CN110433850A - A kind of bimetallic catalyst and the preparation method and application thereof being catalyzed veratryl alcohol hydrogenation deoxidation - Google Patents
A kind of bimetallic catalyst and the preparation method and application thereof being catalyzed veratryl alcohol hydrogenation deoxidation Download PDFInfo
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- CN110433850A CN110433850A CN201910803196.0A CN201910803196A CN110433850A CN 110433850 A CN110433850 A CN 110433850A CN 201910803196 A CN201910803196 A CN 201910803196A CN 110433850 A CN110433850 A CN 110433850A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- OEGPRYNGFWGMMV-UHFFFAOYSA-N (3,4-dimethoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC OEGPRYNGFWGMMV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- 150000002940 palladium Chemical class 0.000 claims abstract description 6
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007385 chemical modification Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229920002101 Chitin Polymers 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 2
- 239000000295 fuel oil Substances 0.000 abstract 1
- 229920005610 lignin Polymers 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 239000002028 Biomass Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of bimetallic catalysts and the preparation method and application thereof for being catalyzed veratryl alcohol hydrogenation deoxidation.The bimetallic catalyst is specifically with CN0.28For catalyst carrier, by palladium salt and chloroplatinic acid (H2PtCl6•H2O CN) is carried on by physics and chemical method0.28On, Pd(II) and Pt(IV) is then reduced to Pd and Pt with ultraviolet catalytic, the suspension of rutile, the dry bimetallic catalyst (Pd-Pt/CN modified to get titanium dioxide after separation of solid and liquid are then added dropwise under ultrasonic agitation state0.28@TiO2).It is restored with photoreduction instead of traditional chemical method in the preparation method of catalyst of the present invention, preparation efficiency is high, at low cost.And bimetallic catalyst of the invention is to the high conversion rate of veratryl alcohol, while good to the selectivity of product, is expected to be applied to lignin cracked oil to be converted into fine chemicals and bio-fuel-oil.
Description
Technical field
The present invention relates to catalyst fields, and in particular to it is a kind of be catalyzed veratryl alcohol hydrogenation deoxidation bimetallic catalyst and its
Preparation method and application.
Background technique
The main problem of 21 century facing mankind is that energy demand is continuously increased, Fossil fuel consumption and extreme climate change
The problems such as.
Current 90% or more the energy both is from non-renewable fossil fuel (coal, former oil and gas).However, fossil
Consuming excessively for fuel is to increase CO in atmosphere2The main reason for discharge amount, therefore greenhouse effects are brought again, threaten all biologies
Existence.Utilize renewable energy (wind energy, solar energy, biomass energy, underground heat and hydroelectric generation etc.) replacing as fossil fuel
Dai Pin, which has become, realizes one of most potential development tactics of sustainable development society.Wherein, (one kind is abundant for biomass energy
Non-fossil carbon source) be capable of providing various valuable function chemicals and high energy density fuel.
The effective valueization of biomass utilizes and is not only to provide useful fuels and chemicals, while can also pass through progress
Photosynthesis and biorefinery technique reduce CO2Discharge amount.Thus, it is expected that the year two thousand thirty, the part of bio-fuel in transport service
Volume is up to 9% or so.It, can also be in sustainable development using natural biomass abundant as the raw material of chemicals production
Promote the development of Green Chemistry under background.
Catalytic hydrogenation treatment method plays very crucial effect during biomass is converted into fuel chemicals.
Heterogeneous solid catalyst has multiple physicochemical property, and high hydrothermal stability, efficient catalytic restore and repeatability,
Homogeneous liquid catalyst is substituted using them, is significantly during biomass higher value application.
In fact, heterogeneous catalysis field accounts for 90% of chemical production processes or so, and the industrial products more than 20% are raw
It produces.Partial size, shape and the porosity of solid catalyst play huge effect in catalysis reaction.
Heterogeneous catalysis is the one kind for converting renewable biomass to the advanced fuel and fine chemicals of sustainable development
Promising technology.Porosity and nanostructure are heterogeneous solid catalyst features the most general, these features determine special
Determine the accessibility in reactivity site, the selectivity of reaction mechanism and required product.Therefore, to the porosity of catalyst and nanometer
The accurate adjustment of structure has become a kind of potential mode of exploitation Novel solid-catalyst, achieves more efficient biomass
Catalyzed conversion.
Catalyst particle form is finely adjusted, especially metal or metal oxide, the electricity of catalyst surface will be optimized
Son and geometrical property.The nano-metal-oxide of controllable shape can preferentially expose exhibiting high surface active crystal face.Therefore, may be used
To enhance the interaction between active site and active material, biomass hydrogenation deoxidation reaction efficiency can effectively improve.
Other than partial size and form, selection of the porosity of solid catalyst for raising catalyst activity and product is controlled
Property is also very important.The pore size of solid catalyst can directly affect the diffusion of active material in biomass conversion reaction
Characteristic.In addition, using specific porous material that can mutually provide specific absorption as the carrier of catalyst for stable catalytic activity
Site.
Due to biomass molecule be it is complicated and highly viscous, use these single mode porous materials to urge as biology correlation
The significant challenge of agent is the obstruction that can encounter mass transfer during the reaction.
Therefore, the research of the porous bimetallic catalyst of support type has caused researcher more and more to pay close attention to.Develop function
The industrial applications that the bimetallic catalyst of energyization is converted into platform chemicals to veratryl alcohol have realistic meaning, while meeting can
The strategic requirement of sustainable development.
Summary of the invention
Status in view of the above technology, the object of the present invention is to provide a kind of bimetallic catalytics for being catalyzed veratryl alcohol hydrogenation deoxidation
Agent and the preparation method and application thereof.The present invention is by palladium salt and chloroplatinic acid (H2PtCl6·H2O it) is loaded by physics and chemical method
In CN0.28On, Pd (II) and Pt (IV) are then reduced to Pd and Pt with ultraviolet catalytic, then under ultrasonic agitation state by
It is added dropwise to the suspension of rutile, the dry bimetallic catalyst (Pd-Pt/ modified to get the titanium dioxide after separation of solid and liquid
CN0.28@TiO2).The problem of can solve using precious metals pd and Pt concerted catalysis oxygenatedchemicals veratryl alcohol hydrogenation deoxidation.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method for the bimetallic catalyst being catalyzed veratryl alcohol hydrogenation deoxidation, comprising the following steps:
(1) by CN0.28It is added to stir-activating in activator, is then washed with water to neutral spare;
(2) CN after taking step (1) to activate0.28It is added to the water, ultrasonic disperse;
(3) palladium salt solution and platinum acid chloride solution are added to CN obtained by step (2) under stirring0.28Surpass in suspension
Sound is to obtain mixed liquor;
(4) mixed liquor obtained by step (3) is irradiated under stirring with ultraviolet light, also by Pd (II) and Pt (IV) catalysis
It originally is Pd and Pt;
(5) alcohol suspension of rutile is added dropwise in the mixture obtained by step (4), is dried in vacuo after separation of solid and liquid
Up to the bimetallic catalyst.
Preferably, step (1) CN0.28Active carbon, graphite phase carbon nitride (g-CN are prepared for chitinX), chemical modification
One of active carbon or two kinds or more.
Preferably, step (1) described activator includes one of nitric acid, ammonium hydroxide, carbonic acid, ammonium hydrogen carbonate, alkali urea solution.
Preferably, step (1) the stir-activating condition are as follows: by 1~10g CN0.28It is placed in 50~500mL5molL-1's
HNO3In solution, activate 24 hours.
Preferably, the power of step (2) ultrasound is 50~100 watts, and the ultrasonic time is 0.5~4.0 hour, into one
Step preferably 4 hours.
Preferably, step (3) described palladium salt be one of palladium acetate, palladium chloride, palladium nitrate, palladium sulfate or two kinds with
On.
Preferably, the time of step (3) ultrasound is 3 hours.
Preferably, the power of step (4) described ultraviolet light is 500~2000 watts, and the reaction time is 0.5~4.0 hour, into
One step preferably 4 hours.
Preferably, the load capacity of palladium is 0.5~40wt% in bimetallic catalyst obtained by step (5), and the load capacity of platinum is
0.5~25wt%, the load capacity of titanium dioxide are 1%~10wt%.
It is further preferred that the load capacity of palladium is 1~10wt%, the load capacity of platinum is 1~10wt%, and titanium dioxide is born
Carrying capacity is 2%~5wt%.
A kind of bimetallic catalyst as made from above-described preparation method.
Application of the above-described bimetallic catalyst in veratryl alcohol hydrogenation deoxidation, comprising the following steps:
Under inert gas protection, solvent and hydrogen source are added in reaction substrate, add the bimetallic catalyst into
Row reaction;The inert gas is one of helium, argon gas, nitrogen;The solvent and hydrogen source are low-carbon alcohols;The reaction bottom
Object is veratryl alcohol;The temperature of the reaction is 150~300 DEG C, and time of reaction is 0.5~10 hour, the pressure of reaction is 2~
10MPa, revolving speed are 500~800rpm.
Compared with prior art, the present invention has the advantage that
1. being restored with photoreduction instead of traditional chemical method in the preparation method of bimetallic catalyst of the present invention, system
It is standby high-efficient, at low cost.
2. bimetallic catalyst of the present invention has the advantages that the high conversion rate of veratryl alcohol and to good product selectivity.
Detailed description of the invention
Fig. 1 a, Fig. 1 b are respectively the transmission electron microscope picture and grain size distribution of 1 gained bimetallic catalyst of embodiment.
Fig. 2 a, Fig. 2 b are respectively the transmission electron microscope picture and grain size distribution of 2 gained bimetallic catalyst of embodiment.
Fig. 3 a, Fig. 3 b are respectively the transmission electron microscope picture and grain size distribution of 3 gained bimetallic catalyst of embodiment.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, the present invention is made further below with reference to embodiment
It is bright.
Embodiment 1
Use biomass resource chitosan 10g as carbon source, 8 hours preparation CN are roasted under the conditions of 600 DEG C0.28;It will
10.0g CN0.28It is added to 50mL5molL-1Stir-activating 24 hours in nitric acid solution, are then washed with deionized water to neutrality
It is spare;Take the above-mentioned CN of 1.0g0.28As in 1 liter of deionized water, ultrasonic disperse 4 hours;It will under stirring
30mL7mmol·L-1Palladium nitrate solution and 30mL3mmolL-1Platinum acid chloride solution (n:n=1:1) be added to above-mentioned CN0.28
In suspension ultrasound 3 hours to obtain mixture;Above-mentioned mixed liquor is shone under stirring with the ultraviolet light that power is 500 watts
It penetrates 4 hours, Pd (II) and Pt (IV) catalysis is reduced to Pd and Pt;0.01g rutile is added dropwise in said mixture
Alcohol suspension, being dried in vacuo after separation of solid and liquid up to the load capacity of palladium is 5wt%, and the load capacity of platinum is 5wt%, titanium dioxide
Load capacity be 1wt% bimetallic catalyst.By Fig. 1 a, Fig. 1 b it is found that the Average Particle Diameters of gained bimetallic catalyst
For 2.79nm.
Embodiment 2
Use biomass resource chitosan 10g as carbon source, 8 hours preparation CN are roasted under the conditions of 600 DEG C0.28;It will
10.0g CN0.28Stir-activating 24 hours in 50mL5molL-1 nitric acid solution are added to, are then washed with deionized water into
Property is spare;Take the above-mentioned CN of 1.0g0.28As in 1 liter of deionized water, ultrasonic disperse 4 hours;It will under stirring
30mL7mmol·L-1Palladium nitrate solution and 30mL6mmolL-1Platinum acid chloride solution (n:n=1:2) be added to above-mentioned CN0.28
In suspension ultrasound 3 hours to obtain mixture;Above-mentioned mixed liquor is shone under stirring with the ultraviolet light that power is 500 watts
It penetrates 4 hours, Pd (II) and Pt (IV) catalysis is reduced to Pd and Pt;0.05g rutile is added dropwise in said mixture
Alcohol suspension, being dried in vacuo after separation of solid and liquid up to the load capacity of palladium is 5wt%, and the load capacity of platinum is 10wt%, titanium dioxide
The load capacity of titanium is the bimetallic catalyst of 5%wt%.By Fig. 2 a, Fig. 2 b it is found that the average grain diameter of gained bimetallic catalyst
Size is 2.94nm.
Embodiment 3
Use biomass resource chitosan 10g as carbon source, 8 hours preparation CN are roasted under the conditions of 600 DEG C0.28;It will
10.0g CN0.28It is added to 50mL5molL-1Stir-activating 24 hours in nitric acid solution, are then washed with deionized water to neutrality
It is spare;Take the above-mentioned CN of 1.0g0.28As in 1 liter of deionized water, ultrasonic disperse 4 hours;It will under stirring
30mL56mmol·L-1Palladium nitrate solution and 30mL12mmolL-1Platinum acid chloride solution (n:n=2:1) be added to it is above-mentioned
CN0.28In suspension ultrasound 3 hours to obtain mixture;The ultraviolet light for being 500 watts with power is by above-mentioned mixed liquor in stirring shape
It is irradiated 4 hours under state, Pd (II) and Pt (IV) catalysis is reduced to Pd and Pt;0.1g golden red is added dropwise in said mixture
The alcohol suspension of stone, it is 40wt% that the load capacity up to palladium is dried in vacuo after separation of solid and liquid, and the load capacity of platinum is 20wt%, two
The load capacity of titanium oxide is 10wt% bimetallic catalyst.By Fig. 3 a, Fig. 3 b it is found that the average grain diameter of gained bimetallic catalyst
Size is 2.73nm.
Catalyst performance evaluation test:
Veratryl alcohol hydrogenation deoxidation is reacted using bimetallic catalyst obtained by embodiment 1-3, specifically: it is protected in argon gas
Under, 40mL isopropanol (solvent and hydrogen source) is added in 2mL veratryl alcohol, bimetallic catalytic obtained by 0.05g embodiment 1-3 is added
Agent is reacted;Reaction temperature is 280 DEG C, and the reaction time is 5 hours, reaction pressure 7.0MPa, revolving speed 800rpm;Reaction
Product is tested and analyzed with gas chromatograph-mass spectrometer.The results are shown in Table 1:
Table 1
As shown in Table 1, bimetallic catalyst of the present invention is to the high conversion rate of veratryl alcohol and to good product selectivity.
Claims (10)
1. a kind of preparation method for the bimetallic catalyst for being catalyzed veratryl alcohol hydrogenation deoxidation, which comprises the following steps:
(1) by CN0.28It is added to stir-activating in activator, is then washed with water to neutral spare;
(2) CN after taking step (1) to activate0.28It is added to the water, ultrasonic disperse;
(3) palladium salt solution and platinum acid chloride solution are added to CN obtained by step (2) under stirring0.28In suspension ultrasound with
Obtain mixed liquor;
(4) mixed liquor obtained by step (3) is irradiated with ultraviolet light under stirring, Pd(II) and Pt(IV) catalysis is reduced to
Pd and Pt;
(5) alcohol suspension of rutile is added dropwise in the mixture obtained by step (4), is dried in vacuo after separation of solid and liquid to obtain the final product
The bimetallic catalyst.
2. preparation method according to claim 1, which is characterized in that step (1) described CN0.28Activity is prepared for chitin
One of charcoal, graphite phase carbon nitride, chemical modification active carbon or two kinds or more.
3. preparation method according to claim 1, which is characterized in that step (1) described activator include nitric acid, ammonium hydroxide,
One of carbonic acid, ammonium hydrogen carbonate, alkali urea solution.
4. preparation method according to claim 1, which is characterized in that activation condition described in step (1) are as follows: by 1 ~ 10g
CN0.28It is placed in 50 ~ 500mL5molL-1HNO3In solution, stir-activating 24 hours.
5. preparation method according to claim 1, which is characterized in that the power of step (2) ultrasound is 50 ~ 100 watts,
The time of ultrasound is 0.5 ~ 4.0 hour.
6. preparation method according to claim 1, which is characterized in that step (3) described palladium salt be palladium acetate, palladium chloride,
One of palladium nitrate, palladium sulfate or two kinds or more.
7. preparation method according to claim 1, which is characterized in that the power of step (4) described ultraviolet light be 500 ~
2000 watts, the reaction time is 0.5 ~ 4.0 hour.
8. preparation method according to claim 1, which is characterized in that palladium is negative in bimetallic catalyst obtained by step (5)
Carrying capacity is 5 ~ 40wt%, and the load capacity of platinum is 5 ~ 25wt%, and the load capacity of titanium dioxide is 1% ~ 10wt%.
9. a kind of bimetallic catalyst as made from the described in any item preparation methods of claim 1-8.
10. application of the bimetallic catalyst as claimed in claim 9 in veratryl alcohol hydrogenation deoxidation, which is characterized in that including with
Lower step:
Under inert gas protection, solvent and hydrogen source are added in reaction substrate, add the bimetallic catalyst and carries out instead
It answers;The inert gas is one of helium, argon gas, nitrogen;The solvent and hydrogen source are low-carbon alcohols;The reaction substrate is
Veratryl alcohol;The temperature of the reaction is 150 ~ 300 DEG C, and the time of reaction is 0.5 ~ 10 hour, and the pressure of reaction is 2 ~ 10 MPa,
Revolving speed is 500 ~ 800 rpm.
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