WO2022134443A1 - 一种碳基固体酸催化剂和制备方法及其应用于生物质水热转化的方法 - Google Patents

一种碳基固体酸催化剂和制备方法及其应用于生物质水热转化的方法 Download PDF

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WO2022134443A1
WO2022134443A1 PCT/CN2021/094791 CN2021094791W WO2022134443A1 WO 2022134443 A1 WO2022134443 A1 WO 2022134443A1 CN 2021094791 W CN2021094791 W CN 2021094791W WO 2022134443 A1 WO2022134443 A1 WO 2022134443A1
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carbon
acid catalyst
based solid
pectin
solid acid
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French (fr)
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王树荣
熊珊珊
徐昊
朱玲君
李允超
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浙江大学
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Priority to JP2022514170A priority Critical patent/JP7339631B2/ja
Priority to US17/622,262 priority patent/US20220395818A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C07D307/50—Preparation from natural products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to the technical field of preparation of green and energy-saving chemical materials, and mainly relates to the use of pectin-rich radical groups, the preparation of carbon-based solid acid catalysts by using common pectin as a precursor, and the addition of aromatic ring matrix ionic resins to strengthen the catalyst effect.
  • the prepared catalyst can be effectively applied to common biomass hydrothermal depolymerization catalytic reaction to achieve the purpose of efficiently producing valuable platform compounds.
  • Bronsted acid (hydrochloric acid, sulfuric acid, acetic acid, bicarbonate, ammonium ion) and Lewis acid (aluminum chloride, ferric chloride, boron trifluoride, niobium pentachloride and trifluoromethanesulfonic acid of lanthanides) Salt) catalysts participate in the catalytic process in the form of molecules or ions, so they can exhibit superior acidic catalytic performance at lower reaction temperatures.
  • liquid acid catalysts are often used. Although they have a large number of active centers, they will seriously corrode equipment, and the liquid catalysts are difficult to recover and reuse. There are also many by-products, and the products are difficult to separate. . Therefore, through the combination of the carrier and the active group, the solid catalyst has Bronsted acid or (and) Lewis acid acidity, forming a solid acid catalyst that is currently being used in the chemical industry and gradually replacing the traditional liquid catalyst.
  • solid acid catalysts have been developed, their large-scale industrial application is also difficult due to the limitation of some influencing factors.
  • supported metal oxide catalysts are often used in various important chemical fields such as hydrogenation, dehydrogenation, hydrogenolysis, synthesis, hydrolysis, and carbonylation.
  • metal catalysts, especially precious metal catalysts have expensive raw materials and high preparation costs, which limit their large-scale industrial application.
  • impurities in the reaction raw materials and solid by-products are easily attached to the surface of the catalyst, resulting in easy deactivation of the catalyst, and the fine powder catalyst is easily lost during the recovery process, resulting in a decrease in the cycle performance of the catalyst. load, its number of active centers is limited, so its activity is limited.
  • carbon-based solid acid catalysts In order to overcome the high cost of metal catalysts and the loss of fine powder catalysts, in recent years, in order to reduce costs and improve the performance of acid catalysts, carbon-based solid acid catalysts have been rapidly developed.
  • the so-called carbon-based catalysts are aromatic hydrocarbons or sugars
  • the compound is not completely carbonized to form a stable polycyclic aromatic hydrocarbon carbon, and then the acid active center is loaded through sulfonation, in which the sulfonic acid group is combined with the polycyclic aromatic hydrocarbon carbon through a covalent bond, which can not only achieve high-strength acidity similar to sulfuric acid, but also sulfonic acid.
  • the group grafting is more stable, and it is a green and energy-saving solid sulfonic acid material with great application potential.
  • the purpose of the present invention is to solve the problems in the prior art, propose a carbon-based solid acid catalyst and a preparation method and a method for its application in the hydrothermal conversion of biomass, using pectin with more active groups as a carbon-based precursor , using carbon-based solid acid enhanced by ionic resin with aromatic ring structure as catalyst to realize the catalytic conversion of biomass hydrothermal depolymerization into high-value platform compounds under mild conditions.
  • the present invention proposes a method for preparing a carbon-based solid acid catalyst.
  • Pectin is used as a carbon-based precursor, the pectin and the ionic resin of the aromatic ring matrix are mixed in a medium and then dried, and the dried resultant is dried. Pyrolysis is carried out, and concentrated sulfuric acid is used for sulfonation treatment to obtain a carbon-based solid acid catalyst.
  • the concrete preparation method comprises the following steps:
  • step S2 drying the obtained material in step S1, pulverizing the obtained material into powder, and pyrolyzing under dry inert gas;
  • step S4 the obtained product of step S3 is diluted with water and filtered, and the filtered residue is washed with water until sulfate ions are no longer detected in the washing water;
  • the concrete preparation method comprises the following steps:
  • the mass ratio of pectin and water is 1:4 ⁇ 10, then add sulfuric acid for activation, and then add the mixture to the ionic resin of the aromatic ring matrix, and the mass ratio of ionic resin and pectin is 1:0.5 ⁇ 3;
  • step S2 Dry the obtained material in step S1, pulverize the obtained black material into powder, and pyrolyze it under dry inert gas for 0.5-3 h;
  • step S3 The solid obtained after the pyrolysis of step S2 is subjected to sulfonation treatment with concentrated sulfuric acid at 20 to 120°C;
  • step S4 the obtained product of step S3 is diluted with water and filtered, and the filtered residue is washed with water until sulfate ions are no longer detected in the washing water;
  • the sulfuric acid is 98% sulfuric acid in mass fraction, and the volume ratio of the added amount of sulfuric acid to water is 1:30; the present invention does not specifically limit pectin, commercially available dry pectin and fresh
  • the prepared moist pectin with moisture can be used.
  • the pectin is fruit pectin, including orange peel pectin, grapefruit peel pectin, lemon peel pectin, apple pectin, and banana peel pectin. one or more.
  • step S2 the product obtained in step S1 is dried to constant weight at 110-120 °C, the pyrolysis is carried out in a horizontal tube furnace, the inert gas is nitrogen, and the pyrolysis temperature is 300-800 °C °C, the time is 1 to 2 hours, preferably the pyrolysis temperature is 300°C, and the time is 1 hour.
  • the mass ratio of the solid obtained after pyrolysis in step S2 to concentrated sulfuric acid is 1:3 to 8, and concentrated sulfuric acid is used to carry out sulfonation treatment in an oil bath with magnetic stirring, and the sulfonation temperature
  • the temperature is 80°C
  • the sulfonation time is 10-48h (preferably 24h)
  • the concentrated sulfuric acid is sulfuric acid with a mass fraction of 98%.
  • the ionic resin of the aromatic ring matrix includes one or more of sulfonic acid styrene-divinylbenzene cation exchange resin and chloromethylated polystyrene resin, sulfonic acid styrene-divinylbenzene
  • the cation exchange resins are preferably Amberlyst type 15 and type 732 strong acid styrene cation exchange resins.
  • the chloromethylated polystyrene resin is preferably a Merrifield polypeptide resin.
  • step S5 drying is performed in an oven, and the temperature is preferably 80°C.
  • the present invention also provides a carbon-based solid acid catalyst prepared by the above preparation method.
  • the catalyst particles are distinct, not easy to run off, and easy to recycle.
  • the present invention also proposes a method for applying the carbon-based solid acid catalyst obtained by the above preparation method to the hydrothermal conversion of biomass. Internal mixing, hydrothermal transformation and obtaining furan-like platform compounds.
  • the organic solvent includes ⁇ -valerolactone (GVL), dimethyl sulfoxide (DMSO), isopropanol, methyl isobutyl (methyl) ketone (MIBK), tetrahydrofuran (THF), N, One or more of N-dimethylformamide (DMF).
  • VL ⁇ -valerolactone
  • DMSO dimethyl sulfoxide
  • MIBK methyl isobutyl (methyl) ketone
  • THF tetrahydrofuran
  • N N-dimethylformamide
  • the product yield is further enhanced by adding a chloride salt, and the chloride salt includes one or more of sodium chloride, potassium chloride, copper chloride, and aluminum chloride. kind.
  • the biomass raw material includes one or more of glucose, xylose, arabinose, cellobiose, inulin, corn starch, fruit peel, and crop straw;
  • the carbohydrate compound includes glucose, xylose, One or more of disaccharides, polysaccharides.
  • the furan-based platform compound is furfural or pentahydroxymethyl furfural.
  • the object of the present invention is to provide a method for preparing a carbon-based solid acid catalyst, which can obtain a carbon-based solid that uses pectin with more active groups and weak acidity as a precursor, and is enhanced by an ionic resin with an aromatic ring structure. Acid is the catalyst.
  • an organic solvent is proposed as the main solvent system. As the main solvent system, the prepared carbon-based solid acid catalyst was used to realize the catalytic conversion of biomass hydrothermal depolymerization into high-value platform compounds under mild conditions.
  • pectin contains a large amount of galacturonic acid, has a considerable number of carboxyl groups, and itself has weak acidity, and the active sites of strong and weak acidity play an important role in the hydrothermal depolymerization of biomass, so pectin is used as the One of the biggest advantages of acidic catalysts is the utilization of their weak acidity.
  • the catalyst recovery rate is close to 90%.
  • the catalyst particles are distinct, not easy to be lost, and easy to recover.
  • the catalyst can also show high performance in the water phase. By adding sodium chloride, the water phase and the organic phase can be separated, and the catalytic performance can be improved, and the water phase and sodium chloride can be recycled.
  • the carbonization temperature is relatively low, and the preparation process is green and environmentally friendly.
  • pectin rich in active groups with weak acidity as a precursor to prepare catalyst supports can not only achieve effective active group grafting, but also provide weak acidity for the hydrothermal depolymerization process.
  • the prepared catalyst can simultaneously realize the hydrothermal conversion of five-carbon sugar and six-carbon sugar, and achieve the purpose of preparing high-value platform compounds.
  • Fig. 1 is the electron microscope image of the carbon-based solid acid catalyst prepared by the embodiment of the present invention 1 with a magnification of 30,000 times;
  • Fig. 2 is the electron microscope image of the carbon-based solid acid catalyst prepared in Example 1 of the present invention, which is magnified 10,000 times;
  • Fig. 4 is the infrared spectrogram of the carbon-based solid acid catalyst prepared in Example 1 of the present invention.
  • FIG. 5 is an infrared spectrogram of the catalyst of Comparative Example 4.
  • the invention uses pectin with a large number of active groups as the carbon-based precursor, and at the same time adds an ionic resin with an aromatic ring structure as a matrix to help expand the liquid phase and improve the availability of acid sites on the surface of the solid acid.
  • an ionic resin with an aromatic ring structure as a matrix to help expand the liquid phase and improve the availability of acid sites on the surface of the solid acid.
  • a high-activity carbon-based solid acid catalyst with strong adaptability and good recovery performance can be obtained.
  • there is no carbon-based solid acid catalyst preparation technology similar to the present invention which uses the same carbon source and uses the aromatic ring matrix ion resin combined with the pectin carbon-based carrier.
  • the effect of the catalyst prepared by the present invention is obviously improved, and it can show good catalytic performance under various reaction conditions.
  • the invention provides a preparation method of a carbon-based solid acid catalyst.
  • Pectin is used as a carbon-based precursor, the pectin and the ionic resin of the aromatic ring matrix are mixed in a medium and then dried, the dried result is pyrolyzed, and the Concentrated sulfuric acid is sulfonated to obtain a carbon-based solid acid catalyst. Include the following steps:
  • step S2 drying the obtained material in step S1, pulverizing the obtained material into powder, and pyrolyzing under dry inert gas;
  • step S3 the solid obtained after step S2 pyrolysis is carried out sulfonation treatment with vitriol oil;
  • the concrete preparation method comprises the following steps:
  • the mass ratio of pectin and water is 1:4 ⁇ 10, then add sulfuric acid for activation, and then add the mixture into the ionic resin of the aromatic ring matrix, and the mass ratio of ionic resin and pectin is 1:0.5 ⁇ 3;
  • the sulfuric acid is 98% sulfuric acid, and the pectin is fruit pectin, including one or more of orange peel pectin, grapefruit peel pectin, lemon peel pectin, apple pectin, and banana peel pectin. kind.
  • step S2 Dry the material obtained in step S1 at 110-120° C. to constant weight, pulverize the obtained black material into powder, and pyrolyze it under dry inert gas for 0.5-3 hours, and the pyrolysis is carried out in a horizontal tube furnace , the pyrolysis temperature is 300 ⁇ 800°C;
  • step S3 The solid obtained after the pyrolysis of step S2 is subjected to sulfonation treatment with concentrated sulfuric acid at 20 to 120°C;
  • step S4 the obtained product of step S3 is diluted with water and filtered, and the filtered residue is washed with water until sulfate ions are no longer detected in the washing water;
  • step S2 the inert gas is nitrogen, the pyrolysis temperature is 300°C, and the time is 1 h.
  • step S3 the mass ratio of the solid obtained after the pyrolysis in step S2 to the concentrated sulfuric acid is 1:3 to 8, and the concentrated sulfuric acid is used for sulfonation treatment in an oil bath with magnetic stirring, and the sulfonation temperature is is 80° C., the sulfonation time is 10-48 h, and the concentrated sulfuric acid is sulfuric acid with a mass fraction of 98%.
  • the ionic resin of the aromatic ring matrix includes one or more of sulfonic acid styrene-divinylbenzene cation exchange resin and chloromethylated polystyrene resin.
  • the present invention also provides a carbon-based solid acid catalyst prepared by the above preparation method.
  • the present invention also proposes a method for applying the carbon-based solid acid catalyst obtained by the above preparation method to the hydrothermal conversion of biomass. Internal mixing, hydrothermal transformation and obtaining furan-like platform compounds.
  • the carbon-based solid acid catalyst and the biomass raw material are mixed in a solvent system and subjected to hydrothermal conversion, wherein the mass ratio of the carbon-based solid acid catalyst to the biomass raw material is 1:1-10, and the reaction temperature is 120-190 °C, the time is 0.5 to 3 hours, the concentration of the raw materials after mixing is 0.012 to 0.32 g/ml, and the solvent system is an organic solvent, water or a mixture of the two.
  • the organic solvent includes ⁇ -valerolactone (GVL), dimethyl sulfoxide (DMSO), isopropanol, methyl isobutyl (methyl) ketone (MIBK), tetrahydrofuran (THF), N, N - One or more of dimethylformamide (DMF).
  • the biomass raw material includes one or more of glucose, xylose, arabinose, cellobiose, inulin, corn starch, fruit peel, and crop straw; the carbohydrate compound includes glucose, xylose, disaccharide, One or more of the polysaccharides.
  • the furan-based platform compound is furfural or pentahydroxymethyl furfural.
  • the product yield is further enhanced by adding a chloride salt, the chloride salt comprising one of sodium chloride, potassium chloride, copper chloride, aluminum chloride or several.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g of xylose and 5ml of ⁇ -valerolactone, react under microwave heating for 1h, and at a reaction temperature of 140 ⁇ 180°C, the furfural yields are all higher than 71mol. %, the highest yield can reach 85mol.%.
  • the catalyst prepared by the present invention has a well-developed pore structure, with a large number of micropores, mesopores and macropore structures, which is very beneficial to the grafting of active groups and the conversion of reactants, and the structure
  • the unit is clear and regular, which is conducive to the regulation of catalyst acidity. Therefore, it is confirmed that pectin is easy to form a reasonable pore structure when used as a carbon-based support, and its advantages and application potential as a solid acid carbon-based support are confirmed.
  • Table 1 shows the acidity test results of the catalyst prepared in Example 1 of the present invention, and the acidity test of pure pectin. The results show that the catalyst prepared by the present invention not only has a reasonable acidity, but also confirms that the pectin itself has a certain degree of acidity. The weak acidity is favorable for the preparation of carbon-based solid acids.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g of xylose and 5ml of ⁇ -valerolactone, and react under microwave heating for 1 hour. At a reaction temperature of 190°C, the yield of furfural is 69.8mol.%.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g xylose, 2ml ⁇ -valerolactone and 3ml deionized water, react under microwave heating for 1h, and at a reaction temperature of 170°C, the furfural yield is 52.9 mol.%.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g xylose, 4ml ⁇ -valerolactone and 1ml deionized water, and add 0.16g NaCl, react under microwave heating for 1h, and at a reaction temperature of 170°C, The furfural yield was 70.6 mol.%.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g of xylose and 5ml of dimethyl sulfoxide, react under microwave heating for 1 hour, and at a reaction temperature of 170°C, the furfural yield is 74.3 mol.%.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.16g of xylose and 5ml of dimethyl sulfoxide, and react under microwave heating for 1 hour. At a reaction temperature of 170 °C, the furfural yields are both 69.2 mol.% .
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g of xylose and 5ml of ⁇ -valerolactone, and react under microwave heating for 1 hour. At a reaction temperature of 170°C, the furfural yield is 77.6 mol.%.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g glucose, 4ml tetrahydrofuran and 1ml deionized water, then add 0.16g NaCl, and react under microwave heating conditions for 1h.
  • the base furfural yield was 33.1 mol.%.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g of xylose and 5ml of ⁇ -valerolactone, react under microwave heating for 0.5h, and at a reaction temperature of 170°C, furfural yield is 70.6mol.%.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g xylose, 4ml ⁇ -valerolactone and 1ml deionized water, and add 0.16g NaCl, react under microwave heating for 1h, and at 170°C reaction temperature, The furfural yield was 68.7 mol.%.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g of xylose and 5ml of ⁇ -valerolactone, and react under microwave heating for 3h. At a reaction temperature of 170°C, the furfural yield is 65.5mol.%.
  • Pectin-like substances can be seen to precipitate during the alcohol addition process. After standing for 20 minutes, filter with nylon cloth, transfer the filter residue to a 100ml beaker, add 30ml of absolute ethanol for washing, and then filter and squeeze with nylon cloth to obtain a wet solution. pectin.
  • the obtained black substance was collected by filtration and washed several times with deionized water until sulfate ions were no longer detected in the washing water.
  • the resulting black solid was dried in an oven at 80°C for 24 hours. Take 0.05g of the obtained black solid into a 10ml test tube, add 0.1g of xylose and 5ml of ⁇ -valerolactone, react under microwave heating for 1h, and at a reaction temperature of 180°C, the furfural yield is 71mol.%.
  • the carbon-based solid acid catalyst prepared with pectin can not only optimize the distribution of acidic sites, but also ensure a sufficiently developed pore structure and abundant free radicals, which is very beneficial to the grafting of active groups.
  • Fig. 5 is the FTIR chart of the catalyst.
  • the characteristic peak of its active group is obviously not as obvious as that of the present invention, especially the characteristic peak of -OH. Its catalytic effect is also proved to be worse than that of this paper.
  • the highest yield is 75.8% at 180° C. for 8 hours, while the catalyst prepared by the present invention can reach 85% of furfural yield at 170° C. for 1 hour. This further proves the superiority of pectin as a carbon-based solid acid carrier.

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Abstract

本发明提出了一种碳基固体酸催化剂和制备方法及其应用于生物质水热转化的方法，其中该碳基固体酸催化剂的制备方法，包括以下步骤：将果胶与水混合，再加入浓硫酸活化，然后将混合物加入芳香环基质的离子树脂中；将获得物干燥，得到的物质粉碎成粉末，在干燥惰性气体下热解；将热解后所获得的固体用浓硫酸进行磺化处理；获得物用水稀释后过滤，过滤后的滤渣用水洗涤，直到洗涤水中不再检测到硫酸盐离子；将过滤所得固体干燥。所制备的催化剂颗粒分明，不易流失，便于回收。并且所制备的催化剂能够同时实现五碳糖和六碳糖的水热转化，实现制备高价值平台化合物的目的。

Description

一种碳基固体酸催化剂和制备方法及其应用于生物质水热转化的方法 【技术领域】
本发明涉及绿色节能化工材料制备的技术领域，主要涉及到利用果胶丰富的自由基团，以常见果胶为前驱体制备碳基固体酸催化剂，加入芳香环基质的离子树脂强化催化剂效果，所制备的催化剂能有效应用于常见生物质水热解聚催化反应，以实现高效生产有价值的平台化合物的目的。
【背景技术】
面对世界性能源短缺和环境污染的问题，人类环保意识和节约能源的意识逐渐加强，因此，化学工业中的污染问题得到了越来越多的关注。为了响应国家“供社会绿色光热，还地球碧水蓝天”的环保能源号召，更多的科学研究者致力于发展绿色节能的原子经济，提倡零排放的反应工程，推荐使用资源丰富且无毒无害的反应原料，追求环境友好的高价值产品。
在化学工业中，固体催化剂逐渐取代了传统的均相催化剂。与均相催化剂相比，固体催化剂易于与反应原料和产物分离，便于回收和循环使用，同时，多相催化剂还具有副产物少，成本较低等优势，因此对能源开发和环境保护等都具有重要意义。目前，一些重要的反应过程，如水解、合成、酯化、脱氢和烷基化反应，都致力于开发绿色高效的酸性催化剂。其中，Bronsted酸(盐酸、硫酸、醋酸、碳酸氢根、铵根离子)和Lewis酸(氯化铝、氯化铁、三氟化硼、五氯化铌以及镧系元素的三氟甲磺酸盐)催化剂，以分子或离子形式参与催化过程，因此能在较低的反应温度下展现优越的酸性催化性能。在传统的化学工艺中，常使用液态的酸性催化剂，其虽具有数目庞大的活性中心，但会对设备腐蚀严重，且液态催化剂难以回收二次利用，还存在副产物多，产品难以分离等问题。因此，通过载体与活性基团的结合，使固体催化剂具有Bronsted酸或(和)Lewis酸酸性，形成现在的化学工业中正在使用，并逐步取代传统液态催化剂的固体酸催化剂。
固体酸催化剂虽然得到了发展，但由于一些影响因素的限制，其大规模的工业化应用也有一定的难度。例如负载型金属氧化物催化剂常应用于加氢、脱氢、氢解、合成、水解、羰基化等多种重要的化工领域。但金属催化剂，尤其是贵金属催化剂原料昂贵，制备成本较高，限制了其大规模工业化应用。此外，反应原料的杂质以及固体副产物容易附着在催化剂表面，导致催化剂容易失活，且粉质较细的催化剂在回收过程中容易流失，导致催化剂的循环性能降低，此外，活性基团通过人为负载，其活性中心数目有限，因此其活性受限。为了克服金属催化剂的高成本，以及粉质较细的催化剂流失现象，近年来，为了降低成本，提高酸性催化剂的性能，碳基固体酸催化剂得到快速发展，所谓碳基催化剂，即将芳烃或糖类化合物不完全碳化，形成稳定的多环芳烃碳，再后续通过磺化负载酸性活性中心，其中磺酸根通过共价键与多环芳烃碳结合，不仅能实现类似硫酸的高强度酸性，且磺酸基团嫁接更为稳定，是一种绿色节能的固态磺酸材料，具有很大的应用潜力。
【发明内容】
本发明的目的就是解决现有技术中的问题，提出一种碳基固体酸催化剂和制备方法及其应用于生物质水热转化的方法，以活性基团较多的果胶为碳基前驱体，以芳香环结构的离子树脂强化性能的碳基固体酸为催化剂，实现在温和条件下将生物质水热解聚催化转化为高价 值平台化合物。
为实现上述目的，本发明提出了一种碳基固体酸催化剂的制备方法，以果胶为碳基前驱体，将果胶与芳香环基质的离子树脂在介质中混合后干燥，将干燥所得物进行热解，使用浓硫酸进行磺化处理，得到碳基固体酸催化剂。
作为优选，具体制备方法包括以下步骤：
S1.将果胶与水混合，再加入硫酸活化，然后将混合物加入芳香环基质的离子树脂中；
S2.将步骤S1的获得物干燥，得到的物质粉碎成粉末，在干燥惰性气体下热解；
S3.将步骤S2热解后所获得的固体用浓硫酸进行磺化处理；
S4.将步骤S3的获得物用水稀释后过滤，过滤后的滤渣用水洗涤，直到洗涤水中不再检测到硫酸根离子；
S5.将过滤所得固体干燥。
作为优选，具体制备方法包括以下步骤：
S1.果胶与水混合的质量比为1：4～10，再加入硫酸活化，然后将混合物加入芳香环基质的离子树脂中，离子树脂与果胶的质量比为1：0.5～3；
S2.将步骤S1的获得物干燥，得到的黑色物质粉碎成粉末，在干燥惰性气体下热解0.5～3h；
S3.将步骤S2热解后所获得的固体用浓硫酸在20～120℃条件下，进行磺化处理；
S4.将步骤S3的获得物用水稀释后过滤，过滤后的滤渣用水洗涤，直到洗涤水中不再检测到硫酸根离子；
S5.将过滤所得固体烘干。
作为优选，步骤S1中，所述硫酸是质量分数为98％的硫酸，硫酸的加入量与水的体积比为1：30；本发明不对果胶做特别限定，市售的干燥果胶以及新制备的带有水分的湿润果胶皆可，作为优选，所述果胶为水果果胶，包括橘皮果胶、柚子皮果胶、柠檬皮果胶、苹果果胶、香蕉皮果胶中的一种或几种。
作为优选，步骤S2中，步骤S1的获得物是在110～120℃下干燥至恒重，所述热解在卧式管式炉中进行，惰性气体为氮气，热解的温度为300～800℃，时间为1～2h，优选热解的温度为300℃，时间为1h。
作为优选，步骤S3中，步骤S2热解后所获得的固体与浓硫酸的质量比为1：3～8，用浓 硫酸在带有磁力搅拌的油浴锅中进行磺化处理，磺化温度为80℃，磺化时间为10～48h(优选24h)，所述浓硫酸为质量分数为98％的硫酸。
作为优选，所述芳香环基质的离子树脂包括磺酸型苯乙烯-二乙烯苯阳离子交换树脂和氯甲基化聚苯乙烯树脂中的一种或几种，磺酸型苯乙烯-二乙烯苯阳离子交换树脂优选Amberlyst 15型和732型强酸苯乙烯阳离子交换树脂。氯甲基化聚苯乙烯树脂优选为Merrifield多肽树脂。
作为优选，步骤S5中在烘箱中进行干燥，温度优选80℃。
此外，本发明还提出了一种采用上述制备方法所制得的碳基固体酸催化剂。该催化剂颗粒分明，不易流失，便于回收。
本发明还提出了一种应用上述制备方法获得的碳基固体酸催化剂应用于生物质水热转化的方法，采用所述碳基固体酸催化剂作为催化剂，与生物质原料或糖类化合物在溶剂系统内混合，水热转化并获得呋喃类平台化合物。
作为优选，将碳基固体酸催化剂与生物质原料在溶剂系统内混合并进行水热转化，其中，碳基固体酸催化剂与生物质原料质量比为1：1～10，反应温度为120～190℃，时间为0.5～3h，混合后原料的浓度为0.012～0.32g/ml，所述溶剂系统为有机溶剂、水或两者混合。
作为优选，所述有机溶剂包括γ-戊内酯(GVL)、二甲基亚砜(DMSO)、异丙醇、甲基异丁基(甲)酮(MIBK)、四氢呋喃(THF)、N、N-二甲基甲酰胺(DMF)中的一种或几种。
作为优选，使用水和有机溶剂两相溶剂系统时，通过加入氯盐进一步加强产物产率，所述氯盐包括氯化钠、氯化钾、氯化铜、氯化铝中的一种或几种。
作为优选，所述生物质原料包括葡萄糖、木糖、阿拉伯糖、纤维二糖、菊粉、玉米淀粉、果皮、作物秸秆中的一种或几种；所述糖类化合物包括葡萄糖，木糖，双糖，多糖中的一种或几种。
作为优选，所述呋喃类平台化合物为糠醛或五羟甲基糠醛。
本发明的目的在于提供一种碳基固体酸催化剂的制备方法，可获得以活性基团较多且本 身具有弱酸性的果胶为前驱体，通过芳香环结构的离子树脂强化性能的碳基固体酸为催化剂。并针对现有碳基催化剂在生物质水热解聚催化反应中的不足之处，包括载体活性较低，酸性活性基团嫁接数目有限，催化剂活性需要进一步优化等问题，提出一种以有机溶剂为主的溶剂系统，使用制备的碳基固体酸催化剂实现在温和条件下将生物质水热解聚催化转化为高价值平台化合物。其中果胶中含有大量的半乳糖醛酸，具有可观的羧基基团数量，本身具有弱酸性，而生物质水热解聚中强弱酸性的活性位点分别发挥重要作用，因此使用果胶作为酸性催化剂的最大优势之一即为其本身的弱酸性的利用。
本发明的有益效果：
1.可实现高达85mol.％的糠醛产率。
2.适用于多种反应参数，140～180℃下即可实现70mol.％的糠醛产率。
3.催化剂回收率接近90％。
本发明具有以下优势：
1.催化剂颗粒分明，不易流失，便于回收。
2.催化剂在水相中亦可展现较高性能，通过加入氯化钠可使水相和有机相分离，并提高催化性能，并且水相和氯化钠可以循环利用。
3.碳化温度相对较低，制备过程绿色环保。
4.使用具有弱酸性的活性基团丰富的果胶作为前驱体制备催化剂载体，不仅能实现有效的活性基团嫁接，载体本身还能为水热解聚过程提供弱酸性。
5.所制备的催化剂能够同时实现五碳糖和六碳糖的水热转化，实现制备高价值平台化合物的目的。
6.生产工艺简单，便于规模化生产。
本发明的特征及优点将通过实施例结合附图进行详细说明。
【附图说明】
图1为本发明实施例1所制备的碳基固体酸催化剂的放大30000倍的电镜图；
图2为本发明实施例1所制备的碳基固体酸催化剂的放大10000倍的电镜图；
图3为反应后的两相溶剂系统，有机相为γ-戊内酯，水相中加入了0.16g氯化钠促使分层，有机：水＝4：1(ml)；
图4为本发明实施例1所制备的碳基固体酸催化剂的红外光谱图；
图5为对比例4的催化剂的红外光谱图。
【具体实施方式】
本发明利用活性基团数目较多的果胶作为碳基前驱体，同时加入以芳香环状结构为基质 的离子树脂帮助膨胀液相，提高固体酸表面酸性位点的可用性，在300～800℃的温和条件下绝氧碳化，经研磨后使用浓硫酸磺化可得到适应性强、回收性能好的高活性碳基固体酸催化剂。从已有的专利技术和文献报道来看，尚未有与本发明类似的技术使用相同碳源，并使用芳香环基质离子树脂与果胶碳基载体结合的碳基固体酸催化剂制备技术。本发明所制备的催化剂效果明显提升，且在多种反应工况下均能展现较好的催化性能，催化剂不易结焦，颗粒分明，便于回收再生，具体效果将在实施例中详细说明。
本发明提出了一种碳基固体酸催化剂的制备方法，以果胶为碳基前驱体，将果胶与芳香环基质的离子树脂在介质中混合后干燥，将干燥所得物进行热解，使用浓硫酸进行磺化处理，得到碳基固体酸催化剂。包括以下步骤：
S1.将果胶与水混合，再加入硫酸活化，然后将混合物加入芳香环基质的离子树脂中；
S2.将步骤S1的获得物干燥，得到的物质粉碎成粉末，在干燥惰性气体下热解；
S3.将步骤S2热解后所获得的固体用浓硫酸进行磺化处理；
S4.将步骤S3的获得物用水稀释后过滤，过滤后的滤渣用水洗涤，直到洗涤水中不再检测到硫酸根离子；
S5.将过滤所得固体干燥。
进一步地，具体制备方法包括以下步骤：
S1.果胶与水混合的质量比为1：4～10，再加入硫酸活化，然后将混合物加入芳香环基质的离子树脂中，离子树脂与果胶的质量比为1：0.5～3；所述硫酸是质量分数为98％的硫酸，所述果胶为水果果胶，包括橘皮果胶、柚子皮果胶、柠檬皮果胶、苹果果胶、香蕉皮果胶中的一种或几种。
S2.将步骤S1的获得物在110～120℃下干燥至恒重，得到的黑色物质粉碎成粉末，在干燥惰性气体下热解0.5～3h，所述热解在卧式管式炉中进行，热解的温度为300～800℃；
S3.将步骤S2热解后所获得的固体用浓硫酸在20～120℃条件下，进行磺化处理；
S4.将步骤S3的获得物用水稀释后过滤，过滤后的滤渣用水洗涤，直到洗涤水中不再检测到硫酸根离子；
S5.将过滤所得固体烘干。
进一步地，步骤S2中，惰性气体为氮气，热解的温度为300℃，时间为1h。
进一步地，步骤S3中，步骤S2热解后所获得的固体与浓硫酸的质量比为1：3～8，用浓硫酸在带有磁力搅拌的油浴锅中进行磺化处理，磺化温度为80℃，磺化时间为10～48h，所述浓硫酸为质量分数为98％的硫酸。
进一步地，所述芳香环基质的离子树脂包括磺酸型苯乙烯-二乙烯苯阳离子交换树脂和氯甲基化聚苯乙烯树脂中的一种或几种。
此外，本发明还提出了一种采用上述制备方法所制得的碳基固体酸催化剂。
本发明还提出了一种应用上述制备方法获得的碳基固体酸催化剂应用于生物质水热转化的方法，采用所述碳基固体酸催化剂作为催化剂，与生物质原料或糖类化合物在溶剂系统内混合，水热转化并获得呋喃类平台化合物。
具体方法：将碳基固体酸催化剂与生物质原料在溶剂系统内混合并进行水热转化，其中，碳基固体酸催化剂与生物质原料质量比为1：1～10，反应温度为120～190℃，时间为0.5～3h，混合后原料的浓度为0.012～0.32g/ml，所述溶剂系统为有机溶剂、水或两者混合。其中，所述有机溶剂包括γ-戊内酯(GVL)、二甲基亚砜(DMSO)、异丙醇、甲基异丁基(甲)酮(MIBK)、四氢呋喃(THF)、N、N-二甲基甲酰胺(DMF)中的一种或几种。所述生物质原料包括葡萄糖、木糖、阿拉伯糖、纤维二糖、菊粉、玉米淀粉、果皮、作物秸秆中的一种或几种；所述糖类化合物包括葡萄糖，木糖，双糖，多糖中的一种或几种。所述呋喃类平台化合物为糠醛或五羟甲基糠醛。
更进一步地，使用水和有机溶剂两相溶剂系统时，通过加入氯盐进一步加强产物产率，所述氯盐包括氯化钠、氯化钾、氯化铜、氯化铝中的一种或几种。
为了更清晰的说明本发明的内容，将以下实施例作详细说明，但是本发明不限于所举实施例，不应以此限制本发明的保护范围。
实施例1：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和5mlγ-戊内酯，在微波加热条件下反应1h，在140～180℃反应温度下，糠醛产率均高于71mol.％，最高产率可达85mol.％。
参阅图1、图2的电镜图，可见本发明所制备的催化剂孔道结构发达，存在大量的微孔、介孔和大孔结构，非常有利于活性基团的嫁接和反应物的转化，且结构单元清晰规整，有利于催化剂酸性调控，因此证实果胶作为碳基载体时，易于形成合理的孔道结构，证实其作为固体酸碳基载体的优势和应用潜力。
参阅图4，红外光谱图中显示催化剂中含有大量的-OH，认为这些羟基主要来源于果胶表面大量的活性基团，且存在大量的弱酸性基团-COOH，此外，催化剂也成功嫁接了数量可观的O＝S＝O基团和-SO 3H基团，证实了果胶作为固体酸碳基载体时，其本身存在的弱酸性和大量的活性基团十分有利于酸性催化剂的制备以及酸性位点的嫁接及合理分布。
表1
Figure PCTCN2021094791-appb-000001
表1为本发明中实施例1所制备的催化剂的酸度测试结果，以及单纯果胶的酸度测试，其结果显示本发明所制备的催化剂不仅具有合理的酸度，同时也证实了果胶本身具有一定的弱酸性，有利于碳基固体酸的制备。
实施例2：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在100℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和5mlγ-戊内酯，在微波加热条件下反应1h，在130℃反应温度下，糠醛产率为57.6mol.％。
实施例3：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在450℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和5mlγ-戊内酯，在微波加热条件下反应1h，在190℃反应温度下，糠醛产率为69.8mol.％。
实施例4：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在800℃干燥氮气下在卧式管式炉中热解0.5h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和2mlγ-戊内酯和3ml去离子水，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率为52.9mol.％。
实施例5：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解3h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和4mlγ-戊内酯和1ml去离子水，并加入0.16gNaCl，在微波加热条件下反应1h，在170℃ 反应温度下，糠醛产率为70.6mol.％。
实施例6：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行36h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和5ml二甲基亚砜，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率为74.3mol.％。
实施例7：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解2h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.16g木糖和5ml二甲基亚砜，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率均为69.2mol.％。
实施例8：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在20℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.10g阿拉伯糖和5ml二甲基亚砜，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率均为32.09mol.％。
实施例9：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和5mlγ-戊内酯，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率为77.6mol.％。
实施例10：
2g干燥苹果果胶与20ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的4g 732强酸苯乙烯阳离子交换树脂中。在110～120℃下干燥24h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g阿拉伯糖和5mlγ-戊内酯，在微波加热条件下反应2h，在170℃反应温度下，糠醛产率为17.1mol.％。
实施例11：
2g干燥苹果果胶与15ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的1g Amberlyst离子树脂中。在110～120℃下干燥24h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行10h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g葡萄糖和4ml四氢呋喃和1ml去离子水，再加入0.16gNaCl，在微波加热条件下反应1h，在160℃反应温度下，5-羟甲基糠醛产率为33.1mol.％。
实施例12：
2g干燥柑橘果胶与20ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g 732强酸苯乙烯阳离子交换树脂中。在110～120℃下干燥24h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在90℃条件下进行48h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.15g木糖和5ml二甲基亚砜，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率为48.8mol.％。
实施例13：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/3g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.01g于10ml的试管中，加入0.1g木糖和5mlγ-戊内酯，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率为68.5mol.％。
实施例14：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和5mlγ-戊内酯，在微波加热条件下反应0.5h，在170℃反应温度下，糠醛产率为70.6mol.％。
实施例15：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和4mlγ-戊内酯和1ml去离子水，并加入0.16gNaCl，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率为68.7mol.％。
实施例16：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行 24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和5mlγ-戊内酯，在微波加热条件下反应3h，在170℃反应温度下，糠醛产率为65.5mol.％。
实施例17：
8g干燥橘皮果胶与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H 2SO 4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和4mlγ-戊内酯和1ml去离子水，并加入0.08gNaCl，在微波加热条件下反应1h，在170℃反应温度下，糠醛产率为66.7mol.％。
实施例18：
称取新鲜柑橘皮20g(干品为8g)，用清水洗净后，放入250ml烧杯中，加120ml水，加热至90℃保温5～10min，使酶失活。用水冲洗后切成3～5mm大小的颗粒，用50℃左右的热水漂洗，直至水为无色，果皮无异味为止。每次漂洗都要把果皮用尼龙布挤干，再进行下一次漂洗。将处理过的果皮粒放入烧杯中，加入0.2mol/的盐酸以浸没果皮为度，调溶液的2.0～2.5之间。加热至90℃，在恒温水浴中保温40min，保温期间要不断地搅动，趁热用垫有尼龙布(100目)的布氏漏斗抽滤，收集滤液。在滤液中加入0.5％～1％的活性炭，加热至80℃，脱色20min，趁热抽滤(如橘皮漂洗干净，滤液清澈，则可不脱色)。滤液冷却后，用6mol/L氨水调至pH 3～4，在不断搅拌下缓缓地加入95％酒精溶液，加入乙醇的量为原滤液体积的1.5倍(使其中酒精的质量分数达50％～60％)。酒精加入过程中即可看到状果胶物质析出，静置20min后，用尼龙布过滤，将滤渣转移至100ml烧杯中，加入30ml无水乙醇洗涤，再用尼龙布过滤、挤压制得湿果胶。将所制的9g湿果胶(也可使用8g干果胶，干果胶的制备方法是将湿果胶放入表面皿中摊开，在60～70℃烘干，将烘干的果胶磨碎过筛，制得干果胶。)与30ml去离子水混合，再加入1ml浓硫酸(98％)，然后将混合物缓慢加入预干燥的8g Amberlyst 15离子树脂中。在110～120℃下干燥48h，得到的黑色物质在300℃干燥氮气下在卧式管式炉中热解1h。用浓硫酸(1g固体/5g H2SO4)在80℃条件下进行24h的磺化处理，加热设备为带有磁力搅拌的油浴锅。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。得到的黑色固体在80℃的烘箱中干燥24小时。取所得的黑色固体0.05g于10ml的试管中，加入0.1g木糖和5mlγ-戊内酯，在微波加热条件下反应1h，在180℃反应温度下，糠醛产率为71mol.％。
对比例1
根据文献(Antonyraj C A,Haridas A.Catalysis Communications,2018,104:101-105.)报道，使用粗质木质素在立式管式炉中，氮气气氛下，于450℃热解1h。取3g所得的热解固体产物于150ml的圆底烧瓶中，加入100ml浓硫酸(98％)，于60℃油浴锅中磁力搅拌18h。用大量的去离子水稀释后，过滤收集得到的黑色物质，用去离子水洗涤数次，直到洗涤水中不再检测硫酸根离子。并于100℃的烘箱中干燥至恒重。取12ml 6.67wt.％木糖溶液(相当于加入的木糖质量为0.08g)，28ml MIBK，与0.2g上述所得催化剂混合，于175℃下反应3h，所得糠醛产率为58.8mol.％。
对比例2
根据文献(王莉，张朱.广州化工.2017，45(18):47-48.)和文献(周文俊,周宇,张霞忠,曾彬.高等学校化学学报.2016,37(4):669-673.)，二者均利用果胶作为载体制备催化剂，通过浸渍法利用果胶吸附活性基团，其与本发明中利用果胶作为碳基前驱体的应用方法完全不同，且果胶对其反应本身无任何催化效果，而本发明利用果胶本身具有的弱酸性，强化了催化剂 系统的酸性强度，并优化了催化剂的强弱酸性位点分布。且对比例文献中应用场合分别为苯甲醛氧化制苯甲酸和Suzuki反应，与本发明所制备催化剂应用的生物质水热转化领域完全不同。
对比例3
根据文献(Ma Y,You S,Jing B,et al.International journal of hydrogen energy.2019,44(31):16624-16638.)和文献(Fan Y,Liu P,Yang Z,et al.Electrochimica acta.2015,163:140-148.)，两篇报道文献利用果胶作为碳源制备了电极材料，但其是利用果胶具有凝胶、乳化和稳定功能，有利于引入二氧化硅模板和Fe物种，形成多孔结构。因此与本发明中的应用场合完全不同，且不同于本发明中充分利用果胶易于形成多孔结构的物理性质和弱酸性及表面活性基团丰富的化学性质，实现了对果胶的综合利用，使用果胶制备的碳基固体酸催化剂不仅能实现酸性位点分布优化，同时能保证足够发达的孔道结构和丰富的自由基，非常有利于活性基团的嫁接。
对比例4
根据文献(梁玉,陈志浩,梁宝炎,等.高等学校化学学报,2016,37(6):1123-1127.)其采用稻壳热解作为碳基固体酸催化剂的载体，催化木糖水热转化生产糠醛。图5为其催化剂的FTIR图，与本发明中的FTIR(图4)相比，其活性基团特征峰明显不如本发明的明显，尤其是-OH的特征峰。其催化效果也证实比本文差，其在180℃，8h时到最高产量75.8％，而本发明所制备的催化剂在170℃，1h时即可达到85％的糠醛产率。这也进一步证明了果胶作为碳基固体酸载体的优越性。
上述实施例是对本发明的说明，不是对本发明的限定，任何对本发明简单变换后的方案均属于本发明的保护范围。

Claims (14)

  1. 一种碳基固体酸催化剂的制备方法，其特征在于：以果胶为碳基前驱体，将果胶与芳香环基质的离子树脂在介质中混合后干燥，将干燥所得物进行热解，使用浓硫酸进行磺化处理，得到碳基固体酸催化剂。
  2. 如权利要求1所述的一种碳基固体酸催化剂的制备方法，其特征在于：
    具体制备方法包括以下步骤：
    S1.将果胶与水混合，再加入硫酸活化，然后将混合物加入芳香环基质的离子树脂中；
    S2.将步骤S1的获得物干燥，得到的物质粉碎成粉末，在干燥惰性气体下热解；
    S3.将步骤S2热解后所获得的固体用浓硫酸进行磺化处理；
    S4.将步骤S3的获得物用水稀释后过滤，过滤后的滤渣用水洗涤，直到洗涤水中不再检测到硫酸根离子；
    S5.将过滤所得固体干燥。
  3. 如权利要求1所述的一种碳基固体酸催化剂的制备方法，其特征在于：具体制备方法包括以下步骤：
    S1.果胶与水混合的质量比为1：4～10，再加入硫酸活化，然后将混合物加入芳香环基质的离子树脂中，离子树脂与果胶的质量比为1：0.5～3；
    S2.将步骤S1的获得物干燥，得到的黑色物质粉碎成粉末，在干燥惰性气体下热解0.5～3h；
    S3.将步骤S2热解后所获得的固体用浓硫酸在20～120℃条件下，进行磺化处理；
    S4.将步骤S3的获得物用水稀释后过滤，过滤后的滤渣用水洗涤，直到洗涤水中不再检测到硫酸根离子；
    S5.将过滤所得固体烘干。
  4. 如权利要求3所述的一种碳基固体酸催化剂的制备方法，其特征在于：步骤S1中，所述果胶包括橘皮果胶、柚子皮果胶、柠檬皮果胶、苹果果胶、香蕉皮果胶中的一种或几种。
  5. 如权利要求3所述的一种碳基固体酸催化剂的制备方法，其特征在于：步骤S2中，所述惰性气体为氮气，热解的温度为300～800℃，时间为1～2h。
  6. 如权利要求3所述的一种碳基固体酸催化剂的制备方法，其特征在于：步骤S3中，步骤S2热解后所获得的固体与浓硫酸的质量比为1：3～8，磺化温度为80℃，磺化时间为10～48h。
  7. 如权利要求2所述的一种碳基固体酸催化剂的制备方法，其特征在于：所述芳香环基质的离子树脂包括磺酸型苯乙烯-二乙烯苯阳离子交换树脂和氯甲基化聚苯乙烯树脂中的一种或几种。
  8. 一种碳基固体酸催化剂，其特征在于：采用如权利要求1-7中任意一项所述的方法制备得到。
  9. 一种如权利要求1-7中任意一项所述的制备方法获得的碳基固体酸催化剂应用于生物质水热转化的方法，其特征在于：采用所述碳基固体酸催化剂作为催化剂，与生物质原料或糖类化合物在溶剂系统内混合，水热转化并获得呋喃类平台化合物。
  10. 如权利要求9所述的一种碳基固体酸催化剂应用于生物质水热转化的方法，其特征在于：将碳基固体酸催化剂与生物质原料在溶剂系统内混合并进行水热转化，其中，碳基固体酸催化剂与生物质原料质量比为1：1～10，反应温度为120～190℃，时间为0.5～3h，混合后原料的浓度为0.012～0.32g/ml，所述溶剂系统为有机溶剂、水或两者混合。
  11. 如权利要求10所述的一种碳基固体酸催化剂应用于生物质水热转化的方法，其特征在于：所述有机溶剂包括γ-戊内酯、二甲基亚砜、异丙醇、甲基异丁基(甲)酮、四氢呋喃、N、N-二甲基甲酰胺中的一种或几种。
  12. 如权利要求10所述的一种碳基固体酸催化剂应用于生物质水热转化的方法，其特征在于：使用水和有机溶剂两相溶剂系统时，通过加入氯盐进一步加强产物产率，所述氯盐包括氯化钠、氯化钾、氯化铜、氯化铝中的一种或几种。
  13. 如权利要求10所述的一种碳基固体酸催化剂应用于生物质水热转化的方法，其特征在于：所述生物质原料包括葡萄糖、木糖、阿拉伯糖、纤维二糖、菊粉、玉米淀粉、果皮、作物秸秆中的一种或几种；所述糖类化合物包括葡萄糖，木糖，双糖，多糖中的一种或几种。
  14. 如权利要求10所述的一种碳基固体酸催化剂应用于生物质水热转化的方法，其特征在于：所述呋喃类平台化合物为糠醛或五羟甲基糠醛。
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