CN106238063B - A kind of glycerine hydrogenation prepares the copper-zinc oxide catalyst and preparation method thereof of propylene glycol - Google Patents
A kind of glycerine hydrogenation prepares the copper-zinc oxide catalyst and preparation method thereof of propylene glycol Download PDFInfo
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- CN106238063B CN106238063B CN201610633345.XA CN201610633345A CN106238063B CN 106238063 B CN106238063 B CN 106238063B CN 201610633345 A CN201610633345 A CN 201610633345A CN 106238063 B CN106238063 B CN 106238063B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 40
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- VODBHXZOIQDDST-UHFFFAOYSA-N copper zinc oxygen(2-) Chemical compound [O--].[O--].[Cu++].[Zn++] VODBHXZOIQDDST-UHFFFAOYSA-N 0.000 title claims description 26
- 239000010949 copper Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 239000002923 metal particle Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 20
- 229960004063 propylene glycol Drugs 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 235000013772 propylene glycol Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 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
- 239000000725 suspension Substances 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 238000001035 drying Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- -1 copper oxide-zinc oxide compound Chemical class 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless 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
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000001291 vacuum drying 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
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 230000035484 reaction time Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 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
- GFCDJPPBUCXJSC-UHFFFAOYSA-N [O-2].[Zn+2].[Cu]=O Chemical compound [O-2].[Zn+2].[Cu]=O GFCDJPPBUCXJSC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 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
- 239000002283 diesel fuel Substances 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
- 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
- 230000001376 precipitating effect Effects 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of glycerine hydrogenations to prepare 1, the Cu ZnO catalyst and preparation method thereof of 2 propylene glycol, catalyst is the Ni metal particle embedded with nano-ZnO, the catalyst of main catalytic active is played by the synergistic effect of Cu and the interfaces ZnO, with metal organic framework compound (Cu (Zn) HKUST 1) for presoma, pass through the catalyst for the Ni metal particle that the nano-ZnO that pyrolysis reduction obtains embeds.It easily grows up under an atmosphere of hydrogen the present invention overcomes copper particle during the control of traditional Cu ZnO catalyst preparation process complexity, the composition of finished catalyst, structure and pattern is difficult and finished catalyst and reduces dispersion degree and lead to catalyst inactivation and specially design.
Description
Technical field
The present invention relates to a kind of preparation method for the copper-zinc oxide catalyst can be used for glycerine hydrogenation, specifically one
Kind glycerine hydrogenation prepares the copper-zinc oxide catalyst and preparation method thereof of 1,2- propylene glycol.
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 resulting in extensive concern.People attempt to use various methods to prepare efficient copper-zinc oxide catalyst
(Science,352(2016)969-974；Catal.Today,272(2016)87-93)；Traditional co-precipitation preparation process can
To obtain higher copper dispersion degree, however because often sodium carbonate or sodium hydroxide is used to do precipitating reagent in preparation process, this
Inevitably bring sodium ion into finished catalyst, and the introducing of sodium ion can seriously inhibit copper-zinc oxide catalyst
Activity (Nature, 531 (2016) 83-87) in the reactions such as methanol-fueled CLC.Therefore, develop it is new, do not introduce sodium ion
The preparation method of copper-zinc oxide catalyst has great importance and application prospect.Kondart etc. is first using supercritical solvent method
Copper-zinc hydrate presoma is first prepared, then the techniques such as drying, roasting, reduction are free of sodium to reach finished catalyst
The purpose (Nature, 531 (2016) 83-87) of ion；However there is complex process, cumbersome, dangerous (overcritical for this method
Condition), expensive starting materials the defects of.
Copper-zinc oxide catalyst had higher initial activity in glycerine hydrogenation reaction, is widely used, from 2007
Just there are document report and patent application, the superfine people of Peking University's bang to find that copper-zinc oxide catalyst is added in glycerin liquid successively
In hydrogen reaction active (Catal.Lett.117 (2007) 62-67)；Chinese patent CN200810011446.9 discloses one
The preparation method of kind Cu-Cr metallic oxide with high specific surface area catalyst and its application in glycerine hydrogenation reaction；
CN200810019133.8 applied it is a kind of containing copper oxide, zinc oxide, aluminium oxide and selected from Y, La, Ce, Pr, Nd, Sm, Eu,
The application of at least one of rare earth elements such as Gd, Tb, Dy or a variety of rare earth oxide catalysts in glycerine hydrogenation reaction；
CN200810072333.X reports a kind of copper zinc catalyst containing carbon nanotube and its application in glycerine hydrogenation reaction
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 used to synthesize the catalyst and its system of 1,2- propylene glycol
Preparation Method；CN201110056530.4 has applied for Cu/MgO catalyst prepared by equi-volume impregnating and its has been reacted in glycerine hydrogenation
In application；CN201110056597.8 has applied for Cu/Al prepared by equi-volume impregnating2O3Catalyst and its in glycerine hydrogenation
Application in reaction；CN201110056529.1 has applied for the Cu/TiO prepared by equi-volume impregnating2Catalyst and its
Technique for applying in glycerine hydrogenation reaction；CN201310181246.9 is reported is used for liquid phase glycerine hydrogenation by raney copper catalyst
Technology；CN201210419541.9 discloses a kind of copper-based catalyst of loaded nano using copper as active constituent, titanium
Or cerium etc. is co-catalyst, the glycerine hydrogenation catalyst prepared using coprecipitation.Catalyst in above-mentioned patent specification
Preparation process mainly has infusion process, coprecipitation, melting-lixiviation process etc..Using these methods during preparing catalyst,
It is difficult composition, structure and the pattern of effectively control catalyst, therefore different researchers can obtain different catalyst, reaction
Effect also is difficult to control and repeat.
The present invention is for current copper-zinc oxide catalyst preparation process complexity, the composition of finished catalyst, structure and pattern
Control is difficult and these catalyst poor repeatability, stability in the reaction that glycerine hydrogenation prepares 1,2- propylene glycol is low etc. asks
It inscribes and proposes solution.Solution proposed by the invention is that one kind is simple, efficiently prepares copper-zinc oxide catalyst
Method, the copper-zinc oxide catalyst obtained using this method for the gas phase hydrogenation of glycerine generate 1,2-PD have it is non-
Often high activity and stability.
Invention content
The present invention be directed to prepare copper-zine oxide composite catalyst process present in current document and patent to introduce sodium
The problems such as ion, preparation method be complicated, expensive starting materials and specially design, it is honest and clean that technique of the invention is not related to sodium ion, raw material
Valence is easy to get, preparation process succinctly easily repeats, the composition of finished catalyst is controllable, morphology controllable, performance is adjustable.It is using the present invention
The copper-zinc oxide catalyst that technique is prepared has very high activity and stability in glycerine gas phase hydrogenation reaction.Letter
It says cleanly, the preparation process of this catalyst is with metal organic framework compound (HKUST-1) for presoma, also by pyrolysis
The Ni metal particle of former and etc. obtained nano-ZnO embedding plays major catalytic by the synergistic effect at Cu and the interfaces ZnO and lives
The catalyst of property.The pattern of this finished catalyst is as shown in Fig. 1.
The present invention is achieved through the following technical solutions：
The invention discloses a kind of copper-zinc oxide catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation, the catalyst
It is the Ni metal particle embedded with nano-ZnO, the catalysis of main catalytic active is played by the synergistic effect of Cu and the interfaces ZnO
Agent.
The invention also discloses the copper-zine oxide catalysis that a kind of glycerine hydrogenation as described in claim 1 prepares propylene glycol
The preparation method of agent passes through pyrolysis reduction with metal organic framework compound (Cu (Zn)-HKUST-1) for presoma
The catalyst of the Ni metal particle of obtained nano-ZnO embedding.
As a further improvement, specific preparation process of the present invention is as follows：
1) it, weighs 2.9 grams of Zinc oxide powders to be scattered in 80 ml deionized waters, stirring is uniform suspended to forming one
After liquid, ultrasound 10 minutes, keep Zinc oxide powder evenly dispersed under room temperature, 300 watts of power；
2) 4.3~17.2 grams of Gerhardites, are weighed, are dissolved in 80 ml deionized waters complete；
3) 7.5~15.0 grams of trimesic acids, are weighed, are dissolved in 260 milliliters of ethyl alcohol complete；
4), after above-mentioned solution prepares completely, 160 milliliters of N, N- dimethylformamide dimethyl acyls are added in the suspension of zinc oxide
Amine is uniformly mixed；
5), the alcoholic solution of the aqueous solution of copper nitrate and trimesic acid is sequentially added in above-mentioned suspension, is vigorously stirred,
Reaction 1 minute；
6) obtained precipitation, is left into solid product through filtering with microporous membrane, is washed three times with absolute ethyl alcohol, every time 50
Milliliter, after be put into vacuum drying oven 120 DEG C of dryings 6 hours；
7), by dried product in the air stream 400 DEG C roasting 4 hours after copper oxide-zinc oxide compound can be obtained,
100 ml/min of air mass flow；
8), by the said goods tabletting, the solid particle of 40~60 mesh sizes is screened, gas-solid phase fixed bed reactors are transferred to
In, head and the tail both ends are sealed with quartz sand；80 milliliters of hydrogen streams per minute are passed through, reduction treatment 1 hour at 350 DEG C, you can
Obtain copper-zine oxide composite catalyst.
As a further improvement, glycerine gas phase hydrogenation reaction of the present invention is in a vertical reaction tube of stainless steel
It is carried out continuously, gas is cooled down through cold-trap after reaction, is collected condensate liquid and is made further material analyzing.
As a further improvement, glycerine hydrogenation reaction temperature of the present invention is at 190-270 DEG C, reaction pressure 5-30
Atmospheric pressure, time of contact 0.1-20 hour, the time of contact are the quality streams of glycerine in catalyst quality/liquid feedstock
Speed.
Beneficial effects of the present invention are as follows：
From metallo-organic framework, (Cu (Zn)-HKUST-1)s are prepared the present invention by roasting and restoring
Catalyst, nano granular of zinc oxide is dispersed in the surface of metallic copper in this catalyst, this to have special pattern
Copper-zinc oxide catalyst reactivity with superelevation in vapor solid glycerin catalytic Hydrogenation is for the reaction of 1,2- propylene glycol
And stability.The present invention be directed to prepare copper-zine oxide composite catalyst process present in current document and patent to introduce
The problems such as sodium ion, preparation method be complicated, expensive starting materials and specially design, technique of the invention is not related to sodium ion, raw material
Cheap and easy to get, preparation process succinctly easily repeats, the composition of finished catalyst is controllable, morphology controllable, performance is adjustable, using the present invention
The copper-zinc oxide catalyst that is prepared of technique there is very high activity and stability in glycerine gas phase hydrogenation reaction.
The present invention overcomes traditional copper-zinc oxide catalyst preparation process complexity, the composition of finished catalyst, structure and shapes
Copper particle easily grows up and reduces dispersion degree and lead to catalyst under an atmosphere of hydrogen in looks control difficulty and finished catalyst
The problems such as inactivation and specially design.Copper-zinc oxide catalyst prepared by the present invention, the gas phase hydrogenation for glycerine prepare 1,2-
In the reaction of propylene glycol, the activity of catalyst is very high, stability is fine, and wherein the selectivity of purpose product 1,2-PD is with sweet
The raising of oily conversion ratio and increase, reach as high as 95.7%.
Description of the drawings
Fig. 1 is the shape appearance figure of copper-zinc oxide catalyst prepared by the present invention；
Fig. 2 is the element composition figure in tangential direction along Fig. 1.
Specific implementation mode
Technical scheme of the present invention is further described below by specific embodiment, but is invented specific interior
Appearance is not limited only to these embodiments.
Embodiment 1
1) it, weighs 2.9 grams of Zinc oxide powders to be scattered in 80 ml deionized waters, stirring is uniform suspended to forming one
After liquid, ultrasound 10 minutes, keep Zinc oxide powder evenly dispersed under room temperature, 300 watts of power；Weigh 4.3 gram of three nitric hydrate
Copper and 7.5 grams of trimesic acids, are dissolved separately in 80 ml deionized waters and 260 milliliters of ethyl alcohol.Wait for that above-mentioned solution has prepared
Quan Hou, is added 160 milliliters of N in the suspension of zinc oxide, and N- dimethylformamide dimethyl amides are uniformly mixed；Then sequentially add nitre
The aqueous solution of sour copper and the alcoholic solution of trimesic acid are vigorously stirred, and are reacted 1 minute.By obtained precipitation through miillpore filter mistake
Filter, leaves solid product, and 120 DEG C of dryings 6 hours are put into vacuum drying oven after washing (every time 50 milliliters) three times with absolute ethyl alcohol；
By dried product, that copper oxide-zinc oxide can be obtained is compound after 400 DEG C of roastings 4 hours in air stream (100 ml/min)
Object.By the said goods tabletting, the solid particle of 40~60 mesh sizes is screened, is transferred in gas-solid phase reactor fixed bed, with quartz
Head and the tail both ends are lived in sand seal；80 milliliters of hydrogen streams per minute are passed through, reduction treatment 1 hour at 350 DEG C, you can obtain copper-oxygen
Change zinc catalyst.
0.1 gram of the catalyst prepared in aforementioned manners is weighed, reaction is carried out continuously in a vertical reaction tube of stainless steel.
Reaction condition：Raw material is the glycerine water solution (1.2 mls/hour) and hydrogen (80 ml/min) that mass content is 20%, instead
Answer 250 DEG C of temperature, 2~100 hours reaction time.The yield of the amount of the substance of 1,2- propylene glycol such as table 1 under the differential responses time
It is shown.
The yield for the 1,2- propylene glycol that the lower successive reaction of 1. 250 degree of table obtains
| Reaction 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
Same catalyst preparation and reaction step in reference embodiment 1, the difference is that glycerine gas phase hydrogenation reaction
Temperature control is 190~250 DEG C, data acquisition time control 2 hours after the reaction.Obtain 1,2- propylene glycol under different time
The yield of the amount of substance is as shown in table 2.
The yield of the 1,2- propylene glycol obtained under 2. different temperatures of table
| 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 and reaction step in embodiment 1, the difference is that when changing the contact of reaction
Between (mass velocity of glycerine in catalyst quality/liquid feedstock), reaction temperature be 190 DEG C, data acquisition time control anti-
It should be 2 hours latter.The yield for obtaining 1,2- propylene glycol under different time is as shown in table 3.
3.190 DEG C of table, using the yield for the 1,2-PD that different times of contact obtain
| 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, the difference is that being added in catalyst preparation process
Gerhardite quality be 4.3 grams to 17.2 grams, that is, when preparing control raw material in cu zn molar ratio be 0.5~
2.0.Catalyst obtained above is prepared to the reaction of 1,2-PD, reaction condition for glycerine gas phase hydrogenation：Catalyst 0.5
Gram, raw material is the glycerine water solution (1.2 mls/hour) and hydrogen (80 ml/min) that mass content is 20%, reaction temperature
190 DEG C, the time control of data acquisition is 2 hours after stable reaction.The yield of 1,2- propylene glycol such as table 4 under the differential responses time
It is shown.
Influence of the cu zn molar ratio to glycerol conversion yield in 4. catalyst preparation materials of table
| 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 in tangential direction along Fig. 1
Composition figure.By Fig. 1 and Fig. 2 it can be found that process route according to the invention, with metallo-organic framework (Cu (Zn)-
HKUST-1 it is) presoma, there is specific pattern by roasting and restoring the copper-zinc oxide catalyst being prepared, this
Nano granular of zinc oxide is dispersed in the surface of metallic copper in catalyst；Wherein, contact area between copper and zinc oxide it is high,
With strong interaction, thus this catalyst activity in the reaction of preparing 1,2-dihydroxypropane by glycerine hydrogenation is high, stability is good.
Listed above is only some specific embodiments of the present invention, it is clear that present invention is not limited to the above embodiments, may be used also
With there are many all changes that deformation, those skilled in the art directly can be exported or be associated from present disclosure
Shape is considered as protection scope of the present invention.
Claims (4)
1. a kind of preparation method of the copper-zinc oxide catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation, which is characterized in that with metal
Organic framework compounds Cu (Zn)-HKUST-1 is presoma, passes through the metal for the nano-ZnO embedding that pyrolysis reduction step obtains
The catalyst of Cu particles, the catalyst are the Ni metal particles of nano-ZnO embedding, and work is cooperateed with by Cu and the interfaces ZnO
With the catalyst for playing main catalytic active.
2. the preparation method of the copper-zinc oxide catalyst of preparing 1,2-dihydroxypropane by glycerine hydrogenation according to claim 1,
It is characterized in that, the specific preparation process is as follows：
1) it, weighs 2.9 grams of Zinc oxide powders to be scattered in 80 ml deionized waters, stirring to one uniform suspension of formation
Afterwards, ultrasound 10 minutes under room temperature, 300 watts of power, keep Zinc oxide powder evenly dispersed；
2) 4.3~17.2 grams of Gerhardites, are weighed, are dissolved in 80 ml deionized waters complete；
3) 7.5~15.0 grams of trimesic acids, are weighed, are dissolved in 260 milliliters of ethyl alcohol complete；
4), after above-mentioned solution prepares completely, 160 milliliters of N of addition in the suspension of zinc oxide, N- dimethylformamide dimethyl amides,
It is uniformly mixed；
5), the alcoholic solution of the aqueous solution of copper nitrate and trimesic acid is sequentially added in above-mentioned suspension, is vigorously stirred, is reacted
1 minute；
6) obtained precipitation, is left into solid product through filtering with microporous membrane, is washed three times with absolute ethyl alcohol, 50 milliliters every time,
After be put into vacuum drying oven 120 DEG C of dryings 6 hours；
7), by dried product in the air stream 400 DEG C roasting 4 hours after copper oxide-zinc oxide compound, air can be obtained
100 ml/min of flow；
8), by the said goods tabletting, the solid particle of 40~60 mesh sizes is screened, is transferred in gas-solid phase reactor fixed bed, with
Quartz sand seals head and the tail both ends；80 milliliters of hydrogen streams per minute are passed through, reduction treatment 1 hour at 350 DEG C, you can obtain
Copper-zine oxide composite catalyst.
3. glycerine hydrogenation according to claim 1 or 2 prepares the preparation side of the copper-zinc oxide catalyst of 1,2- propylene glycol
Method, which is characterized in that glycerine gas phase hydrogenation reaction is carried out continuously in a vertical reaction tube of stainless steel, and gas is through cold after reaction
Trap cools down, and collects condensate liquid and makees further material analyzing.
4. glycerine hydrogenation according to claim 3 prepares the preparation method of the copper-zinc oxide catalyst of propylene glycol, feature
It is, 190-270 DEG C of the reaction temperature, reaction pressure 5-30 atmospheric pressure, time of contact 0.1-20 hour.
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| US4279781A (en) * | 1979-10-09 | 1981-07-21 | United Catalysts Inc. | Catalyst for the synthesis of methanol |
| CN103301843A (en) * | 2012-03-15 | 2013-09-18 | 北京化工大学 | High-dispersion supported copper-based catalyst as well as preparation method and application thereof |
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|---|---|---|---|---|
| US4279781A (en) * | 1979-10-09 | 1981-07-21 | United Catalysts Inc. | Catalyst for the synthesis of methanol |
| CN103301843A (en) * | 2012-03-15 | 2013-09-18 | 北京化工大学 | High-dispersion supported copper-based catalyst as well as preparation method and application thereof |
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