CN1035724C

CN1035724C - Method for producing nickel sulfate and cupric sulfate from mixed nickel-copper material

Info

Publication number: CN1035724C
Application number: CN 92105548
Authority: CN
Inventors: 潘同汉
Original assignee: Individual
Current assignee: Individual
Priority date: 1992-07-06
Filing date: 1992-07-06
Publication date: 1997-08-27
Anticipated expiration: 2007-07-06
Also published as: CN1082512A

Abstract

The present invention relates to a novel method for preparing nickel sulfate and copper sulfate from nickel-copper mixture, which is characterized in that the novel method comprises the steps as follows: firstly, the mixture is added with sulphuric acid and nitric acid, acidified into a mixed hydrothermal solution of nickel sulfate and copper sulfate, and put in a dark room for static chilling; then, copper sulfate separated by crystallization is separated from nickel sulfate which is separated after the discharge of the solution. The method for separating nickel sulfate form copper sulfate has the advantages of simple technology, high utilization rate of raw material, little consumption of auxiliary raw material and reduction of production cost of nickel sulfate and copper sulfate.

Description

Method for producing nickel sulfate and cupric sulfate from mixed nickel-copper material

The invention relates to a kind of method with ambrose alloy compound and nickeliferous copper junk, waste residue, waste water production single nickel salt and copper sulfate.

In industrial production and mine smelting, many nickeliferous copper raw materials, waste material are arranged, all these raw materials can be processed into single nickel salt and copper sulfate, but these raw materials are not fully utilized so far.Its major cause is to separate the method for single nickel salt and copper sulfate now mostly according to Ni (OH) ₂, Cu (OH) ₂, NiCO ₃, CuCO ₃Or NiS, the CuS different pH values when precipitation are separated.Separate single nickel salt and copper sulfate in this way and all want caustic soda or soda ash or sodium sulphite, make copper sulfate change into copper hydroxide, copper sulfate or copper sulfide precipitation and separate out, it is separated with nickel sulfate solution.Adopt this method when the high raw material of Treatment of Copper amount, then produce a large amount of copper ashes, this slag can reduce the rate of recovery of nickel.Adopt this method to carry out the ambrose alloy separation and also will consume a large amount of auxiliary materials, Production Flow Chart is long, and labour intensity is big, has pressed for a kind of more reasonable method and has utilized these raw materials, waste material.

The purpose of this invention is to provide a kind of method of separating the ambrose alloy compound.Adopting this method is not to add the pH value that alkali is adjusted single nickel salt copper sulfate mixing solutions, and the compound precipitation of copper is separated out, and obtains nickel sulfate solution, but utilizes the darkroom crystallization directly to separate single nickel salt and copper sulfate.This method can reduce the consumption of copper nickel, can reduce auxiliary material, can extensively utilize various ambrose alloy raw materials and waste material, simplifies production technique, reduces production costs.

The novel method that the present invention proposes is to find to have the supersaturated solution of the mineral compound of 7 crystal water to have in the immobilized darkroom can crystallization not separate out, and has only exposure, vibration influence when tapping, just the crystallization characteristics design separated out.Single nickel salt is 6 hydrates in time more than 31.5 ℃, and its supersaturated solution can be separated out in the immobilized darkroom in crystallization.Because of being converted into 7 water single nickel salts, its supersaturated solution can not separated out in the immobilized darkroom in crystallization below 31.5 ℃ the time.Copper sulfate is that its supersaturated solution of 5 hydrates can be separated out in the immobilized darkroom in crystallization.So, when the dense hot solution of single nickel salt and copper sulfate is cooled off in the immobilized darkroom, just following situation can appear: only separate out copper sulfate in time more than 31.5 ℃ 1., do not separate out single nickel salt, then continue cooling and also only separate out copper sulfate, single nickel salt can only be stayed in the solution with hypersaturated state, just separates out single nickel salt after emitting solution, and single nickel salt is separated with copper sulfate.2. separate out the compound of single nickel salt and copper sulfate in time more than 31.5 ℃, then just continue to separate out copper sulfate in time below 31.5 ℃, single nickel salt is then stayed in the solution with hypersaturated state, just separates out single nickel salt when tapping.Single nickel salt that crystallization is separated out and copper sulfate compound must be done the 2nd time or darkroom Crystallization Separation more frequently, end when separating out copper sulfate, and single nickel salt is separated with copper sulfate.

The method that the present invention separates the ambrose alloy compound is the mixing hydrothermal solution that earlier compound is become single nickel salt and copper sulfate with the acidifying of sulfuric acid nitric acid, later on hydrothermal solution is changed over to the darkroom crystallisation by cooling, there will be two kinds of situations in crystallisation process: the one, and primary crystallization has been analysed copper sulfate, single nickel salt is then stayed in the solution with hypersaturated state, only after emitting solution, just there is the single nickel salt crystallization to separate out, single nickel salt is separated with copper sulfate.The 2nd, repeatedly copper sulfate is separated out in crystallization, primary crystallization is separated out and is not copper sulfate but the compound of single nickel salt and copper sulfate, just need do the 2nd time so that repeatedly darkroom crystallization, when separating out copper sulfate, crystallization ends, all there is the crystallization from its supersaturated solution of 7 water single nickel salts to separate out when emitting solution after each darkroom crystallization, single nickel salt is separated with copper sulfate.

The temperature of the number of times of darkroom Crystallization Separation single nickel salt and copper sulfate during by the ambrose alloy ratio of raw material, strength of solution and crystallization decided.The ratio of copper is big more in the raw material, and the crystallization number of times is few more; Strength of solution is big more, and the crystallization number of times is many more; Room temperature is low more during crystallization, and the crystallization number of times is few more.

The thick copper sulfate that the darkroom Crystallization Separation is come out can reach more than 96% through washing or recrystallization content, conforms to country-level standard.The crude nickle sulphate that the darkroom Crystallization Separation is come out, content reaches 96.5%, make refinement treatment.Treatment process is earlier crude nickle sulphate to be dissolved in water, and adds nickelous carbonate later on, adjusts the pH value of solution, copper carbonate is precipitated separate out, more after filtration, just to obtain content be single nickel salt more than 98% for evaporation, crystallization.

Provide one to carry out the isolating embodiment of ambrose alloy below with this law:

Accompanying drawing is the production scheme that ambrose alloy separates embodiment.

Present embodiment is got ambrose alloy compound 300 grams of being made up of single nickel salt 200 grams, copper sulfate 100 grams, be 22 ℃ in room temperature and carry out static darkroom Crystallization Separation single nickel salt and copper sulfate, physical record is in following: separate for the first time: above-mentioned compound adds water and is heated to dissolving fully, must mix 280 milliliters of hydrothermal solutions, change darkroom non-shock chilling crystallization later on over to, after 18 hours, carry out solid-liquid separation, get 200 milliliters of solution and some single nickel salts, copper sulfate compound.After the solution exposure 5 hours, separate out crude nickle sulphate 21.6 grams, content 96.3%, the mother liquor of analysing behind the single nickel salt is done to separate for the second time to use.

Separate for the second time: with for the first time separating obtained compound with analyse mother liquor behind the single nickel salt and add water and be heated to fully and dissolve, get 280 milliliters of dense hot solution, change the darkroom crystallization later on over to, after 18 hours, carry out solid-liquid separation, get 220 milliliters of solution and some copper sulfate single nickel salt compounds.Crude nickle sulphate 22.5 grams are separated out in solution exposure after 5 hours, content is 96.5%, analyse single nickel salt after mother liquor do to separate for the third time to use.

Separate for the third time: with the 2nd separating obtained compound with analyse single nickel salt after mother liquor mix, be heated to fully and dissolve, must dense hydrothermal solution 230 milliliters, change darkroom non-shock chilling crystallization later on over to, after 18 hours, carry out solid-liquid separation, get copper sulfate 47 grams, content is 95%, 200 milliliters of solution.Solution exposure after 5 hours crude nickle sulphate 22 grams, content 96.6% analyses that mother liquor is 185 milliliters behind the single nickel salt, this mother liquor is done the 2nd and is taken turns to produce and use.

The purification of above-mentioned crude nickle sulphate and thick copper sulfate: separates by above 3 times, altogether crude nickle sulphate 67.1 grams, average content is 96.5%, thick copper sulfate 47 restrains content 95%.Crude nickle sulphate adds nickelous carbonate (being outer reinforced) to be handled, and gets POV nickel 66 grams, content 99.5%.Thick copper sulfate through washing handle 45 grams, content 96.3%.

In sum, pH value method is separated nickelous sulfate and copper sulphate has the following advantages with adjusting to replace with copper sulphate to separate nickelous sulfate with the darkroom crystallisation:

1. alkali, sulfuric acid consumption amount reduce: with darkroom crystallisation separate sulfur Acid copper does not consume alkali, the sulfuric acid when only needing acidifying. Separate sulfuric acid Nickel only needs alkali and some sulfuric acid of amount of calculation 3%. Adjust pH value method Consume alkali and 2 times of sulfuric acid of ambrose alloy amount of calculation 120%.

2. nickel, copper consumption of raw materials are low: the darkroom crystallisation, and in operation Outside the ambrose alloy of loss minute quantity, it is former not consume in process of production ambrose alloy Material. Adjust pH value method, technological process is long, operating loss is big. Want solution loss ambrose alloy salt when sodium salt is arranged in washing in the production process. Transferring Carry nickel alkali during whole pH in the copper alkali secretly ambrose alloy consumption, spy will be arranged When not being the high raw material of Treatment of Copper amount, consume bigger.

3. technological process is simple: the darkroom crystallisation removes with general acidifying Outside the crystallizer, only need to increase the darkroom, make Crystallization Separation progressively. Adjust pH value method except with the general acidizing crystal equipment, also will increase Add alkalization, wash again acidizing unit, and production procedure is long, work is strong Degree is big.

4. waste residue, waste water are few: darkroom crystallisation ambrose alloy can be whole Reclaim, seldom waste residue, waste water. Adjust pH value method, have a large amount of Sodium salt waste water also has the ambrose alloy waste residue.

Claims

One, a kind of method of producing single nickel salt and copper sulfate with the ambrose alloy compound is characterized in that:

1. become single nickel salt and copper sulfate to mix hydrothermal solution with sulfuric acid, nitric acid, acidifying the ambrose alloy compound.

2. will mix hydrothermal solution changes darkroom non-shock chilling crystallization over to and separates out thick copper sulfate.

3. emit the solution of analysing behind the copper sulfate, just separate out crude nickle sulphate.
Two, according to the described method of producing single nickel salt and copper sulfate with the ambrose alloy compound of claim, it is characterized in that: one (2) describedly changes mixed solution over to darkroom non-shock chilling crystallization to separate out the process of thick copper sulfate can be one or many.