CN113908825B - Solid catalyst containing chromium-magnesium hydrotalcite material composite biochar, and preparation method and application thereof - Google Patents
Solid catalyst containing chromium-magnesium hydrotalcite material composite biochar, and preparation method and application thereof Download PDFInfo
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- CN113908825B CN113908825B CN202111194184.6A CN202111194184A CN113908825B CN 113908825 B CN113908825 B CN 113908825B CN 202111194184 A CN202111194184 A CN 202111194184A CN 113908825 B CN113908825 B CN 113908825B
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- hydrotalcite
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 70
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 67
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 67
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 49
- NACUKFIFISCLOQ-UHFFFAOYSA-N [Mg].[Cr] Chemical compound [Mg].[Cr] NACUKFIFISCLOQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 241000609240 Ambelania acida Species 0.000 claims abstract description 20
- 239000010905 bagasse Substances 0.000 claims abstract description 20
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 38
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000008103 glucose Substances 0.000 claims description 17
- 239000007810 chemical reaction solvent Substances 0.000 claims description 14
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 13
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 13
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 13
- 239000011651 chromium Substances 0.000 claims description 13
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 238000007363 ring formation reaction Methods 0.000 claims description 7
- 150000001844 chromium Chemical class 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 159000000003 magnesium salts Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000002402 hexoses Chemical class 0.000 claims description 4
- 150000002972 pentoses Chemical class 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000003341 Bronsted base Substances 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B01J35/613—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
-
- 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
-
- 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
- C07D307/50—Preparation from natural products
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a solid catalyst of chromium-magnesium-containing hydrotalcite material composite biochar, and a preparation method and application thereof. The preparation method of the solid catalyst comprises the following steps: (1) Dropping NaOH solution into Mg-containing solution 2+ And Cr (V) 3+ In the aqueous solution of (2) until the pH value of the solution is 9-11, filtering and washing the solid after the obtained suspension is aged at constant temperature to obtain Cr-Mg-LDHs hydrotalcite; (2) And (3) fully mixing the Cr-Mg-LDHs hydrotalcite prepared in the step (1) with bagasse, and calcining in a protective gas atmosphere to obtain a solid, namely the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar. According to the invention, the prepared chrome-magnesium hydrotalcite is dispersed by adopting a carbon material, so that the specific surface area of the catalyst is increased, and the catalytic performance of the solid catalyst of the chrome-magnesium hydrotalcite material composite biochar is finally improved, wherein the catalyst has high acid value and high base number.
Description
Technical Field
The invention relates to the technical field of solid catalysts, in particular to a solid catalyst containing chromium-magnesium hydrotalcite material composite biochar, and a preparation method and application thereof.
Background
Various mechanisms of glucose or xylose formation to hydroxymethylfurfural and furfural have been identified and described in numerous documents. Starting from acyclic glucose or xylose, the corresponding ketoses are obtained by 1, 2-hydride displacement or 1, 2-enediol isomerization, which are key intermediates in this mechanism to achieve the cyclisation pathway. In contrast, 1, 2-ene glycol derivatives can provide 2, 3-unsaturated aldehydes as key intermediates. At present, homogeneous catalysts and the like can be adopted in the process of preparing furan compounds such as hydroxymethyl furfural, furfural and the like. Common homogeneous catalysts are sulfuric acid and aluminum chloride. In view of the shortages of homogeneous catalysts in terms of equipment corrosiveness, product separation, waste liquid and waste residue emission and the like, it is necessary to find a catalyst which has high activity and good stability and is easy to separate.
Disclosure of Invention
The invention solves the problems in the prior art, and aims to provide a solid catalyst containing chromium-magnesium hydrotalcite material composite biochar, a preparation method and application thereof, and the solid catalyst is used for catalyzing and synthesizing the hydroxymethylfurfural and the furfural, so that the solid catalyst is convenient to separate from a liquid-phase reaction system, and the yields of the hydroxymethylfurfural and the furfural are respectively up to 94% and 96%.
In order to achieve the above purpose, the invention adopts the following technical scheme: a preparation method of a solid catalyst containing chromium-magnesium hydrotalcite material composite biochar comprises the following steps:
(1) Dropping NaOH solution into Mg-containing solution 2+ And Cr (V) 3+ In the aqueous solution of (2) until the pH value of the solution is 9-11, filtering and washing the solid after the obtained suspension is aged at constant temperature to obtain Cr-Mg-LDHs hydrotalcite;
(2) And (3) mixing the Cr-Mg-LDHs hydrotalcite prepared in the step (1) with bagasse, and calcining in a protective gas atmosphere to obtain a solid, namely the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar.
Preferably, the specific steps of step (1) are: dissolving magnesium salt and chromium salt in water to obtain Mg-containing solution 2+ And Cr (V) 3+ Dropwise adding NaOH solution into the solution until the pH value of the solution reaches 10 to obtain dark green suspension, aging the suspension at 60-100 ℃ for 12-24 hours, and filtering, washing and washing the solid to obtain Cr-Mg-LDHs hydrotalcite.
Further preferably, the magnesium salt is MgCl 2 ·6H 2 O, chromium salt is CrCl 3 ·6H 2 O。
The invention utilizes the acid-base double-function catalytic active sites of the chrome magnesium hydrotalcite to synchronously realize isomerization and cyclization reactions. Wherein the chromium salt serves as a provider of a Lewis acid catalyst center and the magnesium salt serves as a provider of a Bronsted base catalyst center. In addition, the prepared chrome-magnesium hydrotalcite is dispersed by adopting a carbon material, so that the specific surface area of the catalyst is increased, and the catalytic performance of the solid catalyst of the chrome-magnesium hydrotalcite material composite biochar is finally improved.
Preferably, the mass ratio of the Cr-Mg-LDHs hydrotalcite to the bagasse is 1:1-6.
Preferably, the specific conditions for calcination in a protective gas atmosphere are: calcining at 350-450 deg.c for 3.5-4.5 hr under nitrogen protection.
The invention also protects the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar prepared by the preparation method, wherein the chromium/magnesium atomic number ratio of the solid catalyst is 0.32-0.86, and the specific surface area is 85.49-127.15m 2 /g。
The invention firstly adopts a coprecipitation method to prepare a layered hydrotalcite material containing chromium and magnesium, and then bonds the layered hydrotalcite material with mesoporous biochar prepared by taking bagasse as a raw material to prepare the chromium-magnesium-containing hydrotalcite material composite biochar catalyst. The preparation process of the acid-base bifunctional catalyst has high precision, and can prepare a solid catalyst with uniform granularity. The prepared catalyst is easy to recycle, has no corrosion to equipment and is an environment-friendly catalyst. Due to the acid-base double-function catalytic active site, isomerization and cyclization reactions can be synchronously realized. In addition, the bagasse-based mesoporous carbon material is adopted to disperse the prepared chrome magnesium hydrotalcite, so that the specific surface area of the catalyst is improved.
The invention also protects the application of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar in the reaction of preparing furfural and furfural derivatives by dehydration cyclization of hexose and pentose. Aiming at the characteristics of the reaction of producing furfural and furfural derivatives by the dehydration cyclization of hexose and pentose, the invention designs and prepares the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar, and applies the solid catalyst to the dehydration cyclization reaction of hexose and pentose.
Preferably, the preparation method of the furfural and/or the furfural derivative comprises the following steps: glucose, xylose and the solid catalyst are mixed and dissolved in a reaction solvent, wherein the reaction solvent is a mixed solution of deionized water and dimethyl sulfoxide with the volume ratio of 1:3, and the mixed solution reacts for 11-13 hours at the temperature of 95-105 ℃ to obtain the hydroxymethylfurfural and the furfural.
Further preferably, the mass ratio of the glucose to the xylose is 1:1, the mass-volume ratio of the glucose to the reaction solvent is 150:1mg/mL, and the mass ratio of the glucose to the solid catalyst is 7.5:1.
Compared with the prior art, the invention has the beneficial effects that:
(1) Firstly, adopting a coprecipitation method to fix chromium and magnesium in a layered hydrotalcite structure in a hydroxide precipitation mode; and then the chromium-magnesium hydrotalcite material is bonded on the surface of the biochar by utilizing the affinity effect of rich oxygen-containing groups on the surface of the carbon material and strong electronegative metal ions, and meanwhile, the distribution of catalytic activity sites and the specific surface area of the main structure of the catalyst are improved, so that the catalytic performance of the catalyst is improved.
(2) The invention prepares chromium ions into a solid catalyst through hydrotalcite structure, and the solid catalyst is used for replacing homogeneous chromium salt to catalyze dehydration cyclization reaction; the specific surface area of the hydrotalcite-like catalyst is increased by using carbonized biomass raw materials with high specific surface area, and the dispersibility and stability of active centers of the hydrotalcite-like catalyst are improved.
(3) The catalyst prepared by the invention has an acid catalytic center and a base catalytic center, wherein the base catalysis is favorable for the isomerization of the simple substance sugar, so that the structure of the catalyst is easier to dehydrate and cyclize under the action of the acid catalyst, and finally the required product is obtained with high efficiency.
Drawings
FIG. 1 is a graph showing the distribution of the elements of a transmission electron microscope of a solid catalyst of chromium-magnesium-containing hydrotalcite material composite biochar prepared in example 2;
FIG. 2 is a scanning electron microscope image of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar prepared in example 2;
FIG. 3 is a scanning electron microscope image of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar prepared in example 3;
FIG. 4 is a scanning electron microscope image of a solid catalyst of chromium-magnesium-containing hydrotalcite material composite biochar prepared in comparative example 1;
FIG. 5 is a graph showing the ammonia gas temperature programmed desorption of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar prepared in example 2 and the chromium-magnesium-containing hydrotalcite of comparative example 1;
fig. 6 is a carbon dioxide temperature programmed desorption spectrum of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar prepared in example 2 and the chromium-magnesium-containing hydrotalcite of comparative example 1.
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are conventional commercially available products in the art, unless specifically indicated.
The method for characterization of the solid catalyst in the following examples is: the ratio of chromium to magnesium atoms of the prepared catalyst is calculated by adopting an X-ray photoelectron spectroscopy test, and the specific surface area of the prepared catalyst is tested by adopting a BET specific surface area and a void analyzer.
Example 1
The preparation method of the chromium-magnesium-containing hydrotalcite material composite biochar catalyst specifically comprises the following steps:
(1) Preparation of Cr-Mg-LDHs hydrotalcite material: mgCl was dissolved in 250mL deionized water 2 ·6H 2 O and CrCl 3 ·6H 2 O powder, wherein MgCl 2 ·6H 2 O and CrCl 3 ·6H 2 O with the mass ratio of 13:10, dropwise adding 2mol/L NaOH solution into the solution until the pH value of the solution reaches 10, obtaining dark green suspension, aging the suspension at 80 ℃ for 24 hours, filtering the solid, and washing the solid with deionized water to obtain the Cr-Mg-LDHs hydrotalcite material.
(2) Preparation of biochar and compounding of the biochar and Cr-Mg-LDHs hydrotalcite material: pulverizing sun-dried bagasse in a traditional Chinese medicine pulverizer, collecting powder below 400 meshes with a screen, drying in an oven at 80 ℃ for 12 hours to obtain bagasse powder, uniformly mixing the bagasse powder with Cr-Mg-LDHs hydrotalcite material, wherein the mass ratio of the bagasse powder to the Cr-Mg-LDHhydrotalcite is 1:2, placing the mixed powder into a high-temperature atmosphere furnace, calcining for 4 hours at 400 ℃ under the protection of nitrogen, and placing the obtained black powder into a grinding bowl for grinding, thus obtaining the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar. The scanning electron microscope is shown in fig. 1.
The catalyst has a chromium/magnesium atomic number ratio of 0.36 and a specific surface area of 85.49m 2 /g。
Examples 2 to 10:
the preparation steps of the chromium-magnesium-containing hydrotalcite material composite biochar catalyst are the same as in example 1, and the preparation conditions, chromium-magnesium element content and specific surface area of the obtained catalyst are shown in Table 1, which are different from those of example 1. The scanning electron microscope image of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar prepared in the example 2 is shown in fig. 2, and the scanning electron microscope image of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar prepared in the example 3 is shown in fig. 3.
Example 11
The preparation method of the chromium-magnesium-containing hydrotalcite material composite biochar catalyst specifically comprises the following steps:
(1) Preparation of Cr-Mg-LDHs hydrotalcite material: mgCl was dissolved in 250mL deionized water 2 ·6H 2 O and CrCl 3 ·6H 2 O powder, wherein MgCl 2 ·6H 2 O and CrCl 3 ·6H 2 O with the mass ratio of 13:10, dropwise adding 2mol/L NaOH solution into the solution until the pH value of the solution reaches 9, obtaining dark green suspension, keeping the suspension at 60 ℃ for 24 hours at a certain stirring speed, filtering the solid, and washing the solid with deionized water to obtain the Cr-Mg-LDHs hydrotalcite material.
(2) Preparation of biochar and compounding of the biochar and Cr-Mg-LDHs hydrotalcite material: pulverizing sun-dried bagasse in a traditional Chinese medicine pulverizer, collecting powder below 400 meshes with a screen, drying in an oven at 80 ℃ for 12 hours to obtain bagasse powder, uniformly mixing the bagasse powder with Cr-Mg-LDHs hydrotalcite material, wherein the mass ratio of the bagasse powder to the Cr-Mg-LDHhydrotalcite is 1:2, placing the mixed powder into a high-temperature atmosphere furnace, calcining for 4.5 hours at 350 ℃ under the protection of nitrogen, and placing the obtained black powder into a grinding bowl for grinding, thus obtaining the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar.
Example 12:
the preparation method of the chromium-magnesium-containing hydrotalcite material composite biochar catalyst specifically comprises the following steps:
(1) Preparation of Cr-Mg-LDHs hydrotalcite material: mgCl was dissolved in 250mL deionized water 2 ·6H 2 O and CrCl 3 ·6H 2 O powder, wherein MgCl 2 ·6H 2 O and CrCl 3 ·6H 2 O with the mass ratio of 13:10, dropwise adding 2mol/L NaOH solution into the solution until the pH value of the solution reaches 11, obtaining dark green suspension, keeping the suspension at 100 ℃ for 12 hours at a certain stirring speed, filtering the solid, and washing the solid with deionized water to obtain the Cr-Mg-LDHs hydrotalcite material.
(2) Preparation of biochar and compounding of the biochar and Cr-Mg-LDHs hydrotalcite material: pulverizing sun-dried bagasse in a traditional Chinese medicine pulverizer, collecting powder below 400 meshes with a screen, drying in an oven at 80 ℃ for 12 hours to obtain bagasse powder, uniformly mixing the bagasse powder with Cr-Mg-LDHs hydrotalcite material, wherein the mass ratio of the bagasse powder to the Cr-Mg-LDHhydrotalcite is 1:2, placing the mixed powder into a high-temperature atmosphere furnace, calcining for 3.5 hours at 450 ℃ under the protection of nitrogen, and placing the obtained black powder into a grinding bowl for grinding, thus obtaining the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar.
Comparative example 1:
the preparation method of the chromium-magnesium-containing hydrotalcite material directly used as a catalyst comprises the following steps:
MgCl was dissolved in 250mL deionized water 2 ·6H 2 O and CrCl 3 ·6H 2 O powder, wherein MgCl 2 ·6H 2 O and CrCl 3 ·6H 2 O with the mass ratio of 13:10, dropwise adding 2mol/L NaOH solution into the solution until the pH value reaches 10, and obtaining dark green suspension. The suspension was kept at 80 ℃ for 24 hours, and then the solid was filtered and washed with deionized water to prepare hydrotalcite catalyst Cr-Mg-LDH which was not complexed with biochar. A scanning electron microscope image of the solid catalyst is shown in FIG. 4.
The ammonia gas temperature programmed desorption spectra of the solid catalysts of example 2 and comparative example 1 are shown in fig. 5, and as can be seen from the figure, the catalyst prepared in example 2 and the solid catalyst prepared in comparative example 1 both have characteristic peaks representing medium-strength acid and high-strength acid between 400K and 800K, and the prepared catalyst has strong acidity; after being compounded with carbon, the acid strength is even further improved, and a characteristic peak appears above 800K.
The carbon dioxide temperature programmed desorption spectra of the solid catalysts of example 2 and comparative example 1 are shown in fig. 6, and characteristic peaks representing medium-strength alkali and high-strength alkali appear between 400K and 800K for both the catalyst prepared in example 2 and the solid catalyst prepared in comparative example 1, which proves that the prepared catalyst has strong acidity; after being compounded with carbon, the alkali strength is even further improved, and a characteristic peak appears above 800K.
Chromium/magnesium atoms of the catalyst testedThe number ratio was 0.50, the specific surface area was 4.26m 2 /g。
TABLE 1
It can be seen from table 1 that the mass ratio of Mg salt to Cr salt in step (1), the aging temperature in step (1), the aging time in step (1) and the mass ratio of bagasse to hydrotalcite in step (2) have significant influence on the chromium/magnesium atomic number ratio and specific surface area of the prepared solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar. The ratio of chromium to magnesium atoms affects the crystal form integrity of the hydrotalcite structure, and the specific surface area also affects the catalytic activity of the prepared catalyst.
Example 13:
mixing 750mg of glucose, 750mg of xylose and the solid catalyst obtained in example 1, adding the mixture into 5mL of reaction solvent, reacting for 12 hours at 100 ℃ in a mixed solution of deionized water and dimethyl sulfoxide in a volume ratio of 1:3, and respectively obtaining the yields of 44.2% and 62.5% of hydroxymethylfurfural and furfural by liquid chromatography analysis.
Example 14:
mixing 750mg of glucose, 750mg of xylose and the solid catalyst obtained in example 2, adding the mixture into 5mL of reaction solvent, reacting the mixture for 12 hours at 100 ℃ with the volume ratio of deionized water to dimethyl sulfoxide as a mixed solution of 1:3, and carrying out liquid chromatography analysis to obtain the hydroxymethylfurfural and furfural with the yields of 86.3% and 90.4% respectively.
Example 15:
mixing 750mg of glucose, 750mg of xylose and the solid catalyst obtained in comparative example 1, adding the mixture into 5mL of reaction solvent, reacting the mixture for 12 hours at 100 ℃ with the volume ratio of deionized water to dimethyl sulfoxide as a mixed solution of 1:3, and respectively obtaining the yield of 8.4% and 15.2% of hydroxymethylfurfural and furfural by liquid chromatography analysis.
Example 16:
mixing 750mg of glucose, 750mg of xylose and the solid catalyst obtained in comparative example 1, adding the mixture into 5mL of reaction solvent, reacting the mixture at 95 ℃ for 13 hours, wherein the reaction solvent is a mixed solution of deionized water and dimethyl sulfoxide in a volume ratio of 1:3, and the yields of the hydroxymethylfurfural and the furfural are 3.5% and 7.9% respectively through liquid chromatography analysis.
Example 17:
mixing 750mg of glucose, 750mg of xylose and the solid catalyst obtained in comparative example 1, adding the mixture into 5mL of reaction solvent, reacting for 11 hours at 105 ℃ in a mixed solution of deionized water and dimethyl sulfoxide in a volume ratio of 1:3, and carrying out liquid chromatographic analysis to obtain the hydroxymethylfurfural and furfural with the yields of 9.1% and 6.4% respectively.
Example 18:
mixing 750mg of glucose, 750mg of xylose and the solid catalyst obtained in example 1, adding the mixture into 5mL of reaction solvent, reacting the mixture at 95 ℃ for 13 hours, wherein the volume ratio of deionized water to dimethyl sulfoxide is 1:3, and the yields of hydroxymethylfurfural and furfural are 26.5% and 53.6% respectively through liquid chromatography analysis.
Example 19:
mixing 750mg of glucose, 750mg of xylose and the solid catalyst obtained in example 1, adding the mixture into 5mL of reaction solvent, reacting for 11 hours at 105 ℃ in a mixed solution of deionized water and dimethyl sulfoxide in a volume ratio of 1:3, and carrying out liquid chromatographic analysis to obtain the hydroxymethylfurfural and furfural with the yields of 37.4% and 45.7% respectively.
The above examples are only preferred embodiments of the present invention, and it should be noted that the above preferred embodiments should not be construed as limiting the invention, and the scope of the invention should be defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (8)
1. The application of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar in the reaction of preparing furfural and furfural derivatives by the dehydration cyclization of hexose and pentose is characterized in that the preparation method of the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar comprises the following steps:
(1) Dropping NaOH solution into Mg-containing solution 2+ And Cr (V) 3+ In the aqueous solution of (2) until the pH value of the solution is 9-11, filtering and washing the solid after the obtained suspension is aged at constant temperature to obtain Cr-Mg-LDHs hydrotalcite;
(2) And (3) mixing the Cr-Mg-LDHs hydrotalcite prepared in the step (1) with bagasse, and calcining in a protective gas atmosphere to obtain a solid, namely the solid catalyst of the chromium-magnesium-containing hydrotalcite material composite biochar.
2. The use according to claim 1, wherein the specific steps of step (1) are: dissolving magnesium salt and chromium salt in water to obtain Mg-containing solution 2+ And Cr (V) 3+ Dropwise adding NaOH solution into the solution until the pH value of the solution reaches 10 to obtain dark green suspension, aging the suspension at 60-100 ℃ for 12-24 hours, and filtering and washing the solid to obtain Cr-Mg-LDHs hydrotalcite.
3. The use according to claim 2, wherein the magnesium salt is MgCl 2 ·6H 2 O, chromium salt is CrCl 3 ·6H 2 O。
4. The use according to claim 1, wherein the mass ratio of Cr-Mg-LDHs hydrotalcite to bagasse is 1:1-6.
5. The use according to claim 1, characterized in that the specific conditions of calcination in a protective gas atmosphere are: calcining at 350-450 deg.c for 3.5-4.5 hr under nitrogen protection.
6. According to claim 1The application of the catalyst is characterized in that the solid catalyst has a chromium/magnesium atomic number ratio of 0.32-0.86 and a specific surface area of 85.49-127.15m 2 /g。
7. The use according to claim 1, characterized by the steps of: glucose, xylose and the solid catalyst are mixed and dissolved in a reaction solvent, wherein the reaction solvent is a mixed solution of deionized water and dimethyl sulfoxide in a volume ratio of 1:3, and the mixed solution reacts at 95-105 ℃ for 11-13h to obtain hydroxymethylfurfural and furfural.
8. The use according to claim 7, wherein the mass ratio of glucose to xylose is 1:1, the mass/volume ratio of glucose to reaction solvent is 150:1mg/mL, and the mass ratio of glucose to solid catalyst is 7.5:1.
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