CN101531605B - Aminoaliphatic acid flotation agent and preparation method thereof - Google Patents
Aminoaliphatic acid flotation agent and preparation method thereof Download PDFInfo
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- CN101531605B CN101531605B CN2009100617053A CN200910061705A CN101531605B CN 101531605 B CN101531605 B CN 101531605B CN 2009100617053 A CN2009100617053 A CN 2009100617053A CN 200910061705 A CN200910061705 A CN 200910061705A CN 101531605 B CN101531605 B CN 101531605B
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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 through 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 needs in the industry to adopt the floatation process of heating with dispersed relatively poor, 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, unlike polarity be amphoterisation, weak solution from or non-ionized and mix collaborative.
Summary of the invention
Problem to be solved by this invention is to propose a kind of Aminoaliphatic acid flotation agent to 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 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 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; Subsequent use, 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 absolute ethyl alcohol is solvent, adds catalyzer again, charges 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, its carbochain the shortest with the longest eicosanoic acid and the linolenic acid of being respectively; 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 flexibility 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 dependence on temperature greatly.
Description of drawings
Fig. 1 is the infrared absorpting light spectra of Aminoaliphatic acid flotation agent of the present invention.
Like 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 1248.62cm
-1The place is the absorption peak of carbon-nitrogen bond, so the entire compound structure all is confirmed at infrared absorption peak.
Embodiment
Below in conjunction with embodiment the present invention is described further, but can not be as to qualification of the present 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 get saponified, add 80 ℃ of water 100ml and NaOH solution 20ml (15mol/L) continuation insulation reaction half a hour, and 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, and 90～100 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory; Get 80 ℃ of washings of upper strata oily matter 2 times, dry that anhydrous fat is sour;
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, under 110 ℃, reduces pressure 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, is solvent with an amount of absolute ethyl alcohol, adds a spot of yellow soda ash again and makes 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 get saponified, add 80 ℃ of water 200ml and NaOH solution 50ml (12mol/L) continuation insulation reaction half a hour, and 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, and 90～100 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory; Get upper strata oily matter 70-90 ℃ of washing 2 times, dry that anhydrous fat is sour;
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, under 110 ℃, reduces pressure 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, is solvent with an amount of absolute ethyl alcohol, adds a spot of salt of wormwood again and makees 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 get saponified, add 80 ℃ of water 200ml and KOH solution 50ml (12mol/L) continuation insulation reaction half a hour, add an amount of NaCl and leave standstill and saltout 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, and 90～100 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory; Get upper strata oily matter 70-90 ℃ of washing 2 times, dry that anhydrous fat is sour;
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, under 110 ℃, reduces pressure after reaction finishes and takes out de-chlorine hydride and excessive chlorine, promptly obtains chlorinated fatty acid.Again chlorinated fatty acid being placed autoclave, is solvent with an amount of absolute ethyl alcohol, charges 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 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.
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.l. | F | SiO 2 | CO 2 | Fe 2O 3 | Al 2O 3 | Loss on ignition |
| 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 simultaneously with other complexing of metal ion, adds this flotation agent-ammonia fat subsitutes acid again, and useful Collophanite flotation is come out.
Following table be under differing temps through 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 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 recovery reaches 81.50%, and concentrate grade can reach 28.57% under coldcondition, and the recovery reaches 76.11%, all obtain effect preferably.Can know that temperature is little to this flotation agent influence, the grade and the 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 dependence on temperature greatly, practiced thrift the consumption of flotation agent and the required energy consumption of flotation of heating, its effect obviously is superior to 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 (like temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (3)
1. the preparation method of Aminoaliphatic acid flotation agent 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 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; Subsequent use, 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 ℃ fed chlorine down after 8-12 hour, obtained alpha-chloro-fatty acid, and described catalyzer is thionyl chloride or phosphorus pentachloride;
4) the gained alpha-chloro-fatty acid being placed autoclave, is solvent with the absolute ethyl alcohol, adds catalyzer again; Described catalyzer is yellow soda ash or salt of wormwood; Charge into ammonia then, 65-75 ℃ of following mechanical stirring reaction 48 hours, during the uninterrupted ammonia that replenishes; Question response finishes the back and takes out reaction solution and steam ethanol, obtains Aminoaliphatic acid flotation agent.
2. by the preparation method of the described Aminoaliphatic acid flotation agent of claim 1, the concentration that it is characterized in that described strong base solution is 12-18mol/L.
3. by the preparation method of the described Aminoaliphatic acid flotation agent of claim 1, 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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Non-Patent Citations (6)
| Title |
|---|
| .新型α-取代脂肪酸衍生物类磷矿浮选捕收剂.《武汉工程大学学报》.2008,第30卷(第2期),全文. |
| 潘志权 |
| 邓成斌 |
| 马雄伟 |
| 黄齐茂 |
| 黄齐茂;邓成斌;潘志权;马雄伟;.新型α-取代脂肪酸衍生物类磷矿浮选捕收剂.《武汉工程大学学报》.2008,第30卷(第2期),全文. * |
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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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