CN1050367A

CN1050367A - A kind of method of producing single nickel salt

Info

Publication number: CN1050367A
Application number: CN89105173A
Authority: CN
Inventors: 李德斌
Original assignee: Individual
Current assignee: Individual
Priority date: 1989-09-21
Filing date: 1989-09-21
Publication date: 1991-04-03

Abstract

A kind of method of from deactivated catalyzer, extracting metallic nickel production single nickel salt, be characterized in the disused nickel and aluminum catalyst of any nickel content with sulfuric acid reaction to pH=4～5 o'clock, take out reaction solution, put into aluminum removing pool and lime carbonate and be in harmonious proportion pH=5.5～6 o'clock, be aluminium and calcium and generate aluminium hydroxide and calcium sulfate fully and from solution, precipitate and separate out, carry out deironing, dezincification, filtration, evaporation, crystallization, drying, chemical examination, packing etc. then.The invention has the advantages that metallic nickel reclaims thoroughly, can reach 99%, technical process is short, and equipment is simple, and less investment is simple to operate, and quality reaches country-level standard.

Description

A kind of method of producing single nickel salt

The present invention relates to the production method of inorganic chemical product, specifically, relate to the producing and manufacturing technique of single nickel salt.

In the Chemical Manufacture technological process, so that improve yield, increase output in order to improve speed of response, when changing reaction conditions, also must add a certain amount of catalyzer (active catalyst).The active constituent that plays katalysis in the catalyzer generally all is metal or its compound, as: magnesium, zinc, nickel, cobalt, platinum etc.Catalyzer will lose catalytic performance (losing activity) after using certain hour, is commonly called as catalyzer " poisoning ", needs to change raw catalyst.At present, owing to the ratio that reactive metal component in deactivated catalyzer is shared is less, from deactivated catalyzer, extract the restriction that noble metal is subjected to conditions such as extraction process and transportation in addition, although wherein contain a certain amount of valuable or rare metal, nobody shows any interest in because of cost recovery is higher, therefore deactivated catalyzer has just been thrown away in vain, like this, caused certain significant loss from macroscopic view to country, some rare metal or other compound pollute the environment simultaneously, work the mischief to society.

The purpose of this invention is to provide a kind of novel process that metallic nickel is produced single nickel salt of from deactivated catalyzer, extracting, to solve the above-mentioned problem that exists.

The object of the present invention is achieved like this: it is to adopt the disused nickel and aluminum catalyst contain any metallic nickel weight percent heavy with 30～50%() sulfuric acid reaction, generate single nickel salt and Tai-Ace S 150 miscible fluid, when reaction solution PH=4～5, be reaction and finish; Take out reacted mud, stay the block disused nickel and aluminum catalyst that has not reacted, use during reaction to be recycled, the mud that takes out is put into aluminum removing pool, add lime carbonate and react, treat that PH=5.5～6 o'clock are aluminium and calcium and generate aluminium hydroxide and calcium sulfate fully and precipitate and separate out from solution, remove after filtering, it is heavy to remove aluminium mud solution employing 5%(in removing iron flask) potassium permanganate solution removal metallic iron, stir while adding, frontier inspection is looked into, up to there not being iron ion (Fe ²⁺) till the reaction, transfer PH=5.5～6.5 with lime carbonate again, can filter removal.Mud solution behind the removal iron is fed a certain amount of hydrogen sulfide, feed lime carbonate simultaneously, reduce acid number PH=3～5, zinc sulphide is fully precipitated, filter then and remove.And then evaporate, crystallization, drying and packing.Above-mentioned reaction ratio will according in the useless catalyst the gram-equivalent number of nickeliferous aluminium, obtain used sulfuric acid gram-equivalent number, again the sulfuric acid amount of being tried to achieve is made that to contain acid 30～60%(heavy) dilute sulphuric acid participate in reaction, but useless catalyst is worth excessive about 10% than the theory of computation, because of useless catalyst is a lumpy material, the reaction back the useless catalyst of the reaction do not participated in to recycle, and can not run off.

It is short that technology of the present invention has flow line, simple to operate, separates thoroughly rate of recovery height, low cost and other advantages.The present invention adopts the adverse current filter cake in addition, reduces the loss of nickel as far as possible, thereby has saved a large amount of clear water, prevents the excessive expansion of lower concentration washings, can't recycle.

Below in conjunction with accompanying drawing specific embodiments of the invention are described further:

Fig. 1 is a process flow diagram of the present invention.

Referring to Fig. 1, concrete technical process of the present invention is:

The waste nickel aluminium catalyst that 1. will contain certain nickel amount adds retort, it is heavy to add the 50%(that is mixed with lower concentration washing water (back narration) again) dilute sulphuric acid, heated and stirred, when reaction solution PH=4, promptly think to react and finish, emit the reaction back and generate thin mud, does not participate in the useless catalyst of reaction and stay in the jar at jar end, prepares next reaction cycle and use.

The mud of 2. emitting is put into except that aluminium pot adds lime carbonate under continuous stirring state and is transferred pH value 5.5～6, can filter.

3. mud is pressed into plate-and-frame filter press, filters, filtrate is sent into except that iron flask, carries out deironing, dezincifies again, and the filter cake in filter washs, and adopts the washing of countercurrent washing method.

4. the solution after deironing being dezincified is concentrated into 42 ° of Be(degree Beaume), carry out crystallization, drying, chemical examination, packing, promptly finish whole process of production.

5. spent catalyst and sulfuric acid proportioning are not done concrete digital requirement, because of material is the blocks of solid material, so participating in the spent catalyst of reaction should be excessive as far as possible, so not only can increase speed of response, nor can cause significant loss, because reactant is the blocks of solid material, and resultant is superfine mud, so the spent catalyst that reaction back not have react is easy to separate with the mud of reaction back generation, reuses circulating reaction after the lumpy material separation that does not have to have reacted.

6. iron removal: the potassium permanganate solution with 5%, add and remove in the iron flask, the limit adds, stir on the limit, frontier inspection is looked into, up to there not being iron ion Fe ²⁺Till the reaction, transfer pH value=5.5～6.5 with lime carbonate again, can filter, check that the method for ferrous ion is: get 5 milliliters of test solutions, put into cuvette, drip 0.5% high-potassium ferricyanide solution to test solution, if any iron ion Fe ²⁺, the test solution colour developing, as do not have the nondiscoloration of iron ion test solution.

7. the solution after the deironing is dezincified, feed hydrogen sulfide to solution, till not having zine ion.Solution with deironing, after dezincifying filters at last, filtrate is sent into evaporating pan evaporate, and during solution evaporation to 42 ° Be, takes out and carries out crystallization, drying, dry packing in pot.

Above-mentioned countercurrent washing filter cake, be to contain insoluble substances such as a large amount of aluminium hydroxide and calcium sulfate except that the later reaction solution of aluminium, mud is pressed into flame filter press to be filtered, its filtrate is stored in except that iron flask, its filter cake is not discharged in the filter and directly washs, and its objective is the single nickel salt of cleaning in the filter cake, in order to avoid drain with filter cake, its filter cake washing liquid recycles as water of productive use, has avoided the loss of single nickel salt.

Claims

1, a kind of production method of single nickel salt, it is characterized in that it is to adopt the same sulfuric acid reaction of disused nickel and aluminum catalyst that contains metallic nickel, generate the mixing solutions of single nickel salt and Tai-Ace S 150, being reaction when reaction solution PH=4～5 finishes, take out reacted mud, stay the block disused nickel and aluminum catalyst (reaction to be recycled) that has not reacted, the mud that takes out is put into aluminum removing pool, adding lime carbonate reacts, question response liquid PH=5.5～6 o'clock, be aluminium and calcium and generate aluminium hydroxide and calcium sulfate fully and from solution, precipitate and separate out, remove metallic iron again, impurity such as zinc filter then, evaporation, crystallization, dry and packing.

2, the production method of single nickel salt according to claim 1, it is characterized in that reaction ratio will according in the useless catalyst the gram-equivalent number of nickeliferous aluminium, obtain used sulfuric acid gram-equivalent number, again the sulfuric acid of being tried to achieve is made that to contain acid 30～60%(heavy) dilution heat of sulfuric acid participate in reaction, but useless catalyst is worth excessive about 10% than the theory of computation, because of useless catalyst is a lumpy material, the reaction back the useless catalyst of the reaction do not participated in to recycle, and can not run off.

3, the production method of single nickel salt according to claim 1 is characterized in that: removing metallic iron is to adopt 5% potassium permanganate solution, adds and removes in the iron flask, stirs while adding, frontier inspection looks into, and up to nothing iron ion Fe arranged ²⁺, transferring PH=5.5～6.5 with lime carbonate again, can filter.