CN115367720A - Method for preparing high-purity calcium hydrophosphate - Google Patents
Method for preparing high-purity calcium hydrophosphate Download PDFInfo
- Publication number
- CN115367720A CN115367720A CN202210049876.XA CN202210049876A CN115367720A CN 115367720 A CN115367720 A CN 115367720A CN 202210049876 A CN202210049876 A CN 202210049876A CN 115367720 A CN115367720 A CN 115367720A
- Authority
- CN
- China
- Prior art keywords
- solution
- phosphoric acid
- calcium
- calcium hydrophosphate
- hydrophosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 38
- 239000011575 calcium Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000000243 solution Substances 0.000 claims abstract description 65
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 45
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000292 calcium oxide Substances 0.000 claims abstract description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012043 crude product Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004042 decolorization Methods 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 22
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000006115 defluorination reaction Methods 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 claims 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229960005069 calcium Drugs 0.000 description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229960003563 calcium carbonate Drugs 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/322—Preparation by neutralisation of orthophosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention discloses a method for preparing high-purity calcium hydrophosphate, which comprises the following steps; step one, taking a phosphoric acid crude product solution, adding active carbon into the solution, and carrying out decolorization treatment at the temperature of 30-43 ℃; step two, after the decolorization is finished, filtering out activated carbon, pouring the phosphoric acid crude product solution into an oscillator, adding an extracting agent into the phosphoric acid crude product solution, and starting the oscillator until the mixed solution in the oscillator is layered; and step three, carrying out back extraction on the extract phase in the step two by using deionized water, and concentrating under vacuum. Compared with the prior art, the method has the advantages that: the invention saves more resources and construction cost; the method adopts an acid-base neutralization method, and utilizes the phosphoric acid solution and the calcium oxide solution to prepare the calcium hydrophosphate solution, so that the phosphoric acid solution has higher purity and less impurities; the method has the advantages of simple process and simple and convenient operation, and the prepared calcium hydrophosphate is higher in purity.
Description
Technical Field
The invention relates to the technical field of calcium hydrophosphate production and processing, in particular to a method for preparing high-purity calcium hydrophosphate.
Background
Calcium hydrogen phosphate, white monocase crystal system crystal powder, no bad smell and no smell, and is one excellent food grade additive capable of promoting body's metabolism, strengthening physique, preventing osteoporosis, etc. The existing food grade calcium hydrophosphate, including the medicine grade, has insufficient purity and contains a certain amount of non-metallic fluoride and a plurality of harmful heavy metals. Due to the technical characteristics of the existing production process, the product has more burning residues, and the product also contains calcium dihydrogen phosphate, tricalcium phosphate or calcium carbonate and other impurity components, so that the purity of calcium hydrophosphate is not high enough.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the technical difficulties and provide a method for preparing high-purity calcium hydrophosphate with higher purity.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing high-purity calcium hydrogen phosphate, which comprises the following steps;
step one, taking a phosphoric acid crude product solution, adding activated carbon into the phosphoric acid crude product solution, and carrying out decolorization treatment at the temperature of 30-43 ℃;
step two, after the decolorization is finished, filtering out activated carbon, pouring the phosphoric acid crude product solution into an oscillator, adding an extracting agent into the phosphoric acid crude product solution, and starting the oscillator until the mixed solution in the oscillator is layered;
step three, carrying out back extraction on the extract phase in the step two by using deionized water, and concentrating under vacuum to obtain a purified phosphoric acid solution;
step four, carrying out desulfurization and defluorination treatment on the purified phosphoric acid solution obtained in the step three to obtain a refined phosphoric acid solution;
step five, calcining the crude limestone at the temperature of 600-800 ℃ for 60-80 min to prepare refined calcium oxide;
step six, putting the refined calcium oxide in the step five into a slurry preparation pool and adding water to prepare a calcium oxide solution;
step seven, slowly adding the purified and refined phosphoric acid solution obtained in the step four into the calcium oxide solution obtained in the step six, and stirring while adding to ensure that calcium oxide and phosphoric acid fully react at the temperature of 60-75 ℃ to obtain a calcium hydrophosphate solution;
pumping the calcium hydrophosphate solution into a roller dryer for drying to prepare a calcium hydrophosphate solid;
step nine, putting the calcium hydrophosphate solid obtained in the step eight into a crusher to be crushed to obtain calcium hydrophosphate powder;
and step ten, screening the calcium hydrogen phosphate powder obtained in the step nine, wherein the calcium hydrogen phosphate powder with qualified particle size is a finished product, and putting the unqualified calcium hydrogen phosphate powder into the crusher again for secondary crushing.
The extraction in the second step is carried out at the temperature of 35-45 ℃.
The ph of the calcium hydrophosphate solution in the seventh step is 5.6 to 6.5.
The screening in the step ten is to pass through a 400-mesh screen.
And the mass fraction of water in the calcium hydrophosphate finished product in the step ten is 3-6%.
Compared with the prior art, the invention has the advantages that:
1. the invention saves more resources and construction cost;
2. the method adopts an acid-base neutralization method, and utilizes the phosphoric acid solution and the calcium oxide solution to prepare the calcium hydrophosphate solution, so that the phosphoric acid solution has higher purity and less impurities;
3. the method has the advantages of simple process and simple and convenient operation, and the prepared calcium hydrophosphate has higher purity.
Detailed Description
The present invention will be described in further detail with reference to embodiments.
Example 1
A method for preparing high-purity calcium hydrogen phosphate, which comprises the following steps;
step one, taking a phosphoric acid crude product solution, adding activated carbon into the phosphoric acid crude product solution, and carrying out decolorization treatment at the temperature of 33 ℃;
step two, after the decolorization is finished, filtering out activated carbon, pouring the phosphoric acid crude product solution into an oscillator, adding an extracting agent into the phosphoric acid crude product solution, starting the oscillator, and layering the mixed solution in the oscillator at the temperature of 38 ℃;
step three, carrying out back extraction on the extract phase in the step two by using deionized water, and concentrating under vacuum to obtain a purified phosphoric acid solution;
step four, carrying out desulfurization and defluorination treatment on the purified phosphoric acid solution obtained in the step three to obtain a refined phosphoric acid solution;
step five, calcining the crude limestone at 650 ℃ for 68min to prepare refined calcium oxide;
step six, putting the refined calcium oxide obtained in the step five into a slurry mixing pool and adding water to prepare a calcium oxide solution;
step seven, slowly adding the purified and refined phosphoric acid solution obtained in the step four into the calcium oxide solution obtained in the step six, and stirring while adding the purified and refined phosphoric acid solution to ensure that calcium oxide and phosphoric acid fully react at the temperature of 65 ℃ to obtain a calcium hydrophosphate solution with the pH of 5.6;
pumping the calcium hydrophosphate solution into a roller dryer for drying to prepare a calcium hydrophosphate solid;
step nine, putting the calcium hydrophosphate solid obtained in the step eight into a crusher to be crushed to obtain calcium hydrophosphate powder;
and step ten, sieving the calcium hydrogen phosphate powder in the step nine by using a 400-mesh sieve, wherein the calcium hydrogen phosphate powder with qualified particle size is a finished product, the mass fraction of water in the finished calcium hydrogen phosphate product is 6%, and the unqualified calcium hydrogen phosphate product is put into a crusher again for secondary crushing.
Example 2
A method for preparing high-purity calcium hydrogen phosphate, which comprises the following steps;
step one, taking a phosphoric acid crude product solution, adding activated carbon into the solution, and carrying out decolorization treatment at the temperature of 43 ℃;
step two, after the decolorization is finished, filtering out activated carbon, pouring the phosphoric acid crude product solution into an oscillator, adding an extracting agent into the phosphoric acid crude product solution, starting the oscillator, and layering the mixed solution in the oscillator at the temperature of 45 ℃;
step three, carrying out back extraction on the extract phase in the step two by using deionized water, and concentrating under vacuum to obtain a purified phosphoric acid solution;
step four, carrying out desulfurization and defluorination treatment on the purified phosphoric acid solution obtained in the step three to obtain a refined phosphoric acid solution;
step five, calcining the crude limestone at 800 ℃ for 80min to prepare refined calcium oxide;
step six, putting the refined calcium oxide in the step five into a slurry preparation pool and adding water to prepare a calcium oxide solution;
step seven, slowly adding the purified and refined phosphoric acid solution obtained in the step four into the calcium oxide solution obtained in the step six, and stirring while adding the purified and refined phosphoric acid solution to ensure that calcium oxide and phosphoric acid fully react at the temperature of 75 ℃ to obtain a calcium hydrophosphate solution with the ph of 6;
pumping the calcium hydrophosphate solution into a roller dryer for drying to prepare a calcium hydrophosphate solid;
step nine, putting the calcium hydrophosphate solid obtained in the step eight into a crusher to be crushed to obtain calcium hydrophosphate powder;
and step ten, sieving the calcium hydrogen phosphate powder in the step nine by using a 400-mesh sieve, wherein the calcium hydrogen phosphate powder with qualified particle size is a finished product, the mass fraction of water in the finished calcium hydrogen phosphate product is 3%, and the unqualified calcium hydrogen phosphate product is put into a crusher again for secondary crushing.
The invention and its embodiments have been described above, without this being limitative. Without departing from the spirit of the invention, a person skilled in the art shall appreciate that embodiments similar to the above-described embodiments may be devised without inventing, and the invention shall fall within the scope of the claims.
Claims (5)
1. A method for preparing high-purity calcium hydrophosphate is characterized by comprising the following steps: the preparation method of the high-purity calcium hydrophosphate comprises the following steps;
step one, taking a phosphoric acid crude product solution, adding activated carbon into the phosphoric acid crude product solution, and carrying out decolorization treatment at the temperature of 30-43 ℃;
step two, after the decolorization is finished, filtering out activated carbon, pouring the phosphoric acid crude product solution into an oscillator, adding an extracting agent into the phosphoric acid crude product solution, and starting the oscillator until the mixed solution in the oscillator is layered;
step three, carrying out back extraction on the extract phase in the step two by using deionized water, and concentrating under vacuum to obtain a purified phosphoric acid solution;
step four, carrying out desulfurization and defluorination treatment on the purified phosphoric acid solution obtained in the step three to obtain a refined phosphoric acid solution;
step five, calcining the crude limestone at the temperature of 600-800 ℃ for 60-80 min to prepare refined calcium oxide;
step six, putting the refined calcium oxide in the step five into a slurry preparation pool and adding water to prepare a calcium oxide solution;
step seven, slowly adding the purified and refined phosphoric acid solution obtained in the step four into the calcium oxide solution obtained in the step six, and stirring while adding the purified and refined phosphoric acid solution to ensure that calcium oxide and phosphoric acid fully react at the temperature of 60-75 ℃ to obtain a calcium hydrophosphate solution;
pumping the calcium hydrophosphate solution into a roller dryer for drying to prepare a calcium hydrophosphate solid;
step nine, putting the calcium hydrophosphate solid obtained in the step eight into a crusher for crushing to obtain calcium hydrophosphate powder;
and step ten, screening the calcium hydrogen phosphate powder obtained in the step nine, wherein the calcium hydrogen phosphate powder with qualified particle size is a finished product, and putting the unqualified calcium hydrogen phosphate powder into the crusher again for secondary crushing.
2. A process for the preparation of high purity dibasic calcium phosphate according to claim 1, wherein: the extraction in the second step is carried out at the temperature of 35-45 ℃.
3. A process for the preparation of high purity dibasic calcium phosphate according to claim 1, wherein: and the ph of the calcium hydrophosphate solution in the seventh step is 5.6 to 6.5.
4. A process for the preparation of high purity dibasic calcium phosphate according to claim 1, wherein: the screening in the step ten is to pass through a 400-mesh screen.
5. A process for the preparation of high purity dibasic calcium phosphate according to claim 1, wherein: and the mass fraction of water in the calcium hydrophosphate finished product in the step ten is 3-6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210049876.XA CN115367720A (en) | 2022-01-17 | 2022-01-17 | Method for preparing high-purity calcium hydrophosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210049876.XA CN115367720A (en) | 2022-01-17 | 2022-01-17 | Method for preparing high-purity calcium hydrophosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115367720A true CN115367720A (en) | 2022-11-22 |
Family
ID=84060374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210049876.XA Pending CN115367720A (en) | 2022-01-17 | 2022-01-17 | Method for preparing high-purity calcium hydrophosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115367720A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018032911A1 (en) * | 2016-08-15 | 2018-02-22 | 东江环保股份有限公司 | Method for preparing feed grade calcium hydrophosphate from waste liquid comprising phosphoric acid |
| CN108046228A (en) * | 2017-12-29 | 2018-05-18 | 四川绵竹三佳饲料有限责任公司 | A kind of preparation method of high-purity phosphoric acid hydrogen calcium |
| CN108726499A (en) * | 2018-08-01 | 2018-11-02 | 蒋华民 | A kind of food-grade calcium hydrogen phosphate and preparation method thereof |
| CN110395704A (en) * | 2018-04-24 | 2019-11-01 | 四川大学 | The method of phosphoric acid by wet process coproduction PHOSPHORIC ACID TECH.GRADE potassium dihydrogen and calcium hydrophosphate fodder |
| CN111717904A (en) * | 2019-03-22 | 2020-09-29 | 云南善施化工有限公司 | Production method of calcium hydrogen phosphate |
-
2022
- 2022-01-17 CN CN202210049876.XA patent/CN115367720A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018032911A1 (en) * | 2016-08-15 | 2018-02-22 | 东江环保股份有限公司 | Method for preparing feed grade calcium hydrophosphate from waste liquid comprising phosphoric acid |
| CN108046228A (en) * | 2017-12-29 | 2018-05-18 | 四川绵竹三佳饲料有限责任公司 | A kind of preparation method of high-purity phosphoric acid hydrogen calcium |
| CN110395704A (en) * | 2018-04-24 | 2019-11-01 | 四川大学 | The method of phosphoric acid by wet process coproduction PHOSPHORIC ACID TECH.GRADE potassium dihydrogen and calcium hydrophosphate fodder |
| CN108726499A (en) * | 2018-08-01 | 2018-11-02 | 蒋华民 | A kind of food-grade calcium hydrogen phosphate and preparation method thereof |
| CN111717904A (en) * | 2019-03-22 | 2020-09-29 | 云南善施化工有限公司 | Production method of calcium hydrogen phosphate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103496685B (en) | The method of continuous seepage calcium hydrophosphate fodder | |
| CN108642304B (en) | Comprehensive recovery method of lithium iron phosphate waste | |
| CN113307243B (en) | Method for preparing iron phosphate by recycling mother liquor | |
| CN113104827B (en) | Method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution | |
| CN102502721B (en) | Method for preparing lithium carbonate through extracting lithium from lithium ore | |
| CN109775679A (en) | A kind of preparation method of the ferric phosphate of high-purity high-pressure solid LiFePO4 | |
| CN101985694A (en) | Preparation method for recovering high-purity yttrium europium from fluorescent powder scrap | |
| WO2013174061A1 (en) | Method for preparing high quality feed grade calcium hydrogen phosphate using by-product waste acid from titanium dioxide production | |
| CN102675082B (en) | Preparation method of calcium propionate by egg shell | |
| CN114906830A (en) | Method for controllably preparing battery-grade iron phosphate from pyrite cinder | |
| CN114014294B (en) | Method for preparing lithium iron phosphate by using pyrite and lithium iron phosphate material | |
| CN101708860B (en) | Method for preparing high-purity ultrafine barium carbonate | |
| CN101585547B (en) | Method for preparing ammonium sulfate as fertilizer by phosphogypsum through ball milling | |
| CN115367720A (en) | Method for preparing high-purity calcium hydrophosphate | |
| CN101824542A (en) | Comprehensive utilization method of titanium dioxide waste acid by sulfuric acid process | |
| CN116969427A (en) | Process for recycling phosphoric acid, iron and lithium from lithium iron phosphate battery powder | |
| CN111717904A (en) | Production method of calcium hydrogen phosphate | |
| CN115784188A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| CN115744851A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| CN109252050A (en) | A method of the vanadium extraction again of the dephosphorization mud of byproduct containing vanadium | |
| CN104627974A (en) | Method for producing battery grade iron phosphate | |
| CN105858717B (en) | A kind of preparation method of the basic lead sulphate battery additive of nanoscale four | |
| CN105732154A (en) | Method for preparing potassium fertilizer from potassium feldspar | |
| CN114350952B (en) | Method for recycling gypsum slag in calcified vanadium extraction process | |
| CN112899502B (en) | Method for treating high-calcium black-white tungsten mixed ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221122 |
|
| RJ01 | Rejection of invention patent application after publication |