CN112570006A - Novel supported polyacid catalyst and application thereof in preparation of furfural - Google Patents
Novel supported polyacid catalyst and application thereof in preparation of furfural Download PDFInfo
- Publication number
- CN112570006A CN112570006A CN201910927150.XA CN201910927150A CN112570006A CN 112570006 A CN112570006 A CN 112570006A CN 201910927150 A CN201910927150 A CN 201910927150A CN 112570006 A CN112570006 A CN 112570006A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- zsm
- polyacid
- furfural
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
The invention relates to a novel supported polyacid catalyst and application thereof in furfural preparation, wherein the catalyst is a polyacid compound with a Keggin structure, and the polyacid compound with the Keggin structure has a general formula as follows: xH3PW12O40ZSM-5(38) (x is 5% -50%). The preparation method of the catalyst comprises the steps of weighing molecular sieve ZSM-5(38) and a compound H3PW12O40A compound H3PW12O40Pouring into a reactor, adding water, stirring, dripping polyacid into ZSM-5(38), stirring, standing, filtering, drying, and sintering to obtain the catalyst. Adding biomass powder, catalyst and lithium bromide/water system into thick-wall pressure-resistant bottle, reacting to generate furfural, centrifuging to separate out catalyst, extracting with dichloromethane, and reducing pressureAnd (5) distilling. The catalyst has high catalytic performance, and is easy to separate from the reaction system and reuse.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation and application, and particularly relates to a novel nano solid supported heteropoly acid catalyst. Meanwhile, the invention also relates to the application of the nano catalyst in the aspect of preparing furfural.
Technical Field
Energy is related to the survival and development of human beings, and is the life line of national economy. In the face of the enormous pressure of energy crisis and environmental destruction, the development of renewable clean energy has become a focus of attention in many countries of the world for the sustainable development of human society. Since then, the development of the biomass industry has become an important development strategy in China. Biomass is an organic substance formed by photosynthesis of green plants, mainly including sugars (such as monosaccharides, starch, and the like), straws, lignocellulose, grease, and the like, and is an inexhaustible resource treasury.
Hemicellulose, as the second largest component of lignocellulosic biomass, can be converted into a variety of platform compounds due to the diversity of its basic building blocks. The pentose in the hemicellulose can be converted into furfural through dehydration. The product can be used as an industrial synthesis raw material and a solvent, and can be converted into various high-value C4-C5 chemicals such as 2-methyltetrahydrofuran, furfuryl alcohol, 1-pentanol, 2-methylfuran and the like. Is widely used in the fields of medicine, chemical industry, energy and the like.
Therefore, the development and utilization of furfural and high-value downstream chemicals thereof have wide prospects. However, the current industrial production of furfural has the problems of low yield, serious environmental pollution and the like, and can not meet the requirements of the industrial development of furfural in a new period. Therefore, the development of an efficient and green furfural preparation technology, the development of furfural downstream products with high added values and the expansion of the application field of furfural have important practical significance for promoting the development of the furfural industry in China.
The acid catalytic hydrolysis process is a main method for producing furfural at present, and the reaction systems commonly used in recent years are as follows: water, organic solvents (e.g., dimethyl sulfoxide, gamma-valerolactone, etc.), water/organic solvent biphasic systems (e.g., water/tetrahydrofuran, water/toluene, water/methyl isobutyl ketone, water/cyclopentyl methyl ether, water/butanol, etc.), organic ionic liquids: (1-butyl-3-methylimidazole) [ BMIM ] Cl and the like. The organic ionic liquid has high cost and is not environment-friendly. In addition, at present, few reports are made on furfural preparation by using inorganic ionic liquid as biomass conversion.
Heteropolyacids (HPAs) having unique acid properties and higher than concentrated H2SO4The acid strength more than one hundred times is increasingly noticed as a green acid catalyst. Meanwhile, the molecular sieve catalyst, especially the zeolite molecular sieve, has the characteristics of solid acidity, better hydrothermal stability, shape-selective catalysis of pore diameter and the like, and is widely used for preparing the furfural. At present, the research of preparing the furfural catalyst by taking the heteropoly acid loaded molecular sieve as biomass conversion does not exist, and the heteropoly acid loaded molecular sieve can improve the acidic property of the molecular sieve, so that the yield of furfural is improved.
Disclosure of Invention
The invention aims to provide a novel supported polyacid catalyst and application thereof in furfural preparation, wherein the catalyst has high catalytic performance, and is easy to separate from a reaction system and reuse.
The technical scheme of the invention is as follows:
a novel supported polyacid catalyst is a polyacid compound with a Keggin structure, and the polyacid compound with the Keggin structure has a general formula:
xH3PW12O40/ZSM-5(38) (x＝5％～50％)。
a novel supported polyacid catalyst, said polyacid compound preferably being:
5％H3PW12O40ZSM-5(38) or
10％H3PW12O40ZSM-5(38) or
15％H3PW12O40ZSM-5(38) or
20％H3PW12O40ZSM-5(38) or
25％H3PW12O40/ZSM-5(38)
A preparation method of a novel supported polyacid catalyst comprises the following steps of: 0.05 to 0.5 respectivelyTaking molecular sieve ZSM-5(38) and compound H3PW12O40A compound H3PW12O40Pouring the mixture into a reactor, adding a certain amount of water according to an equal volume impregnation method, stirring for dissolving, then dropwise adding the polyacid solution into ZSM-5(38) powder, stirring while dropwise adding, stirring for 30min after dissolving, standing the reaction system for 24h, separating out a light yellow solid, filtering and drying, placing the solid in a muffle furnace, and sintering at the temperature of 250-550 ℃ for 4-6 h to obtain the supported polyacid catalyst for preparing furfural.
A method for preparing furfural by using a novel supported polyacid catalyst comprises the steps of adding 0.05-0.15 g of biomass powder, 0.15-0.75 mmol of the catalyst and 6mL of LiBr/water system in a mass ratio of 1: 1-1: 10 into a thick-wall pressure-resistant bottle, setting a reaction temperature to be 130-180 ℃, reacting for 4-8 hours, hydrolyzing biomass to obtain furfural, centrifugally separating out the catalyst after the reaction is finished, repeatedly converting, extracting the product furfural with dichloromethane, and distilling water at 40 ℃ under reduced pressure to obtain the product.
The invention has the beneficial effects that:
the polyoxometallate with a Keggin structure is used as a catalyst, so that a plurality of technical problems can be solved in the process of converting hemicellulose into furfural:
polyacid of Keggin structure as
Acid, which is helpful for xylose isomerization reaction and can satisfy xylose dehydration reaction, and the molecular sieve has Lewis acid and
acidic, optionally with polyacids
The acidic synergistic effect improves the catalytic performance.
2. The polyacid system is a solid acid catalyst. The polyacid supported solid catalyst is used as a heterogeneous phase reaction catalyst in a reaction system, is easy to separate from the reaction system, does not produce a large amount of polluted sewage, can be repeatedly used, and reduces the use cost of the catalyst.
3. The polyacid supported solid reacts in a nano system. The polyacid supported solid is self-assembled into a nano reactor in water, so that the reaction activity is improved.
4. The adjustability of the catalytic activity of the polyacid supported solid catalyst.
5. Inorganic ionic liquids (such as lithium bromide hydrate) have properties similar to organic ionic liquids, but are cheaper and more environmentally friendly than organic ionic liquids.
The invention discloses a supported polyacid catalyst for catalyzing hemicellulose to furfural, which is a polyacid compound with a Keggin structure and a zeolite molecular sieve ZSM-5; the catalyst is used for catalyzing and preparing furfural. The catalyst has high catalytic activity, repeatability and wide raw material applicability. The whole preparation process generates no waste water, and is green and environment-friendly.
Drawings
FIG. 1 shows 10% H of a supported polyacid catalyst3PW12O40IR spectrum of/ZSM-5 (38).
Fig. 2 shows the optimal yield of furfural from xylose, xylan, hemicellulose and corn stover, respectively.
Detailed Description
The invention provides a polyacid supported catalyst which is used in furfural preparation. To achieve this, the following embodiments are implemented.
According to the mass ratio of 1: 0.05-0.5 weight of molecular sieve ZSM-5(38) and polyacid compound H3PW12O40(ii) a Polyacid compound H3PW12O40Pouring the mixture into a reactor, adding a certain amount of water according to an equal volume impregnation method, stirring for dissolving, then dropwise adding the polyacid solution into ZSM-5(38) powder, stirring while dropwise adding, stirring for 30min after dissolving, standing the reaction system for 24h, separating out a light yellow solid, filtering and drying, placing the solid in a muffle furnace, and sintering at the temperature of 250-550 ℃ for 4-6 h to obtain the polyacid supported catalyst for preparing furfural.
The method for preparing the furfural by catalyzing biomass hydrolysis by using the polyacid supported catalyst for preparing the furfural provided by the invention comprises the following steps: adding biomass powder (0.05-0.15 g), a catalyst (0.15-0.75 mmol) and 6mL of LiBr/water (mass ratio is 1: 1-1: 10) into a thick-wall pressure-resistant bottle, setting the reaction temperature to be 130-180 ℃, and reacting for 4-8 h, so that biomass is hydrolyzed to obtain furfural. After the reaction, the catalyst was separated by centrifugation and the conversion was repeated. Extracting the product furfural with dichloromethane, and distilling at 40 ℃ under reduced pressure to evaporate water to obtain the product.
The biomass can be selected from xylose, xylan, hemicellulose, corn stalk, or mixture of several biomasses.
Example 1
According to the mass ratio of 1: 0.1 weighing molecular sieve ZSM-5(38) and polyacid compound H respectively3PW12O40(ii) a Polyacid compound H3PW12O40Pouring the mixture into a reactor, adding 2.7ml of water according to an equal-volume impregnation method, stirring and dissolving, then dropwise adding a polyacid solution into ZSM-5(38) powder, stirring while dropwise adding, stirring for 30min after dissolving, standing a reaction system for 24h, precipitating a light yellow solid, filtering and drying, placing the solid in a horse kettle furnace, and calcining for 4h at 250 ℃ to obtain the polyacid supported catalyst for preparing furfural.
Mixing xylose powder 0.15g, 0.75mmol 10% H3PW12O40The catalyst/ZSM-5 (38) was placed in a thick-walled pressure-resistant bottle, and 6ml of a 10% LiBr/water solution was added thereto, followed by heating and stirring. The reaction temperature is 130 ℃ and the reaction time is 4 h. After the reaction is finished, cooling, and then putting the reaction mixture into a centrifugal tube for centrifugal separation, wherein the clear liquid contains furfural, and the precipitate is the catalyst. The conversion rate of xylose is close to 100%, and the yield of furfural is 79.3%.
Example 2
According to the mass ratio of 1: 0.2 weighing molecular sieve ZSM-5(38) and polyacid compound H respectively3PW12O40(ii) a Polyacid compound H3PW12O40Pouring into a reactor, adding 2.7ml of water by an equal volume impregnation method, stirring for dissolving, dropwise adding the polyacid solution into the ZSM-5(38) powder while stirring, stirring for 30min after dissolving, and reactingAnd standing the reaction system for 24 hours to separate out a faint yellow solid, filtering and drying the faint yellow solid, putting the faint yellow solid in a kettle furnace, and calcining the faint yellow solid for 4 hours at 300 ℃ to obtain the polyacid supported catalyst for preparing the furfural.
Mixing xylose powder 0.10g, 0.75mmol 10% H3PW12O40The catalyst/ZSM-5 (38) was placed in a thick-walled pressure-resistant bottle, and 6ml of a 20% LiBr/water solution was added thereto, followed by heating and stirring. The reaction temperature is 150 ℃, and the reaction time is 5 h. After the reaction is finished, cooling, and then putting the reaction mixture into a centrifugal tube for centrifugal separation, wherein the clear liquid contains furfural, and the precipitate is the catalyst. The conversion rate of xylose is close to 100 percent, and the yield of furfural is 75.15 percent.
Example 3
According to the mass ratio of 1: 0.3 molecular sieve ZSM-5(38) and polyacid compound H were weighed separately3PW12O40(ii) a Polyacid compound H3PW12O40Pouring the mixture into a reactor, adding 2.7ml of water according to an equal-volume impregnation method, stirring and dissolving, then dropwise adding a polyacid solution into ZSM-5(38) powder, stirring while dropwise adding, stirring for 30min after dissolving, standing a reaction system for 24h, precipitating a light yellow solid, filtering and drying, placing the solid in a horse kettle furnace, and calcining for 4h at 350 ℃ to obtain the polyacid supported catalyst for preparing furfural.
Mixing xylose powder 0.15g, 0.75mmol 10% H3PW12O40The catalyst/ZSM-5 (38) was placed in a thick-walled pressure-resistant bottle, and 6ml of a 30% LiBr/water solution was added thereto, followed by heating and stirring. The reaction temperature is 180 ℃, and the reaction time is 6 h. After the reaction is finished, cooling, and then putting the reaction mixture into a centrifugal tube for centrifugal separation, wherein the clear liquid contains furfural, and the precipitate is the catalyst. The conversion rate of xylose is close to 100%, and the yield of furfural is 55.19%.
Claims (4)
1. A novel supported polyacid catalyst is characterized in that: the polyacid compound with a Keggin structure has a general formula as follows:
xH3PW12O40/ZSM-5(38)(x＝5％～50％)。
2. a novel supported polyacid catalyst is characterized in that: the polyacid compound is preferably:
5％H3PW12O40ZSM-5(38) or
10％H3PW12O40ZSM-5(38) or
15％H3PW12O40ZSM-5(38) or
20％H3PW12O40ZSM-5(38) or
25％H3PW12O40/ZSM-5(38)。
3. A preparation method of a novel supported polyacid catalyst is characterized by comprising the following steps: according to the mass ratio of 1: 0.05-0.5 respectively weighing molecular sieve ZSM-5(38) and compound H3PW12O40A compound H3PW12O40Pouring the mixture into a reactor, adding a certain amount of water according to an equal volume impregnation method, stirring for dissolving, then dropwise adding the polyacid solution into ZSM-5(38) powder, stirring while dropwise adding, stirring for 30min after dissolving, standing the reaction system for 24h, separating out a light yellow solid, filtering and drying, placing the solid in a muffle furnace, and sintering at the temperature of 250-550 ℃ for 4-6 h to obtain the supported polyacid catalyst for preparing furfural.
4. A method for preparing furfural by using a novel supported polyacid catalyst is characterized by comprising the following steps:
adding 0.05-0.15 g of biomass powder, 0.15-0.75 mmol of catalyst and 6mL of LiBr/water system in a mass ratio of 1: 1-1: 10 into a thick-wall pressure-resistant bottle, setting a reaction temperature of 130-180 ℃, reacting for 4-8 h, hydrolyzing the biomass to obtain furfural, after the reaction is finished, centrifugally separating out the catalyst, repeatedly converting, extracting the product furfural with dichloromethane, and distilling water under reduced pressure at 40 ℃ to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910927150.XA CN112570006A (en) | 2019-09-27 | 2019-09-27 | Novel supported polyacid catalyst and application thereof in preparation of furfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910927150.XA CN112570006A (en) | 2019-09-27 | 2019-09-27 | Novel supported polyacid catalyst and application thereof in preparation of furfural |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112570006A true CN112570006A (en) | 2021-03-30 |
Family
ID=75110138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910927150.XA Pending CN112570006A (en) | 2019-09-27 | 2019-09-27 | Novel supported polyacid catalyst and application thereof in preparation of furfural |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112570006A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242270A (en) * | 2013-05-28 | 2013-08-14 | 华东理工大学 | Method for preparing furfural compounds from biomass |
| CN105418561A (en) * | 2015-12-07 | 2016-03-23 | 南京工业大学 | Method for preparing 2,5-furandicarboxylic acid by supported bifunctional catalyst by catalyzing fructose |
| CN107540642A (en) * | 2017-10-12 | 2018-01-05 | 河南省科学院能源研究所有限公司 | A kind of method that furfural and levulic acid are prepared using biomass clean hydrolysis |
-
2019
- 2019-09-27 CN CN201910927150.XA patent/CN112570006A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242270A (en) * | 2013-05-28 | 2013-08-14 | 华东理工大学 | Method for preparing furfural compounds from biomass |
| CN105418561A (en) * | 2015-12-07 | 2016-03-23 | 南京工业大学 | Method for preparing 2,5-furandicarboxylic acid by supported bifunctional catalyst by catalyzing fructose |
| CN107540642A (en) * | 2017-10-12 | 2018-01-05 | 河南省科学院能源研究所有限公司 | A kind of method that furfural and levulic acid are prepared using biomass clean hydrolysis |
Non-Patent Citations (3)
| Title |
|---|
| KAKASAHEB Y. NANDIWALE, ET AL: "HPW Anchored Meso-HZ-5, a Novel Catalyst for Selective Synthesis of Ethyl Levulinate Biofuel by Alcoholysis of Biomass-Derived Furfuryl Alcohol", 《ENVIRONMENTAL PROGRESS & SUSTAINABLE ENERGY》 * |
| SHIQIANG ZHAO, ET AL: "Direct Production of Ethyl Levulinate from Carbohydrates Catalyzed by H-ZSM-5 Supported Phosphotungstic Acid", 《BIORESOURCES》 * |
| 姜亚洁,等: "疏水性固体酸H3PW12O40/HZSM25", 《北京化工大学学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | Recent progress in furfural production from hemicellulose and its derivatives: Conversion mechanism, catalytic system, solvent selection | |
| CN101381351B (en) | Method for coproduction of 5-hydroxymethyl-furfural, acetylpropionic acid and formic acid by high temperature catalytic dehydration of glucose in formic acid | |
| CN101402658B (en) | Method for thermal degradation of cellulose with ion liquid solvent catalysis | |
| CN109467542A (en) | A kind of method that fiber biomass direct liquefaction prepares levulic acid and furfural | |
| CN103193623B (en) | Method for catalytic preparation of acetylpropionic acid in one step by using waste residues obtained by producing xylose | |
| CN105498801A (en) | Preparation method of sulfated carbonized corn cob catalyst and method for preparing furfural from xylose in presence of catalyst | |
| CN110407779A (en) | The method for preparing 5 hydroxymethyl furfural as raw material using biomass | |
| CN103694203A (en) | Method of catalyzing fructose by cellulose base sulfonic acid catalyst to prepare 5-hydroxymethyl furfural | |
| CN106902877B (en) | A kind of polyacid catalyst and preparation method thereof and application method | |
| CN105597757B (en) | Magnetic oxygenated graphen catalyst and preparation method thereof and its application | |
| CN112570006A (en) | Novel supported polyacid catalyst and application thereof in preparation of furfural | |
| CN102492559A (en) | Method for preparing biodiesel in novel alkaline ionic liquid | |
| Quereshi et al. | Catalytic conversion of lignocellulosic biomass into fuels and value-added chemicals | |
| CN102675086B (en) | Method for preparing levulinic acid from steam explosion produced straw short fiber by adding polymerization inhibitor and performing solid acid catalysis | |
| Ma et al. | Preparation, characterization and application of sulfonated mesoporous hollow carbon microspheres | |
| CN109499612B (en) | Polyacid catalyst and preparation method and application thereof | |
| CN103214438A (en) | Method for preparing 5-hydroxymethylfurfural with grape as raw mateiral | |
| CN101982541A (en) | Method for jointly producing biodiesel and lactic acid | |
| CN109628652A (en) | A method of xylose is prepared by the one step catalysis of hemicellulose in corn stover | |
| CN105503789A (en) | Method for catalytic conversion of xylose into furfural by use of montmorillonite-supported metal ion solid acid | |
| CN106278876B (en) | The method that levulic acid compound is prepared by the one step catalysis of corncob hydrolytic residue | |
| CN105214725A (en) | Carbohydrate effectively changes into the green catalysis method of 5 hydroxymethyl furfural | |
| Zhang et al. | Catalytic conversion of carbohydrates into 5-ethoxymethylfurfural using γ-AlOOH and CeO 2@ B 2 O 3 catalyst synergistic effect | |
| CN112473736B (en) | Supported polyacid catalyst and application thereof in preparation of levulinate | |
| CN112321546A (en) | Method for converting hemicellulose into acetal and furfural in low-boiling-point solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |