CN102863008B - Method for producing high-purity zinc oxide by ammonia method using low-grade zinc oxide ores - Google Patents
Method for producing high-purity zinc oxide by ammonia method using low-grade zinc oxide ores Download PDFInfo
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- CN102863008B CN102863008B CN201210358029.8A CN201210358029A CN102863008B CN 102863008 B CN102863008 B CN 102863008B CN 201210358029 A CN201210358029 A CN 201210358029A CN 102863008 B CN102863008 B CN 102863008B
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- zinc oxide
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- oxide ore
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 191
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 73
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000002386 leaching Methods 0.000 claims abstract description 83
- 239000011701 zinc Substances 0.000 claims abstract description 56
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000001994 activation Methods 0.000 claims abstract description 22
- 230000004913 activation Effects 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- 239000011021 lapis lazuli Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 6
- 235000010755 mineral Nutrition 0.000 abstract description 6
- 239000011707 mineral Substances 0.000 abstract description 6
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- -1 sodium fluorosilicate Chemical compound 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 1
- 239000000920 calcium hydroxide Substances 0.000 abstract 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 1
- 235000011116 calcium hydroxide Nutrition 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 229910052793 cadmium Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 235000010265 sodium sulphite Nutrition 0.000 description 6
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical class [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 235000004416 zinc carbonate Nutrition 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011667 zinc carbonate Substances 0.000 description 4
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 239000004110 Zinc silicate Substances 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 3
- 235000019352 zinc silicate Nutrition 0.000 description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DNGCSGDMYSRLAR-UHFFFAOYSA-N [C+4].N.N Chemical compound [C+4].N.N DNGCSGDMYSRLAR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004137 mechanical activation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for producing high-purity zinc oxide by an ammonia method using low-grade zinc oxide ores. The method comprises the following steps of: adding 3-5% of slaked lime to low-grade zinc oxide ores to be treated for performing mixing and activation before leaching, controlling water in the mixture at 8-10% by mass percentage, adding 0.3-0.5kg of sodium fluorosilicate to per cubic meter of leaching agent, and preferably adding surfactant and dicyandiamide, wherein an ammonia pre-distillation step can be further added simultaneously, therefore, on the one hand, the leaching speed and the leaching rate of zinc in the low-grade zinc oxide ores are increased, and on the other hand, a lower calcination temperature is preferred, zinc oxide with a greater specific surface area and with the purity up to 99.7% and more can be obtained, and the obtained zinc oxide has high economic value; in addition, the treatment method is low in energy consumption and high in efficiency, and the leaching agent can be recycled. The final leaching residues after performing leaching treatment do not damage the original composition and structure of minerals and can still be used to brick-making, thereby achieving economical and environmental-friendly dual purposes.
Description
Technical field
The present invention relates to a kind of production method of zinc oxide, particularly a kind of production method of high-purity zinc oxide.
Background technology
The production of zinc oxide product at present is generally carried out roasting with the high ore deposit of zinc content and is become zinc baking sand to make raw material, because it is higher containing zinc rate, lixiviate is relatively easy.Along with exploitation all the year round, higher-grade mineral resources is fewer and feweri, and grade also reduces gradually, and now oneself starts to note the utilization of zinc oxide ore to people.But zinc oxide ore is conventionally containing zinc rate, lower (valuable element content Zn is below 30%; Pb 0.15%; Cu 0.008%; Mn 0.06%), and complicated component, there is gangue content ferric oxide, silicon oxide, calcium oxide, high (the about Fe respectively of content of magnesia in ore mainly with smithsonite, franklinite and lapis calaminaris
2o
34-7%; SiO
23-5%; CaO30-32%; MgO 7-8%).Comprehensive reutilization is worth little, and ore dressing, acidleach to zinc is all more difficult, and beneficiation cost is high, is the long-standing great technical barrier of domestic and international ore dressing.The method of the lixiviate of recent domestic to zinc oxide ore mostly, is used containing the solution of zinc sulfate of strong acid zinc oxide ore is leached, although zinc leaching rate increases, but the iron, the silicon amount that enter solution are also high, deironing difficulty, consumption amount of reagent is large, and it is many that washings is taken away zinc.China's publication, as CN1477217 A improves aforesaid method, first adopts the solution of sulfur acid zinc pH=3-4 to carry out neutrality leaching, then carries out low Ore Leaching technique.But franklinite, lapis calaminaris decompose slowly in low sour situation, and the problems such as leaching efficiency is low, cost is high, environmental pollution still exist.Many metallargists both domestic and external think, zinc content should not be processed by wet-leaching technique separately lower than 20% zinc oxide ore.
Optimal method is that the selectivity of carrying out zinc leaches, and zinc is entered in solution, and zinc obtains valuable recycling.
On the other hand, high pure zinc oxide generally refers to that the massfraction of zinc oxide is more than 99.7%, high-purity zinc oxide is the indispensable a kind of high-tech raw material of modern industry, of many uses, be mainly used in the tens of kinds of industry and enterprises such as glass, feed, pottery, dyestuff, paint, papermaking, rubber, agricultural chemicals, oil refining, zinc-plated, special steel material, alloy, science and techniques of defence, no matter be glass, papermaking, or rubber, oil refining etc. are all in great demand to zinc oxide, and purity requirement is very high.
Produce at present the method for high-purity zinc oxide, it is mainly indirect method, indirect method is generally take zinc ingot metal as raw material, pass through electrolytic reduction, or high-temperature gasification, atmospheric oxidation again condensation collection makes zinc oxide, different zinc ingot metal raw materials, the zinc oxide purity of producing is also different, and this technique is mainly produced the zinc oxide of 99.5%--99.7%.
Ammonia process is a kind of common method of preparing zinc oxide, the general step of ammonia process (ammonia-carbon ammonium associating lixiviation process is produced zinc oxide) comprising at present: use ammonia-carbon ammonium to combine leaching to material containing zinc and make zinc ammonia complex liquid, make zinc oxide product through purification, ammonia still process crystallization, drying and calcining, general zinc oxide content 95-98%.
This traditional ammonia process is prepared zinc oxide and is never applied to the processing of low-grade zinc oxide ore, and major cause is:
1. because mineral are low containing zinc rate, silt content is high, and leach liquor is low containing zinc concentration, and leaching agent consumption is large, and cost is high, and enterprise cannot bear.
2. because of impurity component complexity, the conforming product rate of production is low, the low deficiency in economic performance of product price.
3. when conventional means leaches, the leaching yield of zinc ore is low, and waste is large, and the value of zinc ore is not used and embodies.
In addition, ammonia leaching process is produced in zinc oxide process at present, after analysing ammonia, all crystallize out with zinc subcarbonate, decomposition temperature is high, and (zinc hydroxide just makes approximately 125 ℃ of temperature theoretical decomposition, approximately 300 ℃ of zinc carbonates), for obtaining high purity product, must guarantee sufficiently high decomposition temperature, general control temperature more than 500 ℃, just can make zinc subcarbonate decompose completely.As the Chinese patent application that application number is 200610130477.7, calcining temperature is up to 550 ℃.High-temperature calcination has a strong impact on the specific surface area of zinc oxide and dispersiveness, mobility, then affects its Application Areas.
In sum, for the processing of low-grade zinc oxide ore, how in the low mineral of zinc content, effectively to leach zinc wherein, and obtain high-purity zinc oxide, overcome the shortcoming of traditional method simultaneously, become industry technical barrier urgently to be resolved hurrily.
Summary of the invention
One of the object of the invention is: for the problem of above-mentioned existence, provide a kind of method of effectively utilizing low-grade zinc oxide ore to prepare high-purity zinc oxide.
The technical solution used in the present invention is such: a kind of method of utilizing low-grade zinc oxide ore to produce high-purity zinc oxide, comprises the following steps successively:
Activation, leaching low-grade zinc oxide ore, purification and impurity removal, ammonia still process crystallization and drying and calcining, wherein
Before leaching low-grade zinc oxide ore step, in pending low-grade zinc oxide ore, add white lime to obtain compound, and carry out admixture activation, the amount of the white lime adding, by weight, for the 3-5% of low-grade zinc oxide ore, in described compound, the quality percentage composition of water is controlled at 8-10%;
Low-grade zinc oxide ore after admixture activation is leached as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent
3volumetric molar concentration c (NH
3)=5.5-7mol/L, CO
3 2volumetric molar concentration c (CO
3 2-)=0.95-1.2 mol/L adds 0.3-0.5kg Sodium Silicofluoride in every cubic metre of leaching agent.
Purification and impurity removal, ammonia still process crystallization and drying and calcining step all adopt current common ammonia process to prepare the processing parameter of zinc oxide.
The technology that first the present invention prepares existing ammonia process zinc oxide is applied to the processing to low-grade zinc oxide ore, simultaneously, on the technique basis of existing ammonia process, before ammonia soaks step, activating pretreatment is carried out in ore deposit, method is: low-grade zinc oxide ore and dry hydrate carry out admixture activation at least 36 hours in advance, in leaching agent, adds appropriate Sodium Silicofluoride simultaneously.
Because the gangue content oxidation content of calcium and magnesium of low-grade zinc oxide ore is high, can not leach with acid system, not only acid consumes greatly, also makes a large amount of calcium, magnesium stripping, purifies difficulty.So the present invention adopts ammonia process to leach, dry hydrate plays loose, the fluffy use that turns into mineral, in ore, the ultrafine particulate of gangue also plays certain deadening effect to leaching agent, in order to address this problem, present inventor draws by great many of experiments: appropriate silicofluoric acid is received and can be abolished ultrafine particulate to containing zinc particle package action, realize ultrafine particulate layering floating, thereby zinc is exposed, it is more fully immersed in leach liquor.By the mechanical activation of preactivated and ball milling and the adding of promoting agent (Sodium Silicofluoride, SDS etc.) of raw material, obtain higher leaching yield.
Wherein:
Chemical reaction in admixture activation process is:
Ca(OH)
2+ZnCO
3+ →CaCO
3↓+ Zn(OH)
2
Fe
3+ +3OH
- →Fe(OH)
3↓
The chemical equation of leaching step is:
ZnO+nNH
3 +H
2O→［Zn(NH
3)n］
2++2OH
-
ZnFe
2O
4 +nNH
3+4H
2O→［Zn(NH
3)n］
2++2Fe(OH)
3 ↓+2OH
-
ZnFe
2O
4 +nNH
3+H
2O→［Zn(NH
3)n］
2++Fe
2O
3↓+2OH
-
Zn
2SiO
4 +2nNH
3→ 2［Zn(NH
3)n］
2+ + SiO
4 4-
ZnSiO
3+ nNH
3 +2NH
4HCO
3→［Zn(NH
3)n］CO
3+ SiO
2·H
2O+(NH
4)
2CO
3
Zn(OH)
2 +nNH
3 →［Zn(NH
3)n］
2++2OH
-
ZnCO
3+ nNH
3 →［Zn(NH
3)n］CO
3
Wherein n=1～4;
The reaction occurring in purification and impurity removal process:
S
2O
8 2-+ Mn
2++ 2NH
3·H
2O + H
2O→ Mn O（OH）
2↓ + 2NH
4 ++2SO
4 2-+ 2H
+
S
2O
8 2-+2Fe
2+ +6H
2O →2SO
4 2-+ 2Fe(OH)
3↓+ 6H
+
AsO
4 3- + Fe
3- → FeAsO
4↓
AsO
3 3- + S
2O
8 2-+ H
2O → 2SO
4 2- + AsO
4 3-+ 2H
+
2H
3AsO
3 + 8Fe(OH)
3 → (Fe
2O
3)
4As
2O
3·5H
2O↓ +10H
2O
M
2++ S
2→ MS ↓ M represents Cu
2+, Pb
2+, Cd
2+, Ni
2+hg
2+plasma
As
3+ + S
2-→As
2S
3↓
Y
2++ Zn → Zn
2+wherein Y representative of+Y: Cu
2+, Pb
2+, Cd
2+, Ni
2+plasma;
The reaction equation of ammonia still process step:
［Zn(NH
3)
i］
2++2OH
-= Zn(OH)
2↓+ iNH
3↑ i =1～4
［Zn(NH
3)
4］CO
3+H
2O→ZnCO
3·2Zn(OH)
2·H
2O↓+16NH
3↑
The chemical equation of drying and calcining:
Zn(OH)
2→ZnO + H
2O↑
ZnCO
3·2Zn(OH)
2·H
2O → 3ZnO +3H
2O↑ +CO
2↑
As preferably: be also added with the Dicyanodiamide of 0.5-1kg and the tensio-active agent of 0.03-0.05kg (SDS) in every cubic metre of ammoniacal liquor-ammonium fluid leaching agent.
Decreasing by surfactant surface energy, with Sodium Silicofluoride mating reaction, the coating function that can abolish ultrafine particulate improves leaching agent penetrating power, further improves the rate of recovery of zinc.
As preferably: the Dicyanodiamide that is added with 0.5-1kg at the leaching agent of every cubic metre.
Dicyanodiamide, as ammonia stablizer, can reduce the volatilization of ammonia in leaching process, improves Working environment, reduces the loss of ammonia.
As preferably: in the time of the pending low-grade zinc oxide ore of leaching, adopt ball milling, and guarantee that in ball mill, extraction time is 50～60 minutes, ball mill outlet material is all by 140 mesh sieves.
Utilize ball milling wet extraction, destroyed ore crystalline network (mechanical activation) and combined with the chemical activation of tensio-active agent and dry hydrate, reach higher leaching velocity and leaching yield.
As preferably: before purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid obtaining after leaching is heated to 95-105 ℃ and analyses ammonia, until c (NH in leaching liquid
3)≤3mol/L, is then oxidized completely by adding 2-4kg ammonium persulphate in the leaching liquid of every cubic metre and stirring.Type of heating adopts the mode of indirect heating.As c (NH
3when)≤3mol/L, zinc ammonia complex liquid approaches saturated, does not make zinc separate out simultaneously.
The reaction that pre-ammonia still process process occurs:
NH
3·H
2O+NH
4HCO
3 →2NH
3↑+CO
2↑+2H
2O
（NH
4）
4SiO
4→ SiO
2↓+ 2NH
3↑+2H
2O
Ammonium persulphate is as oxygenant, except impurity such as de-iron, manganese.
Increase pre-ammonia still process step, remove too much free ammonia on the one hand, reduced the complex ability of ammonia, because raise temperature, make silicate colloid and impurity thereof doubt coagulation and form sediment, thereby foreign ion is removed simultaneously, being beneficial to purification, is to make one of high purity product reason; Can remove on the other hand carbanions a large amount of in solution, in subsequent processing complex liquid deamination crystallisation process, be conducive to hydrolysis and obtain zinc hydroxide nucleus, reduce the composition of zinc carbonate, can make one of product reason that specific surface area is large.
As preferably: the wherein mixing ore deposit of one or more in smithsonite that described low-grade zinc oxide ore is is 8%～30% containing zinc massfraction, franklinite ore deposit, lapis calaminaris.
Two of object of the present invention, is to provide a kind of high purity and high performance zinc oxide, and the technical scheme adopting is: on aforesaid technical scheme basis, the temperature of drying and calcining adopts 250-350 ℃.
Due to technical scheme of the present invention, after ammonia still process crystallisation step, what obtain is mainly zinc hydroxide, the decomposition temperature of zinc hydroxide is lower than zinc subcarbonate, adopt the temperature of 250-350 ℃ to calcine, can obtain the zinc oxide product of purity at 99.7% above bigger serface, specific surface area>=60m
2/ g, low temperature calcination dispersiveness, mobility are all more excellent.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows: ammonia process is applied to the processing of low-grade zinc oxide ore, and existing ammonia process is carried out to adaptation, before leaching, increase activation step and in the time of leaching, added Sodium Silicofluoride, tensio-active agent and Dicyanodiamide, improved on the one hand zinc leaching velocity and the leaching yield in low-grade zinc oxide ore.On the other hand, the present invention preferably adopts lower calcining temperature, can obtain can reaching more than 99.7% compared with the zinc oxide while purity of bigger serface, has very high economic worth; In addition, treatment process energy consumption of the present invention is low, efficiency is high, leaching agent recycle.Soak slag through leaching the end of processing, do not destroy original mineral composition structure, still can brickmaking etc. have reached economic environmental protection dual purpose.
Embodiment
The present invention is described in detail below.
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
Raw material: Yunnan oxidized ore 1
#, its composition is: Zn15.48%. Fe18. 20%. Si027. 94%, its zinc thing coordinates and is divided into zinc carbonate 9.49%, zinc silicate 2. 12%. zinc sulphide 0. 7 3%, automolite 3.14 %.
Method for the preparation of high-purity zinc oxide:
(1) activation: get 500g oxidized ore 1
#, adding 15g white lime to obtain compound, and carry out admixture activation, in described compound, the quality percentage composition of water is controlled at 8%, and the admixture activation time is 36 hours;
(2) leaching: the low-grade zinc oxide ore after admixture activation is leached as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent
3volumetric molar concentration c (NH
3)=5.5mol/L, CO
3 2-volumetric molar concentration c (CO
3 2-)=1.2 mol/L adds Sodium Silicofluoride by the amount of adding 0.3kg Sodium Silicofluoride in every cubic metre of leaching agent in leaching agent; Adding up to leaching time is 3 hours, and temperature is 25-40 ℃; After solid-liquid separation, 69.7 grams, zinc in gained zinc ammonia complex liquid; The leaching yield of zinc oxide ore zinc is 90.1%;
(3) purification and impurity removal: add 2.1g potassium permanganate to stir 0.5h in gained zinc ammonia complex liquid, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of deposit C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filters, and filtrate adds KMnO
4consumption is 2.7 times of Fe amount, and 80 ℃ of temperature stir 1h (detecting Fe, Mn qualified), filter, and filtrate adds zinc powder by 2.5 times of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and temperature 60 C, filters, and obtains refined liquid;
(4) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process, vapour pressure import 0.5KMPa/cm in ammonia distiller
2, 105 ℃ of solution temperatures, until ［ Zn
2+when ］=1.5g/L, stop ammonia still process, the emulsion obtaining carries out solid-liquid separation, and filter cake is by the washing of liquid-solid ratio 5:1 clear water, and washing time 1h, refilters separation, obtains filter cake;
(5) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 400 ℃ of retort furnace calcining 40min, sampling detects and obtains purity ZnO%=99.72%, specific surface area 63m
2the high-purity zinc oxide powder of/g.
Embodiment 2
Raw material: oxidized ore 2
#, its composition is: Zn9.67%. Fe19.33%. Si026. 63%, its zinc thing of CaO28.34% coordinates and is divided into zinc carbonate 12.28%, zinc silicate 2. 37%. zinc sulphide 0. 8 2%, automolite 3. 20%.
Method for the preparation of high-purity zinc oxide:
(1) activation: get 500g oxidized ore 2
#, adding 25g white lime to obtain compound, and carry out admixture activation, in described compound, the quality percentage composition of water is controlled at 9%, and the admixture activation time is 36 hours;
(2) leaching: the low-grade zinc oxide ore after admixture activation is leached as leaching agent with 1500ml ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent
3volumetric molar concentration c (NH
3)=7mol/L, CO
3 2-volumetric molar concentration c (CO
3 2-)=1.2 mol/L, adds respectively Sodium Silicofluoride, SDS and Dicyanodiamide by the amount of Dicyanodiamide of the surfactant SDS, the 0.5kg that add 0.5kg Sodium Silicofluoride, 0.05kg in every cubic metre of leaching agent respectively; In the time of leaching, adopt ball milling, and guarantee that in ball mill, extraction time is 60 minutes, ball mill outlet material is all by 140 mesh sieves, and adding up to leaching time is 3 hours, and temperature is 25-40 ℃; 44.28 grams, zinc in gained zinc ammonia complex liquid; The leaching yield 91.58% of zinc oxide ore zinc;
(3) pre-ammonia still process: the leaching liquid obtaining after leaching is heated to 95 ℃ and analyses ammonia, until c (NH in leaching liquid
3)=2.8mol/L, then by adding 4kg ammonium persulphate in the leaching liquid of every cubic metre and stirring;
(4) purification and impurity removal: add 1.33g potassium permanganate to stir 0.5h in gained zinc ammonia complex liquid, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of deposit C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filters, and filtrate adds KMnO
4consumption is 3.5 times of Fe amount, and 80 ℃ of temperature stir 1h (detecting Fe, Mn qualified), filter, and filtrate adds zinc powder by 2.5 times of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and temperature 60 C, filters, and obtains refined liquid;
(5) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process, vapour pressure import 0.6KMPa/cm in ammonia distiller
2, 108 ℃ of solution temperatures, until ［ Zn
2+when ］=1.5g/L, stop ammonia still process, the emulsion obtaining carries out solid-liquid separation, and filter cake is by the washing of liquid-solid ratio 5:1 clear water, and washing time 1h, refilters separation, obtains filter cake;
(6) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 300 ℃ of retort furnace calcining 60min, sampling detects and obtains purity ZnO%=99.82%, specific surface area 68m
2the high-purity zinc oxide powder of/g.
Embodiment 3
Raw material: zinc oxide ore 3
#, its composition is: Zn13.6%. Fe18.67%. Si027.83%, its zinc thing of CaO29.92% coordinates and is divided into zinc carbonate 7.96%, zinc silicate 2. 21%. zinc sulphide 0.76%, automolite 2.67%.
Method for the preparation of high-purity zinc oxide:
(1) activation: get 1t zinc oxide ore 3
#, adding 40kg white lime to obtain compound, and carry out admixture activation, in described compound, the quality percentage composition of water is controlled at 10%, and the admixture activation time is 42 hours;
(2) leaching: the low-grade zinc oxide ore after admixture activation is leached as leaching agent with 3000L ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent
3volumetric molar concentration c (NH
3)=5.6mol/L, CO
3 2-volumetric molar concentration c (CO
3 2-)=1.05 mol/L, adds respectively Sodium Silicofluoride, SDS and Dicyanodiamide by the amount of Dicyanodiamide of the surfactant SDS, the 1kg that add 0.4kg Sodium Silicofluoride, 0.1kg in every cubic metre of leaching agent respectively; In the time of leaching, adopt ball milling, and guarantee that in ball mill, extraction time is 80 minutes, ball mill outlet material is all by 140 mesh sieves, and adding up to leaching time is 3.5 hours, and temperature is 25-40 ℃; 124.86 kilograms, zinc in gained zinc ammonia complex liquid, the zinc leaching rate 91.8% of low-grade zinc oxide;
(3) pre-ammonia still process: the leaching liquid obtaining after leaching is heated to 105 ℃ and analyses ammonia, until c (NH in leaching liquid
3)=2.6mol/L, then by adding 2kg ammonium persulphate in the leaching liquid of every cubic metre and stirring;
(4) purification and impurity removal: add 3.75kg potassium permanganate to stir 0.8h, add a small amount of polyacrylamide solution (4mg/L) to filter, filtrate adds sodium sulphite by 1.2 times of the theoretical amount of deposit C u, Cd, the required sodium sulphite of Pb, temperature, 70 ℃, churning time 2h, filter, filtrate adds KMnO
4consumption is 3.5 times of Fe amount, and 80 ℃ of temperature stir 1h (detecting Fe, Mn qualified), filter, and filtrate adds zinc powder by 2.5 times of displacement Cu, Cd, the required theoretical zinc powder of Pb, stirs 30min, and temperature 60 C, filters, and obtains refined liquid;
(5) ammonia still process crystallization: gained refined liquid is inserted and carried out ammonia still process, vapour pressure import 0.8KMPa/cm in ammonia distiller
2, 108 ℃ of solution temperatures, until ［ Zn
2+when ］=1.5g/L, stop ammonia still process, the emulsion obtaining carries out solid-liquid separation, and filter cake is by the washing of liquid-solid ratio 5:1 clear water, and washing time 1h, refilters separation, obtains filter cake;
(6) drying and calcining: 105 ℃ of filter cakes are dry, obtain powder, through 250 ℃ of retort furnace calcining 80min, sampling detects and obtains purity ZnO%=99.86%, specific surface area 78m
2the high-purity zinc oxide powder of/g.
Claims (7)
1. utilize low-grade zinc oxide ore to produce a method for high-purity zinc oxide, comprise the following steps:
Leaching low-grade zinc oxide ore, purification and impurity removal, ammonia still process crystallization and drying and calcining, is characterized in that:
Before leaching low-grade zinc oxide ore step, in pending low-grade zinc oxide ore, add white lime to obtain compound, and carry out admixture activation, the amount of the white lime adding, by weight, for the 3-5% of low-grade zinc oxide ore, in described compound, the quality percentage composition of water is controlled at 8-10%;
Low-grade zinc oxide ore after admixture activation is leached as leaching agent with ammoniacal liquor-ammonium fluid; Wherein, NH in described leaching agent
3volumetric molar concentration c (NH
3)=5.5-7mol/L, CO
3 2-volumetric molar concentration c (CO
3 2-)=0.95-1.2 mol/L adds 0.3-0.5kg Sodium Silicofluoride in every cubic metre of leaching agent.
2. a kind of low-grade zinc oxide ore that utilizes is produced the method for high-purity zinc oxide according to claim 1, it is characterized in that: the tensio-active agent that is also added with 0.05-0.1kg in every cubic metre of leaching agent.
3. a kind of low-grade zinc oxide ore that utilizes is produced the method for high-purity zinc oxide according to claim 2, it is characterized in that: the Dicyanodiamide that is added with 0.5-1kg at the leaching agent of every cubic metre.
4. a kind of low-grade zinc oxide ore that utilizes is produced the method for high-purity zinc oxide according to claim 1, it is characterized in that: in the time leaching pending low-grade zinc oxide ore, adopt ball milling, and guaranteeing that in ball mill, extraction time is 50～60 minutes, ball mill outlet material is all by 140 mesh sieves.
5. a kind of low-grade zinc oxide ore that utilizes is produced the method for high-purity zinc oxide according to claim 1, it is characterized in that: before purification and impurity removal step, carry out pre-ammonia still process, method is: the leaching liquid obtaining after leaching is heated to 95-105 ℃ and analyses ammonia, until c (NH in leaching liquid
3)≤3mol/L, then by adding 2-4kg ammonium persulphate in the leaching liquid of every cubic metre and stirring.
6. a kind of low-grade zinc oxide ore that utilizes is produced the method for high-purity zinc oxide according to claim 1, it is characterized in that: the wherein mixing ore deposit of one or more in smithsonite that described low-grade zinc oxide ore is is 8%～30% containing zinc massfraction, franklinite ore deposit, lapis calaminaris.
7. a kind of low-grade zinc oxide ore that utilizes is produced the method for high-purity zinc oxide according to claim 1, it is characterized in that: the temperature of described drying and calcining is 250-350 ℃.
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