CN101531605A - Aminoaliphatic acid flotation agent and preparation method thereof - Google Patents
Aminoaliphatic acid flotation agent and preparation method thereof Download PDFInfo
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- CN101531605A CN101531605A CN200910061705A CN200910061705A CN101531605A CN 101531605 A CN101531605 A CN 101531605A CN 200910061705 A CN200910061705 A CN 200910061705A CN 200910061705 A CN200910061705 A CN 200910061705A CN 101531605 A CN101531605 A CN 101531605A
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Abstract
The invention relates to an aminoaliphatic acid flotation agent and a preparation method thereof, wherein the method comprises the following steps: 1) selecting rapeseed oil, alkaline solution, concentrated sulphuric acid, chlorine and ammonia in terms of reaction mol ratio for standby use; 2) saponifying rapeseed oil by alkaline solution, then salting-out, washing and filtering the saponified substance by adding NaCl after reaction, adding the concentrated sulphuric acid into the obtained saponified product, agitating, separating and washing the resultant product with hot water, and then drying to obtain anhydrous fatty acid; 3) placing the anhydrous fatty acid in a reaction container, introducing chlorine in the presence of catalyst so as to obtain alpha-chloroaliphatic acid; and 4) putting the chloroaliphatic acid in a high pressure reaction kettle, adding in catalyst, then introducing ammonia gas, agitating, taking the reaction solution out and evaporating the ethanol after the reaction is finished so as to obtain the aminoaliphatic acid flotation agent. The invention improves the water solubility of the flotation agent, increases the conductivity of the compound and improves the surface activity; and the floatation can be carried out in hard water at low temperature so that the dependency of the flotation agent on temperature is decreased greatly.
Description
Technical field
The present invention relates to a kind of flotation agent, the concrete a kind of Aminoaliphatic acid flotation agent and preparation method thereof that relates to.
Background technology
China's phosphate rock resource is abundant, but low-grade lean ore in wherein more than 90% being must just can reach the requirement of phosphor resource processing by sorting to upgrade.Flotation process can effectively improve the phosphorus ore grade as the topmost method that sorts Rock Phosphate (72Min BPL), and fatty acid collecting agent is adopted in the flotation of phosphate ores at present more.But this type of collecting agent solubility at normal temperatures and dispersed relatively poor, the industrial need adopted the floatation process of heating, and this causes phosphorus concentrate production cost significantly to increase.Therefore, the development resistance to low temperature is good, and the good new collector of flotation performance has great importance.Development of flotation reagent in recent years or the main trend of selecting for use be polyfunctional groupization, functional group's center variation, polyoxyethylene groupsization, heteropolarity be amphoterisation, weak solution from or nonionicization and mix collaborative.
Summary of the invention
Problem to be solved by this invention is to propose a kind of Aminoaliphatic acid flotation agent at above-mentioned prior art, its good water solubility, and temperature is little to its flotation effect influence, and the flotation agent product cost is low.
Another object of the present invention is the preparation method who proposes Aminoaliphatic acid flotation agent.
The present invention is adopted solution to be by the problem of the above-mentioned proposition of solution: Aminoaliphatic acid flotation agent, it is characterized in that it mainly is prepared from by rapeseed oil, strong base solution, the vitriol oil, chlorine and ammonia, the mol ratio of each raw material is: rapeseed oil: strong base solution: the vitriol oil: chlorine: ammonia=1:4.0-5.3:2.0-3.2:9-12:9-12, described strong base solution are sodium hydroxide solution or potassium hydroxide solution.
Press such scheme, preferably the mol ratio of each raw material is: rapeseed oil: strong base solution: the vitriol oil: chlorine: ammonia=1:5:2.5:10:10.
The solution that the Aminoaliphatic acid flotation agent preparation method adopts is: the preparation method of Aminoaliphatic acid flotation agent includes the next coming in order step:
1) mol ratio by rapeseed oil, strong base solution, the vitriol oil, chlorine, ammonia is that 1:4.0-5.3:2.0-3.2:9-12:9-12 prepares rapeseed oil, strong base solution, the vitriol oil, chlorine and ammonia, standby, described strong base solution is sodium hydroxide solution or potassium hydroxide solution;
2) under 80-100 ℃, with strong base solution saponification rapeseed oil, after question response finishes, the saponified adding NaCl of gained is saltoutd, wash then, suction filtration gets saponification resultant, the saponification resultant of gained adds the vitriol oil at normal temperatures, at 80-100 ℃ of following mechanical stirring 1.5-3h, separatory, hot wash obtains anhydrous fat acid after the drying;
3) with step 2) acid of gained anhydrous fat places reaction vessel, and under the catalyst action, 90-100 ℃ feeds chlorine down after 8-12 hour, obtains alpha-chloro-fatty acid;
4) the gained alpha-chloro-fatty acid is placed autoclave, with the dehydrated alcohol is solvent, add catalyzer again, charge into ammonia then, 65-75 ℃ of following mechanical stirring reaction 48 hours, uninterruptedly replenish ammonia during this time, question response finishes the back and takes out reaction solution and steam ethanol, obtains Aminoaliphatic acid flotation agent.
Press such scheme, the described catalyzer of step 3) is thionyl chloride or phosphorus pentachloride.
Press such scheme, the described catalyzer of step 4) is yellow soda ash or salt of wormwood.
Press such scheme, the concentration of described strong base solution is 12-18mol/L
Press such scheme, the concentration of described concentrated sulfuric acid solution is 8-12mol/L.
The general structure of product of the present invention is:
R is to be the hydrochloric ether of 10-22 for carbonatoms in the formula, because raw material is rapeseed oil, the lipid acid after the saponification acidolysis is mixed fatty acid, the shortest and the longest eicosanoic acid and the linolenic acid of being respectively of its carbochain, so R is a carbonatoms is the hydrochloric ether of 10-22, carboxylic acid α bit substituent is-NH
2Base.
The present invention compared with prior art has the following advantages: strengthened anionic activity because the α of carboxylic acid replaces, improved the water-soluble of flotation agent, increased the specific conductivity of compound, reduced surface tension, increased foaming properties, improved surfactivity; Increase is to Ca
2+, Mg
2+Isoionic adaptability can be carried out flotation at a lower temperature with in the hard water; Two polar groups are in the ortho position simultaneously, and flotation agent polar group one end section is increased, and can strengthen the selectivity of medicament, and after hydrophilic polar group was introduced in the α position, the solvability of flotation agent in water increased, and it is reduced greatly to dependence on temperature.
Description of drawings
Fig. 1 is the infrared absorpting light spectra of Aminoaliphatic acid flotation agent of the present invention.
As Fig. 1, at 1462.96cm
-1And 1412.35cm
-1Strong absorption peak be the absorption band of COO-, owing to the result in α-ammonia generation makes the frequency of the two keys of carbon-oxygen move 10～20cm to high frequency treatment
-1, so at 1731.35cm
-1There is the strong absorption peak of the two keys of carbon-oxygen at the place, at 3331.76cm
-1And 3190.93cm
-1Two absorption bands of place's nitrogen-hydrogen bond are amino characteristic strips, at 1248.62em
-1The place is the absorption peak of carbon-nitrogen bond, so the entire compound structure all is confirmed at infrared absorption peak.
Embodiment
The invention will be further described below in conjunction with embodiment, but can not be as limitation of the invention.
Embodiment 1
Add rapeseed oil 0.3mol in the 1L beaker, mechanical stirring and heating, 80 ℃ add NaOH solution 80ml (15mol/L) down, 90-100 ℃ of insulation reaction to the product no oil bloom in cold water that take a morsel occur promptly getting saponified, add 80 ℃ of water 100ml and NaOH solution 20ml (15mol/L) and continue insulation reaction half an hour, adding NaCl leaves standstill and saltouts 5 hours, get the saponified washing in upper strata (water yield can not as many as produce jelly) suction filtration and get saponification resultant, the saponification resultant of gained adds concentrated sulfuric acid solution 60ml (12mol/L) at normal temperatures, 90～100 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory, get 80 ℃ of upper strata oily matter washing 2 times, dry anhydrous fat acid;
The acid of gained anhydrous fat places the 1L there-necked flask, adds the catalyzer thionyl chloride, heats to 90-100 ℃ of logical chlorine (0.1L/min) 3mol, reduces pressure under 110 ℃ after reaction finishes and takes out de-chlorine hydride and excessive chlorine, promptly obtains alpha-chloro-fatty acid.The gained alpha-chloro-fatty acid is placed autoclave, with an amount of dehydrated alcohol is solvent, add a spot of yellow soda ash again and make catalyzer, charge into the ammonia of 2-3MPa then, 65-75 ℃ of following mechanical stirring reaction 48 hours, during the uninterrupted ammonia that replenishes, feed ammonia 3mol altogether, question response finishes the back and takes out reaction solution and steam ethanol, obtains alpha-amino group acid type flotation at low temperature collecting agent, promptly is Aminoaliphatic acid flotation agent of the present invention.
Embodiment 2
Add rapeseed oil 0.6mol in the 2L beaker, mechanical stirring and heating, 90 ℃ add NaOH solution 200ml (12mol/L) down, 90-100 ℃ of insulation reaction to the product no oil bloom in cold water that take a morsel occur promptly getting saponified, add 80 ℃ of water 200ml and NaOH solution 50ml (12mol/L) and continue insulation reaction half an hour, adding NaCl leaves standstill and saltouts 5 hours, get the saponified washing in upper strata (water yield can not as many as produce jelly) suction filtration and get saponification resultant, the saponification resultant of gained adds vitriol oil 185ml (8mol/L) at normal temperatures, 90～100 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory, get upper strata oily matter 70-90 ℃ of washing 2 times, dry anhydrous fat acid;
The acid of gained anhydrous fat places the 2L there-necked flask, adds the catalyzer thionyl chloride, heats to 90-100 ℃ of logical chlorine (0.1L/min) 6mol, reduces pressure under 110 ℃ after reaction finishes and takes out de-chlorine hydride and excessive chlorine, promptly obtains chlorinated fatty acid.The gained alpha-chloro-fatty acid is placed autoclave, with an amount of dehydrated alcohol is solvent, add a spot of salt of wormwood again and make catalyzer, charge into the ammonia of 2-3MPa then, 65-75 ℃ of following mechanical stirring reaction 48 hours, during the uninterrupted ammonia that replenishes, feed ammonia 6mol altogether, question response finishes the back and takes out reaction solution and steam ethanol, promptly obtains Aminoaliphatic acid flotation agent of the present invention.
Embodiment 3
Add rapeseed oil 0.6mol in the 2L beaker, mechanical stirring and heating, 90 ℃ add KOH solution 200ml (12mol/L) down, 90-100 ℃ of insulation reaction to the product no oil bloom in cold water that take a morsel occur promptly getting saponified, add 80 ℃ of water 200ml and KOH solution 50ml (12mol/L) and continue insulation reaction half an hour, adding an amount of NaCl leaves standstill and saltouts 5 hours, get the saponified washing in upper strata (water yield can not as many as produce jelly) suction filtration and get saponification resultant, the saponification resultant of gained adds vitriol oil 185ml (8mol/L) at normal temperatures, 90～100 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory, get upper strata oily matter 70-90 ℃ of washing 2 times, dry anhydrous fat acid;
The acid of gained anhydrous fat places the 2L there-necked flask, adds the catalyzer phosphorus pentachloride, heats to 90-100 ℃ of logical chlorine (0.1L/min) 6mol, reduces pressure under 110 ℃ after reaction finishes and takes out de-chlorine hydride and excessive chlorine, promptly obtains chlorinated fatty acid.Again chlorinated fatty acid is placed autoclave, with an amount of dehydrated alcohol is solvent, charge into the ammonia of 2-3MPa, under the effect of catalyzer carbonic acid potassium, 70 ℃ of left and right sides mechanical stirring reactions 48 hours, during uninterruptedly mend fair ammonia, feed ammonia 6mol altogether, question response finishes the back and takes out reaction solution and steam ethanol, promptly obtains Aminoaliphatic acid flotation agent of the present invention.
Select collophanite to carry out flotation with embodiment 1 prepared Aminoaliphatic acid flotation agent to low-grade refractory in the Yunnan, its ore chemistry consists of:
| Analysis project | P 2O 5 | MgO | CaO | A.I. | F | SiO 2 | CO 2 | Fe 2O 3 | Al 2O 3 | Burn a large amount of |
| Content (%) | 20.78 | 1.45 | 30.39 | 38.60 | 1.68 | 36.53 | 2.74 | 1.77 | 1.50 | 4.34 |
The method of direct flotation adds yellow soda ash and regulates the pH value and suppress Ca
2+, Mg
2+, water glass suppresses silicate, and Sodium hexametaphosphate 99 plays a dispersion agent, stops thin ore particle to be assembled, and with other complexing of metal ion, adds this flotation agent-ammonia fat subsitutes acid more simultaneously, and useful Collophanite flotation is come out.
Following table be under differing temps by obtaining data behind the one thick two single-minded closed circuit flow experiment of sweeping again and again that simply top-ups:
| Temperature/℃ | Concentrate yield | Concentrate grade/% | The concentrate rate of recovery/% |
| 31～33℃ | 58.89 | 28.72 | 81.50 |
| 10～12℃ | 54.15 | 28.57 | 76.11 |
We can see that concentrate grade can reach 28.72% at normal temperatures by above data, and the rate of recovery reaches 81.50%, and concentrate grade can reach 28.57% under cold condition, and the rate of recovery reaches 76.11%, all obtain effect preferably.Temperature is little to this flotation agent influence as can be known, and the grade and the rate of recovery are all more stable between 10-33 ℃, and effect is relatively good.Show that this flotation agent normal temperature low-temperature water-soluble is good, dispersiveness in the phosphorus ore ore pulp has obtained tangible improvement, it is reduced greatly to dependence on temperature, saved the consumption of flotation agent and the required energy consumption of flotation of heating, its effect obviously is better than general oleic-acid flotation agent.
Each cited raw material of the present invention can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (7)
1, Aminoaliphatic acid flotation agent, it is characterized in that it mainly is prepared from by rapeseed oil, strong base solution, the vitriol oil, chlorine and ammonia, the mol ratio of each raw material is: rapeseed oil: strong base solution: the vitriol oil: chlorine: ammonia=1:4.0-5.3:2.0-3.2:9-12:9-12, described strong base solution are sodium hydroxide solution or potassium hydroxide solution.
2, by the described Aminoaliphatic acid flotation agent of claim 1, it is characterized in that the mol ratio of each raw material is: rapeseed oil: strong base solution: the vitriol oil: chlorine: ammonia=1:5:2.5:10:10.
3, the preparation method of the described Aminoaliphatic acid flotation agent of claim 1 is characterized in that including the next coming in order step:
1) mol ratio by rapeseed oil, strong base solution, the vitriol oil, chlorine, ammonia is that 1:4.0-5.3:2.0-3.2:9-12:9-12 prepares rapeseed oil, strong base solution, the vitriol oil, chlorine and ammonia, standby, described strong base solution is sodium hydroxide solution or potassium hydroxide solution;
2) under 80-100 ℃, with strong base solution saponification rapeseed oil, after question response finishes, the saponified adding NaCl of gained is saltoutd, wash then, suction filtration gets saponification resultant, the saponification resultant of gained adds the vitriol oil at normal temperatures, at 80-100 ℃ of following mechanical stirring 1.5-3h, separatory, hot wash obtains anhydrous fat acid after the drying;
3) with step 2) acid of gained anhydrous fat places reaction vessel, and under the catalyst action, 90-100 ℃ feeds chlorine down after 8-12 hour, obtains alpha-chloro-fatty acid;
4) the gained alpha-chloro-fatty acid is placed autoclave, with the dehydrated alcohol is solvent, add catalyzer again, charge into ammonia then, 65-75 ℃ of following mechanical stirring reaction 48 hours, uninterruptedly replenish ammonia during this time, question response finishes the back and takes out reaction solution and steam ethanol, obtains Aminoaliphatic acid flotation agent.
4, by the preparation method of the described Aminoaliphatic acid flotation agent of claim 3, it is characterized in that the described catalyzer of step 3) is thionyl chloride or phosphorus pentachloride.
5, by the preparation method of claim 3 or 4 described Aminoaliphatic acid flotation agents, it is characterized in that the described catalyzer of step 4) is yellow soda ash or salt of wormwood.
6, by the preparation method of claim 3 or 4 described Aminoaliphatic acid flotation agents, the concentration that it is characterized in that described strong base solution is 12-18mol/L.
7, by the preparation method of claim 3 or 4 described Aminoaliphatic acid flotation agents, the concentration that it is characterized in that described concentrated sulfuric acid solution is 8-12mol/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100617053A CN101531605B (en) | 2009-04-21 | 2009-04-21 | Aminoaliphatic acid flotation agent and preparation method thereof |
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|---|---|
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| CN101531605B CN101531605B (en) | 2012-07-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721856A (en) * | 2013-12-17 | 2014-04-16 | 广西大学 | Garnet inhibitor preparation 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 |
-
2009
- 2009-04-21 CN CN2009100617053A patent/CN101531605B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721856A (en) * | 2013-12-17 | 2014-04-16 | 广西大学 | Garnet inhibitor preparation method |
| CN103721856B (en) * | 2013-12-17 | 2015-12-02 | 广西大学 | A kind of preparation method of Garnet inhibitor |
| 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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| CN101531605B (en) | 2012-07-04 |
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Application publication date: 20090916 Assignee: Hubei E'zhong Ecological Engineering Co., Ltd. Assignor: Wuhan Institute of Technology Contract record no.: 2016420000027 Denomination of invention: Aminoaliphatic acid flotation agent and preparation method thereof Granted publication date: 20120704 License type: Exclusive License Record date: 20161020 |
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