CN103721854A - Combinatorial method for novel foaming agent with high selectivity and high foaming characteristics - Google Patents
Combinatorial method for novel foaming agent with high selectivity and high foaming characteristics Download PDFInfo
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- CN103721854A CN103721854A CN201310744548.2A CN201310744548A CN103721854A CN 103721854 A CN103721854 A CN 103721854A CN 201310744548 A CN201310744548 A CN 201310744548A CN 103721854 A CN103721854 A CN 103721854A
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- foaming agent
- foaming
- tetraethylene glycol
- flotation
- butyl alcohol
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Abstract
The invention specifically relates to a combinatorial method for surfactant composition, namely, foaming agent with high selectivity and high foaming characteristics. The combinatorial method is characterized in that.
Description
Technical field
The invention belongs to mineral manufacture field, relate to a kind of combined method of foaming agent-surface activator composition.
Background technology
Froth flotation is, by the surface nature difference of different minerals, the not same-action of liquids and gases in ore pulp is realized to sorting.Wherein bubble is carrier, and mineral grain is carrier.By a kind of namely foaming agent of floating agent, obtaining stabilise bubbles is the prerequisite that flotation can efficiently be carried out.The disposal ability of flotation device or flotation column and economic indicator, froth bed thickness or water yield with the fluid dynamics parameter in collecting district as inflation rate, at most, in Air Bubble Size and distribution situation and selected district have direct relation.Although the physical features such as the foaming mode of above-mentioned parameter and floatation equipment, foam maker aperture, fluid flow pattern, air quality are relevant, but the use of floating agent is the kind of foaming agent especially, for the each flotation performance parameter in twoth district, there is more directly effect.Kind, the importance of quantity in froth flotation of foaming agent are more and more getting the nod in recent years.
Foaming agent is a kind of heteropolarity surfactant, by polar group and nonpolar group two parts, formed, thereby can directed absorption and arrangement on gas-liquid interface.Foaming agent is closely related with the character of these two groups.In flotation, foaming agent mainly contains two purposes: good fluid dynamics parameter (being high selectivity) is provided in collecting district and sufficient depth of foam and water yield (being high foaming characteristic) is provided in selected district.The most of foaming agents that have at present industrial value in international coverage, all belong to two compound family categories widely: a class is that (chemical general formula is C to fatty alcohol
nh
2n+1oH) and an other class ether alcohol class (chemical general formula C
nh
2n+1(C
3h
6o)
moH or C
nh
2n+1(C
2h
4o)
1oH).In alcohols foaming agent, foremost is methyl anyl alcohol (being that isobutyl group methyl benzyl must alcohol, MIBC), and its chemical constitution is C
6h
13oH, industrially produces in a large number, and feature is selectively good thereby be widely used in metallic ore flotation, has accounted in the international market the half of foaming agent consumption.And the DowFroth250 that U.S.'s Dow Chemical (Dow Chemicals) company produces is as the most famous one in ether alcohol class foaming agent, in ore dressing circle, enjoy great prestige very many.Its feature is that consumption is few, flotation speed fast, frothing capacity is more stable.On international market, the output of ether alcohol class and aliphatic alcohols foaming agent accounts for the more than 90% of the total consumption of metallic ore floatation frother.Two class foaming agents can share a general formula and represent its chemical constitution: R (X)
noH, wherein R represents H or alkane chain C
nh
2n+1, X represents expoxy propane (PO, or C
3h
6o) or oxirane (EO, or C
2h
4o).
Identify the effect quality of foaming agent, should depend primarily on its selective and foaming characteristic.Selective good performance characteristic is that the controlled easy control of bubble stabilizes, Air Bubble Size, the foaming rate of climb are slower; The performance characteristic that foaming characteristic is good is that froth bed is stable, water yield is large.Although the foaming agent such as MIBC and DowFroth250 is used extensively, but how to take into account high selectivity and high foaming characteristic, how to make in other words two specific characters roll into one, and can follow according to demand and reach independent control selective or foaming characteristic by adjusting wherein a kind of foaming agent dosage, be the difficult point of foaming agent research and selection aspect always.In general, aliphatic alcohols foaming agent to the control of selective aspect better but foaming characteristic is poor; And the foaming characteristic of ether alcohol class foaming agent better but selectively not strong.Both can not take into account and just can not make floatation indicators reach optimization.But, experimental results demonstrate the just simple two kinds of dissimilar foaming agents of combination that add, as mixed DowFroth250 and MIBC, can not play the effect of 1+1; On the contrary, even can obviously reduce flotation efficiency.However, since this possible research and development application direction is used in the mixing (or combination) that proposes medicament in the international ore dressing meeting in Stockholm in 1945, as the mode of simple, an easy row, instant effect, the mixing of medicament is used and has been caused that people's concern is also developed rapidly.
(being also composite reagent) used in the mixing of floating agent, and object is the cooperative effect improving between medicament.
And the cooperative effect of medicament can be defined as: in the multicomponent system of two or more floating agent composition, floatation indicators is significantly greater than the index sum that each medicament is used separately under the same conditions.Compared with collecting agent, the mixed research of foaming agent is more late.The mixed foaming agent in flotation workshop is abroad comparatively extensive, as the copper ore floatation workshop of the U.S. has, more than 50% uses two kinds of foaming agents simultaneously; Triethoxybutane and methyl anyl alcohol intermixture are used in Zambia workshop.A part facts have proved the mixed generally than using and can obtain better effect separately of medicament.The practice that it should be noted that not all pharmacy mix is all successful; In most of situation, foaming agent is mixed, and what present is without cooperative effect or anti-synergistic effect.Canada once tried out in certain workshop the mixing foaming agent of glycol polypropylene and methyl anyl alcohol, cause organizing front two grooves in flotation cell and occur the ore deposit liquid level decline non-foam generation of serious last two grooves of ' race groove ' phenomenon, greatly affected final economy and production target.The kind that China's foaming agent is used is relatively less, and foaming agent is mixed also in research and starting stage.
Mixed foaming agent is studied development in recent years rapidly and is formed system.Main Viewpoints is that, at the fundamental property that mixes main foaming agent decision bubble in foaming agent, auxiliary foaming agent affects other character of flotation as water yield.In consumption adjustment, foaming agent total amount can change, but the ratio of main and auxiliary foaming agent is generally constant.Also have some recent studies ons to find, under a kind of environment of specific foaming agent, the surfactant that adds some itself to there is no foamability, can produce good cooperative effect, much bigger while using this kind of foaming agent separately as foamability ratio.Much sortings facts have proved, after medicament combination, compared with independent use, what result had can improve the rate of recovery, and what have can improve concentrate grade, and what have can improve flotation rate.Foaming agent is mixed can also reduce its reagent consumption because produce cooperative effect.
However, the mixed research of existing foaming agent also has many deficiencies, and the one, do not carry out the system research of relation between foaming agent molecular structure-flotation performance.Only have on this basis, could rationally propose according to object purposes candidate scheme the checking of mixed foaming agent kind; The 2nd, do not have can characterize means and the parameter of foaming agent on flotation performance impact in broad sense.Existing most of research can only prove that the mixed foaming agent scheme of its recommendation can produce cooperative effect in certain concrete mineral sampling test by non-quantification means, and by the sample ore of final acquisition, calculates concentrate grade, the rate of recovery etc. and carry out side confirmation conclusion.The method limitation is strong, does not possess dissemination; The 3rd, between foaming agent, the research of interactional mechanism is considerably less.
Intuitively, the assessment of the selective and foaming characteristic of foaming agent should be started with on the impact of flotation bubble from foaming agent molecule, that is: 1) control Air Bubble Size, slows down bubble merging; 2) extend bobble rise velocity and the time of staying in ore pulp; 3) reinforced foam layer is stablized and water yield.Measurement and the characterization method of corresponding above foaming agent performance, by 1) bubble observation analysis cabin, measure the big or small D that bubbles
32; 2) gas-liquid ratio analyzer, measures gas liquid ratio E
greflect bubble floating speed; 3) water reclaims automatic measuring unit, monitoring water yield J
wOcomplete.
The mixed object of research foaming agent is to find a kind of foaming agent combined method, can take into account its high selectivity and high foaming characteristic two aspects.Even can be by adjusting the dosage of main and auxiliary foaming agent/surfactant under some extreme cases, realize independent its object selective or foaming characteristic of controlling.
Summary of the invention
The object of the invention is to, propose a kind of assembled scheme of foaming agent/surfactant.Described foaming agent combination can be suited measures to local conditions, and according to the variation of processing the conditions such as the granularity of ore, the inflation rate of floatation equipment, each single foaming agent dosage in combining by adjustment, distinguishes the independent selective and foaming characteristic of optimizing foaming agent of controlling.
For realizing above-mentioned object, medicament provided by the invention technical scheme mixed and checking is as follows:
Step 1: bubble astrodome, gas-liquid ratio analyzer and water are installed respectively and are reclaimed automatic measuring unit in top, middle part and the bottom of 3.5mx0.1m flotation column, by increase gradually n-butyl alcohol (C in flotation column in water-gas binary system
4h
10the mode of concentration O) is measured its critical merger concentration (seeing Fig. 1);
Cloth rapid 2: select a part of representational n-butyl alcohol concentration from low to high as flotation column initial concentration; Progressively increase tetraethylene glycol (C
8h
18o
5) concentration; Under each concentration conditions, measure Air Bubble Size (Fig. 2), gas liquid ratio (Fig. 3) and water yield (Fig. 4);
Step 3: gather measurement data and analyzed.Test result proves: 1) rising of tetraethylene glycol concentration on Air Bubble Size without impact; 2) increase of tetraethylene glycol concentration and gas liquid ratio, and water yield increase to direct ratio; 3), when n-butyl alcohol concentration is critical merger concentration, when tetraethylene glycol concentration is greater than 120ppm, gas liquid ratio and water yield are all without obviously promoting; 4) under identical tetraethylene glycol concentration conditions, increase n-butyl alcohol concentration and make it be greater than critical merger concentration, gas liquid ratio and water yield are without obvious lifting;
Step 4: according to result and consider reagent cost, determine that n-butyl alcohol is main foaming agent, determine the Air Bubble Size in collecting district; Tetraethylene glycol is auxiliary foaming agent, affects the froth bed thickness in ascent rate and the selected district of bubble in collecting district; In most of the cases, n-butyl alcohol concentration 80ppm, tetraethylene glycol 120ppm can reach optimum efficiency (being high selectivity and high foaming characteristic); Under the extreme cases such as, mineral clay content height large at mineral grain, the consumption of main and auxiliary foaming agent is adjustable;
Step 5: use same flotation conditions and process, take fluid dynamics parameter as foundation, make comparisons with the most widely used several commercial foaming agents on international market, result verification the superiority (the results detailed in Table) of combination of n-butyl alcohol and tetraethylene glycol, be gas liquid ratio larger (mapping bobble rise velocity is less, selectively better) and water yield larger (mapping frothing capacity is better).
Table 11-butanols/tetraethylene glycol combination and the application assessment result table of other commercial foaming agent in flotation
* at critical radius, produce the respective value in concentration
1 is provided by Canadian Aldrich-Sigma company.
2 are provided by U.S. Flottec company
3 are provided by U.S. Dow Chemical company
4 are provided by Switzerland Nasaco company
Described test reaction conditions is: floatation process is the circulatory system; 28 liters of ore pulp amounts in post; Room temperature (20-22 ℃) condition; Aqueous vapor two-phase; Inflation rate 0.5cm/s; The pore size of bubble generator is 5 microns; Displacement 1600 ml/min; Foam layer height is constant O.5 centimetre.
Described Air Bubble Size refers to the Sauter average diameter size (D of all bubble samples of collecting
32), computing formula is
wherein D
ifor the average diameter of single isolated bubbles.
Described gas liquid ratio refers in the collecting district of flotation the ratio of gas (bubble) volume and liquid (ore pulp) volume in fixed volume, and computing formula is
general range territory is 4～20%.
Described water yield refers to per surface area drainage rates J
wO.
Described critical merger concentration refers to a specific concentrations of foaming agent, in flotation along with the increase of foaming agent concentration, bubble merging degree reduces, and while finally reaching a specific concentrations, bubble merging stops.During foaming agent is used as lower than this concentration, the unstable size of bubble is unequal; Higher than this concentration, cost increases and may cause the reverse of foaming agent performance to play minus effect.
The combined method of foaming agent-surface activator composition of the present invention, has following characteristics:
The present invention choose two kinds of simple substance foaming agents or the surfactant n-butyl alcohols of use and tetraethylene glycol chemical constitution is simple and easy to degraded, without collecting effect, smell low nontoxic, wide material sources easily obtain, relative low price;
2. the assembled scheme of two kinds of compositions of the present invention is easy to operate in actual use, practical;
3. experimental results show that all kinds of mineral grains surface to n-butyl alcohol and tetraethylene glycol without suction-operated, the outer other kinds main flow floating agent of foaming agent and n-butyl alcohol and tetraethylene glycol are without cooperative effect;
The present invention generate novel foaming agent compared with traditional foaming agent, fluid dynamics parameter (Air Bubble Size
D
32, gas liquid ratio E
gwith water yield J
wO) index better embodied the two excellent of selective and foaming characteristic,
Can obtain in practice good income.
Accompanying drawing explanation
Fig. 1: the mensuration of the Air Bubble Size of n-butyl alcohol and critical merger concentration;
Fig. 2: the impact of the combined concentration of n-butyl alcohol and tetraethylene glycol on bubble;
Fig. 3: the impact of the combined concentration of n-butyl alcohol and tetraethylene glycol on gas liquid ratio;
Fig. 4: the impact of the combined concentration of n-butyl alcohol and tetraethylene glycol on water yield.
The specific embodiment
Below in conjunction with accompanying drawing, specific embodiment is elaborated.Should be emphasized that, following explanation is only exemplary, rather than in order to limit the scope of the invention and to apply.
The mineral sample providing take Brisbane ,Australia JKMRC mining industry laboratory is as raw ore.Sample ore belongs to dip-dye type Skarn Cu ore.According to multielement analysis result, main valuable mineral is chalcopyrite, pyrite, bornite, vitreous copper; Gangue has silicate mineral as quartz, the saturating stone of brightness, sericite, chlorite etc., and a small amount of carbonate mineral is as dolomite, calcite.In ore, also contain a small amount of clay mineral, easily argillization.Chalcopyrite disseminated grain size is 0.0006～0.05mm.20% left and right chalcopyrite is 10～20 μ m and is distributed in gangue mineral or pyrite.This ore belongs to difficult ore dressing.
The flotation column of 3.5 meters of high 10 cm diameters for experiment, bubble generator is 5 μ m porous metals foam makers.Float test is long run test, and sulphide ore bulk flotation collecting agent is ethyl xanthate, and PH adjusting agent is lime.Flotation column inflation rate is 0.75cm/s, and giving ore deposit speed is 1200mL/min, and foam layer height is made as 5cm.The grinding particle size entering before roughing flotation accounts for 85% for-74 μ m.
In order to check foaming agent of the present invention-surfactant combination (n-butyl alcohol concentration 80ppm, tetraethylene glycol 120ppm) effectiveness, in the situation that other condition is consistent and other commercial foaming agent (MIBC of being used herein) contrast.The comparing result demonstration that sulfide flotation is roughly selected, in the situation that sulphide ore character is substantially the same, productive rate has improved 7.18 percentage points, and concentrate copper recovery has improved 6.48 percentage points (referring to following table 2).
Result is roughly selected in the bulk flotation of table 2-sulphide ore
The sample coal providing take Canadian BC province Elk Valley Coal (EVC) company is as raw coal.Ature of coal is rich coal, middle iso flotability, and easily argillization, containing ash content 24.67%, carbon 68.77%, sulphur 1.17%.Ash content Mineral Component has quartz, clay mineral, pyrite and fraction carbonate mineral.Grade aspect ash content mainly concentrate on-0.1mm fine fraction and+1mm coarse fraction between.
The flotation column of 3.5 meters of high 10 cm diameters for experiment, bubble generator is 5 μ m porous metals foam makers.Float test is long run test, and floatability and the hydrophobicity of coal are better, does not need to add collecting agent and adjusting agent.PH value remains on 7.1 left and right in process of the test.Flotation column inflation rate is 0.5cm/s, and giving ore deposit speed is 1200mL/min, and foam layer height is made as 5cm.The feed particle size of coal separation accounts for 75% for-0.15mm.
In order to check foaming agent of the present invention-surfactant combination (n-butyl alcohol concentration 80ppm, tetraethylene glycol 120ppm) effectiveness, in the situation that other condition is consistent and other commercial foaming agent (MIBC of being used herein) contrast.The contrast of coal separation result shows, in the case of the selected character of coal basic the same, use n-butyl alcohol and tetraethylene glycol to combine not only clean coal yield and improved 3 percentage points nearly, and floatation clean coal ash content declined 0.4 percentage point (referring to following table 3).
Table 3-coal floatation result
Above-described embodiment is the preferred embodiment of the present invention, but embodiments of the present invention are not restricted to the described embodiments, and the change that other any the present invention of not deviating from does all should be equivalent substitute mode, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (3)
1. a combined method that is used as the combination foaming agent that can have high selectivity and high foaming characteristic characteristic concurrently, is characterized in that n-butyl alcohol (C
4h
10o) be the main foaming agent of flotation, determine collecting district Air Bubble Size; Tetraethylene glycol (C
8h
18o
5) as auxiliary foaming agent, affect the foamability in collecting district bobble rise velocity and selected district.Order of addition is tetraethylene glycol after first n-butyl alcohol.
2. the combined method of a kind of foaming agent-surface activator composition according to claim 1, is characterized in that, it is n-butyl alcohol 80ppm that the best of said composition is added concentration, tetraethylene glycol 120ppm.
3. the combined method of a kind of foaming agent-surface activator composition according to claim 1, it is characterized in that, according to the difference of the character condition of processing mineral, the adjustable range of the interpolation concentration of said composition is n-butyl alcohol 60-100ppm, tetraethylene glycol 90-150ppm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085827A (en) * | 1993-01-08 | 1994-04-27 | 常熟市白雀助剂厂 | Foaming agent for flotation of rare-earth ore and preparation method thereof |
| CN102614994A (en) * | 2012-03-30 | 2012-08-01 | 河南省核力科技发展有限公司 | Foaming agent for mineral flotation and preparation method thereof |
| CN102716810A (en) * | 2012-06-21 | 2012-10-10 | 冯益生 | Foaming agent for flotation |
-
2013
- 2013-12-31 CN CN201310744548.2A patent/CN103721854A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085827A (en) * | 1993-01-08 | 1994-04-27 | 常熟市白雀助剂厂 | Foaming agent for flotation of rare-earth ore and preparation method thereof |
| CN102614994A (en) * | 2012-03-30 | 2012-08-01 | 河南省核力科技发展有限公司 | Foaming agent for mineral flotation and preparation method thereof |
| CN102716810A (en) * | 2012-06-21 | 2012-10-10 | 冯益生 | Foaming agent for flotation |
Non-Patent Citations (1)
| Title |
|---|
| WEI ZHANG等: "Determining independent control of dual-frother systems-Gas holdup, bubble size and water overflow rate", 《MINERALS ENGINEERING》 * |
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Application publication date: 20140416 |