CN105854896A - Mn-Fe-Al composite metal oxide and application of Mn-Fe-Al composite metal oxide to catalyzing hydrolysis reaction on celluloses - Google Patents
Mn-Fe-Al composite metal oxide and application of Mn-Fe-Al composite metal oxide to catalyzing hydrolysis reaction on celluloses Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 29
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 20
- 235000010980 cellulose Nutrition 0.000 title abstract description 27
- 239000002131 composite material Substances 0.000 title abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 title abstract description 10
- 150000004706 metal oxides Chemical class 0.000 title abstract 8
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000001913 cellulose Substances 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 14
- 239000004005 microsphere Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002905 metal composite material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 235000013877 carbamide Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 150000003672 ureas Chemical group 0.000 claims 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052700 potassium Inorganic materials 0.000 abstract description 3
- 239000011591 potassium Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000006184 cosolvent Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 229910016874 Fe(NO3) Inorganic materials 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 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 description 10
- 239000008103 glucose Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 7
- 239000011973 solid acid Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 229910020015 Nb W Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910009378 Zn Ca Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- -1 such as Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000036962 time dependent Effects 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses Mn-Fe-Al composite metal oxide and application of the Mn-Fe-Al composite metal oxide to catalyzing hydrolysis reaction on celluloses. A method includes that Mn(NO3) 2 and Fe(NO3) 3 are used as raw materials, amorphous gamma-Al2O3 micro-spheres are used as carriers, urea or potassium borohydride or hydrazine hydrate is used as a precipitant, mixed solution with deionized water and ethyl alcohol is used as a co-solvent, a series of Mn-Fe-Al composite metal precipitates are prepared by means of hydrothermal reaction and are calcined at high temperatures to obtain a series of Mn-Fe-Al composite metal oxide, and then the Mn-Fe-Al composite metal oxide is used as a cellulose hydrolysis catalyst to catalyze the hydrolysis reaction on the celluloses. The Mn-Fe-Al composite metal oxide and the application have the advantages that preparation conditions can be microscopically regulated and controlled, so that the series of Mn-Fe-Al composite metal oxide can be controllably prepared, the cellulose hydrolysis properties can be macroscopically regulated and controlled, and the efficient and stable cellulose hydrolysis catalyst can be screened; the catalyst can be easily separated from reactants and products.
Description
Technical field
The invention belongs to the preparing technical field of metal composite oxide, particularly to the compound gold of a kind of Mn-Fe-Al
Belong to oxide and the application of catalyzing cellulose hydrolysis reaction thereof.
Background technology
Along with the increase day by day of petroleum resources demand with it is by excessive application, at present, reduce environmental pollution
Petroleum resources are replaced to become one of the highest problem of society attention rate with finding new material.Wherein,
Cellulose is as a kind of regenerative resource, due to advantages such as its yield are big, cheap it is considered to be very likely generation
For one of non-renewable raw material of fossil energy.Root is it is estimated that current nature produces 200,000,000,000 tons every year
Wooden biomass energy, due to photosynthetic existence, wherein contains 3 × 1018The energy of KJ, is the whole world one
About 10 times of year energy resource consumption.Therefore many countries have had begun to corresponding project, the such as U.S.
Energy agriculture, the ethanol plan of Brazil, the regenerative resource scheme of India, sunlight program of Japan etc..?
In the industry that whole cellulose converts, its hydrolysis generates the emphasis and point of penetration that glucose is the refining of whole biomass.
It is known that cellulosic molecule is consisted of β-Isosorbide-5-Nitrae glycosidic bond bonding numerous glucose molecules, with
Time cellulosic molecule in have substantial amounts of hydrogen bond.Due to structure that cellulose is special cause its have supramolecular structure and
Bigger mechanical strength.The most conventional cellulose hydrolyst has enzyme, supercritical water, mineral acid, ion
Liquid and solid acid catalyst.Solid acid catalysis cellulose hydrolysis at present generates glucose and receives more and more
Paying close attention to, because solid acid catalyst has many advantages compared with liquid catalyst, such as, product can be easily separated,
Recyclable, the corrosion to reactor is little, and very important point uses solid acid catalyst to environment exactly simultaneously
Impact smaller.So, currently used solid acid catalyst catalyzing cellulose hydrolysis generates glucose and has become
For one of focus.The kind of concrete solid acid catalyst has, metal composite oxide, based on polymer
Acid, sulfonation carbylic acid, heteropoly acid and H-type zeolite etc..
Aluminium oxide is at pottery, and abrasive material, medicine, adsorbent, the field such as catalyst and carrier thereof has and uses widely.
The Woelm Alumina being wherein used as catalyst and carrier thereof is commonly referred to as activated alumina, be a kind of porous,
The solid material of high degree of dispersion, has the biggest surface area, adsorptivity.
At document Angewandte Chemie, in 2010,122:1146-1150, Domen et al. is prepared for mesoporous
The catalyst that Nb W oxide hydrolyzes as cellulose, wherein Nb3W7Catalyst has the highest catalysis activity.
At document Petrochemical Technology, in 2011,40:43-4, Fang et al. is prepared for nano level
Zn Ca Fe O composite metallic oxide catalyst, in cellulose hydrolysis, the conversion ratio of cellulose reaches
42.6%, the selectivity of glucose has reached 69.2%.Additionally, due to iron oxides has paramagnetism, this catalysis
Agent can realize the sharp separation between catalyst and reactant by simple Magnetic filter technology.These catalysis
Agent all has good catalytic performance, but the active component of catalyst easily runs off during reaction, and
And catalyst is difficult to separate with product.Therefore, reduce the loss of catalyst activity component and realize catalyst and be prone to
It is separated into the problem in order to solution is presently required.
Summary of the invention
It is an object of the invention to provide a kind of Mn-Fe-Al metal composite oxide and catalyzing cellulose hydrolysis is anti-
The application answered.In the Mn-Fe-Al metal composite oxide of preparation, the percentage composition of Mn is 10%-30%, Fe
Percentage composition be about 10%, specific surface area is at 160m2/g-180m2Between/g.
The method is with Mn (NO3)2、Fe(NO3)3As raw material, with unformed γ-Al2O3Microsphere as carrier,
With carbamide, potassium borohydride or hydrazine hydrate as precipitant, using the mixed solution of deionized water and ethanol as cosolvent,
Hydro-thermal reaction is prepared for a series of Mn-Fe-Al composition metal precipitate, obtains one after high-temperature calcination
The Mn-Fe-Al metal composite oxide of series, then as the catalyst of cellulose hydrolysis, to cellulose
Hydrolysis is catalyzed.The method can be combined by regulating and controlling to realize series Mn-Fe-Al to the microcosmic of preparation condition
The controlled preparation of oxide, and then realize the macro adjustments and controls of its cellulose hydrolysis property, filter out efficient, stable
Cellulose hydrolyst.
The preparation method of Mn-Fe-Al metal composite oxide of the present invention, its concrete processing step is as follows:
(1) preparation total concentration is the Mn (NO of 1-3mol/L3)2With Fe (NO3)3Mixing salt solution, and addition is heavy
Shallow lake agent, precipitant and Fe (NO3)3Mol ratio be 3:1-1:1, ultrasonic be completely dissolved after two solution mixing, add
Unformed γ-the Al of 0.2-1g/mL2O3Microsphere impregnates 1-2 hour, then proceeds in hydrothermal reaction kettle,
React 12-24 hour under conditions of 100-150 DEG C, react product centrifugation, deionized water and second after terminating
Alcohol mixed solvent supersound washing, to neutral, be dried under conditions of 60-70 DEG C and obtain Mn-Fe-Al in 12-36 hour
Composition metal precipitate；
(2) Mn-Fe-Al composition metal precipitate prepared by step (1) is placed in Muffle furnace, with 2-5 DEG C/min
Heating rate be warming up to 400-600 DEG C, calcining at constant temperature 4-6 hour, furnace cooling is down to room temperature afterwards, obtains
Mn-Fe-Al metal composite oxide.
The mol ratio of described Mn (NO3) 2 and Fe (NO3) 3 is 1-5.
Described precipitant is carbamide, potassium borohydride or hydrazine hydrate.
The Mn-Fe-Al metal composite oxide of above-mentioned preparation is applied to catalyzing cellulose hydrolysis reaction.Its reaction
Condition is: weigh 0.1-0.5gMn-Fe-Al metal composite oxide as catalyst, 0.1-0.5g cellulose, amount
Take 20-500mL deionized water, add in autoclave, with air in nitrogen discharge reactor, at 100-160 DEG C
Under conditions of react 2-6 hour.
It is an advantage of the current invention that: with low-cost Mn (NO3)2, Fe (NO3)3·9H2O, unformed γ-Al2O3
Microsphere and precipitant are raw material, with precipitant at unformed γ-Al2O3Microsphere surface fabricated in situ Mn-Fe-Al is multiple
Alloy belongs to the precipitate precursor as metal composite oxide, synthesizes Mn-Fe-Al combined oxidation through high-temperature calcination
Thing, realizes series Mn-Fe-Al composite oxides by the relative amount of metal ion in selective regulation presoma
Adjustable control standby, and then realize its cellulose hydrolyzation catalysis performance regulation and control (productivity of product 30%-60% it
Between), screening is for efficient, stable catalyst.There is strong interaction before this catalyst and carrier to lead
Cause the adhesion between catalyst activity component and carrier relatively strong, be difficult to during reaction run off.Simultaneously with
Powder body catalyst is compared, and this catalyst is due at unformed γ-Al2O3Microsphere surface growth in situ, solid catalyst
Inherently there is the characteristic being easily isolated, contain ferrum oxide species in the catalyst simultaneously, utilize the magnetic of ferrum oxide
Property is advantageously in the separation of catalyst, and therefore this catalyst is prone to be separated from each other with reactant and product.
Accompanying drawing explanation
Fig. 1 is that in the embodiment of the present invention 1, embodiment 2 and embodiment 3, Mn-Fe-Al metal composite oxide is urged
The XRD spectra of agent；
Fig. 2 be in the embodiment of the present invention 2 Mn-Fe-Al O composite metallic oxide catalyst at cellulose hydrolysis
The time dependent curve of middle productivity；
Fig. 3 is that in the embodiment of the present invention 2, Mn-Fe-Al composite oxide catalysts is urged in cellulose hydrolysis
The figure of agent reusability.
Detailed description of the invention
Embodiment 1
Weigh mass fraction 50%Mn (NO3)2Solution 3.5790g, Fe (NO3)3·9H2O 4.0402g, unformed
γ-Al2O3Microsphere 5g, carbamide 1.2012g are raw material；By Mn (NO3)2、Fe(NO3)3·9H2O and carbamide are ultrasonic
It is dissolved in together in 7.5ml deionized water, after being completely dissolved, adds unformed γ-Al2O3Microsphere, impregnates 1 hour；
Adding the raw material into afterwards in hydrothermal reaction kettle, react 12 hours under conditions of 120 DEG C, reaction will after terminating
Product centrifugation, deionized water and alcohol mixed solvent supersound washing, to neutral, are dried under conditions of 70 DEG C
24 hours, finally give Mn-Fe-Al composition metal precipitate.By the Mn-Fe-Al composition metal precipitation of preparation
Thing is placed in Muffle furnace, at 400 DEG C, sinters to heat up under the heating rate of 2 DEG C/min, constant temperature 4 hours,
Furnace cooling is slowly dropped to room temperature afterwards, obtains Mn-Fe-Al metal composite oxide.The wherein percentage ratio of Mn
Content is 11.2%, and the degree of Fe is 10.3%, and the specific surface area of sample is 169m2/g。
Weigh 0.2g Mn-Fe-Al composite oxides, 0.2g microcrystalline Cellulose, measure 20mL deionized water, add
Enter and have in the reactor of polytetrafluoroethylliner liner to 100mL, after reactor is hunted leak, use nitrogen inflation/deflation
10 times, after being drained by the air in still, the pressure drained by nitrogen in holding still is normal pressure, at 120 DEG C of bars
Reacting 4 hours under part, the productivity of glucose is 31.7%.
Embodiment 2
Weigh mass fraction 50%Mn (NO3)2Solution 7.1580g, Fe (NO3)3·9H2O 4.0402g, unformed
γ-Al2O3Microsphere 5g, carbamide 2.4024g are raw material, and condition same as in Example 1 prepares Mn-Fe-Al
Composition metal precipitate, obtains Mn-Fe-Al metal composite oxide through 400 DEG C of roastings.The wherein percentage of Mn
Being 18.5% than content, the degree of Fe is 11.4%, and the specific surface area of sample is 166m2/g.Identical
Reaction condition under, after reacting 4 hours, the productivity of glucose is 58.1%.
Embodiment 3
Weigh mass fraction 50%Mn (NO3)2Solution 10.7370g, Fe (NO3)3·9H2O 4.0402g, unformed
γ-Al2O3Microsphere 5g, carbamide 3.6036g are raw material, and condition same as in Example 1 prepares Mn-Fe-Al
Composition metal precipitate, obtains Mn-Fe-Al metal composite oxide through 400 DEG C of roastings.The wherein percentage of Mn
Being 23.2% than content, the degree of Fe is 10.8%, and the specific surface area of sample is 170m2/g.Identical
Reaction condition under, after reacting 4 hours, the productivity of glucose is 45.4%.
Embodiment 4
Weigh mass fraction 50%Mn (NO3)2Solution 7.1580g, Fe (NO3)3·9H2O 4.0402g, unformed
γ-Al2O3Microsphere 5g, sodium borohydride 0.7566g are raw material, and condition same as in Example 1 prepares Mn-Fe-Al
Composition metal precipitate, obtains Mn-Fe-Al metal composite oxide through 400 DEG C of roastings.At identical reaction bar
Under part, after reacting 4 hours, the productivity of glucose is 34.5%.
Embodiment 5
Weigh mass fraction 50%Mn (NO3)2Solution 7.1580g, Fe (NO3)3·9H2O 4.0402g, unformed
γ-Al2O3Microsphere 5g, sodium borohydride 1.0012g are raw material, and condition same as in Example 1 prepares Mn-Fe-Al
Composition metal precipitate, obtains Mn-Fe-Al metal composite oxide through 400 DEG C of roastings.At identical reaction bar
Under part, after reacting 4 hours, the productivity of glucose is 28.7%.
Claims (5)
1. the preparation method of a Mn-Fe-Al metal composite oxide, it is characterised in that its concrete technique
Step is as follows:
(1) preparation total concentration is the Mn (NO of 1-3mol/L3)2With Fe (NO3)3Mixing salt solution, and addition is heavy
Shallow lake agent, precipitant and Fe (NO3)3Mol ratio be 3:1-1:1, ultrasonic be completely dissolved after two solution mixing, add
Unformed γ-the Al of 0.2-1g/mL2O3Microsphere impregnates 1-2 hour, then proceeds in hydrothermal reaction kettle,
React 12-24 hour under conditions of 100-150 DEG C, react product centrifugation, deionized water and second after terminating
Alcohol mixed solvent supersound washing, to neutral, be dried under conditions of 60-70 DEG C and obtain Mn-Fe-Al in 12-36 hour
Composition metal precipitate；
(2) Mn-Fe-Al composition metal precipitate prepared by step (1) is placed in Muffle furnace, with 2-5 DEG C/min
Heating rate be warming up to 400-600 DEG C, calcining at constant temperature 4-6 hour, furnace cooling is down to room temperature afterwards, obtains
Mn-Fe-Al metal composite oxide.
Preparation method the most according to claim 1, it is characterised in that described Mn (NO3) 2 He
The mol ratio of Fe (NO3) 3 is 1-5.
Preparation method the most according to claim 1, it is characterised in that described precipitant is carbamide, boron
Hydrofining or hydrazine hydrate.
4. the Mn-Fe-Al metal composite oxide prepared according to the arbitrary described method of claim 1-3 is urged
The application of cellulose hydrolysis.
Application the most according to claim 4, it is characterised in that its reaction condition is: weigh
0.1-0.5gMn-Fe-Al metal composite oxide, as catalyst, 0.1-0.5g cellulose, measures 20-500mL
Deionized water, adds in autoclave, with air in nitrogen discharge reactor, under conditions of 100-160 DEG C
React 2-6 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108246307A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of Fe-Mn selective hydrogenation catalysts, preparation method and applications |
| CN108636410A (en) * | 2018-05-14 | 2018-10-12 | 福州大学 | A kind of preparation method and applications of the Fe2O3 doping aluminium oxide hollow microsphere with porous structure |
| CN114392745A (en) * | 2021-12-13 | 2022-04-26 | 鲁东大学 | Method for preparing Fe-transition metal-Al composite metal oxide and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102240557A (en) * | 2011-05-12 | 2011-11-16 | 南京工业大学 | Catalyst containing nickel-iron-manganese compound oxide for processing industrial waste gas and preparation method thereof |
| US20130267411A1 (en) * | 2012-03-26 | 2013-10-10 | Brigham Young University, | Single reaction synthesis of texturized catalysts |
| CN103721668A (en) * | 2012-10-10 | 2014-04-16 | 中国科学院大连化学物理研究所 | Gasoline ultra-deep desulfurization adsorbent and application thereof |
| CN104128181A (en) * | 2014-07-03 | 2014-11-05 | 昆明理工大学 | Catalyst preparation method and application |
| CN104190250A (en) * | 2014-09-04 | 2014-12-10 | 昆明理工大学 | Purification method of methyne phosphate |
-
2016
- 2016-05-11 CN CN201610310892.4A patent/CN105854896B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102240557A (en) * | 2011-05-12 | 2011-11-16 | 南京工业大学 | Catalyst containing nickel-iron-manganese compound oxide for processing industrial waste gas and preparation method thereof |
| US20130267411A1 (en) * | 2012-03-26 | 2013-10-10 | Brigham Young University, | Single reaction synthesis of texturized catalysts |
| CN103721668A (en) * | 2012-10-10 | 2014-04-16 | 中国科学院大连化学物理研究所 | Gasoline ultra-deep desulfurization adsorbent and application thereof |
| CN104128181A (en) * | 2014-07-03 | 2014-11-05 | 昆明理工大学 | Catalyst preparation method and application |
| CN104190250A (en) * | 2014-09-04 | 2014-12-10 | 昆明理工大学 | Purification method of methyne phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 刘炼伟等，: ""超(亚)临界水热合成法制备复合金属氧化物脱硫剂"", 《化工进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108246307A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of Fe-Mn selective hydrogenation catalysts, preparation method and applications |
| CN108636410A (en) * | 2018-05-14 | 2018-10-12 | 福州大学 | A kind of preparation method and applications of the Fe2O3 doping aluminium oxide hollow microsphere with porous structure |
| CN114392745A (en) * | 2021-12-13 | 2022-04-26 | 鲁东大学 | Method for preparing Fe-transition metal-Al composite metal oxide and application thereof |
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