CN115418022B - Ultrahigh crosslinked adsorption resin, preparation method thereof and application thereof in separation of products in biomass hydrolysate - Google Patents
Ultrahigh crosslinked adsorption resin, preparation method thereof and application thereof in separation of products in biomass hydrolysate Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 80
- 229920005989 resin Polymers 0.000 title claims abstract description 80
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000926 separation method Methods 0.000 title claims abstract description 26
- 239000002028 Biomass Substances 0.000 title claims abstract description 19
- 239000000413 hydrolysate Substances 0.000 title claims abstract description 19
- 239000000047 product Substances 0.000 title claims abstract description 10
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000004005 microsphere Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 29
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims abstract description 24
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 claims abstract description 15
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
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- 238000001914 filtration Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
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- 230000000694 effects Effects 0.000 abstract description 2
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- 239000012071 phase Substances 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
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- PYMYPHUHKUWMLA-VAYJURFESA-N aldehydo-L-arabinose Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-VAYJURFESA-N 0.000 description 3
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
- C08F212/18—Chlorine
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an ultra-high crosslinking adsorption resin, a preparation method thereof and application thereof in separation of products in biomass hydrolysate. The preparation method of the adsorption resin comprises the following steps: (1) Mixing water, a dispersing agent and methylene blue, heating until the dispersing agent is dissolved to obtain a water phase, adding an oil phase consisting of chloromethyl styrene, divinylbenzene, benzoyl peroxide and a pore-forming agent into the water phase, starting mechanical stirring, slowly heating to 80-95 ℃, reacting for 6-12 h, performing solid-liquid separation, alternately washing with ethanol and water to obtain a solid product, and removing impurities to obtain chloromethyl crosslinked polystyrene microspheres; (2) Swelling chloromethyl crosslinked polystyrene microsphere in1, 2-dichloroethane with solid-to-liquid ratio of 1:3-1:8, adding catalyst, maintaining the system temperature at 40-48 ℃ for 1.5-2.5h, heating to 60-80 ℃ for heat preservation reaction for 3-9 h, and separating solid from liquid to obtain the solid which is the ultra-high crosslinked adsorption resin. The invention applies the ultra-high crosslinking adsorption resin to separating furfural from biomass hydrolysate, and has good effect.
Description
Technical field:
the invention relates to the technical field of functional polymer materials, in particular to an ultrahigh crosslinked adsorption resin, a preparation method thereof and application thereof in separation of products in biomass hydrolysate.
The background technology is as follows:
Lignocellulose is the most abundant biomass resource on earth, consisting mainly of cellulose, hemicellulose and lignin. Wherein, hemicellulose can be depolymerized and degraded to prepare furfural. Furfural is an important platform compound, has active chemical properties, and can be used in various industries such as plastic modifiers, medicines, industrial chemicals, fragrances, solvents, pesticide intermediates, lubricating oil additives and the like. About 9 hundred million tons of straw waste are produced annually in China. Therefore, the method for preparing the furfural from the straws by a chemical conversion method has wide application prospect. However, during the hydrolysis of straw to produce furfural, a range of other compounds are formed. To obtain furfural with higher purity, the degradation product mixture must be separated and purified. The physical adsorption method has the advantages of low energy consumption, simple equipment and the like, so that the method has good industrial application prospect. The excellent adsorption performance of the adsorbent is a key factor limiting the industrial application of the physical adsorption method. The adsorbents commonly used at present mainly comprise active carbon, active clay, granular clay, adsorbent resin and the like. The activated carbon has the largest specific surface area, mainly comprises micropores, and is mainly adsorbed by virtue of Van der Waals force, but has poor selectivity, and the adsorbed activated carbon is not easy to regenerate and is easy to cause solid waste pollution; nonmetallic mineral adsorbents such as activated clay, granular clay and the like are low in cost, but the specific surface area of the nonmetallic mineral adsorbents is generally small, the adsorption selectivity is poor, and the nonmetallic mineral adsorbents cannot be reused. Compared with the adsorbent, the adsorbent resin has the advantages of adjustable surface property, controllable structure, stable physical and chemical properties, easy regeneration and general recycling.
The traditional adsorption resin mainly comprises macroporous adsorption resin and gel adsorption resin, is an artificially synthesized high polymer with a porous three-dimensional structure, has excellent adsorption performance, and is widely applied to various fields such as wastewater treatment, medicament separation and purification, chromatographic analysis filling materials and the like. With the continuous development of the field of the synthesis of the adsorption resin, davankov and the like utilize linear polystyrene or low-crosslinking styrene-divinylbenzene copolymer to carry out post-crosslinking through Fridel-Crafts reaction to synthesize a large-mesh average Kong Ben ethylene copolymer, which is called ultra-high crosslinking resin. Compared with macroporous adsorption resin, the super-crosslinked porous polymer has the characteristics of high specific surface area, high porosity and the like, and further has the advantages of high thermal stability, light weight, controllable pore diameter and the like, so that the super-crosslinked porous polymer becomes a new research hot spot in the adsorption and separation fields.
Although the ultra-high crosslinked adsorption resin has better adsorption performance, chloromethyl ether (crosslinking agent, strong carcinogenicity) is required to be used for preparing the ultra-high crosslinked adsorption resin conventionally, and the preparation process is not environment-friendly. The Chinese patent CN102875719A discloses a preparation method of 10-100 micrometers chloromethylated crosslinked polystyrene microsphere, adopts an emulsion polymerization method to prepare the microsphere with the outer layer of chloromethylated crosslinked polystyrene in two steps, has the particle size range of 10-60 micrometers, and is applied to the fields of chromatographic separation, biomedicine, paint, printing ink and the like. The Chinese patent CN110627753A discloses a method for circularly preparing levulinic acid and furfural, which adopts polystyrene, polyacrylate and polyacrylamide super-crosslinked adsorption resins to adsorb/desorb to prepare levulinic acid and furfural, wherein the super-crosslinked adsorption resins all adopt the principle of crosslinking by double bonds, and self-crosslinking of the double bonds of uncrosslinked divinylbenzene is utilized to prepare the super-crosslinked adsorption resins. The ultrahigh crosslinked adsorption resin disclosed in the prior art inevitably uses chloromethyl ether in the preparation process, and the microsphere particle size and specific surface area of the ultrahigh crosslinked adsorption resin are small, so that the adsorption of substances is not facilitated.
The invention comprises the following steps:
the invention solves the problems existing in the prior art, provides the ultra-high crosslinking adsorption resin, the preparation method thereof and the application thereof in separating products in biomass hydrolysate, designs and synthesizes the ultra-high crosslinking adsorption resin aiming at the characteristics of the structure, the molecular size, the surface polarity and the like of furfural, is used for adsorbing and separating the furfural in the biomass hydrolysate, has the advantages of high adsorption capacity, rapidness and the like, and simultaneously uses low-carbon alcohols (methanol, ethanol and the like) as a regeneration solvent, so that the ultra-high crosslinking adsorption resin is environment-friendly, and the solvent can be reused.
The invention aims to provide a preparation method of an ultrahigh crosslinked adsorption resin, which comprises the following steps:
(1) Preparation of chloromethyl crosslinked polystyrene microspheres: mixing and heating water, a dispersing agent and methylene blue solution until the dispersing agent is dissolved to obtain a water phase, adding an oil phase consisting of monomer chloromethyl styrene, a cross-linking agent divinylbenzene, an initiator benzoyl peroxide and a pore-forming agent into the water phase, starting mechanical stirring, slowly heating to 80-95 ℃, reacting for 6-12 h, performing solid-liquid separation, alternately washing ethanol and water to obtain a solid product, and removing impurities to obtain chloromethyl cross-linked polystyrene microspheres;
(2) Preparation of ultra-high crosslinked adsorption resin: swelling the chloromethyl crosslinked polystyrene microsphere obtained in the step (1) in 1, 2-dichloroethane, wherein the solid-liquid ratio is 1:3-1:8, adding a catalyst, maintaining the system temperature at 40-48 ℃ for 1.5-2.5h, heating to 60-80 ℃ for heat preservation reaction for 3-9 h, and carrying out solid-liquid separation to obtain the solid which is the ultrahigh crosslinked adsorption resin.
The invention adopts suspension polymerization technology, and obtains chloromethyl crosslinked polystyrene microspheres with different pore structures and pore size distribution by regulating and controlling the dosage of monomer chloromethyl styrene and crosslinking agent divinylbenzene and the type and dosage of pore-forming agent; then carrying out Fu Kehou crosslinking reaction on the microspheres to obtain the ultra-high crosslinking adsorption resin with different structures. The invention avoids using strong cancerogenic substances such as chloromethyl ether and the like, and the preparation process of the ultra-high crosslinking adsorption resin is environment-friendly.
Compared with the prior art, the invention avoids the use of chloromethyl ether, can obtain larger microsphere particle size and higher specific surface area, has the particle size range of 0.42-0.85 mm (being convenient for solid-liquid separation and recycling), and has the specific surface area of 480-1190 m 2/g.
Preferably, the dispersing agent in the step (1) is polyvinyl alcohol and/or gelatin, and the pore-forming agent is selected from more than one of toluene, n-heptane, cyclohexane, liquid paraffin and isobutanol. When the dispersing agent is a mixture of polyvinyl alcohol and gelatin, the mass ratio of the polyvinyl alcohol to the gelatin is 1:1. In the aqueous phase, the mass ratio of the dispersing agent to water is 0.0025:1, the volume ratio of the methylene blue solution to water is 0.0007:1, and the mass fraction of the methylene blue in the methylene blue solution is 1wt%.
Preferably, in the step (1), the mass fraction of divinylbenzene in chloromethyl styrene is 10 to 60 weight percent, and the mass ratio of the pore-forming agent to chloromethyl styrene is 0.63 to 1.6:1, based on 100 weight percent of chloromethyl styrene. The benzoyl peroxide accounts for 1 to 4 weight percent of the chloromethyl styrene.
Preferably, the catalyst in the step (2) is anhydrous aluminum chloride, and the dosage of the anhydrous aluminum chloride is 0.75-3% of the mass of the 1, 2-dichloroethane. The solid-to-liquid ratio refers to the mass-to-volume ratio of chloromethyl crosslinked polystyrene microspheres to 1, 2-dichloroethane, and the unit is g/mL.
Preferably, the specific steps of the step (2) are as follows: swelling the chloromethyl crosslinked polystyrene microsphere obtained in the step (1) in 1, 2-dichloroethane, adding a catalyst, maintaining the system temperature at 45 ℃ for 2 hours, heating to 70 ℃ for heat preservation reaction for 6 hours, and then carrying out solid-liquid separation to obtain the solid which is the ultrahigh crosslinked adsorption resin.
The invention also protects the ultra-high crosslinking adsorption resin obtained by the preparation method, wherein the particle size distribution of the ultra-high crosslinking adsorption resin is 0.42-0.85 mm, the specific surface area is 480-1190 m 2/g, the total pore volume is 0.9-1.5 m 3/g, and the average pore diameter is 4-7 nm.
The invention also protects the application of the ultra-high crosslinked adsorption resin in separating products in the biomass hydrolysate.
Preferably, the product separation is specifically furfural separation.
Preferably, the biomass hydrolysate is bagasse hydrolysate, straw hydrolysate or eucommia hydrolysate.
Preferably, the application comprises the following steps:
(1) Taking biomass hydrolysate, adding the ultrahigh crosslinked adsorption resin into the biomass hydrolysate according to the addition amount of 5-20% of the mass of the biomass hydrolysate, and performing shaking and filtering, and performing solid-liquid separation;
(2) Eluting the resin adsorbed in the step (1) by adopting a low-carbon alcohol solution to enrich furfural;
(3) And (3) washing the resin eluted in the step (2) by pure water, and recycling the washed resin to the step (1).
The lower alcohol includes methanol, ethanol, etc., and is preferably eluted with an ethanol solution having a mass fraction of 95%.
Compared with the prior art, the invention has the following advantages: the ultra-high crosslinking adsorption resin prepared by the invention has larger particle size, can be regulated and controlled, has larger specific surface area and pore volume, and contains micropores, mesopores and macropore structures. The application of the ultra-high crosslinked adsorption resin in separating furfural from biomass hydrolysate has good effect, and particularly has great application potential in separating furfural from biomass hydrolysate such as bagasse, straw, eucommia bark and the like.
The specific embodiment is as follows:
the following examples are further illustrative of the invention and are not intended to be limiting thereof.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention. Unless otherwise indicated, the experimental materials and reagents herein are all commercially available products conventional in the art.
Example 1
The preparation method of the ultra-high crosslinking adsorption resin comprises the following steps:
(1) Preparation of chloromethyl crosslinked polystyrene microsphere
In a 1000ml three-necked flask equipped with mechanical stirring, thermometer and condenser: 480g of water, 1.2g of polyvinyl alcohol and 0.34mL of 1wt% methylene blue solution, and heating until the polyvinyl alcohol is dissolved to obtain a water phase; adding an oil phase containing 190g of chloromethyl styrene, 20g of divinylbenzene, 2g of benzoyl peroxide, 60g of toluene and 60g of n-heptane into the water phase, starting mechanical stirring, regulating the stirring speed to be 150rpm, slowly heating to 80 ℃, reacting for 12 hours, carrying out solid-liquid separation, alternately washing with ethanol and water for multiple times to obtain a solid product, and removing the pore-forming agent and impurities remained in a resin pore canal through Soxhlet extraction to obtain chloromethyl crosslinked polystyrene microspheres.
(2) Preparation of ultra-high crosslinked adsorption resin
Swelling the chloromethyl crosslinked polystyrene microsphere obtained in the step (1) in 1, 2-dichloroethane, wherein the solid-liquid ratio of the chloromethyl crosslinked polystyrene microsphere to the 1, 2-dichloroethane is 1:3, adding anhydrous aluminum chloride serving as a catalyst and accounting for 0.75% of the mass of the 1, 2-dichloroethane, maintaining the system temperature at 45 ℃ for 2 hours, heating to 80 ℃ for heat preservation reaction for 3 hours, and carrying out solid-liquid separation to obtain the solid which is the ultrahigh crosslinked adsorption resin.
The particle size distribution of the prepared ultra-high crosslinked adsorption resin is 0.42-0.65 mm, the specific surface area is 480.56m 2/g, the total pore volume is 0.986m 3/g, and the average pore diameter is 7.9nm.
The bagasse hydrolysate consists of: d-glucose 8.843g/L; d-xylose, 0.897g/L; l-arabinose, 0.545g/L; formic acid 6.383g/L; acetic acid 8.122g/L; levulinic acid, 9.569g/L; furfural, 7.204g/L.
The obtained ultra-high crosslinked adsorption resin is used for adsorbing furfural in bagasse hydrolysate, and comprises the following steps: adding ultra-high crosslinked adsorption resin with the addition amount of 20% of the bagasse hydrolysate by mass, oscillating for 3 hours at constant temperature, filtering, and separating solid from liquid; eluting the adsorbed resin by adopting 95% (w/w, g/g) ethanol, and enriching furfural; and washing the eluted resin microspheres by pure water, so as to recycle the ultra-high crosslinked adsorption resin.
The adsorption capacity of the catalyst for furfural is 90.5mg/g, the desorption yield of the catalyst for furfural is 95.5%, and the sugar loss is 1.82%.
Example 2
The preparation method of the ultra-high crosslinking adsorption resin comprises the following steps:
(1) Preparation of chloromethyl crosslinked polystyrene microsphere
In a 1000ml three-necked flask equipped with mechanical stirring, thermometer and condenser: 480g of water, 1.2g of gelatin and 0.34mL of 1wt% methylene blue solution, and heating until the gelatin is dissolved to obtain a water phase; an oil phase comprising 50g chloromethylstyrene, 30g divinylbenzene, 2g benzoyl peroxide, 40g isobutanol and 40g cyclohexane was added to the aqueous phase, and mechanical stirring was started and the stirring speed was adjusted to 150rpm. Slowly heating to 95 ℃, reacting for 6 hours, carrying out solid-liquid separation, alternately washing with ethanol and water for a plurality of times to obtain a solid product, and removing residual impurities of a pore-forming agent and a resin pore canal through Soxhlet extraction to obtain chloromethyl crosslinked polystyrene microspheres.
(2) Preparation of ultra-high crosslinked adsorption resin
Swelling the chloromethyl crosslinked polystyrene microsphere obtained in the step (1) in 1, 2-dichloroethane, wherein the solid-liquid ratio of the chloromethyl crosslinked polystyrene microsphere to the 1, 2-dichloroethane is 1:8, adding 3% of anhydrous aluminum chloride serving as a catalyst by mass of the 1, 2-dichloroethane, maintaining the system temperature at 45 ℃ for 2 hours, heating to 60 ℃, preserving heat, reacting for 9 hours, and carrying out solid-liquid separation to obtain the solid which is the ultrahigh crosslinked adsorption resin.
The particle size distribution of the prepared ultra-high crosslinked adsorption resin is 0.6-0.85 mm, the specific surface area is 890.56m 2/g, the total pore volume is 1.289m 3/g, and the average pore diameter is 5.9nm.
The rice straw hydrolysate comprises the following components: d-glucose 4.321g/L; d-xylose, 1.068g/L; l-arabinose, 0.599g/L; formic acid 7.251g/L; acetic acid 6.298g/L; levulinic acid 10.652g/L; furfural, 7.051g/L.
The obtained ultra-high crosslinking adsorption resin is used for adsorbing furfural in rice straw hydrolysate, and comprises the following steps: adding super-crosslinking adsorption resin with an addition amount of 15% of the mass of the rice straw hydrolysate, oscillating for 3 hours at constant temperature, filtering, and separating solid from liquid; eluting the adsorbed resin by adopting 95% (w/w, g/g) ethanol, and enriching furfural; and washing the eluted resin microspheres by pure water, so as to recycle the ultra-high crosslinked adsorption resin.
The adsorption capacity of the catalyst for furfural is 110.9mg/g, the desorption yield of the catalyst for furfural is 94.2%, and the sugar loss is 1.66%.
Example 3
The preparation method of the ultra-high crosslinking adsorption resin comprises the following steps:
(1) Preparation of chloromethyl crosslinked polystyrene microsphere
In a 1000ml three-necked flask equipped with mechanical stirring, thermometer and condenser: 480g of water, 0.6g of polyvinyl alcohol, 0.6g of gelatin and 0.34mL of 1wt% methylene blue solution are heated until the polyvinyl alcohol and the gelatin are dissolved, and an aqueous phase is obtained. An oil phase comprising 95g of chloromethylstyrene, 35g of divinylbenzene, 2g of benzoyl peroxide, 60g of toluene and 60g of liquid paraffin was added to the aqueous phase, and mechanical stirring was started and the stirring speed was adjusted to 150rpm. Slowly heating to 85 ℃, reacting for 9 hours, carrying out solid-liquid separation, alternately washing with ethanol and water for a plurality of times to obtain a solid product, and removing residual impurities of a pore-forming agent and a resin pore canal through Soxhlet extraction to obtain chloromethyl crosslinked polystyrene microspheres.
(2) Preparation of ultra-high crosslinked adsorption resin
Swelling the chloromethyl crosslinked polystyrene microsphere obtained in the step (1) in a1, 2-dichloroethane solution, wherein the solid-to-liquid ratio of the chloromethyl crosslinked polystyrene microsphere to the 1, 2-dichloroethane is 1:5, adding anhydrous aluminum chloride serving as a catalyst with the mass of 2.25% of the 1, 2-dichloroethane, maintaining the system temperature at 45 ℃ for 2 hours, heating to 70 ℃ for heat preservation reaction for 6 hours, and carrying out solid-liquid separation to obtain the solid which is the ultra-high crosslinked adsorption resin.
The particle size distribution of the prepared ultra-high crosslinked adsorption resin is 0.5-0.65 mm, the specific surface area is 1190m 2/g, the total pore volume is 1.5m 3/g, and the average pore diameter is 4.1nm.
The eucommia ulmoides hydrolysis liquid comprises the following components: d-glucose 4.809g/L; d-xylose, 0.675g/L; l-arabinose, 0.241g/L; formic acid 4.077g/L; acetic acid 3.933g/L; levulinic acid 7.273g/L; furfural, 5.482g/L.
The obtained ultra-high crosslinking adsorption resin is used for adsorbing furfural in eucommia ulmoides hydrolysate, and comprises the following steps: adding ultra-high crosslinked adsorption resin with an addition amount of 5% of the mass of eucommia ulmoides hydrolysis liquid, oscillating for 3 hours at constant temperature, filtering, and separating solid from liquid; eluting the adsorbed resin by adopting 95% (w/w, g/g) ethanol, and enriching furfural; and washing the eluted resin microspheres by pure water, so as to recycle the ultra-high crosslinked adsorption resin.
The adsorption capacity of the catalyst for furfural is 136.6mg/g, the desorption yield of the catalyst for furfural is 94.0%, and the sugar loss is 1.71%.
The above embodiments are only described to assist in understanding the technical solution of the present invention and its core idea, and it should be noted that it will be obvious to those skilled in the art that several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (3)
1. The application of the ultra-high crosslinked adsorption resin in separating products in biomass hydrolysate is characterized in that the product separation is specifically furfural separation, and the application specifically comprises the following steps:
a. Adding the ultrahigh crosslinked adsorption resin into the biomass hydrolysate according to the addition amount of 5-20% of the mass of the biomass hydrolysate, oscillating and filtering, and carrying out solid-liquid separation;
b. eluting the resin adsorbed in the step a by adopting a low-carbon alcohol solution to enrich furfural;
c. Washing the resin eluted in the step b by pure water, and recycling the washed resin to the step a;
the particle size distribution of the ultra-high crosslinked adsorption resin is 0.42-0.85 mm, the specific surface area is 480-1190 m 2/g, the total pore volume is 0.98-1.5 m 3/g, the average pore diameter is 4-7 nm, and the preparation method of the ultra-high crosslinked adsorption resin comprises the following steps:
(1) Preparation of chloromethyl crosslinked polystyrene microspheres: mixing and heating water, a dispersing agent and methylene blue solution until the dispersing agent is dissolved to obtain a water phase, adding an oil phase consisting of monomer chloromethyl styrene, a cross-linking agent divinyl benzene, an initiator benzoyl peroxide and a pore-foaming agent into the water phase, starting mechanical stirring, slowly heating to 80-95 ℃, reacting for 6-12 h, carrying out solid-liquid separation to obtain a solid product, removing impurities to obtain chloromethyl cross-linked polystyrene microspheres, wherein the dispersing agent is polyvinyl alcohol and/or gelatin, the pore-foaming agent is selected from more than one of toluene, n-heptane, cyclohexane, liquid paraffin and isobutanol, the mass fraction of divinyl benzene accounts for 10-60 wt% of chloromethyl styrene, the mass fraction of the pore-foaming agent and chloromethyl styrene accounts for 0.63-1.6:1, and the mass fraction of benzoyl peroxide accounts for 1-4 wt% of chloromethyl styrene according to the mass percentage of chloromethyl styrene being 100%;
(2) Preparation of ultra-high crosslinked adsorption resin: swelling chloromethyl crosslinked polystyrene microspheres obtained in the step (1) in 1, 2-dichloroethane, wherein the solid-liquid ratio is 1:3-1:8, adding a catalyst, keeping the system temperature at 40-48 ℃ for 1.5-2.5h, heating to 60-80 ℃ for heat preservation reaction for 3-9 h, and carrying out solid-liquid separation to obtain solid which is ultrahigh crosslinked adsorption resin, wherein the catalyst is anhydrous aluminum chloride, and the dosage of the anhydrous aluminum chloride is 0.75-3% of the mass of the 1, 2-dichloroethane.
2. The use according to claim 1, wherein step (2) comprises the specific steps of: swelling the chloromethyl crosslinked polystyrene microsphere obtained in the step (1) in 1, 2-dichloroethane, adding a catalyst, maintaining the system temperature at 45 ℃ for 2 hours, heating to 70 ℃ for heat preservation reaction for 6 hours, and then carrying out solid-liquid separation to obtain the solid which is the ultrahigh crosslinked adsorption resin.
3. The use according to claim 1, wherein the biomass hydrolysate is bagasse hydrolysate, straw hydrolysate or eucommia hydrolysate.
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| CN110627753A (en) * | 2019-09-16 | 2019-12-31 | 中国科学院广州能源研究所 | Method for circularly preparing levulinic acid and furfural |
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| CN102391407A (en) * | 2011-09-26 | 2012-03-28 | 南京大学 | Ultrahigh crosslinked resin for separating and recovering medium and high concentration volatile organic compounds (VOCs), and preparation method and application of resin |
| CN110627753A (en) * | 2019-09-16 | 2019-12-31 | 中国科学院广州能源研究所 | Method for circularly preparing levulinic acid and furfural |
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