CN104307640B - A kind of collecting agent of phosphate reverse flotation calcite - Google Patents
A kind of collecting agent of phosphate reverse flotation calcite Download PDFInfo
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- CN104307640B CN104307640B CN201410622082.3A CN201410622082A CN104307640B CN 104307640 B CN104307640 B CN 104307640B CN 201410622082 A CN201410622082 A CN 201410622082A CN 104307640 B CN104307640 B CN 104307640B
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Abstract
The present invention is a kind of phosphate reverse flotation collecting agent, and this collecting agent is made up of the component of following mass percent: 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%.This collecting agent is applicable to phosphate reverse flotation calcite.This collecting agent, compared with fatty acid collecting agent, has the strongest 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 tradition flotation process phosphorus ore, the shortcomings such as collecting ability is the best, the response rate is low, reagent cost is high, on mineral processing index, show obvious superiority simultaneously, obtain new breakthrough.
Description
Technical field
The invention belongs to phosphate rock floating field, be specifically related to the high selective collecting agent of reverse flotation calcite in phosphorus ore.
Background technology
At present, the phosphorus fine ore of the overwhelming majority is to be obtained by ore dressing.The purpose of ore dressing is the stone-like pulse ore deposit in removing phosphorus ore
Thing.In the flotation of apatite, siliceous mineral and carbonate mineral are modal gangue contents.Siliceous mineral mainly quartz
Or cristobalite, clay mineral and other is such as Anhydrite and Muscovitum etc..Clay mineral in the ore dressing of phosphorus ore with using scouring, desliming more
Remove etc. mode；Quartz, calcedony etc. also show the floatability more poor than apatite in flotation, even if disseminated grain size is fine,
Relatively good choosing, can be removed by direct flotation.Carbonate gangue is mainly calcite and dolomite.White Cloud Mountain
Typically using reverse flotation in flotation of phosphate rock, suppression phosphate reverse flotation White Cloud Mountain de-magging, because the floatability of dolomite is better than
Phosphate, the most in acid condition.The current comparative maturity of this technique, can be removed to concentrate by the collophane containing MgO4 ~ 5%
Containing below MgO0.8%.The ground such as China's Haikou, Kunming, peacefulness, Yichang build up large-scale flotation mill, all use this flotation work
Skill, effect is notable.
From phosphate mineral such as francolite, to isolate calcite and to always consider it is extremely difficult.Both ore deposits
Thing belongs to identical cation type, is all Ca2+.This point is different from dolomite, and dolomite is except containing Ca2+, also Mg2+.These are two years old
Planting mineral all can use cloudy sub-collecting agent such as fatty acid etc. to be allowed to float, and in the range of pH widely, has the most close
Floatability.In apatite and calcite system, under certain condition, Calcite Surface converts to apatite, changes condition, phosphorus
Lime stone surface can also change into calcite.It is relatively difficult that this results in separation calcite from phosphate ore.
Hu Yuehua, Wang Dian assistant is at " α amido aryl phosphoric acids flotation phosphate lime stone and the research of calcite " (" non-ferrous metal "
The first phase in February, 1992) show: in alkaline medium, α amido aryl phosphoric acids is relatively big in the adsorbance of Calcite Surface, right
Calcite has stronger Pu to receive ability, less at apatite surface excess, more weak to the collecting ability of apatite.At α amine
In base aryl phosphoric acids solution, apatite increases with Calcite Surface negative electricity current potential.Solution equilibria calculates and ir data table
Bright, the active component of a mono-amido aryl phosphoric acids flotation harvesting adduction is (R1 R2N R3 CH P( O )O 2H)-in square solution
There is chemisorbed in stone surface.Sort collophane stone by α amido aryl phosphoric acids, can obtain containing P2O523.06 %, the response rate
The rough concentrate of 89.9%, effective more than oxidized paraffin wax soap.But collecting agent α amido aryl phosphoric acids price is much more expensive, close
Become difficulty, it is clear that the improper collecting agent making cheap rock phosphate in powder.Somebody with dodecylphosphoric acid disodium salt in square solution
Stone apatite system does collecting agent, but DeGrain, collecting agent all has certain collecting ability to two kinds of mineral, selects
Property is poor.
Summary of the invention
The technical problem to be solved is for reverse flotation calcite in phosphorus ore in prior art, and collecting agent selects
Property poor, the problems such as collecting effect is bad, it is provided that a kind of efficient, selectivity is good, soluble in water, phosphorus ore that production cost is low
In collecting agent to reverse flotation calcite.
The technical problem to be solved is to be realized by following technical scheme.The present invention is a kind of phosphorus ore
Collecting agent in reverse floatation, 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 formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R1COO(CH2CH2O)nM
Wherein: R1Representing the alkyl of 6 ~ 18 carbon atoms, n=3 ~ 5, M is Ka or Na；
The formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R2O(CH2CH2O)nP=O(OM)2
Wherein: R2Representing the alkyl of 6 ~ twelve carbon atom, n=3 ~ 5, M is Ka or Na.
The formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R3O(CH2CH2O)nH
Wherein: R3Represent 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
Ratio 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: be simply mixed under the conditions of 40 ~ 80 DEG C
?.
The collecting agent of a kind of phosphate reverse flotation calcite of the present invention can be as the reverse flotation of calcite in phosphorus ore
In the purposes of collecting agent.
Compared with prior art, the collecting agent of the present invention has the advantage that this hybrid collector is with two kinds of aniones
Collecting agent (aliphatic acid polyethenoxy base ester salt, alkyl polyoxyethylene base ether phosphoric acid monoester salt) is main, is equipped with two kinds of nonionic tables
Face activating agent (aliphatic alcohol polyethenoxy base ether, span 20) forms, based on anionic collector nonionic surfactant altogether
Absorption and the mechanism adsorbed of interting, test through substantial amounts of Chemicals, and the test of actual Ore, and result of the test shows the moon
Polyoxyethylene groups in ion collecting agent (aliphatic acid polyethenoxy base ester salt, alkyl polyoxyethylene base ether phosphoric acid monoester salt) reduces
The electrostatic repulsion of polar group, association between beneficially two kinds collecting agents, it is equipped with aliphatic alcohol polyethenoxy base ether, span 20 non-
Ionic surface active agent, forms collecting agent nonionic surfactant " co-adsorption ", owing to the effect of " co-adsorption " is further
Promote the association of anionic collector thin film, and the interspersed absorption between medicament significantly enhances the critical micell of collecting agent
Concentration, both common effects make the surface activity of medicament be significantly improved, and then show table between the medicament of combination
The best synergism.
Containing substantial amounts of oxyethylene group group in collecting agent of the present invention, good water solubility, resistance to hard water is strong, and consumption is little.Collecting
Agent has good selectivity collecting ability, it is possible to efficient flotation calcite, weak to phosphate collecting ability.Collecting of the present invention
Agent, compared with fatty acid collecting agent, has the strongest collecting ability and high selectivity；Collecting with α amido aryl phosphoric acids class
Agent is compared, cheap, and consumption is little, draws materials conveniently.When this collecting agent overcomes the calcite in tradition flotation process phosphorus ore, catch
The shortcomings such as receipts ability is the best, the response rate is low, reagent cost is high, show obvious superiority on mineral processing index simultaneously, obtain
New breakthrough.
Accompanying drawing explanation
Fig. 1 is the response rate graph of a relation of collector dosage and francolite and calcite.
Detailed description of the invention
The concrete technical scheme of the present invention described further below, in order to those skilled in the art is further understood that
The present invention, and do not constitute 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 formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R1COO(CH2CH2O)nM
Wherein: R1Representing the alkyl of 6 ~ 18 carbon atoms, n=5, M are Ka；
The formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R2O(CH2CH2O)nP=O(OM)2
Wherein: R2Representing the alkyl of 6 ~ twelve carbon atom, n=3, M are Na.
The formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R3O(CH2CH2O)nH
Wherein: R3Represent 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 formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R1COO(CH2CH2O)nM
Wherein: R1Representing the alkyl of 6 ~ 18 carbon atoms, n=3, M are Ka or Na；
The formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R2O(CH2CH2O)nP=O(OM)2
Wherein: R2Representing the alkyl of 6 ~ twelve carbon atom, n=5, M are Ka or Na.
The formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R3O(CH2CH2O)nH
Wherein: R3Represent 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 formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R1COO(CH2CH2O)nM
Wherein: R1Representing the alkyl of 6 ~ 18 carbon atoms, n=4, M are Ka or Na；
The formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R2O(CH2CH2O)nP=O(OM)2
Wherein: R2Representing the alkyl of 6 ~ twelve carbon atom, n=4, M are Ka or Na.
The formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R3O(CH2CH2O)nH
Wherein: R3Represent 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 is carried out on XFG hanging trough flotator.The 2.0g raw ore sample weighed is thin brilliant phosphorus ash
Stone and calcite quality press the aggregate sample of 1:1 proportioning, put in 50ml flotation cell, add 40ml distilled water, after the 2min that sizes mixing, use
After sulphuric acid regulation pH=5, (quality proportioning is: lauric acid polyoxyethylene groups ester sodium salt 60%(gathers to add collecting agent of the present invention
Right 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%) stirring 3min, flotation 5min, collector dosage and francolite and the recovery of calcite
The relation of rate 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, quartzy and a small amount of white clouds
Stone.Raw ore contains P2O525.67%, MgO0.83%, by raw ore after being ground to-200 mesh content 70%, adds sulphuric acid 2500g/t raw ore and adjusts
After pH, add sodium hexameta phosphate 300g/t and do inhibitor, add hybrid collector 1200g/t raw ore (matter of the present invention
Amount proportioning be: palmitic acid polyoxyethylene groups ester sodium salt 70%(polymerization degree n=5), dodecyl polyoxyethylene ether phosphate monoester potassium
Salt 20%(polymerization degree n=5), tetradecyl alchohol polyoxyethylene ether (polymerization degree n=7) 5%, span 20 5%) carry out laboratory flotation examination
Test, phosphorus concentrate can be obtained at normal temperatures after using a thick essence containing P2O531.22%, 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 contains P2O527.52%, MgO0.66%,
By raw ore after being ground to-200 mesh content 50%, after adding sulphuric acid 1500g/t raw ore tune pH, add sodium hexameta phosphate 450g/t
Doing inhibitor, (quality proportioning is: stearic acid polyoxyethylene base ester to add hybrid collector 1500g/t raw ore of the present invention
Potassium salt (polymerization degree n=3) 40%, octyl group polyoxyethylene ether phosphate monoester sodium salt (polymerization degree n=5) 40%, lauryl alcohol polyoxyethylene
Base ether (polymerization degree n=10) 10%, span 20 10%) carry out laboratory float test, at normal temperatures after using a thick essence
Phosphorus concentrate can be obtained containing P2O533.58%, MgO0.79%, flotation recovery rate 90.50%.
Claims (4)
1. a phosphate reverse flotation collecting agent, it is characterised 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 formula of described aliphatic acid polyethenoxy base ester salt is as follows:
R1COO(CH2CH2O)nM
Wherein: R1Representing the alkyl of 6～18 carbon atoms, n=3～5, M are Ka or Na；
The formula of described alkyl polyoxyethylene base ether phosphoric acid monoester salt is as follows:
R2O(CH2CH2O)nP=O (OM)2
Wherein: R2Representing the alkyl of 6～twelve carbon atom, n=3～5, M are Ka or Na；
The formula of described aliphatic alcohol polyethenoxy base ether is as follows:
R3O(CH2CH2O)nH
Wherein: R3Represent the alkyl of 6～18 carbon atoms, n=7～15.
A kind of phosphate reverse flotation collecting agent the most according to claim 1, it is characterised in that: the percentage by weight of each raw material
For:
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 the most according to claim 1, it is characterised in that: the percentage by weight of each raw material
For:
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. a kind of phosphate reverse flotation collecting agent described in claim 1 or 2 or 3 is as catching in the reverse flotation of calcite in phosphorus ore
Receive the purposes of agent.
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| CA3046326C (en) | 2016-12-23 | 2023-11-07 | Akzo Nobel Chemicals International B.V. | Collector composition for froth flotation of phosphate ores |
| 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 |
| CN112638540B (en) * | 2018-08-30 | 2023-11-14 | 巴斯夫欧洲公司 | Enrichment of phosphate from phosphate-containing ores |
| 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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| DE10024667C2 (en) * | 2000-05-18 | 2002-02-28 | Clariant Gmbh | Preparations for the treatment of phosphate ore |
| CN101797536B (en) * | 2010-01-06 | 2014-07-02 | 云南省化工研究院 | Collophanite flotation collector and method for preparing same |
| DE102010004893A1 (en) * | 2010-01-19 | 2011-07-21 | Clariant International Limited | Flotation reagent for magnetite- and / or hematite-containing iron ores |
| CN102580860A (en) * | 2012-02-27 | 2012-07-18 | 河南省岩石矿物测试中心 | Molybdenite flotation collector |
| CN103357509B (en) * | 2013-07-12 | 2014-12-24 | 武汉工程大学 | Reverse flotation collecting agent of cellophane and preparation method thereof |
| CN103990550B (en) * | 2014-05-28 | 2016-05-25 | 中蓝连海设计研究院 | A kind of collophane direct flotation collecting agent and preparation method thereof and purposes and application process |
| CN104107762B (en) * | 2014-06-20 | 2017-08-04 | 北京矿冶研究总院 | Low-temperature-resistant collophanite reverse flotation collecting agent and preparation method thereof |
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