CN104801426B - A kind of Schiff bases caproate mineral floating collecting agent and its preparation method and application - Google Patents
A kind of Schiff bases caproate mineral floating collecting agent and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Schiff bases caproate mineral floating collecting agent and its preparation method and application, the Schiff bases caproate has aliphatic group and carbon-to-nitrogen double bon and carboxyl structure simultaneously, it is by after caprolactam hydrolysis, ammonium aldehyde condensation reaction is carried out with fatty aldehyde to prepare, which has good water solubility, good dispersion, the characteristics of strong to the selective adsorption capacity of target minreal, be used as the flotation collector of bauxite, ilmenite, scheelite, wolframite, Rare Earth Mine, tin ore, fluorite ore or manganese carbonate ore, can effectively FLOTATION SEPARATION go out valuable mineral；Additionally, the preparation method flow process of Schiff bases caproate is simple, easily-controlled operation, low cost, product yield is high, it is easy to accomplish industrial production.
Description
Technical field
The present invention relates to a kind of Schiff bases caproate mineral floating collecting agent and its preparation method and application, belongs to mineral
Flotation field.
Background technology
Aliphatic acid and its soaps are due to containing active carboxyl functional group, effectively dividing useful mineral with gangue
Open, be the excellent non-sulfide ore flotation collector of a class.As higher fatty acids is solid at normal temperatures, water is insoluble in, is used
Inconvenience, therefore the saturated fatty acid of conventional oleic acid, linoleic acid, leukotrienes, ready denier oil acid and liquid, in industrial floatation process
In at present most commonly oleic acid and its modified product and oxidized paraffin wax soap.Chinese patent (Publication No. CN102921537A) is public
A kind of method of use oleic acid flotation limonite is opened；Chinese patent (Publication No. CN102600985A) discloses one kind by oil
After acid, oxidized paraffin wax soap and aliphatic acid mix in proportion, the collecting agent of resaponifying is used for ilmenite, iron oxide ore flotation
Method；Chinese patent (Publication No. CN101585016) discloses one kind oleic acid and makees collecting agent, with starch, sodium sulphate, salt
Inhibitor of the sour, calgon as barite mineral, the method to low grade fluorite and barite FLOTATION SEPARATION；Chinese patent
(Publication No. CN101712014A) discloses a kind of various with alkaline oleic acid, neutral oleic acid and acid oleic acid segmentation flotation respectively
The method of class impurity single type fluorite ore；Chinese patent (Publication No. CN103657860A) discloses one kind oxidized paraffin wax soap
With the method for collecting agent floating and enriching zinc silicate mineral under acid condition of dodecyl sodium sulfate interworking；Chinese patent
(Publication No. CN101648157 and CN101757983A) disclose it is a kind of with comprising oleic acid fatty acid mixed flotation it is black,
The method of scheelite；Chinese patent (Publication No. CN102302982A) discloses one kind and reclaims white tungsten from gneiss type ore
The beneficiation method of ore deposit；Chinese patent (Publication No. CN102716811A) is disclosed with cotton oil acid and rape oil acid mixed acid flotation water
The method of dissolubility weathering phosphorite ore；Chinese patent (Publication No. CN102962144A) discloses one kind saponification degree about
For the method for 50% oleic acid flotation bauxite.
Oleic acid is welcome by mineral floating producer as collecting agent is deep as collecting ability is strong, use range wide, but
Also there is obvious shortcoming in flotation, i.e. poor, poor dispersion of selective not high, freezing tolerance etc.；And oxidized paraffin wax soap conduct
Though the substitute of oleic acid has low price, the advantages of flotation results are affected little by slurry temperature, flotation when there is also alone
Performance is not so good as oleic acid, poor selectivity, the low shortcoming of concentrate grade.For different to ore deposit property, climate characteristic and oleic acid, oxygen
The deficiency of fossil waxes soaps collecting agent, development of new, efficient collecting agent become one of focus of technique of preparing development.
There is the report of amino acids schiff bases at present, which is mainly formed into metal complex, these schiff base metals coordinate
Thing has preferable biologically active and catalysis activity, can be used for biomedicine field or chemical catalysis field.Amino acids seat
Husband's alkali is typically generated by aldehydes or ketones and amino acid reaction, is particularly easy to hydrolyze, is generally required and synthesize in anhydrous conditions
Arrive.By obtained from fatty aldehydes or ketones amino-acid schiff base due to its stability it is poor, seldom have document report.European patent is (public
The number of opening is WO 2008/127760A1) disclose a kind of system of the amino-acid schiff base by obtained from n-octaldehyde and lysine react
Preparation Method, however, it was found that this amino acid is unstable, will soon be agglomerated into grease.Samy B.Said are reported by containing virtue
The aldehyde of fragrant ring and tert-butylamine reaction prepare the yield of schiff bases more than 80%, but, when with fatty aldehyde (such as 2- ethyl -2-
Hexenoic aldehyde) with tert-butylamine reaction prepares corresponding schiff bases when, as the schiff bases is unstable and is oxidized easily, cannot get
Sterling (Samy B.Said, Jacek Mlochowski, the Jacek Skariewski.Synthesis of 2- of the schiff bases
Alkyl-3-vinyloxaziridines as Potential Antitumor Agents.Liebigs Annalen der
Chemie,1990(5),461-464.)。
The research of amino acids schiff bases is related to, the amino acids schiff bases containing aromatic rings (formula 3) is only limitted to, and it is this kind of
Schiff bases mainly shows good application prospect in fields such as medical science, catalysis, analytical chemistry, electrochemistry and magnetics, and Schiff
The preparation method of bases soap and the application as collecting agent in flotation not yet appear in the newspapers at present.
The content of the invention
All there is selective not high, freeze proof energy for the flotation collector such as oleic-acid in prior art and oxidized paraffin wax soaps
The defects such as power is poor, poor dispersion, the purpose of the present invention be provide one it is similar when have aliphatic group and carbon-to-nitrogen double bon and
The Schiff bases caproate of carboxyl structure, which has good selective absorption, and good water solubility to non-sulfide ore, dispersiveness
It is good, can use as mineral floating collecting agent.
It is to provide a kind of simple flow process, easily-controlled operation, low cost, prepare in high yield that another object of the present invention is
The method of Schiff bases caproate mineral floating collecting agent.
It is the application for providing the Schiff bases caproate mineral floating collecting agent that a further object of the invention is, should
Schiff bases caproate has water-soluble and good dispersion, strong to non-sulfide ore collecting ability, the characteristics of selective good, it is adaptable to
The flotation collecting of multi mineral.
To solve defect of the prior art, the invention provides a kind of Schiff bases caproate mineral floating collecting agent,
With 1 structure of formula：
Wherein,
R is C3～C11Alkyl or alkylene；
M is Na+Or K+。
In preferred Schiff bases caproate mineral floating collecting agent, R is C7Alkyl or alkylene.
More preferably in Schiff bases caproate mineral floating collecting agent, R is C7Straight chain or branched alkyl or
Person C7Monoene alkyl.
Most preferably in Schiff bases caproate mineral floating collecting agent, R is n-heptyl, 1- ethyls n-pentyl or 1- second
Base -1,2- pentenyls.
The Schiff bases caproate of the present invention has imido grpup and carboxylic acid, the mesh of imido grpup and carboxyl to mineral surfaces simultaneously
Mark element has collaboration chelating suction-operated, considerably increases the collecting ability to target minreal.Preferred Schiff bases caproic acid
There is in salt mineral floating collecting agent carboxyl and the fat-based of suitable length to be more beneficial for improving its hydrophily and flotation collecting
Dispersive property in journey.
Present invention also offers the method for preparing Schiff bases caproate mineral floating collecting agent, by caprolactam in temperature
Be hydrolyzed in NaOH and/or potassium hydroxide solution for 80～105 DEG C ring-opening reaction, obtains amino caproate；Amino
Caproate and the aldehyde compound with 2 structure of formula, under acid catalysis, carry out ammonium aldehyde condensation reaction at a temperature of 90～120 DEG C,
Obtain final product；
Wherein,
R is C3～C11Alkyl or alkylene.
In preferred scheme, R is C7Alkyl or alkylene；More preferably it is C7Straight chain or branched alkyl or
Person C7Monoene alkyl；Most preferably n-heptyl, 1- ethyls n-pentyl or 1- ethyl -1,2- pentenyls.
In preferred scheme, in potassium hydroxide and/or sodium hydroxide solution, NaOH and/or potassium hydroxide and water rubs
You are than being 1:1～1:2.
In preferred scheme, potassium hydroxide and/or NaOH and the mol ratio of caprolactam are 1:1.
In preferred scheme, ammonium aldehyde condensation reaction adds water entrainer or water absorbing agent to be used for removing ammonium aldehyde condensation reaction generation
Water.
More preferably in scheme, water entrainer is benzene, toluene, at least one in chloroform.The present invention is in ammonium aldehyde condensation reaction
During add water entrainer, after the completion of question response, vacuum distillation removes the azeotropic mixture of water and water entrainer.
More preferably in scheme, water absorbing agent is Anhydrous potassium carbonate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride, 4A
At least one in molecular sieve.The present invention adds water absorbing agent in ammonium aldehyde condensation reaction, after the completion of question response, filters while hot
Remove the water absorbing agent after water suction.
In preferred scheme, acid catalyst is the concentrated sulfuric acid, concentrated hydrochloric acid, glacial acetic acid, at least one in p-methyl benzenesulfonic acid.
In preferred scheme, the time that hydrolysis reaction is carried out is 0.5～3h.
In preferred scheme, the time that ammonium aldehyde condensation reaction is carried out is 2～5h.
In preferred scheme, aldehyde compound is 1 with the mol ratio of amino caproate:1～1.3:1.
In preferred scheme, amino caproate is slow or is reacted in being dividedly in some parts aldehyde compound.
The caprolactam that the present invention is adopted, is added by its first pre- heat fusing during use for commercially available convenient source
Potassium hydroxide and/or sodium hydroxide solution are hydrolyzed reaction.
The preparation method of the Schiff bases caproate mineral floating collecting agent of the present invention, including step in detail below：
(1) the hydrolysis reaction of caprolactam：Caprolactam is added in reaction vessel, temperature of reactor is raised to
More than 80 DEG C, it is liquid to melt caprolactam, and NaOH and/or potassium hydroxide solution are added to liquid caprolactam
In, maintain temperature that 0.5～3h is reacted at 80～105 DEG C, after being cooled to room temperature, that is, obtain flaxen solid 6-aminocaprolc acid
Sodium and/or 6-aminocaprolc acid potassium；Wherein, NaOH and/or potassium hydroxide and the mol ratio of caprolactam are 1:1；Hydroxide
Sodium and/or potassium hydroxide and the mol ratio of water are 1:1～1:2；
(2) the ammonium aldehyde condensation reaction of 6-aminocaprolc acid salt and aldehyde compound：Aldehydes chemical combination is sequentially added in reaction vessel
Thing, acid catalyst and water entrainer or water absorbing agent, are dividedly in some parts or are slowly added to solid 6-aminocaprolc acid sodium under agitation, fed
Bi Hou, reacts 2～5h under conditions of 90～120 DEG C, and aldehyde compound is 1 with the mol ratio of amino caproate:1～1.3:1；
(3) post-process：If using water absorbing agent, after the completion of ammonium aldehyde condensation reaction, water absorbing agent is filtered out while hot, room is cooled to
Wen Hou, separates out solid matter, and respectively with acetone and absolute ether washed solid 2～3 times, vacuum drying obtains final product Schiff bases
Caproate mineral floating collecting agent；If using water entrainer, after the completion of ammonium aldehyde condensation reaction, vacuum distillation removes water entrainer, analysis
Go out solid matter, respectively with acetone and absolute ether washed solid 2～3 times, be drying to obtain Schiff bases caproate mineral
Flotation collector.
Present invention also offers the application of Schiff bases caproate mineral floating collecting agent, the application be by Schiff bases oneself
Hydrochlorate mineral floating collecting agent is applied to bauxite, ilmenite, scheelite, wolframite, Rare Earth Mine, tin ore, fluorite ore or carbonic acid
The FLOTATION SEPARATION of valuable mineral in manganese ore ore.
In preferred application process, adding during flotation is entered in ore carries out grinding process or after ore grinding includes
Schiff bases caproate mineral floating collecting agent is sized mixing in interior floating agent, goes out to have by froth flotation method FLOTATION SEPARATION
Use mineral；Wherein, Schiff bases caproate mineral collector is added in the ratio of 50～1600g/t ores.
More preferably in application process, the pH of ore slurry is maintained in froth flotation in the range of 6～12.
More preferably in application process, in ore slurry granularity be -200 mesh ore account for whole ore quality 50%～
90%.
The Schiff bases caproate of the present invention can be used separately as collecting agent, or is made with other floating agent compoundings
With.
Hinge structure, the beneficial effect that the present invention brings：The present invention obtain first it is a kind of have simultaneously imino group and
Carboxyl, and the Schiff bases caproate with fat chain structure.Its imido grpup and carboxyl have to the metal ion of mineral surfaces
Collaboration chelating suction-operated, considerably increases the collecting ability to target minreal；And the fat of carboxyl therein and adaptation length
Alkyl is more beneficial for improving its hydrophily and the dispersive property during flotation collecting.The Schiff bases caproate is caught as flotation
Receive agent and be applied to mineral floating, selective good, collecting ability is strong, the features such as dispersiveness and good water solubility.In hinge structure
The deficiencies such as normal fat acid treatment freezing tolerance is poor, poor dispersion, the Schiff bases caproate of the present invention have fabulous water
Dissolubility, is conducive to dissolving of the medicament in ore pulp, convenient use to can be widely applied to the flotation collecting of non-sulfide ore, especially fit
For the flotation collecting of the mineral such as bauxite, ilmenite, scheelite, wolframite, Rare Earth Mine, tin ore, fluorite ore, manganese carbonate ore.
What is more important, the Schiff bases caproate of the present invention are easily hydrolyzed to fatty aldehyde and 6-aminocaprolc acid in acid medium
Salt, after this causes flotation, mineral easily carry out reagent removal process.In addition, the preparation method of Schiff bases caproate, flow process is simple, behaviour
Make easy to control, low cost.
Description of the drawings
【Fig. 1】For 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate infrared spectrogram.
【Fig. 2】For 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate hydrogen nuclear magnetic resonance spectrogram.
【Fig. 3】It is 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate one roughing fluorite process chart.
【Fig. 4】It is 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate one roughing ilmenite process chart.
【Fig. 5】For 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate Scheelite Flotation ore deposit process chart.
【Fig. 6】For 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate flotation bauxite process chart.
【Fig. 7】For 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate flotation manganese carbonate ore process chart.
Specific embodiment
Following examples are intended to further illustrate the present invention, are not the further restrictions to protection scope of the present invention.
In embodiment 1～12, unless otherwise specified all parts and percentages refer both to quality.
Embodiment 1
Preparation of 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate：
5.66 parts of caprolactams are added in the reactor with agitating device, are melted under conditions of temperature is for 80 DEG C
Change, separately take during 2 parts of solid sodium hydroxides are dissolved in 3 parts of distilled water and be made into aqueous slkali, the aqueous slkali is added to melted oneself in
In acid amides liquid, 100 DEG C are warming up to, stirring reaction 2h, the white solid separated out after being cooled to room temperature are 6-aminocaprolc acid sodium.
Sequentially add in reactor 7.56 parts of 2- ethyl -2- hexenoic aldehydes, 0.48 part of p-methyl benzenesulfonic acid, 60 parts of toluene and on
The obtained 6-aminocaprolc acid sodium of hydrolysis is stated, water knockout drum is loaded onto, 3h is reacted under conditions of reaction temperature is for 115 DEG C, decompression is steamed
After toluene is removed in distillation, solid uses respectively washing 2 times of absolute ether and acetone successively, and gained Orange red solid is in 50 DEG C of vacuum desiccators
In be dried 24h, obtain 11.82 parts of solid, yield is 90.57%.Infrared spectrograms of the Fig. 1 for product, Fig. 2 are common for the nuclear-magnetism of product
Shake hydrogen spectrogram.
Embodiment 2
Preparation of 6- (2- ethyl -2- alkene hexyls) imines for sodium n-caproate：
11.32 parts of caprolactams are added in the reactor with agitating device, by which under conditions of temperature is for 80 DEG C
Melt, separately take during 4 parts of solid sodium hydroxides are dissolved in 6 parts of distilled water and be made into aqueous slkali, the aqueous slkali is added to oneself that melted
In lactams liquid, 100 DEG C are warming up to, stirring reaction 2h, the white solid separated out after being cooled to room temperature are 6-aminocaprolc acid
Sodium.
Sequentially add in reactor 15.12 parts of 2- ethyl -2- hexenoic aldehydes, 0.95 part of p-methyl benzenesulfonic acid, 80 parts of toluene and
6-aminocaprolc acid sodium obtained by above-mentioned hydrolysis, loads onto water knockout drum, reacts 4h, reduce pressure under conditions of reaction temperature is for 115 DEG C
After toluene is distilled off, solid uses respectively washing 2 times of absolute ether and acetone, gained Orange red solid to be vacuum dried in 50 DEG C successively
24h is dried in device, 23.82 parts of solid is obtained, yield is 91.26%.
Embodiment 3
Preparation of the n-octyl imines for sodium n-caproate：
11.32 parts of caprolactams are added in the reactor with agitating device, by which under conditions of temperature is for 80 DEG C
Melt, separately take during 4 parts of solid sodium hydroxides are dissolved in 6 parts of distilled water and be made into aqueous slkali, the aqueous slkali is added to oneself that melted
In lactams liquid, 100 DEG C are warming up to, stirring reaction 2h, the white solid separated out after being cooled to room temperature are 6-aminocaprolc acid
Sodium.
15.12 parts of n-octaldehydes, 0.95 part of p-methyl benzenesulfonic acid, 80 parts of toluene are sequentially added in reactor, is instilled at 100 DEG C
The 6-aminocaprolc acid sodium liquid of the melting obtained by above-mentioned hydrolysis, after being added dropwise to complete, loads onto water knockout drum, is 115 in reaction temperature
4h is reacted under conditions of DEG C, after vacuum distillation removes toluene, solid uses respectively washing 2 times of absolute ether and acetone successively, and gained is yellow
Color solid is dried 24h in 50 DEG C of vacuum desiccators, obtains 25.65 parts of solid, and yield is 97.53%.
Embodiment 4
Preparation of 6- (2- ethylhexyls) imines for sodium n-caproate：
5.66 parts of caprolactams are added in the reactor with agitating device, are melted under conditions of temperature is for 80 DEG C
Change, separately take during 2 parts of solid sodium hydroxides are dissolved in 3 parts of distilled water and be made into aqueous slkali, the aqueous slkali is added to melted oneself in
In acid amides liquid, 100 DEG C are warming up to, stirring reaction 2h, the white solid separated out after being cooled to room temperature are 6-aminocaprolc acid sodium.
7.68 parts of 2- ethyl hexanals, 0.48 part of p-methyl benzenesulfonic acid, 45 parts of toluene and above-mentioned water are sequentially added in reactor
The obtained 6-aminocaprolc acid sodium of solution, loads onto water knockout drum, under conditions of reaction temperature is for 115 DEG C reacts 4h, and vacuum distillation is removed
After removing toluene, solid uses respectively washing 2 times of absolute ether and acetone, gained faint yellow solid to do in 50 DEG C of vacuum desiccators successively
Dry 24h, obtains 10.82 parts of solid, and yield is 82.28%.
The front of conventional enuatrol flotation agent in the Schiff bases caproate prepared to embodiment 1～4 and prior art
Orbital energy is compared：
Theoretical according to molecular design of collector, Schiff bases caproate has higher selective collecting energy than oleate
Power.Using 03 softwares of Gaussian, using the B3LYP methods and 6-31G (d) base groups of density functional theory, to schiff bases caproic acid
The advanced linear orbital energy of sodium and enuatrol is calculated, as a result as shown in table 1.From table 1 it follows that the highest of enuatrol is accounted for
High 4kJ/mol of HOMO energy according to track (HOMO) energy ratio schiff bases sodium n-caproate or so, illustrates that enuatrol gives transition metal unit
The ability that element provides electronics is slightly strong；But lowest unoccupied molecular orbital (LUMO) the energy ratio enuatrol LUMO energy of schiff bases sodium n-caproate is low
More than 100kJ/mol, illustrates that schiff bases sodium n-caproate is formed instead than the d orbital electron that enuatrol is easier to receive transition metal atoms
Feedback π keys, are conducive to strengthening coordination selectivity of the schiff bases sodium n-caproate to transition metal.
The advanced linear orbital energy of 1 collecting agent molecule of table compares
Embodiment 5
6- (2- ethyl -2- alkene hexyls) application of the imines for sodium n-caproate on fluorite：
Certain fluorite green ore CaF2Grade 38.92%, ore grinding to -200 mesh account for 60%, are placed in flotation cell, in sodium carbonate
Consumption 1400g/t, waterglass consumption 400g/t, collector dosage 500g/t are carried out under conditions of 30 DEG C of flotation temperature once thick
Industry is elected to be, flotation process figure is shown in accompanying drawing 3.6- (2- ethyl -2- alkene hexyls) imines in the present invention is for sodium n-caproate collecting agent
2 are shown in Table with the flotation contrast and experiment of conventional enuatrol collecting agent.From table, when flotation temperature is 30 DEG C, 6- (2- second
Base -2- alkene hexyls) imines is higher than traditional enuatrol to the flotation recovery rate of fluorite 1.89 percentage points for sodium n-caproate, CaF2Product
Improve 0.53 percentage point in position.
Collecting agent flotation fluorite contrast and experiment when 2 flotation temperature of table is 30 DEG C
| Collector dosage (g/t raw ores) | Rough concentrate CaF2Grade (%) | CaF2The rate of recovery (%) |
| Enuatrol 500 | 80.88 | 96.05 |
| 6- (2- ethyl -2- alkene hexyls) imines is for sodium n-caproate 500 | 81.41 | 97.94 |
Embodiment 6
6- (2- ethyl -2- alkene hexyls) application of the imines for sodium n-caproate in ilmenite flotation：
Certain ferrotianium green ore TiO2Grade 22.85%, ore grinding to -200 mesh account for 60%, are placed in flotation cell, use in sulfuric acid
Amount 1800g/t, collector dosage 1500g/t, carry out one roughing operation, flotation process under conditions of 30 DEG C of flotation temperature
Figure is shown in accompanying drawing 4.6- (2- ethyl -2- alkene hexyls) imines in the present invention is for sodium n-caproate collecting agent and conventional enuatrol collecting agent
Flotation contrast and experiment be shown in Table 3.From table, when flotation temperature is 30 DEG C, 6- (2- ethyl -2- alkene hexyls) imines is for oneself
Sour sodium is higher than traditional enuatrol to the flotation recovery rate of ilmenite 2.01 percentage points, TiO2Grade improves 0.63 percentage
Point.
Collecting agent flotation ilmenite contrast and experiment when 3 flotation temperature of table is 30 DEG C
Embodiment 7
6- (2- ethyl -2- alkene hexyls) application of the imines for sodium n-caproate in Scheelite Flotation：
Certain scheelite raw ore tungsten grade WO30.47%, grinde ore to -200 mesh accounts for 80%, carries out desulfurization flotation first,
Desulfurization flotation presses per ton oily to ore deposit addition 40g butyl xanthates, 10g butylamine black powders, 36g foaming agents 2, then adds to ore deposit by per ton
Enter 3000g sodium carbonate, 2500g waterglass, 500g collecting agents and carry out white tungsten to roughly select operation, scan and add 100g to catch to ore deposit by per ton
Agent is received, primary cleaning adds 500g waterglass, recleaning by per ton to ore deposit to add 300g waterglass, flotation work to ore deposit by per ton
Skill flow chart is shown in accompanying drawing 5.6- (2- ethyl -2- alkene hexyls) imines in the present invention is for sodium n-caproate collecting agent and conventional oxidation stone
The flotation contrast and experiment of wax soap 731 is shown in Table 4.From table, 6- (2- ethyl -2- alkene hexyls) imines is for sodium n-caproate dialogue tungsten
The flotation recovery rate of ore deposit is than 731 high 3.35 percentage points traditional of oxidized paraffin wax soap, WO3Grade improves 0.39 percentage point.
4 collecting agent Scheelite Flotation ore deposit contrast and experiment of table
Embodiment 8
6- (2- ethyl -2- alkene hexyls) application of the imines for sodium n-caproate on bauxite flotation：
Certain bauxite contains Al2O365.15%, SiO210.27%, ore grinding to -200 mesh accounts for 80%, is placed in flotation cell,
Sodium carbonate amount 4000g/t, calgon consumption 60g/t, 6- (2- ethyl -2- alkene hexyls) imines is for sodium n-caproate or enuatrol
With carry out one roughing operation under the conditions of benzyl hydroximic acid sodium combined capturing and collecting agent consumption 1000g/t to bauxite, obtain aluminium coarse-fine
Ore deposit, flotation process figure are shown in accompanying drawing 6, and flotation results are shown in Table 5.From table, combine and make with enuatrol and benzyl hydroximic acid sodium
With comparing, 6- (2- ethyl -2- alkene hexyls) imines is once thick to bauxite when being applied in combination for sodium n-caproate and benzyl hydroximic acid sodium
Al after choosing2O3The rate of recovery improve 3.10 percentage points, alumina silica ratio improve 0.57.
Table 56- (2- ethyl -2- alkene hexyls) imines is for sodium n-caproate flotation bauxite contrast and experiment
Embodiment 9
6- (2- ethyl -2- alkene hexyls) application of the imines for sodium n-caproate in manganese carbonate ore flotation：
Certain manganese carbonate ore magnetic tailing manganese grade 7.58%, ore grinding to -200 mesh account for 80%, roughly select and add to ore deposit by per ton
3000g sodium carbonate, 2500g waterglass, 1000g collecting agents, scan and add 500g waterglass, 200g collecting agent to ore deposit by per ton,
Primary cleaning adds 500g waterglass, recleaning by per ton to ore deposit to add 300g waterglass, floatation process stream to ore deposit by per ton
Journey figure is shown in accompanying drawing 7.6- (2- ethyl -2- alkene hexyls) imines in the present invention is for sodium n-caproate collecting agent and conventional enuatrol collecting
The flotation contrast and experiment of agent is shown in Table 6.From table, 6- (2- ethyl -2- alkene hexyls) imines is for sodium n-caproate to manganese carbonate ore
Flotation recovery rate than enuatrol improve 1.78 percentage points, concentrate manganese grade improve 1.69 percentage points.
The flotation contrast and experiment of 6 manganese carbonate ore magnetic tailing of table
| Collecting agent species | Concentrate manganese grade (%) | Manganese recovery ratio (%) |
| Enuatrol | 16.56 | 80.62 |
| 6- (2- ethyl -2- alkene hexyls) imines is for sodium n-caproate | 18.25 | 82.40 |
Claims (9)
1. a kind of application of Schiff bases caproate mineral floating collecting agent, it is characterised in that be applied to bauxite, ilmenite,
The FLOTATION SEPARATION of valuable mineral in scheelite, wolframite, Rare Earth Mine, tin ore, fluorite ore or manganese carbonate ore；
Described Schiff bases caproate mineral floating collecting agent has 1 structure of formula：
Wherein,
R is C3～C11Alkyl or alkylene；
M is Na+Or K+。
2. the application of Schiff bases caproate mineral floating collecting agent according to claim 1, it is characterised in that R is C7's
Alkyl or alkylene.
3. the application of Schiff bases caproate mineral floating collecting agent according to claim 2, it is characterised in that R is for just
Heptyl, 1- ethyls n-pentyl or 1- ethyl -1,2- pentenyls.
4. the application of Schiff bases caproate mineral floating collecting agent according to claim 1, it is characterised in that：Described
Being prepared via a method which of Schiff bases caproate mineral floating collecting agent obtains：Caprolactam is 80～105 DEG C in temperature
NaOH and/or potassium hydroxide solution in be hydrolyzed ring-opening reaction, obtain amino caproate；Amino caproate with have
The aldehyde compound of 2 structure of formula, under acid catalysis, carries out ammonium aldehyde condensation reaction at a temperature of 90～120 DEG C, obtains final product；
Wherein,
R is C3～C11Alkyl or alkylene.
5. the application of Schiff bases caproate mineral floating collecting agent according to claim 4, it is characterised in that described
In potassium hydroxide and/or sodium hydroxide solution, NaOH and/or potassium hydroxide and the mol ratio of water are 1:1～1:2；Hydroxide
Potassium and/or NaOH and the mol ratio of caprolactam are 1:1.
6. the application of Schiff bases caproate mineral floating collecting agent according to claim 4, it is characterised in that described
Ammonium aldehyde condensation reaction adds water entrainer or water absorbing agent to be used for removing the water of ammonium aldehyde condensation reaction generation.
7. the application of Schiff bases caproate mineral floating collecting agent according to claim 6, it is characterised in that described
Water entrainer is benzene, toluene, at least one in chloroform；Described water absorbing agent is Anhydrous potassium carbonate, anhydrous magnesium sulfate, anhydrous slufuric acid
At least one in sodium, anhydrous calcium chloride, 4A molecular sieves.
8. the application of Schiff bases caproate mineral floating collecting agent according to claim 4, it is characterised in that described
Acid catalyst is the concentrated sulfuric acid, concentrated hydrochloric acid, glacial acetic acid, at least one in p-methyl benzenesulfonic acid；Described hydrolysis reaction is carried out
Time be 0.5～3h；The time that described ammonium aldehyde condensation reaction is carried out is 2～5h.
9. the application of Schiff bases caproate mineral floating collecting agent according to claim 1, it is characterised in that in ore
Adding during flotation is entered in carrying out grinding process or after ore grinding includes that Schiff bases caproate mineral floating collecting agent exists
Interior floating agent is sized mixing, and goes out valuable mineral by froth flotation method FLOTATION SEPARATION；Wherein, Schiff bases caproate flotation
Collecting agent is added in the ratio of 50～1600g/t ores.
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