CN104307640A - Collecting agent for phosphorite reverse flotation calcite - Google Patents
Collecting agent for phosphorite reverse flotation calcite Download PDFInfo
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- CN104307640A CN104307640A CN201410622082.3A CN201410622082A CN104307640A CN 104307640 A CN104307640 A CN 104307640A CN 201410622082 A CN201410622082 A CN 201410622082A CN 104307640 A CN104307640 A CN 104307640A
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- collecting agent
- calcite
- reverse flotation
- base ether
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Abstract
The invention discloses a collecting agent for phosphorite reverse flotation calcite, the collecting agent is composed of the components in following mass percent: 40-80% of fatty acid polyoxyethylene ester salt, 14-50% of alkyl polyoxyethylene ether phosphate monoester salt, 5-20% of fatty alcohol polyoxyethylene ether and 1-20% of span 20. The collecting agent is suitable for phosphorite reverse flotation calcite. Compared with the fatty acid collecting agent, the collecting agent has strong collecting capability and high selectivity; compared with the alpha-amido aryl phosphoric acid collecting agent, the price is low, the dosage is little, and the material is convenient. The collecting agent overcomes the defects of processing calcite in phosphorite by conventional flotation processing method that the collecting capability is poor, the recovery rate is low and the medicine cost is high. The collecting agent has obvious superiority on indicators in beneficiation and has new breakthrough.
Description
Technical field
The invention belongs to phosphate rock floating field, be specifically related to the collecting agent of the high selectivity of reverse flotation calcite in phosphorus ore.
Background technology
At present, the phosphorus fine ore of the overwhelming majority is obtained by ore dressing.The object of ore dressing is the gangue mineral removed in phosphorus ore.In the flotation of apatite, siliceous mineral and carbonate mineral are modal gangue contents.Siliceous mineral is quartz or cristobalite, clay mineral and other is as feldspar and mica etc. mainly.Clay mineral removes by modes such as adopting scouring, desliming more in the ore dressing of phosphorus ore; Quartz, calcedony etc. also show the floatability more poor than apatite in flotation, even if disseminated grain size is fine, generally still relatively good choosing, can be removed by direct flotation.Carbonate gangue is calcite and dolomite mainly.White Cloud Mountain generally adopts reverse flotation in flotation of phosphate rock, suppresses phosphate reverse flotation White Cloud Mountain de-magging, because the floatability of dolomite is better than phosphate, especially in acid condition.The current comparative maturity of this technique, can be removed to concentrate containing below MgO0.8% by the collophane containing MgO4 ~ 5%.The ground such as China's Haikou, Kunming, peacefulness, Yichang builds up large-scale flotation mill, all adopts this floatation process, Be very effective.
Will isolate calcite from phosphate mineral such as francolite always thinks very difficult.These two kinds of mineral belong to identical cation type, are all Ca
2+.This point is different from dolomite, and dolomite is except containing Ca
2+, also have Mg
2+.The all available the moon collecting agent of these two kinds of mineral such as aliphatic acid etc. makes it to float, and within the scope of pH widely, has very close floatability.In apatite and calcite system, under certain condition, Calcite Surface transforms to apatite, and change condition, apatite surface also can change into calcite.It is more difficult that this just causes from phosphate ore, be separated calcite.
Hu Yuehua, Wang Dian assistant showed in " research of α-amido aryl phosphoric acids flotation phosphate lime stone and calcite " (" non-ferrous metal " first phase in February, 1992): in alkaline medium, α-amido aryl phosphoric acids is larger in the adsorbance of Calcite Surface, stronger Pu is had to receive ability to calcite, less at apatite surface excess, more weak to the collecting ability of apatite.In α-amido aryl phosphoric acids solution, apatite and Calcite Surface negative electricity current potential increase.Solution equilibria calculates and ir data shows, the active principle of a mono-amido aryl phosphoric acids flotation harvesting adduction is (R
1r
2n R
3cH P (O) O
2h)-in Calcite Surface generation chemisorbed.Sort collophane stone by α-amido aryl phosphoric acids, can obtain containing P
2o
523.06 %, the rough concentrate of the rate of recovery 89.9%, effective more than oxidized paraffin wax soap.But collecting agent α-amido aryl phosphoric acids price is very expensive, synthesis difficulty, the obviously improper collecting agent making cheap rock phosphate in powder.Somebody does collecting agent with dodecylphosphoric acid disodium salt in calcite-apatite system, but DeGrain, collecting agent all has certain collecting ability, poor selectivity to two kinds of mineral.
Summary of the invention
Technical problem to be solved by this invention is for reverse flotation calcite in phosphorus ore in prior art, collecting agent poor selectivity, the problems such as collecting effect is bad, provide the collecting agent to reverse flotation calcite in a kind of efficient, selective good, soluble in water, phosphorus ore that production cost is low.
Technical problem to be solved by this invention is realized by following technical scheme.The present invention is a kind of phosphate reverse flotation collecting agent, is characterized in: this collecting agent is made up of the raw material of following percentage by weight:
Aliphatic acid polyethenoxy base ester salt 40 ~ 80%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 14 ~ 50%;
Aliphatic alcohol polyethenoxy base ether 5 ~ 20%;
Span 20 1 ~ 10%;
The general formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R
1COO(CH
2CH
2O)
nM
Wherein: R
1represent the alkyl of 6 ~ 18 carbon atoms, n=3 ~ 5, M is Ka or Na;
The general formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R
2O(CH
2CH
2O)
nP=O(OM)
2
Wherein: R
2represent the alkyl of 6 ~ twelve carbon atom, n=3 ~ 5, M is Ka or Na.
The general formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R
3O(CH
2CH
2O)
nH
Wherein: R
3represent the alkyl of 6 ~ 18 carbon atoms, n=7 ~ 15.
A kind of phosphate reverse flotation collecting agent of the present invention, further: the preferred weight percent of each raw material is:
Aliphatic acid polyethenoxy base ester salt 55 ~ 65%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 20 ~ 32%;
Aliphatic alcohol polyethenoxy base ether 10 ~ 15%;
Span 20 3 ~ 7%.
A kind of phosphate reverse flotation collecting agent of the present invention, further: the further preferred weight percent of each raw material is: aliphatic acid polyethenoxy base ester salt 55%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 30%;
Aliphatic alcohol polyethenoxy base ether 10%;
Span 20 5%.
The preparation method of a kind of phosphate reverse flotation collecting agent of the present invention is: simply mix under 40 ~ 80 DEG C of conditions.
The collecting agent of a kind of phosphate reverse flotation calcite of the present invention can as the purposes of the collecting agent in the reverse flotation of calcite in phosphorus ore.
Compared with prior art, collecting agent of the present invention has the following advantages: this hybrid collector is with two kinds of anionic collector (aliphatic acid polyethenoxy base ester salt, alkyl polyoxyethylene base ether phosphoric acid monoester salt) be main, be equipped with two kinds of non-ionic surface active agents (aliphatic alcohol polyethenoxy base ether, span 20) composition, based on anionic collector-non-ionic surface active agent eutectoid content and the mechanism of adsorbing of interting, test through a large amount of Chemicals, and the test of actual ore, result of the test shows anionic collector (aliphatic acid polyethenoxy base ester salt, alkyl polyoxyethylene base ether phosphoric acid monoester salt) in polyoxyethylene groups reduce the electrostatic repulsion of polar group, be conducive to the association between two kinds of collecting agents, be equipped with aliphatic alcohol polyethenoxy base ether, span 20 non-ionic surface active agent, form collecting agent-non-ionic surface active agent " eutectoid content ", effect due to " eutectoid content " further promotes the association of anionic collector film, and the interspersed absorption between medicament significantly enhances the critical micelle concentration of collecting agent, both actings in conjunction make the surface-active of medicament be significantly improved, and then show combine medicament between show good synergy.
Containing a large amount of oxyethylene group groups in collecting agent of the present invention, good water solubility, resistance to hard water is strong, and consumption is little.Collecting agent has good selective collecting ability, can the calcite of flotation efficiently, weak to phosphate collecting ability.Collecting agent of the present invention, compared with fatty acid collecting agent, has very strong collecting ability and high selectivity; Compared with the collecting agent of α-amido aryl phosphoric acids class, cheap, consumption is little, draws materials conveniently.When this collecting agent overcomes the calcite in traditional flotation process phosphorus ore, the shortcomings such as collecting ability is not good, the rate of recovery is low, reagent cost is high, show obvious superiority simultaneously, obtain new breakthrough on mineral processing index.
Accompanying drawing explanation
Fig. 1 is the rate of recovery graph of a relation of collector dosage and francolite and calcite.
Detailed description of the invention
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Embodiment 1, a kind of phosphate reverse flotation collecting agent, this collecting agent is made up of the raw material of following percentage by weight:
Aliphatic acid polyethenoxy base ester salt 40%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 50%;
Aliphatic alcohol polyethenoxy base ether 5%;
Span 20 5%;
The general formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R
1COO(CH
2CH
2O)
nM
Wherein: R
1represent the alkyl of 6 ~ 18 carbon atoms, n=5, M are Ka;
The general formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R
2O(CH
2CH
2O)
nP=O(OM)
2
Wherein: R
2represent the alkyl of 6 ~ twelve carbon atom, n=3, M are Na.
The general formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R
3O(CH
2CH
2O)
nH
Wherein: R
3represent the alkyl of 6 ~ 18 carbon atoms, n=7.
Embodiment 2, a kind of phosphate reverse flotation collecting agent, this collecting agent is made up of the raw material of following percentage by weight:
Aliphatic acid polyethenoxy base ester salt 80%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 14%;
Aliphatic alcohol polyethenoxy base ether 5%;
Span 20 1%;
The general formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R
1COO(CH
2CH
2O)
nM
Wherein: R
1represent the alkyl of 6 ~ 18 carbon atoms, n=3, M are Ka or Na;
The general formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R
2O(CH
2CH
2O)
nP=O(OM)
2
Wherein: R
2represent the alkyl of 6 ~ twelve carbon atom, n=5, M are Ka or Na.
The general formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R
3O(CH
2CH
2O)
nH
Wherein: R
3represent the alkyl of 6 ~ 18 carbon atoms, n=15.
Embodiment 3, a kind of phosphate reverse flotation collecting agent, this collecting agent is made up of the raw material of following percentage by weight:
Aliphatic acid polyethenoxy base ester salt 55%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 15%;
Aliphatic alcohol polyethenoxy base ether 20%;
Span 20 10%;
The general formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R
1COO(CH
2CH
2O)
nM
Wherein: R
1represent the alkyl of 6 ~ 18 carbon atoms, n=4, M are Ka or Na;
The general formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R
2O(CH
2CH
2O)
nP=O(OM)
2
Wherein: R
2represent the alkyl of 6 ~ twelve carbon atom, n=4, M are Ka or Na.
The general formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R
3O(CH
2CH
2O)
nH
Wherein: R
3represent the alkyl of 6 ~ 18 carbon atoms, n=7 ~ 15.
Embodiment 4, a kind of phosphate reverse flotation collecting agent, this collecting agent is made up of the raw material of following percentage by weight:
Aliphatic acid polyethenoxy base ester salt 60%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 27%;
Aliphatic alcohol polyethenoxy base ether 10%;
Span 20 3%.
Embodiment 5, a kind of phosphate reverse flotation collecting agent, this collecting agent is made up of the raw material of following percentage by weight:
Aliphatic acid polyethenoxy base ester salt 55%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 30%;
Aliphatic alcohol polyethenoxy base ether 10%;
Span 20 5%.
Embodiment 6, a kind of phosphate reverse flotation collecting agent flotation experiments two:
Artificial mixed ore flotation experiments carries out on XFG hanging trough flotator.The 2.0g raw ore sample taken is francolite and the calcite quality aggregate sample by 1:1 proportioning, put into 50ml flotation cell, add 40ml distilled water, size mixing after 2min, after regulating pH=5 with sulfuric acid, add collecting agent of the present invention (quality proportioning is: laurate polyoxyethylene groups ester sodium salt 60%(polymerization degree n=3), dodecyl polyoxyethylene ether phosphate monoester sodium salt 25%(polymerization degree n=3), lauryl alcohol polyoxyethylene ether 10%(polymerization degree n=10), span 20 5%) stir 3min, flotation 5min, the relation of the rate of recovery of collector dosage and francolite and calcite is shown in Fig. 1.
Embodiment 7, a kind of phosphate reverse flotation collecting agent flotation experiments three:
Somewhere, Yunnan phosphorite ore, essential mineral content is francolite, calcite, quartz and a small amount of dolomite.Raw ore is containing P
2o
525.67%, MgO0.83%, by raw ore after being ground to-200 order content 70%, after adding sulfuric acid 2500g/t raw ore tune pH, add calgon 300g/t again and make inhibitor, add hybrid collector 1200g/t raw ore of the present invention (quality proportioning is: palmitic acid polyoxyethylene groups ester sodium salt 70%(polymerization degree n=5), dodecyl polyoxyethylene ether phosphate monoester sylvite 20%(polymerization degree n=5), tetradecyl alchohol polyoxyethylene ether (polymerization degree n=7) 5%, span 20 5%) carry out laboratory float test, phosphorus concentrate can be obtained at normal temperatures containing P after adopting a thick essence
2o
531.22%, MgO0.90%, flotation recovery rate 86.43%.
Embodiment 8, a kind of phosphate reverse flotation collecting agent flotation experiments four:
Certain chiltern francolite ore deposit external, main gangue mineral is calcite.Raw ore is containing P
2o
527.52%, MgO0.66%, by raw ore after being ground to-200 order content 50%, after adding sulfuric acid 1500g/t raw ore tune pH, add calgon 450g/t again and make inhibitor, (quality proportioning is: stearic acid polyoxyethylene base ester sylvite (polymerization degree n=3) 40% to add hybrid collector 1500g/t raw ore of the present invention, octyl group polyoxyethylene ether phosphate monoester sodium salt (polymerization degree n=5) 40%, lauryl alcohol polyoxyethylene ether (polymerization degree n=10) 10%, span 20 10%) carry out laboratory float test, phosphorus concentrate can be obtained at normal temperatures containing P after adopting a thick essence
2o
533.58%, MgO0.79%, flotation recovery rate 90.50%.
Claims (4)
1. a phosphate reverse flotation collecting agent, is characterized in that: this collecting agent is made up of the raw material of following percentage by weight:
Aliphatic acid polyethenoxy base ester salt 40 ~ 80%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 14 ~ 50%;
Aliphatic alcohol polyethenoxy base ether 5 ~ 20%;
Span 20 1 ~ 10%;
The general formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R
1COO(CH
2CH
2O)
nM
Wherein: R
1represent the alkyl of 6 ~ 18 carbon atoms, n=3 ~ 5, M is Ka or Na;
The general formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R
2O(CH
2CH
2O)
nP=O(OM)
2
Wherein: R
2represent the alkyl of 6 ~ twelve carbon atom, n=3 ~ 5, M is Ka or Na;
The general formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R
3O(CH
2CH
2O)
nH
Wherein: R
3represent the alkyl of 6 ~ 18 carbon atoms, n=7 ~ 15.
2. a kind of phosphate reverse flotation collecting agent according to claim 1, is characterized in that: the percentage by weight of each raw material is:
Aliphatic acid polyethenoxy base ester salt 55 ~ 65%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 20 ~ 32%;
Aliphatic alcohol polyethenoxy base ether 10 ~ 15%;
Span 20 3 ~ 7%.
3. a kind of phosphate reverse flotation collecting agent according to claim 1, is characterized in that: the percentage by weight of each raw material is:
Aliphatic acid polyethenoxy base ester salt 55%;
Alkyl polyoxyethylene base ether phosphoric acid monoester salt 30%;
Aliphatic alcohol polyethenoxy base ether 10%;
Span 20 5%.
4. the collecting agent of a kind of phosphate reverse flotation calcite described in claim 1 or 2 or 3 is as the purposes of the collecting agent in the reverse flotation of calcite in phosphorus ore.
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| CN201410622082.3A CN104307640B (en) | 2014-11-07 | 2014-11-07 | A kind of collecting agent of phosphate reverse flotation calcite |
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| CN107262289A (en) * | 2017-06-19 | 2017-10-20 | 湖北富邦科技股份有限公司 | A kind of liquid reverse flotation is except collecting agent of calcite and preparation method thereof |
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| CN112638540A (en) * | 2018-08-30 | 2021-04-09 | 巴斯夫欧洲公司 | Phosphate enrichment from phosphate-containing ores |
| CN114057420A (en) * | 2021-11-18 | 2022-02-18 | 中国水利水电第七工程局有限公司 | Non-retarding phosphorous slag powder for cement-based material and preparation method thereof |
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| CN111330744B (en) * | 2018-12-19 | 2022-05-27 | 中蓝连海设计研究院有限公司 | Flotation method and pretreatment method for phosphate rock containing calcite |
| CN114057420A (en) * | 2021-11-18 | 2022-02-18 | 中国水利水电第七工程局有限公司 | Non-retarding phosphorous slag powder for cement-based material and preparation method thereof |
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