CN109046362A - A kind of preparation method and applications of carbon-coated nano CuZnAl catalyst - Google Patents
A kind of preparation method and applications of carbon-coated nano CuZnAl catalyst Download PDFInfo
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- CN109046362A CN109046362A CN201811082471.6A CN201811082471A CN109046362A CN 109046362 A CN109046362 A CN 109046362A CN 201811082471 A CN201811082471 A CN 201811082471A CN 109046362 A CN109046362 A CN 109046362A
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Abstract
The present invention is a kind of preparation method and applications of carbon-coated nano CuZnAl catalyst.Method includes the following steps: carbon based material is mixed with metallic compound, ethyl alcohol is added, obtains slurry after stirring；Dry 20-28h, obtains the presoma of carbon encapsulated material；200-700 DEG C of heating obtains charing compound；It is then added in concentrated hydrochloric acid, the charing compound activated；It roasts under nitrogen protection, obtains carbon-coated nano-copper base catalyst；The advantages of present invention adds hydrogen to prepare neopentyl glycol for hydroxy pivalin aldehyde, while active high and anti-current is lost.
Description
Technical field
The invention belongs to catalysis technical fields, and in particular to a kind of hydroxy pivalin aldehyde adds hydrogen to prepare the carbon coating of neopentyl glycol
The preparation method of nano CuZnAl catalyst.
Background technique
Neopentyl glycol can be used for producing polyester resin, polyurethane etc. as a kind of industrial chemicals that purposes is very extensive,
It can be used for production polyester powder coating, polyurethane foam plastics, surfactant, synthesis plasticizer, printing ink, insulation
All multi-products such as material, polymerization inhibitor, aeroengine oil product additive.It is answered in fields such as automobile, weaving, medicine, coating and petroleum
With extensive, Selective Separation naphthenic base hydrocarbon and aromatic hydrocarbons, wide market can be used for.
Neopentyl glycol industrialized production route includes isobutylaldehyde route and halogenated propyl alcohol route.Currently, due to halogenated propyl alcohol
The raw material of route is rare, this method is not easy to realize industrialization, and the production of neopentyl glycol does not use halogenated propyl alcohol route generally in the world.
Isobutylaldehyde route can be divided into sodium formate method and condensation hydrogenation method according to the restoring method of hydroxy pivalin aldehyde.Sodium formate
Method is the earliest method for realizing industrialized production neopentyl glycol, is that reaction condition is mild, equipment investment is small, but sodium formate method will make
With a large amount of first acid and alkalis, a large amount of waste water are generated, carrying capacity of environment is big, and byproduct formic acid sodium content is higher, and post-processing is complicated, makes to produce
Object purity is not high, and economic benefit is low.Therefore, most of producers have used more clean and environmental protection, more efficient contracting both at home and abroad
Close hydrogenation method.
In condensation hydrogenation method, there are commonly copper system and nickel system and noble metal catalysts for hydroxy pivalin aldehyde hydrogenation catalyst.
Although there is noble metal catalyst preferable catalytic activity and catalytic stability to lead to increased costs since price is higher, because
And it uses less.Nickel catalyst is then mainly two kinds of Raney's nickel of Raney's nickel or modification, although nickel catalyst can be
There is preferable conversion ratio under high temperature, the reaction that hydroxy pivalin aldehyde itself decomposes also easily occurs and generates isobutylaldehyde and formaldehyde, to make
At the decline of selectivity of neopentyl glycol.On the other hand, there are also the disadvantages of complicated is post-processed, these are all limited nickel catalyst significantly
The development of nickel catalyst.And copper-based catalysts have good selectivity and activity, and cheap, are current industry
Upper common catalyst.
Catalyst disclosed in CN104258869A is copper-zinc-aluminium-tin-alkaline-earth metal, and hydrogenation reaction temperature is 120-
140 DEG C, reaction pressure 3-5MPa, catalyst reduction is restored in the mixed gas of nitrogen and hydrogen, but hydrogenation reaction
Air speed it is lower.Catalyst disclosed in CN102513107A is copper-diatomite support catalyst, uses copper sulphate for copper source,
Adding hydrogen to prepare the reaction density of neopentyl glycol is 150-170 DEG C, and reaction temperature is higher, needs more energy.CN101579629A
Disclose a kind of CuO/ZnO/Al2O3The preparation method of catalyst, Cu2+, Zn2+, Al3+Molar ratio be 3/2-8/0.5-1.5,
The granularity of active ingredient copper can be adjusted arbitrarily in the range of 5nm-20nm, can be used for continuous production.CN1294570A is disclosed
A kind of copper-based catalysts, with TiO2For inorganic carrier, be used for carboxyl compound catalytic hydrogenation, tabletting be at 300-600 DEG C,
It consumes energy higher, the processing time is long.CN103130611A discloses a kind of CuO/ZnO/Al2O3Copper-based catalysts, ratio 27:
50:23, hydrogenation conditions are 160-170 DEG C, and pressure 4MPa, required temperature and pressure are higher, to device requirement height.
The hydroxy pivalin aldehyde hydrogenation catalyst of open report is mostly the copper-based catalysts prepared with the precipitation method.And current hydroxyl
The synthesis of neovaleraldehyde uses organic amine (trimethylamine or triethylamine is catalyst) as catalysis using formaldehyde and isobutylaldehyde as raw material
It is the main reason for causing activity of hydrocatalyst component to be lost that agent, active ingredient copper and organic amine, which form complex compound,.Tradition is heavy
The problems such as copper-based catalysts mechanical strength of shallow lake method preparation is lower, and active component is easy loss, dispersion degree is low.Therefore, traditional copper
There is the problems such as being easy inactivation, activity decline is very fast in base catalyst.
In conclusion neopentyl glycol wide market, supply falls short of demand for domestic neopentyl glycol, and domestic substantially using formic acid
Sodium method route prepares neopentyl glycol, and the route is high compared with condensation hydrogenation process costs, and environmental protection pressure is big, but by hydrogenation catalyst
It influences, condensation hydrogenation route development speed is slow.Therefore, develop low cost, high activity, highly selective, high mechanical strength and surely
Qualitative catalyst has great significance to the technical study of condensation hydrogenation neopentyl glycol.
Summary of the invention
It is an object of the present invention to provide a kind of carbon-coated nano CuZnAl catalyst for deficiency present in current techniques
Preparation method and applications.Traditional copper-based catalysts in conjunction with the preparation process of carbon encapsulated material, are prepared for carbon by the present invention
CuZnAl catalyst is coated, and adds hydrogen to prepare neopentyl glycol for hydroxy pivalin aldehyde.Compared with traditional copper-based catalysts, the present invention
Carbon coating CuZnAl catalyst high and anti-current active simultaneously the advantages of losing.
In view of the advantage of carbon-coated nano metal, the present invention provides a kind of carbon-coated nano copper-based catalysts, utilizes this side
The catalyst that method is prepared is applied to hydroxy pivalin aldehyde and adds in the reaction of hydrogen neopentyl glycol, obtains very high reactivity, choosing
Selecting property and stability.
The present invention is realized by following technical proposal:
A kind of preparation method of carbon-coated nano CuZnAl catalyst, comprising the following steps:
(1) carbon based material is mixed with metallic compound, adds ethyl alcohol, after stirring 20-28h under 60-100 DEG C of water-bath,
Obtain slurry；
Wherein, the metallic compound is copper-containing compound, zinc compound and aluminum contained compound；Molar ratio is copper:
Zinc: aluminium=0.9-1.2:0.9-1.2:0.3-0.7；The carbon based material is carbon black or its presoma；Carbon based material additional amount
It is the 20-50wt% of metallic compound gross mass, mass ratio is ethyl alcohol: (carbon based material+metallic compound)=3-7:1；
(2) slurry is heated to 60-90 DEG C under stiring, keeps temperature, until slurry is in paste, then dries 20-28h,
Obtain the presoma of carbon encapsulated material；
(3) under nitrogen protection, the presoma for the carbon encapsulated material that upper step obtains is warming up to the rate of 3-10 DEG C/min
200-700 DEG C, temperature 3-6h is kept, stops heating, is taken out after temperature drops to 80 DEG C or less, obtains charing compound；
(4) step (3) charing compound is added in the container equipped with concentrated hydrochloric acid, 40-50h is stirred after sealing, is obtained
The charing compound of activation；Wherein, mass ratio carbonizes mixture: concentrated hydrochloric acid=1:8-14；
(5) compound after activation obtained by step (4) is washed with deionized, filtered, until filtrate is in neutrality；
(6) step (5) products therefrom is dried, is then roasted under nitrogen protection, arrived using grinding, granulation
Carbon-coated nano-copper base catalyst；The partial size of the catalyst is 10-20 mesh；
The nitrogen protection of the step (3) is to be passed through nitrogen by the rate of 20-200ml/min；
The mass concentration of concentrated hydrochloric acid described in step (4) is 16-37%；
The nitrogen flow rate of nitrogen protection is 50-200ml/min in the step (6)；
Carbon black is acetylene carbon black in the step (1)；Carbon black presoma is solid-state carbon source or liquid carbon source, and described consolidates
State carbon source is one of sucrose, glucose, starch and cyclodextrin or a variety of；The liquid carbon source is polyvinyl alcohol, tetramethyl
One of base benzene, maleic anhydride and cetyl trimethylammonium bromide, two or more；
The copper-containing compound is one of copper nitrate, copper chloride and copper acetate or a variety of；Zinc compound is nitre
One of sour zinc, zinc chloride and zinc acetate are a variety of；Aluminum contained compound be one of aluminum nitrate, aluminium chloride and aluminium acetate or
It is a variety of；
The application of the carbon-coated nano CuZnAl catalyst adds hydrogen to prepare new penta 2 for fixed bed hydroxy pivalin aldehyde
Alcohol.
The following steps are included:
(1) catalyst reduction activates: catalyst being placed in fixed bed reactors, in 100KPa-3MPa pressure, hydrogen
Content is to keep 1-5h at room temperature under the atmosphere of 10%-100%；Then 150-300 is warming up to the rate of 5-20 DEG C/min
DEG C, and 1-5h is kept, final reduction obtains active catalyst；
(2) hydroxy pivalin aldehyde catalytic hydrogenation prepares neopentyl glycol: at 120-200 DEG C, to the fixation for being mounted with catalyst
Bed reactor is passed through hydrogen and raw material aldehyde liquid, with 2-3h-1Liquid hourly space velocity (LHSV), 1-10min residence-time conditions under carry out it is anti-
It answers；Wherein, the pressure of hydrogen is 1.5-4MPa, and the molar ratio of material being passed through is hydrogen: hydroxy pivalin aldehyde=1.5-5:1；
The raw material aldehyde liquid is that condensation prepares hydroxy pivalin aldehyde product or hydroxyl obtained in hydroxy pivalin aldehyde technique
The organic solution of base neovaleraldehyde product, wherein the quality of hydroxy pivalin aldehyde is the 25-95% for accounting for hydroxy pivalin aldehyde product quality；
When for the organic solution of hydroxy pivalin aldehyde product, the quality of organic solvent is the 40- of the organic solution quality of solid product
80%；
The solvent of the organic solution containing hydroxy pivalin aldehyde of the step (2) be ethyl alcohol, methanol, butanol, pentane, oneself
One of alkane and hexamethylene, two or more.
Substantive distinguishing features of the invention are as follows:
Traditional hydroxy pivalin aldehyde hydrogenation catalyst of current open report is passed through after mixing the nitrate of the metals such as copper
Titration generate precipitating, be then fired, be granulated and etc. prepare copper-based catalysts.The shortcomings that for traditional copper-based catalysts, this
It is literary innovative by traditional copper-based catalysts in conjunction with the preparation process of carbon encapsulated material, using ethyl alcohol as solvent, by copper, zinc, aluminium
Compound, be stirred as paste.Then carbon black or its presoma is added to prepare through charing, washing, roasting and granulation etc.
At carbon coating copper-based catalysts.
Compared with traditional copper-based catalysts, carbon coating CuZnAl catalyst while active high the advantages of being lost with anti-current.
Beneficial effects of the present invention:
(1) add hydrogen system new hydroxy pivalin aldehyde using the porous carbon coating nano CuZnAl catalyst material of the method preparation
The reaction process of pentanediol has very high reactivity and selectivity；
(2) catalyst granules that this method is prepared has more duct and active site, for metal and hydrogen and reacts
Effective contact of raw material provides channel；
(3) the catalytic mechanical intensity that this method is prepared is high, and active component should not be lost, and stability is good, in 400h
The conversion ratio that may remain in 95% or more, is suitably applied fixed bed reactors, substantially increases reaction efficiency；
(4) this method preparation catalyst in nano metal partial size < 100nm, preferably 20-50nm；
(5) for the present invention for hydroxy pivalin aldehyde catalytic hydrogenation neopentyl glycol in fixed bed, active metal copper dispersion degree is high,
Catalytic activity is good, and selectivity and stability are greatly improved, and reduces esterification and is etherified the generation of side reaction.It is surveyed in performance
In examination, reaction can make under lower pressure, higher liquid hourly space velocity (LHSV) and lower hydrogen-aldehyde rate hydroxy pivalin aldehyde high conversion rate in
97%, selectivity of neopentyl glycol is higher than 98%, and can be with stable operation 400h or more.
Catalyst is living when reduction rear catalyst of the present invention prepares neopentyl glycol for hydroxy pivalin aldehyde catalytic hydrogenation
Property it is high, the conversion ratio of HPA is greater than 97%, NPG and is selectively greater than 98%, and has good stability, being capable of stable operation
400h or more, and there is stronger mechanical strength, after stable operation 400h, catalyst appearance is complete, catalyst recovery yield
There is no the loss of active ingredient copper greater than 99%, and in operation.
Specific embodiment
Embodiment 1
The preparation of catalyst:
(1) by copper nitrate, zinc nitrate, aluminum nitrate, 1:1:0.5 is mixed in molar ratio, then by metallic compound gross mass
Acetylene carbon black is added in 25wt%, then is in mass ratio ethyl alcohol: ethyl alcohol is added in (carbon based material+metallic compound)=5:1, and stirring is mixed
It closes for 24 hours, obtains slurry；
(2) slurry obtained by step (1) is heated to 80 DEG C and stirs 1h, make ethanol evaporation to mixture in paste, then
Drying for 24 hours, obtains the presoma of carbon-coated nano CuZnAl catalyst at 70 DEG C；
(3) the resulting presoma 40g of step (2) is carbonized under the nitrogen protection of 50ml/min rate, with 5 DEG C/min liter
Temperature is to 400 DEG C, and constant temperature 4h, then takes out after temperature naturally rings to 80 DEG C or less, obtains charing compound；
(4) concentrated hydrochloric acid that the compound after step (3) charing is 37% with mass fraction is mixed by solid-liquid mass ratio 1:10
It closes, and stirring 48h is fully sealed in a reservoir compound activation will be carbonized；
(5) by step, (the charing compound of 4) Suo get Alto activation wash repeatedly with 1L deionized water, is filtered, up to filtrate
PH is 7；
(6) 80 DEG C of drying in air dry oven by step (5) products therefrom, then in the nitrogen protection of 200ml/min
1. lower 500 DEG C of roastings 4h arrives carbon-coated nano CuZnAl catalyst using grinding, granulation (20-40 mesh).
Catalyst reduction: 1. catalyst is loaded with fixed bed reactors in, wherein fixed bed reactors length be 44cm,
Diameter is 1cm, loads 10-20 mesh quartz sand 10-15ml, loaded catalyst 5ml in reactor bottom first, and use 5ml
40 mesh quartz sand dilute catalysts, then be packed full with the quartz sand of 20-30ml.Catalyst is used first using preceding needing to restore
Pure hydrogen normal pressure, 100ml/min flow velocity under keep 1h, reactor is then warming up to 250 DEG C with the rate of 10 DEG C/min,
After heating in the case where pure hydrogen flow velocity is the atmosphere of 20mL/min, 250 DEG C of reduction 5h are kept.
Reaction raw materials are new from the impure hydroxyl that industrial base catalysis is prepared by formaldehyde and isobutylaldehyde through condensation method
Valeral product, wherein product does not need to refine and directly use, and with ethyl alcohol (the i.e. ethyl alcohol quality that quality is feedstock solution 50%
Equal to impure hydroxy pivalin aldehyde product) it is used as solvent to be dissolved as feedstock solution.Feedstock solution specifically comprises 50wt% second
Other components (the first of alcohol, 25wt%HPA, 20wt% isooctanol, 1.2wt%NPG, 3.1wt%1115 ester and 0.7wt%
Aldehyde, isobutylaldehyde etc.), in pure hydrogen atmosphere, gas pressure 3MPa, reaction temperature is 160 DEG C, hydrogen flow rate 50ml/min, liquid
Body flow velocity be 1.2ml/min (residence time 4.17min) under conditions of reacted.
Embodiment 2
Catalyst preparation:
(1) by copper nitrate, zinc nitrate, aluminum nitrate, 2:1:0.5 is mixed in molar ratio, and metallic compound gross mass is then added
25wt% be added acetylene carbon black, then in mass ratio be ethyl alcohol: (carbon based material+metallic compound)=5:1 be added ethyl alcohol, stirring
Mixing for 24 hours, obtains slurry；
(2) slurry obtained by step (1) is heated to 80 DEG C and stirs 1h, make ethanol evaporation to the mixture of step (1) be in
Paste, drying for 24 hours, obtains the presoma of carbon-coated nano CuZnAl catalyst at 70 DEG C；
(3) the mixture 40g of step (2) is carbonized under the nitrogen protection of 50ml/min rate, is warming up to 5 DEG C/min
400 DEG C, and constant temperature 4h, it is then taken out after temperature naturally rings to 80 DEG C or less, obtains charing compound；
(4) the compound object that step (3) carbonize is mixed with the concentrated hydrochloric acid of 37wt% by solid-liquid mass ratio 1:5, and held
Stirring 48h is fully sealed in device so that compound activation will be carbonized；
(5) the charing compound after activation obtained by step (4) washed repeatedly with 1L deionized water, filtered, until filtrate
PH value be 7；
(6) by step (5) products therefrom, 80 DEG C of dry 12h are baked in air dry oven, then in 200ml/min
The lower 500 DEG C of roastings 6h of nitrogen protection, using grinding, be granulated (20-40 mesh) to get to carbon-coated nano CuZnAl be catalyzed
Agent is 2..
Remaining condition is referring to embodiment 1.
Embodiment 3
The preparation of catalyst:
(1) by copper nitrate, zinc nitrate, aluminum nitrate, 1:1:0.5 is mixed in molar ratio, and metallic compound gross mass is then added
25wt% be added acetylene carbon black, then in mass ratio be ethyl alcohol: (carbon based material+metallic compound)=5:1 be added ethyl alcohol, stirring
Mixing is placed on for 24 hours in 80 DEG C of water-baths, obtains slurry；
(2) slurry obtained by step (1) is heated to 80 DEG C and stirs 1h, make ethanol evaporation to the mixture of step (1) be in
Paste, drying for 24 hours, obtains the presoma of carbon-coated nano CuZnAl catalyst at 70 DEG C；
(3) the presoma 40g of step (2) is carbonized under the nitrogen protection of 50ml/min rate, is warming up to 5 DEG C/min
600 DEG C, and constant temperature 4h, it is then taken out after temperature naturally rings to 80 DEG C or less, obtains charing compound；
(4) compound after step (3) charing is mixed with 37% concentrated hydrochloric acid by solid-liquid mass ratio 1:10, and container again
Stirring 48h is fully sealed inside compound activation will be carbonized；
(5) the charing compound after activation obtained by step (4) washed repeatedly with 1L deionized water, filtered, until filtrate
PH is 7；
(6) by step (5) products therefrom, 80 DEG C of dry 12h are in air dry oven to be baked to, then in 200ml/
The lower 500 DEG C of roastings 8h of the nitrogen protection of min arrives carbon-coated nano CuZnAl using grinding, granulation (20-40 mesh)
Catalyst is 3..
Remaining condition is referring to embodiment 1.
Embodiment 4
The preparation of catalyst:
(1) general, copper nitrate, zinc nitrate, aluminum nitrate in molar ratio 1:1:0.5 mix, then be added the total matter of metallic compound
Acetylene carbon black is added in the 35wt% of amount, then is in mass ratio ethyl alcohol: ethyl alcohol is added in (carbon based material+metallic compound)=5:1, stirs
It mixes mixing for 24 hours, obtains slurry；
(2) slurry obtained by step (1) is heated to 80 DEG C and stirs 1h, make ethanol evaporation to the mixture of step (1) be in
Paste, drying for 24 hours, obtains the presoma of carbon-coated nano CuZnAl catalyst at 70 DEG C；
(3) the gained presoma 40g of step (2) is carbonized under the nitrogen protection of 50ml/min rate, with 5 DEG C/min liter
Temperature is to 400 DEG C, and constant temperature 4h, then takes out after temperature drops to 80 DEG C or less, obtains charing compound；
(4) mixture after step (3) charing is mixed with the concentrated hydrochloric acid of 37wt% by solid-liquid mass ratio 1:10, and completely
Sealing stirring 48h will be will carbonize compound activation；
(5) the charing compound after activation obtained by step (4) washed repeatedly with 1L deionized water, filtered, until filtrate
PH be 1；
(6) by step (5) products therefrom, 80 DEG C of dry 12h are baked in air dry oven, then in 200ml/min
The lower 500 DEG C of roastings 8h of nitrogen protection, using grinding, be granulated (20-40 mesh) to get to carbon-coated nano CuZnAl be catalyzed
Agent is 4..
Remaining condition is referring to embodiment 1.
Embodiment 5
The preparation of catalyst:
(1) by copper nitrate, zinc nitrate, aluminum nitrate, 0.3:1:1:0.5 is mixed in molar ratio, and it is total that metallic compound is then added
Acetylene carbon black is added in the 15wt% of quality, then is in mass ratio ethyl alcohol: ethyl alcohol is added in (carbon based material+metallic compound)=5:1,
It is stirred 24 small h and obtains slurry；
(2) slurry obtained by step (1) is heated to 80 DEG C and stirs 1h, make ethanol evaporation to the mixture of step (1) be in
Paste, drying for 24 hours, obtains the presoma of carbon-coated nano CuZnAl catalyst at 70 DEG C；
(3) the resulting presoma 40g of step (2) is carbonized under the nitrogen protection of 50ml/min rate, with 5 DEG C/min liter
Temperature is to 400 DEG C, and constant temperature 4h, then takes out after temperature naturally rings to 80 DEG C or less, obtains charing compound；
(4) compound after step (3) charing is mixed with the concentrated hydrochloric acid of 37wt% by solid-liquid mass ratio 1:10, and held
Stirring 48h is fully sealed in device so that compound activation will be carbonized；
(5) the charing compound after activation obtained by step (4) washed repeatedly with 1L deionized water, filtered, until filtrate
PH be 7；
(6) by step (5) products therefrom, 80 DEG C of dry 12h are baked in air dry oven, then in 200ml/min
The lower 500 DEG C of roastings 8h of nitrogen protection, using grinding, be granulated (20-40 mesh) to get to carbon-coated nano CuZnAl be catalyzed
Agent is 5..
Remaining condition is referring to embodiment 1.
Reaction result is by gas Chromatographic Determination, and gas chromatograph model: Shimadzu 223-60602A, carrier gas are nitrogen, uses
Low pole capillary chromatographic column, temperature programming are initial 150 DEG C, stop 2min, and 5 DEG C/min is warming up to 250 DEG C, stop 10min,
200 DEG C of inlet temperature, 250 DEG C of column temperature.Conversion ratio and selectivity are calculated using area normalization method.To above-described embodiment 1-5's
Activity is tested, as a result as shown in table 1 below.
The activity and selectivity of 1 catalyst of table
By above-mentioned table 1 it is found that when copper zinc-aluminium molar ratio is 1:1:0.5, conversion ratio and NPG the selection performance of HPA reaches
Most preferably, the activity and stability of catalyst be will affect when increasing or reducing content of carbon black, 150 DEG C of carbonization temperature is conducive to urge
The raising of agent stability prevents the loss of active component.The activity and optimal stability of catalyst 1., in remaining condition and reality
Apply example 1 under the same conditions, hydroxy pivalin aldehyde conversion ratio reaches 97%, and selectivity of neopentyl glycol is higher than 98%, and real by recycling
It tests it is found that 1. catalyst recovery yield is greater than 99% and is determined by XRD after stable operation 400h by catalyst in embodiment 1
Its active site is Cu0, and determine that the element of catalyst forms Cu:Zn:Al=1:1:0.5 by EDS.
Many transition metal are all traditional effective catalysts, will more improve its catalytic activity after its nanosizing.But it receives
The environmental stability of rice corpuscles is not good enough to again limit its application.These transition metal are wrapped in carbon shell to keep by the present invention
Metallic catalyst improves its service life under the precursor of high activity, and in particular to arrives carbon-coated nano CuZnAl catalyst
Catalysis hydroxy pivalin aldehyde adds hydrogen neopentyl glycol.
The partial size of carbon-coated nano metallic catalyst reduces with the increase of carbon black and the mass ratio of metal.Carbon black is added
It is thick to increase carbon shell when measuring too high, is unfavorable for reactant and is contacted with active.And the additional amount of carbon black it is too low when be unfavorable for being formed
The core-shell structure of catalyst is unfavorable for improving the surface nature of active component, such as porosity, and specific surface area and is urged at mechanical strength
The dispersion degree of active ingredient copper and stability etc. in agent, and then reduce catalytic activity.Synergistic effect between nucleocapsid is conducive to
The activity of catalyst, yield, selectivity etc..
The present invention obtains carbon-clad metal catalyst while having the characteristic and the interior characteristic covered with gold leaf belonged to of special construction carbon-coating.
Therefore, using the catalyst not only mechanical strength with higher of this method preparation, while facilitating the dispersion of active ingredient copper,
And improve catalyst activity.Meanwhile carbon-coating can effectively prevent the loss of active component, solve copper-based catalysts initial activity
Higher, activity declines fast problem.Carbon-coated nano CuZnAl catalyst has production cost low, and mechanical strength is big, catalysis effect
Rate is high, and selectivity of product is high, and the good advantage of stability adds hydrogen neopentyl glycol to have applied to fixed-bed catalytic hydroxy pivalin aldehyde
Good catalytic effect.
Unaccomplished matter of the present invention is well-known technique.
Claims (10)
1. a kind of preparation method of carbon-coated nano CuZnAl catalyst, it is characterized in that method includes the following steps:
(1) carbon based material is mixed with metallic compound, adds ethyl alcohol, after stirring 20-28h under 60-100 DEG C of water-bath, obtained
Slurry；
Wherein, the metallic compound is copper-containing compound, zinc compound and aluminum contained compound；Molar ratio is copper: zinc: aluminium
=0.9-1.2:0.9-1.2:0.3-0.7；The carbon based material is carbon black or its presoma；Carbon based material additional amount is metal
The 20-50wt% of compound gross mass, mass ratio are ethyl alcohol: (carbon based material+metallic compound)=3-7:1；
(2) slurry is heated to 60-90 DEG C under stiring, keeps temperature, until slurry is in paste, 20-28h is then dried, obtains
The presoma of carbon encapsulated material；
(3) under nitrogen protection, the presoma for the carbon encapsulated material that upper step obtains is warming up to 200- with the rate of 3-10 DEG C/min
700 DEG C, temperature 3-6h is kept, stops heating, is taken out after temperature drops to 80 DEG C or less, obtains charing compound；
(4) step (3) charing compound is added in the container equipped with concentrated hydrochloric acid, 40-50h is stirred after sealing, is activated
Charing compound；Wherein, mass ratio carbonizes mixture: concentrated hydrochloric acid=1:8-14；
(5) compound after activation obtained by step (4) is washed with deionized, filtered, until filtrate is in neutrality；
(6) step (5) products therefrom is dried, is then roasted under nitrogen protection, arrive carbon packet using grinding, granulation
The nano-copper base catalyst covered；The partial size of the catalyst is 10-20 mesh.
2. the preparation method of carbon-coated nano CuZnAl catalyst as described in claim 1, it is characterized in that the step (3)
Nitrogen protection be to be passed through nitrogen by the rate of 20-200ml/min；The nitrogen flow rate of nitrogen protection is 50- in the step (6)
200ml/min。
3. the preparation method of carbon-coated nano CuZnAl catalyst as described in claim 1, it is characterized in that step (4) is described
Concentrated hydrochloric acid mass concentration be 16-37%.
4. the preparation method of carbon-coated nano CuZnAl catalyst as described in claim 1, it is characterized in that the step
(1) carbon black is acetylene carbon black in；Carbon black presoma is solid-state carbon source or liquid carbon source, and the solid-state carbon source is sucrose, grape
One of sugar, starch and cyclodextrin are a variety of；The liquid carbon source is polyvinyl alcohol, durol, maleic anhydride
One of with cetyl trimethylammonium bromide, two or more.
5. the preparation method of carbon-coated nano CuZnAl catalyst as described in claim 1, it is characterized in that the cupric
Compound is one of copper nitrate, copper chloride and copper acetate or a variety of；Zinc compound is zinc nitrate, zinc chloride and zinc acetate
One of or it is a variety of；Aluminum contained compound is one of aluminum nitrate, aluminium chloride and aluminium acetate or a variety of.
6. the application of carbon-coated nano CuZnAl catalyst as described in claim 1, it is characterized in that new for fixed bed hydroxyl
Valeral adds hydrogen to prepare neopentyl glycol.
7. the application of carbon-coated nano CuZnAl catalyst as claimed in claim 6, it is characterized in that the following steps are included:
(1) catalyst reduction activates: catalyst being placed in fixed bed reactors, in 100KPa-3MPa pressure, hydrogen content
To keep 1-5h at room temperature under the atmosphere of 10%-100%；Then it is warming up to 150-300 DEG C with the rate of 5-20 DEG C/min,
And 1-5h is kept, final reduction obtains active catalyst；
(2) hydroxy pivalin aldehyde catalytic hydrogenation prepares neopentyl glycol: anti-to the fixed bed for being mounted with catalyst at 120-200 DEG C
Device is answered to be passed through hydrogen and raw material aldehyde liquid, with 2-3h-1Liquid hourly space velocity (LHSV) under reacted；Wherein, the pressure of hydrogen is 1.5-
4MPa, the molar ratio of material being passed through are hydrogen: hydroxy pivalin aldehyde=1.5-5:1.
8. the application of carbon-coated nano CuZnAl catalyst as claimed in claim 7, it is characterized in that the reaction in step (2) stops
Staying the time is 1-10min.
9. the application of carbon-coated nano CuZnAl catalyst as claimed in claim 7, it is characterized in that the raw material aldehyde liquid
The organic solution of hydroxy pivalin aldehyde product or hydroxy pivalin aldehyde product obtained in hydroxy pivalin aldehyde technique is prepared for condensation,
Wherein, the quality of hydroxy pivalin aldehyde is the 25-95% for accounting for hydroxy pivalin aldehyde product quality；When for the organic of hydroxy pivalin aldehyde product
When solution, the quality of organic solvent is the 40-80% of the organic solution quality of solid product.
10. the application of carbon-coated nano CuZnAl catalyst as claimed in claim 9, it is characterized in that described is new containing hydroxyl
The solvent of the organic solution of valeral be one of ethyl alcohol, methanol, butanol, pentane, hexane and hexamethylene, two or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152676A (en) * | 2019-05-21 | 2019-08-23 | 太原理工大学 | A kind of anti-sintering metal method for preparing catalyst |
| CN110480004A (en) * | 2019-08-29 | 2019-11-22 | 南京理工大学 | The method that hydro-thermal method prepares carbon-coated aluminum nanoparticles |
| CN115228477A (en) * | 2022-07-25 | 2022-10-25 | 广东工业大学 | Carbon-coated copper-zinc-aluminum catalyst and preparation method and application thereof |
| CN116173967A (en) * | 2022-11-07 | 2023-05-30 | 广东工业大学 | Carbon-encapsulated copper-zinc-aluminum catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001028964A2 (en) * | 1999-10-20 | 2001-04-26 | Saudi Basic Industries Corporation | A liquid phase catalytic hydrogenation process to convert aldehydes to the corresponding alcohols |
| CN102311313A (en) * | 2011-07-06 | 2012-01-11 | 上海焦化有限公司 | Neopentyl glycol preparation method utilizing catalytic hydrogenation by copper zinc aluminium catalyst |
| CN103272606A (en) * | 2013-06-06 | 2013-09-04 | 昆明理工大学 | Preparation method for carbon coated nano copper-based catalyst |
-
2018
- 2018-09-17 CN CN201811082471.6A patent/CN109046362A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001028964A2 (en) * | 1999-10-20 | 2001-04-26 | Saudi Basic Industries Corporation | A liquid phase catalytic hydrogenation process to convert aldehydes to the corresponding alcohols |
| CN102311313A (en) * | 2011-07-06 | 2012-01-11 | 上海焦化有限公司 | Neopentyl glycol preparation method utilizing catalytic hydrogenation by copper zinc aluminium catalyst |
| CN103272606A (en) * | 2013-06-06 | 2013-09-04 | 昆明理工大学 | Preparation method for carbon coated nano copper-based catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110152676A (en) * | 2019-05-21 | 2019-08-23 | 太原理工大学 | A kind of anti-sintering metal method for preparing catalyst |
| CN110480004A (en) * | 2019-08-29 | 2019-11-22 | 南京理工大学 | The method that hydro-thermal method prepares carbon-coated aluminum nanoparticles |
| CN115228477A (en) * | 2022-07-25 | 2022-10-25 | 广东工业大学 | Carbon-coated copper-zinc-aluminum catalyst and preparation method and application thereof |
| CN115228477B (en) * | 2022-07-25 | 2023-11-07 | 广东工业大学 | Carbon-coated copper-zinc-aluminum catalyst and preparation method and application thereof |
| CN116173967A (en) * | 2022-11-07 | 2023-05-30 | 广东工业大学 | Carbon-encapsulated copper-zinc-aluminum catalyst and preparation method and application thereof |
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