CN101792513B - Polymer material, preparation method thereof and application thereof to oil removal - Google Patents
Polymer material, preparation method thereof and application thereof to oil removal Download PDFInfo
- Publication number
- CN101792513B CN101792513B CN2010101020146A CN201010102014A CN101792513B CN 101792513 B CN101792513 B CN 101792513B CN 2010101020146 A CN2010101020146 A CN 2010101020146A CN 201010102014 A CN201010102014 A CN 201010102014A CN 101792513 B CN101792513 B CN 101792513B
- Authority
- CN
- China
- Prior art keywords
- oil
- water
- hours
- preparation
- organic
- 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.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides polymer material comprising matrix polymer and a hydrophilic group or hydrophilic groups on matrix polymer. The matrix polymer is formed by the polymerization of organic compound containing -C=C- and organic compound containing -C=C-...-C=C-, wherein the number of the C in the organic compound containing -C=C- is 2 to 10, and the number of the C in the organic compound containing -C=C-...-C=C- is 4-15. The hydrophilic group or hydrophilic groups can be one or more of the sulfonic acid group, the cyano group, the tertiary amine group, the quaternary ammonium group or the hydroxyl group. The polymer material has larger specific surface area, the matrix of the polymer material is hydrophilic, and the surface of the polymer material is provided with a certain number of hydrophilic groups. When the oil film has a certain thickness, the oil film can be separated from the surface of the spheroidal material under the action of the drag force of the water stream to become large oil droplets to ascend to the water level. The polymer material has good oil removal effect, avoids various avoid side effects caused by the addition of the demulsifier. The polymer material does not need to be regenerated and can be used for removing oil continuously.
Description
Technical field
The present invention relates to degreasing technique, be specifically related to a kind of macromolecular material as the oil removing coalescence material, the preparation method of this macromolecular material and use this macromolecular material to carry out the method for oil removing oily(waste)water.
Background technology
Oily(waste)water is meant the waste water that contains fat and various oils, is accompanied by various life activities in production and produces, like the surplus liquid of the extraction in petrochemical industry water of condensation, the hydrometallurgy, steamer water ballast and food industrial wastewater etc.If oily(waste)water is not handled and is directly entered river, lake meeting polluted-water; Influence hydrobiont existence; Influence natural landscape; Be used for agricultural irrigation and then can stop up interstices of soil, hinder crop growth, the carcinogenic hydrocarbon in the oil also can be detrimental to health through food chain through the enrichment of fish, shellfish.
Common deoiling method has membrane filter method, air supporting method, biological process, absorption method and coalescence method etc.Membrane filter method needs bigger hydraulic pressure, thereby equipment and capital construction cost are higher; Air supporting method and biological process can produce secondary pollution in treating processes, also need subsequent technique, and oil-contg is still higher relatively in the water outlet; Typical case's representative of absorption method is charcoal absorption; Though oil suction is respond well; But must regenerate after the adsorptive capacity that reaches capacity, use steam through activated carbon adsorption layer oil wash to be taken off, not only regenerative process is loaded down with trivial details; And the higher waste water of the oil concentration that obtains behind the wash-out still can't directly utilize, and discharging still can work the mischief; The coalescence method is to utilize the difference of profit two relative coalescence material avidity to carry out isolating method; When oily(waste)water passed through coalescence material, elaioleucite was caught to be stranded in material surface and the hole by aggregate material and is formed oil film, when oil film increases to certain thickness; Oil film comes off under waterpower and buoyancy; Merging is agglomerated into bigger elaioleucite, utilizes the density of oil littler than water, with gravitational separation process elaioleucite is separated from water.
The key of coalescence method is a coalescence material; Like Vestolen PP 7052 (PP), SE (PVC); But Vestolen PP 7052 often is made into polypropylene fiber, and SE receives the very tiny of restriction particle of polymerization technique to be Powdered, and these coalescence materials need elevated pressures or special-purpose member when using; Complex operation, deoiling effect are not good.
Summary of the invention
The problem that the present invention solves is to provide a kind of macromolecular material, and it is simple to operate to use it to adsorb oil removing, and oil removal rate is high.The present invention also provides by the preparation method of this macromolecular material and has used this macromolecular material oily(waste)water to be carried out the method for oil removing.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of macromolecular material is made up of matrix polymer and the hydrophilic radical that is positioned on the matrix polymer;
Said matrix polymer be contain-organic cpds of C=C-with contain-C=C-... The organic cpds of-C=C-is polymerized, and the quantity of C is 2～10 in the organic cpds of said containing-C=C-; Said containing-C=C-... The quantity of C is 4～15 in the organic cpds of-C=C-;
Said hydrophilic radical is one or more in sulfonic group, cyanic acid, tertiary amine groups, quaternary ammonium group or the hydroxyl.
As preferably; The organic cpds of said containing-C=C-be ethene, propylene, butylene, penta rare, oneself is rare, iso-butylene, isopentene, dissident's alkene, vinylbenzene, vinyl toluene, vinylformic acid; Methyl acrylate, methylacrylic acid, one or more in the TEB 3K.
As preferably, said containing-C=C-... The organic cpds of-C=C-is a dibutene, limonene, isoprene, two hexenes, dissident's diene, divinylbenzene, kautschin, Diethylene Glycol divinyl ether, one or more in the alloocimene.
A kind of preparation method of said macromolecular material may further comprise the steps:
A, will comprise the water of water, dispersion agent and dispersion aids and comprise said-C=C-organic cpds, contain-organic cpds of C=C-and the oil phase of initiator mix, and carries out suspension polymerization, processes matrix polymer,
The weight ratio composition that said water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2; The weight ratio composition that said oil phase contains is to contain-organic cpds of C=C-: contain-organic cpds of C=C-: initiator=0.75～0.98: 0.02～0.25: 0.003～0.01, and the weight ratio of oil phase and water is 1: 4～6;
B, use aminating agent to carry out amination or carry out sulfonation with sulphonating agent to the matrix polymer of step a;
C, place the solution that forms with organic solvent dissolution alkene nitrile compounds to carry out after polymerization the product of step b, the concentration of alkene nitrile compounds is 0.2wt%～15wt% in the solution, and the weight ratio of the product of step b and alkene nitrile compounds is 1: 3～6,
Said alkene nitrile compounds is 3～8 aliphatic olefin nitrile for the C number; In the heteroaromatic alkene nitrile compound of the aromatic series alkene nitrile compound of C number≤8 or C number≤8 one or more, said organic solvent is for the C number is the assorted aromatic hydrocarbon of aromatic hydrocarbon, C number≤16 of 4～16 aliphatic hydrocarbon, C number≤16, in the industrial solvent one or more;
D, in the product of step c, to add quality be that its 3 times～6 times halohydrocarbon carries out boiling, and said halohydrocarbon is one or more in the assorted aromatic hydrocarbons of halo of halogenated aromatic or C number≤10 of 1～10 halogenated aliphatic hydrocarbon, C number≤10 for the C number.
As preferably, suspension polymerization is specially each composition is added in the reaction kettle among the said step a, in reaction kettle, feeds pressurized air or nitrogen; Make that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reaction kettle, be warming up to 70 ℃～90 ℃, be incubated 2 hours～24 hours; Be warming up to 100 ℃～150 ℃ again; Be incubated 4 hours～36 hours, washing then, dry, screening, collecting granularity is the spherical matrix polymer of 0.2mm～1.35mm.
As preferably; Dispersion agent among the said step a is one or both in inorganic dispersant or the organic dispersing agent; Said inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and said organic dispersing agent is a kind of several kinds in Z 150PH, gelatin, CMC 99.5 or the polyacrylate.
As preferably, the dispersion aids among the said step a is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, X 2073, calcium mahogany sulfonate, petroleum sodium sulfonate or the barium stearate.
As preferably, the initiator among the said step a is one or more in organic peroxy compound, inorganic peroxy compounds or the azo cpd.
As preferably, said initiator is peroxo-two acyl classes, peroxo-two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
As preferably, amination described in the said step b is specially matrix polymer and the chloromethylation reagent react that step a is obtained, and introduces chloromethyl, again product and aminating agent is carried out amination reaction.
As preferably, sulphonating agent is sulphur trioxide, mass concentration greater than in 60% sulfuric acid, chlorsulfonic acid or the thionamic acid one or more among the said step b.
As preferably, after polymerization is specially and uses the said alkene nitrile compounds of said organic solvent dissolution among the said step c, puts into the product of step b again, and temperature of reaction is 80 ℃～120 ℃, and pressure is not more than 0.5MPa, polymerization 2 hours～10 hours.
As preferably, the alkene nitrile compounds is that vinyl cyanide, crotononitrile, pentenenitrile, propylene halide nitrile, halo crotononitrile, halo pentenenitrile, hydroxyl substituted acrylonitrile, hydroxyl replace one or more in crotononitrile or the aryl substituted acrylonitrile among the said step c.
As preferably, organic solvent is in 4～16 straight-chain paraffin, branched paraffin, naphthenic hydrocarbon, No. 120 solvent oils, No. 180 solvent oils, No. 190 solvent oils, No. 200 solvent oils or No. 260 solvent oils one or more for the C number among the said step c.
As preferably, halohydrocarbon described in the said steps d is one or more in tetracol phenixin, ethylene dichloride, difluoro ethylene dichloride, tetrachloroethane, the ethylene dibromide.
As preferably, stewing temperature is 50 ℃～150 ℃, and cooking time is 2 hours～24 hours, and gauge pressure is 0.1MPa～1.0MPa.
A kind of deoiling method that uses said macromolecular material to oily(waste)water may further comprise the steps:
1., said macromolecular material is packed in the coalescence degreaser;
2., make oily(waste)water pass through the coalescence degreaser after the filling in the last step;
3., be separated in and collect the oil that obtains in the collecting tank of coalescence degreaser.
As preferably, said step 2. in, oily(waste)water is 10 ℃～80 ℃ through the temperature of coalescence degreaser, the oily(waste)water flow is 2BV/h～30BV/h.
As preferably, 3. said step is specially when oil reservoir in the said collecting tank reaches 5 centimetres～10 centimetres, and oil slick is scraped.
The matrix of macromolecular material provided by the invention is oil loving, can catch small oil droplet, and the surface has the hydrophilic radical of some amount again simultaneously; Macromolecular material inside also has a large amount of spaces, has bigger specific surface area, when oily(waste)water touches this macromolecular material; Oil content can be trapped in the surface of spheroidal material, forms one deck oil film gradually, because the existence of hydrophilic radical on the macromolecular material; When oil film reaches certain thickness under the effect of current drag force; The surface that oil film just can break away from the spheroidal material becomes the larger oil droplet liter to liquid level, and deoiling effect is fine, has avoided adding the various spinoffs that emulsion splitter brought.And this macromolecular material does not need regeneration, can continuous service.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
A kind of macromolecular material provided by the invention is made up of matrix polymer and the hydrophilic radical that is positioned on the matrix polymer, matrix polymer be contain-organic cpds of C=C-with contain-C=C-... The organic cpds of-C=C-is polymerized.Contain-organic cpds of C=C-in the quantity of C be 2～10, be preferably ethene, propylene, butylene, penta rare, oneself is rare, iso-butylene, isopentene, dissident's alkene, vinylbenzene, vinyl toluene, vinylformic acid, methyl acrylate; Methylacrylic acid, one or more in the TEB 3K contain-C=C-... The quantity of C is 4～15 in the organic cpds of-C=C-; Be preferably dibutene, limonene, isoprene; Two hexenes, dissident's diene, divinylbenzene; Kautschin, Diethylene Glycol divinyl ether, one or more in the alloocimene; Hydrophilic radical is one or more in sulfonic group, cyanic acid, tertiary amine groups, quaternary ammonium group or the hydroxyl.
The preparation method of macromolecular material provided by the invention comprises:
A, will comprise the water of water, dispersion agent and dispersion aids and comprise said-C=C-organic cpds, contain-organic cpds of C=C-and the oil phase of initiator mix, and carries out suspension polymerization, processes matrix polymer,
The weight ratio composition that said water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2; The weight ratio composition that said oil phase contains is to contain-organic cpds of C=C-: contain-organic cpds of C=C-: initiator=0.75～0.98: 0.02～0.25: 0.003～0.01, and the weight ratio of oil phase and water is 1: 4～6.
Dispersion agent is one or both in inorganic dispersant or the organic dispersing agent; Said inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and said organic dispersing agent is a kind of several kinds in Z 150PH, gelatin, CMC 99.5 or the polyacrylate.Dispersion aids is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, X 2073, calcium mahogany sulfonate, petroleum sodium sulfonate or the barium stearate.
Initiator is one or more in organic peroxy compound, inorganic peroxy compounds or the azo cpd, is preferably peroxo-two acyl classes, peroxo-two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
Suspension polymerization is specially each composition is added in the reaction kettle, in reaction kettle, feeds pressurized air or nitrogen, makes that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reaction kettle; Be warming up to 70 ℃～90 ℃; Be incubated 2 hours～24 hours, be warming up to 100 ℃～150 ℃ again, be incubated 4 hours～36 hours; Washing then, dry, screening, collecting granularity is the spherical matrix polymer of 0.2mm～1.35mm.
B, use aminating agent to carry out amination or carry out sulfonation with sulphonating agent to the matrix polymer of step a.Amination is specially matrix polymer and the chloromethylation reagent react that step a is obtained, and introduces chloromethyl, again product and aminating agent is carried out amination reaction.Sulphonating agent is sulphur trioxide, concentration greater than in 60% sulfuric acid, chlorsulfonic acid or the thionamic acid one or more, is preferably mass concentration and is 100%～106% oleum or in the sulphur trioxide one or both.
C, place the solution that forms with organic solvent dissolution alkene nitrile compounds to carry out after polymerization the product of step b, the concentration of alkene nitrile compounds is 0.2wt%～15wt% in the solution, and the weight ratio of the product of step b and alkene nitrile compounds is 1: 3～6.
The alkene nitrile compounds is 3～8 aliphatic olefin nitrile for the C number; In the heteroaromatic alkene nitrile compound of the aromatic series alkene nitrile compound of C number≤8 or C number≤8 one or more are preferably vinyl cyanide, crotononitrile, pentenenitrile, propylene halide nitrile, halo crotononitrile, halo pentenenitrile, hydroxyl substituted acrylonitrile, hydroxyl and replace in crotononitrile or the aryl substituted acrylonitrile one or more.
Organic solvent is for the C number is the assorted aromatic hydrocarbon of aromatic hydrocarbon, C number≤16 of 4～16 aliphatic hydrocarbon, C number≤16, in the industrial solvent one or more, is preferably in 4～16 straight-chain paraffin, branched paraffin, naphthenic hydrocarbon, No. 120 solvent oils, No. 180 solvent oils, No. 190 solvent oils, No. 200 solvent oils or No. 260 solvent oils one or more.
After polymerization is specially and uses the said alkene nitrile compounds of said organic solvent dissolution, puts into the product of step b again, and temperature of reaction is 80 ℃～120 ℃, and pressure is not more than 0.5MPa, polymerization 2 hours～10 hours.
D, in the product of step c, to add quality be that its 3 times～6 times halohydrocarbon carries out boiling; Halohydrocarbon is one or more in the assorted aromatic hydrocarbons of halo of halogenated aromatic or C number≤10 of 1～10 halogenated aliphatic hydrocarbon, C number≤10 for the C number, is preferably in tetracol phenixin, ethylene dichloride, difluoro ethylene dichloride, tetrachloroethane, the ethylene dibromide one or more.
Stewing temperature is 50 ℃～150 ℃, and cooking time is 2 hours～24 hours, and gauge pressure is 0.1MPa～1.0MPa.
Use macromolecular material provided by the invention to the method that oily(waste)water carries out oil removing, comprising:
1., said macromolecular material is packed in the coalescence degreaser, coalescence degreaser is well known in the art.
2., make the coalescence degreaser after oily(waste)water passes through in the last step to fill, the temperature through coalescence degreaser is 10 ℃～80 ℃, the oily(waste)water flow is 2BV/h～30BV/h.Can see behind general operation 10h～30h that larger oil droplet gushes out from the surface of macromolecular material, the oil-contg in the water outlet generally can be below the near 5ppm.
3., be separated in and collect the oil that obtains in the collecting tank of coalescence degreaser, be specially when oil reservoir in the said collecting tank reaches 5 centimetres～10 centimetres, oil slick is scraped.Carry out the isolating while at the oil that collection is obtained, coalescence degreaser continues to keep operation.Macromolecular material provided by the invention need not carry out desorption and activation, can move continuously, and the oil that from water, removes can be recycled.
The matrix of macromolecular material provided by the invention is oil loving, can catch small oil droplet, and the surface has the hydrophilic radical of some amount again simultaneously, comprises in sulfonic group, cyanic acid, tertiary amine groups, quaternary ammonium group or the hydroxyl one or more.Macromolecular material is fairly regular spheroidal, has similar particle diameter, the about 1.2g/cm of density
3, there is a large amount of spaces inside, has bigger specific surface area, and splendid deoiling effect is arranged, and can avoid adding the various spinoffs that emulsion splitter brings.When oily(waste)water touches this macromolecular material; Oil content can be trapped in the surface of spheroidal material; Surface through material behind 2h～10h can form one deck oil film gradually; Because the existence of hydrophilic radical on the macromolecular material, under the effect of current drag force, the surface that oil film just can break away from the spheroidal material becomes the larger oil droplet liter to liquid level when oil film reaches certain thickness; The size of particles of macromolecular material excellent mechanical intensity and homogeneous has guaranteed that coalescence degreaser can steady running, can not cause hydraulic pressure to increase or flow gets clogged.
Use the method for macromolecular material oil removing provided by the invention strong to the flexibility of former water, can be used for oil-containing 100ppm～3000ppm, pH is 2～12 sewage, and the water outlet oleaginousness after the processing is less than 5ppm, and oil removal rate is greater than 99%, and oil recovery rate is greater than 95%.
Embodiment 1:
(1) polymerization: in 50 liters polymeric kettle, add 18 liters of pure water; Be heated to 45 ℃; Under whipped state, add 10g magnesiumcarbonate, 20g gelatin and 0.15g methylene blue respectively, stir the back and add the oil phase that mixes by 3kg vinylbenzene, 1kg divinylbenzene, 20g Lucidol.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.02MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 80 ℃, is incubated 12 hours, is warming up to 100 ℃ again, insulation 20h, and filtration, washing, drying, screening obtain the Archon 2.57kg that granularity is 0.5-0.8mm.
(2) sulfonation: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, add 10kg 105% oleum, be warming up to 110 ℃; Be incubated 16 hours, cooling slowly drips pure water; Still completely back is extracted 1/3 liquid out; Continue to drip pure water, be operated to so that sulfuric acid concentration is less than 5% in the still, a large amount of pure water are washed till neutrality.Drying gets resin 4.18kg.
(3) after polymerization: the 20g vinyl cyanide is dissolved in 10 liters of No. 120 solvent oils.In 50 liters of reaction kettles, the resin after the sulfonation is soaked in this solution, slowly be warming up to 70 ℃, stir, be incubated 5 hours and make resin swelling.Add the 0.3g Lucidol, be warming up to 100 ℃, polymerization 4 hours.Filter, washing, drying gets resin 5.72kg.
(4) ethylene dichloride boiling: the resin adding that step (3) obtains is equipped with in 50 liters of reaction kettles of reflux exchanger, adds 15 liters of ethylene dichloride again, be warming up to 90 ℃, and kept the still internal pressure 0.3MPa8 hour, be cooled to 15 ℃.The centrifugal surface water that removes is got 9.86kg coalescence material finished product.
Get 1 liter of this resin and directly pack in the glass coalescence degreaser, assessment is to the removal ability of oil droplet in the water.When oily liq up stream during through the resin fill district, oil-like emulsions and droplet are extracted catches; When oil accumulation when a certain amount of, form larger oil droplet, taken away by current, larger oil droplet is along with up current, through the specific device of oil eliminator, profit separates automatically, oil is directly delivered to the rich oil dynamic layer and is assembled, and come-up is to the oil reservoir district of installing the top; Water is exported from the side water outlet continuously.The oil that assemble at the top can be discharged from the top through manually or automatically controlling.
Entry oleaginousness 2000ppm, water outlet oleaginousness 5ppm.Flow velocity 4BV/h, moving has stable generation of big oil droplet and come-up after 20 hours, but does not need the operation of manipulation of regeneration long-time continuous.
Embodiment 2:
(1) polymerization: in 50 liters polymeric kettle, add 20 liters of pure water; Be heated to 40 ℃; Under whipped state, add 10g lime carbonate, 20g Z 150PH and 0.15g calcium mahogany sulfonate respectively, stir the back and add the oil phase that mixes by 3kg propylene, 1kg isoprene, 20g Diisopropyl azodicarboxylate.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.04MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 90 ℃, is incubated 9 hours, is warming up to 120 ℃ again, insulation 18h, and filtration, washing, drying, screening obtain the Archon 2.78kg that granularity is 0.5-0.8mm.
(2) sulfonation: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, add the 10kg sulphur trioxide, be warming up to 110 ℃; Be incubated 16 hours, cooling slowly drips pure water; Still completely back is extracted 1/3 liquid out; Continue to drip pure water, be operated to so that sulfuric acid concentration is less than 5% in the still, a large amount of pure water are washed till neutrality.Drying gets resin 4.06kg.
(3) after polymerization: the 50g crotononitrile is dissolved in 10 liters of pentanes.In 50 liters of reaction kettles, the resin after the sulfonation is soaked in this solution, slowly be warming up to 70 ℃, stir, be incubated 7 hours and make resin swelling.Add the 0.5g Diisopropyl azodicarboxylate, be warming up to 100 ℃, polymerization 6 hours.Filter, washing, drying gets resin 6.10kg.
(4) tetracol phenixin boiling: the resin adding that step (3) obtains is equipped with in 50 liters of reaction kettles of reflux exchanger, adds 15 liters of tetracol phenixin again, be warming up to 80 ℃, and kept the still internal pressure 0.2MPa10 hour, be cooled to 15 ℃.The centrifugal surface water that removes is got 11.44kg coalescence material finished product.
Get 1 liter of this resin and directly pack in the glass reinforced plastic coalescence degreaser, carry out oil removing, entry oleaginousness 1000ppm, water outlet oleaginousness 3ppm.Flow velocity 6BV/h, moving has stable generation of big oil droplet and come-up after 15 hours, but does not need the operation of manipulation of regeneration long-time continuous.
Embodiment 3:
(1) polymerization: in 50 liters polymeric kettle, add 20 liters of pure water; Be heated to 40 ℃; Under whipped state, add 12g magnesiumcarbonate, 25g Xylo-Mucine and 0.18g calcium dodecylbenzene sulphonate respectively, stir the back and add the oil phase that mixes by 3.6kg isopentene, 1.2kg Diethylene Glycol divinyl ether, 25g Sodium Persulfate.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.05MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 90 ℃, is incubated 9 hours, is warming up to 120 ℃ again, insulation 20h, and filtration, washing, drying, screening obtain the Archon 3.02kg that granularity is 0.5-0.8mm.
(2) sulfonation: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, and adding 10kg mass concentration is 105% oleum, is warming up to 120 ℃; Be incubated 18 hours, cooling slowly drips pure water; Still completely back is extracted 1/3 liquid out; Continue to drip pure water, be operated to so that sulfuric acid concentration is less than 5% in the still, a large amount of pure water are washed till neutrality.Drying gets resin 4.21kg.
(3) after polymerization: the 50g chloroacrylonitrile is dissolved in 10 liters of No. 180 solvent oils.In 50 liters of reaction kettles, the resin after the sulfonation is soaked in this solution, slowly be warming up to 70 ℃, stir, be incubated 7 hours and make resin swelling.Add the 0.4g Diisopropyl azodicarboxylate, be warming up to 100 ℃, polymerization 8 hours.Filter, washing, drying gets resin 6.45kg.
(4) difluoro ethylene dichloride boiling: the resin adding that step (3) obtains is equipped with in 50 liters of reaction kettles of reflux exchanger, adds 15 liters of difluoro ethylene dichloride again, be warming up to 100 ℃, and kept still internal pressure 0.4MPa 10 hours, be cooled to 15 ℃.The centrifugal surface water that removes is got 11.63kg coalescence material finished product.
Get 1 liter of this resin and directly pack in the steel coalescence degreaser, carry out oil removing, entry oleaginousness 500ppm, water outlet oleaginousness 2ppm.Flow velocity 10BV/h, moving has stable generation of big oil droplet and come-up after 30 hours, but does not need the operation of manipulation of regeneration long-time continuous.
Embodiment 4:
(1) polymerization: in 50 liters polymeric kettle, add 18 liters of pure water; Be heated to 45 ℃; Under whipped state, add 10g magnesiumcarbonate, 20g gelatin and 0.15g methylene blue respectively, stir the back and add the oil phase that mixes by 3kg vinyl toluene, 1kg kautschin, 20g Lucidol.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.02MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 80 ℃, is incubated 12 hours, is warming up to 100 ℃ again, insulation 20h, and filtration, washing, drying, screening obtain the Archon 2.35kg that granularity is 0.5-0.8mm.
(2) amination: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, add the 10kg chloromethyl ether, temperature is controlled at 60 ℃, stirs 6h; In still, add 10 liters of entry again, Trimethylamine 99 5kg stirs 1h, adds mass concentration again and be 1 liter in 30% sodium hydroxide; Be warming up to 80 ℃, insulation 20h, cooling; Add washing to neutral, drying, resin 4.13kg.
(3) after polymerization: the 22g pentenenitrile is dissolved in 10 liters of No. 200 solvent oils.In 50 liters of reaction kettles, the resin after the sulfonation is soaked in this solution, slowly be warming up to 70 ℃, stir, be incubated 5 hours and make resin swelling.Add the 0.3g Lucidol, be warming up to 100 ℃, polymerization 4 hours.Filter, washing, drying gets resin 5.42kg.
(4) tetrachloroethane boiling: the resin adding that step (3) obtains is equipped with in 50 liters of reaction kettles of reflux exchanger, adds 15 liters of tetrachloroethane again, be warming up to 90 ℃, and kept the still internal pressure 0.3MPa8 hour, be cooled to 15 ℃.The centrifugal surface water that removes is got 9.86kg coalescence material finished product.
Get 1 liter of this resin and directly pack in the steel coalescence degreaser, assessment is to the removal ability of oil droplet in the water.When oily liq up stream during through the resin fill district, oil-like emulsions and droplet are extracted catches; When oil accumulation when a certain amount of, form larger oil droplet, taken away by current, larger oil droplet is along with up current, through the specific device of oil eliminator, profit separates automatically, oil is directly delivered to the rich oil dynamic layer and is assembled, and come-up is to the oil reservoir district of installing the top; Water is exported from the side water outlet continuously.The oil that assemble at the top can be discharged from the top through manually or automatically controlling.
Entry oleaginousness 2000ppm, water outlet oleaginousness 5ppm.Flow velocity 10BV/h, moving has stable generation of big oil droplet and come-up after 20 hours, but does not need the operation of manipulation of regeneration long-time continuous.
Embodiment 5:
(1) polymerization: in 50 liters polymeric kettle, add 18 liters of pure water; Be heated to 50 ℃; Under whipped state, add 8g barium stearate, 22g ZX-I and 0.15g methylene blue respectively, stir the back and add the oil phase that mixes by 4.5kg methylacrylic acid, 1.5kg alloocimene, 25g Lucidol.The capping still feeds clean pressurized air in reaction kettle, keeping the interior gaseous pressure of still is 0.02MPa.Unlatching is stirred, and the liquid pearl is transferred to suitable granularity, is warming up to 80 ℃, is incubated 12 hours, is warming up to 120 ℃ again, insulation 22h, and filtration, washing, drying, screening obtain the Archon 3.26kg that granularity is 0.5-0.8mm.
(2) amination: the spheroid that obtains after the polymerization is added in 50 liters of reaction kettles, add 10kg methyl alcohol, temperature is controlled at 60 ℃, stirs 4h; In still, add 10 liters of entry again, ammoniacal liquor 8kg stirs 1h, adds mass concentration again and be 1 liter in 30% sodium hydroxide; Be warming up to 70 ℃, insulation 20h, cooling; Add washing to neutral, drying, resin 5.49kg.
(3) after polymerization: 22g chloro crotononitrile is dissolved in 10 liters of hexanaphthenes.In 50 liters of reaction kettles, the resin after the sulfonation is soaked in this solution, slowly be warming up to 70 ℃, stir, be incubated 5 hours and make resin swelling.Add the 0.3g Lucidol, be warming up to 100 ℃, polymerization 4 hours.Filter, washing, drying gets resin 6.11kg.
(4) ethylene dibromide boiling: the resin adding that step (3) obtains is equipped with in 50 liters of reaction kettles of reflux exchanger, adds 20 liters of ethylene dibromides again, be warming up to 80 ℃, and kept the still internal pressure 0.3MPa10 hour, be cooled to 15 ℃.The centrifugal surface water that removes is got 10.08kg coalescence material finished product.
Get 1 liter of this resin and directly pack in the steel coalescence degreaser, assessment is to the removal ability of oil droplet in the water.When oily liq up stream during through the resin fill district, oil-like emulsions and droplet are extracted catches; When oil accumulation when a certain amount of, form larger oil droplet, taken away by current, larger oil droplet is along with up current, through the specific device of oil eliminator, profit separates automatically, oil is directly delivered to the rich oil dynamic layer and is assembled, and come-up is to the oil reservoir district of installing the top; Water is exported from the side water outlet continuously.The oil that assemble at the top can be discharged from the top through manually or automatically controlling.
Entry oleaginousness 2500ppm, water outlet oleaginousness 3ppm.Flow velocity 10BV/h, moving has stable generation of big oil droplet and come-up after 16 hours, but does not need the operation of manipulation of regeneration long-time continuous.
Can see through embodiment, use macromolecular material size of particles provided by the invention and can control that have oleophilicity and wetting ability simultaneously, deoiling effect is good, need not regenerate, and can move continuously.
More than macromolecular material provided by the present invention and preparation method thereof and the application in oil removing have been carried out detailed introduction.Used concrete example among this paper principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (16)
1. the preparation method of a macromolecular material; May further comprise the steps: a, will comprise the water of water, dispersion agent and dispersion aids and comprise said-C=C-organic cpds, contain-C=C-... The organic cpds of-C=C-and the oil phase of initiator mix; Carry out suspension polymerization; Process matrix polymer
The weight ratio composition that said water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2; The weight ratio composition that said oil phase contains is to contain-organic cpds of C=C-: contain-C=C-... The organic cpds of-C=C-: initiator=0.75～0.98: 0.02～0.25: 0.003～0.01, the weight ratio of oil phase and water is 1: 4～6;
B, use aminating agent to carry out amination or carry out sulfonation with sulphonating agent to the matrix polymer of step a;
C, place the solution that forms with organic solvent dissolution alkene nitrile compounds to carry out after polymerization the product of step b, the concentration of alkene nitrile compounds is 0.2wt%～15wt% in the solution, and the weight ratio of the product of step b and alkene nitrile compounds is 1: 3～6,
Said alkene nitrile compounds is 3～8 aliphatic olefin nitrile for the C number; Or in the heteroaromatic alkene nitrile compound of C number≤8 one or more, said organic solvent is for the C number is the assorted aromatic hydrocarbon of aromatic hydrocarbon, C number≤16 of 4～16 aliphatic hydrocarbon, C number≤16, in the industrial solvent one or more;
D, in the product of step c, to add quality be that its 3 times～6 times halohydrocarbon carries out boiling, and said halohydrocarbon is one or more in the assorted aromatic hydrocarbons of halo of halogenated aromatic or C number≤10 of 1～10 halogenated aliphatic hydrocarbon, C number≤10 for the C number;
Said macromolecular material is made up of matrix polymer and the hydrophilic radical that is positioned on the matrix polymer; Said matrix polymer be contain-organic cpds of C=C-with contain-C=C-... The organic cpds of-C=C-is polymerized, and the quantity of C is 2～10 in the organic cpds of said containing-C=C-; Said containing-C=C-... The quantity of C is 4～15 in the organic cpds of-C=C-; Said hydrophilic radical is one or more in sulfonic group, cyanic acid, tertiary amine groups, quaternary ammonium group or the hydroxyl;
The organic cpds of said containing-C=C-be ethene, propylene, butylene, penta rare, oneself is rare, iso-butylene, isopentene, dissident's alkene, vinylbenzene, vinyl toluene, vinylformic acid, methyl acrylate, methylacrylic acid, one or more in the TEB 3K;
Said containing-C=C-... The organic cpds of-C=C-is a dibutene, limonene, isoprene, two hexenes, dissident's diene, divinylbenzene, kautschin, Diethylene Glycol divinyl ether, one or more in the alloocimene.
2. preparation method according to claim 1 is characterized in that, suspension polymerization is specially each composition is added in the reaction kettle among the said step a; In reaction kettle, feed pressurized air or nitrogen; Make that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reaction kettle, be warming up to 70 ℃～90 ℃, be incubated 2 hours～24 hours; Be warming up to 100 ℃～150 ℃ again; Be incubated 4 hours～36 hours, washing then, dry, screening, collecting granularity is the spherical matrix polymer of 0.2mm～1.35mm.
3. preparation method according to claim 1 and 2; It is characterized in that; Dispersion agent among the said step a is one or both in inorganic dispersant or the organic dispersing agent; Said inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and said organic dispersing agent is a kind of several kinds in Z 150PH, gelatin, CMC 99.5 or the polyacrylate.
4. preparation method according to claim 1 and 2; It is characterized in that the dispersion aids among the said step a is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, X 2073, calcium mahogany sulfonate, petroleum sodium sulfonate or the barium stearate.
5. preparation method according to claim 1 and 2 is characterized in that, the initiator among the said step a is one or more in organic peroxy compound, inorganic peroxy compounds or the azo cpd.
6. preparation method according to claim 5 is characterized in that, said initiator is peroxo-two acyl classes, peroxo-two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
7. preparation method according to claim 1 is characterized in that, amination described in the said step b is specially matrix polymer and the chloromethylation reagent react that step a is obtained, and introduces chloromethyl, again product and aminating agent is carried out amination reaction.
8. preparation method according to claim 1 is characterized in that, sulphonating agent is sulphur trioxide, mass concentration greater than in 60% sulfuric acid, chlorsulfonic acid or the thionamic acid one or more among the said step b.
9. preparation method according to claim 1 is characterized in that, after polymerization is specially and uses the said alkene nitrile compounds of said organic solvent dissolution among the said step c; Put into the product of step b again; Temperature of reaction is 80 ℃～120 ℃, and pressure is not more than 0.5MPa, polymerization 2 hours～10 hours.
10. according to claim 1 or 9 described preparing methods; It is characterized in that the alkene nitrile compounds is one or more in vinyl cyanide, crotononitrile, pentenenitrile, propylene halide nitrile, halo crotononitrile, halo pentenenitrile, hydroxyl substituted acrylonitrile, hydroxyl replacement crotononitrile or the aryl substituted acrylonitrile among the said step c.
11. according to claim 1 or 9 described preparing methods; It is characterized in that organic solvent is in 4～16 straight-chain paraffin, branched paraffin, naphthenic hydrocarbon, No. 120 solvent oils, No. 180 solvent oils, No. 190 solvent oils, No. 200 solvent oils or No. 260 solvent oils one or more for the C number among the said step c.
12. preparation method according to claim 1 is characterized in that, halohydrocarbon described in the said steps d is one or more in tetracol phenixin, ethylene dichloride, difluoro ethylene dichloride, tetrachloroethane, the ethylene dibromide.
13., it is characterized in that stewing temperature is 50 ℃～150 ℃ according to claim 1 or 12 described preparing methods, cooking time is 2 hours～24 hours, gauge pressure is 0.1MPa～1.0MPa.
14. the macromolecular material of preparing method's preparation of using each described macromolecular material of claim 1 to 13 is characterized in that the deoiling method of oily(waste)water, may further comprise the steps:
1., said macromolecular material is packed in the coalescence degreaser;
2., make oily(waste)water pass through the coalescence degreaser after the filling in the last step;
3., be separated in and collect the oil that obtains in the collecting tank of coalescence degreaser.
15. deoiling method according to claim 14 is characterized in that, said step 2. in, oily(waste)water is 10 ℃～80 ℃ through the temperature of coalescence degreaser, the oily(waste)water flow is 2BV/h～30BV/h.
16. deoiling method according to claim 14 is characterized in that, 3. said step is specially when oil reservoir in the said collecting tank reaches 5 centimetres～10 centimetres, and oil slick is scraped.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101020146A CN101792513B (en) | 2010-01-28 | 2010-01-28 | Polymer material, preparation method thereof and application thereof to oil removal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101020146A CN101792513B (en) | 2010-01-28 | 2010-01-28 | Polymer material, preparation method thereof and application thereof to oil removal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101792513A CN101792513A (en) | 2010-08-04 |
| CN101792513B true CN101792513B (en) | 2012-03-07 |
Family
ID=42585450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101020146A Active CN101792513B (en) | 2010-01-28 | 2010-01-28 | Polymer material, preparation method thereof and application thereof to oil removal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101792513B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134344B (en) * | 2010-12-22 | 2012-07-25 | 朱同德 | Biparental high polymer coalescence degreasing material as well as preparation and application thereof |
| CN102875717B (en) * | 2011-08-26 | 2014-06-04 | 中化化工科学技术研究总院 | Synthetic resin, and preparation method and application thereof |
| CN102558416A (en) * | 2011-12-27 | 2012-07-11 | 王颖华 | Metal-doped high molecular material and preparation method thereof and application thereof to ammonia nitrogen removal |
| CN103623709B (en) * | 2013-11-11 | 2015-07-01 | 华南理工大学 | Oxidized graphene-modified super-hydrophilic super-oleophobic oil-water separation film and preparation method and application thereof |
| CN103771560B (en) * | 2014-01-16 | 2015-09-02 | 江苏集贤绿色化学科技研究院有限公司 | A kind of oilfield sewage treatment agent and preparation method thereof |
| CN105709460A (en) * | 2016-04-25 | 2016-06-29 | 中国科学院新疆理化技术研究所 | Preparation method of cellulose-based fiber material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080210A (en) * | 1992-06-16 | 1994-01-05 | 南开大学 | Synthetic and the application of saponin selective adsorption resin |
| CN1760219A (en) * | 2005-10-21 | 2006-04-19 | 天津大学 | Method for preparing microspheres of rigid, cross linked porous polyacrylamide |
| CN1772774A (en) * | 2005-11-08 | 2006-05-17 | 南京大学 | Synthesis of composite functional super high cross-linked adsorbing resin containing sulfo radical |
| CN1865302A (en) * | 2006-04-25 | 2006-11-22 | 南京大学 | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method |
-
2010
- 2010-01-28 CN CN2010101020146A patent/CN101792513B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080210A (en) * | 1992-06-16 | 1994-01-05 | 南开大学 | Synthetic and the application of saponin selective adsorption resin |
| CN1760219A (en) * | 2005-10-21 | 2006-04-19 | 天津大学 | Method for preparing microspheres of rigid, cross linked porous polyacrylamide |
| CN1772774A (en) * | 2005-11-08 | 2006-05-17 | 南京大学 | Synthesis of composite functional super high cross-linked adsorbing resin containing sulfo radical |
| CN1865302A (en) * | 2006-04-25 | 2006-11-22 | 南京大学 | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| TOSHIKAZU ONO etc..Lipophilic polyelectrolyte gels as super-absorbent polymers for nonpolar organic solvents.《nature materials》.2007,第6卷第429-432页. * |
| 滕元勋等.聚结器处理含微粒油废水.《铀矿选冶》.中国知网,1981,第42页第2段-第45页第2段、表3-6. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101792513A (en) | 2010-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101792513B (en) | Polymer material, preparation method thereof and application thereof to oil removal | |
| US7597809B1 (en) | Methods for removal of oil and other contaminants from water | |
| CN107096391B (en) | A method of the preparation method of underwater superoleophobic and oily lower super-hydrophobic film and its continuously separate light oil/water/heavy oil mixture | |
| CN101486515B (en) | Oily wastewater treatment method and whole set apparatus thereof | |
| Yang et al. | Robust membranes with tunable functionalities for sustainable oil/water separation | |
| CN103086472A (en) | High-temperature sewage treatment reverse demulsifier of ultra-heavy oil | |
| CN109652118A (en) | A kind of process system and process washing desalination and water-oil separating | |
| CA1139250A (en) | Process for separating oils or petroleum hydrocarbons from solid or solid/liquid material | |
| WO2016178597A1 (en) | Substance for removing oils from soil and hard surfaces, and method for using said substance (variants) | |
| CN107001089A (en) | The processing of recovered water, the recovered water particularly obtained from the chemical enhanced DP technology using Tackified polymeric | |
| US9718704B2 (en) | Polysaccharide microgels for cleaning water of petroleum and petroleum products and method for using same (variants) | |
| CN103450467A (en) | Multi-branch structure demulsifier of aromatic ring core | |
| CN102875717B (en) | Synthetic resin, and preparation method and application thereof | |
| CN109384341A (en) | Semi-coke high concentrated organic wastewater recycling treatment system and method | |
| CN102134344B (en) | Biparental high polymer coalescence degreasing material as well as preparation and application thereof | |
| CN104946303A (en) | Method for selectively separating phenol mixture from oil | |
| CN103380085A (en) | Water treatment system and water treatment method | |
| CN114105342A (en) | Coal chemical wastewater dephenolization pretreatment system and treatment method thereof | |
| CN115368577A (en) | Hyperbranched polyether grafted polystyrene maleic anhydride oil-water synchronous demulsification water purifier | |
| CN102558416A (en) | Metal-doped high molecular material and preparation method thereof and application thereof to ammonia nitrogen removal | |
| CN101795980A (en) | Method for treatment of water comprising non-polar compounds | |
| CN102307814A (en) | Polymer recovery and recycle | |
| US20160257578A1 (en) | Resin-made porous particles and water treatment process using same | |
| CN108070400A (en) | A kind of alkylation | |
| CN106139647B (en) | Metal ion-purposes of the Polybenzoxazine micro-nano ball as water-oil separating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |