CN107126957A - A kind of catalyst of 1,2 propane diols selective oxidation lactic acid and its preparation method and application - Google Patents
A kind of catalyst of 1,2 propane diols selective oxidation lactic acid and its preparation method and application Download PDFInfo
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 239000004310 lactic acid Substances 0.000 title claims abstract description 28
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 235000013772 propylene glycol Nutrition 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of catalyst of 1,2 propane diols selective oxidation lactic acid, it is with rich in { 001 } crystal face anatase TiO2For carrier, load active component Au Au/TiO2Catalyst, active component A u high degree of dispersion, the mass content for loading Au is 0.1~5%.With TiO2{ 001 } it is the Au/TiO of carrier2Catalyst prepares the catalytic performance of lactic acid to 1,2 propane diols selective oxidation preferably, and the consumption of noble metal is few, so as to reduce the cost of catalyst preparation.The invention discloses its preparation method.
Description
Technical field
TiO the present invention relates to one kind using preferential exposure as { 001 }2Loaded noble metal catalyst for carrier and its
Application in 1,2- propane diols selective oxidation lactic acid.
Background technology
Lactic acid is a kind of important fine chemical product, can be widely applied to food, cosmetics, tobacco, weaving and leather
Deng field.Lactic acid is the primary raw material of synthesized degradable high polymer material PLA (PLA).PLA is a kind of collection biological absorbable
Property, biological degradability and biocompatibility in the green thermoplastic polyester of one, with good hot formability, mechanical strength and
Modulus of elasticity.Lactic acid demand there are about 120 kt every year in worldwide, and demand is still increasing year by year.Current lactic acid
Production method is mainly fermentation method and chemical synthesis.Fermentation method is simple because of technique, and raw material is sufficient, and development is more early, is a kind of ratio
More ripe production method of lectic acid, its yield is about more than the 70% of world's production of lactic acid amount.But the fermentation method cycle is long, can only between
Have a rest or semi-continuous production, and the lactic acid quality of domestic fermentation method production does not reach international standard.Chemical synthesis produces lactic acid
Can on a large scale, continuously it produce, synthesizing lactic acid has also obtained Food and Drug Administration (FDA) accreditation in the U.S..Compare
Although fermentation process, chemical manufacturing process has higher reaction rate, but toxic gas is produced in production process, easily pollutes ring
Border.
Glycerine is as the byproduct of biodiesel, and with being continuously increased for yield of biodiesel, the glycerine of generation is serious
It is superfluous.1,2-PD is prepared by hydrogenolysis process using cheap glycerine as raw material, one is provided for 1,2-PD
The new green syt route of bar, the production line has realized industrialization.And selectivity can be passed through using 1,2- propane diols as raw material
Oxidation reaction prepares lactic acid.Exploitation synthesizes 1,2-PD from glycerine, and then continues to prepare the technology path of lactic acid, not only may be used
To solve the problem of glycerol production is superfluous, glycerol derivatives added value is improved, the production cost of biodiesel is reduced, can also be
Develop the raw material that degradable high polymer material PLA provides non-petroleum chemical industry route, therefore tool is of great significance.
TiO2Be widely used in light-catalyzed reaction because it there is good bio-compatibility, it is chemical inertness, stronger
The low characteristic of oxidation susceptibility, cost, therefore as most potential semiconductor light-catalyst.The research such as Taustuer finds expensive
Metal and Ti atoms or Ti4+Between easily form key, be due to metal and carrier strong interaction (SMSI) (S.J.Tauster,
S.C.Fung,R.L.Garten,Journal of the American Chemical Society,1978,100(1):170-
174.).Just because of this property, causes numerous scholars to TiO2For the research of the loaded catalyst of carrier.In many
In commercial Application, such as petrochemical industry, environment, food, pharmacy etc., metal nanoparticle load are extensive on an metal oxide
In heterogeneous catalyst.It is mutual between optimal catalytic performance and metal and metal oxide carrier in catalytic reaction
Act on close association (G.A.Somorijai, Y.Li, Introduction to Surface Chemistry and
Catalysis,2010.).Liu etc. have studied with the TiO of different preferential exposures2For the Au/TiO of carrier2Catalyst
(L.C.Liu,C.Y.Ge, W.X.Zou,et al.Phys Chem Chem Phys,2015,17,5133).Deng etc. have studied
With (101), the TiO of (001) exposure2For the MnO of carrierx/TiO2Catalyst reduces SCR research to NO selective catalysis,
It was found that MnOx/TiO2(001) SCR catalytic activity is better than MnOx/TiO2(101), further study showed that, Mn3+It is used as master
The species wanted enter TiO2(001) the relatively low hole position of the octahedra degree of polymerization, causes catalyst to have relatively low NH3Oxidation activity
Higher SCR catalytic activity (S.C.Deng, T.T.Meng, B.L.Xu, F.Gao, Y.H.D, L.Y, Y.N.Fan, ACS
Catal,2016,6,5807-5815).Nikolaos etc. prepares 5%Au/TiO by the method for dipping2(P25) catalyst, is used
In the evaluation to 1,2-PD selective oxidation lactic acid, when reaction temperature is 60 DEG C, oxygen pressure is 10bar, during reaction
Between be 4h, the conversion ratio of 1,2-PD is 27%, the selectivity of lactic acid for 91.5% (D.Nikolaos, A.L-S.Jose,
M.Sankar,et al.,Green Chem,2009,11,1209-1216.).The TiO of commodity2(P25) composition is 80%
Anatase and 20% rutile, using it as the Au/TiO of carrier2Catalyst is for 1,2- propane diols selective oxidation lactic acid
Reactivity worth it is poor, cost is high.
The content of the invention
It is an object of the invention to provide one kind with rich in { 001 } crystal face anatase TiO2Urged for the carried noble metal of carrier
The preparation method and its application to 1,2-PD selective oxidation lactic acid of agent and catalyst, to overcome prior art to deposit
Deficiency.
The catalyst is with the TiO of preferential exposure2(001) catalyst for being carrier loaded active component A u, is used in combination
In the reaction of 1,2- propane diols selective oxidation lactic acid.
Technical scheme is as follows：
A kind of catalyst of 1,2-PD selective oxidation lactic acid, it is with rich in { 001 } crystal face anatase TiO2
For carrier, load active component Au Au/TiO2Catalyst, active component A u high degree of dispersion, the mass content for loading Au is
0.1~5%, preferably 0.3~1.5%.
A kind of preparation method of above-mentioned catalyst, it is to prepare Au/TiO by deposition-precipitation method2{ 001 } catalyst, its
Preparation method is as follows：By a certain amount of HAuCl4Mixed with water, the heating stirring under 80 DEG C of water-baths, add carrier/TiO2{ 001 },
The pH of solution is adjusted to 7-8, filtration washing with NaOH or urea liquid, 2h is dried in 110 DEG C of degree, is calcined 2h at 300 DEG C, most
Afterwards in 200 DEG C of logical H2Reductase 12 h, obtains Au/TiO2{ 001 } catalyst.
Described TiO2{ 001 } preparation of carrier：
TiO2(001) prepared by HF- hydro-thermal methods：With 20ml Ti (OC4H9)4100 ml poly- four are blended in 3.2ml HF
In fluorine water heating kettle, then in 200 DEG C of hydro-thermal process 24h, collect white precipitate, by ethanol and distillation water washing fluorine ion,
110 DEG C of dry 24h obtain TiO2(001)。
Active component in the catalyst takes suitable method assembling/load/to be attached to the TiO of different exposures2
(101)、TiO2(100)、TiO2(001) on carrier, the catalyst of active component high degree of dispersion is prepared, as a means of comparing.
The catalyst is used for the reaction of 1,2- propane diols selective oxidation lactic acid.
With the TiO of different exposures2For the Au/TiO of carrier2Catalyst is to 1,2- propane diols selective oxidation lactic acid
Reaction condition is：Using the 1,2-PD aqueous solution as raw material, 1,2-PD concentration is 0.01~2mol/L, and reaction system is added
NaOH solution, NaOH concentration is 0.01~5mol/L, is passed through O2, the MPa of reaction pressure 0.1~1.0, reaction temperature 25~100
DEG C, 0.1~8h of reaction time.It is preferred that reaction condition be：1,2-PD concentration is 0.01~1mol/L, and NaOH concentration is
0.1~2mol/L, O20.1~0.5MPa of reaction pressure, 50~100 DEG C of reaction temperature, 1~4h of reaction time.
Present invention discover that the TiO with 001 preferential exposure2The preparation method of carrier is simple, using it as the Au/ of carrier
TiO2Catalyst prepares the catalytic performance of lactic acid to 1,2-PD selective oxidation preferably, and the consumption of noble metal is few, so as to
To reduce the cost of catalyst preparation.
Figure of description
The preferential exposure that Fig. 1 is prepared is the TiO of (001)2Electron microscope.
Embodiment
The following examples are only used for that the present invention is specifically described.Embodiment is not intended to the usage range of the present invention
In the condition for being limited in embodiment narration.
Embodiment 1：
48ml butyl titanates, 126ml n-butanols, 14ml acetic acid are slowly added to deionized water under the conditions of mixing
12ml.By formed gel aging 24h at room temperature, then in 110 DEG C of dryings, 500 DEG C of roasting 4h obtain carrier TiO2(101)。
From accompanying drawing 1, that this method is prepared is the TiO that preferential exposure is { 101 }2。
Embodiment 2：
20ml Ti(OC4H9)4It is blended in 3.2ml HF in 100ml polytetrafluoro water heating kettles, then in 200 DEG C of hydro-thermal process
24h, the white precipitate of collection, by ethanol and distillation water washing fluorine ion, carrier TiO is obtained in 110 DEG C of dry 24h2(001)。
That this method is prepared is the TiO that preferential exposure is { 001 }2。
Embodiment 3：
Under being stirred continuously in frozen water, by 6.6mlTiCl4It is added in HCl/water solution, then 5.5wt% ammoniacal liquor is molten
Liquid is added in above-mentioned solution and constantly stirred, and is adjusted above-mentioned pH value of solution to 7 with 10ml 4wt% ammonia spirits, in room temperature
Lower aging 2h, then by suspension filtration washing, obtains Ti (OH)4Presoma.With 0.5g (NH4)2SO4Be dissolved into 15ml water and
In 15ml isopropanols, and by 2.0g Ti (OH)4Add in above-mentioned solution, after being well mixed, be transferred into 50ml polytetrafluoro
Water heating kettle, heats 24h at 180 DEG C, reaction product is washed for several times with water and ethanol, finally TiO is obtained in 80 DEG C of dry 6h2
{100}。
Embodiment 4：
By 19.1mg/ml HAuCl4The aqueous solution 0.67ml, 49.3ml H2O is added in beaker, and 80 DEG C are heated in a water bath simultaneously
Constantly stirring, then adds TiO2{ 100 } carrier 1g, is adjusted the pH of solution to 7 with 1mol/L NaOH.Then 2h is stirred,
Filtration washing, in 100 DEG C of dry 2h, is then warming up to 300 DEG C of roasting 2h with 3 DEG C/min, is subsequently passed 80 DEG C of steam roastings
2h, is down to after room temperature and leads to H2And 200 DEG C of reductase 12 h are warming up to 2 DEG C/min, obtain 1.3%Au/TiO2(100) catalyst.
Embodiment 5：
By 19.1mg/ml HAuCl4The aqueous solution 0.67ml, 49.3ml H2O is added in beaker, and 80 DEG C are heated in a water bath simultaneously
Constantly stirring, then adds the TiO of embodiment 22(001) carrier 1g, is adjusted the pH of solution to 7 with 1mol/L NaOH.So
After stir 2h, filtration washing, in 100 DEG C of dry 2h, is then warming up to 300 DEG C of roasting 2h with 3 DEG C/min, is subsequently passed 80 DEG C of water
Steam is calcined 2h, is down to after room temperature and leads to H2And 200 DEG C of reductase 12 h are warming up to 2 DEG C/min, obtain 1.3%Au/TiO2(001) urge
Agent.
Embodiment 6：
By 19.1mg/ml HAuCl4The aqueous solution 0.78ml, 1.2ml H2O is added in beaker, and then ultrasonic 10min adds
The TiO of embodiment 32(101) carrier 1g, ultrasonic 2h, then filtration washing, in 100 DEG C of dry 2h, is then heated up with 3 DEG C/min
To 300 DEG C of roasting 2h, 80 DEG C of steam roasting 2h are subsequently passed, is down to after room temperature and leads to H2And it is warming up to 200 DEG C also with 2 DEG C/min
Former 2h, obtains 1.5%Au/TiO2{ 101 } catalyst.
Embodiment 7：
19.1mg/ml HAuCl4Aqueous solution 0.52ml is added in beaker, then by 1%wt polyvinylpyrrolidones (PVP)
1.2g is added in above-mentioned solution and constantly stirred, and 2.4ml, 0.1mol/L NaBH are then added dropwise at 25 DEG C4Solution,
Aging 30min, then adds the TiO of embodiment 32(101) carrier 1g, stir 2h, filtration washing, it is drying over night at 120 DEG C on.
Obtain 1.0%Au/TiO2(101) catalyst.
Embodiment 8：
19.1mg/ml HAuCl4Aqueous solution 0.52ml is added in beaker, is constantly stirred under 80 DEG C of water-baths, then will
1%wt polyvinyl alcohol (PVA) 1.2g is added in above-mentioned solution and constantly stirred, and 2.4ml, 0.1mol/L then is being added dropwise
NaBH4Then solution, aging 30min adds the TiO of embodiment 12(100) carrier 1g, stirs 2h, filtration washing, at 120 DEG C
On drying over night, 300 DEG C of roasting 2h are then warming up to 3 DEG C/min, 80 DEG C of steam roasting 2h is subsequently passed, obtains 1.0%
Au/TiO2(100) catalyst.
Embodiment 9：
By 19.1mg/ml HAuCl4The aqueous solution 0.78ml, 1.22ml H2O is added in beaker, and then ultrasonic 10min adds
The TiO of embodiment 22(001) carrier 1g, is adjusted pH value of solution to 7 with 0.1mol/L NaOH, ultrasonic 2h, then filtration washing,
In 100 DEG C of dry 2h, 300 DEG C of roasting 2h are then warming up to 3 DEG C/min, 80 DEG C of steam roasting 2h is subsequently passed, is down to room
Wen Houtong H2And 200 DEG C of reductase 12 h are warming up to 2 DEG C/min, obtain 1.0%Au/TiO2(001) catalyst.
Embodiment 10 (comparative example)：
By 19.1mg/ml HAuCl4The aqueous solution 0.78ml, 1.22ml H2O is added in beaker, and then ultrasonic 10min adds
Commodity TiO2Carrier 1g, is adjusted pH value of solution to 7 with 0.1mol/L NaOH, ultrasonic 2h, then filtration washing, in 100 DEG C of dryings
2h, is then warming up to 300 DEG C of roasting 2h with 3 DEG C/min, is subsequently passed 80 DEG C of steam roasting 2h, is down to after room temperature and leads to H2And with
2 DEG C/min is warming up to 200 DEG C of reductase 12 h, obtained 1.0%Au/TiO2Catalyst.
Embodiment 11：
By the catalyst in 0.05g embodiments 4, the 10ml 0.5mol/L 1,2-PDs aqueous solution and the mol/L of 5ml 1
The NaOH aqueous solution is added in stainless steel cauldrons of the 100ml with polytetrafluoroethyllining lining, is passed through O20.3MPa, reaction temperature
90 DEG C, reaction time 4h, magnetic agitation speed 500r/min.Reaction terminate after by gas-chromatography, liquid chromatogram analyzes original
Material, the composition of product.
Catalyst in embodiment 4-7 is also reacted by above-mentioned condition.
Reactivity worth is shown in Table 1, shows with the TiO of different preferential exposures2(101)、TiO2(100)、TiO2(001) it is load
The Au/TiO of body2Catalyst is better than with commodity TiO to the catalytic performance of 1,2- propane diols selective oxidation lactic acid2For carrier
Au/TiO2Catalyst.
Each catalyst 1,2- propane diols selective oxidation lactic acid reactivity worth of table 1.
Claims (4)
1. a kind of catalyst of 1,2-PD selective oxidation lactic acid, it is characterized in that：It is with rich in { 001 } crystal face rutile titania
Ore deposit TiO2For carrier, load active component Au Au/TiO2Catalyst, active component A u high degree of dispersion, the quality for loading Au contains
Measure as 0.1~5%.
2. the catalyst described in claim 1, it is characterized in that：The described mass content for loading Au is 0.3~1.5%.
3. the preparation method of catalyst described in a kind of claim 1, it is characterized in that：It is to prepare Au/TiO by deposition-precipitation method2
{ 001 } catalyst, its preparation method is as follows：By a certain amount of HAuCl4Mix, the heating stirring under 80 DEG C of water-baths, add with water
Carrier/TiO2{ 001 }, the pH of solution is adjusted to 7-8, filtration washing with NaOH or urea liquid, 2h is dried in 110 DEG C of degree,
2h is calcined at 300 DEG C, finally in 200 DEG C of logical H2Reductase 12 h, the mass content that must load Au is 0.1~5%Au/TiO2{ 001 } urge
Agent.
4. application of the catalyst in 1,2- propane diols selective oxidation lactic acid described in claim 1.
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| CN108187692A (en) * | 2018-01-08 | 2018-06-22 | 山东大学 | A kind of nano titania porous ceramic catalyst of supported bi-metallic and its preparation method and application |
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| CN102249892A (en) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | Method for preparing lactic acid by catalytic oxidation of 1,2-propylene glycol |
| CN104193615A (en) * | 2014-05-16 | 2014-12-10 | 江苏大学 | Catalytic oxidation method for 1,2-propanediol |
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| CN102249892A (en) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | Method for preparing lactic acid by catalytic oxidation of 1,2-propylene glycol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108187692A (en) * | 2018-01-08 | 2018-06-22 | 山东大学 | A kind of nano titania porous ceramic catalyst of supported bi-metallic and its preparation method and application |
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