CN109364932A - A kind of bimetallic catalyst, preparation method and applications - Google Patents
A kind of bimetallic catalyst, preparation method and applications Download PDFInfo
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- CN109364932A CN109364932A CN201811369252.6A CN201811369252A CN109364932A CN 109364932 A CN109364932 A CN 109364932A CN 201811369252 A CN201811369252 A CN 201811369252A CN 109364932 A CN109364932 A CN 109364932A
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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
- B01J23/835—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 germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
The invention discloses a kind of bimetallic catalysts, preparation method and applications, the catalyst is a kind of porous bimetallic catalyst of shell-type of caged, wherein the shell of catalyst is made of cobalt and copper nano particles, the mass ratio of cobalt and copper is 65-70:30-35, and the partial size of catalyst is 20-30nm.Preparation method is simple for catalyst in the present invention, easy to operate, and bimetallic catalyst is the catalyst of Styryl oxide as catalytic oxidation of phenylethene, and styrene catalyzed conversion ratio reaches as high as 98%.
Description
Technical field
The present invention relates to catalyst technical fields, and in particular to a kind of bimetallic catalyst, preparation method and applications.
Background technique
Epoxides is a kind of orgnnic comopounds with oxygen-containing three-membered ring, annual output close to 30,000,000 tons, year amplification
Amount is up to 5%, by can get serial alcohol, aldehyde and ethers target chemical product to its epoxy group selective opening or conversion.Its
In, Styryl oxide (SO) is a kind of important fine chemicals, can be used as epoxy resin diluent, ultraviolet absorbing agent and increasing
Pastil etc. uses in fields such as high molecular material, coating and perfume synthesis.In addition, SO is attached by the height that catalytic hydrogenation reaction obtains
Value added bata-phenethyl alcohol can large-scale application in food and daily chemical industry, and its demand rises year by year, year amplification be up to 8%.
SO is mainly reacted by epoxidation of styrene and is obtained at present, and traditional preparation methods are homogeneous oxidizing method, according to institute
Halogenohydrin method and peroxide acid oxidation can be divided into using the difference of oxygen source.Wherein there are the separation of product difficulty and halogen waste water to hold for halogenohydrin method
The problem of easily causing environmental pollution does not meet the demand for development of green chemical industry.Peroxide acid oxidation is with organic peroxide acid
It (RCOOOH) is oxidant, it is expensive, is not suitable for large-scale industrial production and generates a large amount of byproduct organic acids
(RCOOH), separating difficulty is larger.
To solve the above problems, with environmentally protective and inexpensive O2, tert-butyl hydroperoxide (TBHP) substitute traditional oxygen
Agent, loaded noble metal catalyst, under the action of heterogeneous catalysis material epoxidation vinyl benzene prepare the technique of SO gradually by
Extensive concern and research to people.Therefore urgent need prepares that a kind of activity is higher, catalyst of excellent catalytic effect.
Summary of the invention
A kind of catalysis the purpose of the present invention is to provide bimetallic catalyst, preparation method and applications, in the present invention
Preparation method is simple for agent, easy to operate, the high catalytic efficiency of catalyst.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention provides a kind of bimetallic catalyst, which is a kind of porous bimetallic catalytic of shell-type of caged
Agent, shell are made of cobalt and copper nano particles, and the mass ratio of cobalt and copper is 65-70:30-35, and the partial size of catalyst is 20-
30nm。
The present invention also provides a kind of preparation methods of bimetallic catalyst, comprising the following steps: by carbon ball suspension and
The acid solution of pink salt mixes, and filters, and drying obtains the first product；The mixed solution of first product and cobalt salt and mantoquita is carried out
Ion-exchange reactions obtains the second product；Second product is roasted, bimetallic catalyst is obtained.
The invention also provides a kind of applications of bimetallic catalyst, are catalyzed oxygen for the bimetallic catalyst as styrene
Turn to the catalyst of Styryl oxide.
The beneficial effects of the present invention are:
The present invention also provides a kind of bimetallic catalyst and its working method, the preparation method of the catalyst in the present invention
Simple and easy, easy to operate, styrene conversion rate reaches as high as 98%, and Styryl oxide selectivity is up to 90%.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Bimetallic catalyst provided in an embodiment of the present invention is specifically described below.
The embodiment of the present invention provides a kind of bimetallic catalyst, which is that a kind of porous bimetallic of shell-type of caged is urged
Agent, shell are made of cobalt and copper nano particles, and the mass ratio of cobalt and copper is 65-70:30-35, and the partial size of catalyst is 20-
30nm。
The embodiment of the present invention provides a kind of bimetallic catalyst, and the catalyst is attached on carbon ball surface first using carbon ball as carrier
Cobalt ions and copper ion, roasting removal carbon ball, obtain a kind of porous bimetallic catalyst of shell-type of caged, which has
Magnetism, the later period rate of recovery are high (rate of recovery can reach 98%)；The shell catalyst specific surface area of caged and reaction duct are big, catalysis
It is active high.
The embodiment of the invention also provides a kind of preparation methods of bimetallic catalyst, comprising the following steps: hangs carbon ball
The mixing of the acid solution of supernatant liquid and pink salt, is filtered, and drying obtains the first product；The mixing of first product and cobalt salt and mantoquita is molten
Liquid carries out ion-exchange reactions, obtains the second product；Second product is roasted, bimetallic catalyst is obtained.
The acid solution of carbon ball suspension and pink salt is stirred in the embodiment of the present invention, tin ion is made to be attached to carbon ball
Surface is filtered, and drying obtains the first product；Cobalt salt and mantoquita mixed solution are added in the first above-mentioned product, stirring is mixed
It closes, ion-exchange reactions occurs for the cobalt ions and copper ion in the tin ion and solution on carbon ball surface, obtains the attachment of carbon ball surface
The compound carbon ball of the double activity center of cobalt ions and copper ion, obtains the second product；The second above-mentioned product is roasted, is gone
Except the carrier carbon ball inside complex microsphere, a kind of porous bimetallic catalyst of shell-type of caged is obtained.
In some embodiments, cobalt salt is at least one of cobalt nitrate hexahydrate, cobalt sulfate and four water cobalt acetates,
Mantoquita is at least one of copper nitrate, copper chloride and copper acetate, and pink salt is at least one of stannic chloride or stannous chloride.
In some embodiments, the first product is obtained by following steps: by the hydrochloric acid solution of carbon ball suspension and pink salt
The mass ratio of mixing, carbon ball and pink salt is 0.8-1.2, stirs 40-60min, is washed with distilled water filtering until supernatant is close
Colourless, then 50-80 DEG C of holding 20-40min in baking oven again, obtains the first product.
In some embodiments, the acid solution of pink salt is obtained by following steps: pink salt and 0.01-0.03M hydrochloric acid are surpassed
Sound mixes ultrasound 10-15min.
Carbon ball suspension is mixed with the hydrochloric acid solution of pink salt in the embodiment of the present invention, carbon ball makes tin ion as carrier
It is attached to the surface of carbon ball, in order to enable tin ion to be covered with the surface of carbon ball, the mass ratio of carbon ball and pink salt is 0.5-2.5,
Preferably 1.0-2.0, more preferably 0.8-1.2, extra pink salt can be washed removing in subsequent washing process.
In some embodiments, ion-exchange reactions specifically: by the mixed solution of the first product and cobalt salt and mantoquita
Ultrasonic mixing 10-15min adds the sodium formate solution of 0.15-0.20M, carries out ion-exchange reactions.
In some embodiments, the mass ratio of cobalt salt and mantoquita is 65-70:30-35, and the time of ion-exchange reactions is
5-7h。
In some embodiments, distilled water and ethyl alcohol is used to wash respectively repeatedly after ion-exchange reactions, it is dry in vacuum
It is dried within holding 10-12 hours for 100-120 DEG C in dry case.
In the embodiment of the present invention, the first product is mixed with cobalt salt and mantoquita mixed solution, in the alkalinity that sodium formate provides
In environment, cobalt ions and copper ion and tin ion are replaced, and cobalt, copper ion and carbon ball directly form chemical bond force, be firmly attached to
Then carbon ball washes away tin ion with second alcohol and water etc., and be washed till solution neutral condition, make carbon ball area load cobalt ions and copper from
The bimetallic ion of son, i.e. carbon ball surface have double activity center, then wash, dry, and obtain the second product.
In some embodiments, the maturing temperature of the second product is 400-500 DEG C, time 3-6h.
The second product is roasted in the embodiment of the present invention, roasting can remove internal carrier carbon ball, and shell is cobalt
It is no so that a kind of porous bimetallic catalyst of the shell-type for obtaining caged, maturing temperature cannot be too high with copper bi-metal nano particle
It is then easy to happen the oxidation of metal, thereby reduces catalytic activity, maturing temperature is too low, then can not make the carbon inside complex microsphere
Ball is removed.
The present invention also provides a kind of applications of bimetallic catalyst, are catalyzed bimetallic catalyst as Styryl oxide
Agent.
The bimetallic catalyst prepared in the embodiment of the present invention shows higher styrene conversion rate and Styryl oxide
Selectivity, catalytic performance is prominent, is expected to realize effective substitution of Precious Metals Resources, has great industrial application value.At present
Cobalt and copper bi-metal composite oxides are used to have no as the application of catalyst epoxidation of styrene synthesizing epoxy vinylbenzene
Report.The method for preparing catalyst is simple, cost is relatively low and environmental-friendly.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Commercially available carbon ball is bought, deionized water dissolving is added, and keep its evenly dispersed with ultrasonic echography, as solution A.
Again, then it is good to measure configured in advance in 500mL three neck round bottom flask for precise 300mg stannous chloride
60mL, 0.02M hydrochloric acid are added in flask, dissolve stannous chloride sufficiently with ultrasonic echography 10 minutes, are labeled as B solution.By A
Solution mixes Quick mechanical with B solution and stirs 60 minutes.Filtering is washed with distilled water until supernatant is close to colourless, is then dried again
It is kept for 30 minutes for 50 DEG C in case.
Precise 65mg cobalt nitrate and 45mg copper nitrate are added in 250mL there-necked flask, and it is super that 150mL deionized water is added
Sound forms clear solution, then adds the resulting product of step, continues ultrasound 10 minutes in ultrasonic wave, is then added prior
The sodium formate solution 40mL of configured 0.15M.
Finally, mechanical stirring is filtered after 7 hours at normal temperature, is washed repeatedly, be put into respectively with distilled water and ethyl alcohol
It keeps drying for 12 hours for 120 DEG C in vacuum oven, then in Muffle furnace, 400 DEG C are roasted 5 hours, obtain bimetallic catalyst,
Bimetallic catalyst is 96% to styrene conversion rate, Styryl oxide selectivity 88%.
Embodiment 2
Commercially available carbon ball is bought, deionized water dissolving is added, and keep its evenly dispersed with ultrasonic echography, as solution A.
Again, then it is good to measure configured in advance in 500mL three neck round bottom flask for precise 300mg stannous chloride
60mL, 0.02M hydrochloric acid are added in flask, dissolve stannous chloride sufficiently with ultrasonic echography 10 minutes, are labeled as B solution.By A
Solution mixes Quick mechanical with B solution and stirs 60 minutes.Filtering is washed with distilled water until supernatant is close to colourless, is then dried again
It is kept for 30 minutes for 50 DEG C in case.
Precise 65mg cobalt nitrate and 45mg copper nitrate are added in 250mL there-necked flask, and it is super that 150mL deionized water is added
Sound forms clear solution, then adds the resulting product of step, continues ultrasound 10 minutes in ultrasonic wave, is then added prior
The sodium formate solution 40mL of configured 0.15M.
Finally, mechanical stirring is filtered after 7 hours at normal temperature, is washed repeatedly, be put into respectively with distilled water and ethyl alcohol
It keeps drying for 12 hours for 120 DEG C in vacuum oven, then in Muffle furnace, 45 0 DEG C are roasted 5 hours, obtain bimetallic catalytic
Agent, for bimetallic catalyst to styrene conversion rate 97%, Styryl oxide is selectively 89%.
Embodiment 3
Firstly, weigh glucose 12.0g be added 200mL beaker in, take the distilled water of 80mL make its sufficiently dissolve formed it is clear
Then solution is transferred in autoclave by clear solution, reaction kettle is kept for 4 hours at 180 DEG C.It takes out and is used after cooling with steaming
Distilled water and ethanol washing filtering.Products therefrom is dried at 60 DEG C in vacuum oven.
Secondly, the carbon ball that the above-mentioned drying of 300mg is formed is added in 200mL single necked round bottom flask, deionized water is added
100mL dissolution, and keep its evenly dispersed with ultrasonic echography, as solution A.
Again, then it is good to measure configured in advance in 500mL three neck round bottom flask for precise 300mg stannous chloride
60mL, 0.02M hydrochloric acid are added in flask, dissolve stannous chloride sufficiently with ultrasonic echography 10 minutes, are labeled as B solution.By A
Solution mixes Quick mechanical with B solution and stirs 60 minutes.Filtering is washed with distilled water until supernatant is close to colourless, is then dried again
It is kept for 30 minutes for 50 DEG C in case.
Precise 65mg cobalt nitrate and 35mg copper nitrate are added in 250mL there-necked flask, and it is super that 150mL deionized water is added
Sound forms clear solution, then adds the resulting product of step, continues ultrasound 10 minutes in ultrasonic wave, is then added prior
The sodium formate solution 40mL of configured 0.15M.
Finally, mechanical stirring is filtered after 7 hours at normal temperature, is washed repeatedly, be put into respectively with distilled water and ethyl alcohol
It keeps drying for 12 hours for 120 DEG C in vacuum oven, then in Muffle furnace, 480 DEG C are roasted 5 hours, obtain bimetallic catalyst,
Bimetallic catalyst is 98% to styrene conversion rate, and Styryl oxide is selectively 90%.
Embodiment 4
Firstly, weigh glucose 20.0g be added 200mL beaker in, take the distilled water of 80mL make its sufficiently dissolve formed it is clear
Then solution is transferred in autoclave by clear solution, reaction kettle is kept for 4 hours at 180 DEG C.It takes out and is used after cooling with steaming
Distilled water and ethanol washing filtering.Products therefrom is dried at 60 DEG C in vacuum oven.
Secondly, the carbon ball that the above-mentioned drying of 400mg is formed is added in 200mL single necked round bottom flask, deionized water is added
100mL dissolution, and keep its evenly dispersed with ultrasonic echography, as solution A.
Again, then it is good to measure configured in advance in 500mL three neck round bottom flask for precise 600mg stannous chloride
120mL, 0.02M hydrochloric acid are added in flask, dissolve stannous chloride sufficiently with ultrasonic echography 10 minutes, are labeled as B solution.It will
Solution A mixes Quick mechanical with B solution and stirs 60 minutes.It is washed with distilled water filtering until supernatant is close to colourless, then again
It is kept for 30 minutes for 50 DEG C in baking oven.
Precise 75mg cobalt nitrate and 25mg copper nitrate are added in 250mL there-necked flask, and it is super that 150mL deionized water is added
Sound forms clear solution, then adds the resulting product of step, continues ultrasound 10 minutes in ultrasonic wave, is then added prior
The sodium formate solution 40mL of configured 0.15M.
Finally, mechanical stirring is filtered after 7 hours at normal temperature, is washed repeatedly, be put into respectively with distilled water and ethyl alcohol
It keeps drying for 12 hours for 120 DEG C in vacuum oven, then in Muffle furnace, 500 DEG C are roasted 5 hours, obtain bimetallic catalyst,
Bimetallic catalyst is 98% to styrene conversion rate, and Styryl oxide is selectively 90%.
Comparative example 1
Firstly, weigh glucose 12.0g be added 200mL beaker in, take the distilled water of 80mL make its sufficiently dissolve formed it is clear
Then solution is transferred in autoclave by clear solution, reaction kettle is kept for 4 hours at 180 DEG C.It takes out and is used after cooling with steaming
Distilled water and ethanol washing filtering.Products therefrom is dried at 60 DEG C in vacuum oven.
Secondly, the carbon ball that the above-mentioned drying of 300mg is formed is added in 200mL single necked round bottom flask, deionized water is added
100mL dissolution, and keep its evenly dispersed with ultrasonic echography, as solution A.
Again, then it is good to measure configured in advance in 500mL three neck round bottom flask for precise 300mg stannous chloride
60mL, 0.02M hydrochloric acid are added in flask, dissolve stannous chloride sufficiently with ultrasonic echography 10 minutes, are labeled as B solution.By A
Solution mixes Quick mechanical with B solution and stirs 60 minutes.Filtering is washed with distilled water until supernatant is close to colourless, is then dried again
It is kept for 30 minutes for 50 DEG C in case.
Precise 65mg cobalt nitrate is added in 250mL there-necked flask, and addition 150mL deionized water is ultrasonically formed transparent molten
Then liquid adds the resulting product of step, continue ultrasound 10 minutes in ultrasonic wave, and it is good that configured in advance is then added
The sodium formate solution 40mL of 0.15M.
Finally, mechanical stirring is filtered after 7 hours at normal temperature, is washed repeatedly, be put into respectively with distilled water and ethyl alcohol
It keeps drying for 12 hours for 120 DEG C in vacuum oven, then in Muffle furnace, 480 DEG C are roasted 5 hours, obtain Co catalysts, cobalt is urged
Agent is 75% to styrene conversion rate, and Styryl oxide is selectively 80%.
To sum up, a kind of preparation method of bimetallic catalyst is provided in the embodiment of the present invention, comprising the following steps: the present invention
Additionally provide a kind of preparation method of bimetallic catalyst, comprising the following steps: mix the acid solution of carbon ball suspension and pink salt
It closes, filters, drying obtains the first product；The mixed solution of first product and cobalt salt and mantoquita is subjected to ion-exchange reactions, is obtained
To the second product；Second product is roasted, bimetallic catalyst is obtained.In tin ion and solution by making the attachment of carbon ball surface
Cobalt ions and copper ion occur ion-exchange reactions, obtain the double activity center of the bimetallic ion of cobalt ions and copper ion
Compound carbon ball；The carrier carbon ball inside removal is roasted again, obtains a kind of porous bimetallic catalyst of shell-type of caged.
The present invention has the following beneficial effects:
Bimetallic catalyst preparation cost in the present invention is low, and preparation facilitates succinct, overcomes existing to styrene epoxy
Type and the type for changing catalyst are more, but product yield is not relatively high and catalyst recycling is difficult, or to improve the rate of recovery
The defect of third party's auxiliary material must be added；The catalyst of preparation of the embodiment of the present invention has magnetism, and the later period rate of recovery is high, returns
Yield can reach 98%；The shell catalyst specific surface area of caged and reaction duct are big, and catalytic activity is high.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of bimetallic catalyst, which is characterized in that the catalyst is a kind of porous bimetallic catalyst of shell-type of caged,
The shell is made of cobalt and copper nano particles, and the mass ratio of the cobalt and copper is 65-70:30-35, the partial size of the catalyst
For 20-30nm.
2. the preparation method of bimetallic catalyst according to claim 1, which comprises the following steps: by carbon
The mixing of the acid solution of ball suspension and pink salt, is filtered, and drying obtains the first product；By first product and cobalt salt and mantoquita
Mixed solution carry out ion-exchange reactions, obtain the second product；Second product is roasted, the bimetallic catalytic is obtained
Agent.
3. the preparation method of bimetallic catalyst according to claim 2, which is characterized in that the cobalt salt is six water nitric acid
At least one of cobalt, cobalt sulfate and four water cobalt acetates, the mantoquita be copper nitrate, copper chloride and copper acetate at least
One kind, the pink salt are at least one of stannic chloride or stannous chloride.
4. the preparation method of bimetallic catalyst according to claim 2, which is characterized in that first product is by following
Step obtains: the hydrochloric acid solution of carbon ball suspension and pink salt being mixed, the mass ratio of the carbon ball and the pink salt is 0.8-
1.2, stir 40-60min, be washed with distilled water filtering until supernatant is close to colourless, then again in baking oven 50-80 DEG C keep
20-40min obtains first product.
5. the preparation method of bimetallic catalyst according to claim 4, which is characterized in that the acid solution of the pink salt
It is obtained by following steps: the pink salt and 0.01-0.03M hydrochloric ultrasonic wave is mixed into ultrasound 10-15min.
6. the preparation method of bimetallic catalyst according to claim 2, which is characterized in that the ion-exchange reactions tool
Body are as follows: by the mixed solution ultrasonic mixing 10-15min of first product and the cobalt salt and the mantoquita, add 0.15-
The sodium formate solution of 0.20M carries out ion-exchange reactions.
7. the preparation method of bimetallic catalyst according to claim 6, which is characterized in that the cobalt salt and the mantoquita
Mass ratio be 65-70:30-35, time of the ion-exchange reactions is 5-7h.
8. the preparation method of bimetallic catalyst according to claim 6, which is characterized in that the ion-exchange reactions it
It is washed repeatedly with distilled water and ethyl alcohol, is dried within holding 10-12 hours for 100-120 DEG C in vacuum oven respectively afterwards.
9. the preparation method of bimetallic catalyst according to claim 2, which is characterized in that the roasting of second product
Temperature is 400-500 DEG C, time 3-6h.
10. a kind of application of the bimetallic catalyst as described in claim any one of 1-9, which is characterized in that by double gold
Metal catalyst is the catalyst of Styryl oxide as catalytic oxidation of phenylethene.
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