是普通铁精矿、普通铁精矿直接还原铁，普通铁精矿烧结矿、普通铁精矿球团矿、普通铁精矿金属化球团、普通铁精矿含碳预还原球团、钢渣、锌冶炼渣、焦炭冶炼烟尘与尘泥、钢铁烟尘与尘泥、含镍冶炼渣、铜渣、铅冶炼渣、铜渣、锡冶炼渣、赤泥、脱钠后高钙赤泥、煤粉灰、硫酸烧渣中的一种或几种；所述钢铁烟尘与尘泥包括高炉瓦斯泥、转炉尘泥、电炉尘泥、热或冷轧污泥、烧结粉尘、球团粉尘、出铁厂集尘、高炉瓦斯灰、电炉除尘灰、轧钢氧化铁皮；The iron-containing material is ordinary iron concentrate, ordinary iron concentrate direct reduced iron, ordinary iron concentrate sintered ore, ordinary iron concentrate pellet, ordinary iron concentrate metallized pellet, ordinary iron concentrate carbon-bearing pre- Reducing pellets, steel slag, zinc smelting slag, coke smelting soot and dust, steel soot and dust, nickel smelting slag, copper slag, lead smelting slag, copper slag, tin smelting slag, red mud, high calcium after desodium One or more of red mud, coal dust ash, sulfuric acid slag; the steel dust and dust including blast furnace gas mud, converter dust mud, electric furnace dust, hot or cold rolling sludge, sintering dust, pellets Dust, dust collection in ironworks, blast furnace gas ash, electric furnace dust ash, rolled steel oxide scale;

所述含氟物料是萤石、CaF₂或含氟高炉渣中的一种或几种。The fluorine-containing material is one or more of fluorite, CaF ₂ or fluorine-containing blast furnace slag.
如权利要求2所述的方法，其特征在于，所述含铜物料、含铁物料和含氟物料均为球团或粉状物料或制粒；其中，粉状物料的粒度≤150μm，粒状物料粒度为5～25mm，粉状物料以喷吹的方式喷入，粒状物料以喷吹或投料的方式加入，载入气体为0～1200℃的氩气、氮气、还原性气体、氧化性气体中的一种或多种；所述的喷吹方式为采用耐火喷枪***熔渣或置于反应熔渣上部或侧面或底部吹入中的一种或几种；所述的碱性物料为石灰粉、赤泥、脱钠后高钙赤泥、电石渣、白云石粉或生石灰粉中的一种或几种；所述的碱性含铁物料为CaO/SiO₂>1的含铁物料、碱性烧结矿、碱性铁精矿、铁合金炉渣、钢渣、碱性预还原球团、碱性金属化球团、钢渣或高炉渣中的一种或几种；所述酸性物料为硅石、粉煤灰、煤矸石中的一种或多种；所述酸性含铁物料为CaO/SiO₂≤1的含铁物料、酸性烧结矿、酸性铁精矿、酸性预还原球团、酸性金属化球团、铜渣、含铅炉渣、锌冶炼渣、镍冶炼渣、锡冶炼渣、铁合金渣、高炉渣中的一种或几种。The method according to claim 2, wherein the copper-containing material, the iron-containing material and the fluorine-containing material are pellets or powdery materials or granulation; wherein, the granular material has a particle size of ≤150 μm, and the granular material The particle size is 5~25mm, the powdery material is sprayed by spraying, and the granular material is added by spraying or feeding, and the gas is loaded into argon gas, nitrogen gas, reducing gas and oxidizing gas of 0-1200 °C. One or more of the following methods; the injection method is one or several types in which a refractory spray gun is inserted into the slag or placed in the upper portion or the side or bottom of the reaction slag; the alkaline material is lime powder. One or more of red mud, high calcium red mud, calcium carbide slag, dolomite powder or quicklime powder after de-sodium removal; the basic iron-containing material is CaO/SiO ₂ >1 iron-containing material, alkaline One or more of sinter, alkaline iron concentrate, iron alloy slag, steel slag, alkaline pre-reduction pellet, alkaline metallized pellet, steel slag or blast furnace slag; the acidic material is silica, fly ash One or more of coal gangue; the acidic iron-containing material is CaO/SiO ₂ ≤1 Iron material, acid sinter, acid iron concentrate, acid pre-reduction pellet, acid metallized pellet, copper slag, lead slag, zinc smelting slag, nickel smelting slag, tin smelting slag, iron alloy slag, blast furnace slag One or several.
如权利要求1-7中任一项所述的方法，其特征在于，所述步骤S2分离回收中，进行如下处理：The method according to any one of claims 1 to 7, wherein the step S2 is separated and recovered, and the following processing is performed:

含有热态或冷态所述富铜相，送往转炉或吹炼炉炼铜或缓冷破碎磁选分离金属铁后再送往转炉或吹炼炉炼铜或经磁选分离金属铁或不经磁选分离金属铁后，直接还原，还原产物经磁选分离金属铁后，再送往转炉或吹炼炉炼铜； Containing the copper-rich phase in a hot or cold state, sent to a converter or a blowing furnace for copper smelting or slow cooling and magnetic separation to separate the metal iron, and then sent to a converter or a blowing furnace for copper smelting or magnetic separation to separate metal iron or not After separation of the metal iron by magnetic separation, the reduction product is directly separated by magnetic separation, and then sent to a converter or a blowing furnace for copper smelting;

所述含锌组分与含铅组分，以氧化物形式进入烟尘；The zinc-containing component and the lead-containing component enter the soot as an oxide;

所述含铁硅酸盐矿物相和/或所述富铁相，进行如下方法A-G中的任一种处理；The iron-containing silicate mineral phase and/or the iron-rich phase is subjected to any of the following methods A-G;

方法A：水淬或空冷后，直接用于水泥原料；Method A: directly after water quenching or air cooling, used for cement raw materials;

方法B：部分或全部所述含铁硅酸盐矿物相和/或所述富铁相返回到反应熔渣中作为热态冶金熔剂；Method B: part or all of the iron-containing silicate mineral phase and/or the iron-rich phase is returned to the reaction slag as a hot metallurgical flux;

方法C：用于浇筑微晶玻璃或作为矿渣棉；Method C: for pouring glass ceramics or as slag wool;

方法D：所述含铁硅酸盐矿物相和/或所述富铁相保留在熔炼反应装置内或将其倒入保温装置，向熔渣中，吹入温度为0～1200℃的预热氧化性气体，并保证熔渣温度>1450℃；当熔渣氧化亚铁重量百分比含量<1％，获得氧化后的熔渣；所述氧化后的熔渣直接空冷或水淬，用作矿渣水泥、水泥调整剂、水泥生产中的添加剂或水泥熟料；Method D: The iron-containing silicate mineral phase and/or the iron-rich phase remains in the smelting reaction device or is poured into the heat preservation device, and the preheating at a temperature of 0 to 1200 ° C is blown into the slag. Oxidizing gas, and ensure that the slag temperature is >1450 ° C; when the slag oxidized ferrous iron content percentage <1%, the oxidized slag is obtained; the oxidized slag is directly air-cooled or water quenched, used as slag cement , cement conditioner, additive in cement production or cement clinker;

方法E、用于生产高附加值的水泥熟料，方法如下：Method E, for producing high value-added cement clinker, the method is as follows:

E-1、将所述含铁硅酸盐矿物相和/或所述富铁相保留在熔炼反应装置内或将熔渣倒入保温装置，向熔渣中，加入熔融钢渣、石灰、石灰石、铁合金炉渣、粉煤灰、碱性铁贫矿、铝土矿、熔融高炉渣、赤泥、脱钠后赤泥或电石渣中的一种或几种，充分混合，获得熔渣混合物料；E-1, retaining the iron-containing silicate mineral phase and/or the iron-rich phase in the smelting reaction device or pouring the slag into the heat preservation device, and adding molten steel slag, lime, limestone, One or more of ferroalloy slag, fly ash, alkaline iron ore, bauxite, molten blast furnace slag, red mud, red mud after desoda or calcium carbide slag, thoroughly mixed to obtain slag mixture;

E-2、向上熔渣混合物料中吹入预热温度为0～1190℃的氧化性气体，并保证熔渣混合物料温度>1440℃；当氧化亚铁重量百分比含量<1％，获得氧化后的熔渣；E-2, the slag mixture mixture is blown into an oxidizing gas having a preheating temperature of 0 to 1190 ° C, and the temperature of the slag mixture is >1440 ° C; when the weight percentage of ferrous oxide is <1%, the oxidation is obtained. Slag

E-3、对所述氧化后的熔渣，进行空冷或水淬，制得高附加值的水泥熟料；E-3, performing air cooling or water quenching on the oxidized slag to obtain a high value-added cement clinker;

方法F：所述含铁硅酸盐矿物相和/或所述富铁相熔渣作为高炉炼铁原料或直接还原炼铁原料：将含铁硅酸盐矿物相和/或所述富铁相的熔渣空冷、水淬或缓冷后，用作高炉炼铁或直接还原炼铁原料，直接还原后，采用磁选分离或电炉熔分，磁选产物为金属铁与尾矿，电炉熔分，产物为铁水与熔渣；Method F: the iron-containing silicate mineral phase and/or the iron-rich phase slag as a blast furnace ironmaking raw material or a direct reduction ironmaking raw material: an iron-containing silicate mineral phase and/or the iron-rich phase After the slag is air-cooled, water-quenched or slow-cooled, it is used as a blast furnace ironmaking or direct reduction ironmaking raw material. After direct reduction, magnetic separation or electric furnace melting is used, and the magnetic separation product is metal iron and tailings, and the electric furnace is melted. The product is molten iron and slag;

或将所述含铁硅酸盐矿物相和/或所述富铁相的熔渣倒入保温装置后，采用以下方法进行分离：熔渣改性后磁选分离：向保温装置中的熔渣，吹入0～1200℃的预热的氧化性气体，并保证其熔渣温度>1250℃，完成熔渣中磁铁矿的转化；将上述氧化后的熔渣缓冷至室温，破碎、磁选，产物为磁铁矿精矿与尾矿，尾矿作为建筑材料；Or after pouring the iron-silicate-containing mineral phase and/or the iron-rich phase slag into the heat preservation device, separating by the following method: magnetic separation after slag modification: slag into the heat preservation device , blowing a preheated oxidizing gas at 0-1200 ° C, and ensuring that the slag temperature is >1250 ° C, completing the conversion of magnetite in the slag; slowly cooling the oxidized slag to room temperature, crushing, magnetic Selected, the product is magnetite concentrate and tailings, tailings as building materials;

方法G：所述含铁熔渣进行还原炼铁，包括如下步骤：Method G: The iron-containing slag is subjected to reduction ironmaking, comprising the following steps:

G-1、将所述含铁硅酸盐矿物相和/或所述富铁相的熔渣保留在熔炼反应装置内或将熔渣倒入保温装置，向熔融态熔渣中加入含铁物料、还原剂，进行熔融还原，实时监测反应熔渣，通过调控同时满足条件：反应熔渣的温度为1350～1650℃和反应熔渣的碱度CaO/SiO₂比值＝0.6～2.4，获得反应完成后的熔渣；G-1, retaining the iron-containing silicate mineral phase and/or the iron-rich phase slag in the smelting reaction device or pouring the slag into the heat preservation device, and adding the iron-containing material to the molten slag The reducing agent is subjected to smelting reduction, and the reaction slag is monitored in real time, and the conditions are satisfied by the regulation: the temperature of the reaction slag is 1350 to 1650 ° C and the alkalinity of the reaction slag is CaO / SiO ₂ ratio = 0.6 to 2.4, and the reaction is completed. After the slag;

其中，控制反应熔渣的温度的方法为：Among them, the method of controlling the temperature of the reaction slag is:

当反应熔渣的温度＜1350℃，通过反应装置自身的加热，或向熔渣中加入燃料与预热的氧化性气体，使反应熔渣的温度达到1350～1650℃；When the temperature of the reaction slag is <1350 ° C, the heating of the reaction device itself, or the addition of fuel and preheated oxidizing gas to the slag, so that the temperature of the reaction slag reaches 1350 ~ 1650 ° C;

当反应熔渣的温度＞1350℃，向反应熔渣中加入冶金熔剂、含铁物料或含氟物料中的一种或几种，使反应熔渣的温度达到1350～1650℃；其中，所述冶金熔剂为含CaO或SiO₂的矿物；When the temperature of the reaction slag is >1350 ° C, one or more of a metallurgical flux, an iron-containing material or a fluorine-containing material is added to the reaction slag to bring the temperature of the reaction slag to 1350 to 1650 ° C; wherein The metallurgical flux is a mineral containing CaO or SiO ₂ ;

控制反应熔渣的碱度的方法为：The method of controlling the alkalinity of the reaction slag is:

当反应熔渣中碱度CaO/SiO₂比值<0.6时，向熔渣中加入碱性物料和/或碱性含铁物料；When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is less than 0.6, an alkaline material and/or an alkaline iron-containing material is added to the slag;

当反应熔渣中碱度CaO/SiO₂比值>2.4时，向熔渣中加入酸性物料和/或酸性含铁物料； When the ratio of alkalinity CaO/SiO ₂ in the reaction slag is >2.4, an acidic material and/or an acidic iron-containing material is added to the slag;

G-2、所述G-1中熔融还原时还需向熔渣中喷吹0～1200℃预热后的氧化性气体进行熔融还原，形成还原后的熔渣；G-2, in the G-1, in the smelting reduction, the oxidizing gas preheated by 0 to 1200 ° C is sprayed into the slag to be smelted and reduced to form a reduced slag;

G-3、分离回收：采用以下方法中的一种：G-3, separation and recovery: use one of the following methods:

方法Ⅰ：将还原后的混合熔渣倒入保温渣罐，冷却至室温，获得缓冷渣；其中，金属铁沉降到反应装置的底部，形成铁坨，将剩余缓冷渣中含金属铁层，破碎至粒度20～400μm，磨矿，磁选分离出剩余金属铁与尾矿；Method I: Pour the mixed slag after reduction into a heat preservation slag tank, and cool to room temperature to obtain slow cooling slag; wherein, the metal iron is settled to the bottom of the reaction device to form iron slag, and the remaining chilled slag contains metal iron layer , crushed to a particle size of 20 to 400 μm, grinding, magnetic separation to separate the remaining metal iron and tailings;

方法Ⅱ：还原后的混合熔渣，冷却沉降，渣-金分离，获得铁水与还原后的熔渣；所述还原后的熔渣，按照方法A～E中的一种或几种方法进行熔渣处理；所述铁水，送往转炉或电炉炼钢；Method II: the mixed slag after reduction, cooling and sedimentation, separation of slag-gold, obtaining molten iron and reduced slag; and the slag after reduction is melted according to one or several methods of methods A to E Slag treatment; the molten iron is sent to a converter or an electric furnace for steelmaking;

或含有所述富铁相层进行水淬或空冷或倒入保温装置缓冷经人工分拣与重选结合获得，作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料或浮选提铜原料或磁选分离金属铁后作为炼铜或直接还原炼铁的原料；浮选产物为含铜精矿与铁精矿，铜精矿返回炼铜***，铁精矿作为高炉炼铁原料或直接还原炼铁原料或熔融还原炼铁原料；其中，在直接还原过程中，还原产物磁选分离后，获得金属铁与尾矿，尾矿返回炼铜***；所述直接还原过程采用转底炉、隧道窑、车底路、竖炉、回转窑或感应炉，利用气基或煤基还原，气基还原采用天然气和/或煤气，煤基还原采用无烟煤、烟煤、褐煤、焦煤、焦粉或焦炭中的一种或几种，控制还原温度为900～1400℃，控制碱度CaO/SiO₂比值＝0.8～1.5。Or containing the iron-rich phase layer for water quenching or air cooling or pouring into a heat preservation device, slow cooling by manual sorting and re-election, as a blast furnace ironmaking raw material or direct reduction ironmaking raw material or smelting reduction ironmaking raw material or flotation Copper extraction raw materials or magnetic separation and separation of metal iron as raw materials for copper smelting or direct reduction ironmaking; flotation products are copper-containing concentrates and iron concentrates, copper concentrates are returned to copper smelting system, iron concentrates are used as blast furnace ironmaking raw materials Or directly reducing the ironmaking raw material or the smelting reduction ironmaking raw material; wherein, in the direct reduction process, after the magnetic reduction of the reduced product, the metal iron and the tailings are obtained, and the tailings are returned to the copper smelting system; Furnace, tunnel kiln, undercarriage, shaft furnace, rotary kiln or induction furnace, using gas-based or coal-based reduction, gas-based reduction using natural gas and/or gas, coal-based reduction using anthracite, bituminous coal, lignite, coking coal, coke breeze Or one or more of coke, the controlled reduction temperature is 900-1400 ° C, and the control alkalinity CaO / SiO ₂ ratio = 0.8 ~ 1.5.
如权利要求8的方法，其特征在于，所述氧化性气体为预热的空气、氧气、富氧空气、氮气-空气、氩气-空气、氧气-氮气、氧气-氩气中的一种，所述预热的温度为0～1200℃；The method of claim 8 wherein said oxidizing gas is one of preheated air, oxygen, oxygen-enriched air, nitrogen-air, argon-air, oxygen-nitrogen, oxygen-argon. The preheating temperature is 0 to 1200 ° C;

所述燃料与还原剂为固体、液体或气体中的一种或多种，以喷吹或投料的方式喷入，所述喷吹载入气体为预热的氧化性气体、氮气或氩气中的一种或多种，所述预热的温度为0～1200℃；所述固体燃料与还原剂为煤粉、焦粉、焦炭、粉煤灰、烟煤或无烟煤中的一种或多种，形状为粒状或粉状，粒状物料粒度为5～25mm，粉状物料粒度为≤150μm，所述液体燃料与还原剂为重油，气体燃料与还原剂为煤气和/或天然气。The fuel and the reducing agent are one or more of a solid, a liquid or a gas, which is sprayed or fed, and the injected gas is preheated in an oxidizing gas, nitrogen or argon. One or more of the preheating temperature is 0 to 1200 ° C; the solid fuel and the reducing agent are one or more of coal powder, coke powder, coke, fly ash, bituminous coal or anthracite. The shape is granular or powdery, the granular material has a particle size of 5 to 25 mm, the powdery material has a particle size of ≤150 μm, the liquid fuel and the reducing agent are heavy oil, and the gaseous fuel and the reducing agent are gas and/or natural gas.
如权利要求1所述的方法，其特征在于，在所述步骤S1中，所述混合均匀为自然混合或搅拌混合，搅拌方式为氩气搅拌、氮气搅拌、氮气-氩气混合气搅拌、还原性气体搅拌、氧化性气体、电磁搅拌或机械搅拌中的一种或几种；The method according to claim 1, wherein in the step S1, the mixing is uniformly performed by natural mixing or stirring, and the stirring mode is argon stirring, nitrogen stirring, nitrogen-argon gas mixture stirring, reduction. One or more of gas agitation, oxidizing gas, electromagnetic stirring or mechanical agitation;

在所述步骤S2中，所述沉降为自然沉降或旋转沉降或离心沉降；进行冷却沉降时的冷却方式为自然冷却或旋转冷却或离心冷却，所述分离时，用重力分选法是摇床分选、溜槽分选或者二者相结合。 In the step S2, the sedimentation is natural sedimentation or spin sedimentation or centrifugal sedimentation; the cooling mode when cooling sedimentation is natural cooling or rotary cooling or centrifugal cooling, and the gravity sorting method is a shaker. Sorting, chute sorting or a combination of the two.