CN105601494B - A kind of method of nanometer of propane diols of copper catalysis 1,2 oxidation - Google Patents
A kind of method of nanometer of propane diols of copper catalysis 1,2 oxidation Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 230000003647 oxidation Effects 0.000 title claims abstract description 39
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 24
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 5
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 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 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- -1 Polyethylene Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 235000013772 propylene glycol Nutrition 0.000 abstract description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract description 14
- 239000004310 lactic acid Substances 0.000 abstract description 12
- 235000014655 lactic acid Nutrition 0.000 abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 abstract description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- AHTSCRNWVSEMPI-UHFFFAOYSA-N gold;methane Chemical compound C.[Au] AHTSCRNWVSEMPI-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- OSFGNZOUZOPXBL-UHFFFAOYSA-N nitric acid;trihydrate Chemical class O.O.O.O[N+]([O-])=O OSFGNZOUZOPXBL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of method of 1,2 propane diols catalysis oxidations, refer in particular to using metal nano copper as catalyst, the method that the propane diols of catalysis oxidation 1,2 prepares lactic acid.The catalyst of nano-copper used in this method is prepared using wet-chemical reducing process, is controlled the size of copper particle in course of reaction by using different organic modifiers, is effectively improved catalyst activity.Non-noble metal nano copper is applied in the reaction of 1,2 propane diols catalysis oxidations, compared with the noble metal such as Au, Pd, Pt, substantially reduces catalyst cost.1,2 propane diols method for oxidation are simple in invention, and catalyst amount is few, and catalytic activity is high, is easy to separate with product, while have the advantages of recycling performance is good, there is preferable industrial application value.
Description
Technical field
The present invention relates to 1,2-PD catalytic oxidation technologies field, refers in particular to a kind of nanometer copper catalysis 1,2-PD oxidation
The method for preparing lactic acid.
Background technology
Lactic acid is the green chemical that a kind of demand is big, widely used, and biodegradable modeling is produced by raw material of lactic acid
Expect, green solvent, oxidizing chemical, meet the market demand of its rapid growth.At present lactic acid mainly with glucose, starch,
Sucrose etc. is that raw material is produced by fermentation method, or is prepared by chemical synthesis.However, traditional fermentation method cost
Height, reaction rate is low, downstream product separation and purification difficult；Chemical synthesis uses noxious material HCN, is unfavorable for environmental protection, because
This, finding efficient, green a novel material route and synthetic method has important Research Significance.
As biodiesel largely produces, glycerine is 10% or so as by-product yields, and this make it that glycerol production is quick
Improve.Glycerine is produced the 1,2-PD that yield is more than 90% by hydrogenolysis and light can realized compared with 1,3-PD, but
Constantly expand large-scale production, and 1,2- at home as dimethyl carbonate coproduction 1,2-PD prepares carbonate device
Propane diols reduces in the demand side of solvent and unsaturated-resin, and 1,2-PD faces the problem of drug on the market.Therefore, 1,2-
Propane diols can be as a kind of novel material for preparing lactic acid.
At present, 1,2-PD selective catalytic oxidation prepares the technology of lactic acid and is concentrated mainly on Study of Catalyst.Prati
Deng (Gold on Carbon as a New Catalyst for Selective Liquid Phase Oxidation of
Diols, J.Catal.176 (1998) 552-560.) report using 1%Au/C catalyst in O2Pressure is 0.3MPa, reaction temperature
Spend and reacted for catalysis oxidation 1,2-PD under conditions of 90 DEG C, after reacting 1h, 1,2-PD conversion ratio reaches 78%, lactic acid
Selectivity reaches 100%.They also found catalytic activity of the particle size to Au catalyst in 1,2- propane diols oxidation reactions
Significantly affect.The technology reaction condition is gentle, and catalyst has high catalytic activity, but is used as reaction using noble metal Au
Active component, cause needed for cost it is higher the problems such as, be extremely difficult to commercial Application requirement.
The content of the invention
It is an object of the invention to provide a kind of method for preparing lactic acid using Nanometer Copper catalysis oxidation 1,2- propane diols.This
Invent the reaction to carry out in autoclave, the use of oxygen is oxidant under catalyst action.Catalyst in course of reaction
Dosage is few, and catalyst not easy in inactivation, has good stability in use.
The present invention is achieved through the following technical solutions：
Step 1: added in autoclave water-soluble containing certain density 1,2- propane diols, the mixing of sodium hydroxide
Liquid, a certain amount of nanometer of copper catalyst is added, lead to N2Emptied, be then turned on agitating device；
Step 2: system obtained by step 1 is heated to reaction temperature；It is passed through certain pressure oxygen to be reacted, reaction knot
Shu Hou, reaction product carry out acidification, using gas-chromatography, efficient liquid phase chromatographic analysis and result of calculation.
In step 1,1,2-PD concentration is 0.2~0.7mol/L in the mixed aqueous solution, and naoh concentration is
0.5~1.2mol/L；
In step 1, the quality of nanometer copper catalyst is 0.07~0.24g.
In step 1, the volume ratio of described reaction solution and autoclave is 1:5, stir speed (S.S.) 600rpm；
In step 2, described oxygen pressure is 0.5~1.5MPa, and reaction temperature is 140~200 DEG C, and the reaction time is
4h。
In step 2, the acidification of described reaction product refer to concentrated hydrochloric acid by the pH of product be adjusted to 2~3 it
Between.
Nanometer copper catalyst of the present invention passes through wet-chemical reducing process under conditions of using organic solvent as dressing agent
It is prepared, specific preparation method is carried out as steps described below：
A certain amount of organic modifier and nitrate trihydrate copper is weighed first, is dissolved in absolute ethyl alcohol by 30min ultrasounds point
Dissipate, when reactant mixture is heated to 60 DEG C, NaOH ethanol solutions are added dropwise dropwise, the pH value for adjusting reaction solution is
8.0, continue heating response liquid afterwards to 80 DEG C, hydrazine hydrate absolute ethyl alcohol weak solution is then added dropwise dropwise, under magnetic stirring instead
The nano copper particle of preparation should be cooled to room temperature after certain time and be stored in ethanol solution, pre- place is needed before use
Reason, repeatedly washed, centrifuged with absolute ethyl alcohol, dried.
The organic modifier is citric acid (CA), Tween-80 (Tween-80), cetyl trimethylammonium bromide
Or Polyethylene glycol-2000 (PEG-2000) (CTAB).
The organic modifier quality is that the concentration of 20%, the NaOH ethanol solutions of nitrate trihydrate copper mass is 1.0mol/
L。
The concentration of the hydrazine hydrate absolute ethyl alcohol weak solution is 0.1mol/L.
The mass concentration of the hydrazine hydrate is 85%, reaction time 2h.
The nanometer copper catalyst of the present invention controls copper particle in preparation process by using different organic modifiers
Size, effectively improve catalyst activity.
Beneficial effects of the present invention：
(1) present invention uses non-noble metal nano copper that prepared by 1,2-PD catalysis oxidation into breast as catalyst first
Acid, compared with the noble metal such as Au, Pd, Pt, catalyst cost is substantially reduced, there is preferable industrial application value.
(2) nanometer copper catalyst of the present invention has dosage few, is catalyzed during the course of the reaction without activation process
It is active high, good product selectivity, it is easy to the advantages that product separation and recycling performance are good.
(3) the nanometer copper catalyst that the present invention uses in the preparation, can be controlled by using different organic modifiers
The size of copper particle, so as to improve catalyst activity.
Brief description of the drawings：
Fig. 1 is the nanometer Cu prepared by the present inventionCTABThe TEM figures of catalyst.
Embodiment：
It is below presently preferred embodiments of the present invention, better understood when the present invention, but embodiments of the invention are not limited to
This, while its shown data does not represent the limitation to feature of present invention scope.
Embodiment 1
(1) preparation of nanometer copper catalyst
2.42g nitrate trihydrates copper is weighed first and 0.484g cetyl trimethylammonium bromides (CTAB) dissolve in 100ml's
Being ultrasonically treated 30min in absolute ethyl alcohol, under normal temperature makes it all dissolve, and adds four-hole boiling flask and is heated to 60 DEG C, then will configuration
1.0mol/L NaOH ethanol solutions (ultrasonic dissolution) be added dropwise to above-mentioned mixed liquor dropwise, regulation pH value is 8.0；Continue afterwards
Then heating response liquid is added dropwise 100ml0.1mol/L hydrazine hydrate alcohol dilute solutions, reacts 2h under magnetic stirring dropwise to 80 DEG C
After prepare Nanometer Copper (CuCTAB), it is cooled to room temperature and is stored in ethanol solution.Need to pre-process before use, with anhydrous second
Alcohol is repeatedly washed, centrifuged, drying.
Fig. 1 is nanometer CuCTABThe TEM figures of catalyst.As illustrated, the Nanometer Copper prepared when using CTAB as dressing agent is
Spheric granules, the particle size range of particle is 0.44~10.32nm, and average grain diameter is about 7.18nm, the results showed that, this experiment condition
The copper catalyst of lower preparation is nano-scale particle.
(2) 1,2- propane diols catalytic oxidation:
1,2-PD, the mixed aqueous solution of sodium hydroxide are added first in 1L autoclaves, wherein 1,2- the third two
Determining alcohol is 0.4mol/L, naoh concentration 0.8mol/L；0.12g nanometer copper catalysts are added, stirring makes it scattered
Uniformly.Reaction unit is installed, nitrogen purging 15min is passed through and is emptied, be then turned on agitating device, stir speed (S.S.)
600rpm, when reaction temperature rises to 180 DEG C, it is passed through 1.0MPa O2Start to react；After reaction 4h terminates, to obtained product
Acidification is carried out, using gas-chromatography, efficient liquid phase chromatographic analysis and result of calculation, the results are shown in Table 1.
Embodiment 2
Nanometer copper catalyst is prepared using the same method of embodiment 1, but it is respectively CA, Tween- to change organic modifier
80, PEG-2000, prepare CuCA、CuTween-80、CuPEG-2000Nanocatalyst, catalyst aoxidize the process of 1,2-PD
Using method same as Example 1, you can obtain different modifying agent and prepare nanometer copper catalyst to 1,2-PD catalysis oxygen
Change the influence of reaction, the results are shown in Table 1, from the conversion ratio of 1,2-PD, Cu nano particles are catalyzed the anti-of 1,2-PD
Answer speed that there is order below CuCA>CuCTAB>CuTween-80>CuPEG-2000.When with CuCTABWhen nano particle is catalyst, 1,2-
The conversion ratio of propane diols is 84.3%, lactic acid, and the selectivity of formic acid and acetic acid is respectively 53.8%, 15.6%, 30.6%, lactic acid
Yield be 45%, with catalyst CuCA, CuTween-80, CuPEG-2000Compare, the yield highest of lactic acid.
The different modifying agent of table 1 prepares influence of the nanometer copper catalyst to 1,2- propane diols catalytic oxidations
Embodiment 3
Nanometer Cu is prepared using the same method of embodiment 1CTABCatalyst, the process of catalysis oxidation 1,2-PD use
Method same as Example 1, the concentration for only changing 1,2-PD is respectively 0.2mol/L, 0.7mol/L, you can 1 is obtained,
Influence of the 2- PG concentrations to 1,2-PD catalytic oxidation, the results are shown in Table 2.
Influence of the 1,2- PG concentrations of table 2 to 1,2- propane diols catalytic oxidations
Embodiment 4
Nanometer Cu is prepared using the same method of embodiment 1CTABCatalyst, the process of catalysis oxidation 1,2-PD use
Method same as Example 1, it is respectively 140 DEG C, 160 DEG C, 200 DEG C only to change reaction temperature, you can obtains reaction temperature pair
The influence of 1,2-PD catalytic oxidation, the results are shown in Table 3.
Influence of the reaction temperature of table 3 to 1,2- propane diols catalytic oxidations
Embodiment 5
Nanometer Cu is prepared using the same method of embodiment 1CTABCatalyst, the process of catalysis oxidation 1,2-PD use
Method same as Example 1, it is respectively 0.5MPa, 1.5MPa only to change oxygen pressure, you can obtains different oxygen pressures pair
The influence of 1,2-PD catalytic oxidation, the results are shown in Table 4.
Influence of the oxygen pressure of table 4 to 1,2- propane diols catalytic oxidations
Embodiment 6
Nanometer Cu is prepared using the same method of embodiment 1CTABCatalyst, the process of catalysis oxidation 1,2-PD use
Method same as Example 1, it is respectively 0.5mol/L, 1.2mol/L only to change naoh concentration, you can obtains hydroxide
Influence of the na concn to 1,2-PD catalytic oxidation, the results are shown in Table 5.
Influence of the naoh concentration of table 5 to 1,2- propane diols catalytic oxidations
Embodiment 7
Nanometer Cu is prepared using the same method of embodiment 1CTABCatalyst, the process of catalysis oxidation 1,2-PD use
Method same as Example 1, it is respectively 0.07g, 0.24g only to change catalyst amount, you can catalyst amount is obtained to 1,
The influence of 2- propane diols catalytic oxidations, the results are shown in Table 6.
Influence of the catalyst amount of table 6 to 1,2- propane diols catalytic oxidations
Claims (9)
1. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation, it is characterised in that comprise the following steps：
Step 1: added in autoclave containing certain density 1,2-PD, the mixed aqueous solution of sodium hydroxide, then
A certain amount of nanometer of copper catalyst is added, leads to N2Emptied, be then turned on agitating device；
Step 2: system obtained by step 1 is heated to reaction temperature；It is passed through certain pressure oxygen to be reacted, reaction terminates
Afterwards, reaction product carries out acidification, using gas-chromatography, efficient liquid phase chromatographic analysis and result of calculation.
2. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation according to claim 1, it is characterised in that step 1
In, 1,2-PD concentration is 0.2~0.7mol/L in the mixed aqueous solution, and naoh concentration is 0.5~1.2mol/L,
The quality of nanometer copper catalyst is 0.07~0.24g.
3. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation according to claim 1, it is characterised in that step 1
In, the volume ratio of described reaction solution and autoclave is 1:5, stir speed (S.S.) 600rpm.
4. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation according to claim 1, it is characterised in that step 2
In, described oxygen pressure is 0.5~1.5MPa, and reaction temperature is 140~200 DEG C, reaction time 4h.
5. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation according to claim 1, it is characterised in that step 2
In, the acidification of described reaction product refers to the pH of product is adjusted between 2~3 with concentrated hydrochloric acid.
6. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation according to claim 1, it is characterised in that described to receive
Rice copper catalyst is prepared by following steps：
A certain amount of organic modifier and nitrate trihydrate copper is weighed first, is dissolved in absolute ethyl alcohol by 30min ultrasonic disperses, when
When reactant mixture is heated to 60 DEG C, NaOH ethanol solutions are added dropwise dropwise, the pH value for adjusting reaction solution is 8.0, it
Continue heating response liquid afterwards to 80 DEG C, hydrazine hydrate absolute ethyl alcohol weak solution is then added dropwise dropwise, reaction is certain under magnetic stirring
The nano copper particle of preparation is cooled to room temperature after time and is stored in ethanol solution, needs to pre-process before use, with nothing
Water-ethanol is repeatedly washed, centrifuged, drying.
7. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation according to claim 6, it is characterised in that described to have
Machine dressing agent is citric acid, Tween-80, cetyl trimethylammonium bromide or Polyethylene glycol-2000.
8. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation according to claim 6, it is characterised in that described to have
Machine dressing agent quality is that the concentration of 20%, the NaOH ethanol solutions of nitrate trihydrate copper mass is 1.0mol/L.
9. the method for a kind of nanometer of copper catalysis 1,2-PD oxidation according to claim 6, it is characterised in that the water
The concentration for closing hydrazine absolute ethyl alcohol weak solution is 0.1mol/L；The mass concentration of the hydrazine hydrate is 85%, reaction time 2h.
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