CN113289604A - Preparation method and application of biomass coke-doped zirconium lanthanum magnesium aluminum solid acid catalyst - Google Patents
Preparation method and application of biomass coke-doped zirconium lanthanum magnesium aluminum solid acid catalyst Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000011973 solid acid Substances 0.000 title claims abstract description 23
- -1 zirconium lanthanum magnesium aluminum Chemical compound 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000571 coke Substances 0.000 claims abstract description 23
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006276 transfer reaction Methods 0.000 claims abstract description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000009901 transfer hydrogenation reaction Methods 0.000 abstract description 5
- 239000002841 Lewis acid Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 150000007517 lewis acids Chemical class 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229940058352 levulinate Drugs 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method and application of a biomass coke-doped zirconium lanthanum magnesium aluminum solid acid catalyst, wherein the preparation method comprises the following steps: (1) oxidizing the biomass coke and concentrated nitric acid or fuming nitric acid under the heating condition, and further filtering and washing to obtain a carbon material; (2) soaking a corresponding carbon material serving as a carrier in a zirconium, lanthanum, magnesium and aluminum salt solution, and drying a soaked sample; (3) the biomass coke doped zirconium, lanthanum, magnesium and aluminum solid acid catalyst is obtained by roasting in a tubular furnace. And subsequently, applying the solid acid catalyst to the hydrogen transfer hydrogenation reaction of the biomass derivative compound furfural. According to the invention, the biomass coke is used, rich oxygen-containing functional groups are introduced after oxidation treatment, and then zirconium, lanthanum, magnesium and aluminum are loaded by an impregnation method, so that rich acid sites, especially Lewis acid sites, are successfully introduced. The catalyst shows excellent hydrogen transfer hydrogenation performance in the hydrogen transfer reaction of biomass derivative compound furfural and has good circulation stability.
Description
Technical Field
The invention belongs to the field of solid acid catalyst preparation technology and application, and particularly relates to a preparation method and application of a biomass coke doped zirconium lanthanum magnesium aluminum solid acid catalyst.
Background
With the increasing depletion of non-renewable resources, such as coal, petroleum, etc., more and more attention is being focused on the development of green, renewable resources. Biomass has received great attention as an important renewable resource, which mainly includes lignocellulosic biomass. Through biomass cracking and thermochemical hydrolysis, biomass can be converted into bio-oil, biomass coke, high value-added compounds and the like. For example, biomass, such as corn cobs and the like, can produce furfural by means of hydrolysis. Furfural, as an important biomass-based platform compound, can be further converted into valuable chemicals such as furfuryl alcohol, tetrahydrofurfuryl alcohol, levulinate and the like through hydrogenation, acid catalysis and other modes. Therefore, development and utilization of biomass resources are of great importance.
For hydrolysis of biomass, it requires the participation of an acid catalyst. Commonly used acid catalysts include homogeneous acids (e.g., hydrochloric acid, sulfuric acid, etc.) as well as heterogeneous acids. Since homogeneous acid catalysts have problems of difficulty in recovery, environmental pollution, and strong corrosiveness to reaction apparatuses, more research has been focused on the development and use of environment-friendly heterogeneous acid catalysts, such as metal oxides, cation-exchange sulfonic acid resins, zeolite molecular sieves, sulfuric acid-supported oxide solid superacids, ionic liquids, and the like. However, most of the solid acid catalysts have complicated preparation processes, insufficient raw material sources, high production cost, and are not suitable for large-scale production. For carbon-based catalysts, because carbon materials are widely available and conform to the green chemistry concept, great attention needs to be paid to development and design of carbon-based catalysts.
Meanwhile, the solid acid catalyst can be applied to hydrogen transfer hydrogenation reaction due to the existence of Lewis acid and Bronsted acid sites. Furfural is an important biomass platform compound, which can be upgraded into high value-added chemicals by a hydrogenation mode, and in order to avoid the use of hydrogen, hydrogen transfer hydrogenation reaction receives more and more attention, so that it is necessary to develop an environment-friendly bifunctional solid acid catalyst to realize the hydrogenation conversion utilization of furfural. The carbon-based catalyst has important application prospect, and has the advantages of wide source, low production cost and the like.
Disclosure of Invention
The invention aims to provide a preparation method and application of a biomass coke-doped zirconium lanthanum magnesium aluminum solid acid catalyst aiming at the defects of the prior art.
The invention discloses a preparation method of a biomass coke doped zirconium lanthanum magnesium aluminum solid acid catalyst, which comprises the following steps:
(1) mixing the biomass coke with concentrated nitric acid or fuming nitric acid, carrying out hydrothermal treatment at 60-120 ℃, then filtering, washing, recovering, and drying at 60-130 ℃ to obtain a carbon material;
(2) soaking the carbon material obtained in the step 1 in aqueous solution of zirconium, lanthanum, magnesium and aluminum salt for 12-36 h, and then drying in an oven at 60-130 ℃ for 6-20 h.
(3) And (3) placing the dried sample obtained in the step (2) in a tubular furnace, and heating and roasting in an inert atmosphere to obtain the biomass coke zirconium-doped lanthanum magnesium aluminum solid acid catalyst.
Preferably, the biomass coke in the step (1) is obtained by cracking biomass such as agricultural and forestry waste.
1. Preferably, the zirconium, lanthanum, magnesium and aluminum source in step (2) are one of salts such as nitrates or chlorides.
Preferably, the calcination temperature in step (3) is 400-800 ℃.
2. The invention further provides an application of the biomass coke-doped zirconium lanthanum magnesium aluminum solid acid catalyst, which is applied to the hydrogen transfer reaction of biomass derivative furfural, wherein the reaction temperature is 100-200 ℃, and the reaction time is 1-10 h.
Aiming at the defects in the prior art, the invention has the following advantages:
(1) the biomass coke is selected as the raw material, has wide sources and low cost, and is suitable for large-scale production.
(2) Zirconium, lanthanum, magnesium and aluminum are loaded by an impregnation method, so that the Lewis acid sites are successfully introduced, and the zirconium lanthanum magnesium aluminum base catalyst with double functions is designed and obtained.
(3) The catalyst is oxidized, and rich oxygen-containing functional groups are introduced, so that the subsequent impregnation of zirconium, lanthanum, magnesium and an aluminum source and the stabilization of active sites in the roasting process can be facilitated on one hand; on the other hand, the catalyst can be beneficial to improving the catalytic activity of the catalyst, and the oxygen-containing functional group can be used as an adsorption site to enhance the adsorption of the catalyst to a substrate and improve the hydrogenation performance of the catalyst.
Drawings
Fig. 1 is an abstract drawing.
FIG. 2 shows the results of acid amount and specific surface area of the solid acid catalyst of biomass coke doped with magnesium aluminum zirconium obtained in examples 1 to 4.
FIG. 3 is a product distribution diagram of hydrogen transfer hydrogenation of furfural catalyzed by the biomass coke-doped zirconium lanthanum magnesium aluminum solid acid catalyst obtained in example 5.
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
Mixing the biomass coke with concentrated nitric acid, stirring for 1 h at 80 ℃, then filtering and washing to be neutral, and then transferring to an oven at 100 ℃ for drying treatment. The dried sample is used as a catalyst carrier, and is stirred and soaked for 24 hours at room temperature with a solution of zirconium nitrate, lanthanum nitrate, magnesium nitrate and aluminum nitrate with the load of 20%, and then is dried for 12 hours in an oven at 100 ℃. And roasting the obtained sample in a 500 ℃ tubular furnace under a nitrogen atmosphere for 4 hours to prepare the biomass coke zirconium-doped magnesium aluminum solid acid catalyst, wherein the specific surface area and the acid amount of the catalyst are shown in figure 2.
Example 2
Mixing the biomass coke with concentrated nitric acid, stirring for 1 h at 80 ℃, then filtering and washing to be neutral, and then transferring to an oven at 100 ℃ for drying treatment. The dried sample is used as a catalyst carrier, and is stirred and soaked for 24 hours at room temperature with a solution of zirconium nitrate, lanthanum nitrate, magnesium nitrate and aluminum nitrate with the load of 20%, and then is dried for 12 hours in an oven at 100 ℃. And roasting the obtained sample in a tube furnace at 600 ℃ for 4 hours under the nitrogen atmosphere, so as to prepare the biomass coke zirconium-doped magnesium aluminum solid acid catalyst, wherein the specific surface area and the acid amount of the catalyst are shown in figure 2.
Example 3
Mixing the biomass coke with concentrated nitric acid, stirring for 1 h at 80 ℃, then filtering and washing to be neutral, and then transferring to an oven at 100 ℃ for drying treatment. The dried sample is used as a catalyst carrier, and is stirred and soaked for 24 hours at room temperature with a solution of zirconium nitrate, lanthanum nitrate, magnesium nitrate and aluminum nitrate with the load of 20%, and then is dried for 12 hours in an oven at 100 ℃. The obtained sample is roasted in a 700 ℃ tube furnace under the nitrogen atmosphere for 4 hours, so that the biomass coke zirconium-doped magnesium-aluminum solid acid catalyst is prepared, and the specific surface area and the acid amount of the catalyst are shown in figure 2.
Example 4
Mixing the biomass coke with concentrated nitric acid, stirring for 1 h at 80 ℃, then filtering and washing to be neutral, and then transferring to an oven at 100 ℃ for drying treatment. The dried sample is used as a catalyst carrier, and is stirred and soaked for 24 hours at room temperature with a solution of zirconium nitrate, lanthanum nitrate, magnesium nitrate and aluminum nitrate with the load of 20%, and then is dried for 12 hours in an oven at 100 ℃. And roasting the obtained sample in a 800 ℃ tubular furnace under a nitrogen atmosphere for 4 hours to prepare the biomass coke zirconium-doped magnesium aluminum solid acid catalyst, wherein the specific surface area and the acid amount of the catalyst are shown in figure 2.
Example 5
The prepared catalyst is applied to the hydrogen transfer reaction of furfural, the reaction temperature is 150 ℃, the reaction time is 3 h, the addition amount of furfural is 0.2 g, the addition amount of the catalyst is 20 mg, the volume of isopropanol is 5 mL, and the product distribution of furfural hydrogen transfer is shown in figure 3.
Claims (5)
1. A preparation method and application of a biomass coke doped zirconium lanthanum magnesium aluminum solid acid catalyst are characterized by comprising the following steps:
(1) mixing the biomass coke with concentrated nitric acid or fuming nitric acid, carrying out hydrothermal treatment at 60-120 ℃, then filtering, washing, recovering, and drying at 60-130 ℃ to obtain a carbon material;
(2) soaking the carbon material obtained in the step 1 in aqueous solution of zirconium, lanthanum, magnesium and aluminum salt for 12-36 h, and then drying in an oven at 60-130 ℃ for 6-20 h;
(3) and (3) placing the dried sample obtained in the step (2) in a tubular furnace, and heating and roasting in an inert atmosphere to obtain the biomass coke zirconium-doped lanthanum magnesium aluminum solid acid catalyst.
2. The method according to claim 1, wherein the biomass char in step (1) is obtained by cracking biomass such as agricultural and forestry waste.
3. The method of claim 1, wherein the zirconium, lanthanum, magnesium and aluminum source in step (2) is one of nitrate or chloride salts.
4. The method as claimed in claim 1, wherein the calcination temperature in step (3) is 400-800 ℃.
5. The application of the biomass coke doped zirconium lanthanum magnesium aluminum solid acid catalyst as claimed in claim 1, is characterized in that: the method is applied to the hydrogen transfer reaction of biomass derivative furfural, the reaction temperature is 100-200 ℃, and the reaction time is 1-10 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114307617A (en) * | 2022-02-25 | 2022-04-12 | 太原理工大学 | Copper oxide composite desulfurizer and preparation method and application thereof |
| CN114345117A (en) * | 2022-02-25 | 2022-04-15 | 太原理工大学 | Ferric oxide composite desulfurizer and preparation method and application thereof |
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