CN115850695A - Bio-based water-based polyether amine high-molecular polymer and preparation method and application thereof - Google Patents
Bio-based water-based polyether amine high-molecular polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a bio-based waterborne polyether amine high molecular polymer and a preparation method and application thereof, wherein the bio-based waterborne polyether amine high molecular polymer is prepared from the following raw materials in parts by weight: 80-10 parts of epichlorohydrin, 0.36-0.6 part of glycol, 0.7-1.4 parts of boron trifluoride tetrahydrofuran complex, 30-45 parts of tetrahydrofuran, 260-320 parts of polyethylene polyamine, 50-80 parts of cottonseed protein intermediate and 150-300 parts of methanol. The polymer of the invention not only retains the inherent non-toxic harmless, biocompatibility, degradability and other excellent performances of tannin and cottonseed protein, but also has a positive charge in each structural unit of a molecular chain, has uniform charge distribution, can more effectively neutralize the excessive negative charge carried by the microflocs, promotes the formation and growth of the flocs, improves the structure of the flocs, further improves the pollutant adsorption capacity and flocculation sedimentation performance, and has wider application field.
Description
Technical Field
The invention relates to the technical field of flocculants, and particularly relates to a bio-based water-based polyether amine high polymer and a preparation method and application thereof.
Background
At present, with the increasing demand of people on environmental protection, more and more environment-friendly materials are developed and applied to water treatment. The bio-based flocculant is a natural organic polymer flocculant and can be divided into three categories according to the chemical composition, namely protein, cellulose, polysaccharide and other carbohydrate flocculants. The bio-based flocculant using plant protein or chitosan as a main raw material is a natural environment-friendly flocculant which can be modified and compounded and then used for sewage treatment. Compared with the traditional chemical flocculant, the natural organic flocculant has the advantages of safety, stability, reproducibility, no secondary pollution, biodegradability and the like. But the molecular structure is in a compact crystalline state and insoluble in water and most organic solvents due to the strong hydrogen bonding action existing in the molecules and among the molecules, which greatly limits the application of the organic solvent.
The cottonseed protein is a high protein product prepared by removing down and husks from cottonseeds, soaking in oil once at low temperature, draining, and then removing toxic substances (gossypol). At present, the cottonseed protein production process needs detoxification treatment, and wet meal subjected to solvent detoxification treatment mostly adopts a heating evaporation process to dry the wet meal, so that finished product protein is prepared. Patent application No. 200510124534.6 introduces a cottonseed protein production method, which comprises the following steps: the cottonseed protein extraction is completed in a leacher by using a mixed solvent of No. 6 solvent and methanol 1.5; and extruding the wet meal by an extruder, and drying by a disc dryer to obtain the finished cottonseed protein. The production process is simple, the loss is less, the energy consumption is low, the cost is low, high-quality cottonseed protein with the protein free gossypol content of less than 400ppm and the protein solubility of more than 55 percent can be obtained, and the continuous industrial production is easy to realize; however, the cottonseed protein in the prior art has the defect of poor net-capturing adsorption performance, and the application range of the cottonseed protein is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a bio-based water-based polyether amine high polymer and a preparation method and application thereof, the polymer not only retains the inherent excellent performances of tannin and cottonseed protein, such as innocuity, biocompatibility, degradability and the like, but also has a positive charge in each structural unit of a molecular chain, the charge distribution is uniform, the excessive negative charge carried by micro flocs can be neutralized more effectively, the formation and growth of the flocs are promoted, the structure of the flocs is improved, the pollutant adsorption capacity and the flocculation settling property are improved, and the application field is wider.
The invention provides a bio-based waterborne polyether amine high molecular polymer, which is prepared from the following raw materials in parts by weight: 80-10 parts of epichlorohydrin, 0.36-0.6 part of glycol, 0.7-1.4 parts of boron trifluoride tetrahydrofuran complex, 30-45 parts of tetrahydrofuran, 260-320 parts of polyethylene polyamine, 50-80 parts of cottonseed protein intermediate and 150-300 parts of methanol.
In the invention, as a preferred embodiment, the bio-based waterborne polyether amine high molecular polymer is prepared from the following raw materials in parts by weight: 90 parts by weight of epichlorohydrin, 0.36-0.6 part by weight of ethylene glycol, 0.7-1.4 parts by weight of boron trifluoride tetrahydrofuran complex, 30-45 parts by weight of tetrahydrofuran, 260-320 parts by weight of polyethylene polyamine, 50-80 parts by weight of cottonseed protein intermediate and 150-300 parts by weight of methanol.
In the invention, as a preferred embodiment, the bio-based water-based polyether amine high molecular polymer is prepared from the following raw materials in parts by weight: 90 parts by weight of epichlorohydrin, 0.6 part by weight of ethylene glycol, 1.4 parts by weight of boron trifluoride tetrahydrofuran complex, 45 parts by weight of tetrahydrofuran, 280 parts by weight of polyethylene polyamine, 70 parts by weight of cottonseed protein intermediate, and 300 parts by weight of methanol.
In the invention, as a preferred embodiment, the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 2-4 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 45-55 parts of water.
In the present invention, as a preferred embodiment, the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 5-10 parts of urea, 2-4 parts of 2-mercaptoethanol, 2-4 parts of NaOH,30-50 parts of condensed tannin and 90 parts of water.
The second aspect of the invention also provides a preparation method of the bio-based waterborne polyether amine high molecular polymer, which comprises the following steps: adding a tetrahydrofuran solvent with the formula amount into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, adding ethylene glycol and a boron trifluoride tetrahydrofuran complex with the formula amount, reducing the temperature to below 10 ℃, slowly dropwise adding epoxy chloropropane diluted with tetrahydrofuran with the formula amount for 6-8h, reacting for 12h after dropwise adding to obtain polyepichlorohydrin, then adding a cottonseed protein intermediate, polyethylene polyamine and methanol with the formula amount, reacting for 2-3h under stirring at 50 ℃, subsequently heating to 90 ℃, reacting for 3-5h, and cooling at room temperature to obtain a target product.
In the present invention, as a preferred embodiment, the preparation method of the cottonseed protein intermediate comprises the steps of condensing tannin modified cottonseed protein: mixing the cottonseed protein, the depolymerized condensed tannin, 1,2, 3-glycerol triglycidyl ether and water according to the formula ratio, and stirring for 6-8 hours at normal temperature to obtain a cottonseed protein intermediate.
In the present invention, as a preferred embodiment, a depolymerization step of the condensed tannin is further included: adding urea, 2-mercaptoethanol, naOH, condensed tannin and water in formula amounts into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in water bath, reacting for 2-4h, and continuing stirring the solution at normal temperature for 15h to obtain the depolymerized condensed tannin.
In the present invention, as a preferred embodiment, the method further comprises a pretreatment step: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for multiple times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging; placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight; and (3) grinding the dried cottonseed meal again and sieving the cottonseed meal with a 200-mesh sieve to obtain the cottonseed protein.
The third aspect of the invention also provides an application of the bio-based waterborne polyether amine high molecular polymer as a flocculant.
Compared with the prior art, the invention has the beneficial effects that: the bio-based waterborne polyether amine high molecular polymer can be used as a flocculating agent. On one hand, the condensed tannin and cottonseed protein retain inherent excellent performances of innocuity, biocompatibility, degradability, macromolecular adsorption and the like, and meanwhile, because the tannin has a certain steric hindrance due to the large relative molecular weight and has poor reactivity with other molecules, the tannin is treated by utilizing green environment-friendly urea and 2-mercaptoethanol, the steric hindrance of the condensed tannin is reduced, and the reactivity is increased; on the other hand, the polyepichlorohydrin with relatively large molecular weight is synthesized to be used as a cross-linking agent, not only the polyepichlorohydrin and the polyethylene polyamine are subjected to cross-linking polycondensation reaction, but also the catechol group on the condensed tannin and the NH on the cottonseed protein chain and the polyethylene polyamine are utilized 2 The groups react to form a double-crosslinked network structure to enhance the net trapping and sweeping effect, so that the polymer molecular chain is longer, the branching degree is high, a more developed network structure is formed, the bridging effect and the electric neutralization effect on oil drops are stronger, the emulsified oil drops are easier to contact, original natural surfactants on the surface of oil water are replaced, the oil drops are extruded to promote coalescence, and the floating or sinking is promoted. Furthermore, the cottonseed protein intermediate disclosed by the invention has the advantages that the condensed tannin is treated by utilizing green and environment-friendly urea and 2-mercaptoethanol, the steric hindrance of the condensed tannin is reduced, the reaction activity of the condensed tannin is increased, the depolymerized condensed tannin solution is uniformly dispersed in the cottonseed protein, the net structure is increased, and the net catching adsorption performance is further enhanced.
Drawings
FIG. 1 is a graph showing the effect of different dosages of bio-based waterborne polyetheramine high molecular weight polymer on the transmittance of kaolin solution in example 3;
FIG. 2 is a graph comparing the oil removing effect of bio-based aqueous polyetheramine high molecular weight polymer of example 3 and a market comparison sample on polymer-containing wastewater;
FIG. 3 is a graph comparing the flocculation effect of bio-based waterborne polyetheramine high molecular weight polymers of examples 1-4 on kaolin suspensions.
Detailed Description
The invention is further described with reference to the drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict. Except as specifically noted, the materials and equipment used in this example are commercially available.
A bio-based water-based polyether amine high molecular polymer is prepared from the following raw materials in parts by weight: 80-10 parts of epichlorohydrin, 0.36-0.6 part of glycol, 0.7-1.4 parts of boron trifluoride tetrahydrofuran complex, 30-45 parts of tetrahydrofuran, 260-320 parts of polyethylene polyamine, 50-80 parts of cottonseed protein intermediate and 150-300 parts of methanol.
As a preferable embodiment, the bio-based waterborne polyether amine high molecular polymer is prepared from the following raw materials in parts by weight: 90 parts by weight of epichlorohydrin, 0.36-0.6 part by weight of ethylene glycol, 0.7-1.4 parts by weight of boron trifluoride tetrahydrofuran complex, 30-45 parts by weight of tetrahydrofuran, 260-320 parts by weight of polyethylene polyamine, 50-80 parts by weight of cottonseed protein intermediate and 150-300 parts by weight of methanol.
As a preferable embodiment, the bio-based waterborne polyether amine high molecular polymer is prepared from the following raw materials in parts by weight: 90 parts by weight of epichlorohydrin, 0.6 part by weight of ethylene glycol, 1.4 parts by weight of boron trifluoride tetrahydrofuran complex, 45 parts by weight of tetrahydrofuran, 280 parts by weight of polyethylene polyamine, 70 parts by weight of cottonseed protein intermediate, and 300 parts by weight of methanol.
As a preferred embodiment, the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 2-4 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 45-55 parts of water.
As a preferred embodiment, the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 5-10 parts of urea, 2-4 parts of 2-mercaptoethanol, 2-4 parts of NaOH,30-50 parts of condensed tannin and 90 parts of water.
The second aspect of the invention also provides a preparation method of the bio-based waterborne polyether amine high molecular polymer, which comprises the following steps: adding a tetrahydrofuran solvent with the formula amount into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, then adding ethylene glycol with the formula amount and a boron trifluoride tetrahydrofuran complex with the formula amount, reducing the temperature to be below 10 ℃, slowly dropwise adding epoxy chloropropane diluted by tetrahydrofuran with the formula amount, dropwise adding for 6-8h, reacting for 12h after dropwise adding to obtain polyepichlorohydrin, then adding a cottonseed protein intermediate, polyethylene polyamine and methanol with the formula amount, stirring at 50 ℃ for 2-3h, subsequently heating to 90 ℃, reacting for 3-5h, and cooling at room temperature to obtain a target product.
As a preferred embodiment, the preparation method of the cottonseed protein intermediate comprises the following steps of: mixing the cottonseed protein, the depolymerized condensed tannin, 1,2, 3-glycerol triglycidyl ether and water according to the formula ratio, and stirring for 6-8h at normal temperature to obtain a cottonseed protein intermediate.
As a preferred embodiment, it further comprises a step of depolymerisation of the condensed tannin: adding urea, 2-mercaptoethanol, naOH, condensed tannin and water in formula amounts into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in water bath, reacting for 2-4h, and continuing stirring the solution at normal temperature for 15h to obtain the depolymerized condensed tannin.
As a preferred embodiment, the method further comprises the step of preprocessing: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for multiple times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging; placing the centrifuged cottonseed meal in an oven, and drying the cottonseed meal to constant weight at 60 ℃; and (3) grinding the dried cottonseed meal again and sieving the cottonseed meal with a 200-mesh sieve to obtain the cottonseed protein.
The third aspect of the invention also provides an application of the bio-based waterborne polyether amine high molecular polymer as a flocculant.
The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application.
Example 1:
the embodiment provides a preparation method of a bio-based waterborne polyether amine high molecular polymer, which comprises the following steps:
1) Pretreatment of cottonseed meal: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for three times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging. Placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight. And grinding the dried cottonseed meal again through a 200-mesh screen to be used as an intermediate product base material.
2) Depolymerization of condensed tannins: adding 5 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 2 parts by weight of NaOH,30 parts by weight of condensed tannin and 90 parts by weight of water into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in a water bath, reacting for 4 hours, and continuing to stir the solution at normal temperature for 15 hours to obtain the depolymerized condensed tannin.
3) Condensed tannin modified cottonseed protein: weighing 8 parts by weight of pretreated cottonseed protein, 5 parts by weight of depolymerized condensed tannin, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether and 50 parts by weight of water, and stirring at normal temperature for 6-8 hours to obtain a cottonseed protein intermediate.
4) Adding 45 parts by weight of tetrahydrofuran solvent, then adding 0.36 part by weight of ethylene glycol and 0.7 part by weight of boron trifluoride tetrahydrofuran complex into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, cooling to below 10 ℃, slowly adding 90 parts by weight of epoxy chloropropane diluted by 45 parts by weight of tetrahydrofuran dropwise for 6 hours, reacting for 12 hours after dropwise addition to obtain polyepichlorohydrin, then adding 50 parts by weight of cottonseed protein intermediate, 280 parts by weight of polyethylene polyamine and 150 parts by weight of methanol, stirring at 50 ℃ for reaction for 3 hours, subsequently heating to 90 ℃, reacting for 3 hours, cooling at room temperature to obtain a target product, and adding water for dilution according to the required solid content.
Example 2
The embodiment provides a preparation method of a bio-based waterborne polyether amine high molecular polymer, which comprises the following steps: the method comprises the following steps:
1) Pretreatment of cottonseed meal: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for three times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging. Placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight. And grinding the dried cottonseed meal again through a 200-mesh screen to be used as an intermediate product base material.
2) Depolymerization of condensed tannins: adding 10 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 4 parts by weight of NaOH, 50 parts by weight of condensed tannin and 90 parts by weight of water into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in a water bath, reacting for 4 hours, and continuing to stir the solution at normal temperature for 15 hours to obtain depolymerized condensed tannin.
3) Condensed tannin modified cottonseed protein: weighing 15 parts by weight of pretreated cottonseed protein, 10 parts by weight of depolymerized condensed tannin, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether and 50 parts by weight of water, and stirring for 8 hours at normal temperature to obtain a cottonseed protein intermediate.
4) Adding 40 parts by weight of tetrahydrofuran solvent, adding 0.5 part by weight of ethylene glycol and 1.2 parts by weight of boron trifluoride tetrahydrofuran complex into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, cooling to below 10 ℃, slowly dropwise adding 90 parts by weight of epichlorohydrin diluted by 40 parts by weight of tetrahydrofuran, dropwise adding for 6 hours, reacting for 12 hours after dropwise adding to obtain polyepichlorohydrin, adding 80 parts by weight of cottonseed protein intermediate, 320 parts by weight of polyethylene polyamine and 280 parts by weight of methanol, stirring at 50 ℃ for reaction for 3 hours, subsequently heating to 90 ℃, reacting for 5 hours, cooling at room temperature to obtain a target product, and adding water for dilution according to the required solid content.
Example 3
The embodiment provides a preparation method of a bio-based waterborne polyether amine high molecular polymer, which comprises the following steps:
1) Pretreatment of cottonseed meal: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for three times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging. Placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight. And grinding the dried cottonseed meal again through a 200-mesh screen to be used as an intermediate product base material.
2) Depolymerization of condensed tannins: adding 8 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 4 parts by weight of NaOH, 40 parts by weight of condensed tannin and 90 parts by weight of water into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in a water bath, reacting for 3 hours, and continuing to stir the solution for 15 hours at normal temperature to obtain depolymerized condensed tannin.
3) Condensed tannin modified cottonseed protein: weighing 10 parts by weight of pretreated cottonseed protein, 8 parts by weight of depolymerized condensed tannin, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether and 50 parts by weight of water, and stirring for 8 hours at normal temperature to obtain a cottonseed protein intermediate.
4) Adding 45 parts by weight of tetrahydrofuran solvent, adding 0.6 part by weight of ethylene glycol and 1.4 parts by weight of boron trifluoride tetrahydrofuran complex into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, cooling to below 10 ℃, slowly adding 45 parts by weight of tetrahydrofuran diluted epichlorohydrin 90 parts by weight, dropwise adding for 7 hours, reacting for 12 hours after dropwise adding to obtain polyepichlorohydrin, adding 70 parts by weight of cottonseed protein intermediate, 280 parts by weight of polyethylene polyamine and 300 parts by weight of methanol, stirring at 50 ℃ for reaction for 3 hours, subsequently heating to 90 ℃, reacting for 5 hours, cooling at room temperature to obtain a target product, and adding water for dilution according to the required solid content.
Example 4
The embodiment provides a preparation method of a bio-based waterborne polyether amine high molecular polymer, which comprises the following steps:
1) Pretreatment of cottonseed meal: grinding oil-squeezed cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for three times, preparing 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min while stirring, cooling to room temperature, and centrifuging. Placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight. And grinding the dried cottonseed meal again through a 200-mesh screen to be used as an intermediate product base material.
2) Depolymerization of condensed tannins: adding 6 parts by weight of urea, 3 parts by weight of 2-mercaptoethanol, 3 parts by weight of NaOH, 45 parts by weight of condensed tannin and 90 parts by weight of water into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating in a water bath to 65 ℃, reacting for 2 hours, and continuing to stir the solution at normal temperature for 15 hours to obtain depolymerized condensed tannin.
3) Condensed tannin modified cottonseed protein: weighing 12 parts by weight of pretreated cottonseed protein, 8 parts by weight of depolymerized condensed tannin, 3 parts by weight of 1,2, 3-glycerol triglycidyl ether and 50 parts by weight of water, and stirring for 8 hours at normal temperature to obtain a cottonseed protein intermediate.
4) Adding 30 parts by weight of tetrahydrofuran solvent, then adding 0.4 part by weight of ethylene glycol and 1.0 part by weight of boron trifluoride tetrahydrofuran complex into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, cooling to below 10 ℃, slowly adding 30 parts by weight of tetrahydrofuran diluted epichlorohydrin by 90 parts by weight, dropwise adding for 8 hours, reacting for 12 hours after dropwise adding to obtain polyepichlorohydrin, then adding 60 parts by weight of cottonseed protein intermediate, 260 parts by weight of polyethylene polyamine and 200 parts by weight of methanol, stirring at 50 ℃ for reaction for 2 hours, subsequently heating to 90 ℃, reacting for 3 hours, cooling at room temperature to obtain a target product, and adding water for dilution according to the required solid content.
In conclusion, the bio-based water-based polyether amine high polymer prepared by using the cottonseed protein intermediate as a raw material can be used as a flocculant. On one hand, the condensed tannin and cottonseed protein retain inherent excellent performances of innocuity, biocompatibility, degradability, macromolecular adsorption and the like, and meanwhile, because the tannin has a certain steric hindrance due to the large relative molecular weight and has poor reactivity with other molecules, the tannin is treated by utilizing green environment-friendly urea and 2-mercaptoethanol, the steric hindrance of the condensed tannin is reduced, and the reactivity is increased; on the other hand, the polyepichlorohydrin with relatively large molecular weight is synthesized to be used as a cross-linking agent, not only the polyepichlorohydrin and the polyethylene polyamine are subjected to cross-linking polycondensation reaction, but also the catechol group on the condensed tannin and the NH on the cottonseed protein chain and the polyethylene polyamine are utilized 2 The groups react to form a double-crosslinked network structure to enhance the net trapping and sweeping effect, so that the polymer molecular chain is longer, the branching degree is high, a more developed network structure is formed, the bridging effect and the electric neutralization effect on oil drops are stronger, the emulsified oil drops are easier to contact, original natural surfactants on the surface of oil water are replaced, the oil drops are extruded to promote coalescence, and the floating or sinking is promoted.
And (3) performance testing:
1. the high molecular polymer of the embodiment 3 is prepared into a diluent with 20 percent of solid content, a certain amount of flocculant mother liquor is slowly added into 1g/L kaolin suspension under the continuous stirring of a cantilever stirrer, the timing is started, firstly, the solution is stirred for a certain time at a high rotating speed of 200r/min, then, the rotating speed is reduced to 100r/min, the stirring is carried out for 5min, after the stirring is finished, the stirrer is closed, the solution is allowed to stand for 5min, a certain amount of clear liquid below 1cm away from the liquid level is absorbed by a rubber head dropper, and the light transmittance (T percent) of the solution is measured at the wavelength of 550nm by using an ultraviolet UV-4802 type spectrophotometer. The effect of the polymer addition on the flocculation effect was examined and the results are shown in FIG. 1.
As can be seen from FIG. 1, before the addition amount of the high molecular polymer in example 3 is 20mg/L, the light transmittance (T%) and the addition amount are in positive correlation, when the addition amount is small, the positive charges generated by the self-made polymer molecules are not enough to neutralize the negative charges carried by the kaolin particles, the electric neutralization effect is weak, and most of the particles form flocs to be eliminated by virtue of the net-swatting sweeping and adsorption bridging mechanisms. However, with the continuous addition of the self-made polymer molecules, the surfaces of the particles are wrapped by the self-made polymer molecules, so that the steric hindrance is increased, the colloid protection is generated, the self-made polymer molecules cannot play the role, and the particles cannot be removed in a large amount, so that the light transmittance T% of the solution is greatly reduced, and the optimal addition of the polymer to the kaolin solution is 20mg/L in combination with the above description.
2. In order to compare the difference of the oil removing effect of the polymer-containing wastewater between the home-made polymer and the commercially available comparative sample, the final treatment effect of the polymer-containing wastewater was compared with the oil removing rate of the polymer-containing wastewater after adding the high molecular polymer of example 3 at a temperature of 60 ℃ under other conditions, as shown in fig. 2.
As can be seen from FIG. 2, after the polymer-containing wastewater added with the high molecular polymer of example 3 is treated, the oil removal rate increases and then decreases with the increase of the addition amount, the optimal addition amount is 15mg/L, and the removal rate reaches 86.2%. Compared with the prior art, the market comparison sample can be further improved when the adding amount is increased, the maximum removal rate can only reach 58.1 percent, the adding amount is 25mg/L, and is more than half of that of the high molecular polymer in the embodiment 3, so that the effect superior to that of the market comparison sample can be obtained due to the optimization of the developed double-net structure such as high branching degree, long molecular chain and the like and the high molecular weight and the like of the high molecular polymer in the embodiment 3 under the condition of low dosage, and the market comparison sample has better economical efficiency.
3. Under certain conditions (room temperature), several equal parts of 100 ml kaolin suspension (1 g/L) are taken, 0.5mg, 1.0mg, 1.5mg, 2.0mg, 2.5mg and 3.0mg of each self-made polymer (such as example 1, example 2, example 3 and example 4) are respectively taken to treat the kaolin suspension in a beaker, the pH is 7-8, the kaolin suspension is rapidly stirred at the speed of 200rad min < -1 > for 1min, then the kaolin suspension is slowly stirred at the speed of 100rad min < -1 > for 5min, the stirring is stopped, the kaolin suspension is kept still for settling for a moment, and the residual turbidity of the sample is measured. The influence of different contents of different self-made polymers in kaolin suspension on the flocculation performance is respectively inspected, and the index for evaluating the flocculation performance is the flocculation rate. The calculation formula of the flocculation rate is shown as follows:
in the formula:
e% is the flocculation rate;
N 0 is the turbidity of kaolin suspension before adding the medicament;
N 1 the turbidity of the high-collar soil suspension after the addition of the medicament is shown.
As can be seen from FIG. 3, with the increase of the added amount, the flocculation effect of the four self-made polymers on the kaolin suspension is increased; when the optimal dosage is 15mg/L, the flocculation rate of the self-made polymer in example 3 reaches 95.3 percent, which is higher than that of other self-made polymers with the same quantity and is also higher than the highest flocculation rate of other self-made polymers with different dosages. Because in the self-made polymer structure, the inherent excellent performances of macromolecular adsorption and the like of condensed tannin and cottonseed protein are kept, and the double-crosslinked network structure formed by functional groups on the molecular structure and polyamine has more grafted positive charges, the self-made polymer has strong electric neutralization capacity with colloidal particles, and the self-made polymer is more favorable for capturing the bridged suspended particles.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. The bio-based waterborne polyether amine high molecular polymer is characterized by being prepared from the following raw materials in parts by weight: 80-10 parts of epichlorohydrin, 0.36-0.6 part of glycol, 0.7-1.4 parts of boron trifluoride tetrahydrofuran complex, 30-45 parts of tetrahydrofuran, 260-320 parts of polyethylene polyamine, 50-80 parts of cottonseed protein intermediate and 150-300 parts of methanol.
2. The bio-based waterborne polyether amine high molecular polymer of claim 1, wherein the bio-based waterborne polyether amine high molecular polymer is prepared from the following raw materials in parts by weight: 90 parts by weight of epichlorohydrin, 0.36-0.6 part by weight of ethylene glycol, 0.7-1.4 parts by weight of boron trifluoride tetrahydrofuran complex, 30-45 parts by weight of tetrahydrofuran, 260-320 parts by weight of polyethylene polyamine, 50-80 parts by weight of cottonseed protein intermediate and 150-300 parts by weight of methanol.
3. The bio-based aqueous polyether amine high molecular polymer as claimed in claim 2, wherein the bio-based aqueous polyether amine high molecular polymer is prepared from the following raw materials in parts by weight: 90 parts by weight of epichlorohydrin, 0.6 part by weight of ethylene glycol, 1.4 parts by weight of boron trifluoride tetrahydrofuran complex, 45 parts by weight of tetrahydrofuran, 280 parts by weight of polyethylene polyamine, 70 parts by weight of cottonseed protein intermediate, and 300 parts by weight of methanol.
4. The bio-based aqueous polyether amine high molecular polymer as claimed in claim 1, wherein the cottonseed protein intermediate is prepared from the following raw materials in parts by weight: 8-15 parts of cottonseed protein, 2-4 parts of 1,2, 3-glycerol triglycidyl ether, 5-10 parts of depolymerized condensed tannin and 45-55 parts of water.
5. The bio-based waterborne polyether amine high molecular polymer of claim 4, wherein the depolymerized condensed tannin is prepared from the following raw materials in parts by weight: 5-10 parts of urea, 2-4 parts of 2-mercaptoethanol, 2-4 parts of NaOH,30-50 parts of condensed tannin and 90 parts of water.
6. A method for preparing the bio-based waterborne polyether amine high molecular polymer as claimed in any one of claims 1-5, comprising the steps of: adding a tetrahydrofuran solvent with the formula amount into a flask with a thermometer, a stirrer, a water separator and a reflux condenser, then adding ethylene glycol with the formula amount and a boron trifluoride tetrahydrofuran complex with the formula amount, reducing the temperature to be below 10 ℃, slowly dropwise adding epoxy chloropropane diluted by tetrahydrofuran with the formula amount, dropwise adding for 6-8h, reacting for 12h after dropwise adding to obtain polyepichlorohydrin, then adding a cottonseed protein intermediate, polyethylene polyamine and methanol with the formula amount, stirring at 50 ℃ for 2-3h, subsequently heating to 90 ℃, reacting for 3-5h, and cooling at room temperature to obtain a target product.
7. The method for preparing a bio-based waterborne polyether amine high polymer as claimed in claim 6, wherein the method for preparing the cottonseed protein intermediate comprises the steps of condensing tannin to modify cottonseed protein: mixing the cottonseed protein, the depolymerized condensed tannin, 1,2, 3-glycerol triglycidyl ether and water according to the formula ratio, and stirring for 6-8 hours at normal temperature to obtain a cottonseed protein intermediate.
8. The method of claim 7, further comprising a condensation tannin depolymerization step: adding urea, 2-mercaptoethanol, naOH, condensed tannin and water in formula amounts into a flask with a thermometer, a stirrer and a water separator in sequence, stirring, heating to 65 ℃ in water bath, reacting for 2-4h, and continuously stirring the solution at normal temperature for 15h to obtain the depolymerized condensed tannin.
9. The method for preparing a bio-based waterborne polyetheramine high molecular polymer of claim 8, further comprising a pretreatment step of: grinding oil-extracted cottonseed meal into powder by a grinder, sieving with a 200-mesh sieve, washing with water for multiple times, preparing a 40% cottonseed meal solution, preheating in a 80-85 deg.C water bath for 30min, stirring the cottonseed meal solution continuously during the treatment process, cooling to normal temperature after preheating, and centrifuging; placing the centrifuged cottonseed meal in an oven, and drying at 60 ℃ to constant weight; and (3) grinding the dried cottonseed meal again and sieving the cottonseed meal with a 200-mesh sieve to obtain the cottonseed protein.
10. Use of a bio-based waterborne polyetheramine high molecular weight polymer as claimed in any one of claims 1 to 5 as a flocculant.
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