CN1152550A - Method for producing barium hydroxide from carbonate type barium ore - Google Patents
Method for producing barium hydroxide from carbonate type barium ore Download PDFInfo
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- CN1152550A CN1152550A CN 96117772 CN96117772A CN1152550A CN 1152550 A CN1152550 A CN 1152550A CN 96117772 CN96117772 CN 96117772 CN 96117772 A CN96117772 A CN 96117772A CN 1152550 A CN1152550 A CN 1152550A
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- barium
- carbonate
- ore
- producing
- barium hydroxide
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- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 229910001863 barium hydroxide Inorganic materials 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229910052788 barium Inorganic materials 0.000 title claims description 43
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims description 40
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims description 11
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 18
- 239000011707 mineral Substances 0.000 claims description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010428 baryte Substances 0.000 claims description 11
- 229910052601 baryte Inorganic materials 0.000 claims description 11
- 239000004575 stone Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical group C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003830 anthracite Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000035939 shock Effects 0.000 claims description 5
- 239000002802 bituminous coal Substances 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910021532 Calcite Inorganic materials 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 33
- 239000000463 material Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 5
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 abstract description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 22
- 235000010755 mineral Nutrition 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 11
- 239000002893 slag Substances 0.000 description 11
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000001553 barium compounds Chemical class 0.000 description 5
- 229910052916 barium silicate Inorganic materials 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910001626 barium chloride Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000004135 Bone phosphate Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 2
- 229910052676 chabazite Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- -1 1.69% of others Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZYTUJDHYVZOBJE-UHFFFAOYSA-N Cl.[Ba] Chemical compound Cl.[Ba] ZYTUJDHYVZOBJE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- QLZFCZLKIVFFCM-UHFFFAOYSA-N [Si]([O-])([O-])([O-])[O-].[Si]([O-])([O-])([O-])[O-].[Si]([O-])([O-])([O-])[O-].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2] Chemical compound [Si]([O-])([O-])([O-])[O-].[Si]([O-])([O-])([O-])[O-].[Si]([O-])([O-])([O-])[O-].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2].[Ba+2] QLZFCZLKIVFFCM-UHFFFAOYSA-N 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for producing barium hydroxide from carbonate barium ore, which is characterized in that carbonate barium ore is used as a raw material, carbon is used as a reducing agent, the carbonate barium ore and the carbon are prepared into powder, the powder is uniformly mixed and then placed in a heat-resistant container with good sealing performance, the heat-resistant container is placed in a kiln to be calcined at the temperature of 1100-1400 ℃, preferably 1250-1300 ℃, calcined materials are leached by water after calcination, solid-liquid separation is carried out to obtain leaching liquid and leaching residue, and the leaching liquid is concentrated or directly cooled and crystallized to obtain barium hydroxide octahydrate. Simple process, low production cost, no pollution and suitability for large-scale industrial production.
Description
The invention relates to a method for producing barium hydroxide, in particular to a method for producing barium hydroxide by using carbonate type barium ore.
The traditional method for producing barium hydroxide uses barite as raw material, firstly processes it into barium sulfide (BaS), then reacts with manganese dioxide (MnO2) and zinc oxide (ZnO) or uses ion exchange method to obtain barium hydroxide. Barium carbonate (BaCO3), barium oxide (BaO), and barium silicate (Ba3SiO5) can also be prepared from BaS, and then processed into barium hydroxide. However, the most common method adopted in the current domestic and foreign industrial production is to prepare barium chloride (Bacl2) from barium sulfide (BaS) and then react the barium chloride with caustic soda (NaOH) to produce barium hydroxide. These methods have problems of complicated process, long flow, high cost, sulfur pollution, etc. Conventional BaCO3Production of Ba (OH)2The method is to mix industrial BaCO3Calcining at high temperature to convert into BaO, hydrolyzing to obtain Ba (OH)2The reaction is as follows:
In view of the above, the present invention aims to provide a method for producing barium hydroxide from carbonate barium ore, which has the advantages of simple process, low production cost, no pollution and suitability for large-scale industrial production.
The method of the invention is to take carbonate barium ore as raw material, use carbon as reducing agent, make the two into powder, mix them evenly, put them into heat-resisting container with good sealing performance, then put the heat-resisting container into 1100-1400 deg.C, preferably 1250-1300 deg.C to calcine, calcine the material, leach with water, preferably leach under 70 deg.C to boiling condition, solid-liquid separation is leach liquor and leaching residue, the leach liquor is concentrated or directly cooled and precipitated to get barium hydroxide octahydrate, its reaction formula is:
the above-mentioned carbonate barium ore is heavy toxic (BaCO)3) Barium disintegrable [ BaCa (CO3)2]]Mainly contains chabazite alkaline earth stone [ Ca7Ba6(CO3)13]]Barite (BaSO4), and Alumino-barium [ Ba2Al6Si5O19 (OH). 3H2O]And gangue minerals (quartz, dolomite, calcite, carbon and the like), wherein the weight percentages of the components are as follows:
barium disintegrable rock 17-95
Witherite 0-83
0-30 parts of rhombohedral alkaline earth stone
0-30% of barite
Alumino-barium stone 0-15
The gangue minerals 0-30 are different from single witherite minerals and have unique mineral combination, structure, physical and chemical characteristics and thermal performance characteristics.
The carbonate type barium ore and the carbonaceous reducing agent are made into powder and then directly filled into a heat-resistant container or added with an adhesive for pelletizing and then filled into the heat-resistant container, wherein the adhesive can be organic (flour, corn, wild plants and the like) or inorganic (barium cement and the like) adhesive.
The carbonate type barium ore and the carbonaceous reducing agent have the powder milling particle size of-2 mm to-200 meshes, preferably-80 meshes.
The carbonaceous reducing agent can adopt anthracite, bituminous coal or coke powder, the anthracite is economic and has good reducing effect, the carbonaceous reducing agent is the best reducing agent, the coke has good reducing effect, and the bituminous coal or other carbonaceous reducing agents can also be used in places lacking the anthracite or the coke, and can effectively decompose CO released by mineral powder2Reducing the carbon into CO, and simultaneously requiring that the content of the fixed carbon of the reducing agents is high, and the impurities brought into the forged material and the product are less when the consumption of the reducing agents for fixing the carbon is less.
The weight of the carbonaceous reducing agent is 5-20% of that of the carbonate type barium ore.
The heat-resistant container is a crucible which has good sealing performance, high thermal shock resistance, high temperature resistance and strong alkali corrosion resistance, can be made of high-density and low-porosity ceramics, graphite and other materials, and can be made of lithium and rare earth (neodymium and praseodymium) high thermal shock resistance crucibles in order to ensure the high temperature strength, rapid cooling and heat resistance and strong alkali corrosion resistance of the crucible.
The upper part of the crucible is preferably provided with an exhaust hole with the diameter of 2-5mm, the concentration of CO in the reaction container can be reduced, so that CO gas in the crucible can be exhausted, and the calcining furnace is controlled to operate at negative pressure or zero pressure in a high-fire heat preservation area, so that the CO gas in the crucible can be smoothly exhausted through the exhaust hole, and the conversion rate of the barium element is improved.
The calcining kiln can adopt a coal-fired tunnel kiln, a pushed slab kiln or a down draft kiln, the temperature of a burning zone is preferably 1250-; negative or zero pressure operation.
The slag may be added with chloride salt for low temperature chlorination roasting or added with ammonium chloride solution for direct leaching to produce barium chloride dihydrate, and the water soluble barium compound produced after the ore material is added with reductant and calcined includes barium oxide, barium silicate, small amount of incompletely crystallized barium trisilicate, barium sulfide and residual barium carbonate. Barium oxide hydrolyzes to form barium hydroxide, and barium disilicate (2 BaO. SiO2) reacts withTribarium silicate (3 BaO. SiO)2) When in hydrolysis, one part and two parts of BaO are respectively released and hydrated to generate Ba (OH)2The rest BaO is mixed with SiO2With barium metasilicate (BaO. SiO)2) The residue is left in the slag, so that chlorine salt is added into the leached slagas an auxiliary material for low-temperature chloridizing roasting or directly reacting with NH4Cl solution reacts to generate barium chloride dihydrate [ or further converted to BaCO3·Ba(OH)2And other barium compounds]The secondary slag is used for manufacturing barium slag bricks, cement mineralizers and the like.
The invention adopts witherite (BaCO)3) And barium disintegrable [ BaCa (CO)]3)2]Mainly accompanied by a small amount of chabazite [ Ca]7Ba6(CO3)13]The barium carbonate is carbonate type barium ore, the barium dissolution stone begins to decompose (lose weight) at 675 ℃, and the calcium carbonate gradually dissociates to separate out CO2The crystal structure of the baryte and the internal structure of the ore are destroyed, thereby accelerating the process of the decomposition reaction,so the decomposition temperature is obviously lower than that of single witherite ore and industrial grade barium carbonate.
Pressure data for alkaline earth carbonate decomposition indicate: barium carbonate is largely decomposed into BaO and CO under normal pressure (101326Pa)2Is 1270 c, the column is heated above 1360 c in order to decompose completely as quickly as possible. However, this reaction is a reversible reaction, and BaCO is generated as the temperature in the furnace decreases3The decomposition products (BaO) can absorb CO in the furnace and in the air2Recombination into BaCO3. Additionally, BaCO3The minimum eutectic point of the BaO system is 1030 ℃, and other low-melting components in the mineral aggregate can be partially melted on the surface of the block at high temperature to form an impermeable shell which hinders the decomposition process. On the other hand, the strong base corrosiveness of BaO at high temperature also puts special requirements on the materials of the calcining furnace lining and the crucible. The high temperature, reversible reaction, surface melting and strong base corrosion form four technical difficulties in the production of barium hydroxide from barium carbonate. Theoretically, the reduction calcination of barium carbonate with carbon helps to solve the above-mentioned difficulties. At this time, the reaction was carried out according to the following formula: the overall reaction is:
the above-mentioned charcoaling reduction reaction can be spontaneously carried out at a temperature of 990.55 deg.C, based on thermodynamic data and equilibrium constant counts at 25 deg.C and standard atmospheric pressure, taking into account the relationship between melting, entropy change and temperature. Because the invention selects the process scheme of adding carbon to reduce and calcine, but in order to accelerate the reaction and avoid the surface melting of the mineral aggregate, the optimum calcining temperature is determined to be between 1250 and 1300 ℃ through a plurality of tests.
The reducing agent is mainly required to have high fixed carbon content, and can effectively decompose CO released by mineral powder2Reducing the carbon into CO, and simultaneously, the dosage of the fixed carbon high reducing agent is less, and the impurities brought into the forged material and the product are less. The volatile matter content is required to be low because the volatile matter of the coal is often more harmful to mineral aggregate decompositionThe hydrocarbon of (2). And the coal with high volatile matter has low ignition point and the reduction effect cannot be lasting. The reducing agent also requires that the ash content is not too high, otherwise, the impurities in the calcined material are high, particularly 5 percent of the ash content of the coal is silicon dioxide, the silicon dioxide is easy to combine with barium carbonate in the mineral powder to form barium silicate, and the yield of water-soluble barium is reduced. Therefore, the invention firstly pushes the anthracite which is economic and easy to obtain and has good reduction effect as the best reducing agent. Secondly, coke reduction is also very effective, but is expensive and bituminous or other carbonaceous reducing agents can be used in areas lacking the above resources. The invention adopts the crucible made of ceramic, graphite and other materials with high density and low porosity. In order to ensure the high temperature strength, quenching and quenching heat resistance and strong alkali corrosion resistance of the crucible, a lithium and rare earth (neodymium, praseodymium) high heat shock resistance crucible is developed on the basis of a common clay crucible, and the thermal expansion coefficients of the lithium and rare earth (neodymium, praseodymium) high heat shock resistance crucible are less than 2 multiplied by 10-6The temperature is/DEG C or nearly zero, which is an ideal crucible material for implementing the process. In addition, in order to reduce the CO concentration in the reaction vessel, it is preferable to provide a 2-5mm vent hole above the crucible in accordance with the charging amount and sealing degree of the crucible to discharge the CO gas in the crucible. Meanwhile, the calcining furnace is controlled to operate under the negative pressure or zero pressure in the high-fire heat preservation area, so that CO gas in the crucible can be smoothly discharged through the exhaust hole, and the conversion rate of the barium element is improved. The most important advantage of the invention is that it uses coal which is economical and easy to obtain as energy source, and selects open flame or muffle type coal burning tunnel kiln, pusher kiln ordown-draft kiln which is low in cost as calcining furnace type. Thus greatly improving the economic benefit of the invention and laying a solid foundation for large-scale industrial productionAnd (4) the foundation is compensated.
The water-soluble barium compound generated after the ore material is added with the reducing agent and calcined comprises the following components: barium oxide, barium disilicate and a small amount of poorly crystallized tribasic barium silicate and barium sulfide. Barium hydroxide is produced after hydrolysis of barium oxide, and barium disilicate (2 BaO. SiO)2) With tribasic barium silicate (3 BaO. SiO)2) When in hydrolysis, one part and two parts of BaO are respectively released and hydrated to generate Ba (OH)2The rest BaO is mixed with SiO2Compounding with barium metasilicate (BaO. SiO)2) In the form of residues in the slag. After barium sulfide is hydrolyzed, barium hydroxide is generatedBarium hydrosulfide. CaCO abundantly occurring in ore3Calcined to CaO, and Ca (OH) is generated during hydrolysis2. According to the solubility difference of alkaline earth metal hydroxide under different temperatures, the solubility of barium hydroxide is increased to the maximum extent above 80 ℃, so that the calcined material needs to be heated to a slightly boiling state during leaching, and is preferably kept above 80 ℃ during filtering and separation. And Ca (OH)2The solubility of (A) is just reduced along with the increase of the temperature, and Ca (OH) can be filtered by using heat preservation2The barium hydroxide is left in the slag in a precipitate mode, so that the purity of the barium hydroxide product is greatly improved. The invention recommends the adoption of three-stage heating (slight boiling) stirring leaching, the first stage is according to 1: 4 of clinker and water, the leaching time is 15-30 min; the second and third stages are respectively half of the water amount added in the first stage, the leaching time is 10-15min, and the amount of the slurry and the stirring force are increased and decreased according to the needs. The first-stage leaching solution can be directly used for preparing a barium hydroxide product; the second and third stage leaching solutions are combined and used for the first stage leaching in the next round. The above steps are repeated in a circulating way to form a closed circulation system for continuous production.
The barium compounds of the leaching residue after water leaching are mainly barium carbonate and barium metasilicate which are not completely decomposed. The weight of the barium-containing composite material is 30-50% of the weight of the ore, and the residual barium accounts for BaCO3If 40-45% of the slag is used for returning material calcination, the yield of barium is only about 30%; if discharged as waste residue, not only a large amount of BaCO is lost3Resources, land occupation and environmental pollution. The invention designs that the leaching residue is added with chloride salt as an auxiliary material and is chloridized and roasted at low temperature or the leaching residue is directly mixed with NH4Cl solution reaction to produce barium chloride dihydrate [ or further converting to BaCO3、Ba(OH)2And other barium compounds]And the secondary slag is used for manufacturing barium slag bricks, cement mineralizers and the like. The auxiliary materials suitable for the chloridizing roasting process are as follows: CaCl2，NH4Cl、MgCl2And salt production by-product bladderBars, etc. in an amount of the residual BaCO in the leaching residue3Conversion of the total amount (or by total alkalinity) to BaCl2Theoretical amount of chloride salt required (or corresponding chloride). The roasting temperature is below 800℃, and the roasting time is selected according to the quantity of the charging materials, the roasting mode, the heating condition and the like, and is generally more than 2 hours. Leaching of clinkerA three-stage heating stirring circulating leaching mode is adopted, the solid-liquid ratio is 1: 2-4, and the time is 20-40 min. The immersion liquid is evaporated, concentrated, cold separated, crystallized, separated and dried to obtain the barium chloride dihydrate product. The quality can be more than the standard of first-class products of the national standard GB 1617-89.
The barium hydrochloride leaching residue can also be added with NH with the theoretical amount required by the reaction being three times excessive according to the method for producing and preparing barium chloride by the carbonate barium ore full wet method4And (3) carrying out boiling stirring leaching on the Cl solution with the concentration of 2-4 MOl/L and the solid-liquid ratio of 1: 3-8 in a container with the internal and external heating for enhancing the reaction, concentrating and crystallizing the leaching solution to obtain barium chloride dihydrate, wherein the yield of barium element is 85-95%, and the product quality can reach the standard of the national first-class product.
The invention has simple process, low production cost and no pollution, and is suitable for large-scale industrial production.
The following examples are presented, but the scope of the invention is not limited to the following examples:
example 1:
ore grade BaCO376.39%, mineral composition of 51.20% baryta stone, 4.5% rhombohedral alkaline earth stone, 39.59% witherite, 10.5% barite and other 3.66%. Particle size-100 mesh, weight 2076.65 g. 254.83g of anthracite powder (-100 meshes) (the carbon content is 120 percent), the bulk materials are respectively filled into ordinary porcelain crucibles with four side faces provided with 2mm exhaust holes after being mixed uniformly, and are calcined for 45min in a 60m open flame type coal-fired tunnel kiln at 1260 ℃, so as to obtain 1657g of clinker, and the conversion rate of barium carbonate into barium hydroxide is 71.85 percent through testing.
Adding water into sample No. 1 at a solid-to-liquid ratio of 1: 4, boiling, stirring, leaching for 15min to obtain first stage leaching solution, evaporating for 1h, cold separating for 12h, and centrifuging to obtain 323.4g of barium hydroxide octahydrate crystal. The leached residue is twice and three-stage re-leached separately with half of the water amount added in the first stage leaching, and the leached liquid is used in the next stage leaching. The four samples (four-wheel) are leached, evaporated, concentrated and crystallized by cold separation to obtainBa(OH)2·8H21462.4g of qualified product with the content of O being more than 98 percent, 144.6g of the mother liquor remained, and the total yield of 1607g of barium is 64.93 percent.
Example 2:
ore grade BaCO379.53%, the mineral composition is: 22.73 percent of barnacite, 64.45 percent of witherite, 2.92 percent of barite, 2.74 percent of dolomite, 0.76 percent of strontianite and the balance of 6.40 percent. Particle size-200 mesh, weight 40 g. Adding metallurgical coke powder (granularity-0.2 mm)4.34g (carbon content 120%), flour 0.8g (carbon content 2%) and proper amount of water, kneading into round balls with diameter of 8-12mm, baking, loading into sealed graphite crucible, calcining in muffle furnace at 1250 deg.C for 40min to obtain clinker 33.7g, and testing the conversion rate of barium to 81.39%.
Example 3:
ore grade BaCO375.15%,the mineral composition is: 65.01% of baryta stone, 32.02% of witherite, 1.28% of barite, 1.69% of others, particle size of-80 meshes and weight of 1996 g. 236g of anthracite (granularity-100 meshes) is added (the carbon content is 120%). After mixing uniformly, the bulk materials are loaded into four ceramic common crucibles and calcined in a 12m coal-fired pushed slab kiln at 1260 ℃ for 40min to obtain 1687.5g of clinker, and the test shows that the conversion rate of barium is 61.70%.
Example 4:
ore grade BaCO361.27%, the mineral composition is: 90.30% barytite, 2.17% rhombohedral alkaline earth, 3.15% alumino-silica barium, 2.27% barite and other 2.11%. The particle size is 100 meshes, the weight is 1000g, 140g of bituminous coal powder (the carbon content is 150%) with the same particle size is added, the mixture is uniformly mixed and then is put into a lithium heat-resistant crucible, and the mixture is calcined for 45min at 1250 ℃ in an open flame type coal-fired down-draft kiln, so that 863g of clinker is obtained, and the barium conversion rate is 58.73% through a test.
Example 5:
is the leaching residue after barium hydroxide production, BaCO340.01 percent, CaO9.71 percent, MgO1.10 percent, particle size of-200 meshes and weight of 375 g. Adding industrial grade CaCl2105.44g (100 percent of theoretical dosage) are mixed evenly, and then bulk materials are loaded into a graphite crucible and put into a coal-fired muffle tunnel kiln at 700 DEG CCalcining for 2 hours and 30 minutes. Adding water into the clinker, boiling, stirring and leaching, carrying out solid-liquid separation, concentrating the leaching solution, and crystallizing to obtain 153g of a qualified barium chloride dihydrate product. 16g of the mother liquor remained, and the total amount was 169g and the barium conversion rate was 91.00%.
Example 6:
is the leaching residue after barium hydroxide production, BaCO338.42％，CaO10.13％，MgO1.08%, particle size-200 mesh, weight 371 g. Addition of NH4345.64g of agricultural ammonium chloride having a Cl content of 93% (which is 200% of theory) were added with 1615ml of water to prepare a 4mol/L strength solution. Boiling, stirring and leaching for 3h, filtering to remove residues, concentrating the leaching solution, and performing cold crystallization to obtain 159.31g of barium chloride dihydrate product, wherein the barium conversion rate is 90.30%, and the product quality reaches the GB1617-89 high-class product standard. The mother liquor can be used for the next cycle leaching, and the secondary slag can be used for manufacturing barium slag bricks and the like for comprehensive utilization.
Claims (10)
1. A process for preparing barium hydroxide from carbonate-type barium ore includes such steps as pulverizing the carbonate-type barium ore as raw material, mixing with carbon as reducer, calcining at 1100-1400 deg.C (1250-1300 deg.C), immersing in water, boiling, solid-liquid separation to obtain immersion liquid and dregs, concentrating or direct cold educing and crystallizing.
2. The method for producing barium hydroxide from carbonate barium ore according to claim 1, wherein said carbonate barium ore is mainly witherite or barite and is accompanied by alkaline earth stones, barite, alumino-silica barium stone and gangue minerals, and the minerals of said ore comprise (by weight%):
barium disintegrable rock 17-95
Witherite 0-83
0-30 parts of rhombohedral alkaline earth stone
0-30% of barite
Alumino-barium stone 0-15
Gangue mineral 0-30
The gangue minerals include quartz, dolomite, calcite, and carbon.
3. The method for producing barium hydroxide as claimed in claim 1, wherein the carbonate type barium ore and the carbonaceous reducing agent are pulverized and then directly charged or charged with a binder for pelletizing and then charged into a heat-resistant container for calcination.
4. The method for producing barium hydroxide according to claim 1, wherein the carbonate type barium ore and the carbonaceous reducing agent are pulverized to have a particle size of-2 mm to-200 mesh, preferably-80 mesh.
5. The method for producing barium hydroxide from carbonate-type barium ore according to claim 1, wherein said carbonaceous reducing agent is anthracite, bituminous coal or coke.
6. The method for producing barium hydroxide from carbonate-type barium ore according to claim 1, wherein the weight of said carbonaceous reducing agent is about 5 to 20% of the weight of carbonate-type barium ore.
7. The method for producing barium hydroxide from carbonate barium ore according to claim 1, wherein the heat-resistant container is a crucible having good sealing property, high thermal shock resistance, high temperature resistance, and strong alkali corrosion resistance.
8. The method for producing barium hydroxide from carbonate type barium ore according to claim 7, wherein saidcrucible is preferably provided with a vent hole having a diameter of 2 to 5mm at the upper portion thereof.
9. The method for producing barium hydroxide from carbonate-type barium ore according to claim 1, wherein said calcining kiln is a coal-fired tunnel kiln, a pushed slab kiln or a down draft kiln.
10. The method for producing barium hydroxide according to claim 1, wherein chloride salt is added to said leached residue to perform low temperature chlorination roasting or ammonium chloride solution is added to directly leach the leached residue to produce barium chloride dihydrate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723428B (en) * | 2010-01-15 | 2011-12-07 | 贵州红星发展股份有限公司 | Method for preparing low strontium barium hydroxide |
| CN102923748A (en) * | 2012-11-30 | 2013-02-13 | 长沙矿冶研究院有限责任公司 | Method for preparing barium hydroxide by using barium carbonate |
| CN118954565A (en) * | 2024-10-18 | 2024-11-15 | 山东辰安化学有限公司 | A preparation process of barium hydroxide octahydrate |
-
1996
- 1996-11-08 CN CN 96117772 patent/CN1152550A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723428B (en) * | 2010-01-15 | 2011-12-07 | 贵州红星发展股份有限公司 | Method for preparing low strontium barium hydroxide |
| CN102923748A (en) * | 2012-11-30 | 2013-02-13 | 长沙矿冶研究院有限责任公司 | Method for preparing barium hydroxide by using barium carbonate |
| CN102923748B (en) * | 2012-11-30 | 2014-07-23 | 长沙矿冶研究院有限责任公司 | Method for preparing barium hydroxide by using barium carbonate |
| CN118954565A (en) * | 2024-10-18 | 2024-11-15 | 山东辰安化学有限公司 | A preparation process of barium hydroxide octahydrate |
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