CN104801426A - Schiff base caproate mineral flotation collecting agent as well as preparation method and application thereof - Google Patents
Schiff base caproate mineral flotation collecting agent as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Schiff base caproate mineral flotation collecting agent, a preparation method thereof and application thereof. A Schiff base caproate has an aliphatic group and a carbon-nitrogen double bond and carboxyl structure and is prepared by performing ammonia aldehyde condensation reaction on hydrolyzed caprolactam and aliphatic aldehyde. The Schiff base caproate has the characteristics of good water solubility, high dispersibility and high selective adsorption capacity to a target mineral, serves as the flotation collecting agent of bauxite, ilmenite, scheelite, wolframite, rare earth mine, tin ore, fluorite ore or manganese carbonate ore, and can effectively float and separate available minerals; furthermore, the preparation method of the Schiff base caproate is simple in process, easy in control on operation, low in cost, and high in product yield, and industrial production is easy to realize.
Description
Technical field
The present invention relates to a kind of Schiff bases caproate mineral floating collecting agent and its preparation method and application, belong to mineral floating field.
Background technology
Useful mineral, due to containing active carboxyl functional group, can separate with gangue by aliphatic acid and soap class effectively thereof, are the non-sulfide ore flotation collectors that a class is excellent.Because higher fatty acids is solid at normal temperatures, be insoluble in water, use inconvenience, therefore the saturated fatty acid of conventional oleic acid, linoleic acid, leukotrienes, ready denier oil acid and liquid, the most frequently used at present in industrial floatation process is oleic acid and modified product thereof and oxidized paraffin wax soap.Chinese patent (publication number is CN102921537A) discloses a kind of method of oleic acid flotation limonite; Chinese patent (publication number is CN102600985A) discloses a kind of method of collecting agent for ilmenite, iron oxide ore flotation being mixed rear resaponifying by oleic acid, oxidized paraffin wax soap and aliphatic acid in proportion; Chinese patent (publication number is CN101585016) discloses one oleic acid and makes collecting agent, with starch, sodium sulphate, hydrochloric acid, calgon as the inhibitor of barite mineral, to the method for low grade fluorite and barite FLOTATION SEPARATION; Chinese patent (publication number is CN101712014A) discloses a kind of method using alkaline oleic acid, neutral oleic acid and acid oleic acid segmentation flotation Multicategory-impurity single fluorite ore deposit respectively; Chinese patent (publication number is CN103657860A) discloses the method for collecting agent floating and enriching zinc silicate mineral under acid condition of a kind of oxidized paraffin wax soap and dodecyl sodium sulfate interworking; Chinese patent (publication number is CN101648157 and CN101757983A) discloses that a kind of fatty acid mixed flotation with comprising oleic acid is black, the method for scheelite; Chinese patent (publication number is CN102302982A) discloses a kind of beneficiation method reclaiming scheelite from gneiss type ore; Chinese patent (publication number is CN102716811A) discloses the method with cotton oil acid and rape oil acid mixed acid flotation water-soluble weathering phosphorite ore; Chinese patent (publication number is CN102962144A) discloses a kind of method that saponification degree is about the oleic acid flotation bauxite of 50%.
Oleic acid as collecting agent because collecting ability is strong, the wide and dark welcome by mineral floating producer of the scope of application, but in flotation, also there is obvious shortcoming, namely selective not high, freezing tolerance is poor, dispersiveness is bad; Though and oxidized paraffin wax soap has low price as the substitute of oleic acid, flotation results affects the advantages such as little by slurry temperature, when also existing alone, flotation performance is not as oleic acid, poor selectivity, the shortcomings such as concentrate grade is low.For the different deficiencies of giving ore deposit character, climate characteristic and oleic acid, oxidized paraffin wax soap class collecting agent, development of new, efficiently collecting agent become one of focus of technique of preparing development.
Have the report of amino acids schiff bases at present, it mainly makes metal complex, and these schiff base metal complexes have good biologically active and catalytic activity, can be used for biomedicine field or chemical catalysis field.Amino acids schiff bases is normally reacted by aldehydes or ketones and amino acid and is generated, and is especially easily hydrolyzed, generally needs to synthesize in anhydrous conditions to obtain.The amino-acid schiff base obtained by fatty aldehydes or ketones, due to its poor stability, seldom has bibliographical information.European patent (publication number is WO 2008/127760A1) discloses a kind of preparation method being reacted the amino-acid schiff base obtained by n-octaldehyde and lysine, but finds, this seed amino acid is unstable, will soon be agglomerated into grease.Aldehyde and tert-butylamine reaction that Samy B.Said reports by containing aromatic rings prepare the productive rate of schiff bases more than 80%, but, when react with fatty aldehyde (as 2-ethyl-2-hexenoic aldehyde) and tert-butylamine prepare corresponding schiff bases time, because this schiff bases is unstable and easily oxidized, can not get sterling (the Samy B.Said of this schiff bases, Jacek Mlochowski, Jacek Skariewski.Synthesisof 2-Alkyl-3-vinyloxaziridines as Potential Antitumor Agents.Liebigs Annalen derChemie, 1990 (5), 461-464.).
There is the research about amino acids schiff bases, be only limitted to the amino acids schiff bases (formula 3) containing aromatic rings, and this kind of schiff bases mainly shows good application prospect in fields such as medical science, catalysis, analytical chemistry, electrochemistry and magnetics, and the preparation method of Schiff bases soap and also there is not been reported at present as the application of collecting agent in flotation.
Summary of the invention
Selective not high, the defect such as freezing tolerance is poor, dispersiveness is bad is all there is for flotation collectors such as oleic-acid in prior art and oxidized paraffin wax soap classes, the object of the invention is to be to provide one roughly the same time there is the Schiff bases caproate of aliphatic group and carbon-to-nitrogen double bon and carboxyl structure, it has good selective absorption to non-sulfide ore, and good water solubility, good dispersion, can use as mineral floating collecting agent.
Another object of the present invention be to provide that a kind of flow process is simple, method that easily-controlled operation, low cost, high yield prepare Schiff bases caproate mineral floating collecting agent.
A further object of the invention is the application being to provide described Schiff bases caproate mineral floating collecting agent, this Schiff bases caproate has water-soluble and good dispersion, strong to non-sulfide ore collecting ability, selective good feature, is applicable to the flotation collecting of multi mineral.
For solving defect of the prior art, the invention provides a kind of Schiff bases caproate mineral floating collecting agent, there is formula 1 structure:
Wherein,
R is C
3~ C
11alkyl or alkylene;
M is Na
+or K
+.
In preferred Schiff bases caproate mineral floating collecting agent, R is C
7alkyl or alkylene.
More preferably in Schiff bases caproate mineral floating collecting agent, R is C
7straight chain or branched alkyl or C
7monoene alkyl.
In most preferred Schiff bases caproate mineral floating collecting agent, R is n-heptyl, 1-ethyl n-pentyl or 1-ethyl-1,2-pentenyl.
Schiff bases caproate of the present invention has imido grpup and carboxylic acid simultaneously, and imido grpup and the object element of carboxyl to mineral surfaces have collaborative chelating suction-operated, considerably increase the collecting ability to target minreal.The fat-based in preferred Schiff bases caproate mineral floating collecting agent with carboxyl and suitable length is more conducive to improving the dispersive property in its hydrophily and flotation collecting process.
Present invention also offers the method preparing Schiff bases caproate mineral floating collecting agent, be hydrolyzed caprolactam in temperature is the NaOH of 80 ~ 105 DEG C and/or potassium hydroxide solution ring-opening reaction, obtains amino caproate; Amino caproate and the aldehyde compound with formula 2 structure, under acid catalysis, carry out ammonium aldehyde condensation reaction, to obtain final product at 90 ~ 120 DEG C of temperature;
Wherein,
R is C
3~ C
11alkyl or alkylene.
In preferred scheme, R is C
7alkyl or alkylene; Be more preferably C
7straight chain or branched alkyl or C
7monoene alkyl; Most preferably be n-heptyl, 1-ethyl n-pentyl or 1-ethyl-1,2-pentenyl.
In preferred scheme, in potassium hydroxide and/or sodium hydroxide solution, the mol ratio of NaOH and/or potassium hydroxide and water is 1:1 ~ 1:2.
In preferred scheme, the mol ratio of potassium hydroxide and/or NaOH and caprolactam is 1:1.
In preferred scheme, ammonium aldehyde condensation reaction adds water entrainer or water absorbing agent and is used for removing the water that ammonium aldehyde condensation reaction generates.
More preferably in scheme, water entrainer is at least one in benzene, toluene, chloroform.The present invention adds water entrainer in ammonium aldehyde condensation reaction, and after question response completes, decompression distillation is except anhydrating and the azeotropic mixture of water entrainer.
More preferably in scheme, water absorbing agent is at least one in Anhydrous potassium carbonate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride, 4A molecular sieve.The present invention adds water absorbing agent in ammonium aldehyde condensation reaction, after question response completes, crosses the water absorbing agent after filtering water suction while hot.
In preferred scheme, acid catalyst is at least one in the concentrated sulfuric acid, concentrated hydrochloric acid, glacial acetic acid, p-methyl benzenesulfonic acid.
In preferred scheme, it is 0.5 ~ 3h that hydrolysis reacts the time of carrying out.
In preferred scheme, the time that ammonium aldehyde condensation reaction is carried out is 2 ~ 5h.
In preferred scheme, the mol ratio of aldehyde compound and amino caproate is 1:1 ~ 1.3:1.
In preferred scheme, amino caproate slowly or in batches joins in aldehyde compound and reacts.
The caprolactam that the present invention adopts is commercially available convenient source, by its first pre-heat fusing in use procedure, then adds potassium hydroxide and/or sodium hydroxide solution and to be hydrolyzed reaction.
The preparation method of Schiff bases caproate mineral floating collecting agent of the present invention, comprises following concrete steps:
(1) the hydrolysis reaction of caprolactam: caprolactam is joined in reaction vessel, temperature of reactor is raised to more than 80 DEG C, caprolactam is made to melt as liquid, NaOH and/or potassium hydroxide solution are joined in liquid caprolactam, holding temperature reacts 0.5 ~ 3h at 80 ~ 105 DEG C, after being cooled to room temperature, namely obtain flaxen solid 6-aminocaprolc acid sodium and/or 6-aminocaprolc acid potassium; Wherein, the mol ratio of NaOH and/or potassium hydroxide and caprolactam is 1:1; The mol ratio of NaOH and/or potassium hydroxide and water is 1:1 ~ 1:2;
(2) the ammonium aldehyde condensation reaction of 6-aminocaprolc acid salt and aldehyde compound: add aldehyde compound, acid catalyst and water entrainer or water absorbing agent successively in reaction vessel, under agitation add in batches or slowly add solid 6-aminocaprolc acid sodium, after reinforced, under the condition of 90 ~ 120 DEG C, react 2 ~ 5h, the mol ratio of aldehyde compound and amino caproate is 1:1 ~ 1.3:1;
(3) post processing: if use water absorbing agent, then, after ammonium aldehyde condensation reaction completes, filter out water absorbing agent while hot, after being cooled to room temperature, separate out solid matter, use acetone and absolute ether washed solid 2 ~ 3 times respectively, namely vacuum drying obtains Schiff bases caproate mineral floating collecting agent; If use water entrainer, then after ammonium aldehyde condensation reaction completes, decompression distillation removing water entrainer, separates out solid matter, uses acetone and absolute ether washed solid 2 ~ 3 times respectively, be drying to obtain Schiff bases caproate mineral floating collecting agent.
Present invention also offers the application of Schiff bases caproate mineral floating collecting agent, this application is FLOTATION SEPARATION Schiff bases caproate mineral floating collecting agent being applied to valuable mineral in bauxite, ilmenite, scheelite, wolframite, Rare Earth Mine, tin ore, fluorite ore or manganese carbonate ore ore.
In preferred application process, carry out at ore entering in grinding process or after ore grinding and add the floating agent comprising Schiff bases caproate mineral floating collecting agent in the process of flotation and size mixing, go out valuable mineral by froth flotation method FLOTATION SEPARATION; Wherein, Schiff bases caproate mineral collector adds in the ratio of 50 ~ 1600g/t ore.
More preferably in application process, maintain the pH of ore slurry when froth flotation in 6 ~ 12 scopes.
More preferably in application process, in ore slurry, granularity is that-200 object ores account for 50% ~ 90% of whole ore quality.
Schiff bases caproate of the present invention can use as collecting agent separately, or use composite with other floating agent.
Hinge structure, the beneficial effect that the present invention brings: the present invention obtains one first and has imino group and carboxyl simultaneously, and there is the Schiff bases caproate of fat chain structure.Its imido grpup and the metal ion of carboxyl to mineral surfaces have collaborative chelating suction-operated, considerably increase the collecting ability to target minreal; And carboxyl wherein is more conducive to improving the dispersive property in its hydrophily and flotation collecting process with the aliphatic group adapting to length.This Schiff bases caproate is applied to mineral floating as flotation collector, selective good, and collecting ability is strong, the features such as dispersiveness and good water solubility.The deficiencies such as in hinge structure, normal fat acid treatment freezing tolerance is poor, dispersiveness is bad, Schiff bases caproate of the present invention has fabulous water-soluble, be conducive to the dissolving of medicament in ore pulp, easy to use, the flotation collecting of non-sulfide ore can be widely used in, be specially adapted to 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, Schiff bases caproate of the present invention is easily hydrolyzed to fatty aldehyde and 6-aminocaprolc acid salt in acid medium, and after this makes flotation, mineral easily carry out reagent removal process.In addition, the preparation method of Schiff bases caproate, flow process is simple, easily-controlled operation, cost are low.
Accompanying drawing explanation
[Fig. 1] is for 6-(2-ethyl-2-alkene hexyl) imines is for the infrared spectrogram of sodium n-caproate.
[Fig. 2] is for 6-(2-ethyl-2-alkene hexyl) imines is for the hydrogen nuclear magnetic resonance spectrogram of sodium n-caproate.
[Fig. 3] is for 6-(2-ethyl-2-alkene hexyl) imines is for sodium n-caproate one roughing fluorite process chart.
[Fig. 4] is for 6-(2-ethyl-2-alkene hexyl) imines is for sodium n-caproate one roughing ilmenite process chart.
[Fig. 5] is for 6-(2-ethyl-2-alkene hexyl) imines is for the process chart in sodium n-caproate Scheelite Flotation ore deposit.
[Fig. 6] is for 6-(2-ethyl-2-alkene hexyl) imines is for the process chart of sodium n-caproate flotation bauxite.
[Fig. 7] is for 6-(2-ethyl-2-alkene hexyl) imines is for the process chart of sodium n-caproate flotation manganese carbonate ore.
Detailed description of the invention
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 numbers and percentage all refer to quality.
Embodiment 1
6-(2-ethyl-2-alkene hexyl) imines is for the preparation of sodium n-caproate:
5.66 parts of caprolactams are joined in the reactor of band agitating device, melted under the condition of 80 DEG C, separately get 2 parts of solid sodium hydroxides and be dissolved in proportionaling alkali-forming solution in 3 parts of distilled water, this aqueous slkali is joined in the caprolactam liquid melted, be warming up to 100 DEG C, stirring reaction 2h, the white solid of separating out after being cooled to room temperature is 6-aminocaprolc acid sodium.
7.56 parts of 2-ethyl-2-hexenoic aldehydes, 0.48 part of p-methyl benzenesulfonic acid, 60 parts of toluene and the 6-aminocaprolc acid sodium obtained by said hydrolyzed is added successively in reactor, load onto water knockout drum, be react 3h under the condition of 115 DEG C in reaction temperature, after decompression distillation removing toluene, solid respectively washs 2 times with absolute ether and acetone successively, gained Orange red solid is dry 24h in 50 DEG C of vacuum desiccators, obtains solid 11.82 parts, and productive rate is 90.57%.Fig. 1 is the infrared spectrogram of product, and Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of product.
Embodiment 2
6-(2-ethyl-2-alkene hexyl) imines is for the preparation of sodium n-caproate:
11.32 parts of caprolactams are joined in the reactor of band agitating device, melted under the condition of 80 DEG C, separately get 4 parts of solid sodium hydroxides and be dissolved in proportionaling alkali-forming solution in 6 parts of distilled water, this aqueous slkali is joined in the caprolactam liquid melted, be warming up to 100 DEG C, stirring reaction 2h, the white solid of separating out after being cooled to room temperature is 6-aminocaprolc acid sodium.
15.12 parts of 2-ethyl-2-hexenoic aldehydes, 0.95 part of p-methyl benzenesulfonic acid, 80 parts of toluene and the 6-aminocaprolc acid sodium obtained by said hydrolyzed is added successively in reactor, load onto water knockout drum, be react 4h under the condition of 115 DEG C in reaction temperature, after decompression distillation removing toluene, solid respectively washs 2 times with absolute ether and acetone successively, gained Orange red solid is dry 24h in 50 DEG C of vacuum desiccators, obtains solid 23.82 parts, and productive rate is 91.26%.
Embodiment 3
N-octyl imines is for the preparation of sodium n-caproate:
11.32 parts of caprolactams are joined in the reactor of band agitating device, melted under the condition of 80 DEG C, separately get 4 parts of solid sodium hydroxides and be dissolved in proportionaling alkali-forming solution in 6 parts of distilled water, this aqueous slkali is joined in the caprolactam liquid melted, be warming up to 100 DEG C, stirring reaction 2h, the white solid of separating out after being cooled to room temperature is 6-aminocaprolc acid sodium.
15.12 parts of n-octaldehydes, 0.95 part of p-methyl benzenesulfonic acid, 80 parts of toluene are added successively in reactor, the 6-aminocaprolc acid sodium liquid of the melting obtained by said hydrolyzed is instilled at 100 DEG C, after being added dropwise to complete, loading onto water knockout drum, is react 4h under the condition of 115 DEG C in reaction temperature, after decompression distillation removing toluene, solid respectively washs 2 times with absolute ether and acetone successively, gained yellow solid is dry 24h in 50 DEG C of vacuum desiccators, obtains solid 25.65 parts, and productive rate is 97.53%.
Embodiment 4
6-(2-ethylhexyl) imines is for the preparation of sodium n-caproate:
5.66 parts of caprolactams are joined in the reactor of band agitating device, melted under the condition of 80 DEG C, separately get 2 parts of solid sodium hydroxides and be dissolved in proportionaling alkali-forming solution in 3 parts of distilled water, this aqueous slkali is joined in the caprolactam liquid melted, be warming up to 100 DEG C, stirring reaction 2h, the white solid of separating out after being cooled to room temperature is 6-aminocaprolc acid sodium.
7.68 parts of 2-ethyl hexanals, 0.48 part of p-methyl benzenesulfonic acid, 45 parts of toluene and the 6-aminocaprolc acid sodium obtained by said hydrolyzed is added successively in reactor, load onto water knockout drum, be react 4h under the condition of 115 DEG C in reaction temperature, after decompression distillation removing toluene, solid respectively washs 2 times with absolute ether and acetone successively, gained faint yellow solid is dry 24h in 50 DEG C of vacuum desiccators, obtains solid 10.82 parts, and productive rate is 82.28%.
The advanced linear orbital energy of enuatrol flotation agent conventional in the Schiff bases caproate prepare embodiment 1 ~ 4 and prior art compares:
Theoretical according to molecular design of collector, Schiff bases caproate has stronger selective collecting ability than oleate.Utilize Gaussian 03 software, adopt B3LYP method and 6-31G (d) the base group of density functional theory, calculate the advanced linear orbital energy of schiff bases sodium n-caproate and enuatrol, result is as shown in table 1.As can be seen from Table 1, HOMO energy height about the 4kJ/mol of highest occupied molecular orbital (HOMO) the energy Ratios schiff bases sodium n-caproate of enuatrol, illustrates that enuatrol provides the ability of electronics slightly strong to transition metal; But low more than the 100kJ/mol of the lowest unoccupied molecular orbital of schiff bases sodium n-caproate (LUMO) energy Ratios enuatrol LUMO energy, illustrate that the d orbital electron of schiff bases sodium n-caproate transition metal atoms more acceptant than enuatrol forms backdonation, be conducive to strengthening the coordination of schiff bases sodium n-caproate to transition metal selective.
The advanced linear orbital energy of table 1 collecting agent molecule compares
Embodiment 5
6-(2-ethyl-2-alkene hexyl) imines is for the application of sodium n-caproate on fluorite:
Certain fluorite ore raw ore CaF
2grade 38.92%, ore grinding to-200 orders account for 60%, and be placed in flotation cell, at sodium carbonate amount 1400g/t, waterglass consumption 400g/t, collector dosage 500g/t, carry out one roughing operation under the condition that flotation temperature is 30 DEG C, and flotation process figure is shown in accompanying drawing 3.6-(2-ethyl-2-alkene hexyl) imines in the present invention for the flotation contrast and experiment of sodium n-caproate collecting agent and conventional enuatrol collecting agent in table 2.From table, when flotation temperature is 30 DEG C, 6-(2-ethyl-2-alkene hexyl) imines is higher than traditional enuatrol 1.89 percentage points to the flotation recovery rate of fluorite for sodium n-caproate, CaF
2grade improves 0.53 percentage point.
Collecting agent flotation fluorite contrast and experiment when table 2 flotation temperature is 30 DEG C
| Collector dosage (g/t raw ore) | Rough concentrate CaF 2Grade (%) | CaF 2The rate of recovery (%) |
| Enuatrol 500 | 80.88 | 96.05 |
| 6-(2-ethyl-2-alkene hexyl) imines is for sodium n-caproate 500 | 81.41 | 97.94 |
Embodiment 6
6-(2-ethyl-2-alkene hexyl) imines is for the application of sodium n-caproate in ilmenite flotation:
Certain ilmenite raw ore TiO
2grade 22.85%, ore grinding to-200 orders account for 60%, and be placed in flotation cell, at sulfuric acid dosage 1800g/t, collector dosage 1500g/t, carries out one roughing operation under the condition that flotation temperature is 30 DEG C, and flotation process figure is shown in accompanying drawing 4.6-(2-ethyl-2-alkene hexyl) imines in the present invention for the flotation contrast and experiment of sodium n-caproate collecting agent and conventional enuatrol collecting agent in table 3.From table, when flotation temperature is 30 DEG C, 6-(2-ethyl-2-alkene hexyl) imines is higher than traditional enuatrol 2.01 percentage points to the flotation recovery rate of ilmenite for sodium n-caproate, TiO
2grade improves 0.63 percentage point.
Collecting agent flotation ilmenite contrast and experiment when table 3 flotation temperature is 30 DEG C
Embodiment 7
6-(2-ethyl-2-alkene hexyl) imines is for the application of sodium n-caproate in Scheelite Flotation:
Certain scheelite raw ore tungsten grade WO
30.47%, grinde ore to-200 orders account for 80%, first desulfurization flotation is carried out, desulfurization flotation adds 40g butyl xanthate, 10g butylamine black powder, 36g foaming agent No. 2 oil by per ton to ore deposit, then by per tonly adding 3000g sodium carbonate to ore deposit, 2500g waterglass, 500g collecting agent carry out white tungsten and roughly select operation, scan and add 100g collecting agent by per ton to ore deposit, primary cleaning adds 500g waterglass by per ton to ore deposit, recleaning adds 300g waterglass by per ton to ore deposit, and flotation process figure is shown in accompanying drawing 5.6-(2-ethyl-2-alkene hexyl) imines in the present invention for the flotation contrast and experiment of sodium n-caproate collecting agent and conventional oxidized paraffin wax soap 731 in table 4.From table, 6-(2-ethyl-2-alkene hexyl) imines is higher than traditional oxidized paraffin wax soap 731 3.35 percentage points to the flotation recovery rate of scheelite for sodium n-caproate, WO
3grade improves 0.39 percentage point.
Table 4 collecting agent Scheelite Flotation ore deposit contrast and experiment
Embodiment 8
6-(2-ethyl-2-alkene hexyl) imines is for the application of sodium n-caproate on bauxite flotation:
Certain bauxite is containing Al
2o
365.15%, SiO
210.27%, ore grinding to-200 orders account for 80%, be placed in flotation cell, at sodium carbonate amount 4000g/t, calgon consumption 60g/t, 6-(2-ethyl-2-alkene hexyl) imines carries out one roughing operation under sodium n-caproate or enuatrol and benzyl hydroximic acid sodium combined capturing and collecting agent consumption 1000g/t condition to bauxite, obtains aluminium rough concentrate, flotation process figure is shown in accompanying drawing 6, and flotation results is in table 5.From table, to combinationally use with benzyl hydroximic acid sodium with enuatrol and compare, to Al after bauxite one roughing when 6-(2-ethyl-2-alkene hexyl) imines combinationally uses for sodium n-caproate and benzyl hydroximic acid sodium
2o
3the rate of recovery improve 3.10 percentage points, alumina silica ratio improve 0.57.
Table 56-(2-ethyl-2-alkene hexyl) imines is for sodium n-caproate flotation bauxite contrast and experiment
Embodiment 9
6-(2-ethyl-2-alkene hexyl) imines is for the application of sodium n-caproate in manganese carbonate ore flotation:
Certain manganese carbonate ore magnetic tailing manganese grade 7.58%, ore grinding to-200 orders account for 80%, roughly select and add 3000g sodium carbonate, 2500g waterglass, 1000g collecting agent by per ton to ore deposit, scan and add 500g waterglass, 200g collecting agent by per ton to ore deposit, primary cleaning adds 500g waterglass by per ton to ore deposit, recleaning adds 300g waterglass by per ton to ore deposit, and flotation process figure is shown in accompanying drawing 7.6-(2-ethyl-2-alkene hexyl) imines in the present invention for the flotation contrast and experiment of sodium n-caproate collecting agent and conventional enuatrol collecting agent in table 6.From table, 6-(2-ethyl-2-alkene hexyl) imines improves 1.78 percentage point to the flotation recovery rate of manganese carbonate ore than enuatrol for sodium n-caproate, and concentrate manganese grade improves 1.69 percentage points.
The flotation contrast and experiment of table 6 manganese carbonate ore magnetic tailing
| Collecting agent kind | Concentrate manganese grade (%) | Manganese recovery ratio (%) |
| Enuatrol | 16.56 | 80.62 |
| 6-(2-ethyl-2-alkene hexyl) imines is for sodium n-caproate | 18.25 | 82.40 |
Claims (10)
1. a Schiff bases caproate mineral floating collecting agent, is characterized in that, has formula 1 structure:
Wherein,
R is C
3~ C
11alkyl or alkylene;
M is Na
+or K
+.
2. Schiff bases caproate mineral floating collecting agent according to claim 1, is characterized in that, R is C
7alkyl or alkylene.
3. Schiff bases caproate mineral floating collecting agent according to claim 2, is characterized in that, R is n-heptyl, 1-ethyl n-pentyl or 1-ethyl-1,2-pentenyl.
4. prepare the method for Schiff bases caproate mineral floating collecting agent according to claim 1, it is characterized in that, caprolactam is hydrolyzed ring-opening reaction in temperature is the NaOH of 80 ~ 105 DEG C and/or potassium hydroxide solution, obtains amino caproate; Amino caproate and the aldehyde compound with formula 2 structure, under acid catalysis, carry out ammonium aldehyde condensation reaction, to obtain final product at 90 ~ 120 DEG C of temperature;
Wherein,
R is C
3~ C
11alkyl or alkylene.
5. method according to claim 4, is characterized in that, in described potassium hydroxide and/or sodium hydroxide solution, the mol ratio of NaOH and/or potassium hydroxide and water is 1:1 ~ 1:2; The mol ratio of potassium hydroxide and/or NaOH and caprolactam is 1:1.
6. method according to claim 4, is characterized in that, described ammonium aldehyde condensation reaction adds water entrainer or water absorbing agent and is used for removing the water that ammonium aldehyde condensation reaction generates.
7. method according to claim 6, is characterized in that, described water entrainer is at least one in benzene, toluene, chloroform; Described water absorbing agent is at least one in Anhydrous potassium carbonate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride, 4A molecular sieve.
8. method according to claim 4, is characterized in that, described acid catalyst is at least one in the concentrated sulfuric acid, concentrated hydrochloric acid, glacial acetic acid, p-methyl benzenesulfonic acid; It is 0.5 ~ 3h that described hydrolysis reacts the time of carrying out; The time that described ammonium aldehyde condensation reaction is carried out is 2 ~ 5h.
9. the application of the Schiff bases caproate mineral floating collecting agent described in any one of claims 1 to 3, it is characterized in that, be applied to the FLOTATION SEPARATION of valuable mineral in bauxite, ilmenite, scheelite, wolframite, Rare Earth Mine, tin ore, fluorite ore or manganese carbonate ore.
10. application according to claim 9, it is characterized in that, carry out at ore entering in grinding process or after ore grinding and add the floating agent comprising Schiff bases caproate mineral floating collecting agent in the process of flotation and size mixing, go out valuable mineral by froth flotation method FLOTATION SEPARATION; Wherein, Schiff bases caproate flotation collector adds in the ratio of 50 ~ 1600g/t ore.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510226788.2A CN104801426B (en) | 2015-05-07 | 2015-05-07 | A kind of Schiff bases caproate mineral floating collecting agent and its preparation method and application |
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| CN201510226788.2A CN104801426B (en) | 2015-05-07 | 2015-05-07 | A kind of Schiff bases caproate mineral floating collecting agent and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105880034A (en) * | 2016-04-22 | 2016-08-24 | 北京矿冶研究总院 | Ilmenite chelating collector |
| CN107520058A (en) * | 2017-08-23 | 2017-12-29 | 中南大学 | A kind of rutile ore dressing composite reagent and its beneficiation method |
| CN115090422A (en) * | 2022-06-17 | 2022-09-23 | 山东理工大学 | Amino acid type collecting agent and preparation method and application thereof |
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| CN102276608A (en) * | 2011-06-27 | 2011-12-14 | 陕西科技大学 | Method for synthesizing tetrahydro-beta-carboline diketopiperazine compound |
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| CN102276608A (en) * | 2011-06-27 | 2011-12-14 | 陕西科技大学 | Method for synthesizing tetrahydro-beta-carboline diketopiperazine compound |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105880034A (en) * | 2016-04-22 | 2016-08-24 | 北京矿冶研究总院 | Ilmenite chelating collector |
| CN105880034B (en) * | 2016-04-22 | 2019-02-05 | 北京矿冶研究总院 | Ilmenite chelating collector |
| CN107520058A (en) * | 2017-08-23 | 2017-12-29 | 中南大学 | A kind of rutile ore dressing composite reagent and its beneficiation method |
| CN107520058B (en) * | 2017-08-23 | 2019-05-17 | 中南大学 | A kind of rutile ore dressing composite reagent and its beneficiation method |
| CN115090422A (en) * | 2022-06-17 | 2022-09-23 | 山东理工大学 | Amino acid type collecting agent and preparation method and application thereof |
| CN115090422B (en) * | 2022-06-17 | 2024-04-26 | 山东理工大学 | Amino acid type collector, and preparation method and application thereof |
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| CN104801426B (en) | 2017-04-05 |
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