Hydrophilic acid retardant resin as well as preparation method and application thereof

Abstract

The invention relates to the technical field of adsorption separation resin materials, and discloses hydrophilic acid retardant resin and a preparation method thereof. A functional monomer, a cross-linking agent and an initiator are prepared into an oil phase, a dispersing agent and water are prepared into a water phase, a suspension polymerization method is combined with a tubular injection technology to prepare resin base balls, and the resin base balls are washed and dried to obtain dry resin balls; reacting the dry resin balls with a halogenating reagent under the action of a catalyst to obtain halogen resin balls; and finally, reacting the resin halogen balls with an amination reagent to prepare the hydrophilic acid retardant resin. According to the preparation method disclosed by the invention, the hydrophilic monovinyl monomer is introduced into the functional monomer, and the mass ratio of the hydrophilic monovinyl monomer to the amination reagent is (1-2): 1, so that when the prepared hydrophilic acid retardant resin is used for separating sugar and acid, the acid can be quickly washed out, the water consumption is reduced, and the retention time of the acid on the resin is greatly shortened; the strong acid tailing phenomenon is avoided, and the service life of the hydrophilic acid retardant resin is prolonged.

Description

Technical Field

[0001] The present invention relates to the field of adsorption separation resin materials, and particularly relates to a hydrophilic acid-blocking resin, a preparation method thereof, and an application thereof. Background Art

[0002] The ion retardation method was initially proposed by Hatch and Dillon in 1963 during the process of separating acids and their corresponding acid salts. When applied to the separation of acid and non-acid mixtures, it is called acid retardation. The acid-blocking resin used for acid retardation separation has a greater affinity for acids. It retards the acids in the resin, while the acid salts are eluted first, and then the acids are also eluted from the resin. This process follows two equilibriums, one is the Donnan equilibrium, and the other is the charge balance. When these two equilibriums are disrupted, the mixed solution is separated.

[0003] U.S. Patent Document US5,968,362 discloses a method for separating acids and sugars from the acid hydrolysis step of biomass. This process uses an anion exchange resin or an ion exclusion chromatography material in a simulated moving bed to retain the acids in the hydrolysis products. U.S. Patent Document US5,628,907 discloses the separation of acid-sugar mixtures using ion exclusion chromatography, and the separation of glucose and sulfuric acid under different feed concentrations and different operating modes, using several resins with different degrees of divinylbenzene (DVB) crosslinking. Although the above methods can achieve the separation of sugars and acids using conventional anion exchange resins, a long sulfuric acid tail is generated during the elution process, causing the resin to be immersed in strong acid for a longer time and shortening the service life of the resin. Summary of the Invention

[0004] In view of this, the present invention provides a preparation method of a hydrophilic acid-blocking resin. The hydrophilic acid-blocking resin prepared thereby does not produce a strong acid tail during the elution process for separating non-ionic compounds and acids, greatly shortening the retention time of strong acid in the resin, achieving rapid separation of acids, and extending the resin life.

[0005] The present invention also provides an application of the above hydrophilic acid-blocking resin in separating sugar acids.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a preparation method of a hydrophilic acid-blocking resin, including the following steps:

[0008] (1) Prepare an oil phase by mixing a functional monomer, a crosslinking agent, and an initiator, and prepare an aqueous phase by mixing a dispersant and water. Use suspension polymerization combined with a tube jetting technique to prepare resin-based spheres, wash and dry them to obtain resin dry spheres;

[0009] (2) Under the action of a catalyst, react the resin dry beads with a halogenating reagent to obtain resin halogen beads;

[0010] (3) React the resin halogen beads with an aminating reagent to prepare a hydrophilic acid-blocking resin;

[0011] The functional monomer includes a hydrophobic monovinyl monomer and a hydrophilic monovinyl monomer;

[0012] The mass ratio of the hydrophilic monovinyl monomer to the aminating reagent is 1-2:1.

[0013] In an alternative embodiment, the mass ratio of the hydrophobic monovinyl monomer to the hydrophilic monovinyl monomer is 100:5-30, preferably 100:10-20.

[0014] In an alternative embodiment, the hydrophobic monovinyl monomer is at least one of styrene, acetoxystyrene, and p-chloromethylstyrene.

[0015] In an alternative embodiment, the hydrophilic monovinyl monomer is at least one of 2-hydroxyethyl acrylate, vinyl acetate, hydroxyethylacrylamide, and 4-hydroxybutyl vinyl ether.

[0016] In an alternative embodiment, the temperature of the amination reaction is 30°C-70°C, and the reaction time is 2h-12h.

[0017] In an alternative embodiment, in step (3), the aminating reagent is an alkylolamine; preferably, the alkylolamine is at least one of N,N-dimethylethanolamine, N-methylethanolamine, and diethanolamine.

[0018] In an alternative embodiment, the crosslinking agent is at least one of divinylbenzene and p,p'-divinyl-1,2-diphenylethane.

[0019] In an alternative embodiment, the initiator is at least one of lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, and azobisisoheptonitrile.

[0020] In an alternative embodiment, the dispersant is at least one of polyvinyl alcohol, gelatin, and celluloses; preferably, the celluloses include at least one of hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl cellulose.

[0021] In an alternative embodiment, the crosslinking agent is 2%-30% of the mass of the functional monomer.

[0022] In an alternative embodiment, the initiator is 0.6%-2% of the mass of the functional monomer.

[0023] In an alternative embodiment, the ratio of the mass of the dispersant to the volume of the water is 1:25-200, and the proportional relationship is g / mL.

[0024] In an alternative embodiment, in step (1), the difference between the injection speed of the aqueous phase and the injection speed of the oil phase is 0-10 mL / min.

[0025] In an alternative embodiment, in step (1), the diameter of the needle nozzle is 50 μm-200 μm.

[0026] In an alternative embodiment, in step (1), the curing temperature is 40°C-110°C.

[0027] In an alternative embodiment, in step (1), it further includes a step of washing away the dispersant with water.

[0028] When the hydrophilic monovinyl monomer is vinyl acetate, it further includes a step of hydrolysis with an alkaline solution to hydrolyze the ester group in vinyl acetate into a hydroxyl group.

[0029] In an alternative embodiment, the alkaline reagent in the alkaline solution is at least one of sodium hydroxide, potassium hydroxide, and sodium carbonate; and / or

[0030] In an alternative embodiment, in the alkaline solution, the mass concentration of the alkaline reagent is 20%-50%.

[0031] In an alternative embodiment, in step (2), the halogenating reagent is at least one of chloromethyl ether, a mixture of HCl solution and formaldehyde, and bromomethyl ether.

[0032] In an alternative embodiment, in step (2), when the halogenating reagent is a mixture of HCl solution and formaldehyde, the volume ratio of the HCl solution to formaldehyde is 1:1-5; the mass concentration of the HCl solution is 10%-30%.

[0033] In an alternative embodiment, in step (2), the catalyst is at least one of zinc chloride, aluminum chloride, iron chloride, boron trifluoride, niobium pentachloride, and trifluoromethanesulfonate.

[0034] In an alternative embodiment, in step (2), the halogenation reaction further includes a reaction solvent, and the reaction solvent is at least one of methylal, methanol, ethanol, acetone, toluene, isopropanol, and ether.

[0035] In an alternative embodiment, in step (2), the mass ratio of the resin dry bulb, the catalyst, the halogenating reagent, and the solvent is 1: 0.5-3: 0.5-7: 2-3.

[0036] In an alternative embodiment, in step (2), the temperature of the halogenation reaction is 40 °C - 85 °C, and the reaction time is 1 h - 12 h.

[0037] In an alternative embodiment, in step (3), the temperature of the amination reaction is 30 °C - 70 °C, and the reaction time is 2 h - 12 h.

[0038] Second, the present invention provides a hydrophilic acid-blocking resin prepared by the above method.

[0039] In an alternative embodiment, the ratio of the hydroxyl group to the amino group content in the hydrophilic acid-blocking resin is 1: 3-6, preferably 1: 4-5.

[0040] In an alternative embodiment, the particle size of the hydrophilic acid-blocking resin is 250 um - 330 um.

[0041] In an alternative embodiment, the uniformity coefficient of the hydrophilic acid-blocking resin is ≤ 1.15.

[0042] In an alternative embodiment, the strong base mass exchange capacity of the hydrophilic acid-blocking resin is 1.0 mmol / g - 3.0 mmol / g.

[0043] In an alternative embodiment, the wet apparent density of the hydrophilic acid-blocking resin is 0.67 g / cm 3 - 0.73 g / cm 3 .

[0044] In an alternative embodiment, the wet true density of the hydrophilic acid-blocking resin is 1.0 g / cm 3 - 1.2 g / cm 3 .

[0045] In an alternative embodiment, the resin water content of the hydrophilic acid-blocking resin is 20% - 30%.

[0046] Third, the present invention provides an application of the above hydrophilic acid-blocking resin in the separation of biomass non-ionic organic compounds and acids.

[0047] In an alternative embodiment, the acid is at least one of sulfuric acid, hydrochloric acid, acetic acid, and maleic acid.

[0048] In an alternative embodiment, the non-ionic organic compound is at least one of glucose, xylose, fructose, and galactose.

[0049] In an alternative embodiment, the mass concentration of the acid is 5 wt% - 50 wt%.

[0050] In an alternative embodiment, the mass concentration of the non-ionic organic compound is 5 wt% - 25 wt%.

[0051] Compared with the prior art, the technical solution of the present invention has the following advantages:

[0052] 1. The preparation method of the hydrophilic acid-blocking resin provided by the present invention comprises formulating a functional monomer, a cross-linking agent, and an initiator into an oil phase, formulating a dispersant and water into an aqueous phase, and preparing resin-based spheres by suspension polymerization combined with a tube jetting technique. After washing and drying, resin dry spheres are obtained; then, under the action of a catalyst, the resin dry spheres are reacted with a halogenating reagent to obtain resin halogen spheres; finally, the resin halogen spheres are reacted with an aminating reagent to prepare the hydrophilic acid-blocking resin. In the preparation method of the present invention, a hydrophilic monovinyl monomer is introduced into the functional monomer, and the mass ratio of the hydrophilic monovinyl monomer to the aminating reagent is 1 - 2:1. When the hydrophilic acid-blocking resin prepared by the present invention is used for separating sugar and acid, the acid can be quickly washed out, reducing water consumption and significantly shortening the residence time of the acid on the resin, avoiding the phenomenon of strong acid tailing, and being beneficial to extending the service life of the hydrophilic acid-blocking resin.

[0053] The preparation method of the hydrophilic acid-blocking resin provided by the present invention is simple, low in cost, convenient to operate, and easy to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0055] Figure 1 It is a comparison diagram of the elution curves of the hydrophilic acid-blocking resin prepared in Example 1 of the present invention for separating sulfuric acid and xylose for 1 time and 500 times. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0056] The following embodiments are provided to better further understand the present invention. It is not limited to the best embodiment, and does not limit the content and protection scope of the present invention. Any product obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with those of other prior arts and being the same as or similar to the present invention falls within the protection scope of the present invention.

[0057] For those without specific experimental steps or conditions noted in the examples, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments without the manufacturer noted, they are all conventional reagent products that can be obtained through commercial purchase.

[0058] To solve the problems existing in the above related technologies, the preparation method of the hydrophilic acid-blocking resin provided by the present invention is as follows: an oil phase is prepared by mixing a functional monomer, a cross-linking agent, and an initiator, and an aqueous phase is prepared by mixing a dispersant and water. The resin-based spheres are prepared by suspension polymerization combined with a tubular injection technique, and the resin dry spheres are obtained after washing and drying. Then, under the action of a catalyst, the resin dry spheres are reacted with a halogenating reagent to obtain resin halogen spheres. Finally, the resin halogen spheres are reacted with an aminating reagent to prepare the hydrophilic acid-blocking resin. In the preparation method of the present invention, a hydrophilic mono-vinyl monomer is introduced into the functional monomer, and the mass ratio of the hydrophilic mono-vinyl monomer to the aminating reagent is 1-2:1. When the hydrophilic acid-blocking resin prepared by the present invention is used for separating sugar and acid, the acid can be quickly washed out, reducing water consumption and greatly shortening the residence time of the acid on the resin, avoiding the phenomenon of strong acid tailing, and being beneficial to extending the service life of the hydrophilic acid-blocking resin. By controlling the addition amounts of the hydrophilic mono-vinyl monomer and the aminating reagent, the ratio of hydrophilic groups and amino groups in the resin is controlled. The positive charge of the amino group content blocks the acid, enabling the hydrophilic acid-blocking resin to play an acid-blocking role during the elution process. The hydrophilic mono-vinyl monomer prevents the acid from generating a long strong acid tail, greatly shortening the retention time of the strong acid on the hydrophilic acid-blocking resin and realizing the rapid recovery of the acid. Therefore, the service life of the hydrophilic acid-blocking resin is improved, and it has potential applications in the field of separating biomass non-ionic organic compounds and acids.

[0059] The preparation method of the hydrophilic acid-blocking resin prepared by the present invention is simple, low in cost, easy to operate, and easy to industrialize.

[0060] It can be understood that the term "mono-vinyl monomer" in the present invention refers to a compound having one polymerizable vinyl functional group.

[0061] The following further describes the present invention in detail with specific examples, and these examples should not be construed as limiting the scope claimed by the present invention.

[0062] Example 1

[0063] This example provides a preparation method of a hydrophilic acid-blocking resin, including the following steps:

[0064] (1) Prepare an oil phase system by mixing 100 g of styrene, 20 g of 63% (w / w) divinylbenzene, and 30 g of 2-hydroxyethyl acrylate. Keep the temperature at 30 °C, and add 1.2 g of benzoyl peroxide (BPO) to the oil phase and stir to dissolve. Dissolve 12 g of gelatin and 6 g of hydroxyethyl cellulose in 500 mL of water, mix well, and keep the temperature at 50 °C. Control the oil phase flow rate at 2 mL / min, the water phase flow rate at 4 mL / min, and the diameter of the needle nozzle at 110 μm for spraying, and cure at 80 °C, then wash to obtain resin-based spheres;

[0065] (2) Stir the resin-based spheres in water at 60 °C for 8 h to remove the dispersant, and then dry at 60 °C to obtain dry resin spheres;

[0066] (3) Weigh 100 g of the dry resin spheres, add 200 g of methylal, 100 g of chloromethyl ether, and 50 g of zinc chloride as a catalyst, and stir at 43 °C for 12 h to obtain resin chlorine spheres;

[0067] (4) Weigh 100 g of the resin chlorine spheres, add 30 g of N,N-dimethylethanolamine, stir and swell at room temperature for 2 h, then react at 30 °C for 12 h, and wash with water to obtain a hydrophilic acid-blocking resin. The ratio of the hydroxyl group to the amino group content in the resin is 1:3.5, the particle size is 250 μm - 320 μm, the uniformity coefficient is 1.15, the strong base mass exchange capacity is 2.4 mmol / g, the wet apparent density is 0.716 g / cm 3 , and the wet true density is 1.17 g / cm 3 , the water content of the resin is 24.3%, and the ionic form is chloride form.

[0068] Example 2

[0069] This example provides a method for preparing a hydrophilic acid-blocking resin, which includes the following steps:

[0070] (1) Prepare an oil phase system by mixing 100 g of styrene, 30 g of 63% (w / w) divinylbenzene, and 20 g of vinyl acetate. Keep the temperature at 30 °C, and add 1.2 g of BPO to the oil phase and stir to dissolve. Dissolve 12 g of gelatin and 6 g of hydroxyethyl cellulose in 500 mL of water, mix well, and keep the temperature at 50 °C. Control the oil phase flow rate at 1 mL / min, the water phase flow rate at 4 mL / min, and the diameter of the needle nozzle at 50 μm for spraying, and cure at 80 °C, then wash to obtain resin-based spheres;

[0071] (2) Stir the resin-based spheres in water at 60 °C for 8 h to remove the dispersant, dry at 60 °C, and then hydrolyze in 300 mL of 30% potassium hydroxide solution at 80 °C for 12 h to obtain dry resin spheres.

[0072] (3) Weigh 100 g of dry resin balls, add 200 g of methylal, 100 g of chloromethyl methyl ether, and 50 g of zinc chloride as a catalyst, stir at 43 °C for 12 h to obtain resin chlorine balls;

[0073] (4) Weigh 100 g of resin chlorine balls, add 20 g of N,N-dimethylethanolamine, stir and swell at room temperature for 2 h, then react at 30 °C for 12 h, wash with water to obtain a hydrophilic acid-blocking resin. The ratio of the hydroxyl group to the amino group content in the resin is 1:5, the particle size is 250 - 320 μm, the uniformity coefficient is 1.12, the strong base mass exchange capacity is 2.25 mmol / g, and the wet apparent density is 0.721 g / cm 3 , and the wet true density is 1.18 g / cm 3 , the water content of the resin is 24.8%, and the ionic form is chloride form.

[0074] Example 3

[0075] This example provides a preparation method of a hydrophilic acid-blocking resin, including the following steps:

[0076] (1) Prepare an oil phase system by mixing 100 g of styrene, 25 g of 63% (w / w) divinylbenzene, and 25 g of 4-hydroxybutyl vinyl ether, keep the temperature at 30 °C, and add 1.2 g of BPO to the oil phase and stir to dissolve; dissolve 12 g of gelatin and 6 g of hydroxyethyl cellulose in 500 mL of water, mix evenly, and keep the temperature at 50 °C; control the oil phase flow rate at 1 mL / min, the water phase flow rate at 5 mL / min, and the nozzle diameter of the injection needle at 80 μm for injection, and cure at 80 °C, then wash to obtain resin-based balls;

[0077] (2) Stir the resin-based balls in water at 60 °C for 8 h to remove the dispersant, and dry at 60 °C to obtain dry resin balls;

[0078] (3) Weigh 100 g of dry resin balls, add 200 g of methylal, 100 g of chloromethyl methyl ether, and 50 g of zinc chloride as a catalyst, and stir at 43 °C for 12 hours to obtain resin chlorine balls;

[0079] (4) Weigh 100 g of resin chlorine balls, add 25 g of N,N-dimethylethanolamine, stir and swell at room temperature for 2 h, then react at 30 °C for 12 h, wash with water to obtain a hydrophilic acid-blocking resin. The ratio of the hydroxyl group to the amino group content in the resin is 1:4.3, the particle size is 250 - 320 μm, the uniformity coefficient is 1.12, the strong base mass exchange capacity is 2.36 mmol / g, and the wet apparent density is 0.718 g / cm 3 , and the wet true density is 1.16 g / cm 3 , the water content of the resin is 25.1%, and the ionic form is chloride form.

[0080] Example 4

[0081] This embodiment provides a method for preparing a hydrophilic acid-blocking resin, which includes the following steps:

[0082] (1) Prepare an oil-phase system by mixing 1000 kg of styrene, 200 kg of 63% (w / w) divinylbenzene, and 300 kg of vinyl acetate. Keep the temperature at 30°C, and add 12 kg of BPO to the oil phase and stir to dissolve it. Dissolve 120 kg of gelatin and 60 kg of hydroxyethyl cellulose in 5000 L of water, mix evenly, and keep the temperature at 50°C. Control the oil-phase flow rate at 5 L / min, the water-phase flow rate at 5 L / min, and the diameter of the needle nozzle at 140 μm for spraying, and cure at 80°C, then wash to obtain resin-based spheres;

[0083] (2) Boil the resin-based spheres in water at 60°C to remove the dispersant, dry them at 60°C, and then hydrolyze them in 3000 L of 30% sodium carbonate solution at 80°C for 12 h to obtain dry resin spheres;

[0084] (3) Weigh 1000 kg of dry resin spheres, add 2000 kg of methylal, 1000 kg of chloromethyl ether, and 500 kg of zinc chloride as a catalyst, and stir at 43°C for 12 h to obtain resin chloride spheres;

[0085] (4) Weigh 1000 kg of resin chloride spheres, add 200 kg of N,N-dimethylethanolamine, stir and swell at room temperature for 2 h, then react at 30°C for 12 h, and wash with water to obtain a hydrophilic acid-blocking resin. The ratio of the hydroxyl group to the amino group content in the resin is 1:3.3, the particle size is 250 μm - 320 μm, the uniformity coefficient is 1.13, the strong-base mass exchange capacity is 2.33 mmol / g, the wet apparent density is 0.718 g / cm 3 , and the wet true density is 1.18 g / cm 3 , the water content of the resin is 24.6%, and the ionic form is chloride form.

[0086] Example 5

[0087] This embodiment provides a method for preparing a hydrophilic acid-blocking resin, which includes the following steps:

[0088] (1) Prepare an oil-phase system by mixing 100 g of acetoxystyrene, 2.1 g of 98% (w / w) p,p'-divinyl-1,2-diphenylethane, and 5 g of hydroxyethylacrylamide. Keep the temperature at 30°C, and add 2.1 g of potassium persulfate to the oil phase and stir to dissolve it. Dissolve 5 g of polyvinyl alcohol in 500 mL of water, mix evenly, and keep the temperature at 50°C. Control the oil-phase flow rate at 1 L / min, the water-phase flow rate at 9 L / min, and the diameter of the needle nozzle at 170 μm, and carry out spraying, and cure at 110°C, then wash to obtain resin-based spheres;

[0089] (2) Boil the resin-based spheres in water at 60 °C to remove the dispersant, and then dry them at 60 °C to obtain dry resin spheres.

[0090] (3) Weigh 100 g of the dry resin spheres, add 200 g of methanol, 100 g of a mixture of HCl solution and formaldehyde (the volume ratio of HCl solution to formaldehyde is 1:2, and the mass concentration of the HCl solution is 30%), and 50 g of aluminum chloride as a catalyst, and stir at 60 °C for 8 h to obtain resin chlorine spheres.

[0091] (4) Weigh 100 g of the resin chlorine spheres, add 5 g of N,N-diethanolamine, stir and swell at room temperature for 2 h, then react at 50 °C for 6 h, and wash with water to obtain a hydrophilic acid-blocking resin. The ratio of the hydroxyl group to the amino group content in the resin is 1:3, the particle size is 250 - 320 μm, the uniformity coefficient is 1.13, the strong base mass exchange capacity is 2.26 mmol / g, the wet apparent density is 0.715 g / cm 3 , and the wet true density is 1.16 g / cm 3 , the water content of the resin is 25.4%, and the ionic form is chloride form.

[0092] Example 6

[0093] This example provides a preparation method of a hydrophilic acid-blocking resin, which includes the following steps:

[0094] (1) Prepare an oil-phase system by mixing 100 g of p-chloromethylstyrene, 33 g of 63% (w / w) divinylbenzene, and 10 g of hydroxyethyl acrylamide, keep the temperature at 30 °C, and add 0.66 g of azobisisoheptonitrile to the oil phase and stir to dissolve; dissolve 2.5 g of hydroxypropyl cellulose in 500 mL of water, mix evenly, and keep the temperature at 50 °C; control the oil-phase flow rate at 3 L / min, the water-phase flow rate at 8 L / min, and the diameter of the injection needle orifice at 200 μm for injection, and cure at 40 °C, then wash to obtain resin-based spheres.

[0095] (2) Boil the resin-based spheres in water at 60 °C to remove the dispersant, and then dry them at 60 °C to obtain dry resin spheres.

[0096] (3) Weigh 100 g of the dry resin spheres, add 300 g of toluene, 50 g of bromomethyl ether, and 50 g of niobium pentachloride as a catalyst, and stir at 85 °C for 4 h to obtain resin bromine spheres.

[0097] (4) Weigh 100 g of resin chloro balls, add 10 g of N-methylethanolamine, stir and swell at room temperature for 2 h, then react at 70 °C for 2 h, and wash with water to obtain a hydrophilic acid-blocking resin. The ratio of the hydroxyl group to the amino group in the resin is 1:3.5, the particle size is 250 μm - 330 μm, the uniformity coefficient is 1.15, the strong base mass exchange capacity is 2.34 mmol / g, and the wet apparent density is 0.716 g / cm 3 , and the wet true density is 1.17 g / cm 3 , the water content of the resin is 25.6%, and the ionic form is bromide form.

[0098] Comparative Example 1

[0099] This comparative example provides a preparation method of a hydrophilic acid-blocking resin, which is basically the same as the steps of Example 1, except that 130 g of styrene is used instead of 100 g of styrene and 30 g of 2-hydroxyethyl acrylate.

[0100] Comparative Example 2

[0101] This comparative example provides a preparation method of a hydrophilic acid-blocking resin, which is basically the same as the steps of Example 1, except that 130 g of 2-hydroxyethyl acrylate is used instead of 100 g of styrene and 30 g of 2-hydroxyethyl acrylate.

[0102] Comparative Example 3

[0103] This comparative example provides a preparation method of a hydrophilic acid-blocking resin, which is basically the same as the steps of Example 1, except that the mass of the 2-hydroxyethyl acrylate is 60 g, so that the ratio of the hydrophilic hydroxyl group to the amino group in the hydrophilic acid-blocking resin is 1:2.

[0104] Comparative Example 4

[0105] This comparative example provides a preparation method of a hydrophilic acid-blocking resin, which is basically the same as the steps of Example 1, except that the mass of the 2-hydroxyethyl acrylate is 5 g, so that the ratio of the hydrophilic hydroxyl group to the amino group in the hydrophilic acid-blocking resin is 1:8.

[0106] Experimental Example 1

[0107] Use the hydrophilic acid-blocking resin prepared in the above examples to separate sugar acid, which specifically includes the following steps:

[0108] Column packing: Pack the hydrophilic acid-blocking resin prepared in the above examples and comparative examples into a chromatography column with a jacket for heat preservation, the temperature is 50 °C, the height-diameter ratio of the chromatography column is 40:1, and the resin packing volume is 500 mL.

[0109] Column equilibration: Rinse and equilibrate the column with deionized water at a flow rate of 1.5 BV / h.

[0110] Sample loading: The mass concentration of glucose in the sugar-acid separation feed liquid is 10 wt%, the mass concentration of sulfuric acid is 40 wt%, 0.2 BV of the separation feed liquid is taken, and the flow rate is 2 BV / h for injection into the chromatography column.

[0111] Elution with the mobile phase: After sample loading, deionized water is used for elution at a flow rate of 2 BV / h. Samples are taken in segments to detect the sulfuric acid and glucose contents in each segment until no substance flows out. The separation effect is shown in Table 1.

[0112] Table 1 Sugar-acid separation effects of each example and comparative example

[0113] Sulfuric acid yield (%) Glucose yield (%) Example 1 97.2 97.8 Example 2 97.6 98.2 Example 3 96.5 97.2 Example 4 96.8 97.1 Example 5 95.8 96.6 Example 6 95.3 96.8 Comparative Example 1 78.2 94.3 Comparative Example 2 92.5 93.8 Comparative Example 3 93.1 85.6 Comparative Example 4 88.5 92.3

[0114] Experimental Example 2

[0115] The hydrophilic acid-blocking resin prepared in the above examples and comparative examples was used for sugar-acid separation, which was basically the same as the steps of Experimental Example 1, except that the mass concentration of xylose in the sugar-acid separation feed liquid was 6 wt%, the mass concentration of sulfuric acid was 35 wt%, 0.25 BV of the separation feed liquid was taken, and the separation effect is shown in Table 2.

[0116] Table 2 Sugar-acid separation effects of each example and comparative example

[0117]

[0118]

[0119] The results show that as can be seen from Table 1 and Table 2, after eluting the sugar-acid with the hydrophilic acid-blocking resin prepared in Examples 1-6, the sulfuric acid recovery rate is over 95%, and the recovery rate of xylose or glucose is over 96%. After Experimental Example 2 was repeated 500 times, the sulfuric acid recovery rate could still remain over 95%, and the xylose recovery rate was over 96%. For Comparative Example 1, the sulfuric acid recovery rate obtained after eluting 5 BV was over 78%; the recovery rate of xylose or glucose was over 93%. This is because of the hydrophobic effect of the benzene ring, which causes a long sulfuric acid tail to be generated during the elution process of sulfuric acid, resulting in a decrease in the sulfuric acid recovery rate. For Comparative Example 2, there was no separation effect between xylose and sulfuric acid after repeating 33 times. This is because the strong sulfuric acid damaged the resin structure of the acrylate system, resulting in a sharp reduction in the lifespan. For Comparative Example 3, the sulfuric acid recovery rate obtained after eluting 5 BV was over 93%; the recovery rate of xylose or glucose was over 85%. This is because the resin in Comparative Example 3 had stronger hydrophilicity, and during the elution process, the sulfuric acid flowed out faster, resulting in a worse separation effect between sulfuric acid and xylose or glucose. For Comparative Example 4, the sulfuric acid recovery rate obtained after eluting 5 BV was over 88%; the recovery rate of xylose or glucose was over 92%. This is because the proportion of hydrophilic monomers in the resin of Comparative Example 4 decreased, resulting in poorer hydrophilicity, which caused sulfuric acid to tail during the elution process.

[0120] From Figure 1 It can be seen that after repeating 500 times, the separation effect of the resin has little difference, indicating that the hydrophilic acid-blocking resin prepared by the present invention has a long service life.

[0121] Experimental Example 3

[0122] The hydrophilic acid-blocking resin prepared in Example 1 was immersed in a sugar-acid feed solution with a mass concentration of glucose of 10 wt% and a mass concentration of sulfuric acid of 40 wt%, placed in an oven at 65 degrees, and left for more than 6 months. After reinstalling the column, the separation effect of sugar acid can still maintain a sulfuric acid yield of more than 95%; the glucose yield is more than 96%, indicating that the hydrophilic acid-blocking resin prepared by the present invention has a long service life.

[0123] Obviously, the above embodiments are merely examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A method for preparing a hydrophilic acid-blocking resin, characterized in that, It includes the following steps: (1) Prepare an oil phase by mixing a functional monomer, a crosslinking agent, and an initiator, and prepare an aqueous phase by mixing a dispersant and water. Use suspension polymerization combined with a tubular injection technique to prepare resin-based spheres, wash and dry them to obtain dry resin spheres; (2) React the dry resin spheres with a halogenating reagent under the action of a catalyst to obtain resin halogen spheres; (3) React the resin halogen spheres with an aminating reagent to prepare a hydrophilic acid-blocking resin; The functional monomer includes a hydrophobic monovinyl monomer and a hydrophilic monovinyl monomer; The mass ratio of the hydrophilic monovinyl monomer to the aminating reagent is 1-2:

1.

2. The preparation method of the hydrophilic acid-blocking resin according to claim 1, characterized in that, The mass ratio of the hydrophobic monovinyl monomer to the hydrophilic monovinyl monomer is 100:5-30, preferably 100:10-20; and / or, The hydrophobic monovinyl monomer is at least one of styrene, acetoxystyrene, and p-chloromethylstyrene; and / or, The hydrophilic monovinyl monomer is at least one of 2-hydroxyethyl acrylate, vinyl acetate, hydroxyethyl acrylamide, and 4-hydroxybutyl vinyl ether.

3. The preparation method of the hydrophilic acid-blocking resin according to claim 1, characterized in that, In step (3), the temperature of the amination reaction is 30°C-70°C, and the reaction time is 2h-12h; and / or, The aminating reagent is an alkyl alkanolamine; preferably, the alkyl alkanolamine is at least one of N,N-dimethylethanolamine, N-methylethanolamine, and diethanolamine.

4. The preparation method of the hydrophilic acid-blocking resin according to claim 1, characterized in that, The crosslinking agent is at least one of divinylbenzene and p,p'-divinyl-1,2-diphenylethane; and / or, The initiator is at least one of lauroyl peroxide, benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, and azobisisoheptonitrile; and / or, The dispersant is at least one of polyvinyl alcohol, gelatin, and celluloses; preferably, the celluloses include at least one of hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl cellulose; and / or, The crosslinking agent is 2%-30% of the mass of the functional monomer; and / or, The initiator is 0.6%-2% of the mass of the functional monomer; and / or, The mass ratio of the dispersant to the volume of water is 1:25-200, and the ratio is g / mL.

5. The preparation method of the hydrophilic acid-blocking resin according to claim 1, characterized in that, In step (1), the difference between the injection speed of the aqueous phase and the injection speed of the oil phase is 0-10 mL / min; and / or, The diameter of the nozzle of the injection needle is 50μm-200μm; and / or, The curing temperature is 40°C-110°C; and / or, In step (1), it also includes a step of washing away the dispersant with water; and / or, When the hydrophilic monovinyl monomer is vinyl acetate, it also includes a step of hydrolysis with an alkaline solution; The alkaline reagent in the alkaline solution is at least one of sodium hydroxide, potassium hydroxide, and sodium carbonate; and / or, In the alkaline solution, the mass concentration of the alkaline reagent is 20%-50%.

6. The preparation method of the hydrophilic acid-blocking resin according to claim 1, wherein In step (2), the halogenating reagent is at least one of chloromethyl ether, a mixture of HCl solution and formaldehyde, and bromomethyl ether; When the halogenating reagent is a mixture of HCl solution and formaldehyde, the volume ratio of the HCl solution to formaldehyde is 1:1 - 5; the mass concentration of the HCl solution is 10% - 30%; and / or, the catalyst is at least one of zinc chloride, aluminum chloride, iron chloride, boron trifluoride, niobium pentachloride, trifluoromethanesulfonate; and / or, the halogenation reaction further includes a reaction solvent, and the reaction solvent is at least one of methylal, methanol, ethanol, acetone, toluene, isopropanol, ether; and / or, the mass ratio of the resin dry balls, catalyst, halogenating reagent, and solvent is 1:0.5 - 3:0.5 - 7:2 - 3; and / or, the temperature of the halogenation reaction is 40°C - 85°C, and the reaction time is 1h - 12h.

7. A hydrophilic acid-blocking resin, characterized in that, Prepared by the preparation method according to any one of claims 1 - 6.

8. The hydrophilic acid-blocking resin according to claim 7, wherein In the hydrophilic acid-blocking resin, the ratio of the hydroxyl group content to the amino group content is 1:3 - 6, preferably 1:4 - 5; and / or, the particle size of the hydrophilic acid-blocking resin is 250um - 330um; and / or, the uniformity coefficient of the hydrophilic acid-blocking resin is ≤1.15; and / or, the strong base mass exchange capacity of the hydrophilic acid-blocking resin is 1.0 mmol / g - 3.0 mmol / g; and / or, The wet apparent density of the hydrophilic acid-blocking resin is 0.67 g / cm 3 - 0.73 g / cm 3 ; and / or, The wet true density of the hydrophilic acid-blocking resin is 1.0 g / cm 3 -1.2 g / cm 3 ; and / or, the resin water content of the hydrophilic acid-blocking resin is 20% - 30%.

9. Use of the hydrophilic acid-blocking resin according to claim 7 or 8 in the separation of biomass non-ionic organic compounds and acids.

10. The application according to claim 9, characterized in that, The acid is at least one of sulfuric acid, hydrochloric acid, acetic acid, maleic acid; and / or, the non-ionic organic compound is at least one of glucose, xylose, fructose, galactose; and / or, the mass concentration of the acid is 5wt% - 50wt%; and / or, the mass concentration of the non-ionic organic compound is 5wt% - 25wt%.

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