CN106238063A - A kind of glycerine hydrogenation Cu ZnO catalyst preparing propylene glycol and preparation method thereof - Google Patents
A kind of glycerine hydrogenation Cu ZnO catalyst preparing propylene glycol and preparation method thereof Download PDFInfo
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- CN106238063A CN106238063A CN201610633345.XA CN201610633345A CN106238063A CN 106238063 A CN106238063 A CN 106238063A CN 201610633345 A CN201610633345 A CN 201610633345A CN 106238063 A CN106238063 A CN 106238063A
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- catalyst
- copper
- zinc oxide
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- VODBHXZOIQDDST-UHFFFAOYSA-N copper zinc oxygen(2-) Chemical compound [O--].[O--].[Cu++].[Zn++] VODBHXZOIQDDST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 239000008187 granular material Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 235000013772 propylene glycol Nutrition 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- GFCDJPPBUCXJSC-UHFFFAOYSA-N [O-2].[Zn+2].[Cu]=O Chemical compound [O-2].[Zn+2].[Cu]=O GFCDJPPBUCXJSC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 150000003639 trimesic acids Chemical class 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 2
- 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 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- OCKHUPCREYAULF-UHFFFAOYSA-N n,n-dimethylformamide;n-methylmethanamine Chemical compound CNC.CN(C)C=O OCKHUPCREYAULF-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N Vilsmeier-Haack reagent Natural products CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- -1 N, N-dimethylformamide dimethyl acyls Amine Chemical class 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- JOHINUCSOJCMIE-UHFFFAOYSA-N O.[Zn].[Cu] Chemical compound O.[Zn].[Cu] JOHINUCSOJCMIE-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 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
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- B01J35/396—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
Abstract
The invention discloses a kind of glycerine hydrogenation and prepare 1, Cu ZnO catalyst of 2 propylene glycol and preparation method thereof, catalyst is with the Ni metal granule of nano-ZnO embedding, the synergism relying on Cu Yu ZnO interface plays the catalyst of main catalytic active, with metal organic framework compound (Cu (Zn) HKUST 1) as presoma, the catalyst of the Ni metal granule that the nano-ZnO obtained by steps such as pyrolysis reduction is embedded.Instant invention overcomes traditional copper Zinc oxide catalytic complicated process of preparation, the composition of finished catalyst, structure and morphology control difficulty, and in finished catalyst, copper granule is the most easily grown up and reduced dispersion and cause the problems such as catalysqt deactivation and custom-designed.
Description
Technical field
The present invention relates to the preparation method of a kind of copper-zinc oxide catalyst that can be used for glycerine hydrogenation, specifically one
Plant glycerine hydrogenation copper-zinc oxide catalyst preparing 1,2-propylene glycol and preparation method thereof.
Background technology
Copper-zinc oxide catalyst is in methanol-fueled CLC, water-gas shift, nitrous oxides selectivity reduction and biomass conversion etc.
Field is widely used；In recent years, copper-zinc oxide catalyst answering in the selective hydrogenation of biological diesel oil byproduct glycerin
With also result in extensive concern.People attempt have employed various method to prepare efficient copper-zinc oxide catalyst
(Science,352(2016)969-974；Catal.Today,272(2016)87-93)；Traditional co-precipitation preparation technology can
To obtain higher copper dispersion, but because preparation process often uses sodium carbonate or sodium hydroxide to do precipitant, this
In finished catalyst, inevitably bring sodium ion into, and the introducing of sodium ion can seriously suppress copper-zinc oxide catalyst
Activity (Nature, 531 (2016) 83-87) in the reactions such as methanol-fueled CLC.Therefore, develop new, do not introduce sodium ion
The preparation method of copper-zinc oxide catalyst has great importance and application prospect.Kondart etc. use supercritical solvent method first
First preparing copper-zinc hydrate presoma, then the technique such as drying, roasting, reduction is to reach finished catalyst without sodium
The purpose (Nature, 531 (2016) 83-87) of ion；But this method also exists complex process, (supercritical loaded down with trivial details, dangerous
Condition), the defect such as expensive starting materials.
Copper-zinc oxide catalyst has higher initial activity in glycerine hydrogenation reacts, is widely used, from 2007
Having document report and patent application the most successively, the superfine people of Peking University's bang finds, copper-zinc oxide catalyst is added at glycerin liquid
In hydrogen reaction active (Catal.Lett.117 (2007) 62-67)；Chinese patent CN200810011446.9 discloses one
Plant the preparation method of Cu-Cr metallic oxide with high specific surface area catalyst and the application in glycerine hydrogenation reacts thereof；
CN200810019133.8 applied for a kind of containing copper oxide, zinc oxide, aluminium oxide and selected from Y, La, Ce, Pr, Nd, Sm, Eu,
At least one in the rare earth elements such as Gd, Tb, Dy or the application in glycerine hydrogenation reacts of the multiple rare earth oxide catalyst；
CN200810072333.X reports a kind of copper zinc catalyst containing CNT and the application in glycerine hydrogenation reacts thereof
Technology；CN200980112844.2 discloses a kind of cupric, glycerine hydrogenation technique in the presence of grained catalyst；
CN201110438039.8 provides CuO ZnO-B2O3/Al2O3Catalyst is for synthesizing catalyst and the system thereof of 1,2-propylene glycol
Preparation Method；CN201110056530.4 has applied for Cu/MgO catalyst prepared by equi-volume impregnating and has reacted at glycerine hydrogenation
In application；CN201110056597.8 has applied for Cu/Al prepared by equi-volume impregnating2O3Catalyst and at glycerine hydrogenation
Application in reaction；CN201110056529.1 has applied for the Cu/TiO prepared by equi-volume impregnating2Catalyst and
Technique for applying in glycerine hydrogenation reaction；CN201310181246.9 reports and raney copper catalyst is used for liquid phase glycerine hydrogenation
Technology；CN201210419541.9 discloses a kind of loaded nano cuprio catalyst using copper as active component, titanium
Or cerium etc. is promoter, use glycerine hydrogenation catalyst prepared by coprecipitation.Catalyst in above-mentioned patent specification
Preparation technology mainly has infusion process, coprecipitation, melted-solvent extraction method etc..Use these methods during preparing catalyst,
Being difficult to effectively control the composition of catalyst, structure and pattern, the most different researcheres can obtain different catalyst, its reaction
Effect also is difficult to control and repeat.
The present invention is directed to current copper-zinc oxide catalyst complicated process of preparation, the composition of finished catalyst, structure and pattern
Control that difficulty and these catalyst poor repeatability, stability in glycerine hydrogenation prepares the reaction of 1,2-propylene glycol are low etc. asks
Inscribe and propose solution.Solution proposed by the invention is that one prepares copper-zinc oxide catalyst simply, efficiently
Method, use the copper-zinc oxide catalyst that obtains of this method to generate 1,2-PD for the gas phase hydrogenation of glycerol and have non-
The highest activity and stability.
Summary of the invention
The present invention be directed to prepare copper-zine oxide composite catalyst process present in current document and patent and can introduce sodium
The problems such as ion, preparation method complexity, expensive starting materials and custom-designed, it is honest and clean that the technique of the present invention is not related to sodium ion, raw material
Valency is easy to get, preparation technology the most easily repeats, the composition of finished catalyst is controlled, morphology controllable, performance are adjustable.Use the present invention's
The copper-zinc oxide catalyst that technique prepares has the highest activity and stability in glycerol gas phase hydrogenation reaction.Letter
Saying, the preparation technology of this catalyst is as presoma with metal organic framework compound (HKUST-1) cleanly, by pyrolysis also
The Ni metal granule of the nano-ZnO embedding that the step such as former obtains, the synergism at Cu Yu ZnO interface is relied on to play major catalytic work
The catalyst of property.The pattern of this finished catalyst is as shown in Figure 1.
The present invention is achieved through the following technical solutions:
The invention discloses the copper-zinc oxide catalyst of a kind of preparing 1,2-dihydroxypropane by glycerine hydrogenation, described catalyst
It is with the Ni metal granule of nano-ZnO embedding, relies on the synergism at Cu Yu ZnO interface to play the catalysis of main catalytic active
Agent.
The invention also discloses a kind of glycerine hydrogenation as claimed in claim 1 and prepare the copper-zine oxide catalysis of propylene glycol
The preparation method of agent, with metal organic framework compound (Cu (Zn)-HKUST-1) as presoma, by steps such as pyrolysis reduction
The catalyst of the Ni metal granule of the nano-ZnO embedding obtained.
As improving further, concrete preparation process of the present invention is as follows:
1), weighing 2.9 grams of Zinc oxide powders and be scattered in 80 ml deionized water, stirring is uniform suspended to forming one
After liquid, under room temperature, the power of 300 watts ultrasonic 10 minutes, make Zinc oxide powder dispersed；
2), weigh 4.3～17.2 grams of Gerhardites, dissolve completely in 80 ml deionized water；
3), weigh 7.5～15.0 grams of trimesic acids, dissolve completely in 260 milliliters of ethanol；
4), after above-mentioned solution prepares completely, the suspension of zinc oxide adds 160 milliliters of N, N-dimethylformamide dimethyl acyls
Amine, mix homogeneously；
5), the aqueous solution of copper nitrate and the alcoholic solution of trimesic acid are sequentially added in above-mentioned suspension, are stirred vigorously,
React 1 minute；
6), by the precipitation that obtains through filtering with microporous membrane, solid product is left, with absolute ethanol washing three times, each 50
Milliliter, after put in vacuum drying oven 120 DEG C and be dried 6 hours；
7), by available copper oxide-zinc oxide complex after dried product in the air stream 400 DEG C of roastings 4 hours,
Air mass flow 100 ml/min；
8), by the said goods tabletting, the solid particle of screening 40～60 mesh sizes, the solid phase fixed bed reactor of gas is proceeded to
In, seal head and the tail two ends with quartz sand；It is passed through 80 milliliters of hydrogen streams per minute, reduction treatment 1 hour at 350 DEG C,
Obtain copper-zine oxide composite catalyst.
As improving further, glycerol gas phase hydrogenation reaction of the present invention is in a vertical reaction tube of rustless steel
Being carried out continuously, after reaction, gas cools down through cold-trap, collects condensed fluid and makees further material analyzing.
As improving further, glycerine hydrogenation reaction temperature of the present invention at 190-270 DEG C, reaction pressure 5-30
Atmospheric pressure, 0.1-20 hour time of contact, described time of contact is the quality stream of glycerol in catalyst quality/liquid feedstock
Speed.
Beneficial effects of the present invention is as follows:
From metallo-organic framework, (Cu (the Zn)-HKUST-1) prepares the present invention through roasting and reduction
Catalyst, in this catalyst, nano granular of zinc oxide is dispersed in the surface of metallic copper, and this have special pattern
Copper-zinc oxide catalyst has the reactivity of superelevation in the reaction for 1,2-propylene glycol of the vapor solid glycerin catalytic Hydrogenation
And stability.The present invention be directed to prepare copper-zine oxide composite catalyst process present in current document and patent can introduce
The problems such as sodium ion, preparation method complexity, expensive starting materials and custom-designed, the technique of the present invention is not related to sodium ion, raw material
Cheap and easy to get, preparation technology the most easily repeats, the composition of finished catalyst is controlled, morphology controllable, performance are adjustable, uses the present invention
The copper-zinc oxide catalyst for preparing of technique there is in glycerol gas phase hydrogenation reaction the highest activity and stability.
Instant invention overcomes tradition copper-zinc oxide catalyst complicated process of preparation, the composition of finished catalyst, structure and shape
Looks control difficulty, and in finished catalyst, copper granule is the most easily grown up and reduced dispersion and cause catalyst
The problems such as inactivation and custom-designed.Copper-zinc oxide catalyst prepared by the present invention, the gas phase hydrogenation for glycerol prepares 1,2-
In the reaction of propylene glycol, the activity of catalyst is the highest, stability fine, and wherein the selectivity of purpose product 1,2-PD is with sweet
The oil raising of conversion ratio and increase, reach as high as 95.7%.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of copper-zinc oxide catalyst prepared by the present invention；
Fig. 2 is the elementary composition figure along Fig. 1 in tangential direction.
Detailed description of the invention
Below by being embodied as example, technical scheme is further described, but invention is concrete interior
Hold and be not limited only to these embodiments.
Embodiment 1
1), weighing 2.9 grams of Zinc oxide powders and be scattered in 80 ml deionized water, stirring is uniform suspended to forming one
After liquid, under room temperature, the power of 300 watts ultrasonic 10 minutes, make Zinc oxide powder dispersed；Weigh 4.3 gram of three nitric hydrate
Copper and 7.5 grams of trimesic acids, be dissolved separately in 80 ml deionized water and 260 milliliters of ethanol.Treat that above-mentioned solution has prepared
Quan Hou, adds 160 milliliters of N, N-dimethylformamide dimethyl amide, mix homogeneously in the suspension of zinc oxide；It is sequentially added into nitre subsequently
The acid aqueous solution of copper and the alcoholic solution of trimesic acid are stirred vigorously, and react 1 minute.By the precipitation that obtains through microporous filter membrane mistake
Filter, leaves solid product, with putting into 120 DEG C dry 6 hours in vacuum drying oven after absolute ethanol washing three times (each 50 milliliters)；
By dried product in air stream (100 ml/min) after 400 DEG C of roastings 4 hours available copper oxide-zinc oxide be combined
Thing.By the said goods tabletting, the solid particle of screening 40～60 mesh sizes, proceed in gas-solid phase reactor fixed bed, with quartz
Head and the tail two ends are lived in sand seal；It is passed through 80 milliliters of hydrogen streams per minute, reduction treatment 1 hour at 350 DEG C, i.e. can get copper-oxygen
Change zinc catalyst.
Weigh the catalyst 0.1 gram prepared in aforementioned manners, in a vertical reaction tube of rustless steel, be carried out continuously reaction.
Reaction condition: raw material be mass content be glycerine water solution (1.2 mls/hour) and the hydrogen (80 ml/min) of 20%, instead
Answer temperature 250 DEG C, response time 2～100 hours.The yield of the amount of the material of 1,2-propylene glycol such as table 1 under the differential responses time
Shown in.
The yield of the 1,2-propylene glycol that the lower successive reaction of 1. 250 degree of table obtains
| Response time/hour | 2 | 10 | 30 | 50 | 80 | 100 |
| 1,2-propylene glycol yield/mol% | 85.7 | 85.0 | 83.0 | 82.9 | 81.8 | 79.9 |
Embodiment 2
With reference to the same catalyst preparation in embodiment 1 and reactions steps, except for the difference that glycerol gas phase hydrogenation reaction
It is 190～250 DEG C that temperature controls, and data acquisition time controls 2 hours after the reaction.Obtain 1,2-propylene glycol under different time
The yield of the amount of material is as shown in table 2.
The yield of the 1,2-propylene glycol obtained under table 2. different temperatures
| Reaction temperature/DEG C | 190 | 210 | 230 | 250 |
| 1,2-propylene glycol yield/mol% | 37.2 | 57.5 | 73.2 | 85.7 |
Embodiment 3
With reference to the same catalyst preparation in embodiment 1 and reactions steps, when except for the difference that changing the contact of reaction
Between (mass velocity of glycerol in catalyst quality/liquid feedstock), reaction temperature is 190 DEG C, and data acquisition time controls instead
Should be latter 2 hours.Obtain the yield of 1,2-propylene glycol under different time as shown in table 3.
3.190 DEG C of table, uses the yield of the 1,2-PD obtained different time of contact
| Time of contact/hour | 0.42 | 1.0 | 2.1 |
| 1,2-propylene glycol yield/mol% | 37.2 | 61.9 | 86.2 |
Embodiment 4
With reference to the preparation process of the similar catalyst in embodiment 1, except for the difference that add in catalyst preparation process
Gerhardite quality be 4.3 grams to 17.2 grams, control when i.e. preparing the molar ratio of cu zn in raw material be 0.5～
2.0.Catalyst obtained above is used for glycerol gas phase hydrogenation and prepares the reaction of 1,2-PD, reaction condition: catalyst 0.5
Gram, raw material be mass content be glycerine water solution (1.2 mls/hour) and hydrogen (80 ml/min), the reaction temperature of 20%
190 DEG C, the time of data acquisition controls after stable reaction 2 hours.The yield of 1,2-propylene glycol such as table 4 under the differential responses time
Shown in.
The cu zn mol ratio impact on glycerol conversion yield in table 4. catalyst preparation materials
| Cu zn molar ratio in catalyst preparation materials | 0.5 | 1.0 | 2.0 |
| 1,2-propylene glycol yield/mol% | 86.2 | 60.8 | 44.6 |
Fig. 1 is the shape appearance figure of copper-zinc oxide catalyst prepared by the present invention；Fig. 2 is the element along Fig. 1 in tangential direction
Composition diagram.By Fig. 1 and Fig. 2 it is found that according to the present invention process route, with metallo-organic framework (Cu (Zn)-
HKUST-1) being presoma, the copper-zinc oxide catalyst prepared through roasting and reduction has specific pattern, this
In catalyst, nano granular of zinc oxide is dispersed in the surface of metallic copper；Wherein, contact area between copper and zinc oxide high,
There is strong interaction, thus this catalyst activity in the reaction of preparing 1,2-dihydroxypropane by glycerine hydrogenation is high, good stability.
Listed above is only some specific embodiments of the present invention, it is clear that the invention is not restricted to above example, also may be used
To have many deformation, all changes that those of ordinary skill in the art can directly derive from present disclosure or associate
Shape, is all considered as protection scope of the present invention.
Claims (5)
1. the copper-zinc oxide catalyst of a preparing 1,2-dihydroxypropane by glycerine hydrogenation, it is characterised in that described catalyst is to receive
The Ni metal granule of rice ZnO embedding, relies on the synergism at Cu Yu ZnO interface to play the catalyst of main catalytic active.
2. a preparation method for the copper-zinc oxide catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation as claimed in claim 1,
It is characterized in that, be as presoma with metal organic framework compound (Cu (Zn)-HKUST-1), by steps such as pyrolysis reduction
The catalyst of the Ni metal granule of the nano-ZnO embedding obtained.
The preparation method of the copper-zinc oxide catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation the most according to claim 2, its
Being characterised by, described concrete preparation process is as follows:
1), weighing 2.9 grams of Zinc oxide powders and be scattered in 80 ml deionized water, stirring is to forming a uniform suspension
After, under room temperature, the power of 300 watts ultrasonic 10 minutes, make Zinc oxide powder dispersed；
2), weigh 4.3～17.2 grams of Gerhardites, dissolve completely in 80 ml deionized water；
3), weigh 7.5～15.0 grams of trimesic acids, dissolve completely in 260 milliliters of ethanol；
4), after above-mentioned solution prepares completely, the suspension of zinc oxide adds 160 milliliters of N, N-dimethylformamide dimethyl amide,
Mix homogeneously；
5), the aqueous solution of copper nitrate and the alcoholic solution of trimesic acid are sequentially added in above-mentioned suspension, are stirred vigorously, reaction
1 minute；
6), by the precipitation that obtains through filtering with microporous membrane, solid product is left, with absolute ethanol washing three times, each 50 milliliters,
After put in vacuum drying oven 120 DEG C and be dried 6 hours；
7), by available copper oxide-zinc oxide complex after dried product in the air stream 400 DEG C of roastings 4 hours, air
Flow 100 ml/min；
8), by the said goods tabletting, the solid particle of screening 40～60 mesh sizes, proceed in gas-solid phase reactor fixed bed, with
Quartz sand seals head and the tail two ends；Being passed through 80 milliliters of hydrogen streams per minute, at 350 DEG C, reduction treatment 1 hour, the most available
Copper-zine oxide composite catalyst.
4. the preparation side of the copper-zinc oxide catalyst of 1,2-propylene glycol is prepared according to the glycerine hydrogenation described in Claims 2 or 3
Method, it is characterised in that described glycerol gas phase hydrogenation reaction is carried out continuously in a vertical reaction tube of rustless steel, gas after reaction
Body cools down through cold-trap, collects condensed fluid and makees further material analyzing.
Glycerine hydrogenation the most according to claim 4 prepares the preparation method of the copper-zinc oxide catalyst of propylene glycol, its feature
It is, described reaction temperature 190-270 DEG C, reaction pressure 5-30 atmospheric pressure, 0.1-20 hour time of contact, described contact
Time is the mass velocity of glycerol in catalyst quality/liquid feedstock.
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| CN109772321A (en) * | 2017-11-13 | 2019-05-21 | 中国科学院福建物质结构研究所 | A kind of copper Si catalyst and its preparation and application based on metal organic frame |
| CN109772331A (en) * | 2019-03-01 | 2019-05-21 | 浙江大学 | A kind of glycerine hydrogenation prepares CoFe catalyst of propenyl and its preparation method and application |
| CN112892598A (en) * | 2021-01-26 | 2021-06-04 | 烟台市友利化工科技有限公司 | Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst |
| CN115646498A (en) * | 2022-10-20 | 2023-01-31 | 浙江大学 | High-stability copper-based catalyst for ethanol dehydrogenation and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109772321A (en) * | 2017-11-13 | 2019-05-21 | 中国科学院福建物质结构研究所 | A kind of copper Si catalyst and its preparation and application based on metal organic frame |
| CN109772321B (en) * | 2017-11-13 | 2021-07-16 | 中国科学院福建物质结构研究所 | Copper-silicon catalyst based on metal organic framework and preparation and application thereof |
| CN109772331A (en) * | 2019-03-01 | 2019-05-21 | 浙江大学 | A kind of glycerine hydrogenation prepares CoFe catalyst of propenyl and its preparation method and application |
| CN112892598A (en) * | 2021-01-26 | 2021-06-04 | 烟台市友利化工科技有限公司 | Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst |
| CN112892598B (en) * | 2021-01-26 | 2022-05-24 | 烟台市友利化工科技有限公司 | Preparation method of sec-butyl alcohol dehydrogenation MOF catalyst |
| CN115646498A (en) * | 2022-10-20 | 2023-01-31 | 浙江大学 | High-stability copper-based catalyst for ethanol dehydrogenation and preparation method thereof |
| CN115646498B (en) * | 2022-10-20 | 2024-02-02 | 浙江大学 | High-stability copper-based catalyst for ethanol dehydrogenation and preparation method thereof |
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