CN102120197A - Mineral floatation foaming agent and preparation method thereof - Google Patents
Mineral floatation foaming agent and preparation method thereof Download PDFInfo
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- CN102120197A CN102120197A CN2010105600206A CN201010560020A CN102120197A CN 102120197 A CN102120197 A CN 102120197A CN 2010105600206 A CN2010105600206 A CN 2010105600206A CN 201010560020 A CN201010560020 A CN 201010560020A CN 102120197 A CN102120197 A CN 102120197A
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Abstract
The invention discloses a mineral floatation foaming agent and a preparation method thereof. The mineral flotation foaming agent is prepared from the raw materials of fatty alcohol with a branch chain and epoxy chloropropane by epoxidation and sulfonation. One end of the foaming agent has polar groups of -OH and -SO3H, and the other end of the foaming agent has fatty alcohol sulfonate with straight chain alkyls or branch chain alkyls of different carbon atoms. The raw materials of the mineral flotation foaming agent are widely available and cheap, the synthesis process is simple, the synthesis conditions are mild, the reaction is easy to control, and the industrialization is easy to realize. The foaming agent has good aerophily and hydrophily as well as excellent foaming performance. The degradation speed of the foaming agent is higher than that of the terpineol with an annular structure, thereby being favorable for environmental protection. Compared with the existing product, the mineral recovery rate is increased by 0.5-2%, and the using cost is lowered by 10-20%.
Description
Technical field
The invention belongs to the ore floatation technique field, be specifically related to a kind of mineral flotation foaming agent.Simultaneously, the invention still further relates to the preparation method of this foaming agent.
Background technology
Foaming agent is one of main medicament of ore floatation.The a large amount of at present foaming agents that use in China mine are terpinols, generally more kinds are not available in enterprise, therefore, and when considering from the raising of medicament angle or improving sorting index, people often pay attention to working from aspects such as collecting agent, adjustment agent, and have ignored the dynamic role of foaming agent.Long term studies shows that the performance of foaming agent is significant to the influence of floatation indicators.Foaming agent generally is the surface reactive material of heteropolarity.Containing polar group in molecular structure, as hydroxyl-OH, is nonpolar group at the other end of molecule, as alkyl-R.Because the asymmetry of foaming agent molecular structure, in the ore pulp of foaming agent is arranged, charge into a large amount of air after, the foaming agent molecule will preferentially be adsorbed on the gas-water interface.Hydrophobic nonpolar group tries hard to move into the water surface in the leaving water, and hydrophilic polar group part then tries hard to enter in the water.
Because it is active that the chemism of alcohols can not show a candle to carboxylic acids, so this class foaming agent does not have collecting and has only foaming characteristic.The solubility of alcohols foaming agent is generally bigger, so lather quickness is fast, foam is sticking, and froth breaking is easy, does not have a collecting, is difficult for carrying secretly the thin mud of gangue in foam, is beneficial to the raising grade of ore.As containing hydroxyl, ether (polar group that two classes are desirable), hydration is strong in the foaming agent, no collecting effect, and the influence of pH value is little, contains sulfonic group, and foamability is strong, and close solidity is strong.Synthetic branched fatty alcohol floatation frother through sulfonation, etherificate has frothing capacity preferably.
The widest a kind of floatation frother of external use is a methyl isobutyl carbinol, also claims methyl anyl alcohol, code name MIBC.This product is to be that raw material forms through condensation with acetone, because acetone need obtain by grain fermentation and through cumene method production, and cost of material height not only, and also domestic production technology does not reach requirement yet.At present, the MIBC floatation frother there is no production at home, all relies on import, and high cost is very limited its application.In the prior art, Chinese patent CN1403206A once disclosed " a kind of mineral foaming agent and preparation thereof ", to contain branched alcohol and oxirane or propylene oxide foaming agent.But this method need be carried out under high temperature, hyperbaric environment, and reaction condition is comparatively harsh, and final products are not with sulfonic group, so foam performance is unsatisfactory.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of reaction condition gentleness is provided, is easy to control, conversion ratio height, mineral flotation foaming agent that frothing capacity is good.
The present invention also aims to provide a kind of method for preparing described mineral flotation foaming agent.
Purpose of the present invention is achieved by the following technical programs.
Except as otherwise noted, percentage of the present invention is percetage by weight.
A kind of mineral flotation foaming agent is characterized in that: described foaming agent be an end have-OH (hydroxyl) ,-SO
3The polar group of H (sulfonic group), the other end have the fatty alcohol ether sulfonate of nonpolar group of the straight or branched alkyl of different carbon atoms.
The preparation method of described mineral flotation foaming agent comprises the steps:
1, branched fatty alcohol is mixed according to weight ratio 1: 1～4 with epoxychloropropane, add the triethyl benzyl ammonia chloride account for mixed material weight 0.1%～0.5% or TBAB as catalyst, add account for mixed material weight 10%～35%, concentration is the sodium hydroxide solution of percetage by weight 30%～60%, stirring reaction is 2～5 hours under 50～90 ℃ of conditions, be cooled to room temperature, unreacted epoxychloropropane is removed in distillation, obtains the chloro fat alcohol ether; Described branched fatty alcohol is a kind of in isopropyl alcohol, isobutanol or the tert-butyl alcohol;
2, the chloro fat alcohol ether that step (1) is obtained at room temperature stirs the sodium hydroxide solution that adds 0.5～2mol/L, and the sodium hydroxide solution addition is 10%～20% of a chloro fat alcohol ether weight, stirs 0.5～1 hour, obtains fatty alcohol epoxy radicals ether;
3, with sodium sulfite with make saturated solution after sodium hydrogensulfite mixes by mass ratio at 5: 1, the fatty alcohol epoxy radicals ether that obtains according to weight ratio 1: 1～3 and step (2) mixes again, under 50～80 ℃ of temperature, reacted 0.5～2 hour, be cooled to room temperature, at pressure is reduction vaporization 0.5～1 hour under 0.06～0.08MPa condition, adds 10～15ml isopropyl alcohol, leaves standstill 18～30 hours, leach the inorganic salts that are precipitated out, promptly obtain required mineral flotation foaming agent.
Compare with prior art, the present invention has the following advantages:
Though some are arranged in 1 prior art is the report of the synthetic floatation frother in basis with the industrial chemicals, but really realize the few of the industrialization and the marketization, reason or be the production cost height, or be the difficult control of production technology, severe reaction conditions, or raw material is limited etc.The present invention is that raw material prepares a kind of floatation frother efficiently by epoxidation, sulfonation with branched fatty alcohol and epoxychloropropane, and its raw material sources are extensive, and are inexpensive, and synthesis technique is simple, synthesis condition gentleness, easy control of reaction system, easily industrialization.
2, floatation frother one end of the present invention has the nonpolar group of alkyl, and the other end has hydroxyl, ether and sulfonic polar group, makes foaming agent possess good close gas and hydrophilicity, is a kind of excellent performance, floatation frother efficiently.
3, this foaming agent is that raw material is synthetic with the fatty alcohol, is chain structure, and is faster than the terpinol degradation speed of circulus, helps environmental protection.
4, owing to the excellent frothing capacity of this foaming agent, lower than general foaming agent consumption in mineral floating, mineral recovery rate exceeds 0.5%～2%;
5, because the advantage of aspects such as cost of material, production technology, properties of product obtains under the identical rate of recovery situation at mineral, floatation frother of the present invention is than the use cost low 10%～20% of like product.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail, but protection scope of the present invention is not limited to this.
Embodiment 1
Getting isopropyl alcohol 10g and epoxychloropropane 30g puts in the round-bottomed flask of 150ml, stirring and evenly mixing adds triethyl benzyl ammonia chloride 0.10g and mass concentration and is 40% sodium hydroxide solution 12ml successively, is heated to 60～65 ℃, continue to stir 3 hours, reaction finishes product is cooled to room temperature.Then product is placed the Rotary Evaporators decompression distillation to go out the intact epoxychloropropane of unreacted, get product chloro fat alcohol ether.Get chloro fat alcohol ether 30g and put in the round-bottomed flask of 100ml, stir and slowly add the sodium hydroxide solution 5g of 1.0mol/L, stirring reaction 50min under the room temperature obtains fatty alcohol epoxy radicals ether.With sodium sulfite with make saturated solution after sodium hydrogensulfite mixes by mass ratio at 5: 1.Getting fatty alcohol epoxy radicals ether 10g, sodium sulfite and sodium hydrogensulfite saturated solution 20g joins in the round-bottomed flask of 100ml successively, be heated with stirring to 55～60 ℃, continue to stir 1 hour, be cooled to room temperature after having reacted, and product placed Rotary Evaporators, at pressure is reduction vaporization 40min under the 0.08MPa condition, steams 75%～85% moisture.Enriched product adds the 10ml isopropyl alcohol and stirs, and leaves standstill 24 hours, removes by filter sediment, promptly gets fatty alcohol ether sulfonate foaming agent product.This product frothing capacity is stable, is applicable in the flotation of general copper-sulphide ores, copper mine tailing.
Embodiment 2
Getting isobutanol 12g and epoxychloropropane 30g puts in the round-bottomed flask of 150ml, stirring and evenly mixing adds TBAB 0.10g and mass concentration and is 50% sodium hydroxide solution 15ml successively, is heated to 70～75 ℃, continue to stir 4 hours, reaction finishes product is cooled to room temperature.Then product is placed the Rotary Evaporators decompression distillation to go out the intact epoxychloropropane of unreacted, get product chloro fat alcohol ether.Get chloro fat alcohol ether 30g and put in the round-bottomed flask of 100ml, stir and slowly add the sodium hydroxide solution 6g of 0.8mol/L, stirring reaction 60min under the room temperature obtains fatty alcohol epoxy radicals ether.With sodium sulfite with make saturated solution after sodium hydrogensulfite mixes by mass ratio at 5: 1.Getting fatty alcohol epoxy radicals ether 10g, sodium sulfite and sodium hydrogensulfite saturated solution 25g joins in the round-bottomed flask of 100ml successively, be heated with stirring to 60～65 ℃, continue to stir 1.5 hours, be cooled to room temperature after having reacted, and product to Rotary Evaporators, at pressure is reduction vaporization 50min under the 0.07MPa condition, steams 75%～85% moisture; Enriched product adds the 12ml isopropyl alcohol and stirs, and leaves standstill 18 hours, removes by filter sediment, promptly gets fatty alcohol ether sulfonate foaming agent product.This product micro air bubble is more, and it is highly high to bubble, and is applicable to the flotation of plumbous zinc ore, copper concentrate.
Embodiment 3
Getting tert-butyl alcohol 10g and epoxychloropropane 25g puts in the round-bottomed flask of 150ml, stirring and evenly mixing adds TBAB 0.15g and mass concentration and is 60% sodium hydroxide solution 15ml successively, is heated to 80～85 ℃, continue to stir 5 hours, reaction finishes product is cooled to room temperature.Then product is put the Rotary Evaporators decompression distillation and go out the intact epoxychloropropane of unreacted, get product chloro fat alcohol ether.Get chloro fat alcohol ether 25g and put in the round-bottomed flask of 100ml, stir and slowly add the sodium hydroxide solution 2.5g of 0.5mol/L, stirring reaction 30min under the room temperature obtains fatty alcohol epoxy radicals ether.With sodium sulfite with make saturated solution after sodium hydrogensulfite mixes by mass ratio at 5: 1, getting above-mentioned fatty alcohol epoxy radicals ether 12g, saturated solution 36g joins in the round-bottomed flask of 150ml successively, be heated with stirring to 60～65 ℃, continue to stir 0.5 hour, be cooled to room temperature after having reacted, and product placed Rotary Evaporators, and be reduction vaporization 60min under the 0.08MPa condition at pressure, steam 75%～85% moisture; Enriched product is added the 15ml isopropyl alcohol stir, left standstill 30 hours, remove by filter sediment, promptly get fatty alcohol ether sulfonate foaming agent product.This product frothing capacity is good, and stability better can be used for the flotation of copper sulfide, cupric oxide ore.
Application Example
The embodiment of the invention 3 gained floatation frothers and terpinol (2
#Oil), the comparing result in MIBC flotation ore deposit see Table 1, table 2.
Table 1 embodiment 3 and terpinol (2
#Oil) result of flotation copper mine
Annotate: two kinds of all collecting agents of method flotation are butyl xanthate 500g/t in the table.
The result of table 2 embodiment 3 and MIBC flotation zinc concentrate
Annotate: two kinds of all collecting agents of method flotation are butyl xanthate 600g/t in the table.
Claims (2)
1. mineral flotation foaming agent, it is characterized in that: described foaming agent is that an end has hydroxyl, sulfonic polar group, the other end has the fatty alcohol ether sulfonate of nonpolar group of the straight or branched alkyl of different carbon atoms.
2. prepare the method for the described mineral flotation foaming agent of claim 1, comprise the steps:
(1) branched fatty alcohol is mixed according to weight ratio 1: 1～4 with epoxychloropropane, add the triethyl benzyl ammonia chloride account for mixed material weight 0.1%～0.5% or TBAB as catalyst, add account for mixed material weight 10%～35%, concentration is the sodium hydroxide solution of percetage by weight 30%～60%, stirring reaction is 2～5 hours under 50～90 ℃ of conditions, be cooled to room temperature, unreacted epoxychloropropane is removed in distillation, obtains the chloro fat alcohol ether; Described branched fatty alcohol is a kind of in isopropyl alcohol, isobutanol or the tert-butyl alcohol;
(2) the chloro fat alcohol ether that step (1) is obtained at room temperature stirs the sodium hydroxide solution that adds 0.5～2mol/L, and the sodium hydroxide solution addition is 10%～20% of a chloro fat alcohol ether weight, stirs 0.5～1 hour, obtains fatty alcohol epoxy radicals ether;
(3) with sodium sulfite with make saturated solution after sodium hydrogensulfite mixes by mass ratio at 5: 1, the fatty alcohol epoxy radicals ether that obtains according to weight ratio 1: 1～3 and step (2) mixes again, under 50～80 ℃ of temperature, reacted 0.5～2 hour, be cooled to room temperature, at pressure is reduction vaporization 0.5～1 hour under 0.06～0.08MPa condition, adds 10～15ml isopropyl alcohol, leaves standstill 18～30 hours, leach the inorganic salts that are precipitated out, promptly obtain required mineral flotation foaming agent.
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Cited By (4)
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| CN103819314A (en) * | 2013-12-31 | 2014-05-28 | 张炜 | Preparation method for acyclic compound used as foaming agent |
| CN106693268A (en) * | 2015-11-12 | 2017-05-24 | 上海汇友精密化学品有限公司 | Water-series fire extinguishing agent |
| CN107138289A (en) * | 2017-06-26 | 2017-09-08 | 新沂市中诺新材料科技有限公司 | A kind of cationic selects flotation frother |
| CN108212538A (en) * | 2018-01-31 | 2018-06-29 | 中南大学 | A kind of alkyl thioether group alcohol compound and preparation method and application |
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| US7427588B2 (en) * | 2007-01-12 | 2008-09-23 | Paul Daniel Berger | Ether sulfonate surfactants and process for making same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819314A (en) * | 2013-12-31 | 2014-05-28 | 张炜 | Preparation method for acyclic compound used as foaming agent |
| CN106693268A (en) * | 2015-11-12 | 2017-05-24 | 上海汇友精密化学品有限公司 | Water-series fire extinguishing agent |
| CN107138289A (en) * | 2017-06-26 | 2017-09-08 | 新沂市中诺新材料科技有限公司 | A kind of cationic selects flotation frother |
| CN107138289B (en) * | 2017-06-26 | 2019-07-12 | 乌拉特前旗西沙德盖钼业有限责任公司 | A kind of cationic selects flotation frother |
| CN108212538A (en) * | 2018-01-31 | 2018-06-29 | 中南大学 | A kind of alkyl thioether group alcohol compound and preparation method and application |
| CN108212538B (en) * | 2018-01-31 | 2019-04-26 | 中南大学 | A kind of alkyl thioether group alcohol compound and the preparation method and application thereof |
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