CN104722295A - Catalyst for catalysis of biological oil hydrodeoxygenation reaction in water phase or water-oil two phase - Google Patents
Catalyst for catalysis of biological oil hydrodeoxygenation reaction in water phase or water-oil two phase Download PDFInfo
- Publication number
- CN104722295A CN104722295A CN201310704290.3A CN201310704290A CN104722295A CN 104722295 A CN104722295 A CN 104722295A CN 201310704290 A CN201310704290 A CN 201310704290A CN 104722295 A CN104722295 A CN 104722295A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- water
- oil
- phase
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention in particular relates to a hollow carbon sphere supported nano palladium catalyst used for catalysis of biological oil hydrodeoxygenation reaction in water phase or water-oil two phase, a hollow carbon sphere (CM) is used as a carrier, and the carbon sphere supported palladium nano particle (Pd / CM) catalyst can be synthesized by the impregnation reduction method by use of PdCl2 as a precursor. The Pd / CM catalyst can be effectively dispersed in water, can also form Pickering emulsion in a water-oil two phase system, and can be sued for efficient catalysis of biological oil hydrodeoxygenation reaction in water phase or water-oil two phase, the obtained product is easy to separate, and the catalyst can be recycled.
Description
Technical field
The present invention be more particularly directed to a kind of hollow carbon balls loaded nanometer palladium catalyst for catalysis biological oil hydrogenation deoxidation reaction in aqueous phase or water oil two-phase.
Background technology
Along with the consumption day by day of the fossil fuels such as oil, find a kind of alternative fuel source and become more and more urgent.In recent decades, the bio oil produced by lignocellulose has attracted the concern of more and more people.Reproducible living beings can produce bio oil through pyrolysis, and bio oil generally has the oxygen content up to 60%.Therefore the oxygen content of bio oil must be reduced, to improve its calorific value and stability.In numerous methods, catalytic hydrodeoxygenation is considered to the most effective method of one.Catalytic hydrodeoxygenation is under high-pressure situations, is got rid of by oxygen by hydrogen from bio oil, finally obtains the high-quality product oil being similar to crude oil.
The bio oil deriving from living beings is a kind of very complicated material, and it can partly be dissolved in water, also can partly be dissolved in hydrocarbon solvent.From the angle of practical application, the catalytic hydrogenation reaction carried out at aqueous phase or water oil two-phase system will be more meaningful.But conventional catalyst can only be dissolved in oil phase mostly, be difficult to play catalytic action in aqueous phase or water oil two-phase system.Therefore, find a kind of can aqueous phase or water oil two-phase system in catalysis biological oil hydrogenation deoxidation reaction catalyst just seem particularly important.
Summary of the invention
The object of the present invention is to provide a kind of carbon ball supported palladium nanoparticle catalyst (Pd/CM) that can realize the reaction of catalysis biological oil hydrogenation deoxidation at aqueous phase or water oil two-phase system.This catalyst is easily prepared, can be dispersed in water, in water oil two-phase, form pickering emulsion.Catalyst efficiency is high, recoverable.
The preparation method of described Pd/CM catalyst comprises the steps:
The hollow carbon balls (concrete preparation method is shown in Chinese invention patent 200910237792.3) obtained by saccharomycete hydrothermal carbonization, as carrier, then uses the method synthetic catalyst of dipping reduction: by support C M and presoma PdCl
2be added to the water ultrasonic disperse, then adds reducing agent, stirring reaction.Carry out centrifuge washing after reaction terminates, namely vacuum drying obtains target product Pd/CM catalyst.
Described CM:PdCl
2=1: 10-1: 20 (mass ratioes).
Described reducing agent is sodium borohydride or formaldehyde.
Above-mentioned Pd/CM catalyst can be dispersed in water, can form pickering emulsion in water oil two-phase.Biological oil hydrodeoxygenation reaction can be carried out in above-mentioned aqueous phase or water oil two-phase.
Described biological oil hydrodeoxygenation reaction experiment step is: bio oil joined in above-mentioned aqueous phase or water oil two-phase, then transferred in high-pressure reactor by mixed solution.Air in reactor nitrogen purges displacement, then passes into hydrogen, improves pressure.At a certain temperature, stirring reaction 1-3 hour.After reaction terminates, solution with ethyl acetate extracts, and detects with GC-FID.
Described Hydrogen Vapor Pressure is 50-300psi.
Described reaction temperature is 50-150 DEG C.
Feature of the present invention:
1. catalyst can be dispersed in water, can form pickering emulsion in water oil two-phase.
2. the method be applicable to biological oil hydrodeoxygenation reaction, catalyst can aqueous phase or water oil two-phase in efficiently catalytic reaction carry out, the easily separated extraction of product, convenient catalyst recycle.
Detailed description of the invention
Experimental technique in following embodiment, if no special instructions, is conventional method.Test material in following embodiment, if no special instructions, is and purchases available from conventional chemical reagent shop.Vanillic aldehyde is a kind of common typical bio-oil components, mainly below reacts for the hydrogenation deoxidation of vanillic aldehyde, and in water oil two phase reaction, choose decahydronaphthalenes as oil phase is example, is convenient to understand the present invention better, but does not limit the present invention.
Case study on implementation 1, the reaction of application Pd/CM catalysis aqueous phase vanillic aldehyde hydrogenation deoxidation
(1) preparation of Pd/CM catalyst
1.0g hollow carbon balls is joined in 50mL water, then add 0.05g PdCl
2, carry out ultrasonic disperse dipping, this this dispersion backward adds 1mL and contains 0.01gNaBH
4the reducing agent aqueous solution, stirring reaction 0.5h.Carry out centrifuge washing after reaction terminates, namely vacuum drying 24h obtains Pd/CM catalyst.
(2) catalytic performance
The Pd/CM catalyst of 155g vanillic aldehyde and 0.5g is dispersed in the water of 30ml.Then mixed liquor is transferred in reactor.Reactor nitrogen purges 5min, by the air displacement of the inside.Then reactor leads to pressurized with hydrogen to 150psi.2h is reacted under the condition of temperature 100 DEG C with magnetic agitation 650rpm.After reaction terminates, product and matrix ethyl acetate extract, and then detect with GC-FID.The conversion ratio of raw material is 100%, and the selective of product 2-methoxyl group-4-methylphenol is 100%.
Case study on implementation 2, the reaction of application Pd/CM catalytic water oil two-phase vanillic aldehyde hydrogenation deoxidation
(1) preparation of Pd/CM catalyst
With the step 1 of embodiment 1.
(2) catalytic performance
The Pd/CM catalyst of 155g vanillic aldehyde and 0.5g is dispersed in the decahydronaphthalenes of 20mL and the water of 10mL.Ultrasonic disperse is until there is obvious pickering emulsion layer to be formed.Then mixed liquor is transferred in reactor.Reactor nitrogen purges 5min, by the air displacement of the inside.Then reactor leads to pressurized with hydrogen to 200psi.2h is reacted under the condition of temperature 100 DEG C with magnetic agitation 650rpm.After reaction terminates, product and matrix ethyl acetate extract, and then detect with GC-FID.The conversion ratio of raw material is 100%, and the selective of product 2-methoxyl group-4-methylphenol is 95%.
Case study on implementation 3, the reaction of application Pd/CM catalytic water oil two-phase vanillic aldehyde hydrogenation deoxidation
(1) preparation of Pd/CM catalyst
1.0g hollow carbon balls is joined in 50mL water, then add 0.05g PdCl
2, carry out ultrasonic disperse dipping, this this dispersion backward adds the reducing agent aqueous solution that 3mL contains 37-40% formaldehyde, stirring reaction 0.5h.Carry out centrifuge washing after reaction terminates, namely vacuum drying 24h obtains Pd/CM catalyst.
(2) catalytic performance
The Pd/CM catalyst of 155g vanillic aldehyde and 0.5g is dispersed in the decahydronaphthalenes of 10mL and the water of 20mL.Ultrasonic disperse is until there is obvious pickering emulsion layer to be formed.Then mixed liquor is transferred in reactor.Reactor nitrogen purges 5min, by the air displacement of the inside.Then reactor leads to pressurized with hydrogen to 300psi.2h is reacted under the condition of temperature 100 DEG C with magnetic agitation 650rpm.After reaction terminates, product and matrix ethyl acetate extract, and then detect with GC-FID.The conversion ratio of raw material is 100%, and the selective of product 2-methoxyl group-4-methylphenol is 100%.
Claims (6)
1. a hollow carbon balls loaded nanometer palladium catalyst, is characterized in that, the preparation method of described catalyst comprises the steps: carrier hollow carbon balls (CM) and a certain amount of PdCl
2add be added to the water (in the quality of Pd, the targeted loads amount of Pd is 1-10%), then add reducing agent, stirring reaction.Carry out centrifuge washing after reaction terminates, namely vacuum drying obtains Pd/CM catalyst.
2. prepare the method for Pd/CM catalyst as claimed in claim 1, it is characterized in that: described reducing agent is sodium borohydride or formaldehyde, makes PdCl
2with the amount of substance ratio of reducing agent be: 1: 4-1: 10..
3. the Pd/CM catalyst as described in claim 1-2, is characterized in that: described catalyst can be dispersed in water, in water oil two-phase, form pickering emulsion.
4. the Pd/CM catalyst as described in claim 1-3, is characterized in that: described catalyst can react by the hydrogenation deoxidation of catalysis biological oil in aqueous phase or water oil two-phase.
5. Pd/CM biological oil hydrodeoxygenation reaction as claimed in claim 4, is characterized in that: described Hydrogen Vapor Pressure is 50-300psi.
6. Pd/CM biological oil hydrodeoxygenation reaction as claimed in claim 4, is characterized in that: described reaction temperature is 50-150 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310704290.3A CN104722295A (en) | 2013-12-20 | 2013-12-20 | Catalyst for catalysis of biological oil hydrodeoxygenation reaction in water phase or water-oil two phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310704290.3A CN104722295A (en) | 2013-12-20 | 2013-12-20 | Catalyst for catalysis of biological oil hydrodeoxygenation reaction in water phase or water-oil two phase |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104722295A true CN104722295A (en) | 2015-06-24 |
Family
ID=53447070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310704290.3A Pending CN104722295A (en) | 2013-12-20 | 2013-12-20 | Catalyst for catalysis of biological oil hydrodeoxygenation reaction in water phase or water-oil two phase |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104722295A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111266107A (en) * | 2020-03-18 | 2020-06-12 | 河北工业大学 | Preparation method and application of resin carbon sphere supported palladium catalyst |
| CN112675840A (en) * | 2021-01-11 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | Catalyst for nitroaniline and preparation method thereof |
| CN114656337A (en) * | 2022-04-22 | 2022-06-24 | 陕西科技大学 | Method for preparing 2-methoxy-4-methylphenol from biomass-based vanillin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891326A (en) * | 2012-10-23 | 2013-01-23 | 南京交通职业技术学院 | Nitrogen-doped hollow carbon ball loaded palladium-based catalyst and preparation method thereof, and alcohol fuel cell applying same |
| CN103130599A (en) * | 2011-11-24 | 2013-06-05 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin from animal and plant oil and waste animal and plant oil |
-
2013
- 2013-12-20 CN CN201310704290.3A patent/CN104722295A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130599A (en) * | 2011-11-24 | 2013-06-05 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin from animal and plant oil and waste animal and plant oil |
| CN102891326A (en) * | 2012-10-23 | 2013-01-23 | 南京交通职业技术学院 | Nitrogen-doped hollow carbon ball loaded palladium-based catalyst and preparation method thereof, and alcohol fuel cell applying same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111266107A (en) * | 2020-03-18 | 2020-06-12 | 河北工业大学 | Preparation method and application of resin carbon sphere supported palladium catalyst |
| CN111266107B (en) * | 2020-03-18 | 2022-12-20 | 河北工业大学 | Preparation method and application of resin carbon sphere supported palladium catalyst |
| CN112675840A (en) * | 2021-01-11 | 2021-04-20 | 浙江工业大学上虞研究院有限公司 | Catalyst for nitroaniline and preparation method thereof |
| CN114656337A (en) * | 2022-04-22 | 2022-06-24 | 陕西科技大学 | Method for preparing 2-methoxy-4-methylphenol from biomass-based vanillin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Okoye et al. | Synthesis of oxygenated fuel additives via glycerol esterification with acetic acid over bio-derived carbon catalyst | |
| Zhang et al. | Biodiesel production direct from high acid value oil with a novel magnetic carbonaceous acid | |
| Chen et al. | Magnetically recyclable cellulose-derived carbonaceous solid acid catalyzed the biofuel 5-ethoxymethylfurfural synthesis from renewable carbohydrates | |
| Liu et al. | Catalytic conversion of biomass into chemicals and fuels over magnetic catalysts | |
| Du et al. | Conversion of biomass‐derived levulinate and formate esters into γ‐valerolactone over supported gold catalysts | |
| Xing et al. | Effect of acidity and porosity of alkali-treated ZSM-5 zeolite on eugenol hydrodeoxygenation | |
| Zhou et al. | Cobalt catalysts: very efficient for hydrogenation of biomass-derived ethyl levulinate to gamma-valerolactone under mild conditions | |
| CN105289592A (en) | Method for preparing gamma-valerolactone by acetylpropionic acid catalytic hydrogenation | |
| Jiang et al. | Promotional effect of F for Pd/HZSM-5 catalyst on selective HDO of biobased ketones | |
| Yun et al. | Low‐temperature and highly efficient conversion of saccharides into formic acid under hydrothermal conditions | |
| CN101579637B (en) | Method for preparing molecular sieve solid acid catalyst used for preparing ethylene by ethanol dehydration | |
| Ma et al. | Catalytic depolymerization of lignin for liquefied fuel at mild condition by rare earth metals loading on CNT | |
| CN106866589B (en) | A kind of preparation method of gamma-valerolactone | |
| Park et al. | Fractionation of lignocellulosic biomass over core–shell Ni@ Al2O3 catalysts with formic acid as a cocatalyst and hydrogen source | |
| Ning et al. | Selective upgrading of biomass-derived benzylic ketones by (formic acid)–Pd/HPC–NH2 system with high efficiency under ambient conditions | |
| CN103691429B (en) | Catalyst for rapid pyrolysis and liquefaction of biomass as well as preparation method and application thereof | |
| Shimin et al. | One step preparation of sulfonated solid catalyst and its effect in esterification reaction | |
| CN104722295A (en) | Catalyst for catalysis of biological oil hydrodeoxygenation reaction in water phase or water-oil two phase | |
| US10377728B2 (en) | Method for preparing 2,5-dimethylfuran by directly catalyzing carbohydrate using modified Pd/C | |
| Qian et al. | Selective production of levoglucosenone by catalytic pyrolysis of cellulose mixed with magnetic solid acid | |
| Shi et al. | Preparation of heterogeneous interfacial catalyst benzimidazole-based acid ILs@ MIL-100 (Fe) and its application in esterification | |
| Zhang et al. | Catalytic Hydrogenation for Bio‐Oil Upgrading by a Supported NiMoB Amorphous Alloy | |
| Zhang et al. | Preparation of core-shell structure magnetic carbon-based solid acid and its catalytic performance on hemicellulose in corncobs | |
| CN112717939A (en) | Emulsion Ni/ZrO for catalytic hydrogenation upgrading of caprylic acid2Process for preparing catalyst | |
| CN106987285B (en) | A kind of method that multi phase state prepares high alcohol bio-fuel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150624 |
|
| RJ01 | Rejection of invention patent application after publication |