CN101792513A - 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
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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, as the surplus liquid of the extraction in petrochemical industry water of condensation, the hydrometallurgy, steamer water ballast and food industrial wastewater etc.If not handled, oily(waste)water directly do not enter 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 by food chain by the enrichment of fish, shellfish.
Common deoiling method has membrane filter method, air supporting method, biological process, absorption method and coalescent 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 oil wash to be taken off by activated carbon adsorption layer, 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; Coalescent method is to utilize the difference of profit two relative coalescence material avidity to carry out isolating method, when oily(waste)water passes through coalescence material, elaioleucite is 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 coalescent method is a coalescence material, as polypropylene (PP), polyvinyl chloride (PVC), but polypropylene often is made into polypropylene fiber, polyvinyl chloride is subjected to the very tiny of restriction particle of polymerization technique to be Powdered, 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, the oil removal rate height.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 of matrix polymer and the hydrophilic radical that is positioned on the matrix polymer;
Described matrix polymer be contain-organic compound of C=C-with contain-C=C-... the organic compound of-C=C-is polymerized, and the quantity of C is 2～10 in the organic compound of described containing-C=C-; Described containing-C=C-... the quantity of C is 4～15 in the organic compound of-C=C-;
Described hydrophilic radical is one or more in sulfonic group, cyano group, tertiary amine groups, quaternary ammonium group or the hydroxyl.
As preferably, the organic compound of described 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, methacrylic acid, one or more in the methyl methacrylate.
As preferably, described containing-C=C-... the organic compound 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 described macromolecular material may further comprise the steps:
A, will comprise the water of water, dispersion agent and dispersion aids and comprise described-C=C-organic compound, contain-organic compound of C=C-and the oil phase of initiator mix, and carries out suspension polymerization, makes matrix polymer,
The weight ratio composition that described water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2, the weight ratio composition that described oil phase contains is to contain-organic compound of C=C-: contain-organic compound 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,
Described 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, described 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, to add quality in the product of step c be that its 3 times～6 times halohydrocarbon carries out boiling, and described halohydrocarbon is one or more in the assorted aromatic hydrocarbons of halo of the halogenated aromatic of 1～10 halogenated aliphatic hydrocarbon, C number≤10 or C number≤10 for the C number.
As preferably, suspension polymerization is specially each composition is added in the reactor among the described step a, in reactor, feed pressurized air or nitrogen, make that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reactor, 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 described step a is one or both in inorganic dispersant or the organic dispersing agent, described inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and described organic dispersing agent is a kind of several in polyvinyl alcohol, gelatin, carboxymethyl cellulose or the polyacrylate.
As preferably, the dispersion aids among the described step a is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, Sodium dodecylbenzene sulfonate, calcium mahogany sulfonate, petroleum sodium sulfonate or the barium stearate.
As preferably, the initiator among the described step a is one or more in organic peroxy compound, inorganic peroxy compounds or the azo-compound.
As preferably, described initiator is peroxidation two acyl classes, peroxidation two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
As preferably, amination described in the described 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 described step b.
As preferably, after polymerization is specially and uses the described alkene nitrile compounds of described organic solvent dissolution among the described 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 described 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 described step c.
As preferably, halohydrocarbon described in the described 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 described macromolecular material to oily(waste)water may further comprise the steps:
1., described 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, described step 2. in, oily(waste)water is 10 ℃～80 ℃ by the temperature of coalescence degreaser, the oily(waste)water flow is 2BV/h～30BV/h.
As preferably, 3. described step is specially when oil reservoir in the described 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, 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, 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, deoiling effect is fine, has avoided adding the various side effects 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, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
A kind of macromolecular material provided by the invention is made of matrix polymer and the hydrophilic radical that is positioned on the matrix polymer, matrix polymer be contain-organic compound of C=C-with contain-C=C-... the organic compound of-C=C-is polymerized.Contain-organic compound 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, methacrylic acid, in the methyl methacrylate one or more, contain-C=C-... the quantity of C is 4～15 in the organic compound of-C=C-, be preferably dibutene, limonene, isoprene, two hexenes, dissident's diene, divinylbenzene, kautschin, the Diethylene Glycol divinyl ether, one or more in the alloocimene; Hydrophilic radical is one or more in sulfonic group, cyano group, 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 described-C=C-organic compound, contain-organic compound of C=C-and the oil phase of initiator mix, and carries out suspension polymerization, makes matrix polymer,
The weight ratio composition that described water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2, the weight ratio composition that described oil phase contains is to contain-organic compound of C=C-: contain-organic compound 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, described inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and described organic dispersing agent is a kind of several in polyvinyl alcohol, gelatin, carboxymethyl cellulose or the polyacrylate.Dispersion aids is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, Sodium dodecylbenzene sulfonate, 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-compound, is preferably peroxidation two acyl classes, peroxidation two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
Suspension polymerization is specially each composition is added in the reactor, in reactor, feed pressurized air or nitrogen, make that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reactor, 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 described alkene nitrile compounds of described 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, to add quality in the product of step c be that its 3 times～6 times halohydrocarbon carries out boiling, halohydrocarbon is one or more in the assorted aromatic hydrocarbons of halo of the halogenated aromatic of 1～10 halogenated aliphatic hydrocarbon, C number≤10 or 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., described 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 by 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 described 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 removes from water 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, cyano group, 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 side effects 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, 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, 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 liquid stream gets clogged.
Use the method for macromolecular material oil removing provided by the invention strong to the adaptability 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 evenly the back and add the oil phase that mixes by 3kg vinylbenzene, 1kg divinylbenzene, 20g benzoyl peroxide.The capping still feeds clean pressurized air in reactor, 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 reactors, 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 reactors, 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 benzoyl peroxide, 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 reactors 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, by 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 continuously from the side water outlet.The oil that assemble at the top can be discharged from the top by 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 polyvinyl alcohol and 0.15g calcium mahogany sulfonate respectively, stir evenly 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 reactor, 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 reactors, 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 reactors, 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 reactors 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 evenly 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 reactor, 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 reactors, adding 10kg mass concentration is 105% oleum, be 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 reactors, 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 reactors 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 evenly the back and add the oil phase that mixes by 3kg vinyl toluene, 1kg kautschin, 20g benzoyl peroxide.The capping still feeds clean pressurized air in reactor, 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 reactors, add the 10kg chloromethyl ether, temperature is controlled at 60 ℃, stir 6h, in still, add 10 liters of entry again, Trimethylamine 99 5kg, stir 1h, add mass concentration again and be 1 liter in 30% sodium hydroxide, be warming up to 80 ℃, insulation 20h, cooling, add and be washed to neutrality, drying, resin 4.13kg.
(3) after polymerization: the 22g pentenenitrile is dissolved in 10 liters of No. 200 solvent oils.In 50 liters of reactors, 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 benzoyl peroxide, 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 reactors 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, by 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 continuously from the side water outlet.The oil that assemble at the top can be discharged from the top by 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 sodium polyacrylate and 0.15g methylene blue respectively, stir evenly the back and add the oil phase that mixes by 4.5kg methacrylic acid, 1.5kg alloocimene, 25g benzoyl peroxide.The capping still feeds clean pressurized air in reactor, 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 reactors, add 10kg methyl alcohol, temperature is controlled at 60 ℃, stir 4h, in still, add 10 liters of entry again, ammoniacal liquor 8kg, stir 1h, add mass concentration again and be 1 liter in 30% sodium hydroxide, be warming up to 70 ℃, insulation 20h, cooling, add and be washed to neutrality, drying, resin 5.49kg.
(3) after polymerization: 22g chloro crotononitrile is dissolved in 10 liters of hexanaphthenes.In 50 liters of reactors, 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 benzoyl peroxide, 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 reactors 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, by 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 continuously from the side water outlet.The oil that assemble at the top can be discharged from the top by 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 by embodiment, use macromolecular material size of particles provided by the invention and can control that have lipophilicity 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 are described in detail.Used specific case herein 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 (19)
1. a macromolecular material is characterized in that, is made of matrix polymer and the hydrophilic radical that is positioned on the matrix polymer;
Described matrix polymer be contain-organic compound of C=C-with contain-C=C-... the organic compound of-C=C-is polymerized, and the quantity of C is 2～10 in the organic compound of described containing-C=C-; Described containing-C=C-... the quantity of C is 4～15 in the organic compound of-C=C-;
Described hydrophilic radical is one or more in sulfonic group, cyano group, tertiary amine groups, quaternary ammonium group or the hydroxyl.
2. macromolecular material according to claim 1, it is characterized in that, the organic compound of described 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, methacrylic acid, one or more in the methyl methacrylate.
3. macromolecular material according to claim 1 is characterized in that, described containing-C=C-... the organic compound 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.
4. the preparation method of each described macromolecular material of claim 1 to 3 may further comprise the steps:
A, will comprise the water of water, dispersion agent and dispersion aids and comprise described-C=C-organic compound, contain-organic compound of C=C-and the oil phase of initiator mix, and carries out suspension polymerization, makes matrix polymer,
The weight ratio composition that described water contains is a water: dispersion agent: dispersion aids=800～1000: 0.5～3.0: 0.05～0.2, the weight ratio composition that described oil phase contains is to contain-organic compound of C=C-: contain-organic compound 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,
Described 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, described 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, to add quality in the product of step c be that its 3 times～6 times halohydrocarbon carries out boiling, and described halohydrocarbon is one or more in the assorted aromatic hydrocarbons of halo of the halogenated aromatic of 1～10 halogenated aliphatic hydrocarbon, C number≤10 or C number≤10 for the C number.
5. preparation method according to claim 4, it is characterized in that, suspension polymerization is specially each composition is added in the reactor among the described step a, in reactor, feed pressurized air or nitrogen, make that pressure remains under the barotropic state of gauge pressure smaller or equal to 0.5MPa in the reactor, 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.
6. according to claim 4 or 5 described preparation methods, it is characterized in that, dispersion agent among the described step a is one or both in inorganic dispersant or the organic dispersing agent, described inorganic dispersant is one or more in silicate, carbonate or the phosphoric acid salt, and described organic dispersing agent is a kind of several in polyvinyl alcohol, gelatin, carboxymethyl cellulose or the polyacrylate.
7. according to claim 4 or 5 described preparation methods, it is characterized in that the dispersion aids among the described step a is one or more in sodium lauryl sulphate, calcium dodecylbenzene sulphonate, Sodium dodecylbenzene sulfonate, calcium mahogany sulfonate, petroleum sodium sulfonate or the barium stearate.
8. according to claim 4 or 5 described preparation methods, it is characterized in that the initiator among the described step a is one or more in organic peroxy compound, inorganic peroxy compounds or the azo-compound.
9. preparation method according to claim 8 is characterized in that, described initiator is peroxidation two acyl classes, peroxidation two alkanes, peroxyesters, Diisopropyl azodicarboxylate or persulphate.
10. preparation method according to claim 4 is characterized in that, amination described in the described 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.
11. preparation method according to claim 4 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 described step b.
12. preparation method according to claim 4, it is characterized in that, after polymerization is specially and uses the described alkene nitrile compounds of described organic solvent dissolution among the described step c, put into the product of step b again, temperature of reaction is 80 ℃～120 ℃, pressure is not more than 0.5MPa, polymerization 2 hours～10 hours.
13. according to claim 4 or 12 described preparation 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 described step c.
14. according to claim 4 or 12 described preparation 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 described step c.
15. preparation method according to claim 4 is characterized in that, halohydrocarbon described in the described steps d is one or more in tetracol phenixin, ethylene dichloride, difluoro ethylene dichloride, tetrachloroethane, the ethylene dibromide.
16., it is characterized in that stewing temperature is 50 ℃～150 ℃ according to claim 4 or 15 described preparation methods, cooking time is 2 hours～24 hours, gauge pressure is 0.1MPa～1.0MPa.
17. a deoiling method that uses each described macromolecular material of claim 1 to 3 to oily(waste)water is characterized in that, may further comprise the steps:
1., described 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.
18. deoiling method according to claim 17 is characterized in that, described step 2. in, oily(waste)water is 10 ℃～80 ℃ by the temperature of coalescence degreaser, the oily(waste)water flow is 9BV/h～30BV/h.
19. deoiling method according to claim 17 is characterized in that, 3. described step is specially when oil reservoir in the described collecting tank reaches 5 centimetres～10 centimetres, and oil slick is scraped.
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| CN102134344A (en) * | 2010-12-22 | 2011-07-27 | 朱同德 | Biparental high polymer coalescence degreasing material as well as preparation and application thereof |
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| CN1033560C (en) * | 1992-06-16 | 1996-12-18 | 南开大学 | Synthesis and application of saponin selective adsorption resin |
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| CN102134344A (en) * | 2010-12-22 | 2011-07-27 | 朱同德 | Biparental high polymer coalescence degreasing material as well as preparation and application thereof |
| CN102134344B (en) * | 2010-12-22 | 2012-07-25 | 朱同德 | Biparental high polymer coalescence degreasing material as well as preparation and application thereof |
| CN102875717A (en) * | 2011-08-26 | 2013-01-16 | 中化化工科学技术研究总院 | Synthetic resin, and preparation method and application thereof |
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