CN103193923B - Preparation method and application of pervaporation separation material based on polyacrylate resin - Google Patents
Preparation method and application of pervaporation separation material based on polyacrylate resin Download PDFInfo
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- CN103193923B CN103193923B CN201210006178.8A CN201210006178A CN103193923B CN 103193923 B CN103193923 B CN 103193923B CN 201210006178 A CN201210006178 A CN 201210006178A CN 103193923 B CN103193923 B CN 103193923B
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Abstract
A preparation method of a pervaporation separation material based on polyacrylate resin. The method comprises the following steps: step one, preparing water, a dispersing agent and a surface active agent into an aqueous solution under the conditions of heating and stirring; step two, preparing monomers, an initiator and a crosslinking agent into a monomer solution; and step three, adding the aqueous solution into a reaction vessel, heating while stirring, then adding monomer solution into the reaction vessel, maintaining the temperature, stirring for reaction, curing, cooling to the room temperature, filtering, washing and drying to a constant weight, and crushing into particles to obtain the separation material based on pervaporation polyacrylate resin. In addition, the invention also provides application of the material prepared by the preparation method provided by the invention to a pervaporation separation device.
Description
[technical field]
The present invention relates to a kind of preparation method and application of the infiltration evaporation parting material based on polyacrylate resin.
[background technology]
Pervaporation Technology develops a kind of new separation technology rapidly over nearly twenty or thirty year.Infiltration evaporation sepn process by the restriction that liquid phase is gentle, therefore not may be used for traditional Liquid liquid Separation system as reluctant in rectifying, as removing of minor amount of water in Azeotrope separation, organism.Infiltration evaporation often needs to rely on separatory membrane to realize, and comprises multiple polymers film and inorganic material film, and its principle is nothing more than relying on the regular micropore of film inside optionally to hold certain or certain class material realizes separating substances by film.Infiltrating and vaporizing membrane is divided into water preferentially preferentially to pass through film by film and organism.But, be no matter organism preferentially by film or water preferentially by film, the preparation technology of film itself is loaded down with trivial details, and cost is higher.On the other hand, material is comparatively large by pressure drop during film, needs film both sides to there is pressure reduction, therefore needs pressurization or has certain vacuum tightness at opposite side, and its process is complicated, and running cost is higher, and especially energy consumption is higher.
[summary of the invention]
Based on this, be necessary to provide a kind of preparation method the preparation method and application of the relatively simple infiltration evaporation parting material based on polyacrylate resin.
Based on a preparation method for the infiltration evaporation parting material of polyacrylate resin, comprise the steps:
Step one, water, dispersion agent and tensio-active agent are mixed with aqueous phase solution under the condition of heated and stirred, wherein, the mass percent of described dispersion agent is 0.5% ~ 1%, add that quality is described water 0.1% ~ 0.2% of described tensio-active agent;
Step 2, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer by mass percent be the methyl methacrylate of 30% ~ 50%, the ethyl propenoate of 10% ~ 20% and 30% ~ 60% butyl acrylate form, add that quality is described monomer 0.3% ~ 0.5% of described initiator, add that quality is described monomer 0.1% ~ 0.2% of described linking agent; And
Step 3, described aqueous phase solution is joined in reaction vessel, be heated to 75 DEG C ~ 85 DEG C under agitation, described monomer solution joins in described reaction vessel by the ratio being then 1: 2 ~ 1: 5 according to the volume ratio of described monomer solution and described aqueous phase solution, holding temperature is at 80 DEG C ~ 85 DEG C, with the speed stirring reaction 3 ~ 4 hours of 150 ~ 250rpm, temperature is risen to 90 DEG C of slakings 1 hour, filter after being down to room temperature, washing, dry to constant weight, be ground into the particle that particle diameter is 0.5mm ~ 2mm, obtain the described infiltration evaporation parting material based on polyacrylate resin.
In a preferred embodiment, in step one, described dispersion agent is gelatin.
In a preferred embodiment, in step one, described tensio-active agent is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
In a preferred embodiment, in step 2, described initiator is dibenzoyl peroxide and N, N-Diisopropyl azodicarboxylate.
In a preferred embodiment, in step 2, described linking agent is Vinylstyrene or ethylene glycol diacrylate.
According to the application of material in infiltration evaporation tripping device that the preparation method of the above-mentioned infiltration evaporation parting material based on polyacrylate resin obtains.
Based on a preparation method for the infiltration evaporation parting material of polyacrylate resin, comprise the steps:
Step one, dispersion agent is dissolved in solvent is mixed with dispersant solution, wherein, add that quality is described solvent 1% ~ 3% of described dispersion agent;
Step 2, Jiang Shui, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer is that the Hydroxyethyl acrylate of 20% ~ 40% and the vinylformic acid of 60% ~ 80% are formed by mass percent, the volume ratio of described monomer and water is 1: 1, add that quality is described monomer 0.5% ~ 1% of described initiator, add that quality is described monomer 0.2% ~ 0.5% of described linking agent; And
Step 3, dispersant solution is joined in reaction vessel, be heated to 55 DEG C ~ 60 DEG C under agitation, described monomer solution joins in described reaction vessel by the ratio being then 1: 3 ~ 1: 5 according to the volume ratio of described monomer solution and described dispersant solution, holding temperature is at 65 DEG C, with the speed stirring reaction 3 ~ 4 hours of 150 ~ 200rpm, temperature is risen to 70 DEG C of slakings 1 hour, filter after being down to room temperature, washing, dry to constant weight, be ground into the particle that particle diameter is 0.4mm ~ 1mm, obtain the described infiltration evaporation parting material based on polyacrylate resin.
In a preferred embodiment, in step one, described solvent is normal heptane or whiteruss.
In a preferred embodiment, in step one, described dispersion agent is calcium phosphate or calcium phosphate powder.
In a preferred embodiment, in step 2, described initiator is Potassium Persulphate-sodium bisulfite.
In a preferred embodiment, in step 2, described linking agent is N,N methylene bis acrylamide.
According to the application of material in infiltration evaporation tripping device that the preparation method of the above-mentioned infiltration evaporation parting material based on polyacrylate resin obtains.
Based on a preparation method for the infiltration evaporation parting material of polyacrylate resin, comprise the steps:
Step one, by monomer and water according to 1: 1 volume ratio be mixed with monomer solution, wherein said monomer is that the Hydroxyethyl acrylate of 20% ~ 40% and the vinylformic acid of 60% ~ 80% are formed by mass percent;
Step 2, be the initiator solution of 1% by water-soluble for initiator formation mass concentration;
Step 3, described monomer solution is joined in reaction vessel, be heated to 60 DEG C under agitation, then according to described monomer solution quality 2% ~ 5% ratio add described initiator solution, question response liquid becomes sticky to when cannot continue to stir, moved into by reaction solution in baking oven, slaking 1 hour at 70 DEG C, filters after being down to room temperature, washs, dries to constant weight, be ground into the particle that particle diameter is 3mm ~ 5mm, obtain the described infiltration evaporation parting material based on polyacrylate resin.
In a preferred embodiment, in step 2, described initiator is Potassium Persulphate-sodium bisulfite.
According to the application of material in infiltration evaporation tripping device that the preparation method of the above-mentioned infiltration evaporation parting material based on polyacrylate resin obtains.
Above-mentioned infiltration evaporation parting material is the infiltration evaporation parting material based on polyacrylate resin, it can realize optionally absorbing certain or certain type organic in water or in mixing organism, and limit organic vaporization rate by the cross-linked network structure of polyacrylate resin inside thus change water and organic gas-liquid phase equilibrium, realize organic abstraction and purification a small amount of in water with rectifying coupling.In addition, relative to traditional infiltrating and vaporizing membrane, the above-mentioned infiltration evaporation parting material technical maturity based on polyacrylate resin, simple.
[accompanying drawing explanation]
By the more specifically explanation of the preferred embodiments of the present invention shown in accompanying drawing, above-mentioned and other object of the present invention, Characteristics and advantages will become more clear.Reference numeral identical in whole accompanying drawing indicates identical part, and does not deliberately draw accompanying drawing by physical size equal proportion convergent-divergent, focuses on purport of the present invention is shown.
Fig. 1 is the structural representation of the infiltration evaporation separating device of an embodiment.
[embodiment]
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the infiltration evaporation separating device 100 of an embodiment comprises electric heater 1, container for storing liquid 2, knockout tower 3, condenser 4, return line 5 and discharge nozzle 6.
Electric heater 1 is for heating the stoste to be separated in container for storing liquid 2.Knockout tower 3 is made up of glass, and its inside is filled with infiltration evaporation parting material 31.In the present embodiment, the internal diameter of knockout tower 3 is 50mm, and length is 1m.The infiltration evaporation parting material 31 of filling is divided into three sections, every section of about 20mm, support, and the distance between maintaining segment section is about 100mm, distributes for gas again between section and section with Stainless Steel Cloth.The top of knockout tower 3 is provided with discharge port and refluxing opening (sign).Condenser 4 is connected with refluxing opening with discharge port with return line 5 respectively by discharging pipeline 41, and discharge nozzle 6 is connected with return line 5.Return line 5 and discharge nozzle 6 are also provided with under meter and valve.
During use, stoste to be separated in container for storing liquid 2 is heated into steam by electric heater 1, mixing steam is by knockout tower 3, and the infiltration evaporation of the infiltration evaporation parting material through filling is separated the organism that can realize usual way is difficult to be separated and carries out the removal that effective separation maybe can realize a small amount of water in organism.
Above-mentioned infiltration evaporation parting material is the infiltration evaporation parting material based on polyacrylate resin, it can realize optionally absorbing certain or certain type organic in water or in mixing organism, as optionally absorbed the materials such as the water-soluble of trace or the sl. sol. ketone of water, ester class, and limit organic vaporization rate by the cross-linked network structure of polyacrylate resin inside thus change water and organic gas-liquid phase equilibrium, realize organic abstraction and purification a small amount of in water with rectifying coupling; Also the abstraction and purification of certain type organic in organism mixing solutions can be realized by the selective absorbing of polyacrylate resin to certain type organic.
Above-mentioned infiltration evaporation parting material is the infiltration evaporation parting material based on polyacrylate resin, and wherein polyacrylic ester can select methyl acrylate, ethyl propenoate, butyl acrylate etc.Can different Polyacrylate monomer be selected to generate corresponding polyacrylate polymers according to different separation systems.Its preparation process can select suspend poly-, inverse suspension polymerization and solution polymerization, and makes material to certain organism or glassware for drinking water selectively absorptive character by the adjustment of monomer component.Be described below by concrete preparation method.
The preparation method of the infiltration evaporation parting material based on polyacrylate resin of embodiment one, comprises the steps:
Step one, water, dispersion agent and tensio-active agent are mixed with aqueous phase solution under the condition of heated and stirred, wherein, the mass percent of described dispersion agent is 0.5% ~ 1%, add that quality is described water 0.1% ~ 0.2% of described tensio-active agent.
Wherein, described dispersion agent is gelatin.Described tensio-active agent can select anionic surfactant, such as, can be Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
Step 2, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer by mass percent be the methyl methacrylate of 30% ~ 50%, the ethyl propenoate of 10% ~ 20% and 30% ~ 60% butyl acrylate form, add that quality is described monomer 0.3% ~ 0.5% of described initiator, add that quality is described monomer 0.1% ~ 0.2% of described linking agent.
Wherein, described initiator is dibenzoyl peroxide (BPO) and N, N-Diisopropyl azodicarboxylate (AIBN).Described linking agent is Vinylstyrene or ethylene glycol diacrylate.
Step 3, described aqueous phase solution is joined in reaction vessel (such as with stirring and the reaction flask of reflux), be heated to 75 DEG C ~ 85 DEG C under agitation, described monomer solution joins in described reaction vessel by the ratio being then 1: 2 ~ 1: 5 according to the volume ratio of described monomer solution and described aqueous phase solution, holding temperature is at 80 DEG C ~ 85 DEG C, with the speed stirring reaction 3 ~ 4 hours of 150 ~ 250rpm, temperature is risen to 90 DEG C of slakings 1 hour, filter after being down to room temperature, wash three times with water, with washing with alcohol once after, dry to constant weight, be ground into the particle that particle diameter is 0.5mm ~ 2mm, obtain the infiltration evaporation parting material based on polyacrylate resin.
The infiltration evaporation parting material obtained by above-mentioned preparation method can realize being separated of the close alcohol of boiling point and aromatic hydrocarbons (such as methyl alcohol and benzene, methyl alcohol and tetrahydrofuran (THF)).
The preparation method of the infiltration evaporation parting material based on polyacrylate resin of embodiment two, comprises the steps:
Step one, dispersion agent is dissolved in solvent is mixed with dispersant solution, wherein, add that quality is described solvent 1% ~ 3% of described dispersion agent.
Described dispersion agent is calcium phosphate or calcium phosphate powder.Described solvent is normal heptane or whiteruss.
Step 2, Jiang Shui, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer is that the Hydroxyethyl acrylate of 20% ~ 40% and the vinylformic acid of 60% ~ 80% are formed by mass percent, the volume ratio of described monomer and water is 1: 1, add that quality is described monomer 0.5% ~ 1% of described initiator, add that quality is described monomer 0.2% ~ 0.5% of described linking agent.
Described initiator is redox initiator, such as Potassium Persulphate-sodium bisulfite.Described linking agent is N,N methylene bis acrylamide.
Step 3, dispersant solution is joined in reaction vessel (such as with stirring and the reaction flask of reflux), be heated to 55 DEG C ~ 60 DEG C under agitation, described monomer solution joins in described reaction vessel by the ratio being then 1: 3 ~ 1: 5 according to the volume ratio of described monomer solution and described dispersant solution, holding temperature is at 65 DEG C, with the speed stirring reaction 3 ~ 4 hours of 150 ~ 200rpm, temperature is risen to 70 DEG C of slakings 1 hour, filter after being down to room temperature, after water and ethanol repetitive scrubbing three times, dry to constant weight, be ground into the particle that particle diameter is 0.4mm ~ 1mm, obtain the infiltration evaporation parting material based on polyacrylate resin.
The infiltration evaporation parting material obtained by above-mentioned preparation method can realize some can form dewatering of organism (such as the ethyl acetate) of azeotropic point with water, can also realize removing of the minor amount of water in some organism (such as tetrahydrofuran (THF)) that infinitely can dissolve each other with water.
The preparation method of the infiltration evaporation parting material based on polyacrylate resin of embodiment three, comprises the steps:
Step one, by monomer and water according to 1: 1 volume ratio be mixed with monomer solution, wherein said monomer is that the Hydroxyethyl acrylate of 20% ~ 40% and the vinylformic acid of 60% ~ 80% are formed by mass percent.
Step 2, be the initiator solution of 1% by water-soluble for initiator formation mass concentration.
Described initiator is Potassium Persulphate-sodium bisulfite.
Step 3, described monomer solution is joined in reaction vessel, be heated to 60 DEG C under agitation, then according to described monomer solution quality 2% ~ 5% ratio add described initiator solution, question response liquid becomes sticky to when cannot continue to stir, reaction solution is moved in baking oven, slaking 1 hour at 70 DEG C, filter after being down to room temperature, after water and ethanol repetitive scrubbing three times, dry to constant weight, be ground into the particle that particle diameter is 3mm ~ 5mm, obtain the infiltration evaporation parting material based on polyacrylate resin.
The infiltration evaporation parting material obtained by above-mentioned preparation method can realize some can form dewatering of organism (such as the ethyl acetate) of azeotropic point with water, can also realize removing of the minor amount of water in some organism (such as tetrahydrofuran (THF)) that infinitely can dissolve each other with water.
The present invention selects infiltration evaporation parting material based on polyacrylate resin as the packing material of knockout tower, and its preparation method more for convenience.Utilize polyacrylate resin, the resin especially with certain degree of crosslinking (0.05 ~ 0.2%) is optionally swelling in its specific good solvent and absorb the feature of specific solvent, changes organism and water and balancing each other between organism and organism by the cross-linked network result of polymeric inner to the restriction of organism free diffusing.Such as in the methyl alcohol containing a small amount of benzene, because of benzene (good solvent of polyacrylic ester) can be preferential, optionally impel polymers swell and enter in the network structure of polymeric inner, and when vaporizing because its speed diffusing to gas-particle two-phase interface is restricted, thus itself and balancing each other of methyl alcohol are affected, the benzene of (namely relative to solution phase) small amount is vaporized and transfers steam to.And methyl alcohol is the poor solvent of polyacrylate resin, cannot enter in polymeric system, therefore the gas-liquid phase equilibrium of methyl alcohol is less is affected, thus with the infiltration evaporation parting material based on polyacrylate resin for filler and in the knockout tower of device, can tower top obtain benzene concentration lower than 1% methanol product.Because polyacrylate resin realizes by the selectivity of organism to polymkeric substance is swelling organic separation, and swelling in some organism or organic solvent of polymkeric substance is the characteristic property of polymeric system, therefore less demanding, spherical, the even pulverous resin of particulate state of this infiltration evaporation sepn process preparation to acrylate resin all can use.
In addition, comparatively infiltrating and vaporizing membrane is low for the separation factor of polyacrylate resin itself, after therefore polyacrylate resin being prepared into particulate state, the state such as spherical, it can being packed into fixed bed as filler, can realizing good separating effect equally.And fixed-bed process is ripe, gas percent of pass is high, pressure drop is little.Can realize without the need to applying pressure in fixed bed both sides.In addition, because above-mentioned parting material device becomes the fixed bed form of comparative maturity, its technical maturity, equipment are simple, and running cost is lower, are convenient to maximize and commercialization popularization.
Illustrate with specific embodiment below.
Embodiment 1
Preparation aqueous phase solution: water, dispersion agent, tensio-active agent be wiring solution-forming under condition of heating and stirring.Wherein dispersion agent is gelatin, and content is 0.5%; Tensio-active agent is Sodium dodecylbenzene sulfonate, and consumption is 0.1% of quality.
Preparation monomer solution, wherein containing monomer, initiator, linking agent.Wherein monomer is methyl methacrylate, ethyl propenoate and butyl acrylate.Concrete ratio is methyl methacrylate 30%; Ethyl propenoate 10%; Butyl acrylate 60%.Linking agent selects dibenzoyl peroxide (BPO) and N, N-Diisopropyl azodicarboxylate (AIBN), and consumption is 0.3% of monomer mass.Vinylstyrene selected by linking agent, and consumption is 0.1% of monomer.
The volume ratio of monomer solution and aqueous phase solution controls 1: 2.
Aqueous phase solution be added to backflow and whipping appts reaction flask in, be heated to 75 DEG C under agitation, maintenance stirring velocity, the monomer solution prepared once is added.Be warming up to temperature of reaction 80 DEG C, temperature, after 3 hours, is risen to 90 DEG C of slakings one hour by maintenance stirring (150rpm) and thermotonus.By reacting the resin filter obtained after being cooled to normal temperature, washing three times with water, by washing with alcohol post-drying to constant weight, being ground into the particle that particle diameter is 0.5mm ~ 2mm, obtain the described infiltration evaporation parting material based on polyacrylate resin.
Embodiment 2
Preparation aqueous phase solution: water, dispersion agent, tensio-active agent be wiring solution-forming under condition of heating and stirring.Wherein dispersion agent is gelatin, and content is 1%; Tensio-active agent is sodium lauryl sulphate, and consumption is 0.2% of quality.
Preparation monomer solution, wherein containing monomer, initiator, linking agent.Wherein monomer is methyl methacrylate, ethyl propenoate and butyl acrylate.Concrete ratio is methyl methacrylate 50%; Ethyl propenoate 20%; Butyl acrylate 30%.Linking agent selects dibenzoyl peroxide (BPO) and N, N-Diisopropyl azodicarboxylate (AIBN), and consumption is 0.5% of monomer mass.Ethylene glycol diacrylate selected by linking agent, and consumption is 0.2% of monomer.
The volume ratio of monomer solution and aqueous phase solution controls 1: 5.
Aqueous phase solution be added to backflow and whipping appts reaction flask in, be heated to 85 DEG C under agitation, maintenance stirring velocity, the monomer solution prepared once is added.Be warming up to temperature of reaction 85 DEG C, temperature, after 4 hours, is risen to 90 DEG C of slakings one hour by maintenance stirring (250rpm) and thermotonus.By reacting the resin filter obtained after being cooled to normal temperature, washing three times with water, by washing with alcohol post-drying to constant weight, being ground into the particle that particle diameter is 0.5mm ~ 2mm, obtain the described infiltration evaporation parting material based on polyacrylate resin.
Embodiment 3
Preparation dispersant solution: wherein containing normal heptane and dispersion agent.Dispersion agent selects calcium phosphate, and consumption is 1% of dispersant solution.
Preparation water-soluble mono liquid solution: water, monomer, initiator and linking agent are mixed with homogeneous phase solution.Wherein monomer and water volume ratio are 1: 1, and monomer is Hydroxyethyl acrylate 20% and vinylformic acid 80%; Initiator adopts redox type initiator, i.e. Potassium Persulphate-sodium bisulfite, and consumption is 0.5% of amount of monomer; Linking agent is N,N methylene bis acrylamide, and its consumption is 0.2% of amount of monomer.
The volume ratio of monomer solution and dispersant solution controls between 1: 3.
Dispersant solution is added with stir and reflux reaction flask in, be heated to 55 DEG C under agitation, maintenance stirring velocity, the monomer solution prepared once is added.Be warming up to temperature of reaction 65 DEG C, temperature, after 3 hours, is risen to 70 DEG C of slakings one hour by maintenance stirring and thermotonus.By reacting the resin filter that obtains after being cooled to normal temperature, after washing with alcohol three times, wash three post-dryings by massive laundering for subsequent use to constant weight.Control stir speed (S.S.) (150rpm-200rpm) and can obtain the different rosin products of particle diameter with dispersant dosage, the ultimate size of the resin synthesized by the present embodiment is 0.4-1mm.
Embodiment 4
Preparation dispersant solution: wherein containing whiteruss and dispersion agent.Dispersion agent selects calcium phosphate powder, and consumption is 2% of dispersant solution.
Preparation water-soluble mono liquid solution: water, monomer, initiator and linking agent are mixed with homogeneous phase solution.Wherein monomer and water volume ratio are 1: 1, and monomer is Hydroxyethyl acrylate 30% and vinylformic acid 70%; Initiator adopts redox type initiator, i.e. Potassium Persulphate-sodium bisulfite, and consumption is 0.6% of amount of monomer; Linking agent is N,N methylene bis acrylamide, and its consumption is 0.3% of amount of monomer.
The volume ratio of monomer solution and dispersant solution controls between 1: 4.
Dispersant solution is added with stir and reflux reaction flask in, be heated to 56 DEG C under agitation, maintenance stirring velocity, the monomer solution prepared once is added.Be warming up to temperature of reaction 65 DEG C, temperature, after 3 hours, is risen to 70 DEG C of slakings one hour by maintenance stirring and thermotonus.By reacting the resin filter that obtains after being cooled to normal temperature, after washing with alcohol three times, wash three post-dryings by massive laundering for subsequent use to constant weight.Control stir speed (S.S.) (150rpm-200rpm) and can obtain the different rosin products of particle diameter with dispersant dosage, the ultimate size of the resin synthesized by the present embodiment is 0.4-1mm.
Embodiment 5
Preparation dispersant solution: wherein containing normal heptane and dispersion agent.Dispersion agent selects calcium phosphate, and consumption is 3% of dispersant solution.
Preparation water-soluble mono liquid solution: water, monomer, initiator and linking agent are mixed with homogeneous phase solution.Wherein monomer and water volume ratio are 1: 1, and monomer is Hydroxyethyl acrylate 40% and vinylformic acid 80%; Initiator adopts redox type initiator, i.e. Potassium Persulphate-sodium bisulfite, and consumption is 0.8% of amount of monomer; Linking agent is N,N methylene bis acrylamide, and its consumption is 0.4% of amount of monomer.
The volume ratio of monomer solution and dispersant solution controls between 1: 5.
Dispersant solution is added with stir and reflux reaction flask in, be heated to 58 DEG C under agitation, maintenance stirring velocity, the monomer solution prepared once is added.Be warming up to temperature of reaction 65 DEG C, temperature, after 4 hours, is risen to 70 DEG C of slakings one hour by maintenance stirring and thermotonus.By reacting the resin filter that obtains after being cooled to normal temperature, after washing with alcohol three times, wash three post-dryings by massive laundering for subsequent use to constant weight.Control stir speed (S.S.) (150rpm-200rpm) and can obtain the different rosin products of particle diameter with dispersant dosage, the ultimate size of the resin synthesized by the present embodiment is 0.4-1mm.
Embodiment 6
Preparation dispersant solution: wherein containing liquid paraffin and dispersion agent.Dispersion agent selects calcium phosphate powder, and consumption is 2.5% of dispersant solution.
Preparation water-soluble mono liquid solution: water, monomer, initiator and linking agent are mixed with homogeneous phase solution.Wherein monomer and water volume ratio are 1: 1, and monomer is Hydroxyethyl acrylate 30% and vinylformic acid 70%; Initiator adopts redox type initiator, i.e. Potassium Persulphate-sodium bisulfite, and consumption is 1% of amount of monomer; Linking agent is N,N methylene bis acrylamide, and its consumption is 0.5% of amount of monomer.
The volume ratio of monomer solution and dispersant solution controls between 1: 5.
Dispersant solution is added with stir and reflux reaction flask in, be heated to 60 DEG C under agitation, maintenance stirring velocity, the monomer solution prepared once is added.Be warming up to temperature of reaction 65 DEG C, temperature, after 4 hours, is risen to 70 DEG C of slakings one hour by maintenance stirring and thermotonus.By reacting the resin filter that obtains after being cooled to normal temperature, after washing with alcohol three times, wash three post-dryings by massive laundering for subsequent use to constant weight.Control stir speed (S.S.) (150rpm-200rpm) and can obtain the different rosin products of particle diameter with dispersant dosage, the ultimate size of the resin synthesized by the present embodiment is 0.4-1mm.
Embodiment 7
Monomer and water are mixed with monomer solution, and monomer and water volume ratio are 1: 1.Monomer is Hydroxyethyl acrylate 20% and vinylformic acid 80%.Be added to by monomer solution in reaction beaker, be heated to 60 DEG C in water bath with thermostatic control, add initiator solution (initiator is 1% of Potassium Persulphate and sodium bisulfite) under agitation, add-on is 2% of monomer solution.When the aqueous solution becomes sticky and cannot stir, reaction solution is moved into baking oven, oven temperature maintains 70 degree, and slaking was taken out after one hour.After block for gained rosin products water and ethanol repetitive scrubbing three times, resin is inserted oven for drying to constant weight.It is that the particulate state of 3-5mm is for subsequent use that rosin products is crushed to yardstick.
Embodiment 8
Monomer and water are mixed with monomer solution, and monomer and water volume ratio are 1: 1.Monomer is Hydroxyethyl acrylate 30% and vinylformic acid 70%.Be added to by monomer solution in reaction beaker, be heated to 60 DEG C in water bath with thermostatic control, add initiator solution (initiator is Potassium Persulphate and sodium bisulfite, and mass concentration is 1%) under agitation, add-on is 3% of monomer solution.When the aqueous solution becomes sticky and cannot stir, reaction solution is moved into baking oven, oven temperature maintains 70 degree, and slaking was taken out after one hour.After block for gained rosin products water and ethanol repetitive scrubbing three times, resin is inserted oven for drying to constant weight.It is that the particulate state of 3-5mm is for subsequent use that rosin products is crushed to yardstick.
Embodiment 9
Monomer and water are mixed with monomer solution, and monomer and water volume ratio are 1: 1.Monomer is Hydroxyethyl acrylate 40% and vinylformic acid 60%.Be added to by monomer solution in reaction beaker, be heated to 60 DEG C in water bath with thermostatic control, add initiator solution (initiator is Potassium Persulphate and sodium bisulfite, and mass concentration is 1%) under agitation, add-on is 4% of monomer solution.When the aqueous solution becomes sticky and cannot stir, reaction solution is moved into baking oven, oven temperature maintains 70 degree, and slaking was taken out after one hour.After block for gained rosin products water and ethanol repetitive scrubbing three times, resin is inserted oven for drying to constant weight.It is that the particulate state of 3-5mm is for subsequent use that rosin products is crushed to yardstick.
Embodiment 10
Monomer and water are mixed with monomer solution, and monomer and water volume ratio are 1: 1.Monomer is Hydroxyethyl acrylate 30% and vinylformic acid 70%.Be added to by monomer solution in reaction beaker, be heated to 60 DEG C in water bath with thermostatic control, add initiator solution (initiator is Potassium Persulphate and sodium bisulfite, and mass concentration is 1%) under agitation, add-on is 5% of monomer solution.When the aqueous solution becomes sticky and cannot stir, reaction solution is moved into baking oven, oven temperature maintains 70 degree, and slaking was taken out after one hour.After block for gained rosin products water and ethanol repetitive scrubbing three times, resin is inserted oven for drying to constant weight.It is that the particulate state of 3-5mm is for subsequent use that rosin products is crushed to yardstick.
The infiltration evaporation parting material based on polyacrylate resin prepared by embodiment 1 ~ 10 is respectively charged into as filler and is separated in tower body, make infiltration evaporation knockout tower and be respectively used to separation of methanol-benzene, ethyl acetate-water and tetrahydrofuran (THF)-aqueous systems.During separation, the temperature heated in setting electric heater is 70 DEG C, and maintenance mixture is boiling state, and opens the water of condensation in overhead condenser.From overhead extraction sample under the certain reflux ratio of maintenance or full discharging situation, measure the benzene content or water content determined wherein with chromatography of gases.Test result is as following table.
Table 1
Can be drawn by table 1, by using the fixed bed device loaded as filler based on the infiltration evaporation parting material of polyacrylate resin, and realize being separated by its ORGANIC SOLVENT MIXTURES that conventional distillation process can be difficult to be separated boiling point close (methyl alcohol and benzene) by the vaporization of system and the process of osmosis in fixed bed separately; Can realize organic dewater (ethyl acetate and water form azeotrope) that certain and water formed to azeotropic, and its removal process can once complete, technique is simple.Its result is also better than azeotropic distillation; Also removing (tetrahydrofuran (THF) infinitely can dissolve each other with water, and conventional distillation is also difficult to remove wherein contained a small amount of water or minor amount of water) of a small amount of water in the organism infinitely dissolved each other with water or minor amount of water can be realized.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (3)
1., based on a preparation method for the infiltration evaporation parting material of polyacrylate resin, it is characterized in that, comprise the steps:
Step one, water, dispersion agent and tensio-active agent are mixed with aqueous phase solution under the condition of heated and stirred, wherein, the mass percent of described dispersion agent is 0.5% ~ 1%, add that quality is described water 0.1% ~ 0.2% of described tensio-active agent; Described dispersion agent is gelatin; Described tensio-active agent is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate;
Step 2, monomer, initiator and linking agent are mixed with monomer solution, wherein, described monomer by mass percent be the methyl methacrylate of 30% ~ 50%, the ethyl propenoate of 10% ~ 20% and 30% ~ 60% butyl acrylate form, add that quality is described monomer 0.3% ~ 0.5% of described initiator, add that quality is described monomer 0.1% ~ 0.2% of described linking agent; Described initiator is dibenzoyl peroxide and N, N-Diisopropyl azodicarboxylate; Described linking agent is Vinylstyrene or ethylene glycol diacrylate; And
Step 3, described aqueous phase solution is joined in reaction vessel, be heated to 75 DEG C ~ 85 DEG C under agitation, described monomer solution joins in described reaction vessel by the ratio being then 1:2 ~ 1:5 according to the volume ratio of described monomer solution and described aqueous phase solution, holding temperature is at 80 DEG C ~ 85 DEG C, with the speed stirring reaction 3 ~ 4 hours of 150 ~ 250rpm, temperature is risen to 90 DEG C of slakings 1 hour, filter after being down to room temperature, washing, dry to constant weight, be ground into the particle that particle diameter is 0.5mm ~ 2mm, obtain the described infiltration evaporation parting material based on polyacrylate resin.
2. according to the application of material in infiltration evaporation tripping device that the preparation method of the infiltration evaporation parting material based on polyacrylate resin according to claim 1 obtains.
3. an infiltration evaporation tripping device, comprises knockout tower, it is characterized in that, is filled with the material obtained according to the preparation method of the infiltration evaporation parting material based on polyacrylate resin according to claim 1 in described knockout tower.
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| CN105461667A (en) * | 2016-01-08 | 2016-04-06 | 上海博丹环境工程技术股份有限公司 | Treatment method and system for recycling tetrahydrofuran in solution discharged in parecoxib normal-phase workshop section |
| CN107096399A (en) * | 2016-02-22 | 2017-08-29 | 深圳市启德环保科技有限公司 | A kind of high pressure resistant porous polymer PMMA filter membrane materials |
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