CN103395811A - Method for producing barium hydroxide and calcium hydroxide with barium sulfate waste slag - Google Patents
Method for producing barium hydroxide and calcium hydroxide with barium sulfate waste slag Download PDFInfo
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- CN103395811A CN103395811A CN2013103079701A CN201310307970A CN103395811A CN 103395811 A CN103395811 A CN 103395811A CN 2013103079701 A CN2013103079701 A CN 2013103079701A CN 201310307970 A CN201310307970 A CN 201310307970A CN 103395811 A CN103395811 A CN 103395811A
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- barium
- solid
- slag
- hydroxide
- barium sulfate
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Abstract
The invention belongs to the field of technical research and development of treatment of three wastes (waste gas, waste water and industrial residue) and resource reuse in chemical industry production, mainly relates to a problem of comprehensively recycling barium slag generated in the production process of barium sulfate, and particularly relates to a method for producing barium hydroxide and calcium hydroxide with barium sulfate waste slag. According to the main technical scheme, the method comprises the following steps: acidifying barium slag with industrial hydrochloric acid, preparing baking-free bricks by using treated insoluble solid waste slag I, conveying soluble pickle liquor into a purification tank, adding slaked lime Ca(OH)2 to remove a small amount of impurities of iron, aluminum, silicon and the like, performing the waste slag treatment on insoluble solid II after secondary separation, and adding purification liquid to industrial caustic soda to react and separate, wherein a part of solid Ca(OH)2 is used for purification and the other part of solid Ca(OH)2 is used as a product; and cooling liquid I to crystallize barium hydroxide, returning and evaporating mother liquor after centrifugal separation, and performing vacuum drying on the solid to obtain the barium hydroxide product. The method is a practical treatment and utilization method; according to the method, relatively considerable economic value can be created and the waste slag in chemical industry is also treated, so that the environmental pollution is controlled, especially, the barium sulfate waste slag is thoroughly controlled and secondary pollution and environment-friendly hidden danger are avoided.
Description
Technical field
The present invention relates to the comprehensive reutilization technology of the barium waste residue of barium sulfate production process generation, prepare simultaneously industrial hydrogen barium oxide and calcium hydroxide product and non-burning brick method.Production technique is to soak the barium sulfate waste residue with technical hydrochloric acid, pickling liquor adds coproduct hydrogen calcium oxide purifying treatment, scavenging solution adds industrial sodium hydroxide reaction manufacture hydrated barta and calcium hydroxide, and the barium slag after processing is further made non-burning brick, accomplishes the trade waste recycling.This technology belongs to comprehensive regulation barium sulfate waste residue field.
Background technology
Employing is with barite (main component BaSO
4) be raw material, at high temperature reduction with carbon becomes barium sulphide, then produces barium salt after the water leaching, and the solid residue of leaching is barium waste residue (being called for short the barium sulfate waste residue), and one ton of barium sulfate of every production can produce 1-2 ton barium sulfate waste residue, and its solubility in acid barium salt is (with BaCO
3Meter) generally 15～30%, water soluble barium salt (in BaS) l% left and right.The barium sulfate waste residue is piled up for a long time, not only takies a large amount of soils, and brings pollution to environment, and the barium sulphide in waste residue and sour molten barium also directly produce toxic action to soil.Utilize the useful composition in waste residue, eliminate the pollution of barium sulfate waste residue to environment, it is turned waste into wealth, take the barium sulfate waste residue as raw material, extract barium ion and produce the hydrated barta product, while coproduct hydrogen calcium oxide, bits after the extraction barium ion are produced non-burning brick again, the real comprehensive utilization that realizes the barium sulfate waste residue.
Summary of the invention
First 100 kilograms of barium sulfate waste residues are put into to the acid-leaching reaction tank, add about 200 kg of water, then slowly add 100-300 kilogram 15% hydrochloric acid, adjust pH value 2～4, be heated to 40-80 ℃ of reaction after 2-5 hour, with plate-and-frame filter press, carry out solid-liquid separation, liquid imports purification pot, and it is 7～8 that solid washes pH value with water.Obtain solid sulphuric acid barium waste residue and be used for preparing non-burning brick, solution further purifies in purification pot, add white lime Ca (OH)
2, pH value is adjusted to 8～14, and after separating, solid slag returns the barium sulfate waste residue to process, and liquid enters and adds the alkali reaction tank, is heated to 60-90 ℃, adds the industrial sodium hydroxide of 20-100 kilogram 30%, and after the reaction certain hour, sheet frame separates, solid Ca (OH)
2A part is for purifying, and a part is for the preparation of becoming product, and liquid evaporation goes out barium hydroxide to crystallisation by cooling after finite concentration, and after centrifugation, mother liquor returns to evaporation, solid Ba (OH)
28H
2O carries out vacuum-drying and finally obtains the barium hydroxide product.
Reaction principle: the barium sulfate waste residue that barium sulfate is produced extracts barium ion with hydrochloric acid reaction, then makes hydrated barta coproduct hydrogen calcium oxide simultaneously with the liquid caustic soda reaction, and it is non-burning brick that the bits of finally having carried barium ion and flyash etc. mix production.
Reaction equation is:
BaCO
3+HCl=BaCl
2+H
2O+CO
2
CaCO
3+HCl=CaCl
2+H
2O+CO
2
BaCl
2+2NaOH+8H
2O=Ba(OH)
28(H
2O)+2NaCl
CaCl
2+2NaOH=Ca(OH)
2+2NaCl
The present invention compared with prior art has following advantage:
Respectively produce at present the barium slag of the producer of barium sulfate and do not recycle, environment had both been polluted in long-term accumulation, encroached on again farmland.Utilize discarded Industry Waste barium slag to produce hydrated barta and calcium hydroxide, after processing, do non-burning brickly, therefore reach recycling, comprehensive regulation environment, increase the factory economy benefit.
The accompanying drawing explanation
Fig. 1 is production technological process of the present invention
Example:
Example one: first 100Kg barium slag is put into to the acid-leaching reaction tank, add the water of 200Kg, then slowly drip 5-20Kg hydrochloric acid, adjust pH value 2～4, heat 40-80 ℃ of reaction after 2 hours, with plate-and-frame filter press, carry out solid-liquid separation, liquid imports purification pot, and it is 7～8 that solid washes pH value with water.Obtain solid sulphuric acid barium waste residue and be used for preparing non-burning brick, solution further purifies in purification pot, add white lime Ca (OH)
2, pH value is adjusted to 8～14, and after separating, solid slag returns the barium sulfate waste residue to process, and liquid enters and adds the alkali reaction tank, is heated to 60-90 ℃, adds a certain amount of industrial caustic soda, and after the reaction certain hour, sheet frame separates, solid Ca (OH)
2A part is for purifying, and a part is for the preparation of magnesium hydroxide, and liquid evaporation goes out hydrated barta to crystallisation by cooling after finite concentration, and after centrifugation, mother liquor returns to evaporation, solid Ba (OH)
28H
2O carries out vacuum-drying and finally obtains the hydrated barta product.
Example two: first 200Kg barium slag is put into to the acid-leaching reaction tank, add 400Kg water, then slowly drip 5-30Kg hydrochloric acid, adjust pH value 2～4, heat 40-80 ℃ of reaction after 3 hours, with plate-and-frame filter press, carry out solid-liquid separation, liquid imports purification pot, and it is 7～8 that solid washes pH value with water.Obtain solid sulphuric acid barium waste residue and be used for preparing non-burning brick, solution further purifies in purification pot, add white lime Ca (OH)
2, pH value is adjusted to 8～14, and after separating, solid slag returns the barium sulfate waste residue to process, and liquid enters and adds the alkali reaction tank, is heated to 60-90 ℃, adds a certain amount of industrial caustic soda, and after the reaction certain hour, sheet frame separates, solid Ca (OH)
2A part is for purifying, and a part is for the preparation of magnesium hydroxide, and liquid evaporation goes out hydrated barta to crystallisation by cooling after finite concentration, and after centrifugation, mother liquor returns to evaporation, solid Ba (OH)
28H
2O carries out vacuum-drying and finally obtains the hydrated barta product.
Example three: first 300Kg barium slag is put into to the acid-leaching reaction tank, add 600Kg water, then slowly drip 5-50Kg hydrochloric acid, adjust pH value 2～4, heat 40-80 ℃ of reaction after 5 hours, with plate-and-frame filter press, carry out solid-liquid separation, liquid imports purification pot, and it is 7～8 that solid washes pH value with water.Obtain solid sulphuric acid barium waste residue and be used for preparing non-burning brick, solution further purifies in purification pot, add white lime Ca (OH)
2, pH value is adjusted to 8～14, and after separating, solid slag returns the barium sulfate waste residue to process, and liquid enters and adds the alkali reaction tank, is heated to 60-90 ℃, adds a certain amount of industrial caustic soda, and after the reaction certain hour, sheet frame separates, solid Ca (OH)
2A part is for purifying, and a part is for the preparation of magnesium hydroxide, and liquid evaporation goes out hydrated barta to crystallisation by cooling after finite concentration, and after centrifugation, mother liquor returns to evaporation, solid Ba (OH)
28H
2O carries out vacuum-drying and finally obtains the hydrated barta product.
Barium slag transformation efficiency:
Slag after the reaction washing, its sour molten barium transformation efficiency is at 50-100% by analysis.
Claims (1)
1. method of producing hydrated barta and calcium hydroxide with the barium sulfate waste residue is characterized in that comprising the following steps:
Step 1: the barium slag adds hydrochloric acid to carry out acidification reaction, and part by weight is barium slag: hydrochloric acid=1:3, and namely 100 kilograms of slags add 50-300 kilogram hydrochloric acid, is heated to 40-80 ℃ of reaction 2-5 hour;
Solid-liquid separation, solid is done non-burning brick, and liquid is pickling liquor;
Step 2: according to impurity and calcium hydroxide molecular mass ratio, add 30-100 kilogram calcium hydroxide to purify the resulting pickling liquor of step 1, solid-liquid separation, solid slag is done non-burning brick, and liquid is scavenging solution;
Step 3: the scavenging solution of step 2 is heated to 60-90 ℃, then adds the sodium hydroxide 20-100 kilogram reaction of 30% concentration to prepare hydrated barta and calcium hydroxide, solid-liquid separation;
Step 4: step 3 is separated the solid hydrogen calcium oxide washing drying that obtains and is obtained product, after the barium hydroxide solution evaporation, and crystallisation by cooling, centrifugation, solid drying obtains the hydrated barta product, and mother liquor returns to the vapo(u)rization system recycle;
Step 5: the solid barium slag that step 1 is obtained adds gypsum, stone, cement, lime etc., and mixing moulding is made non-burning brick.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103079701A CN103395811A (en) | 2013-07-22 | 2013-07-22 | Method for producing barium hydroxide and calcium hydroxide with barium sulfate waste slag |
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|---|---|---|---|
| CN2013103079701A CN103395811A (en) | 2013-07-22 | 2013-07-22 | Method for producing barium hydroxide and calcium hydroxide with barium sulfate waste slag |
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|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104561561A (en) * | 2014-12-04 | 2015-04-29 | 东北大学 | Innocent treatment method for barium-containing waste residues |
| CN105236783A (en) * | 2015-10-10 | 2016-01-13 | 南风化工集团股份有限公司 | Barium sulfate waste residue comprehensive utilization method and wall filling material |
| 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 |
| CN106830038A (en) * | 2017-03-31 | 2017-06-13 | 青岛红蝶新材料有限公司 | The production technology of electronic grade high-purity barium hydroxide |
| CN110775995A (en) * | 2019-12-04 | 2020-02-11 | 新晃鲁湘钡业有限公司 | Treatment method for producing building material by using barium-containing slag mud |
| CN115010158A (en) * | 2022-06-27 | 2022-09-06 | 中国科学院过程工程研究所 | Method for preparing barium hydroxide by alkali fusion roasting of barite |
-
2013
- 2013-07-22 CN CN2013103079701A patent/CN103395811A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104561561A (en) * | 2014-12-04 | 2015-04-29 | 东北大学 | Innocent treatment method for barium-containing waste residues |
| CN104561561B (en) * | 2014-12-04 | 2016-07-27 | 东北大学 | A kind of the Barium Residue method for innocent treatment |
| CN105236783A (en) * | 2015-10-10 | 2016-01-13 | 南风化工集团股份有限公司 | Barium sulfate waste residue comprehensive utilization method and wall filling material |
| CN105236783B (en) * | 2015-10-10 | 2017-08-01 | 南风化工集团股份有限公司 | Barium sulfate waste residue method of comprehensive utilization and wall filler |
| 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 |
| CN106830038A (en) * | 2017-03-31 | 2017-06-13 | 青岛红蝶新材料有限公司 | The production technology of electronic grade high-purity barium hydroxide |
| CN106830038B (en) * | 2017-03-31 | 2018-03-13 | 青岛红蝶新材料有限公司 | The production technology of electronic grade high-purity barium hydroxide |
| CN110775995A (en) * | 2019-12-04 | 2020-02-11 | 新晃鲁湘钡业有限公司 | Treatment method for producing building material by using barium-containing slag mud |
| CN115010158A (en) * | 2022-06-27 | 2022-09-06 | 中国科学院过程工程研究所 | Method for preparing barium hydroxide by alkali fusion roasting of barite |
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Application publication date: 20131120 |