CN102887494A - Method for preparing zinc phosphate by using low-grade zinc oxide ore - Google Patents
Method for preparing zinc phosphate by using low-grade zinc oxide ore Download PDFInfo
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Abstract
The invention relates to a method for preparing zinc phosphate by using low-grade zinc oxide ores, belonging to the technical field of inorganic chemical industry. Using low-grade zinc oxide ore as raw material, ammonia-ammonium salt leaching and purifying to obtain ammonia leaching purification liquor, adding precipitant to make reaction to produce intermediate deposit of zinc-ammonium double salt, then making the intermediate completely dissolve, making liquid-liquid reaction with trisodium phosphate solution to produce zinc phosphate solid deposit, drying so as to obtain PO4 3-The content is more than or equal to 45 percent, Zn2+The high-purity powdery zinc phosphate dihydrate product with the content of more than or equal to 45 percent and the content of zinc phosphate of more than 98 percent can be used as a raw material for high-grade anticorrosive paint. The invention has simple process, rich raw material sources and low price, adopts a liquid-liquid reaction mode, has fast reaction speed of the raw materials, no wrapping phenomenon, easy washing of the product, fine granularity (+ 45um is less than or equal to 0.5 percent), and more than 92 percent of product yield, can promote the development and utilization of low-grade zinc oxide ore, and greatly reduces the production cost of zinc phosphate products.
Description
Technical field
The present invention relates to a kind of preparation method of zinc phosphate, in particular to a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate, belong to technical field of inorganic chemical industry.
Background technology
Zinc phosphate has another name called phosphorus zinc white, is widely used in the antirust industry of coating.Coating also is a kind of pollution-free rustproof pigment of early being used with zinc phosphate.Its principle is that phosphoric acid zinc salt coating can form in the metallic surface the fine and close coverture of the not dynamic tunicle of one deck, makes metal surface passivation, plays the protecting group surface and is not corroded the purpose that reaches antirust.
Through the years of researches development, the method for preparing at present zinc phosphate mainly contains two kinds: a kind of is direct method, namely with high-grade zinc oxide (ZnO 〉=99.7%) and industrial phosphoric acid (H
3PO
4〉=85%) direct reaction obtains; This method is higher for the quality requirements of raw material zinc oxide, owing to be solid-liquid reaction, the zinc phosphate of generation easily at unreacted zinc oxide surface the parcel phenomenon occurs, and affects the transformation efficiency of zinc oxide, reduces the quality of zinc phosphate product.Simultaneously, high-grade zinc oxide is expensive, and the expense of raw material zinc oxide accounts for 70% of production cost, has directly increased thus the production cost of zinc phosphate product.Another kind is double decomposition, i.e. indirect method, be with zinc sulfate directly and SODIUM PHOSPHATE, MONOBASIC or sodium phosphate hot solution stirring reaction make; This method production technique is relatively complicated, easily produces a large amount of water-soluble impurities, product washing difficulty, and too high so that quality product is difficult to control because of water-soluble substances, purity can't be guaranteed.
Application number 200910114623.0 discloses a kind of method of producing high-purity zinc phosphate, as raw material take soluble zinc salt, soluble carbonate salt or supercarbonate, in the aqueous solution, react under the certain condition and generate zinc carbonate or zinc subcarbonate precipitation, and then generate zinc phosphate with phosphatase reaction, product yield reaches more than 95%, phosphate dihydrate zinc content is more than 98%, wherein sulfate radical content is less than 0.05%, chloride ion content is less than 0.05%, plumbous≤0.0025%, cadmium≤0.0025% can be used as the high grade paint raw material.The method belongs to indirect method, and take the solubility inorganic zinc salt as raw material, raw material sources are limited, and cost is relatively high, can't realize the docking of existing zinc oxide ore ammonia-ammonium salt soaking technology is used.In addition, (the Yunnan chemical such as old Beam, the 3rd phase of calendar year 2001) the employing low-grade zinc oxide is raw material, ammonia-carbon ammonium mixed solution is solvent, with the zinc oxide extraction and cleaning, be converted into water-soluble zinc ammonium complex again with phosphatase reaction, realize liquid-liquid reactions, also exist raw materials cost higher, the limited shortcoming of originating, and also the product foreign matter content is higher.
China has abundant zinc oxide ore resource, is mainly used in extracting metallic zinc, but along with increasing to the metallic zinc demand of the world, higher-grade zinc oxide mineral products resource is also continually developed and exhaustion thereupon.Therefore, utilize economically low-grade zinc oxide ore resource tool to be of great significance.The present invention prepares the method for zinc phosphate take low-grade zinc oxide ore as raw material, have no so far report.
Summary of the invention
The present invention is intended to overcome defects, and a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate is provided.The raw material sources of the method are abundant, and technique is simple, and the product foreign matter content is low, and yield is high, and cost is lower.
For achieving the above object, the concrete technical scheme taked of the present invention is as follows:
A kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate, it is characterized in that: take low-grade zinc oxide ore as raw material, leach, purify acquisition ammonia through ammonia-ammonium salt and soak scavenging solution, soak in ammonia and to add precipitation agent in the scavenging solution, stirring at normal temperature reaction 30～50min, leave standstill 10～20min, after liquid-solid separation, obtain zinc ammonium double salt intermediate; Zinc ammonium double salt intermediate is water-soluble, be mixed with the solution that concentration is 30～70wt%, press again Zn in the zinc ammonium double salt intermediate
2+: Na
3PO
4Mol ratio is 1:0.56～0.66, the trisodium phosphate solution of configuration concentration 25～50wt%, and under 60～90 ℃ whipped state, trisodium phosphate solution is slowly joined zinc ammonium double salt intermediate insulation reaction 30～50min, then filter, filter cake is dried 1～3h through washing, under 110～130 ℃ and is namely obtained PO
4 3-Content 〉=45%, Zn
2+High-purity powdery phosphate dihydrate zinc product that content 〉=45%, heavy metal content are extremely low.
The zinc content of described low-grade zinc oxide ore≤14%.
Described precipitation agent is quality than the sulfuric acid of concentration 98% or the quality hydrochloric acid than concentration 36.5%.
Described precipitation agent soaks scavenging solution Zn by ammonia
2+: H
2SO
4Or HCl is the molar mass ratio adding of 1:2.03～2.56.
Described zinc ammonium double salt intermediate through obtaining after the liquid-solid separation can be for subsequent use behind 1～2.5h at 60～80 ℃, oven dry.Zinc ammonium double salt intermediate after the drying also can be directly as the elementary inorganic chemical product of zinc ammonium double salt except for the preparation of the zinc phosphate.
It is take ammonia-ammonia sulfate solution or ammonia-ammonium chloride solution as leaching agent that described low-grade zinc oxide ore ammonia soaks scavenging solution, and the zinc oxide ore leach liquor adds excessive Zn powder reaction 60～100min at normal temperatures, after solid-liquid separation, gained ammonia soak solution again with H
2O
2, Fe
2(SO
4)
3Solution is pressed the volume ratio of 1000:1～4:5～30, at 40～70 ℃ of lower reaction 60～120min, obtains after solid-liquid separation.
The leaching condition of described ammonia-ammonia sulfate solution is: leaching agent concentration 3.2mol/L, NH
3: NH
4 +Mol ratio 1:1; 40 ℃ of extraction temperatures; Liquid-solid ratio L:S=3.5:1; Extraction time 2h.
The leaching condition of described ammonia-ammonium chloride solution is: leaching agent concentration 4.5 mol/L, NH
3: NH
4 +Mol ratio 1:1; 35 ℃ of extraction temperatures; Liquid-solid ratio L:S=2.5:1; Extraction time 1h.
The consumption of described excessive Zn powder is the required theoretical amount zinc powder of replacement(metathesis)reaction occurs for foreign metal ion and Zn in the leach liquor 8～14 times, to remove heavy metal Pb in the leach liquor, Cu, Cd, Co.
Described H
2O
2Concentration be 30wt%, Fe
2(SO
4)
3The concentration of solution is 1.5wt%.
Ammonia behind the described purification and impurity removal soaks scavenging solution raw material Pb≤4mg/L, Gd≤0.15mg/L, As≤0.30mg/L.
The yield of described high-purity phosphate dihydrate zinc product reaches more than 92%, and zinc phosphate content is more than 98%, Pb content ﹤ 0.008%, Cd content ﹤ 0.001%.
The invention has the advantages that:
1, the present invention is take low-grade zinc oxide ore as raw material, and its raw material sources are abundant, and are cheap, not only promoted the development and use of low-grade zinc oxide ore, and the production cost of zinc phosphate product reduce greatly.
2, the present invention soaks scavenging solution with sulfuric acid or hydrochloric acid as precipitation agent and ammonia and reacts and generate zinc ammonium double salt intermediate precipitation, after this intermediate is water-soluble, again trisodium phosphate solution is slowly added wherein, what adopt is the liquid-liquid reactions mode, raw material reaction speed is fast, there is not the parcel phenomenon, product easily washs, fine size (+45um≤0.5%), not only the yield of zinc phosphate product (by purifying rear liquid to product) reaches more than 92%, and can obtain purity also more than 98%, low (the Pb content ﹤ 0.008% of beavy metal impurity content, Cd content ﹤ 0.001%) zinc phosphate product.
3, the present invention adopts ammonia-ammonia sulfate solution or ammonia-ammonium chloride solution as leaching agent, and under corresponding leaching condition, leach low-grade zinc oxide ore (zinc leaching rate reaches 85%), easy by removal of impurities in ammonia-ammonium salt solution, guaranteed that not only the ammonia behind the purification and impurity removal soaks the very low (Pb≤4.00mg/L of harmful ion content in the scavenging solution, Cd≤0.15mg/L, As≤0.30mg/L), and make quality product be easier to just reach the specification of quality of one-level zinc phosphate product.
4, technique of the present invention is simple, is easy to suitability for industrialized production, can obtain preferably economic benefit.
Description of drawings
Fig. 1 is process flow diagram of the present invention
Embodiment
Embodiment 1
Ammonia at low-grade zinc oxide ore soaks in the scavenging solution, presses Zn in the scavenging solution
2+: H
2SO
4The molar mass that is 1:2.03～2.56 is than adding sulfuric acid (concentration 98%), and stirring at normal temperature reaction 35～40min filters after leaving standstill 10～15min, obtains solid sulphuric acid zinc ammonium, and for subsequent use in 65～75 ℃ of oven dry 1～2h; Then it is 40～60% the aqueous solution that the zinc sulfate ammonium after will drying is mixed with concentration, presses zinc sulfate ammonium Zn again
2+: Na
3PO
4Mol ratio is 1:0.56～0.66, configuration concentration is 25～50% trisodium phosphate solution, and this solution slowly joined in the zinc sulfate ammonium solution, insulation reaction 35～45min under 75～85 ℃ of whipped states, then filter, filter cake is dried 2h～2.5h with the 150ml water washing, under 115～125 ℃ and is namely obtained PO
4 3-Content 〉=45%, Zn
2+High-purity phosphate dihydrate zinc product of content 〉=45%.
Embodiment 2
Measure ammonia-ammonia sulfate and leach scavenging solution (main chemical compositions is as shown in table 1) 300ml, add in the 1L flat bottom beaker, press scavenging solution Zn
2+: H
2SO
4Be the molar mass of 1:2.53 than adding sulfuric acid (concentration 98%), stirring reaction 40min at normal temperatures filters after leaving standstill 10min, obtains solid sulphuric acid zinc ammonium; In the 400mL flat bottom beaker, the zinc sulfate ammonium is mixed with the aqueous solution of concentration 30%, presses Zn
2+: Na
3PO
4Mol ratio is 1:0.56, configuration concentration is 50% trisodium phosphate solution, and this solution slowly joined in the zinc sulfate ammonium solution, at 75 ℃ of lower insulation reaction 30min that stir, after filtration, filter cake is with after the 150ml water washing, obtains four water zinc phosphate white product, again in 110 ℃ of oven dry 3h, obtain the phosphate dihydrate zinc product, record PO in the product
4 3-Content is 45.01%, Zn
2+Content is 45.09%.Product yield is 92.08%.
Table 1 ammonia-ammonia sulfate leaches scavenging solution and forms and content (mg/L)
| Component | Pb | Ni | Cu | Cd | Co | As | Sb | Fe | Zn* |
| Content | 3.64 | 0.15 | 0.13 | 0.13 | 0.88 | 0.30 | 0.014 | 0.20 | 40.83 |
* represent that measure unit is g/L
Embodiment 3
Measure ammonia-ammonia sulfate and leach scavenging solution (main chemical compositions is as shown in table 1) 300ml, add in the 1L flat bottom beaker, press scavenging solution Zn
2+: H
2SO
4For the molar mass of 1:2.03 than the sulfuric acid precipitation agent that adds concentration 98%, stirring reaction 50min at normal temperatures filters after leaving standstill 15min, obtains solid sulphuric acid zinc ammonium, and is for subsequent use at 70 ℃ of oven dry 2h; Then the zinc sulfate ammonium after will drying in the 400mL flat bottom beaker is mixed with the aqueous solution of concentration 60%, presses Zn
2+: Na
3PO
4Mol ratio is 1:0.62, configuration concentration is 25% trisodium phosphate solution, and this solution slowly joined in the zinc sulfate ammonium solution, at 60 ℃ of lower insulation reaction 50min that stir, after filtration, filter cake is with after the 150ml water washing, obtains four water zinc phosphate white product, again in 130 ℃ of oven dry 1.5h, obtain the phosphate dihydrate zinc product, record PO in the product
4 3-Content is 45.11%, Zn
2+Content is 45.22%, and product yield is 92.40%.
Embodiment 4
Measure ammonia-ammonia sulfate and leach scavenging solution (main chemical compositions is as shown in table 1) 300ml, add in the 1L flat bottom beaker, press scavenging solution Zn
2+: H
2SO
4Be the molar mass of 1:2.21 than adding sulfuric acid (concentration 98%), stirring reaction 45min at normal temperatures filters after leaving standstill 20min, obtains solid sulphuric acid zinc ammonium, and is for subsequent use at 60 ℃ of oven dry 2.5h; Then the zinc sulfate ammonium after will drying in the 400mL flat bottom beaker is mixed with the aqueous solution of concentration 70%, presses Zn
2+: Na
3PO
4Mol ratio is 1:0.66, configuration concentration is 30% trisodium phosphate solution, and this solution slowly joined in the zinc sulfate ammonium solution, stir insulation reaction 40min at 85 ℃, after filtration, filter cake is with after the 150ml water washing, obtains four water zinc phosphate white product, again in 120 ℃ of oven dry 2h, obtain the phosphate dihydrate zinc product, record PO in the product
4 3-Content is 45.15%, Zn
2+Content is 46.02%, and product yield is 92.55%.
Embodiment 5
Measure ammonia-ammonia sulfate and leach scavenging solution (main chemical compositions is as shown in table 1) 300ml, add in the 1L flat bottom beaker, press scavenging solution Zn
2+: H
2SO
4Be the molar mass of 1:2.15 than adding sulfuric acid (concentration 98%), stirring reaction 30min at normal temperatures filters after leaving standstill 20min, gets solid sulphuric acid zinc ammonium; In the 400mL flat bottom beaker, the zinc sulfate ammonium is mixed with the aqueous solution of concentration 50%, presses Zn
2+: Na
3PO
4Mol ratio is 1:0.64, configuration concentration is 40% trisodium phosphate solution, and this solution slowly joined in the zinc sulfate ammonium solution, at 90 ℃ of lower insulation reaction 40min that stir, after filtration, filter cake is with after the 150ml water washing, obtains four water zinc phosphate white product, again in 130 ℃ of oven dry 1h, obtain the phosphate dihydrate zinc product, record PO in the product
4 3-Content is 45.00%, Zn
2+Content is 46.19%, and product yield is 94.37%.
Table 2 ammonia-ammonia sulfate leaches scavenging solution and forms and content (mg/L)
| Component | Pb | Ni | Cu | Cd | Co | As | Sb | Fe | Zn* |
| Content | 3.58 | 0.12 | 0.19 | 0.6 | 0.85 | 0.54 | 0.019 | 0.34 | 40.20 |
* represent that measure unit is g/L
Embodiment 6
Measure ammonia-ammonia sulfate and leach scavenging solution (main chemical compositions is as shown in table 1) 300ml, add in the 1L flat bottom beaker, press scavenging solution Zn
2+: H
2SO
4Be that 1:2.03 adds sulfuric acid (concentration 98%), stirring reaction 30min at normal temperatures filters after leaving standstill 20min, obtains solid sulphuric acid zinc ammonium, and is for subsequent use at 80 ℃ of oven dry 2h; Then the zinc sulfate ammonium is mixed with the aqueous solution of concentration 50% after will drying in the 400mL flat bottom beaker, presses Zn
2+: Na
3PO
4Mol ratio is 1:0.66, configuration concentration is 35% trisodium phosphate solution, and this solution slowly joined in the zinc sulfate ammonium solution, at 85 ℃ of lower insulation reaction 50min that stir, after filtration, filter cake is with after the 150ml water washing, obtains four water zinc phosphate white product, again in 110 ℃ of oven dry 3h, obtain the phosphate dihydrate zinc product, record PO in the product
4 3-Content is 45.40%, Zn
2+Content is 45.45% zinc phosphate product.Product yield is 92.01%.
Embodiment 7
Measure ammonia-oronain and leach scavenging solution (main chemical compositions is as shown in table 3) 300ml, add in the 1L flat bottom beaker, press scavenging solution Zn
2+: HCl be the molar mass of 1:2.51 than adding hydrochloric acid (concentration 36.5%), stirring reaction 40min at normal temperatures filters after leaving standstill 20min, obtains the solid zinc ammonium chloride, and is for subsequent use at 60 ℃ of oven dry 2h; Then in the 400mL flat bottom beaker, will dry the aqueous solution that post chlorization zinc ammonium is mixed with concentration 50%, press Zn
2+: Na
3PO
4Mol ratio is 1:0.66, configuration concentration is 40% trisodium phosphate solution, and this solution slowly joined in the zinc ammonium chloride solution, at 75 ℃ of lower insulation reaction 50min that stir, after filtration, filter cake is with after the 150ml water washing, obtains four water zinc phosphate white product, again in 110 ℃ of oven dry 3h, obtain the phosphate dihydrate zinc product, record PO in the product
4 3-Content is 45.10%, Zn
2+Content is 45.30%, and product yield is 92.65%.
Table 3 ammonia-ammonium chloride leaches scavenging solution and forms and content (mg/L)
| Component | Pb | Ni | Cu | Cd | Co | As | Sb | Fe | Zn* |
| Content | 0.14 | 0.1 | 0.1 | 0.1 | 0.1 | 0.20 | 0.02 | 0.22 | 71.91 |
* represent that measure unit is g/L.
Claims (10)
1. method of utilizing low-grade zinc oxide ore to prepare zinc phosphate, it is characterized in that: take low-grade zinc oxide ore as raw material, leach, purify acquisition ammonia through ammonia-ammonium salt and soak scavenging solution, soak in ammonia and to add precipitation agent in the scavenging solution, stirring at normal temperature reaction 30～50min, leave standstill 10～20min, after liquid-solid separation, obtain zinc ammonium double salt intermediate; Zinc ammonium double salt intermediate is water-soluble, be mixed with the solution that concentration is 30～70wt%, press again Zn in the zinc ammonium double salt intermediate
2+: Na
3PO
4Mol ratio is 1:0.56～0.66, the trisodium phosphate solution of compound concentration 25～50wt%, and under 60～90 ℃ whipped state, trisodium phosphate solution is slowly joined insulation reaction 30～50min in the zinc ammonium double salt midbody solution, then filter, filter cake namely obtains PO through washing, at 110～130 ℃ of lower dry 1～3h
4 3-Content 〉=45%, Zn
2+High-purity powdery phosphate dihydrate zinc product of content 〉=45%, Pb content ﹤ 0.008%, Cd content ﹤ 0.001%.
2. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 1 is characterized in that: the zinc content of described low-grade zinc oxide ore≤14%.
3. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 1 is characterized in that: described precipitation agent is quality than the sulfuric acid of concentration 98% or the quality hydrochloric acid than concentration 36.5%.
4. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 1 and 2, it is characterized in that: described precipitation agent soaks scavenging solution Zn by ammonia
2+: H
2SO
4Or HCl is the molar mass ratio adding of 1:2.03～2.56.
5. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 1 is characterized in that: described zinc ammonium double salt intermediate through obtaining after the liquid-solid separation is for subsequent use behind 60～80 ℃, oven dry 1～2.5h.
6. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 1, it is characterized in that: it is as leaching agent take ammonia-ammonia sulfate solution or ammonia-ammonium chloride solution that described low-grade zinc oxide ore ammonia soaks scavenging solution, the zinc oxide ore leach liquor adds excessive Zn powder reaction 60～100min at normal temperatures, after solid-liquid separation, it is 30wt%H with concentration again that gained ammonia soaks solution
2O
2, 1.5 wt%Fe
2(SO
4)
3Solution is pressed the volume ratio of 1000:1～4:5～30, at 40～70 ℃ of lower reaction 60～120min, obtains after solid-liquid separation.
7. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 6, it is characterized in that: the leaching condition of described ammonia-ammonia sulfate solution is: leaching agent concentration 3.2mol/L, NH
3: NH
4 +Mol ratio 1:1; 40 ℃ of extraction temperatures; Liquid-solid ratio L:S=3.5:1; Extraction time 2h.
8. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 6, it is characterized in that: the leaching condition of described ammonia-ammonium chloride solution is: leaching agent concentration 4.5 mol/L, NH
3: NH
4 +Mol ratio 1:1; 35 ℃ of extraction temperatures; Liquid-solid ratio L:S=2.5:1; Extraction time 1h.
9. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 6, it is characterized in that: the consumption of described excessive Zn powder is the required theoretical amount zinc powder of replacement(metathesis)reaction occurs for foreign metal ion and Zn in the leach liquor 8～14 times, to remove heavy metal Pb in the leach liquor, Cu, Cd, Co.
10. a kind of method of utilizing low-grade zinc oxide ore to prepare zinc phosphate according to claim 1, it is characterized in that: described ammonia soaks scavenging solution raw material Pb≤4mg/L, Gd≤0.15mg/L, As≤0.30mg/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116022759A (en) * | 2022-12-30 | 2023-04-28 | 昆明精粹工程技术有限责任公司 | A method for producing high-quality zinc phosphate by utilizing low-grade zinc ore |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4207301A (en) * | 1978-03-14 | 1980-06-10 | Alexeeva Olga V | Process for producing zinc phosphate |
| CN1065685A (en) * | 1992-04-28 | 1992-10-28 | 中南工业大学 | Zinc oxide preparing process by ammonia method |
-
2012
- 2012-11-14 CN CN201210455288.2A patent/CN102887494B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4207301A (en) * | 1978-03-14 | 1980-06-10 | Alexeeva Olga V | Process for producing zinc phosphate |
| CN1065685A (en) * | 1992-04-28 | 1992-10-28 | 中南工业大学 | Zinc oxide preparing process by ammonia method |
Non-Patent Citations (2)
| Title |
|---|
| 唐谟堂等: "硫铵法制取等级氧化锌", 《中国有色金属学报》, vol. 8, no. 1, 31 March 1998 (1998-03-31) * |
| 程华月: "氧化锌矿氨法直接制取磷酸锌", 《万方数据知识服务平台》, 25 April 2005 (2005-04-25) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116022759A (en) * | 2022-12-30 | 2023-04-28 | 昆明精粹工程技术有限责任公司 | A method for producing high-quality zinc phosphate by utilizing low-grade zinc ore |
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