CN1074464C

CN1074464C - New process for recovering metals of indium, iron, silver and tin from high-indium high-iron zinc preparation concentrate

Info

Publication number: CN1074464C
Application number: CN99106190A
Authority: CN
Inventors: 沈奕林; 覃庶宏
Original assignee: Individual
Current assignee: Individual
Priority date: 1999-05-04
Filing date: 1999-05-04
Publication date: 2001-11-07
Anticipated expiration: 2019-05-04
Also published as: CN1272553A

Abstract

The present invention relates to technology for recovering metal, such as indium, ferrum, silver, tin, etc., from zinc ore concentrate with high indium and ferrum, which comprises the following steps: jarosite slag containing the indium and slag leached in hot acid are treated in a reduction furnace such as a reverberatory furnace or a zinc white furnace, etc., wherein the zinc ore concentrate with high indium and ferrum is leached in the hot acid so that the zinc, the indium and the ferrum are separated from the silver and the tin to obtain silver and tin enriched leached slag; the ferrum and the indium are deposited by a jarosite method so that the zinc is separated from the indium and the ferrum to obtain silver and tin enriched ferric alum slag; after the ferric alum slag is reduced in the reduction furnace by a reducing agent, the ferrum and the indium are respectively separated and recovered, and the silver and the tin are recovered.

Description

New process for recovering metals such as the indium of high indium high-iron zinc sulfide concentrate, iron, silver, tin

The present invention relates to the comprehensive recovery of high indium high-iron zinc sulfide concentrate dilute metal in smelting process.

At present, in various wet method smelting process, because the iron level of high indium high-iron zinc sulfide concentrate is up to more than 10%, indium iron separation difficulty.So the ubiquity indium recovery is low, technical process is long, the production cost height, and scum can't be handled, and silver is difficult to difficult problems such as recovery.At present, the wet processing flow process of handling high indium high-iron zinc sulfide concentrate has three kinds.

First kind of technology is zinc ore concentrate to be carried out neutrality leach after oxidizing roasting, and leached mud obtains containing the low-grade zinc oxide of indium 0.1-0.3% through the rotary kiln reduction volatilization, go out with acidleach again, add the replacement slag that the zinc dust precipitation minuent contains indium 1-5%, carry out acidleach again, indium is carried in extraction then.Because iron content height, influence the liquid-solid separation in the zinc hydrometallurgy, so, this technical process can not the high indium high-iron zinc sulfide concentrate of individual curing, but to join the low indium zinc ore concentrate of a certain proportion of low iron, so just influenced processing power, also reduced the rate of recovery of indium simultaneously, the rate of recovery of its indium generally has only 30%.

Second kind of technology be zinc ore concentrate after oxidizing roasting, carry out hot acid and leach, indium enters leach liquor, adopt centrifugal extractor directly from solution, to carry indium then, raffinate must return the zinc electrolytic system, and there are the following problems for this technology: the one, and raffinate contains organic phase, influences the electrodeposition of zinc; The 2nd, the emulsification of when extraction is serious, the production cost height of indium; The 3rd, extracting system is not easy with the zinc metallurgy system balancing.Because problems, so the manufacturer that uses is few at present.

The third technology is with after the roasting of zinc ore concentrate process, carries out hot acid and leaches, and adopts the heavy iron of jarosite process, contains the iron vitriol slag of indium 0.15-0.2% separately.Then it is decomposed roasting, carry out acidleach again, indium is carried in extraction.This flow process exists technology long, and facility investment is big, production cost height, the secondary pollution of iron oxide red slag, and problem such as indium recovery is low.

Purpose of the present invention just provides a kind of reduced investment, and high efficiency can reclaim valuable metals such as indium, iron, silver, tin, and helps overcoming the new production process of secondary pollution.

Solution of the present invention is performed such: with after the oxidizing roasting of high indium high-iron zinc sulfide concentrate process, adopt hot acid to leach earlier, make the indium more than 95% enter solution, metals such as silver, tin are stayed and have been obtained the first step enrichment in the leached mud; 98% indium entered iron vitriol slag in the solution with the heavy iron of jarosite process second step, had finished separating of zinc and iron, indium, and indium has obtained the first step enrichment in iron vitriol slag like this, and iron vitriol slag contains indium can reach 0.2-0.5%; The 3rd step reacted according to Stephen Bourdow, the reduction with carbon method is handled and is contained the indium iron vitriol slag, can in various reduction stoves such as rotary kiln, reverberatory furnace, Furnace for obtaining white zinc, carry out, obtain containing the oxidation material of indium 1-5%, make indium obtain enrichment for the second time, finished indium iron and separated, obtain the slag of iron content more than 35% simultaneously, can be used for ironmaking, system cement, field such as bake bricks, iron is recycled fully; The 4th step was carried out acidleach to containing the indium material, and indium is carried in extraction then.

In addition, the leached mud of argentiferous, tin also reduction with carbon method is respectively handled, and contains indium in this leached mud and also reaches 0.1-0.13%, can reclaim.Obtain the slag that argentiferous is 0.5-0.8%, can be used as silver preparation concentrate, wherein tin content also can reach 1-8%, has realized that like this silver, tin reclaim.

Embodiment of the present invention are such: earlier with the oxidizing roasting of high indium high-iron zinc sulfide concentrate process fluidizing furnace, mainly contained the roasting sand of zinc oxide.It is to exist with the wustite that is not soluble in dilute sulphuric acid or the form of silicate that part zinc, indium and iron are wherein arranged, then with zinc roasting sand as raw material, smelt according to the process flow sheet in the accompanying drawing 1.

In the technical process of accompanying drawing 1, after zinc roasting sand leached through a series of sulfuric acid, the zinc more than 95%, indium and iron entered solution system, and silver, tin and lead are stayed in the leached mud, have realized the first step enrichment; Add sylvite or ammonium salt,, the iron that contains in zinc, indium and the ferrous solution is separated from solution with the solid form of jarosite (or ammonium jarosite) as vitriol or carbonate.Wherein there is 98% indium also to enter in the solid siderotil, from solution, separates with iron with the form of alum.Zinc still is retained in the solution, enters in the following zinc metallurgy system, and indium obtains preliminary enrichment in siderotil, and iron vitriol slag contains indium and reaches 0.2-0.3%; Handle iron vitriol slag and the leached mud that contains indium respectively with rotary kiln, further separate indium, iron, silver, tin and lead.Add a certain proportion of reductive agent such as coke powder or go back raw coal in rotary kiln, reductive agent is 1: 3 to 2: 3 (weight) with the ratio of material.The temperature of control kiln, iron vitriol slag in rotary kiln by different temperature bands successively dewater, sulphate decomposition and reactions such as oxidation, reduction, wherein dehydration temperaturre is 35 0 ℃-500 ℃, the temperature of sulphate decomposition and oxidation is 500 ℃-900 ℃, the temperature of reduction reaction is 1100 ℃-1350 ℃, can obtain containing the volatilization material of indium 1-5% through above-mentioned processing, and iron and silver and tin are retained in respectively in rich silver-colored, the scruff (argentiferous 0.5-0.8%, tin 5-10%) of rotary kiln scum (iron content is up to more than 35%) and rotary kiln.Originally the precious metals such as indium, iron, silver and tin that were difficult to reclaim application in the high indium high-iron zinc sulfide concentrate are reclaimed fully, and the indium purity that wherein electric indium recovery obtains has realized no waste sludge discharge 99.99%.

The advantage of technology of the present invention is: 1. the rate of recovery height of indium reaches 70% (from zinc concentrate Calculate); 2. the rate of recovery of zinc, iron, silver is up to more than 95%; 3. whole smelting process flow process Short, reduced investment, the easy balance of system is produced stable; 4. the cost of extraction of indium is low; 5. do not have Waste sludge discharge.

Claims

1. one kind is reclaimed indium in high indium high-iron zinc sulfide concentrate, iron, silver, the technology of metals such as tin, this technology is included in rotary kiln, handle jarosite slag and the hot acid leached mud that contains indium in the reduction furnace such as reverberatory furnace or Furnace for obtaining white zinc, wherein high indium high-iron zinc sulfide concentrate leaches through hot acid, zinc, indium, iron and silver, tin separates the leached mud that obtains enrichment silver and tin, with the heavy iron of jarosite process, indium, reach zinc and indium, iron separates, obtain being rich in the iron vitriol slag of indium and iron, iron vitriol slag successively dewaters by different temperature bands in rotary kiln, sulphate decomposition and oxidation, reactions such as reduction, wherein dehydration temperaturre is 350 ℃-500 ℃, the temperature of sulphate decomposition and oxidation is 500 ℃-900 ℃, the temperature of reduction reaction is 1100 ℃-1350 ℃, can realize iron respectively through after the above-mentioned processing, indium separates and reclaims and realize the recovery of silver and tin.

2. according to the technology of claim 1, it is characterized in that the ratio of reductive agent and material is 1: 3 to 2: 3 (weight) in the reduction reaction.

3. according to the technology of claim 2, it is characterized in that reductive agent is coke or goes back raw coal.