CN1050531A - The production method of Strontium carbonate powder - Google Patents

Abstract

The invention relates to the lazurite is the method for raw material production Strontium carbonate powder.Taked the deliming pre-treatment, selected for use bicarbonate of ammonia to carry out conversion reaction as transforming agent.Remove barium purifying treatment and precipitation and produce technologies such as pure strontium carbonate product.Whole technological process is simple, and is pollution-free, and total production cost is than soda ash, and the volatile salt method is lower.Its transformation efficiency reaches more than 95%, and total recovery reaches more than 94%, and the content of Strontium carbonate powder reaches the U.S. up to more than 97% in the product, Japan, and the industrial standards of the Soviet Union can be used as colour picture tube shell frit.

Description

The production method of Strontium carbonate powder

The invention relates to the preparation method of Strontium carbonate powder, it is that raw material (major ingredient is a Strontium Sulphate) is produced highly pure strontium carbonate that this method is particularly suitable for the lazurite.

Strontium carbonate powder is used as the raw material of light industry, chemical industry, medicine and electronic industry widely.Especially as the raw material of strontium magneticsubstance,, be used as colour picture tube tube panel frit because of it has shielding effect to X ray.The prior art of producing Strontium carbonate powder has: carbon reduction method, high-temperature decomposition (＞1500 ℃) and double decomposition.Carbon reduction method exists that the strontium yield is low, ore utilizes unreasonable and problem such as three-waste pollution is serious.High-temperature decomposition, though the quality product height, energy consumption is very high.Double decomposition mainly contains employing soda ash and makes transforming agent and adopt volatile salt to make two kinds of transforming agents, and it is transforming agent that Japan special permission communique JP-7351895 adopts volatile salt exactly.The soda ash method is because soda ash is in short supply, and high price causes the product cost height, add that the corrodibility of soda ash causes equipment loss big greatly, and energy consumption is also big.Though it is good than soda ash to adopt volatile salt to make transforming agent, unsatisfactory part is also arranged: volatile salt easily decomposes ammonification, carbonic acid gas, water.Volatile salt has the intensive hydrolytic action in solution:

(the first step hydrolysis)

Therefore must add ammoniacal liquor separates to prevent water.Volatile salt easily is dehydrated into ammonium carbamate in cold soln:

And ammonium carbamate is not generate precipitation with the alkaline earth metal carbonate reaction.Thereby, adopt volatile salt to make transforming agent separately, its consumption is very big, otherwise will add a large amount of ammoniacal liquor in case hydrolysis.Certainly will cause cost to increase like this.

For this reason, the objective of the invention is to design a kind of processing method of producing Strontium carbonate powder, and by seeking new transforming agent and suitable calcium remover and barium removal agent, and corresponding technological conditions realizes above-mentioned purpose.

Take a broad view of prior art, the technical solution that the present invention proposes is: select for use bicarbonate of ammonia to make transforming agent, whole technology is by pre-treatment, conversion reaction, and purifying treatment and pure strontium carbonate product are produced and are waited four procedures composition.Existing division is as follows:

1, pre-treatment: the main purpose of this operation is deliming.The lazurite grind into powder is crossed (100 order), added calcium remover, controlled temperature is 60～90 ℃ of reactions 0.5～2 hour, and visual response filters, washs and be sent to next procedure after finishing.Above-mentioned calcium remover can adopt any in concentrated hydrochloric acid, concentrated nitric acid, the vitriol oil, and the consumption of calcium remover is controlled at 125～175% of theoretical amount.

2, conversion reaction: this operation is a key of the present invention, and the key of decision transformation efficiency adopts bicarbonate of ammonia to make transforming agent.To mix mutually with solid ammonium bicarbonate in the presence of ammonium hydroxide through pretreated lazurite, control reaction temperature was carried out conversion reaction 3.5～7 hours at 65～80 ℃, and visual response finishes, and throw out washing, drying can be obtained the Strontium carbonate powder crude product.The consumption of its ammonium hydroxide is controlled at lazurite amount 120～180%, and the consumption of bicarbonate of ammonia is controlled at lazurite amount 130～170%.

3, purifying treatment: this operation is mainly except that barium and deironing design.With the Strontium carbonate powder crude product dissolving with hydrochloric acid of gained, and controlled temperature is 60～90 ℃, treats that precipitation fully after the dissolving, adds barium removal agent, adds ammonium hydroxide again to pH=6～8 deironing after removing barium, after filtration, washing abandons filter residue and get the strontium chloride scavenging solution.The concentration of above-mentioned hydrochloric acid is controlled at 8～12N, and add-on is controlled at 103～110% of theoretical amount.The consumption of barium removal agent is controlled at 20～50% of theoretical amount, and barium removal agent adopts any in potassiumchromate, Sodium chromate, potassium bichromate, sodium dichromate 99, the ammonium sulfate.

4, pure strontium carbonate product is produced:

Above-mentioned strontium chloride scavenging solution control is heated to 50～80 ℃, in the presence of ammonium hydroxide, add saturated ammonium bicarbonate soln, carry out the Strontium carbonate powder precipitin reaction, after reacting completely, filtering, wash to strontium carbonate product does not have the chlorine root, row oven dry again, grind pure strontium carbonate product.The consumption of above-mentioned ammonium hydroxide is controlled at 102～120% of theoretical amount, and the add-on of unsaturated carbonate hydrogen ammonium solution is controlled at 102～120% of theoretical amount.

So far, technology narration of the present invention finishes.

The present invention has reached its intended purposes owing to adopted bicarbonate of ammonia to make transforming agent, and whole technological process is simple, and production unit is not had particular requirement, does not have corrosion phenomenon, and waste water can be recycled, three-waste free pollution.Total cost of the present invention only is 80% of a soda ash method, has also reduced about 10% than the volatile salt method.And bicarbonate of ammonia is China's distinctive " little nitrogenous fertilizer " product, and the source is sufficient.Adopt technology of the present invention, its ore transformation efficiency can reach more than 95%, purifies yield and can reach more than 98%, and total recovery can reach more than 94%, and the content of product strontium carbonate reaches more than 97%.The industrial standards (" table 2 " is the standard and the quality product of these three countries) that surpasses the U.S., Japan, the Soviet Union fully.

The embodiment of the invention is as follows:

Example 1, get Sichuan and produce lazurite 1000 grams (powder) and add about 130 milliliters concentrated hydrochloric acid, in 1 hour after-filtration of 75～85 ℃ of reactions, washing by theoretical amount 140%.Press 130% of lazurite amount again and add the ammonium hydroxide of about 120 grams and press lazurite amount 150% and add solid ammonium bicarbonate 640 grams, in 65～75 ℃ of reactions after 5 hours after with throw out filtration, washing, drying Strontium carbonate powder crude product 760 restrains.Amount by theoretical amount 106% adds about 1600 milliliters 9N hydrochloric acid again, at 80～85 ℃ of solubilizing reactions, treat that solubilizing reaction fully adds about 12 grams of ammonium sulfate by 35% of theoretical amount in the back, and then add 1: 1 ammonium hydroxide in right amount to pH=6～8, precipitation is by elimination, wash the strontium chloride scavenging solution.When being heated to 55～60 ℃, the ammonium hydroxide that adds about 80 grams by theoretical amount 109%, with add about 1900 milliliters bicarbonate of ammonia saturated solution by theoretical amount 110%, after precipitin reaction is carried out 1 hour, filter, wash, dry, grind strontium carbonate product 653.2 grams.This example yield, quality product situation are seen " table 1 ", " table 2 ".

Example 2, get Sichuan and produce lazurite 50 grams (powder) and add about 6 milliliters concentrated hydrochloric acid by theoretical amount 130%, controlled temperature is in 0.5 hour after-filtration of 80～85 ℃ of reactions, washing.Press 140% of lazurite amount again and add about 6.44 ammonium hydroxide that restrain and press the solid ammonium bicarbonate that lazurite amount 160% adds about 34.4 grams, after 5 hours, will get Strontium carbonate powder crude product 33.8 grams after sedimentation and filtration, washing, the drying in reaction under 65～70 ℃.Add about 80 milliliters 10N hydrochloric acid by theoretical amount 110% again, at 80～90 ℃ of solubilizing reactions, solubilizing reaction back fully adds about 1.72 grams of potassium bichromate by theoretical amount 45%, the ammonium hydroxide that adds 1: 1 then is to pH=6～7, the elimination precipitation, get the strontium chloride scavenging solution after the washing, when heating and being controlled at 60～70 ℃, add about 4.4 grams of ammonium hydroxide by theoretical amount 120%, with add about 98 milliliters of bicarbonate of ammonia saturated solution by theoretical amount 115%, after the precipitin reaction 0.5 hour, filter, wash, dry, grind to such an extent that strontium carbonate product 32.2 restrains.Yield and quality product situation are seen " table 1 ", " table 2 ".

Example 3, get Sichuan and produce lazurite 200 grams (powder) and add about 16 milliliters of concentrated nitric acid, after 1.5 hours, filter, wash 70～80 ℃ of reactions by theoretical amount 165%.Press about 29 grams of lazurite amount 160% adding ammonium hydroxide again and press about 142 grams of lazurite amount 165% adding solid ammonium bicarbonate, control conversion reaction temperature is 70～75 ℃, reacts after 5 hours filtration, washing, dry Strontium carbonate powder crude product 136 grams that get.Add about 250 milliliters of 12N hydrochloric acid by theoretical amount 103% again, the solubilizing reaction temperature is that 75～85 ℃ of solubilizing reactions add about 2 grams of potassiumchromate by theoretical amount 20% in the back fully, the ammonium hydroxide that adds 1: 1 subsequently again is to pH=6～8, the precipitation of elimination subsequently, wash the strontium chloride scavenging solution.Control again when being heated to 65～75 ℃ and add the ammonium hydroxide of about 16 grams and, after reaction is carried out 0.5 hour, filter, wash, dry, grind to such an extent that strontium carbonate product 131 restrains by the about 360 milliliters bicarbonate of ammonia saturated solution of theoretical amount 105% adding by theoretical amount 110%.This example yield and quality product situation are seen " table 1 ", " table 2 ".

Claims (5)

1, a kind of is raw material with the lazurite, through pre-treatment, and the processing method that four procedures such as use that transforming agent conversion reaction, purifying treatment, pure strontium carbonate product are produced are produced Strontium carbonate powder, feature of the present invention is:

1,1, pre-treatment is to take to add calcium remover and controlled temperature in 0.5～2 hour technologies of 60～90 ℃ of reactions, wherein the add-on of calcium remover is 125～175% of a theoretical amount, can adopt concentrated hydrochloric acid or concentrated nitric acid or the vitriol oil to make calcium remover,

1,2, conversion reaction is to adopt bicarbonate of ammonia to make transforming agent, pretreated lazurite is mixed mutually with solid ammonium bicarbonate in the presence of ammonium hydroxide, in 3.5～7 hours technology of 65～80 ℃ of reactions, wherein the consumption of ammonium hydroxide is 120～180% of a lazurite amount, the consumption of bicarbonate of ammonia is 130～170% of a lazurite amount

1,3, purifying treatment is the hydrochloric acid that adds 8～12N, controlled temperature is in 60～90 ℃ of solubilizing reactions, back adding barium removal agent reacts completely, add the technology of ammonium hydroxide subsequently again to PH=6～8, wherein the consumption of hydrochloric acid is controlled at 103～110% of theoretical amount, the barium removal agent consumption is controlled at 20～50% of theoretical amount, and barium removal agent can adopt potassiumchromate or Sodium chromate or potassium bichromate or sodium dichromate 99 or ammonium sulfate

1,4, to produce be that the control of strontium chloride scavenging solution is heated to 50～80 ℃ to pure strontium carbonate product, in the presence of ammonium hydroxide, add the technology that the bicarbonate of ammonia saturated solution reacts, wherein the consumption of ammonium hydroxide is controlled at 102～120% of theoretical amount, and the add-on of bicarbonate of ammonia saturated solution is controlled at 102～120% of theoretical amount.

2, pretreatment technology according to claim 1, the consumption that it is characterized in that calcium remover is 130～165% of a theoretical amount, and Controllable Temperature is built in 70～85 ℃, and calcium remover can be selected concentrated nitric acid or concentrated hydrochloric acid for use.

3, converting reaction process according to claim 1, the consumption that it is characterized in that ammonium hydroxide is 130～160% of a lazurite amount, and the consumption of bicarbonate of ammonia is 150～165% of a lazurite amount, and temperature is 65～75 ℃.

4, purification process technique according to claim 1 is characterized in that hydrochloric acid can select 9～12N for use, and the solubilizing reaction temperature is 75～85 ℃, and the barium removal agent consumption is 20～45% of a theoretical amount, and barium removal agent can be selected ammonium sulfate or potassiumchromate or potassium bichromate for use.

5, pure strontium carbonate product reparation technology according to claim 1, the consumption that it is characterized in that ammonium hydroxide is 109～120% of a theoretical consumption, and bicarbonate of ammonia saturated solution add-on is 105～115% of a theoretical amount, and temperature is 65～75 ℃