CN107416881A - Calcium aluminium byproduct generation technique in barium sulfate preparation process - Google Patents

Calcium aluminium byproduct generation technique in barium sulfate preparation process Download PDF

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Publication number
CN107416881A
CN107416881A CN201710617760.0A CN201710617760A CN107416881A CN 107416881 A CN107416881 A CN 107416881A CN 201710617760 A CN201710617760 A CN 201710617760A CN 107416881 A CN107416881 A CN 107416881A
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China
Prior art keywords
calcium
solution
hydroxide
aluminium
barium sulfate
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CN201710617760.0A
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Inventor
雷军强
李玉秋
覃稳梅
韦倩梅
莫晓君
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XIANGZHOU COUNTY SCIENCE TECHNOLOGY INFORMATION RESEARCH INSTITUTE
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XIANGZHOU COUNTY SCIENCE TECHNOLOGY INFORMATION RESEARCH INSTITUTE
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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
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The present invention discloses calcium aluminium byproduct generation technique in a kind of barium sulfate preparation process, including traditional approach aluminium refinement and calcium byproduct generation, step 1：Iron hydroxide, magnesium hydrate precipitate are filtrated to get after hydrogenation sodium hydroxide solution, is sodium metaaluminate, calcium hydroxide in solution；Step 2：After precipitation is filtered out, carbon dioxide is passed through into solution；Step 3：After being passed through carbon dioxide, aluminum hydroxide precipitation and calcium bicarbonate solution are obtained, evaporative precipitation thing obtains anhydrous alumina crystal after filtering, and molten state aluminum oxide is obtained under high temperature, and electrolyzing fused state aluminum oxide obtains pure aluminum；Step 4：60 DEG C of 700 DEG C of evaporation calcium bicarbonate solutions, obtain calcium carbonate solid；The present invention solves the problems such as wasting of resources, environmental pollution, makes full use of available resources in waste residue, so as to save the cost of company's processing waste residue, and generates a series of concomitant outputs, has the advantages of Green Chemistry, cheap.

Description

Calcium aluminium byproduct generation technique in barium sulfate preparation process
Technical field
The invention belongs to barium sulfate preparation process byproduct generation technology field, it is related to a kind of barium sulfate preparation process Middle calcium aluminium byproduct generation technique.
Background technology
Contain multi mineral composition, by taking the barite deposit of Suizhou as an example, its chemical analysis of mineral result in natural barite ore deposit For：BaSO4 94.78%, acid-soluble material 2.1%, Si 0.72%, organic carbon 0.56%, Ca 0.43%, Fe 0.12%, Al 0.10%, Mg 0.17%.In chemical industry barium sulfate preparation process, substantial amounts of waste residue and liquid can be usually produced, these waste residue and liquids contain abundant The element such as silico-calcium magnesium-aluminum-iron, be not only one to local environment if just being discharged without effective processing The serious burden of kind, and economic interests of its loss are also quite huge, and existing production technology is for such waste residue waste material Only carry out simple except acid treatment is just discharged, it is clear that be irrational processing method；Aluminium calcium constituent is by effective in waste residue and liquid Extraction, can carry out benefit conversion, form auxiliary production product.
Domestic patent database disclosed wastewater recycling process and device skill in some similar barium sulfate productions in recent years Art is reported：
【Application number】ZL2015106494160,【Title】Vulcanized sodium wastewater recycling process and device in a kind of barium sulfate production, 【Publication number】CN105236783A, vulcanized sodium wastewater recycling process and device in a kind of barium sulfate production are disclosed, including it is following Step and corresponding device：Dilute vulcanization waste liquor of sodium is taken, adds sulfuric acid to neutralize；Hydrogen sulfide is absorbed with vulcanized sodium spray column；Toward sodium sulphate Hydrogen peroxide is added in solution, it is sulphur to make to be dissolved in the Oxidation of Hydrogen Sulfide in metabisulfite solution；Filter metabisulfite solution；Finally by sulphur Sour sodium weak solution is led in disc tube reverse osmosis (dt-ro) membranous system or high-pressure flat plate membranous system and concentrated, and concentrate is back to use sulfuric acid In barium production, clear liquid can be discharged directly, but utilization of this method for useful element in waste liquid is more superficial.
The content of the invention
The present invention provides a kind of waste liquid recycling, Green Chemistry, cheap calcium aluminium byproduct generation technique, solves to pass The problem of wasting of resources of system mode and environmental pollution.
Calcium aluminium byproduct generation technique in barium sulfate preparation process of the present invention, including the refinement of traditional approach aluminium and the pair of calcium The generation of product, it is characterised in that：
Step 1：Sodium hydroxide solution is hydrogenated with into barium sulfate waste liquid, filters, obtains iron hydroxide, magnesium hydrate precipitate, in solution For sodium metaaluminate, calcium hydroxide, ionic equation is：
Fe3++3OH-=Fe(OH)3, Mg2++2OH-=Mg(OH)2, Ca2++2OH-= Ca (OH)2 ,
Al3+ + 3OH- = Al(OH)3, Al (OH)3 + OH- = AlO2- + 2H2O；
Step 2：It is sodium metaaluminate in solution, calcium hydroxide after precipitation is filtered out, the titanium dioxide being now passed through into solution Carbon, meta-aluminic acid root can produce aluminum hydroxide precipitation, and ionic equation is：
2ALO2-+3H2O+CO2=2AL(OH)3↓+CO3 2-, Ca2++2CO2=Ca(HCO3)2；
Step 3：Aluminum hydroxide precipitation is evaporated to obtain anhydrous alundum (Al2O3) crystal, and obtains molten state oxidation at high temperature Aluminium, electrolyzing fused state aluminum oxide obtain pure aluminum, and chemical equation is：
2Al2O3=4Al+3O2；
Step 4：60 DEG C of -700 DEG C of evaporation calcium bicarbonate solutions, obtain calcium carbonate solid, chemical equation is：
Ca(HCO3)2==CaCO3 + CO2↑+H2O 。
It is 2 that carbon dioxide is passed through in described step two with metal ion in solution mol ratio:1；Step 4 is evaporated When temperature range be 60 DEG C -120 DEG C.
The present invention is taken full advantage of the element remained in waste liquid, is utilized each element using the collection of aluminium and the byproduct of calcium Unique property separates it, protects environment, reduces cost, using waste liquid as raw material, so as to giving up for the company of having saved Liquid processing cost, advantageously produced in company, generate a series of concomitant outputs, certain benefit can be produced, there is work Skill is simple, Green Chemistry, it is cheap the advantages of.
Brief description of the drawings
Fig. 1 is the calcium aluminium byproduct generation process chart of the present invention.
Embodiment
With reference to specific drawings and examples, the invention will be further described.
Example 1
As shown in figure 1, calcium aluminium byproduct generation technique in a kind of barium sulfate preparation process, including traditional method for treating waste liquid, aluminium Refinement and calcium byproduct generation technique,
Step 1：Sodium hydroxide solution is hydrogenated with into barium sulfate waste liquid, filters, obtains iron hydroxide, magnesium hydrate precipitate, in solution For sodium metaaluminate, calcium hydroxide, ionic equation is：
Fe3++3OH-=Fe(OH)3, Mg2++2OH-=Mg(OH)2, Ca2++2OH-= Ca (OH)2 ,
Al3+ + 3OH- = Al(OH)3, Al (OH)3 + OH- = AlO2- + 2H2O；
Step 2：It is sodium metaaluminate in solution, calcium hydroxide after precipitation is filtered out, the titanium dioxide being now passed through into solution Carbon, meta-aluminic acid root can produce aluminum hydroxide precipitation, and ionic equation is：
2ALO2-+3H2O+CO2=2AL(OH)3↓+CO3 2-, Ca2++2CO2=Ca(HCO3)2；
Step 3：Aluminum hydroxide precipitation is evaporated to obtain anhydrous alundum (Al2O3) crystal, and obtains molten state oxidation at high temperature Aluminium, electrolyzing fused state aluminum oxide obtain pure aluminum, and chemical equation is：
2Al2O3=4Al+3O2；
Step 4：60 DEG C of evaporation calcium bicarbonate solutions, obtain calcium carbonate solid, chemical equation is：
Ca(HCO3)2==CaCO3 + CO2↑+H2O 。
Example 2
As shown in figure 1, calcium aluminium byproduct generation technique in a kind of barium sulfate preparation process, including traditional method for treating waste liquid, aluminium Refinement and calcium byproduct generation technique,
Step 1：Sodium hydroxide solution is hydrogenated with into barium sulfate waste liquid, filters, obtains iron hydroxide, magnesium hydrate precipitate, in solution For sodium metaaluminate, calcium hydroxide, ionic equation is：
Fe3++3OH-=Fe(OH)3, Mg2++2OH-=Mg(OH)2, Ca2++2OH-= Ca (OH)2 ,
Al3+ + 3OH- = Al(OH)3, Al (OH)3 + OH- = AlO2- + 2H2O；
Step 2：It is sodium metaaluminate in solution, calcium hydroxide after precipitation is filtered out, the titanium dioxide being now passed through into solution Carbon, carbon dioxide are 2 with metal ion in solution mol ratio:1, meta-aluminic acid root can produce aluminum hydroxide precipitation, ion side Formula is：
2ALO2-+3H2O+CO2=2AL(OH)3↓+CO3 2-, Ca2++2CO2=Ca(HCO3)2；
Step 3：Aluminum hydroxide precipitation is evaporated to obtain anhydrous alundum (Al2O3) crystal, and obtains molten state oxidation at high temperature Aluminium, electrolyzing fused state aluminum oxide obtain pure aluminum, and chemical equation is：
2Al2O3=4Al+3O2；
Step 4：100 DEG C of evaporation calcium bicarbonate solutions, obtain calcium carbonate solid, chemical equation is：
Ca(HCO3)2==CaCO3 + CO2↑+H2O 。

Claims (2)

1. calcium aluminium byproduct generation technique in barium sulfate preparation process, including traditional approach aluminium refinement and calcium byproduct life Into, it is characterised in that：
Step 1：Sodium hydroxide solution is hydrogenated with into barium sulfate waste liquid, filters, obtains iron hydroxide, magnesium hydrate precipitate, in solution For sodium metaaluminate, calcium hydroxide, ionic equation is：
Fe3++3OH-=Fe(OH)3, Mg2++2OH-=Mg(OH)2, Ca2++2OH-= Ca (OH)2 ,
Al3+ + 3OH- = Al(OH)3, Al (OH)3 + OH- = AlO2- + 2H2O；
Step 2：It is sodium metaaluminate in solution, calcium hydroxide after precipitation is filtered out, the titanium dioxide being now passed through into solution Carbon, meta-aluminic acid root can produce aluminum hydroxide precipitation, and ionic equation is：
2ALO2-+3H2O+CO2=2AL(OH)3↓+CO3 2-, Ca2++2CO2=Ca(HCO3)2；
Step 3：Aluminum hydroxide precipitation is evaporated to obtain anhydrous alundum (Al2O3) crystal, and obtains molten state oxidation at high temperature Aluminium, electrolyzing fused state aluminum oxide obtain pure aluminum, and chemical equation is：
2Al2O3=4Al+3O2；
Step 4：60 DEG C of -700 DEG C of evaporation calcium bicarbonate solutions, obtain calcium carbonate solid, chemical equation is：
Ca(HCO3)2==CaCO3 + CO2↑+H2O。
2. calcium aluminium byproduct generation technique in barium sulfate preparation process as claimed in claim 1, it is characterised in that：Described step It is 2 that carbon dioxide is passed through in rapid two with metal ion in solution mol ratio:1；Step 4 evaporate when temperature range be 60 DEG C- 120℃。
CN201710617760.0A 2017-07-26 2017-07-26 Calcium aluminium byproduct generation technique in barium sulfate preparation process Pending CN107416881A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111908511A (en) * 2019-05-16 2020-11-10 清华大学 Method for removing calcium and magnesium ions in production of high-purity manganese sulfate
CN112010454A (en) * 2019-05-30 2020-12-01 上海顺樊环保科技有限公司 Electroplating nickel-containing wastewater treatment and recovery method

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Publication number Priority date Publication date Assignee Title
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CN103738988A (en) * 2013-12-26 2014-04-23 张延大 Method for preparing slagging desulfurizing agent by utilizing industrial waste residue resource
CN103936046A (en) * 2014-04-30 2014-07-23 东北大学 Later-addition ore calcification transformation method in aluminum oxide production process
CN105883873A (en) * 2016-04-20 2016-08-24 航天推进技术研究院 Sulfuric acid hot leaching based method for extracting aluminum oxide from fly ash
CN106103360A (en) * 2014-02-26 2016-11-09 奥图泰(芬兰)公司 The method of sulfate is removed from waste water

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103303952A (en) * 2012-03-06 2013-09-18 中国科学院过程工程研究所 Method for linked preparation of sodium aluminate and production of silica-based material by means of high-alumina fly ash low-temperature liquid-phase alkali dissolving
CN103738988A (en) * 2013-12-26 2014-04-23 张延大 Method for preparing slagging desulfurizing agent by utilizing industrial waste residue resource
CN106103360A (en) * 2014-02-26 2016-11-09 奥图泰(芬兰)公司 The method of sulfate is removed from waste water
CN103936046A (en) * 2014-04-30 2014-07-23 东北大学 Later-addition ore calcification transformation method in aluminum oxide production process
CN105883873A (en) * 2016-04-20 2016-08-24 航天推进技术研究院 Sulfuric acid hot leaching based method for extracting aluminum oxide from fly ash

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111908511A (en) * 2019-05-16 2020-11-10 清华大学 Method for removing calcium and magnesium ions in production of high-purity manganese sulfate
CN112010454A (en) * 2019-05-30 2020-12-01 上海顺樊环保科技有限公司 Electroplating nickel-containing wastewater treatment and recovery method

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Application publication date: 20171201