CN109529912A - Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof - Google Patents
Furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst and preparation method thereof Download PDFInfo
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- CN109529912A CN109529912A CN201811624827.4A CN201811624827A CN109529912A CN 109529912 A CN109529912 A CN 109529912A CN 201811624827 A CN201811624827 A CN 201811624827A CN 109529912 A CN109529912 A CN 109529912A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000010949 copper Substances 0.000 title claims abstract description 38
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 14
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 13
- 229910002637 Pr6O11 Inorganic materials 0.000 claims abstract description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- -1 lanthanide metal oxide Chemical class 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 9
- 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 description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 231100000331 toxic Toxicity 0.000 claims description 2
- 230000002588 toxic effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 230000001133 acceleration Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011943 nanocatalyst Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 229960004643 cupric oxide Drugs 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002604 ultrasonography 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of furfural hydrogenations to prepare furfuryl alcohol composite nanostructure copper catalyst, and the catalyst is Cu/@- CeO2/SBA‑15、Cu/@‑La2O3/ SBA-15 or Cu/@- Pr6O11/ SBA-15, the preparation method of the catalyst includes first preparing lanthanide metal oxide film layer coated on SBA-15 molecular sieve with the precipitation method, composite carrier is formed after washed filtering, drying and calcination, the active component elemental copper being supported on composite carrier is prepared with impregnation-reduction method again, obtains the composite nanostructure copper catalyst；The weight of the lanthanide metal oxide is 10wt%~30wt% of composite carrier, and the weight of the elemental copper is 8wt%~12wt% of total catalyst weight.Catalyst of the invention has the advantages that high furfural high conversion rate, furfuryl alcohol selectivity, cheap, environmental protection, catalytic condition are mild.
Description
Technical field
The present invention relates to a kind of novel composite nano catalyst and preparation method thereof, especially a kind of furfural hydrogenation prepares chaff
Alcohol composite nanostructure copper catalyst and preparation method thereof.
Background technique
Furfuryl alcohol is widely used in as a kind of important Organic Chemicals and prepares synthetic fibers and synthetic rubber, while
It is raw material important in fuel, coating and pesticide preparation.Nowadays, furfuryl alcohol is mainly derived from the deep processing of furfural, by chaff
The further selection of aldehyde adds hydrogen and obtains, and extremely meets the social theory of sustainable development.Therefore develop it is a kind of efficiently, it is cheap,
The catalyst of environmental protection has important economic value and practical significance.
Currently, furfuraldehyde hydrogenation catalyst mostly uses single oxide carrier or porous mass class carrier, for example,
CN105148923A discloses a kind of molecular-layer deposition method and prepares metallic copper-oxide (Cu-MOx) hydrogenation catalyst preparation
A series of method, including urging using carbon nanotube, carbon fiber, graphene, SBA-15, gama-alumina or titanium dioxide as carrier
Agent.Since these methods are complicated for operation, operating condition is harsh, so being not easy commercial introduction.Patent CN1398670A and patent
CN1562477A individually discloses a kind of Cu-Cr catalyst containing precious metals pt and Pd, although which has preferably
Catalytic activity, but involve great expense and pollute environment.And patent CN106732706A also discloses a kind of chaff containing rare earth element
Aldehyde hydrogenating catalyst, although catalyst series catalytic activity with higher, catalytic condition is harsher, i.e., temperature is
220 DEG C of pressure are 7Mpa, to improve operating condition and equipment manufacturing cost, and in catalyst active sites copper oxide accounting it is high
Up to 70wt%, it is low to reflect utilization rate of the copper oxide in catalysis.
In view of existing furfural hydrogenation is prepared in the technique of furfuryl alcohol, catalyst occupies sizable cost.Therefore, ability
Domain needs the furfural hydrogenation of more new constructions to prepare furfuryl alcohol catalyst.
Summary of the invention
The purpose of the present invention is to provide a kind of novel composite nano catalyst and preparation method thereof, to solve background technique
The problem of middle proposition.
To achieve the above object, the present invention provides a kind of furfural hydrogenations to prepare the catalysis of furfuryl alcohol composite nanostructure copper
Agent, the catalyst are Cu/@- CeO2/SBA-15、Cu/@-La2O3/ SBA-15 or Cu/@- Pr6O11/ SBA-15, the catalysis
The preparation method of agent includes first preparing lanthanide metal oxide film layer with the precipitation method to be coated on SBA-15 molecular sieve, washed mistake
Composite carrier is formed after filter, drying and calcination, then the active component being supported on composite carrier is prepared with impregnation-reduction method
Elemental copper obtains the composite nanostructure copper catalyst；The weight of the lanthanide metal oxide is composite carrier
10wt%~30wt%, and the weight of the elemental copper is 8wt%~12wt% of total catalyst weight.
Novel composite nano catalyst according to the present invention, it is preferable that the catalyst does not contain noble metal gold, silver, platinum；
The catalyst does not contain toxic metals chromium.
Novel composite nano catalyst according to the present invention, it is preferable that reducing agent used in the impregnation-reduction method is
Hydrazine hydrate.
Novel composite nano catalyst according to the present invention, it is preferable that the lanthanide metal oxide prepares raw material choosing
From lanthanum nitrate, cerous nitrate or praseodymium nitrate.
The present invention also provides a kind of preparation methods of novel composite nano catalyst comprising following steps:
1) solution containing lanthanide series is prepared, and a certain amount of SBA-15 is added and is mixed evenly；
2) under sonic oscillation, it is 7.5-9 that the addition ammonium hydroxide of mixed liquor obtained by step 1), which is adjusted pH value, and continues stirring one
Section time t, rear standing a period of time t '；
3) mixed liquor washing filtering, the dry, calcining obtained step 2), obtains composite carrier CeO2/SBA-15、
La2O3/ SBA-15 or Pr6O11/SBA-15；
4) under the action of lasting stirring, product and copper nitrate solution, polyvinylpyrrolidone K- that step 3) is obtained
30 are uniformly mixed at 75-85 DEG C, and it is 8~9 that mixed solution ammonium hydroxide, which adjusts pH value, and dropwise addition hydrazine hydrate continues stirring and is allowed to abundant
Reaction, products therefrom is washed, filters, obtains Cu/@- CeO after vacuum drying2/SBA-15、Cu/@-La2O3/SBA-15、
Cu/@-Pr6O11/ SBA-15 catalyst.
The preparation method of novel composite nano catalyst according to the present invention, it is preferable that lanthanide series is dense in step 1)
Degree is 0.02~0.05mol/L.
The preparation method of novel composite nano catalyst according to the present invention, it is preferable that ammonia concn is 1.5 in step 2)
~2mol/L, adding speed are 1~4.5ml/min, and mixing time t is 4~6h, and whipping temp is 75-85 DEG C, time of repose t '
For 2h or more.
The preparation method of novel composite nano catalyst according to the present invention, it is preferable that product is in 75- described in step 3)
Dry 12~15h, CeO at 85 DEG C2/SBA-15、La2O3/SBA-15、Pr6O11/ SBA-15 is respectively at calcining 1 at 400~600 DEG C
~3h, 2~6h is calcined at 500~700 DEG C, at 400~600 DEG C obtained by 1~5h of calcining.
The preparation method of novel composite nano catalyst according to the present invention, it is preferable that it is rapid 4) in nitric acid copper concentration be
0.02~0.08mol/L, copper nitrate, polyvinylpyrrolidone, hydrazine hydrate molar ratio be 1:5:8~10, ammonia concn 1.5
~2mol/L.
The preparation method of novel composite nano catalyst according to the present invention, it is preferable that the stirring in step 4) is in temperature
Degree is to carry out at 40~60 DEG C, and mixing time is 6~7h, and the product is in 70~90 DEG C of vacuum dry 12h or more.
Compared with the prior art, a kind of novel composite nano catalyst of the invention is used for catalytic hydrogenation, in particular for
Furfural selection plus hydrogen are prepared in furfuryl alcohol reaction, are had the advantage that
1, reaction condition is mild, and reaction temperature is low (120 DEG C), H needed for reaction process2Pressure is low (1.0MPa).
2、Cu/@-CeO2/SBA-15、Cu/@-La2O3/SBA-15、Cu/@-Pr6O11The catalyst such as/SBA-15 all have compared with
High catalytic activity (> 95%), and keep excellent selectivity (> 97%).
3, the series composite nano structure catalyst more single SBA-15, CeO2Equal carried catalysts have higher
Catalytic activity.
4, this catalyst has the characteristics that cheap, environmental protection.
5, the present invention has the advantages that large specific surface area, skeleton structure are stable and inner surface is easy to modify using SBA-15,
Both and have the characteristics that stronger adsorption capacity and strong reducing power using lanthanide metal oxide, combined in certain method
Complex carrier is formed, then the elemental copper of reduction-state has obtained a kind of performance as active component in load on the complex carrier
Excellent catalyst, the catalyst prepare competitiveness with higher in furfuryl alcohol production in furfural hydrogenation.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
Below with reference to figure, the present invention is described in further detail.
Detailed description of the invention
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is a kind of XRD diagram of novel composite nano catalyst of the present invention；
Specific embodiment
The embodiment of the present invention is described in detail below in conjunction with attached drawing, but the present invention can be limited according to claim
Fixed and covering multitude of different ways is implemented.
Embodiment 1:
1,20%CeO2The preparation of/SBA-15 composite carrier, specifically: preparing and contain 26ml deionized water and 0.378g nitre
The solution of sour cerium adds 0.6g SBA-15 molecular sieve, and stirs 4h at 80 DEG C；Mixed liquor is moved in sonic oscillation,
The ammonia spirit for adding 1.5~2mol/L after 20min with the speed of 1~4.5ml/min, adjusting pH value is 7.5~8.5；It is subsequent
Continuous move at 80 DEG C of water-bath is stirred, and 12h is stood after 4~6h；Acquired solution is washed with deionized, is filtered, and in drying box
Middle 12~15h of drying, after by product in 500 DEG C of calcining 2h to get 20%CeO2/ SBA-15 complex carrier.
2,10Cu/@- 20%CeO2/ SBA-15 catalyst preparation, specifically: taking 0.482g PVP K-30
It is dissolved in 32ml ethylene glycol, the 20%CeO of 0.5g is added2/ SBA-15 composite carrier is uniformly mixed；Take tri- water nitre of 0.212g
Sour copper dissolution is added in above-mentioned mixed liquor in 12ml water in ultrasound, and 30min is moved back to stirring at 80 DEG C of water-bath, after 4h
The ammonia spirit of 1.5~2mol/L is added with the speed of 1~4.5ml/min, adjusting pH value is 8~9, in bath temperature 40~60
0.58ml hydrazine hydrate to be added at DEG C, continues 6~7h of stirring, acquired solution dehydrated alcohol and deionized water are washed, are filtered, and 80 DEG C
Vacuum drying 12h obtains 10Cu/@- 20%CeO2/ SBA-15 catalyst.
Embodiment 2:
Other than the mass content of CeO2 in composite carrier is replaced with shown in table 1, remaining step and condition and reality
It is identical to apply example 1.
Embodiment 3:
In addition to by 10Cu/@- 20%CeO2Except the mass content of Cu replaces with shown in table 1 in/SBA-15 catalyst,
Remaining step and condition are identical as example 1.
Embodiment 4
In addition to by CeO in composite carrier2Replace with La2O3For shown in table 1, remaining step is identical as example 1.
Embodiment 5:
In addition to by CeO in composite carrier2Replace with Pr6O11For shown in table 1, remaining step is identical as example 1.
Table 1
Comparative example 1
10%Cu/SBA-15 catalyst preparation, specifically: 0.482g PVP K-30 being taken to be dissolved in 32ml second
In glycol, the SBA-15 molecular sieve that 0.5g is added is uniformly mixed；Take 0.212g nitrate trihydrate copper dissolution in 12ml water, Yu Chaosheng
In be added in above-mentioned mixed liquor, 30min is moved back to stirring at 80 DEG C of water-bath, is added after 4h with the speed of 1~4.5ml/min
The ammonia spirit of 1.5~2mol/L, adjusting pH value is 8~9, and 0.58ml hydrazine hydrate is added at 40~60 DEG C of bath temperature, after
6~7h of continuous stirring, acquired solution dehydrated alcohol and deionized water are washed, are filtered, and 80 DEG C of vacuum drying 12h obtain 10%Cu/
SBA-15 catalyst.
Comparative example 2
In addition to carrier S BA-15 is replaced with CeO2Outside, remaining step and condition and ratio 1 are identical.
Embodiment 6
The catalyst prepared in above-described embodiment 1~5, comparative example 1~2 is used to be catalyzed furfural selective hydrogenation reaction.It takes
1.6mmol furfural, 0.15g catalyst and 15mL isopropanol are passed through H in autoclave2Displace the air in reaction kettle
Afterwards, H is closed2Valve is passed through H after temperature in the kettle reaches 120 DEG C of reaction temperatures2(1.0MPa) opens stirring (950-
1050rpm) start to react, react 4h, after reaction, cooling centrifugation, reaction solution carries out gas chromatographic analysis.Experimental result ginseng
It is shown in Table 2.
Table 2
As seen from the above embodiment, the catalyst of different quality containing prepared by this method is for furfural selective hydrogenation
It reacts active.The scope of the invention is not limited to above embodiments, as long as controlling catalyst activity component quality point
Several and reaction condition prepares furfuryl alcohol for furfural hydrogenation reaction and can reach good catalytic effect.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of furfural hydrogenation prepares furfuryl alcohol composite nanostructure copper catalyst, which is characterized in that the catalyst is Cu/@-
CeO2/SBA-15、Cu/@-La2O3/ SBA-15 or Cu/@- Pr6O11/ SBA-15, the preparation method of the catalyst include first with
The precipitation method prepare lanthanide metal oxide film layer coated on SBA-15 molecular sieve, are formed after washed filtering, drying and calcination
Composite carrier, then the active component elemental copper being supported on composite carrier is prepared with impregnation-reduction method, it obtains described compound
Nanostructure copper catalyst；The weight of the lanthanide metal oxide is 10wt%~30wt% of composite carrier, and described
The weight of elemental copper is 8wt%~12wt% of total catalyst weight.
2. catalyst according to claim 1, which is characterized in that the catalyst does not contain noble metal gold, silver, platinum；Institute
Catalyst is stated without containing toxic metals chromium.
3. catalyst according to claim 1, which is characterized in that reducing agent used in the impregnation-reduction method is water
Close hydrazine.
4. catalyst according to claim 1, which is characterized in that the raw material for preparing of the lanthanide metal oxide is selected from nitre
Sour lanthanum, cerous nitrate or praseodymium nitrate.
5. a kind of preparation method of catalyst according to any one of claims 1 to 4, which is characterized in that it includes as follows
Step:
1) solution containing lanthanide series is prepared, and a certain amount of SBA-15 is added and is mixed evenly；
2) under sonic oscillation, when the addition ammonium hydroxide of mixed liquor obtained by step 1) being adjusted pH value as 7.5-9, and continuing one section of stirring
Between t, it is rear to stand a period of time t '；
3) mixed liquor washing filtering, the dry, calcining obtained step 2), obtains composite carrier CeO2/SBA-15、La2O3/
SBA-15 or Pr6O11/SBA-15；
4) under the action of lasting stirring, product that step 3) is obtained and copper nitrate solution, PVP K-30 in
It is uniformly mixed at 75-85 DEG C, it is 8~9 that mixed solution ammonium hydroxide, which adjusts pH value, and dropwise addition hydrazine hydrate continues stirring and is allowed to sufficiently anti-
It answers, products therefrom is washed, filters, obtains Cu/@- CeO after vacuum drying2/SBA-15、Cu/@-La2O3/SBA-15、Cu/@-
Pr6O11/ SBA-15 catalyst.
6. preparation method according to claim 5, which is characterized in that in step 1) concentration of lanthanide series be 0.02~
0.05mol/L。
7. preparation method according to claim 5, which is characterized in that ammonia concn is 1.5~2mol/L in step 2), is added
Acceleration is 1~4.5ml/min, and mixing time t is 4~6h, and whipping temp is 75-85 DEG C, and time of repose t ' is 2h or more.
8. preparation method according to claim 5, which is characterized in that product described in step 3) is dry at 75-85 DEG C
12~15h, CeO2/SBA-15、La2O3/SBA-15、Pr6O11/ SBA-15 respectively at 400~600 DEG C calcine 1~3h, 500~
2~6h is calcined at 700 DEG C, at 400~600 DEG C obtained by 1~5h of calcining.
9. preparation method according to claim 5, which is characterized in that in step 4) nitric acid copper concentration be 0.02~
0.08mol/L, copper nitrate, polyvinylpyrrolidone, hydrazine hydrate molar ratio be 1:5:8~10, ammonia concn be 1.5~
2mol/L。
10. preparation method according to claim 5, which is characterized in that it is 40~60 that the stirring in step 4), which is in temperature,
It is carried out at DEG C, mixing time is 6~7h, and the product is in 70~90 DEG C of vacuum dry 12h or more.
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