CN101856636B - Chlorinated fatty acid tartaric ester flotation agent and preparation method thereof - Google Patents
Chlorinated fatty acid tartaric ester flotation agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a flotation agent, in particular relating to a chlorinated fatty acid tartaric ester flotation agent and a preparation method thereof. The chlorinated fatty acid tartaric ester flotation agent is characterized by being prepared from the raw materials of soybean oil, strong base solution, concentrated sulfuric acid, chlorine, thionyl chloride, anhydrous tartaric acid and synergist with the molar ratio of 1.0: (9.8-12.3): (4.8-5.6): (5.5-6.4): (1.4-2.2): (1.7-2.2): (0.03-0.08). The flotation agent prepared by the method has good floating effect, small influence from temperature, easily obtained raw materials and low price.
Description
Technical field
The present invention relates to a kind of flotation agent and preparation method thereof, the concrete a kind of chlorinated fatty acid flotation agent and preparation method thereof that relates to.
Background technology
Mid low grade phosphate rock in China's phosphorus ore is many, and rich ore is few, and average grade only has 17%, and the selecting and purchasing difficulty is large, and the enrichment cost is high.Therefore, the technical research of raising phosphorus ore grade is extremely urgent.One adopts floatation to improve the phosphorus ore grade.Common used carboxylic acids collecting agent, because it is difficult for dispersion at normal temperatures, the collecting poor-performing, effect is undesirable, often needs ore pulp is heated, and causes beneficiation cost to increase.Find out that thus the development resistance to low temperature is good, and the good new collector of flotation performance has great importance.The in recent years development of floating agent or the main trend of selecting be polyfunctional group, functional group's center variation, polyoxyethylene groups, heteropolarity be amphoterisation, weak solution from or non-ionic and mix collaborative.
Summary of the invention
The object of the present invention is to provide a kind of chlorinated fatty acid tartaric ester flotation agent and preparation method thereof, the flotation effect of the flotation agent of the method preparation is better, temperature influence is little.
For achieving the above object, the technical solution used in the present invention is: chlorinated fatty acid tartaric ester flotation agent, it is characterized in that it is prepared from by comprising soybean oil, strong base solution, the concentrated sulfuric acid, chlorine, thionyl chloride, anhydrous tartaric acid and synergist raw material, the mol ratio of each raw material is: soybean oil: strong base solution: the concentrated sulfuric acid: chlorine: thionyl chloride: anhydrous tartaric acid: synergist=1.0: (9.8-12.3): (4.8-5.6): (5.5-6.4): (1.4-2.2): (1.7-2.2): (0.03-0.08).
Described strong base solution is sodium hydroxide solution or potassium hydroxide solution, and the concentration of solution is 12-18mol/L; The concentrated sulfuric acid uses after distilled water diluting becomes concentration to be 8-12mol/L.
Press such scheme, preferably the mol ratio of each raw material is: soybean oil: sodium hydroxide solution: the concentrated sulfuric acid: chlorine: thionyl chloride: anhydrous tartaric acid: synergist=1.0: 10.3: 5.3: 6.0: 2.0: 1.9: 0.06
The preparation method of above-mentioned chlorinated fatty acid tartaric ester flotation agent is characterized in that it includes following steps:
1) mol ratio by each raw material is: soybean oil: strong base solution: the concentrated sulfuric acid: chlorine: thionyl chloride: anhydrous tartaric acid: synergist=1.0: (9.8-12.3): (4.8-5.6): (5.5-6.4): (1.4-2.2): (1.7-2.2): (0.03-0.08), prepare soybean oil, strong base solution, the concentrated sulfuric acid, chlorine, thionyl chloride, anhydrous tartaric acid and synergist, for subsequent use;
2) under 80-100 ℃, with strong base solution saponification soybean oil, reaction 3-24h after question response finishes, saltouts the saponified adding NaCl of gained, and press soybean oil: sodium chloride=1.0: 1.2-1.4 adds NaCl; Then, get that the upper strata is saponified to be washed, suction filtration gets saponification resultant; It is the sulfuric acid solution of 8-12mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution at normal temperatures, at 80-100 ℃ of lower mechanical agitation 1.5-3h, leaves standstill separatory, get upper strata grease with hot water (70-90 ℃ of water) washing, obtain free-of-liquid fat acid after the drying;
3) by soybean oil: catalyst=0.3mol: (0.01-0.02) mol chooses catalyst, get step 2) acid of gained free-of-liquid fat places reaction vessel, add catalyst, heat simultaneously in mechanical agitation, after passing into chlorine 8-12 hour under 90-100 ℃, obtain alpha-chloro-fatty acid, add thionyl chloride again, reaction obtains acyl chlorides;
4) with anhydrous N, dinethylformamide (DMF) is solvent, add dry anhydrous tartaric acid, be made into the tartaric acid solution that concentration is 2.2mol/L, add thermal agitation, with constant pressure funnel with step 3) the gained acyl chlorides slowly is added dropwise in the tartaric acid solution, in 80-90 ℃ of lower little stirring and refluxing 16 hours of boiling, cooling water washing, steaming desolventizes, drying obtains compound; Add synergist in the compound, mix, obtain chlorinated fatty acid tartaric ester flotation agent (being the alpha-chloro-fatty acid tartrate).
Press such scheme, step 3) described catalyst is thionyl chloride or phosphorus pentachloride.When making catalyst, consumption is few, so step 1) in thionyl chloride only as the reactant consumption.
Press such scheme, described strong base solution is sodium hydroxide solution or potassium hydroxide solution, and the concentration of solution is 12-18mol/L.
Described synergist is Tween-40 (Tween-40) or Tween-20 (Tween-20).
The general structure of product chlorinated fatty acid tartaric ester flotation agent of the present invention is:
R is that carbon number is the chlorohydrocarbon of 10-22 in the formula, because raw material is soybean oil, the aliphatic acid after the saponification acidolysis is fatty acid mixed, and the shortest and the longest arachidic acid and the leukotrienes of being respectively of its carbochain is the chlorohydrocarbon of 10-22 so R is carbon number.
Compared with prior art, the invention has the beneficial effects as follows: because the α of carboxylic acid replaces the activity that has strengthened anion, improve the water-soluble of flotation agent, increased the electrical conductivity of compound, reduced surface tension, increased foaming properties, improved surface-active; Increase is to Ca
2+, Mg
2+Isoionic adaptability can be carried out flotation under lower temperature (20-25 ℃) and in the hard water; Two polar groups are in the ortho position simultaneously, flotation agent polar group one end section is increased, can strengthen the selective of medicament, after hydrophilic polar group is introduced in the α position, the dissolubility of flotation agent in water increased, and its dependence to temperature is reduced greatly, and temperature influence is little, flotation need not heating (namely not needing to heat), and flotation effect is better.Raw material of the present invention is easy to get, and is cheap.
Description of drawings
Fig. 1 is the infrared absorpting light spectra of chlorinated fatty acid tartaric ester flotation agent of the present invention.
The specific embodiment
The invention will be further described below in conjunction with embodiment, but can not be as limitation of the invention.
Embodiment 1:
The preparation method of chlorinated fatty acid tartaric ester flotation agent, it includes following steps:
Add soybean oil 0.3mol in the 1L beaker, mechanical agitation and heating, 80 ℃ of lower NaOH solution 200m L (15mol/L) that add, 90 ℃ of insulation reaction to products that take a morsel occur (namely fully saponified without oil bloom in cold water, time is about 3h), add 80 ℃ of water 100m L and NaOH solution 30mL (15mol/L) and continue insulation reaction half an hour, obtain saponified; Leave standstill to the NaCl of saponified middle adding 0.4mol and to saltout 5 hours, get the saponified washing in upper strata (water yield can not as many as produce jelly), suction filtration gets saponification resultant; It is the sulfuric acid solution of 12mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution 125mL (12mol/L) at normal temperatures, and 90 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory, get upper strata grease with 80 ℃ of washings 2 times, dry that free-of-liquid fat is sour;
Upper step product free-of-liquid fat acid places the 1L there-necked flask, adds 0.02mol catalyst thionyl chloride, passes into chlorine (0.1L/min) 1.7mol when being warming up to 90 ℃ under stirring, pass into chlorine after 12 hours, be down to normal temperature, obtain alpha-chloro-fatty acid, slowly drip thionyl chloride (SOCl
2) 0.45mol, stir and be warming up to 80 ℃, little 2 hours (described little boiling refers to that temperature is 80 ℃) of refluxing of boiling, decompression is pumped to liquid without bubble, namely gets acyl chlorides;
To the anhydrous N of 300m L, add anhydrous tartaric acid powder 0.66mol in the dinethylformamide (DMF), [take anhydrous DMF (DMF) as solvent, the concentration of this moment is 2.2mol/L], obtain tartaric acid solution (tartaric anhydrous DMF solution); Gained acyl chlorides of upper step is splashed in the tartaric acid solution with constant pressure funnel, and 80-90 ℃ of lower little return stirring 16 hours (described little boiling refers to that temperature is 80-90 ℃) that boils with 300mL washing 3 times, steams solvent DMF respectively, and drying obtains compound; Add the Tween-40 (synergist) of 0.009mol in the compound, mix, obtain product (chlorinated fatty acid tartaric ester flotation agent).
Fig. 1 is the infrared absorpting light spectra of the chlorinated fatty acid tartaric ester flotation agent that obtains of the embodiment of the invention 1, and as shown in Figure 1, the strong absworption peak of the two keys of carbon-oxygen should be at 1711.23cm
-1About, but because the impact of alpha-chloro, so that the frequency of the two keys of carbon-oxygen moves 10～30cm to high frequency treatment
-1, so at 1728.54cm
-1There is the strong absworption peak of the two keys of carbon-oxygen at the place.Carbon-chlorine key is at 732.13cm
-1And 650.17cm
-1There are two absworption peaks at the place.1380.89cm
-1Absworption peak and 1090.30cm
-1The absworption peak of carbon-oxygen singly-bound be the characteristic peak of hydroxyl, at 1200.05cm
-1And 1049.30cm
-1The place is the absworption peak of carbon-oxygen-carbon ester bond.1273.31cm
-1Absworption peak and 1131.95cm
-1The absworption peak of carbon-oxygen singly-bound be the characteristic peak of hydroxyl, 3375.38cm
-1The place on the tartaric acid-the resulting feature broad peak of association of OH.So the infrared absorption peak of whole compound structure all is confirmed, illustrate that the compound that is synthesized namely is target product.The product that Fig. 1 susceptible of proof present embodiment 1 obtains is chlorinated fatty acid tartaric ester.
Select collophane to carry out flotation with embodiment 1 prepared chlorinated fatty acid tartaric ester flotation agent to low-grade refractory in the Hubei, its ore chemistry consists of:
| Analysis project | P 2O 5 | MgO | CaO | SiO 2 | CO 2 | Fe 2O 3 | Al 2O 3 | F |
| Mass fraction/% | 17.09 | 5.29 | 35.4 | 25.8 | 6.62 | 1.99 | 1.91 | 1.49 |
The method of direct flotation adds sodium carbonate and regulates the pH value and suppress Ca
2+, Mg
2+, sodium metasilicate suppresses silicate, and calgon plays a dispersant, stops thin ore particle to be assembled, and with other complexing of metal ion, adds this flotation agent-chlorinated fatty acid tartaric ester, with useful Collophanite flotation out simultaneously again.
The contrast experiment obtains data through the one roughing temperature:
| Temperature/ |
15 | 20 | 25 | 30 | 35 |
| Grade/% | 22.76 | 22.01 | 21.87 | 21.98 | 21.37 |
| The rate of recovery/% | 73.1 | 80.7 | 81.8 | 85.9 | 87.4 |
Known that by above data concentrate grade can reach 22.76% at low temperatures, the rate of recovery is 73.15%, and concentrate grade can reach 22.01% under the normal temperature, and the rate of recovery is 80.7%, and flotation effect is all better.And heating there is no much improvement to flotation effect.Flotation results shows, in the chloro tartaric acid monoesters of anionic, the introducing of-Cl has increased the sterically hindered of the nonpolar part of medicament, makes medicament be difficult to form micelle in the aqueous solution, so have good dispersiveness, the introducing of-COOH has strengthened the selective and collecting of medicament, the introducing of-OH, improve medicament water-soluble (in the experimentation according to experience paired observation gained good water solubility), strengthened foaming characteristic.Both reduce cost, had again good flotation performance, obviously be better than one oleic-acid flotation agent.
Embodiment 2:
The preparation method of chlorinated fatty acid tartaric ester flotation agent, it includes following steps:
Add soybean oil 0.6mol in the 2L beaker, mechanical agitation and heating, 90 ℃ of lower NaOH solution 400mL (12mol/L) that add, 100 ℃ of insulation reaction to products that take a morsel occur namely getting saponified (namely fully saponified without oil bloom in cold water, time is about 3h), add 80 ℃ of water 200mL and NaOH solution 100mL (12mol/L) and continue insulation reaction half an hour, obtain saponified; Leave standstill to saponified middle adding 0.8molNaCl and to 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; It is the sulfuric acid solution of 8mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution 400mL (8mol/L) at normal temperatures, and 100 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory, get upper strata grease with 90 ℃ of washings 2 times, dry that free-of-liquid fat is sour;
Upper step product free-of-liquid fat acid places the 1L there-necked flask, add 0.03-0.04mol catalyst thionyl chloride, pass into chlorine (0.1L/min) 3.7mol when being warming up to 90 ℃ under stirring, pass into chlorine after 8 hours, be down to normal temperature, slowly drip thionyl chloride (SOCl
2) 1mol, stir and be warming up to 78-82 ℃, little 2 hours (described little boiling refers to that temperature is 78-82 ℃) of refluxing of boiling, decompression is pumped to liquid without bubble, namely gets acyl chlorides;
To the anhydrous N of 500mL, add anhydrous tartaric acid powder 1.1mol[in the dinethylformamide (DMF) with anhydrous N, dinethylformamide (DMF) is solvent, and the concentration of this moment is 2.2mol/L], obtain tartaric acid solution (tartaric anhydrous DMF solution); Gained acyl chlorides of upper step is splashed in the tartaric acid solution with constant pressure funnel, and 80-90 ℃ of lower little return stirring 16 hours of boiling with 300ml washing 3 times, steams solvent DMF respectively, and drying obtains compound; Add the Tween-40 (synergist) of 0.024mol in the compound, mix, obtain product (chlorinated fatty acid tartaric ester flotation agent).
Embodiment 3:
The preparation method of chlorinated fatty acid tartaric ester flotation agent, it includes following steps:
Add soybean oil 0.6mol in the 2L beaker, mechanical agitation and heating, 80 ℃ of lower KOH solution 400mL (12mol/L) that add, it (is that saponification is complete that 80 ℃ of insulation reaction to products that take a morsel occur without oil bloom in cold water, time is about 4h), add 80 ℃ of water 200m L and KOH solution 100mL (12mol/L) and continue insulation reaction half an hour, obtain saponified; Leave standstill to saponified middle adding 0.8molNaCl and to 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; It is the sulfuric acid solution of 8mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution 400ml (8mol/L) at normal temperatures, and 90 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory, get upper strata grease with 70 ℃ of washings 2 times, dry that free-of-liquid fat is sour;
Upper step product free-of-liquid fat acid places the 1L there-necked flask, adds 0.03-0.04mol catalyst thionyl chloride, passes into chlorine (0.1L/min) 3.3mol when being warming up to 90 ℃ under stirring, and chlorine was down to normal temperature after 9 hours, slowly dripped thionyl chloride (SOCl
2) 1mol, stir and be warming up to 78-82 ℃, little 2 hours (described little boiling refers to that temperature is 78-82 ℃) of refluxing of boiling, decompression is pumped to liquid without bubble, namely gets acyl chlorides;
To the anhydrous N of 545ml, add anhydrous tartaric acid powder 1.2mol[in the dinethylformamide (DMF) with anhydrous N, dinethylformamide (DMF) is solvent, and the concentration of this moment is 2.2mol/L], obtain tartaric acid solution (tartaric anhydrous DMF solution); Gained acyl chlorides of upper step is splashed in the tartaric acid solution with constant pressure funnel, and 80-90 ℃ of lower little return stirring 16 hours of boiling with 300mL washing 3 times, steams solvent DMF respectively, and drying obtains compound; Add the Tween-20 (synergist) of 0.036mol in the compound, mix, obtain product (chlorinated fatty acid tartaric ester flotation agent).
Embodiment 4:
The preparation method of chlorinated fatty acid tartaric ester flotation agent, it includes following steps:
Add soybean oil 0.6mol in the 2L beaker, mechanical agitation and heating, 90 ℃ of lower NaOH solution 400mL (12mol/L) that add, 100 ℃ of insulation reaction to products that take a morsel occur namely getting saponified (namely fully saponified without oil bloom in cold water, time is about 4h), add 80 ℃ of water 200mL and NaOH solution 115mL (12mol/L) and continue insulation reaction half an hour, obtain saponified; Leave standstill to saponified middle adding 0.8molNaCl and to 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; It is the sulfuric acid solution of 8mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution 398mL (8mol/L) at normal temperatures, and 100 ℃ are incubated mechanical stirring reaction 3 hours, leave standstill separatory, get upper strata grease and wash 2 times with 80 ℃, drying obtains free-of-liquid fat acid;
Upper step product free-of-liquid fat acid places the 1L there-necked flask, add 0.03-0.04mol catalyst thionyl chloride, pass into chlorine (0.1L/min) 3.6mol when being warming up to 90 ℃ under stirring, pass into chlorine after 10 hours, be down to normal temperature, slowly drip thionyl chloride (SOCl
2) 1.2mol, stir and be warming up to 78-82 ℃, little 2 hours (described little boiling refers to that temperature is 78-82 ℃) of refluxing of boiling, decompression is pumped to liquid and namely gets acyl chlorides without bubble;
In the anhydrous DMF of 518mL (DMF), add anhydrous tartaric acid powder 1.14mol, obtain tartaric acid solution (tartaric anhydrous DMF solution, the concentration of this moment is 2.2mol/L); Gained acyl chlorides of upper step is splashed in the tartaric acid solution with constant pressure funnel, and 80-90 ℃ of lower little return stirring 16 hours of boiling with 300mL washing 3 times, steams solvent DMF respectively, and drying obtains compound; Add the Tween-20 (synergist) of 0.036mol in the compound, mix, obtain product (chlorinated fatty acid tartaric ester flotation agent).
Embodiment 5:
The preparation method of above-mentioned chlorinated fatty acid tartaric ester flotation agent, it includes following steps:
1) mol ratio by each raw material is: soybean oil: strong base solution: the concentrated sulfuric acid: chlorine: thionyl chloride: anhydrous tartaric acid: synergist=1.0: 9.8: 4.8: 5.5: 1.4: 1.7: 0.03, prepare soybean oil, strong base solution, the concentrated sulfuric acid, chlorine, thionyl chloride, anhydrous tartaric acid and synergist, for subsequent use; Described strong base solution is sodium hydroxide solution, and the concentration of solution is 12mol/L;
2) under 80 ℃, with strong base solution saponification soybean oil, reaction 3h after question response finishes, saltouts saponified the addings NaCl of gained, presses soybean oil: sodium chloride=1.0: 1.2 adding NaCl; Then, get that the upper strata is saponified to be washed, suction filtration gets saponification resultant; It is the sulfuric acid solution of 8mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution at normal temperatures, at 80 ℃ of lower mechanical agitation 1.5h, leaves standstill separatory, get upper strata grease with hot water (70 ℃ of water) washing, obtain free-of-liquid fat acid after the drying;
3) by soybean oil: catalyst=0.3mol: 0.01mol chooses catalyst, get step 2) acid of gained free-of-liquid fat places reaction vessel, add catalyst, heat simultaneously in mechanical agitation, pass into chlorine under 90 ℃ after 8 hours, obtain alpha-chloro-fatty acid, add thionyl chloride again, reaction obtains acyl chlorides; Described catalyst is thionyl chloride;
4) with anhydrous N, dinethylformamide (DMF) is solvent, add dry anhydrous tartaric acid, be made into the tartaric acid solution that concentration is 2.2mol/L, add thermal agitation, with constant pressure funnel with step 3) the gained acyl chlorides slowly is added dropwise in the tartaric acid solution, in 80 ℃ of lower little stirring and refluxing 16 hours of boiling, cooling water washing, steaming desolventizes, drying obtains compound; Add synergist (Tween-40) in the compound, mix, obtain product (chlorinated fatty acid tartaric ester flotation agent).
Embodiment 6:
The preparation method of above-mentioned chlorinated fatty acid tartaric ester flotation agent, it includes following steps:
1) mol ratio by each raw material is: soybean oil: strong base solution: the concentrated sulfuric acid: chlorine: thionyl chloride: anhydrous tartaric acid: synergist=1.0: 12.3: 5.6: 6.4: 2.2: 2.2: 0.08, prepare soybean oil, strong base solution, the concentrated sulfuric acid, chlorine, thionyl chloride, anhydrous tartaric acid and synergist, for subsequent use; Described strong base solution is potassium hydroxide solution, and the concentration of solution is 18mol/L;
2) under 100 ℃, with strong base solution saponification soybean oil, reaction 24h after question response finishes, saltouts saponified the addings NaCl of gained, presses soybean oil: sodium chloride=1.0: 1.4 adding NaCl; Then, get that the upper strata is saponified to be washed, suction filtration gets saponification resultant; It is the sulfuric acid solution of 12mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution at normal temperatures, at 100 ℃ of lower mechanical agitation 3h, leaves standstill separatory, get upper strata grease with hot water (90 ℃ of water) washing, obtain free-of-liquid fat acid after the drying;
3) by soybean oil: catalyst=0.3mol: 0.02mol chooses catalyst, get step 2) acid of gained free-of-liquid fat places reaction vessel, add catalyst, heat simultaneously in mechanical agitation, pass into chlorine under 100 ℃ after 12 hours, obtain alpha-chloro-fatty acid, add thionyl chloride again, reaction obtains acyl chlorides; Described catalyst is phosphorus pentachloride;
4) with anhydrous N, dinethylformamide (DMF) is solvent, add dry anhydrous tartaric acid, be made into the tartaric acid solution that concentration is 2.2mol/L, add thermal agitation, with constant pressure funnel with step 3) the gained acyl chlorides slowly is added dropwise in the tartaric acid solution, in 90 ℃ of lower little stirring and refluxing 16 hours of boiling, cooling water washing, steaming desolventizes, drying obtains compound; Add synergist (Tween-20) in the compound, mix, obtain product (chlorinated fatty acid tartaric ester flotation agent).
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of technological parameter (such as temperature, time etc.), interval value can both realize the present invention, do not enumerate one by one embodiment at this.
Claims (6)
1. chlorinated fatty acid tartaric ester flotation agent, it is characterized in that it is prepared from by soybean oil, strong base solution, the concentrated sulfuric acid, chlorine, thionyl chloride, anhydrous tartaric acid and synergist, the mol ratio of each raw material is: soybean oil: strong base solution: the concentrated sulfuric acid: chlorine: thionyl chloride: anhydrous tartaric acid: synergist=1.0:(9.8-12.3): (4.8-5.6): (5.5-6.4): (1.4-2.2): (1.7-2.2): (0.03-0.08);
Described synergist is Tween-40 or Tween-20;
1) under 80-100 ℃, with strong base solution saponification soybean oil, reaction 3-24h after question response finishes, saltouts the saponified adding NaCl of gained, and press soybean oil: sodium chloride mol ratio=1.0:1.2-1.4 adds NaCl; Then, get that the upper strata is saponified to be washed, suction filtration gets saponification resultant; It is the sulfuric acid solution of 8-12mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution at normal temperatures, at 80-100 ℃ of lower mechanical agitation 1.5-3h, leaves standstill separatory, get upper strata grease hot wash, obtain free-of-liquid fat acid after the drying;
2) by soybean oil: catalyst=0.3mol:(0.01-0.02) mol chooses catalyst, gets the acid of step 1) gained free-of-liquid fat and places reaction vessel, adds catalyst, heat simultaneously in mechanical agitation, after passing into chlorine 8-12 hour under 90-100 ℃, add thionyl chloride, reaction obtains acyl chlorides again;
3) with anhydrous N, dinethylformamide is solvent, add dry anhydrous tartaric acid, be made into the tartaric acid solution that concentration is 2.2mol/L, add thermal agitation, with constant pressure funnel with step 2) the gained acyl chlorides slowly is added dropwise in the tartaric acid solution, in 80-90 ℃ of lower little stirring and refluxing 16 hours of boiling, cooling water washing, steaming desolventizes, drying obtains compound; Add synergist in the compound, mix, obtain chlorinated fatty acid tartaric ester flotation agent.
2. chlorinated fatty acid tartaric ester flotation agent according to claim 1, it is characterized in that: described strong base solution is sodium hydroxide solution or potassium hydroxide solution, the concentration of solution is 12-18mol/L.
3. chlorinated fatty acid tartaric ester flotation agent according to claim 1, it is characterized in that: the mol ratio of each raw material is: soybean oil: strong base solution: the concentrated sulfuric acid: chlorine: thionyl chloride: anhydrous tartaric acid: synergist=1.0:10.3:5.3:6.0:2.0:1.9:0.06.
4. the preparation method of chlorinated fatty acid tartaric ester flotation agent as claimed in claim 1 is characterized in that it includes following steps:
1) mol ratio by each raw material is: soybean oil: strong base solution: the concentrated sulfuric acid: chlorine: thionyl chloride: anhydrous tartaric acid: synergist=1.0:(9.8-12.3): (4.8-5.6): (5.5-6.4): (1.4-2.2): (1.7-2.2): (0.03-0.08), prepare soybean oil, strong base solution, the concentrated sulfuric acid, chlorine, thionyl chloride, anhydrous tartaric acid and synergist, for subsequent use; Described synergist is Tween-40 or Tween-20;
2) under 80-100 ℃, with strong base solution saponification soybean oil, reaction 3-24h after question response finishes, saltouts the saponified adding NaCl of gained, and press soybean oil: sodium chloride mol ratio=1.0:1.2-1.4 adds NaCl; Then, get that the upper strata is saponified to be washed, suction filtration gets saponification resultant; It is the sulfuric acid solution of 8-12mol/L that the concentrated sulfuric acid becomes concentration through distilled water diluting, the saponification resultant of gained adds sulfuric acid solution at normal temperatures, at 80-100 ℃ of lower mechanical agitation 1.5-3h, leaves standstill separatory, get upper strata grease hot wash, obtain free-of-liquid fat acid after the drying;
3) by soybean oil: catalyst=0.3mol:(0.01-0.02) mol chooses catalyst, gets step 2) acid of gained free-of-liquid fat places reaction vessel, adds catalyst, heat simultaneously in mechanical agitation, after passing into chlorine 8-12 hour under 90-100 ℃, add thionyl chloride, reaction obtains acyl chlorides again;
4) with anhydrous N, dinethylformamide is solvent, add dry anhydrous tartaric acid, be made into the tartaric acid solution that concentration is 2.2mol/L, add thermal agitation, slowly be added dropwise to step 3) gained acyl chlorides in the tartaric acid solution with constant pressure funnel, in 80-90 ℃ of lower little stirring and refluxing 16 hours of boiling, cooling water washing, steaming desolventizes, drying obtains compound; Add synergist in the compound, mix, obtain chlorinated fatty acid tartaric ester flotation agent.
5. the preparation method of chlorinated fatty acid tartaric ester flotation agent according to claim 4, it is characterized in that: the described catalyst of step 3) is thionyl chloride or phosphorus pentachloride.
6. the preparation method of chlorinated fatty acid tartaric ester flotation agent according to claim 4, it is characterized in that: described strong base solution is sodium hydroxide solution or potassium hydroxide solution, the concentration of solution is 12-18mol/L.
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| CN 201010194504 CN101856636B (en) | 2010-06-08 | 2010-06-08 | Chlorinated fatty acid tartaric ester flotation agent and preparation method thereof |
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| CN102302983B (en) * | 2011-05-31 | 2013-06-19 | 武汉工程大学 | Quaternary ammonium salt hydroximic acid phosphorus ore floatation collecting agent and preparation method thereof |
| CN106378263B (en) * | 2016-09-27 | 2018-06-22 | 中国地质科学院郑州矿产综合利用研究所 | Low-alkali-consumption scheelite collecting agent and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0106787A2 (en) * | 1982-10-14 | 1984-04-25 | Sherex Chemical Company, Inc. | Promoters for froth flotation of coal |
| CN101429120A (en) * | 2008-11-27 | 2009-05-13 | 武汉工程大学 | Chloro-fatty acid lemon acid ester flotation agent and method for producing the same |
| CN101549327A (en) * | 2009-05-05 | 2009-10-07 | 武汉工程大学 | Composite floating chemical and method for preparing same |
| CN101698160A (en) * | 2009-10-26 | 2010-04-28 | 中南大学 | Sulfide flotation collector and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6799682B1 (en) * | 2000-05-16 | 2004-10-05 | Roe-Hoan Yoon | Method of increasing flotation rate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0106787A2 (en) * | 1982-10-14 | 1984-04-25 | Sherex Chemical Company, Inc. | Promoters for froth flotation of coal |
| CN101429120A (en) * | 2008-11-27 | 2009-05-13 | 武汉工程大学 | Chloro-fatty acid lemon acid ester flotation agent and method for producing the same |
| CN101549327A (en) * | 2009-05-05 | 2009-10-07 | 武汉工程大学 | Composite floating chemical and method for preparing same |
| CN101698160A (en) * | 2009-10-26 | 2010-04-28 | 中南大学 | Sulfide flotation collector and preparation method |
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