CN113214531B - Hydrophobic/hydrophilic interpenetrating network resin and preparation and application thereof - Google Patents
Hydrophobic/hydrophilic interpenetrating network resin and preparation and application thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The invention discloses a method for refining and decoloring xylose mother liquor by utilizing hydrophobic/hydrophilic interpenetrating network resin, which comprises the following steps: (1) adding the oil phase mixture into the water phase to prepare macroporous resin; (2) swelling the prepared macroporous resin, putting the swollen macroporous resin into a polyvinyl alcohol solution, reacting, washing with water, extracting a pore-forming agent, and drying to obtain the double-hydrophobic interpenetrating network resin; (3) and (3) adding a trimethylamine hydrochloride solution into the interpenetrating network resin prepared in the step (2) to carry out amination reaction, and washing with water to neutrality after leaching to obtain the hydrophobic/hydrophilic type interpenetrating network resin. The hydrophobic/hydrophilic interpenetrating network resin prepared by the invention has stable adsorption performance, decolouring rate of xylose mother liquor of more than 97 percent, strong selectivity, reducing sugar retention rate of more than 99 percent, simple operation, good effect and low cost.
Description
Technical Field
The invention relates to the technical field of resin preparation, in particular to a hydrophobic/hydrophilic interpenetrating network resin and preparation and application thereof.
Background
The functional sugar has the effects of low calorie, providing nutrition, promoting and improving physiological functions, improving human immunity and the like, and is mainly represented by functional sugar alcohol, functional dietary fiber and functional oligosaccharide. Among the functional sugar alcohols, xylitol is the most representative substance, and is generally prepared by catalytic hydrogenation of xylose in industry. The biomass for producing the reduced xylose comprises straw agricultural and forestry waste, core-shell agricultural and forestry waste, agricultural and forestry stem block and the like, wherein the ratio of the straw agricultural and forestry waste is the largest.
The agricultural and forestry waste is hydrolyzed or enzymolyzed with dilute acid to obtain xylose hydrolysate, and the xylose is prepared through refining, concentration and crystallization, and this produces great amount of residual dark brown ropy liquid, i.e. xylose mother liquor. If the xylose mother liquor is counted by mass fraction, the xylose content is 40-52%, the arabinose content is 25-32%, the glucose content is 10-18%, the galactose content is 10-16% and the impurity content is 3-7%. Because the xylose mother liquor contains a large amount of reducing monosaccharide and has a relatively dark color, the contained xylose cannot be crystallized or chromatographically separated and recovered, and can only be sold to caramel pigment enterprises at the price of 10 percent of the crystallized xylose, thereby greatly reducing the economic benefit of xylose production. Therefore, the method effectively removes color sources in the xylose mother liquor, fully recovers the reducing monosaccharide component in the mother liquor, improves the xylose production benefit, and is a problem which needs to be concerned by the functional sugar industry.
The pigment in the xylose mother liquor can be removed by methods such as activated carbon adsorption, membrane separation, ion exchange resin and the like.
The activated carbon is a highly aromatized carbonaceous material, has a developed internal pore structure and a large specific surface area, can effectively and selectively eliminate inhibitors in hydrolysate, has the characteristics of safety, no toxicity, high adsorbability and the like, does not influence the concentration of sugar liquor in a downstream section, and is an important decolorizing agent in the sugar production field at home and abroad. CN107893132A discloses a method and a device for producing xylose, which takes wood fibers such as corncobs, bagasse and the like as raw materials, and the raw materials are hydrolyzed by acid to obtain xylose hydrolysate, and the xylose hydrolysate is decolorized by active carbon and then is subjected to secondary impurity removal and decolorization by chromatography and a nanofiltration membrane. However, the process is complicated, and after the hydrolysate is decolorized by active carbon, secondary refining is needed by a nanofiltration membrane.
Membrane separation based on a pore size screening mechanism is a new application of sugar liquor decoloring and refining, partial substances permeate a membrane layer and are intercepted under the action of driving forces (such as pressure difference, concentration difference and potential difference), and component recovery or feed liquor concentration is realized. The technology avoids consuming acid or active carbon in the decoloring process and avoids a large amount of phase transformation energy in the evaporation and concentration process in the concentration process. CN111440903A discloses a process and a system for producing xylose products by using corncobs, wherein, after continuous chromatographic separation and reverse osmosis concentration treatment are carried out on a pretreated xylose hydrolysate, the xylose hydrolysate is sent to nanofiltration membrane equipment for decolorization and degumming treatment, and the light transmittance of the obtained sugar solution is 65-75%. Although the method and the device used by the method can effectively deacidify, the method has more working procedures and complicated operation and cannot well remove the pigment and separate the sugar components.
The ion exchange resin is a synthetic spherical polymer with certain exchangeable functional groups on the surface; when the surface of the solute is contacted with the solution, the solute is gathered on the solid-liquid surface to generate adsorption action under the action of surface energy; has the advantages of stable mechanical strength, double functions of ion exchange and adsorption, good regeneration performance and the like, and is a mainstream method for refining and decoloring in the sugar manufacturing field. The ion exchange resin has proper pore size and proper functional groups, and can remove colored substances from sugar solution by chemical adsorption and physical adsorption (such as hydrophobic effect, pi-pi stacking effect, etc.). Meanwhile, the ion exchange resin can also adsorb other impurities (such as salt substances, organic acid and the like), so that the purity of the sugar solution after decolorization is improved.
CN 103614435 a discloses a method for preparing xylo-oligosaccharide from bagasse, which comprises obtaining crude xylan solution by enzymolysis, and obtaining purified sugar solution by a decolorization and desalination system with activated carbon column and anion-cation exchange column connected in series. However, the method needs to be connected with an activated carbon column in series, has the problem of solid waste treatment, does not study the problem of sugar loss in desalting and decoloring, and does not give the performance attenuation condition of the regenerated resin.
In conclusion, although the conventional decoloring and refining method can effectively remove pigments, inorganic ions and the like, the defects are very obvious, such as low decoloring rate, poor selectivity, high sugar loss rate, decolorant and the like. As artificially designed, structurally tunable ion exchange resins have been considered the most potent decolorizing media, but the key issue is the adsorption capacity for specific compounds. The pigment in the xylose mother liquor has both hydrophilic part and hydrophobic structure, and the common decolorizing resin has single structure, low adsorption capacity to the pigment and poor selectivity. Therefore, the design and synthesis of the xylose mother liquor decolorizing resin with high adsorption capacity and strong selectivity are the key points of research in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrophobic/hydrophilic interpenetrating network resin and preparation and application thereof. The hydrophobic/hydrophilic interpenetrating network resin prepared by the invention has stable adsorption performance, decolouring rate of xylose mother liquor of more than 97 percent, strong selectivity, reducing sugar retention rate of more than 99 percent, simple operation, good effect and low cost.
The technical scheme of the invention is as follows:
a preparation method of hydrophobic/hydrophilic interpenetrating network resin comprises the following steps:
(1) adding the oil phase mixture into the water phase for suspension polymerization, washing with water, extracting a pore-forming agent, and drying to obtain macroporous resin;
(2) swelling the macroporous resin prepared in the step (1), putting the swollen macroporous resin into a polyvinyl alcohol solution, heating to 80-90 ℃ while stirring, reacting, washing with water, extracting a pore-forming agent, and drying to obtain the double-hydrophobic interpenetrating network resin;
(3) and (3) adding a trimethylamine hydrochloride solution into the double-hydrophobic type interpenetrating network resin prepared in the step (2) to carry out amination reaction, washing with an HCl solution, washing with water to neutrality, washing with an NaOH solution, and washing with water to neutrality to obtain the hydrophobic/hydrophilic type interpenetrating network resin.
Further, in the step (1), the mass ratio of the oil phase mixture to the water phase is (0.5-1): 2-3.
Further, in the step (1), the oil phase mixture consists of a monomer, a pore-forming agent and an initiator, and the mass ratio of the monomer to the pore-forming agent to the initiator is 1 (2-3) to (0.005-0.02).
Further, the monomer is divinylbenzene; the pore-foaming agent consists of toluene, xylene and n-heptane, and the mass ratio of the toluene, the xylene and the n-heptane is (1-3): 1; the initiator is dibenzoyl peroxide.
Further, in the step (1), the water phase consists of polyvinyl alcohol and a NaCl solution, and the mass concentration of the polyvinyl alcohol in the water phase is 0.5-2%; the mass concentration of NaCl in the water phase is 2-5%.
Further, in the step (1), the suspension polymerization method is as follows: adding the oil phase mixture into the water phase according to the mass ratio, stirring at 140-170 r/min, heating to 90-98 ℃ at 20-30 ℃/h, and reacting at constant temperature for 5-8 h; the water washing is carried out for 2-5 times by using water at 70-80 ℃.
Further, in the step (1) and the step (2), the extraction of the pore-forming agent is carried out in a Soxhlet extractor, and the used reagent is one or more of acetone and petroleum ether; the drying temperature is 40-60 ℃, and the drying time is 10-15 h.
Further, in the step (2), the reagent for swelling is composed of a pore-foaming agent and a monomer; the mass ratio of the pore-foaming agent to the monomer is (1.5-3): 1, the monomer consists of glycidyl methacrylate and triallyl isocyanurate, the mass ratio of the glycidyl methacrylate to the triallyl isocyanurate to the macroporous resin prepared in the step (1) is (7-9): 1-3): 10, the pore-foaming agent consists of butyl acetate and n-heptane, and the mass ratio of the butyl acetate to the n-heptane is (2-4): 1; the swelling time is 15-24 h; the mass concentration of the polyvinyl alcohol solution is 0.5-2%; the stirring speed is 100-150 r/min; the temperature rising speed is 1-3 ℃/min; the reaction time is 10-15 h; the water washing is carried out for 2-5 times by using water at 70-80 ℃.
Further, in the step (3), the mass concentration of the trimethylamine hydrochloride solution is 40-60%; the temperature of the amination reaction is 70-90 ℃, and the reaction time is 9-12 h; the molar concentration of the HCl solution is 0.5-1.5 mol/L; the molar concentration of the NaOH solution is 0.5-1.5 mol/L; the leaching time is 1-3 h.
The application of the hydrophobic/hydrophilic interpenetrating network resin can be used for decoloring xylose mother liquor, and the specific method comprises the following steps:
(1) loading the prepared hydrophobic/hydrophilic interpenetrating network resin into an adsorption column with the height-diameter ratio of (15-25): 1;
(2) filtering the xylose mother liquor to remove insoluble impurities, and diluting the xylose mother liquor to 25-30 DEG Bx with water;
(3) taking 15-20 BV of the xylose mother liquor pretreated in the step (2), passing through the adsorption column prepared in the step (1) at the working temperature of 40 ℃ at the flow rate of 1-4 BV/h, and collecting the xylose mother liquor passing through the adsorption column;
(4) desorbing and regenerating the resin by using an eluant;
the eluent is an aqueous solution composed of NaOH solution and absolute ethyl alcohol in a volume ratio of (4-6) to 1, and the mass concentration of the NaOH solution is 1-3%; the dosage of the eluent is 3-5 BV; the flow rate of desorption is 3-6 BV/h.
The beneficial technical effects of the invention are as follows:
(1) the hydrophobic/hydrophilic interpenetrating network resin prepared by the invention has stable adsorption performance, and can adsorb color source substances by utilizing the hydrophobic (or pi-pi accumulation effect), static electricity, hydrogen bonds and other effects, thereby greatly improving the adsorption capacity of the resin on pigment substances in xylose mother liquor. The sugar liquor decolorization rate can reach more than 97%, the selectivity is strong, the retention rate of reducing sugar reaches more than 99%, the defects of the traditional decolorization resin are overcome, and the defects of low decolorization rate, poor selectivity, weak pollution resistance and the like of the common resin are effectively overcome.
(2) The hydrophobic/hydrophilic interpenetrating network resin is easy to regenerate, the eluent uses sodium hydroxide with lower concentration, the acid-base consumption is low, the regeneration performance is good, the decolorization rate is still kept above 95% after the resin is recycled for more than 5 times, and a novel alternative adsorption decolorization medium is provided for the decolorization and refining of xylose mother liquor.
(3) The invention overcomes some defects in the prior art, has moderate specific surface area and proper pore size distribution, can well reduce the loss of sugar in the refining process, and has simple operation, good effect and low cost.
Drawings
FIG. 1 is an infrared spectrum of the hydrophobic/hydrophilic interpenetrating network resin prepared in example 1 of the present invention.
FIG. 2 is a distribution diagram of the pore diameters of the hydrophobic/hydrophilic interpenetrating network resin prepared in example 1 of the present invention.
FIG. 3 is a UV spectrum of the resin prepared in example 2 of the present invention before and after decolorizing xylose mother liquor.
FIG. 4 is the adsorption isotherm of the hydrophobic/hydrophilic interpenetrating network resin prepared in example 2 of the present invention for pigments in xylose mother liquor.
FIG. 5 shows the adsorption kinetics of the hydrophobic/hydrophilic interpenetrating network resin prepared in example 3 of the present invention on pigments in xylose mother liquor.
FIG. 6 shows the results of the repeated use of the hydrophobic/hydrophilic interpenetrating network resin prepared in example 3 of the present invention for decoloring xylose mother liquor.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example 1
A hydrophobic/hydrophilic interpenetrating network resin is prepared by the following steps:
adding an oil phase mixture consisting of a monomer, a pore-forming agent and an initiator in a mass ratio of 1:2:0.005 into a water phase containing 0.5% of polyvinyl alcohol and 2% of NaCl for suspension polymerization, wherein the mass ratio of the oil phase mixture to the water phase is 0.5:2, the monomer is divinylbenzene, the pore-forming agent is toluene, xylene and n-heptane, the mass ratio of the toluene, the xylene and the n-heptane is 1:1:1, and the initiator is dibenzoyl peroxide. The suspension polymerization is as follows: the temperature is raised to 90 ℃ at the speed of 20 ℃/h while stirring at 140r/min, and then the reaction is carried out for 5h at constant temperature. After the reaction is finished, washing the mixture for 2 times by hot water at 70 ℃, extracting a pore-forming agent by using a Soxhlet extractor, and drying the mixture for 10 hours at 40 ℃ by using acetone as a solvent to obtain macroporous resin; swelling the prepared macroporous resin for 15h, wherein a reagent used for swelling consists of a monomer and a pore-forming agent; the mass ratio of the pore-foaming agent to the monomer is 1.5:1, the monomer consists of glycidyl methacrylate and triallyl isocyanurate, the mass ratio of the glycidyl methacrylate to the triallyl isocyanurate to the macroporous resin is 9:1:10, the pore-foaming agent consists of butyl acetate and n-heptane, and the mass ratio of the butyl acetate to the n-heptane is 2: 1. Adding polyvinyl alcohol solution with mass concentration of 0.5%, heating to 80 ℃ at 1 ℃/min while stirring at 100r/min, reacting for 10h, washing for 2 times with hot water at 70 ℃, extracting a pore-forming agent by using a Soxhlet extractor, wherein the solvent is acetone, and finally drying for 10h at 40 ℃ to obtain the hydrophobic/hydrophilic interpenetrating network resin; and adding 40% trimethylamine hydrochloride solution into the prepared hydrophobic/hydrophilic interpenetrating network resin solution for amination reaction, reacting for 9 hours at 70 ℃, leaching for 1 hour by using 0.5mol/L HCl, washing to be neutral, leaching for 1 hour by using 0.5mol/L NaOH, and washing to be neutral to obtain the hydrophobic/hydrophilic interpenetrating network resin.
Loading the prepared hydrophobic/hydrophilic interpenetrating network resin into an adsorption column with the height-diameter ratio of 15:1, filtering the xylose mother liquor to remove insoluble impurities, diluting the xylose mother liquor to 25-degree Bx with water to obtain a pretreated xylose mother liquor, allowing the pretreated 15BV xylose mother liquor to pass through the adsorption column at the working temperature of 40 ℃ and the flow rate of 1BV/h, collecting the decolorized xylose mother liquor, and measuring the absorbance (A) 450nm ) Calculating the decolorization rate and the reducing sugar retention rate; the eluent is 1 percent NaOH solution and absolute ethyl alcohol with the volume ratio of 4:1, desorption regeneration is carried out on the resin at the flow rate of 3BV/h, and the dosage of the eluent is 3 BV.
Example 2
A hydrophobic/hydrophilic interpenetrating network resin is prepared by the following steps:
adding an oil phase mixture consisting of a monomer, a pore-forming agent and an initiator in a mass ratio of 1:2.5:0.015 into a water phase containing 1.5% of polyvinyl alcohol and 4% of NaCl for suspension polymerization, wherein the mass ratio of the oil phase mixture to the water phase is 0.75:2.5, the monomer is divinylbenzene, the pore-forming agent is toluene, xylene and n-heptane, the mass ratio of the toluene, the xylene and the n-heptane is 2:2:1, and the initiator is dibenzoyl peroxide. The suspension polymerization is as follows: the temperature is raised to 94 ℃ at the speed of 25 ℃/h while stirring at 155r/min, and then the reaction is carried out for 6h at constant temperature. After the reaction is finished, washing the mixture for 3 times by using hot water at the temperature of 75 ℃, extracting a pore-forming agent by using a Soxhlet extractor, wherein the solvent is petroleum ether, and drying the mixture for 13 hours at the temperature of 50 ℃ to obtain macroporous resin; swelling the prepared macroporous resin for 20 hours, wherein a reagent used for swelling consists of a monomer and a pore-forming agent; the mass ratio of the pore-foaming agent to the monomer is 2:1, the monomer consists of glycidyl methacrylate and triallyl isocyanurate, the mass ratio of the glycidyl methacrylate to the triallyl isocyanurate to the macroporous resin is 8:2:10, the pore-foaming agent consists of butyl acetate and n-heptane, and the mass ratio of the butyl acetate to the n-heptane is 3: 1. Adding a polyvinyl alcohol solution with the mass concentration of 1.5%, heating to 85 ℃ at the speed of 2 ℃/min while stirring at 125r/min, reacting for 13h, washing for 3 times with hot water at the temperature of 75 ℃, extracting a pore-forming agent by using a Soxhlet extractor, wherein the solvent is petroleum ether, and finally drying for 13h at the temperature of 50 ℃ to obtain the hydrophobic/hydrophilic interpenetrating network resin; and adding 50% trimethylamine hydrochloride solution into the prepared hydrophobic/hydrophilic interpenetrating network resin for amination reaction, reacting for 11h at 80 ℃, leaching for 2h by using 1.0mol/L HCl, washing to be neutral, leaching for 2h by using 1.0mol/L NaOH, and washing to be neutral to obtain the hydrophobic/hydrophilic interpenetrating network resin.
Loading the prepared hydrophobic/hydrophilic interpenetrating network resin into an adsorption column with the height-diameter ratio of 20:1, filtering the xylose mother liquor to remove insoluble impurities, diluting the xylose mother liquor to 27.5 ℃ Bx with water to obtain a pretreated xylose mother liquor, allowing the pretreated 17BV xylose mother liquor to pass through the adsorption column at the working temperature of 40 ℃ and the flow rate of 3BV/h, collecting the decolorized xylose mother liquor, and measuring the absorbance (A) 450nm ) And calculating the decolorization rate and the reducing sugar retention rate, wherein the eluent is 2% NaOH solution and absolute ethyl alcohol in a volume ratio of 5:1, the resin is desorbed and regenerated at a flow rate of 5BV/h, and the using amount of the eluent is 4 BV.
Example 3
A hydrophobic/hydrophilic interpenetrating network resin is prepared by the following steps:
adding an oil phase mixture consisting of a monomer, a pore-forming agent and an initiator in a mass ratio of 1:3:0.02 into a water phase containing 2% of polyvinyl alcohol and 5% of NaCl for suspension polymerization, wherein the mass ratio of the oil phase mixture to the water phase is 1:3, the monomer is divinylbenzene, the pore-forming agent is toluene, xylene and n-heptane, the mass ratio of the toluene, the xylene and the n-heptane is 3:3:1, and the initiator is dibenzoyl peroxide. The suspension polymerization is as follows: heating to 98 ℃ at the speed of 30 ℃/h while stirring at 170r/min, and reacting for 8h at constant temperature. After the reaction is finished, washing the mixture for 5 times by hot water at the temperature of 80 ℃, extracting a pore-forming agent by using a Soxhlet extractor, drying the mixture for 15 hours at the temperature of 60 ℃ to obtain macroporous resin, wherein the solvent is petroleum ether; swelling the prepared macroporous resin for 24 hours, wherein a reagent used for swelling consists of a pore-foaming agent and a monomer; the mass ratio of the pore-foaming agent to the monomer is 3:1, the monomer consists of glycidyl methacrylate and triallyl isocyanurate, the mass ratio of the glycidyl methacrylate to the triallyl isocyanurate to the macroporous resin is 7:3:10, the pore-foaming agent consists of butyl acetate and n-heptane, and the mass ratio of the butyl acetate to the n-heptane is 4: 1. Adding a polyvinyl alcohol solution with the mass concentration of 2%, heating to 90 ℃ at the speed of 3 ℃/min while stirring at 150r/min, reacting for 15h, washing for 5 times with hot water at the temperature of 80 ℃, extracting a pore-forming agent by using a Soxhlet extractor, and finally drying for 15h at the temperature of 60 ℃ to obtain the hydrophobic/hydrophilic interpenetrating network resin; and adding 60% trimethylamine hydrochloride solution into the prepared hydrophobic/hydrophilic interpenetrating network resin for amination reaction, reacting for 12 hours at 90 ℃, leaching for 3 hours by using 1.5mol/L HCl, washing to be neutral, leaching for 3 hours by using 1.5mol/L NaOH, and washing to be neutral to obtain the hydrophobic/hydrophilic interpenetrating network resin.
Loading the prepared hydrophobic/hydrophilic interpenetrating network resin into an adsorption column with the height-diameter ratio of 25:1, filtering the xylose mother liquor to remove insoluble impurities, diluting the xylose mother liquor to 30-degree Bx with water to obtain a pretreated xylose mother liquor, allowing the pretreated 20BV xylose mother liquor to pass through the adsorption column at the working temperature of 40 ℃ and the flow rate of 4BV/h, collecting the decolorized xylose mother liquor, and measuring the absorbance (A) 450nm ) And calculating the decolorization rate and the reducing sugar retention rate, wherein the eluent is 3 percent NaOH solution and absolute ethyl alcohol with the volume ratio of 6:1, the resin is desorbed and regenerated at the flow rate of 6BV/h, and the using amount of the eluent is 5 BV.
Comparative example 1
The preparation method of the macroporous resin comprises the following steps:
adding an oil phase mixture consisting of a monomer, a pore-forming agent and an initiator in a mass ratio of 1:2.5:0.015 into a water phase containing 1.5% of polyvinyl alcohol and 4% of NaCl for suspension polymerization, wherein the mass ratio of the oil phase mixture to the water phase is 0.75:2.5, the monomer is divinylbenzene, the pore-forming agent is toluene, xylene and n-heptane, the mass ratio of the toluene, the xylene and the n-heptane is 2:2:1, and the initiator is dibenzoyl peroxide. The suspension polymerization is as follows: while stirring at 155r/min, heating to 94 ℃ at a speed of 25 ℃/h, and reacting at constant temperature for 6 h. After the reaction is finished, washing the mixture for 3 times by using hot water at the temperature of 75 ℃, extracting a pore-forming agent by using a Soxhlet extractor, wherein the solvent is petroleum ether, and drying the mixture for 13 hours at the temperature of 50 ℃ to obtain the macroporous resin.
Loading the prepared macroporous resin into an adsorption column at a height-diameter ratio of 20:1, filtering xylose mother liquor to remove insoluble impurities, diluting the xylose mother liquor to 27.5 ℃ Bx with water to obtain pretreated xylose mother liquor, allowing the pretreated 17BV xylose mother liquor to pass through a column bed at a working temperature of 40 ℃ and a flow rate of 3BV/h, collecting decolorized xylose mother liquor, and measuring the absorbance (A) 450nm )。
Comparative example 2
The preparation method of the polymethacrylic acid strong base resin comprises the following steps:
preparing a pore-foaming agent and a monomer in a mass ratio of 2:1, wherein the monomer consists of glycidyl methacrylate and triallyl isocyanurate, the mass ratio of the glycidyl methacrylate to the triallyl isocyanurate is 8:2, the pore-foaming agent consists of butyl acetate and n-heptane, the mass ratio of the butyl acetate to the n-heptane is 3:1, the pore-foaming agent is put into a polyvinyl alcohol solution with the mass concentration of 1.5%, the temperature is raised to 85 ℃ at 2 ℃/min while stirring at 125r/min, the reaction is carried out for 13h, after the mixture is washed for 3 times by hot water at 75 ℃, a Soxhlet extractor is used for extracting the pore-foaming agent, the used solvent is petroleum ether, and the drying is carried out to obtain the polyglycidyl methacrylate resin; and adding 50% trimethylamine hydrochloride solution into the prepared resin for amination reaction, reacting for 11h at 80 ℃, leaching for 2h by using 1.0mol/L HCl, washing to be neutral by using water, leaching for 2h by using 1.0mol/L NaOH, and washing to be neutral by using water to obtain the hydrophilic strong base resin.
Loading the prepared resin into an adsorption column, wherein the height-diameter ratio is 20:1, filtering the xylose mother liquor to remove insoluble impurities, diluting the xylose mother liquor to 27.5 ℃ Bx with water to obtain pretreated xylose mother liquor, passing the pretreated 17BV xylose mother liquor through a column bed at the working temperature of 40 ℃ at the flow rate of 3BV/h, collecting the decolorized xylose mother liquor, and measuring the absorbance at 450 nm.
Comparative example 3
Putting a commercially available 201X 7 resin into an adsorption column at a height-diameter ratio of 20:1, filtering a xylose mother liquor to remove insoluble impurities, diluting the xylose mother liquor to 27.5 ℃ Bx with water to obtain a pretreated xylose mother liquor, passing 17BV of the pretreated xylose mother liquor through a column bed at a working temperature of 40 ℃ and a flow rate of 3BV/h, collecting the decolorized xylose mother liquor, and measuring the absorbance at 450 nm.
Comparative example 4
Loading sugar activated carbon powder into an adsorption column at a height-diameter ratio of 20:1, filtering xylose mother liquor to remove insoluble impurities, diluting the xylose mother liquor to 27.5 DEG Bx with water to obtain pretreated xylose mother liquor, passing 17BV of the pretreated xylose mother liquor through a column bed at a working temperature of 40 ℃ at a flow rate of 3BV/h, collecting decolorized xylose mother liquor, and measuring the absorbance at 450 nm.
Test example:
the properties of the hydrophobic/hydrophilic interpenetrating network resin prepared in examples 1 to 3 and the resin prepared in comparative examples 1 to 2, such as pore size, particle size, etc., were measured using a fully automatic specific surface area and gap analyzer, and the results of the measurements are shown in table 1.
And (3) determining the decolorization rate and the sugar retention rate of the xylose mother liquor:
the xylose mother liquor before and after decolorization in examples 1 to 3 and comparative examples 1 to 4 was collected, and the absorbance of the xylose mother liquor before and after decolorization was measured by an ultraviolet spectrophotometer (A) 450nm ) And calculating the decolorization rate through the absorbance, wherein the calculation formula of the decolorization rate is shown as a formula (1).
In the formula, A 0 Is the absorbance value of the xylose mother liquor under 450nm before decolorization, and A is the absorbance value of the xylose mother liquor under 450nm after decolorization.
Collecting the xylose mother liquor before and after decolorization in examples 1-3 and comparative examples 1-4, measuring the content of sugar in the xylose mother liquor before and after decolorization by using high performance liquid chromatography, and calculating the sugar retention rate, wherein the calculation formula is shown as the following formula (2):
in the formula, C 0 The content of sugar before decolorization and the content of sugar after decolorization of C are respectively expressed in mg/mL.
The results of measurement of the decolorization ratio and the sugar retention ratio of the xylose mother liquor are shown in table 1.
TABLE 1
The infrared spectrogram of the hydrophobic/hydrophilic interpenetrating network resin prepared in the embodiment 1 of the invention is shown in fig. 1, and the infrared spectrogram of the interpenetrating polydivinylbenzene/polyglycidyl methacrylate aminated resin (PDVB/PMATAM) not only retains the characteristic absorption peak of Polydivinylbenzene (PDVB), but also is at 1728cm -1 A characteristic absorption peak of carbonyl appears at 3500cm -1 The peak is a wide peak, which is the stretching vibration absorption peak of-OH, and 1058cm -1 The stretching vibration peak is the C-N bond generated after resin amination reaction, which shows that the prepared resin has the properties of polydivinylbenzene resin (PDVB) network (namely hydrophobic effect and pi-pi stacking effect) and the properties of resin (PMATAM) network after the amination of the polyglycidyl methacrylate (namely electrostatic, hydrogen bond and other effects). The hydrophobic/hydrophilic interpenetrating network resin prepared by the method can adsorb substances with hydrophobic structures (such as pigments with benzene ring structures) in pigments through hydrophobic effect and pi-pi stacking effect, and can adsorb substances such as organic acids and furfural in sugar solution through electrostatic and hydrogen bonds. Therefore, the resin has strong decolorizing capability and large adsorption capacity. In addition, the hydrophobic/hydrophilic interpenetrating network resin prepared by the invention has moderate specific surface area, and the reducing sugar component can be well reserved. The total sugar content of the xylose mother liquor before decolorization is 288.9mg/mL, wherein the total sugar content comprises 34.7mg/mL of glucose, 52mg/mL of arabinose and 202.2mg/mL of xylose, and the total sugar content of the xylose mother liquor after decolorization is more than 287mg/mL, wherein the total sugar content comprises 34.4mg/mL of glucose, 51.7mg/mL of arabinose and 202mg/mL of xylose.
FIG. 2 is a diagram showing the pore size distribution before and after the interpenetration of the hydrophobic/hydrophilic type interpenetrating network resin prepared in example 1 of the present application. As can be seen from FIG. 2, the prepared resin has the advantages that the pore diameter is mostly distributed in the mesoporous range, the prepared resin contains abundant micropores, and the special pore structure enables the resin to have strong decolorizing capacity and high sugar retention rate.
FIG. 3 is a graph showing the comparison of UV before and after the resin prepared in example 2 of the present invention decolorizes the xylose mother liquor, and it can be seen that the absorbance of the decolorized xylose mother liquor is significantly reduced in the range of 400-600 nm.
FIG. 4 is the adsorption isotherm of the hydrophobic/hydrophilic interpenetrating network resin prepared in example 2 on the pigment in the xylose mother liquor, from which it can be seen that the temperature rise is favorable for the adsorption of the resin, and the adsorption curve more conforms to the Langmuir model.
FIG. 5 shows the adsorption kinetics of the hydrophobic/hydrophilic interpenetrating network resin prepared in example 3 on pigments in xylose mother liquor, and it can be seen that the decolorization rate of the sugar liquor reaches 90% or more in 10min, which indicates that the adsorption rate of the hydrophobic/hydrophilic interpenetrating network resin prepared by the present invention is very fast.
Fig. 6 shows the result of the repeated use of the hydrophobic/hydrophilic interpenetrating network resin prepared in example 3 for the decolorization of the xylose mother liquor, and as shown in the figure, after 5 times of cyclic use, the decolorization rate is still maintained above 95%, the total sugar retention rate is higher than 98%, and meanwhile, the stable structure, good repeatability and easy regeneration of the resin are also demonstrated.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. The preparation method of the hydrophobic/hydrophilic interpenetrating network resin is characterized by comprising the following steps:
(1) adding the oil phase mixture into the water phase for suspension polymerization, washing with water, extracting a pore-forming agent, and drying to obtain macroporous resin;
(2) swelling the macroporous resin prepared in the step (1), putting the swollen macroporous resin into a polyvinyl alcohol solution, heating to 80-90 ℃ while stirring, reacting, washing with water, extracting a pore-forming agent, and drying to obtain the double-hydrophobic interpenetrating network resin;
(3) adding a trimethylamine hydrochloride solution into the interpenetrating network resin prepared in the step (2) for amination reaction, washing with an HCl solution, washing with water to neutrality, finally washing with an NaOH solution, and washing with water to neutrality to obtain the hydrophobic/hydrophilic type interpenetrating network resin;
in the step (1), the oil phase mixture consists of a monomer, a pore-forming agent and an initiator, and the mass ratio of the monomer to the pore-forming agent to the initiator is 1: (2-3) 0.005-0.02;
the monomer is divinylbenzene; the pore-foaming agent consists of toluene, xylene and n-heptane, and the mass ratio of the toluene to the xylene to the n-heptane is as follows: (1-3) 1-3; the initiator is dibenzoyl peroxide;
in the step (2), the reagent for swelling consists of a pore-foaming agent and a monomer; the mass ratio of the pore-foaming agent to the monomer is (1.5-3): 1, the monomer consists of glycidyl methacrylate and triallyl isocyanurate, the mass ratio of the glycidyl methacrylate to the triallyl isocyanurate to the macroporous resin prepared in the step (1) is (7-9): 1-3): 10, the pore-foaming agent consists of butyl acetate and n-heptane, and the mass ratio of the butyl acetate to the n-heptane is (2-4): 1; the swelling time is 15-24 h; the mass concentration of the polyvinyl alcohol solution is 0.5-2%; the stirring speed is 100-150 r/min; the temperature rising speed is 1-3 ℃/min; the reaction time is 10-15 h; the water washing is carried out for 2-5 times by using water at 70-80 ℃.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the oil phase mixture to the water phase is (0.5-1) to (2-3).
3. The preparation method according to claim 1, wherein in the step (1), the aqueous phase consists of polyvinyl alcohol and NaCl solution, and the mass concentration of the polyvinyl alcohol in the aqueous phase is 0.5-2%; the mass concentration of NaCl in the water phase is 2-5%; the suspension polymerization method comprises the following steps: adding the oil phase mixture into the water phase according to the mass ratio, stirring at 140-170 r/min, heating to 90-98 ℃ at 20-30 ℃/h, and reacting at constant temperature for 5-8 h; the water washing is carried out for 2-5 times by using water at 70-80 ℃.
4. The preparation method according to claim 1, wherein in the steps (1) and (2), the extraction of the pore-forming agent is performed in a Soxhlet extractor, and the used reagent is one or more of acetone and petroleum ether; the drying temperature is 40-60 ℃, and the drying time is 10-15 h.
5. The preparation method according to claim 1, wherein in the step (3), the mass concentration of the trimethylamine hydrochloride solution is 40-60%; the temperature of the amination reaction is 70-90 ℃, and the reaction time is 9-12 h; the molar concentration of the HCl solution is 0.5-1.5 mol/L; the molar concentration of the NaOH solution is 0.5-1.5 mol/L; the leaching time is 1-3 h.
6. A hydrophobic/hydrophilic interpenetrating network resin prepared by the preparation method of any one of claims 1 to 5.
7. The application of the hydrophobic/hydrophilic interpenetrating network resin of claim 6, wherein the hydrophobic/hydrophilic interpenetrating network resin can be used for decoloring xylose mother liquor by the following specific method:
(1) loading the prepared hydrophobic/hydrophilic interpenetrating network resin into an adsorption column with the height-diameter ratio of (15-25): 1;
(2) filtering the xylose mother liquor to remove insoluble impurities, and diluting the xylose mother liquor to 25-30 DEG Bx with water;
(3) and (3) taking 15-20 BV of the xylose mother liquor pretreated in the step (2), passing through the adsorption column in the step (1) at the working temperature of 40 ℃ at the flow rate of 1-4 BV/h, and collecting the xylose mother liquor passing through the adsorption column.
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| AU2010217189A1 (en) * | 2009-02-24 | 2011-09-08 | The University Of Sydney | Polymer particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU2010217189A1 (en) * | 2009-02-24 | 2011-09-08 | The University Of Sydney | Polymer particles |
| CN109762109A (en) * | 2019-02-18 | 2019-05-17 | 南开大学 | A kind of poly 4 vinyl pyridine function base resin and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| 一种强碱性阴离子交换树脂的合成与结构表征;张金辉等;《武汉工程大学学报》;20090131;第31卷(第1期);62-68 * |
| 聚（GMA-DVB-TAIC）型连续床的制备及其对蛋白质的色谱分离性能;张敏莲等;《离子交换与吸附》;20000630(第3期);199-206 * |
| 高选择性吸附树脂结构设计及在天然产物提取分离中的应用;张丽轩等;《高分子通报》;20130131(第1期);1-12 * |
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