CN110653071A - Rare earth collecting agent and preparation method thereof - Google Patents
Rare earth collecting agent and preparation method thereof Download PDFInfo
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- CN110653071A CN110653071A CN201910983763.5A CN201910983763A CN110653071A CN 110653071 A CN110653071 A CN 110653071A CN 201910983763 A CN201910983763 A CN 201910983763A CN 110653071 A CN110653071 A CN 110653071A
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- rare earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
Abstract
The invention discloses a rare earth collecting agent and a preparation method thereof. 2-hydroxy-3-naphthoic acid and p-methylbenzoic acid are respectively put into an enamel reaction kettle, methanol and concentrated sulfuric acid are added, the mixture is heated to 65 +/-1 ℃ and refluxed for 36-40 hours, excessive methanol is evaporated for standby, the remainder is 2-hydroxy-3-methyl naphthoate and p-methyl benzoate, the two esters are respectively put into a crystallization tank and a barrel, then the two esters are put into the enamel reaction kettle, methyl benzoate tap water and hydroxylamine hydrochloride are added, the temperature is raised to 25-50 ℃ for reaction for about 6 hours, liquid alkali is dripped during the reaction, the pH value is always kept at 10, the mixture is cooled to about 20 ℃ after the reaction is finished, diluted sulfuric acid is added for acidification until the pH value is 5, and the mixture is put into a plastic barrel for collecting the rare earth agent. Compared with the original collecting agent, the invention changes the chemical reagent of the formula, has slightly lower cost, better selectivity to rare earth minerals and stronger collecting capability.
Description
Technical Field
The invention relates to a flotation rare earth mineral, in particular to a rare earth collecting agent and a preparation method thereof.
Background
China is rich in rare earth resources, and the rare earth reserves account for 33% of the total reserves in the world. The main method for selecting rare earth minerals from rare earth-containing ores is a flotation method.
At present, most of rare earth flotation reagents used in Baiyunebo ore are hydroximic acid composite reagents, but certain difference exists between selectivity and collection of different reagents, and the difference between the selectivity and the collection is mainly reflected by the recovery rate of rare earth and the grade of selected rare earth concentrate, for example, for the rare earth flotation of strong magnetic middlings of lean oxidized ore in Baiyunebo after weak magnetic-strong magnetic separation, the yield of the rare earth of the original reagent is 75.8%, and the grade of the rare earth concentrate is 56.1%.
Disclosure of Invention
The technical problem solved by the invention is to provide the rare earth collecting agent and the preparation method thereof, the recovery rate of the rare earth collecting agent is improved by 2-4% and the grade of rare earth concentrate is improved by 2-4.4% in a flotation process compared with that of a raw chemical agent.
The technical scheme is as follows:
the invention comprises the following materials by weight percent:
the rare earth collector comprises the following components in percentage by weight: 30-60% of 2-hydroxy-3-naphthalene hydroxamic acid, 10-30% of p-methyl benzohydroxamic acid and 20-50% of benzohydroxamic acid.
The preparation method of the rare earth collector comprises the following steps:
(1) putting 300-500 kg of 2-hydroxy-3-naphthoic acid into an enamel reaction kettle, then adding 700-1100 kg of methanol with the weight percentage concentration of 99.9% and 50-80 kg of sulfuric acid with the weight percentage concentration of 98%, then heating to 65 +/-1 ℃, refluxing for 36-40 hours, then evaporating excessive methanol for later use, and putting the remainder of 2-hydroxy-3-naphthoic acid methyl ester into a crystallization tank for natural crystallization for 45-55 hours;
(2) putting 250-400 kg of p-methylbenzoic acid into an enamel reaction kettle, adding 450-920 kg of methanol with the weight percentage concentration of 99.9% and 40-74 kg of sulfuric acid with the weight percentage concentration of 98%, heating to 65 +/-1 ℃, refluxing for 36-40 hours, evaporating excessive methanol, putting the excessive methanol into a barrel for later use, and putting the remainder of methyl p-methylbenzoate into a plastic barrel;
(3) taking 300-600 kg of crystallized 2-hydroxy-3-methyl naphthoate obtained in the step (1), then taking 100-300 kg of p-methyl benzoate obtained in the step (2), putting the p-methyl benzoate into an enamel reaction kettle, adding 200-500 kg of methyl benzoate, adding 1000-2800 kg of water, then adding 280-900 kg of hydroxylamine hydrochloride with the weight percentage concentration of 99%, heating to 25-50 ℃ for reacting for about 6 hours, dropwise adding 30% liquid alkali during the reaction, keeping the pH 10 all the time, cooling to about 20 ℃ after the reaction is finished, acidifying with the weight percentage concentration of 25-30% sulfuric acid until the pH is 5, and putting the acidified sulfuric acid into a plastic bucket to obtain the rare earth collecting agent.
The invention has the technical effects that:
the rare earth flotation reagent obtained by the invention is brownish yellow suspension which is easy to disperse in ore pulp, has stable chemical property, no corrosiveness and non-inflammable products, and has no quality change after being stored in a shade place for a long time.
Compared with the original rare earth collecting agent, the rare earth collecting agent has better selective collecting property and higher rare earth recovery rate and rare earth concentrate grade.
For example, for the rare earth flotation of the strong magnetic middlings of the lean oxide ores in Baiyunebo after the weak magnetic-strong magnetic separation, the yield of the rare earth of the original reagent is 75.8 percent, and the grade of the rare earth concentrate is 56.1 percent. The invention has the advantages that the yield of the rare earth is 77.4 percent, and the grade of the selected rare earth concentrate is 60.5 percent.
Compared with the original pesticide rare earth recovery rate, the rare earth collecting agent of the invention improves 2-4% and the rare earth concentrate grade improves 2-4.4% in different flotation processes.
Detailed Description
The following description sufficiently illustrates specific embodiments of the invention to enable those skilled in the art to practice and reproduce it.
Example 1
The invention comprises the following materials by weight percent:
2 hydroxy-3 naphthalene hydroxamic acid 40%
P-benzohydroxamic acid 10%
Benzohydroxamic acid 50%
The preparation method comprises the following steps:
(1) weighing 400kg of 2-hydroxy-3-naphthoic acid, placing the 2-hydroxy-3-naphthoic acid into an enamel reaction kettle, adding 900kg of methanol with a weight percentage concentration of 99.9% and 75 kg of concentrated sulfuric acid with a weight percentage concentration of 98%, heating to 65 +/-1 ℃, refluxing (methanol vapor is condensed by a condenser and then returns to the reaction kettle) for 37 hours, evaporating excessive methanol (methanol vapor is condensed by the condenser and returns to another container) for standby, and placing the rest of 2-hydroxy-3-naphthoic acid methyl ester into a crystallization tank for natural crystallization for 50 hours.
(2) 300kg of p-methyl benzoic acid is put into an enamel reaction kettle, 820kg of methanol with the weight percentage concentration of 99.9 percent is added, 64kg of concentrated sulfuric acid with the weight percentage concentration of 98 percent is heated to 65 +/-1 ℃ for reflux (methanol steam is condensed by a condenser and then returns to the reaction kettle) for 37 hours, and excessive methanol is evaporated out (the methanol steam is condensed by the condenser and returns to another container) and is put into a barrel for standby. The remainder is methyl p-methylbenzoate and is put into a plastic bucket.
(3) Taking 400kg of crystallized 2-hydroxy-3-methyl naphthoate obtained in the step (1), then taking 100kg of methyl p-methylbenzoate obtained in the step (2), putting the methyl p-methylbenzoate into an enamel reaction kettle, adding 500kg of methyl benzoate, adding 2000kg of tap water, then adding 510kg of hydroxylamine hydrochloride with the weight percentage of 99%, heating to 50 ℃ for reaction for 6 hours, dropwise adding a sodium hydroxide solution with the weight percentage concentration of 30% during the reaction, keeping the pH value at 10 all the time, cooling to about 20 ℃ after the reaction is finished, adding sulfuric acid with the weight percentage concentration of 25% to acidify to the pH value at 5, and putting the acidified solution into a plastic barrel to obtain the rare earth collector.
The reagent is used for carrying out the rare earth flotation experiment on the strong magnetic middlings of the middlings lean oxidized ores of bayan obo from inner Mongolia after the middlings lean oxidized ores are subjected to weak magnetic-strong magnetic separation in a dressing plant, and the minerals contain 8.21% of fluorine carbon cerium, 3.38% of monazite, 16.87% of fluorite and hematite, feldspar, mica, spodumene and amphibole.
The experiment is carried out on the premise of the original process flow, the grinding fineness and the pulp concentration, a primary coarse and secondary fine production flow is adopted, the water is returned from the tailings of the ore dressing, the water quality is circulated for many times, the ion content is high, the hardness is high, and the pH value is 5.5-6.
Results of the experiment
| The rare earth content of the raw ore% | Content of rare earth in ore concentrate% | Content of rare earth in tailings% | The recovery rate is high | |
| Raw medicine | 11.85 | 56.12 | 2.25 | 75.87 |
| Rare earth collector and foaming agent | 10.72 | 60.58 | 1.76 | 77.43 |
The test result shows that the medicament has better collecting property and strong selectivity compared with the original medicament, and the grade of the rare earth concentrate and the recovery rate of the rare earth are obviously improved.
Example 2
The invention comprises the following materials by weight percent:
2 hydroxy-3 naphthalene hydroxamic acid 50%
P-benzohydroxamic acid 20%
Benzohydroxamic acid 30%
The preparation method comprises the following steps:
(1) weighing 500kg of 2-hydroxy-3-naphthoic acid, putting the 2-hydroxy-3-naphthoic acid into an enamel reaction kettle, adding 1100kg of methanol with the weight percentage concentration of 99.9% and 80kg of sulfuric acid with the weight percentage concentration of 98%, heating to 65 +/-1 ℃, refluxing (methanol steam is condensed by a condenser and then returns to the reaction kettle) for 40 hours, evaporating excessive methanol (methanol steam is condensed by the condenser and returns to another container) for standby, and putting the remainder 2-hydroxy-3-naphthoic acid methyl ester into a crystallization tank for natural crystallization for 49 hours.
(2) 300kg of p-methyl benzoic acid is put into an enamel reaction kettle, 820kg of methanol with the weight percentage concentration of 99.9 percent and 58kg of concentrated sulfuric acid with the weight percentage concentration of 98 percent are added to be heated and refluxed (methanol steam is condensed by a condenser and then returns to the reaction kettle) for 40 hours, excessive methanol is distilled out (the methanol steam is condensed by the condenser and returns to another container), and the remainder is methyl p-methyl benzoate which is put into a plastic bucket.
(3) 400kg of crystalline methyl 2-hydroxy-3-naphthoate (1) was taken. And (3) putting 160kg of methyl p-methylbenzoate in the step (2) into an enamel reaction kettle, adding 240kg of methyl benzoate, adding 1600kg of tap water, adding 380kg of 99% hydroxylamine hydrochloride by weight, heating to 49 ℃ for reacting for 6 hours, dropwise adding a 30% sodium hydroxide solution by weight during the reaction, keeping the pH value at 10 all the time, cooling to 20 ℃ after the reaction is finished, acidifying with sulfuric acid with the weight percentage concentration of 27% to the pH value at 5, and putting the sulfuric acid into a plastic barrel to obtain the rare earth collector.
The raw ore of rare earth of Douglas badugi is tested by the medicament, and the raw ore contains 8.56 percent of rare earth REO, has high impurity content and great sorting difficulty.
Results of the experiment
| The rare earth content of the raw ore% | Content of rare earth in ore concentrate% | Content of rare earth in tailings% | The recovery rate is high | |
| Raw medicine | 9.25 | 46.18 | 2.85 | 52.43 |
| Rare earth collector and foaming agent | 9.11 | 48.85 | 2.45 | 54.67 |
The experimental results show that: for Damaoqi rare earth ore medicament, the rare earth grade and the yield are obviously improved for the original medicament.
Example 3
The invention comprises the following materials by weight percent:
2 hydroxy-3 naphthalene hydroxamic acid 30%
P-methylbenzyl hydroxamic acid 30 percent
Benzohydroxamic acid 40%
The preparation method comprises the following steps:
(1) weighing 300kg of 2-hydroxy-3-naphthoic acid, putting the 2-hydroxy-3-naphthoic acid into an enamel reaction kettle, adding 700kg of methanol with the weight percentage concentration of 99.9% and 50kg of concentrated sulfuric acid with the weight percentage concentration of 98%, heating to 65 +/-1 ℃, refluxing (methanol steam is condensed by a condenser and then returns to the reaction kettle) for 39 hours, evaporating excessive methanol (methanol steam is condensed by the condenser and returns to another container) for standby, and putting the remainder 2-hydroxy-3-naphthoic acid methyl ester into a crystallization tank for natural crystallization for 48 hours.
(2) 350kg of p-methyl benzoic acid is put into an enamel reaction kettle, 900kg of methanol with the weight percentage concentration of 99.9 percent is added, 70kg of concentrated sulfuric acid with the weight percentage concentration of 98 percent is heated to 65 +/-1 ℃ for refluxing (methanol steam is condensed by a condenser and then returns to the reaction kettle) for 39 hours, excessive methanol is evaporated out (the methanol steam is condensed by the condenser and returns to another container), and the remainder is methyl p-methyl benzoate which is put into a plastic bucket.
(3) 300kg of crystalline methyl 2-hydroxy-3-naphthoate (1) was collected. And (3) putting 300kg of methyl p-methylbenzoate in the step (2) into an enamel reaction kettle, adding 400kg of methyl benzoate, adding 2000kg of tap water, adding 550kg of hydroxylamine hydrochloride with the weight percentage of 99%, heating to 48 ℃, reacting for 6 hours, dropwise adding a sodium hydroxide solution with the weight percentage concentration of 30% during the reaction, keeping the pH value at 10 all the time, cooling to about 20 ℃ after the reaction is finished, acidifying with 29% diluted sulfuric acid with the weight percentage concentration to the pH value at 5, and putting the acidified solution into a plastic barrel to obtain the rare earth collecting agent.
The raw materials of the medicament are from bayan obo iron ore tailings minerals, and the ingredients of the medicament are complex, such as fluorite, apatite, nonmagnetic iron minerals, mica, pyroxene and amphibole.
The experiment is carried out on the premise of not changing the field process flow, the grinding fineness and the pulp concentration, and flotation equipment is adopted for comparison of raw medicines.
Results of the experiment
| The rare earth content of the raw ore% | Content of rare earth in ore concentrate% | Content of rare earth in tailings% | The recovery rate is high | |
| Raw medicine | 9.07 | 56.95 | 2.58 | 45.87 |
| Rare earth collector and foaming agent | 9.17 | 60.35 | 2.00 | 50.05 |
The result shows that the method has stronger advantages in improving the grade and yield of the rare earth concentrate for the iron-dressing tailings with complex bayan obo components.
It should be understood that the above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention, and the present invention should be covered thereby. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (2)
1. A rare earth collector is characterized by comprising the following components in percentage by weight: 30-60% of 2-hydroxy-3-naphthalene hydroxamic acid, 10-30% of p-methyl benzohydroxamic acid and 20-50% of benzohydroxamic acid.
2. A preparation method of a rare earth collector is characterized by comprising the following steps:
(1) putting 300-500 kg of 2-hydroxy-3-naphthoic acid into an enamel reaction kettle, then adding 700-1100 kg of methanol with the weight percentage concentration of 99.9% and 50-80 kg of sulfuric acid with the weight percentage concentration of 98%, then heating to 65 +/-1 ℃, refluxing for 36-40 hours, then evaporating excessive methanol for later use, and putting the remainder of 2-hydroxy-3-naphthoic acid methyl ester into a crystallization tank for natural crystallization for 45-55 hours;
(2) putting 250-400 kg of p-methylbenzoic acid into an enamel reaction kettle, adding 450-920 kg of methanol with the weight percentage concentration of 99.9% and 40-74 kg of sulfuric acid with the weight percentage concentration of 98%, heating to 65 +/-1 ℃, refluxing for 36-40 hours, evaporating excessive methanol, putting the excessive methanol into a barrel for later use, and putting the remainder of methyl p-methylbenzoate into a plastic barrel;
(3) taking 300-600 kg of crystallized 2-hydroxy-3-methyl naphthoate obtained in the step (1), then taking 100-300 kg of p-methyl benzoate obtained in the step (2), putting the p-methyl benzoate into an enamel reaction kettle, adding 200-500 kg of methyl benzoate, adding 1000-2800 kg of water, then adding 280-900 kg of hydroxylamine hydrochloride with the weight percentage concentration of 99%, heating to 25-50 ℃ for reacting for about 6 hours, dropwise adding 30% liquid alkali during the reaction, keeping the pH 10 all the time, cooling to about 20 ℃ after the reaction is finished, acidifying with the weight percentage concentration of 25-30% sulfuric acid until the pH is 5, and putting the acidified sulfuric acid into a plastic bucket to obtain the rare earth collecting agent.
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| CN2019106260081 | 2019-07-11 | ||
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| CN110653071A true CN110653071A (en) | 2020-01-07 |
| CN110653071B CN110653071B (en) | 2021-06-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276276A (en) * | 2021-07-05 | 2022-04-05 | 天津天宝翔科技有限公司 | Chelating rare earth collecting agent and preparation method thereof |
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| US4929393A (en) * | 1988-03-28 | 1990-05-29 | Cyanamid Canada Inc. | 1,4-Disubstituted-2,3,5,6-tetrahydroxy-1,4-diphosphorinanes and their oxides or sulfides |
| CN1386586A (en) * | 2002-06-24 | 2002-12-25 | 赵越凡 | Process for synthesizing composite collector for dressing rare-earth ore |
| CN101524670A (en) * | 2009-04-03 | 2009-09-09 | 包头市林峰稀土化工有限公司 | Rare earth collector |
| CN106008266A (en) * | 2016-05-20 | 2016-10-12 | 中国地质科学院矿产综合利用研究所 | Green preparation method of hydroximic acid rare earth flotation reagent |
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2019
- 2019-10-16 CN CN201910983763.5A patent/CN110653071B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4929393A (en) * | 1988-03-28 | 1990-05-29 | Cyanamid Canada Inc. | 1,4-Disubstituted-2,3,5,6-tetrahydroxy-1,4-diphosphorinanes and their oxides or sulfides |
| CN1386586A (en) * | 2002-06-24 | 2002-12-25 | 赵越凡 | Process for synthesizing composite collector for dressing rare-earth ore |
| CN101524670A (en) * | 2009-04-03 | 2009-09-09 | 包头市林峰稀土化工有限公司 | Rare earth collector |
| CN106008266A (en) * | 2016-05-20 | 2016-10-12 | 中国地质科学院矿产综合利用研究所 | Green preparation method of hydroximic acid rare earth flotation reagent |
Non-Patent Citations (1)
| Title |
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| 车丽萍 等: "羟肟酸类捕收剂在稀土矿物浮选中的应用及发展", 《稀土》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276276A (en) * | 2021-07-05 | 2022-04-05 | 天津天宝翔科技有限公司 | Chelating rare earth collecting agent and preparation method thereof |
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