CN106944263B - A kind of Collophane anti-floatation collector and its preparation method and application method - Google Patents
A kind of Collophane anti-floatation collector and its preparation method and application method Download PDFInfo
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- CN106944263B CN106944263B CN201710222637.9A CN201710222637A CN106944263B CN 106944263 B CN106944263 B CN 106944263B CN 201710222637 A CN201710222637 A CN 201710222637A CN 106944263 B CN106944263 B CN 106944263B
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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
- B03D1/018—Mixtures of inorganic and organic compounds
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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
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Abstract
The invention discloses a kind of Collophane anti-floatation collector and its preparation method and application methods, belong to SOLID MINERAL RESOURCES sorting technology field.The present invention is to depressurize five line phenol extraction oil, diluent, oleum, sodium hydroxide etc. as raw material, after feedstock oil and diluent are mixed by certain mass percent, oleum is fed into reaction kettle sulfonation, washing is stirred after sulfonating reaction, stratification, it takes organic layer to be once saponified in saponification kettle, sulfonate is made；Sulfonate obtained is carried out to compound resulting mixture by certain mass percent with soybean oleic acid, through secondary saponification to get anionic high calcium (magnesium) matter Collophane anti-floatation collector.Medicament preparation process is simple, and adaptable (temperature, pH values of pulp etc.), resistance to mud is good, floatation indicators are high and stablize, it is low in cost, nontoxic, it is applied to the flotation of high calcium (magnesium) collophane, is remarkably improved phosphorus concentrate grade (P2O5) and the rate of recovery, and reduce its impurity content.
Description
Technical field
The invention belongs to SOLID MINERAL RESOURCES sorting technology fields, more specifically to a kind of high magnesium or high calcium glue phosphorus
Ore inverse flotation collecting agent and its preparation method and application method.
Background technique
Flotation is the main method of flotation of phosphate rock, can be divided into direct flotation, reverse flotation and anti-~direct flotation etc., flotation effect
Quality depend primarily on collecting agent used.In early days, collecting agent used generally uses oxidized paraffin wax soap, tall oil in phosphate rock floating
Equal fatty acid and its soaps collecting agent recycling phosphate and carbonate, but the selectivity of the type collecting agent is poor, to hard
The adaptability of water and flotation at low temperature is poor, and to keep fatty acid collecting agent well dispersed, phosphate rock floating need to usually heat flotation, work
Skill is more demanding.
With large-scale developing and utilizing for phosphate rock resource, the phosphorus ore of rich ore and Yi Xuan are gradually decreased, the remaining overwhelming majority
For middle-low grade appositional pattern phosphorus ore rock, because it is complicated at mine property, grade is low, and 90% or more rock phosphate in powder also contains a large amount of carbonic acid
The gangue minerals such as salt, silicate cause beneficiation cost height, difficulty big.For a long time, for high calcium (magnesium) matter collophane ore dressing skill
The developmental research of art and floating agent is always the research emphasis and difficult point of ore dressing scientific worker.
Current relatively effective collophane ore-dressing technique, including flotation, gravity treatment, heavymedia separation, magnetoelectricity ore dressing, roasting~
Digestion, chemical mineral processing etc., wherein floatation beneficiating efficiency highest, is most common beneficiation method.For high calcium (magnesium) collophane,
Due to its valuable mineral and the mutual symbiosis of gangue mineral, package, disseminated grain size is thin, and most of phosphorus ores need ore grinding to granularity before sorting
Monomer dissociation is just able to achieve for 90% or more -0.074mm.Phosphate minerals and gangue mineral carbonate mineral surface property become simultaneously
Same, floatability approaches, and two kinds of mineral floatings separation is caused to become extremely difficult.Numerous results of study show for high calcium (magnesium)
Collophane, most effective beneficiation method are reverse flotation and roasting~digestion process.
(1) this process flow of single reverse floatation process is simple, at low cost, can efficiently separate the gangues such as collophane and dolomite
The removal rate of mineral, dolomite may be up to 80 or more, low high calcium (magnesium) the glue phosphorus of high suitable for content of magnesia and siliceous content
Mine ore dressing.Its flotation mechanism is: using inhibitor, (pH is 4.0~5.0) inhibits Phosphate minerals in weak acidic medium, then utilizes
Fatty acid collecting agent flotation calcic (magnesium) mineral.The premise that this technology can be successfully applied is, it is necessary to which selective good catches
Receive agent and inhibitor.
(2) rock phosphate in powder that this technique of roasting~digestion process is suitble to carbonate mineral content high, belongs to chemical mineral processing, makees
With mechanism are as follows: under the conditions of 900 DEG C of high-temperature roastings, the carbonate mineral in rock phosphate in powder is chemically reacted, and releases CO2Gas
Body, then plus water digestion makes CaO, MgO aquation, generates the Ca (OH) of microfine2With Mg (OH)2Precipitating finally uses desliming, divides
Deliming, magnesium hydroxide are gone in grade operation, achieve the purpose that rock phosphate in powder decalcification (magnesium) is enriched with.But roasting~digestion process is to high magnesium
(calcium) collophane has certain limitation, especially as SiO in rock phosphate in powder2When content is more than 5%, technique cannot be used,
Otherwise it is difficult to ensure the grade of final phosphorus concentrate, therefore can only just use floatation.
In order to guarantee the using effect of floatation, the selection of collecting agent is most important.Currently, height commonly used in the prior art
Calcium (magnesium) matter Collophane anti-floatation collector mainly includes following four type:
(1) fatty acid anionic collector
Fatty acid collecting agent is that foremost oxide mineral collector and high magnesium (calcium) matter collophane are most common anti-floating
One of collecting agent is selected, this kind of collecting agent mainly has: oleic acid and its esters, tall oil and oxidized paraffin wax soap etc..Fatty acid collecting
The most significant feature of agent is that source is wide, but existing fatty acid collecting agent not readily dissolves, and the bad adaptability in hard water, flotation
Selectivity is relatively poor, and concentrate grade is low, and the rate of recovery is low, it is difficult to meet technical requirements, seldom use single fat acids at present
Collecting agent carries out flotation to high magnesium (calcium) matter collophane.
(2) amphoteric collector
So-called amphoteric collector refers in cation in acid intermediate value, is in anion in alkaline intermediate value, is a kind of same
When with anion and cation heteropolar collector, common are diethylamine ethyl xanthogenate, 8~oxyquinoline etc..It is reported that
Finland Mondgy B M. utilizes alkyl~N~methyl glycine flotation high calcium (magnesium) rock phosphate in powder, as Beneficiation Feed Grade (P2O5) be
4.0%, (MgO) is 14.7%, using the single reverse floatation process of one roughing triple cleaning, can get phosphorus concentrate grade (P2O5)
It is 35.0%, impurity (MgO) is 1.6%.Studies have shown that amphoteric collector has preferable selection than fatty acid collecting agent
Property, floatation indicators are preferable, but its reagent cost is too high, and synthesis technology is complicated, it is difficult to industrially large-scale application.
(3) modified fat acid collector
Modified fat acid collector is a kind of collecting agent of current research and application at most, such collecting agent is mainly logical
Unsaturated bond in passing fatty acid in a certain amount of concentrated sulfuric acid of addition and chlorine, with fatty acid molecule reacts, and makes fat
Acid is modified, to be conducive to improve the water solubility and selectivity of fatty-acid collector.It is ground by Lianyungang Design and Research Institute (Lanai Engineering Co.)
The modified collecting agent of the PA series fatty acid of system exploitation has very carbonate containing type rock phosphate in powder under the conditions of pH is 4.0~5.0
Good sorting is giving mine grade (P in Weng'an biota commerical test2O5) when being 30.98%, by reverse flotation, make final
Concentrate grade (P2O5) it is increased to 36.18%.But the medicament still exists in practical applications, and flotation temperature is high, tailings grade is high,
The problems such as rate of recovery is low.
(4) composite class collecting agent
So-called mixing class collecting agent, refers to the limitation due to single fat acid collector itself, using a kind of and more
Kind fatty acid of different nature is compounded with its derivative or neutral oil, so that reaching improves its flotation performance, is improved floating
Select the purpose of index.Composite class collecting agent has been widely used for the flotation of rock phosphate in powder at present.India scholar once uses oleic acid and coal
Oil is compounded, and the high magnesium of flotation (calcium) rock phosphate in powder obtains grade (P2O5) it is 37.48%, the phosphorus that impurity (MgO) is 1.27%
Concentrate.It is reported that thering is scholar to compound using enuatrol with ammonium oleate, using reverse flotation head grade (P2O5) mentioned from 27.48%
Height is to 38.10%, the rate of recovery 85.20%, but in its gained concentrate impurity MgO content it is higher.
In conclusion above-mentioned all types of existing collecting agents can more or less exist, collecting agent usage amount is big, reagent cost is high,
Or flotation selectivity is poor, or bad adaptability more sensitive to sludge, the problems such as flotation at low temperature effect is poor, especially to high magnesium (calcium)
The separating effect of apatite and carbonate mineral is worse in rock phosphate in powder, it is difficult to meet requirement.In addition some collecting agents also contain
There is a certain amount of noxious material, environment can be caused centainly to pollute.
Summary of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome deficiency existing for existing high magnesium (calcium) rock phosphate in powder collecting agent, a kind of glue is provided
Phosphate reverse flotation collecting agent and preparation method thereof, the present invention, which prepares gained collecting agent, can be realized phosphorus in high magnesium or high calcium rock phosphate in powder
Lime stone and carbonate mineral efficiently separate, and floatation indicators are high and stablize, while preparation process is simple, low in cost and nontoxic.
It is a further object to provide the application methods of above-mentioned collophane stone collecting agent, can using this method
On the basis of guaranteeing to high magnesium (calcium) collophane stone flotation effect, the low temperature resistance and selectivity of collecting agent are greatly improved.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
First, a kind of preparation method of Collophane anti-floatation collector of the invention, comprising the following steps:
(1) decompression five line phenol extraction oil mix being placed in reaction kettle with gasoline, agitating and heating, then to reaction
Addition sulfonating agent carries out sulfonation in kettle, obtains sulfonated products；
(2) gained sulfonated products are stirred washing and stratification, organic layer is taken to carry out saponification, sulfonic acid is made
Salt；
(3) gained sulfonate and soybean oleic acid are re-dubbed mixture, through secondary saponification, that is, obtain anion of the invention
Type Collophane anti-floatation collector.
Further, the mixing mass ratio of five line phenol of decompression extraction oil and gasoline is (1~4) in the step (1): (1
~2), the temperature of agitating and heating is 20 DEG C~30 DEG C.
Further, the sulfonating agent in the step (1) uses oleum, and sulfonation temperature is 50 DEG C~70 DEG C, sulphur
The change time is 1h~3h, and the oil content of gained sulfonated products is 57 ± 2wt%.
Further, SO in the sulfonating agent oleum3Mass fraction be 15wt%~30wt%.
Further, the mass ratio of organic layer and saponification agent is (4~10): (1~2) in the step (2), and is saponified
Process pH is controlled between 8~11.
Further, use NaOH solution as saponification agent in the step (2).
Further, the mass ratio of sulfonate and soybean oleic acid is (4~10): (1~2) in the step (3).
Second, a kind of Collophane anti-floatation collector of the invention, the collecting agent is prepared using method of the invention
It obtains, which includes three kinds of organic matter, neutral oil and inorganic salts components, and the matter of organic matter, neutral oil and inorganic salts
Measuring percentage is respectively 35%~50%, 30%~45% and 10%~30%, and wherein hydrocarbon molecule amount is 400~600.
Third, a kind of application method of Collophane anti-floatation collector of the invention, its step are as follows:
(1) content that flotation is -0.074mm to the grinding fineness of mine accounts for the 70%~82% of total amount；
(2) levigate ore pulp obtains rougher concentration and rougher tailings, wherein roughing process conditions are as follows: sodium carbonate through roughing
Dosage is 1500-3000g/t, and action time 2-5min, collector dosage is 350g/t~500g/t, action time 2-
5min；
(3) obtained rougher tailings is carried out scanning operation 1, obtain scanning chats 1 and scans tailing 1, scanned chats 1 and return
Return upper one layer of roughing operation；Wherein rougher tailings, which is scanned, does not add any medicament.
(4) gained is scanned tailing 1 to be scanned for the second time, chats 2 and true tailings are scanned in acquisition, scan the return of chats 2
Upper one layer scans operation 1；It wherein scans for the second time and does not add any medicament.
(5) rougher concentration for obtaining step (2) carries out selected, obtains selected chats and final concentrate, selected chats returns
Return upper one layer of roughing operation；Wherein rougher concentration is selected does not add any medicament.
3. beneficial effect
Using technical solution provided by the invention, compared with prior art, have the following beneficial effects:
(1) preparation method of a kind of Collophane anti-floatation collector of the invention, with depressurize five line phenol extraction oil, gasoline,
Oleum, sodium hydroxide etc. are raw material, carry out sulfonation processing after feedstock oil and gasoline mixing, then layered gained organic layer
It carries out saponification process and sulfonate is made；Sulfonate obtained is compounded with soybean oleic acid, and through secondary saponification to get this hair
Bright anionic high calcium (magnesium) matter Collophane anti-floatation collector, the collecting agent can be realized phosphorus in high magnesium or high calcium rock phosphate in powder
Lime stone and carbonate mineral efficiently separate, and compared with existing high calcium (magnesium) Collophane anti-floatation collector, have stronger suitable
Ying Xing can satisfy different type, the flotation demand of heterogeneity rock phosphate in powder, and the resistance to mud of collecting agent is good, and floatation indicators are steady
Fixed, pharmaceutical use is few, and production cost is low.
(2) preparation method of a kind of Collophane anti-floatation collector of the invention, by reaction raw materials and its proportion and
Reaction process parameter optimizes, and so as to which collecting agent is effectively ensured while with good collecting effect, improves
The stability of its flotation froth, and adaptability of the gained collecting agent to the adaptability of floatation process, especially to pH values of pulp variation
Relatively strong, floatation indicators are high；The collecting agent is also higher to the adaptability of flotation temperature simultaneously, and especially flotation at low temperature effect is good.
(3) a kind of preparation method of Collophane anti-floatation collector of the invention can by optimizing to preparation process
To effectively prevent sulfonate in preparation process that coking, charing occurs, to significantly improve the performance and conversion ratio of product, and should
Preparation process is simple, and preparation gained collecting agent main component is sulfonic acid and fatty acid, and effect on environment is small, belongs to green product.
(4) application method of a kind of Collophane anti-floatation collector of the invention is swept by using thick~essence~bis-
Closed circuit single reverse floatation process, and specific process parameter is optimized, so as to effectively improve gained phosphorus concentrate
Grade and the rate of recovery, and reduce the impurity content in recycling phosphorus concentrate.
(5) application method of a kind of Collophane anti-floatation collector of the invention, by height (magnesium) calcium collophane of the invention
Collecting agent in reverse floatation is used to carry out reverse flotation experiment to Guizhou phosphorus ore, as Beneficiation Feed Grade (P2O5) it is that 21.58%, (MgO) is
4.48%, closed circuit single reverse floatation process is swept using thick~essence~bis-, can get phosphorus concentrate grade (P2O5) it is 34.11%,
The excellent measure that impurity (MgO) is 0.24%, compared with the collecting agent in reverse floatation that scene uses, P2O5Concentrate grade improves 2.25
Percentage point, the rate of recovery improves 0.35 percentage point.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the application method of Collophane anti-floatation collector of the invention.
Specific embodiment
When carrying out ore dressing processing to high calcium (magnesium) matter collophane using reverse flotation method, the type of flotation agent is for mineral point
It is most important from effect.And in existing common collecting agent, fatty acid collecting agent not readily dissolves, the bad adaptability in hard water, floats
Choosing selectivity is relatively poor, and concentrate grade is low, and the rate of recovery is low, it is difficult to meet technical requirements；Amphoteric collector is caught than fatty acid
Receiving agent has preferable selectivity, and floatation indicators are preferable, but its reagent cost is too high, and synthesis technology is complicated, it is difficult to industrially
Large-scale application；Modified fat acid collector equally exists flotation temperature height, tailings grade height, the rate of recovery in practical applications
The problems such as low.Meanwhile the above existing common collecting agent mostly exists that bad dispersibility, molten point are high, solubility is small, stability in hard water is poor,
Selectivity is bad, needs the defects of heating.
For problem above existing for existing collecting agent, inventor is by lot of experiments to reaction raw materials and its proportion
It is optimized with reaction process parameter, final preparation gained collecting agent can be realized apatite in high magnesium or high calcium rock phosphate in powder
With efficiently separating for carbonate mineral, and the resistance to mud of the collecting agent it is good, have foamability is strong, collecting ability is strong, it is adaptable,
The advantages such as synthesis cost is low, floatation indicators are high and stablize, while its preparation process is simple, low in cost and nontoxic.It will be of the invention
Gained collecting agent and anionic surfactant or nonionic surfactant combinations use, and substantially increase the anti-of the collecting agent
Cryogenic property, simultaneous selection also greatly improve.The preparation method of high calcium (magnesium) matter Collophane anti-floatation collector of the invention,
Specifically includes the following steps:
(1) be (1~4) according to mass ratio with gasoline by decompression five line phenol extraction oil: (1~2), which mix, to be placed in instead
It answers in kettle, the agitating and heating at 20 DEG C~30 DEG C, then adds oleum into reaction kettle as sulfonating agent and carry out sulfonation, obtain
Obtain sulfonated products, SO in oleum used3Mass fraction be 15wt%~30wt%.Wherein, sulfonation temperature be 50 DEG C~
70 DEG C, sulfonation time is 1h~3h, and the oil content of gained sulfonated products is 57 ± 2wt%.
(2) gained sulfonated products are stirred washing and stratification, take organic layer to carry out saponification, using NaOH
Solution is as saponification agent, and the mass ratio of organic layer and saponification agent is (4~10): (1~2), and saponification process pH control is 8~11
Between, sulfonate is obtained, the reaction equation of sulfonate preparation is as follows:
R·H+SO3→RSO3H
R·SO3H+NaOH→RSO3Na+H2O
Inventor has found that coking, charing phenomenon easily occur during the preparation process for sulfonate, thus shadow in the course of the research
The using effect of gained collecting agent is rung, this is also the major issue that the present invention needs to solve.And use method of the invention
It can effectively prevent sulfonate that coking, charing occurs, be conducive to improve conversion ratio and properties of product.
(3) be in mass ratio (4~10) with soybean oleic acid by gained sulfonate: (1~2) compounds resulting mixture, through secondary
Saponification, that is, obtain anionic Collophane anti-floatation collector of the invention, and the present invention prepares gained collecting agent mainly by organic
Object, neutral oil and inorganic salts composition, and the mass percent of organic matter, neutral oil and inorganic salts be respectively 35%~50%,
30%~45% and 10%~30%, wherein hydrocarbon molecule amount is 400~600.
The present invention prepares the application method of gained collecting agent, and its step are as follows:
(1) content that flotation is -0.074mm to the grinding fineness of mine accounts for the 70%~82% of total amount；
(2) levigate ore pulp obtains rougher concentration and rougher tailings, wherein roughing process conditions are as follows: sodium carbonate through roughing
Dosage is 2000g/t, and action time 2min, collector dosage is 350g/t~500g/t, action time 3min；
(3) obtained rougher tailings is carried out scanning operation 1, obtain scanning chats 1 and scans tailing 1, scanned chats 1 and return
Return upper one layer of roughing operation；Wherein rougher tailings, which is scanned, does not add any medicament.
(4) gained is scanned tailing 1 to be scanned for the second time, chats 2 and true tailings are scanned in acquisition, scan the return of chats 2
Upper one layer scans operation 1；It wherein scans for the second time and does not add any medicament.
(5) rougher concentration for obtaining step (2) carries out selected, obtains selected chats and final concentrate, selected chats returns
Return upper one layer of roughing operation；Wherein rougher concentration is selected does not add any medicament.
When present invention preparation gained collecting agent is used for the flotation of high calcium (magnesium) matter collophane, by using a thick~essence
~bis- sweep closed circuit single reverse floatation process, and optimize to specific process parameter, so as to effectively improve gained phosphorus
The grade and the rate of recovery of concentrate, and reduce the impurity content in recycling phosphorus concentrate.
To further appreciate that the contents of the present invention, now in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of preparation method of the Collophane anti-floatation collector of the present embodiment, comprising the following steps:
It (1) is in mass ratio that 1:2 mix being placed in reaction kettle with gasoline by decompression five line phenol extraction oil, stirring adds
Heat, heating temperature are 25 DEG C, and oleum is then added into reaction kettle as sulfonating agent progress sulfonation, in oleum used
SO3Mass fraction be 15wt%, sulfonation temperature be 50 DEG C, sulfonation time 1h, obtain sulfonated products, gained sulfonated products
Oil content is 57wt%.
(2) gained sulfonated products are stirred washing and stratification, using NaOH solution as saponification agent to organic
Layer carries out saponification process, is made sulfonate, and the mass ratio of organic layer and NaOH solution is 4:2, and saponification process pH=8.
(3) in mass ratio it is that 10:1 compounds resulting mixture with soybean oleic acid by gained sulfonate, through secondary saponification, that is, obtains
Final anionic Collophane anti-floatation collector, organic matter, neutral oil in collecting agent in reverse floatation obtained by the present embodiment and
The mass percent of inorganic salts is respectively 50%, 30% and 10%, and wherein hydrocarbon molecule amount is about 500.
The existing collecting agent of the present embodiment preparation gained collecting agent in reverse floatation and scene is respectively adopted to low-grade high magnesium calcium glue
Phosphorus ore carries out flotation processing, and experiment process is that thick-one essence-two is swept, and sulfuric acid is inhibitor, in conjunction with Fig. 1, detailed process are as follows:
(1) content that flotation is -0.074mm to the grinding fineness of mine accounts for the 70%~82% of total amount；
(2) levigate ore pulp obtains rougher concentration and rougher tailings, wherein roughing process conditions are as follows: sodium carbonate through roughing
Dosage is 2000g/t, action time 2min, collector dosage 350g/tg/t, action time 3min；
(3) obtained rougher tailings is carried out scanning operation 1, obtain scanning chats 1 and scans tailing 1, scanned chats 1 and return
Return upper one layer of roughing operation；Wherein rougher tailings, which is scanned, does not add any medicament.
(4) gained is scanned tailing 1 to be scanned for the second time, chats 2 and true tailings are scanned in acquisition, scan the return of chats 2
Upper one layer scans operation 1；It wherein scans for the second time and does not add any medicament.
(5) rougher concentration for obtaining step (2) carries out selected, obtains selected chats and final concentrate, selected chats returns
Return upper one layer of roughing operation；Wherein rougher concentration is selected does not add any medicament.
Above-mentioned experimental data comparing result is as shown in table 1 below, as can be seen from Table 1, the reverse flotation collecting used with scene
Agent is compared, and is remarkably improved P using the collecting agent of the present embodiment2O5Concentrate grade and its rate of recovery, and reduce the impurity in concentrate
(MgO) content.
Certain the low-grade high magnesium calcium Collophane anti-floatation collector comparative test result (%) of table 1
Embodiment 2
A kind of preparation method of the Collophane anti-floatation collector of the present embodiment, comprising the following steps:
It (1) is in mass ratio that 4:1 mix being placed in reaction kettle with gasoline by decompression five line phenol extraction oil, stirring adds
Heat, heating temperature are 20 DEG C, and oleum is then added into reaction kettle as sulfonating agent progress sulfonation, in oleum used
SO3Mass fraction be 25wt%, sulfonation temperature be 65 DEG C, sulfonation time 2h, obtain sulfonated products, gained sulfonated products
Oil content is 55wt%.
(2) gained sulfonated products are stirred washing and stratification, using NaOH solution as saponification agent to organic
Layer carries out saponification process, is made sulfonate, and the mass ratio of organic layer and NaOH solution is 10:1, and saponification process pH=11.
(3) in mass ratio it is that 4:1 compounds resulting mixture with soybean oleic acid by gained sulfonate, through secondary saponification, that is, obtains
Final anionic Collophane anti-floatation collector.Organic matter, neutral oil and inorganic in the present embodiment preparation gained collecting agent
The mass percent of salt is respectively 35%, 33% and 30%, and wherein hydrocarbon molecule amount is 400.
By collectors application obtained by the present embodiment in the flotation of high calcium collophane, step is substantially the same as embodiment 1, difference master
It is: roughing process conditions in step (2) in the present embodiment are as follows: sodium carbonate amount 1500g/t, action time 5min,
Collector dosage is 500g/t, action time 2min, and experimental result is closer to embodiment 1.
Embodiment 3
A kind of preparation method of the Collophane anti-floatation collector of the present embodiment, comprising the following steps:
It (1) is in mass ratio that 3:2 mix being placed in reaction kettle with gasoline by decompression five line phenol extraction oil, stirring adds
Heat, heating temperature are 30 DEG C, and oleum is then added into reaction kettle as sulfonating agent progress sulfonation, in oleum used
SO3Mass fraction be 30wt%, sulfonation temperature be 70 DEG C, sulfonation time 3h, obtain sulfonated products, gained sulfonated products
Oil content is 59wt%.
(2) gained sulfonated products are stirred washing and stratification, using NaOH solution as saponification agent to organic
Layer carries out saponification process, is made sulfonate, and the mass ratio of organic layer and NaOH solution is 7:1, and saponification process pH=9.
(3) in mass ratio it is that 2:1 compounds resulting mixture with soybean oleic acid by gained sulfonate, through secondary saponification, that is, obtains
Final anionic Collophane anti-floatation collector.Organic matter, neutral oil and inorganic in the present embodiment preparation gained collecting agent
The mass percent of salt is respectively 38%, 45% and 14%, and wherein hydrocarbon molecule amount is 600.
By collectors application obtained by the present embodiment in the flotation of high calcium collophane, step is substantially the same as embodiment 1, difference master
It is: roughing process conditions in step (2) in the present embodiment are as follows: sodium carbonate amount 3000g/t, action time 4min,
Collector dosage is 450g/t, action time 5min, and experimental result is closer to embodiment 1.
Claims (7)
1. a kind of preparation method of Collophane anti-floatation collector, which comprises the following steps:
(1) decompression five line phenol extraction oil mix being placed in reaction kettle with gasoline, agitating and heating, then into reaction kettle
It adds sulfonating agent and carries out sulfonation, obtain sulfonated products；Wherein depressurize five line phenol extraction oil with the mixing mass ratio of gasoline be (1~
4): (1~2), the temperature of agitating and heating are 20 DEG C~30 DEG C, and the sulfonating agent uses oleum, sulfonation temperature is 50 DEG C~
70 DEG C, sulfonation time is 1h~3h, and the oil content of gained sulfonated products is 57 ± 2wt%；
(2) gained sulfonated products are stirred washing and stratification, organic layer is taken to carry out saponification, sulfonate is made；
(3) gained sulfonate and soybean oleic acid are re-dubbed mixture, through secondary saponification, that is, obtain that anionic collophane is counter to float
Select collecting agent.
2. a kind of preparation method of Collophane anti-floatation collector according to claim 1, it is characterised in that: the sulfonation
SO in agent oleum3Mass fraction be 15wt%~30wt%.
3. a kind of preparation method of Collophane anti-floatation collector according to claim 1 or 2, it is characterised in that: described
The mass ratio of organic layer and saponification agent is (4~10): (1~2) in step (2), and saponification process pH control is between 8~11.
4. a kind of preparation method of Collophane anti-floatation collector according to claim 3, it is characterised in that: the step
(2) using NaOH solution as saponification agent in.
5. a kind of preparation method of Collophane anti-floatation collector according to claim 3, it is characterised in that: the step
(3) mass ratio of sulfonate and soybean oleic acid is (4~10): (1~2) in.
6. a kind of Collophane anti-floatation collector, it is characterised in that: the collecting agent is using any one of claim 1-5 institute
What the method stated was prepared, which includes three kinds of organic matter, neutral oil and inorganic salts components, and organic matter, neutral oil
Mass percent with inorganic salts is respectively 35%~50%, 30%~45% and 10%~30%, and wherein hydrocarbon molecule amount is 400
~600.
7. a kind of application method of Collophane anti-floatation collector as claimed in claim 6, which is characterized in that its step is such as
Under:
(1) content that flotation is -0.074mm to the grinding fineness of mine accounts for the 70%~82% of total amount；
(2) levigate ore pulp obtains rougher concentration and rougher tailings, wherein roughing process conditions are as follows: sodium carbonate amount through roughing
For 1500-3000g/t, action time 2-5min, collector dosage is 350g/t~500g/t, action time 2-5min；
(3) obtained rougher tailings is carried out scanning operation 1, obtain scanning chats 1 and scans tailing 1, scanned chats 1 and return
One layer of roughing operation；Wherein rougher tailings, which is scanned, does not add any medicament；
(4) gained is scanned tailing 1 to be scanned for the second time, chats 2 and true tailings are scanned in acquisition, are scanned chats 2 and are returned to upper one
Layer scans operation 1；It wherein scans for the second time and does not add any medicament；
(5) rougher concentration obtained step (2) carries out selected, selected chats and final concentrate is obtained, on selected middling recurrence
One layer of roughing operation；Wherein rougher concentration is selected does not add any medicament.
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| CN110152889A (en) * | 2019-06-04 | 2019-08-23 | 瓮福（集团）有限责任公司 | A kind of silicon calcium quality ore Counterfloatating desiliconization removal of impurities combined capturing and collecting agent and its preparation method and application |
| CN110293006B (en) * | 2019-07-19 | 2021-08-10 | 宜都兴发化工有限公司 | Beneficiation method for reducing sesquioxide in collophanite |
| CN110369155B (en) * | 2019-08-29 | 2021-09-14 | 北京矿冶科技集团有限公司 | Double-reaction impurity removal method for collophanite |
| CN111482277B (en) * | 2020-06-23 | 2022-06-10 | 四川省地质矿产勘查开发局成都综合岩矿测试中心 | Collecting agent for magnesium-silicon phosphate rock mixed reverse flotation, preparation method and beneficiation method |
| CN114749281B (en) * | 2022-03-22 | 2023-07-14 | 张艺蓬 | Calcium gangue zinc oxide ore mixed collector, preparation method and use method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962828A (en) * | 1997-10-15 | 1999-10-05 | Custom Chemicals Corporation | Enhanced flotation reagents for beneficiation of phosphate ores |
| CN1249213A (en) * | 1998-09-26 | 2000-04-05 | 冶金工业部马鞍山矿山研究院 | Process for preparing floatation collector of sillimanite |
| CN101955450A (en) * | 2009-07-20 | 2011-01-26 | 中国石油天然气股份有限公司 | Petroleum sulfonate composition, preparation method and application thereof |
| CN104117435A (en) * | 2014-08-07 | 2014-10-29 | 张家口市凯盛选矿药剂有限公司 | Preparation method for titanic iron ore floatation collecting agent |
| CN105233966A (en) * | 2015-10-08 | 2016-01-13 | 云南磷化集团有限公司 | Chemical magnesium removal and phosphorite reverse flotation coupling technology |
| CN106269286A (en) * | 2016-08-24 | 2017-01-04 | 武汉工程大学 | A kind of preparation method of alpha-sulfonated fatty acid phosphate reverse flotation collecting agent |
-
2017
- 2017-04-07 CN CN201710222637.9A patent/CN106944263B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962828A (en) * | 1997-10-15 | 1999-10-05 | Custom Chemicals Corporation | Enhanced flotation reagents for beneficiation of phosphate ores |
| CN1249213A (en) * | 1998-09-26 | 2000-04-05 | 冶金工业部马鞍山矿山研究院 | Process for preparing floatation collector of sillimanite |
| CN101955450A (en) * | 2009-07-20 | 2011-01-26 | 中国石油天然气股份有限公司 | Petroleum sulfonate composition, preparation method and application thereof |
| CN104117435A (en) * | 2014-08-07 | 2014-10-29 | 张家口市凯盛选矿药剂有限公司 | Preparation method for titanic iron ore floatation collecting agent |
| CN105233966A (en) * | 2015-10-08 | 2016-01-13 | 云南磷化集团有限公司 | Chemical magnesium removal and phosphorite reverse flotation coupling technology |
| CN106269286A (en) * | 2016-08-24 | 2017-01-04 | 武汉工程大学 | A kind of preparation method of alpha-sulfonated fatty acid phosphate reverse flotation collecting agent |
Non-Patent Citations (2)
| Title |
|---|
| 石油磺酸盐的试验研究;马鞍山矿山研究院药剂室石油磺酸组;《矿产综合利用》;19800301(第01期);第76-80,89页 |
| 胶磷矿组合捕收剂的浮选性能研究;赵和平等;《化工矿物与加工》;20160315(第3期);第1-3,7页 |
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