CN103613614B - A kind of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds and methods for making and using same thereof - Google Patents
A kind of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds and methods for making and using same thereof Download PDFInfo
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Abstract
The invention discloses a kind of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds and methods for making and using same thereof, its structure is such as formula shown in I, its preparation method is: 2-ethyl-2-hexenoic aldehyde and Hypophosporous Acid, 50 or hypophosphite addition reaction occur under an acidic catalyst existent condition and generate 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid and oxidant reaction generate 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is used as bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, the flotation collector in fluorite ore or lithium ore deposit, consumption is 30 ~ 600g/t, controlling flotation solution ph is 4 ~ 12, effectively can realize being separated of target minreal and gangue mineral.
Description
Technical field
The invention belongs to technical field of beneficiation, relate to a kind of compound and preparation method thereof being used as mineral floating collecting agent newly, and this compound in bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or the flotation of lithium ore deposit as the application of collecting agent.
Background technology
The collecting agent of Long carbon chain, owing to having hydroxyl and the phosphonic acid functional groups of polarity, is a kind of excellent oxide mineral collector.Alkyl phosphonic acid is very weak for silicate minerals collecting ability, while flotation, adds suitable inhibitor, as starch, dextrin, Sodium salts humic acids or water glass etc., just can be successfully separated with gangue mineral by valuable mineral.Oxide mineral collector the most frequently used at present in industrial floatation process is oleic acid and modified product thereof.Patent CN101648157A and CN101757983A discloses that a kind of mixed fatty acid flotation with comprising oleic acid is black, the method for sheelite; Patent CN102302982A discloses a kind of beneficiation method reclaiming sheelite from leaf gneiss type ore; Because of its low price, wide material sources and be subject to the welcome of mineral floating producer, but in flotation, also there is obvious shortcoming, the shortcomings such as namely selectivity is not high, freezing tolerance is poor, dispersiveness is bad in oleic-acid collecting agent; Phosphonic acid based collecting agent also has a large amount of patent disclosure as a kind of Novel Titanium iron ore, rutile ore selective copper collector: collecting agent patent CN1047462A discloses a kind of method of 1-hydroxyl-1,1-bis phosphoric acid flotation zircon; CN106327A discloses the method for a kind of α-nitroso-group phosphonic acid ester as pyrite collecting agent; Patent CN102500462A discloses the method for phosphoric acid class and the composite flotation rutile of hydroximic acid; Patent CN101879479A discloses styryl phosphonic acid, oxidized paraffin wax soap, lipid acid, tal fibre wet goods medicament for the method for floating of eclogite rutile ore; External also have a large amount of patent and document to disclose the method for floating of diisobutyl dithiophosphinic acids sodium to sulphide ores and association rare precious metal about the report of phosphorus acid collector to sulphide ores, oxidized ore and complicated ore flotation: patent US5411148; Patent US4561970 discloses the mineral floating method of diisobutyl dithiophosphinic acids sodium for complex system.Problems such as polluting large, technical process complexity, preparation difficulty is there is in above-mentioned phosphonic acid based collecting agent production process.
The invention provides a kind of novel flotation collector, relate to the preparation of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds and the application in bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or the flotation of lithium ore deposit thereof.The collecting agent of present patent application due to have carbon-carbon double bond and and branched structure, fusing point is less than-15 DEG C, and compared with the collecting agents such as traditional lipid acid, oxidized paraffin wax soap, its use range is more wide, and operating environment is looser; The collecting agent that present method is produced has hydroxyl and phosphonate group bipolarity group, mineral surface metalloform-selective is adsorbed, make bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit sorting mineral effective, the rate of recovery and concentrate quality is high, sorting pH value range is wide, do not need the advantages such as flotation of heating.This catenanes hydroxy unsaturated acid has suitable hydrophobic carbon chain (C
8) and double-hydrophilic configuration, have a hydroxyl and a phosphonate group in its molecule, be a kind of brand-new compound, having no it has bibliographical information.
Summary of the invention
The object of this invention is to provide a kind of new Alpha-hydroxy unsaturated alkyl phosphinic acid compounds and preparation method thereof, and provide this compound to be applied to the floatation process in bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit, in order to strengthen method to the collecting ability of valuable mineral in ore, thus realize target minreal and be separated with the efficient flotation separation of its gangue mineral.
The object of the invention is to be realized by following manner:
A kind of Alpha-hydroxy unsaturated alkyl phosphinic acid compounds, structure is such as formula shown in I:
The preparation method of described Alpha-hydroxy unsaturated alkyl phosphinic acid compounds, comprises the following steps:
Under acid catalyst existent condition, Hypophosporous Acid, 50 or hypophosphite and 2-ethyl-2-hexenoic aldehyde generation addition reaction, extracting and separating, distillation, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid can be obtained, 2-ethyl-2-hexenoic aldehyde structure is such as formula shown in II, and 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid structure is as shown in formula III;
(2) 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid and oxygenant generation oxidizing reaction, separatory, can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids;
The acid catalyst of addition reaction comprise in hydrochloric acid, sulfuric acid one or both, its consumption is no more than 30% of 2-ethyl-2-hexenoic aldehyde quality.
The solvent of addition reaction and oxidizing reaction comprises one or more in methyl alcohol, ethanol, water, Isosorbide-5-Nitrae-dioxane, acetonitrile, acetone, tetrahydrofuran (THF); The temperature of reaction of addition reaction is 60 ~ 100 DEG C, reaction times 1 ~ 6h; The temperature of oxidizing reaction is 0 ~ 50 DEG C, reaction times 0.5 ~ 8h.
Hypophosporous Acid, 50 used in addition reaction or hypophosphite comprise: one or more in Hypophosporous Acid, 50, sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite, and the mol ratio of Hypophosporous Acid, 50 or hypophosphite and 2-ethyl-2-hexenoic aldehyde is 1 ~ 3:1.
The solvent used in extraction process comprises one or more in ethyl acetate, ether, toluene, propyl carbinol, tetrahydrofuran (THF) or chloroform; Its consumption is 20% ~ 60% of addition reaction bulk product, and extraction temperature is 10 ~ 40 DEG C, and extraction progression is 1 ~ 3.
The oxygenant of oxidizing reaction comprise in clorox, dimethyl sulfoxide (DMSO), hydrogen peroxide, air, oxygen one or several, the mol ratio of oxygenant and 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid is 1 ~ 3:1.When taking dimethyl sulfoxide (DMSO) as oxygenant, adding the iodine being no more than dimethyl sulfoxide (DMSO) quality 20% is catalyzer; After oxidizing reaction completes, add KI solution washing and remove iodine, the mass concentration of the KI aqueous solution is 5% ~ 20%, KI consumption is 50% ~ 70% of iodine quality.
Also carry out cancellation reaction to stop Strong oxdiative reaction if desired after oxidizing reaction in aforesaid method, the reagent used comprise in sodium bisulfite, Sulfothiorine or Hypophosporous Acid, 50 one or several, its consumption is no more than oxygenant consumption.
The application method of described Alpha-hydroxy unsaturated alkyl phosphinic acid compounds, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is directly added or adds sodium hydroxide solution and is made into salt, as bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit flotation collector.Collector dosage is 30 ~ 600g/t, and flotation solution ph is 4 ~ 12.
Above-mentioned preparation method changes as follows further in detail:
(1) preparation of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid: add concentrated hydrochloric acid, solvent, Hypophosporous Acid, 50 or hypophosphite, 2-ethyl-2-hexenoic aldehyde, stirring reaction, after reaction terminates, be extracted with ethyl acetate, extraction progression is 3, and separatory, gets supernatant liquid, underpressure distillation, namely obtains 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid.
(2) preparation of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids: add oxygenant in 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, stirs, after having reacted, adds saturated NaHSO
3solution, till making starch-kalium iodide test paper test constant basket, leaves standstill separatory, gets supernatant liquid, can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids.
The Alpha-hydroxy unsaturated alkyl phosphinic acid compounds tool that the present invention is used as bauxite, ilmenite, rutile ore, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit flotation collector has the following advantages:
(1) contain a straight chain in this Alpha-hydroxy unsaturated alkyl Phosphonic acid molecules, and straight chain has an ethyl and carbon-carbon double bond structure, be conducive to the hydrophobization of mineral surface, and make it be easy to stick to bubble, to mineral, there is stronger collecting ability.
(2) contain a hydroxyl and a phosphonate group in this Alpha-hydroxy unsaturated alkyl Phosphonic acid molecules, there is double-hydrophilic group, be conducive to collecting agent and mineral generation adsorption, to valuable mineral, there is stronger collecting ability.(3) this Alpha-hydroxy unsaturated alkyl phosphinic acid compounds has branched-chain alkene structure, and fusing point is less than 15 DEG C, is conducive to the dissolving of medicament in ore pulp and dispersion, does not need flotation of heating.
Accompanying drawing illustrates:
Fig. 1 is the infrared spectrogram of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids;
Fig. 2 is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
31p nmr spectrum;
Fig. 3 is the process flow sheet of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids flotation fluorite;
Fig. 4 is the process flow sheet of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids flotation ilmenite;
Fig. 5 is the process flow sheet of 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids Flotation of Cassiterite.
Embodiment
The present invention is further illustrated by the following example, but not by the restriction of these embodiments.In embodiment, unless otherwise specified all numbers and percentage ratio all refer to quality.
The preparation of embodiment 11-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid
By 4.4 parts of 2-ethyl-2-hexenoic aldehydes, 40 parts of Isosorbide-5-Nitrae-dioxane, 7 parts of Hypophosporous Acid, 50,2 part of 20% dilute sulphuric acid fully mixes, 80 DEG C of stirring reaction 5h, with 1.4 parts of extraction into ethyl acetate 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, extraction temperature is 30 DEG C, extracts 3 times, separatory, get supernatant liquid underpressure distillation removing ethyl acetate, distillation temperature is 50 DEG C, and vacuum tightness is 0.098MPa, residuum is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, productive rate 75.2%.
The preparation of embodiment 21-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid
By 4.4 parts of 2-ethyl-2-hexenoic aldehydes, 40 parts of Isosorbide-5-Nitrae-dioxane, 7 parts of Hypophosporous Acid, 50,1 part of 37% concentrated hydrochloric acid fully mixes, 80 DEG C of stirring reaction 5h, with 1.4 parts of extraction into ethyl acetate 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, extraction temperature is 30 DEG C, extracts 3 times, separatory, get supernatant liquid underpressure distillation removing ethyl acetate, distillation temperature is 50 DEG C, and vacuum tightness is 0.098MPa, residuum is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, productive rate 83.5%.
The preparation of embodiment 31-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid
By 4.4 parts of 2-ethyl-2-hexenoic aldehydes, 40 parts of ethanol, 7 parts of Hypophosporous Acid, 50,1 part of hydrochloric acid fully mixes, 80 DEG C of stirring reaction 5h, with 1.4 parts of extraction into ethyl acetate 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, extraction temperature is 30 DEG C, extract 3 times, separatory, get supernatant liquid underpressure distillation removing ethyl acetate, distillation temperature is 55 DEG C, vacuum tightness is 0.098MPa, and residuum is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, productive rate 70.6%.
The preparation of embodiment 41-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
Be added drop-wise to the 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid that 4.4 parts of embodiments 1 are obtained under being stirred by 10 part of 10% clorox, stirred at ambient temperature reaction 6h, adds saturated NaHSO
3solution, to the constant basket of starch-kalium iodide test paper, leaves standstill separatory, gets upper organic phase drying, namely obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, productive rate 89%.
The preparation of embodiment 51-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
Be added drop-wise to 4.4 parts of embodiments 1 under being stirred by 10 part of 30% hydrogen peroxide and obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, stirred at ambient temperature reaction 6h, adds saturated NaHSO
3solution, to the constant basket of starch-kalium iodide test paper, leaves standstill separatory, gets upper organic phase drying, namely obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, productive rate 92%.
The preparation of embodiment 61-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
By 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid obtained for 4.4 parts of embodiments 1, under agitation add 3.6 parts of dimethyl sulfoxide (DMSO) in batches, 0.5 part of iodine, 65 DEG C of stirring reaction 5h, by filtrate with 3 parts of 10%KI solution washings, leave standstill separatory, get upper organic phase underpressure distillation and can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, productive rate 94%, its infrared spectrum is shown in Fig. 1,1445cm
-1, 1148cm
-1for P=O stretching vibration peak, 3468cm
-1for the stretching vibration peak of-OH, 2940cm
-1for CH
3or CH
2stretching vibration peak, 1637cm
-1for C=C stretching vibration peak;
31p nucleus magnetic resonance figure is shown in Fig. 2,1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids
31pNMR (CD
3cOCD
3/ H
3pO
4) chemical displacement value is 32.8.
The application of embodiment 7,1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids on fluorite is roughly selected
Certain quartz-fluorite ore raw ore CaF
2grade 38.83%, grinding fineness-200 order accounts for 60%, is placed in flotation cell, at sodium carbonate amount 1400g/t, water glass consumption 400g/t, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids consumption 450g/t, carry out flotation under the condition that room temperature is 10 DEG C, flotation process figure is shown in Fig. 3.The flotation contrast and experiment of the 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids collecting agent in the present invention and conventional oleic collector is in table 1.From table, at 10 DEG C, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is higher than traditional oleic acid 16.09 percentage points for the flotation recovery rate of fluorite.
At table 110 DEG C, collecting agent roughly selects fluorite contrast and experiment
Collector dosage (g/t raw ore) | CaF 2Grade (%) | CaF 2The rate of recovery (%) |
Oleic acid 450 | 85.93 | 70.41 |
1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids 450 | 82.48 | 83.28 |
The application of embodiment 81-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids in ilmenite flotation
Ilmenite sample is taken from Xuan Tai factory of Pan Gangtai industry company coarse fraction flotation production line and is floated titanium raw ore (coarse grain production line floats sulphur mine tailing), head grade TiO
222.48%, granularity is-74 μm and accounts for 65%, by per tonly adding 1800g sulfuric acid to ore deposit, 800g1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 200g2 oil carries out ilmenite and roughly selects flotation, scan and add 200g1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 50g2 oil by per ton to ore deposit, primary cleaning adds 350g sulfuric acid by per ton to ore deposit, recleaning adds 250g sulfuric acid by per ton to ore deposit, triple cleaning adds 200g sulfuric acid by per ton to ore deposit, four times selected adds 100g sulfuric acid by per ton to ore deposit, and flotation process figure is shown in accompanying drawing 4.TiO is obtained after one roughing, once purging selection, four selected operations
2grade 47.03%, the ilmenite concentrate of the rate of recovery 82.78%.The flotation contrast and experiment of the 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids collecting agent in the present invention and conventional vinylbenzene phosphoric acid is in table 2.From table 2,1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is higher than traditional vinylbenzene phosphoric acid 7.69 percentage points for the flotation recovery rate of ilmenite.
Table 2 collecting agent flotation ilmenite contrast and experiment
Collecting agent | Ilmenite concentrate TiO 2Grade (%) | The rate of recovery (%) |
Vinylbenzene phosphoric acid | 47.12 | 75.09 |
1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids | 47.03 | 82.78 |
The application of embodiment 91-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids in tin ore flotation
Certain technics of cassiterite clay raw ore tin grade 1.38%, granularity is-19 μm and accounts for 95%, by per tonly adding 1000g sodium carbonate to ore deposit, 700g Xylo-Mucine, 1000g1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 24g2 oil roughly selects, scan and add 500g1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids, 12g2 oil by per ton to ore deposit, primary cleaning adds 200g Xylo-Mucine by per ton to ore deposit, recleaning adds 150g Xylo-Mucine by per ton to ore deposit, and flotation process figure is shown in accompanying drawing 5.Tin grade 21.46% is obtained, the tin rough concentrate of the rate of recovery 91.22% after one roughing, once purging selection, twice selected operation.The flotation contrast and experiment of the 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids collecting agent in the present invention and conventional Using Salicyl Hydroximic Acid is in table 3.From table, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is higher than traditional Using Salicyl Hydroximic Acid 3.64 percentage points for the flotation recovery rate of tin ore.
Table 3 collecting agent flotation tin ore contrast and experiment
Collecting agent | Tin concentrate grade (%) | The tin rate of recovery (%) |
Using Salicyl Hydroximic Acid | 20.91 | 87.58 |
1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids | 21.46 | 91.22 |
Claims (3)
1. a preparation method for 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, is characterized in that, comprise the following steps:
1) by 4.4 parts of 2-ethyl-2-hexenoic aldehydes, 40 parts of Isosorbide-5-Nitrae-dioxane, 7 parts of Hypophosporous Acid, 50,2 part of 20% dilute sulphuric acid fully mixes, 80 DEG C of stirring reaction 5h, with 1.4 parts of extraction into ethyl acetate 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, extraction temperature is 30 DEG C, extracts 3 times, separatory, get supernatant liquid underpressure distillation removing ethyl acetate, distillation temperature is 50 DEG C, and vacuum tightness is 0.098MPa, and residuum is 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid;
2) step 1 is added drop-wise under being stirred 10 part of 10% clorox) obtained 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, stirred at ambient temperature reaction 6h, adds saturated NaHSO
3solution, to the constant basket of starch-kalium iodide test paper, leaves standstill separatory, gets upper organic phase drying, namely obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids;
Or be added drop-wise to step 1 under being stirred 10 part of 30% hydrogen peroxide) obtained 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, stirred at ambient temperature reaction 6h, adds saturated NaHSO
3solution, to the constant basket of starch-kalium iodide test paper, leaves standstill separatory, gets upper organic phase drying, namely obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids;
Or by 4.4 parts of steps 1) obtained 1-hydroxyl-2-ethyl-2-hexene-1-phosphonous acid, under agitation add 3.6 parts of dimethyl sulfoxide (DMSO) in batches, 0.5 part of iodine, 65 DEG C of stirring reaction 5h, by filtrate with 3 parts of 10%KI solution washings, leave standstill separatory, get upper organic phase underpressure distillation and can obtain 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids; Its structure is such as formula shown in I:
2. the application method of an Alpha-hydroxy unsaturated alkyl phosphinic acid compounds, it is characterized in that, 1-hydroxyl-2-ethyl-2-hexene-1-phosphonic acids is directly added or adds sodium hydroxide solution and is made into salt, as bauxite, ilmenite, rutile, sheelite, wolframite, rare-earth mineral, tin ore, fluorite ore or lithium ore deposit flotation collector; Described Alpha-hydroxy unsaturated alkyl phosphinic acid compounds structure is such as formula shown in I:
3. application method according to claim 2, is characterized in that, collector dosage is 30 ~ 600g/t, and flotation solution ph is 4 ~ 12.
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CN106674274B (en) * | 2016-02-29 | 2019-04-26 | 中蓝连海设计研究院有限公司 | A kind of phosphate mineral inhibitor and preparation method thereof and purposes |
CN106378263B (en) * | 2016-09-27 | 2018-06-22 | 中国地质科学院郑州矿产综合利用研究所 | Low-alkali-consumption scheelite collecting agent and application thereof |
CN108623627B (en) * | 2018-07-03 | 2019-07-09 | 中南大学 | A kind of preparation method and application of styryl phosphonate monoester |
CN109402389B (en) * | 2018-11-05 | 2020-07-14 | 中南大学 | Method for treating scheelite in normal-pressure acidic system |
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