CN111729674A - Preparation of magnetic nano solid acid and application of magnetic nano solid acid in lignocellulose hydrolysis - Google Patents
Preparation of magnetic nano solid acid and application of magnetic nano solid acid in lignocellulose hydrolysis Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
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- 239000003054 catalyst Substances 0.000 claims abstract description 13
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- 238000000034 method Methods 0.000 claims abstract description 11
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- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 6
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- 239000000843 powder Substances 0.000 claims abstract description 6
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- 238000005485 electric heating Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
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- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
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- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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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
- 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
- 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
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
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- Engineering & Computer Science (AREA)
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Abstract
A method for hydrolyzing lignocellulose with magnetic nano solid acid comprises collecting FeCl3·6H2Dissolving O in ethylene glycol, adding sodium acetate and polyethylene glycol, uniformly mixing, placing in a high-pressure reaction kettle, heating, washing, dispersing in deionized water to obtain magnetic nano Fe3O4Dispersing, adding anhydrous ethanol and ammonia water, dispersing again, stirring in water bath, adding TEOS, reacting for 1 hr, and treating to obtain Fe with shell structure3O4‑SiO2Adding the powder into a round-bottom flask, adding benzyl alcohol and toluene, mixing, treating and drying, adding trichloromethane and chlorosulfonic acid, and treating to obtain solid acid; adding the magnetic nano solid acid and the dried cellulose into water or ionic liquid solution, recovering the catalyst after reaction, and filtering to obtain the hydrolysis sugar solution of the lignocellulose. The solid acid prepared by the invention has simple preparation process, low cost and good hydrolysis effectAnd the recycling of waste acid is avoided, and the pollution to the environment is avoided.
Description
Technical Field
The invention belongs to the field of biomass conversion, and particularly relates to preparation of magnetic nano solid acid and application of the magnetic nano solid acid in lignocellulose hydrolysis.
Background
Lignocellulose is a renewable resource and is extremely abundant on earth. However, at present, a large amount of the feed is burnt except a small amount of the feed is used as animal feed, which not only causes waste of resources, but also causes environmental pollution. In recent years, with the rapid development of economy, the problem of shortage of fossil resources is becoming more serious, and effective utilization and conversion of lignocellulose are at the forefront.
Lignocellulose such as corn straw is mainly composed of cellulose, hemicellulose and lignin, wherein the cellulose and the hemicellulose can be hydrolyzed into monosaccharide and other chemicals, and can be further prepared into ethanol, acetone, butanol, furfural, 5-hydroxymethylfurfural, xylitol, levulinic acid and the like. The hydrolysis process is a key step in the conversion of lignocellulose. The hydrolysis method is divided into enzymatic hydrolysis and acid hydrolysis. The method for hydrolyzing lignocellulose by using biological enzyme is environment-friendly, but has high cost and low hydrolysis efficiency at present. The hydrolysis of lignocelluloses, such as H, is carried out industrially mainly by means of mineral acids2SO4HF, hydrochloric acid and the like, which have the advantages of high acid strength, good catalytic activity, low price and the like, but the generated waste acid is difficult to recover, can cause environmental pollution and simultaneously corrode equipment. The solid acid is used as a novel catalyst, is easy to separate from a solvent, can realize the repeated use of the acid, and is environment-friendly. However, the use of solid acids for lignocellulose hydrolysis presents new problems. Lignocellulose is insoluble in water and is not highly soluble in ionic liquids. Solid acid hydrolysis of lignocellulose in water or ionic liquid medium is a solid-solid phase reaction, which cannot be fully contacted, and has low hydrolysis efficiency. In addition, because the lignin contained in the lignocellulose can not be hydrolyzed by acid to generate residues, the smaller the solid acid particles are, the more the raw materials can be contacted, the hydrolysis efficiency can be improved, but the more the separation difficulty of the lignin and the residues after the reaction is, the higher the separation difficulty is.
Disclosure of Invention
The invention aims to provide a preparation method of magnetic nano solid acid and application of the magnetic nano solid acid in lignocellulose hydrolysis, and the magnetic nano solid acid is used for the hydrolysis of lignocellulose.
The invention is realized by the following technical scheme: a preparation method of magnetic nano solid acid comprises the following specific steps:
(1) taking FeCl3·6H2Dissolving O in ethylene glycol, adding sodium acetate and polyethylene glycol, stirring for 30 minutes under the action of magnetic force, uniformly mixing, placing the solution in a high-pressure reaction kettle, heating in a 200 ℃ oven for 8 hours, washing after the reaction is finished, and dispersing in deionized water to obtain magnetic nano Fe3O4For standby;
(2) taking the magnetic nano Fe in the step (1)3O4Dispersing in a conical flask, adding absolute ethyl alcohol and ammonia water, sealing, and performing ultrasonic treatment to obtain nanometer Fe3O4Dispersing uniformly, placing into water bath kettle, mechanically stirring, adding appropriate amount of TEOS, stirring for reaction for 1 h, separating with magnet, washing, and vacuum drying to obtain shell structure Fe3O4-SiO2；
(3) Taking dry Fe3O4-SiO2Adding the powder into a round-bottom flask, adding benzyl alcohol and toluene, ultrasonically dispersing, heating and refluxing by an electric heating sleeve, cleaning and drying, putting the dried product into the round-bottom flask, adding trichloromethane and chlorosulfonic acid, refluxing for 2 h, cleaning and drying to obtain the magnetic nano solid acid Fe3O4-SiO2-SO3H。
Further preferably, the washing agents in the washing in the step (1) and the washing in the step (2) are both ethanol and water.
Further optimization, the concentration of the ammonia water in the step (2) is 5%, and the adding amount of TEOS is 0.2-0.8 mL.
Further optimization, the adding amount of the chlorosulfonic acid in the step (3) is 0.2-1 mL.
The method for hydrolyzing lignocellulose by using magnetic nano solid acid comprises the following specific steps: magnetic nano solid acid Fe3O4-SiO2-SO3Adding H and dried cellulose into water or ionic liquid solution according to the proportion of 0.5-2.5(g/g), reacting in an oil bath kettle at 90-150 ℃ for 3-7H, recovering the catalyst through an external magnetic field, and filtering to obtain the hydrolyzed sugar solution of lignocellulose.
The invention has the beneficial effects that:
Fe3O4-SiO2the shell layer can not only play a role in protecting magnetic cores, but also can be used for connecting sulfonic acid groups and magnetic nano solid acid Fe3O4-SiO2-SO3When the H is added to hydrolyze cellulose, the solid acid can be recovered by adding a magnetic field, so that the problem of solid acid separation is solved. The solid acid catalyst has the advantages of relatively simple preparation process, mild conditions, low cost and good hydrolysis effect.
Drawings
FIG. 1 is a scanning electron microscope image of magnetic nano solid acid.
Detailed Description
The technical solution of the present invention will be further explained by the following detailed description with reference to the accompanying drawings.
In order to make the objects, technical solutions and novel points of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Taking 1.35g FeCl3·6H2Dissolving O in 40mL of ethylene glycol, adding 3.6g of sodium acetate and 1g of polyethylene glycol, magnetically stirring for 30min, placing the mixed solution in a high-pressure reaction kettle, heating in a 200 ℃ oven for 8h, washing with ethanol and water for three times respectively, and dispersing in deionized water to obtain magnetic nano Fe3O4Magnetic nano Fe3O4Dispersed in an Erlenmeyer flask and 80 mL of anhydrousSealing ethanol and 4 mL ammonia water, and performing ultrasonic treatment for 5min to obtain nanometer Fe3O4Dispersing uniformly, placing into 50 deg.C water bath, mechanically stirring, adding 0.2 mL TEOS, stirring for reaction for 1 h, separating with magnet after stirring, washing with ethanol and water for 3 times respectively, and vacuum drying to obtain shell structure Fe3O4-SiO2；
1g of dry Fe is taken3O4-SiO2Adding the powder into a round-bottom flask, adding 5 mL of benzyl alcohol and 20 mL of toluene, ultrasonically dispersing, heating and refluxing by an electric heating sleeve, cleaning and drying, putting 1g of the dried product into the round-bottom flask, adding 20 mL of trichloromethane and 0.2 mL of chlorosulfonic acid, refluxing for 2 h, cleaning and drying to obtain the magnetic nano solid acid Fe3O4-SiO2-SO3H, the solid acid has magnetism, the surface of the solid acid has sulfonic acid groups, and the amount of the solid acid is 2.07 mmol/g-1。
Example 2
Taking 1.35g FeCl3·6H2Dissolving O in 40mL of ethylene glycol, adding 3.6g of sodium acetate and 1g of polyethylene glycol, magnetically stirring for 30min, placing the mixed solution in a high-pressure reaction kettle, heating in a 200 ℃ oven for 8h, washing with ethanol and water for 3 times respectively, and dispersing in deionized water to obtain magnetic nano Fe3O4Magnetic nano Fe3O4Dispersing in a conical flask, adding 80 mL of anhydrous ethanol and 4 mL of ammonia water, sealing, and performing ultrasonic treatment for 5min to obtain nanometer Fe3O4Dispersing uniformly, placing into 50 deg.C water bath, mechanically stirring, adding 0.2 mL TEOS, stirring for reaction for 1 h, separating with magnet after stirring, washing with ethanol and water for 3 times respectively, and vacuum drying to obtain shell structure Fe3O4-SiO2；
1g of dry Fe is taken3O4-SiO2Adding the powder into a round-bottom flask, adding 5 mL of benzyl alcohol and 20 mL of toluene, ultrasonically dispersing, heating and refluxing by an electric heating sleeve, cleaning, drying, adding 1g of the dried product into the round-bottom flask, adding 20 mL of trichloromethane and 0.6 mL of chlorosulfonic acid, refluxing for 2h, cleaning and drying to obtain the magnetic nano solid acid Fe3O4-SiO2-SO3H, the solid acid has magnetism, the surface of the solid acid has sulfonic acid groups, and the amount of the solid acid is 3.36 mmol/g-1。
Example 3
Taking 1.35g FeCl3·6H2Dissolving O in 40mL of ethylene glycol, adding 3.6g of sodium acetate and 1g of polyethylene glycol, magnetically stirring for 30min, placing the mixed solution in a high-pressure reaction kettle, heating in a 200 ℃ oven for 8h, washing with ethanol and water for three times respectively, and dispersing in deionized water to obtain magnetic nano Fe3O4Magnetic nano Fe3O4Dispersing in a conical flask, adding 80 mL of anhydrous ethanol and 4 mL of ammonia water, sealing, and performing ultrasonic treatment for 5min to obtain nanometer Fe3O4Dispersing uniformly, placing into 50 deg.C water bath, mechanically stirring, adding 0.2 mL TEOS, stirring for reaction for 1 h, separating with magnet after stirring, washing with ethanol and water for 3 times, and vacuum drying to obtain shell structure Fe3O4-SiO2；
1g of dry Fe is taken3O4-SiO2Adding the powder into a round-bottom flask, adding 5 mL of benzyl alcohol and 20 mL of toluene, ultrasonically dispersing, heating and refluxing by an electric heating sleeve, cleaning and drying, putting 1g of the dried product into the round-bottom flask, adding 20 mL of trichloromethane and 1 mL of chlorosulfonic acid, refluxing for 2 h, cleaning and drying to obtain the magnetic nano solid acid Fe3O4-SiO2-SO3H, the solid acid has magnetism, the surface of the solid acid has sulfonic acid groups, and the amount of the solid acid is 3.10 mmol/g-1。
Example 4
The nano magnetic solid acid catalyst prepared according to the above example 2 and the dried microcrystalline cellulose are added into 10mL of aqueous solution according to the proportion of 2.5(g/g), the mixture reacts in an oil bath kettle at the temperature of 90 ℃ for 7h, the catalyst is recovered through an additional magnet, and the hydrolyzed sugar solution is obtained through filtration, wherein the hydrolysis rate of the cellulose is 59.62%.
Example 5
The nano magnetic solid acid catalyst prepared according to the above example 2 and the dried microcrystalline cellulose were added to 10mL of [ Bmim ] Cl ionic liquid solution in a proportion of 1.5(g/g), reacted for 7 hours in an oil bath at a temperature of 150 ℃, the catalyst was recovered by adding a magnet, and a hydrolyzed sugar solution was obtained by filtration, the hydrolysis rate of the cellulose was 70.38%.
Example 6
The nano magnetic solid acid catalyst prepared according to the example 2 and the corn stalk fiber are added into 10mL of aqueous solution according to the proportion of 2(g/g), the mixture reacts for 7 hours in an oil bath kettle at the temperature of 150 ℃, the catalyst is recovered by using a magnet, and the hydrolyzed sugar solution is obtained by filtering, wherein the hydrolysis rate of the holocellulose in the corn stalk is 89.97%.
Example 7
The nano magnetic solid acid catalyst prepared according to the embodiment 2 and dried corn stalks are added into 10mL of [ Bmim ] Cl ionic liquid solution according to the proportion of 2(g/g), the mixture reacts for 7 hours in an oil bath kettle at the temperature of 150 ℃, the catalyst is recovered by using a magnet, and hydrolyzed sugar liquor is obtained by filtering, wherein the hydrolysis rate of holocellulose in the corn stalks is 97.04%.
An electron microscope image of solid acid particles prepared by the method of the invention is shown in fig. 1, the solid acid has a nanometer size, the solid acid prepared in the embodiment 2 is applied to cellulose hydrolysis, wherein the [ Bmim ] Cl ionic liquid solution is used as a reaction medium in the embodiment 5 and the embodiment 7, the aqueous solution is used as a reaction medium in the embodiment 4 and the embodiment 6, the solubility of cellulose and lignocellulose in the [ Bmim ] Cl ionic liquid solution is larger, the contact between the solid acid and raw materials is facilitated, and the hydrolysis rate is higher. Cellulose and lignocellulose are basically insoluble in aqueous solution, and are solid-solid reaction processes, and the phenomenon of nonuniform reaction is easy to occur in solid-phase reaction, so that the hydrolysis rate of the former is obviously higher than that of the latter. The holocellulose of the corn straw refers to the sum of cellulose and hemicellulose in the straw, the hemicellulose is easier to be hydrolyzed by acid compared with the cellulose, and a space gap generated after the hemicellulose is hydrolyzed is beneficial to the contact of the cellulose in the raw material and solid acid, so that the hydrolysis of the cellulose is promoted.
While the foregoing shows and describes the operation, general principles, essential features and advantages of the invention, it will be understood by those skilled in the art that the invention is not limited by the foregoing embodiments, which are merely illustrative of the principles of the invention, but is capable of numerous changes and modifications within the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (5)
1. The preparation method of the magnetic nano solid acid is characterized by comprising the following specific steps of:
(1) taking FeCl3·6H2Dissolving O in ethylene glycol, adding sodium acetate and polyethylene glycol, stirring under the action of magnetic force for 15-40min, mixing well, placing the solution in a high-pressure reaction kettle, heating in an oven at 18-220 deg.C for 7-10h, washing after the reaction is finished, dispersing in deionized water to obtain magnetic nano Fe3O4For standby;
(2) taking the magnetic nano Fe in the step (1)3O4Dispersing in a conical flask, adding absolute ethyl alcohol and ammonia water, sealing, and performing ultrasonic treatment to obtain nanometer Fe3O4Dispersing uniformly, placing into water bath kettle, mechanically stirring, adding appropriate amount of TEOS, stirring for reaction for 0.5-1.5 hr, separating with magnet, washing, and vacuum drying to obtain shell structure Fe3O4-SiO2；
(3) Taking dry Fe3O4-SiO2Adding the powder into a round-bottom flask, adding benzyl alcohol and toluene, ultrasonically dispersing, heating and refluxing by an electric heating sleeve, cleaning and drying, putting the dried product into the round-bottom flask, adding trichloromethane and chlorosulfonic acid, refluxing for 1-3 h, cleaning and drying to obtain the magnetic nano solid acid Fe3O4-SiO2-SO3H。
2. The method for preparing a magnetic nano solid acid according to claim 1, wherein the washing agents in the steps (1) and (2) are ethanol and water.
3. The method for preparing a magnetic nano solid acid according to claim 1, wherein the concentration of the ammonia water in the step (2) is 5%, and the amount of the added TEOS is 0.2-0.8 mL.
4. The method for preparing a magnetic nano solid acid according to claim 1, wherein the chlorosulfonic acid is added in an amount of 0.2 to 1 mL in the step (3).
5. The method for hydrolyzing lignocellulose by using magnetic nano solid acid is characterized in that the magnetic nano solid acid is prepared by using the preparation method of any one of claims 1 to 4, and the specific method for hydrolyzing lignocellulose by using magnetic nano solid acid is as follows: magnetic nano solid acid Fe3O4-SiO2-SO3Adding H and dried cellulose into water or ionic liquid solution according to the proportion of 0.5-2.5(g/g), reacting in an oil bath kettle at 90-150 ℃ for 3-7H, recovering the catalyst through an external magnetic field, and filtering to obtain the hydrolyzed sugar solution of lignocellulose.
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| CN115475656A (en) * | 2022-09-05 | 2022-12-16 | 河南科技大学 | Preparation method of magnetic solid acid and application of magnetic solid acid in biomass hydrolysis |
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