CN113772741A - Method for producing iron oxide black by liquid phase synthesis - Google Patents
Method for producing iron oxide black by liquid phase synthesis Download PDFInfo
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- CN113772741A CN113772741A CN202111041352.8A CN202111041352A CN113772741A CN 113772741 A CN113772741 A CN 113772741A CN 202111041352 A CN202111041352 A CN 202111041352A CN 113772741 A CN113772741 A CN 113772741A
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- Prior art keywords
- iron oxide
- oxide black
- liquid phase
- black
- producing
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000007791 liquid phase Substances 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 32
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 32
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 32
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000006228 supernatant Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 4
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 abstract description 9
- 239000001034 iron oxide pigment Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- 239000000243 solution Substances 0.000 description 36
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000007259 addition reaction Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a method for producing iron oxide black by liquid phase synthesis, belonging to the technical field of iron oxide pigment production. The invention provides a method for producing iron oxide black by liquid phase addition, which mainly comprises the following steps: in the same reaction kettle, a plurality of batches of iron oxide black are produced, and the iron oxide black generated in the previous batch is reserved each time and is used as a crystal nucleus generated by the iron oxide black in the next batch; the specific method for producing the iron oxide black of each batch comprises the following steps: preheating ferrous sulfate solution and alkali liquor, adding into a reaction kettle, maintaining the temperature at 70-95 ℃, introducing air to generate iron oxide black, settling the iron oxide black after the reaction is finished, and skimming supernatant. Experiments prove that the method can improve the chemical stability and the chromaticity quality of the iron oxide black, effectively improve the quality of the iron oxide black product and have extremely high industrial application value.
Description
Technical Field
The invention belongs to the technical field of production of iron oxide pigments, and particularly relates to a method for producing iron oxide black by liquid phase synthesis.
Background
Black iron oxide with molecular formula of Fe3O4Black powder of Fe2O3The addition product of FeO and FeO is insoluble in water, has magnetism, high coloring power and covering power, no toxicity and no pollution. The iron oxide black is used as an industrial raw material, is widely applied to the technical fields of coatings, cosmetics and biomedicines, and has wide development prospect.
The current common production process of iron oxide black in China mainly comprises the following steps:
an addition method comprises the following steps: mixing ferrous sulfate solution with liquid alkali (NaOH) and reactingShould produce Fe (OH)2Adding proper amount of iron yellow leftover (FeSO) in proportion3) Performing an addition reaction at 95-100 deg.C (reaction time about 68h) to obtain iron oxide black. The method has the defects of long reaction time, high energy consumption and light coloring power of the product.
A precipitation oxidation method: neutralizing the purified ferrous sulfate solution with liquid alkali to generate Fe (OH)2And then heating to 85-95 ℃, introducing air for oxidation (having a stirring function) to obtain iron oxide black slurry, and filtering, washing, drying, finely grinding and blending to obtain an iron oxide black product. The direct oxidation method is an innovation for the addition method, and the coloring of the product is higher than that of the addition method.
An ammonia method: adding ammonia water into the purified ferrous sulfate solution, and controlling the pH of the solution to be about 9-10 to obtain a solution containing Fe (OH)2And (NH)4)2SO4The colloidal solution of (4). Then heating to 70-80 ℃, introducing air for oxidation (having a stirring function) to obtain iron oxide black slurry, and filtering, washing, drying, finely grinding and blending to obtain an iron oxide black product; the filtrate is evaporated to prepare ammonium sulfate. Although the quality of the iron oxide black prepared by the method can reach the national first-grade product standard, the production cost is reduced, and the by-product (NH) is generated4)25O4Can be recycled as fertilizer, but has certain environmental pollution because the volatilization of free ammonia in the solution is inevitably caused in the production process.
The precipitation oxidation method is the most used iron oxide black production method at present by combining various factors, but can be improved according to the change of specific production conditions, and has the possibility of improving the production efficiency and the product quality.
Disclosure of Invention
In view of the above problems in the prior art, the technical problem to be solved by the present invention is to provide a method for producing black iron oxide by liquid phase synthesis.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for producing black iron oxide by liquid phase synthesis comprises the following steps: and (3) carrying out a plurality of batches of black iron oxide production in the same reaction kettle, and keeping the black iron oxide produced in the previous batch each time to be used as a crystal nucleus for the production of the black iron oxide in the next batch.
Further, the specific method for producing the iron oxide black of each batch comprises the following steps: preheating ferrous sulfate solution and alkali liquor, adding into a reaction kettle, maintaining the temperature at 70-95 ℃, introducing air to generate iron oxide black, settling the iron oxide black after the reaction is finished, and skimming supernatant.
Further, the temperature of the preheating is 70 ℃.
Further, the air introducing speed is 25-35M3/min。
Further, the concentration of the ferrous sulfate solution is 0.5-10%.
Further, the plurality of batches are 5-8 batches.
Compared with the prior art, the invention has the beneficial effects that:
the method for producing the iron oxide black through liquid phase addition, provided by the invention, is characterized in that a plurality of batches of iron oxide black production are carried out in the same reaction kettle, the iron oxide black generated in the previous batch is reserved each time and is used as a crystal nucleus generated by the iron oxide black in the next batch, and the steps are repeated, so that the chemical stability and the chromaticity quality of the iron oxide black are improved, the quality of the iron oxide black product is effectively improved, and the method has a very high industrial application value. The method can particularly effectively recover and utilize low-concentration ferrous sulfate, and the existing method for producing 1 ton of iron oxide red can generate a large amount of about 20 tons of mother liquor (also called process water and waste water), wherein the main components of the mother liquor are ferrous sulfate with the content of about 0.5 percent and other miscellaneous salts. The method of the invention can further utilize the ferrous sulfate in the mother liquor with high efficiency.
Detailed Description
The invention is further described with reference to specific examples.
Example 1:
adding 0.5% ferrous sulfate solution preheated to 70 deg.C into reaction kettle, maintaining at 70-95 deg.C, introducing 25M air3Adding NaOH solution, ferrous sulfate and sodium hydroxide under the condition of minForming reaction to generate ferroferric oxide, stopping stirring after the reaction is finished, settling and gathering the ferroferric oxide at the bottom of the reaction kettle, removing supernatant after the settling is finished, keeping the generated ferroferric oxide in the reaction kettle, continuously adding 0.5 percent ferrous sulfate solution preheated to 70 ℃ into the reaction kettle, adding NaOH solution, and introducing 25M of air3And/min, keeping the temperature at 70-95 ℃ to continuously generate ferroferric oxide. And performing reaction to generate ferroferric oxide-ferroferric oxide sedimentation-supernatant removal circulation for 3 times in a reaction kettle, collecting and cleaning the sediment, and performing conventional filter pressing, drying and grinding to obtain the iron oxide black.
Example 2:
adding 0.5% ferrous sulfate solution preheated to 70 deg.C into reaction kettle, maintaining at 80-95 deg.C, introducing air 30M3Adding NaOH solution under the condition of min, carrying out addition reaction on ferrous sulfate and sodium hydroxide to generate ferroferric oxide, stopping stirring after the reaction is finished, settling and gathering the ferroferric oxide at the bottom of the reaction kettle, removing supernatant after the settlement is finished, keeping the generated ferroferric oxide in the reaction kettle, continuously adding 0.5% ferrous sulfate solution preheated to 70 ℃ into the reaction kettle, adding NaOH solution, and introducing air at the rate of 30M3And/min, keeping the temperature at 70-95 ℃ to continuously generate ferroferric oxide. And performing reaction to generate ferroferric oxide-ferroferric oxide sedimentation-supernatant removal circulation for 5 times in a reaction kettle, collecting and cleaning the sediment, and performing conventional filter pressing, drying and grinding to obtain the iron oxide black.
Example 3:
adding 0.5% ferrous sulfate solution preheated to 70 deg.C into reaction kettle, maintaining at 80-95 deg.C, introducing air 30M3Adding NaOH solution under the condition of min, carrying out addition reaction on ferrous sulfate and sodium hydroxide to generate ferroferric oxide, stopping stirring after the reaction is finished, settling and gathering the ferroferric oxide at the bottom of the reaction kettle, removing supernatant after the settlement is finished, keeping the generated ferroferric oxide in the reaction kettle, continuously adding 0.5% ferrous sulfate solution preheated to 70 ℃ into the reaction kettle, adding NaOH solution, and introducing air at the rate of 30M3Min, keeping the temperature at 70-95 deg.CAnd generating ferroferric oxide. And performing reaction to generate ferroferric oxide-ferroferric oxide sedimentation-supernatant removal circulation for 8 times in a reaction kettle, collecting and cleaning the sediment, and performing conventional filter pressing, drying and grinding to obtain the iron oxide black.
Example 4:
adding 2% ferrous sulfate solution preheated to 70 deg.C into reaction kettle, maintaining at 70-95 deg.C, introducing air 30M3Adding NaOH solution under the condition of min, carrying out addition reaction on ferrous sulfate and sodium hydroxide to generate ferroferric oxide, stopping stirring after the reaction is finished, settling and gathering the ferroferric oxide at the bottom of the reaction kettle, removing supernatant after the settling is finished, keeping the generated ferroferric oxide in the reaction kettle, continuously adding 0.5% ferrous sulfate solution preheated to 70 ℃ into the reaction kettle, adding NaOH solution, introducing air, and keeping the temperature at 70-95 ℃ to continuously generate the ferroferric oxide. And performing reaction to generate ferroferric oxide-ferroferric oxide sedimentation-supernatant removal circulation for 6 times in a reaction kettle, collecting and cleaning the sediment, and performing conventional filter pressing, drying and grinding to obtain the iron oxide black.
Example 5:
adding 5% ferrous sulfate solution preheated to 70 deg.C into reaction kettle, maintaining at 70-95 deg.C, introducing air 30M3Adding NaOH solution under the condition of min, carrying out addition reaction on ferrous sulfate and sodium hydroxide to generate ferroferric oxide, stopping stirring after the reaction is finished, settling and gathering the ferroferric oxide at the bottom of the reaction kettle, removing supernatant after the settlement is finished, keeping the generated ferroferric oxide in the reaction kettle, continuously adding 0.5% ferrous sulfate solution preheated to 70 ℃ into the reaction kettle, adding NaOH solution, and introducing 30M air3And/min, keeping the temperature at 70-95 ℃ to continuously generate ferroferric oxide. And performing reaction to generate ferroferric oxide-ferroferric oxide sedimentation-supernatant removal circulation for 6 times in a reaction kettle, collecting and cleaning the sediment, and performing conventional filter pressing, drying and grinding to obtain the iron oxide black.
Example 6:
adding 10% ferrous sulfate solution preheated to 70 deg.C into reaction kettle, maintaining at 70-95 deg.C, introducingAir 30M3Adding NaOH solution under the condition of min, carrying out addition reaction on ferrous sulfate and sodium hydroxide to generate ferroferric oxide, stopping stirring after the reaction is finished, settling and gathering the ferroferric oxide at the bottom of the reaction kettle, removing supernatant after the settlement is finished, keeping the generated ferroferric oxide in the reaction kettle, continuously adding 0.5% ferrous sulfate solution preheated to 70 ℃ into the reaction kettle, adding NaOH solution, and introducing air at the rate of 30M3And/min, keeping the temperature at 70-95 ℃ to continuously generate ferroferric oxide. And performing reaction to generate ferroferric oxide-ferroferric oxide sedimentation-supernatant removal circulation for 6 times in a reaction kettle, collecting and cleaning the sediment, and performing conventional filter pressing, drying and grinding to obtain the iron oxide black.
Example 7:
the iron oxide blacks prepared in examples 1 to 6 were tested for stability and color index, and it was found that in examples 1 to 3, the stability of the iron oxide black gradually increased with the increase of the number of cycles, but the color index of the iron oxide blacks in examples 2 and 3 was better than that in example 1, and the color was more pure black. In examples 4 to 6, the stability of the iron oxide black is slightly reduced with the increase of the concentration of the ferrous sulfate solution to 10%, and the color index is slightly different between the concentration of the ferrous sulfate solution of 2% and the concentration of the ferrous sulfate solution of 5%, which is slightly lower than that of example 2 and slightly better than that of example 6.
Claims (6)
1. The liquid phase synthesis process of producing black iron oxide features that several batches of black iron oxide are produced in the same reactor while maintaining the black iron oxide produced in the previous batch as the crystal nucleus for the next batch.
2. The method for producing black iron oxide through liquid phase addition according to claim 1, wherein the specific method for producing each batch of black iron oxide is as follows: preheating ferrous sulfate solution and alkali liquor, adding into a reaction kettle, maintaining the temperature at 70-95 ℃, introducing air to generate iron oxide black, settling the iron oxide black after the reaction is finished, and skimming supernatant.
3. The method for producing black iron oxide by liquid phase addition according to claim 2, wherein the temperature of the preheating is 70 ℃.
4. The method for producing black iron oxide by liquid phase addition according to claim 2, wherein the air is introduced at a rate of 25 to 35M3/min。
5. The method for producing black iron oxide by liquid phase addition according to claim 2, wherein the concentration of the ferrous sulfate solution is 0.5 to 10%.
6. The method for producing black iron oxide by liquid phase addition according to claim 2, wherein the number of batches is 5 to 8 batches.
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| CN202111041352.8A CN113772741A (en) | 2021-09-06 | 2021-09-06 | Method for producing iron oxide black by liquid phase synthesis |
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| CN202111041352.8A CN113772741A (en) | 2021-09-06 | 2021-09-06 | Method for producing iron oxide black by liquid phase synthesis |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB433333A (en) * | 1934-05-03 | 1935-08-13 | Joseph Williams Ayers | Improvements in black oxide of iron |
| GB1441043A (en) * | 1974-02-21 | 1976-06-30 | Laporte Industries Ltd | Process for the production of iron oxide |
| US4090888A (en) * | 1975-04-24 | 1978-05-23 | Bayer Aktiengesellschaft | Production of black iron oxide pigments |
| CN1709985A (en) * | 2005-06-08 | 2005-12-21 | 刘世琦 | Method for producing iron oxide black |
| CN102139927A (en) * | 2011-01-17 | 2011-08-03 | 升华集团德清华源颜料有限公司 | High-purity iron oxide black pigment and production method thereof |
| CN102689931A (en) * | 2012-06-11 | 2012-09-26 | 上海宝齐氧化铁有限公司 | Method for producing iron oxide black from desiliconized sludge cake by one-step process |
| CN103333523A (en) * | 2013-06-08 | 2013-10-02 | 安徽天泰环保科技有限公司 | Method for preparing black iron oxide wrapped with silicon dioxide |
| CN104071850A (en) * | 2013-03-25 | 2014-10-01 | 北京三聚环保新材料股份有限公司 | Preparation method for iron oxide black |
| CN107200359A (en) * | 2016-03-17 | 2017-09-26 | 北京中金瑞丰环保科技有限公司 | A kind of iron oxide pigment and its production method |
-
2021
- 2021-09-06 CN CN202111041352.8A patent/CN113772741A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB433333A (en) * | 1934-05-03 | 1935-08-13 | Joseph Williams Ayers | Improvements in black oxide of iron |
| GB1441043A (en) * | 1974-02-21 | 1976-06-30 | Laporte Industries Ltd | Process for the production of iron oxide |
| US4090888A (en) * | 1975-04-24 | 1978-05-23 | Bayer Aktiengesellschaft | Production of black iron oxide pigments |
| CN1709985A (en) * | 2005-06-08 | 2005-12-21 | 刘世琦 | Method for producing iron oxide black |
| CN102139927A (en) * | 2011-01-17 | 2011-08-03 | 升华集团德清华源颜料有限公司 | High-purity iron oxide black pigment and production method thereof |
| CN102689931A (en) * | 2012-06-11 | 2012-09-26 | 上海宝齐氧化铁有限公司 | Method for producing iron oxide black from desiliconized sludge cake by one-step process |
| CN104071850A (en) * | 2013-03-25 | 2014-10-01 | 北京三聚环保新材料股份有限公司 | Preparation method for iron oxide black |
| CN103333523A (en) * | 2013-06-08 | 2013-10-02 | 安徽天泰环保科技有限公司 | Method for preparing black iron oxide wrapped with silicon dioxide |
| CN107200359A (en) * | 2016-03-17 | 2017-09-26 | 北京中金瑞丰环保科技有限公司 | A kind of iron oxide pigment and its production method |
Non-Patent Citations (1)
| Title |
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Application publication date: 20211210 |