CN101429114B - Chloro-sodium soap/sylvite flotation agent and method for producing the same - Google Patents
Chloro-sodium soap/sylvite flotation agent and method for producing the same Download PDFInfo
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- CN101429114B CN101429114B CN2008101979358A CN200810197935A CN101429114B CN 101429114 B CN101429114 B CN 101429114B CN 2008101979358 A CN2008101979358 A CN 2008101979358A CN 200810197935 A CN200810197935 A CN 200810197935A CN 101429114 B CN101429114 B CN 101429114B
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- flotation agent
- fatty acid
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- chlorine
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Abstract
The invention relates to a chlor-sodium soap/sylvine floatation agent and a preparation method thereof. The floatation agent is mainly prepared from colza oil, a strong alkali solution, concentrated sulfuric acid and chlorine; the molar ratio of raw materials of the colza oil, to the strong alkali solution to the concentrated sulfuric acid to the chlorine is 1 to 10.2-12.9 to 4.2-5.4 to 9-12. Compared with the prior art, the method has the following advantages: for alpha substitution (-Cl or-OH), the alpha substitution of carboxylic acid strengthens the activity of anions, improves the chelating capacity of the floatation agent, increases the electric conductivity of a compound, reduces surface tension, increases the foam performance and improves surface activity; the adaptability to Ca<2+> ions and Mg<2+> ions is increased so that floatation can be carried out at lower temperature in hard water; if two polar groups are in or the position, the section on one end of the polar group of the floatation agent is increased to strengthen the selectivity of a drug; after a hydrophilic polar group is introduced to the alpha position, the dependence of the floatation agent on the temperature is greatly reduced.
Description
Technical field
The present invention relates to a kind of flotation agent, the concrete a kind of chlorinated fatty acid sodium/sylvite flotation agent and preparation method thereof that relates to.
Background technology
The phosphate rock resource of China accounts for the world 30%, wherein mostly be the difficult ore dressing of low taste greatly, at present, fatty acid flotation agent is adopted in the flotation of phosphate ores more, but the shortcoming of common fatty acids flotation flotation agent is poor selectivity, floatation indicators is low when low to flotation temperature sensitivity, temperature, and especially during the flotation mid low grade phosphate rock, heating up to increase energy consumption, increasing the flotation agent consumption can increase cost and make the liquid waste disposal difficulty, thereby causes phosphorus concentrate price not possess competitive power.Flotation reagent development 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, in flotation reagent, be subjected to paying close attention to widely.
Summary of the invention
Problem to be solved by this invention is to propose a kind of chlorinated fatty acid sodium/sylvite 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 chlorinated fatty acid sodium/sylvite flotation agent.
The present invention is adopted solution to be by the problem of the above-mentioned proposition of solution: chlorinated fatty acid sodium/sylvite flotation agent, it is characterized in that it mainly is prepared from by rapeseed oil, strong base solution, the vitriol oil, chlorine, the mol ratio of each raw material is: rapeseed oil: strong base solution: the vitriol oil: chlorine=1:10.2-12.9:4.2-5.4:9-12, 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=1.0:12:4.5:9.
The solution that chlorinated fatty acid sodium/sylvite flotation agent preparation method adopts is: the preparation method of chlorinated fatty acid sodium/sylvite flotation agent includes the next coming in order step:
1) mol ratio by rapeseed oil, strong base solution, the vitriol oil, chlorine is that 1:10.2-12.9:4.2-5.4:9-12 prepares rapeseed oil, strong base solution, the vitriol oil and chlorine, and is standby;
2) under 80-100 ℃, strong base solution saponification rapeseed oil with the 35-40% that accounts for total strong base solution quality, 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) remaining strong base solution solution is added in the reaction vessel, mechanical stirring, little back flow reaction 2 hours of boiling adds the NaCl solid and saltouts, the solid product that obtains after filtration, after the oven dry chlorinated fatty acid sodium/sylvite flotation agent.
Press such scheme, the described catalyzer of step 3) is a thionyl chloride.
Press such scheme, described strong base solution is sodium hydroxide solution or potassium hydroxide solution, and the concentration of 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 that carbonatoms is the hydrochloric ether of 10-22 in the formula, because raw material is rapeseed oil (or its tankage), lipid acid after the saponification acidolysis is mixed fatty acid, and the shortest and the longest eicosanoic acid and the linolenic acid of being respectively of its carbochain is the hydrochloric ether of 10-22 so R is a carbonatoms.Carboxylic acid α position replace and can be (Cl or-OH), carboxylic acid sodium salt, sylvite can.
The present invention compared with prior art has the following advantages: since be the α of carboxylic acid replace (Cl or-OH), the α replacement of carboxylic acid has strengthened anionic activity, improve the one-tenth chela ability of flotation agent, increased the specific conductivity of compound, reduced surface tension, increase foaming properties, improved surfactivity; Increase is to Ca
2+, Mg
2+Isoionic adaptability can be carried out flotation in lesser temps and hard water; If two polar groups are in the ortho position, flotation agent polar group one end section is increased, can strengthen the selectivity of medicament, 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 the embodiment of the invention 1 gained chloro fat acid sodium-salt flotation agent.
As Fig. 1, at 1561.32cm
-1And 1463.07cm
-1Strong absorption peak be COO
-Absorption band, owing to the result of alpha-chloro makes the frequency of the two keys of carbon-oxygen move 10～20cm to high frequency treatment
-1, so at 1734.15cm
-1There is the strong absorption peak of the two keys of carbon-oxygen at the place, and carbon-chlorine key is at 727.00cm
-1And 655.30cm
-1There are two absorption peaks, 1378.04cm in the place
-1Absorption peak and 1099.16cm
-1The single bonded absorption peak of carbon-oxygen be the characteristic peak of hydroxyl, 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.
Add rapeseed oil 0.3mol in the 1L beaker, mechanical stirring and heating, 80 ℃ add NaOH solution 1.2mol (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 0.1mol 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 1.5mol (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, add the catalyzer thionyl chloride, heat to 90-100 ℃ of logical chlorine (0.1L/min) 3mol, after finishing, reaction obtains chlorinated fatty acid, to wherein adding NaOH solution 2mol, be incubated little boiling and refluxed 2 hours, adding NaCl leaves standstill and saltouts 5 hours, get the saponified washing suction filtration in upper strata, the dry chloro fat acid sodium-salt flotation agent that gets.
Embodiment 2
Add rapeseed oil 0.6mol in the 2L beaker, mechanical stirring and heating, 90 ℃ add NaOH solution 2mol (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 0.6mol 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 2.7mol (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, add catalyzer, heat to 90-100 ℃ of logical chlorine (0.1L/min) 5.4mol, after finishing, reaction obtains chlorinated fatty acid, to wherein adding NaOH solution 4.5mol, be incubated little boiling and refluxed 3 hours, adding NaCl leaves standstill and saltouts 5 hours, get the saponified washing suction filtration in upper strata, the dry chloro fat acid sodium-salt flotation agent that gets.
Embodiment 3
Add rapeseed oil 0.6mol in the 2L beaker, mechanical stirring and heating, 90 ℃ add KOH solution 2mol (18mol/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 0.3mol 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 3.2mol (10mol/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, add catalyzer, heat to 90-100 ℃ of logical chlorine (0.1L/min) 7.2mol, after finishing, reaction obtains chlorinated fatty acid, to wherein adding KOH solution 4.0mol, be incubated little boiling and refluxed 3 hours, adding NaCl leaves standstill and saltouts 5 hours, get the saponified washing suction filtration in upper strata, the dry chloro fat acid sodium-salt flotation agent that gets.
With embodiment 1 prepared chloro fat acid sodium-salt flotation agent certain collophanite is carried out flotation, not several main components and percentage composition before the flotation:
| Component | P 2O 5 | MgO | SiO 2 | Al 2O 3 | Fe 2O 3 |
| Massfraction | 0.2039 | 0.0256 | 0.2634 | 0.0308 | 0.025 |
The method of direct flotation adds yellow soda ash adjusting pH value and suppresses Ca
2+, Mg
2+, water glass suppresses SiO
2, Sodium hexametaphosphate 99 suppresses various metals, adds this flotation agent-chloro fat acid sodium-salt flotation agent again, with useful collophanite emersion.
The contrast experiment obtains data through the one roughing temperature:
| Temperature/℃ | 16 | 19 | 22 | 25 | 30 |
| Grade/% | 24.35 | 24.43 | 24.74 | 25.10 | 24.97 |
| The rate of recovery/% | 84.3 | 85.1 | 86.4 | 87.3 | 90.2 |
We can see that temperature is little to this flotation agent influence by data, and the grade and the rate of recovery are all more stable between 15-30 ℃, and effect is relatively good.
Test P through one thick one single-minded sweeping under the normal temperature
2O
5Content can reach 27.9%, and the rate of recovery reaches 94% and obtains effect preferably.Flotation results shows 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.
Claims (4)
1. the preparation method of chlorinated fatty acid sodium/sylvite 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 is 1: 10.2-12.9: 4.2-5.4: 9-12 prepares rapeseed oil, strong base solution, the vitriol oil and chlorine, and standby, described strong base solution is sodium hydroxide solution or potassium hydroxide solution;
2) under 80-100 ℃, strong base solution saponification rapeseed oil with the 35-40% that accounts for total strong base solution quality, 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) remaining strong base solution is added in the reaction vessel, mechanical stirring, little back flow reaction 2 hours of boiling adds the NaCl solid and saltouts, the solid product that obtains after filtration, after the oven dry chlorinated fatty acid sodium/sylvite flotation agent.
2. by the preparation method of the described chlorinated fatty acid sodium of claim 1/sylvite flotation agent, it is characterized in that the described catalyzer of step 3) is a thionyl chloride.
3. by the preparation method of claim 1 or 2 described chlorinated fatty acid sodium/sylvite flotation agent, the concentration that it is characterized in that described sodium hydroxide solution or potassium hydroxide solution is 12-18mol/L.
4. by the preparation method of claim 1 or 2 described chlorinated fatty acid sodium/sylvite flotation agent, the concentration that it is characterized in that described concentrated sulfuric acid solution is 8-12mol/L.
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| CN101429114B true CN101429114B (en) | 2011-12-07 |
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| CN102240602B (en) * | 2010-05-12 | 2014-08-13 | 北京君致清科技有限公司 | Method for using collector prepared from illegal cooking oil in flotation and desilication of iron ore |
| CN102240603B (en) * | 2010-05-12 | 2014-08-13 | 北京君致清科技有限公司 | Method for floatation of apatite using collector prepared from illegal cooking oils |
| CN102240605B (en) * | 2010-05-12 | 2014-08-13 | 北京君致清科技有限公司 | Preparation method, application and using process of floating agent prepared from drainage oil |
| CN103331212B (en) * | 2013-07-12 | 2014-12-24 | 武汉工程大学 | Carbonate phosphorite reverse flotation collecting agent and preparation method thereof |
| CN103357509B (en) * | 2013-07-12 | 2014-12-24 | 武汉工程大学 | Reverse flotation collecting agent of cellophane and preparation method thereof |
| CN103357510B (en) * | 2013-07-26 | 2014-12-24 | 武汉工程大学 | Cellophane positive flotation collector and preparation method of cellophane positive flotation collector |
| 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 (1)
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|---|---|---|---|---|
| CN1579641A (en) * | 2003-08-12 | 2005-02-16 | 贵州福泉市华美磷业有限责任公司 | Oxidized ore floating collector |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1579641A (en) * | 2003-08-12 | 2005-02-16 | 贵州福泉市华美磷业有限责任公司 | Oxidized ore floating collector |
Non-Patent Citations (2)
| Title |
|---|
| 王荣.用氯化的方法改善脂肪酸类捕收剂的浮选性能.《矿产综合利用》.1992,1-4. * |
| 黄齐茂等.新型a-取代脂肪酸衍生物类磷矿浮选捕收剂(I).《武汉工程大学学报》.2008,第30卷(第2期),15-17. * |
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