阅读说明：本技术 一种综合回收钨冶炼除钼渣中铜、钼、钨、硫的方法 (Method for comprehensively recovering copper, molybdenum, tungsten and sulfur in molybdenum removal slag in tungsten smelting ) 是由 刘旭恒 赵中伟 陈星宇 李江涛 何利华 熊家金 邓立勤 于 2019-10-16 设计创作，主要内容包括：本发明公开的一种综合回收钨冶炼除钼渣中铜、钼、钨、硫的方法,包括以下步骤：将除钼渣破碎磨细后置于反应炉中,升温至500～800℃,同时按照一定流速通入氯气至反应结束,得到氯化铜和气态产物；将所得气态产物先降温至380～420℃,得到单质硫磺；再降温至280～320℃,得到氯化钨产品；最后降温至25～50℃,得到氯化钼产品。本发明提供的方法实现了除钼渣中铜、钼、钨、硫的彻底分离,得到的氯化铜可返回钨冶炼的除钼工序,实现了钨冶炼系统中铜资源的循环利用,有利于降低钨冶炼的生产成本,且工艺流程短,操作简单,处理成本较低,易于工业化推广。(The invention discloses a method for comprehensively recovering copper, molybdenum, tungsten and sulfur in tungsten smelting molybdenum-removing slag, which comprises the following steps: crushing and grinding the molybdenum-removing slag, placing the crushed and ground molybdenum-removing slag in a reaction furnace, heating to 500-800 ℃, and introducing chlorine gas at a certain flow rate until the reaction is finished to obtain copper chloride and gaseous products; cooling the obtained gaseous product to 380-420 ℃ to obtain elemental sulfur; cooling to 280-320 ℃ to obtain a tungsten chloride product; and finally, cooling to 25-50 ℃ to obtain a molybdenum chloride product. The method provided by the invention realizes the complete separation of copper, molybdenum, tungsten and sulfur in the molybdenum removal slag, the obtained copper chloride can return to the molybdenum removal process of tungsten smelting, the recycling of copper resources in a tungsten smelting system is realized, the production cost of tungsten smelting is favorably reduced, the process flow is short, the operation is simple, the treatment cost is lower, and the industrial popularization is easy.)

1. A method for comprehensively recovering copper, molybdenum, tungsten and sulfur in molybdenum removal slag in tungsten smelting is characterized by comprising the following steps: crushing and grinding the molybdenum-removing slag, placing the crushed and ground molybdenum-removing slag in a reaction furnace, heating to 500-800 ℃, and introducing chlorine gas at a certain flow rate until the reaction is finished to obtain copper chloride and gaseous products; cooling the obtained gaseous product to 380-420 ℃ to obtain elemental sulfur; cooling to 280-320 ℃ to obtain a tungsten chloride product; and finally, cooling to 25-50 ℃ to obtain a molybdenum chloride product.

2. The method for comprehensively recovering copper, molybdenum, tungsten and sulfur in the molybdenum removal slag from tungsten smelting according to claim 1, characterized in that in the step 1), the molybdenum removal slag is crushed and ground to a particle size of 100 meshes or more and 95%.

3. The method for comprehensively recovering the copper, the molybdenum, the tungsten and the sulfur in the molybdenum slag through tungsten smelting according to claim 1, wherein in the step 1), the flow rate of chlorine gas is 0.5-5L/min, and the time of chlorine gas introduction is 1-4 h.

4. The method for comprehensively recovering copper, molybdenum, tungsten and sulfur in the molybdenum slag removed by tungsten smelting according to any one of claims 1 to 3, characterized by comprising the following steps:

1) crushing and grinding the molybdenum-removing slag until the granularity is more than or equal to 95 percent and then putting the crushed molybdenum-removing slag into a boat, putting the boat into a tubular electric furnace, heating the tubular electric furnace to 500-800 ℃, and simultaneously introducing chlorine gas at the flow rate of 0.5-5L/min until the reaction is finished, wherein the reaction time is 1-4 h, so as to obtain a gaseous product;

2) introducing the gaseous product obtained in the step 1) into a first-stage constant-temperature storage tank, and maintaining the temperature of the first-stage constant-temperature storage tank at 380-420 ℃; introducing gas discharged from the first-stage constant-temperature storage tank into a second-stage constant-temperature storage tank, and maintaining the temperature of the second-stage constant-temperature storage tank at 280-320 ℃; introducing gas discharged from the second section of constant-temperature storage tank into a third section of constant-temperature storage tank, and maintaining the temperature of the third section of constant-temperature storage tank at 25-50 ℃; gas discharged from the third section of constant-temperature storage tank is absorbed by alkali liquor and then is discharged;

3) and cooling the tubular electric furnace, the first section of constant temperature storage tank, the second section of constant temperature storage tank and the third section of constant temperature storage tank to room temperature, obtaining copper chloride from the boat, obtaining elemental sulfur from the first section of constant temperature storage tank, obtaining a tungsten chloride product from the second section of constant temperature storage tank, and obtaining a molybdenum chloride product from the third section of constant temperature storage tank.

Technical Field

The invention relates to the technical field of rare metal tungsten smelting, in particular to a method for comprehensively recovering copper, molybdenum, tungsten and sulfur in tungsten smelting molybdenum-removing slag.

Background

The chemical properties of tungsten and molybdenum are similar, so that molybdenum is usually associated with tungsten concentrate. And the tungsten smelting product APT has very high requirement on the content of molybdenum (less than or equal to 20 mg/kg). Therefore, the separation of tungsten and molybdenum becomes a key process in the tungsten smelting process. At present, more than 80% of APT manufacturers in China adopt a selective precipitation method to remove molybdenum. The method has high molybdenum removal effect and simple operation, but the produced molybdenum removal sulfide slag contains a large amount of valuable metals such as copper, molybdenum, tungsten and the like, and has high recovery value.

At present, domestic manufacturers mostly adopt an alkaline leaching method to leach molybdenum and tungsten in molybdenum removal slag, then carry out acidification on a leaching solution to recover molybdenum, and merge the residual tungsten-containing solution into a tungsten smelting system. The method is simple to operate, but has the defects of low leaching rate of tungsten and molybdenum, incomplete tungsten and molybdenum separation and the like, a large amount of acid and alkali is consumed in the process, and the reagent cost is high. And a few enterprises adopt a combined process of a fire method and a wet method to treat the molybdenum-removed slag, firstly, the molybdenum-removed slag is oxidized and roasted, then, alkali liquor is used for leaching tungsten and molybdenum, and copper is left in the leached slag. A significant disadvantage of this process is the SO content during calcination₂The pollution problem of the flue gas, and the process flow is longer and the production cost is higher. Therefore, at present, most tungsten smelting enterprises stack the molybdenum-removing slag in a warehouse for a long time. With the increasing requirement of environmental protection, the molybdenum removal slag is listed as a dangerous waste list, and how to efficiently treat the molybdenum removal slag to realize the economic and efficient recovery of valuable metals in the molybdenum removal slag becomes the current situationThe prior tungsten smelting process is very important.

Disclosure of Invention

In view of the above, the invention aims to provide a method for comprehensively recovering copper, molybdenum, tungsten and sulfur in molybdenum removal slag in tungsten smelting. According to the invention, the molybdenum removing slag reacts with chlorine at 500-800 ℃, reaction products are recovered in a sectional cooling mode, products such as copper chloride, molybdenum chloride, tungsten chloride and elemental sulfur are respectively obtained, the obtained copper chloride can return to a molybdenum removing process of tungsten smelting, the recycling of copper resources in a tungsten smelting system is realized, the obtained tungsten chloride, molybdenum chloride and the like are important raw materials facing the application field of new materials, and the high-valued recycling of the tungsten and molybdenum resources in the molybdenum removing slag is facilitated; the sulfur is finally produced in the form of elemental sulfur, the added value is high, and the storage and the transportation are convenient. The method is simple to operate, easy to industrially popularize, can realize the separation and recovery of copper, molybdenum, tungsten and sulfur in the molybdenum-removing slag in one step, has high recovery rate of valuable resources, can change the molybdenum-removing slag into valuables, and has very obvious economic benefit and environmental benefit.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a method for comprehensively recovering copper, molybdenum, tungsten and sulfur in molybdenum-removing slag in tungsten smelting comprises the following steps: crushing and grinding the molybdenum-removing slag, placing the crushed and ground molybdenum-removing slag in a reaction furnace, heating to 500-800 ℃, and introducing chlorine gas at a certain flow rate until the reaction is finished to obtain copper chloride and gaseous products; cooling the obtained gaseous product to 380-420 ℃ to obtain elemental sulfur; cooling to 280-320 ℃ to obtain a tungsten chloride product; and finally, cooling to 25-50 ℃ to obtain a molybdenum chloride product.

Preferably, in the step 1), the molybdenum removal slag is crushed and ground to a particle size of 100 meshes or more than 95%.

Preferably, in the step 1), the flow rate of the chlorine gas is 0.5-5L/min, and the time of the chlorine gas is 1-4 h.

Preferably, the method comprises the following steps:

1) crushing and grinding the molybdenum-removing slag until the granularity is more than or equal to 95 percent and then putting the crushed molybdenum-removing slag into a boat, putting the boat into a tubular electric furnace, heating the tubular electric furnace to 500-800 ℃, and simultaneously introducing chlorine gas at the flow rate of 0.5-5L/min until the reaction is finished, wherein the reaction time is 1-4 h, so as to obtain a gaseous product;

2) introducing the gaseous product obtained in the step 1) into a first-stage constant-temperature storage tank, and maintaining the temperature of the first-stage constant-temperature storage tank at 380-420 ℃; introducing gas discharged from the first-stage constant-temperature storage tank into a second-stage constant-temperature storage tank, and maintaining the temperature of the second-stage constant-temperature storage tank at 280-320 ℃; introducing gas discharged from the second section of constant-temperature storage tank into a third section of constant-temperature storage tank, and maintaining the temperature of the third section of constant-temperature storage tank at 25-50 ℃; gas discharged from the third section of constant-temperature storage tank is absorbed by alkali liquor and then is discharged;

3) and cooling the tubular electric furnace, the first section of constant temperature storage tank, the second section of constant temperature storage tank and the third section of constant temperature storage tank to room temperature, obtaining copper chloride from the boat, obtaining elemental sulfur from the first section of constant temperature storage tank, obtaining a tungsten chloride product from the second section of constant temperature storage tank, and obtaining a molybdenum chloride product from the third section of constant temperature storage tank.

Compared with the traditional molybdenum slag removing treatment process, the invention has the beneficial effects that:

1) the method realizes the complete separation of copper, molybdenum, tungsten and sulfur in the molybdenum removal slag, the obtained copper chloride can return to the molybdenum removal process of tungsten smelting, the recycling of copper resources in a tungsten smelting system is realized, and the production cost of tungsten smelting is favorably reduced.

2) Short process flow, simple operation, low treatment cost and easy industrial popularization.

3) The resource utilization and high-value utilization of the molybdenum-removing slag have obvious economic and ecological benefits.

Detailed Description

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.