CN1052147A - Oxide compound is produced - Google Patents

Abstract

The present invention relates to the processing of inorganic mineral, produce metal oxide from metallic sulfide (the particularly sulfide of antimony) specifically.This method is to use the suitable leaching agent leaching mineral earlier, makes then to leach the material hydrolysis.Improvement separates the leaching material earlier before being included in hydrolysis from leaching agent.Separate the most handy crystallization.But this improve one's methods can use nontoxic and inexpensive agents, the reaction conditions a large amount of reagent of not harsher recirculation and solvent, intermediate product active high, end product quality is good and the secondary product that also can obtain economic worth.

Description

Oxide compound is produced

The present invention relates to the processing of inorganic mineral.More particularly, the present invention relates to produce metal oxide from metallic sulfide.The present invention is specially adapted to produce weisspiessglanz from the mineral of stibiated sulfide.

From the antimony sulfide concentrate, produce sb oxide and proposed many methods.

For example, the pyrometallurgy of producing sb oxide is a roasting brightness antimony concentrate in air, and this will produce the flores of evaporable sb oxide.

The shortcoming of this method is: as the common volatilization of the impurity such as compound, trace sulfide and sulfurous gas of arsenic oxide, lead and iron with carry secretly; Impure oxide compound need be handled again, just high purity product can be obtained; Must handle with absorption process or other method with the sulfurous gas that produces, to avoid topsoil.

Hydrometallurgy also proposes, and as United States Patent (USP) 2,331,395 is described.This method is referred to as " method at sunshine (Sunshine process) ", and wherein metallic antimony is from antimony leaching liquid electrolytic recovery.This leaching liquid is to get with the leaching of sodium sulphite selectivity from stibiated sulfide concentrate.In the Soviet Union and China similar electrolysis process has been described also.

But this electrolytic process only limits to produce metal, and it also will further be handled could generate oxide compound.In addition, also need additional treatment step for the sulphur component that reclaims original feed.For example, in above-mentioned relevant electrolytic process, sodium sulphite is recovered and recycled in the leaching liquid by crystallization usually.

The method of another prior art also comprises with ammonium sulfide selectivity leaching brightness antimony concentrate, reclaims sulfide (as United States Patent (USP) 3,883,635 is described) by the distillation of leaching liquid then.After this make the sulfide of recovery be converted into oxide compound and sulphur by the digestion in nitric acid.The shortcoming of this method is an ammonium sulfide frowziness when actually operating, and the elementary sulfur by product economic worth that obtains is also little.

United States Patent (USP) 3,944 has been introduced the chlorination of brightness antimony concentrate in 653, obtains butter of antimony and sulphur or hydrogen sulfide by product.Antimony chloride (behind the distillation purifying) is by being hydrolyzed to sb oxide.But can not look to initial chlorinating step is selectively to antimony, therefore need carry out purifying to the intermediate product of butter of antimony.In addition, chlorination generally also obtains the not high sulphur by product of economic worth.

French Patent 7,608,963rd is with calcium chloride, SO ₂With oxygen etch antimony concentrate to be converted into muriate.Gained muriate distillation method purifying is hydrolyzed to oxide compound then.Sulphur is finally got rid of with sulphate waste.

Also having other method, is with hydrogen chloride gas etch brightness antimony concentrate, obtains the antimony chloride intermediate product.After it carried out distillation purifying, the mat hydrolysis made antimony chloride be converted into oxide compound.Sulphur in the concentrate is converted into hydrogen sulfide, then is converted into sodium sulphite again.The total cost of these class methods may be higher.

Except that aforesaid method, also proposing some other conversion butter of antimony is the method for weisspiessglanz.For example United States Patent (USP) 3,917, and 793 have described being lower than and make the butter of antimony hydrolysis produce light-stable senarmontite (Senarmontite) under the condition of 40 ℃ and pH7-10.More early can be with reference to United States Patent (USP) 3,883,635, this patent has been described the final heat treatment step that comprises oxide compound such as heat to 500 ℃.

The method of all above-mentioned prior aries generally all has one or two shortcoming: the operational difficulty of toxic reagent or by product; Produce the necessary harsh reaction conditions of final quality products and obtain the low by product of economic worth simultaneously.In addition, for the art methods of using acidolysis, this acidifying has also destroyed remaining leaching agent, and this leaching agent be as before the leaching liquid recirculation from hydrolysising by-product regeneration it must have.This more increases the complicacy and the cost of these technology.

Catalogue of the present invention be to overcome or improve at least one or more problems that above-mentioned technology exists and a kind of method of producing the high pure metal oxide compound is provided, this method can prolong the useful life of employed reagent in method to greatest extent.

Set up present method particularly, be before metallic material is further handled, earlier metal-containing material is separated from leaching liquid, (1) a large amount of leach liquors that do not consume can reclaim and immediately as leaching liquid recirculation like this, simultaneously its original leaching capacity keeps and (2) isolated metal-containing material reveals tangible high reactivity for thereafter processing list basically.

According to the present invention, provide a kind of method from metallic material produce metal oxide.Described method is to leach described metallic material with a kind of suitable leaching agent earlier, and Jin Qu material is hydrolyzed then, and wherein before being hydrolyzed, described leaching material is separated from described leaching agent earlier.

Best, described metal-containing material is to separate from described leaching agent with crystallization process.

Better be to leach described metal-containing material with a kind of sulphide salt solution.Better described sulphide salt or sodium sulphite or the sulfide of described metal.The sodium polysulphide salt that best described sulphide salt is described metal.

Best, before hydrolysis, the crystallization of the described sodium Metal 99.5 sulphide salt of gained is converted into the muriate of described metal after separation.

Different along with the character of used reactant and quality, obviously reaction conditions required for the present invention also can change to some extent.But in general find: the present invention is particularly suitable for preparing the trioxide of high-purity antimony from the mineral that contain antimony sulfide.

Best, from its concentrate, leach antimony sulfide with the antimony sulfide sodium leaching aqueous solution.This leaching liquid is to prepare by add sodium sulphite liquid in stibnite concentrate at the very start.Leaching liquid is easy to filter.The gained slag can be handled with ordinary method, to reclaim contained precious metal.From a large amount of antimony sulfide sodium solid of leaching liquid crystallization, remaining antimony sulfide sodium then reuses as a component of recirculation leaching liquid in solution.But solid has extracted sodium sulphite owing to (using antimony) shifts so far from leaching liquid before this, therefore needs to add sodium sulphite and replenish in the recirculation leaching liquid, still recovers original composition when making it return leaching workshop section.

By with acid-respons, make antimony sulfide sodium solid be converted into butter of antimony, sodium sulphite and hydrogen sulfide.The vitriol oil that need add q.s makes sodium be converted into sodium sulfate and also need add the azeotropic hydrochloric acid of being roughly of q.s and makes antimony be converted into butter of antimony.(staff in present technique field it will be appreciated that: salt and sulfuric acid can be used to produce on the spot hydrochloric acid).The hydrogen sulfide that discharges in the reaction for example can then be absorbed in the sodium hydroxide.From gained liquid through the recyclable sodium sulfate of acidification step.

The butter of antimony vlil.And air-blowing gets rid of soluble sulfide, and the water with q.s is hydrolyzed then, obtains five oxygen dichloride (pentoxydichloride) of antimony, Sb ₄O ₅Cl ₂And hydrochloric acid, but its recirculation after evaporation concentration is used.

Five oxygen dichloride of antimony can be converted into the trioxide of antimony by hydrolysis, are preferably under the alkaline condition to react with it with for example alkali of ammonia, sodium hydroxide or yellow soda ash.

Understand used reagent and the reaction conditions of each step of the inventive method in the following embodiments specifically.In this embodiment, all temperature is a centigradetemperature, and the technology language has the general implication of this area.The thick product of the reaction of gained can be used wherein described method, also can use other currently known methods purifying of this area.

Embodiment

The initial preparation of leaching liquid

530 gram (65%Sb) stibnite concentrates join 444 gram technical pure (60%Na ₂S) sodium sulphite liquid is heated to 80 ℃ in the solution of 1100 ml distilled waters.Fierce the mixing of these slurries is incorporated in 80-95 ℃ of maintenance 30 minutes.

Antimony sulfide sodium solid crystal is come out.This solid filters then to remove liquid.

The preparation that continues of leaching liquid

After isolating solid, in the gained leach liquor, add the commercially pure sodium sulphite (60%Na of 47 grams ₂S) regulate the concentration of sodium sulphite, and be heated to 80 ℃, add 137 gram (65%Sb) sulfide concentrates again, the fierce mixing until abundant dissolving.Slurries as above-mentioned filtration leaching obtain residue and leaching liquid.

The recovery of antimony sulfide sodium

Concentrate this leaching liquid, antimony sulfide sodium solid crystal is come out, it roughly consists of NaSbS ₂, say and join the reagent in the leaching: Na in quality ₂S and Sb ₂S ₃Content is roughly suitable.

Be converted into butter of antimony

Hydrochloric acid with 0.3 mole sulfuric acid and 6 moles makes antimony sulfide sodium solid reflux.Liquid is removed residue in a small amount after filtration.

Generate the oxychlorination thing

Add distilled water and make the liquid hydrolysis that contains butter of antimony and hydrochloric acid, obtain five oxygen dichloride, i.e. Sb of antimony ₄O ₅Cl ₂White fine crystallization precipitation.Remove by filter leaching liquid.

The oxychlorination thing is converted into oxide compound

At room temperature sodium carbonate solution reacts with the oxychlorination thing of the arsenic, lead, iron and the sulphur that contain trace impurity, can get white ANTIMONY TRIOXIDE SB 203 99.8 PCT.

Use the inventive method, the particularly stibiated concentrate of containing metal can be converted into high-purity metal oxide.Other valuable product be can also obtain, sulfide, sulfohydrate and vitriol comprised.

Recovery and purifying workshop section in beginning, this method is to use the selectivity leaching to metallic material, therefore then can in the general structured material relevant, carry out recovery, can avoid for the unite demand of necessary high capacity material of the high-temp chlorination system of prior art from solution with hot alkaline solution.This step also provides the leaching and the purification phase of this method simultaneously, and need not additional purifying, and this is usually requisite for the wide spectrum dissolving with chlorination or hydrochloric acid etching afterwards.

The present invention is particularly suitable for leaching the material of containing metal sulfide, with the inventive method after above-mentioned recovery and purifying workshop section, metallic sulfide with low-grade hydrochloric acid reaction in can be converted into metal chloride.The hydrogen sulfide that discharges can reclaim by for example absorption in sodium hydroxide, and it can further be handled and be used for recirculation and sale.

In following workshop section, under the condition of control, make metal chloride liquid generation hydrolysis, generate the oxychlorination thing of metal.This program can make the most of hydrochloric acid recirculation (behind the dope) that produces in the reaction be used for the workshop section of front.

In last workshop section, under alkaline condition, make metal oxychlorination thing hydrolysis and obtain metal oxide.

Have the many advantages that are better than prior art from the above-mentioned the present invention of being understood that: use (1) Nontoxic and inexpensive reagent, (2) reaction condition temperature closes; (3) a large amount of agent/solvent recycle and because intermediate product reactivity height, thereby just only need less reagent in the follow-up workshop section of this method, and above-mentioned two factors all can make the totle drilling cost of method reduce; (4) obtain the final products of high-quality and the secondary species that (5) obtain having economic worth.

Certainly, be appreciated that above-described embodiment just for illustrating the present invention, in not departing from the scope of the present invention that limits such as claims, can propose various variations to details.

Claims (15)

1, from the method for metallic material produce metal oxide, this method is to leach metallic material with suitable leaching agent earlier, the material of such leaching is hydrolyzed, and the material of wherein said leaching was separated from described leaching agent earlier before being hydrolyzed.

2, according to the process of claim 1 wherein that the material of described leaching is to separate from described leaching agent by crystallization.

3, according to the method for claim 1 or 2, wherein said metallic material is the material of containing metal sulfide.

4,, wherein the leaching of the material of described containing metal sulfide is carried out with sulphide salt solution according to the method for claim 3.

5, according to the method for claim 4, wherein said sulphide salt is the sulfide of described metal.

6, according to the method for claim 5, wherein said described metallic sulfide is the sodium polysulphide of described metal.

7, according to the method for claim 6, wherein said described sodium Metal 99.5 sulfide is by the prepared in reaction of material that contains described metallic sulfide and sodium sulphite.

8, according to arbitrary method among the claim 4-6, wherein after the material of described leaching is isolated earlier, remaining described sulphide salt is as a component of described leaching agent and recirculation in the solution.

9, according to arbitrary method among the claim 1-8, the described leaching material after wherein separating before described hydrolysis is carried out, is converted into the muriate of described metal.

10, according to the method for claim 9, the muriate of wherein said metal is hydrolyzed to the oxide compound of described metal.

11, according to arbitrary method among the claim 1-10, wherein said metallic material is an antimony-containing mineral.

12, according to the method for claim 11, wherein said mineral are mineral of stibiated sulfide.

13, according to the prepared metal oxide of arbitrary method among the claim 1-12.

14, according to claim 1 basically with reference to the described method of the embodiment of the invention.

15, the metal oxide for preparing with reference to the described method of the embodiment of the invention basically.