CN109437285A - A kind of method of environmentally protective production germanium dioxide - Google Patents
A kind of method of environmentally protective production germanium dioxide Download PDFInfo
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- CN109437285A CN109437285A CN201811467465.2A CN201811467465A CN109437285A CN 109437285 A CN109437285 A CN 109437285A CN 201811467465 A CN201811467465 A CN 201811467465A CN 109437285 A CN109437285 A CN 109437285A
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- germanium
- acid
- liquid
- gas
- germanium dioxide
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 58
- 229940119177 germanium dioxide Drugs 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 230000001681 protective effect Effects 0.000 title claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 35
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003546 flue gas Substances 0.000 claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 23
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 238000002386 leaching Methods 0.000 claims abstract description 22
- 229920001864 tannin Polymers 0.000 claims abstract description 20
- 239000001648 tannin Substances 0.000 claims abstract description 20
- 235000018553 tannin Nutrition 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 52
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000000746 purification Methods 0.000 claims description 27
- 239000002893 slag Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 24
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000009423 ventilation Methods 0.000 claims description 6
- 239000003500 flue dust Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000011109 contamination Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/02—Germanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to field of material technology, provide a kind of method of environmentally protective production germanium dioxide.This method comprises: (1) leaches recycling lead, zinc；(2) tannin acid recovery；(3) it pre-processes；(4) it is crushed；(5) salt Ore Leaching；(6) it distills；(7) multiple to steam；(8) it hydrolyzes；(9) it dries；(10) abraum salt acid recovery；(11) liquid acid multi-stage flue gas absorbs；(12) the heating distillation of mixed acid；(13) retort gas condenses to obtain hydrochloric acid.Not only germanium leaching rate is high for the germanium dioxide that this method is prepared, the purity is high of germanium dioxide, and the problem of be able to solve residue contamination in germanium dioxide production process, so that waste and old hydrochloric acid, sulfuric acid is recycled, it reduces production cost and is also conducive to environmental protection, realize environmentally protective production germanium dioxide.
Description
Technical field
The invention belongs to field of material technology, specifically, being related to a kind of method of environmentally protective production germanium dioxide.
Background technique
Content of the germanium in the earth's crust is about 0.0007%, is one of the element most dispersed in the earth's crust.Germanium resource amount is in the whole world
It is poorer, and distribution concentrate very much, a large amount of germanium be present in dispersity the silicate mine of various metals, sulfide mine with
And in various types of coals.
In the production process of germanium dioxide, tannin germanium mine raw material can generate flue dust, tail gas in 600-700 DEG C of pretreatment
(such as sulfur dioxide gas, exhaust gas, water vapour etc. after organic matter processing).Hydrochloric acid is largely used as leaching agent, is being produced
Industry Waste hydrochloric acid is generated with the meeting not avoided in manufacturing process, just have leached mud accumulation in distillation process and multiple steaming process and is given up
Hydrochloric acid is placed, and the hydrogen chloride in associated metal and waste hydrochloric acid in slag can't be efficiently used by not only polluting environment, causes resource
Waste increases cost.
Summary of the invention
For deficiency above-mentioned in the prior art, the object of the present invention is to provide a kind of environmentally protective production titanium dioxides
The method of germanium；Not only germanium leaching rate is high for the germanium dioxide that this method is prepared, the purity is high of germanium dioxide, and is able to solve
In germanium dioxide production process the problem of residue contamination, waste and old hydrochloric acid, sulfuric acid is enable to recycle, it is also sharp to reduce production cost
In environmental protection, environmentally protective production germanium dioxide is realized.
In order to achieve the above object, the solution that the present invention uses is:
A kind of method of environmentally protective production germanium dioxide, comprising: (1) leach recycling lead, zinc: being 250- by concentration
The ammonium chloride solution of 270g/L is that 4-6:1 is mixed according to liquid-solid ratio (m/m) with tannin germanium, and control pH value is that 2.5-3.2 is soaked
1h out obtains leachate and leached mud；Leachate carries out synthetical recovery；(2) it is molten that oxalic acid tannin acid recovery: is added into leached mud
Liquid obtains mixed solution, and oxalic acid additional amount is the 4.5-5% of mixed solution quality, and control pH value is 8.5-9.5, reacts and is
1.5h obtains rich germanium slag and tannin recovered liquid；(3) pre-process: rich germanium slag, which is pre-processed in 650-680 DEG C through rotary kiln, to be aoxidized
Germanium；(4) it is crushed: germanium oxide is broken into germania particle；(5) salt Ore Leaching: by germania particle and hydrogen chloride according to solid-liquid
Than mixing for 1:4-6 (m/m), and it is passed through chlorine, controlled at 70-75 DEG C, be stirred, reacted 35-40min, mixed
Compound extract；(6) it distills: being stirred leachate, control heating temperature is 88-92 DEG C, distills 2-4h, it is molten to obtain germanium tetrachloride
Liquid and waste hydrochloric acid；(7) multiple to steam；Successively carry out primary purification and secondary purification；Primary purification includes: to pass through germanium tetrachloride solution
Hot steam heating distillation, control heating temperature are 90-92 DEG C, obtain a germanium tetrachloride solution；Secondary purification includes: will be primary
Germanium tetrachloride solution electrified regulation, control heating temperature are 85-87 DEG C, obtain pure germanium tetrachloride solution；In secondary purification process
Middle generation foreign gas is discharged after vent gas treatment is up to standard；(8) it hydrolyzes: by deionized water and pure germanium tetrachloride solution according to volume
Than reactor tank is added for 4-6:1, control reaction temperature is 20 DEG C of liquid to after white precipitate occur and hydrolyze；(9) it dries: will be white
Precipitating is dried after being washed, and obtains germanium dioxide powder；(10) abraum salt acid recovery: to waste hydrochloric acid carry out filters pressing, solid-liquor separation,
Obtain solid slag and liquid acid；For solid slag after NaOH is leached, obtained solid carries out synthetical recovery, and gained liquid sends step back to
(6)；(11) liquid acid multi-stage flue gas absorbs: into liquid acid, room temperature injects sulfuric acid relieving haperacidity flue gas, when sulfuric acid concentration reaches 50%
Stop ventilation afterwards, obtains mixed acid and the first tail gas；Relieving haperacidity flue gas is absorbed through lye again after multistage absorption, and the first tail gas enters
Relieving haperacidity flue gas process is recycled；(12) the heating distillation of mixed acid: 82 DEG C are greater than in vapo(u)rizing temperature to mixed acid, distillation
The interior pressure of device is that 0.3-0.4Mpa is distilled, liquid and retort gas after being distilled；The amount of steaming of hydrochloric acid in retort gas
For the 33-34% of mixed acid quality；The concentration of sulfuric acid is 75-76% in liquid after distillation, and chlorine ion concentration is less than 0.1%；(13)
Retort gas condenses to obtain hydrochloric acid.
The beneficial effect of the method for the environmentally protective production germanium dioxide of one kind provided by the invention is:
(1) in the method for this kind provided by the invention environmentally protective production germanium dioxide, the entire production of germanium dioxide is all
It is carried out in reaction kettle, distillation container, the closed environments such as pipeline, the germanium dioxide that this method is prepared not only germanium leaching rate
Height, the purity is high of germanium dioxide, and the problem of be able to solve residue contamination in germanium dioxide production process；Can by waste residue into
Row recovery processing, both can solve problem of environmental pollution, moreover it is possible to recycle valuable metal therein (such as zinc recovering for producing zinc ingot metal,
Lead enriching and recovering can be sold to the producer etc. of needs in the form of low-grade ore), cost is reduced, it is not only environmentally friendly, also
Rationally utilize resource.
(2) method of this kind provided by the invention environmentally protective production germanium dioxide, can solve germanium dioxide production process
The problem of waste acid treatment；Spent acid reuse, changes harmful to treasure, and high economic effect is also brought while solving environmental issue for enterprise
Benefit, it is very considerable with prospect using field, there is huge investment repayment value.
(3) method of this kind provided by the invention environmentally protective production germanium dioxide, can make sulfuric acid relieving haperacidity flue gas obtain
Combined governance, and Joint Production goes out industrial production raw material sulfuric acid, saves production cost.
Detailed description of the invention
Fig. 1 is process flow chart provided by the invention.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The method of production germanium dioxide environmentally protective to one kind provided in an embodiment of the present invention is specifically described below.
A kind of method of environmentally protective production germanium dioxide, referring to Fig. 1, including:
(1) leach recycling lead, zinc: by concentration be 250-270g/L ammonium chloride solution and tannin germanium according to liquid-solid ratio (m/
M) it is mixed for 4-6:1, control pH value is that 2.5-3.2 carries out leaching 1h, obtains leachate and and leached mud；Leachate is integrated
Recycling；In acid condition, lead and chloride ion will form complex compound and enter leachate, and zinc then enters leaching in the form of zinc chloride
In liquid.After leachate send synthetical recovery, zinc can be used for producing zinc ingot metal, and lead can be enriched with into the sale of lead mud.
(2) tannin acid recovery: oxalic acid solution is added into leached mud and obtains mixed solution, oxalic acid additional amount is mixed solution
The 4.5-5% of quality, control pH value are 8.5-9.5, react for 1.5h, obtain rich germanium slag and tannin recovered liquid；Germanium and oxalic acid network
Conjunction property is stronger than tannic acid, and oxalic acid is oxidized easily decomposition.
(3) pre-process: rich germanium slag pre-processes to obtain germanium oxide through rotary kiln in 650-680 DEG C；It, can in above-mentioned temperature
Organic matter and moisture in rich germanium slag are removed, and sulfur-containing compound is decomposed into sulfur dioxide.The flue dust and sulfur dioxide of generation are logical
Cross the spray removal of lye spray column.
(4) it is crushed: germanium oxide is broken into germania particle with crusher, to increase surface area, improve and leach in process
The leaching rate of germanium, to improve the productivity of germanium.Since volume of smoke can be generated in shattering process, using bag-type dust equipment
Flue dust is removed, dust removal efficiency can reach 99.9%.
(5) salt Ore Leaching: germania particle is mixed with hydrogen chloride according to solid-to-liquid ratio for 1:4-6 (m/m), while by close
Stopped pipe road is passed through micro chlorine；The hypochlorous acid that chlorine can generate after reacting with water, hypochlorous acid can part be in oxidic raw materials
It is dissolved in the germanium metal of hydrochloric acid, then improves leaching rate.It controlled at 70-75 DEG C, is stirred, reacts simultaneously 35-40min, obtain
To the mixing leachate containing germanium tetrachloride and hydrogen chloride.
(6) it distills: being stirred leachate in distillation still, control heating temperature is 88-92 DEG C, distills 2-4h；Using
Condenser pipe collects the germanium tetrachloride gas distilled, obtains germanium tetrachloride solution, removes other metal impurities；Part hydrochloric acid exists
Hydrogen chloride gas is formed when distillation, hydrogen chloride gas enters in the tail gas absorption groove equipped with 15-20% hydrochloric acid solution, then is pumped into alkali
Liquid spray column spray handles rear discharge up to standard.Vinasse in distillation still is waste hydrochloric acid.
(7) multiple to steam；Successively carry out primary purification and secondary purification；Primary purification includes: by germanium tetrachloride solution through overheating
Steam heating distillation, control heating temperature are 90-92 DEG C, obtain a germanium tetrachloride solution；Secondary purification includes: by one time four
Chlorination germanium solution electrified regulation, control heating temperature are 85-87 DEG C, obtain pure germanium tetrachloride solution；During secondary purification
Foreign gas is generated through vent gas treatment heel row up to standard.
(8) it hydrolyzes: deionized water and pure germanium tetrachloride solution is 4-6:1 addition reactor tank according to volume ratio and stirred,
Control reaction temperature is 20 DEG C of liquid to after white precipitate occur and hydrolyze；Send liquid after hydrolysis back to multiple steaming step.
(9) it dries: being dried after white precipitate is washed, obtain germanium dioxide powder.
(10) abraum salt acid recovery: filters pressing is carried out to waste hydrochloric acid, solid-liquor separation obtains solid slag and liquid acid；Solid slag warp
After NaOH is leached, obtained solid carries out synthetical recovery, and gained liquid sends step (6) back to.
(11) liquid acid multi-stage flue gas absorbs: into liquid acid, room temperature injects sulfuric acid relieving haperacidity flue gas, the SO in flue gas3With water
React (SO3+H2O=H2SO4) sulfuric acid solution is generated, stop ventilation after sulfuric acid concentration reaches 50%, obtains mixed acid and first
Tail gas；Relieving haperacidity flue gas is absorbed through lye again after multistage absorption, and the first tail gas enters relieving haperacidity flue gas process and recycled.
(12) the heating distillation of mixed acid: 82 DEG C are greater than in vapo(u)rizing temperature to mixed acid, the interior pressure of distiller is 0.3-
0.4Mpa is distilled, liquid and retort gas after being distilled；The amount of steaming of hydrochloric acid is the 33- of mixed acid quality in retort gas
34%；The concentration of sulfuric acid is 75-76% in liquid after distillation, and chlorine ion concentration is less than 0.1%.
(13) by adding distilled water to retort gas, condensed, and control the mass fraction of condensation hydrochloric acid total acidity >
31% (being measured by AA7050 atomic absorption spectrophotometer), is up to state standards, as this technique finished industrial hydrochloric acid；It is cold
The second tail gas generated during solidifying is delivered to step (11) and carries out circular treatment into relieving haperacidity flue gas process.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of method of environmentally protective production germanium dioxide, comprising: (1) leach recycling lead, zinc: being 250g/L's by concentration
Ammonium chloride solution is that 4:1 is mixed according to liquid-solid ratio (m/m) with tannin germanium, and control pH value carries out leaching 1h for 2.5, obtains leachate
And leached mud；Leachate carries out synthetical recovery；(2) tannin acid recovery: being added oxalic acid solution into leached mud and obtain mixed solution,
Oxalic acid additional amount is the 4.5% of mixed solution quality, and control pH value is 8.5, is reacted for 1.5h, obtains rich germanium slag and tannin recycling
Liquid；(3) pre-process: rich germanium slag pre-processes to obtain germanium oxide through rotary kiln in 650 DEG C；(4) it is crushed: germanium oxide is broken into oxidation
Germanium particle；(5) salt Ore Leaching: germania particle is mixed with hydrogen chloride according to solid-to-liquid ratio for 1:4 (m/m), and is passed through chlorine, is controlled
Temperature processed is 70 DEG C, is stirred, and 35min is reacted, and obtains mixing leachate；(6) it distills: being stirred leachate, control adds
Hot temperature is 88 DEG C, distills 4h, obtains germanium tetrachloride solution and waste hydrochloric acid；(7) multiple to steam；It successively carries out primary purification and secondary mentions
It is pure；Primary purification includes: to heat germanium tetrachloride solution through superheated steam to distill, and control heating temperature is 90 DEG C, is obtained primary
Germanium tetrachloride solution；Secondary purification includes: by a germanium tetrachloride solution electrified regulation, and controlling heating temperature is 85 DEG C, is obtained
Pure germanium tetrachloride solution；Foreign gas is generated during secondary purification to be discharged after vent gas treatment is up to standard；(8) it hydrolyzes: will go
Ionized water and pure germanium tetrachloride solution are that 4:1 is added reactor tank according to volume ratio, and control reaction temperature is 20 DEG C to there is white
Liquid after precipitating and hydrolysis；(9) it dries: being dried after white precipitate is washed, obtain germanium dioxide powder；(10) waste hydrochloric acid returns
It receives: filters pressing being carried out to waste hydrochloric acid, solid-liquor separation obtains solid slag and liquid acid；Solid slag after NaOH is leached, obtained solid into
Row synthetical recovery, gained liquid send step (6) back to；(11) liquid acid multi-stage flue gas absorbs: into liquid acid, room temperature injects sulfuric acid
Relieving haperacidity flue gas stops ventilation after sulfuric acid concentration reaches 50%, obtains mixed acid and the first tail gas；Relieving haperacidity flue gas is through multistage absorption
It is absorbed again through lye afterwards, the first tail gas enters relieving haperacidity flue gas process and recycled；(12) the heating distillation of mixed acid: to mixed
It is 85 DEG C that acid, which is closed, in distillation temperature, and the interior pressure of distiller is that 0.3Mpa is distilled, liquid and retort gas after being distilled；Distillation
The amount of steaming of hydrochloric acid is the 33% of mixed acid quality in gas；The concentration of sulfuric acid is 75% in liquid after distillation, and chlorine ion concentration is
0.8%；(13) retort gas condenses to obtain hydrochloric acid.
Embodiment 2
A kind of method of environmentally protective production germanium dioxide, comprising: (1) leach recycling lead, zinc: being 270g/L's by concentration
Ammonium chloride solution is that 6:1 is mixed according to liquid-solid ratio (m/m) with tannin germanium, and control pH value carries out leaching 1h for 3.2, obtains leachate
And leached mud；Leachate carries out synthetical recovery；(2) tannin acid recovery: being added oxalic acid solution into leached mud and obtain mixed solution,
Oxalic acid additional amount is the 5% of mixed solution quality, and control pH value is 9.5, is reacted for 1.5h, obtains rich germanium slag and tannin recycling
Liquid；(3) pre-process: rich germanium slag pre-processes to obtain germanium oxide through rotary kiln in 680 DEG C；(4) it is crushed: germanium oxide is broken into oxidation
Germanium particle；(5) salt Ore Leaching: germania particle is mixed with hydrogen chloride according to solid-to-liquid ratio for 1:6 (m/m), and is passed through chlorine, is controlled
Temperature processed is 75 DEG C, is stirred, and 40min is reacted, and obtains mixing leachate；(6) it distills: being stirred leachate, control adds
Hot temperature is 92 DEG C, distills 2h, obtains germanium tetrachloride solution and waste hydrochloric acid；(7) multiple to steam；It successively carries out primary purification and secondary mentions
It is pure；Primary purification includes: to heat germanium tetrachloride solution through superheated steam to distill, and control heating temperature is 92 DEG C, is obtained primary
Germanium tetrachloride solution；Secondary purification includes: by a germanium tetrachloride solution electrified regulation, and controlling heating temperature is 87 DEG C, is obtained
Pure germanium tetrachloride solution；Foreign gas is generated during secondary purification to be discharged after vent gas treatment is up to standard；(8) it hydrolyzes: will go
Ionized water and pure germanium tetrachloride solution are that 6:1 is added reactor tank according to volume ratio, and control reaction temperature is 20 DEG C to there is white
Liquid after precipitating and hydrolysis；(9) it dries: being dried after white precipitate is washed, obtain germanium dioxide powder；(10) waste hydrochloric acid returns
It receives: filters pressing being carried out to waste hydrochloric acid, solid-liquor separation obtains solid slag and liquid acid；Solid slag after NaOH is leached, obtained solid into
Row synthetical recovery, gained liquid send step (6) back to；(11) liquid acid multi-stage flue gas absorbs: into liquid acid, room temperature injects sulfuric acid
Relieving haperacidity flue gas stops ventilation after sulfuric acid concentration reaches 50%, obtains mixed acid and the first tail gas；Relieving haperacidity flue gas is through multistage absorption
It is absorbed again through lye afterwards, the first tail gas enters relieving haperacidity flue gas process and recycled；(12) the heating distillation of mixed acid: to mixed
It is 83 DEG C that acid, which is closed, in vapo(u)rizing temperature, and the interior pressure of distiller is that 0.4Mpa is distilled, liquid and retort gas after being distilled；It steams
The amount of steaming for evaporating hydrochloric acid in gas is the 34% of mixed acid quality；The concentration of sulfuric acid is 6% in liquid after distillation, and chlorine ion concentration is
0.7%；(13) retort gas condenses to obtain hydrochloric acid.
Embodiment 3
A kind of method of environmentally protective production germanium dioxide, comprising: (1) leach recycling lead, zinc: being 260g/L's by concentration
Ammonium chloride solution and tannin germanium are that 5:1 mix according to liquid-solid ratio (m/m), and control pH value is 3 to carry out leaching 1h, obtain leachate with
Leached mud；Leachate carries out synthetical recovery；(2) tannin acid recovery: being added oxalic acid solution into leached mud and obtain mixed solution, grass
Sour additional amount is the 4.7% of mixed solution quality, and control pH value is 9, reacts for 1.5h, obtains rich germanium slag and tannin recovered liquid；
(3) pre-process: rich germanium slag pre-processes to obtain germanium oxide through rotary kiln in 660 DEG C；(4) it is crushed: germanium oxide is broken into germanium oxide
Particle；(5) salt Ore Leaching: germania particle is mixed with hydrogen chloride according to solid-to-liquid ratio for 1:5 (m/m), and is passed through chlorine, is controlled
Temperature is 72 DEG C, is stirred, and 38min is reacted, and obtains mixing leachate；(6) it distills: being stirred leachate, control heating
Temperature is 90 DEG C, distills 3h, obtains germanium tetrachloride solution and waste hydrochloric acid；(7) multiple to steam；It successively carries out primary purification and secondary mentions
It is pure；Primary purification includes: to heat germanium tetrachloride solution through superheated steam to distill, and control heating temperature is 91 DEG C, is obtained primary
Germanium tetrachloride solution；Secondary purification includes: by a germanium tetrachloride solution electrified regulation, and controlling heating temperature is 86 DEG C, is obtained
Pure germanium tetrachloride solution；Foreign gas is generated during secondary purification to be discharged after vent gas treatment is up to standard；(8) it hydrolyzes: will go
Ionized water and pure germanium tetrachloride solution are that 5:1 is added reactor tank according to volume ratio, and control reaction temperature is 20 DEG C to there is white
Liquid after precipitating and hydrolysis；(9) it dries: being dried after white precipitate is washed, obtain germanium dioxide powder；(10) waste hydrochloric acid returns
It receives: filters pressing being carried out to waste hydrochloric acid, solid-liquor separation obtains solid slag and liquid acid；Solid slag after NaOH is leached, obtained solid into
Row synthetical recovery, gained liquid send step (6) back to；(11) liquid acid multi-stage flue gas absorbs: into liquid acid, room temperature injects sulfuric acid
Relieving haperacidity flue gas stops ventilation after sulfuric acid concentration reaches 50%, obtains mixed acid and the first tail gas；Relieving haperacidity flue gas is through multistage absorption
It is absorbed again through lye afterwards, the first tail gas enters relieving haperacidity flue gas process and recycled；(12) the heating distillation of mixed acid: to mixed
It is 90 DEG C that acid, which is closed, in vapo(u)rizing temperature, and the interior pressure of distiller is that 0.2Mpa is distilled, liquid and retort gas after being distilled；It steams
The amount of steaming for evaporating hydrochloric acid in gas is the 33% of mixed acid quality；The concentration of sulfuric acid is 75% in liquid after distillation, chlorine ion concentration
It is 0.6%；(13) retort gas condenses to obtain hydrochloric acid.
Experimental example 1
Experimental method: the leaching rate for the germanium dioxide that embodiment 1-3 is prepared is shown in Table 1:
Table 1
| Group number | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Leaching rate (%) | 97.57 | 97.99 | 98.12 |
From the data in table 1, it can be seen that being prepared into using the method for environmentally protective production germanium dioxide provided in an embodiment of the present invention
The leaching rate of the germanium dioxide arrived is high.
Experimental example 2
Experimental method: using icp ms detection embodiment 1-3 preparation to germanium dioxide in
The content of associated metal the results are shown in Table shown in 2:
Table 2
From the data in table 2, it can be seen that being prepared into using the method for environmentally protective production germanium dioxide provided in an embodiment of the present invention
To germanium dioxide in associated metal content significantly reduce.
Experimental example 3
Experimental method: using spectrophotometer embodiment 1-3 preparation to germanium dioxide in chlorine element and moisture contain
Amount, the results are shown in Table shown in 3:
Table 3
| Component | 1 | 2 | 3 |
| Cl | 0.029 | 0.031 | 0.035 |
| Moisture | 0.11 | 0.20 | 0.20 |
From the data in table 3, it can be seen that being prepared into using the method for environmentally protective production germanium dioxide provided in an embodiment of the present invention
To germanium dioxide in chlorine element and the content of moisture it is few.
In conclusion using the method for environmentally protective production germanium dioxide provided by the invention；This method not only can solve
In germanium dioxide production process the problem of residue contamination, moreover it is possible to so that waste and old hydrochloric acid, sulfuric acid is recycled, reduce and be produced into
This is also conducive to environmental protection, realizes environmentally protective production germanium dioxide.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of method of environmentally protective production germanium dioxide, it is characterised in that: include:
(1) recycling lead, zinc are leached: being according to liquid-solid ratio (m/m) by ammonium chloride solution and tannin germanium that concentration is 250-270g/L
4-6:1 mixing, control pH value are that 2.5-3.2 carries out leaching 1h, obtain leachate and leached mud；The leachate integrates back
It receives；
(2) tannin acid recovery: oxalic acid solution is added in Xiang Suoshu leached mud and obtains mixed solution, oxalic acid additional amount is the mixing
The 4.5-5% of solution quality, control pH value are 8.5-9.5, react for 1.5h, obtain rich germanium slag and tannin recovered liquid；
(3) pre-process: the richness germanium slag pre-processes to obtain germanium oxide through rotary kiln in 650-680 DEG C；
(4) it is crushed: the germanium oxide is broken into germania particle；
(5) salt Ore Leaching: the germania particle is mixed with hydrogen chloride according to solid-to-liquid ratio for 1:4-6 (m/m), and is passed through chlorine
Gas is stirred controlled at 70-75 DEG C, reacts 35-40min, obtains mixing leachate；
(6) it distills: stirring the mixing leachate, control heating temperature is 88-92 DEG C, distills 2-4h, it is molten to obtain germanium tetrachloride
Liquid and waste hydrochloric acid；
(7) multiple to steam；Successively carry out primary purification and secondary purification；The primary purification includes: to pass through the germanium tetrachloride solution
Superheated steam heating distillation, control heating temperature are 90-92 DEG C, obtain a germanium tetrachloride solution；The secondary purification includes:
By the germanium tetrachloride solution electrified regulation, controlling heating temperature is 85-87 DEG C, obtains pure germanium tetrachloride solution；Two
Foreign gas is generated in secondary purification process to be discharged after vent gas treatment is up to standard；
(8) it hydrolyzes: reactor tank is added according to volume ratio for 4-6:1 in deionized water and the pure germanium tetrachloride solution, control is anti-
Answering temperature is 20 DEG C of liquid to after white precipitate occur and hydrolyze；
(9) it dries: being dried after the white precipitate is washed, obtain germanium dioxide powder；
(10) abraum salt acid recovery: filters pressing is carried out to the waste hydrochloric acid, solid-liquor separation obtains solid slag and liquid acid；The solid
For slag after NaOH is leached, obtained solid carries out synthetical recovery, and gained liquid sends step (6) back to；
(11) liquid acid multi-stage flue gas absorbs: room temperature injects sulfuric acid relieving haperacidity flue gas in Xiang Suoshu liquid acid, when sulfuric acid concentration reaches
Stop ventilation after 50%, obtains mixed acid and the first tail gas；The relieving haperacidity flue gas is absorbed through lye again after multistage absorption, described
First tail gas enters relieving haperacidity flue gas process and is recycled；
(12) the heating distillation of mixed acid: 82 DEG C are greater than in vapo(u)rizing temperature to the mixed acid, the interior pressure of distiller is 0.3-
0.4Mpa is distilled, liquid and retort gas after being distilled；The amount of steaming of hydrochloric acid is the mixed acid in the retort gas
The 33-34% of quality；The concentration of sulfuric acid is 75-76% in liquid after the distillation, and chlorine ion concentration is less than 0.1%；
(13) retort gas condenses to obtain hydrochloric acid.
2. the method for environmentally protective production germanium dioxide according to claim 1, it is characterised in that: step is also wrapped in (3)
It includes and the sulfur dioxide and flue dust that pre-process through rotary kiln is passed through into the spray removal of lye spray column.
3. the method for environmentally protective production germanium dioxide according to claim 1, it is characterised in that: set using bag-type dust
It is standby to remove the flue dust generated in step (4).
4. the method for environmentally protective production germanium dioxide according to claim 1, it is characterised in that: in step (6), also wrap
It includes: collecting the germanium tetrachloride gas distilled using condenser pipe, obtain germanium tetrachloride solution, remove other metal impurities；Portion
Hydrochloric acid is divided to form hydrogen chloride gas in distillation, the hydrogen chloride gas enters the tail gas absorption equipped with 15-20% hydrochloric acid solution
In slot, then it is pumped into lye spray column spray, handles rear discharge up to standard.
5. the method for environmentally protective production germanium dioxide according to claim 3, it is characterised in that: generate step (8)
Hydrolysis after liquid enter steam step again.
6. the method for environmentally protective production germanium dioxide according to claim 1, it is characterised in that: in step (13), lead to
It crosses to the retort gas and adds distilled water, and control mass fraction > 31% of condensation hydrochloric acid total acidity.
7. the method for environmentally protective production germanium dioxide according to claim 1, it is characterised in that: cold in step (13)
The second tail gas generated during solidifying is delivered to step (11) and carries out circular treatment into relieving haperacidity flue gas process.
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| CN115109929A (en) * | 2022-01-21 | 2022-09-27 | 昆明理工大学 | Method for directly preparing coarse germanium dioxide from tannin germanium slag |
| CN115536055A (en) * | 2022-09-27 | 2022-12-30 | 昆明理工大学 | Method for preparing germanium dioxide from zinc hydrometallurgy inorganic germanium slag |
| CN116732356A (en) * | 2023-08-15 | 2023-09-12 | 昆明理工大学 | Method for synchronously leaching and precipitating germanium in zinc suboxide smoke dust |
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Address after: 625400 Zhuma Industrial Park, Huilong Township, Shimian County, Ya'an City, Sichuan Province Patentee after: Sichuan Sihuan Zinc Germanium Technology Co.,Ltd. Address before: 625400 Zhuma Industrial Park, Huilong Township, Shimian County, Ya'an City, Sichuan Province Patentee before: SIHUAN ZINC & GERMANIUM TECHNOLOGY Co.,Ltd. |
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Address after: 625400 Sichuan Shimian Industrial Park, Huilong Town, Shimian County, Ya'an City, Sichuan Province Patentee after: Sichuan Shengtun Zinc Germanium Technology Co.,Ltd. Address before: 625400 Zhuma Industrial Park, Huilong Township, Shimian County, Ya'an City, Sichuan Province Patentee before: Sichuan Sihuan Zinc Germanium Technology Co.,Ltd. |