CN102583487A - Method for preparing barium chloride by using witherite tailings and barium residues - Google Patents
Method for preparing barium chloride by using witherite tailings and barium residues Download PDFInfo
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- CN102583487A CN102583487A CN2011104630001A CN201110463000A CN102583487A CN 102583487 A CN102583487 A CN 102583487A CN 2011104630001 A CN2011104630001 A CN 2011104630001A CN 201110463000 A CN201110463000 A CN 201110463000A CN 102583487 A CN102583487 A CN 102583487A
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Abstract
The invention relates to a method for preparing barium chloride by using witherite tailings and barium residues, belonging to the technical field of fine chemical engineering. According to the method, the witherite tailings or the barium residues are used as raw materials, and hydrochloric acid solution is used for dissolving and leaching in two steps. The method comprises the following steps of: 1, dissolving to remove impurity elements such as calcium, iron, strontium and the like in an ethanol aqueous medium in a lower liquid-solid ratio, and filtering and separating to obtain solid phases with undissolved substance such as barium, silicon and the like; and 2, dissolving the solid phases obtained in the step 1 in a higher liquid-solid ratio to obtain barium chloride solution, and crystallizing and drying to obtain industrial-grade qualified products of barium chloride; or, adding oxalic acid into the obtained barium chloride solution, regulating a pH value to remove precipitates formed by a trace of calcium and strontium, concentrating and crystallizing the solution, washing off chloride on the surface by means of anhydrous ethanol, and thus obtaining the high-purity barium chloride. According to the method, the energy consumption in the preparation of the barium chloride is lower, the barium in the tailings or the barium residues can be recycled, the damage of the tailings or the barium residues to the environment is reduced, and the income of enterprises is increased.
Description
Technical field
The present invention relates to the fine chemical technology field, specifically use witherite mine tailing barium slag to produce the method for bariumchloride as raw material.The recycling and the nothing that are applicable to witherite mine tailing barium slag poison processing.
Background technology
There is the generation of low-grade mine tailing in witherite barium ore deposit and deposits in mining and ore dressing process, and the mining wet method of witherite barium is produced in the hydrated barta process, can produce a large amount of barium content at 20～30% barium slag.The harmless treatment of barium slag has seriously restricted the development of barium salt company.At present mainly adopt the technology of storing up of building a dam for the processing of mine tailing barium slag.
Barium is a kind of deleterious heavy metal element; Mine tailing barium slag is being stored up in the process for a long time; Erosion and the effect of hypergene geochemistry through rainwater; Receive effects such as temperature, water, organic matter, atmosphere, soda acid and interface chemistry, the barium element very easily dissolves from solid particulate and is discharged in the surrounding enviroment, causes the heavy metal contamination of water body, soil and vegetation.Because the mine tailing barium slag that produces can not get timely processing, the man barium salt of domestic existing number company is in end-of-life state.
Summary of the invention
The objective of the invention is to having the way that most of producers build a dam and store up witherite mine tailing barium slag now, providing a kind of is the method that raw material is produced bariumchloride with mine tailing barium slag, not only can turn waste into wealth but also can preserve the ecological environment.It is low, easy and simple to handle that this method has a production cost, characteristics such as product yield recovery height.
The objective of the invention is to realize like this: witherite mine tailing barium slag is produced the method for bariumchloride, is raw material with witherite barium slag, uses hydrochloric acid soln to dissolve leaching in two steps, and bullion can obtain salable product after removal of impurities, and concrete step is following:
(1) 100 mesh sieves are crossed in the broken back of witherite mine tailing barium ground-slag; In ethanol-water media with concentration 1～1.6mol/L hydrochloric acid soln; Under 65～75 ℃ of temperature, in solid-to-liquid ratio 1: 0.5～1.5 ratios, under 100～300 rev/mins of conditions of mixing speed; Reacted 2～3 hours, and got solid phases such as baric and silicon insolubles behind the filtration washing.
The solid matter that (2) will be obtained by (1), in solid-to-liquid ratio 1: 6～8 ratios, under 200～400 rev/mins of conditions of mixing speed, reacted 2～3 hours under 65～75 ℃ of temperature with 1.8～2.2mol/L hydrochloric acid soln, and the filtering and concentrating crystallization obtains the bariumchloride salable product.
(3) with (2) gained salable product bariumchloride recrystallization; Regulate pH value 2～3; Add and press bariumchloride: oxalic acid=1: 0.5～1 precipitation agent eliminating minute strontium and calcium, filter the back condensing crystal, through bariumchloride: 90 ℃ of freeze-day with constant temperature obtained bariumchloride I series products after washed absolute ethyl alcohol=1: 0.2～0.4.
After the present invention adopts technique scheme, have the following advantages:
(1) adopt the two-step approach leaching, dust removal rate is high, and product purity reaches more than 99.9%, and operating performance is easy, and steady quality is reliable;
(2) the barium recovery is high in the witherite, surpasses 95%, has both protected environment, has increased income again;
(3) the inventive method newly added equipment is simple, thereby the expense of reducing investment outlay is convenient to industrial production and is applied;
(4) can not produce new pollutent in the production process, so can not pollute to environment.
The inventive method can be widely used in the recycling and the toxicological harmless of barium in the various witherite mine tailings to be handled, and also can be used for the witherite is raw material, the recycling of the barytic enterprise of wet method hydrogen manufacturing barium slag.Adopt the product of the inventive method preparation can extensively reach national bariumchloride standard, as industrial chemicals.
Description of drawings
Combine accompanying drawing that the present invention is done further explain at present.
Fig. 1 produces the process flow sheet of the method for bariumchloride for witherite mine tailing barium slag according to the invention.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
The concrete steps of method that witherite mine tailing barium slag is produced bariumchloride are following:
Instance 1: witherite mine tailing barium slag is produced bariumchloride; 100 mesh sieves are crossed in the broken back of witherite mine tailing barium ground-slag, in ethanol-water media with concentration 1mol/L hydrochloric acid soln, under 65 ℃ of temperature; In 1: 0.5 ratio of solid-to-liquid ratio; Under 100 rev/mins of conditions of mixing speed, reacted 2 hours, get solid phases such as baric and silicon insolubles behind the filtration washing.The solid matter that obtains is used the 1.8mol/L hydrochloric acid soln, under 65 ℃ of temperature, in 1: 6 ratio of solid-to-liquid ratio, under 200 rev/mins of conditions of mixing speed, reacted 2 hours, the crystallization of gained solution filtering and concentrating obtains the bariumchloride salable product.With gained bariumchloride recrystallization, regulate pH value 2～3, add bariumchloride: oxalic acid=1: 0.5 precipitation agent eliminating minute strontium and calcium, filter the back condensing crystal, obtain the higher degree bariumchloride through 90 ℃ of freeze-day with constant temperature of absolute ethanol washing.
Instance 2: 100 mesh sieves are crossed in the broken back of witherite mine tailing barium ground-slag, in ethanol-water media with concentration 1.6mol/L hydrochloric acid soln, under 75 ℃ of temperature; In 1: 1.5 ratio of solid-to-liquid ratio; Under 300 rev/mins of conditions of mixing speed, reacted 3 hours, get solid phases such as baric and silicon insolubles behind the filtration washing.Resulting solid matter is used the 2.2mol/L hydrochloric acid soln, under 75 ℃ of temperature, in 1: 8 ratio of solid-to-liquid ratio; Under 400 rev/mins of conditions of mixing speed, reacted 3 hours, the crystallization of solution filtering and concentrating obtains the bariumchloride bullion; With institute's gained bullion bariumchloride recrystallization, regulate pH value 3, add bariumchloride: oxalic acid=1: 1 precipitation agent eliminating minute strontium and calcium; Filter the back condensing crystal, obtain higher degree bariumchloride product through 90 ℃ of freeze-day with constant temperature of absolute ethanol washing.
Instance 3: 100 mesh sieves are crossed in the broken back of witherite mine tailing barium ground-slag, in ethanol-water media with concentration 1mol/L hydrochloric acid soln, under 70 ℃ of temperature; In 1: 0.5 ratio of solid-to-liquid ratio; Under 200 rev/mins of conditions of mixing speed, reacted 2 hours, get solid phases such as baric and silicon insolubles behind the filtration washing.Resulting solid matter is used the 2mol/L hydrochloric acid soln, under 70 ℃ of temperature, in 1: 7 ratio of solid-to-liquid ratio; Under 300 rev/mins of conditions of mixing speed, reacted 2.5 hours, the crystallization of gained solution filtering and concentrating obtains the bariumchloride bullion; With institute's gained bullion bariumchloride recrystallization, regulate pH value 3, add bariumchloride: oxalic acid=1: 0.7 precipitation agent eliminating minute strontium and calcium; Filter the back condensing crystal, obtain higher degree bariumchloride product through 90 ℃ of freeze-day with constant temperature of absolute ethanol washing.
Experimental result
1, it is following with low concentration hydrochloric acid each element in the witherite mine tailing barium slag to be removed the result for the first time:
2, following with higher concentration hydrochloric acid for the second time to witherite mine tailing barium slag leaching result:
Know from above experimental result: the present invention uses low concentration hydrochloric acid higher to element clearances such as calcium, iron, strontium the witherite mine tailing barium slag for the first time; Avoided the once isolating again trouble of leaching; For the second time with the witherite mine tailing barium slag of higher concentration hydrochloric acid after to removal of impurities leach can obtain barium total recovery more than 95%, the total barium content of the solid phase residue of formation is especially little.
The solution direct crystallization that obtains after the secondary leaching can be met salable product in GB/T 1617-2002 " industrial chlorinating titanate " standard, and the product that obtains behind its purifying is satisfied I series products standard.Therefore, adopt the inventive method can increase recycling, can play environmental-protection function again barium.
Claims (5)
1. one kind prepares the method for bariumchloride with witherite mine tailing barium slag, it is characterized in that concrete step is following:
(1) 100 mesh sieves are crossed in the broken back of witherite mine tailing barium ground-slag; In ethanol-water media with concentration 1～1.6mol/L hydrochloric acid soln; Under 65～75 ℃ of temperature, in solid-to-liquid ratio 1: 0.5～1.5 ratios, under 100～300 rev/mins of conditions of mixing speed; Reacted 2～3 hours, and got solid phases such as baric and silicon insolubles behind the filtration washing.
The solid matter that (2) will be obtained by (1), in solid-to-liquid ratio 1: 6～8 ratios, under 200～400 rev/mins of conditions of mixing speed, reacted 2～3 hours under 65～75 ℃ of temperature with 1.8～2.2mol/L hydrochloric acid soln, and the filtering and concentrating crystallization obtains the bariumchloride salable product.
(3) with (2) gained salable product bariumchloride recrystallization; Regulate pH value 2～3; Add and press bariumchloride: oxalic acid=1: 0.5～1 precipitation agent eliminating minute strontium and calcium, filter the back condensing crystal, through bariumchloride: 90 ℃ of freeze-day with constant temperature obtained the bariumchloride product after washed absolute ethyl alcohol=1: 0.2～0.4.
2. according to the described method for preparing bariumchloride with witherite mine tailing barium slag of claim 1; It is characterized in that adopting two step leaching methods; The first step is to use the hydrochloric acid than small proportion to remove impurity such as strontium, calcium, iron earlier, filters solid part excessively and adopts for second step obtained bariumchloride with the dissolving with hydrochloric acid of larger proportion.
3. prepare the method for bariumchloride according to claim 1 is described with witherite mine tailing barium slag, the concrete steps of method that it is characterized in that preparing with witherite mine tailing barium slag bariumchloride are following:
Witherite mine tailing barium slag is produced bariumchloride; 100 mesh sieves are crossed in the broken back of witherite mine tailing barium ground-slag, in ethanol-water media with concentration 1mol/L hydrochloric acid soln, under 65 ℃ of temperature; In 1: 0.5 ratio of solid-to-liquid ratio; Under 100 rev/mins of conditions of mixing speed, reacted 2 hours, get solid phases such as baric and silicon insolubles behind the filtration washing.The solid matter that obtains is used the 1.8mol/L hydrochloric acid soln, under 65 ℃ of temperature, in 1: 6 ratio of solid-to-liquid ratio, under 200 rev/mins of conditions of mixing speed, reacted 2 hours, the crystallization of gained solution filtering and concentrating obtains the bariumchloride salable product.With gained bariumchloride recrystallization, regulate pH value 2～3, add bariumchloride: oxalic acid=1: 0.5 precipitation agent eliminating minute strontium and calcium, filter the back condensing crystal, obtain the higher degree bariumchloride through 90 ℃ of freeze-day with constant temperature of absolute ethanol washing.
4. prepare the method for bariumchloride according to claim 1 is described with witherite mine tailing barium slag, the concrete steps of method that it is characterized in that preparing with witherite mine tailing barium slag bariumchloride are following:
100 mesh sieves are crossed in the broken back of witherite mine tailing barium ground-slag, in ethanol-water media with concentration 1.6mol/L hydrochloric acid soln, under 75 ℃ of temperature; In 1: 1.5 ratio of solid-to-liquid ratio; Under 300 rev/mins of conditions of mixing speed, reacted 3 hours, get solid phases such as baric and silicon insolubles behind the filtration washing.Resulting solid matter is used the 2.2mol/L hydrochloric acid soln, under 75 ℃ of temperature, in 1: 8 ratio of solid-to-liquid ratio; Under 400 rev/mins of conditions of mixing speed, reacted 3 hours, the crystallization of solution filtering and concentrating obtains the bariumchloride bullion; With gained bullion bariumchloride recrystallization, regulate pH value 3, add bariumchloride: oxalic acid=1: 1 precipitation agent eliminating minute strontium and calcium; Filter the back condensing crystal, obtain higher degree bariumchloride product through 90 ℃ of freeze-day with constant temperature of absolute ethanol washing.
5. prepare the method for bariumchloride according to claim 1 is described with witherite mine tailing barium slag, the concrete steps of method that it is characterized in that preparing with witherite mine tailing barium slag bariumchloride are following:
100 mesh sieves are crossed in the broken back of witherite mine tailing barium ground-slag, in ethanol-water media with concentration 1mol/L hydrochloric acid soln, under 70 ℃ of temperature; In 1: 0.5 ratio of solid-to-liquid ratio; Under 200 rev/mins of conditions of mixing speed, reacted 2 hours, get solid phases such as baric and silicon insolubles behind the filtration washing.Resulting solid matter is used the 2mol/L hydrochloric acid soln, under 70 ℃ of temperature, in 1: 7 ratio of solid-to-liquid ratio; Under 300 rev/mins of conditions of mixing speed, reacted 2.5 hours, the crystallization of gained solution filtering and concentrating obtains the bariumchloride bullion; With gained bullion bariumchloride recrystallization, regulate pH value 3, add bariumchloride: oxalic acid=1: 0.7 precipitation agent eliminating minute strontium and calcium; Filter the back condensing crystal, obtain higher degree bariumchloride product through 90 ℃ of freeze-day with constant temperature of absolute ethanol washing.
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| CN2011104630001A CN102583487A (en) | 2011-12-30 | 2011-12-30 | Method for preparing barium chloride by using witherite tailings and barium residues |
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| CN2011104630001A CN102583487A (en) | 2011-12-30 | 2011-12-30 | Method for preparing barium chloride by using witherite tailings and barium residues |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271347A (en) * | 2015-10-16 | 2016-01-27 | 重庆市川渝矿业有限责任公司 | Method for preparing high-purity barium salt by using witherite-barytocalcite industrial waste residues |
| CN106734056A (en) * | 2016-11-22 | 2017-05-31 | 贵州红星发展大龙锰业有限责任公司 | A kind of barium dregs innocent treatment method |
| CN109279638A (en) * | 2018-12-11 | 2019-01-29 | 宜昌华昊新材料科技有限公司 | The method that calcium witherite mineral produces barium chloride |
| CN109336158A (en) * | 2018-12-11 | 2019-02-15 | 宜昌华昊新材料科技有限公司 | The method that high calcium witherite mineral produces barium chloride |
| CN110000187A (en) * | 2019-03-20 | 2019-07-12 | 贵州红星发展股份有限公司 | A kind of barium dregs innocent treatment method |
-
2011
- 2011-12-30 CN CN2011104630001A patent/CN102583487A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271347A (en) * | 2015-10-16 | 2016-01-27 | 重庆市川渝矿业有限责任公司 | Method for preparing high-purity barium salt by using witherite-barytocalcite industrial waste residues |
| CN105271347B (en) * | 2015-10-16 | 2017-04-12 | 重庆市川渝矿业有限责任公司 | Method for preparing high-purity barium salt by using witherite-barytocalcite industrial waste residues |
| CN106734056A (en) * | 2016-11-22 | 2017-05-31 | 贵州红星发展大龙锰业有限责任公司 | A kind of barium dregs innocent treatment method |
| CN109279638A (en) * | 2018-12-11 | 2019-01-29 | 宜昌华昊新材料科技有限公司 | The method that calcium witherite mineral produces barium chloride |
| CN109336158A (en) * | 2018-12-11 | 2019-02-15 | 宜昌华昊新材料科技有限公司 | The method that high calcium witherite mineral produces barium chloride |
| CN110000187A (en) * | 2019-03-20 | 2019-07-12 | 贵州红星发展股份有限公司 | A kind of barium dregs innocent treatment method |
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Application publication date: 20120718 |