CN111939953A - Preparation method of MXene-based catalyst for preparing furfural with high selectivity - Google Patents

Preparation method of MXene-based catalyst for preparing furfural with high selectivity Download PDF

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CN111939953A
CN111939953A CN202010825301.3A CN202010825301A CN111939953A CN 111939953 A CN111939953 A CN 111939953A CN 202010825301 A CN202010825301 A CN 202010825301A CN 111939953 A CN111939953 A CN 111939953A
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mxene
based catalyst
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dispersion liquid
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CN111939953B (en
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姚志通
罗琦予
唐俊红
徐少丹
刘洁
黄进刚
韩伟
吴卫红
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Hangzhou Dianzi University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64Pore diameter
    • B01J35/6472-50 nm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20Carbon compounds
    • B01J27/22Carbides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235Nitrogen containing compounds
    • B01J31/0244Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235Nitrogen containing compounds
    • B01J31/0254Nitrogen containing compounds on mineral substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64Pore diameter
    • B01J35/65150-500 nm
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34Heterocyclic 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
    • C07D307/38Heterocyclic 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
    • C07D307/40Radicals substituted by oxygen atoms
    • C07D307/46Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

The invention discloses a preparation method of an MXene-based catalyst for preparing furfural with high selectivity. The method mainly comprises the following steps: multilayer titanium carbide MXene was dispersed in water to obtain a dispersion A. Chloroiridic acid was added to the dispersion liquid a, and 1-butyl-3-methylimidazolium tetrafluoroborate was added while performing ultrasonic dispersion to obtain a dispersion liquid B. Adjusting the pH value of the dispersion liquid B to 10-12, reacting for 1-5 h, then filtering, washing and drying to obtain a dispersion liquid B with a surface alkaline constant Kb and an acid constant Ka ratio of 1.0-2.0: MXene-based catalyst with 1, 30-250 nm pore diameter structure. The method synthesizes the MXene-based catalyst for preparing the furfural with high selectivity by using the chloroiridic acid as an active metal raw material and the layered MXene as a catalyst framework, and has the advantages of simple preparation process, high furfural selectivity and yield in biomass pyrolysis liquid products, easiness in large-scale production and the like.

Description

Preparation method of MXene-based catalyst for preparing furfural with high selectivity
Technical Field
The invention belongs to the technical field of biomass recycling, and particularly relates to a preparation method of an MXene-based catalyst for preparing furfural with high selectivity.
Background
The technology for preparing high-quality bio-oil by biomass rapid catalytic pyrolysis can realize the preparation of chemicals and liquid fuels, and is considered to be one of effective ways for realizing fossil energy substitution. However, the bio-oil has the defects of complex components, high oxygen content, difficult separation and the like, and can be used as alternative fuel after catalytic upgrading. To improve bio-oil yield and target product selectivity, it is important to select a suitable catalyst. Microporous (such as ZSM-5, Y-type and type zeolite, etc.) and mesoporous molecular sieves (such as MCM-41, MSU, SBA-15, etc.) are ideal catalysts for preparing aromatic hydrocarbon by catalytic rapid thermal cracking due to the advantages of regular pore channel structures, good hydrothermal stability, proper acidity, ideal shape-selective catalytic selectivity, etc. In some researches, modification researches are carried out on rice straw pyrolysis oil steam by using HZSM-5 as a catalyst and adopting a fluidized bed pyrolysis and fixed bed catalytic device. As a result, it was found that the bio-oil yield was reduced from 28.5% to 7.2% after passing the oil vapor through the catalyst bed, and the oxygen content was correspondingly reduced from 40.2% to 14.5%. In addition, the catalytic pyrolysis research of pine sawdust is carried out by respectively using P-type, Y-type, mordenite and ZSM-5 as catalysts. The results show that the components of the bio-oil are greatly influenced by the structure and acidity of the zeolite molecular sieve, the bio-oil ketones and polycyclic aromatic hydrocarbon compounds obtained by using the ZSM-5 catalyst are increased, and the acids and alcohols are reduced; as acid sites increase, oil yield decreases and water and aromatic heterocyclic compounds increase. But the single micropore structure of the microporous molecular sieve leads to overlarge mass transfer resistance in the reaction process, thereby not only limiting the reaction rate and the effective utilization of active sites, but also increasing carbon deposition in the reaction process. The deactivation of the carbon deposition of the catalyst is a selective catalytic process with acid catalysis, the carbon deposition is a very complex polycyclic compound, the determination of the chemical composition and the structure is difficult, and the factors influencing the carbon deposition mainly comprise the pore structure of the catalyst, the distribution of acid sites and the operating conditions. For the microporous or mesoporous ZSM-5 molecular sieve catalyst, the main reason for the reduction of the activity is that the acid sites on the outer surface of the catalyst are active sites of coking reaction, and the generated macromolecular coke causes the blockage of catalyst pore channels, so that the activity of the catalyst is rapidly reduced. Therefore, the development of a novel catalyst is a key factor for improving the quality of the bio-oil and the yield and selectivity of chemicals, and the improvement of the catalytic performance of the catalyst has important significance for the biomass catalytic pyrolysis technology.
MXene is a very attractive two-dimensional material due to its unusual structure and properties. They have the formula Mn+1XnTx(N-1-3) wherein M is a transition metal (e.g., Ti, V, Nb, Mo, etc.), X is a C or N element, and T represents a chemical group such as-OH, -O, -Cl, and-F. Having broad chemical and structural change properties makes them attractive for example for high conductivity associated with high electron density states near the fermi level, excellent hydrophilicity, good mechanical stability and abundant surface chemistry by grafting chemical groups. The advantages enable MXene to have wide application prospects in the fields such as energy storage, catalysis, transparent electronic devices, separation membranes, sensors, composite material reinforcement, electromagnetic shielding, biomedicine and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an MXene-based catalyst for preparing furfural with high selectivity.
The method mainly comprises the following steps:
dispersing multiple layers of titanium carbide MXene in water to obtain a dispersion liquid A; the solid-to-liquid ratio of the multilayer titanium carbide MXene to water is 1: 100-300, unit is g/ml;
step (2), adding chloroiridic acid and 1-butyl-3-methylimidazole tetrafluoroborate into the dispersion liquid A in sequence, and performing ultrasonic dispersion to obtain a dispersion liquid B; wherein the solid-to-liquid ratio of the chloroiridic acid to the dispersion liquid A is 0.3-1: 100 in g/ml; the volume ratio of the 1-butyl-3-methylimidazole tetrafluoroborate to the dispersion liquid A is 1-10: 100, respectively;
and (3) adjusting the pH value of the dispersion liquid B to 10-12 by using sodium hydroxide, reacting for 1-5 h, filtering, washing and drying to obtain a dispersion liquid B with a surface alkaline constant Kb and an acid constant Ka ratio of 1.0-2.0: MXene-based catalyst with 1, 30-250 nm pore diameter structure.
The method synthesizes the MXene-based catalyst for preparing furfural with high selectivity by using chloroiridic acid as an active metal raw material and layered MXene as a catalyst framework. The ratio of the surface basic constant Kb to the acid constant Ka of the prepared catalyst is 1.0-2.0: 1, the catalyst has proper acidity and alkalinity, and simultaneously has a porous channel structure with the aperture of 30-250 nm, so that the mass transfer resistance is small in the catalytic reaction process, and oxygen-containing biomass macromolecules can quickly enter a catalyst pore channel to be directionally cut, so that the catalyst has good selectivity for furfural, and the defects of complex preparation process, low catalytic performance, easy coking and inactivation and the like of the traditional zeolite molecular sieve are overcome.
Detailed Description
The present invention is further illustrated by the following examples, but the content of the present invention is not limited to the contents of the examples.
Example 1:
(1) 1g of multi-layered titanium carbide MXene was dispersed in 100mL of water to obtain a dispersion A.
(2) To 100ml of the dispersion A were added 0.3g of chloroiridic acid and 1ml of 1-butyl-3-methylimidazolium tetrafluoroborate, and ultrasonic dispersion was carried out to obtain a dispersion B.
(3) Adjusting the pH value of the dispersion liquid B to 10 by using sodium hydroxide, reacting for 1h, filtering, washing and drying to obtain a solution with the surface alkaline constant Kb and the acid constant Ka being 1.0: MXene-based catalyst with 1, 30-100 nm pore diameter structure.
(4) The rice hull is used as a raw material, the catalyst is adopted to carry out pyrolysis reaction for 4 hours at 400 ℃, and a liquid product is collected. The yield of the liquid product is 41.2 percent, and the content of the 5-hydroxymethylfurfural is 40.5 percent.
Example 2:
(1) 1g of multi-layered titanium carbide MXene was dispersed in 300mL of water to obtain a dispersion A.
(2) Adding 1g of chloroiridic acid and 10ml of 1-butyl-3-methylimidazolium tetrafluoroborate into 100ml of the dispersion A, and performing ultrasonic dispersion to obtain a dispersion B;
(3) adjusting the pH value of the dispersion liquid B to be 12 by using sodium hydroxide, reacting for 5 hours, filtering, washing and drying to obtain a solution with the surface alkaline constant Kb and the acid constant Ka being 2.0: MXene-based catalyst with 1, 50-150 nm pore diameter structure;
(4) the wood dust is used as a raw material, the catalyst is adopted to carry out pyrolysis reaction for 6 hours at 500 ℃, and a liquid product is collected. The yield of the liquid product is 43.1 percent, and the content of the 5-hydroxymethylfurfural is 44.5 percent.
Example 3:
(1) 1g of multi-layered titanium carbide MXene was dispersed in 200mL of water to obtain a dispersion A.
(2) To 100ml of the dispersion A were added 0.5g of chloroiridic acid and 3ml of 1-butyl-3-methylimidazolium tetrafluoroborate, and ultrasonic dispersion was carried out to obtain a dispersion B.
(3) Adjusting the pH value of the dispersion liquid B to 10 by using sodium hydroxide, reacting for 2 hours, filtering, washing and drying to obtain a solution with the surface alkaline constant Kb and the acid constant Ka being 1.3: 1, MXene-based catalyst with pore diameter structure of 80-200 nm;
(4) the wheat straw is used as a raw material, the catalyst is adopted to carry out pyrolysis reaction for 8 hours at 450 ℃, and a liquid product is collected. The yield of the liquid product is 46.5 percent, and the content of the 5-hydroxymethylfurfural is 41.7 percent.
Example 4:
(1) 1g of multi-layered titanium carbide MXene was dispersed in 250ml of water to obtain a dispersion A.
(2) To 100ml of the dispersion A were added 0.6g of chloroiridic acid and 7ml of 1-butyl-3-methylimidazolium tetrafluoroborate, and ultrasonic dispersion was carried out to obtain a dispersion B.
(3) Adjusting the pH value of the dispersion liquid B to 11.5 by using sodium hydroxide, reacting for 4 hours, filtering, washing and drying to obtain a solution with the surface alkaline constant Kb and the acid constant Ka being 1.8: MXene-based catalyst with 1, 30-110 nm pore diameter structure;
(4) animal wastes and sludge are used as raw materials, the catalyst is adopted to carry out pyrolysis reaction for 6 hours at 480 ℃, and liquid products are collected. The yield of the liquid product is 42.5 percent, and the content of the 5-hydroxymethylfurfural is 41.3 percent.
Example 5:
(1) 1g of multi-layered titanium carbide MXene was dispersed in 250ml of water to obtain a dispersion A.
(2) To 100ml of the dispersion A were added 0.9g of chloroiridic acid and 8ml of 1-butyl-3-methylimidazolium tetrafluoroborate, and ultrasonic dispersion was carried out to obtain a dispersion B.
(3) Adjusting the pH value of the dispersion liquid B to 10.5 by using sodium hydroxide, reacting for 4.5h, then filtering, washing and drying to obtain a solution with the surface alkaline constant Kb and the acid constant Ka being 1.0: MXene-based catalyst with 1, 40-130 nm pore diameter structure.
(4) The method takes vinasse and mushroom dregs as raw materials, adopts the catalyst of the invention to carry out pyrolysis reaction for 6.5 hours at 650 ℃, and collects liquid products. The yield of the liquid product is 41.3 percent, and the content of the 5-hydroxymethylfurfural is 40.2 percent.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.

Claims (5)

1. A method for preparing MXene-based catalyst for preparing furfural with high selectivity is provided, wherein the ratio of alkali constant Kb and acid constant Ka on the surface of MXene-based catalyst is 1.0-2.0: 1, 30-250 nm aperture structure; the method is characterized by comprising the following steps:
dispersing multiple layers of titanium carbide MXene in water to obtain a dispersion liquid A;
step (2), adding chloroiridic acid and 1-butyl-3-methylimidazole tetrafluoroborate into the dispersion liquid A in sequence, and performing ultrasonic dispersion to obtain a dispersion liquid B;
and (3) adjusting the pH value of the dispersion liquid B to 10-12, reacting for 1-5 h, and then filtering, washing and drying to obtain the MXene-based catalyst.
2. The method for preparing the MXene-based catalyst for preparing furfural with high selectivity according to claim 1, wherein the solid-to-liquid ratio of the multi-layer titanium carbide MXene to water is 1: 100 to 300 (g/ml).
3. The method for preparing the MXene-based catalyst for highly selectively preparing furfural according to any one of claims 1 to 2, wherein the solid-to-liquid ratio of chloroiridic acid to the dispersion liquid A is 0.3 to 1: 100 (g/ml).
4. The method for preparing the MXene-based catalyst for preparing furfural with high selectivity according to any one of claims 1 to 2, wherein the volume ratio of the 1-butyl-3-methylimidazolium tetrafluoroborate to the dispersion A is 1-10: 100.
5. an MXene-based catalyst having a ratio of surface basic constant Kb to acid constant Ka of 1.0 to 2.0: 1, 30-250 nm aperture structure; prepared by the method of any one of claims 1 to 4.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113457701A (en) * 2021-06-08 2021-10-01 西安交通大学 MXene-based catalyst and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN102766119A (en) * 2012-08-14 2012-11-07 中国科学技术大学 Method for preparing 5-methylfurfural
US20130172583A1 (en) * 2011-12-28 2013-07-04 E I Du Pont De Nemours And Company Process for the production of furfural
CN108793166A (en) * 2018-07-10 2018-11-13 中国科学院宁波材料技术与工程研究所 Composite material, its preparation method and the application of the compound MXenes of B metal
CN109796016A (en) * 2019-02-26 2019-05-24 北京化工大学 A method of regulation MXene nanoscale twins spacing
CN110404532A (en) * 2019-09-02 2019-11-05 北京邮电大学 A kind of method that wet-chemical polishing prepares noble metal cluster or monatomic catalyst
CN111302992A (en) * 2020-02-26 2020-06-19 淮阴师范学院 Mercapto aryl functionalized MXene material and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130172583A1 (en) * 2011-12-28 2013-07-04 E I Du Pont De Nemours And Company Process for the production of furfural
CN102766119A (en) * 2012-08-14 2012-11-07 中国科学技术大学 Method for preparing 5-methylfurfural
CN108793166A (en) * 2018-07-10 2018-11-13 中国科学院宁波材料技术与工程研究所 Composite material, its preparation method and the application of the compound MXenes of B metal
CN109796016A (en) * 2019-02-26 2019-05-24 北京化工大学 A method of regulation MXene nanoscale twins spacing
CN110404532A (en) * 2019-09-02 2019-11-05 北京邮电大学 A kind of method that wet-chemical polishing prepares noble metal cluster or monatomic catalyst
CN111302992A (en) * 2020-02-26 2020-06-19 淮阴师范学院 Mercapto aryl functionalized MXene material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113457701A (en) * 2021-06-08 2021-10-01 西安交通大学 MXene-based catalyst and preparation method and application thereof

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