CN101134596A - Technique for producing fine barium sulfate by barite sulfuric acid process - Google Patents
Technique for producing fine barium sulfate by barite sulfuric acid process Download PDFInfo
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- CN101134596A CN101134596A CNA2006100321807A CN200610032180A CN101134596A CN 101134596 A CN101134596 A CN 101134596A CN A2006100321807 A CNA2006100321807 A CN A2006100321807A CN 200610032180 A CN200610032180 A CN 200610032180A CN 101134596 A CN101134596 A CN 101134596A
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- barium sulfate
- sulfuric acid
- barite
- technique
- barium
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Abstract
The present invention discloses sulfuric acid process of producing refined barium sulfate with barite, and belongs to the field of chemical technology. The process includes the following main technological steps: producing black ash containing barium sulfate with coal calcining barite; soaking black ash containing barium sulfate in water to obtain barium sulfate solution; adding sulfuric acid into the barium sulfate solution to obtain slurry with barium sulfate precipitant; and dewatering the slurry, stoving and crushing to obtain refined barium sulfate product. The refined barium sulfate product has low cost, and may be applied widely in high grade paint, etc. and the production process is harmless and has environment friendship and high marketability.
Description
Technical field
The invention belongs to chemical technology field, being specifically related to a kind of is the production technique that raw material is produced fine barium sulfate, i.e. technique for producing fine barium sulfate by barite sulfuric acid process with the barite.
Background technology
Existing is that the method for raw material production barium sulfate mainly contains barite mirabilite method, bariumchloride mirabilite method etc. with the barite, and the main weak point of these processing methodes is that environmental pollution is heavy and be difficult to solve, and product specification is low, has limited the expansion of barium sulfate Application Areas; The complex manufacturing that has, the cost height.
Summary of the invention
Purpose of the present invention will overcome the prior art deficiency exactly, providing that innoxious production, product specification height, adjustable grain can be controlled and reach to a kind of environmental pollution, technology is simple, cost is low is that raw material is produced the fine barium sulfate production technique with the barite, i.e. technique for producing fine barium sulfate by barite sulfuric acid process.
For achieving the above object, technical scheme of the present invention is that this technique for producing fine barium sulfate by barite sulfuric acid process comprises following processing step:
A generates the grey black of Containing Sulfur barium with the coal calcination barite;
B. the grey black of this Containing Sulfur barium of being soaked in water gets barium sulfide solution;
C. in this barium sulfide solution, add sulfuric acid and generate process white slurry and hydrogen sulfide;
D. this barium sulfate slurry is dewatered, is dried, pulverizes the fine barium sulfate finished product.
The used coal of described calcining barite is a hard coal, and the weight ratio of barite and hard coal is 1: 0.26, and the two is pulverized mixed calcining,
Describedly be controlled at 1100-1200 ℃ with the bar temperature of coal calcination.
Described is 2 hours with the bar calcination time of coal calcination.
The water of the grey black of the described Containing Sulfur barium that is soaked in water is hot water, and water temperature is controlled at 75-85 ℃.
The weight ratio of the water of the grey black of the described Containing Sulfur barium that is soaked in water and the grey black of Containing Sulfur barium is 1: 0.1.
The described sulfuric acid that adds in barium sulfide solution is the vitriol oil, and the weight ratio of the barium sulphide and the vitriol oil is 1: 0.55-0.65.Sulfuric acid concentration is big more, reacts slow more, and the particle diameter that generates barium sulfate is more little; Sulfuric acid concentration is more little, reacts fast more, and the particle diameter that generates barium sulfate is big more.Sulfate liquid is carried out closed circulation and is used.
It is described that to add sulfuric acid in barium sulfide solution be under agitation condition.
Adding the vitriolic stirring velocity under the described agitation condition in barium sulfide solution is that per minute 300 changes.
The main chemical reactions of described technology is as follows:
BaSO
4+2C→BaS+2CO
2↑
BaS
x+H
2O→Ba(SH)
2+Ba(OH)
2
Ba(SH)
2+H
2SO
4→BaSO
4↓+H
2S↑
Ba(OH)
2+H
2SO
4→BaSO
4↓+H
2O↑
Major ingredient is CO in the flue gas that calcining produces
2, CO, N
2With a small amount of SO
2And dust, adopt dry method dust and foam fly-ash separator to remove SO
2
The major ingredient of leaching back residue is unconverted barite, coal ash, silicon-dioxide and a spot of BaS, its principal pollutant BaS, take to prevent that at slag place face shop impervious barrier it from permeating the ground, lower is built pond for recovering in the slag field, and the water recovery that bits are oozed out is used to leach BaS, makes not pollute.
The hydrogen sulfide that reaction generates is transported in the calcining furnace through roots blower and burns, and generates sulphur through three grades of condensers, convertor, trap, and yield is more than 95%.The waste gas that this process produces mainly is water vapor, hydrogen sulfide and sulfurous gas, with the hydrogen sulfide in the activated carbon adsorption waste gas, makes emission compliance before advancing smokestack.
A waste water that is produced becomes acid ph value=5, adds alkali and regulates pH=7, returns to be used to leach barium sulphide; Two times waste water alkalizes recycle, and several all after dates are regulated pH=7, return to mend and make the leaching water, and waste water does not efflux.
Described processing step can carry out under normal pressure.
With existing technology relatively, the fine barium sulfate that adopts the present invention to produce, color and luster is fair and clear, alternative titanium dioxide on the colourity; Its product grain warp can reach 0.1 micron, and adjustable, and Application Areas is further widened, and can be used for high-grade paint etc.; Adopt the factory of technology of the present invention not far far from vitriol works and barite mine, the sulfate liquid of its production process is carried out closed circulation and is used, do not efflux, no contaminated wastewater, waste gas mainly is hydrogen sulfide, be reduced into sulphur recovery by the dry dedusting technology device, make the flue dust qualified discharge, thereby realized the innoxious production of fine barium sulfate; Product cost is lower than existing technology, has the very strong market competitiveness.
Embodiment
Embodiment 1
Barite and hard coal are pulverized mixing by 1: 0.26 weight ratio, drop into calcining in the calcining converter, temperature is controlled at 1200 ℃, and calcination time is 2 hours, and the thick barium sulphide of generation Containing Sulfur barium about 60% is commonly called as " grey black ";
Above-mentioned thick barium sulphide (grey black) is put into the leaching groove with 80 ℃ of hot-water soaks, and the weight ratio of the grey black of water and Containing Sulfur barium is 1: 0.1, produces the barium sulfide solution that contains BaS110g/L-135g/L, is commonly called as " sulphur water ";
Press 1: 0.65 weight ratio of the barium sulphide and the vitriol oil, under the agitation condition that per minute 300 changes, carry out successive reaction in reactor, this process pH value is controlled at about 5, generates white precipitate barium sulfate slurry and hydrogen sulfide;
Filter cake behind the barium sulfate slurry filter-press dehydration is added alkali by customer requirements to be regulated pH value (being generally 10-11), oven dry, pulverizing and promptly gets the fine barium sulfate finished product;
Major ingredient is CO in the flue gas that calcining produces
2, CO, N
2With a small amount of SO
2And dust, adopt dry method dust and foam fly-ash separator to remove SO
2Wherein the foam fly-ash separator is used in the NaOH solution and SO
2Reaction formula: SO
2+ 2NaOH → Na
2SO
3+ H
2O
The major ingredient of the residue after the leaching is unconverted barite, coal ash, silicon-dioxide and a small amount of BaS (below 0.5%), its principal pollutant are BaS, take to prevent that at slag place face shop impervious barrier it from permeating the ground, lower is built pond for recovering in the slag field, and the water recovery that bits are oozed out is used to leach BaS.
The hydrogen sulfide that reaction generates is transported in the calcining furnace through roots blower and burns, and generates sulphur through three grades of condensers, convertor, trap, and yield is more than 95%.The waste gas that this process produces mainly is water vapor, hydrogen sulfide and sulfurous gas, with the hydrogen sulfide in the activated carbon adsorption waste gas, makes emission compliance before advancing smokestack.
One time and two times waste water being produced, wherein waste water becomes acid (PH=5), enters to add alkali in the waste water stirred pot and adjust to neutrality (PH=7), returns to make the leaching barium sulphide and use; Two times waste water is alkalescence, recycles, and enters after several cycles to adjust PH=7 in the waste water stirred pot, is restored to and replenishes the leaching water in the waste water tank, and waste water is not effluxed.
Embodiment 2
Barite and hard coal are pulverized mixing by 1: 0.26 weight ratio, drop into calcining in the calcining converter, temperature is controlled at 1100 ℃, and calcination time is 2 hours, and the thick barium sulphide of generation Containing Sulfur barium about 60% is commonly called as " grey black ";
Above-mentioned thick barium sulphide (grey black) is put into the leaching groove with 85 ℃ of hot-water soaks, and the weight ratio of the grey black of water and Containing Sulfur barium is 1: 0.1, produces the barium sulfide solution that contains BaS110g/L-135g/L, is commonly called as " sulphur water ";
Press 1: 0.60 weight ratio of the barium sulphide and the vitriol oil, under the agitation condition that per minute 300 changes, carry out successive reaction in reactor, this process pH value is controlled at about 5, generates white precipitate barium sulfate slurry and hydrogen sulfide;
Filter cake behind the barium sulfate slurry filter-press dehydration is added alkali by customer requirements to be regulated pH value, oven dry, pulverizing and promptly gets the fine barium sulfate finished product;
The processing of the waste gas that is produced, residue and waste water is identical with embodiment 1.
Embodiment 3
Barite and hard coal are pulverized mixing by 1: 0.26 weight ratio, drop into calcining in the calcining converter, temperature is controlled at 1150 ℃, and calcination time is 2 hours, and the thick barium sulphide of generation Containing Sulfur barium about 60% is commonly called as " grey black ";
Above-mentioned thick barium sulphide (grey black) is put into the leaching groove with 75 ℃ of hot-water soaks, and the weight ratio of the grey black of water and Containing Sulfur barium is 1: 0.1, produces the barium sulfide solution that contains BaS110g/L-135g/L, is commonly called as " sulphur water ";
Press 1: 0.55 weight ratio of the barium sulphide and the vitriol oil, under the agitation condition that per minute 300 changes, carry out successive reaction in reactor, this process pH value is controlled at about 5, generates white precipitate barium sulfate slurry and hydrogen sulfide;
Filter cake behind the barium sulfate slurry filter-press dehydration is added alkali by customer requirements to be regulated pH value, oven dry, pulverizing and promptly gets the fine barium sulfate finished product;
The processing of the waste gas that is produced, residue and waste water is identical with embodiment 1.
Claims (9)
1. technique for producing fine barium sulfate by barite sulfuric acid process, it is characterized in that: it comprises the steps:
A. generate the grey black of Containing Sulfur barium with the coal calcination barite;
B. the grey black of this Containing Sulfur barium of being soaked in water gets barium sulfide solution;
C. in this barium sulfide solution, add sulfuric acid and generate process white slurry and hydrogen sulfide;
D. this barium sulfate slurry is dewatered, is dried, pulverizes the fine barium sulfate finished product.
2. technique for producing fine barium sulfate by barite sulfuric acid process according to claim 1 is characterized in that: described is hard coal with the bar coal of coal calcination.
3. technique for producing fine barium sulfate by barite sulfuric acid process according to claim 1 is characterized in that: describedly be controlled at 1100-1200 ℃ with the bar temperature of coal calcination.
4. technique for producing fine barium sulfate by barite sulfuric acid process according to claim 1 is characterized in that: described is 2 hours with the bar calcination time of coal calcination.
5. technique for producing fine barium sulfate by barite sulfuric acid process according to claim 1 is characterized in that: the described used water that is soaked in water is hot water, and water temperature is controlled at 75-85 ℃.
6. technique for producing fine barium sulfate by barite sulfuric acid process according to claim 1 is characterized in that: the described water that is soaked in water is 1 to 0.1 with the weight ratio of the grey black of Containing Sulfur barium.
7. technique for producing fine barium sulfate by barite sulfuric acid process according to claim 1 is characterized in that: the described sulfuric acid that adds in barium sulfide solution is the vitriol oil, and the weight ratio of the barium sulphide and the vitriol oil is 1: 0.55-0.65.
8. technique for producing fine barium sulfate by barite sulfuric acid process according to claim 1 is characterized in that: described to add sulfuric acid in barium sulfide solution be under agitation condition.
9. technique for producing fine barium sulfate by barite sulfuric acid process according to claim 8 is characterized in that: adding the vitriolic stirring velocity under the described agitation condition in barium sulfide solution is that per minute 300 changes.
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|---|---|---|---|
| CNA2006100321807A CN101134596A (en) | 2006-08-31 | 2006-08-31 | Technique for producing fine barium sulfate by barite sulfuric acid process |
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|---|---|---|---|
| CNA2006100321807A CN101134596A (en) | 2006-08-31 | 2006-08-31 | Technique for producing fine barium sulfate by barite sulfuric acid process |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010078821A1 (en) * | 2009-01-06 | 2010-07-15 | 重庆科昌科技有限公司 | Method for preparing subsphaeroidal barium sulfate by sulfuric acid process and its use in copper foil substrate |
| WO2010078820A1 (en) * | 2009-01-06 | 2010-07-15 | 重庆科昌科技有限公司 | Titania composite and preparing method thereof |
| CN102505082A (en) * | 2011-11-02 | 2012-06-20 | 欧阳隆章 | Method and device for extracting barium and barium salt from ore |
| CN103693671A (en) * | 2013-12-19 | 2014-04-02 | 贵州红星发展股份有限公司 | Submicron flake-shaped barium sulfate and preparation method thereof |
| CN104326499A (en) * | 2014-10-13 | 2015-02-04 | 南风化工集团股份有限公司 | Method for improving sodium sulfide solution concentration by leaching black ash for three times |
| CN106976900A (en) * | 2017-04-14 | 2017-07-25 | 河北科技大学 | A kind of preparation method of powdery paints barium sulfate |
| CN107673387A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of efficiently barium salt production line |
| CN107673388A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of hydrogen sulfide recycling system barium salt production line |
| CN107673386A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of barium sulfate leaches groove barium salt production line |
| CN107720799A (en) * | 2017-11-03 | 2018-02-23 | 荆门市双创专利技术服务有限公司 | A kind of barium salt production line with carbonators |
| EP3219673A4 (en) * | 2014-11-10 | 2018-06-13 | Sakai Chemical Industry Co., Ltd. | Barium sulfate powder production method and barium sulfate powder |
| CN108773850A (en) * | 2018-07-13 | 2018-11-09 | 贵州紫云月华新材料有限公司 | A kind of barite deposit agent production method and its technique |
| CN110092357A (en) * | 2019-04-23 | 2019-08-06 | 贵州红星发展股份有限公司 | A kind of preparation method of high-purity barium sulphide |
| CN112250100A (en) * | 2020-09-11 | 2021-01-22 | 河津市鑫特化工有限公司 | Preparation method of barium sulfate |
-
2006
- 2006-08-31 CN CNA2006100321807A patent/CN101134596A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010078821A1 (en) * | 2009-01-06 | 2010-07-15 | 重庆科昌科技有限公司 | Method for preparing subsphaeroidal barium sulfate by sulfuric acid process and its use in copper foil substrate |
| WO2010078820A1 (en) * | 2009-01-06 | 2010-07-15 | 重庆科昌科技有限公司 | Titania composite and preparing method thereof |
| CN102505082A (en) * | 2011-11-02 | 2012-06-20 | 欧阳隆章 | Method and device for extracting barium and barium salt from ore |
| CN102505082B (en) * | 2011-11-02 | 2013-08-21 | 欧阳隆章 | Method and device for extracting barium and barium salt from ore |
| CN103693671A (en) * | 2013-12-19 | 2014-04-02 | 贵州红星发展股份有限公司 | Submicron flake-shaped barium sulfate and preparation method thereof |
| CN104326499A (en) * | 2014-10-13 | 2015-02-04 | 南风化工集团股份有限公司 | Method for improving sodium sulfide solution concentration by leaching black ash for three times |
| CN104326499B (en) * | 2014-10-13 | 2016-04-27 | 南风化工集团股份有限公司 | By the method for three molten leaching grey black raising sodium sulfide solution concentration |
| EP3219673A4 (en) * | 2014-11-10 | 2018-06-13 | Sakai Chemical Industry Co., Ltd. | Barium sulfate powder production method and barium sulfate powder |
| CN106976900A (en) * | 2017-04-14 | 2017-07-25 | 河北科技大学 | A kind of preparation method of powdery paints barium sulfate |
| CN106976900B (en) * | 2017-04-14 | 2019-04-05 | 河北科技大学 | A kind of preparation method of powdery paints barium sulfate |
| CN107673387A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of efficiently barium salt production line |
| CN107673388A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of hydrogen sulfide recycling system barium salt production line |
| CN107673386A (en) * | 2017-11-03 | 2018-02-09 | 荆门市双创专利技术服务有限公司 | A kind of barium sulfate leaches groove barium salt production line |
| CN107720799A (en) * | 2017-11-03 | 2018-02-23 | 荆门市双创专利技术服务有限公司 | A kind of barium salt production line with carbonators |
| CN108773850A (en) * | 2018-07-13 | 2018-11-09 | 贵州紫云月华新材料有限公司 | A kind of barite deposit agent production method and its technique |
| CN110092357A (en) * | 2019-04-23 | 2019-08-06 | 贵州红星发展股份有限公司 | A kind of preparation method of high-purity barium sulphide |
| CN112250100A (en) * | 2020-09-11 | 2021-01-22 | 河津市鑫特化工有限公司 | Preparation method of barium sulfate |
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Open date: 20080305 |