CN103056033B - Coal slime microemulsion collecting agent and preparation method thereof - Google Patents
Coal slime microemulsion collecting agent and preparation method thereof Download PDFInfo
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- CN103056033B CN103056033B CN201310032524.4A CN201310032524A CN103056033B CN 103056033 B CN103056033 B CN 103056033B CN 201310032524 A CN201310032524 A CN 201310032524A CN 103056033 B CN103056033 B CN 103056033B
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- collecting agent
- light diesel
- coal slime
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- coal
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- 239000003245 coal Substances 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000004530 micro-emulsion Substances 0.000 title abstract description 4
- 239000002283 diesel fuel Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004064 cosurfactant Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims description 15
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005352 clarification Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- -1 alkyl hydroxybenzene Chemical compound 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims description 2
- 238000005188 flotation Methods 0.000 abstract description 17
- 239000003995 emulsifying agent Substances 0.000 abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract 3
- 229930195733 hydrocarbon Natural products 0.000 abstract 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract 3
- 239000002994 raw material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007957 coemulsifier Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses a coal slime microemulsion collecting agent. The coal slime microemulsion collecting agent is composed, by mass percent: 6%-15% of hydrocarbon oil, 2%-6% of main emulsifying agent, 2-4% of cosurfactant, and the balance being water. The hydrocarbon oil is light diesel oil selected from number 10 light diesel oil, number 0 light diesel oil, number -10 light diesel oil, number -20 light diesel oil or number -35 light diesel oil. The main emulsifying agent is alkylphenol polyethenoxy ether surfactant. Cosurfactant is at least selected from one of C4-C8 alcohol. Since collecting agent is applied in coal slime flotation, hydrocarbon oil dosage is saved beneficially, and oil saving ratio can reach more than 30% on the premise that clean coal yield and ash content are almost the same.
Description
Technical field
Patent of the present invention relates to coal slime flotation technical field, relates in particular to a kind of coal slime microemulsified collecting agent.
Background technology
Coal is the most important energy of China, and from class, although coal resources in China coal class is complete, each coal is composed the situation of depositing and showed difference.Rare Kinds of Coal Resources refer in the actual coal resources reserves of China compose deposit less, simultaneously again to the Chinese national economy categories of coal playing an important role that runs and develops.Deposit utilization reality with reference to coal resources in China criteria for classification (GB5751-86) and the each coal tax of coal resources, in coal resources, coal for coking, high-quality anthracite and other special coal types surely belong to the Rare Kinds in coal resources.For a long time, owing to being subject to the impact of coal industry tradition development model, this part resource fails efficiently to be utilized, especially the sorting utilization of the rare coal slime of high-quality existing problems at most, caused Rare Kinds of Coal Resources consume too fast, waste the facts such as serious.
Along with the raising of mining mechanization degree and a large amount of introducings of dual medium cyclone dressing technique, in the processing and utilization process of the rare coal resources of high-quality, coal slime proportion increases gradually, and at present coal slime accounts for raw coal and enter the 10-30% of the amount of washing.Because coal slime has good native floatability, therefore, flotation is the technology the most widely that slime separation adopts.Flotation is to realize sorting according to the difference of mineral surfaces physicochemical properties.
At present, in coal slime flotation process, conventionally to add nonpolar neutral hydrocarbon-type oil, as kerosene and diesel oil etc., it forms oil film as adsorption of collector in the surface of coal grain, strengthen the hydrophobicity on coal grain surface, make it firmly stick to bubble surface and form mineral laden bubble, and then separate with hydrophilic spoil, realize the object of sorting.
Hydrocarbon-type oil is insoluble in water, dispersed poor in water, can only exist with the form of oil droplet (>1mm), and the coal particle size of flotation is generally below 0.5mm, the probability that the oil droplet size disperseing causes itself and coal grain to collide compared with conference declines, and reduces flotation efficiency, in addition, excessive oil droplet also can, by more tiny coal grain excessive adsorption, cause the waste of medicament.
For solving hydrocarbon-type oil collecting agent bad dispersibility, technological deficiency that flotation efficiency is low, China Patent Publication No. CN101722111A(application number: 201010034074.9) disclose a kind of coal slime flotation collector and preparation method thereof, it is made up of the material of following mass percent: kerosene and/or light diesel fuel 20%-50%, primary emulsion 1%-5%, coemulsifier 0.006%-0.015%, surplus is water; Wherein, described primary emulsion is the mixture of polyoxyethylene sorbitan fatty acid ester and fatty acid esters of sorbitan, and the HLB value of described primary emulsion is between 12.8-14.3; Described coemulsifier is selected from the mixture that neopelex or sodium sulfate of polyethenoxy ether of fatty alcohol and neopelex are mixed to get with mass ratio 1: 0.5-2.Although this coal slime flotation collector can improve floating smart productive rate, also has following defect: the one, because this coal slime collecting agent belongs to the category of emulsion, therefore, poor stability, the problem of depositing at short notice " breakdown of emulsion ", lost efficacy after " breakdown of emulsion ", be difficult for storage, unfavorablely use by industry spot.The 2nd, the oil droplet size of emulsion collecting agent is larger, is generally 0.5mm left and right, still has in actual use the problem that collecting agent consumption is large.
There is at present scholar to propose collecting agent to carry out the technology of microemulsified and emulsification, such as national coal separation academic meeting paper in 2005 is concentrated and has been published one piece about " emulsification of collecting agent and micro-emulsion technology ", wherein discuss and utilized RM and SLL surfactant, as emulsifying agent, collecting agent is carried out to emulsification, thereby solved collecting agent because of the loose low technological deficiency of the poor flotation efficiency of property.The document has been carried out microemulsified to collecting agent on the surface, in fact, the RM that it adds and SLL surfactant are to use as emulsifying agent, collecting agent after treatment is the same with above-mentioned patent documentation, also be the category that belongs to emulsion, do not solve equally poor stability and the large technical problem of collecting agent consumption.
Summary of the invention
In order to overcome the large and poor technological deficiency of hydrocarbon-type oil collecting agent flotation effect of emulsus class collecting agent poor stability, collecting agent consumption simultaneously, the invention provides the coal slime microemulsified collecting agent of the high and remarkable in economical benefits of a kind of good stability, flotation efficiency.
The present invention provides the micro emulsifying method of this coal slime collecting agent simultaneously.
For achieving the above object, coal slime collecting agent of the present invention is made up of the material of following mass percent:
Hydrocarbon-type oil 6%～15%, primary emulsion 2%～6%, cosurfactant 2～4%, surplus is water, wherein:
Described hydrocarbon-type oil is light diesel fuel, can be selected from following at least one: No. 10 light diesel fuels, No. 0 light diesel fuel ,-No. 10 light diesel fuels ,-No. 20 light diesel fuels and-No. 35 light diesel fuels;
Described primary emulsion is induced by alkyl hydroxybenzene polyethenoxy ether class surfactant (trade name OP series), is at least selected from following one: OP-4, OP-7, OP-9 and OP-10.
Described cosurfactant is at least selected from following one: C4～C8 alcohol, and take n-amyl alcohol and n-hexyl alcohol as good.
Preparation method of the present invention is: by the ratio mixing on request of above-mentioned hydrocarbon-type oil, primary emulsion and cosurfactant, on magnetic stirring apparatus, stir in advance, add water while stirring, to transparent clarification, then within the scope of 20-40 ℃, adopt ultrasonic generator to proceed to disperse 5-10 minute, supersonic generator supersonic frequency is 20-40KHz.
Advantage of the present invention is:
In chemical field, the performance of material depends on choosing of raw material on the one hand, the more important thing is the proportioning ratio of each raw material, in disclosed existing document, prepare collecting agent raw material hydrocarbon-type oil value ratio used generally all higher, fettered by this, guiding those skilled in the art are in the time developing new collecting agent, only expect choosing more optimal material, nobody goes to think otherwise possibility.The present invention overcomes this technology prejudice, a kind of and the diverse technical scheme of collecting agent technical conceive have in the past been proposed, courageously reduce hydrocarbon-type oil value ratio, choose new emulsifying agent, then be aided with surfactant, make the not only good dispersion of collecting agent preparing, and stability is strong, compared with the collecting agent of emulsus, under the clean coal yield prerequisite substantially suitable with ash content, rate of economizing gasoline can reach more than 30%.Collectors application of the present invention, in coal slime flotation, is conducive to save hydrocarbon-type oil consumption, increases economic efficiency.
After testing, collecting agent oil droplet size of the present invention, below 100nm, can significantly improve the dispersiveness of hydrocarbon-type oil in water; Place and within 6 months, also there is no above significant change, appearance transparent clarification, good stability, and preparation method is simple.
Accompanying drawing explanation
Fig. 1 adopts the particle diameter distribution situation of oil droplet in the coal slime collecting agent of the present invention that dynamic light scattering measures.
Tu Zhong particle diameter unit is nanometer (nm).
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is illustrated, following examples are intended to further illustrate the present invention, and unrestricted the present invention.
Embodiment mono-
Raw material :-No. 10 light diesel fuel 1g, OP-4 is 0.82g, n-amyl alcohol 0.48g, water 12.95g.
Preparation method: No. 0 light diesel fuel, OP-7 and n-amyl alcohol are mixed, on magnetic stirring apparatus, stir in advance, limit adds waterside and stirs, be stirred to transparent clarification, then adopt ultrasonic generator to proceed to disperse 5-10 minute, ultrasonic generator supersonic frequency adopts 20KHz, and preparation process temperature is controlled at 20 ℃.The collecting agent oil droplet size preparing is at 85nm
Embodiment bis-
Raw material: No. 0 light diesel fuel 1g, OP-7 is 0.39g, n-amyl alcohol 0.25g, water 8.63g.
Preparation method is identical with embodiment mono-, and different is that preparation process temperature is controlled at 30 ℃, and ultrasonic generator supersonic frequency adopts 28KHz.The collecting agent oil droplet size preparing is at 53nm.
Embodiment tri-
Raw material: No. 0 light diesel fuel 1g, OP-10 is 0.29g, n-amyl alcohol 0.18g, water 5.2g.
Preparation method is identical with embodiment mono-, and different is that preparation process temperature is controlled at 40 ℃, and ultrasonic generator supersonic frequency adopts 40KHz.The collecting agent oil droplet size preparing is at 38nm.
Fig. 1 adopts the particle diameter distribution situation of oil droplet in the coal slime collecting agent of the present invention that dynamic light scattering measures, and as can be seen from the figure, the particle diameter of collecting agent of the present invention is less than 100nm.
In order to verify advantage of the present invention, choose the microemulsified collecting agent of No. 0 diesel oil and three embodiment of the present invention to carrying out flotation with a collection of coal slime, flotation effect is as following table.
As can be seen from the table, during with No. 0 diesel oil and collecting agent coal slurry flotation of the present invention, clean coal yield and ash content are substantially suitable, but because hydrocarbon-type oil content in collecting agent of the present invention is very low, wherein embodiment mono-content is 6.56%, embodiment bis-content are 9.73%, embodiment tri-content are 15.0%, thereby can calculate, and are reaching under the clean coal yield and ash content prerequisite being equal to, compare with No. 0 diesel oil of simple use, the rate of economizing gasoline of collecting agent of the present invention can reach more than 30%.
Claims (3)
1. a coal slime microemulsified collecting agent, is characterized in that, it is to be made up according to following preparation method of the material of following mass percent: hydrocarbon-type oil 6%～15%, and primary emulsion 2%～6%, cosurfactant 2～4%, surplus is water, wherein:
Described hydrocarbon-type oil is light diesel fuel, is selected from No. 10 light diesel fuels, No. 0 light diesel fuel ,-No. 10 light diesel fuels ,-No. 20 light diesel fuels or-No. 35 light diesel fuels;
Described primary emulsion is induced by alkyl hydroxybenzene polyethenoxy ether class surfactant, and trade name OP series, is at least selected from following one: OP-4, OP-7, OP-9 and OP-10;
Described cosurfactant is at least selected from following one: C4～C8 alcohol;
The oil droplet size of this coal slime microemulsified collecting agent is below 100nm, preparation method is, by the ratio mixing on request of hydrocarbon-type oil, primary emulsion and cosurfactant, on magnetic stirring apparatus, stir in advance, add water while stirring, be stirred to transparent clarification, then within the scope of 20-40 ℃, adopt ultrasonic generator to proceed to disperse 5-10 minute, supersonic generator supersonic frequency is 20-40KHz.
2. coal slime microemulsified collecting agent as claimed in claim 1, is characterized in that, described cosurfactant is n-amyl alcohol or n-hexyl alcohol.
3. prepare the method for coal slime microemulsified collecting agent claimed in claim 1 for one kind, it is characterized in that, by the ratio mixing on request of hydrocarbon-type oil, primary emulsion and cosurfactant, on magnetic stirring apparatus, stir in advance, add water while stirring, be stirred to transparent clarification, then within the scope of 20-40 ℃, adopt ultrasonic generator to proceed to disperse 5-10 minute, supersonic generator supersonic frequency is 20-40KHz.
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| CN104259011A (en) * | 2014-09-02 | 2015-01-07 | 长沙明鹏科技有限公司 | Coal compound flotation agent |
| CN104525383A (en) * | 2014-12-31 | 2015-04-22 | 淮北华星工贸有限责任公司 | Efficient floatation reagent for coal slime |
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| CN111558466B (en) * | 2020-04-28 | 2022-08-23 | 西北矿冶研究院 | Nanoscale emulsified diesel oil collecting agent for separating unburned carbon and tail ash in fly ash and preparation method thereof |
| CN114471956B (en) * | 2021-12-27 | 2023-03-17 | 中国矿业大学 | Coal flotation capsule slow-release collecting agent and preparation method and application thereof |
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| CN85106071A (en) * | 1985-08-14 | 1986-01-10 | 轻工业部日用化学工业科学研究所 | Oil-in-water emulsion used in flotation of coal slurry |
| US8469197B2 (en) * | 2008-08-19 | 2013-06-25 | Tata Steel Limited | Blended frother for producing low ash content clean coal through flotation |
| CN101940981A (en) * | 2010-08-07 | 2011-01-12 | 武贵丙 | Highly watered micro-emulsified diesel oil additive, preparation method and application thereof |
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