CN107626349A - A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid - Google Patents
A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid Download PDFInfo
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Abstract
The present invention relates to the production process that a kind of direct liquid phase oxidation of toluene prepares phenmethylol, benzaldehyde and benzoic acid.Specifically under the concerted catalysis effect of load-type ion liquid and metal-organic framework material (MOFs), using toluene as raw material, hydrogen peroxide is oxidant, and in gentle reaction system, phenmethylol, benzaldehyde and benzoic acid are prepared by high selectivity liquid phase controlled oxidation reaction.The catalyst preparation of the present invention is easy, can be reused with good recovery, and chemo-selective is high, and reaction condition is gentle, simple to operate, and dioxygen water use efficiency is high, is a kind of efficient, environment-friendly method.
Description
Technical field
The present invention relates to load-type ion liquid and metal-organic framework materials (MOFs) catalysis toluene liquid-phase selectively to control
Oxygenerating prepares the new method of phenmethylol, benzaldehyde and benzoic acid, belongs to chemical technology field.
Technical background
Phenmethylol, benzaldehyde and benzoic acid are very important chemical products, having many uses industrially, extensively should
Synthesis for compounds such as dyestuff, medicine intermediate, agricultural chemicals.Toluene is as the main production in PETROLEUM PROCESSING and coal chemical industry simultaneously
Thing, toluene is subjected to deep processing generation high value added product such as phenmethylol, benzaldehyde and benzoic acid etc. and had great importance.Mesh
Before, the main method for producing phenmethylol, benzaldehyde and benzoic acid using toluene has chlorination toluene Hydrolyze method, gas phase oxidation of toluene method
With liquid-phase oxidation of toluene method.Chlorination toluene Hydrolyze method is industrially to produce benzoic acid by-product phenmethylol and benzene at present in three kinds of methods
The most widely used method of formaldehyde.But there is more deficiency in this method：Technological process is grown, and product separation is difficult, atom profit
It is low with rate, sour gas and debirs are discharged, cause serious environmental pollution.Gas phase oxidation of toluene method part overcomes toluene
The deficiency of chlorinolysis, but the major defect of this method is embodied in：Toluene conversion is low, and toluene recovery utilizes tired in tail gas
Difficulty, product yield is low, and selectivity is low superoxidized generation, production cost height.
In recent years, toluene liquid-phase selective oxidation prepares phenmethylol, benzaldehyde and benzoic acid by domestic and international chemical work
The extensive concern of person, it is the new focus of toluene alkylation technique research and development.With molecular oxygen and hydrogen peroxide as oxidant, to environment
Endanger small, there is the characteristics of cleaning ambient close friend.Air (oxygen) liquid-phase oxidation of toluene method (CN101613269A,
JP2003286210A, US6495726B1) the advantages of be that reaction condition is gentle, but higher is required to consersion unit, and instead
Answer that conversion ratio is relatively low, expensive catalyst.Hydrogen peroxide toluene liquid-phase selective oxidation phenmethylol, benzaldehyde and benzoic acid
(Z.Guo,B.Liu,Q.Zhang,W.Deng,Y.Wang,Y.Yang,Chem.Soc.Rev.,2014,43,3480；X.Wang,
J.Wu, M.Zhao, Y.Lv, G.Li, C.Hu, J.Phys.Chem.C, 2009,113,14270), by-product only in course of reaction
Thing is water, has the advantages that high conversion rate, process route are short, Atom economy is high, therefore is considered as that one kind has extensive answer
With the clean preparation method of prospect.
Because heterogeneous catalysis has the advantages that easily separated, the good and repeatable utilization of catalyst stability, therefore have
Chemist is applied heterogeneous catalysis on hydrogen peroxide liquid phase selective oxidation toluene.Such as：CN101972646A
Using the transition metal vanadate Co-V-O catalyst of preparation, hydrogen peroxide is oxidant, passes through liquid phase oxidation toluene, knot at 60 DEG C
The conversion ratio of fruit toluene is close to 50%, and the selectivity of benzaldehyde is about 70%, and benzyl alcohol selective is about 13%.Liu etc.
(Appl.Catal.A:Gen., 2012,425-426,191) find using HZSM-5-0.20 molecular sieves as catalyst, hydrogen peroxide is
Oxidant, water are solvent, and 90-95 DEG C is reacted 5 hours, toluene conversion only 32%, and the choosing of benzaldehyde, phenmethylol and benzoic acid
Selecting property only has 25%, 20.8% and 27.5%, while the also generation of 22.3% accessory substance phenolic compound respectively.Xia etc.
(Catal.Commun., 2016,86,72) makees catalyst with the V-Mo-Fe-O prepared, and hydrogen peroxide is oxidant, in 80 DEG C of progress
Liquid phase oxidation reaction, toluene conversion are only 40.3%, and benzaldehyde is selectively 84.5%.Silva etc. is with complex [Fe
(BMPA)Cl3] it is catalyst (J.Mol.Catal.A:Chem., 2017,426,564), hydrogen peroxide is oxidant, and acetonitrile is molten
Agent, benzaldehyde highest yield is only 10.5%, its selectivity only 36%, and phenmethylol yield is only less than 4%, its selectivity
For 13%, while also a large amount of accessory substances such as phenol quinone peroxide etc. generates.
In a word, at present in toluene alkylation method, there is that catalyst activity is not high, reaction selectivity is relatively low, technique
The defects of complicated.
The content of the invention
The purpose of the present invention be develop the toluene direct oxidation phenmethylol of high conversion high selectivity a kind of, benzaldehyde and
The green method of benzoic acid.
To achieve these goals, the present invention provides a kind of hydrogen peroxide toluene liquid-phase selective oxidation phenmethylol, benzene first
The new method of aldehyde and benzoic acid, i.e., using toluene as raw material, 30% hydrogen peroxide is oxidant, metal-modified ZSM-5 molecular sieve load
Type ionic liquid and metal-organic framework materials (MOFs) are catalyst, and the selectivity control of toluene is realized under condition of no solvent
Oxidation reaction.
Above-mentioned promoter metal-organic framework materials (MOFs) are MIL-53 (Fe), MIL-53 (Cr), MIL-53
(Al), one kind in Ce-MIL-101 (Fe), Ce-MIL-101 (Cr).And divided with the transition metal modified ZSM-5 of Mn, Cu, Co, Fe
Son sieve supported imidazole ion liquid is major catalyst.
It is prepared by the transition metal modified ZSM-5 molecular sieve supported imidazole ion liquid of Mn, Cu, Co, Fe used in the present invention
Chemical principle and structure it is as follows：
Formula intermediate ion liquid anion can be chlorine, FeCl4,CuCl3,CuClBr,SnCl3Anion.Transition metal M
Can be Mn, Cu, Co, Fe.The reaction principle of formula M-ZSM-5@IL [anion] catalyst comprises the following steps：
(1) imidazoles and 3- chloropropyl triethoxysilanes are in toluene solvant, and back flow reaction 20-25 is small at 90-110 DEG C
When, then add after triethylamine and continue reaction 2 hours, recycling design, dry intermediate 1,
(2) intermediate 1 and 1- chlorohexanes are in toluene, the back flow reaction 10-15 hours at 90-110 DEG C, recycling design,
Dry intermediate 2,
(3) intermediate 2 and metal modified molecular screen M-ZSM-5 is in toluene, and back flow reaction 20-25 is small at 90-110 DEG C
When, filtering, dry ionic liquid 3,
(4) ionic liquid 3 continues anti-with the backflow of iron chloride, copper chloride, cuprous bromide or stannous chloride in acetonitrile solvent
Filtering, acetonitrile washing, dry, obtain supported imidazole ion liquid catalyst after answering 24 hours.
In step (1), imidazoles, 3- chloropropyl triethoxysilanes, the mol ratio of triethylamine are 1：0.5-5：0.5-5；
More preferably, imidazoles, 3- chloropropyl triethoxysilanes, the mol ratio of triethylamine are 1：1：1.
In step (2), the mol ratio of intermediate 1 and 1- chlorohexanes is 1：0.5-2；
More preferably, the mol ratio of intermediate 1 and 1- chlorohexanes is 1：1.
In step (3), intermediate 2 and metal modified molecular screen M-ZSM-5 mass ratio is 1-3：1
More preferably, intermediate 2 and metal modified molecular screen M-ZSM-5 mass ratio is 1.5：1
In above-mentioned course of reaction, the toluene solvant added is excessive.
The mol ratio of material used in the present invention is toluene：30% hydrogen peroxide=1:1~6, major catalyst dosage is toluene matter
The 1~10% of amount, co-catalyst dosage is 0.01~1.0g, and described material is pressed with MOFs and load-type ion liquid catalyst
Fed intake according to ratio and mix reaction.
Reaction temperature of the present invention is 25~70 DEG C.
Reaction time of the present invention is 0.5~8 hour.
Major catalyst of the present invention is the molecular sieve carried type imidazoles iron chloride salt ionic liquids of M-ZSM-5, M-ZSM-5 points
Son sieve support type imidazoles copper chloride ionic liquid, the molecular sieve carried type imidazoles chlorine cuprous bromide ionic liquids of M-ZSM-5, M-
One kind in ZSM-5 molecular sieve support type imidazoles stannous chloride ionic liquid.
A kind of transition metal modified ZSM-5 molecular sieve supported imidazole ion liquid of the present invention and MOFs concerted catalysis
The method of toluene hydrogen peroxide liquid phase controlled oxidation phenmethylol, benzaldehyde and benzoic acid, after reaction terminates, cooling and standings, catalysis
Agent particle is sunken to drag, and catalyst is recovered by filtration can be without i.e. recyclable reuse be handled, by toluene：30% hydrogen peroxide
=1:1~6 ratio, which feeds intake, carries out next group catalytic oxidation.
The catalytic oxidation principle of the present invention is as follows：
According to the method provided by the invention for preparing phenmethylol, benzaldehyde and benzoic acid, its key technology is using preparation
The molecular sieve carried type imidazole ion liquids of modification M-ZSM-5 and MOFs concerted catalysis toluene hydrogen peroxide liquid phase controlled oxidation reaction
Obtain phenmethylol, benzaldehyde and benzoic acid.
The present invention uses transition metal modified ZSM-5 molecular sieve supported imidazole ion liquid major catalyst and co-catalyst
MOFs is as heterogeneous catalysis system, and under mild conditions, catalysis toluene hydrogen peroxide liquid phase controlled oxidation prepares phenmethylol, benzene
Formaldehyde and benzoic acid, test result indicates that the conversion ratio and phenmethylol of toluene, the selectivity of benzaldehyde and benzoic acid and yield can
To be significantly improved.
Compared with prior art, its advantage is the present invention：(1) the molecular sieve carried type imidazole ion liquids of M-ZSM-5 are used
With MOFs catalyst, it is easy to prepare, and catalytic activity is high, and stability is good, can be recycled.(2) reaction is heterogeneous concerted catalysis
Oxidation, product and catalyst separation are simple, and catalyst can be reused conveniently in recovery.(3) whole reaction system green high-efficient,
Reaction condition is gentle, and selectivity of product is high, and dioxygen water use efficiency is high, solvent-free environment-friendly.
Embodiment
Implementation below is only the description to best mode for carrying out the invention, is not had to the scope of the present invention any
Limitation, it is further explained by means of the following examples the essence of the present invention.
The preparation of catalyst：
(1) imidazoles (1mol) and 3- chloropropyl triethoxysilanes (1mol) are in toluene (800mL) solvent, at 105 DEG C
Lower back flow reaction 22 hours, then add after triethylamine (1mol) and continue reaction 2 hours, recycling design, dry intermediate 1,
(2) then 1 (0.5mol) and 1- chlorohexanes (0.5mol) are in toluene (350mL), the back flow reaction 12 at 105 DEG C
Hour, recycling design, dry intermediate 2,
(3) in intermediate 2 (0.05mol) and metal modified molecular screen M-ZSM-5 (15g) toluene (300mL), at 105 DEG C
Lower back flow reaction 24 hours, filtering, dry ionic liquid 3,
(4) ionic liquid 3 (10g) continue in acetonitrile (100mL) solvent with iron chloride (0.02mol), copper chloride
(0.02mol), cuprous bromide (0.02mol) or stannous chloride (0.02mol) back flow reaction 24 hours,
(5) filtering, acetonitrile washing, dry, obtain supported imidazole ion liquid major catalyst 4.It is followed successively by：M-ZSM-5 points
Son sieve support type imidazoles iron chloride salt ionic liquid, the molecular sieve carried type imidazoles copper chloride ionic liquids of M-ZSM-5, M-ZSM-
5 molecular sieve carried type imidazoles chlorine cuprous bromide ionic liquids, the molecular sieve carried type imidazoles stannous chloride salt ion liquid of M-ZSM-5
Body.
Embodiment 1
In reaction flask, toluene (1mol), load-type ion liquid Mn-ZSM-5@IL [CuCl are added3] (5.5g),
MIL-53 (Fe) (0.15g), is slowly added to 30% hydrogen peroxide (1.1mol) under stirring, after 50 DEG C continue stirring reactions 3.5 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 87%, benzaldehyde selectivity 74%, benzene first
Sour selectivity 24%, phenmethylol and other selectivity of product 2%.
Embodiment 2
In reaction flask, toluene (1mol), load-type ion liquid Cu-ZSM-5@IL [CuCl are added3] (6.0g),
MIL-53 (Fe) (0.2g), is slowly added to 30% hydrogen peroxide (1mol) under stirring, after at 55 DEG C continue stirring reaction 3 hours.It is cold
But catalyst, is recovered by filtration.GC-MS analysis results show that toluene conversion 78%, benzaldehyde selectivity 82%, phenmethylol selects
Selecting property 10%, benzoic acid and other selectivity of product 8%.
Embodiment 3
In reaction flask, toluene (1mol), load-type ion liquid Co-ZSM-5@IL [CuCl are added3] (5.5g),
MIL-53 (Fe) (0.3g), is slowly added to 30% hydrogen peroxide (1.1mol) under stirring, after 55 DEG C continue stirring reactions 2.5 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 84%, benzaldehyde selectivity 87%, benzene first
Alcohol selectivity 5%, benzoic acid and other selectivity of product 8%.
Embodiment 4
In reaction flask, toluene (1mol), load-type ion liquid Fe-ZSM-5@IL [CuCl are added3] (6.0g),
MIL-53 (Fe) (0.25g), is slowly added to 30% hydrogen peroxide (1.2mol) under stirring, after at 50 DEG C continue stirring reaction 2 hours.
Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 90%, benzaldehyde selectivity 80%, phenmethylol
Selectivity 2%, benzoic acid and other selectivity of product 18%.
Embodiment 5
In reaction flask, toluene (1mol), load-type ion liquid Co-ZSM-5@IL [CuCl are added3] (5.5g),
MIL-53 (Cr) (0.35g), is slowly added to 30% hydrogen peroxide (1.1mol) under stirring, after at 45 DEG C continue stirring reaction 2 hours.
Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 86%, benzaldehyde selectivity 85%, phenmethylol
Selectivity 10%, benzoic acid and other selectivity of product 5%.
Embodiment 6
In reaction flask, toluene (1mol), load-type ion liquid Co-ZSM-5@IL [CuCl are added3] (6.0g),
Ce-MIL-101 (Fe) (0.5g), is slowly added to 30% hydrogen peroxide (1mol) under stirring, after 50 DEG C continue stirring reactions 3 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 92%, benzaldehyde selectivity 75%, benzene first
Alcohol selectivity 23%, benzoic acid and other selectivity of product 2%.
Embodiment 7
In reaction flask, toluene (1mol), load-type ion liquid Co-ZSM-5@IL [CuCl are added3] (8.0g),
MIL-53 (Al) (0.8g), is slowly added to 30% hydrogen peroxide (1.2mol) under stirring, after at 65 DEG C continue stirring reaction 5 hours.
Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 62%, benzaldehyde selectivity 79%, phenmethylol
Selectivity 8%, benzoic acid and other selectivity of product 13%.
Embodiment 8
In reaction flask, toluene (1mol), load-type ion liquid Cu-ZSM-5@IL [CuCl are added3] (5.0g),
Ce-MIL-101 (Cr) (1.0g), is slowly added to 30% hydrogen peroxide (1.1mol) under stirring, after 40 DEG C continue stirring reactions 6 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 83%, benzyl alcohol selective 47%, benzene first
Aldehyde selectivity 45%, benzoic acid and other selectivity of product 8%.
Embodiment 9
In reaction flask, toluene (1mol), load-type ion liquid Cu-ZSM-5@IL [CuCl are added3] (8.0g),
Ce-MIL-101 (Cr) (0.7g), is slowly added to 30% hydrogen peroxide (1.1mol) under stirring, after 40 DEG C continue stirring reactions 8 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 85%, benzyl alcohol selective 59%, benzene first
Aldehyde selectivity 38%, benzoic acid and other selectivity of product 3%.
Embodiment 10
In reaction flask, toluene (1mol), load-type ion liquid Co-ZSM-5@IL [SnCl are added3] (7.0g),
Ce-MIL-101 (Cr) (0.8g), is slowly added to 30% hydrogen peroxide (1.1mol) under stirring, after 60 DEG C continue stirring reactions 4 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 85%, benzaldehyde selectivity 83%, benzene first
Alcohol selectivity 8%, benzoic acid and other selectivity of product 9%.
Embodiment 11
In reaction flask, toluene (1mol), load-type ion liquid Co-ZSM-5@IL [SnCl are added3] (6.0g),
Ce-MIL-101 (Cr) (0.9g), is slowly added to 30% hydrogen peroxide (1.3mol) under stirring, after 55 DEG C continue stirring reactions 5 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 92%, benzaldehyde selectivity 90%, benzene first
Sour selectivity 8%, phenmethylol and other selectivity of product 2%.
Embodiment 12
In reaction flask, toluene (1mol), load-type ion liquid Fe-ZSM-5@IL [FeCl are added4] (8.0g),
Ce-MIL-101 (Fe) (0.6g), is slowly added to 30% hydrogen peroxide (3mol) under stirring, after 605 DEG C continue stirring reactions 7 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 90%, benzoic acid selectivity 91%, benzene first
Aldehyde and other selectivity of product 9%.
Embodiment 13
In reaction flask, toluene (1mol), load-type ion liquid Mn-ZSM-5@IL [FeCl are added4] (9.0g),
Ce-MIL-101 (Fe) (0.8g), is slowly added to 30% hydrogen peroxide (4mol) under stirring, after 60 DEG C continue stirring reactions 5 it is small
When.Cool down, catalyst is recovered by filtration.GC-MS analysis results show, toluene conversion 94%, benzoic acid selectivity 93%, benzene first
Aldehyde and other selectivity of product 7%.
Embodiment 14
Catalyst in embodiment 3 is reclaimed, catalytic reaction is carried out by each condition in embodiment 3, reuses recovery
Catalyst 3 times, experimental result show that catalyst activity does not subtract, toluene conversion 76~84%, benzaldehyde selectivity 82~87%.
Embodiment 15
Catalyst in embodiment 11 is reclaimed, catalytic reaction is carried out by each condition in embodiment 11, reuses back
Receive catalyst 4 times, experimental result shows that catalyst activity does not subtract toluene conversion 86~92%, benzaldehyde selectivity 85~
90%.
Embodiment 16
Catalyst in embodiment 13 is reclaimed, catalytic reaction is carried out by each condition in embodiment 13, reuses back
Receive catalyst 4 times, experimental result shows that catalyst activity does not subtract, toluene conversion 90~94%, benzoic acid selectivity 90~
93%.
Claims (10)
1. a kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid, it is characterised in that be specially transition metal modified ZSM-
5 molecular sieve carried type imidazole ion liquids, concrete structure are as follows：
2. the catalyst for preparing phenmethylol, benzaldehyde and benzoic acid described in claim 1, it is characterised in that it is described it is cloudy from
Sub- anion is chlorion compound, specially FeCl4, CuCl3, CuClBr, SnCl3In any one；Described transition gold
Category M is Mn, Cu, Co, any one in Fe.
3. the catalyst for preparing phenmethylol, benzaldehyde and benzoic acid described in claim 2, it is characterised in that described chlorine from
Muonic catalysis agent is SnCl3, transition metal M Co.
4. the preparation method of the catalyst described in claim 1-3 any one, it is characterised in that comprise the following steps：
(1) imidazoles and 3- chloropropyl triethoxysilanes are in toluene solvant, the back flow reaction 20-25 hours at 90-110 DEG C,
Then add after triethylamine and continue reaction 2 hours, recycling design, dry intermediate 1,
(2) intermediate 1 and 1- chlorohexanes are in toluene, the back flow reaction 10-15 hours at 90-110 DEG C, recycling design, drying
Intermediate 2 is obtained,
(3) intermediate 2 and metal modified molecular screen M-ZSM-5 is in toluene, the back flow reaction 20-25 hours at 90-110 DEG C,
Filtering, dry ionic liquid 3,
(4) ionic liquid 3 continue in acetonitrile solvent with iron chloride, copper chloride, cuprous bromide or stannous chloride back flow reaction 24
Filtering, acetonitrile washing, dry, obtain supported imidazole ion liquid catalyst after hour.
5. the method described in claim 4, it is characterised in that
In step (1), imidazoles, 3- chloropropyl triethoxysilanes, the mol ratio of triethylamine are 1：0.5-5：0.5-5, further
Preferably, imidazoles, 3- chloropropyl triethoxysilanes, the mol ratio of triethylamine are 1：1：1；
In step (2), the mol ratio of intermediate 1 and 1- chlorohexanes is 1：0.5-2,
More preferably, the mol ratio of intermediate 1 and 1- chlorohexanes is 1：1；
In step (3), intermediate 2 and metal modified molecular screen M-ZSM-5 mass ratio is 1-3：1,
More preferably, intermediate 2 and metal modified molecular screen M-ZSM-5 mass ratio is 1.5：1；
In above-mentioned course of reaction, the toluene solvant added is excessive.
6. using the method for the catalyst preparation phenmethylol described in claim 1-3 any one, benzaldehyde and benzoic acid, it is special
Sign is, using toluene as raw material, 30% hydrogen peroxide is oxidant, through adding transition metal modified ZSM-5 molecular sieve support type miaow
After oxazolinium ion liquid major catalyst and co-catalyst MOFs, under condition of no solvent, at a temperature of 25~70 DEG C, stirring reaction
Filtered after 0.5~8 hour, obtain product phenmethylol, benzaldehyde and benzoic acid after separation successively.
7. according to the method for claim 4, it is characterised in that described co-catalyst is metal-organic framework materials
(MOFs) MIL-53 (Fe), MIL-53 (Cr), MIL-53 (Al), Ce-MIL-101 (Fe), Ce-MIL-101 (Cr), are specifically included
In any one.
8. according to the method for claim 4, it is characterised in that the mol ratio of material used is toluene：30% hydrogen peroxide=
1:1~6, transition metal modified ZSM-5 molecular sieve supported imidazole ion liquid major catalyst dosage for toluene quality 1~
10%, co-catalyst MOFs dosage are the 0.01~1.0% of toluene quality.
9. according to the method for claim 1, it is characterised in that the temperature of reaction is adjusted between 25~70 DEG C, when sponsoring
Agent is Co-ZSM-5@IL [SnCl3], co-catalyst be Ce-MIL-101 (Cr), temperature control is at 55~60 DEG C.
10. according to the method for claim 1, it is characterised in that the reaction time to be adjusted between 0.5~8 hour, works as master
Catalyst is Co-ZSM-5@IL [SnCl3], co-catalyst be Ce-MIL-101 (Cr), the reaction time was controlled at 4~5 hours.
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| WO2020051955A1 (en) | 2018-09-10 | 2020-03-19 | 大连理工大学 | Method for preparing benzyl alcohol and homologues by means of catalytic conversion of lower alcohol and catalyst used |
| CN113735746A (en) * | 2021-09-07 | 2021-12-03 | 三峡大学 | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid |
| CN115805101A (en) * | 2021-09-13 | 2023-03-17 | 中国石油化工股份有限公司 | Catalyst for preparing hydroxy arone and preparation method and application thereof |
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| CN113735746A (en) * | 2021-09-07 | 2021-12-03 | 三峡大学 | Preparation method of 2-nitro-4-methylsulfonylbenzoic acid |
| CN115805101A (en) * | 2021-09-13 | 2023-03-17 | 中国石油化工股份有限公司 | Catalyst for preparing hydroxy arone and preparation method and application thereof |
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