CN106492808A - A kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction and preparation method - Google Patents
A kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction and preparation method 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 a kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction and preparation method, the catalyst is by binary composite oxides SiO2‑Al2O3Constitute 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 the Ni/SiO of porous2‑Al2O3Composite catalyst, the catalyst has the advantages that big specific surface area, active metal Ni good dispersions, acidic site concentration are big, in the reaction of Syringa oblata Lindl. phenol hydrogenation deoxidation, have reactivity height, target product selectivity good, the conversion ratio of Syringa oblata Lindl. phenol is close to 100%, and cyclohexane selectivity reaches as high as 98.2%.
Description
Technical field：
The present invention relates to catalyst technical field, and in particular to a kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction
And preparation method.
Background technology：
As increasingly reducing for fossil resource is increasingly serious with environmental problem, lignin is got over as a kind of Renewable resource
More to be paid close attention to by people.Lignin molecule is by three kinds of guaiacyl propane, Syringa oblata Lindl. base propane and p-hydroxyphenyl propane
The three-dimensional high molecular polymer that phenylpropyl alcohol alkyl structure unit is bonded at random, wherein C-O ehter bonds connected mode constitute about 2/3, its
Remaining for C-C keys.By these connecting keys that rupture, can obtain containing aromatic radical, methoxyl group, phenol (alcohol) hydroxyl, carbonyl, carboxyl etc.
The small molecule depolymerization product of several functions group.These micromolecular compounds C/H content ratios are close with oil, in high-quality liquid
The field such as fuel and high valuable chemicals preparation has great application potential.But compared to aromatic hydrocarbons, these lignin solutions
Poly- product contains very high oxygen element content, it is impossible to be directly used as liquid fuel.
Hydrogenation deoxidation (HDO) reaction can completely remove oxygen element, add more protiums, make lignin depolymerization product
Higher calorific value and more preferable chemical stability is obtained, is a kind of very promising processing method.Prior art document report will
(NiMo, the CoMo such as sulfuration is carried on aluminium oxide, activated carbon, silicon dioxide, silicon to the traditional Hydrobon catalyst of petrochemical industry
On the carriers such as sour aluminum) the hydrogenation deoxidation technique of lignin depolymerization product and bio oil is applied to, however, sulphurized catalyst is relative
Unstable, and add sulfur-containing compound in catalystic converter system (such as H2S, 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 shortcoming, such as Rh, Pt, Pd of support type etc., but
Catalyst service life is not long, and noble metal price is high, inhibits on a large scale should 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 need the synergism of acidic site realize completely hydrogenation deoxidation.
Content of the invention：
It is an object of the invention to provide a kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction and preparation method, this is urged
Agent is by binary composite oxides SiO2-Al2O3Constitute 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 the Ni/SiO of porous2-Al2O3Composite catalyst, the catalysis
Agent has the advantages that big specific surface area, active metal Ni good dispersions, acidic site concentration are big, anti-in Syringa oblata Lindl. phenol hydrogenation deoxidation
Have reactivity height, target product selectivity good in answering, the conversion ratio of Syringa oblata Lindl. phenol is close to 100%, and hexamethylene is selected
Selecting property reaches as high as 98.2%.
The present invention is achieved by the following technical programs：
A kind of catalyst of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reaction, the catalyst is by binary composite oxides SiO2-
Al2O3Constitute with active metal Ni, the binary composite oxides SiO2-Al2O3The ratio of middle Si and Al molal quantitys is 1:3～7, gold
The loading of category Ni is 20wt.%；The preparation method of the catalyst is comprised the following steps：
(1) 7.2-8.3 gram of Ni (NO is weighed3)2·6H2O is dissolved in 700ml ethanol-water mixed solvents, according to Ni/
SiO2-Al2O3In composite catalyst, the mol ratio of each component weighs Al (NO3)3·9H2O is dissolved in alcohol-water；Add poly- second
4-8 gram of 0.5-1.5 gram of alkene pyrrolidone and cetyl trimethylammonium bromide, stir；Ethanol in ethanol-water mixed solvent
Volume ratio with water is 1:1～4:3；
(2) after being added dropwise over ammonia under ultrasound condition, 10min is placed；Then the positive silicon of 20ml is added dropwise under ultrasound condition
Acetoacetic ester, under agitation aging more than the 48h of room temperature；
(3) filter, be washed with deionized precipitation, be ground after drying, 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 of middle Si and Al molal quantitys is preferably 5～7.
The ammonia is preferably the ammonia that mass fraction is 25%.
The present invention adds polyvinylpyrrolidone as stabilizer, adds cetyl trimethylammonium bromide to live as surface
Property agent, under ultrasound condition, be then added dropwise over excessive ammonia, make W metal formed complex disperse in the solution, be subsequently adding
Tetraethyl orthosilicate, has through precipitation and the catalyst that obtains of post processing that specific surface area is big, active metal Ni good dispersions, acidic site
The advantages of point concentration is big.
The high degree of dispersion of active metal Ni can effectively improve hydrogenolysis and hydrogenation reaction catalysis activity；SiO2Can be to catalyst
Carry out specific surface area dilatation, and and Al2O3Mutually coordination forms the acidic site for being conducive to hydrogenation deoxidation reaction to carry out.
The present invention also protects described Ni/SiO2-Al2O3Catalyst prepares hexamethylene in catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation
In purposes.
The purposes specifically includes following steps：Using decahydronaphthalene as solvent, in Ni/SiO2-Al2O3Under catalyst action
180-210 DEG C, react under 2MPa atmosphere of hydrogen.
Preferably in stainless steel cauldron add 20ml decahydronaphthalenes as solvent, 0.2g Syringa oblata Lindl.s phenol be raw material,
0.1gNi/SiO2-Al2O3Catalyst, under the conditions of 200-210 DEG C, reacts 2h under 2MPa atmosphere of hydrogen.
Beneficial effects of the present invention are as follows：
(1) present invention passes through step-by-step precipitation method by binary oxide SiO2-Al2O3With the active metal Ni systems of being entrenched togather
Standby Ni/SiO2-Al2O3Composite catalyst, the catalyst for obtaining have that specific surface area is big, active metal Ni good dispersions, acidic site
The advantages of point concentration is big, hydrogenation deoxidation catalysis activity is high.
(2) present invention prepares the catalyst that the raw materials used cheap, preparation method of catalyst is simple, obtain and is being catalyzed purple
In the reaction of eugenol hydrogenation deoxidation, reactivity is high, and good product selectivity, the conversion ratio of Syringa oblata Lindl. phenol are close to 100%, hexamethylene
Selectivity reaches as high as 98.2%.
Description of the drawings：
Fig. 1 is the Ni/SiO that embodiment 1 is obtained2-Al2O3The stereoscan photograph of catalyst.
Fig. 2 is the Ni/SiO that embodiment 1 is obtained2-Al2O3The transmission electron microscope photo of catalyst.
Specific embodiment：
The following is and the present invention is further illustrated, rather than limitation of the present invention.
Embodiment 1：The loading of W metal is 20wt.%, Si:The ratio of Al molal quantitys is 5:The preparation side of 1 catalyst
Method and its catalytic performance test
Preparation method is comprised the following steps：
1st step：Weigh 7.55g Ni (NO3)2·6H2O, 6.50g Al (NO3)3·9H2O, is dissolved in the second of 700ml
(ethanol and water volume ratio 4 in alcohol-water mixed solvent：3) 1g polyvinylpyrrolidones (PVP), are added as stabilizer and 6g ten
Six alkyl trimethyl ammonium bromides (CTAB) stir as surfactant.
2nd step：The ammonia 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min afterwards；In ultrasound condition
Under be added dropwise over the tetraethyl orthosilicate (TEOS) of 20ml, room temperature under agitation, aging more than 48h；
3rd step：Filter, precipitation is leached, is washed with deionized, 12h is dried in 80 DEG C of baking ovens, ground after terminating
Mill, 500 DEG C of calcining 6h in Muffle furnace, under an atmosphere of hydrogen, 550 DEG C reduce 4h, and the loading for obtaining W metal is finally
20wt.%, Si:The ratio of Al molal quantitys is 5:1 catalyst, referred to as 20%Ni/SiO2-Al2O3(Si：Al=5:1) it is catalyzed
Agent, its specific surface area are 445.86m2g-1.
The 20%Ni/SiO that embodiment 1 is obtained2-Al2O3(Si：Al mol ratios 5:1) scanning electron microscope (SEM) photograph of catalyst and transmission
Electron microscope is referring to Fig. 1 and Fig. 2.Catalyst activity W metal manufactured in the present embodiment has good dividing as can be drawn from Figure 2
Scattered property.
Catalytic performance test：20ml decahydronaphthalene conducts are added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L materials
Solvent, 0.2g Syringa oblata Lindl.s phenol be raw material, 0.1g catalyst, under 2MPa atmosphere of hydrogen react 2h.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 Syringa oblata Lindl. phenol
Embodiment 2：The loading of W metal is 20wt.%, Si:The ratio of Al molal quantitys is 5:The preparation side of 1 catalyst
Method and its catalytic performance test.
The present embodiment and the difference of embodiment 1 are that the amount of stabilizer and surfactant is different.
Preparation method is comprised the following steps：
1st step：Weigh 7.55g Ni (NO3)2·6H2O, 6.50g Al (NO3)3·9H2O, is dissolved in the second of 700ml
(ethanol and water volume ratio 4 in alcohol water mixed solvent：3) 0.5g polyvinylpyrrolidones (PVP), are added as stabilizer and 4g ten
Six alkyl trimethyl ammonium bromides (CTAB) stir as surfactant.
2nd step：The ammonia 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min afterwards；In ultrasound condition
Under be added dropwise over the tetraethyl orthosilicate (TEOS) of 20ml, room temperature under agitation, aging more than 48h；
3rd step：Filter, precipitation is leached, is washed with deionized, 12h is dried in 80 DEG C of baking ovens, ground after terminating
Mill, 500 DEG C of calcining 6h in Muffle furnace, under an atmosphere of hydrogen, 550 DEG C reduce 4h, and the loading for obtaining W metal is finally
20wt.%, Si:The ratio of Al molal quantitys is 5:1 catalyst, referred to as 20%Ni/SiO2-Al2O3(Si：Al=5:1) (1) urges
Agent.
Catalytic performance test：20ml decahydronaphthalene conducts are added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L materials
Solvent, 0.2g Syringa oblata Lindl.s phenol be raw material, 0.1g catalyst, under 2MPa atmosphere of hydrogen react 2h.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 Syringa oblata Lindl. phenol
Embodiment 3：The loading of W metal is 20wt.%, Si:The ratio of Al molal quantitys is 5:The preparation side of 1 catalyst
Method and its catalytic performance test.
The present embodiment is that with the difference of embodiment 1 stabilizer is different with the amount of surfactant, and ethanol-
In water mixed solvent, alcohol water is than different.
Preparation method is comprised the following steps：
1st step：Weigh 7.55g Ni (NO3)2·6H2O, 6.50g Al (NO3)3·9H2O, is dissolved in the second of 700ml
(ethanol and water volume ratio 1 in alcohol-water mixed solvent：1) 1.5g polyvinylpyrrolidones (PVP), are added as stabilizer and 8g
Cetyl trimethylammonium bromide (CTAB) stirs as surfactant.
2nd step：The ammonia 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min afterwards；In ultrasound condition
Under be added dropwise over the tetraethyl orthosilicate (TEOS) of 20ml, room temperature under agitation, aging more than 48h；
3rd step：Filter, precipitation is leached, is washed with deionized, 12h is dried in 80 DEG C of baking ovens, ground after terminating
Mill, 500 DEG C of calcining 6h in Muffle furnace, under an atmosphere of hydrogen, 550 DEG C reduce 4h, and the loading for obtaining W metal is finally
20wt.%, Si:The ratio of Al molal quantitys is 5:1 catalyst, referred to as 20%Ni/SiO2-Al2O3(Si：Al=5:1) (2) urge
Agent.
Catalytic performance test：20ml decahydronaphthalene conducts are added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L materials
Solvent, 0.2g Syringa oblata Lindl.s phenol be raw material, 0.1g catalyst, under 2MPa atmosphere of hydrogen react 2h.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 Syringa oblata Lindl. phenol
The loading of 4 W metal of embodiment is 20wt.%, Si:The ratio of Al molal quantitys is 3:The preparation method of 1 catalyst
And its catalytic performance test
Preparation method is comprised the following steps：
1st step：Weigh 8.30g Ni (NO3)2·6H2O, 10.9g Al (NO3)3·9H2O, is dissolved in the second of 700ml
(ethanol and water volume ratio 4 in alcohol-water mixed solvent：3) 1g polyvinylpyrrolidones (PVP), are added as stabilizer and 6g ten
Six alkyl trimethyl ammonium bromides (CTAB) stir as surfactant.
2nd step：The ammonia 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min afterwards；In ultrasound condition
Under be added dropwise over the tetraethyl orthosilicate (TEOS) of 20ml, room temperature under agitation, aging more than 48h；
3rd step：Filter, precipitation is leached, is washed with deionized, 12h is dried in 80 DEG C of baking ovens, ground after terminating
Mill, 500 DEG C of calcining 6h in Muffle furnace, under an atmosphere of hydrogen, 550 DEG C of reduction 4h obtain 20%Ni/SiO finally2-Al2O3
(Si：Al mol ratios 3:1) catalyst.
Catalytic performance test：20ml decahydronaphthalene conducts are added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L materials
Solvent, 0.2g Syringa oblata Lindl.s phenol be raw material, 0.1g catalyst, under 2MPa atmosphere of hydrogen react 2h.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 Syringa oblata Lindl. phenol
The loading of 5 W metal of embodiment is 20wt.%, Si:The ratio of Al molal quantitys is 7:The preparation method of 1 catalyst
And its catalytic performance test
Preparation method is comprised the following steps：
1st step：Weigh 7.24g Ni (NO3)2·6H2O, 4.65g Al (NO3)3·9H2O, is dissolved in the second of 700ml
(ethanol and water volume ratio 4 in alcohol-water mixed solvent：3) 1g polyvinylpyrrolidones (PVP), are added as stabilizer and 6g ten
Six alkyl trimethyl ammonium bromides (CTAB) stir as surfactant.
2nd step：The ammonia 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min afterwards；In ultrasound condition
Under be added dropwise over the tetraethyl orthosilicate (TEOS) of 20ml, room temperature under agitation, aging more than 48h；
3rd step：Filter, precipitation is leached, is washed with deionized, 12h is dried in 80 DEG C of baking ovens, ground after terminating
Mill, 500 DEG C of calcining 6h in Muffle furnace, under an atmosphere of hydrogen, 550 DEG C of reduction 4h obtain 20%Ni/SiO finally2-Al2O3
(Si：Al mol ratios 7:1) catalyst.
Catalytic performance test：20ml decahydronaphthalene conducts are added in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L materials
Solvent, 0.2g Syringa oblata Lindl.s phenol be raw material, 0.1g catalyst, under 2MPa atmosphere of hydrogen react 2h.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 Syringa oblata Lindl. phenol
Reference examples 1：
Reference implementation example 1, difference are not add tetraethyl orthosilicate.
Preparation method is comprised the following steps：
1st step：Weigh 7.55g Ni (NO3)2·6H2O, 6.50g Al (NO3)3·9H2O, is dissolved in the second of 700ml
(ethanol and water volume ratio 4 in alcohol-water mixed solvent：3) 1g polyvinylpyrrolidones (PVP), are added as stabilizer and 6g ten
Six alkyl trimethyl ammonium bromides (CTAB) stir as surfactant.
2nd step：The ammonia 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min afterwards.In stirring condition
Lower room temperature, aging more than 48h；
3rd step：Filter, precipitation is leached, is washed with deionized, 12h is dried in 80 DEG C of baking ovens, ground after terminating
Mill, 500 DEG C of calcining 6h in Muffle furnace, under an atmosphere of hydrogen, 550 DEG C of reduction 4h obtain 20%Ni/Al finally2O3Catalyst.
Catalytic effect is referring to table 6.
Reference examples 2：
This reference examples is not add aluminum nitrate with the difference of embodiment 1.
Preparation method is comprised the following steps：
1st step：Weigh 7.55g Ni (NO3)2·6H2O, is dissolved in (ethanol in the ethanol-water mixed solvent of 700ml
With water volume ratio 4：3) 1g polyvinylpyrrolidones (PVP), are added as stabilizer and 6g cetyl trimethylammonium bromide
(CTAB) as surfactant, stir.
2nd step：The ammonia 120ml of 25wt.% is added dropwise under ultrasound condition, places 10min afterwards；In ultrasound condition
Under be added dropwise over the tetraethyl orthosilicate (TEOS) of 20ml, room temperature under agitation, aging more than 48h；
4th step：Filter, precipitation is leached, is washed with deionized, 12h is dried in 80 DEG C of baking ovens, ground after terminating
Mill, 500 DEG C of calcining 6h in Muffle furnace, under an atmosphere of hydrogen, 550 DEG C of reduction 4h obtain 20%Ni/SiO finally2Catalyst.
The catalytic performance test of reference examples 1 and 2：Add in the high-temperature high-pressure reaction kettle of 50ml Stainless steel 316 L materials
Used as solvent, 0.2g Syringa oblata Lindl.s phenol is raw material to 20ml decahydronaphthalenes, and 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 bases catalyst to Syringa oblata Lindl. phenol
From embodiment 1, reference examples 1 and reference examples 2：SiO2Can carry out specific surface area dilatation to catalyst, and with
Al2O3Mutually coordination forms the acidic site for being conducive to hydrogenation deoxidation reaction to carry out, the present invention in the reaction of Syringa oblata Lindl. phenol hydrogenation deoxidation
Good with reactivity height, target product selectivity, cyclohexane selectivity is up to 98.2%.
The specific surface area Property comparison of table 7Ni base catalyst
Can obtain from table 7, the 20%Ni/SiO that embodiment 1 is obtained2-Al2O3There is very high specific surface area and conjunction
Suitable pore-size distribution.With 20%Ni/SiO2And 20%Ni/Al2O3Compare, the 20%Ni/SiO that embodiment 1 is obtained2-Al2O3Not only
There is 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 forms the acidic site for being conducive to hydrogenation deoxidation reaction to carry out.
Claims (6)
1. the catalyst that a kind of catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation reacts, it is characterised in that the catalyst is by binary combined oxidation
Thing SiO2-Al2O3Constitute with active metal Ni, the binary composite oxides SiO2-Al2O3The ratio of middle Si and Al molal quantitys is 1:
3～7, the loading of W metal is 20wt.%；The preparation method of the catalyst is comprised the following steps：
(1) 7.2-8.3 gram of Ni (NO is weighed3)2·6H2O is dissolved in 700ml ethanol-water mixed solvents, according to Ni/SiO2-
Al2O3In composite catalyst, the mol ratio of each component weighs Al (NO3)3·9H2O is dissolved in alcohol-water；Add polyvinyl pyrrole
4-8 gram of alkanone 0.5-1.5 gram and cetyl trimethylammonium bromide, stir；Second alcohol and water in ethanol-water mixed solvent
Volume ratio is 1:1～4:3；
(2) after being added dropwise over ammonia under ultrasound condition, 10min is placed；Then the positive silicic acid second of 20ml is added dropwise under ultrasound condition
Ester, under agitation aging more than the 48h of room temperature；
(3) filter, be washed with deionized precipitation, be ground after drying, 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. the catalyst that catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation according to claim 1 reacts, it is characterised in that the catalysis
Binary composite oxides SiO in agent2-Al2O3The ratio of middle Si and Al molal quantitys is 5～7.
3. the catalyst that catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation according to claim 1 and 2 reacts, it is characterised in that described
Ammonia is ammonia that mass fraction is 25%.
4. the Ni/SiO in claims 1 to 3 described in any claim2-Al2O3Catalyst is de- in catalysis Syringa oblata Lindl. phenol hydrogenation
Oxygen prepares the purposes in hexamethylene.
5. according to the Ni/SiO described in claim 42-Al2O3Catalyst prepares hexamethylene in catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation
In purposes, it is characterised in that using decahydronaphthalene as solvent, in Ni/SiO2-Al2O3180-210 DEG C under catalyst action, 2MPa
React under atmosphere of hydrogen.
6. according to the Ni/SiO described in claim 52-Al2O3Catalyst prepares hexamethylene in catalysis Syringa oblata Lindl. phenol hydrogenation deoxidation
In purposes, it is characterised in that in stainless steel cauldron add 20ml decahydronaphthalenes as solvent, 0.2g Syringa oblata Lindl.s phenol for original
Material, 0.1g Ni/SiO2-Al2O3Catalyst, under the conditions of 200-210 DEG C, reacts 2h under 2MPa atmosphere of hydrogen.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| 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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