CN108816226A - A kind of preparation and application of the load type gold catalyst for 5 hydroxymethyl furfural oxidative synthesis 2,5- furandicarboxylic acid - Google Patents
A kind of preparation and application of the load type gold catalyst for 5 hydroxymethyl furfural oxidative synthesis 2,5- furandicarboxylic acid Download PDFInfo
- Publication number
- CN108816226A CN108816226A CN201810497936.8A CN201810497936A CN108816226A CN 108816226 A CN108816226 A CN 108816226A CN 201810497936 A CN201810497936 A CN 201810497936A CN 108816226 A CN108816226 A CN 108816226A
- Authority
- CN
- China
- Prior art keywords
- hydroxymethyl furfural
- catalyst
- load type
- type gold
- furandicarboxylic acid
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the preparations and application of a kind of load type gold catalyst for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid.The carrier of the load type gold catalyst is CeO2Oxide, ZrO2The Ce of oxide or different ratioxZr1‑xO composite oxides (X value is 0.7~0.9), the mass fraction of carrier is 97%~99.5%, and the mass fraction of golden component is 0.5%~3%.Gold content is lower in the load type gold catalyst, and utilization efficiency is higher, and support material is cheap and easy to get, and catalyst entirety preparation process is simple.The load type gold catalyst is for being catalyzed 5 hydroxymethyl furfural oxidative synthesis 2, in the reaction of 5- furandicarboxylic acid, reaction condition is mild, it is environmentally friendly, catalytic activity is higher, and by the pH value in the proportion of Ce and Zr in adjusting carrier and the golden component loading process of activity, it can effectively regulate and control the selectivity of 2,5-furandicarboxylic acid.When reaction temperature is 70~100 DEG C, oxygen pressure is 0.5~1.5MPa, and the reaction time is 2~4 hours, and the conversion ratio of 5 hydroxymethyl furfural can reach 100%, and the selectivity of 2,5-furandicarboxylic acid can reach 97.3%.
Description
Technical field
The present invention relates to a kind of load type gold catalysts for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid
Preparation and application.
Background technique
The advantages that biomass resource has abundance, cheap, environmentally protective, reproducibility, is ideal fossil
Substitution of resources product.5 hydroxymethyl furfural is a kind of biomass hardware and software platform converted by biomass carbohydrates catalysis oxidation
Object is closed, the reactions such as oxidation, reduction, polymerization, hydrolysis can occur and generate a series of product.Wherein, the oxygen of 5 hydroxymethyl furfural
Change the important intermediate that product 2,5-furandicarboxylic acid is biopolymer, fine chemicals and medicine.And 2,5- furans
Dioctyl phthalate is similar to the structure of terephthalic acid (TPA), it is considered to be a kind of biological poly ester monomer with application prospect can be replaced
For conventional petroleum base polyester monocase terephthalic acid (TPA) for synthesizing common naval stores in life production.
Generally using potassium permanganate, potassium bichromate or high price lead compound etc. as oxidation in traditional oxidation process
Agent belongs to metering oxidation reaction, needs to consume a large amount of oxidants, and atom utilization is low, and generates a large amount of harmful by-products.Oxygen
Gas is used for catalytic oxidation process as a kind of oxidant from a wealth of sources, cheap and easy to get and environmental-friendly, can effectively solve
The certainly above problem is widely used.In recent years, it is that chemistry is lazy to gold that the fast development of Au catalyst, which revolutionizes people,
The understanding of property.Au catalyst is extensively studied applied to Oxidation of Carbon Monoxide, water-gas conversion, alcohol oxidation, oxidative esterification etc.
Reaction.Load type gold catalyst activity mainly by carrier, gold particle size and shape and gold and carrier between phase
The influence of the factors such as interaction, and these factors are influenced by preparation method.
Summary of the invention
The purpose of the present invention is to provide a kind of loads for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid
The preparation and application of type Au catalyst.
The present invention provides a kind of load type gold catalyst for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid
Preparation method, condition and steps are as follows：
(1) carrier is prepared.Weigh the cerium nitrate hexahydrate (AR) of certain mass or the mixture of zirconyl nitrate (AR) or both
It is dissolved in 50mL dehydrated alcohol, cerium nitrate hexahydrate and the molar ratio of zirconyl nitrate are (7: 3)~(9: 1) in mixture.It is stirring
Under be slowly added to citric acid complexing agent, the molar ratio of citric acid and metal cation is (1: 1), is put into 60 DEG C of water-bath, temperature
Degree persistently stirs 3 hours after stablizing, and then cools down 30 minutes at room temperature.Mixed solution is rotated at 50 DEG C and is evaporated, is then existed
Bulk solids are dried to obtain at 100 DEG C.Obtained solid is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min,
It is roasted at 500 DEG C 2 hours, then cooled to room temperature, takes out solid abrasive into powder, obtain CeO2、ZrO2Or different ratio
CexZr1-xO composite oxide carrier (X value is 0.7~0.9).
(2) load type gold catalyst is prepared.It is 0.5%~3% according to the mass fraction of golden component in the catalyst, weighs
The gold chloride of certain mass is dissolved in 50mL secondary water, and adjusting pH with NaOH solution is 4.91~7.32, is put into 60 DEG C of water-bath
In, the carrier of corrresponding quality is slowly added under stirring, temperature persistently stirs 1 hour after stablizing.Then it cools down 40 minutes at room temperature
After filtered, the solid obtained with ammonia scrubbing in filtrate until, without chloride ion, then with secondary water washing solid 2~3 times, taking out
After dry that solid is 12 hours dry at 65 DEG C, obtained solid grind into powder obtains load type gold catalyst.
The present invention provides a kind of load type gold catalyst for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid
Application, condition and steps are as follows：
5 hydroxymethyl furfural, NaOH and the catalyst for weighing certain mass are added in polytetrafluoroethyllining lining, wherein 5-
The molar ratio of hydroxymethylfurfural and NaOH are (1: 4)~(1: 1), the molar ratio of golden component in 5 hydroxymethyl furfural and catalyst
(100: 1)~(1000: 1) are added 10mL secondary water and dissolve 5 hydroxymethyl furfural and NaOH, then in polytetrafluoroethylene (PTFE)
Lining sealing is in a high pressure reaction kettle.Reaction kettle is placed in 70~100 DEG C of oil bath, etc. temperature stablize after be filled with 0.5~
The oxygen (99.999%) of 1.5MPa, is persistently stirred to react 2~4 hours.After reaction, reaction kettle is placed on cold in ice-water bath
But 40 minutes, subsequent slow pressure release opened reaction kettle, is separated by filtration liquid and catalyst solid after reaction, carried out to filtrate high
Effect liquid phase chromatogram analysis, determines the conversion ratio of 5 hydroxymethyl furfural and the selectivity of 2,5-furandicarboxylic acid.
Beneficial effects of the present invention：Gold content is lower in load type gold catalyst, and utilization efficiency is higher, and support material is cheap
It is easy to get, catalyst entirety preparation process is simple.Load type gold catalyst is for being catalyzed 5 hydroxymethyl furfural oxidative synthesis 2,5- furan
In dioctyl phthalate of muttering reaction, reaction condition is mild, and environmentally friendly, catalytic activity is higher, and by adjusting Ce and Zr in carrier
Proportion and the golden component loading process of activity in pH value, can effectively regulate and control the selectivity of 2,5-furandicarboxylic acid.5-
The conversion ratio of hydroxymethylfurfural can reach 100%, and the selectivity of 2,5-furandicarboxylic acid can reach 97.3%.
Specific embodiment
Embodiment 1
(1) carrier is prepared.It weighs 6.5133g cerium nitrate hexahydrate (AR) to be dissolved in 50mL dehydrated alcohol, slowly add under stirring
Enter 2.8818g citric acid complexing agent, be put into 60 DEG C of water-bath, temperature persistently stirs 3 hours after stablizing, then cold at room temperature
But 30 minutes.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain bulk solids at 100 DEG C.By obtained solid
It is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, roasted 2 hours at 500 DEG C, then naturally cool to room
Temperature takes out solid abrasive into powder, obtains CeO2Oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 5.92 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst A.
Embodiment 2
(1) carrier is prepared.It weighs 8.0930g zirconyl nitrate (AR) to be dissolved in 50mL dehydrated alcohol, be slowly added under stirring
6.725g citric acid complexing agent is put into 60 DEG C of water-bath, and temperature persistently stirs 3 hours after stablizing, and then cools down 30 at room temperature
Minute.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain bulk solids at 100 DEG C.Obtained solid is put into
In Muffle furnace, 500 DEG C are warming up to the rate of 2 DEG C/min, is roasted 2 hours at 500 DEG C, then cooled to room temperature, takes
Solid abrasive obtains ZrO at powder out2Oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 5.92 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst B.
Embodiment 3
(1) carrier is prepared.Weigh 7.8160g cerium nitrate hexahydrate (AR) and 0.4625g zirconyl nitrate (AR) be dissolved in 50mL without
In water-ethanol, it is slowly added to 3.8424g citric acid complexing agent under stirring, is put into 60 DEG C of water-bath, temperature is persistently stirred after stablizing
It mixes 3 hours, then cools down 30 minutes at room temperature.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain at 100 DEG C
Bulk solids.Obtained solid is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, it is small that 2 are roasted at 500 DEG C
When, then cooled to room temperature, takes out solid abrasive into powder, obtains Ce0.9Zr0.1O2Composite oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 4.91 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst C.
Embodiment 4
(1) carrier is prepared.Weigh 7.8160g cerium nitrate hexahydrate (AR) and 0.4625g zirconyl nitrate (AR) be dissolved in 50mL without
In water-ethanol, it is slowly added to 3.8424g citric acid complexing agent under stirring, is put into 60 DEG C of water-bath, temperature is persistently stirred after stablizing
It mixes 3 hours, then cools down 30 minutes at room temperature.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain at 100 DEG C
Bulk solids.Obtained solid is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, it is small that 2 are roasted at 500 DEG C
When, then cooled to room temperature, takes out solid abrasive into powder, obtains Ce0.9Zr0.1O2Composite oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 5.39 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst D.
Embodiment 5
(1) carrier is prepared.Weigh 7.8160g cerium nitrate hexahydrate (AR) and 0.4625g zirconyl nitrate (AR) be dissolved in 50mL without
In water-ethanol, it is slowly added to 3.8424g citric acid complexing agent under stirring, is put into 60 DEG C of water-bath, temperature is persistently stirred after stablizing
It mixes 3 hours, then cools down 30 minutes at room temperature.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain at 100 DEG C
Bulk solids.Obtained solid is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, it is small that 2 are roasted at 500 DEG C
When, then cooled to room temperature, takes out solid abrasive into powder, obtains Ce0.9Zr0.1O2Composite oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 5.92 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst E.
Embodiment 6
(1) carrier is prepared.Weigh 7.8160g cerium nitrate hexahydrate (AR) and 0.4625g zirconyl nitrate (AR) be dissolved in 50mL without
In water-ethanol, it is slowly added to 3.8424g citric acid complexing agent under stirring, is put into 60 DEG C of water-bath, temperature is persistently stirred after stablizing
It mixes 3 hours, then cools down 30 minutes at room temperature.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain at 100 DEG C
Bulk solids.Obtained solid is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, it is small that 2 are roasted at 500 DEG C
When, then cooled to room temperature, takes out solid abrasive into powder, obtains Ce0.9Zr0.1O2Composite oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 6.50 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst F.
Embodiment 7
(1) carrier is prepared.Weigh 7.8160g cerium nitrate hexahydrate (AR) and 0.4625g zirconyl nitrate (AR) be dissolved in 50mL without
In water-ethanol, it is slowly added to 3.8424g citric acid complexing agent under stirring, is put into 60 DEG C of water-bath, temperature is persistently stirred after stablizing
It mixes 3 hours, then cools down 30 minutes at room temperature.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain at 100 DEG C
Bulk solids.Obtained solid is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, it is small that 2 are roasted at 500 DEG C
When, then cooled to room temperature, takes out solid abrasive into powder, obtains Ce0.9Zr0.1O2Composite oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 7.32 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst G.
Embodiment 8
(1) carrier is prepared.Weigh 5.2107g cerium nitrate hexahydrate (AR) and 0.6938g zirconyl nitrate (AR) be dissolved in 50mL without
In water-ethanol, it is slowly added to 2.8818g citric acid complexing agent under stirring, is put into 60 DEG C of water-bath, temperature is persistently stirred after stablizing
It mixes 3 hours, then cools down 30 minutes at room temperature.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain at 100 DEG C
Bulk solids.Obtained solid is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, it is small that 2 are roasted at 500 DEG C
When, then cooled to room temperature, takes out solid abrasive into powder, obtains Ce0.8Zr0.2O2Composite oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 5.92 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst H.
Embodiment 9
(1) carrier is prepared.Weigh 6.0791g cerium nitrate hexahydrate (AR) and 1.3874g zirconyl nitrate (AR) be dissolved in 50mL without
In water-ethanol, it is slowly added to 3.8424g citric acid complexing agent under stirring, is put into 60 DEG C of water-bath, temperature is persistently stirred after stablizing
It mixes 3 hours, then cools down 30 minutes at room temperature.Mixed solution is rotated at 50 DEG C and is evaporated, is then dried to obtain at 100 DEG C
Bulk solids.Obtained solid is put into Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, it is small that 2 are roasted at 500 DEG C
When, then cooled to room temperature, takes out solid abrasive into powder, obtains Ce0.7Zr0.3O2Composite oxide carrier.
(2) load type gold catalyst is prepared.It is 1% according to the mass fraction of golden component in the catalyst, weighs 0.0213g
Gold chloride is dissolved in 50mL secondary water, is 5.92 with NaOH solution adjusting pH, is put into 60 DEG C of water-bath, slowly adds under stirring
Enter 0.6g carrier, temperature persistently stirs 1 hour after stablizing.Then cooling is filtered after forty minutes at room temperature, uses ammonia scrubbing
Obtained solid in filtrate at 65 DEG C until, without chloride ion, then with secondary water washing solid 2~3 times, doing solid after draining
Dry 12 hours, obtained solid grind into powder obtained load type gold catalyst I.
Embodiment 10
It weighs 0.1g 5 hydroxymethyl furfural and 0.1269g NaOH is added in polytetrafluoroethyllining lining, 10mL bis- is added
Secondary water dissolves 5 hydroxymethyl furfural and NaOH, then in a high pressure reaction kettle polytetrafluoroethyllining lining sealing.By reaction kettle
Be placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen (99.999%) of 1MPa, be persistently stirred to react 3 hours.Reaction
After, reaction kettle is placed in ice-water bath to 40 minutes cooling, subsequent slow pressure release, opening reaction kettle, after being separated by filtration reaction
Liquid and catalyst solid carry out efficient liquid phase chromatographic analysis to filtrate, and the conversion ratio of 5- hydroxymethylfurfural is 91.3%, 2,
The selectivity of 5- furandicarboxylic acid is 9.9%.
Embodiment 11
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312gCe0.9Zr0.1O2Composite oxide carrier adds
Enter into polytetrafluoroethyllining lining, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethylene (PTFE)
Liner seals in a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 94.2%, and the selectivity of 2,5-furandicarboxylic acid is 5.5%.
Embodiment 12
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst A is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen (99.999%) of 1MPa,
It is persistently stirred to react 3 hours.After reaction, reaction kettle is placed in ice-water bath to 40 minutes cooling, subsequent slow pressure release, opening
Reaction kettle is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis, 5 hydroxymethyl furfural to filtrate
Conversion ratio be 100%, the selectivity of 2,5-furandicarboxylic acid is 83.4%.
Embodiment 13
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst B is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 100%, and the selectivity of 2,5-furandicarboxylic acid is 62.3%.
Embodiment 14
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst C is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 100%, and the selectivity of 2,5-furandicarboxylic acid is 66.6%.
Embodiment 15
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst D is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen (99.999%) of 1MPa,
It is persistently stirred to react 3 hours.After reaction, reaction kettle is placed in ice-water bath to 40 minutes cooling, subsequent slow pressure release, opening
Reaction kettle is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis, 5 hydroxymethyl furfural to filtrate
Conversion ratio be 100%, the selectivity of 2,5-furandicarboxylic acid is 87.5%.
Embodiment 16
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst E is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 100%, and the selectivity of 2,5-furandicarboxylic acid is 97.3%.
Embodiment 17
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst F is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 100%, and the selectivity of 2,5-furandicarboxylic acid is 69.6%.
Embodiment 18
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst G is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen (99.999%) of 1MPa,
It is persistently stirred to react 3 hours.After reaction, reaction kettle is placed in ice-water bath to 40 minutes cooling, subsequent slow pressure release, opening
Reaction kettle is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis, 5 hydroxymethyl furfural to filtrate
Conversion ratio be 100%, the selectivity of 2,5-furandicarboxylic acid is 43.6%.
Embodiment 19
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst H is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen (99.999%) of 1MPa,
It is persistently stirred to react 3 hours.After reaction, reaction kettle is placed in ice-water bath to 40 minutes cooling, subsequent slow pressure release, opening
Reaction kettle is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis, 5 hydroxymethyl furfural to filtrate
Conversion ratio be 100%, the selectivity of 2,5-furandicarboxylic acid is 88.8%.
Embodiment 20
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst I is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 100%, and the selectivity of 2,5-furandicarboxylic acid is 85.3%.
Embodiment 21
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst E is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 80 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 99.6%, and the selectivity of 2,5-furandicarboxylic acid is 90.5%.
Embodiment 22
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst E is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 70 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 99.7%, and the selectivity of 2,5-furandicarboxylic acid is 42.1%.
Embodiment 23
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst E is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 0.5MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 100%, and the selectivity of 2,5-furandicarboxylic acid is 86.8%.
Embodiment 24
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst E is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1.5MPa
(99.999%), it is persistently stirred to react 3 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 100%, and the selectivity of 2,5-furandicarboxylic acid is 97.8%.
Embodiment 25
Weigh 0.1g 5 hydroxymethyl furfural, 0.1269g NaOH and 0.0312g load type gold catalyst E is added to poly- four
In vinyl fluoride liner, 10mL secondary water is added and dissolves 5 hydroxymethyl furfural and NaOH, then polytetrafluoroethyllining lining is sealed
In a high pressure reaction kettle.Reaction kettle is placed in 90 DEG C of oil bath, etc. temperature stablize after be filled with the oxygen of 1MPa
(99.999%), it is persistently stirred to react 2 hours.After reaction, reaction kettle is placed on cooling 40 minutes in ice-water bath, it is then slow
Reaction kettle is opened in slow pressure release, is separated by filtration liquid and catalyst solid after reaction, carries out efficient liquid phase chromatographic analysis to filtrate,
The conversion ratio of 5 hydroxymethyl furfural is 100%, and the selectivity of 2,5-furandicarboxylic acid is 76.6%.
Claims (4)
1. a kind of preparation method of the load type gold catalyst for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid,
The carrier for being characterized in that the load type gold catalyst is CeO2Oxide, ZrO2The Ce of oxide or different ratioxZr1-xO is compound
Oxide (X value be 0.7~0.9), the mass fraction of carrier are 97%~99.5%, the mass fraction of golden component is 0.5%~
3%.
2. a kind of load type gold for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid as described in claim 1 is urged
The preparation method of agent, it is characterised in that the preparation condition of the carrier and steps are as follows：By cerium nitrate hexahydrate or zirconyl nitrate
Or both mixture be dissolved in dehydrated alcohol, be slowly added to citric acid under stirring, stirred 3 hours at 60 DEG C, after room temperature is cooling
Mixed solution rotation is evaporated, it is then dry at 100 DEG C, it is finally putting into Muffle furnace, is roasted 2 hours at 500 DEG C, it is cooling
Grinding obtains support powder, and cerium nitrate hexahydrate and the molar ratio of zirconyl nitrate are (7: 3)~(9: 1), lemon in the mixture
The molar ratio of acid and metal cation is (1: 1).
3. a kind of load type gold for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid as described in claim 1 is urged
The preparation method of agent, it is characterised in that the preparation condition of the catalyst and steps are as follows：In the catalyst according to golden component
Mass fraction configure aqueous solution of chloraurate, adjusting pH with NaOH solution is that corrresponding quality is added at 4.91~7.32,60 DEG C
Carrier simultaneously stirs 1 hour, filters after room temperature is cooling, with ammonia scrubbing solid until in filtrate without chloride ion, at 65 DEG C after draining
Lower drying 12 hours, grinding obtain catalyst fines.
4. a kind of load type gold for 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid as described in claim 1-3
The application of catalyst, it is characterised in that the condition of 5 hydroxymethyl furfural oxidative synthesis 2,5-furandicarboxylic acid and steps are as follows：Claim
5 hydroxymethyl furfural, NaOH and the catalyst of amount certain mass are added in polytetrafluoroethyllining lining, and a certain amount of secondary water is added
5 hydroxymethyl furfural and NaOH are dissolved, then in a high pressure reaction kettle by polytetrafluoroethyllining lining sealing.Reaction kettle is heated to 70
~100 DEG C and it is filled with the oxygen of 0.5~1.5MPa, is then persistently stirred to react 2~4 hours.After reaction, cooling pressure release,
It is separated by filtration, liquid and catalyst solid after being reacted.The molar ratio of the 5 hydroxymethyl furfural and NaOH are (1: 4)~(1
: 1), and molar ratio (100: 1)~(1000: 1) of golden component in 5 hydroxymethyl furfural and catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810497936.8A CN108816226B (en) | 2018-05-22 | 2018-05-22 | Preparation and application of supported gold catalyst for synthesizing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810497936.8A CN108816226B (en) | 2018-05-22 | 2018-05-22 | Preparation and application of supported gold catalyst for synthesizing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108816226A true CN108816226A (en) | 2018-11-16 |
| CN108816226B CN108816226B (en) | 2021-09-24 |
Family
ID=64148307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810497936.8A Active CN108816226B (en) | 2018-05-22 | 2018-05-22 | Preparation and application of supported gold catalyst for synthesizing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108816226B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213368A (en) * | 2021-12-15 | 2022-03-22 | 中国科学院大连化学物理研究所 | Method for preparing furan dicarboxylic acid by oxidizing 5-hydroxymethylfurfural with composite catalyst |
| CN114260012A (en) * | 2021-12-28 | 2022-04-01 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for preparing 2,5-furandicarboxylic acid, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10205873A1 (en) * | 2002-02-13 | 2003-08-21 | Zsw | Au catalysts supported by metal oxides, processes for their production and their use |
| CN101612578A (en) * | 2008-06-24 | 2009-12-30 | 中国人民解放军63971部队 | Nano catalyst of a kind of eliminating formaldehyde at room temperature and preparation method thereof |
| CN102134089A (en) * | 2011-02-01 | 2011-07-27 | 大连海事大学 | Fusiform large-scale cerium based composite oxide powder and preparation method thereof |
| CN102309960A (en) * | 2011-06-03 | 2012-01-11 | 中南大学 | Preparation method of CeO2-ZrO2 material with highly ordered mesoporous pore canal |
| WO2013163547A1 (en) * | 2012-04-27 | 2013-10-31 | E. I. Du Pont De Nemours And Company | Production of alpha, omega-diols |
| CN107855133A (en) * | 2016-09-22 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing support type little particle Au catalyst |
-
2018
- 2018-05-22 CN CN201810497936.8A patent/CN108816226B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10205873A1 (en) * | 2002-02-13 | 2003-08-21 | Zsw | Au catalysts supported by metal oxides, processes for their production and their use |
| CN101612578A (en) * | 2008-06-24 | 2009-12-30 | 中国人民解放军63971部队 | Nano catalyst of a kind of eliminating formaldehyde at room temperature and preparation method thereof |
| CN102134089A (en) * | 2011-02-01 | 2011-07-27 | 大连海事大学 | Fusiform large-scale cerium based composite oxide powder and preparation method thereof |
| CN102309960A (en) * | 2011-06-03 | 2012-01-11 | 中南大学 | Preparation method of CeO2-ZrO2 material with highly ordered mesoporous pore canal |
| WO2013163547A1 (en) * | 2012-04-27 | 2013-10-31 | E. I. Du Pont De Nemours And Company | Production of alpha, omega-diols |
| CN107855133A (en) * | 2016-09-22 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing support type little particle Au catalyst |
Non-Patent Citations (2)
| Title |
|---|
| ONOFRE CASANOVA ET AL.: "Biomass into Chemicals: Aerobic Oxidation of 5-Hydroxymethyl-5-Hydroxymethyl-2-furfural into 2,5-Furandicarboxylic Acid with Gold Nanoparticle Catalysts", 《CHEMSUSCHEM》 * |
| 明彩兵等: "Pt负载的铈锆固溶体的催化性能与表征", 《环境科学与技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213368A (en) * | 2021-12-15 | 2022-03-22 | 中国科学院大连化学物理研究所 | Method for preparing furan dicarboxylic acid by oxidizing 5-hydroxymethylfurfural with composite catalyst |
| CN114260012A (en) * | 2021-12-28 | 2022-04-01 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for preparing 2,5-furandicarboxylic acid, preparation method and application |
| CN114260012B (en) * | 2021-12-28 | 2023-06-30 | 中国华能集团清洁能源技术研究院有限公司 | Catalyst for preparing 2,5-furandicarboxylic acid, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108816226B (en) | 2021-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107365286B (en) | Method for synthesizing 2, 5-furandicarboxylic acid | |
| CN108525697A (en) | A kind of alkalinity high-dispersion loading type Pt base nano-catalysts and its preparation and application | |
| CN110368928B (en) | Catalyst for synthesizing benzaldehyde by oxidizing benzyl alcohol and preparation method and application thereof | |
| CN111375404B (en) | P-type titanium dioxide/n-type tungsten trioxide heterojunction catalyst, preparation method thereof and application thereof in photochemical synthesis of fuel | |
| CN108816226A (en) | A kind of preparation and application of the load type gold catalyst for 5 hydroxymethyl furfural oxidative synthesis 2,5- furandicarboxylic acid | |
| CN105968075B (en) | A kind of method that photochemical catalytic oxidation HMF prepares DFF | |
| CN104190401B (en) | Molybdenum based composite metal oxidate catalyst for glycerine synthesizing propylene alcohol and preparation method thereof | |
| CN106699703B (en) | Method for preparing 5-hydroxymethylfurfural by catalyzing biomass sugar with zirconium phosphate loaded titanium dioxide | |
| CN108440262B (en) | Method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase | |
| CN113101941B (en) | Preparation method of cobalt-molybdenum catalyst and application of cobalt-molybdenum catalyst in catalyzing levulinic acid hydrogenation reaction | |
| KR20050053644A (en) | Method for producing acrylic acid from propane, in the presence of molecular oxygen | |
| CN108043461A (en) | It is a kind of to use g-C3N4/ UiO-66/NiPt catalyst is to the method for levulic acid catalytic hydrogenation | |
| CN111185247A (en) | Multi-element composite titanium oxide cluster (PTCs) CdSPCN-777 hydrogen production photocatalyst by water decomposition | |
| CN107987041A (en) | A kind of method of synthesis 2,5- furandicarboxylic acids | |
| CN106944050A (en) | A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application | |
| CN110256230A (en) | Efficient catalytic glycerol prepares catalyst of glyceric acid and preparation method thereof under the conditions of a kind of alkali-free | |
| CN113121481A (en) | Ruthenium-based catalyst and method for preparing 2, 5-furandicarboxylic acid by using same | |
| CN104801311A (en) | MoO3/NiO/TiO2 solid acid catalyst and preparation method thereof | |
| CN111253230B (en) | Method for preparing 3-hydroxymethylcyclopentanone by hydrogenating 5-hydroxymethylfurfural under catalysis of water phase | |
| CN108855158A (en) | A kind of preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst | |
| CN113786837A (en) | Method for preparing cyclopentanone and cyclopentanol through furfural hydrogenation rearrangement | |
| CN109251126A (en) | A kind of method of cyclohexane oxidation KA oil | |
| CN113877612A (en) | Multifunctional catalyst compounded by FeMo component and VPO component, and preparation method and application thereof | |
| CN109999776B (en) | Modified montmorillonite catalyst for catalyzing biomass sugar to prepare 5-hydroxymethylfurfural, and preparation method and application thereof | |
| EP2769766A1 (en) | Methanation catalyst of carbon dioxide, preparation method and usage of same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |