CN1093756A - From copper slag, reclaim the method for metals such as tin, copper, lead, zinc - Google Patents

Abstract

The present invention is a kind of method that reclaims metals such as tin, copper, lead, zinc from copper slag, adopt the hot stove in ore deposit retailoring copper slag at high temperature, produce the alloy of oxide powder and zinc and tin, lead, copper, iron, adopt oxidizing roasting, selectivity sulfuric acid to leach this alloy and produce tindioxide, lead sulfate mixing slag and copper sulfate, ferric sulfate mixed solution, the retailoring after desulfurization of tin, lead skim gets scolding tin, and mixed solution send electrolysis to get electrolytic copper after the deironing of ammonium jarosite method.

Description

From copper slag, reclaim the method for metals such as tin, copper, lead, zinc

The present invention is a kind of method to copper slag secondary resource comprehensive reutilization, relates to the electrosmelting technology of copper slag of multiple metals such as containing tin, copper, lead, zinc and the separating technology of these complex alloys.

Contain tin in the copper slag, copper, plumbous, multiple valuable metal such as zinc, its potential utility value is than higher, but because its complicated component, grade is relatively low, so metal smelting wherein can't be come out with prior art, so not only cause a large amount of secondary resource wastes, and polluted environment, for a long time, people once attempted to come it is reclaimed by the whole bag of tricks, but all do not achieve success, copper slag is to be in discarded situation always, in general, will restore valuable metal in low-grade copper waste residue, its conventional means is to carry out under the condition of high reductibility, certainly will cause the reduction of a large amount of iron like this, the complicacy of the reduction of iron and products obtained therefrom composition makes the product of this refinement not have commercial value.

The objective of the invention is to invent and a kind ofly copper slag is handled with electric furnace smelting method, obtain the alloy of oxide powder and zinc and tin, copper, lead, iron, adopt operations such as oxidation roast, the leaching of sulfuric acid selectivity, ammonium jarosite deironing that this alloy is separated then, reach the purpose that reclaims product.

The present invention constitutes like this: utilize electric furnace smelting method, copper slag under being 1250～1400 ℃, the condition of coke ratio 2～5%, fluorite 2～8%, temperature is smelted (generally speaking, the content of each metallic element is in the copper slag: tin 2～5%, copper 2～8%, zinc 1～5%, plumbous 1～3%, iron 10～20% or the like), produce the alloy of the oxide powder and zinc that contains ZnO75～90% and tin, copper, lead, iron; At this moment, in this alloy, contain tin 30～45%, copper 10～25%, lead 10～20%, iron 8～20%; Carry out oxidizing roasting with obtaining under the condition that alloy is in 750～850 ℃, the purpose of oxidizing roasting is to make each metallic element be transformed into high oxide, control Sn in the calcining ²⁺＜1%; Under 85～95 ℃, liquid-solid ratio equal 1: 3, the condition of 2～4 hours time this oxide compound being carried out two sections adverse current selectivity sulfuric acid then leaches, thereby make tin, lead, separate with copper, iron, vitriolic adding mode is anti-the leaching, at this moment, control vitriolic concentration is no more than 100 grams per liters, leach liquor is through filtering the mixed solution of back output tin, lead skim and copper sulfate, ferric sulfate, at this moment, in the tin lead skim, contain about Sn40%, plumbous about 20%, contain Cu50～100 grams per liters in Fe＜8%, Cu＜1%, the copper-bath, Fe30～50 grams per liters.At last tin, lead skim are carried out the pyrogenic process desulfurization in rotary kiln, use the electric furnace reducing and smelting again, output scolding tin contains Sn60～70%, Pb20～30% in the scolding tin; The mixed solution of copper sulfate, ferric sulfate under temperature is 90～95 ℃, the condition of pH value 1.5～2, is added bicarbonate of ammonia (NH ₄HCO ₃) add-on is 45～55% of total iron-holder, adjusts pH value to 1.5～2 with milk of lime, and iron is generated ammonium jarosite, reaches copper, the isolating purpose of iron.Handle copper-bath according to common process, produce electrolytic copper.

Compared with prior art, the technology of the present invention is simple, be convenient to operation, low production cost, and is safe and reliable, make the depleted copper slag to make a silk purse out of a sow's ear on the one hand, reduced the pollution of environment on the other hand, the present invention is easy to promote, and has good society, economic benefit.

Embodiments of the invention: get 13 tons of copper slags, allocate 40 kilograms of coke powders, 65 kilograms in fluorite into, in the hot stove in 1800 kilovolt-amperes ore deposit, carry out 18 hours reducing and smeltings, produce 220 kilograms of oxide powder and zincs (containing ZnO85%), produce 1 ton of alloy; With ball mill alloy is pulverized to 60 orders, carry out the oxidation roast in homemade rotary kiln, 780 ℃ of temperature, 3 hours time, output calcining (contain Sn for 1.25 tons ²⁺0.8%), these 1.25 tons of calcinings being put into volume is 5.5m ³Leaching vat in leach, 88 ℃ of extraction temperatures, 4 hours time, add 920 kilograms in sulfuric acid (add at twice, two sections adverse currents leach), produce 900 kilograms of tin lead skims, produce leach liquor 4m ³, contain Cu78 grams per liter, Fe25 grams per liter, Sn0.3 grams per liter, Pb trace in the leach liquor, the leaching yield of the leaching yield of Cu＞96.5%, Fe＞65%, after 870 ℃ of rotary kiln desulfurization, the tin lead skim contains S0.8%, above-mentioned 4m with the tin lead skim of above-mentioned sulfur-bearing 4.5% ³Leach liquor 95 ℃ of temperature, is transferred pH value to 1.5～2.0 with milk of lime, adds NH ₄HCO ₃50 kilograms after behind 2 hours heavy alum, it is 75 grams per liters that solution contains Cu, contains the Fe1.8 grams per liter; Get 900 kilograms of tin lead skims, allocate 100 kilograms of coke powders, 130 kilograms in lime into, 200 kilograms of silica sands were said reductase 12 0 hour at 650 kilovolt-amperes electric furnace, 460 kilograms of tinsels, wherein contain Sn71%, Pb26%, other 3%, through refining and after joining lead No. 60 scolding tin; Send electrolysis with the leach liquor after the deironing, can get 270 kilograms of electrolytic coppers.

Claims (3)

1, a kind of method that from copper slag, reclaims metals such as tin, copper, lead, zinc, it is characterized in that: utilize electric furnace smelting method, copper slag is smelted under temperature is 1250～1400 ℃, the condition of coke ratio 2～5%, fluorite 2～8%, produced the alloy of the oxide powder and zinc that contains ZnO75～90% and tin, copper, lead, iron.

2, according to the described this method that from copper slag, reclaims metals such as tin, copper, lead, zinc of claim 1, it is characterized in that: will obtain carrying out the oxidation roast under the condition that alloy is in 750～850 ℃, and make each metallic element be transformed into high oxide like this; Under 85～95 ℃, liquid-solid ratio equal 1: 3, the condition of 2～4 hours time this oxide compound being carried out two sections adverse current selectivity sulfuric acid then leaches, vitriolic adding mode is anti-the leaching, at this moment, control vitriolic concentration is no more than 100 grams per liters, like this, obtain containing tin, lead skim and copper sulfate, the ferric sulfate mixed solution of tindioxide, lead sulfate.

3, according to claim 1 or the 2 described this methods that from copper slag, reclaim metals such as tin, copper, lead, zinc, it is characterized in that: the mixed solution of copper sulfate, ferric sulfate under temperature is 90～95 ℃, the condition of PH1.5～2, is added bicarbonate of ammonia (NH ₄HCO ₃), add-on is 45～55% of total iron-holder, adjusts pH value to 1.5～2 with milk of lime, and iron is generated ammonium jarosite, reaches copper, the isolating purpose of iron.