CN109336158A - The method that high calcium witherite mineral produces barium chloride - Google Patents
The method that high calcium witherite mineral produces barium chloride Download PDFInfo
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- CN109336158A CN109336158A CN201811507676.4A CN201811507676A CN109336158A CN 109336158 A CN109336158 A CN 109336158A CN 201811507676 A CN201811507676 A CN 201811507676A CN 109336158 A CN109336158 A CN 109336158A
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- calcium
- barium
- chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses the method that high calcium witherite mineral produces barium chloride, the raw material including following parts by weight proportion: 100KG barium carbonate content is between 40%-55%, high calcium witherite mineral of the calcium carbonate content in 25%-30%, the concentrated hydrochloric acid that concentration is 32%.The method that the high calcium witherite mineral produces barium chloride, utilize common-ion effect, it is reacted using concentrated hydrochloric acid, concentrated hydrochloric acid is taken to be reacted with the ore, the calcium chloride that reaction generates will be all dissolved in the water that hydrochloric acid is brought into, and the barium chloride generated only has the water that is dissolved in of only a few, the overwhelming majority is present in solid form in barium slag, pass through by-pass filtration, the liquid of filtering is liquid calcium chloride, remove calcium chloride, filter residue enters back into beater tub and is beaten with water, barium chloride in barium slag is all leached, obtain the very high barium chloride liquid of purity, crystallization is evaporated with this barium liquid again, obtained product purity is high, and yield is big, ton product steam consumption and power consumption are low.
Description
Technical field
Field is produced the present invention relates to barium chloride, specially the high calcium witherite mineral method of producing barium chloride.
Background technique
Barium chloride is the crystal of white, soluble easily in water, is slightly soluble in hydrochloric acid and nitric acid, is insoluble in ethyl alcohol and ether, easy to moisture absorption,
It need to be sealed, the reagent that performs an analysis, dehydrating agent and barium salt processed, and industrial for electronics, instrument and metallurgy etc., be mainly used for gold
Belong to heat treatment, barium salt manufacture and electronic instrument, be also used for making heat treatment agent in machining, measure sulfate and selenate etc.,
Chromatography, spot analysis measure platinum, water softener and textile dyeing.
To this Chinese patent CN105967216B propose method for producing barium chloride, this method using ball mill by barium slag with
Water or dilute barium chloride solution are ground together to be slurried, and hydrochloric acid is added in gained slurry, reacts to obtain barium chloride mixed solution, terminal PH
Gained mixed solution is separated by filtration, the recycling of slag abandoning by value control in 6.5-7.5, and wash water is used for ball mill, is mixed limpid molten
Liquid is used for subsequent processing, hydrogen peroxide is added in acquired solution, oxidation makes to vulcanize sulfate ion and sulfurous acid ion is converted to sulphur
Acid ion removes, and for oxidation of divalent iron ion at ferric ion, the present invention is effectively utilized barium slag, the barium chloride purity of preparation
Height, however as a large amount of exploitations of witherite, the high witherite of barium carbonate content is fewer and fewer, although high calcium content yield is more,
But because barium chloride is at high cost to utilize for production, so the production method is difficult to tackle the problem at its root.
Witherite acidification technique produces barium chloride, in order to guarantee product quality, generally uses the low strontium of low calcium, barium carbonate content
Witherite greater than 60% is produced, but continuing to increase with yield, and high-quality ore reserve is fewer and fewer, it is low-grade and
Calcium carbonate content is big greater than 25% witherite amount, and is mainly distributed on Shaanxi Province Ankang City periphery, and this mineral surface is in ash
Color, canescence or white, between barium carbonate content 40%-55%, calcium carbonate content is between 25%-30%, conventional production
Method is to react ore with hydrochloric acid, obtains barium chloride and calcium chloride mixing liquid, then produce chlorination by evaporative crystallization
Barium, using in this ore production process, since calcium carbonate content is high in ore, calcium chloride concentration will be up to 150- in reaction solution
200g/L, and barium chloride concentration can only achieve 150g/L or so, this reaction solution is evaporated crystallization, chlorine in the barium chloride of production
Changing calcium content will severely exceed, and cannot reach the corresponding quality standard of country, and low output, the steam consumption and electricity of unit product
It can consume greatly, the direct cost of product will improve 300 yuan or so, and therefore, the witherite mineral of this high calcium content is basic, and nobody asks
Saliva, resource cannot be utilized effectively, and many mines all suffer from the situation for stopping exploitation because of stockpiling of unsold product, develop a kind of be suitble to
In the ore production barium chloride method be extremely urgent.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides the method that high calcium witherite mineral produces barium chloride, has high calcium
Witherite mineral can low cost a large amount of the advantages of producing barium chloride, solve continuing to increase with yield, high-quality ore reserve
It is fewer and fewer, the problem of witherite of low-grade and calcium carbonate content greater than 25% is difficult to be utilized.
(2) technical solution
For realize above-mentioned high calcium witherite mineral can low cost largely produce the purposes of barium chloride, the present invention provides following technology
Scheme: the raw material including following parts by weight proportion: between 40%-55%, calcium carbonate content exists 100KG barium carbonate content
The high calcium witherite mineral of 25%-30%, the concentrated hydrochloric acid that concentration is 32%.
Preferably, the raw material including following parts by weight proportion: 100KG barium carbonate content is between 40%-55%, carbonic acid
High calcium witherite mineral of the calcium content in 25%-30%, the concentrated hydrochloric acid that concentration is 26%.
Preferably, the raw material including following parts by weight proportion: 100KG barium carbonate content is between 40%-55%, carbonic acid
High calcium witherite mineral of the calcium content in 25%-30%, the concentrated hydrochloric acid that concentration is 38%.
Preferably, the raw material including following parts by weight proportion: 100KG barium carbonate content is between 40%-55%, carbonic acid
High calcium witherite mineral of the calcium content in 25%-30%, the concentrated hydrochloric acid that concentration is 44%.
Another technical problem to be solved by the present invention is that providing the preparation side that high calcium witherite mineral produces the method for barium chloride
Method, comprising the following steps:
1) the clean placement ventilation of the high calcium witherite mineral of 100KG is taken to dry spare.
2) the high salt concentration acid solution of sufficient amount is imported in reactor tank, and the high calcium witherite mineral in step 1) is put into
In reactor tank, until the fully reacting of high calcium witherite mineral.
3) mixed liquor after complete reaction, is obtained into filter residue and liquid calcium chloride by by-pass filtration.
4) filter residue obtained after filtering is poured into beater tub, carries out mashing work, by mixed liquor by secondary filtration, obtained
To the very high barium chloride solution of purity.
5) by gained barium chloride solution in step 4), it is evaporated crystallization, obtains the high chlorination crystal of barium first time.
(3) beneficial effect
Compared with prior art, the present invention provides the methods that high calcium witherite mineral produces barium chloride, have following beneficial
Effect:
1, the method that high calcium witherite mineral produces barium chloride is reacted using common-ion effect using concentrated hydrochloric acid,
The general concentration of the hydrochloric acid of high concentration is 32% or so, takes concentrated hydrochloric acid to be reacted with the ore, reacts the chlorination of generation
Calcium will be all dissolved in the water that hydrochloric acid is brought into, and concentration reaches 250g/L or more, and the barium chloride generated only has the molten of only a few
Xie Yushui, concentration are 50-60g/L or so, and the overwhelming majority is present in solid form in barium slag, after the reaction was completed, first pass through one
Grade filtering, the liquid of filtering are liquid calcium chloride (wherein having partial oxidation barium), remove calcium chloride, and filter residue enters back into beater tub use
Water is beaten, by barium slag barium chloride all leach, obtain the very high barium chloride liquid of purity (calcium chloride content 20g/L with
Under), barium chloride concentration 320g/L or more, then it is evaporated crystallization with this barium liquid, obtained product purity is high, and yield is big, ton
Product steam consumption and power consumption are low.
2, the method that high calcium witherite mineral produces barium chloride, is produced using this method, can not only obtain high-purity
Barium chloride, and can also use high calcium witherite ore, raw ore it is more adaptable.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
Embodiment one:
The method that high calcium witherite mineral produces barium chloride, the raw material including following parts by weight proportion:.
High calcium witherite mineral produces the preparation method of the method for barium chloride, comprising the following steps: 100KG barium carbonate content exists
Between 40%-55%, high calcium witherite mineral of the calcium carbonate content in 25%-30%, the concentrated hydrochloric acid that concentration is 32%.
1) take 100KG barium carbonate content between 40%-55%, high calcium witherite of the calcium carbonate content in 25%-30%
Dry spare in the clean placement ventilation of mine.
2) the high salt concentration acid solution that sufficient amount concentration is 32% is imported in reactor tank, and the high calcium in step 1) is malicious
Scheelite mine is put into reactor tank, until the fully reacting of high calcium witherite mineral.
3) mixed liquor after complete reaction, is obtained into filter residue and liquid calcium chloride by by-pass filtration.
4) filter residue obtained after filtering is poured into beater tub, carries out mashing work, by mixed liquor by secondary filtration, obtained
To the very high barium chloride solution of purity.
5) by gained barium chloride solution in step 4), it is evaporated crystallization, obtains the high chlorination crystal of barium first time.
In entire production process, the liquid calcium chloride concentration in step 3) mixed liquor is 300g/L, and barium chloride concentration is 15g/
L, the calcium chloride concentration in step 4) mixed liquor are 10g/L, and barium chloride concentration is 400g/L.
Embodiment two:
The method that high calcium witherite mineral produces barium chloride, the raw material including following parts by weight proportion:.
High calcium witherite mineral produces the preparation method of the method for barium chloride, comprising the following steps: 100KG barium carbonate content exists
Between 40%-55%, high calcium witherite mineral of the calcium carbonate content in 25%-30%, the concentrated hydrochloric acid that concentration is 26%.
High calcium witherite mineral produces the preparation method of the method for barium chloride, comprising the following steps: 100KG barium carbonate content exists
Between 40%-55%, high calcium witherite mineral of the calcium carbonate content in 25%-30%, the concentrated hydrochloric acid that concentration is 26%.
1) take 100KG barium carbonate content between 40%-55%, high calcium witherite of the calcium carbonate content in 25%-30%
Dry spare in the clean placement ventilation of mine.
2) the high salt concentration acid solution that sufficient amount concentration is 26% is imported in reactor tank, and the high calcium in step 1) is malicious
Scheelite mine is put into reactor tank, until the fully reacting of high calcium witherite mineral.
3) mixed liquor after complete reaction, is obtained into filter residue and liquid calcium chloride by by-pass filtration.
4) filter residue obtained after filtering is poured into beater tub, carries out mashing work, by mixed liquor by secondary filtration, obtained
To the very high barium chloride solution of purity.
5) by gained barium chloride solution in step 4), it is evaporated crystallization, obtains the high chlorination crystal of barium first time.
In entire production process, the liquid calcium chloride concentration in step 3) mixed liquor is 100g/L, and barium chloride concentration is 10g/
L, the calcium chloride concentration in step 4) mixed liquor are 200g/L, and barium chloride concentration is 150g/L.
Embodiment three:
The method that high calcium witherite mineral produces barium chloride, the raw material including following parts by weight proportion:.
High calcium witherite mineral produces the preparation method of the method for barium chloride, comprising the following steps: 100KG barium carbonate content exists
Between 40%-55%, high calcium witherite mineral of the calcium carbonate content in 25%-30%, the concentrated hydrochloric acid that concentration is 38%.
1) take 100KG barium carbonate content between 40%-55%, high calcium witherite of the calcium carbonate content in 25%-30%
Dry spare in the clean placement ventilation of mine.
2) the high salt concentration acid solution that sufficient amount concentration is 38% is imported in reactor tank, and the high calcium in step 1) is malicious
Scheelite mine is put into reactor tank, until the fully reacting of high calcium witherite mineral.
3) mixed liquor after complete reaction, is obtained into filter residue and liquid calcium chloride by by-pass filtration.
4) filter residue obtained after filtering is poured into beater tub, carries out mashing work, by mixed liquor by secondary filtration, obtained
To the very high barium chloride solution of purity.
5) by gained barium chloride solution in step 4), it is evaporated crystallization, obtains the high chlorination crystal of barium first time.
In entire production process, the liquid calcium chloride concentration in step 3) mixed liquor is 312g/L, and barium chloride concentration is 25g/
L, the calcium chloride concentration in step 4) mixed liquor are 8g/L, and barium chloride concentration is 376g/L.
Example IV:
The method that high calcium witherite mineral produces barium chloride, the raw material including following parts by weight proportion:.
High calcium witherite mineral produces the preparation method of the method for barium chloride, comprising the following steps: 100KG barium carbonate content exists
Between 40%-55%, high calcium witherite mineral of the calcium carbonate content in 25%-30%, the concentrated hydrochloric acid that concentration is 44%.
1) take 100KG barium carbonate content between 40%-55%, high calcium witherite of the calcium carbonate content in 25%-30%
Dry spare in the clean placement ventilation of mine.
2) the high salt concentration acid solution that sufficient amount concentration is 44% is imported in reactor tank, and the high calcium in step 1) is malicious
Scheelite mine is put into reactor tank, until the fully reacting of high calcium witherite mineral.
3) mixed liquor after complete reaction, is obtained into filter residue and liquid calcium chloride by by-pass filtration.
4) filter residue obtained after filtering is poured into beater tub, carries out mashing work, by mixed liquor by secondary filtration, obtained
To the very high barium chloride solution of purity.
5) by gained barium chloride solution in step 4), it is evaporated crystallization, obtains the high chlorination crystal of barium first time.
In entire production process, the liquid calcium chloride concentration in step 3) mixed liquor is 322g/L, and barium chloride concentration is 86g/
L, the calcium chloride concentration in step 4) mixed liquor are 5g/L, and barium chloride concentration is 352g/L.
It is compared by aforementioned four embodiment the data obtained result it is found that the concentration of high salt concentration acid solution is 32%
When, obtained chlorination crystal of barium is most pure, and it is minimum to distill the calcium chloride crystals that crystallization is precipitated.
The beneficial effects of the present invention are: being reacted using common-ion effect using concentrated hydrochloric acid, the hydrochloric acid of high concentration
General concentration is 32% or so, and concentrated hydrochloric acid is taken to be reacted with the ore, reacts the calcium chloride of generation for whole dissolutions
In the water that hydrochloric acid is brought into, concentration reaches 250g/L or more, and the barium chloride generated only has the water that is dissolved in of only a few, and concentration is
50-60g/L or so, the overwhelming majority are present in solid form in barium slag, after the reaction was completed, first pass through by-pass filtration, filtering
Liquid is liquid calcium chloride (wherein having partial oxidation barium), removes calcium chloride, and filter residue enters back into beater tub and is beaten with water, will
Barium chloride in barium slag all leaches, and obtains the very high barium chloride liquid (calcium chloride content 20g/L or less) of purity, barium chloride concentration
320g/L or more, then be evaporated crystallization with this barium liquid, obtained product purity is high, and yield is big, ton product steam consumption and
Power consumption is low, is produced using this method, can not only obtain high-purity barium chloride, and can also use the poison weight of high calcium
Stone ore stone, raw ore it is more adaptable.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. the method that high calcium witherite mineral produces barium chloride, which is characterized in that the raw material including following parts by weight proportion:
100KG barium carbonate content is between 40%-55%, high calcium witherite mineral of the calcium carbonate content in 25%-30%, concentration 32%
Concentrated hydrochloric acid.
2. the method that high calcium witherite mineral according to claim 1 produces barium chloride, which is characterized in that including following weight
The raw material of number proportion: 100KG barium carbonate content is between 40%-55%, high calcium poison weight of the calcium carbonate content in 25%-30%
Stone ore, the concentrated hydrochloric acid that concentration is 26%.
3. the method that high calcium witherite mineral according to claim 1 produces barium chloride, which is characterized in that including following weight
The raw material of number proportion: 100KG barium carbonate content is between 40%-55%, high calcium poison weight of the calcium carbonate content in 25%-30%
Stone ore, the concentrated hydrochloric acid that concentration is 38%.
4. the method that high calcium witherite mineral according to claim 1 produces barium chloride, which is characterized in that including following weight
The raw material of number proportion: 100KG barium carbonate content is between 40%-55%, high calcium poison weight of the calcium carbonate content in 25%-30%
Stone ore, the concentrated hydrochloric acid that concentration is 44%.
5. the preparation method that high calcium witherite mineral produces the method for barium chloride, which comprises the following steps:
1) the clean placement ventilation of the high calcium witherite mineral of 100KG is taken to dry spare；
2) the high salt concentration acid solution of sufficient amount is imported in reactor tank, and the high calcium witherite mineral in step 1) is put into reaction
In tank, until the fully reacting of high calcium witherite mineral；
3) mixed liquor after complete reaction, is obtained into filter residue and liquid calcium chloride by by-pass filtration；
4) filter residue obtained after filtering is poured into beater tub, carries out mashing work, by mixed liquor by secondary filtration, obtained pure
Spend very high barium chloride solution；
5) by gained barium chloride solution in step 4), it is evaporated crystallization, obtains the high chlorination crystal of barium first time.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110095373A (en) * | 2019-03-26 | 2019-08-06 | 玉溪新兴钢铁有限公司 | The detection method of barium carbonate content in a kind of witherite |
| CN112591781A (en) * | 2020-12-31 | 2021-04-02 | 宜昌华昊新材料科技有限公司 | Process for producing electronic grade barium chloride by using low-grade witherite ore |
| CN113405879A (en) * | 2021-08-19 | 2021-09-17 | 中国农业科学院农业环境与可持续发展研究所 | Method for improving extraction rate of organic phosphorus in calcareous soil and detection effect of liquid-phase 31P-NMR |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110095373A (en) * | 2019-03-26 | 2019-08-06 | 玉溪新兴钢铁有限公司 | The detection method of barium carbonate content in a kind of witherite |
| CN112591781A (en) * | 2020-12-31 | 2021-04-02 | 宜昌华昊新材料科技有限公司 | Process for producing electronic grade barium chloride by using low-grade witherite ore |
| CN113405879A (en) * | 2021-08-19 | 2021-09-17 | 中国农业科学院农业环境与可持续发展研究所 | Method for improving extraction rate of organic phosphorus in calcareous soil and detection effect of liquid-phase 31P-NMR |
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Application publication date: 20190215 |