CN106955506A - The high stable state of big flux is used for the super hydrophilic three-dimensional porous base material of water-oil separating - Google Patents
The high stable state of big flux is used for the super hydrophilic three-dimensional porous base material of water-oil separating Download PDFInfo
- Publication number
- CN106955506A CN106955506A CN201710127690.0A CN201710127690A CN106955506A CN 106955506 A CN106955506 A CN 106955506A CN 201710127690 A CN201710127690 A CN 201710127690A CN 106955506 A CN106955506 A CN 106955506A
- Authority
- CN
- China
- Prior art keywords
- water
- base material
- sponge
- hydrophilic
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The present invention relates to the super hydrophilic three-dimensional porous base material that a kind of big high stable state of flux is used for water-oil separating, the micro/nano level hydrophilic material base sponge that the three-dimensional porous base material is prepared using doping method in situ is support, functional modification is carried out to it with the hydrophilic hydrogel for adding preservative, and strengthening the adhesive force of hydrophilic hydrogel and the intensity of sponge with hydrophilic black cement, whole preparation process mainly includes blending foaming, absorption filling, dry solidification and processing four steps of combination.The present invention is not the pattern progress with the adsorption/desorption of traditional oil absorption material when being used for water-oil separating based on hydrophily three-dimensional porous sponge base material, but using the base material as water resistance oil filtering layer, the conditions such as the quantity of thickness, the area of substrate combination part and increase substrate combination part by adjusting base material unit, reach the purpose of the profit processing of the high stable state of big flux by way of water pump draws water, lightweight oil water mixture and heavy oil water mixture are applicable.
Description
Technical field
The invention belongs to functional material technical field, and in particular to a kind of big high stable state of flux is used for the parent of water-oil separating
Aqueous three-dimensional porous base material.
Background technology
Ship ballast water, the infiltration of gas station's oil tank, oil refining, plant equipment processing, the leakage of rivers oil plant, ocean leakage
The oil water mixture of the staggering amounts of generation such as oil, oilfield water extraction, shale oil exploitation, realizes point of oil and water in oil water mixture
Quick, efficient process from especially a large amount of oil water mixtures are key subjects that current field of Environment Protection faces.Low cost
Realize oil water mixture efficiently separate on the one hand can reclaim oil plant be used for reproduction utilize, oil water mixture can be reduced
Processing cost, i.e., reduction production and processing cost bring economic benefit, on the other hand for environment improvement with protect have greatly
Benifit, thereby increases good social benefit.
In recent years, substantial amounts of exploratory development is concentrated mainly on the work(constructed with hydrophobic oleophilic oil or oleophobic water-wet behavior surface
Mode of the base materials such as sponge, screen cloth or fabric based on suction-desorption and filtering can be changed and realize oil water mixture.Such as Chinese patent CN
103342827 B disclose a kind of preparation method of hydrophobic/lipophilpolyurethane polyurethane sponge, and this method is prepared based on crystalline flake graphite
Expanded graphite, then through concentrated nitric acid long-time reflow treatment, and the ultrasonic a few hours in the mixed solution of ammoniacal liquor and ethanol, after will use
What the polyurethane sponge immersion that acetone and deionized water are cleaned by ultrasonic was obtained enters in graphene ethanol solution, takes out and reached after drying
The purpose of oleophilic drainage, and then for water-oil separating.This method process is complicated and uses that concentrated nitric acid and acetone etc. is high-risk, high toxicity
Reagent, brings extra problem of environmental pollution, substantially increases production cost.Simultaneously between graphene and sponge without or only
There is a small amount of functional group's connection, undoubtedly can largely be come off during oil suction-extruding de-oiling, this not only makes the performance of sponge big
Big reduction, but also understand contaminated product and water body because of coming off for graphene, cause extra pollution threat.
The B of Chinese patent CN 102953268 disclose a kind of preparation of super oleophilic and super hydrophobic oil-water separation terylene textile
Method, its elder generation, for solvent, by the regulation of ammoniacal liquor, hydrochloric acid, is prepared with methanol, n-hexane etc. and is based on tetraethyl orthosilicate and hexamethyl
The hydrophobic Ludox of disilazane, then dacron carried out in above-mentioned hydrophobic Ludox to pad processing, it can obtain
The Polyester Textiles of the super-hydrophobic water-oil separating of oleophylic must be surpassed.
The sponge for water-oil separating of above-mentioned preparation and Polyester Textiles, are the hydrophobic-lipophilics based on material surface
Characteristic.Under the working condition that the oil water mixture of a small amount of or small area is only applicable to for the former, while needing special equipment
Suction deoiling treatment is carried out to sponge, treatment effeciency is not high；For the latter, it is adapted to the substantial amounts of oil water mixture of processing, but to preparing
Technological requirement is too high, because must accomplish firm covering of the functional material to fabric face 100%, otherwise the flaw of a little
Just have oil product to pass through, and then the content of oil product in water after processing is significantly increased, and have necessarily to the clarity of oil water mixture
Requirement, i.e., can not contain obvious impurity, including particle, suspension, oil emulsion etc., otherwise can cause the obstruction of mesh, enter
And cause flux to substantially reduce, fabric certainly will be carried out and frequently changed.These factors all restrict the practical application of similar products.
The content of the invention
The present invention, which is based on the sponges such as polyurethane sponge, polyvinylalcohol sponge, melamine sponge, has great amount of hydroxy group, amino etc.
Labile functional groups, it is easy to be based on the active forces such as hydrogen bond with polyvinyl alcohol based hydrogel and be closely linked, reach that sponge is hydrophilic
Property purpose, the mechanical strength of sponge can be strengthened by adding a certain amount of hydrophily black cement, and the addition of a certain amount of preservative is also
The service life of base material can be extended and separative efficiency is kept.Big flux high stable state of the present invention based on this preparation is used for water-oil separating
The three-dimensional porous base material of hydrophily, carry out be not during water-oil separating with the progress of the pattern of the adsorption-desorption of traditional sorbing material, and
It is using the base material as filter layer, by adjusting the thickness of base material unit, the area of substrate combination part and increase substrate combination part
The conditions such as quantity, realized by way of pumping draws water or filters the high stable state of big flux profit processing purpose, to light oil-
Aqueous mixtures and mink cell focus-aqueous mixtures are applicable.
Specific technical scheme is, the micro/nano level that super hydrophilic three-dimensional porous base material of the invention is prepared with doping method in situ
Hydrophilic material base sponge is support, and functional modification is carried out to it with the hydrophilic hydrogel for adding preservative, and with hydrophilic
Black cement enhancing hydrophilic hydrogel adhesive force and the intensity of sponge, whole preparation process mainly includes,
1st, blending-foaming：By micro/nano level hydrophilic material, such as hydrophilic silicon oxides, hydrophily graphite oxide, hydrophily oxygen
The one or more of graphite alkene, hydrophilic nano titanium dioxide, hydrophilic nano zinc oxide etc., pass through the side such as stirring, ultrasound
Formula is scattered in the primary raw materials of sponge foaming such as polyurethane sponge, melamine sponge, polyvinylalcohol sponge；Micro/nano level hydrophily
Material can use low temperature plasma surface grafting technology to be pre-processed to increase its surface hydrophilicity functional group, plasma spoke
According to power be 50-300 W, exposure time be 0.5-5 min, vacuum be 30 Pa-120 Pa, doping relative to
The mass fraction of sponge foaming primary raw material is 0.01-0.5 %, and the specification of foam sponge is spongioplasm per square inch
（PPI）More than 40, shape, thickness and area can be constructed according under practical application working condition with special dies.
2nd, absorption-filling：1）First by heating, the crosslinking method such as gamma-rays, ultraviolet irradiation prepares mass concentration and is
0.1-2% hydrophilic polyethene alcohol based aquagel aqueous solution, can be polyvinyl alcohol hydrogel, polyvinyl alcohol-glutaraldehyde
Cross-linked hydrogel, polyvinyl alcohol-formaldehyde cross-linked hydrogel or polyvinyl alcohol-tannic acid cross-linked hydrogel.In above-mentioned hydrogel
The micro/nano level hydrophilic material of the addition preparation of part steps 1 simultaneously makes it be uniformly dispersed to strengthen hydrophily and construct coarse table circle
Face structure, micro/nano level hydrophilic material is 0.02-0.5% relative to the mass fraction of hydrogel solution；2）Preparing poly- second
A certain amount of preservative can be added during the enol aqueous solution or hydrophilic hydrogel solution, such as sorbic acid, benzoic acid, to hydroxyl
Yl benzoic acid, salicylic acid etc., the structure of hydrogel and sponge bracket caused by the breeding to suppress mushroom in use
Destruction, and then extend the service life of base material and keep separative efficiency, wherein the quality of the preservative added is relative to poly- second
The 1-5% of enol dry powder；3）Add the black cement relative to above-mentioned polyvinyl alcohol based hydrogel aqueous solution gross mass 15-35%
And be sufficiently stirred for；4）Polyurethane sponge, polyvinylalcohol sponge, melamine sponge etc. have the active official such as great amount of hydroxy group, amino because of it
Can group, it is easy to be based on the active force such as hydrogen bond with polyvinyl alcohol based hydrogel and be closely linked, thus by step 1 obtain it is specific
The sponge of shape is immersed in the polyvinyl alcohol based hydrogel aqueous solution of above-mentioned preparation, and by face pressed several times until sponge absorbing liquid
Body keeps 1-10 min to saturated mode.
3rd, dehydration-solidification：, can after taking-up when being mixed with black cement in base material after adsorption saturation state to be achieved
1-7 angel's cement solidification of holding in room temperature or 15-55 DEG C of environment is first placed in, electricity consumption blowing warm air drying afterwards, vacuum
The modes such as heat drying, infrared radiation heating or microwave irradiation heating slough moisture and make resin solidification, drying process control temperature
Spend in the range of 60-160 DEG C, during dehydration, polyvinyl alcohol based hydrogel gradually solidifies in the surface of sponge skeleton
On, that is, obtain hydrophily three-dimensional porous sponge base material.Absorption-filling and dehydration-curing schedule may be repeated 1-2 time.
4th, processing-combination：Obtained hydrophilic porous base material can process-be combined into suitable operating mode with reference to practical situations
Under the conditions of oily-water seperating equipment, using it is preceding in water soak 10-30min after, hydrophily sponge reach water saturation inhale
It is attached, you can be used for the quick separating of oil and water in a variety of oil water mixtures by way of water pump draws water or filters.
Compared with prior art, the advantage of the invention is that：
The present invention has the labile functional groups such as great amount of hydroxy group, amino based on sponge, it is easy to be based on hydrogen with polyvinyl alcohol based hydrogel
The active forces such as key are closely linked, and the adhesive force and the sponge that add further to enhance hydrogel of hydrophilic black cement
Intensity, with this prepare the high stable state of big flux be used for water-oil separating the three-dimensional porous base material of hydrophily, with preparing hydrophobic-lipophilic circle
Facestock material is compared, and the process engineering is simple, stably, low cost, no high poison, the use of high-risk reagent.
The present invention based on hydrophily three-dimensional porous sponge base material be used for water-oil separating when be not with traditional oil absorption material
The pattern of adsorption-desorption is carried out, but using the base material as water-oil resistance filtering layer, by the thickness, the base material that adjust base material unit
The condition such as the area of sub-assembly and the quantity of increase substrate combination part, reaches the high stable state of big flux by way of water pump draws water
Light oil-aqueous mixtures and mink cell focus-aqueous mixtures are applicable by the purpose of profit processing.
The present invention with the addition of a certain amount of anti-during polyvinyl alcohol water solution or hydrophilic hydrogel solution is prepared
Rotten agent, suppresses the breeding of mushroom in use, it is therefore prevented that hydrogel and sponge bracket it is destructurized, extend base material
Service life and keep base material separative efficiency.
The micro/nano level hydrophilic nanoparticles that the present invention adulterates in blending-foaming and absorption-filling step, it is such as hydrophilic
Property nano titanium oxide and hydrophilic nano zinc oxide etc., not only enhance hydrophilic-oleophobic performance of base material, and due to dioxy
Changing titanium and zinc oxide has good photocatalysis performance, i.e., certain superoxide anion and hydroxyl can be produced under illumination condition
The reactive groups such as ion, these groups can effectively kill and suppress the breeding of bacterium, thus slow down base material and be etched speed, with
Preservative synergy and then the service life that base material can be greatly prolonged.
Embodiment
The present invention is described in further detail with reference to embodiments.
Embodiment 1
The high stable state of big flux is used for the preparation of the three-dimensional porous base material of hydrophily of water-oil separating：
Step one：Hydrophilic silicon oxides are distributed to the primary raw material melamine formaldehyde resin of melamine sponge by stirring
In, ~ 50 PPI hydrophilic silicon oxides original position doping melamine sponge, the addition of silica are made after microwave radiation technology foaming
The mass percent measured relative to resin is~0.1 %；
Step 2：The polyvinyl alcohol that 1750+50 type polyvinyl alcohol is dissolved in into preparation mass fraction 0.65 % in 95 DEG C of water is transparent
The aqueous solution, adds the P-hydroxybenzoic acid relative to polyvinyl alcohol quality 2% and is completely dissolved it, while adding relative to poly-
The hydrophilic nano silica of vinyl alcohol quality 8%, keeps under the conditions of 55-60 DEG C, stirs；It is slowly added to quality point
Several 5 % boric acid aqueous solution, quick stirring is untill having white flock insoluble matter to occur and do not dissolve, and acquisition is mixed with hydrophily
The polyvinyl alcohol of silica-boric acid cross-linked hydrogel solution；
Step 3：Based on prepared melamine sponge, constructed with the mode of cutting outside dimension for the mm of 130 mm × 110 ×
80 mm, inside dimension are the mm size sponge substrates of the mm of 110 mm × 90 × 60, and are dipped in the polyethylene prepared
In alcohol-boric acid cross-linked hydrogel aqueous solution, take out, sloughed with the electrically heated mode of blowing warm air in base material after adsorption saturation
Moisture, obtains hydrophilic silicon oxides-polyvinyl alcohol-boronate hydrophily melamine sponge substrate, and surrounding is kept during dehydration-solidification
Environment temperature is 95~100 DEG C；
Step 4：Above-mentioned gained melamine sponge substrate is soaked in running water after 20 min, using peanut oil-water system to treat point
From mixture（Profit initial volume ratio is 20：80）, the processing flux that single assembly is calculated by way of water pump draws water is water
The m of flux 0.43~0.453 h-1, the content of oil product is 16-22 ppm in water sample after separation.
Embodiment 2
It is embodied with reference to embodiment 1, difference is：
Step 2：1750+50 type polyvinyl alcohol is dissolved in the poly- second that the % of water white transparency mass fraction 0.65 is prepared in 95 DEG C of water
The enol aqueous solution, while adding the sorbic acid relative to the % of polyvinyl alcohol quality 1.5 and being completely dissolved it；Keep 60-
Under the conditions of 65 DEG C, 5 mg mL of the volume 2% relative to polyvinyl alcohol water solution are added-1Graphene oxide dispersion and matter
The % of fraction 4 glutaraldehyde water solution is measured, the wherein volume of glutaraldehyde water solution is 1 with respect to the volume ratio of polyvinyl alcohol water solution:
40, continue to add the black cement relative to above-mentioned hydrogel solution gross mass 20% after 30 min of stirring and be sufficiently stirred for, mixed
There is oxidation used in the scattered polyvinyl alcohol-glutaraldehyde cross-linked hydrogel solution of the graphene oxide of black cement, the present embodiment
Graphene is made for oxidation-reduction method（J. Am. Chem. Soc., 1958, 80, 1339 ; J. Am. Chem.
Soc., 2009, 131, 13490）；After adsorption saturation state to be achieved, it is placed in after taking-up in 35 DEG C of environment and places 3 angel's water
Mud solidifies, and sloughs moisture in sponge under 100 DEG C in the way of electric heating forced air drying environment afterwards.With prepared hydrophily melamine
Based on sponge substrate, it is that the mm of the mm of 180 mm × 170 × 80, inside dimension are 160 that outside dimension is constructed with the mode of cutting
The base material of the mm sizes of the mm of mm × 150 × 65；
Step 3：Respectively using peanut oil-water system and diesel fuel-water as mixture to be separated（Profit initial volume ratio is 20：
80）, the base material obtained is first soaked into 20 min in running water, then measure by way of pumping is fetched water the place of single assembly
Reason flux is the m of water flux 0.99 ~ 1.053 h-1With 1.15 ~ 1.18 m3 h-1, extract the content of oil product in water sample after separation
Respectively 19-29 ppm and 14-21 ppm.
Embodiment 3
It is embodied with reference to embodiment 1, difference is：
Step one：The micro Nano material of addition is hydrophilic nano titanium dioxide, and low temperature plasma surface is first being used before
Grafting technology is pre-processed to increase its surface hydrophilicity functional group, and plasma irradiation power is 120 W, and exposure time is 1
Min, vacuum is 50 Pa
Step 3：What is obtained is nano titanium oxide-polyvinyl alcohol-boronate hydrophily melamine sponge substrate；
Step 4：Using sewing machine oil-water system as mixture to be separated, profit initial volume ratio remains as 20：80, same size
Under the conditions of, the processing flux of single assembly is 0.49 ~ 0.53 m3 h-1, the content of oil product is 20-28 in water sample after separation
ppm；Outdoor has under illumination condition, after 30 days, and the processing flux of the sponge based devices is the m of water flux 0.43 ~ 0.473 h-1,
The content of oil product is 25-32 ppm in water sample after separation；After 60 days, the processing flux of the sponge based devices is water flux 0.40
~ 0.44 m3 h-1, the content of oil product is 26-37 ppm in water sample after separation.
Embodiment 4
Step one：The melamine sponge that sponge is commercially available 40 PPI and 60 PPI that can directly buy.By 1750+50 type polyvinyl alcohol
The polyvinyl alcohol transparent aqueous solution that the % of mass fraction 0.85 is prepared in 95 DEG C of water is dissolved in, while adding relative to polyvinyl alcohol
The benzoic acid of quality 3% is simultaneously completely dissolved it；At 50 DEG C add relative to polyvinyl alcohol water solution quality 15% black cement simultaneously
It is sufficiently stirred for, obtains the polyvinyl alcohol-aqueous mixtures for being mixed with black cement；
Step 2：40 commercially available PPI and 60 PPI melamine sponge are directly immersed in the above-mentioned 0.85 % poly- second for being mixed with black cement
In enol-aqueous mixtures solution, it is placed in 35 DEG C of environment and is placed after 3 angel's cement solidifications with electricity after adsorption saturation, after taking-up
Moisture in sponge is sloughed under 100 DEG C of environment of mode that hot blast is dried, black cement-polyvinyl alcohol-melamine sponge substrate is obtained..
Step 3：It is that the mm of the mm of 180 mm × 170 × 80, inside dimension are 160 mm that outside dimension is constructed with the mode of cutting
The oily-water seperating equipment of the mm sizes of × 150 mm × 65, soaks after 15 min in water, is surveyed by way of pumping is fetched water
The content of oil product is in water sample after the processing flux of calculation single assembly and separation：For 40 PPI black cements-polyvinyl alcohol-melamine
Sponge substrate, water flux is 1.49 ~ 1.57 m3 h-1, filtrate oil content be 31-37 ppm（Peanut oil-water system）And water
Flux is 1.66 ~ 1.69 m3 h-1, filtrate oil content be 27-35 ppm（Diesel fuel-water system）；For 60 PPI Heisui River
Mud-polyvinyl alcohol-melamine sponge substrate, water flux is 0.92 ~ 0.96 m3 h-1, filtrate oil content be 11-17 ppm（Flower
Raw oil-water system）It is 0.98 ~ 1.05 m with water flux3 h-1, filtrate oil content be 14-22 ppm（Diesel fuel-water system）,
The initial volume ratio of oil product and water is 20 in above oil water mixture：80.
Embodiment 5
It is embodied with reference to embodiment 1, difference is：
Step one：Sponge is direct commercially available commercially available 50 PPI polyurethane sponge；
Step 2：The polyvinyl alcohol that 1750+50 type polyvinyl alcohol is dissolved in into preparation mass fraction 0.8 % in 95 DEG C of water is transparent
The aqueous solution, while adding the salicylic acid relative to polyvinyl alcohol quality 5% and being completely dissolved it；Keep 65-70 DEG C of conditions
Under, the % of mass fraction 10 tannin aqueous acid, and the ultraviolet lamp for being 365nm with wavelength are slowly added to, 5 cm lamps are away from irradiation
20 seconds, it is further continued for being slowly stirred 30 min, obtains polyvinyl alcohol-tannic acid cross-linked hydrogel solution；
Step 3：What is obtained is polyvinyl alcohol-tannin acidic group hydrophilic polyurethane sponge base material；
Step 4：Based on gained polyurethane sponge base material, outside dimension is constructed with the mode of cutting for 130 mm × 110
The mm of mm × 80, inside dimension are the oily-water seperating equipment of the mm sizes of the mm of 110 mm × 90 × 60, and 20 are soaked in water
After min, using methyl-silicone oil-aqueous systems as mixture to be separated（Profit initial volume ratio is 20：80）, the side drawn water by water pump
The processing flux of formula measuring and calculating single assembly is the m of water flux 0.62 ~ 0.693 h-1, the content of oil product is 31 in water sample after separation
- 38 ppm。
Embodiment 6
It is embodied with reference to embodiment 3, difference is：
Step 4：Using sewing machine oil-water system as mixture to be separated, profit initial volume ratio remains as 15：85, same size
Under the conditions of, the processing flux of single assembly is the m of water flux 0.73 ~ 0.763 h-1, the content of oil product is 21 in water sample after separation
- 27 ppm. treat base material operation 10 hours daily, and after running 60 days, it is passed through into forced air drying respectively under the conditions of 65 DEG C
And vacuum drying is sloughed after moisture again, the separation of the oil water mixture of sewing machine oil-water system, the first initial body of profit are re-used for
Product ratio remains as 15：85, the processing flux of single assembly is the m of water flux 0.71 ~ 0.743 h-1, oil product in water sample after separation
Content be 25-33 ppm.
In addition to the implementation, present invention additionally comprises have other embodiment, all use equivalents or equivalence replacement
The technical scheme that mode is formed, all should fall within the scope of the hereto appended claims.
Claims (10)
1. a kind of high stable state of big flux is used for the super hydrophilic three-dimensional porous base material of water-oil separating, it is characterised in that：This is three-dimensional porous
The micro/nano level hydrophilic material base sponge that base material is prepared using doping method in situ is support, to add the hydrophily water-setting of preservative
Glue carries out functional modification to it, and strengthens the adhesive force of hydrophilic hydrogel and the intensity of sponge with hydrophilic black cement, whole
Individual preparation process mainly includes blending-foaming, absorption-filling, drying-solidification and the step of processing-combination four.
2. a kind of big high stable state of flux according to claim 1 is used for the three-dimensional porous base material of Superhydrophilic of water-oil separating,
It is characterized in that：The micro/nano level hydrophilic material of doping includes hydrophilic silicon oxides, hydrophily graphite oxide, hydrophily oxygen
One or more in graphite alkene, hydrophilic nano titanium dioxide, hydrophilic nano zinc oxide etc..
3. a kind of big high stable state of flux according to claim 2 is used for the three-dimensional porous base material of hydrophily of water-oil separating, its
It is characterised by：Described micro/nano level hydrophilic material further can be located in advance using low temperature plasma surface grafting technology
Reason is to increase its surface hydrophilicity functional group, and plasma irradiation power is 50-300 W, and exposure time is 0.5-5 min,
Vacuum is 30 Pa -120 Pa.
4. a kind of big high stable state of flux according to claim 1 is used for the three-dimensional porous base material of hydrophily of water-oil separating, its
It is characterised by：The doping of described micro/nano level hydrophilic material is relative to the mass fraction of sponge foaming primary raw material
0.01-0.5 %, and be scattered in by way of stirring, ultrasound in primary raw material；Described sponge is polyurethane sponge, close
Amine sponge, polyvinylalcohol sponge, specification are spongioplasm per square inch（PPI）More than 40.
5. a kind of big high stable state of flux according to claim 1 is used for the three-dimensional porous base material of hydrophily of water-oil separating, its
It is characterised by：Hydrogel can be polyvinyl alcohol hydrogel, polyvinyl alcohol-boric acid crosslinking in described hydrophilic hydrogel solution
Hydrogel, Polyvinyl alcohol-borax cross-linked hydrogel, polyvinyl alcohol-glutaraldehyde cross-linked hydrogel, polyvinyl alcohol-formaldehyde crosslinking water
The one or more of gel, polyvinyl alcohol-tannic acid cross-linked hydrogel etc., wherein crosslinking method include heating, gamma-rays, ultraviolet
Line is irradiated, and the mass concentration of the prepared polyvinyl alcohol based hydrogel aqueous solution is 0.1-2%；Optionally pass through simultaneously
The part that the mode of stirring and ultrasound is disperseed in micro/nano level hydrophilic material is in wherein, and micro/nano level hydrophilic material is relative
In hydrogel solution mass fraction be 0.02-0.5%.
6. a kind of big high stable state of flux according to claim 5 is used for the three-dimensional porous base material of hydrophily of water-oil separating, its
It is characterised by：A certain amount of preservative can be added during polyvinyl alcohol water solution or hydrophilic hydrogel solution is prepared,
Preservative includes sorbic acid, benzoic acid, P-hydroxybenzoic acid, salicylic acid, and the quality of the preservative of addition is relative to polyvinyl alcohol
The percentage amounts of dry powder are 1-5%.
7. a kind of big high stable state of flux according to claim 5 is used for the three-dimensional porous base material of hydrophily of water-oil separating, its
It is characterised by：Add the black cement of the quality 15-35% relative to the polyvinyl alcohol based hydrogel aqueous solution and be sufficiently stirred for.
8. a kind of big high stable state of flux according to claim 1 is used for the three-dimensional porous base material of hydrophily of water-oil separating, its
It is characterised by：Sponge material is immersed into polyvinyl alcohol based hydrogel solution or the polyvinyl alcohol based hydrogel solution of black cement is mixed with
In, after adsorption saturation state to be achieved, can be first placed in when being mixed with black cement in base material, after taking-up room temperature or 15-
1-7 angel's cement solidification is kept in 55 DEG C of environment, is taken out afterwards and the drying of electricity consumption blowing warm air, vacuum and heating drying, red
The mode of external irradiation heating or microwave irradiation heating sloughs moisture and makes resin solidification, and it is 60-160 that drying process, which controls temperature,
In the range of DEG C, during dehydration, polyvinyl alcohol based hydrogel gradually solidifies on the surface of sponge skeleton, that is, obtains parent
Aqueous three-dimensional porous sponge base material.
9. a kind of big high stable state of flux according to claim 7 is used for the three-dimensional porous base material of hydrophily of water-oil separating, its
It is characterised by：The sponge base base material of prepared hydrogel modification can be molded in sponge foaming by template according to the actual requirements
Or the mode of later stage machining is constructed suitable for the water-oil separating base material under different working conditions.
10. a kind of big high stable state of flux according to claim 8 is used for the three-dimensional porous base material of hydrophily of water-oil separating, its
It is characterised by：The three-dimensional porous base material of gained hydrophily should first soak 10-30 min using preceding in water, reach water
After saturation absorption is swelled, you can the quick separating for profit, it is adaptable to edible oil-water, machine oil-water, diesel fuel-water, silicone oil-
The oil mixing with water objects systems such as water, low content Crude oil-water；The area and base of thickness, substrate combination part according to single base material unit
The conditions such as the quantity of material sub-assembly, the processing flux to oil water mixture is the m of water flux 0.1-303 h-1, separative efficiency is big
In 99.99 %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710127690.0A CN106955506A (en) | 2017-03-06 | 2017-03-06 | The high stable state of big flux is used for the super hydrophilic three-dimensional porous base material of water-oil separating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710127690.0A CN106955506A (en) | 2017-03-06 | 2017-03-06 | The high stable state of big flux is used for the super hydrophilic three-dimensional porous base material of water-oil separating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106955506A true CN106955506A (en) | 2017-07-18 |
Family
ID=59470067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710127690.0A Pending CN106955506A (en) | 2017-03-06 | 2017-03-06 | The high stable state of big flux is used for the super hydrophilic three-dimensional porous base material of water-oil separating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106955506A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108080045A (en) * | 2017-12-27 | 2018-05-29 | 北京百奥芯科技有限公司 | A kind of hydrophilically modified method of fluid channel inside micro-fluidic chip |
| CN108671585A (en) * | 2018-05-29 | 2018-10-19 | 大连理工大学 | A kind of preparation method of super hydrophilic net for water-oil separating |
| CN108786183A (en) * | 2018-05-29 | 2018-11-13 | 大连理工大学 | A kind of preparation method of super-hydrophobic-super oleophylic net for water-oil separating |
| CN109296839A (en) * | 2018-10-12 | 2019-02-01 | 江苏天润管业有限公司 | A kind of strong closed type buried corrosion-resistant insulating tube and preparation method thereof |
| CN110407993A (en) * | 2018-04-26 | 2019-11-05 | 祯佶祥实业股份有限公司 | The permeable graphene sponge of oil suction |
| US11306164B2 (en) | 2019-04-02 | 2022-04-19 | King Fahd University Of Petroleum And Minerals | Water purification material for petrochemicals |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433822A (en) * | 2008-12-10 | 2009-05-20 | 郑国炉 | Air purification material and preparation method thereof as well as produced art ware or material for decoration |
| CN101875006A (en) * | 2010-04-30 | 2010-11-03 | 中国科学院长春应用化学研究所 | Solid-phase microextraction material composite and electrode material composite |
| CN103157299A (en) * | 2013-03-26 | 2013-06-19 | 清华大学 | Oil-water separation mesh film with acid-base salt stabilizing function and with underwater super-oleophobic property and preparation method thereof |
| CN103316507A (en) * | 2013-06-06 | 2013-09-25 | 华南理工大学 | Super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane, and preparation method and application thereof |
| CN103626171A (en) * | 2013-11-28 | 2014-03-12 | 中国科学技术大学 | Preparation method of oil-water separation material |
| CN104107562A (en) * | 2014-05-29 | 2014-10-22 | 南京大学 | Hydrogel microstructure template-based multifunctional superhydrophobic coating |
| CN105289330A (en) * | 2015-12-01 | 2016-02-03 | 天津工业大学 | Preparation method of concrete hollow fiber membrane capable of being used as support |
| WO2016017713A1 (en) * | 2014-07-30 | 2016-02-04 | 三菱マテリアル株式会社 | Oil and water separation device and drainage system |
| CN106310957A (en) * | 2015-07-03 | 2017-01-11 | 天津工业大学 | Nanometer fiber-reinforced hydrogel filter membrane and preparation method thereof |
| CN106337283A (en) * | 2016-09-21 | 2017-01-18 | 江苏盖姆纳米材料科技有限公司 | Preparation method of hydrophilic mesh cloth or fabric applicable to oil-water separation |
-
2017
- 2017-03-06 CN CN201710127690.0A patent/CN106955506A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433822A (en) * | 2008-12-10 | 2009-05-20 | 郑国炉 | Air purification material and preparation method thereof as well as produced art ware or material for decoration |
| CN101875006A (en) * | 2010-04-30 | 2010-11-03 | 中国科学院长春应用化学研究所 | Solid-phase microextraction material composite and electrode material composite |
| CN103157299A (en) * | 2013-03-26 | 2013-06-19 | 清华大学 | Oil-water separation mesh film with acid-base salt stabilizing function and with underwater super-oleophobic property and preparation method thereof |
| CN103316507A (en) * | 2013-06-06 | 2013-09-25 | 华南理工大学 | Super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane, and preparation method and application thereof |
| CN103626171A (en) * | 2013-11-28 | 2014-03-12 | 中国科学技术大学 | Preparation method of oil-water separation material |
| CN104107562A (en) * | 2014-05-29 | 2014-10-22 | 南京大学 | Hydrogel microstructure template-based multifunctional superhydrophobic coating |
| WO2016017713A1 (en) * | 2014-07-30 | 2016-02-04 | 三菱マテリアル株式会社 | Oil and water separation device and drainage system |
| CN106310957A (en) * | 2015-07-03 | 2017-01-11 | 天津工业大学 | Nanometer fiber-reinforced hydrogel filter membrane and preparation method thereof |
| CN105289330A (en) * | 2015-12-01 | 2016-02-03 | 天津工业大学 | Preparation method of concrete hollow fiber membrane capable of being used as support |
| CN106337283A (en) * | 2016-09-21 | 2017-01-18 | 江苏盖姆纳米材料科技有限公司 | Preparation method of hydrophilic mesh cloth or fabric applicable to oil-water separation |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108080045A (en) * | 2017-12-27 | 2018-05-29 | 北京百奥芯科技有限公司 | A kind of hydrophilically modified method of fluid channel inside micro-fluidic chip |
| CN110407993A (en) * | 2018-04-26 | 2019-11-05 | 祯佶祥实业股份有限公司 | The permeable graphene sponge of oil suction |
| CN108671585A (en) * | 2018-05-29 | 2018-10-19 | 大连理工大学 | A kind of preparation method of super hydrophilic net for water-oil separating |
| CN108786183A (en) * | 2018-05-29 | 2018-11-13 | 大连理工大学 | A kind of preparation method of super-hydrophobic-super oleophylic net for water-oil separating |
| CN108786183B (en) * | 2018-05-29 | 2020-12-11 | 大连理工大学 | Preparation method of super-hydrophobic-super-oleophilic net for oil-water separation |
| CN108671585B (en) * | 2018-05-29 | 2021-04-20 | 大连理工大学 | Preparation method of super-hydrophilic net for oil-water separation |
| CN109296839A (en) * | 2018-10-12 | 2019-02-01 | 江苏天润管业有限公司 | A kind of strong closed type buried corrosion-resistant insulating tube and preparation method thereof |
| US11306164B2 (en) | 2019-04-02 | 2022-04-19 | King Fahd University Of Petroleum And Minerals | Water purification material for petrochemicals |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106955506A (en) | The high stable state of big flux is used for the super hydrophilic three-dimensional porous base material of water-oil separating | |
| Khuluk et al. | Removal of methylene blue by adsorption onto activated carbon from coconut shell (Cocous Nucifera L.) | |
| CN104857934B (en) | A kind of method and its application that nano zero valence iron suspension is prepared with green tea | |
| CN106179249B (en) | A kind of preparation method of concave convex rod cellulose composite adsorption microballoon | |
| CN107081134A (en) | A kind of modified hair keratin adsorbent and preparation method and application | |
| CN105597667B (en) | The preparation method of suspension ball-type concave convex rod adsorbent and its application for handling heavy metals in industrial wastewater | |
| CN102671646B (en) | Method for preparing adsorbing material for disposing oily sewage | |
| CN103785345B (en) | A kind of support type manganese dioxide adsorbent and utilize the method for its pretreatment aniline waste water | |
| CN105399977A (en) | Method for preparing reusable oil-absorbing sponge | |
| CN108339521A (en) | A kind of sodium alginate-MOFs complex microsphere preparation methods of absorption heavy metal arsenic | |
| CN103464111B (en) | Softex kw modification walnut shell adsorbent and its preparation method and application | |
| CN106943999A (en) | A kind of graphene modified attapulgite earth adsorbing and preparation method | |
| CN105289495B (en) | Using adsorbing the method that the useless clay mineral reaction in-situ after dyestuff prepares multifunctional composite | |
| CN101601991A (en) | Remove biomass adsorbent and preparation, application and the renovation process of lead ion in the waste water | |
| CN105797596A (en) | Preparation method of filter membrane for water purification | |
| CN108905983A (en) | A kind of preparation method of the Beta-cyclodextrin-based material of sodium alginate-for handling intermetallic composite coating waste water | |
| CN103495399A (en) | Preparation method and application of sludge activated carbon | |
| CN110423620B (en) | Synergistic remediation composite treating agent for soil nitrobenzene pollution | |
| CN100579648C (en) | Process for preparing As-dispelling sorbent for sea-changed red mud porcelain granule and application method thereof | |
| CN108325499A (en) | A kind of preparation method and application for the sodium bentonite modified as modifying agent using cationic-type polyacrylamide and 4 bromide | |
| CN106140095B (en) | The modified preparation and application of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure | |
| CN108341990A (en) | A kind of simple, the super-hydrophobic composite material of low cost preparation method | |
| CN104826608A (en) | Method for degrading orange II in wastewater by using porous chitosan gel beads prepared by using amino protection-modification-release method | |
| Liang et al. | Regeneration of spent bleaching clay by ultrasonic irradiation and its application in methylene blue adsorption | |
| CN109647356A (en) | A kind of preparation method and its application in removal waste water in anions and canons dyestuff at the same time of both sexes adsorbent material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170718 |
|
| RJ01 | Rejection of invention patent application after publication |