CN106944263A - 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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- CN106944263A CN106944263A CN201710222637.9A CN201710222637A CN106944263A CN 106944263 A CN106944263 A CN 106944263A CN 201710222637 A CN201710222637 A CN 201710222637A CN 106944263 A CN106944263 A CN 106944263A
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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 method, belong to SOLID MINERAL RESOURCES sorting technology field.The present invention is to depressurize five line phenol tapped oils, diluent, oleum, NaOH etc. for raw material, after feedstock oil and diluent are mixed by certain mass percent, oleum is fed into reactor sulfonation, sulfonating reaction stirs washing after terminating, stratification, take organic layer to carry out a saponification in saponification kettle, sulfonate is made；Obtained sulfonate and soybean oleic acid are subjected to compounding resulting mixture by certain mass percent, through secondary saponification, anionic high calcium (magnesium) matter Collophane anti-floatation collector is produced.Medicament preparation technology is simple, strong adaptability (temperature, pH values of pulp etc.), and resistance to mud is good, floatation indicators are high and stably, it is with low 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 field, 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 technology
Flotation is the main method of flotation of phosphate rock, can be divided into direct flotation, reverse flotation and anti-~direct flotation etc., its flotation effect
Quality depend primarily on collecting agent used.In early days, collecting agent used typically uses oxidized paraffin wax soap, tall oil in phosphate rock floating
Phosphate and carbonate are reclaimed Deng aliphatic acid and its soaps collecting agent, but the selectivity ratios of the type collecting agent are poor, to hard
The adaptability of water and flotation at low temperature is poor, to make fatty acid collecting agent well dispersed, and phosphate rock floating need to generally heat flotation, work
Skill requires higher.
With large-scale developing and utilizing for phosphate rock resource, rich ore and Yi Xuan phosphorus ore are gradually decreased, the remaining overwhelming majority
For middle-low grade appositional pattern phosphorus ore rock, because it is complicated into ore deposit property, grade is low, and more than 90% rock phosphate in powder also contains substantial amounts 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, are the most frequently used beneficiation methods.For high calcium (magnesium) collophane,
Due to its valuable mineral and the mutual symbiosis of gangue mineral, parcel, disseminated grain size is thin, and most of phosphorus ores need ore grinding to granularity before sorting
Monomer dissociation could be realized for~0.074mm more than 90%.Phosphate minerals and gangue mineral carbonate mineral surface nature become simultaneously
Same, floatability is approached, and causes two kinds of mineral floatings to separate the extremely difficult of change.Numerous results of study show, for high calcium (magnesium)
Collophane, maximally effective beneficiation method is reverse flotation and roasting~digestion process.
(1) this technological process of single reverse floatation process is simple, and low cost can efficiently separate the gangues such as collophane and dolomite
Mineral, the removal rate of dolomite may be up to more than 80, it is adaptable to which content of magnesia is high and high calcium (magnesium) glue phosphorus that siliceous content is low
Ore deposit ore dressing.Its flotation mechanism is：Using inhibitor, (pH is 4.0~5.0) suppresses 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) this technique of roasting~digestion process is adapted to the high rock phosphate in powder of carbonate mineral content, belongs to chemical mineral processing, and it is made
It is with mechanism：Under the conditions of 900 DEG C of high-temperature roastings, the carbonate mineral in rock phosphate in powder chemically reacts, and discharges CO2Gas
Body, the digestion that then adds water makes CaO, MgO aquation, generates the Ca (OH) of microfine2With Mg (OH)2Precipitation, finally uses desliming, divides
Deliming, magnesium hydroxide are removed in level operation, reach the purpose of rock phosphate in powder decalcification (magnesium) enrichment.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%, it is impossible to use technique,
Otherwise the grade of final phosphorus concentrate is difficult to ensure that, therefore can only just use floatation.
In order to ensure the using effect of floatation, the selection of collecting agent is most important.At present, 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 foremost oxide mineral collector, and being also that high magnesium (calcium) matter collophane is the most frequently used instead floats
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
Agent most outstanding feature is that source is wide, but existing fatty acid collecting agent is not readily dissolved, 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, and single fat acids is seldom used at present
Collecting agent carries out flotation to high magnesium (calcium) matter collophane.
(2) amphoteric collector
So-called amphoteric collector refers to be in cation in acid intermediate value, is in anion in alkaline intermediate value, is a kind of same
When the heteropolar collector with anion and cation, common are diethylamine ethyl xanthogenate, 8~oxyquinoline etc..It is reported that
Finland Mondgy B M. utilize alkyl~N~methyl Gly flotation high calcium (magnesium) rock phosphate in powder, as Beneficiation Feed Grade (P2O5) be
4.0%th, (MgO) is 14.7%, using the single reverse floatation process of one roughing triple cleaning, can obtain phosphorus concentrate grade (P2O5)
For 35.0%, its impurity (MgO) is 1.6%.Research shows that amphoteric collector has preferable selection than fatty acid collecting agent
Property, preferably, but its reagent cost is too high for floatation indicators, and synthesis technique is complicated, it is difficult to industrially large-scale application.
(3) modified fat acid collector
Modified fat acid collector is current research and the most class collecting agent of application, and such collecting agent is mainly logical
Unsaturated bond in passing aliphatic acid in a certain amount of concentrated sulfuric acid of addition and chlorine, with fatty acid molecule reacts, and makes fat
Acid is modified, so as to be conducive to improving the water-soluble and selective of fatty-acid collector.Ground by Lianyungang Design and Research Institute (Lanai Engineering Co.)
The PA series fatty acids of system exploitation are modified collecting agent, under the conditions of pH is 4.0~5.0, have very to carbonate containing type rock phosphate in powder
Good sorting, in Weng’an biota commerical test, is giving ore deposit grade (P2O5) when being 30.98%, by reverse flotation, make final
Concentrate grade (P2O5) bring up to 36.18%.But still there is flotation temperature height, tailings grade height in actual applications in the medicament,
The low problem of the rate of recovery.
(4) composite class collecting agent
So-called mixing class collecting agent, refers to the limitation in itself due to single fat acid collector, using a kind of and many
Plant aliphatic acid of different nature to be compounded with its derivative or neutral oil, so as to reach its flotation performance of improvement, improve floating
Select the purpose of index.Current composite class collecting agent has been widely used for the flotation of rock phosphate in powder.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%, impurity (MgO) is 1.27% phosphorus
Concentrate.It is reported that thering is scholar to be compounded using enuatrol with ammonium oleate, using reverse flotation head grade (P2O5) carried from 27.48%
Height to 38.10%, the rate of recovery is 85.20%, but its gained concentrate in impurity MgO content it is higher.
In summary, above-mentioned all types of existing collecting agents can more or less have that collecting agent usage amount is big, reagent cost is high,
Or flotation selectivity is poor, more sensitive to sludge, or the problems such as bad adaptability, flotation at low temperature effect difference, 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 use requirement.Some other collecting agents also contain
There is a certain amount of noxious material, certain pollution can be caused to environment.
The content of the invention
1. the invention technical problem to be solved
It is an object of the invention to overcome the shortcomings of that existing high magnesium (calcium) rock phosphate in powder collecting agent has that there is provided a kind of glue
Phosphate reverse flotation collecting agent and preparation method thereof, the present invention, which prepares gained collecting agent, can realize phosphorus in high magnesium or high calcium rock phosphate in powder
Lime stone and carbonate mineral are efficiently separated, and floatation indicators are high and stably, while preparation technology is simple, it is with low cost and nontoxic.
, can using this method it is a further object to provide the application process of above-mentioned collophane stone collecting agent
On the basis of ensureing to high magnesium (calcium) collophane stone flotation effect, the low temperature resistivity energy and selectivity of collecting agent are greatly improved.
2. technical scheme
To reach above-mentioned purpose, the technical scheme that the present invention is provided is：
First, a kind of preparation method of Collophane anti-floatation collector of the present invention, comprises the following steps：
(1) five line phenol tapped oils of decompression and gasoline mix being placed in reactor, agitating heating, then to reaction
Addition sulfonating agent carries out sulfonation in kettle, obtains sulfonated products；
(2) gained sulfonated products are stirred washing and stratification, take organic layer 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 the anion of the present invention
Type Collophane anti-floatation collector.
Further, the mixing quality ratio of five line phenol tapped oils of decompression and gasoline is (1~4) in the step (1):(1
~2), the temperature of its agitating 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) in the step (2):(1~2), and saponification
Process pH is controlled between 8~11.
Further, saponification agent is used as using NaOH solution in the step (2).
Further, sulfonate and the mass ratio of soybean oleic acid are (4~10) in the step (3):(1~2).
Second, a kind of Collophane anti-floatation collector of the present invention, the collecting agent is prepared using the method for the present invention
Obtain, the collecting agent includes organic matter, three kinds of components of neutral oil and inorganic salts, and the matter of organic matter, neutral oil and inorganic salts
It is respectively 35%~50%, 30%~45% and 10%~30% to measure percentage, and wherein hydrocarbon molecule amount is 400~600.
Third, a kind of application process of Collophane anti-floatation collector of the present invention, its step is as follows：
(1) flotation for~0.074mm content accounts for the 70%~82% of total amount to the mog of ore deposit；
(2) levigate ore pulp obtains rougher concentration and rougher tailings through roughing, and wherein roughing process conditions are：Sodium carbonate
Consumption is 1500-3000g/t, and action time is 2-5min, and collector dosage is 350g/t~500g/t, and action time is 2-
5min；
(3) obtained rougher tailings is carried out scanning operation 1, obtains scanning chats 1 and scan mine tailing 1, scan chats 1 and return
Return the roughing operation of last layer；Wherein rougher tailings is scanned without any medicament.
(4) gained is scanned into mine tailing 1 through scanning for the second time, chats 2 and true tailings are scanned in acquisition, are scanned chats 2 and are returned
Last layer scans operation 1；Wherein scan for the second time without any medicament.
(5) the rougher concentration progress obtained step (2) is selected, obtains selected chats and final concentrate, selected chats is returned
Return the roughing operation of last layer；Wherein rougher concentration is selected without any medicament.
3. beneficial effect
The technical scheme provided using the present invention, compared with prior art, is had the advantages that：
(1) preparation method of a kind of Collophane anti-floatation collector of the invention, with depressurize five line phenol tapped oils, gasoline,
Oleum, NaOH etc. are raw material, carry out sulfonation processing after feedstock oil and gasoline mixing, then layered gained organic layer
Carry out saponification process and sulfonate is made；Obtained sulfonate is compounded with soybean oleic acid, and through secondary saponification, produces this hair
Bright anionic high calcium (magnesium) matter Collophane anti-floatation collector, the collecting agent can realize phosphorus in high magnesium or high calcium rock phosphate in powder
Lime stone and carbonate mineral are efficiently separated, compared with existing high calcium (magnesium) Collophane anti-floatation collector, with stronger suitable
Ying Xing, disclosure satisfy that 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, medicament usage amount 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 proportioning and
Reaction process parameter optimizes design, so as to which collecting agent is effectively ensured while with good collecting effect, improves
The stability of its flotation froth, and gained collecting agent is to the adaptability of floatation process, the adaptability especially changed to pH values of pulp
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) preparation method of a kind of Collophane anti-floatation collector of the invention, can by being optimized to preparation technology
Effectively to prevent that coking, charing occur for sulfonate in preparation process, so that the performance and conversion ratio of product are significantly improved, and should
Preparation technology is simple, and it is sulfonic acid and aliphatic acid to prepare gained collecting agent main component, and effect on environment is small, belongs to green product.
(4) application process of a kind of Collophane anti-floatation collector of the invention, by using it is one thick~mono- essence~bis- sweep
Closed circuit single reverse floatation process, and design is optimized to specific process parameter, so as to effectively improve gained phosphorus concentrate
Grade and the rate of recovery, and reduce the impurity content reclaimed in phosphorus concentrate.
(5) application process of a kind of Collophane anti-floatation collector of the invention, by height (magnesium) calcium collophane of the present invention
Collecting agent in reverse floatation is used to carry out reverse flotation experiment to Guizhou phosphorus ore, as Beneficiation Feed Grade (P2O5) be for 21.58%, (MgO)
4.48%, using it is one thick~mono- essence~bis- sweep closed circuit single reverse floatation process, phosphorus concentrate grade (P can be obtained2O5) it is 34.11%,
Impurity (MgO) is 0.24% excellent measure, compared with the collecting agent in reverse floatation of onsite application, P2O5Concentrate grade improves 2.25
Percentage point, the rate of recovery improves 0.35 percentage point.
Brief description of the drawings
Fig. 1 is a kind of process chart of the application process of Collophane anti-floatation collector of the present invention.
Embodiment
When carrying out ore dressing processing to high calcium (magnesium) matter collophane using reverse flotation method, the species of flotation agent is for mineral point
It is most important from effect.And in existing conventional collecting agent, fatty acid collecting agent is not readily dissolved, the bad adaptability in hard water is floated
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 technique 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 actual applications
Low problem.Meanwhile, the existing conventional collecting agent of the above mostly has that bad dispersibility, molten point are high, solubility is small, stability in hard water is poor,
Selectivity is bad, need the defects such as heating.
The problem above existed for existing collecting agent, inventor is by lot of experiments to reaction raw materials and its proportioning
Design is optimized with reaction process parameter, the final gained collecting agent for preparing can realize 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, with foamability is strong, collecting ability strong, strong adaptability,
Synthesize low cost and other advantages, floatation indicators are high and stably, while its preparation technology is simple, with low cost and nontoxic.By the present invention
Gained collecting agent is used with anion surfactant or nonionic surfactant combinations, substantially increases the anti-of the collecting agent
Cryogenic property, simultaneous selection is also greatly improved.The preparation method of high calcium (magnesium) matter Collophane anti-floatation collector of the present invention,
Specifically include following steps：
(1) it is (1~4) according to mass ratio that will depressurize five line phenol tapped oils with gasoline:(1~2) mixing is carried out to be placed in instead
Answer in kettle, in agitating heating at 20 DEG C~30 DEG C, oleum is then added into reactor and carries out sulfonation as sulfonating agent, is obtained
Obtain SO in sulfonated products, 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 controls are 8~11
Between, that is, sulfonate is made, reaction equation prepared by the sulfonate is as follows：
R·H+SO3→RSO3H
R·SO3H+NaOH→RSO3Na+H2O
Inventor has found that coking, charing phenomenon easily occur in preparation process for sulfonate, so that shadow in research process
The using effect of gained collecting agent is rung, this is also the major issue that the present invention needs to solve.And use the method for the present invention
It can effectively prevent that sulfonate from occurring coking, charing, be conducive to improving conversion ratio and properties of product.
(3) it is (4~10) in mass ratio by gained sulfonate and soybean oleic acid:(1~2) resulting mixture is compounded, through secondary
Saponification, that is, obtain the anionic Collophane anti-floatation collector of the present invention, it is main by organic that the present invention prepares gained collecting agent
Thing, 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 process of gained collecting agent, and its step is as follows：
(1) flotation for~0.074mm content accounts for the 70%~82% of total amount to the mog of ore deposit；
(2) levigate ore pulp obtains rougher concentration and rougher tailings through roughing, and wherein roughing process conditions are：Sodium carbonate
Consumption is 2000g/t, and action time is 2min, and collector dosage is 350g/t~500g/t, and action time is 3min；
(3) obtained rougher tailings is carried out scanning operation 1, obtains scanning chats 1 and scan mine tailing 1, scan chats 1 and return
Return the roughing operation of last layer；Wherein rougher tailings is scanned without any medicament.
(4) gained is scanned into mine tailing 1 through scanning for the second time, chats 2 and true tailings are scanned in acquisition, are scanned chats 2 and are returned
Last layer scans operation 1；Wherein scan for the second time without any medicament.
(5) the rougher concentration progress obtained step (2) is selected, obtains selected chats and final concentrate, selected chats is returned
Return the roughing operation of last layer；Wherein rougher concentration is selected without any medicament.
It is slightly~mono- smart by using one when collecting agent obtained by of the invention prepare is used for into the flotation of high calcium (magnesium) matter collophane
~bis- sweep closed circuit single reverse floatation process, and optimize design 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 reclaimed in phosphorus concentrate.
To further appreciate that present disclosure, in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of preparation method of Collophane anti-floatation collector of the present embodiment, comprises the following steps：
(1) it is 1 in mass ratio with gasoline that will depressurize five line phenol tapped oils:2 progress mixing are placed in reactor, and stirring adds
Heat, heating-up temperature is 25 DEG C, and oleum is then added into reactor is carried out in sulfonation, oleum used as sulfonating agent
SO3Mass fraction be 15wt%, sulfonation temperature be 50 DEG C, sulfonation time is 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
The mass ratio of layer progress saponification process, obtained sulfonate, organic layer and NaOH solution is 4:2, and saponification process pH=8.
(3) it is 10 in mass ratio by gained sulfonate and soybean oleic acid:1 compounding resulting mixture, through secondary saponification, that is, is obtained
Organic matter, neutral oil in final anionic Collophane anti-floatation collector, 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 present embodiment is respectively adopted and prepares gained collecting agent in reverse floatation with live existing collecting agent 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, and with reference to Fig. 1, its detailed process is：
(1) flotation for~0.074mm content accounts for the 70%~82% of total amount to the mog of ore deposit；
(2) levigate ore pulp obtains rougher concentration and rougher tailings through roughing, and wherein roughing process conditions are：Sodium carbonate
Consumption is 2000g/t, and action time is 2min, and collector dosage is 350g/tg/t, and action time is 3min；
(3) obtained rougher tailings is carried out scanning operation 1, obtains scanning chats 1 and scan mine tailing 1, scan chats 1 and return
Return the roughing operation of last layer；Wherein rougher tailings is scanned without any medicament.
(4) gained is scanned into mine tailing 1 through scanning for the second time, chats 2 and true tailings are scanned in acquisition, are scanned chats 2 and are returned
Last layer scans operation 1；Wherein scan for the second time without any medicament.
(5) the rougher concentration progress obtained step (2) is selected, obtains selected chats and final concentrate, selected chats is returned
Return the roughing operation of last layer；Wherein rougher concentration is selected without 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 with onsite application
Agent is compared, and P is remarkably improved 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 Collophane anti-floatation collector of the present embodiment, comprises the following steps：
(1) it is 4 in mass ratio with gasoline that will depressurize five line phenol tapped oils:1 progress mixing is placed in reactor, and stirring adds
Heat, heating-up temperature is 20 DEG C, and oleum is then added into reactor is carried out in sulfonation, oleum used as sulfonating agent
SO3Mass fraction be 25wt%, sulfonation temperature be 65 DEG C, sulfonation time is 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
The mass ratio of layer progress saponification process, obtained sulfonate, organic layer and NaOH solution is 10:1, and saponification process pH=11.
(3) it is 4 in mass ratio by gained sulfonate and soybean oleic acid:1 compounding resulting mixture, through secondary saponification, that is, is obtained
Final anionic Collophane anti-floatation collector.The present embodiment prepares organic matter, neutral oil and inorganic in 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, the basic be the same as Example 1 of its step, difference master
It is：Roughing process conditions are in step (2) in the present embodiment：Sodium carbonate amount is 1500g/t, and action time is 5min,
Collector dosage is 500g/t, and action time is 2min, and its experimental result is closer to embodiment 1.
Embodiment 3
A kind of preparation method of Collophane anti-floatation collector of the present embodiment, comprises the following steps：
(1) it is 3 in mass ratio with gasoline that will depressurize five line phenol tapped oils:2 progress mixing are placed in reactor, and stirring adds
Heat, heating-up temperature is 30 DEG C, and oleum is then added into reactor is carried out in sulfonation, oleum used as sulfonating agent
SO3Mass fraction be 30wt%, sulfonation temperature be 70 DEG C, sulfonation time is 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
The mass ratio of layer progress saponification process, obtained sulfonate, organic layer and NaOH solution is 7:1, and saponification process pH=9.
(3) it is 2 in mass ratio by gained sulfonate and soybean oleic acid:1 compounding resulting mixture, through secondary saponification, that is, is obtained
Final anionic Collophane anti-floatation collector.The present embodiment prepares organic matter, neutral oil and inorganic in 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, the basic be the same as Example 1 of its step, difference master
It is：Roughing process conditions are in step (2) in the present embodiment：Sodium carbonate amount is 3000g/t, and action time is 4min,
Collector dosage is 450g/t, and action time is 5min, and its experimental result is closer to embodiment 1.
Claims (9)
1. a kind of preparation method of Collophane anti-floatation collector, it is characterised in that comprise the following steps：
(1) five line phenol tapped oils of decompression and gasoline mix being placed in reactor, agitating heating, then into reactor
Add sulfonating agent and carry out sulfonation, obtain sulfonated products；
(2) gained sulfonated products are stirred washing and stratification, take organic layer to carry out saponification, sulfonate is made；
(3) gained sulfonate and soybean oleic acid are re-dubbed mixture, through secondary saponification, that is, obtain the anionic glue of the present invention
Phosphate reverse flotation collecting agent.
2. a kind of preparation method of Collophane anti-floatation collector according to claim 1, it is characterised in that：The step
(1) the mixing quality ratio of five line phenol tapped oils of decompression and gasoline is (1~4) in:(1~2), the temperature of its agitating heating is 20 DEG C
~30 DEG C.
3. a kind of preparation method of Collophane anti-floatation collector according to claim 1, it is characterised in that：The step
(1) sulfonating agent in uses oleum, and sulfonation temperature is 50 DEG C~70 DEG C, and sulfonation time is 1h~3h, gained sulfonated products
Oil content be 57 ± 2wt%.
4. a kind of preparation method of Collophane anti-floatation collector according to claim 3, it is characterised in that：The sulfonation
SO in agent oleum3Mass fraction be 15wt%~30wt%.
5. a kind of preparation method of Collophane anti-floatation collector according to any one of claim 1-4, its feature exists
In：The mass ratio of organic layer and saponification agent is (4~10) in the step (2):(1~2), and saponification process pH controls 8~
Between 11.
6. a kind of preparation method of Collophane anti-floatation collector according to claim 5, it is characterised in that：The step
(2) saponification agent is used as using NaOH solution in.
7. a kind of preparation method of Collophane anti-floatation collector according to claim 5, it is characterised in that：The step
(3) sulfonate and the mass ratio of soybean oleic acid are (4~10) in:(1~2).
8. a kind of Collophane anti-floatation collector, it is characterised in that：The collecting agent is using any one of claim 1-7 institute
What the method stated was prepared, the collecting agent includes organic matter, three kinds of components of neutral oil and inorganic salts, 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.
9. a kind of application process of Collophane anti-floatation collector as claimed in claim 8, it is characterised in that its step is such as
Under：
(1) flotation for~0.074mm content accounts for the 70%~82% of total amount to the mog of ore deposit；
(2) levigate ore pulp obtains rougher concentration and rougher tailings through roughing, and wherein roughing process conditions are：Sodium carbonate amount
For 1500-3000g/t, action time is 2-5min, and collector dosage is 350g/t~500g/t, and action time is 2-5min；
(3) obtained rougher tailings is carried out scanning operation 1, obtains scanning chats 1 and scan mine tailing 1, scanned chats 1 and return
One layer of roughing operation；Wherein rougher tailings is scanned without any medicament.
(4) gained is scanned into mine tailing 1 through scanning for the second time, chats 2 and true tailings are scanned in acquisition, scans chats 2 and return to upper one
Layer scan operation 1；Wherein scan for the second time without any medicament.
(5) the rougher concentration progress obtained step (2) is selected, obtains on selected chats and final concentrate, selected middling recurrence
One layer of roughing operation；Wherein rougher concentration is selected without any medicament.
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