CN111330632A - Preparation method of zirconium modified beta molecular sieve and application of zirconium modified beta molecular sieve in xylose conversion - Google Patents
Preparation method of zirconium modified beta molecular sieve and application of zirconium modified beta molecular sieve in xylose conversion Download PDFInfo
- Publication number
- CN111330632A CN111330632A CN202010370499.0A CN202010370499A CN111330632A CN 111330632 A CN111330632 A CN 111330632A CN 202010370499 A CN202010370499 A CN 202010370499A CN 111330632 A CN111330632 A CN 111330632A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zirconium
- catalyst
- beta molecular
- modified beta
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Abstract
The invention relates to the technical field of catalysts, and particularly relates to a zirconium modified beta molecular sieve catalyst and a preparation method and application thereof. The catalyst is obtained by taking a microporous H-beta molecular sieve with the silicon-aluminum ratio of 25-100 as a raw material and performing metal cation impregnation treatment. The catalyst is used for the reaction of preparing isopropyl levulinate by acid catalytic conversion with xylose as a raw material, the isopropyl levulinate with extremely high yield is generated by the reaction, and the service life of the catalyst is relatively stable.
Description
Technical Field
The invention relates to a preparation method of a zirconium modified beta molecular sieve and application of the zirconium modified beta molecular sieve in xylose conversion.
Background
The levulinic acid is used as a bio-based platform compound, has a wide application range, and can be upgraded into various organic chemicals with high added values. The levulinate ester as an important derivative has wide application prospect in the medical and perfume industries.
The existing preparation of levulinic acid and ester thereof can be prepared from biomass derived hexose, meanwhile, pentose serving as a main hydrolysate of hemicellulose can also be converted to prepare the levulinic acid and ester thereof, but the route is complex, and furfural serving as an intermediate is seriously polymerized. Five-carbon sugar, such as xylose, is dehydrated to generate furfural, and after furfural is hydrogenated to furfuryl alcohol, the subsequent furfuryl alcohol is further hydrolyzed to generate levulinic acid and ester, and the process needs the combined action of a hydrogenation catalyst and an acid catalyst. If a bifunctional catalyst can be designed and prepared, which has both hydrogenation and hydrogen transfer properties, xylose can be converted in one pot to prepare levulinic acid and esters thereof, thereby increasing the overall yield of biomass to levulinic acid and esters thereof.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to prepare a zirconium modified beta molecular sieve, and apply the zirconium modified beta molecular sieve to the conversion of xylose to prepare levulinic acid and ester thereof.
The purpose of the invention is realized by the following technical scheme:
a zirconium modified beta molecular sieve catalyst is prepared from microporous H-beta molecular sieve with Si/Al ratio of 25-100 and zirconium salt solution as impregnating solution through immersing and subsequent treating.
Furthermore, the impregnation method is to load the molecular sieve into zirconium salt solutions with different zirconium loading amounts according to the solid-to-liquid ratio of 1: 2-5, and stir for 12-36 h under certain conditions.
The preparation method of the catalyst comprises the following steps:
(1) taking a microporous H-beta molecular sieve with the silicon-aluminum ratio of 25-100, soaking the microporous H-beta molecular sieve with zirconium salt solutions with different zirconium loading amounts (1%, 2.5%, 5%, 10%, 20% and 30% of zirconium loading amounts) under a certain condition, and then drying;
(2) and (2) treating the molecular sieve obtained in the step (1) according to a solid-liquid ratio of 1: 2-5, adding zirconium chloride solutions with different zirconium loading amounts, stirring the molecular sieve to completely dissolve, soaking at room temperature for 12-36 h, and then drying at 100-150 ℃ for 4 h;
(3) and (3) roasting the dried sample obtained by the treatment in the step (2) at the temperature of 350-650 ℃ for 4-6 h.
Preferably, the zirconium salt solution used for impregnation in the step (1) is a zirconium chloride solution.
Preferably, in the step (2), the soaking time is 12-36 h.
Preferably, in the step (3), the roasting treatment is carried out for 4-6 h at the roasting parameter of 350-650 ℃.
An application of the molecular sieve catalyst prepared by the method is used for preparing levulinic acid and isopropyl levulinate by taking xylose and isopropanol in a mass ratio of 10-50: 1 as raw materials.
Preferably, the reaction temperature is 120-220 ℃, and the reaction pressure is 0.1-7.0 MPa.
The preparation method and the prepared target product have the following advantages and beneficial effects:
the zirconium modified beta molecular sieve bifunctional catalyst developed by the invention can realize direct conversion of xylose into levulinic acid and ester thereof, has remarkable catalytic performance, can greatly slow down polymerization reaction in the reaction process, and can obtain levulinic acid and ester thereof with extremely high yield.
Drawings
FIG. 1 is a scanning electron microscope image and an energy spectrum analysis chart of the zirconium modified beta molecular sieve based catalyst obtained in example 3 of the present invention.
FIG. 2 is a graph showing the yield of levulinic acid and its isopropyl ester catalyzed by zirconium-modified beta molecular sieve catalysts according to examples 4-6 of the invention.
FIG. 3 is a diagram of the catalytic reaction pathways of examples 4-6 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Example 1
Preparation of molecular sieve catalyst: (1) taking a microporous H-beta molecular sieve with a silicon-aluminum ratio of 25, soaking the microporous H-beta molecular sieve in a zirconium salt solution with a zirconium load of 10% at room temperature, and then drying;
(2) and (2) treating the molecular sieve obtained in the step (1) according to a solid-liquid ratio of 1: 2 adding zirconium chloride solution with 10 percent of zirconium loading capacity, firstly stirring the molecular sieve to completely dissolve, soaking for 24 hours at room temperature, and then drying for 4 hours at 120 ℃;
(3) and (3) roasting the dried sample obtained in the step (2) at 400 ℃ for 5 hours.
Example 2
Preparation of molecular sieve catalyst: (1) taking a microporous H-beta molecular sieve with a silicon-aluminum ratio of 25, soaking the microporous H-beta molecular sieve in a zirconium salt solution with a zirconium load of 10% at room temperature, and then drying;
(2) and (2) treating the molecular sieve obtained in the step (1) according to a solid-liquid ratio of 1: 2 adding zirconium chloride solution with 10 percent of zirconium loading capacity, firstly stirring the molecular sieve to completely dissolve, soaking for 24 hours at room temperature, and then drying for 4 hours at 120 ℃;
(3) and (3) roasting the dried sample obtained in the step (2) at 500 ℃ for 5 hours.
Example 3
Preparation of molecular sieve catalyst: (1) taking a microporous H-beta molecular sieve with a silicon-aluminum ratio of 25, soaking the microporous H-beta molecular sieve in a zirconium salt solution with a zirconium load of 10% at room temperature, and then drying;
(2) and (2) treating the molecular sieve obtained in the step (1) according to a solid-liquid ratio of 1: 2 adding zirconium chloride solution with 10 percent of zirconium loading capacity, firstly stirring the molecular sieve to completely dissolve, soaking for 24 hours at room temperature, and then drying for 4 hours at 120 ℃;
(3) roasting the dried sample obtained in the step (2) at 600 ℃ for 5 hours; the scanning electron image and the element distribution diagram of the obtained zirconium modified molecular sieve catalyst are shown in figure 1.
Example 4
The application of the zirconium modified beta molecular sieve in xylose catalytic conversion is as follows:
selecting 0.25 g of xylose as a reaction substrate, adding 9.75 g of isopropanol as a reaction solvent, wherein the using amount of the zirconium modified beta molecular sieve catalyst roasted at 400 ℃ is 0.5 wt%, and the reaction temperature is 190 ℃;
the yield distribution diagram of levulinic acid and isopropyl ester prepared by the zirconium modified beta molecular sieve catalyst in the embodiment of the invention is shown in figure 2, and the catalytic xylose conversion path diagram of the catalyst is shown in figure 3.
Example 5
The application of the zirconium modified beta molecular sieve in xylose catalytic conversion is as follows:
selecting 0.25 g of xylose as a reaction substrate, adding 9.75 g of isopropanol as a reaction solvent, wherein the using amount of the zirconium modified beta molecular sieve catalyst roasted at 500 ℃ is 0.5 wt%, and the reaction temperature is 190 ℃;
the yield distribution diagram of levulinic acid and isopropyl ester prepared by the zirconium modified beta molecular sieve catalyst in the embodiment of the invention is shown in figure 2, and the catalytic xylose conversion path diagram of the catalyst is shown in figure 3.
Example 6
The application of the zirconium modified beta molecular sieve in xylose catalytic conversion is as follows:
selecting 0.25 g of xylose as a reaction substrate, adding 9.75 g of isopropanol as a reaction solvent, wherein the using amount of the zirconium modified beta molecular sieve catalyst roasted at the temperature of 600 ℃ is 0.5 wt%, and the reaction temperature is 190 ℃;
the yield distribution diagram of levulinic acid and isopropyl ester prepared by the zirconium modified beta molecular sieve catalyst in the embodiment of the invention is shown in figure 2, and the catalytic xylose conversion path diagram of the catalyst is shown in figure 3.
Claims (8)
1. A zirconium modified beta molecular sieve catalyst is characterized in that a microporous H-beta molecular sieve with a silicon-aluminum ratio of 25-100 is used as a raw material, a zirconium salt solution is used as an impregnation solution, and the catalyst is synthesized by an impregnation method and is obtained after subsequent treatment.
2. The catalyst of claim 1, wherein the impregnation is carried out by passing the molecular sieve through a solid-to-liquid ratio of 1: 2-5, loading in zirconium salt solutions with different zirconium loading amounts, and stirring for 12-36 h under certain conditions.
3. A method for preparing a catalyst according to any one of claims 1-2, comprising the steps of:
(1) taking a microporous H-beta molecular sieve with the silicon-aluminum ratio of 25-100, soaking the microporous H-beta molecular sieve with zirconium salt solutions with different zirconium loading amounts (1%, 2.5%, 5%, 10%, 20% and 30% of zirconium loading amounts) under a certain condition, and then drying;
(2) adding the molecular sieve obtained by the treatment in the step (1) into zirconium chloride solutions with different zirconium loading amounts according to the solid-to-liquid ratio of 1: 2-5, firstly stirring the molecular sieve to be completely dissolved, soaking at room temperature for 12-36 h, and then drying at the temperature of 100-;
(3) and (3) roasting the dried sample obtained by the treatment in the step (2) at the temperature of 350-650 ℃ for 4-6 h.
4. The method for preparing a catalyst according to claim 3, characterized in that: the zirconium salt solution used for impregnation in the step (1) is a zirconium chloride solution.
5. The method for preparing a catalyst according to claim 3, characterized in that: in the step (2), the dipping time is 12-36 h.
6. The method for preparing a catalyst according to claim 3, characterized in that: in the step (3), the roasting parameter is 350-650 ℃ for 4-6 h.
7. Use of a molecular sieve catalyst prepared by the process of any one of claims 3 to 6, wherein: the method is used for the reaction of preparing levulinic acid and isopropyl levulinate by taking xylose and isopropanol in a mass ratio of 10-50: 1 as raw materials.
8. The use according to claim 7, wherein the reaction temperature is 120 ℃ and 220 ℃ and the reaction pressure is 0.1-7.0 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010370499.0A CN111330632A (en) | 2020-05-06 | 2020-05-06 | Preparation method of zirconium modified beta molecular sieve and application of zirconium modified beta molecular sieve in xylose conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010370499.0A CN111330632A (en) | 2020-05-06 | 2020-05-06 | Preparation method of zirconium modified beta molecular sieve and application of zirconium modified beta molecular sieve in xylose conversion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111330632A true CN111330632A (en) | 2020-06-26 |
Family
ID=71177308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010370499.0A Pending CN111330632A (en) | 2020-05-06 | 2020-05-06 | Preparation method of zirconium modified beta molecular sieve and application of zirconium modified beta molecular sieve in xylose conversion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111330632A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113332973A (en) * | 2021-05-20 | 2021-09-03 | 济南大学 | Preparation method of hydrogenation catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108328624A (en) * | 2018-01-23 | 2018-07-27 | 中国石油大学(北京) | A kind of modified beta molecular sieve and its preparation method and application |
| CN109718843A (en) * | 2018-08-31 | 2019-05-07 | 济南大学 | A kind of preparation and application of novel carbon dioxide methanation catalyst |
| CN110003010A (en) * | 2019-03-29 | 2019-07-12 | 昆明理工大学 | A kind of direct method for preparing levulinate using xylose |
-
2020
- 2020-05-06 CN CN202010370499.0A patent/CN111330632A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108328624A (en) * | 2018-01-23 | 2018-07-27 | 中国石油大学(北京) | A kind of modified beta molecular sieve and its preparation method and application |
| CN109718843A (en) * | 2018-08-31 | 2019-05-07 | 济南大学 | A kind of preparation and application of novel carbon dioxide methanation catalyst |
| CN110003010A (en) * | 2019-03-29 | 2019-07-12 | 昆明理工大学 | A kind of direct method for preparing levulinate using xylose |
Non-Patent Citations (1)
| Title |
|---|
| YUEWEN SHAO ET AL: "Balanced distribution of Brønsted acidic sites and Lewis acidic sites for highly selective conversion of xylose into levulinic acid/ester over Zr-beta catalysts", 《GREEN CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113332973A (en) * | 2021-05-20 | 2021-09-03 | 济南大学 | Preparation method of hydrogenation catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xiao et al. | Efficient conversion of cellulose into biofuel precursor 5-hydroxymethylfurfural in dimethyl sulfoxide–ionic liquid mixtures | |
| Enslow et al. | The kinetics of Brønsted acid-catalyzed hydrolysis of hemicellulose dissolved in 1-ethyl-3-methylimidazolium chloride | |
| JP5344666B2 (en) | Method for producing lactic acid | |
| US20070100162A1 (en) | Process for the liquefaction of lignocellulosic material | |
| JP2016524525A (en) | Co-solvent for producing reaction intermediates from biomass | |
| Feng et al. | Selective catalytic conversion of waste lignocellulosic biomass for renewable value-added chemicals via directional microwave-assisted liquefaction | |
| EP3587431B1 (en) | Method for preparing levoglucosenone by catalytic pyrolysis of biomass | |
| JP6529502B2 (en) | Production of furfural from xylose | |
| Liu et al. | Cascade production of lactic acid from universal types of sugars catalyzed by lanthanum triflate | |
| CN111330632A (en) | Preparation method of zirconium modified beta molecular sieve and application of zirconium modified beta molecular sieve in xylose conversion | |
| Yüksel Özşen | Conversion of biomass to organic acids by liquefaction reactions under subcritical conditions | |
| Zhu et al. | Sulfonated vermiculite-mediated catalysis of reed (phragmites communis) into furfural for enhancing the biosynthesis of 2-furoic acid with a dehydrogenase biocatalyst in a one-pot manner | |
| CN109651307B (en) | Method for preparing furan derivative from fiber type Chinese medicine residues | |
| Lu et al. | Mechanistic role of γ-valerolactone co-solvent to promote ethyl levulinate production from cellulose transformation in ethanol | |
| WO2011129640A2 (en) | Metal catalyst composition for producing furfural derivatives from raw materials of lignocellulosic biomass, and method for producing furfural derivatives using the composition | |
| Wang et al. | Two carriages for efficient furfural production from biomass: Rational design of porous biochar catalyst and clever utilization of butyrolactone-water medium | |
| WO2017084907A1 (en) | Process for converting a feedstock comprising a lignocellulosic biomass using a polyoxometalate salt comprising nickel and tungsten or nickel and molybdenum | |
| CN110227547A (en) | A kind of preparation method and applications of sulfomethylated lignin acid catalyst | |
| Zhao et al. | A new route to improved glucose yields in cellulose hydrolysis | |
| CN113332973A (en) | Preparation method of hydrogenation catalyst | |
| CN113181932B (en) | Difunctional biomass carbon-based catalyst and application thereof in catalytic preparation of levulinate | |
| CN116925014A (en) | Method for preparing 2-methyl furan from biomass raw material | |
| Wang | The Application and Research Progress of Ionic Liquid in Biomass Transformation | |
| CN113649063A (en) | Method for preparing furfural by catalyzing decarbonization of hexose | |
| M Ali et al. | Conversion of Waste Biomass into Valuable Platform Furan-Based-Compounds |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200626 |
|
| WD01 | Invention patent application deemed withdrawn after publication |