CN102838160A - Method utilizing low-grage zinc oxide mine compound waste gypsum to produce nanometer lithopone - Google Patents
Method utilizing low-grage zinc oxide mine compound waste gypsum to produce nanometer lithopone Download PDFInfo
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- CN102838160A CN102838160A CN2012103579553A CN201210357955A CN102838160A CN 102838160 A CN102838160 A CN 102838160A CN 2012103579553 A CN2012103579553 A CN 2012103579553A CN 201210357955 A CN201210357955 A CN 201210357955A CN 102838160 A CN102838160 A CN 102838160A
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Abstract
The invention discloses a method utilizing low-grage zinc oxide mine compound waste gypsum to produce nanometer lithopone. The method comprises the following specific steps of: soaking, purifying, carrying out a metathetical reaction, washing and smashing, leaching out zinc through an ammonia-ammonium sulfate method in a selective manner, and combining an ammonium persulfate deferrization, arsenic removal and sulfurization method and a zinc dust replacement method to remove heavy metal elements such as nickel, copper, lead and cadmium; and carrying out replacement reaction to obtain an nZnS-BaSO4 superfine crystalline press cake, and drying and smashing the crystalline press cake to obtain a nanometer lithopone product. According to the invention, the quality of the lithopone product is good, a zinc raw material used for production is provided by a low-grage zinc oxide mine, and sulfate radical is provided by waste gypsum; and zinc in the low-grage zinc oxide is recycled, resource utilization of the waste gypsum is realized, the waste is changed into wealth, the production cost is low, and the operation is simple.
Description
Technical field
The present invention relates to the production technique of mineral dye zinc sulfide white, be specifically related to a kind of low-grade zinc oxide ore that utilizes and be equipped with the method that waste gypsum is produced nano level zinc sulfide white.
Background technology
Mineral dye zinc sulfide white is also claimed lithopone; It is the mixed crystal of zinc sulphide and permanent white; Have many uniquenesses and good performance; The zinc sulfide white product has formed series product, like high ZnS type, apparent processing type, aqueous dispersion type, sun-proof type, color-type etc., in industrial and agricultural production and daily life, is bringing into play important effect.Be mainly used in coating, paint, thermoplastics, thermosetting resin, paper etc., through surface treatment or TiO
2Coating can the instead of part rutile.
Zinc sulfide white is mainly produced in China at present, and the production overwhelming majority of domestic zinc sulfide white also is to use traditional method, and main raw material is secondary zinc oxide, sulfuric acid and barium sulphide (tiff and coal make through high temperature reduction), uses raw material generally to contain zinc 45%～70%.It is to be that raw material leaches with sulfuric acid to contain zinc 45% above zinc baking sand that the tradition method is produced the zinc sulfide white flow process; Obtain the thick liquid of zinc sulfate; Use potassium permanganate oxidation deironing etc. then; Use the zinc dust precipitation heavy metal again, filter and to obtain the zinc sulfate refined liquid, carry out replacement(metathesis)reaction, press filtration, calcining, rinsing, drying, pulverizing with barium sulphide again and obtain Containing Sulfur zinc dissimilar zinc sulfide white series product more than 30%.Whole process is carried out in acid (PH＜7) environment, consumes a large amount of sulfuric acid, and sulfuric acid has intensive corrodibility; Production unit is required height, and the slag of discharging at last is an acid slag, brings new pollution to environment; And high to ingredient requirement, production cost is high, resulting poor product quality.
Along with development of science and technology, various pigment arise at the historic moment, and mineral dye is being faced with serious challenge, and nano material is the one type of type material with the sight dimension yardstick that is situated between that grows up for 20 end of the centurys, just develops with compound direction towards low dimension at present.Nanometer zinc sulfide white has dropped into industrial production in recent years; It is identical with traditional method that solution of zinc sulfate makes; In organic phase (like benzene etc.), carry out when synthetic, production cost is high, and waste water is difficult to recycle; Production process organic solvent and end soak slag and cause the pollution to environment easily, and its development receives serious limit.
In addition, along with the demand of zn cpds and zinc sulfide white is increasing, the continuous exploitation of China's zinc resource, Mineral resources are poor day by day, thin, assorted, and comprehensive utilization and environmental requirement improve constantly, and people have begun one's study and have hanged down the recovery and utilization technology of zinc raw material.So-called low zinc raw material is mainly low-grade zinc oxide ore.But because the low grade oxidation ore complicated component, the less unsuitable comprehensive extraction and application of other valuable metal (like lead, copper etc.) content, flotation is difficult, and beneficiating efficiency is low, beneficiation cost is high, and flotation mud, sewage, institute's adding medicine are big for environment pollution.And the pyrometallurgical smelting recovery is low, and energy consumption is high, and the product grade of recovery is low; Impurity is high; Deficiency in economic performance, atmospheric pollution are also big and receive the repulsion of national industrial policies, so the ore dressing of low-grade zinc oxide ore, processing and utilization are long-standing great technical barriers both at home and abroad.
In sum, how in the zinc oxide ore of low zinc content, effectively to leach zinc wherein, obtain high-quality nano level zinc sulfide white, overcome the shortcoming that traditional zinc sulfide white is produced simultaneously, become the industry and need to be resolved hurrily and unsolved technical barrier.
Summary of the invention
ThisThe purpose of invention is to overcome the defective that above-mentioned prior art exists; Design a kind of method of utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white; Be used for the zinc of low-grade zinc oxide ore and the sulfate radical in the waste gypsum are recycled; Under ammonia property environment, produce that zinc sulphide and barium sulfate content are high, quality is good, particle diameter is nano level zinc sulfide white.
For realizing above-mentioned purpose, technical scheme of the present invention comprises the steps:
1) leach: low-grade zinc oxide ore and waste gypsum mix, and raw material mass mixture ratio is pressed c (Zn
2+): (SO
4 2-)=0.7～3:1, with ammoniacal liquor-ammonium sulfate liquid leaching, ammonia concn is that 5.0～7.0mol/L, ammonium sulfate concentrations are 0～1mol/L, is under 20～50 ℃ in temperature, leaches 3h～9h, the whole immersion liquid of gained is used for subsequent processing;
The leaching reaction equation is:
ZnO +n NH
3+H
2O+CaSO
4 →［Zn NH
3)n］SO
4 + Ca(OH)
2↓
Zn(OH)
2+ n NH
3 +CaSO
4→［Zn NH
3)n］SO
4 + Ca(OH)
2↓
ZnSO
4 + n NH
3→［Zn(NH
3)n］
2++SO
4 2-
ZnFe
2O
4 +n NH
3+4H
2O+CaSO
4→［Zn(NH
3)n］SO
4+2Fe(OH)
3 ↓+ Ca(OH)
2↓
Zn
2SiO
4+2n NH
3 +2H
2O → 2［Zn(NH
3)n］(OH )
2+ SiO
2 ↓
CaSO
4
+ 2 NH
3
·H
2
O → （NH
4
）
2
SO
4
+ Ca(OH)
2
↓
CaSO
4
+ 2 OH
-
→ SO
4
2-
+ Ca(OH)
2
↓
N=1～4 wherein
2) purify: in whole immersion liquid, add ammonium persulphate and carry out disposable iron removal by oxidation; And add the co-precipitation of charcoal absorption arsenic iron and reach the arsenic removal purpose, add SEPIGEL 305 flocculation agent filtering separation before separating, add Sodium Sulphide in the solution after the once oxidation removal of impurities and vulcanize removal of impurities; Filtrating after the sulfuration that separation obtains is replaced with zinc powder; Remove remaining impurity, obtain zinc sulfate ammonia complex liquid, be used for subsequent processing;
Reaction equation is:
5(NH
4)
2S
2O
8+2Mn
2++ 8H
2O → 2NH
4MnO
4+ 4(NH
4)
2SO
4 +16H
++ 6SO
4 2-
S
2O
8 2-+ Mn
2++ 2 NH
3·H
2O + H
2O→MnO(OH)
2↓+2NH
4 2++2SO
4 2-+ 2H
+
S
2O
8 2-+2Fe
2+ +6 NH
3·H
2O →2 SO
4 2-+ 2Fe(OH)
3↓+6NH
4 +
As
2O
3 +3H
2O → 2H
3AsO
3
2H
3AsO
3 + 8Fe(OH)
3 → (Fe
2O
3)
4As
2O
3·5H
2O↓+10H
2O
AsO
4 3- + Fe
3- → FeAsO
4↓
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↓
3) replacement(metathesis)reaction: Sodium Sulphide is dissolved in obtains replacement(metathesis)reaction clear liquid in the zero(ppm) water; And the adding nonionogenic tenside stirs; Slowly it is added in the zinc sulfate ammonia complex liquid then replacement(metathesis)reaction takes place, obtain zinc sulfide white emulsion, filtering separation; Ammoniacal liquor after the separation returns leaching, isolating nZnS-BaSO after transferring ammonia
4The xln filter cake gets into subsequent processing;
［Zn(NH
3)n］SO
4 +BaS→ZnS ↓+ BaSO
4 ↓+nNH
3
［Zn(NH
3)n］(OH )
2+ H
2S → ZnS ↓+2H
2O +nNH
3
4) washing is pulverized: with zero(ppm) water or washing with alcohol nZnS-BaSO
4The xln filter cake, the nZnS-BaSO of filtering separation after the washing
4The xln filter cake carries out drying and crushing, obtains nanometer zinc sulfide white product.
Leach in the step, the zinc massfraction is 5%～35% in the said low-grade zinc oxide ore, and the calcium sulfate massfraction is more than 80% in the waste gypsum.In purifying step, behind the adding ammonium persulphate once oxidation, add the SEPIGEL 305 flocculation agent before the filtering separation in the whole immersion liquid.Be used for flocculation and produce arsenic, iron co-precipitation, remove harmful element.
Preferred version has: in leaching step, add the X 2073 of 0.05kg～0.1kg in ammoniacal liquor-ammoniumsulphate soln of every cubic metre, X 2073 reduces the solution surface ability.
In leaching step, add 0.3～0.5kg Sodium Silicofluoride 98min in ammoniacal liquor-ammoniumsulphate soln of every cubic metre.Add an amount of silicofluoric acid and receive and can abolish one type of ultrafine particulate such as calcium hydroxide that calcium sulfate generates in the switching process of ammonia solution, realize ultrafine particulate delamination come-up containing zinc particulate parcel, thus zinc is exposed, realize soaking molten.
In leaching step, the Dicyanodiamide of adding 0.5～1kg in ammoniacal liquor-ammoniumsulphate soln of every cubic metre through adding Dicyanodiamide, reduces the volatilization of ammonia in the technological process, improves Working environment, reduces the loss waste of ammonia.
The Sodium Sulphide that adds in the purifying step is included as the wherein any or mixture of sodium sulphite, ammonium sulfide or hydrogen sulfide.Most Cu are removed in sulfuration
2+, Pb
2+, Cd
2+, Ni
2+, Hg
2+Etc. heavy metal ion.
Sulfide in the said replacement(metathesis)reaction step is barium sulphide, sodium sulphite, ammonium sulfide or hydrogen sulfide.Nonionogenic tenside is OP-10, is the condenses of NP and oxyethane, and add-on is to add 0.15～0.2kg in every cubic metre the replacement(metathesis)reaction liquid, and 10～40 ℃ of temperature of reaction, stirring velocity are 10～15m/s, chemical combination time 0.5～1h.The adding of nonionogenic tenside utilizes nZnS-BaSO4 fine crystalline nucleation, well is dispersed because nonionogenic tenside has, and can effectively suppress the growth of nucleus.
As preferably: nonionogenic tenside is OP-10; Be the condenses of NP and oxyethane, add-on is to add 0.15～0.2kg, 10～40 ℃ of temperature of reaction in every cubic metre the replacement(metathesis)reaction liquid; Stirring velocity is 10～15m/s, chemical combination time 0.5～1h.
Further: also be added with SDS, form mixed surfactant with OP-10.
Optimized technical scheme also has, and in the zinc sulfide white emulsion of replacement(metathesis)reaction step, adds H
2O
2,Add H
2O
2Massfraction be 10～33%, make zinc sulfide white emulsion desulfurization (being mainly sulfur hydrogen anion ion or elemental sulfur), slowly add H
2O
2Be the water white transparency shape until zinc sulfide white emulsion.Resulting sulfate ion is used for this production technique once more.
Chemical equation is: 4H
2O
2+ HS
-+ OH
-→ SO
4 2-+ 5H
2O
3H
2O
2 + S+ 2OH
- → SO
4 2- + 4H
2O
Advantage of the present invention and beneficial effect are:
First; Ammonia leaching process is as the effective Treatment Technology means of low-grade zinc oxide ore; Under weakly alkaline (PH=8.5～10) ammonia property environment, produce nanometer zinc sulfide white; The oxyhydroxide solubleness of some metallic impurity such as Ca, Mg, Fe, Al is low, and the impurity that in the ammonia-ammonia sulfate selectivity leaches, gets in the whole immersion liquid reduces, thereby guarantees the quality of product; The classical acid legal system is equipped with zinc sulfide white because in the roasting of zinc baking sand, Sodium Sulphide and reduction process, more or less can produce simple substance sulphur and sulphite; It is yellow partially to produce the zinc sulfide white whiteness difference color that obtains; And this patent replacement(metathesis)reaction is carried out in ammonia solution (alkalescence); What oxidation products obtained is sulfate radical, through adding H
2O
2Desulfurization fast, thoroughly needn't just can guarantee the whiteness of product through high-temperature calcination; Lower than the sulfuric acid leaching to equipment requirements, the ordinary steel leaching vat can be accomplished leaching; Solved the low grade oxidation ore complicated component, flotation difficulty, problem such as beneficiating efficiency is low, beneficiation cost is high, and flotation mud, sewage, institute's adding medicine are big for environment pollution realizes the recycling of high value metals zinc.
The second, the present invention provides a large industrialized production technique that production cost is low, efficient, energy-conservation, the constant product quality yearly capacity reaches few hundred thousand tonnes of.Leach zinc through the ammonia process selectivity, and combine ammonium persulphate deironing, sulfuration method and zinc replacement to remove heavy metal elements such as nickel, copper, lead, cadmium, arsenic, replacement(metathesis)reaction obtains nZnS-BaSO
4Fine crystalline body filter cake, convection drying, pulverizing xln without high-temperature calcination, the nanometer zinc sulfide white product that obtains.The products obtained therefrom quality is good, and industry is workable.
The 3rd, be the low-grade zinc oxide raw ore because the present invention produces the zinc raw material of used needs, price is relatively low.Sulfate radical is provided by waste gypsum, and about 2,500 ten thousand tons of the annual discharging of domestic production phosphate fertilizer waste gypsum because using value is little, is generally stacked on the spot or flooded, and poses a big pressure to environment.Utilize waste gypsum to make feedstock production nanometer zinc sulfide white product, both waste gypsum had been realized recycling, make a silk purse out of a sow's ear, simple to operate, again the acid soil of waste gypsum is administered and improved, purified environment.In ammonia gonosome system, carry out during chemical combination, the ammoniacal liquor after synthetic the separation returns leaching, and whole process of production does not have waste water, and the waste residue of production reaches the general solid waste discharge standard of country and effluxes, and is environmental protection " green " type technology.
Embodiment
Below in conjunction with embodiment, specific embodiments of the invention further describes.Following examples only are used for technical scheme of the present invention more clearly is described, and can not limit protection scope of the present invention with this.
Embodiment 1
Get low-grade zinc oxide ore, be staple by quality ratio: Zn21.15%, Fe18.20%, Si0
27.94%, its zinc thing coordinates and is divided into zinc carbonate 13.86%, zinc silicate 2.82%, zinc sulphide 0.73%, franklinite 3.74%.Get the calcium sulfate massfraction and be 93% waste gypsum.
1. leach: produce 1500ml ammoniacal liquor-ammoniumsulphate soln as ammonia leaching solution; Wherein ammonia concn is that 7.0mol/L, ammonium sulfate volumetric molar concentration are 0.5mol/L, adds X 2073, the 0. 5kg Sodium Silicofluoride 98min of 0.05kg, the Dicyanodiamide of 0.5kg by every cubic metre of ammonia leaching solution.Getting zinc oxide ore 3720 gram mixes with waste gypsum 1280 grams and (records the quality proportioning and be ［ Zn
2+］: ［ SO
4 2-］=2.9:1) joins carries out three sections leachings in the above-mentioned ammonia-ammonia sulfate immersion liquid, each section leaching time is 3 hours, after the solid-liquid separation; Obtain the whole immersion liquid (taking away in all the other liquid slags) of 1450ml; Zinc leaching rate 90.02%, the composition of the whole immersion liquid of gained is: Zn83.94 g/L, SO
4 2-88.36 g/L, Pb 1.18 g/L, Cu 0.33 g/L, Cd 0.24 g/L, Fe 0.69 g/L.
2. the preparation of zinc sulfide white: get above-mentioned whole immersion liquid 1000ml in the 2000ml beaker, be heated to 98 ℃, add the 4g ammonium persulphate again and use magnetic stirrer 0.5h; Behind the once oxidation in the solution; Add polyacrylamide solution, the polyacrylamide solution volume is 0.02 ‰, a 1h after-filtration of liquor capacity; Gained filtrating obtains the refining complex liquid of zinc sulfate ammonia behind sulfuration removal of impurities, zinc dust precipitation.
Getting 155.9g barium sulphide (not moisture) and 28.4g sodium sulphite (not moisture) mixes to be dissolved in and obtains replacement(metathesis)reaction liquid in the zero(ppm) water; In this solution, add nonionogenic tenside OP-10 (being the condenses of NP and oxyethane) 0.18g; 25 ℃ of temperature of reaction, stirring velocity are 13m/s, fully stir the 30min mixing; Slowly join then in the refining complex liquid of 1000ml zinc sulfate ammonia, adding massfraction behind the continuation stirring 30min is 10%H
2O
2Desulfurization bleaching, the bleaching after-filtration separate nZnS-BaSO
4The xln filter cake.
Use washing with alcohol nZnS-BaSO
4The xln filter cake; The washing after-filtration, filter cake is pulverized behind 105 ℃ of dry 1h of loft drier, detects zinc, barium productive rate with atomic absorption; Reach 97.6% in zinc; Reach 99% in barium, detect by National Standard Method: the quality product mark reaches 99.4% with zinc sulphide and permanent white summation, and the ZnS massfraction accounts for 38.6%.Barium sulphide particle diameter ratio zinc sulphide particle diameter is big, is respectively 78nm and 32nm, and each item indexs such as tinting strength, oil-absorption(number) surpass GB GB/T1707-1995 B311 type product.
Embodiment 2
Get low-grade zinc oxide ore, calculate according to mass ratio, its composition is: Zn13.6%, Fe19.33%, Si0
26.63%, CaO28.34%, its zinc thing coordinate and are divided into zinc carbonate 10.61%, zinc silicate 1.47%, zinc sulphide 0.42%, automolite 1.10%.Get and contain CaSO
4Massfraction is 89% waste gypsum.
1. leach: produce 1500ml ammoniacal liquor-ammoniumsulphate soln as ammonia leaching solution; Wherein ammonia concn is that 7.0mol/L, ammonium sulfate volumetric molar concentration are 0.3mol/L, adds X 2073, the 0.3kg Sodium Silicofluoride 98min of 0.1kg, the Dicyanodiamide of 1.0kg by every cubic metre of ammonia leaching solution.Zinc oxide ore 3880 grams mix with waste gypsum 1120 grams and (record the quality proportioning and be ［ Zn
2+］: ［ SO
4 2-］=2.0:1) joins and carries out three sections leachings in the above-mentioned ammonia-ammonia sulfate immersion liquid, and each section leaching time is 2 hours, after the solid-liquid separation, obtains the whole immersion liquid (taking away in all the other liquid slags) of 1450ml, zinc leaching rate 89.3%; The composition of whole immersion liquid is: Zn69.45 g/L, SO
4 2-67.8 g/L, Pb 0.98 g/L, Cu 0.09 g/L, Cd 0.61 g/L, Fe0.37 g/L.
2. the preparation of zinc sulfide white: get above-mentioned whole immersion liquid 1000ml in the 2000ml beaker, be heated to 98 ℃, add the 4g ammonium persulphate again and use magnetic stirrer 0.5h; Behind the once oxidation in the solution; Add polyacrylamide solution, the polyacrylamide solution volume is 0.02 ‰, a 1h after-filtration of liquor capacity; Gained filtrating obtains the refining complex liquid of zinc sulfate ammonia behind sulfuration removal of impurities, zinc dust precipitation.
Getting 119.6g barium sulphide (not moisture) and 27.8g sodium sulphite (not moisture) mixes to be dissolved in and obtains replacement(metathesis)reaction liquid in the zero(ppm) water; In this solution, add nonionogenic tenside OP-10 (being the condenses of NP and oxyethane) 0.15g; 10 ℃ of temperature of reaction, stirring velocity are 10m/s, fully stir the 60min mixing; Slowly join then in the refining complex liquid of 1000ml zinc sulfate ammonia, adding massfraction behind the continuation stirring 30min is 20%H
2O
2Desulfurization bleaching, the bleaching after-filtration separate nZnS-BaSO
4The xln filter cake.
Use washing with alcohol nZnS-BaSO
4The xln filter cake; The washing after-filtration, filter cake is pulverized behind 105 ℃ of dry 1h of loft drier, detects zinc, barium productive rate with atomic absorption; Reach 98.2% in zinc; Reach 98.9% in barium, detect by National Standard Method: the quality product mark reaches 99.3% with zinc sulphide and permanent white summation, and the ZnS massfraction accounts for 38.6%.Barium sulphide particle diameter ratio zinc sulphide particle diameter is big, is respectively 91nm and 33nm, and each item indexs such as tinting strength, oil-absorption(number) surpass GB GB/T1707-1995 B311 type product.
Embodiment 3
Get low-grade zinc oxide ore, calculate according to mass ratio, its composition is: Zn8.62%, Fe18.67%, Si027.83%, CaO29.92%, its zinc thing coordinate and are divided into zinc carbonate 4.98%, zinc silicate 1.61%, zinc sulphide 0.66%, automolite 1.37%.Get that to contain the CaSO4 massfraction be 95% waste gypsum.
1. leach: produce 1500ml ammoniacal liquor-ammoniumsulphate soln as ammonia leaching solution; Wherein ammonia concn is that 6.0mol/L, ammonium sulfate volumetric molar concentration are 0.9mol/L, adds X 2073, the 0.45g Sodium Silicofluoride 98min of 0.075g, the Dicyanodiamide of 0.75g by every cubic metre of ammonia leaching solution.Getting butt zinc oxide ore 4020 gram mixes with waste gypsum 980 grams and (records the quality proportioning and be ［ Zn
2+］: ［ SO
4 2-］=1.1:1) joins and carries out three sections leachings in the above-mentioned ammonia-ammonia sulfate immersion liquid, and each section leaching time is 2 hours, after the solid-liquid separation, obtains the whole immersion liquid (taking away in all the other liquid slags) of 1450ml, zinc leaching rate 88.76%; Washing back clear liquid is as joining ammoniacal liquor or inhaling ammonia and recycle, and whole immersion liquid composition is: Zn62.03 g/L, SO
4 2-75.83 g/L, Pb 1.37 g/L, Cu 0.15 g/L, Cd 0.31 g/L, Fe 0.43 g/L.
2. the preparation of zinc sulfide white: get above-mentioned whole immersion liquid 1000ml in the 2000ml beaker, be heated to 98 ℃, add the 4g ammonium persulphate again and use magnetic stirrer 0.5h; Behind the once oxidation in the solution; Add polyacrylamide solution, the polyacrylamide solution volume is 0.02 ‰, a 1h after-filtration of liquor capacity; Gained filtrating obtains the refining complex liquid of zinc sulfate ammonia behind sulfuration removal of impurities, zinc dust precipitation.
133.8g mixing to be dissolved in, barium sulphide (not moisture) and 12.8g sodium sulphite (not moisture) obtains replacement(metathesis)reaction liquid in the zero(ppm) water; In this solution, add nonionogenic tenside OP-10 (being the condenses of NP and oxyethane) 0.2g; 40 ℃ of temperature of reaction, stirring velocity are 15m/s, fully stir the 40min mixing; Slowly join then in the refining complex liquid of 1000ml zinc sulfate ammonia, adding massfraction behind the continuation stirring 30min is 30%H
2O
2Desulfurization bleaching, the bleaching after-filtration separate nZnS-BaSO
4The xln filter cake.
Use washing with alcohol nZnS-BaSO
4The xln filter cake; The washing after-filtration, filter cake is pulverized behind 105 ℃ of dry 1h of loft drier, detects zinc, barium productive rate with atomic absorption; Reach 98.2% in zinc; Reach 99% in barium, detect by National Standard Method: the quality product mark reaches 99.1% with zinc sulphide and permanent white summation, and the ZnS massfraction accounts for 33.4%.Barium sulphide particle diameter ratio zinc sulphide particle diameter is big, is respectively 84nm and 38nm, and each item indexs such as tinting strength, oil-absorption(number) surpass GB GB/T1707-1995 B311 type product.
Claims (9)
1. method of utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white is characterized in that concrete steps are following:
1) leach: low-grade zinc oxide ore and waste gypsum mix, and raw material mass mixture ratio is pressed c (Zn
2+): (SO
4 2-)=0.7～3:1, with ammoniacal liquor-ammonium sulfate liquid leaching, ammonia concn is that 5.0～7.0mol/L, ammonium sulfate concentrations are 0～1.0mol/L, is under 20～50 ℃ in temperature, leaches 3h ~ 9h, the whole immersion liquid of gained is used for subsequent processing;
2) purify: in whole immersion liquid, add ammonium persulphate and carry out disposable iron removal by oxidation; And add the co-precipitation of charcoal absorption arsenic iron, and add SEPIGEL 305 flocculation agent filtering separation before separating, add Sodium Sulphide in the solution after the once oxidation removal of impurities and vulcanize removal of impurities; Filtrating after the sulfuration that separation obtains is replaced with zinc powder; Remove remaining impurity, obtain zinc sulfate ammonia complex liquid, be used for subsequent processing;
3) replacement(metathesis)reaction: Sodium Sulphide is dissolved in obtains replacement(metathesis)reaction clear liquid in the zero(ppm) water; And the adding nonionogenic tenside stirs; Slowly it is added in the zinc sulfate ammonia complex liquid then replacement(metathesis)reaction takes place, obtain zinc sulfide white emulsion, add H again
2O
2The oxidation sweetening bleaching, filtering separation, the ammoniacal liquor after the separation returns leaching, isolating nZnS-BaSO after transferring ammonia
4The xln filter cake gets into subsequent processing;
4) washing is pulverized: with zero(ppm) water or washing with alcohol nZnS-BaSO
4The xln filter cake, the nZnS-BaSO of filtering separation after the washing
4The xln filter cake carries out drying and crushing, obtains nanometer zinc sulfide white product.
2. the method for utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white as claimed in claim 1 is characterized in that, in leaching step, adds the X 2073 of 0.05kg～0.1kg in every cubic metre the ammonia-ammonia sulfate solution.
3. the method for utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white as claimed in claim 1 is characterized in that, in leaching step, adds 0.3～0.5kg Sodium Silicofluoride 98min in every cubic metre the ammonia-ammonia sulfate solution.
4. the method for utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white as claimed in claim 1 is characterized in that, in leaching step, and the Dicyanodiamide of adding 0.5～1kg in every cubic metre the ammonia-ammonia sulfate solution.
5. the method for utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white as claimed in claim 1 is characterized in that, the Sodium Sulphide that adds in the purifying step is included as the wherein any or mixture of sodium sulphite, ammonium sulfide or hydrogen sulfide.
6. the method for utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white as claimed in claim 5 is characterized in that the sulfide in the said replacement(metathesis)reaction step is barium sulphide, sodium sulphite, ammonium sulfide or hydrogen sulfide.
7. the method for utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white as claimed in claim 6; It is characterized in that nonionogenic tenside is OP-10, be the condenses of NP and oxyethane; Add-on is to add 0.15～0.2kg in every cubic metre the replacement(metathesis)reaction liquid; 10～40 ℃ of temperature of reaction, stirring velocity are 10～15m/s, chemical combination time 0.5～1h.
8. the method for utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white as claimed in claim 7 is characterized in that: also be added with SDS, form mixed surfactant with OP-10.
9. like each described method of utilizing low-grade zinc oxide ore to join waste gypsum production nanometer zinc sulfide white of claim 1 to 7, it is characterized in that, in the zinc sulfide white emulsion of replacement(metathesis)reaction step, add H
2O
2
Priority Applications (1)
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| WO2014047765A1 (en) * | 2012-09-25 | 2014-04-03 | 四川巨宏科技有限公司 | Method for producing nanometer lithopone from low-grade zinc oxide ore compound waste gypsum |
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| EP0109486A2 (en) * | 1982-08-02 | 1984-05-30 | The B.F. GOODRICH Company | Recovery of components of a binary azeotrope |
| CN101538648A (en) * | 2009-03-13 | 2009-09-23 | 昆明理工大学 | Method for activating ammonia leaching for high calcium-magnesium zinc oxide ore |
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| EP0109486A2 (en) * | 1982-08-02 | 1984-05-30 | The B.F. GOODRICH Company | Recovery of components of a binary azeotrope |
| CN101760613A (en) * | 2008-12-02 | 2010-06-30 | 中国恩菲工程技术有限公司 | Method for leaching zinc-containing ores |
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| WO2014047765A1 (en) * | 2012-09-25 | 2014-04-03 | 四川巨宏科技有限公司 | Method for producing nanometer lithopone from low-grade zinc oxide ore compound waste gypsum |
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