CN108435185A - A kind of catalyst preparing benzaldehyde for catalysis oxidation benzyl alcohol - Google Patents
A kind of catalyst preparing benzaldehyde for catalysis oxidation benzyl alcohol Download PDFInfo
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- CN108435185A CN108435185A CN201810349311.7A CN201810349311A CN108435185A CN 108435185 A CN108435185 A CN 108435185A CN 201810349311 A CN201810349311 A CN 201810349311A CN 108435185 A CN108435185 A CN 108435185A
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- benzyl alcohol
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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
- B01J23/76—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
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
Abstract
The present invention relates to a kind of catalyst preparing benzaldehyde for catalysis oxidation benzyl alcohol, molecular formula is xCu-yZn/CNTS catalyst, wherein the x is the mass percentage of Ni metal in the catalyst, x is 0.01%~20%；The y is the mass percentages of metal Zn in the catalyst, and y is 0.1%~30%；The catalyst has good temperature tolerance, within the scope of very wide temperature (220 DEG C~400 DEG C), has stable catalytic performance, the stable structure in gas phase successive reaction, service life length and easily-activated regeneration.
Description
Technical field
The invention belongs to field of fine chemical more particularly to a kind of catalysis preparing benzaldehyde for catalysis oxidation benzyl alcohol
Agent.
Background technology
Benzaldehyde is important organic intermediate, can be used for the industries such as medicine, fragrance, dyestuff, food and pesticide, at present work
Industry preparation method mainly has subsegment base dichloro Hydrolyze method, toluene gas phase, liquid phase oxidation to save alcohol oxidizing process, toluene Indirect Electro oxygen
Change method and benzoic acid or its vinegar reduction method.
The application of benzal chloride Hydrolyze method is relatively wide, in particular to toluene is carried out pendant chlorine under proper condition, obtains
Benzal chloride, then benzal chloride is hydrolyzed under acid or alkaline conditions, benzene first can be obtained by finally carrying out rectifying to hydrolyzate
Aldehyde, by-product are benzoic acid, and this method advantage is that reaction is simple, and technical maturity, the disadvantage is that reaction step is more, yield is not high, corrosion
Seriously polluted, three waste discharge is more, does not meet Atom economy.
The vapour phase oxidation process of toluene often makees catalyst with the oxide of the transition metal such as vanadium, key, uranium, iron, using fixed bed
Technique makees oxidant with air or oxygen, is reacted to prepare benzaldehyde, instead under the conditions of high temperature (350~550 DEG C), high-speed
Answer conversion ratio insufficient, selectivity is less than 80%.According to Wu Zebiao et al., fixed-bed process is replaced using membrane reactor, it can be big
Big to improve conversion ratio, for high conversion rate up to 19%, selectivity is 79%.
Benzaldehyde " green " production technology has toluene oxidation method, reduction method and benzyl alcohol direct oxidation method etc..Wherein toluene
Oxidizing process is low since there are product yields, and the defect more than by-product limits its industrial applications, and reduction method is due to adding hydrogen also
Former technique productions cost is excessively high without the market competitiveness.Benzyl alcohol direct oxidation method, due to simple for process, environment friend
Good feature and show good application prospect.Benzyl alcohol direct oxidation method can be divided into two kinds according to the difference of operation temperature,
One is gaseous oxidation methods and liquid oxidatively method.The reaction temperature that vapour phase oxidation process requires is higher, and many catalyst are in 300 DEG C of
With relatively good catalytic activity, and vapour phase oxidation process needs special fixed bed reactors, these are all unfavorable for this method
Heavy industrialization application.Benzyl alcohol liquid phase oxidation depends on the development of catalyst, and technics comparing is simple, reacts item
Part is mild, some catalyst also show relatively good catalytic activity at 90 DEG C.At present benzyl alcohol liquid phase oxidation research compared with
More catalyst mainly has loaded noble metal catalyst, non-noble metal oxide catalyst, heteropoly acid and its supported catalyst
Agent, ionic liquid catalyst systems and carrier-borne transition metal organic complex catalyst.Such as with 3- aminopropyl-triethoxy silicon
Alkane is modified carrier TiO2, as a result, it has been found that:Under identical preparation condition and identical reaction condition, before functionalization
The conversion ratio of the corresponding benzyl alcohol of Pd/TiO2 catalyst be 57.6%, selectivity is 74.1%, and the Pd/ after functionalization
TiO2 catalyst, the conversion ratio of benzyl alcohol are 61.5, and benzaldehyde selectively reaches 81.4, the conversion ratio of catalyst before and after functionalization
It all increases with selectivity.By-product is relatively more on the whole for this kind of catalyst, and the separation of product is more complicated.In addition it crosses
Crossing metal (Cu, Pd, Ru etc.) complex compound catalyst has the activity and selectivity of higher benzyl alcohol selective oxidation producing benzaldehyde,
But in practical applications, such catalyst still have catalyst and product separation are difficult, catalyst is of high cost, catalyst easily from
The problems such as reuniting and inactivating.
In recent years, using molecular oxygen as oxidant, using solid catalyst, fixed bed reactors, gas-solid phase selectivity are utilized
Catalysis oxidation benzyl alcohol generates benzaldehyde, since reaction process is solvent-free, by-product is few, product is easily separated, catalyst reprocessing
Relatively simple and successive reaction is easy to industrialized production, and reaction process is environmentally protective and receives favor.
Temperature is to influence an important factor for benzyl alcohol gas phase selective catalytic oxidation reaction prepares benzaldehyde, and temperature increases meeting
Cause target product benzaldehyde peroxidating to generate benzoic acid, target product selectivity is made to decline, by-product increases, and high temperature is anti-
It answers, energy consumption increases, and security risk increases, and is unfavorable for energy conservation and environmental protection and safety in production, does not meet the strategy of sustainable development.In recent years
Come, low-temperature gaseous phase selective catalytic oxidation benzyl alcohol generates benzaldehyde, and reaction temperature is low, not only contributes to improve purpose product choosing
Selecting property improves the service life of active sites, and energy conservation and environmental protection, and people is caused more and more to pay attention to.
Ag base supported catalysts since preparation method is simple, active component high degree of dispersion, activity is high, selectivity is strong and
Have many advantages, such as that higher active surface area, price are significantly reduced compared with Au base catalyst, is widely used in dimethyl oxalate and adds
The oxidation of hydrogen synthesizing methyl glycolate, formaldehyde is eliminated, the selective oxidation of alkyl-substituted aromatic hydrocarbon synthesizes ketone, aldehydes-alkynes-amine
In the reactions such as the tri compound reaction of class compound, CO oxidations, benzyl alcohol selective preparing benzaldehyde by oxidizing, and show very well
Catalytic performance.
Tsuruya et al. (JournalofCatalysis, 2005,234:308-317) Ag is carried on using infusion process
On SiO2, and use it in the reaction of benzyl alcohol catalytic gas phase oxidation producing benzaldehyde.As a result, it has been found that Ag/SiO2 catalyst pair
Benzyl alcohol gas phase oxidation has preferable catalytic activity.When reaction temperature is 320 DEG C, benzaldehyde yield is 80%, selection
Property is close to 100%.But reaction temperature is far above the vapourizing temperature of benzyl alcohol.
Sawayama et al. (IndEngChemRes, 2006,45:Ag loaded catalysts 8837-8845) are reported to exist
Application in catalytic gas phase oxidation benzyl alcohol producing benzaldehyde.Author has synthesized different carriers (SiO2/ with infusion process in the literature
CaO Ag supported catalysts), and K/Ag/SiO2 catalyst on this basis.System thinking catalyst calcination temperature,
The influence of reaction time and reaction temperature to catalyst activity.Reaction yield is up to 84.2%.Although catalyst compared with
It is very high to the selectivity of benzaldehyde under low temperature, but conversion ratio is unsatisfactory.
A kind of catalyst and preparation method thereof for low-temperature gaseous phase synthesis of benzaldehyde is disclosed in CN102139224A, with
M-Ag-HMS (M is alkali metal, alkaline-earth metal or thulium) is catalyst, reaction temperature at 215 DEG C~220 DEG C,
The conversion ratio of benzyl alcohol reaches 94.71%, and the selectivity of benzaldehyde is 97.56%.However the tolerance of the temperature of catalyst compared with
Difference, when reaction temperature is 320 DEG C, the conversion ratio of benzyl alcohol drops to 64.11%, and the selectivity of benzaldehyde is 95.53%.Ma etc.
People (ChineseJournalofCatalysis, 2013) is prepared for Ag/SBA-15 with infusion process, and is selected for benzyl alcohol gas phase
Oxidative synthesis benzaldehyde is selected, when reaction temperature is 240 DEG C, conversion ratio and selectivity reach 94% or more, due to reaction process
Reunion, loss and the carbon deposit of middle Ag causes its service life shorter.
In conclusion be currently used for gas phase selective catalytic oxidation alcohol prepare corresponding aldehydes or ketones catalyst cannot take into account it is low
Warm, highly selective, high activity, preferable temperature tolerance, cheap and advantage with long service life, and preparation process is multiple
It is miscellaneous.
Invention content
The present invention is to solve the catalyst for being currently used for gas phase selective catalytic oxidation alcohol and preparing corresponding aldehydes or ketones cannot
The problem of taking into account low temperature, highly selective, high activity, preferable temperature tolerance, longer service life, and low-temperature gaseous phase is provided
The method that selective catalytic oxidation benzyl alcohol prepares benzaldehyde.
The molecular formula of catalyst of the present invention is xCu-yZn/CNTS, wherein the x is the matter of Ni metal in the catalyst
Percentage composition is measured, x is 0.01%~20%；The y is the mass percentages of metal Zn in the catalyst, y 0.1%
~30%.
The preparation method of the present invention, carries out according to the following steps：
By CNTS carrier impregnations in Cu2+/Zn2It is then 20 DEG C~100 DEG C and speed in temperature in+mixed aqueous solution
For magnetic agitation 2h under conditions of 60 turns/min~1000 turn/min~for 24 hours, filtering obtains solid catalyst, then will obtain
Solid catalyst to be placed in temperature be dry 1h~48h in 50 DEG C~200 DEG C of baking oven, then be placed at a temperature of 400 DEG C~700 DEG C
1h~for 24 hours is roasted to get to xCu-yZn/CNTS；The wherein x is the mass percentage of Ni metal in the catalyst, x
It is 0.01%~20%；The y is the mass percentages of metal Ag in the catalyst, and y is 0.1%~30%；Described
Cation is Cu2+ and Zn2+, and Cu2+ in the Cu2+/Zn2+ mixed aqueous solutions in Cu2+/Zn2+ mixed aqueous solutions
A concentration of 0.001mol/L~5mol/L, a concentration of 0.001mol/L of Zn2+ in the Cu2+/Zn2+ mixed aqueous solutions~
5mol/L。
The Cu2+ ion sources are any one of copper nitrate, copper chloride, copper bromide, copper sulphate.Zn2+ ion sources
For any one of zinc nitrate, zinc chloride, zinc bromide, zinc sulfate.
Molecular formula is in xCu-yZn/CNTS, and x is preferably 0.1%~10%；The y be metal Zn in the catalyst
Mass percentage, y are 0.1%~5%.
Carbon nanotube also known as Baji-tube mainly constitute several layers to tens of layers coaxial by the carbon atom of hexagonal arrangement
Pipe forms, and is found by Japanese Electronic Speculum scholar Iijima.Once it has been observed that having started the research of carbon nanotube in every field
The content of upsurge, research includes：Preparation, performance and the application of carbon nanotube.By research it is found that vapour deposition process can be with
Synthesizing carbon nanotubes on a large scale so that the cost of carbon nanotube is effectively reduced, this is also that the application of carbon nanotube carries
Solid foundation is supplied.The research of carbon nanotube performance is disclosed：Carbon nanotube is a kind of allotrope of carbon, and aperture can
With from several nanometers to 100nm.Due to it be by graphite develop come, thus still have a large amount of unpaired electrons along tube wall travelling,
In fact, carbon nanotube had not only had the electric conductivity of metal, but also there is semiconducting behavior, is particularly due to certain special defects
It may lead to the same carbon pipe not only property with metal, but also the property with semiconductor.By being introduced on Single Carbon Nanotubes
Defect, then the position by adjusting defect on the carbon nanotubes can change and adjust this of carbon nanotube in very large range
Electrical property.And specific surface area of carbon nanotube is big, hardness is high, has high thermal stability.The particularity of carbon nanotube causes to answer it
Extensive research, it is no exception in catalytic science field.In view of many characteristics of carbon nanotube, people carried out as
The research of catalyst carrier.
The application of the present invention is will to be used to low-temperature gaseous phase selective catalytic oxidation alcohol prepare in corresponding aldehydes or ketones as catalysis
Agent uses.
Catalyst xCu-yZn/CNTS is fitted into atmospheric fixed bed reactor, is squeezed into the alcohol of liquid using charge pump
The benzyl alcohol of liquid is set to completely vaporize in 206 DEG C~300 DEG C of preheating furnace, the alcohol after being vaporized, then with the alcohol after vaporization
Gas flow be X, take the gas flow of oxygen in oxygen source as Y and with the gas flow of N2 be Z by after vaporization alcohol, oxygen source and
N2 is passed into atmospheric fixed bed reactor simultaneously, and successive reaction is to get to phase under conditions of temperature is 210 DEG C~400 DEG C
This formaldehyde answered；The ratio of the gas flow X of this methanol after the vaporization and gas flow Y of oxygen in oxygen source is (0.01
~10):1；The ratio of the gas flow Z of the N2 and gas flow Y of oxygen in oxygen source is (0.01~100):1；Described
Catalyst quality and the rate of charge of the quality of the alcohol after vaporization indicate that weight (hourly) space velocity (WHSV) is 0.01h-1~1000h- with weight (hourly) space velocity (WHSV)
1；The oxygenous mixed gas that the oxygen source is oxygen or volume fraction is m, wherein 50%≤m ＜ 100%.
Advantages of the present invention：
1, for catalyst of the invention using method preparation is soaked, synthesis technology is simple；Intermetallic interaction makes activearm
Divide and be highly dispersed at carrier surface, and the reduction of content of metal has been obviously shortened production cost；
2, catalyst activity of the invention is high, selectivity is strong, with excellent catalytic performance, and product purity is high, reduction point
Cost from purification；And catalyst has good temperature tolerance, and within the scope of very wide temperature (220 DEG C~400 DEG C), tool
There is stable catalytic performance, the stable structure in gas phase successive reaction, service life is long and easily-activated regeneration；
3, the Catalyst packing of the present invention is used for low-temperature gaseous phase selective catalytic oxidation in fixed bed continuous reactor
Alcohol prepares the reaction of corresponding aldehydes or ketones, can realize the low-temperature gaseous phase high-selectivity oxidation of alcohol under the premise of providing greater activity
Corresponding aldehydes or ketones are synthesized, energy consumption is reduced；It is beneficial to the industrialized production for realizing that alcohol gaseous oxidation prepares corresponding aldehydes or ketones, meets green
Colour chemistry demand for development；
4, for the present invention using oxygen as oxygen source, by-product is water, free from environmental pollution.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
The every other implementation that domain those of ordinary skill is obtained without making creative work is added in embodiment, ability
Example, shall fall within the protection scope of the present invention.
【Embodiment 1】
By CNTS carrier impregnations in the mixed aqueous solution of copper nitrate and zinc nitrate, Cu2+'s is dense in the mixed aqueous solution
Degree is 0.3mol/L, a concentration of 3mol/L of Zn2+.Then magnetic force under conditions of temperature is 50 DEG C and speed is 80 turns/min
For 24 hours, filtering obtains solid catalyst for stirring, is then placed in obtained solid catalyst dry in the baking oven that temperature is 100 DEG C
For 24 hours, then 700 DEG C of roasting temperature 3h are placed in get to 0.2%Cu-1.8%Zn/CNTS；
Catalyst 0.2%Cu-1.8%Zn/CNTS is fitted into atmospheric fixed bed reactor, using charge pump by liquid
Alcohol, which is squeezed into 250 DEG C of preheating furnace, makes the benzyl alcohol of liquid completely vaporize, the benzyl alcohol after being vaporized, benzyl alcohol gas flow
Gas flow ratio with oxygen is 1:1 uses internal diameter for 10 millimeters of stainless steel reactor, and loaded catalyst is 10 milliliters, instead
It is 220 DEG C to answer temperature, is reacted under normal pressure, and raw material is 80% benzyl alcohol, air speed 6 hours‐1.Reaction product is distinguished after gas-liquid separation
Analysis, reaction result are shown in Table 1.
【Embodiment 2】
By CNTS carrier impregnations in the mixed aqueous solution of copper nitrate and zinc nitrate, Cu2+'s is dense in the mixed aqueous solution
Degree is 3mol/L, a concentration of 0.2mol/L of Zn2+.Then magnetic under conditions of temperature is 100 DEG C and speed is 200 turns/min
Power stirs for 24 hours, and filtering obtains solid catalyst, and then obtained solid catalyst is placed in the baking oven that temperature is 100 DEG C and is done
It is dry for 24 hours, then be placed in 700 DEG C of roasting temperature 5h to get to 2.3%Cu-0.3%Zn/CNTS；
Catalyst 2.3%Cu-0.3%Zn/CNTS is fitted into atmospheric fixed bed reactor, using charge pump by liquid
Alcohol, which is squeezed into 250 DEG C of preheating furnace, makes the benzyl alcohol of liquid completely vaporize, the benzyl alcohol after being vaporized, benzyl alcohol gas flow
Gas flow ratio with oxygen is 1:1 uses internal diameter for 10 millimeters of stainless steel reactor, and loaded catalyst is 10 milliliters, instead
It is 240 DEG C to answer temperature, is reacted under normal pressure, and raw material is 80% benzyl alcohol, air speed 12 hours‐1.Reaction product is divided after gas-liquid separation
It does not analyze, reaction result is shown in Table 1.
【Embodiment 3】
By CNTS carrier impregnations in the mixed aqueous solution of copper nitrate and zinc nitrate, Cu2+'s is dense in the mixed aqueous solution
Degree is 3mol/L, a concentration of 4.2mol/L of Zn2+.Then magnetic under conditions of temperature is 100 DEG C and speed is 200 turns/min
Power stirs for 24 hours, and filtering obtains solid catalyst, and then obtained solid catalyst is placed in the baking oven that temperature is 100 DEG C and is done
It is dry for 24 hours, then be placed in 600 DEG C of roasting temperature 5h to get to 2.3%Cu-3.8%Zn/CNTS；
Catalyst 2.3%Cu-3.8%Zn/CNTS is fitted into atmospheric fixed bed reactor, using charge pump by liquid
Alcohol, which is squeezed into 250 DEG C of preheating furnace, makes the benzyl alcohol of liquid completely vaporize, the benzyl alcohol after being vaporized, benzyl alcohol gas flow
Gas flow ratio with oxygen is 1:1 uses internal diameter for 10 millimeters of stainless steel reactor, and loaded catalyst is 10 milliliters, instead
It is 260 DEG C to answer temperature, is reacted under normal pressure, and raw material is 80% benzyl alcohol, air speed 10 hours‐1.Reaction product is divided after gas-liquid separation
It does not analyze, reaction result is shown in Table 1.
Table 1
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the range of claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (7)
1. a kind of catalyst preparing benzaldehyde for catalysis oxidation benzyl alcohol, it is characterised in that：The molecular formula of the catalyst
For xCu-yZn/CNTS, wherein the x is the mass percentage of Ni metal in the catalyst, x is 0.01%~20%；Institute
The y stated is the mass percentages of metal Zn in the catalyst, and y is 0.1%~30%.
2. the catalyst according to claim 1 for preparing benzaldehyde for catalysis oxidation benzyl alcohol, it is characterised in that：It will
CNTS carrier impregnations are in Cu2+/Zn2In+mixed aqueous solution, then temperature be 20 DEG C~100 DEG C and speed be 60 turns/min~
Magnetic agitation 2h under conditions of 1000 turns/min~for 24 hours, filtering obtains solid catalyst, the solid catalyst that then will be obtained
It is dry 1h~48h in 50 DEG C~200 DEG C of baking oven to be placed in temperature, then is placed in 400 DEG C~700 DEG C roasting temperature 1h~for 24 hours,
Obtain xCu-yZn/CNTS.
3. the catalyst according to claim 2 for preparing benzaldehyde for catalysis oxidation benzyl alcohol, it is characterised in that：It is described
Cu2+Ion source is any one of copper nitrate, copper chloride, copper bromide, copper sulphate.
4. the catalyst according to claim 2 for preparing benzaldehyde for catalysis oxidation benzyl alcohol, it is characterised in that：Zn2+
Ion source is any one of zinc nitrate, zinc chloride, zinc bromide, zinc sulfate.
5. the catalyst according to claim 2 for preparing benzaldehyde for catalysis oxidation benzyl alcohol, it is characterised in that：X is excellent
It is selected as 0.1%~10%；Y is preferably 0.1%~5%.
6. the catalyst according to claim 2 for preparing benzaldehyde for catalysis oxidation benzyl alcohol, it is characterised in that：It is described
Cu2+/Zn2+Cation is Cu in mixed aqueous solution2+And Zn2+, and Cu in the Cu2+/Zn2+ mixed aqueous solutions2+It is dense
Degree is 0.001mol/L~5mol/L, the Cu2+/Zn2+Zn in mixed aqueous solution2+A concentration of 0.001mol/L~5mol/
L。
7. application of the catalyst in catalysis oxidation benzyl alcohol prepares benzaldehyde as described in claim 1~6.
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Application publication date: 20180824 |