CN1827803A - Iron slag free wet-method zinc smelting and indium extracting method and method for preparing zinc ferrite - Google Patents
Iron slag free wet-method zinc smelting and indium extracting method and method for preparing zinc ferrite Download PDFInfo
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Abstract
The invention relates the non iron slag wet method for zinc metallurgy, refining indium and preparing ferrous acid zinc. In hydrochloric acid system the invention treats middle dipping slag and high dipping slag in which the zinc is removed to refine indium, and then uses the iron and zinc as raw material to make ferrous acid zinc. The method comprises high temperature highly acid deacidizing dipping, removing copper, extracting zinc and indium, displacement indium, extracting iron, deposition and preparing ferrous acid zinc. The method comprises the following characters: canceling the deferrization course, and using all iron and little zinc to make the ferrous acid zinc; refining indium from deacidizing liquid, simplifying the indium reclamation technology, improving recovery ratio, and removing low concentration sulfur dioxide smoke gas and iron slag; high metal leaching ratio when treating middle dipping slag and high dipping slag in hydrochloric acid system, and easy separating and purifying iron and zinc. The invention is important to prepare the high-grade material product, such as ferrous acid zinc, and manganese-zinc soft magnetic ferrite.
Description
[technical field] the present invention relates to the method that hydrometallurgy and material preparation method, particularly slag-free zinc hydrometallurgy are carried indium and produced zinc ferrite.
The method for removing iron that the zinc hydrometallurgy hot acid extract technology that [background technology] is traditional adopts has jarosite process, goethite process, hematite process etc., produces a large amount of scums, and environmental pollution is serious.In China, mostly adopt the jarosite process deironing, its iron level is low, the quantity of slag big, poor stability.Processing for the very high indium zinc ore concentrate of iron content also is to adopt this method, and in order to reclaim indium, iron vitriol slag must further be handled.Earlier with iron vitriol slag drying, reduction volatilization enrichment, from flue dust, reclaim indium as patent ZL99106190 then.Indium, zinc recovery are low, respectively less than 60% and 85%, produce the sulfurous gas and the oxidation scum of big volume low-concentration simultaneously, contaminate environment.For this reason, people such as Tang Motang have proposed the slag-free zinc hydrometallurgy novel process, this method will be soaked the raw material of slag as Mn-Zn soft magnetic ferrite in the conventional wet smelting process, reclaim indium and zinc when producing the coprecipitated powder of soft magnetism, and indium, zinc recovery improve respectively more than 25% and 8%.But problems such as this technology remains in separation of iron zinc and deep purifying difficulty thereof, and logistics capacity is big.
Zinc ferrite has spinel structure, has purposes widely.It not only can be used as the raw material of magneticsubstance, and is a kind of good sweetening agent and better heat-resisting pigment, can also use as catalytic material and absorbing material.But the traditional preparation process method of zinc ferrite is promptly even with pure iron oxide and zinc oxide ground and mixed in proportion based on dry method, calcines down at 900 ℃ then and makes the cost height in 2～4 hours; Nanometer zinc ferrite is produced with wet method, is raw material with pure zinc salt and molysite, and cost is higher.
[summary of the invention] the purpose of this invention is to provide the method that a kind of slag-free zinc hydrometallurgy is carried indium and produced zinc ferrite.This method makes full use of whole iron and a little zinc in the zinc ore, directly is processed into broad-spectrum zinc ferrite, thereby the cancellation iron removal shortens zinc hydrometallurgy and puies forward the indium flow process.
Details are as follows for specific embodiment of the present invention and condition:
1. high temperature peracid, reduction are leached
The high temperature peracid leaches and to carry out in hydrochloric acid system, and its condition is: 60～95 ℃ of temperature, and time 0.5～5h, liquid-solid ratio 3～8: 1, the hydrochloric acid consumption is 1.1～2 times of theoretical consumption, the high oxide of iron such as wustite, Indian red all can decompose and enters high immersion liquid:
Under ferric effect, metallic sulfide also can oxidation dissolution:
Silver finally enters residue with silver chloride, and tin mainly exists with inert cassiterite form, also stay in residue, and indium compound character is similar with the high price iron cpd, all enters leach liquor with the hydrochloric acid effect.
High immersion liquid contains Fe
3+, for the ease of carrying indium and carrying out zinc-iron and separate, must reduce:
Reductive agent can be a gaseous reducing agent, as SO
2Or H
2S; Also can be solid reductant, as iron filings, FeS or zinc sulphide.
The reduction leaching condition is: 60～95 ℃ of temperature, time 0.5～5h, reductive agent consumption are 1.05～2.05 times of theoretical consumption.
2. displacement copper removal
Contain higher cupric ion in the leach liquor, in order to reclaim the Fe in copper and the thorough reduction leach liquor
3+, adopt industrial iron powder substitution copper:
Displacement copper removal condition is: 25～80 ℃ of temperature, time 10-60min, iron powder consumption are 1.2～2.2 times of theoretical consumption.
3. extraction of indium zinc
With TBP extracting zinc indium the liquid behind copper removal:
Extracting zinc indium condition is: 4～60 ℃ of temperature, and time 0.2～10min, pH value 1～5, compare W/O=1: (1～20), organic phase is formed: 10～95%TBP+ sulfonated kerosene, 1～6 grade of extraction progression; Back extraction zinc indium condition is: 5～50 ℃ of temperature, and time 0.2～10min compares W/O=1/ (1～10), and reverse-extraction agent is a pure water, pH value 6～7,1～5 grade of back extraction progression; Zine plate displacement indium gets sponge indium and liquor zinci chloridi, and the sponge indium send the indium treatment process.
4. extraction iron
Liquid is FeCl behind the TBP collection zinc indium
2Solution also contains Cd
2+, Pb
2+, Ca
2+, Mg
2+Deng impurity.For purifying, at first use air, oxygen or liquid chlorine with FeCl
2Solution oxide becomes FeCl
3Solution:
Extract ferric iron with TBP again:
Extraction conditions is: 5～60 ℃ of temperature, and time 0.2～10min, pH value 0～2 is compared W/O=1～20, and organic phase is formed: 10～95%TBP+ sulfonated kerosene, 1～6 grade of extraction progression; Back extraction ferric iron condition is: 5～50 ℃ of temperature, and time 0.2～10min compares W/O=1/ (1～10), and reverse-extraction agent is a pure water, pH value 1～2,1～5 grade of back extraction progression.
5. zinc ferrite preparation
Carry out co-precipitation after 3 described liquor zinci chloridis and 4 described ferric chloride Solutions are mixed according to the zinc ferrite proportioning, its condition is: the metal ion total concn is 0.1～2mol/l, precipitation agent concentration is 0.5～2.5mol/l, precipitation agent is bicarbonate of ammonia, ammoniacal liquor or the mixing of the two, consumption is 1.1～2 times of theoretical consumption, 10～60 ℃ of temperature, endpoint pH are 6～12, and the reaction times is 0.5～5h; Coprecipitated powder washing back dry 8-24h under 60～200 ℃ temperature; At last coprecipitated powder is placed in the retort furnace temperature lower calcination 1～5h at 400～1000 ℃.
The present invention has cancelled the iron removal in the zinc hydrometallurgy, and makes full use of iron and a little zinc in the zinc hydrometallurgy, directly is processed into broad-spectrum zinc ferrite powder, and iron resources obtains the high value utilization; Directly extract indium from reduced liquid, the indium recovery process is simplified greatly, the rate of recovery improves more than 30%, and has eliminated low concentration sulphur dioxide flue gas and the pollution of a large amount of scums to environment, turns waste into wealth, and the iron resources in the zinc ore concentrate is fully used; Soak slag or height in handling in the hydrochloric acid system and soak slag and have the metal leaching rate height, iron zinc thoroughly separates and characteristics such as purification respectively easily, is that the preparation of high-grade material product of main component is significant with iron to zinc ferrite, Mn-Zn soft magnetic ferrite etc.
[description of drawings] Fig. 1 is a process flow diagram of the present invention.
[embodiment]
Having soaked slag in the punch refinery zinc hydrometallurgy factory from the beginning since the embodiment 1 is test portion, and its chemical ingredients sees Table 1.
Table 1 leached mud chemical ingredients w
B/ %
| Raw material | Zn | Fe | In | Pb | Ag | Cu |
| In soak that slag is low to be soaked the slag height and soak the slag zinc ore concentrate | 28.29 18.6 8.21 46.68 | 26.98 21.18 13.76 13.613 | 0.18 0.063 0.028 0.1014 | 1.99 4.62 7.16 - | 0.012 0.102 0.1353 - | 2.12 - - 1.72 |
A: the high temperature peracid leaches with reduction and leaches
The 3375ml concentrated hydrochloric acid is joined in the 825g water, soak slag 1200g in the adding; At 70 ℃ of agitation leach 5h; In reactor, add the 443.7g zinc sulfide concentrates again, continue agitation leach 3h; Filter slip, immersion liquid and washing lotion merged, must the 7660ml leach liquor, its chemical ingredients sees Table 2, with filter cake dry leached mud 280.95g.Be respectively in liquid zinc, iron, indium leaching yield: 93.89%, 94.46%, 97.89%, slag rate 23.4%.
Table 2 leach liquor chemical ingredients
| Element | Zn | Fe | Fe 3+ | Cu | In | Pb | Cd |
| Concentration (g/l) | 66.864 | 47.3 | 1.60 | 3.60 | 0.333 | 1.17 | 0.42 |
B: displacement copper removal
Get above-mentioned leach liquor 5375ml, adding 47.21g iron powder stirs 45min under 30 ℃, filter, and liquid behind the copper removal and washing lotion are merged, and gets filtrate 5485ml, and its chemical ingredients sees Table 3.The copper removal rate reaches more than 99.82%, and the indium rate of loss has only 0.25%, and deleading, cadmium rate are respectively 32.50% and 17.90%.
Composition is learned in liquefaction behind table 3 copper removal
| Element | Zn | Fe | Fe 3+ | Cu | In | Pb | Cd |
| Concentration (g/l) | 65.51 | 51.85 | 0 | 0.0063 | 0.3255 | 0.774 | 0.338 |
C: extraction of indium zinc
Get liquid 1250ml behind the above-mentioned copper removal, in room temperature and be in a ratio of W/O=1: under 5 the condition, with 50%TBP+ sulfonated kerosene three stage countercurrent extracting zinc indiums, mixing time 5min; Organic phase pure water secondary back extraction, back extraction time 2min.Its zinc indium percentage extraction and back extraction ratio are respectively 99.4%, 97.7% and 94.5%, 97.8%, and the iron percentage extraction is less than 0.2%.Liquid is replaced indium with zine plate again after the back extraction, and rate of displacement is 99%.Therefrom soak slag to the sponge indium, the total yield of indium is 92.37%.
D: extraction iron
Raffinate is FeCl
2Solution all is oxidized to FeCl with air with it earlier
3Solution.Get FeCl
3Solution 1000ml is with 30%TBP+ sulfonated kerosene Pyatyi counter-current extraction iron, mixing time 5min; Low sour four-stage counter-current back extraction 4min.Iron percentage extraction and back extraction ratio are respectively 99.7% and 93.4%, and iron content is less than 0.1g/l in the raffinate, and the strip liquor foreign matter content is few.
E: zinc ferrite preparation
With above-mentioned gained ZnCl
2And FeCl
3Solution is according to the proportioning preparation mixing solutions of nFe: nZn=2, dilution, getting the metal ion total concn is the mixing solutions 500ml of 1.5mol/l, with 1.2 times of theoretical amount, concentration is that the ammonium bicarbonate soln of 2mol/l is a precipitation agent, and at 40 ℃ of following co-precipitation 1h, endpoint pH is 6.0.After the filtration, coprecipitated powder is through washing, getting precursor powder 71.2g in 60 ℃ of dry 24h; Getting this powder 10.0g places retort furnace to calcine 5h down at 450 ℃.XRD analysis shows that product is entirely zinc ferrite; Sem analysis finds that the pattern and the granularity of product is better.
Example is executed mode 2: raw material soaks slag for low, and its chemical ingredients sees Table 1.
A: the high temperature peracid leaches with reduction and leaches
The 1600ml concentrated hydrochloric acid is joined in the 400g water, add the low slag 400g that soaks; At 80 ℃ of agitation leach 3h; In reactor, add the 127.6g zinc sulfide concentrates again, continue agitation leach 2h; Filter slip, immersion liquid and washing lotion merged, must the 3650ml leach liquor, its chemical ingredients sees Table 4, with filter cake dry leached mud 103.55g.Be respectively in liquid zinc, iron, indium leaching yield: 95.2%, 96.25%, 98.1%, slag rate 25.89%.
Table 4 leach liquor chemical ingredients
| Element | Zn | Fe | Fe 3+ | Cu | In | Pb |
| Concentration (g/l) | 34.94 | 26.92 | 1.15 | 0.60 | 0.103 | 4.95 |
B: displacement copper removal
Get above-mentioned leach liquor 3000ml, add the 10.5g iron powder, in 50 ℃ of agitation condition underlying recopper 30min, filter, liquid behind the copper removal and washing lotion are merged, get 3080ml liquid, its chemical ingredients sees Table 5.The copper removal rate reaches more than 99.45%, and the indium rate of loss has only 0.11%, and the deleading rate is 34.60%.
Composition is learned in liquefaction behind table 5 copper removal
| Element | Zn | Fe | Fe 3+ | Cu | In | Pb |
| Concentration (g/l) | 34.03 | 27.93 | 0 | 0.0032 | 0.100 | 3.15 |
C: extraction of indium zinc
Get liquid 1250ml behind the above-mentioned copper removal, in room temperature and be in a ratio of W/O=1: under 8 the condition, with 30%TBP+ sulfonated kerosene four-stage counter-current extracting zinc indium, mixing time 6min; Organic phase three grades of back extractions of pure water, back extraction time 3min.Its zinc indium percentage extraction and back extraction ratio are respectively 99.78%, 98.51% and 93.95%, 97.96%, and the iron percentage extraction is less than 0.2%.Strip liquor is replaced indium with zine plate again, and rate of displacement is 99%.Therefrom soak slag to the sponge indium, the total yield of indium is 93.62%.
D: extraction iron
Raffinate is FeCl
2Solution all is oxidized to FeCl with oxygen with it
3Solution.Get FeCl
3Solution 1000ml is with 50%TBP+ sulfonated kerosene four-stage counter-current extraction iron, mixing time 4min; Low sour three stage countercurrent back extraction 3min.Iron percentage extraction and back extraction ratio are respectively 99.8% and 94.1%, and iron content is less than 0.1g/l in the raffinate, and the strip liquor foreign matter content is few.
E: zinc ferrite preparation
With above-mentioned gained ZnCl
2And FeCl
3Solution, according to the proportioning preparation mixing solutions of nFe: nZn=2, dilution, getting the metal ion total concn is the mixing solutions 1000ml of 1.0mol/l, the ammoniacal liquor that with concentration is 1.5mol/l and 1.5 times of theoretical amount be precipitation agent at 30 ℃ of following co-precipitation 3h, endpoint pH is 8.0.After the filtration, coprecipitated powder is through washing, getting precursor powder 95.1g in 80 ℃ of dry 16h; Get this powder 10.0g, place retort furnace to calcine 3h down at 600 ℃.XRD analysis shows that product is entirely zinc ferrite; Sem analysis finds that the pattern and the granularity of product is better.
Embodiment 3: raw material is that height soaks slag, and composition is with embodiment 1.
A: the high temperature peracid leaches with reduction and leaches
The 1120ml concentrated hydrochloric acid is joined in the 280g water, add height and soak slag 200g; At 90 ℃ of agitation leach 1h; In reactor, add the 62.95g zinc sulfide concentrates again, continue agitation leach 1h; Filter slip, immersion liquid and washing lotion merged, must the 2250ml leach liquor, its chemical ingredients sees Table 6, with filter cake dry leached mud 65.2g.Be respectively in liquid zinc, iron, indium leaching yield: 92.67%, 94.33%, 98.5%, slag rate 32.6%.
Table 6 leach liquor chemical ingredients
| Element | Zn | Fe | Fe 3+ | Cu | In | Pb |
| Concentration (g/L) | 18.81 | 15.13 | 0.85 | 1.53 | 0.0525 | 6.36 |
B: displacement copper removal
Get above-mentioned leach liquor 2000ml, add the 9.52g iron powder, in 70 ℃ of agitation condition underlying recopper 15min, filter, liquid behind the copper removal and washing lotion are merged, get 2055ml liquid, its chemical ingredients sees Table 7.The copper removal rate reaches more than 99.68%, and the indium rate of loss has only 0.13%, and deleading is 33.70%.
Composition is learned in liquefaction behind table 7 copper removal
| Element | Zn | Fe | Fe 3+ | Cu | In | Pb |
| Concentration (g/L) | 18.31 | 17.04 | 0 | 0.0048 | 0.051 | 4.10 |
C: extraction of indium zinc
Get liquid 1250ml behind the above-mentioned copper removal, in room temperature and be in a ratio of W/O=1: under 12 the condition, with 15%TBP+ sulfonated kerosene Pyatyi counter-current extraction zinc indium, mixing time 7min; Organic phase pure water level Four back extraction, back extraction time 4min.Its zinc indium percentage extraction and back extraction ratio are respectively 99.23%, 97.42% and 94.75%, 97.54%, and the iron percentage extraction is less than 0.2%.Liquid is replaced indium with zine plate again after the back extraction, and rate of displacement is 99%.Therefrom soak slag to the sponge indium, the total yield of indium is 92.54%.
D: extraction iron
It is FeCl that zinc-iron separates back liquid
2Solution all is oxidized to FeCl with liquid chlorine with it
3Solution.Get FeCl
3Solution 1000ml is with 70%TBP+ sulfonated kerosene three stage countercurrents extraction iron, mixing time 3min; Low sour secondary countercurrent reextraction time 2min.Iron percentage extraction and back extraction ratio are respectively 99.85% and 93.55%, and iron content is less than 0.1g/l in the raffinate, and the liquid foreign matter content is few after the back extraction.
E: zinc ferrite preparation
With above-mentioned gained ZnCl
2And FeCl
3Solution, proportioning preparation mixing solutions according to nFe: nZn=2, dilution, getting the metal ion total concn is the mixed solution 1000ml of 0.5mol/l, with 1.7 times of theoretical amount and the total ammonia concentration bicarbonate of ammonia that is 1.0mol/l and the mixing solutions of ammoniacal liquor is precipitation agent, at 45 ℃ of following co-precipitation 1h, endpoint pH is 7.0.After the filtration, coprecipitated powder is through washing, getting precursor powder 47.5g in 110 ℃ of following dry 8h; Get this powder 10.0g, place retort furnace to calcine 1h down at 800 ℃.XRD analysis shows that product is entirely zinc ferrite; Sem analysis finds that the pattern and the granularity of product is better.
Claims (4)
1. a slag-free zinc hydrometallurgy is carried indium and is produced the method for zinc ferrite, it is characterized in that: processing sulfuric acid soaks in behind most of zinc and soaks slag, low acid leaching residue or high acid leaching residue extraction indium in hydrochloric acid system, and be that raw material is produced zinc ferrite with iron, the zinc resource of carrying behind the indium, in soak slag or height soak slag through the high temperature peracid reduction leach, the iron replacement copper removal, TBP extraction of indium zinc, strip liquor displacement indium, the raffinate Oxidation of Fe
2+, TBP extraction iron, iron trichloride back extraction; Iron(ic) chloride and the preparation of zinc chloride mixing solutions, zinc-iron co-precipitation, drying, calcining make the zinc ferrite powder and extract indium, and with pure ZnCl
2Reclaim unnecessary zinc, concrete processing condition are:
(1) high temperature peracid leaching condition is: 60～95 ℃ of temperature, and time 0.5～5h, liquid-solid ratio 3～8: 1, the hydrochloric acid consumption is 1.1～2 times of theoretical consumption; The reduction leaching condition is: 60～95 ℃ of temperature, and time 0.5～5h, reductive agent consumption are 1.05～2.05 times of theoretical consumption;
(2) leach liquor iron replacement copper removal, its condition is: 25～80 ℃ of temperature, time 10-60min, iron powder consumption are 1.2～2.2 times of theoretical consumption;
(3) liquid TBP extracting zinc indium behind the copper removal, its condition is: 5～60 ℃ of temperature, time 0.2～10min, the pH value is compared W/O=1～20 less than 2, and organic phase is formed: 10～95%TBP+ sulfonated kerosene, 1～6 grade of extraction progression; Back extraction zinc indium condition is: 4～50 ℃ of temperature, and time 0.2～10min compares W/O=1/ (1～10), and reverse-extraction agent is a pure water, pH value 6～7,1～5 grade of back extraction progression; Zine plate displacement indium gets sponge indium and liquor zinci chloridi;
(4) elder generation becomes trivalent with the oxygenant of 1.1～2.0 times of theoretical amount with the oxidation of divalent in the raffinate, extract iron with TBP again, collection iron bar spare is: 5～60 ℃ of temperature, time 0.2～10min, HCl 5～25g/L, compare W/O=1～20, organic phase is formed: 10～95%TBP+ sulfonated kerosene, 1～6 grade of extraction progression; Back extraction iron bar spare is: 4～50 ℃ of temperature, and time 0.2～10min compares W/O=1/ (1～10), and the pH value is less than 5,1～5 grade of back extraction progression;
(5) liquor zinci chloridi and ferric chloride Solution are made the mixing dilute solution by the zinc ferrite proportioning, carry out co-precipitation then, its condition is: the metal ion total concn is 0.1～2mol/l, precipitation agent concentration is 0.5～2.5mol/l, 10～60 ℃ of temperature, pH value are 6～12, and the reaction times is 0.5～5h;
(6) coprecipitated dried bean noodles is dry, calcining preparation zinc ferrite, drying temperature is 60～200 ℃, time 8-24h, calcining temperature is 400～1000 ℃, time 1～5h.
2. method according to claim 1 is characterized in that: described reductive agent is gaseous reducing agent SO
2Or H
2S, or solid reductant iron filings, FeS or zinc sulphide.
3. method according to claim 1 is characterized in that: described oxygenant is H
2O
2, air, oxygen or liquid chlorine.
4. method according to claim 1 is characterized in that: described precipitation agent is bicarbonate of ammonia, ammoniacal liquor or the mixing of the two.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443604C (en) * | 2006-11-20 | 2008-12-17 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Extraction and separation technology for reclaiming main impurity in indium in hydrochloric acid system |
| CN101113490B (en) * | 2007-09-12 | 2010-05-19 | 昆明理工大学 | Method for leaching indium from indium sulfide concentrate |
| CN102660678A (en) * | 2012-05-17 | 2012-09-12 | 四川大学 | Method for selectively separating iron from hydrochloric acid solution containing ferrous chloride |
| CN102719666A (en) * | 2012-06-26 | 2012-10-10 | 中南大学 | Method for removing iron with lead sulfate as vegasite-precipitating agent in wet zinc smelting process |
| CN104480306A (en) * | 2014-12-07 | 2015-04-01 | 金川集团股份有限公司 | Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material |
| CN105543483A (en) * | 2015-12-31 | 2016-05-04 | 中南大学 | Method for efficiently leaching cadmium from neutral leaching residues through zinc hydrometallurgy |
| CN106957965A (en) * | 2017-05-09 | 2017-07-18 | 甘肃有色冶金职业技术学院 | A kind of preparation method of iron oxide product |
| CN108557791A (en) * | 2018-06-08 | 2018-09-21 | 武汉工程大学 | The method for preparing calcium dihydrogen phosphate using low-grade phosphate ore |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1206008A (en) * | 1982-02-24 | 1986-06-17 | Donald R. Weir | Recovery of zinc from zinc-containing sulphidic material |
| CN1074464C (en) * | 1999-05-04 | 2001-11-07 | 沈奕林 | New process for recovering metals of indium, iron, silver and tin from high-indium high-iron zinc preparation concentrate |
-
2006
- 2006-03-30 CN CNB2006100314358A patent/CN100348750C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443604C (en) * | 2006-11-20 | 2008-12-17 | 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 | Extraction and separation technology for reclaiming main impurity in indium in hydrochloric acid system |
| CN101113490B (en) * | 2007-09-12 | 2010-05-19 | 昆明理工大学 | Method for leaching indium from indium sulfide concentrate |
| CN102660678A (en) * | 2012-05-17 | 2012-09-12 | 四川大学 | Method for selectively separating iron from hydrochloric acid solution containing ferrous chloride |
| CN102719666A (en) * | 2012-06-26 | 2012-10-10 | 中南大学 | Method for removing iron with lead sulfate as vegasite-precipitating agent in wet zinc smelting process |
| CN104480306A (en) * | 2014-12-07 | 2015-04-01 | 金川集团股份有限公司 | Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material |
| CN105543483A (en) * | 2015-12-31 | 2016-05-04 | 中南大学 | Method for efficiently leaching cadmium from neutral leaching residues through zinc hydrometallurgy |
| CN106957965A (en) * | 2017-05-09 | 2017-07-18 | 甘肃有色冶金职业技术学院 | A kind of preparation method of iron oxide product |
| CN106957965B (en) * | 2017-05-09 | 2018-08-07 | 甘肃有色冶金职业技术学院 | A kind of preparation method of iron oxide product |
| CN108557791A (en) * | 2018-06-08 | 2018-09-21 | 武汉工程大学 | The method for preparing calcium dihydrogen phosphate using low-grade phosphate ore |
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