CN110508402B - Low-temperature-resistant double-acid-salt rare earth ore flotation collector and preparation method and application thereof - Google Patents
Low-temperature-resistant double-acid-salt rare earth ore flotation collector and preparation method and application thereof Download PDFInfo
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- CN110508402B CN110508402B CN201910871090.4A CN201910871090A CN110508402B CN 110508402 B CN110508402 B CN 110508402B CN 201910871090 A CN201910871090 A CN 201910871090A CN 110508402 B CN110508402 B CN 110508402B
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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
- B03D1/014—Organic compounds containing phosphorus
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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
- B03D2203/04—Non-sulfide ores
- B03D2203/06—Phosphate ores
Abstract
The invention relates to the technical field of ore flotation and collection, and discloses a low-temperature-resistant complex acid salt type rare earth ore flotation and collection agent, which comprises alkyl phosphate sodium, sulfated sodium oleate, a surfactant and an emulsifier; wherein the surfactant comprises sodium dodecyl benzene sulfonate, and the emulsifier comprises OP-10. The collector has the advantages of good low temperature resistance, strong collecting capability, low production cost, small using amount and the like. The invention also discloses a preparation method and application of the collector, wherein the preparation method comprises the following steps: and mixing and stirring the sodium alkyl phosphate, the sulfated sodium oleate, the surfactant and the emulsifier uniformly to obtain the collecting agent. The collecting agent has good separation effect when being particularly applied to silicate phosphate rare earth ores, and meanwhile, a foaming agent is not required to be added in the flotation process, so that the beneficiation cost can be greatly reduced, and the economic benefit and the social benefit of resource utilization are improved.
Description
Technical Field
The invention relates to the technical field of ore flotation and collection, in particular to a low-temperature-resistant complex acid salt type rare earth ore flotation and collection agent and a preparation method and application thereof.
Background
The industrial reserve of the rare earth oxide which has been ascertained in China is 1859 million tons, which accounts for about 23.6 percent of the reserve of the rare earth which has been ascertained in the world, the rare earth resource mineral deposit is complete in type, wide in distribution and relatively centralized, thousands of mineral deposits, mineral spots and mineralization producing areas are discovered in more than two thirds of provinces (regions) in China at present, and are intensively distributed in Baiyunebo, Jiangxi south, Guangdong North, Sichuan Liang mountains, Shandong micro mountains and other places in inner Mongolia to form distribution patterns of north, south, west and east, and the like, and the distribution patterns are distributed in the North, south, west and eastHas the distribution characteristics of north and south. The rare earth industrial minerals are of various types, and the three main minerals for industrially extracting rare earth metals at the present stage are bastnaesite [ RECO ]3F]And monazite [ (RE, Th, Y) PO4]And xenotime [ (Y, RE) PO ]4]. The rare earth metal is widely applied to the fields of clean energy, national defense science and technology, industrial technology, electronic products and the like.
At present, rare earth mines taking bastnaesite as main rare earth minerals mostly adopt one or a mixture of alkyl hydroxamic acid, hydroxamic acid with benzene ring, cycloalkyl hydroxamic acid and naphthyl hydroxamic acid as a collecting agent, and although the collecting agent obtains better indexes in bastnaesite type rare earth flotation, the collecting agent has the defects of high price, large dosage, unsatisfactory single use comprehensive effect, difficult degradation of medicaments with benzene ring and naphthalene ring, difficult meeting of the requirement of environmental protection of ore dressing tailing wastewater and the like; meanwhile, silicate phosphate rare earth ore can not be effectively sorted.
At present, the research, development and application of silicate phosphate rare earth ore collecting agents are only found in chinese patent document cn201711202681.x, application date 20171127, with the name: a phosphosilicate type rare earth ore flotation collector and a preparation method and application thereof are disclosed, and the phosphosilicate type rare earth ore flotation collector is composed of the following materials in parts by mass: 5-15 parts of octyl ether propyl-a-amino-1, 1-diphosphonic acid, 60-80 parts of coconut oil acid, 5-10 parts of hexadecyl sulfonate and 1-3 parts of Tween-60. The above patent documents disclose laboratory normal temperature sorting indexes for silicate phosphate rare earth ore: for a certain ultra-low grade phosphosilicate rare earth ore with 1.48 percent of REO content, a mixture of octyl ether propyl-a-amino-1, 1-diphosphonic acid, coconut oleic acid, hexadecyl sulfonate and Tween-60 is used as a collecting agent in the test through a grinding-flotation process, the using amount is about 0.5 kg/t.raw ore, and the inhibitor is water glass, so that rare earth ore concentrate with 18.43 percent of REO content and 82.99 percent of recovery rate can be obtained.
Because the ore deposit of silicate phosphate rare earth ore is found only near the arctic circle at present, and the perennial temperature of the area where the ore is located is below 10 ℃, the hydrophilicity of the rare earth ore is far stronger than that of the conventional rare earth ore such as bastnaesite and the like, so that a collecting agent with strong collecting capability and low temperature resistance is needed for carrying out flotation separation on the rare earth ore.
The above patent documents provide a collector for flotation separation of silicate phosphate rare earth ore, which can be applied at domestic normal temperature, that is, at about 20 ℃, but a technical scheme about a collector which is resistant to low temperature and can be applied to the industrial utilization field of silicate phosphate rare earth ore is not proposed. When the collector is used in the mining area, the solubility and collecting ability of the collector are drastically reduced.
In conclusion, a collecting agent which has good low-temperature resistance, strong collecting capability, lower production cost and less using amount and has good separation effect particularly when applied to silicate phosphate rare earth ores is needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a low-temperature-resistant complex acid salt type rare earth ore flotation collector so as to achieve the effects of good low-temperature resistance, strong collecting capability, lower production cost, small using amount and good separation effect when being applied to silicate phosphate type rare earth ores.
The purpose of the invention is realized by the following technical scheme: a floatation collector of low-temp. resistant complex-acid-salt rare-earth ore is composed of sodium alkylphosphate, sulfated sodium oleate, surfactant and emulsifier.
Through the technical scheme, the sodium alkyl phosphate is obtained by completely saponifying or partially saponifying alkyl phosphate, so that the effects of improving the selectivity of the sodium alkyl phosphate and the alkyl phosphate and improving the water solubility at low temperature are achieved; the sulfated sodium oleate is obtained by sulfating and saponifying oleic acid serving as a carrier, has strong collecting capacity, is simple in synthesis process and easy to operate, and achieves the effects of improving low temperature resistance and water solubility by introducing sulfate radicals compared with sodium oleate.
Preferably, the collector comprises the following components in parts by weight: 10-25 parts of sodium alkyl phosphate, 60-80 parts of sodium phosphatate, 8-15 parts of surfactant and 0.8-2 parts of emulsifier.
Preferably, the surfactant comprises sodium dodecylbenzenesulfonate.
Through the technical scheme, the sodium dodecyl benzene sulfonate has strong foaming performance and certain collecting performance, and achieves the effect that no foaming agent is required to be added in the flotation process.
Preferably, the emulsifier comprises OP-10.
According to the technical scheme, the emulsifier OP-10 is added, so that the components in the collecting agent are better dissolved with each other, and the effect of making the collecting agent not easy to separate layers is achieved.
Preferably, the preparation method of the sodium alkyl phosphate comprises the following steps: mixing mixed alcohol, pyrophosphoric acid and a solvent, and reacting under heating to obtain alkyl phosphate; mixing the alkyl phosphate with a sodium hydroxide solution with the concentration of 20% to obtain the sodium alkyl phosphate;
the mixed alcohol comprises isooctyl alcohol and n-heptanol, and the mass ratio of the isooctyl alcohol to the n-heptanol is 2: 1-1.5; if the carbon chain of each component in the mixed alcohol is less than 8, the collecting performance of the sodium alkyl phosphate is too poor; the carbon chain of each component is higher than 10, and the collecting performance of the sodium alkyl phosphate is too strong. Isooctyl alcohol and n-heptanol are adopted as components of the mixed alcohol, and the carbon number of the mixed alcohol is 8-10, so that the collecting agent with better collecting performance is obtained.
The solvent is ethanol, the mass ratio of the mixed alcohol to the pyrophosphoric acid to the ethanol is 1 (0.65-0.75) to (1.1-1.3), the mass ratio of the mixed alcohol to the sodium hydroxide solution is 10: 3.5-7, the heating temperature is 40-50 ℃, and the heat preservation time is 3-5 hours.
By the technical scheme, the heating temperature is limited, so that the reaction is fully performed, and the effect of producing a target product is achieved; the heat preservation time is limited, and the effects of ensuring the conversion rate of the target product and improving the yield are achieved.
The chemical reaction equations involved in the synthesis are:
ROPO(OH)2+NaOH——ROP＝O(OH)(ONa)+H2O
ROP＝O(OH)(ONa)+NaOH——ROP＝O(ONa)2+H2O
preferably, the preparation method of the sulfated sodium oleate comprises the following steps: slowly adding concentrated sulfuric acid into the stirred oleic acid at normal temperature, heating and preserving heat, adding a sodium hydroxide solution, and performing saponification reaction to obtain the sulfated sodium oleate; the heating temperature is 40-50 ℃, and the heat preservation time is 60-90 min; the concentration of the sodium hydroxide solution is 20%, and the mass ratio of the sodium hydroxide solution to the oleic acid is 1: 10.
By the technical scheme, the heating temperature is limited, so that the reaction is fully performed, and the effect of producing a target product is achieved; the heat preservation time is limited, and the effects of ensuring the conversion rate of the target product and improving the yield are achieved.
The chemical reaction equations involved in the synthesis are:
CH3(CH2)7CH2CH(SO4H)(CH2)7COOH+NaOH—CH3(CH2)7CH2CH(SO4H)(CH2)7COONa+H2O
the method for preparing the low-temperature-resistant double-acid-salt rare earth ore flotation collecting agent comprises the steps of mixing and stirring the alkyl phosphate sodium, the sulfated sodium oleate, the surfactant and the emulsifier uniformly to obtain the low-temperature-resistant double-acid-salt rare earth ore flotation collecting agent. Wherein the mass ratio of the sodium alkyl phosphate, the sulfated sodium oleate, the surfactant and the emulsifier is (10-25): 60-80): 8-15): 0.8-2.
The application of the low-temperature-resistant complex acid salt rare earth ore flotation collector is used for flotation of complex acid salt rare earth ores.
Preferably, the collector is used for flotation of silicate phosphate rare earth ore.
Preferably, a collector and an auxiliary agent are added into the ore pulp of the rare earth ore for flotation, the auxiliary agent comprises an inhibitor, and the inhibitor is acidified water glass.
The acidified water glass is prepared from water glass and dilute acid, and the modulus of the water glass is 2.3-2.8.
When the modulus of the water glass is lower than 2.3, the inhibiting ability of the inhibitor is too weak, so that the problems of large dosage and increased cost are caused; when the modulus of the water glass is higher than 2.8, the inhibitor has too strong inhibiting ability, which lowers the product yield. Therefore, the modulus of the water glass is limited to 2.3-2.8, and the effect of reducing the cost is achieved while the product yield and the inhibition capability are ensured.
The invention has the beneficial effects that:
1. according to the low-temperature-resistant double-acid-salt rare earth ore flotation collector, the alkyl phosphate sodium is added and is obtained by completely saponifying or partially saponifying alkyl phosphate, so that the effects of improving the selectivity and water solubility of the alkyl phosphate sodium and the alkyl phosphate are achieved.
2. According to the low-temperature-resistant double-acid-salt rare earth ore flotation collector, the sulfated sodium oleate is added, oleic acid is used as a carrier, the collector is obtained through sulfation and saponification, the collecting capacity is high, the synthesis process is simple and easy to operate, and the effects of improving low-temperature resistance and water solubility are achieved through introducing sulfate radicals relative to sodium oleate.
3. According to the low-temperature-resistant double-acid-salt rare earth ore flotation collector, the sodium dodecyl benzene sulfonate and the OP-10 are added, the sodium dodecyl benzene sulfonate has strong foaming performance and also has certain collecting performance, and the effect that a foaming agent is not required to be added in the flotation process is achieved; the OP-10 enables components in the collector to be better dissolved with each other, and meanwhile, the effect that the collector is not easy to delaminate is achieved.
Drawings
FIG. 1 is a flow diagram of a flotation process in an embodiment of the invention.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
Example 1
1. The low-temperature-resistant double-acid-salt rare earth ore flotation collector comprises the following components in parts by weight: 10 parts of sodium alkyl phosphate, 80 parts of sulfated sodium oleate, 8.5 parts of sodium dodecyl benzene sulfonate and 101.5 parts of OP-101.
2. The method for preparing the low-temperature-resistant double-acid-salt rare earth ore flotation collector comprises the following steps:
s1, preparing alkyl sodium phosphate: mixing isooctyl alcohol and n-heptanol (mass ratio is 2:1) to obtain mixed alcohol, putting the mixed alcohol, pyrophosphoric acid and ethanol with the mass ratio of 1:0.65:1.1 into an enamel reaction kettle, heating to 40 ℃, and preserving heat for 5 hours to obtain alkyl phosphate; then adding a 20% NaOH solution into the alkyl phosphate to carry out saponification (the mass ratio of the NaOH solution to the mixed alcohol is 6:10), and finally obtaining sodium alkyl phosphate;
s2, preparing sulfated sodium oleate: adding oleic acid into a three-neck flask, cooling in a water bath, starting stirring, then slowly adding concentrated sulfuric acid (the mass ratio of the oleic acid to the concentrated sulfuric acid is 5:1), and maintaining the reaction temperature at normal temperature through a water bath cooling system; after 30 minutes, adding concentrated sulfuric acid, heating to 40 ℃, keeping the temperature for 90 minutes, and then slowly adding a 10% NaOH solution to carry out saponification reaction (the mass ratio of the NaOH solution to the oleic acid is 1:10), so as to finally obtain sulfated sodium oleate;
s3, preparing a collecting agent: mixing and stirring 10 parts of sodium alkyl phosphate, 80 parts of sulfated sodium oleate, 8.5 parts of sodium dodecyl benzene sulfonate and OP-101.5 parts uniformly to prepare the collector.
3. Application method of collecting agent
In order to verify the flotation separation effect of the low-temperature-resistant double-acid-salt rare earth ore flotation collector on silicate phosphate rare earth ore, an application method experiment is carried out. Silicate phosphate low-grade rare earth ore with raw ore REO grade of 1.55% is selected in an experiment and subjected to flotation separation, and the method comprises the following steps:
-preparation of the material: crushing the rare earth ore until the granularity is less than 3mm, and grinding the crushed rare earth ore by a ball mill to obtain 82% of material with the granularity less than 0.075 mm;
-a flotation process: a single flotation separation process, a rough and sweep three fine flow (as shown in fig. 1);
-flotation conditions: the experiment adopts an XFD type small flotation machine to carry out the flotation test under the condition of normal temperature;
-a dosage regimen: in the first three fine procedures, the dosage of the medicament is as follows:
roughing: 2500g/t of acidified water glass, 500g/t of collecting agent and raw ore;
sweeping: 500g/t of acidified water glass and 120g/t of collecting agent;
first selection: acidifying 200g/t of water glass and 100g/t of collecting agent;
and (3) second fine selection: acidifying water glass 50 g/t. raw ore, and collecting agent 50 g/t. raw ore;
and (3) carrying out third selection: no acidified water glass and collecting agent are added;
wherein the acidified water glass is prepared from water glass and dilute sulfuric acid in a mass ratio of 85:15, and the modulus of the water glass is 2.7.
Example 2
1. The low-temperature-resistant double-acid-salt rare earth ore flotation collector comprises the following components in parts by weight: 12.5 parts of sodium alkyl phosphate, 75 parts of sulfated sodium oleate, 11.5 parts of sodium dodecyl benzene sulfonate and OP-101 parts.
2. The method for preparing the low-temperature-resistant double-acid-salt rare earth ore flotation collector comprises the following steps:
s1, preparing alkyl sodium phosphate: mixing isooctyl alcohol and n-heptanol (mass ratio is 2:1.5) to obtain mixed alcohol, putting the mixed alcohol, pyrophosphoric acid and ethanol with the mass ratio of 1:0.75:1.3 into an enamel reaction kettle, heating to 50 ℃, and preserving heat for 3 hours to obtain alkyl phosphate; then adding a 20% NaOH solution into the alkyl phosphate to carry out saponification (the mass ratio of the NaOH solution to the mixed alcohol is 4.5:10), and finally obtaining sodium alkyl phosphate;
s2, preparing sulfated sodium oleate: adding oleic acid into a three-neck flask, cooling in a water bath, starting stirring, then slowly adding concentrated sulfuric acid (the mass ratio of the oleic acid to the concentrated sulfuric acid is 5:1), and maintaining the reaction temperature at normal temperature through a water bath cooling system; after 50 minutes, adding concentrated sulfuric acid, heating to 50 ℃, keeping the temperature for 60 minutes, and then slowly adding a 10% NaOH solution to carry out saponification reaction (the mass ratio of the NaOH solution to the oleic acid is 1:10), thereby finally obtaining sulfated sodium oleate;
s3, preparing a collecting agent: and mixing and stirring 12.5 parts of sodium alkyl phosphate, 75 parts of sulfated sodium oleate, 11.5 parts of sodium dodecyl benzene sulfonate and OP-101 parts uniformly to prepare the collector.
3. Application method of collecting agent
In order to verify the flotation separation effect of the low-temperature-resistant double-acid-salt rare earth ore flotation collector on silicate phosphate rare earth ore, an application method experiment is carried out. Silicate phosphate low-grade rare earth ore with raw ore REO grade of 1.55% is selected in an experiment and subjected to flotation separation, and the method comprises the following steps:
-preparation of the material: crushing the rare earth ore until the granularity is less than 3mm, and grinding the crushed rare earth ore by a ball mill to obtain 82% of material with the granularity less than 0.075 mm;
-a flotation process: a single flotation separation process, a rough and sweep three fine flow (as shown in fig. 1);
-flotation conditions: the experiment adopts an XFD type small flotation machine, and the flotation test is carried out under the condition that the temperature of ore pulp is 10 ℃;
-a dosage regimen: in the first three fine procedures, the dosage of the medicament is as follows:
roughing: 2500g/t of acidified water glass and 600g/t of collecting agent;
sweeping: acidifying water glass 400 g/t. raw ore, collecting agent 150 g/t. raw ore;
first selection: acidifying 200g/t of water glass and 100g/t of collecting agent;
and (3) second fine selection: acidifying water glass 50 g/t. raw ore, and collecting agent 50 g/t. raw ore;
and (3) carrying out third selection: no acidified water glass and collecting agent are added;
wherein the acidified water glass is prepared from water glass and dilute sulfuric acid in a mass ratio of 85:15, and the modulus of the water glass is 2.3.
Example 3
1. The low-temperature-resistant double-acid-salt rare earth ore flotation collector comprises the following components in parts by weight: 25 parts of sodium alkyl phosphate, 60 parts of sulfated sodium oleate, 14.2 parts of sodium dodecyl benzene sulfonate and 100.8 parts of OP-100.
2. The method for preparing the low-temperature-resistant double-acid-salt rare earth ore flotation collector comprises the following steps:
s1, preparing alkyl sodium phosphate: mixing isooctyl alcohol and n-heptanol (mass ratio is 2:1.25) to obtain mixed alcohol, putting the mixed alcohol, pyrophosphoric acid and ethanol in a mass ratio of 1:0.7:1.2 into an enamel reaction kettle, heating to 45 ℃, and preserving heat for 4 hours to obtain alkyl phosphate; then adding a 20% NaOH solution into the alkyl phosphate to carry out saponification (the mass ratio of the NaOH solution to the mixed alcohol is 5:10), and finally obtaining sodium alkyl phosphate;
s2, preparing sulfated sodium oleate: adding oleic acid into a three-neck flask, cooling in a water bath, starting stirring, then slowly adding concentrated sulfuric acid (the mass ratio of the oleic acid to the concentrated sulfuric acid is 5:1), and maintaining the reaction temperature at normal temperature through a water bath cooling system; after 50 minutes, adding concentrated sulfuric acid, heating to 45 ℃, keeping the temperature for 75 minutes, and then slowly adding a 10% NaOH solution to carry out saponification reaction (the mass ratio of the NaOH solution to the oleic acid is 1:10), thereby finally obtaining sulfated sodium oleate;
s3, preparing a collecting agent: and (3) uniformly mixing and stirring 25 parts of sodium alkyl phosphate, 60 parts of sulfated sodium oleate, 14.2 parts of sodium dodecyl benzene sulfonate and 100.8 parts of OP-100 to obtain the collector.
3. Application method of collecting agent
In order to verify the flotation separation effect of the low-temperature-resistant double-acid-salt rare earth ore flotation collector on silicate phosphate rare earth ore, an application method experiment is carried out. Silicate phosphate low-grade rare earth ore with raw ore REO grade of 1.55% is selected in an experiment and subjected to flotation separation, and the method comprises the following steps:
-preparation of the material: crushing the rare earth ore until the granularity is less than 3mm, and grinding the crushed rare earth ore by a ball mill to obtain 82% of material with the granularity less than 0.075 mm;
-a flotation process: a single flotation separation process, a rough and sweep three fine flow (as shown in fig. 1);
-flotation conditions: the experiment adopts an XFD type small flotation machine, and the flotation test is carried out under the condition that the temperature of ore pulp is 10 ℃;
-a dosage regimen: in the first three fine procedures, the dosage of the medicament is as follows:
roughing: 2500g/t of acidified water glass and 600g/t of collecting agent;
sweeping: acidifying water glass 400 g/t. raw ore, collecting agent 150 g/t. raw ore;
first selection: acidifying 200g/t of water glass and 100g/t of collecting agent;
and (3) second fine selection: acidifying water glass 50 g/t. raw ore, and collecting agent 50 g/t. raw ore;
and (3) carrying out third selection: no acidified water glass and collecting agent are added;
wherein the acidified water glass is prepared from water glass and dilute sulfuric acid in a mass ratio of 85:15, and the modulus of the water glass is 2.3.
Comparative example 1
The indexes of the silicate rare earth ore separated by flotation in the embodiment 1 of the invention are compared with the indexes of the silicate rare earth ore separated by flotation in the comparative example 1, wherein the flotation separation method in the comparative example 1 comprises the following steps: the collecting agent adopts a mixture of octyl ether propyl-a-amino-1, 1-diphosphonic acid, coconut oleic acid, hexadecyl sulfonate and Tween-60, the inhibitor adopts water glass, and other conditions such as the dosage of medicament, the fineness of grinding ore, the adopted process flow and the like are the same as those of the embodiment 1 of the invention. (this comparative example is compared with the prior art and is used for proving that the flotation separation method and the collecting agent used in the invention have better effect).
Comparative example 2
The indexes of the silicate rare earth ore separated by flotation in the embodiment 2 of the invention are compared with the indexes of the silicate rare earth ore separated by flotation in the comparative example 2, wherein the flotation separation method in the comparative example 2 comprises the following steps: the collecting agent consists of the following components: sodium alkyl phosphate, sodium oleate, sodium dodecyl benzene sulfonate and OP-10; other conditions such as the dosage of the medicament, the fineness of grinding ore, the adopted process flow and the like are the same as those of the embodiment 2 of the invention. (sodium oleate is used for replacing the sodium sulfate in the collector of the comparative example, and other conditions are consistent with those in example 2 and are used for proving that the collecting effect of the sodium sulfate in the collector of the scheme is better).
Comparative example 3
The indexes of the silicate rare earth ore separated by flotation in the embodiment 2 of the invention are compared with the indexes of the silicate rare earth ore separated by flotation in the comparative example 3, wherein the flotation separation method in the comparative example 3 comprises the following steps: the collecting agent consists of the following components: phosphoric esters, sodium sulfated oleate, sodium dodecylbenzenesulfonate and OP-10; other conditions such as the dosage of the medicament, the fineness of grinding ore, the adopted process flow and the like are the same as those of the embodiment 2 of the invention. (phosphate esters are used for replacing sodium alkyl phosphate in the collector of the comparative example, and other conditions are consistent with those of example 2, so that the collecting effect of the sodium alkyl phosphate in the collector of the scheme is better).
Comparative example 4
The indexes of the silicate rare earth ore separated by flotation in the embodiment 2 of the invention are compared with the indexes of the silicate rare earth ore separated by flotation in the comparative example 4, wherein the flotation separation method in the comparative example 4 comprises the following steps: the collecting agent consists of the following components: phosphoric esters, sodium oleate, sodium dodecyl benzene sulfonate and OP-10; other conditions such as the dosage of the medicament, the fineness of grinding ore, the adopted process flow and the like are the same as those of the embodiment 2 of the invention. (sodium oleate is used for replacing sodium sulfated sulfate and phosphate esters are used for replacing sodium alkyl phosphate in the collecting agent of the comparison example, other conditions are consistent with those of the embodiment 2, and the conditions are used for proving that the synergistic collecting effect of the sodium sulfated sulfate and the sodium alkyl phosphate in the collecting agent of the scheme is better).
The experimental data of examples 1-3 and comparative examples 1-4 are shown in the following table:
according to the test data, the collecting agent disclosed by the invention has good performance on the silicate phosphate rare earth ore and strong low temperature resistance. Compared with the method of the comparative example 1, the collector disclosed by the invention can realize the utilization of silicate phosphate rare earth ore under the conditions of normal temperature or low temperature, is particularly favorable for the utilization of ore deposits with resources distributed in a low-temperature zone, can reduce the temperature of flotation ore pulp to 10 ℃, reduces the consumption of energy sources, reduces the heating cost, greatly reduces the ore dressing cost and improves the economic benefit and social benefit of resource utilization. Compared with the methods of the comparison examples 2-4, the grade and recovery rate of the silicate phosphate rare earth ore separated by the method of the embodiment 2 are obviously improved, and the fact that the sulfated sodium oleate and the sodium alkyl phosphate are used in the formula of the collecting agent disclosed by the invention is proved to obviously improve the collecting capacity and the low temperature resistance.
In conclusion, the collector disclosed by the invention is good in low-temperature resistance, strong in collecting capability, low in production cost, small in using amount and good in separation effect when applied to silicate phosphate rare earth ores.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The utility model provides a low temperature resistant double acid salt type rare earth ore flotation collector which characterized in that: including sodium alkyl phosphates, sodium sulfated oleates, surfactants, and emulsifiers.
2. The flotation collector for low-temperature-resistant double-acid-salt rare earth ores according to claim 1, is characterized in that: comprises the following components in parts by weight: 10-25 parts of sodium alkyl phosphate, 60-80 parts of sodium phosphatate, 8-15 parts of surfactant and 0.8-2 parts of emulsifier.
3. The flotation collector for low-temperature-resistant double-acid-salt rare earth ores according to claim 1, is characterized in that: the surfactant comprises sodium dodecyl benzene sulfonate.
4. The flotation collector for low-temperature-resistant double-acid-salt rare earth ores according to claim 1, is characterized in that: the emulsifier comprises OP-10.
5. The flotation collector for low-temperature-resistant double-acid-salt rare earth ores according to claim 1, is characterized in that: the preparation method of the sodium alkyl phosphate comprises the following steps: mixing mixed alcohol, pyrophosphoric acid and a solvent, and reacting under heating to obtain alkyl phosphate; mixing the alkyl phosphate with a sodium hydroxide solution to obtain the sodium alkyl phosphate; the mixed alcohol comprises isooctyl alcohol and n-heptanol, and the mass ratio of the isooctyl alcohol to the n-heptanol is 2: 1-1.5.
6. The flotation collector for low-temperature-resistant double-acid-salt rare earth ores according to claim 1, is characterized in that: the preparation method of the sulfated sodium oleate comprises the following steps: slowly adding concentrated sulfuric acid into the stirred oleic acid at normal temperature, heating and preserving heat, adding a sodium hydroxide solution, and performing saponification reaction to obtain the sulfated sodium oleate; the mass ratio of the sodium hydroxide solution to the oleic acid is 1: 10.
7. The preparation method of the low-temperature-resistant double-salt rare earth ore flotation collector as claimed in claims 1 to 6, is characterized in that: the sodium alkyl phosphate, the sulfated sodium oleate, the surfactant and the emulsifier are mixed and stirred uniformly to obtain the sodium alkyl phosphate.
8. The application of the low-temperature-resistant double-acid-salt rare earth ore flotation collector as claimed in claims 1 to 7 is characterized in that: the collecting agent is used for flotation of the double-acid salt rare earth ore.
9. The application of the low-temperature-resistant double-acid-salt rare earth ore flotation collector according to claim 8 is characterized in that: the collecting agent is used for flotation of silicate phosphate rare earth ore.
10. The application of the low-temperature-resistant double-acid-salt rare earth ore flotation collector according to claim 9 is characterized in that: adding a collecting agent and an auxiliary agent into the ore pulp of the rare earth ore for flotation, wherein the auxiliary agent comprises an inhibitor, and the inhibitor is acidified water glass.
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| CN111451001B (en) * | 2020-03-10 | 2021-05-11 | 中国地质科学院矿产综合利用研究所 | Medium-low grade mixed collophanite flotation separation reagent system and application thereof |
| CN111530634B (en) * | 2020-04-24 | 2022-03-22 | 核工业北京化工冶金研究院 | Flotation method of alkaline granite type rare earth ore |
| CN111515029B (en) * | 2020-04-30 | 2022-05-17 | 江西理工大学 | Collecting agent for separating monazite and ilmenite and using method thereof |
| CN112474064B (en) * | 2020-10-23 | 2022-06-24 | 核工业北京化工冶金研究院 | Compound collecting agent and application thereof in complex rare earth ore flotation |
| CN113210135A (en) * | 2021-04-29 | 2021-08-06 | 西部黄金(克拉玛依)矿业科技有限责任公司 | Modified oleic acid type mineral flotation collector and preparation method thereof |
| CN115228621A (en) * | 2022-07-18 | 2022-10-25 | 武汉工程大学 | Mixed collecting agent and application thereof in flotation separation of calcium-magnesium carbonate minerals |
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| JP4351822B2 (en) * | 2002-02-22 | 2009-10-28 | 住鉱コンサルタント株式会社 | A method for the preparation of bastonite from weathered rare earth ores. |
| CN102764700B (en) * | 2012-08-01 | 2013-09-25 | 中钢集团马鞍山矿山研究院有限公司 | Preparation method of low temperature resisting fluorite flotation collector |
| US9266120B2 (en) * | 2013-10-01 | 2016-02-23 | Ecolab Usa Inc | Collectors for mineral flotation |
| CN104607320A (en) * | 2014-11-19 | 2015-05-13 | 四川省地质矿产勘查开发局成都综合岩矿测试中心 | Efficient flotation collector for rare earth ore |
| CN105170338B (en) * | 2015-08-28 | 2017-12-08 | 河南天鸿选矿科技有限公司 | A kind of non-sulfide ore mineral floating collecting agent and its preparation method and application |
| CN106269262B (en) * | 2016-08-10 | 2018-05-22 | 广东省资源综合利用研究所 | A kind of method of microfine Rare Earth Mine carrier flotation |
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| CN107952591B (en) * | 2017-11-27 | 2019-05-10 | 中国地质科学院矿产综合利用研究所 | Phosphosilicate type rare earth ore flotation collector and preparation method and application thereof |
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