CN102179067A - Oil-water separation device and preparation method thereof - Google Patents
Oil-water separation device and preparation method thereof Download PDFInfo
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- CN102179067A CN102179067A CN2011100714811A CN201110071481A CN102179067A CN 102179067 A CN102179067 A CN 102179067A CN 2011100714811 A CN2011100714811 A CN 2011100714811A CN 201110071481 A CN201110071481 A CN 201110071481A CN 102179067 A CN102179067 A CN 102179067A
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Abstract
The invention discloses an oil-water separation device and a preparation method thereof, and belongs to the technical field of chemical process devices. The preparation method comprises the following steps of: alternately putting a foam metal mesh substrate into ethanol and acetone, ultrasonically cleaning, and drying; preparing the required hydrofluoric acid/silver nitrate corrosive liquid; closely combining the foam metal mesh and a silicon chip, immersing in the heated hydrofluoric acid/silver nitrate corrosive liquid, corroding for 5 to 20 minutes, taking out, washing with distilled water, and drying; and soaking the dried device in ethanol solution of a low-surface-energy substance, taking out, washing with distilled water and drying. The device with multiple functions of adsorbing overflowed oil, an oil skimmer and separating oil and water consists of the metal mesh substrate and nano metal silver particles deposited on the surface of the metal mesh substrate, and has the surface modified by the low-surface-energy substance. The device has superhydrophobic/super-oleophilic effect, can be self-cleaned, can bear high temperature of at least 120DEG C, and can collect leaked oil at high temperature. The preparation method is simple, the flow time is short, and the efficiency is high.
Description
Technical field
The invention belongs to chemical technology device technique field, that relate generally to is a kind of multi-functional oily-water seperating equipment and preparation method, and this device has the function of the oil fence, oil spilling absorption, oil skimmer and water-oil separating simultaneously concurrently.
Background technology
The develop rapidly of modern society makes resource and energy problem that the mankind face constantly aggravate.At present, tradition such as the oil easily reserves in power consumption source constantly descend, and rise of the oil price is all constantly affecting human daily life and social activities.For this reason, people have strengthened the exploitation and the utilization of offshore petroleum resources gradually, thereby have caused the serious problems that oil spill accident takes place frequently in the recovery process; Meanwhile, flourish along with the offshore oil trade, the accidents caused extensive concern that caused of leakage of oil that exists in offshore oil transportation and the oil cargo handling process.In addition, in the second phase of Chemical Manufacture and crude oil, the three phase recovery process, water-oil separating also is the problem of high energy consumption, especially how in-situ accomplishes efficient, low energy consumption the oil in the water is collected; Moreover how organic solvent being separated from water efficiently in the laboratory also is one of problem that will solve.
At present, worldwide leakage of oil is collected and is mainly concentrated on modes such as using oil skimmer, asphalt felt and machinery recovery.The principle of various oil skimmers is different, and weir formula oil skimmer is the proportion difference by profit, and the regulating weir open height just in time below oil reservoir, oil is flowed in the oil trap, and water is blocked in the outside.This method is restricted bigger, because we must know the thickness of oil reservoir, and what tend to like this collect is the mixture of profit.Other oil skimmer all is the effect that utilizes oil absorption material, by contacting of lipophilic material and oil spilling, oil spilling is adsorbed onto in the material, and the mode through extruding or scraping blade reclaims oil then, though such method is simpler, efficient is very low, and workload is very big.All be processing also with the oil spilling original position just like spraying detergent and biodegradable method, and not with its recycling.These methods exist shortcomings such as cost height, complicated operation, highly energy-consuming and efficient are low jointly.Therefore, need a kind of multi-functional integrated oily-water seperating equipment of development, make its function that can have the oil fence, oil spilling absorption, oil skimmer and water-oil separating simultaneously concurrently, thereby simplify device and mode that marine oil overflow is handled, improve the efficient that oil spilling is handled, reduce cost, reduce energy consumption.
In modern chemical industry is produced, chemical reaction and separation process are the energy consumption rich anies influential family, particularly separation process in the energy consumption of whole chemical process shared ratio up to 50～70%, and in the investment budgey of petrochemical production process that to large-scale petroleum industry with the chemical reaction is the center, the expense of separator accounts for 50～90% of gross investment.Improvement and optimization along with chemical process, on existing equipment system basis, carry out interior transformation, develop energy-conservation separation new material and be applied to large-size chemical production, not only will also will make contributions to alleviating energy consumption, reducing cost of investment and produce important economic implications for eco-friendly green chemical industry production.In addition, China is the deficient relatively countries of petroleum resources, oil exploration industry presents following characteristics at present: main force oil field enters the exploitation middle and later periods, the oil field composite water cut rises, the treating capacity of oil-polluted water also increases gradually, and the exploitation time, long well water reached more than 90%, and separation costs increases, productivity effect descends, and the volume increase difficulty is big.Thereby the strategy that ensures national Oil Safety also changes from the direction that simple " increasing income " lays equal stress on to " increasing income " and " throttling ", under existing oil storage level, development low-consumption high-efficiency oil product treatment technology, quickening to develop the energy-conservation separating and purifying technology that adapts to the oil field waste processing has become a great demand and has had global challenge problem.
Realize that energy-conservation, water-oil separating efficiently has important Research Significance at aspects such as petrochemical industry, metallurgical manufacturing and marine oil overflow processing, has the important strategic meaning for solving the petroleum resources waste, improve energy utilization rate and reducing environmental pollution.Thereby oily water separation technique is the research focus of aspects such as domestic and international petrochemical industry, using energy source always.Known oil-water separation method mainly contains gravity type separation, centrifugal separation, electric separation, adsorbing separation and dissolved air flotation etc. at present.Wherein, the gravity type separation costs is lower, but can only remove the Free water in the crude oil, and is then powerless for dissolving water and emulsified water.Centrifugal separation can reach the purpose of separating Free water and emulsified water, yet the centrifugation apparatus price is higher, and the regular maintenance difficulty only is applied to lab analysis at present.Electricity takes off when being separated in the higher crude oil emulsion of electricity consumption evaporation process water content, can produce electrical breakdown and can't set up the electric-field intensity of interpolar necessity, can not use separately, can only be as the post-order process of other processing methods.Adsorbing separation and dissolved air flotation exist too separate thoroughly and equipment cost than problems such as height.Therefore, develop the separator of simple separation method, low-cost low energy consumption and original position efficiently organic efficiency be the important directions of following water-oil separating development, also be the bottleneck place of existing method.
Summary of the invention
The object of the invention is to overcome technology loaded down with trivial details in the prior art and complicated implementation process, and provide a kind of preparation method of oily-water seperating equipment of low-cost low energy consumption, realize the original position high efficiente callback of oil content in the chemical process, be applicable to the organic solvent that kerosene, gasoline, diesel oil, machine oil and toluene, carrene etc. do not dissolve each other with water.
A kind of have a multi-functional integrated device of oil spilling absorption, oil skimmer and water-oil separating, it is characterized in that: this device is by the wire netting substrate and be deposited on its surperficial nanometer metallic silver particle and form, and finishing has the low-surface-energy material.
Described metal foam net is nickel foam, foam copper, foamed aluminium and foamed alloy.
Described low-surface-energy material is one of n-dodecyl mercaptan, Stearyl mercaptan, octadecyl trimethicone and fluoro mercaptan and fluoro siloxanes.
The objective of the invention is to realize by following technical measures:
1), foam metal net substrate is alternately put into ethanol and acetone, ultrasonic wave cleans three times, dries in the air dry oven.
2), the required hydrofluoric acid/silver hitrate cautery liquid of preparation: the concentration that corrosive liquid hydrofluoric acid and silver nitrate are joined is respectively: hydrofluoric acid 1.0-6.0mol/L, silver nitrate is at 5-200mmol/L.
3), metal foam net and silicon chip are combined closely, be immersed in 70 ℃ of hydrofluoric acid/silver hitrate cautery solution after the water-baths heating, the metal foam net takes out corrode 5-20min in hydrofluoric acid/silver hitrate cautery solution after, dries behind the distilled water flushing.
4), the device after the oven dry is dipped in the ethanolic solution of low-surface-energy material distilled water flushing oven dry after taking out.Obtain having the multi-functional integrated device of oil spilling absorption, oil skimmer and water-oil separating.
Involved in the present invention is to have the multi-functional integrated oily-water seperating equipment of oil spilling absorption, oil skimmer and water-oil separating, it be utilize no electric electrochemical deposition method with the nanometer metallic silver particle deposition to the metal foam net substrate of getting ready, directly modify self assembly mercaptan monolayer then on the surface.Can observe in the mesh of the recessed injustice of foam metal substrate epirelief and the surface by the SEM of amplifying 25 times, a large amount of deposition of silver is all arranged, and 2000 times effect shows that these silver form some silver bunch with micro nano structure.Such structure can form a kind of super-hydrophobic surface after modifying through the thiol molecule of low-surface-energy, can realize the effect of super oleophylic simultaneously.
Oily-water seperating equipment of the present invention is to have the multi-functional integrated oily-water seperating equipment of oil spilling absorption, oil skimmer and water-oil separating to have multi-functional integrated oily-water seperating equipment, can be widely used in oil, water purified treatment and offshore spilled oil and reclaim.This oily-water seperating equipment is with a wide range of applications equally in fields such as petrochemical industry, industrial and mineral, metallurgy, family expenses, environmental protection.
1, to have a hydrophobic effect good for device of the present invention, and the fireballing characteristics of oleophylic can be used for water-oil separating and leakage of oil and collect.
2, device of the present invention can be widely used in the offshore oil exploitation operation, can continual the oily substance of revealing be reclaimed.
3, device of the present invention can be used for the processing of water sump oil, can realize purified treatment to water resource.
4, device of the present invention, the organic solvent in can separating experiment chamber waste liquid realizes that the classification of waste liquid is handled.
5, device of the present invention is used for handling discarded edible oil in family kitchen, can be efficiently with edible oil, moisture from.
6, device of the present invention has the effect of super-hydrophobic/super-oleophilic, can realize self-cleaning effect.
7, device preparation method of the present invention is simple, and the flow process time is short, the efficient height.
8, device of the present invention can stable operation, can bear at least 120 ℃ high temperature, and at high temperature still can carry out leakage of oil and collect.
9, device of the present invention has universality, and gasoline, kerosene, diesel oil, former wet goods and organic solvent are absorbed recovery.
10, device of the present invention has the advantages that can be recycled, and repeatedly uses the back organic efficiency still can not reduce.
Description of drawings
Fig. 1. the optical photograph figure on the surface of the oily-water seperating equipment of the present invention's preparation;
Fig. 2. the optical photograph figure in kind of the oily-water seperating equipment of the present invention's preparation;
Fig. 3. volume is the shape figure that the water droplet of 4 μ L drips to the oily-water seperating equipment surface of this invention;
Fig. 4. volume is the shape figure that the oil droplet of 4 μ L drips to the oily-water seperating equipment surface of this invention preparation;
Fig. 5. the device of the present invention preparation carry out water-oil separating experiment overlook photo;
Fig. 6. the device of the present invention's preparation carries out the optical photograph of crude oil/water separating experiment.
The specific embodiment
Below in conjunction with examples of implementation and accompanying drawing technical scheme of the present invention is further described:
Embodiment 1:
1, foam nickel screen substrate is alternately put into ethanol and acetone, ultrasonic wave cleans three times, dries in the air dry oven.
2, the required hydrofluoric acid/silver hitrate cautery liquid of preparation.It is respectively hydrofluoric acid 5.0mol/L that hydrofluoric acid and silver nitrate are mixed with concentration, and silver nitrate is at 0.02mol/L.
3,70 ℃ of the temperature of water-bath are set, metal foam net and silicon chip are combined closely, be immersed in the hydrofluoric acid/liquor argenti nitratis ophthalmicus after the heating.
4, take out after the metal foam net was corroded in above-mentioned solution 15 minutes, dry behind the distilled water flushing.
5, the device after the oven dry is dipped in the ethanolic solution of low-surface-energy material lauryl mercaptan 24 hours, takes out back distilled water flushing oven dry, obtains having the super-hydrophobicity/super lipophile device of oil-water separating function.
Foam nickel screen substrate changed do foam copper or foamed aluminium net substrate all can obtain effect same.
Embodiment 2:
1, foam nickel screen substrate is alternately put into ethanol and acetone, ultrasonic wave cleans three times, dries in the air dry oven.
2, the required hydrofluoric acid/silver hitrate cautery liquid of preparation.Getting hydrofluoric acid and silver nitrate, to be mixed with concentration be respectively hydrofluoric acid 4.0mol/L, and silver nitrate is at 0.02mol/L.
3,70 ℃ of the temperature of water-bath are set, metal foam net and silicon chip are combined closely, be immersed in the hydrofluoric acid/liquor argenti nitratis ophthalmicus after the heating.
4, take out after nickel foam was corroded in above-mentioned solution 15 minutes, dry behind the distilled water flushing.
5, the device after the oven dry is dipped in the ethanolic solution of low-surface-energy material lauryl mercaptan 24 hours, takes out back distilled water flushing oven dry.Obtain having the super-hydrophobicity/super lipophile device of oil-water separating function.
Foam nickel screen substrate changed do foam copper or foamed aluminium net substrate all can obtain effect same.
Embodiment 3:
1, foam nickel screen substrate is alternately put into ethanol and acetone, ultrasonic wave cleans three times, dries in the air dry oven.
2, the required hydrofluoric acid/silver hitrate cautery liquid of preparation.Getting 40% hydrofluoric acid and silver nitrate, to be mixed with concentration be respectively hydrofluoric acid 4.6mol/L, and silver nitrate is at 0.05mol/L.
3,70 ℃ of the temperature of water-bath are set, metal foam net and silicon chip are combined closely, be immersed in the hydrofluoric acid/liquor argenti nitratis ophthalmicus after the heating.
4, take out after nickel foam was corroded in above-mentioned solution 10 minutes, dry behind the distilled water flushing.
5, the device after the oven dry is dipped in the ethanolic solution of low-surface-energy material 24 hours, takes out back distilled water flushing oven dry.Obtain having the super-hydrophobicity/super lipophile device of oil-water separating function.
Foam nickel screen substrate changed do foam copper or foamed aluminium net substrate all can obtain effect same.
Embodiment 4:
1, get 50ml toluene, with No. 78 coloring agent dyeing carrying out of solvent blue mark, so that observe.
2, the toluene that dyes is joined in the beaker of the ready 150ml of filling water, then super-hydrophobic/super-oleophilic device of the present invention is put into wherein.
3, with the continuous sucking-off of the toluene of access to plant, toluene in device, no longer occurs and assemble.
4, graduated cylinder is measured the volume of the toluene that reclaims, and calculate recovery rate reaches more than 95%.
Embodiment 5:
1, get 50ml kerosene, with No. 78 coloring agent dyeing carrying out of solvent blue mark, so that observe.
2, the kerosene that dyes is joined in the beaker of the ready 150ml of filling water, then super-hydrophobic/super-oleophilic device of the present invention is put into wherein.
3, with the continuous sucking-off of the kerosene of access to plant, kerosene in device, no longer occurs and assemble.
4, graduated cylinder is measured the volume of the kerosene that reclaims, and calculate recovery rate reaches more than 95%.
Embodiment 6:
1, get the 50ml olive oil, with No. 78 coloring agent dyeing carrying out of solvent blue mark, so that observe.
2, the olive oil that dyes is joined in the beaker of the ready 150ml of filling water, then the super-hydrophobic/super-oleophilic device of the inventive method preparation is put into wherein.
3, with the continuous sucking-off of the olive oil of access to plant, olive oil in device, no longer occurs and assemble.
4, graduated cylinder is measured the volume of the olive oil that reclaims, and calculate recovery rate reaches more than 95%.
Embodiment 7:
1, get the 10ml petroleum crude oil, it is joined in the beaker that fills 150ml water, then the oily-water seperating equipment of the inventive method preparation is put into wherein.
2, the petroleum crude oil that penetrates into device inside is constantly used the suction pipe sucking-off, petroleum crude oil in device, no longer occurs and assemble.
3, graduated cylinder is measured the volume of the petroleum crude oil that reclaims, and calculate recovery rate reaches more than 90%.
Embodiment 8:
1, get the 10ml petroleum crude oil, it is joined in the beaker that fills 150ml water.
2, with emulsifier for mixing beaker PetroChina Company Limited.'s crude oil and water 10min, rotating speed 12,000r/min obtains emulsification shape mixed liquor, extremely unmanageable emulsus oil water mixture in the oil spill accident of simulation deep-sea.
3, the device of the inventive method preparation is put into wherein, the petroleum crude oil that penetrates into device inside is constantly used the suction pipe sucking-off, petroleum crude oil in device, no longer occurs and assemble.
4, graduated cylinder is measured the volume of the petroleum crude oil that reclaims, and calculate recovery rate reaches more than 90%.
The optical photograph figure on the surface of the oily-water seperating equipment of the present invention's preparation sees Fig. 1; The optical photograph figure in kind of the oily-water seperating equipment of the present invention's preparation sees Fig. 2; Volume is that the shape that the water droplet of 4 μ L drips to the oily-water seperating equipment surface of this invention is seen Fig. 3; Volume is that the shape that the oil droplet of 4 μ L drips to the oily-water seperating equipment surface of this invention preparation is seen Fig. 4; The device of the present invention's preparation carries out the photo of overlooking of the experiment of water-oil separating and sees Fig. 5; The device of the present invention's preparation carries out the optical photograph of crude oil/water separating experiment and sees Fig. 6.
Claims (3)
1. one kind has the multi-functional integrated device of oil spilling absorption, oil skimmer and water-oil separating, it is characterized in that: this device is by the wire netting substrate and be deposited on its surperficial nanometer metallic silver particle and form, and finishing has the low-surface-energy material.
2. the preparation method with the multi-functional integrated device of oil spilling absorption, oil skimmer and water-oil separating of claim 1 is characterized in that, may further comprise the steps:
1), foam metal net substrate is alternately put into ethanol and acetone, ultrasonic wave cleans three times, dries in the air dry oven;
2), the required hydrofluoric acid/silver hitrate cautery liquid of preparation: the concentration that corrosive liquid hydrofluoric acid and silver nitrate are joined is respectively: hydrofluoric acid 1.0-6.0mol/L, silver nitrate is at 5-200mmol/L;
3), metal foam net and silicon chip are combined closely, be immersed in 70 ℃ of hydrofluoric acid/silver hitrate cautery solution after the water-baths heating, the metal foam net takes out corrode 5-20min in hydrofluoric acid/silver hitrate cautery solution after, dries behind the distilled water flushing;
4), the device after the oven dry is dipped in the ethanolic solution of low-surface-energy material distilled water flushing oven dry after taking out;
The low-surface-energy material is one of n-dodecyl mercaptan, Stearyl mercaptan, octadecyl trimethicone, fluoro mercaptan and fluoro siloxanes.
3. according to the method for claim 2, it is characterized in that described metal foam net is nickel foam, foam copper, foamed aluminium and foamed alloy.
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| CN2011100714811A CN102179067A (en) | 2011-03-24 | 2011-03-24 | Oil-water separation device and preparation method thereof |
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Cited By (12)
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| CN102657954A (en) * | 2012-04-23 | 2012-09-12 | 中国石油天然气股份有限公司 | Material with water-controlled function and preparation method of same |
| CN102886155A (en) * | 2012-09-20 | 2013-01-23 | 北京航空航天大学 | Bionic construction of metal-foam-based oil-water separation material |
| CN102979066A (en) * | 2012-12-24 | 2013-03-20 | 南昌航空大学 | Device for adsorbing and separating spilled oil on water surface |
| CN104888498A (en) * | 2015-06-12 | 2015-09-09 | 东南大学 | Preparation method of durable super-hydrophobic super-oleophylic foamy copper for oil and water separation |
| CN105080216A (en) * | 2014-05-15 | 2015-11-25 | 浙江强盛滤料有限公司 | Preparation method of composite filter net of metal etching net and metal fiber net |
| CN105344133A (en) * | 2015-12-08 | 2016-02-24 | 上海愚工机械科技有限公司 | Preparation method of oil-water separation membrane |
| CN105582693A (en) * | 2015-12-22 | 2016-05-18 | 北京航空航天大学 | T-type oil-water separation equipment integrating two special wettable materials |
| CN106310719A (en) * | 2016-08-26 | 2017-01-11 | 北京航空航天大学 | High efficiency and continuous oil-water separation device |
| CN106861629A (en) * | 2017-02-14 | 2017-06-20 | 江西中医药大学 | The nickel foam adsorbent of octadecyl modification and its application |
| CN107127468A (en) * | 2017-05-05 | 2017-09-05 | 哈尔滨工业大学深圳研究生院 | A kind of high temperature based on foam copper interconnects the preparation method of solder joint |
| CN108453018A (en) * | 2018-03-22 | 2018-08-28 | 河南科技学院 | Foam copper based on sulfhydryl compound modification and its application |
| CN110052058A (en) * | 2019-04-04 | 2019-07-26 | 华南理工大学 | Modified foam copper of permanent seal cooling based on organopolysilazane modification and the preparation method and application thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102657954A (en) * | 2012-04-23 | 2012-09-12 | 中国石油天然气股份有限公司 | Material with water-controlled function and preparation method of same |
| CN102886155A (en) * | 2012-09-20 | 2013-01-23 | 北京航空航天大学 | Bionic construction of metal-foam-based oil-water separation material |
| CN102886155B (en) * | 2012-09-20 | 2015-01-14 | 北京航空航天大学 | Bionic construction of metal-foam-based oil-water separation material |
| CN102979066A (en) * | 2012-12-24 | 2013-03-20 | 南昌航空大学 | Device for adsorbing and separating spilled oil on water surface |
| CN105080216A (en) * | 2014-05-15 | 2015-11-25 | 浙江强盛滤料有限公司 | Preparation method of composite filter net of metal etching net and metal fiber net |
| CN104888498B (en) * | 2015-06-12 | 2016-06-15 | 东南大学 | A kind of durability super-hydrophobic super-oleophylic foam copper preparation method for oil-water separation |
| CN104888498A (en) * | 2015-06-12 | 2015-09-09 | 东南大学 | Preparation method of durable super-hydrophobic super-oleophylic foamy copper for oil and water separation |
| CN105344133A (en) * | 2015-12-08 | 2016-02-24 | 上海愚工机械科技有限公司 | Preparation method of oil-water separation membrane |
| CN105582693A (en) * | 2015-12-22 | 2016-05-18 | 北京航空航天大学 | T-type oil-water separation equipment integrating two special wettable materials |
| CN105582693B (en) * | 2015-12-22 | 2018-09-11 | 北京航空航天大学 | A kind of T-type oily water separating equipment integrating two kinds of special wellability materials |
| CN106310719A (en) * | 2016-08-26 | 2017-01-11 | 北京航空航天大学 | High efficiency and continuous oil-water separation device |
| CN106861629A (en) * | 2017-02-14 | 2017-06-20 | 江西中医药大学 | The nickel foam adsorbent of octadecyl modification and its application |
| CN107127468A (en) * | 2017-05-05 | 2017-09-05 | 哈尔滨工业大学深圳研究生院 | A kind of high temperature based on foam copper interconnects the preparation method of solder joint |
| CN107127468B (en) * | 2017-05-05 | 2020-02-14 | 哈尔滨工业大学深圳研究生院 | Preparation method of high-temperature interconnection welding spot based on foam copper |
| CN108453018A (en) * | 2018-03-22 | 2018-08-28 | 河南科技学院 | Foam copper based on sulfhydryl compound modification and its application |
| CN110052058A (en) * | 2019-04-04 | 2019-07-26 | 华南理工大学 | Modified foam copper of permanent seal cooling based on organopolysilazane modification and the preparation method and application thereof |
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Application publication date: 20110914 |