CN106492808B - A kind of catalyst and preparation method of the reaction of catalysis lilac phenol hydrogenation deoxidation - Google Patents
A kind of catalyst and preparation method of the reaction of catalysis lilac phenol hydrogenation deoxidation Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
The invention discloses the catalyst and preparation method of a kind of catalysis lilac phenol hydrogenation deoxidation reaction, and the catalyst is by binary composite oxides SiO2‑Al2O3It is formed with active metal Ni, by the method for fractional precipitation by binary composite oxides SiO2‑Al2O3It is entrenched togather with active metal Ni and has synthesized porous Ni/SiO2‑Al2O3Composite catalyst, the catalyst has many advantages, such as that large specific surface area, active metal Ni good dispersion, acidic site concentration are big, have many advantages, such as that reactivity is high, target product selectivity is good in the reaction of lilac phenol hydrogenation deoxidation, for the conversion ratio of lilac phenol close to 100%, cyclohexane selectivity reaches as high as 98.2%.
Description
Technical field:
The present invention relates to catalyst technical fields, and in particular to a kind of catalyst of catalysis lilac phenol hydrogenation deoxidation reaction
And preparation method.
Background technique:
With increasingly reducing for fossil resource and getting worse for environmental problem, lignin is got over as a kind of renewable resource
To be more concerned by people.Lignin molecule is by guaiacyl propane, lilac base propane and three kinds of p-hydroxyphenyl propane
Three-dimensional high molecular polymer made of phenylpropyl alcohol alkyl structure unit is bonded at random, wherein C-O ehter bond connection type accounts about 2/3,
Remaining is C-C key.It is available to contain aromatic radical, methoxyl group, phenol (alcohol) hydroxyl, carbonyl, carboxyl etc. by being broken these connecting keys
The small molecule depolymerization product of multiple functions group.These small molecule compounds C/H content ratio is close with petroleum, in high-quality liquid
The fields such as fuel and high valuable chemicals preparation have great application potential.But compared to aromatic hydrocarbons, these lignin solutions
Poly- product contains very high oxygen element content, cannot be directly used as liquid fuel.
Hydrogenation deoxidation (HDO) reaction can completely remove oxygen element, and more protiums are added, make lignin depolymerization product
Higher calorific value and better chemical stability are obtained, is a kind of very promising processing method.Prior art document report will
The traditional Hydrobon catalyst of petrochemical industry is (as NiMo, CoMo of vulcanization are carried on aluminium oxide, active carbon, silica, silicon
On the carriers such as sour aluminium) it is applied to the hydrogenation deoxidation technique of lignin depolymerization product and bio oil, however, sulphurized catalyst is opposite
It is unstable, and sulfur-containing compound (such as H is added in catalystic converter system2S, thiophene phenol etc.) sulphur pollution can be introduced in the product
Source.The noble metal hydrogenation dehydrogenation catalyst of high catalytic activity can overcome this disadvantage, such as Rh, Pt, Pd of support type, still
Catalyst service life is not grown, and noble metal is at high price, inhibits answering on a large scale for such catalyst to a certain extent
With.Cheap Ni base catalyst is a good selection, but Ni base catalyst needs to have very high active metal dispersion
Degree can just show high catalytic activity, and the synergistic effect of acidic site is needed just to be able to achieve complete hydrogenation deoxidation.
Summary of the invention:
The object of the present invention is to provide the catalyst and preparation method of a kind of catalysis lilac phenol hydrogenation deoxidation reaction, this is urged
Agent is by binary composite oxides SiO2-Al2O3It is formed with active metal Ni, by the method for fractional precipitation by binary composite oxygen
Compound SiO2-Al2O3It is entrenched togather with active metal Ni and has synthesized porous Ni/SiO2-Al2O3Composite catalyst, the catalysis
Agent has many advantages, such as that large specific surface area, active metal Ni good dispersion, acidic site concentration are big, anti-in lilac phenol hydrogenation deoxidation
Have many advantages, such as that reactivity is high, target product selectivity is good in answering, close to 100%, hexamethylene selects the conversion ratio of lilac phenol
Selecting property reaches as high as 98.2%.
The present invention is achieved by the following technical programs:
A kind of catalyst of catalysis lilac phenol hydrogenation deoxidation reaction, the catalyst is by binary composite oxides SiO2-
Al2O3It is formed with active metal Ni, the binary composite oxides SiO2-Al2O3The ratio between middle Si and Al molal quantity are 1:3~7, gold
The loading for belonging to Ni is 20wt.%；The preparation method of the catalyst the following steps are included:
(1) 7.2-8.3 grams of Ni (NO is weighed3)2·6H2O is dissolved in 700ml ethanol-water mixed solvent, according to Ni/
SiO2-Al2O3The molar ratio of each component weighs Al (NO in composite catalyst3)3·9H2O is dissolved in alcohol-water；Poly- second is added
It 0.5-1.5 grams and 4-8 grams of cetyl trimethylammonium bromide of alkene pyrrolidone, stirs evenly；Ethyl alcohol in ethanol-water mixed solvent
Volume ratio with water is 1:1~4:3；
(2) 10min is placed after ammonium hydroxide being added dropwise under ultrasound condition；Then the positive silicon of 20ml is added dropwise under ultrasound condition
Acetoacetic ester, under agitation room temperature aging 48h or more；
(3) it filters, precipitating is washed with deionized, is ground after dry, 500 DEG C of calcining 6h in Muffle furnace, finally
Under an atmosphere of hydrogen, 550 DEG C of reduction 4h, obtain Ni/SiO2-Al2O3Catalyst.
Binary composite oxides SiO in the catalyst2-Al2O3The ratio between middle Si and Al molal quantity are preferably 5~7.
The ammonium hydroxide is preferably the ammonium hydroxide that mass fraction is 25%.
Polyvinylpyrrolidone is added as stabilizer in the present invention, and it is living as surface that cetyl trimethylammonium bromide is added
Property agent, excessive ammonia is then added dropwise under ultrasound condition, make W metal formed complex compound dispersion in the solution, be then added
Ethyl orthosilicate, the catalyst for being precipitated and being post-processed have large specific surface area, active metal Ni good dispersion, acidic site
The advantages that point concentration is big.
The high degree of dispersion of active metal Ni can effectively improve hydrogenolysis and hydrogenation reaction catalytic activity；SiO2It can be to catalyst
Carry out specific surface area dilatation, and and Al2O3Mutually coordination, which is formed, is conducive to the acidic site that hydrogenation deoxidation reaction carries out.
The present invention also protects the Ni/SiO2-Al2O3Catalyst prepares hexamethylene in catalysis lilac phenol hydrogenation deoxidation
In purposes.
The purposes is specifically includes the following steps: using decahydronaphthalene as solvent, in Ni/SiO2-Al2O3Under catalyst action
It 180-210 DEG C, reacts under 2MPa atmosphere of hydrogen.
Preferably in stainless steel cauldron be added 20ml decahydronaphthalene as solvent, 0.2g lilac phenol be raw material,
0.1gNi/SiO2-Al2O3Catalyst reacts 2h under 2MPa atmosphere of hydrogen under the conditions of 200-210 DEG C.
Beneficial effects of the present invention are as follows:
(1) present invention passes through step-by-step precipitation method for binary oxide SiO2-Al2O3With the active metal Ni system of being entrenched togather
Standby Ni/SiO2-Al2O3Composite catalyst, obtained catalyst have large specific surface area, active metal Ni good dispersion, acidic site
The advantages that point concentration is big, hydrogenation deoxidation catalytic activity is high.
(2) it is purple in catalysis to prepare the catalyst that the raw materials used cheap, preparation method of catalyst is simple, obtains by the present invention
In the reaction of eugenol hydrogenation deoxidation, reactivity is high, good product selectivity, and the conversion ratio of lilac phenol is close to 100%, hexamethylene
Selectivity reaches as high as 98.2%.
Detailed description of the invention:
Fig. 1 is the Ni/SiO that embodiment 1 obtains2-Al2O3The stereoscan photograph of catalyst.
Fig. 2 is the Ni/SiO that embodiment 1 obtains2-Al2O3The transmission electron microscope photo of catalyst.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1: the loading of W metal is 20wt.%, and the ratio between Si:Al molal quantity is the preparation side of the catalyst of 5:1
Method and its catalytic performance test
Preparation method the following steps are included:
Step 1: 7.55g Ni (NO is weighed3)2·6H2O, 6.50g Al (NO3)3·9H2O is dissolved in the second of 700ml
In alcohol-water mixed solvent (ethyl alcohol and water volume ratio 4:3), 1g polyvinylpyrrolidone (PVP) is added and is used as stabilizer and 6g ten
Six alkyl trimethyl ammonium bromides (CTAB) are used as surfactant, stir evenly.
Step 2: the ammonium hydroxide 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min later；In ultrasound condition
Under the ethyl orthosilicate (TEOS) of 20ml is added dropwise, room temperature under agitation, aging 48h or more；
Step 3: precipitating is filtered out, is washed with deionized by filtering, dry 12h in 80 DEG C of baking ovens, after ground
Mill, 500 DEG C of calcining 6h in Muffle furnace, finally under an atmosphere of hydrogen, 550 DEG C of reduction 4h, the loading for obtaining W metal is
The ratio between 20wt.%, Si:Al molal quantity is the catalyst of 5:1, referred to as 20%Ni/SiO2-Al2O3(Si:Al=5:1) it is catalyzed
Agent, specific surface area 445.86m2g-1。
The 20%Ni/SiO that embodiment 1 obtains2-Al2O3The scanning electron microscope (SEM) photograph of (Si:Al molar ratio 5:1) catalyst and transmission
Electron microscope is referring to Fig. 1 and Fig. 2.Catalyst activity W metal manufactured in the present embodiment has good point as can be drawn from Figure 2
Dissipate property.
Catalytic performance test: the conduct of 20ml decahydronaphthalene is added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L material
Solvent, 0.2g lilac phenol are raw material, and 0.1g catalyst reacts 2h under 2MPa atmosphere of hydrogen.Catalytic effect is referring to table 1:
1 20%Ni/SiO of table2-Al2O3(Si:Al=5:1) hydrogenation deoxidation result of the catalyst to lilac phenol
Embodiment 2: the loading of W metal is 20wt.%, and the ratio between Si:Al molal quantity is the preparation side of the catalyst of 5:1
Method and its catalytic performance test.
The present embodiment is difference from example 1 is that stabilizer is different with the amount of surfactant.
Preparation method the following steps are included:
Step 1: 7.55g Ni (NO is weighed3)2·6H2O, 6.50g Al (NO3)3·9H2O is dissolved in the second of 700ml
In alcohol water mixed solvent (ethyl alcohol and water volume ratio 4:3), 0.5g polyvinylpyrrolidone (PVP) is added and is used as stabilizer and 4g ten
Six alkyl trimethyl ammonium bromides (CTAB) are used as surfactant, stir evenly.
Step 2: the ammonium hydroxide 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min later；In ultrasound condition
Under the ethyl orthosilicate (TEOS) of 20ml is added dropwise, room temperature under agitation, aging 48h or more；
Step 3: precipitating is filtered out, is washed with deionized by filtering, dry 12h in 80 DEG C of baking ovens, after ground
Mill, 500 DEG C of calcining 6h in Muffle furnace, finally under an atmosphere of hydrogen, 550 DEG C of reduction 4h, the loading for obtaining W metal is
The ratio between 20wt.%, Si:Al molal quantity is the catalyst of 5:1, referred to as 20%Ni/SiO2-Al2O3(Si:Al=5:1) (1) is urged
Agent.
Catalytic performance test: the conduct of 20ml decahydronaphthalene is added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L material
Solvent, 0.2g lilac phenol are raw material, and 0.1g catalyst reacts 2h under 2MPa atmosphere of hydrogen.Catalytic effect is referring to table 2:
2 20%Ni/SiO of table2-Al2O3(Si:Al=5:1) hydrogenation deoxidation result of (1) catalyst to lilac phenol
Embodiment 3: the loading of W metal is 20wt.%, and the ratio between Si:Al molal quantity is the preparation side of the catalyst of 5:1
Method and its catalytic performance test.
The present embodiment difference from example 1 is that, the amount of stabilizer and surfactant is different and ethyl alcohol-
Alcohol water is than different in water mixed solvent.
Preparation method the following steps are included:
Step 1: 7.55g Ni (NO is weighed3)2·6H2O, 6.50g Al (NO3)3·9H2O is dissolved in the second of 700ml
In alcohol-water mixed solvent (ethyl alcohol and water volume ratio 1:1), 1.5g polyvinylpyrrolidone (PVP) is added and is used as stabilizer and 8g
Cetyl trimethylammonium bromide (CTAB) is used as surfactant, stirs evenly.
Step 2: the ammonium hydroxide 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min later；In ultrasound condition
Under the ethyl orthosilicate (TEOS) of 20ml is added dropwise, room temperature under agitation, aging 48h or more；
Step 3: precipitating is filtered out, is washed with deionized by filtering, dry 12h in 80 DEG C of baking ovens, after ground
Mill, 500 DEG C of calcining 6h in Muffle furnace, finally under an atmosphere of hydrogen, 550 DEG C of reduction 4h, the loading for obtaining W metal is
The ratio between 20wt.%, Si:Al molal quantity is the catalyst of 5:1, referred to as 20%Ni/SiO2-Al2O3(Si:Al=5:1) (2) are urged
Agent.
Catalytic performance test: the conduct of 20ml decahydronaphthalene is added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L material
Solvent, 0.2g lilac phenol are raw material, and 0.1g catalyst reacts 2h under 2MPa atmosphere of hydrogen.Catalytic effect is referring to table 3:
3 20%Ni/SiO of table2-Al2O3(Si:Al=5:1) hydrogenation deoxidation result of (2) catalyst to lilac phenol
The loading of 4 W metal of embodiment is 20wt.%, and the ratio between Si:Al molal quantity is the preparation method of the catalyst of 3:1
And its catalytic performance test
Preparation method the following steps are included:
Step 1: 8.30g Ni (NO is weighed3)2·6H2O, 10.9g Al (NO3)3·9H2O is dissolved in the second of 700ml
In alcohol-water mixed solvent (ethyl alcohol and water volume ratio 4:3), 1g polyvinylpyrrolidone (PVP) is added and is used as stabilizer and 6g ten
Six alkyl trimethyl ammonium bromides (CTAB) are used as surfactant, stir evenly.
Step 2: the ammonium hydroxide 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min later；In ultrasound condition
Under the ethyl orthosilicate (TEOS) of 20ml is added dropwise, room temperature under agitation, aging 48h or more；
Step 3: precipitating is filtered out, is washed with deionized by filtering, dry 12h in 80 DEG C of baking ovens, after ground
Mill, 500 DEG C of calcining 6h in Muffle furnace, finally under an atmosphere of hydrogen, 550 DEG C of reduction 4h obtain 20%Ni/SiO2-Al2O3
(Si:Al molar ratio 3:1) catalyst.
Catalytic performance test: the conduct of 20ml decahydronaphthalene is added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L material
Solvent, 0.2g lilac phenol are raw material, and 0.1g catalyst reacts 2h under 2MPa atmosphere of hydrogen.Catalytic effect is referring to table 4:
4 20%Ni/SiO of table2-Al2O3(Si:Al=3:1) hydrogenation deoxidation result of the catalyst to lilac phenol
The loading of 5 W metal of embodiment is 20wt.%, and the ratio between Si:Al molal quantity is the preparation method of the catalyst of 7:1
And its catalytic performance test
Preparation method the following steps are included:
Step 1: 7.24g Ni (NO is weighed3)2·6H2O, 4.65g Al (NO3)3·9H2O is dissolved in the second of 700ml
In alcohol-water mixed solvent (ethyl alcohol and water volume ratio 4:3), 1g polyvinylpyrrolidone (PVP) is added and is used as stabilizer and 6g ten
Six alkyl trimethyl ammonium bromides (CTAB) are used as surfactant, stir evenly.
Step 2: the ammonium hydroxide 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min later；In ultrasound condition
Under the ethyl orthosilicate (TEOS) of 20ml is added dropwise, room temperature under agitation, aging 48h or more；
Step 3: precipitating is filtered out, is washed with deionized by filtering, dry 12h in 80 DEG C of baking ovens, after ground
Mill, 500 DEG C of calcining 6h in Muffle furnace, finally under an atmosphere of hydrogen, 550 DEG C of reduction 4h obtain 20%Ni/SiO2-Al2O3
(Si:Al molar ratio 7:1) catalyst.
Catalytic performance test: the conduct of 20ml decahydronaphthalene is added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L material
Solvent, 0.2g lilac phenol are raw material, and 0.1g catalyst reacts 2h under 2MPa atmosphere of hydrogen.Catalytic effect is referring to table 5:
5 20%Ni/SiO of table2-Al2O3(Si:Al=7:1) hydrogenation deoxidation result of the catalyst to lilac phenol
Reference examples 1:
Reference implementation example 1, the difference is that not adding ethyl orthosilicate.
Preparation method the following steps are included:
Step 1: 7.55g Ni (NO is weighed3)2·6H2O, 6.50g Al (NO3)3·9H2O is dissolved in the second of 700ml
In alcohol-water mixed solvent (ethyl alcohol and water volume ratio 4:3), 1g polyvinylpyrrolidone (PVP) is added and is used as stabilizer and 6g ten
Six alkyl trimethyl ammonium bromides (CTAB) are used as surfactant, stir evenly.
Step 2: the ammonium hydroxide 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min later.In stirring condition
Lower room temperature, aging 48h or more；
Step 3: precipitating is filtered out, is washed with deionized by filtering, dry 12h in 80 DEG C of baking ovens, after ground
Mill, 500 DEG C of calcining 6h in Muffle furnace, finally under an atmosphere of hydrogen, 550 DEG C of reduction 4h obtain 20%Ni/Al2O3Catalyst.
Catalytic effect is referring to table 6.
Reference examples 2:
This reference examples is not difference from example 1 is that add aluminum nitrate.
Preparation method the following steps are included:
Step 1: 7.55g Ni (NO is weighed3)2·6H2O is dissolved in the ethanol-water mixed solvent of 700ml (ethyl alcohol
With water volume ratio 4:3), 1g polyvinylpyrrolidone (PVP) is added and is used as stabilizer and 6g cetyl trimethylammonium bromide
(CTAB) it is used as surfactant, is stirred evenly.
Step 2: the ammonium hydroxide 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min later；In ultrasound condition
Under the ethyl orthosilicate (TEOS) of 20ml is added dropwise, room temperature under agitation, aging 48h or more；
Step 4: precipitating is filtered out, is washed with deionized by filtering, dry 12h in 80 DEG C of baking ovens, after ground
Mill, 500 DEG C of calcining 6h in Muffle furnace, finally under an atmosphere of hydrogen, 550 DEG C of reduction 4h obtain 20%Ni/SiO2Catalyst.
The catalytic performance test of reference examples 1 and 2: it is added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L material
20ml decahydronaphthalene is as solvent, and 0.2g lilac phenol is raw material, 0.1g catalyst, reacts 2h under 2MPa atmosphere of hydrogen.Catalysis effect
Fruit is referring to table 6.
Hydrogenation deoxidation result of the table 6Ni base catalyst to lilac phenol
From embodiment 1, reference examples 1 and reference examples 2: SiO2Can to catalyst carry out specific surface area dilatation, and with
Al2O3Mutually coordination, which is formed, is conducive to the acidic site that hydrogenation deoxidation reaction carries out, the present invention in the reaction of lilac phenol hydrogenation deoxidation
Have many advantages, such as that reactivity is high, target product selectivity is good, cyclohexane selectivity is up to 98.2%.
The specific surface area Property comparison of table 7Ni base catalyst
20%Ni/SiO available from table 7, that embodiment 1 obtains2-Al2O3With very high specific surface area and conjunction
Suitable pore-size distribution.With 20%Ni/SiO2And 20%Ni/Al2O3It compares, the 20%Ni/SiO that embodiment 1 obtains2-Al2O3Not only
With very big specific surface area, and acidic site concentration is big, SiO2Specific surface area dilatation, and and Al can be carried out to catalyst2O3
Mutually coordination, which is formed, is conducive to the acidic site that hydrogenation deoxidation reaction carries out.
Claims (4)
1. a kind of purposes for preparing the catalyst of hexamethylene for being catalyzed lilac phenol hydrogenation deoxidation reaction, which is characterized in that with
Decahydronaphthalene is as solvent, in Ni/SiO2-Al2O3180-210 DEG C under catalyst action, reacted under 2MPa atmosphere of hydrogen；The catalysis
Agent is by binary composite oxides SiO2-Al2O3It is formed with active metal Ni, binary composite oxides SiO2-Al2O3And active metal
Ni, which is entrenched togather, has synthesized porous Ni/SiO2-Al2O3Composite catalyst, the binary composite oxides SiO2-Al2O3In
The ratio between Si and Al molal quantity are 3~7:1, and the loading of W metal is 20wt.%；The specific surface area of catalyst is big, activity is golden
It is big to belong to Ni good dispersion, acidic site concentration, the method for preparing catalyst the following steps are included:
(1) 7.2-8.3 grams of Ni (NO is weighed3)2·6H2O is dissolved in 700ml ethanol-water mixed solvent, according to Ni/SiO2-
Al2O3The molar ratio of each component weighs Al (NO in composite catalyst3)3·9H2O is dissolved in alcohol-water；Polyvinyl pyrrole is added
It 0.5-1.5 grams and 4-8 grams of cetyl trimethylammonium bromide of alkanone, stirs evenly；Second alcohol and water in ethanol-water mixed solvent
Volume ratio is 1:1~4:3；
(2) 10min is placed after ammonium hydroxide being added dropwise under ultrasound condition；Then the positive silicic acid second of 20ml is added dropwise under ultrasound condition
Ester, under agitation room temperature aging 48h or more；
(3) it filters, precipitating is washed with deionized, is ground after dry, 500 DEG C of calcining 6h in Muffle furnace, finally in hydrogen
Under atmosphere is enclosed, 550 DEG C of reduction 4h obtain Ni/SiO2-Al2O3Catalyst.
2. purposes according to claim 1, which is characterized in that binary composite oxides SiO in the catalyst2-Al2O3
The ratio between middle Si and Al molal quantity are 5~7.
3. purposes according to claim 1 or 2, which is characterized in that the ammonium hydroxide is the ammonium hydroxide that mass fraction is 25%.
4. purposes according to claim 1 or 2, which is characterized in that 20ml decahydronaphthalene is added in stainless steel cauldron and makees
It is raw material, 0.1g Ni/SiO for solvent, 0.2g lilac phenol2-Al2O3Catalyst, under the conditions of 200-210 DEG C, 2MPa hydrogen
2h is reacted under atmosphere.
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| CN109806881A (en) * | 2017-11-20 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol |
| CN109967073A (en) * | 2019-04-22 | 2019-07-05 | 广东工业大学 | A kind of metallic catalyst and the preparation method and application thereof |
| CN110694678A (en) * | 2019-10-10 | 2020-01-17 | 天津大学 | Phenol hydrodeoxygenation catalyst, preparation method and application |
| CN114700109A (en) * | 2022-03-08 | 2022-07-05 | 青岛理工大学 | Preparation method of supported Ni-based phenolic compound selective hydrogenation catalyst |
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| CN102794178A (en) * | 2011-05-24 | 2012-11-28 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation thereof |
| CN102430409A (en) * | 2011-08-31 | 2012-05-02 | 中国科学院广州能源研究所 | Catalyst for catalyzing hydrogenation deoxidation reaction of guaiacol and preparation method thereof |
| CN105618058A (en) * | 2014-11-26 | 2016-06-01 | 南京大学 | Method for preparing supported water and heat resistant metallic nickel catalyst |
| CN104923233A (en) * | 2015-06-29 | 2015-09-23 | 中国科学院广州能源研究所 | Core-shell structured catalyst for preparation of cyclohexanol by selective hydrodeoxygenation of catalytic guaiacol |
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