CN1613541A - Filtering and demulsifying material with super-parents characteristic and its preparation and use - Google Patents
Filtering and demulsifying material with super-parents characteristic and its preparation and use Download PDFInfo
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Abstract
A demulsifying filter material with superhydrophilicity and super lipophilicity for demulsifying and filtering the emulsion is prepared from the porous basic material through coating a layer of TiO2 film which contains organic silicon adhesive and can be solidified at ordinary temp, or coating a layer of TiO2 film to be sintered at high temp, or conting a TiO2-SiO2 film to be sintered at high temp, and UV irradiating.
Description
Technical field
The present invention relates to filter the breakdown of emulsion material, particularly have filtration breakdown of emulsion material of super hydrophilic, super oil-wet behavior and its production and use.
Background technology
Emulsion is everlasting to have in daily-use chemical industry, the compound probability widely because of its unique character and is used, simultaneously be again the important pollution sources that composing environment pollutes, as in compound probability, because product forms emulsion or generates in emulsion system, obtain clean product, just need carry out first breakdown of emulsion, adopt traditional breaking method, both increased cost, can not realize environmental friendliness again, increased pollution environment.In petrochemical industry, also reduced the quality of crude oil usually because of the existence of emulsion.As seen, the research of the breakdown of emulsion of emulsion is the problem that an existing most important theories meaning has using value again.
Because emulsifying agent molecule orientation on oil-water interface is adsorbed and formed firm interfacial film, has increased the effective thickness of diffuse double layer simultaneously, and makes the Potential distribution width of electric double layer and steepness increase, thereby make emulsion have suitable stability.Make the emulsion loss of stability, just must manage to eliminate or weaken the ability of emulsifying agent protection emulsion, promptly destroy the adsorbed film on the oil-water interface, reduce dispersed particle with the like charges amount, realize water-oil separating at last, reach the purpose of breakdown of emulsion.And there is the energy consumption height in traditional breaking method, the operating condition harshness, and poor effect causes pollution or the like deficiency easily.In recent years, the embrane method breakdown of emulsion has caused the extensive concern of Chinese scholars, and has obtained certain achievement.The film demulsification technology is normally selected a kind of microporous films of the hydrophilic or oleophylic identical with decentralized photo for use, by granting certain pressure, squeezed broken distortion when making emulsion pass through hole, because membrane material is identical with the decentralized photo compatibility, decentralized photo is wetting to be agglomerated into big liquid pearl thereby make, and plays the effect of breakdown of emulsion.Disclosed as Chinese patent publication number 1218771, when sewage by film when surface, hydrophilic, oleophylic, the balance of various particulates are destroyed, sewage carries out in the film pipe, finishes the breakdown of emulsion of emulsion particle simultaneously, easy construction is easy to operate, water-oil separating efficient height.And for example Chinese patent publication number 1044290 is disclosed, adopts filtration method that oil is carried out desalting and dewatering and handles, and they load strong hydrophilicity polarity in filter porous particulate filter comes breakdown of emulsion, makes in the oil emulsification water particle gather into the bulky grain water droplet and separates.European patent EP 0017283 discloses the micron perforated membrane with oleophylic and hydrophilic microcell, realizes the w/o type emulsion has been carried out the breakdown of emulsion separation.As seen the affine performance with decentralized photo is the key of breakdown of emulsion.
Compare the film breakdown of emulsion material of single parent and common parents' character, the surface has the micropore filtering material of super hydrophilic, super oleophylic, because of its distinctive super parents' surface nature, in theory, should there be better profit knot to assemble interior phase of emulsion or foreign minister's effect, be aided with certain pressure again, the crimp effect of micropore and the fine burr structure on filtering material surface can play the effect of breakdown of emulsion to the effect of puncturing of emulsion micella.The filtering material of super parents' surface nature will be applied to breakdown of emulsion and the separating oil aqueous mixtures is that new application breaks through so will have.
Summary of the invention
One of purpose of the present invention is to provide a kind of new filtration breakdown of emulsion material, and this material has super hydrophilic, super oleophilic characteristics.
A further object of the present invention is to provide the preparation methods of the filtration breakdown of emulsion with super parents' characteristic.
Another object of the present invention is to provide the purposes of filtration breakdown of emulsion material with super parents' characteristic.
Filtration breakdown of emulsion material with super parents' characteristic of the present invention, be to be coated with the ambient temperature curable titanium deoxid film that one deck contains the organosilicon bonding agent at the substrate surface that has 1～10 micron pore structure, wherein the mol ratio of Si: Ti is 0.2～1: 1, or coating one deck needs the titanium deoxid film of high temperature sintering, or apply the titanium dioxide of one deck need high temperature sintering and the laminated film of silica, wherein the mol ratio of titanium dioxide and silica is 3～10: 1.Described titanium dioxide is the titanium dioxide of anatase phase.
Filtration breakdown of emulsion material with super parents' characteristic of the present invention through behind the UV-irradiation, can obtain to continue 5～10 hours super hydrophilic, super oleophilic characteristics.Stopping 5～10 hours super parents' characteristics of ultraviolet lighting can disappear, and behind the ultraviolet lighting, can produce this characteristic again once more.
The employed colloidal sol of filtration breakdown of emulsion material with super parents' characteristic of the present invention can be the commercially available cold curing TiO 2 sol that is added with the organosilicon bonding agent, wherein the mol ratio of Si: Ti is 0.2～1: 1, it also can be the TiO 2 sol that needs high temperature sintering, can also be the complex sol of titanium dioxide and silica, wherein the mol ratio of titanium dioxide and silica be 3～10: 1.
Filtration breakdown of emulsion material with super parents' characteristic of the present invention has the renewable repeated use performance, and resistance to elevated temperatures is good.Can under the temperature about 500～700 ℃, repeat sintering, can remove the organic matter that some are difficult to immersion treatment.
Filtration breakdown of emulsion preparation methods step with super parents' characteristic of the present invention comprises:
(1). the base material that will have 1～10 micron hole is with weak caustic solution or acid soak, ultrasonicly again after water cleans cleanly handles 60 ℃ of left and right sides vacuum drying.
(2). to the super parents' modification of substrate surface that has hole
To be immersed in the colloidal sol through the base material that step (1) obtains with 1～10 micron hole, described colloidal sol is to add an amount of organosilicon binding agent in the anatase titania colloidal sol of commercially available ambient temperature curable, wherein the mol ratio of Si: Ti is 0.2～1: 1, vertically mention base material and after room temperature is placed, soak again, room temperature is placed again, repeats 3～10 times, obtains the filtration breakdown of emulsion material that the top layer contains the titanium deoxid film of different-thickness;
Or
Get the butyl titanate of 10～20 weight portions, be dissolved in the absolute ethyl alcohol of 30～66 weight portions, add 4～8 parts by weight of ethanol amine, stirring at room, add entry and ethanol volume ratio and be 1: 9 mixture 8～10 weight portions, stir, add the molecular weight that contains 0.5～2 weight portion and be ethanolic solution 10～30 weight portions of 1000～5000 polyethylene glycol, continue again to stir, add ethanol 60～100 weight portions, be made into the TiO 2 sol of variable concentrations, stir, get flaxen TiO 2 sol clear liquid;
To be immersed in the flaxen TiO 2 sol clear liquid through the base material that step (1) obtains with 1～10 micron hole, after vertically mentioning base material and in 60～100 ℃ baking oven, placing, soak again, in 60～100 ℃ baking oven, place, soak again, in 60～100 ℃ baking oven, place, repeat 3～10 times, sintering in 500～700 ℃ of muffle furnaces obtains the filtration breakdown of emulsion material that the top layer contains the titanium deoxid film of different-thickness again;
Or
Get the ethyl orthosilicate of 1～3 weight portion, the absolute ethyl alcohol of 4～12 weight portions, the distilled water of 2～6 weight portions, concentration is hydrochloric acid 0.03～0.09 weight portion of 36wt%, mixes, and is heated to about 70 ℃ after the formation mixed liquor again and refluxes, and obtains backflow mixed liquor; Get the acetylacetone,2,4-pentanedione of 9～30 weight portions, the absolute ethyl alcohol of the butyl titanate of 9～30 weight portions and 10～100 weight portions, form mixed liquor, mix stirring again with backflow mixed liquor, add absolute ethyl alcohol 80～100 weight portions then, water 18～60 weight portions, hydrochloric acid 0.54～1.8 weight portion, add the molecular weight contain 0.5～2 weight portion again and be ethanolic solution 8～30 weight portions of 1000～5000 polyethylene glycol, stir, obtain the clear liquid of the complex sol of the titanium dioxide of buff and silica, wherein the ratio of titanium dioxide and silica is 3～10;
To be immersed in through the base material that step (1) obtains in the clear liquid of complex sol of the titanium dioxide of buff and silica with 1～10 micron hole, after vertically mentioning base material and in 60～100 ℃ baking oven, placing, soak again, place in 60～100 ℃ the baking oven, repeat 3～10, sintering in 500～700 ℃ of muffle furnaces obtains the filtration breakdown of emulsion material that the top layer contains the titanium deoxid film of different-thickness again.
Base material among the present invention can be the all-glass paper that has hole, also can be other potsherd that has pore structure, nylon 6, aluminium oxide, Kynoar, polytetrafluoroethylene (PTFE) or synthetic fibers or the like.
Described organosilicon bonding agent can be that organic siliconresin or structural formula are R
1PSiX
q(OR
2)
tHydrolyzable silicon compound and partial hydrolysate thereof, wherein: R
1Be C
1～C
18Alkyl, X is a halogen atom, OR
2Be C
1～C
4Organic alkoxy, p+q+t=4,4 〉=q+t 〉=1.
Described organosilicon bonding agent can be decomposed by the photocatalytic the subject of knowledge and the object of knowledge of titanium dioxide, is about 0.2～1 times of content of titanium dioxide.
The concentration of the cold curing TiO 2 sol that uses among the present invention is 2～20g/l.
The emulsion of using among the present invention, its surfactant are anion surfactant, and the content of surfactant is 0.25wt%～2wt%.
The filtration breakdown of emulsion material with super parents' characteristic of gained of the present invention can obtain to continue super parents' characteristic of 5～10 hours after wavelength is the 365nm UV-irradiation.
The invention discloses a kind of new physics breakdown of emulsion material, this material has super parents' characteristic.Abundant wetting coalescence effect between super parents' material and the emulsion has destroyed the adsorbed film on the oil-water interface, thereby realizes the filtration breakdown of emulsion of emulsion.When oil-in-water (O/W) type emulsion after normal pressure is by super parents' filtering material, compare commercially available hydrophobic oleophylic glass paper, emulsion leaves standstill to the time of clarification and can effectively shorten.When Water-In-Oil (W/O) emulsion normal pressure and super parents' filtering material fully act on, filtration under diminished pressure again contrasts leaving standstill to the time of clarification of commercially available hydrophobic oleophylic glass paper and also can shorten greatly.When Water-In-Oil (W/O) emulsion under reduced pressure by super parents' filtering material, the breakdown of emulsion settling time that the contrast nature leaves standstill shortens greatly, and is suitable with the settling time of commercially available hydrophobic oleophylic glass paper.
Filtration breakdown of emulsion material of the present invention is applicable to Water-In-Oil (W/O) or oil-in-water (O/W) type emulsion.
The filtration breakdown of emulsion process of the filtration breakdown of emulsion material with super parents' characteristic of the present invention is as follows:
1) emulsion type used of the present invention is oil-in-water type (O/W) and water-in-oil type (W/O), adopts mechanical high-speed to stir, and rotating speed is 1400～1600 rev/mins, and wherein water-in-oil type (W/O) adopts the phase conversion method preparation.For increasing the stability of oil-in-water type (O/W) emulsion, in 1 part of surfactant, added the n-butanol of 2.5～4 weight portions as stabilizing agent.
The filtration breakdown of emulsion material with super parents' characteristic that 2) will prepare, be cut into the material that diameter is 70mm, place filter, the emulsion for preparing of measuring certain volume is poured in the filter, make emulsion pass through filtering material under the normal pressure, or after making emulsion and filtering material fully contacting, make emulsion pass through filtering material under the decompression again, make the emulsion of passing through place band scale test tube or conical flask then, investigate water or the oily volume told in the identical time, emulsion is thoroughly clarified the water yield or the oil mass of telling after needed time and the clarification.
Description of drawings
Fig. 1. the structural representation of super parents' filtering material that the present invention uses.
The specific embodiment
Embodiment 1
The hole that precleaning is good is about 3 microns all-glass paper, soak in the concentration of the cold curing that is added with the organosilicon bonding agent is the TiO 2 sol (wherein the mol ratio of Si/Ti is 0.7) of 5.8g/l, airing soaks again, airing repeats five times successively again.Shine in 30 minutes under ultraviolet light then, these two kinds super parents' material number of gained are c, and the filtering material for preparing is cut into the disk that diameter is 70mm.
Get the butyl titanate of 17 weight portions, be dissolved in the absolute ethyl alcohol of 55 weight portions, add 4 parts by weight of ethanol amine, stirring at room, adding volume ratio is 1: 9 the water and mixture 9 weight portions of ethanol, stirred 2 hours, add the molecular weight contain 1 weight portion again and be ethanolic solution 20 weight portions of 2000 polyethylene glycol, continue again to stir, add ethanol 80 weight portions, stir, get flaxen TiO 2 sol clear liquid; The hole that precleaning is good is about 3 microns all-glass paper, soaks in the faint yellow TiO 2 sol clear liquid for preparing, and airing soaks again, and airing repeats five times successively again.Through 550 ℃ of high temperature sinterings 1 hour, under ultraviolet light in the irradiation 30 minutes, these two kinds super parents' material number of gained were d then, and the filtering material of preparation is cut into the disk that diameter is 70mm.
Get 1 part of neopelex, 100 parts of water, 2.5 parts of n-butanols, 10 parts of cyclohexanes are put into the container of belt stirrer, and high-speed stirred forms O/W emulsion.Get the filtering material that a slice cuts and place filter, pour the emulsion 40ml for preparing into, the normal pressure emulsion is by filtering material, collects the emulsion of passing through and changes in the conical flask and leave standstill, and observes the oil mass of telling and clarifies fully the needed time.Wherein selected commercially available hydrophobic glass fibrous paper a for use; Commercially available hydrophobic glass fibrous paper activates the all-glass paper b that handles through cleaning surfaces and hydroxyl again behind 500 ℃ of high temperature sinterings, as the contrast of demulsification, following examples of implementation adopt identical contrast.The breakdown of emulsion result is as shown in table 1.
Table 1
| The filter membrane kind | Do not have | ????a | ????b | ????c | ????d | D considers immersion to be worth doing |
| Thorough settling time (my god) the beginning separation time (my god) branch oil pump capacity (ml) | ????14 ????1 ????2.5 | 12 1 are not | ????14 ????1 ????1.5 | ????13 ????1 ????1 | ????10 ????1 ????1 | 71 are not |
Annotate: " not " expression fails to measure oil volume, may be that oil content is low, be filtered film and sponge most of cause, below identical.
The mensuration of dividing oil pump capacity is after thoroughly clarifying, and measures after soaking 20 minutes under about 60 ℃ hot water, finds no the variation of The apparent phenomenon before and after the hot-water soak.Can find out that from table 1 glass paper c that titanium dioxide surface is handled and the more commercially available glass paper of the demulsification a (the hydrophobic oleophylic is applicable to water-oil separating) of d are good.
Embodiment 2
The preparation method of breakdown of emulsion material c and d is with embodiment 1, and wherein the mol ratio of the Si/Ti that selects for use of breakdown of emulsion material c is 0.5.
1 part of neopelex, 400 parts of water, 10 parts of n-butanols, 40 parts of cyclohexanes are put into the container of belt stirrer, and high-speed stirred forms O/W emulsion.The filtration breakdown of emulsion material stack that three diameters are 70mm is put into and is filtered breaking device, pour the emulsion 40ml that makes into, the normal pressure emulsion is by filtering material, and the emulsion that collection is passed through changes in the conical flask and leaves standstill, and the oil mass that observation is told reaches and clarifies fully the needed time.The breakdown of emulsion result is as shown in table 2.The result shows that the surface is covered with super parents' glass paper c of titanium dioxide film and d can both shorten 7～8 days with the breakdown of emulsion settling time of O/W emulsion, and demulsification is obvious.As seen contrast table 1 increases the usage quantity of filtering material, can improve demulsification.
Table 2
| The filter membrane kind | Do not have | ????a | ????b | ????c | ????d |
| Thorough settling time (my god) the beginning separation time (my god) branch oil pump capacity (ml) | ????13 ????1 ????2 | 10 1 are not | ????12 ????1 ????1.5 | 61 are not | 51 are not |
Embodiment 3
The preparation method of breakdown of emulsion material c and d is with embodiment 1, and wherein the mol ratio of the Si/Ti that selects for use of breakdown of emulsion material c is 0.8, and breakdown of emulsion material d is at 600 ℃ of sintering.
Surfactant changes 4 parts dodecyl sodium sulfate into, and dissolving under heating, and all the other are with example two, the O/W emulsion of formation.Use the filtration breakdown of emulsion material of a slice diameter as 70mm.Table 3 tells us to increase the action time of filtering material and emulsion, can improve demulsification.
Table 3
| The filter membrane kind | Do not have | ????a | ????c | ????d | D* (three times) |
| Thorough settling time (my god) the beginning separation time (my god) branch oil pump capacity (ml) | ??7 ??1 ??2.5 | ????7 ????1 ????0.5 | ????7 ????1 ????0.5 | ????4 ????1 ????0.5 | 1-not |
Annotate: * is meant that emulsion passes through the high temperature titanium film three times repeatedly, increases action time
Embodiment 4
Table 4
| The filter membrane kind | Do not have | ??e | ??d | ????f | ????a | ????g |
| Thoroughly settling time (day) begin separation time (my god) tell clear liquid amount (ml) after 1 day and tell clear liquid amount (ml) after 5 days | ????24 ????1 ????1 ????9.9 | ????17 ????1 ????1 ????10.6 | ????18 ????1 ????1 ????10.4 | ????18 ????1 ????1 ????10.1 | ????19 ????1 ????1 ????10.1 | ????15 ????1 ????1 ????10.8 |
The immersion of breakdown of emulsion material c and d repeats 3 times, and breakdown of emulsion material d is at 600 ℃ of sintering, and all the other preparation methods are with embodiment 1.
The preparation of breakdown of emulsion material e
Get the ethyl orthosilicate of 2 weight portions, the absolute ethyl alcohol of 8 weight portions, the distilled water of 4 weight portions, concentration is hydrochloric acid 0.06 weight portion of 36wt%, mixes, and is heated to about 70 ℃ again and refluxes 2 hours, obtains backflow mixed liquor; Get the acetylacetone,2,4-pentanedione of 17 weight portions, the absolute ethyl alcohol of the butyl titanate of 17 weight portions and 68 weight portions, form mixed liquor, mix with backflow mixed liquor again and stirred 30 minutes, add absolute ethyl alcohol 80 weight portions then, water 34 weight portions, hydrochloric acid 0.6 weight portion add the molecular weight contain 0.5 weight portion and are ethanolic solution 10 weight portions of 2000 polyethylene glycol again, stir, obtain the clear liquid of the complex sol of the titanium dioxide of buff and silica.The base material that will have 3 microns holes is immersed in the complex sol of the buff for preparing, and after vertically mentioning base material and placing in 80 ℃ baking oven, soaks again, place in 80 ℃ the baking oven, repeat 3 times, sintering in 600 ℃ of muffle furnaces shines in 30 minutes under ultraviolet light then again.This super parents' material of gained is cut into the disk that diameter is 70mm, is breakdown of emulsion material e.
1 part of neopelex, 100 parts of water, 4 parts of n-butanols, the O/W emulsion of 30 parts of n-hexanes is put into the container of belt stirrer, and high-speed stirred forms O/W emulsion.Get a slice and filter breakdown of emulsion material c, d, e, put into respectively and filter breaking device, pour the emulsion 40ml that makes into, the normal pressure emulsion is by filtering material, and each takes out 15ml and places graduated test tube to leave standstill through the emulsion behind the breakdown of emulsion material, every day, the volume of clear liquid told in record, and the oil mass that observation is told reaches and clarifies fully the needed time.The breakdown of emulsion experimental result is as shown in table 4.Wherein f refers to after breakdown of emulsion material a carries out breakdown of emulsion experiment, remove emulsion and surfactant after, use behind the ultraviolet lighting again again; G refers to and fills up the commercially available glass paper of one deck on the funnel earlier, and pad is gone up the combination of filtering material e again.As can be seen, the breakdown of emulsion ability of silica containing super parents' film is good slightly with the demulsification that only contains titanium dioxide film, wherein demulsification the best of g.
Embodiment 5
The preparation method of breakdown of emulsion material c and d is with embodiment 1.
Table 5
| The filter membrane kind | Do not have | a | ????d | ??h | ????j | ????d* |
| Thoroughly settling time (my god) begin to tell the clear liquid time (hour) branch oil pump capacity (ml) is divided water yield (ml) after 10 days after 10 days | ????- ????2 ????0.2 ????2 | 24 immediately 4.7 3.2 | ????20 ????18. ????1 ????0.5 | -immediately 1.8 3.1 | ????- ????2 ????0.6 ????2.9 | ????3 ????1 ????- ????- |
* refer to earlier under normal pressure, after emulsion and filter membrane fully act on, suction filtration under reduced pressure again
1 part of neopelex is dissolved in earlier in 30 parts of water, repeatedly adds 90 parts of n-hexanes on a small quantity, puts into the container of belt stirrer, adopts the phase conversion method high-speed stirred to be prepared into the w/o type emulsion.Get a slice respectively and filter breakdown of emulsion material d and contrast material, put into and filter breaking device, pour the emulsion 40ml that makes respectively into, filtering material is passed through in the emulsion decompression, taking out 15ml places graduated test tube to leave standstill through the emulsion behind the breakdown of emulsion material, every day, the volume of clear liquid told in record, observes the water yield and the oil mass told, and clarify fully the needed time.The result is as shown in table 5.Wherein h refers to fill up the commercially available glass paper of one deck a on the funnel earlier, and pad is gone up the combination of the all-glass paper c of room temperature titanium film modification again; J refers to fill up the commercially available glass paper of one deck a on the funnel earlier, and pad is gone up the combination of the all-glass paper d of high temperature sintering titanium film modification again.As can be seen from Table 5, under normal pressure fully after the effect, decompression makes emulsion see through filter membrane the thorough settling time of breakdown of emulsion is shortened greatly again, but commercially available glass paper a can divide water outlet rapidly, and the water content of emulsion is reduced rapidly.Directly decompression is left standstill after filtering emulsion down, finds that hydrophobic glass paper a's that time ratio that the all-glass paper d to the modification of high temperature titanium film clarifies emulsion fully is commercially available is short slightly.As seen titania modified super parents' glass paper has the breakdown of emulsion separating power too to the w/o type emulsion.
Embodiment 6
The immersion of breakdown of emulsion material d and e repeats 5 times, and the mol ratio of titanium dioxide and silica is 7 among the breakdown of emulsion material e, and all the other preparation methods are with embodiment 4.
Make 90 parts of n-hexanes into 100 parts of cyclohexanes, all the other adopt phase conversion method to be prepared into the w/o type emulsion with embodiment 5.Get a slice respectively and filter breakdown of emulsion material d, e and contrast material, put into and filter breaking device, pour the emulsion 40ml that makes respectively into, filtering material is passed through in the emulsion decompression, taking out 15ml places graduated test tube to leave standstill through the emulsion behind the breakdown of emulsion material, every day, the volume of clear liquid told in record, observes the water yield and the oil mass told, and clarify fully the needed time.The breakdown of emulsion result is as shown in table 6.The ability of instant minute water yield of commercially available as can be seen from Table 6 glass paper is better.Though the all-glass paper d of high temperature titanium film modification and the too late commercially available water-oil separating film a of the instant breakdown of emulsion separating power of the glass fiber material e of the compound titanium film modification that contains silica, but the contrast emulsion is static result directly, and the titanium dioxide glass fiber material still has breakdown of emulsion separating power preferably.Different time divides the size of water yield from table 6, and high temperature titanium dioxide glass fiber material d or silica containing composite glass fiber material e can both separate the w/o type emulsion preferably as can be seen.
Table 6
| The filter membrane kind | Do not have | ??d | ????a | ????e | ????k |
| Thorough settling time, (my god) divide oil pump capacity behind the 2h, (ml) divide water yield behind the 14h, (ml) divide water yield after 20 days, (ml) water yield of telling after the clarification, (ml) | -not 0.2 2- | ????- ????0.1 ????1 ????3 ????- | ????14 ????1.4 ????0.6 ????3.1 ????3.1 | ????- ????0.05 ????0.5 ????2.6 ????- | ????- ????0.2 ????0.2 ????1.9 ????- |
Claims (10)
1. filtration breakdown of emulsion material with super parents' characteristic, it is characterized in that: described material is to be coated with the ambient temperature curable titanium deoxid film that one deck contains the organosilicon bonding agent at the substrate surface that has 1～10 micron pore structure, wherein the mol ratio of Si: Ti is 0.2～1: 1, or coating one deck needs the titanium deoxid film of high temperature sintering, or apply the titanium dioxide of one deck need high temperature sintering and the laminated film of silica, wherein the mol ratio of titanium dioxide and silica is 3～10: 1.
2. material as claimed in claim 1 is characterized in that: described titanium dioxide is the titanium dioxide of anatase phase.
3. material as claimed in claim 1 is characterized in that: described base material is all-glass paper, potsherd, nylon 6, aluminium oxide, Kynoar, polytetrafluoroethylene (PTFE) or the synthetic fibers that have hole.
4. material as claimed in claim 1 is characterized in that: described organosilicon bonding agent is that organic siliconresin or structural formula are R
1PSiX
q(OR
2)
tHydrolyzable silicon compound and partial hydrolysate thereof, wherein: R
1Be C
1～C
18Alkyl, X is a halogen atom, OR
2Be C
1～C
4Organic alkoxy, p+q+t=4,4 〉=q+t 〉=1.
5. one kind as each described preparation methods of claim 1～4, and it is characterized in that: described preparation method's step comprises:
(1). clean base material and drying with 1～10 micron hole;
(2). to the super parents' modification of substrate surface that has hole
To be immersed in the colloidal sol through the base material that step (1) obtains with 1～10 micron hole, described colloidal sol is to add organic silicon bonding in the TiO 2 sol of cold curing, wherein the mol ratio of Si: Ti is 0.2～1: 1, mention base material, room temperature is placed, and obtaining the top layer is the filtration breakdown of emulsion material of titanium deoxid film;
Or
Get the butyl titanate of 10～20 weight portions, be dissolved in the absolute ethyl alcohol of 30～66 weight portions, add 4～8 parts by weight of ethanol amine, stirring at room, add entry and ethanol volume ratio and be 1: 9 mixture 8～10 weight portions, stir, add ethanolic solution 10～30 weight portions of the polyethylene glycol that contains 0.5～2 weight portion, continue again to stir, add ethanol 60～100 weight portions, be made into TiO 2 sol, stir, get the TiO 2 sol clear liquid;
To be immersed in through the base material that step (1) obtains in the TiO 2 sol clear liquid with 1～10 micron hole, after mentioning base material and in 60～100 ℃ baking oven, placing, sintering in 500～700 ℃ of muffle furnaces again, obtaining the surface is the filtration breakdown of emulsion material of titanium deoxid film;
Or
Get the ethyl orthosilicate of 1～3 weight portion, the absolute ethyl alcohol of 4～12 weight portions, the distilled water of 2～6 weight portions, hydrochloric acid 0.03～0.09 weight portion mixes, and adds hot reflux again after the formation mixed liquor, obtains backflow mixed liquor; Get the acetylacetone,2,4-pentanedione of 9～30 weight portions, the absolute ethyl alcohol of the butyl titanate of 9～30 weight portions and 10～100 weight portions, form mixed liquor, mix stirring again with backflow mixed liquor, add absolute ethyl alcohol 80～100 weight portions then, water 18～60 weight portions, hydrochloric acid 0.54～1.8 weight portion, ethanolic solution 8～30 weight portions that add the polyethylene glycol that contains 0.5～2 weight portion again, stir, obtain the clear liquid of the complex sol of titanium dioxide and silica, wherein the mol ratio of titanium dioxide and silica is 3～10: 1;
To be immersed in through the base material that step (1) obtains in the clear liquid of complex sol of titanium dioxide and silica with 1～10 micron hole, after mentioning base material and in 60～100 ℃ baking oven, placing, sintering in 500～700 ℃ of muffle furnaces again obtains the filtration breakdown of emulsion material of titanium deoxid film.
6. preparation method as claimed in claim 5 is characterized in that: described organosilicon bonding agent is that organic siliconresin or structural formula are R
1PSiX
q(OR
2)
tHydrolyzable silicon compound and partial hydrolysate thereof, wherein: R
1Be C
1～C
18Alkyl, X is a halogen atom, OR
2Be C
1～C
4Organic alkoxy, p+q+t=4,4 〉=q+t 〉=1.
7. preparation method as claimed in claim 5 is characterized in that: the molecular weight of described polyethylene glycol is 1000～5000.
8. preparation methods as claimed in claim 5 is characterized in that: the base material of described step (1) is further handled with ultrasonic cleaning after water cleans.
9. purposes as each described material of claim 1～4, it is characterized in that: described filtration breakdown of emulsion material with super parents' characteristic is used for the filtration breakdown of emulsion of emulsion.
10. the purposes of material as claimed in claim 9, it is characterized in that: described filtration breakdown of emulsion material is applicable to Water-In-Oil or oil-in-water emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310103150 CN1274386C (en) | 2003-11-05 | 2003-11-05 | Filtering and demulsifying material with super-parents characteristic and its preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310103150 CN1274386C (en) | 2003-11-05 | 2003-11-05 | Filtering and demulsifying material with super-parents characteristic and its preparation and use |
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| CN1274386C CN1274386C (en) | 2006-09-13 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432196A (en) * | 2011-09-22 | 2012-05-02 | 中国航天科技集团公司第五研究院第五一O研究所 | Preparation method of superhydrophilic TiO2/SiO2 porous bilaminar membrane |
| CN102875032A (en) * | 2011-07-15 | 2013-01-16 | 比亚迪股份有限公司 | Sol composition, preparation method thereof, method for forming self-cleaning and anti-reflective film on glass and self-cleaning and anti-reflective glass |
| CN108439627A (en) * | 2018-05-22 | 2018-08-24 | 浙江海牛环境科技股份有限公司 | A kind of process system and method to the demulsification of sewage containing oil emulsion |
| CN109016332A (en) * | 2018-07-12 | 2018-12-18 | 歌尔股份有限公司 | Inorganic non-metallic and the combination of plastics and preparation method thereof |
| CN112680876A (en) * | 2020-12-11 | 2021-04-20 | 厦门保瑞达环保科技有限公司 | Manufacturing method of high-precision plasticized polypropylene fiber felt |
| CN114471176A (en) * | 2021-12-09 | 2022-05-13 | 华南师范大学 | Super-hydrophilic composite membrane for realizing separation of emulsified oil and preparation method and application thereof |
-
2003
- 2003-11-05 CN CN 200310103150 patent/CN1274386C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875032A (en) * | 2011-07-15 | 2013-01-16 | 比亚迪股份有限公司 | Sol composition, preparation method thereof, method for forming self-cleaning and anti-reflective film on glass and self-cleaning and anti-reflective glass |
| CN102875032B (en) * | 2011-07-15 | 2015-09-02 | 比亚迪股份有限公司 | Sol composition and preparation method thereof, form the method for self-cleaning anti-reflection film and self-cleaning anti-reflective glass at glass surface |
| CN102432196A (en) * | 2011-09-22 | 2012-05-02 | 中国航天科技集团公司第五研究院第五一O研究所 | Preparation method of superhydrophilic TiO2/SiO2 porous bilaminar membrane |
| CN102432196B (en) * | 2011-09-22 | 2014-03-26 | 中国航天科技集团公司第五研究院第五一O研究所 | Preparation method of superhydrophilic TiO2/SiO2 porous bilaminar membrane |
| CN108439627A (en) * | 2018-05-22 | 2018-08-24 | 浙江海牛环境科技股份有限公司 | A kind of process system and method to the demulsification of sewage containing oil emulsion |
| CN109016332A (en) * | 2018-07-12 | 2018-12-18 | 歌尔股份有限公司 | Inorganic non-metallic and the combination of plastics and preparation method thereof |
| CN112680876A (en) * | 2020-12-11 | 2021-04-20 | 厦门保瑞达环保科技有限公司 | Manufacturing method of high-precision plasticized polypropylene fiber felt |
| CN112680876B (en) * | 2020-12-11 | 2022-06-14 | 厦门保瑞达环保科技有限公司 | Manufacturing method of high-precision plasticized polypropylene fiber felt |
| CN114471176A (en) * | 2021-12-09 | 2022-05-13 | 华南师范大学 | Super-hydrophilic composite membrane for realizing separation of emulsified oil and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1274386C (en) | 2006-09-13 |
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