CN110302801A - A kind of preparation method and applications of Nanometer Copper/palladium alloy catalysts - Google Patents
A kind of preparation method and applications of Nanometer Copper/palladium alloy catalysts Download PDFInfo
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- CN110302801A CN110302801A CN201910526557.1A CN201910526557A CN110302801A CN 110302801 A CN110302801 A CN 110302801A CN 201910526557 A CN201910526557 A CN 201910526557A CN 110302801 A CN110302801 A CN 110302801A
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
Abstract
Nano-catalytic field of the present invention discloses a kind of preparation method and applications of Nanometer Copper/palladium alloy catalysts.The present invention forms more catalytic active centers with palladium coated copper using chemical precipitation reduction method, and hydrazine hydrate is reducing agent, and polyvinylpyrrolidone is dressing agent, prepares copper palladium composite metal catalyst.And it is used for the reaction that catalysis oxidation 1,2-PD prepares lactic acid, after reaction, the conversion ratio of 1,2-PD after reaction is surveyed with gas chromatograph；The selectivity of various products is surveyed after being acidified with acid with high performance liquid chromatography.PDO conversion ratio reaches 85.9%, and lactic acid selectively reaches 60.1%.
Description
Technical field
The invention belongs to nano-catalytic fields, are related to the preparation method and its catalysis of a kind of Nanometer Copper/palladium composite catalyst
Aoxidize the application of 1,2- propylene glycol.
Background technique
In the past 20 years alcohol on metallic catalyst, aldehyde selective oxidation study to have obtained extensive attention because this kind of anti-
It should be at relatively mild reaction condition (normal pressure, 293~353K), using Pt metal, Pd catalyst, using oxygen as oxygen in liquid phase
Catalytic alcohol, the oxidation reaction of aldehyde and its derivative of agent replace traditional inorganic using environmental-friendly clean oxidant
Oxidant.It is capable of providing a large amount of important fine chemicals and organic synthesis intermediate.
Bimetallic catalytic is research hotspot in recent years, it can not only make up the single of the catalysis of single-metal reforming catalyst
Property, single noble metal problem at high price, nanoparticle agglomeration traits etc..Bimetallic catalyst ratio is using single metal as catalyst
Catalytic activity it is high, and price is lower, and alloyed catalysts are higher than the catalyst activity of simple composite.
In recent years, biomass fuel obtained tremendous development, and the by-product of some products also largely generates, reasonable utilization these
By-product has very important significance to environment-friendly and green development tool.Rationally it is exactly one using 1,2- propylene glycol (PDO) important to grind
Study carefully direction.PDO is one of the by-product of biomass renewable energy, is a kind of chemicals of nontoxic, cheap, high demand.Extensively
Applied to polymer, resin, solvent, liquid detergent, antifreezing agent, food additives and cosmetics.Effect of the PDO in catalyst
Under can be oxidized to aldehyde, carboxylic acid etc., lactic acid is one of important downstream chemical products of PDO.
Lactic acid (LA) is generation during carbohydrate biocatalysis, is functional polymer and degradation plastic
One of base stock has a wide range of applications in industrial circle.Lactic acid preparation method has biological the preparation method and chemical preparation method.It is raw
Object the preparation method mainly utilizes carbohydrate fermentation technology to prepare.But the method reaction rate is low, and water consumption is big, industrial separation
Cost is larger.And a large amount of biological sludges can be generated in reaction process, cause certain environmental pollution.Chemical method, which prepares lactic acid, to be had
Lactic acid is prepared with the method for sulphuric acid hydrolysis again using second eyeball and the reaction of ammonia chloric acid, but this method environmental pollution is larger, is not suitable for
Long-term large-scale production.Another chemical manufacturing process is with Organic biologicals such as bio-renewable glycerol, 1,2- propylene glycol
Oxidation reaction generates lactic acid to raw material under the catalysis of catalyst.This method not will cause environmental pollution, production cost to environment
It is lower, but it is limited by the use of catalyst.A kind of suitable catalyst is found to have a very big significance the production of lactic acid.
Summary of the invention
In view of the problems of the existing technology, the present invention is prepared for a kind of Nanometer Copper/palladium composite catalyst, and for selecting
Catalysis oxidation 1,2- propylene glycol produces lactic acid.The catalyst amount is few, high activity, and has good stability in use.
Technical scheme is as follows:
A kind of preparation method of Nanometer Copper/palladium alloy catalysts, steps are as follows:
(1) first copper nitrate ethanol solution is poured into three-neck flask, and organic modifier polyvinylpyrrolidone second is added
Alcoholic solution is stirred continuously simultaneously heating water bath；
(2) sodium hydroxide ethanol solution is used, the pH to 6.0~8.0 of mixed liquor obtained by regulating step (1) is stirred continuously dense
Contracting, until solution becomes colloid；
(3) into colloid obtained by step (2), it is added dropwise the ethanol solution of hydrazine hydrate with liquid relief pump, 2~3h of stir about,
Nano metal colloidal sol is formed, at this time under alkaline condition, Nanometer Copper surface has negative electrical charge, forms isoelectric point；
(4) palladium chloride ethanol solution is added in the resulting nano metal colloidal sol of step (3), palladium ion is easier at this time
The attachment of Nanometer Copper surface, forms the colloidal solution of electroneutral, continuously adds the sodium hydroxide ethanol solution of 1mol/L, adjust pH to
8.5~10, and hydrazine hydrate solution is added, and be stirred continuously 2~3h, after reaction, washing centrifugation, vacuum drying can obtain
To Nanometer Copper/palladium alloy catalysts.
In step (1), the quality of polyvinylpyrrolidone is the 5% of nitric acid copper mass, and the temperature of heating water bath is 60 DEG C.
In step (2), the concentration of sodium hydroxide ethanol solution is 1mol/L.
In step (3), the concentration of the ethanol solution of hydrazine hydrate is 6~8mol/L, and the amount of the substance of hydrazine hydrate is copper and palladium
10 times of the amount summation of substance, the rate of addition of hydrazine hydrate are 1mL/min.
In step (4), the dosage of palladium chloride are as follows: the molar ratio of Cu and Pd is 100:0.5-7.
Nanometer Copper/palladium alloy catalysts prepared by the present invention are used for the use that catalysis oxidation 1,2- propylene glycol prepares lactic acid
On the way, steps are as follows:
(1) certain density 1,2- propylene glycol is added in the autoclave equipped with thermometer, pressure gauge and blender
Aqueous solution and certain density NaOH solution, solvent are deionized water, then Nanometer Copper/palldium alloy of certain mass is added thereto
Catalyst, then use N2Emptying；
(2) it being brought rapidly up, adjusting revolving speed is 100-200rpm, until the temperature of reaction solution, which reaches reaction temperature, is passed through oxygen,
Revolving speed is adjusted to 400-500rp；
(3) after reaction, it is quickly cooled down, filters and separate solid catalyst, recycled after ethyl alcohol and water washing are dry
It utilizes；N-butanol is added as internal standard compound in liquid after reaction, surveys reaction conversion ratio with gas-chromatography, uses height after reaction solution acid adding
The selectivity of effect liquid phase chromatogram survey lactic acid.
In step (1), 1,2-PD solution concentration is 0.05-0.2mol/L, and the concentration of NaOH solution is 0.05-
The molar ratio of 0.3mol/L, NaOH and 1,2-PD is 1~4:1, Nanometer Copper/palladium alloy catalysts additive amount and 1,2- third
Glycol mass ratio is 0.025-0.06:1.
In step (2), 60-160 DEG C of reaction temperature, reaction time 1-5h.
The reusable number of the Nanometer Copper/palladium alloy catalysts is not less than 10 times.
The invention has the benefit that
Nanometer CuPd alloy composite catalyst prepared by the present invention is not simple metal reduction, forms compound double gold
Metal catalyst, but form the catalyst of alloying.By XRD analysis, the peak value of the standard diffraction peak of CuPd is all had occurred partially
It moves, illustrates that the CuPd alloying trend of method preparation is more obvious.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of catalyst obtained by each embodiment.
Specific embodiment
The following are presently preferred embodiments of the present invention, the present invention better understood when, but the embodiment of the present invention is not limited to
This, while its shown data does not represent the limitation to feature of present invention range.
Embodiment 1:
By 3.624g Gerhardite, 0.0136g anhydrous palladium bichloride, 0.1832g polyvinylpyrrolidone is dissolved in respectively
In 30mL dehydrated alcohol, ultrasonic dissolution.First Gerhardite is transferred in 500mL three-neck flask, is gradually added dropwise 1M's
NaOH ethanol solution adjusts pH to 6.6, and copper ion precipitates completely at this time, and organic modifier polyvinylpyrrolidone is then added,
30min is stirred, then the hydrazine hydrate of 5.5mL 85% is added in 20mL dehydrated alcohol again, is pumped with liquid relief the alcohol of hydrazine hydrate is molten
Liquid 1mL/min is slowly added in three-neck flask, and the copper surface being reduced at this time is in electroneutral, and then continues to adjust pH to 10, is stirred
Mix 2h, the copper surface being reduced at this time is negatively charged, the palladium chloride solution of ultrasonic dissolution is added, the copper surface with negative electrical charge this more
The package for being conducive to palladium ion continues to stir 2h.Entire reaction process is carried out in 60 DEG C of water-bath, wait react knot
Product is centrifuged by Shu Hou, and washing is dried overnight in an oven, catalyst Cu is made100Pd0.5It is spare.
1.5218g 1,2-PD is taken to be added in 200mL volumetric flask, constant volume.It is being furnished with thermometer, pressure gauge and stirring
The PDO for having configured concentration is added in the autoclave of device, 1.6g sodium hydroxide is added, 0.07609g catalyst is added.Group
After installing instrument, it is passed through nitrogen and hunts leak 15 minutes, remove the air in reaction kettle, then pass to high purity oxygen gas and increase to pressure
1Mpa is to slowly warm up to 80-160 DEG C, keeps the temperature lower reaction 1-4h, stirring rate 500r/min；After reaction, by reactant
Material is cooled to room temperature.The content of PDO carries out HPLC points by using gas chromatographic detection in reaction product after being acidified with hydrochloric acid
Analysis.
Embodiment 2: method is with embodiment 1, and the quality of Gerhardite is 3.624g, and the quality of anhydrous palladium bichloride is
0.0266g, the quality of polyvinylpyrrolidone are 0.1825g, and hydrazine hydrate amount is 5.8mL；Catalyst Cu100Pd1 is made, is catalyzed
Agent is tested with embodiment 1.
Embodiment 3: method is with embodiment 1, and the quality of Gerhardite is 3.624g, and the quality of anhydrous palladium bichloride is
0.0798g, the quality of polyvinylpyrrolidone are 0.1852g, and hydrazine hydrate amount is 5.9mL；Catalyst Cu100Pd3 is made, is catalyzed
Agent is tested with embodiment 1.
Embodiment 4: method is with embodiment 1, and the quality of Gerhardite is 3.624g, and the quality of anhydrous palladium bichloride is
0.1330g, the quality of polyvinylpyrrolidone are 0.1878g, and hydrazine hydrate amount is 6.0mL；Catalyst Cu100Pd5 is made, is catalyzed
Agent is tested with embodiment 1.
Embodiment 5: method is with embodiment 1, and the quality of Gerhardite is 3.624g, and the quality of anhydrous palladium bichloride is
0.1862g, the quality of polyvinylpyrrolidone are 0.1905g, and hydrazine hydrate amount is 6.1mL；Catalyst Cu100Pd7 is made, is catalyzed
Agent is tested with embodiment 1.
Embodiment 6: we choose a kind of catalyst, respectively change 1,2-PD concentration, reaction temperature, the reaction time,
Catalyst amount, one of these conditions of NaOH concentration take the experimental method of appeal, carry out catalysis oxidation 1,2-PD
Experiment.As a result as follows:
Fig. 1 is the XRD diffraction pattern of catalyst obtained by each embodiment；As can be seen from Figure 1 nanometer Cu-Pd alloy catalyst
In the standard diffraction peaks of two kinds of metals deviated compared with elemental metals, illustrate there is alloying trend, Cu0Characteristic peak pair
The diffraction crystal face answered is respectively 43.500 °, 50.520 °, 74.201 °.Pd0Characteristic peak corresponding diffraction crystal face difference
40.140°,46.802°,68.215°。Cu100Pd0.5The corresponding diffraction crystal face of the characteristic peak of middle Cu is 43.360 °, offset
0.14°。Cu100Pd1The corresponding diffraction crystal face of the characteristic peak of middle Cu is 43.260 °, deviates 0.24 °, the characteristic peak of Pd is corresponding to spread out
Penetrating crystal face is 40.131 °, deviates 0.009 °.Cu100Pd3The corresponding diffraction crystal face of the characteristic peak of middle Cu is 43.261 °, offset
The corresponding diffraction crystal face of the characteristic peak of 0.239 ° of Pd is 40.358 °, deviates 0.218 °.Cu100Pd5The characteristic peak of middle Cu is corresponding
Diffraction crystal face is 43.279 °, deviates 0.221 °, and the corresponding diffraction crystal face of the characteristic peak of Pd is 40.238 °, deviates 0.098 °.
Cu100Pd7The corresponding diffraction crystal face of the characteristic peak of middle Cu is 43.219 °, deviates 0.281 °, the corresponding diffraction of the characteristic peak of Pd is brilliant
Face is 40.082 °, deviates 0.058 °.Illustrate that there are alloying trend for two kinds of monometallics.Test result:
1 differential responses condition of table is to catalyst Cu100Pd0.5Catalyzed conversion 1,2- propylene glycol prepares the influence of lactic acid
Claims (10)
1. a kind of preparation method of Nanometer Copper/palladium alloy catalysts, which is characterized in that steps are as follows:
(1) first copper nitrate ethanol solution is poured into three-neck flask, and it is molten that organic modifier polyvinylpyrrolidone ethyl alcohol is added
Liquid is stirred continuously simultaneously heating water bath；
(2) sodium hydroxide ethanol solution is used, the pH to 6.0~8.0 of mixed liquor obtained by regulating step (1) is stirred continuously concentration, until
Solution becomes colloid；
(3) into colloid obtained by step (2), the ethanol solution of hydrazine hydrate is added dropwise with liquid relief pump, 2~3h of stir about is formed
Nano metal colloidal sol, at this time under alkaline condition, Nanometer Copper surface have negative electrical charge, form isoelectric point；
(4) palladium chloride ethanol solution is added in the resulting nano metal colloidal sol of step (3), palladium ion is easier in nanometer at this time
The attachment of copper surface, forms the colloidal solution of electroneutral, continuously adds the sodium hydroxide ethanol solution of 1mol/L, adjusts pH to 8.5
~10, and hydrazine hydrate solution is added, and be stirred continuously 2~3h, after reaction, washing centrifugation, vacuum drying can be obtained and receive
Rice copper/palladium alloy catalysts.
2. a kind of preparation method of Nanometer Copper/palladium alloy catalysts as described in claim 1, which is characterized in that step (1)
In, the quality of polyvinylpyrrolidone is the 5% of nitric acid copper mass, and the temperature of heating water bath is 60 DEG C.
3. a kind of preparation method of Nanometer Copper/palladium alloy catalysts as described in claim 1, which is characterized in that step (2)
In, the concentration of sodium hydroxide ethanol solution is 1mol/L.
4. a kind of preparation method of Nanometer Copper/palladium alloy catalysts as described in claim 1, which is characterized in that step (3)
In, the concentration of the ethanol solution of hydrazine hydrate is 6~8mol/L, and the amount of the substance of hydrazine hydrate is the 10 of the amount summation of copper and palladium substance
Times, the rate of addition of hydrazine hydrate is 1mL/min.
5. a kind of preparation method of Nanometer Copper/palladium alloy catalysts as described in claim 1, which is characterized in that step (4)
In, the dosage of palladium chloride are as follows: the molar ratio of Cu and Pd is 100:0.5-7.
6. Nanometer Copper/palladium alloy catalysts prepared by preparation method described in Claims 1 to 5 any one are used for catalysis oxidation
1,2- propylene glycol prepares the purposes of lactic acid.
7. purposes as claimed in claim 6, which is characterized in that steps are as follows:
(1) certain density 1,2- water-propylene glycol is added in the autoclave equipped with thermometer, pressure gauge and blender
Liquid and certain density NaOH solution, solvent are deionized water, then Nanometer Copper/palldium alloy catalysis of certain mass is added thereto
Agent, then use N2Emptying；
(2) it is brought rapidly up, adjusting revolving speed is 100-200rpm, until the temperature of reaction solution, which reaches reaction temperature, is passed through oxygen, will be turned
Speed is adjusted to 400-500rp；
(3) after reaction, it is quickly cooled down, filters and separate solid catalyst, recycled after ethyl alcohol and water washing are dry；
Liquid after reaction is added n-butanol and is used as internal standard compound, with gas-chromatography survey reaction conversion ratio, with efficient liquid after reaction solution acid adding
The selectivity of phase chromatography survey lactic acid.
8. purposes as claimed in claim 7, which is characterized in that in step (1), 1,2-PD solution concentration is 0.05-
0.2mol/L, the concentration of NaOH solution are 0.05-0.3mol/L, and the molar ratio of NaOH and 1,2-PD is 1~4:1, nanometer
Copper/palladium alloy catalysts additive amount and 1,2- propylene glycol mass ratio are 0.025-0.06:1.
9. purposes as claimed in claim 7, which is characterized in that in step (2), 60-160 DEG C of reaction temperature, reaction time are
1-5h。
10. purposes as claimed in claim 7, which is characterized in that the Nanometer Copper/palladium alloy catalysts are reusable
Number is not less than 10 times.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111482184A (en) * | 2020-04-22 | 2020-08-04 | 江苏大学 | Cu/Pd/Au ternary composite metal catalyst and preparation method and application thereof |
| CN113814408A (en) * | 2021-10-08 | 2021-12-21 | 哈尔滨理工大学 | Preparation of CuPd alloy nanocrystalline and component regulation and control method thereof |
| CN117102477A (en) * | 2023-08-01 | 2023-11-24 | 淮安中顺环保科技有限公司 | Copper-palladium alloy nano-particle and preparation method and application thereof |
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