CN111362300A - Method for producing titanium hydrolysate by auxiliary crystallization of ferrous sulfate monohydrate - Google Patents
Method for producing titanium hydrolysate by auxiliary crystallization of ferrous sulfate monohydrate Download PDFInfo
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- CN111362300A CN111362300A CN202010191671.6A CN202010191671A CN111362300A CN 111362300 A CN111362300 A CN 111362300A CN 202010191671 A CN202010191671 A CN 202010191671A CN 111362300 A CN111362300 A CN 111362300A
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- Prior art keywords
- ferrous sulfate
- titanium
- liquid
- sulfate monohydrate
- solution
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000010936 titanium Substances 0.000 title claims abstract description 88
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 88
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 title claims abstract description 40
- 238000002425 crystallisation Methods 0.000 title claims abstract description 32
- 230000008025 crystallization Effects 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000000413 hydrolysate Substances 0.000 title description 3
- 239000007788 liquid Substances 0.000 claims abstract description 78
- 238000005406 washing Methods 0.000 claims abstract description 39
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 239000011268 mixed slurry Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 239000004408 titanium dioxide Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of titanium dioxide production, and discloses a method for producing a hydrolyzed titanium liquid by auxiliary crystallization of ferrous sulfate monohydrate, which comprises the following steps: 1) mixing ferrous sulfate monohydrate and the settled titanium liquid to obtain mixed slurry; 2) introducing the mixed slurry into a crystallizer, and cooling to obtain crystallized slurry; 3) carrying out solid-liquid separation on the crystallized slurry to obtain a hydrolyzed titanium solution and ferrous sulfate heptahydrate; 4) carrying out centrifugal washing on the ferrous sulfate heptahydrate to obtain a ferrous sulfate heptahydrate product and a washing solution; 5) and returning the cleaning solution to the precipitated titanium liquid tank to be mixed with the precipitated titanium liquid for standby. The method uses the ferrous sulfate monohydrate in the production of the hydrolyzed titanium solution, can reduce the crystallization and cooling energy consumption and the titanium solution concentration energy consumption cost, can realize the high-efficiency recycling of the ferrous sulfate monohydrate and the centrifugal washing solution, shortens the production period, and has the characteristics of high efficiency, quickness, energy conservation, consumption reduction and resource utilization.
Description
Technical Field
The invention belongs to the technical field of titanium dioxide production, and particularly relates to a method for producing a hydrolyzed titanium liquid by auxiliary crystallization of ferrous sulfate monohydrate.
Background
Titanium dioxide is widely used in many fields, such as paint, ink, plastic, rubber, paper, ceramic, and synthetic fiber industries, due to its non-toxicity, optimal opacity, optimal whiteness and brightness, and good hiding power and tinting strength. At present, the titanium dioxide in China is mainly produced by a sulfuric acid method.
The production process of titanium dioxide by a sulfuric acid method mainly comprises acidolysis, sedimentation, crystallization, concentration, hydrolysis, bleaching, calcination, coating, vapor powder and the like, the purpose of the crystallization process is to remove ferrous iron in a titanium liquid and remove the ferrous iron in a form of ferrous sulfate crystallization, but the prior titanium dioxide industry mostly applies cooling crystallization, the crystallization process has high energy consumption and low unit crystallizer processing capacity, the concentration of the obtained titanium liquid can not meet the hydrolysis requirement after solid-liquid separation of crystallization slurry, concentration and concentration are also needed, a large amount of energy consumption is consumed, the production period is prolonged, and the method is extremely cost-ineffective. In the production process of titanium sulfate white, a large amount of ferrous sulfate monohydrate containing about 15% of sulfuric acid is produced, and the ferrous sulfate monohydrate is treated separately and then sold, which is both a waste and increases the cost, so that the waste and side-product ferrous sulfate monohydrate is necessary to be recycled. In addition, in the current titanium sulfate white production process, the ferrous sulfate heptahydrate centrifugal washing liquid is returned to the acidolysis leaching section, which is uneconomical and causes more economic waste, so that the optimization of the use route of the centrifugal washing liquid is also necessary.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for producing a titanium hydrolysate by using ferrous sulfate monohydrate auxiliary crystallization, which uses the ferrous sulfate monohydrate for producing the titanium hydrolysate, directly recycles centrifugal washing liquid for precipitating titanium liquid crystallization, and mixes low-temperature ferrous sulfate monohydrate and recycled low-temperature centrifugal washing liquid with high-temperature precipitated titanium liquid, thereby realizing high-efficiency low-energy-consumption cooling of the precipitated titanium liquid and saving the cost of crystallization steam; meanwhile, the ferrous sulfate monohydrate is transformed into ferrous sulfate heptahydrate, so that part of water in the titanium liquid is taken away, the larger grain size of ferrous sulfate crystal is ensured, the concentration of the crystallized titanium liquid can be effectively improved, the concentration required by hydrolysis is reached, the titanium liquid filtered by the rotary table is directly hydrolyzed without concentration, and the concentration cost is saved; the method has the advantages that the centrifugal washing liquid is directly used in the rear-end precipitated titanium liquid crystallization process instead of being used for front-end acidolysis leaching, so that the centrifugal washing liquid is efficiently and quickly recycled, the production period is saved, and comprehensively, the method can reduce the crystallization cooling energy consumption and the titanium liquid concentration energy consumption cost, can realize the efficient recycling of ferrous sulfate monohydrate and the centrifugal washing liquid, shortens the production period, and has the characteristics of high efficiency, quickness and energy conservation.
The invention provides a method for producing a hydrolyzed titanium liquid by ferrous sulfate monohydrate auxiliary crystallization, which comprises the following steps:
1) mixing ferrous sulfate monohydrate and the settled titanium liquid to obtain mixed slurry;
2) introducing the mixed slurry into a crystallizer, and cooling to obtain crystallized slurry;
3) carrying out solid-liquid separation on the crystallized slurry to obtain a hydrolyzed titanium solution and ferrous sulfate heptahydrate;
4) carrying out centrifugal washing on the ferrous sulfate heptahydrate to obtain a ferrous sulfate heptahydrate product and a washing solution;
5) and returning the cleaning solution to the precipitated titanium liquid tank to be mixed with the precipitated titanium liquid for standby.
Preferably, the mass ratio of the ferrous sulfate monohydrate to the precipitated titanium liquid is 1: 15-1: 20. Experiments show that the ferrous sulfate monohydrate and the precipitated titanium liquid are mixed according to the mass ratio, so that the crystallization requirement of the precipitated titanium liquid can be met, and the ferrous sulfate monohydrate is completely crystallized. If the concentration of the crystallized titanium can not meet the requirement of hydrolysis when the ferrous sulfate monohydrate is too low, and if the concentration of the crystallized titanium can not be completely transformed into the ferrous sulfate heptahydrate within a short time when the concentration of the crystallized titanium is too high.
In the invention, the titanium concentration of the settled titanium liquid is 130-plus 135g/L, and after the crystallization and the solid-liquid separation by adopting the method of the invention, the concentration of the crystallized titanium liquid can reach 190-plus 195g/L which is required by hydrolysis.
According to the invention, in the step 2), the cooling conditions include: cooling to 20-25 deg.C, and keeping the temperature for 10 min.
Preferably, in step 3), the crystallization slurry is subjected to solid-liquid separation by a rotary table.
Preferably, in the step 4), during centrifugal washing, the adding proportion of the washing water is 3-5% of the mass of the ferrous sulfate heptahydrate.
The technological parameters which are not limited in the invention are carried out by adopting the conventional mode in the field, such as solid-liquid separation of a rotary table, centrifugal washing and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, ferrous sulfate monohydrate is added into the precipitated titanium liquid for cooling crystallization, so that the crystallization of the precipitated titanium liquid and the crystal transformation of the ferrous sulfate monohydrate into the ferrous sulfate heptahydrate are synchronously carried out, the crystallization and iron removal of the ferrous sulfate monohydrate into the ferrous sulfate heptahydrate and the precipitated titanium liquid are realized, part of water in the titanium liquid is taken away, the concentration of the crystallized titanium liquid is increased, and the concentration of the crystallized titanium liquid is increased by 10-15g/L compared with the original process, so that the concentration required by hydrolysis is reached.
2. The centrifugal washing liquid is directly returned to be mixed with the precipitated titanium liquid, so that the precipitated titanium liquid is quickly cooled, and the centrifugal washing liquid and the added low-temperature ferrous sulfate monohydrate act together, so that the temperature of the precipitated titanium liquid is efficiently and conveniently reduced, and the energy consumption cost of crystallization can be saved.
3. By adopting the method, the crystalline titanium liquid can be directly hydrolyzed without concentration, the concentration process of the crystalline titanium liquid is omitted, the concentration cost is saved, the production period is shortened, the waste ferrous sulfate monohydrate can be reused, and the low-cost production of the titanium sulfate white is realized.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Examples 1-3 are provided to illustrate the process of the present invention for producing a hydrolyzed titanium solution by the assisted crystallization of ferrous sulfate monohydrate.
Example 1
Mixing ferrous sulfate monohydrate and precipitated titanium liquid (titanium concentration is 130 g/L) according to a mass ratio of 1: 15, introducing into a crystallizer, cooling to 20 ℃, preserving heat for 10 minutes, performing solid-liquid separation through a rotary table, measuring the concentration of filtered titanium liquid to be 191g/L, and sending to a titanium liquid hydrolysis tank for later use; and (3) centrifugally washing the rotary table ferrous sulfate heptahydrate by a centrifugal machine, wherein the addition of washing water is 3% of the mass of the ferrous sulfate heptahydrate, so as to obtain a ferrous sulfate heptahydrate product and a centrifugal machine washing solution, and pumping the centrifugal machine washing solution to a precipitated titanium solution tank to be mixed with the precipitated titanium solution.
Example 2
Mixing ferrous sulfate monohydrate and precipitated titanium liquid (titanium concentration is 135 g/L) according to a mass ratio of 1: 20, introducing into a crystallizer, cooling to 25 ℃, preserving heat for 10 minutes, performing solid-liquid separation through a rotary table, measuring the concentration of filtered titanium liquid to be 195g/L, and sending to a titanium liquid hydrolysis tank for later use; and (3) centrifugally washing the rotary table ferrous sulfate heptahydrate by a centrifugal machine, wherein the addition of washing water is 5% of the mass of the ferrous sulfate heptahydrate, so as to obtain a ferrous sulfate heptahydrate product and a centrifugal machine washing solution, and pumping the centrifugal machine washing solution to a precipitated titanium solution tank to be mixed with the precipitated titanium solution.
Example 3
Ferrous sulfate monohydrate and precipitated titanium liquid (titanium concentration is 132 g/L) are introduced into a crystallizer according to the mass ratio of 1: 17, cooled to 23 ℃, kept for 10 minutes, subjected to solid-liquid separation through a rotary table, measured and filtered, and sent to a titanium liquid hydrolysis tank for standby application, wherein the concentration of the filtered titanium liquid is 192 g/L; and (3) centrifugally washing the rotary table ferrous sulfate heptahydrate by a centrifugal machine, wherein the addition of washing water is 4% of the mass of the ferrous sulfate heptahydrate, so as to obtain a ferrous sulfate heptahydrate product and a centrifugal machine washing solution, and pumping the centrifugal machine washing solution to a precipitated titanium solution tank to be mixed with the precipitated titanium solution.
Comparative example 1
Introducing the settled titanium solution (with the titanium concentration of 132 g/L) into a crystallizer, cooling to 23 ℃, preserving the temperature for 10 minutes, then carrying out solid-liquid separation by a turntable, determining the concentration of the obtained filtered titanium solution to be 180g/L, sending the filtered titanium solution to a concentration process, concentrating to 190-195g/L, and then sending the filtered titanium solution to a titanium hydrolysis solution tank for later use; and (3) centrifugally washing the rotary table ferrous sulfate heptahydrate by a centrifugal machine, wherein the addition of washing water is 4% of the mass of the ferrous sulfate heptahydrate, so as to obtain a ferrous sulfate heptahydrate product and a centrifugal machine washing solution, and pumping the centrifugal machine washing solution to an acidolysis leaching process for use.
The embodiment and the comparison of the comparative example show that by the method, the precipitated titanium liquid is efficiently and quickly cooled by mixing the low-temperature ferrous sulfate monohydrate and the low-temperature centrifugal washing liquid with the precipitated titanium liquid, the energy consumption cost of crystallization is saved, meanwhile, the ferrous sulfate monohydrate is transformed into ferrous sulfate heptahydrate in the crystallization process of the titanium liquid, partial water in the titanium liquid is taken away, the concentration of the crystallized titanium liquid is increased to the concentration required by hydrolysis, the crystallized titanium liquid can be directly hydrolyzed without being concentrated, the concentration cost is saved, the production period is shortened, the production cost of titanium dioxide is reduced, the reuse of waste and secondary ferrous sulfate monohydrate and the efficient recycling of the centrifugal washing liquid are realized, and the method is efficient and quick, low in energy consumption and resource utilization.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.
Claims (5)
1. A method for producing a hydrolyzed titanium liquid by ferrous sulfate monohydrate auxiliary crystallization is characterized by comprising the following steps:
1) mixing ferrous sulfate monohydrate and the settled titanium liquid to obtain mixed slurry;
2) introducing the mixed slurry into a crystallizer, and cooling to obtain crystallized slurry;
3) carrying out solid-liquid separation on the crystallized slurry to obtain a hydrolyzed titanium solution and ferrous sulfate heptahydrate;
4) carrying out centrifugal washing on the ferrous sulfate heptahydrate to obtain a ferrous sulfate heptahydrate product and a washing solution;
5) and returning the cleaning solution to the precipitated titanium liquid tank to be mixed with the precipitated titanium liquid for standby.
2. The method for producing the hydrolyzed titanium solution by the auxiliary crystallization of ferrous sulfate monohydrate according to claim 1, characterized in that: the mass ratio of the ferrous sulfate monohydrate to the precipitated titanium liquid is 1: 15-1: 20.
3. The method for producing the hydrolyzed titanium solution by the auxiliary crystallization of ferrous sulfate monohydrate according to claim 1, characterized in that: in the step 2), the cooling conditions include: cooling to 20-25 deg.C, and keeping the temperature for 10 min.
4. The method for producing the hydrolyzed titanium solution by the auxiliary crystallization of ferrous sulfate monohydrate according to claim 1, characterized in that: in the step 3), solid-liquid separation is carried out on the crystallized slurry through a rotary table.
5. The method for producing the hydrolyzed titanium solution by the auxiliary crystallization of ferrous sulfate monohydrate according to claim 1, characterized in that: in the step 4), during centrifugal washing, the adding proportion of washing water is 3-5% of the mass of the ferrous sulfate heptahydrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010191671.6A CN111362300A (en) | 2020-03-18 | 2020-03-18 | Method for producing titanium hydrolysate by auxiliary crystallization of ferrous sulfate monohydrate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010191671.6A CN111362300A (en) | 2020-03-18 | 2020-03-18 | Method for producing titanium hydrolysate by auxiliary crystallization of ferrous sulfate monohydrate |
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| CN202010191671.6A Pending CN111362300A (en) | 2020-03-18 | 2020-03-18 | Method for producing titanium hydrolysate by auxiliary crystallization of ferrous sulfate monohydrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634210A (en) * | 2022-03-17 | 2022-06-17 | 河北惠尔信新材料有限公司 | Treatment system and method for washing mother liquor for producing titanium dioxide by sulfuric acid process |
| CN115159472A (en) * | 2022-07-19 | 2022-10-11 | 杭州安永环保科技有限公司 | A method for concentrating black titanium liquid or waste sulfuric acid in the production process of titanium dioxide by sulfuric acid method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224221A (en) * | 2013-04-14 | 2013-07-31 | 张彭成 | Method for separating sulfuric acid and ferrous sulfate by using ferrous sulfate monohydrate residue |
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2020
- 2020-03-18 CN CN202010191671.6A patent/CN111362300A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224221A (en) * | 2013-04-14 | 2013-07-31 | 张彭成 | Method for separating sulfuric acid and ferrous sulfate by using ferrous sulfate monohydrate residue |
Non-Patent Citations (1)
| Title |
|---|
| 李坚主编: "《轻稀贵金属冶金学》", 31 March 2018, 冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114634210A (en) * | 2022-03-17 | 2022-06-17 | 河北惠尔信新材料有限公司 | Treatment system and method for washing mother liquor for producing titanium dioxide by sulfuric acid process |
| CN115159472A (en) * | 2022-07-19 | 2022-10-11 | 杭州安永环保科技有限公司 | A method for concentrating black titanium liquid or waste sulfuric acid in the production process of titanium dioxide by sulfuric acid method |
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Application publication date: 20200703 |