CN1075468C - Separating and refining process for Co-Mn mixture - Google Patents

Abstract

The present invention provides a method for separating and refining the mixed material of cobalt and manganese, which has the process principle that the mixture which is composed of cobalt carbonate and manganese carbonate and difficult to be separated is dissolved in an acid, and then cobalt sulfide is added to converting the mixture into the mixture of cobalt sulfide and manganese sulfide; with the utilization of the difference between the solubility products of the cobalt sulfide and the manganese sulfide, the cobalt sulfide is separated in one time with the adoption of the techniques of second acid dissolution, filtration, washing, etc., and the solution of the manganese sulfate as a byproduct is produced; the cobalt sulfide as a schwerl solid is dissolved at a specific temperature with the adoption of a mixed acid with a definite proportion to prepare the solution of cobalt chloride with a wide application. The present invention has the advantages that the mixture of the cobalt carbonate and the manganese carbonate can be separated and converted to the product of the solution of the cobalt chloride with high universality, and simultaneously, the product of manganese as a byproduct can be produced.

Description

The separation and refining method of Co-Mn mixture

The present invention relates to reclaim in a kind of Chemical Manufacture the separation and refining method of the separation and refining method, particularly a kind of Co-Mn mixture of solid material.

The cobaltous carbonate and the manganous carbonate solid mixture that reclaim from the tankage that PTA produces can not directly use as finished product, must separate.In the prior art, utilization methods to the cobaltous carbonate Mn mixture is: behind the compound and naphthenic acid reaction with cobaltous carbonate manganese, be dissolved in No. 200 varnish makers' and painters' naphtha and make the G4 cobalt manganese drier, be mainly used in the siccative of various lacquers with oxidation filming, varnish, priming paint.But because the cobaltous carbonate Mn mixture reclaims from the PTA tankage, its cobalt manganese ratio uncertain (seeing Table) is difficult to reach the quality index of G4 siccative; Simultaneously, do not remove because of foreign ions such as the sodium in the raw material, iron and influence its quality product yet.More inconvenient is, product G 4 siccative are difficult to be converted into other products, in case the market requirement descends, then the single contradiction of product is more outstanding.Table: cobalt manganese content analysis * (wt) in the compound

Batch	Co(PPm)	Mn(ppm)
			1	1.09×10 5	1.90×10 5
2	1.01×10 5	1.77×10 5
			3	1.21×10 5	1.71×10 5
4	7.12×10 4	1.23×10 5

^*Cobalt manganese quantitatively adopts atomic absorption spectrometry

What the objective of the invention is to propose in order to overcome the deficiencies in the prior art is a kind of, and separation and purification goes out the separation and refining method of the Co-Mn mixture of cobalt product and manganese product from Co-Mn mixture.

The object of the present invention is achieved like this: the separation and purification step of Co-Mn mixture is:

1, a hypo acid is molten: the dissolving tank of the compound of cobaltous carbonate manganese quantitatively being put into belt stirrer, under normal temperature, normal pressure, quantitatively add dilute sulphuric acid (is 20% as concentration), all dissolve and be converted into the rose vitriol manganese mixed solution of redness until the solid carbonic acid Co-Mn mixture, the pH value of solution is about 4.5.

The quantivative approach of common 20% dilute sulphuric acid is according to the total amount that adds raw material and the content of cobaltous carbonate manganese wherein, calculate theoretical requirement by following chemical equation after, add again 20% excessive.

As the compound 1000g of cobaltous carbonate manganese, contain Co:10% (wt); Mn:18% (wt); 20% (wt) sulfuric acid amount that adds is x, by two formulas down: $1000\×10\%\×\frac{118.9}{58.9}:x_1\×20\%$ 118.9 ∶98.1x ₁=832.9(g) $1000\×18\%\×\frac{115}{55}:x_2\×20\%$

115 ∶98.1x ₂=1605.3(g) x=(x ₁+x ₂)·(1+20％)=2925.7(g)

Two, sulfuration: after treating that cobaltous carbonate manganese all is converted into rose vitriol manganese, in dissolving tank, add sloid alcali sulphide.Stir at normal temperature, the following edged of normal pressure, want the pH value of METHOD FOR CONTINUOUS DETERMINATION solution simultaneously.When pH value progressively was raised to 7, solution was black by red stain, when pH value is 8.5, showed that reaction is all over.With solution left standstill 8 hours, observe the cobaltous sulfide manganese precipitation of black this moment, top is clear liquid.

The quantitative estimation that adds Sodium Sulphide (wherein Containing Sulfur sodium 60%) is by 1.15 times of calculating of theoretical requirement, is as the criterion but finally still measure with reacted PH.The estimation formula is as follows: $1000\×10\%\×\frac{155}{58.9}:x_1$ 155 ∶ 78 x ₁=132.4(g) $1000\×18\%\×\frac{151.1}{55}:x_2$ 151.1 ∶ 78 x ₂=255.3 x=(x ₁+x ₂)×1.15/60％=743(g)

Attention: at the initial stage that adds Sodium Sulphide, during excessive sulfuric acid reaction, emit deleterious hydrogen sulfide in Sodium Sulphide and the solution, should in time collect discharge or with 5% NaOH solution absorption.

3, quadratic acid is molten: the upper clear supernate of cobalt manganese liquid behind the sulfide precipitation in the dissolving tank is taken out 80%, and (that takes out is more thorough, more help reducing the acid consumption of quadratic acid when molten, but easily make the Co-Mn mixture loss of bottom settlings, reduce product yield), quantitatively add dilute sulphuric acid (is 20% as concentration) then.The limit edged fully stirs, and makes wherein manganese sulfide and fully dissolving such as other impurity, and no hydrogen sulfide is emitted (observing no bubble) in solution, pH value is 4 o'clock, shows the solubilizing reaction end.After keeping stirring for some time (as 30 minutes), stop to stir, mixed solution is carried out normal pressure to be filtered, the black cobaltous sulfide filter cake that filters to isolate, need with after dried twice of the deionized water washing, the filter that are equivalent to the filter cake quality, promptly get purified solid cobaltous sulfide wet cake, be the manganese sulfate solution of by-product after filtrate and washings are collected, after the production technique processing of routine, can make manganese product.

The quantitative estimation of dilute sulphuric acid was that by theoretical requirement 1.15 times are definite when quadratic acid was molten, but the terminal point of reaction is as the criterion with above-mentioned observation situation and pH value mensuration situation.Evaluation method is as follows: $1000\×18\%\×\frac{87.1}{55}:x_1\×20\%$ 87.1 ∶98.1x ₁=1605.3(g) x=x ₁·1.15=1846.1(g)

Still handle for the hydrogen sulfide of emitting in the reaction by preceding method.

4, three hypo acids are molten:

The solid cobaltous sulfide generally can not directly use as catalyzer or siccative, need continue to be converted into wieldy cobalt chloride solution.

For this reason, above-mentioned gained cobaltous sulfide filter cake is put into the dissolving tank of belt stirrer, add excessive concentrated hydrochloric acid and an amount of concentrated nitric acid, the add-on of getting nitric acid is 10% of a hydrochloric acid add-on, and the limit edged stirs.Add in the sour dissolution process and should pass through heating in water bath or Electric heating, keep the dissolving tank temperature at 70～90 ℃, after the cobaltous sulfide for the treatment of black all is converted into red cobalt chloride solution, stop agitator after continuing to keep stirring for some time (as 30 minutes), promptly obtain the finished product cobalt chloride solution-liquid cobalt chloride.

30% concentrated hydrochloric acid be that benchmark calculates still quantitatively with the add-on of raw material cobaltous carbonate manganese, and keep 50% excessive.Method of calculation are as follows: $1000\×\frac{91}{58.9}:x_1\×30\%$

91: 2 * 36.5 x ₁=413.1 (g) x=x ₁15=619.7 (g) add-on of concentrated nitric acid is: 619.7 * 10%=62 (g)

The liquid cobalt chloride that contains Co 〉=10% is a kind of good catalyzer, also can be used for electroplating, glass-ceramic is painted, paint drier etc.; In addition, existing at present a lot of sophisticated treatment process are made other cobalt product.As the solid cobalt chloride that after evaporation, crystallization, drying, makes; Can get cobaltous carbonate after directly adding yellow soda ash or bicarbonate of ammonia; Can get cobaltous hydroxide or the like after adding the caustic soda reaction.

The present invention compared with prior art, its remarkable advantage is: the compound of cobaltous carbonate manganese can be separated, be converted into the extremely strong liquid cobalt chloride product of versatility, simultaneously, can get the by-product manganese product.Cobalt contents: Co 〉=10% wherein, the rate of recovery of cobalt is more than 85%.

The invention will be further described below in conjunction with embodiment:

Embodiment one: get cobaltous carbonate Mn mixture 100g, the cobalt manganese content of analyzing in the raw material is (Wt):

Co:10.9％；Mn:19.0％

Cobalt manganese separation and purification step is:

1, a hypo acid is molten:

100g cobaltous carbonate Mn mixture is put into the beaker of 1000ml, install minitype electric mixer on the beaker, the dilute sulphuric acid that under normal temperature, normal pressure, in beaker, quantitatively adds 312g 20% (Wt), the limit edged stirred 30 minutes, treat that solid carbonic acid cobalt manganese all dissolves and be converted into the rose vitriol manganese mixed solution of redness, observe no solid particulate in the beaker, pH value is 4.5 o'clock, represents a hypo acid cementing bundle.

The quantivative approach that adds diluted acid is according to the cobalt manganese content in raw material add-on and the raw material, calculate theoretical requirement by following chemical formula after, add again 20% excessive: $1000\×10.9\%\×\frac{118.9}{58.9}:x_1\×20\%$

118.9 ∶98.1 x ₁=90.8(g) $1000\×\frac{115}{55}:x_2\×20\%$

115 ∶98.1

x ₂=169.4(g)

X=(x ₁+ x ₂) (1+20%)=312.2 (g) ₂Get in fact: 312 (g)

2, sulfuration:

Rose vitriol manganese mixed solution with a hypo acid after molten, continuously stirring also adds sloid alcali sulphide (wherein Containing Sulfur sodium 60%).Beaker should be placed on the place of ventilation air extractor when adding alkali, the timely H2S gas (white liquor of application 5% absorbed when input amount was big) of emitting when reacting of extracting out.

After adding 1.15 times of continuous inputs and abundant dissolving of amount elder generation by theoretical calculated amount of Sodium Sulphide, constantly measure pH value.Speed with each 1g adds alkali, dissolving, survey pH value again, is 8.5 o'clock up to pH value, shows that reaction finishes.Left standstill solution 8 hours, cobaltous sulfide manganese is fully precipitated.

The quantitative estimation method that adds Sodium Sulphide is as follows: $100\×10.9\%\×\frac{155}{58.9}:x_1\×60\%$

155 ∶ 78 x ₁=24.1(g) $100\×19\%\×\frac{151.1}{55}:x_2\×60\%$

151.1: 78 x ₂=44.9 (g) estimator: x=(x ₁+ x ₂) real 86 (g) that add of this test of 1.15=79.4 (g)

3, quadratic acid is molten:

In order to remove impurity such as manganese sulfide and isolate cobaltous sulfide; Earlier the upper clear supernate in the above-mentioned beaker is taken out 80%.Attention: the cobaltous sulfide Mn mixture of bottom settlings thing black can not be extracted, to guarantee the yield of final cobalt product.After upper clear supernate (waste water) extracts, start agitator, add 20% dilute sulphuric acid 195g continuously in beaker, add acid and finish the back and continue to stir 15 minutes, the pH value of measuring solution is 4.5, observes no bubble generation in the solution, shows that manganese sulfide etc. all dissolves.

The quantivative approach that adds acid is 1.15 times of calculating of measuring on demand: $100\×19\%\×\frac{87}{55}:x_1\×20\%$

87: 98.1 x ₁=169.4 (g) estimator is 169.4 * 1.15=194.8 (g)

Get in fact: 195 (g)

The hydrogen sulfide that quadratic acid is emitted when molten is still handled as stated above.

Mixture after the dissolving end is carried out normal pressure filter, solid filter cake is a cobaltous sulfide, and the pink liquid that leaches is a manganese sulfate solution.The filter cake that filters out is washed, filters twice with the 30ml deionized water at every turn, and washing lotion and filtrate collection can prepare manganese product together, and the gained wet cake is cobaltous sulfide.

Above-mentioned wet cake need not oven dry, and wherein moisture (about 40%) does not have influence to reaction and end product quality.

4, three hypo acids are molten:

Cobaltous sulfide wet cake with quadratic acid after molten is all put into the beaker of 1000ml with electronic agitator, simultaneously a small amount of cobaltous sulfide residual on the filter paper is washed in the beaker with deionized water (consumption is not more than 15ml), beaker can and be warming up to 80 ℃ with heating in water bath, starts agitator.

With quantitatively and the concentrated hydrochloric acid for preparing and concentrated nitric acid add continuously in the beaker, keep temperature of reaction in the beaker at 80 ℃, under normal pressure, in time take out the H that emits ₂S gas.

Quantitatively carrying out as follows of mixing acid.Promptly earlier according to cobalt in the initial feed quantitatively, calculate the theoretical amount that needs the concentrated hydrochloric acid of 30% concentration, and keep 50% excessive; And the add-on of nitric acid is 10% of a hydrochloric acid add-on. $100\×10.9\%\×\frac{91}{58.9}:x_1\×30\%$

91: 2 * 36.5x ₁=45 (g) concentrated hydrochloric acid add-on is: 45 * 1.5=67.5 (g) is real to be got: 68g.The concentrated nitric acid add-on is: 68 * 10%=6.8 (g) is real to be got: 7 (g)

After adding the mixing acid 75g of certainty ratio, cobaltous sulfide dissolves rapidly and is converted into red cobalt chloride solution, and after the cobaltous sulfide of black in the solution all was converted into red cobalt chloride solution, continuously stirring also dropwise added the concentrated hydrochloric acid of 30% concentration; The final pH value of regulator solution is 2.5 o'clock, promptly stops to stir and adding acid, obtains liquid cobalt chloride product 95.6g altogether.

By analysis, cobalt contents wherein is 10.04% (wt), and manganese content is 0.08% (wt), meets the requirement of technical grade liquid cobalt chloride product.The rate of recovery of cobalt is: 88%.

Embodiment two:

Get cobaltous carbonate Mn mixture 10kg, the cobalt contents of analyzing wherein is: 12.1% (wt); Manganese content is: 17.1% (wt).

Cobalt manganese separation and purification step is:

1, a hypo acid is molten:

The 10kg mixing raw material is put into 0.1M ³Dissolving tank in.Dissolving tank is made of the porcelain enamel barrel of acid-alkali-corrosive-resisting, on adorn minitype electric mixer and induced draft device, the bottom is provided with the electric heater material in the heating for dissolving groove at any time.

Add the dilute sulphuric acid 30.5kg of 20% (wt) under normal temperature, normal pressure in dissolving tank continuously, the limit edged stirs.Add to continue to keep after acid finishes and stirred 30 minutes, observe no solid particulate in the solution, measuring pH value is 4.5, represents a hypo acid cementing bundle.

The quantivative approach that adds diluted acid is: the theoretical acid that raw material cobaltous carbonate manganese is consumed when reacting with diluted acid, add again 20% excessive.Method of calculation and example (1) are together.

2, sulfuration:

Behind the one hypo acid cementing bundle, do not stop agitator, directly in dissolving tank, add Sodium Sulphide, open the air extractor on dissolving tank top simultaneously, in time discharge the excess acid of hypo acid when molten and the H2S gas of emitting during the Sodium Sulphide reaction.

The amount that adds Sodium Sulphide (Containing Sulfur sodium 60%), be according to the required theoretical consumption of sedimentation cobalt manganese add 15% excessive, the 7.7kg one-time continuous adds altogether, stirring and recording the solution pH value after 15 minutes is 7.5, does not arrive reaction end.

Continue to add alkali with the speed of each 100g again, stirred 15 minutes, survey pH value, when adding to the 5th altogether, the pH value that records is 8.5, shows that reaction finishes, and rose vitriol manganese has been converted into cobaltous sulfide manganese, stops to stir, and free setting is more than 8 hours.

This adds up to and adds Sodium Sulphide 8.2kg.

3, quadratic acid is molten:

With the upper clear supernate (being waste water) of post precipitation in the dissolving tank, take out 80% liquid level after, turn on agitator, one-time continuous add 20% diluted acid 17.6kg (estimator) in groove, add acid and finish the back and continue to stir 15 minutes, recording the solution pH value is 6.Reaction is less than terminal point, and the limit adds acid again, pH value is surveyed on the limit, is 4.5 o'clock to pH value, observes no bubble generation in the solution, shows that manganese sulfide etc. has all dissolved to finish.

The quantivative approach that adds dilute sulphuric acid is: 1.15 times according to the required theoretical consumption of dissolving manganese sulfide estimate add-on one time.Measuring pH value, if greater than 4.5, again with speed, stirring and dissolving 15 minutes, the mensuration pH value of each adding 100g, is 4.5 o'clock until pH value then, stops to add acid.When this test added to the 6th time, recording pH value was 4.5, added up to add sour 18.2kg.

The H that quadratic acid is emitted when molten ₂S gas is still handled as stated above.

Mixed solution after dissolving finishes carries out normal pressure and filters with the terylene filter cloth of 621-90 on B, to filtering the filter cake after doing, all use the deionized water spray, the washed twice that are equivalent to the filter cake amount at every turn, and the total consumption of wash water is 2kg.Washing lotion and filtrate all are collected in standby together.

All wet cakes that filter after finishing are all put into cleaned dissolving tank, and a small amount of filter cake on the filter cloth is washed in the dissolving tank with deionized water.Attention: the deionized water consumption must not surpass the gross weight of filter cake, about 2kg, otherwise, with the sour speed of response when molten of the cobalt contents and next step that influence the finished product.

The gained filter cake is the solid cobaltous sulfide; Washing lotion and the mother liquor collected are fluid sulphuric acid manganese.

4, three hypo acids are molten:

According to the content of cobalt in the raw material, calculate dissolving 30% required hydrochloric acid content of cobaltous sulfide by chemical equation, and add 50% excessive; Add 10% concentrated nitric acid of hydrochloric acid total amount simultaneously, promptly the mass ratio of hydrochloric acid and nitric acid is 10: 1.

According to calculating, this test concentrated hydrochloric acid add-on is: 7.5kg; The concentrated nitric acid add-on is: 0.75kg.

The mixing acid for preparing is total to 8.25kg, adds dissolving tank continuously, lentamente, open bottom heater, top agitator and gas barrier, control reaction temperature is at 80 ℃.After adding the acid end, continue to stir 30 minutes, measuring the solution pH value is 2.5, show that reaction finishes, need not to add on a small quantity acid and regulate pH value that this test obtains liquid cobalt chloride product 10.1kg altogether, analyzing wherein, cobalt contents is: 10.2%, and the cobalt rate of recovery is 85.1%, manganese content is 0.06%.The atomic absorption light spectral method is quantitatively adopted in the analysis of cobalt manganese.

Claims (1)

1, a kind of separation and refining method of Co-Mn mixture is characterized in that the step of separation and purification is:

1.1 a hypo acid is molten: the compound of cobaltous carbonate manganese is put into the dissolving tank of belt stirrer, under normal temperature, normal pressure, add dilute sulphuric acid, all dissolve, and be converted into red cobaltous carbonate manganese mixed solution until the solid carbonic acid Co-Mn mixture;

1.2 sulfuration: add Sodium Sulphide in dissolving tank, stir at normal temperature, the following edged of normal pressure, solution is black by red stain, finishes until reaction, leaves standstill the cobaltous sulfide manganese precipitation for the treatment of black;

1.3 quadratic acid is molten: take out the upper clear supernate in the dissolving tank, add dilute sulphuric acid then, the limit edged stirs, finish until reaction, keep and stop to stir after stirring for some time, mixed solution is carried out normal pressure filter, isolate the cobaltous sulfide filter cake of black, with deionized water the cobaltous sulfide filter cake is washed and promptly to get purified solid cobaltous sulfide wet cake, be the manganese sulfate solution of by-product after filtrate and washings are collected, can make manganese product through conventional production technique;

1.4 three hypo acids are molten: the dissolving tank of the cobaltous sulfide filter cake being put into belt stirrer, add excessive concentrated hydrochloric acid and an amount of concentrated nitric acid, the limit edged stirs, and by heating in water bath or electric heating, keep the dissolving tank temperature at 70～90 ℃, after the cobaltous sulfide for the treatment of black all is converted into red cobalt chloride solution, stop to stir after continuing to stir for some time, promptly get cobalt chloride liquid.