CN1058199A - The manufacture method of high-pruity barium carbonate - Google Patents

Abstract

The present invention is a production method of producing high-pruity barium carbonate, is the further invention of Chinese patent application 89108924.9.The present invention utilizes witherite or general industry barium carbonate and ammonium salt to carry out conversion reaction, generates the soluble barium salt, and again through refrigerated separation, recrystallization purifies, and operations such as drying finally make barium carbonate purity and be the product more than 99.0%.

Description

The manufacture method of high-pruity barium carbonate

The invention belongs to the production method of barium carbonate, the present invention is an industrially preparing process of producing high-pruity barium carbonate furtherly.

As everyone knows, often contain impurity such as lime carbonate, Strontium carbonate powder, barium sulfate and sulfide in the general industry barium carbonate product.Even if content is 99.0% industrial first grade barium carbonate, its content is meant that also barium carbonate, lime carbonate, Strontium carbonate powder resultant are 99.0%.In order to remove these impurity, make high-pruity barium carbonate, usual method is to re-refine with the barium carbonate of industrial first grade.Method commonly used is the method that adopts recrystallization method and add deliming, strontium agent: at first, the barium carbonate of industrial first grade is dissolved in strong acid such as nitric acid or the hydrochloric acid, the carbonate of calcium, strontium, barium all changes in the solution, carry out recrystallization again, barium salt is separated with calcium, strontium salt add high-purity volatile salt then and be settled out barium carbonate, purify, drying obtains product; Perhaps add sodium hydroxide in strong acid solution, adjust pH value and add high-purity volatile salt after removing calcium, strontium impurity, be settled out barium carbonate, purify, drying obtains product.Aforesaid method ubiquity high-pruity barium carbonate yield is low, and problems such as equipment corrosion, and need to use expensive high purity product are therefore from being non-remunerative economically.Thus, the processing method of producing high-pruity barium carbonate at present requires further improvement.

For overcoming the shortcoming that exists in the aforementioned production method, the present invention proposes a new operational path.The present invention can use industrial potassium titanate products production high purity product, also can directly use witherite mineral powder to produce the high-pruity barium carbonate product.Self-evident, directly use witherite mineral powder, will more can embody huge superiority of the present invention.Chinese patent application 89108924.9 has at large been introduced the method for being produced industrial potassium titanate by witherite mineral powder, and the present invention is its further invention, adopts the present invention directly to produce the high-pruity barium carbonate product by witherite mineral powder on its basis.

The present invention is to be 1～5: 1 ratio with mol ratio with witherite mineral powder and the ammonium salt that can make water-insoluble barium in the breeze be converted into the soluble barium salt, liquid-solid ratio is 0～1.5: 1 ratio, under 90～700 ℃, carry out conversion reaction, the volatile salt that produces in the reaction reclaims by condensation and uses, and has specifically described the process of conversion reaction in Chinese patent application 89108924.9.After the reaction, cool off, dilution, separate, cooling temperature is controlled at 10～60 ℃, because barium salt is different with the solubleness and the solubility product of calcium salt and strontium salt, so the barium salt crystallization is separated out with slag and separated with mother liquor together in process of cooling, mother liquor after the refrigerated separation adds the volatile salt that reclaims in the conversion reaction operation, and its amount is preferably Ca ⁺⁺, Sr ⁺⁺The amount 0.8～1.5 times, to remove impurity such as calcium, strontium, to return the conversion reaction operation then to recycle, isolated mother liquor dissolves again in the deionized water of isolated barium salt and slag the most handy 4～10 or the precipitation operation thereafter, filter, slag is got rid of.If there is not particular requirement, the volatile salt that barium salt solution behind the separation slag can directly add the conversion procedure recovery of theoretical amount at least carries out precipitin reaction, be settled out barium carbonate, restore the ammonium salt that adds when to carry out conversion reaction simultaneously, filtering the back mother liquor returns the conversion reaction operation and recycles or be used to dissolve the barium salt operation, the barium carbonate drying that is settled out obtains finished product, and barium carbonate purity can reach more than 98%.If the barium salt solution that will separate behind the slag carries out recrystallization, Tc is controlled between 10～60 ℃, the isolated mother liquor of recrystallization returns the conversion reaction operation and recycles, barium salt behind the recrystallization is again with isolated mother liquor dissolving in 4～10 times deionized water or the precipitation operation, add the volatile salt that reclaims in the conversion procedure of theoretical amount, be settled out barium carbonate, purify after drying and promptly obtain product, barium carbonate purity can reach more than 99.9%.Precipitated barium carbonate is dry at once without purifying, and its barium carbonate purity also can reach more than 99.0%.

The ammonium salt that uses in the conversion reaction can be converted into the soluble barium salt with water-insoluble barium, and then be converted into insoluble barium carbonate, whole process all relies on the variation of this ammonium salts to finish, and they have participated in reaction in variation, and have finally recovered original state.This ammonium salts is a lot, as ammonium chloride, ammonium sulfide, ammonium nitrate, ammonium formiate, ammonium acetate etc.For example, ammonium nitrate and witherite mineral powder are with 1～5: 1 mol ratio, 0～1.5: 1 liquid-solid ratio, carry out conversion reaction under 90～150 ℃, reaction is actually to be carried out with the replacement(metathesis)reaction principle, the volatile salt that produces in the reaction, under temperature of reaction of the present invention, can be easily reclaimed use with the method for condensation with gas phase volatilization, reaction produces nitrate of baryta simultaneously, calcium, impurity such as strontium also are converted into corresponding nitrate, and by refrigerated separation, nitrate of baryta separates with mother liquor together with slag, add the volatile salt that reclaims in the normal conversion reaction operation in the mother liquor of dilution back, can be with calcium, strontium is removed, and returns the conversion reaction operation then and recycles, and isolated mother liquor dissolves again in the operation with 4～10 times deionized water or with precipitating thereafter for nitrate of baryta and slag, nitrate of baryta is soluble in water, and slag is then by removing by filter.Nitrate of baryta solution adds the volatile salt that reclaims in the normal conversion procedure through recrystallization with after dissolving two step operations again, and then nitrate of baryta changes barium carbonate into and precipitates, the ammonium nitrate mother liquor of getting back simultaneously.Mother liquor can return conversion procedure and recycle or be used for dissolution process.Precipitated barium carbonate purifies after drying, obtains barium carbonate purity and be the product more than 99.9%.Certainly,, recrystallization and cleaning section can be saved, barium carbonate purity can be obtained and be the product more than 98% if the user does not have particular requirement.

Using the general industry barium carbonate product is raw material of the present invention, adopts operational path of the present invention, will be easy to make the very high product of barium carbonate purity.For example, with industrial first grade barium carbonate and ammonium nitrate with mol ratio 1～5: 1 ratio, liquid-solid ratio 0.5～1: 1 ratio, under 90～150 ℃, carry out conversion reaction, the volatile salt that produces reclaims use by the method for condensation, and the nitrate that produces carries out refrigerated separation, and nitrate of baryta separates with mother liquor together with some impurity, is incorporated as Ca in the mother liquor of dilution back ⁺⁺, Sr ⁺⁺The volatile salt of measuring 0.8～1.5 times conversion reaction operation recovery can be removed the nitrate of calcium, strontium, returns the conversion reaction operation and recycles.Nitrate of baryta and impurity dissolve again with isolated mother liquor in 4～10 times deionized water or the precipitation operation thereafter, remove by filter impurity, and following operation steps and requirement can obtain ideal high-pruity barium carbonate product with using witherite mineral powder.In fact, using the general industry barium carbonate product is raw material of the present invention, does not generally need can obtain the very high barium carbonate product of purity through recrystallization and cleaning section.

Implement the present invention, particularly directly use witherite mineral powder to implement the present invention, can directly make high-pruity barium carbonate by breeze, this is very worthwhile economically.The ammonium salt that uses as transforming agent is nonexpendable in theory in whole process, and the part that only needs in the actual production to replenish mechanical loss gets final product.The present invention does not need to use strong acid and high purity material, so equipment anticorrosion problem and production cost all are easy to solve and reduce.Conscientiously implement the present invention, actual barium yield is reached more than 90%.

Example 1

Get 100g and contain BaCO ₃80% witherite mineral powder, fineness 180 orders, add ammonium nitrate 116.7g, add water 100g, under 125 ℃ through conversion reaction 1.5 hours, the volatile salt that produces in the reaction reclaims through condensation and uses, reacted material cooling, dilution is filtered, mother liquor is incorporated as the volatile salt that reclaims in 1.0 times of conversion reaction operations of calcium, strontium amount, returns the conversion reaction operation after calcium, strontium precipitation are removed and recycles.Nitrate of baryta and slag dissolve with 6 times deionized water, remove by filter slag, mother liquor returns the conversion reaction operation and recycles behind the recrystallization, the nitrate of baryta crystallization is carried out precipitin reaction with the volatile salt that adds normal conversion reaction operation recovery after 6 times the deionized water dissolving again, obtain barium carbonate sediment and ammonium nitrate mother liquor, mother liquor returns the conversion reaction operation and recycles or be used for dissolution process, and barium carbonate sediment purifies the back drying, and can to obtain containing barium carbonate be 99.90% product.The barium yield is 90%.

Example 2

Get the 100g industrial potassium titanate,, can obtain barium carbonate purity and be 99.92% product, barium yield 98.0% with example 1 identical operations.

Example 3

With example 1 identical must the operation,, can make barium carbonate purity and be 99.2% product without purification.

Example 4

With the operation of example 3, without recrystallization and cleaning section, products obtained therefrom barium carbonate purity is 98.3%, barium yield 95%.

Example 5

The mother liquor identical with the operation of example 1, that conversion reaction operation and dissolution process use circulation to reclaim can get barium carbonate purity and be 99.90% product.

Example 6

Claim that 100g contains BaCO ₃80% witherite, fineness 180 orders are mixed the back 500～700 ℃ of roastings 2 minutes with 60g ammonium chloride, and as follows example 1 can get 99.90% barium carbonate.

Claims (5)

1, a kind of production method of making high-pruity barium carbonate, be that witherite mineral powder or general industry barium carbonate product and the water-insoluble barium that can make of theoretical amount at least are converted into soluble barium salt's ammonium salt, in liquid-solid ratio is 0～1.5: 1, carry out conversion reaction under 90～700 ℃, the volatile salt that produces in the reaction reclaims by condensation and uses, again through separating, add volatile salt and carry out precipitin reaction, filter, purify, dry, it is characterized in that carrying out refrigerated separation after the conversion reaction, barium salt separates with mother liquor together with slag, separate back mother liquor dilution and add the volatile salt that the conversion reaction operation reclaims, remove calcium, returning the conversion reaction operation behind the strontium impurity recycles, barium salt and slag dissolve with isolated mother liquor in deionized water or the precipitation operation, filter, remove and remove slag, barium salt solution carries out dissolving with isolated mother liquor in deionized water or the precipitation operation behind the recrystallization again, the volatile salt that adds the recovery of conversion reaction operation carries out precipitin reaction, perhaps the slagging-off back is without recrystallization and dissolving again, the volatile salt that directly adds the recovery of conversion reaction operation carries out precipitin reaction, the precipitin reaction after-filtration separates, mother liquor returns the conversion reaction operation and recycles or be used for dissolution process, the barium carbonate that is settled out is through purifying after drying, perhaps without purifying convection drying.

2, a kind of the method for claim 1 is characterized in that the isolating temperature of conversion reaction postcooling is controlled at 10～60 ℃.

3, a kind of the method for claim 1 is characterized in that preferably being incorporated as the volatile salt that 0.8～1.5 times conversion reaction operation of Ca, Sr amount reclaims with barium salt and mother liquor after slag separates.

4, a kind of the method for claim 1, the barium salt that it is characterized in that dissolving behind barium salt and slag and the recrystallization is that its amount is 4～10 times of the solid phase amount with isolated mother liquor in deionized water or the precipitation operation.

5, a kind of the method for claim 1 is characterized in that the volatile salt that the conversion reaction operation that adds in the precipitin reaction operation reclaims should be theoretical amount at least.