CN115193470B - Sulfuric acid modified MCM-41 loaded single metal type solid acid catalyst and preparation and application thereof - Google Patents
Sulfuric acid modified MCM-41 loaded single metal type solid acid catalyst and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- -1 Sulfuric acid modified MCM-41 Chemical class 0.000 title claims abstract description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011973 solid acid Substances 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 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 abstract description 47
- 239000008103 glucose Substances 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 15
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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 claims description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 2
- 235000019743 Choline chloride Nutrition 0.000 claims description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 2
- 229960003178 choline chloride Drugs 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 13
- 239000002808 molecular sieve Substances 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 230000002051 biphasic effect Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229930091371 Fructose Natural products 0.000 description 15
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 15
- 239000005715 Fructose Substances 0.000 description 15
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- GAUQOWHNIIHLQU-UHFFFAOYSA-N nitric acid sulfuric acid hydrochloride Chemical compound Cl.O[N+]([O-])=O.OS(O)(=O)=O GAUQOWHNIIHLQU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a sulfuric acid modified MCM-41 supported single metal type solid acid catalyst, and preparation and application thereof. The catalyst of the invention takes all-silicon molecular sieve MCM-41 as a carrier, and adds the active metal aluminum to the neutral MCM-41 molecular sieve through sulfuric acid modification and loading
Description
Technical Field
The invention belongs to the technical field of solid acid catalysis, and particularly relates to a sulfuric acid modified MCM-41 supported single-metal type solid acid catalyst, and preparation and application thereof.
Background
Along with the consumption of fossil energy and environmental pollution, the conversion of biomass into biofuel, which aims at replacing fossil fuel, is receiving a great deal of attention. The lignocellulose biomass is used as only a renewable carbon source, has abundant reserves and low price, can be converted into energy fuels and high added value chemicals, can obtain various renewable bio-based materials through biological, physical or chemical methods, and has important significance for gradually replacing non-renewable fossil energy sources and global sustainable development strategies. The cellulose with the largest content in lignocellulose can be efficiently hydrolyzed into glucose, the glucose is used as the most common hexose to be isomerized into fructose, the fructose is dehydrated to generate the pentahydroxymethyl furfural, and the pentahydroxymethyl furfural can be converted into various fuels and fine chemicals with high added values through selective oxidation, hydrogenation, etherification, condensation and other modes, so that the pentahydroxymethyl furfural is a platform compound with great development prospect. Most of the synthesis of the industrial pentahydroxy methyl furfural has been focused on fructose as a raw material and a homogeneous inorganic acid as a catalyst, and the reaction system has high raw material conversion rate and yield, but the reaction system has problems of high raw material price, difficult product separation, incapability of recovering the homogeneous acid catalyst, corrosion of equipment by liquid acid and the like. Therefore, it is highly necessary to use glucose instead of fructose as a raw material, reduce the raw material cost, and explore an effective heterogeneous catalyst instead of a homogeneous acid catalyst system.
The mesoporous aluminum doped MCM-41 silica catalyst is prepared by the steps of acid hydrolysis and alkali hydrolysis through a sol-gel method by Ignacio Jimez-Morales et al (Applied catalysis. B, environmental,2015, 164:70-76), the glucose conversion rate and the HMF yield in a biphasic system reach 98% and 63%, the catalytic performance of the acid solid is related to the existence of a strong acid site, the yield of the HMF is 46% after the second cycle use, and the catalyst circulation effect is poor. Son Tung Pham et al (chemosphere.2021, 265: 129062) found that the production of pentahydroxymethyl furfural and the conversion of cellulose were strongly dependent on total acid, strong/medium/weak acid ratio andthe acid ratio is that he synthesizes the MCM-41 molecular sieve doped with aluminum by a hydrothermal method, the yield of HMF is 40.56% under the optimal reaction condition, but the acid sites of the catalyst are not more, and the yield of HMF is not high.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the primary purpose of the invention is to provide a preparation method of a sulfuric acid modified MCM-41 supported single metal type solid acid catalyst.
Another object of the present invention is to provide a sulfuric acid modified MCM-41 supported single metal type solid acid catalyst prepared by the above method.
The invention also aims to provide the application of the sulfuric acid modified MCM-41 supported single metal type solid acid catalyst in preparing the pentahydroxy methyl furfural from glucose.
The invention aims at realizing the following technical scheme:
a preparation method of a sulfuric acid modified MCM-41 supported single metal type solid acid catalyst comprises the following steps:
(1) Adding all-silicon MCM-41 carrier into sulfuric acid solution, stirring at 30-70 ℃ for reaction for 5-10 h, filtering, and drying to obtain modified molecular sieve MCM-41/S;
(2) Adding the modified molecular sieve MCM-41/S into an aluminum salt solution, uniformly mixing, dipping, drying and calcining to obtain the sulfuric acid modified molecular sieve supported single metal type solid acid catalyst Al-MCM-41/S.
Preferably, the sulfuric acid solution in the step (1) is a 10-25 wt% sulfuric acid aqueous solution.
Preferably, the volume mass ratio of the sulfuric acid solution in the step (1) to the all-silicon MCM-41 carrier is 5-20 mL:0.5 g to 3g.
Preferably, the water bath temperature in the step (1) is 50 ℃, and the stirring time is 6 hours.
Preferably, the drying temperature in the steps (1) and (2) is 100-110 ℃, and the drying time is 8-12 h.
Preferably, the mass ratio of aluminum in the aluminum salt in the step (2) to the modified molecular sieve MCM-41/S is 2.5-12.5: 100; more preferably 5 to 10:100, most preferably 7.5 to 10:100.
preferably, the concentration of the aluminum salt solution in the step (2) is 0.104-0.521 g/mL, more preferably 0.313g/mL; the mass volume ratio of the modified molecular sieve MCM-41/S to the aluminum salt solution is 0.1-0.5 g: 0.5-3 mL. The aluminum salt in the aluminum salt solution is at least one of aluminum nitrate and aluminum chloride.
Preferably, the uniform mixing in the step (2) means that the ultrasonic oscillation time is 20-30 min.
Preferably, the soaking time in the step (2) is 12-24 hours.
Preferably, the calcining temperature in the step (2) is 400-600 ℃ and the time is 3-7 h; the temperature rising rate is 2-7 ℃/min, more preferably 500 ℃,5h,5 ℃/min.
The sulfuric acid modified MCM-41 supported single metal type solid acid catalyst prepared by the method.
The application of the sulfuric acid modified MCM-41 supported single metal type solid acid catalyst in preparing the pentahydroxy methyl furfural from glucose comprises the following steps:
and uniformly mixing the sulfuric acid modified MCM-41 loaded single-metal type solid acid catalyst, glucose and a solvent, reacting at 170-210 ℃ for 0.5-2.5 hours under the condition of nitrogen or inert gas, ending the reaction, cooling to room temperature, centrifuging, separating solid from liquid, and separating liquid to obtain a water phase and an organic phase, wherein the organic phase contains the pentahydroxy methyl furfural.
Preferably, the sulfuric acid modified MCM-41 supported single metal type solid acid catalyst, glucose and solvent have a proportion of 0.025-0.125 g:0.1 to 0.5g:25 to 45mL, more preferably 0.075 to 0.125g:0.1g:35mL.
Preferably, the solvent is at least one of dimethyl sulfoxide, a mixed solution of water and methyl isobutyl ketone, a mixed solution of choline chloride aqueous solution and methyl isobutyl ketone, and a mixed solution of sodium chloride aqueous solution and methyl isobutyl ketone, and more preferably, the volume ratio is 1:4 to 8, and most preferably, the volume ratio of the mixed solution of the sodium chloride aqueous solution and the methyl isobutyl ketone is 1:6 and 10 to 25 weight percent of sodium chloride aqueous solution and methyl isobutyl ketone.
Preferably, the reaction temperature is 170-190 ℃ and the time is 1-2 h.
Preferably, the reaction is carried out in an autoclave, which is rapidly cooled to room temperature in an ice-water bath, and then the gas in the autoclave is vented in a fume hood.
Compared with the prior art, the invention has the following advantages:
the invention fully and uniformly mixes the active components and the carrier by ultrasonic vibration in the metal loading process, and the carrier MCM-41 molecular sieve has good stability, large specific surface area and pore canal junctionThe synthesis process of the sulfuric acid modified molecular sieve supported single metal type solid acid catalyst is convenient and simple, and the raw materials are cheap and easy to obtain. Modification of neutral MCM-41 molecular sieve directly with sulfuric acid solution and additionAnd the acid site is added by loading low-cost metal aluminum, so that the solid acid catalyst which is easy to separate from a reaction system and has no pollution to the environment is obtained. />The synergistic effect of the acid and the Lewis acid is favorable for the glucose reaction to generate the pentahydroxy methyl furfural, and when the loading capacity of Al is 7.5wt% at 190 ℃, the conversion rate of the glucose in a biphasic reaction system of sodium chloride aqueous solution and methyl isobutyl ketone is up to 98.76%, and the yield of the pentahydroxy methyl furfural is up to 63.71%; after the fourth recycling of the catalyst, the yield of the pentahydroxy methyl furfural is still kept at 54.12%.
Drawings
Fig. 1 is an SEM image and a TEM image of the catalyst obtained in example 3, wherein the SEM image: (a) MCM-41, (b) 7.5Al-MCM-41/S; TEM image: (c) MCM-41, (d) 7.5Al-MCM-41/S.
Fig. 2 is an XRD pattern of the catalyst obtained in example 3.
Fig. 3 is a graph showing the yield of the resulting pentahydroxy methyl furfural by recycling the solid acid catalyst according to the conditions of example 10.
FIG. 4 is an in situ pyridine adsorption infrared spectrum of the solid acid catalyst of example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The specific conditions are not noted in the examples of the present invention, and are carried out according to conventional conditions or conditions suggested by the manufacturer. The raw materials, reagents, etc. used, which are not noted to the manufacturer, are conventional products commercially available.
In the following examples, glucose and pentahydroxymethyl furfural were measured by High Performance Liquid Chromatography (HPLC) analysis, and the calculation method of HPLC detection adopts an external standard method. The sulfuric acid modified MCM-41 supported single metal type solid acid catalyst was characterized by an X-ray diffractometer (X' pert Powder), ultra-high resolution field emission electron microscope (SU 8220), field emission transmission electron microscope (JEM 2100F), and pyridine infrared.
The calculation formula of the yield of the pentahydroxy methyl furfural of the catalytic product in the following examples is: y=amount of substance of pentahydroxy methyl furfural/amount of substance added with glucose x 100%, the calculation formula of fructose is: y=amount of fructose substance/amount of glucose added substance×100%, the calculation formula of the glucose conversion is: c= (amount of added glucose-amount of remaining glucose)/amount of added glucose x 100%.
Examples 1 to 5
Diluting concentrated sulfuric acid into 10% sulfuric acid water solution, weighing 20mL, putting into a beaker, adding 2G of all-silicon MCM-41 molecular sieve, putting into a water bath kettle, magnetically stirring at constant temperature of 50 ℃ for 6 hours, filtering with a G4 glass sand core funnel after the reaction is finished, washing with distilled water to be neutral, and drying in a forced air drying box at 105 ℃ for 10 hours to obtain the modified molecular sieve carrier (MCM-41/S).
Weighing 0.104g, 0.208g, 0.313g, 0.417g and 0.521g of Al (NO) 3 ) 3 ·9H 2 O is dissolved in 5 small beakers by using 1ml of deionized water, 0.3g of sulfuric acid modified molecular sieve carrier is added, stirring is uniform, ultrasonic oscillation is carried out for 30min, standing is carried out at room temperature for 24h, and then the mixture is placed in a muffle furnace for calcination at 500 ℃ for 5h, wherein the heating rate is 5 ℃/min, and the catalyst with the metal Al loading of 2.5, 5, 7.5, 10 and 12.5wt% is obtained and is recorded as xAl-MCM-41/S (x=2.5, 5, 7.5, 10 and 12.5), and the catalyst is shown in table 1.
Adding 0.1g glucose, 0.1g catalyst, 5mL sodium chloride aqueous solution with mass concentration of 20% and 30mL methyl isobutyl ketone into a high-pressure reaction kettle, introducing nitrogen into the high-pressure reaction kettle to replace air in the kettle, reacting at 170 ℃ for 1h, cooling the reaction kettle to room temperature by tap water after the reaction is finished at 600rpm, separating solid from liquid by centrifugation, separating liquid to obtain an organic phase and a water phase, and analyzing a product in the organic phase and the water phase by high performance liquid chromatography, wherein the conversion rate of the obtained glucose, the yield of the pentahydroxy methyl furfural and the yield of the fructose are shown in table 1.
TABLE 1 influence of different loadings on the production of pentahydroxymethyl furfural from glucose
Examples 6 to 9
The modified molecular sieve carrier was prepared by referring to the preparation process of the modified molecular sieve carrier in examples 1 to 5.
1.0417g of Al (NO) was weighed out 3 ) 3 ·9H 2 O is dissolved in a beaker by using 2ml of deionized water, 1g of sulfuric acid modified molecular sieve carrier is added, stirring is uniform, ultrasonic oscillation is carried out for 30min, standing is carried out at room temperature for 24h, then the mixture is placed in a muffle furnace for calcination at 500 ℃ for 5h, wherein the heating rate is 5 ℃/min, and the catalyst with 7.5wt% of metal Al load is obtained and is recorded as 7.5Al-MCM-41/S.
0.1g glucose, 5mL sodium chloride aqueous solution with mass concentration of 20% and 30mL methyl isobutyl ketone are added into a high-pressure reaction kettle, 0.025 g catalyst, 0.05 g catalyst, 0.075g catalyst, 0.1g catalyst and 0.125g catalyst are respectively added in parallel experiments, nitrogen is introduced into the high-pressure reaction kettle to replace air in the kettle, the reaction is carried out at 170 ℃ for 1h at the speed of 600rpm, after the reaction is finished, the reaction kettle is cooled to room temperature by tap water, solid-liquid separation is carried out through centrifugation, liquid is separated to obtain an organic phase and an aqueous phase, and products in the organic phase and the aqueous phase are analyzed by high performance liquid chromatography, so that the glucose conversion rate, the penta-hydroxymethylfurfural yield and the fructose yield are shown in table 2.
TABLE 2 influence of different catalyst dosages on the preparation of pentahydroxy methyl furfural from glucose
| Examples | 6 | 7 | 8 | 3 | 9 |
| Catalyst amount/g | 0.025 | 0.05 | 0.075 | 0.1 | 0.125 |
| Glucose conversion/% | 85.27 | 90.98 | 96.28 | 96.51 | 97.02 |
| Pentahydroxymethyl furfural yield/% | 55.92 | 60.63 | 63.45 | 62.61 | 61.82 |
| Fructose yield/% | 2.01 | 1.57 | 1.03 | 1.02 | 0.92 |
Examples 10 to 11 and comparative examples 1 to 2
A sulfuric acid modified MCM-41 molecular sieve supported catalyst of 7.5wt% Al was prepared in accordance with the catalyst preparation procedure of examples 6-9, designated 7.5Al-MCM-41/S.
Adding 0.1g glucose, 0.075g catalyst, 5mL sodium chloride aqueous solution with mass concentration of 20% and 30mL methyl isobutyl ketone into a high-pressure reaction kettle, introducing nitrogen into the high-pressure reaction kettle to replace air in the kettle, respectively reacting for 1h at 130, 150, 170, 190 and 210 ℃, cooling the reaction kettle to room temperature by using tap water after the reaction is finished, separating liquid into an organic phase and a water phase after solid-liquid separation by centrifugation, and analyzing products in the organic phase and the water phase by using high performance liquid chromatography, wherein the glucose conversion rate, the pentahydroxy methyl furfural yield and the fructose yield are shown in Table 3.
TABLE 3 influence of different reaction temperatures on the preparation of pentahydroxymethyl furfural from glucose
| Comparative example 1 | Comparative example 2 | Example 8 | Example 10 | Example 11 | |
| Reaction temperature/. Degree.C | 130 | 150 | 170 | 190 | 210 |
| Glucose conversion/% | 11.75 | 73.68 | 96.28 | 98.76 | 99.58 |
| Pentahydroxymethyl furfural yield/% | 0.9 | 20.75 | 63.45 | 63.71 | 59.13 |
| Fructose yield/% | 3.12 | 2.95 | 1.03 | 0.50 | 0.03 |
Examples 12 to 15
A sulfuric acid modified MCM-41 molecular sieve supported catalyst of 7.5wt% Al was prepared in accordance with the catalyst preparation procedure of examples 6-9, designated 7.5Al-MCM-41/S.
0.1g glucose, 0.075g catalyst, 5mL sodium chloride aqueous solution with mass concentration of 20% and 30mL methyl isobutyl ketone are added into a high-pressure reaction kettle, nitrogen is introduced into the high-pressure reaction kettle to replace air in the kettle, the reaction is carried out at 190 ℃ for 0.5 h, 1h, 1.5 h, 2h and 2.5h respectively, the rotating speed is 600rpm, after the reaction is finished, the reaction kettle is cooled to room temperature by tap water, solid-liquid separation is carried out through centrifugation, liquid is separated to obtain an organic phase and an aqueous phase, and products in the organic phase and the aqueous phase are analyzed by high performance liquid chromatography, wherein the conversion rate of glucose, the yield of the pentahydroxy methyl furfural and the yield of fructose are shown in Table 4.
Example 10 after the end of the reaction, the catalyst after the reaction was separated by centrifugation, washed with distilled water and ethanol three times, dried, and subjected to the experiment of catalyzing glucose to prepare pentahydroxymethyl furfural according to the conditions of example 10, and thus circulated, the HMF yield of the catalyst used for the first time was 63.71%, the HMF yield after the first time (i.e., used for the second time) was 60.57%, the HMF yield after the second time (i.e., used for the third time) was 58.31%, the HMF yield after the third time (i.e., used for the fourth time) was 55.97%, and the HMF yield after the fourth time (i.e., used for the fifth time) of the prepared solid acid catalyst remained at 54.12%.
TABLE 4 influence of different reaction times on the preparation of pentahydroxymethyl furfural from glucose
| Examples | 12 | 10 | 13 | 14 | 15 |
| Reaction time/h | 0.5 | 1 | 1.5 | 2 | 2.5 |
| Glucose conversion/% | 90.1 | 98.76 | 99.93 | 99.55 | 99.76 |
| Pentahydroxymethyl furfural yield/% | 58.1 | 63.71 | 63.1 | 60.54 | 58.53 |
| Fructose yield/% | 3.12 | 0.50 | 0.11 | 0.05 | 0.04 |
Comparative examples 3 to 4
Respectively diluting hydrochloric acid and nitric acid into aqueous solutions with the mass concentration of 10%, weighing 20mL, putting the aqueous solutions into a beaker, respectively adding 2G of all-silicon MCM-41 molecular sieve, putting the aqueous solutions into a water bath kettle, magnetically stirring the aqueous solutions at the constant temperature of 50 ℃ for 6 hours, filtering the aqueous solutions by using a G4 glass sand core funnel after the reaction is finished, washing the aqueous solutions to be neutral by using distilled water, and drying the aqueous solutions at the temperature of 105 ℃ for 10 hours in a blast drying box to respectively obtain the hydrochloric acid modified molecular sieve carrier and the nitric acid modified molecular sieve carrier.
1.0417g of Al (NO) was weighed out separately 3 ) 3 ·9H 2 O is dissolved in a beaker by using 2ml of deionized water, 1g of hydrochloric acid modified molecular sieve carrier and nitric acid modified molecular sieve carrier are respectively added, uniformly stirred, subjected to ultrasonic vibration for 30min, and placed in a muffle furnace for calcination at 500 ℃ for 5h after standing for 24h at room temperature, wherein the heating rate is 5 ℃/min, and the hydrochloric acid modified catalyst and the nitric acid modified catalyst with the Al loading amount of 7.5wt% are respectively obtained.
0.1g glucose, 0.075g catalyst, 5mL sodium chloride aqueous solution with mass concentration of 20% and 30mL methyl isobutyl ketone are added into a high-pressure reaction kettle, nitrogen is introduced into the high-pressure reaction kettle to replace air in the kettle, the reaction is carried out for 1h at 190 ℃, the rotating speed is 600rpm, after the reaction is finished, the reaction kettle is cooled to room temperature by tap water, solid-liquid separation is carried out by centrifugation, liquid is separated to obtain an organic phase and an aqueous phase, and products in the organic phase and the aqueous phase are analyzed by high performance liquid chromatography, wherein the glucose conversion rate, the yield of the pentahydroxy methyl furfural and the yield of the fructose are shown in table 5.
TABLE 5 influence of different acid modifications on the preparation of pentahydroxymethyl furfural from glucose
| Example 10 | Comparative example 3 | Comparative example 4 | |
| Species of modifying acid | Sulfuric acid | Hydrochloric acid | Nitric acid |
| Glucose conversion/% | 98.76 | 95.08 | 94.11 |
| Pentahydroxymethyl furfural yield/% | 63.71 | 50.29 | 48.53 |
| Fructose yield/% | 0.50 | 1.55 | 1.83 |
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. The application of the sulfuric acid modified MCM-41 supported single-metal type solid acid catalyst in preparing the pentahydroxymethyl furfural from glucose is characterized in that the preparation method of the sulfuric acid modified MCM-41 supported single-metal type solid acid catalyst comprises the following steps:
(1) Adding all-silicon MCM-41 carrier into sulfuric acid solution, stirring at 30-70 ℃ for reaction for 5-10 h, filtering, and drying to obtain modified molecular sieve MCM-41/S;
(2) Adding the modified molecular sieve MCM-41/S into an aluminum salt solution, uniformly mixing, dipping, drying and calcining to obtain a sulfuric acid modified molecular sieve supported single metal type solid acid catalyst Al-MCM-41/S;
the volume mass ratio of the sulfuric acid solution to the all-silicon MCM-41 carrier in the step (1) is 5-20 mL: 0.5-3 g; the sulfuric acid solution in the step (1) is 10-25 wt% sulfuric acid water solution;
in the step (2), the mass ratio of aluminum in the aluminum salt to the modified molecular sieve MCM-41/S is 2.5-12.5: 100; the aluminum salt in the aluminum salt solution is at least one of aluminum nitrate and aluminum chloride;
the application comprises the following steps:
and uniformly mixing the sulfuric acid modified MCM-41 loaded single-metal type solid acid catalyst, glucose and a solvent, reacting at 170-210 ℃ for 0.5-2.5 hours under the condition of nitrogen or inert gas, ending the reaction, cooling to room temperature, centrifuging, separating solid from liquid, and separating liquid to obtain a water phase and an organic phase, wherein the organic phase contains the pentahydroxy methyl furfural.
2. The use of a sulfuric acid modified MCM-41 supported single metal type solid acid catalyst in the manufacture of pentahydroxy methylfurfural from glucose according to claim 1, wherein the concentration of the aluminum salt solution in step (2) is 0.104-0.521 g/mL; the mass volume ratio of the modified molecular sieve MCM-41/S to the aluminum salt solution is 0.1-0.5 g: 0.5-3 mL.
3. The application of a sulfuric acid modified MCM-41 supported single metal type solid acid catalyst in preparing pentahydroxy methyl furfural by glucose, according to claim 1, wherein the uniform mixing in the step (2) means ultrasonic vibration for 20-30 min; the dipping time in the step (2) is 12-24 hours.
4. The application of a sulfuric acid modified MCM-41 supported single metal type solid acid catalyst in preparing pentahydroxy methyl furfural by glucose according to claim 1, wherein the calcining temperature in the step (2) is 400-600 ℃ and the time is 3-7 h; the temperature rising rate is 2-7 ℃/min.
5. The use of a sulfuric acid modified MCM-41 supported single metal type solid acid catalyst in the manufacture of pentahydroxymethyl furfural from glucose according to claim 1, wherein in the application step, the ratio of sulfuric acid modified MCM-41 supported single metal type solid acid catalyst, glucose and solvent is 0.025-0.125 g:0.1 to 0.5g: 25-45 mL; the reaction temperature is 170-190 ℃ and the reaction time is 1-2 h.
6. The use of a sulfuric acid modified MCM-41 supported solid acid catalyst of a single metal type in the manufacture of pentahydroxy methylfurfural from glucose according to claim 1, wherein in the application step, the solvent is at least one of dimethyl sulfoxide, a mixed solution of water and methyl isobutyl ketone, a mixed solution of choline chloride aqueous solution and methyl isobutyl ketone, and a mixed solution of sodium chloride aqueous solution and methyl isobutyl ketone.
7. The application of the sulfuric acid modified MCM-41 supported single metal type solid acid catalyst in preparing the pentahydroxy methyl furfural by glucose according to claim 6, wherein in the application step, the solvent is in a volume ratio of 1: 4-8 of sodium chloride aqueous solution and methyl isobutyl ketone, wherein the concentration of the sodium chloride aqueous solution is 10-25 wt%.
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