CN106673977B - A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, preparation method and applications - Google Patents
A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, preparation method and applications Download PDFInfo
- Publication number
- CN106673977B CN106673977B CN201611118124.5A CN201611118124A CN106673977B CN 106673977 B CN106673977 B CN 106673977B CN 201611118124 A CN201611118124 A CN 201611118124A CN 106673977 B CN106673977 B CN 106673977B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- charcoal
- preparation
- carrier
- acetaldehyde
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
Abstract
The present invention provides a kind of ethyl alcohol direct dehydrogenations to prepare the catalyst of acetaldehyde, preparation method and applications, belongs to chemical industry catalysis technical field.The active component of the catalyst is Cu, and the carrier of catalyst is the oxide coated compound of charcoal；By percentage to the quality, using Cu as active component, active component is 0.1~30wt% of catalyst quality to the component for including in catalyst；Using the oxide coated compound of charcoal as carrier, carrier is 70~99.9wt% of catalyst quality；Wherein, charcoal is 0.5~50wt% of carrier quality, remaining is oxide.Catalyst provided by the invention has very high acetaldehyde selectivity, and acetaldehyde is selectively higher than 92.1%；The catalyst has excellent stability simultaneously, substantially without inactivation in test 40h.
Description
Technical field
The present invention relates to a kind of ethyl alcohol direct dehydrogenations to prepare the catalyst of acetaldehyde, preparation method and applications, belongs to chemical industry
Catalysis technical field.It refers in particular under the conditions of ordinary-pressure gas-phase, carries out the catalyst that alcohol dehydrogenase prepares acetaldehyde.
Background technique
Acetaldehyde is a kind of important aliphatic compound, is widely used in the fields such as agricultural, industry and daily life, is production
(mistake) acetic acid, pentaerythrite, n-butanol, crotonaldehyde, 2-Ethylhexyl Alcohol, pyridine, butanediol, ethyl acetate, trichloroacetaldehyde etc. are more
The raw material of kind important chemical, has very high application value.
At present the synthetic route of acetaldehyde mainly have ethylene method, acetylene hydration process, acetic acid reduction, ethane oxidation method,
CH4With CO synthetic method and Oxidative dehydrogenation of ethanol method.There are equipment corrosion, environmental pollution and Atom economies for above-mentioned acetaldehyde production method
Low a series of problems.China's bio-ethanol yield increases year by year, cheap, prepares acetaldehyde using ethyl alcohol direct dehydrogenation, together
When by-product hydrogen route meet the requirement of energy sustainable development.And this method mild, atom economy with reaction condition
Property high, environmental-friendly, gas-liquid the advantages that being easily isolated, be the following important acetaldehyde production route.
Ethyl alcohol direct dehydrogenation prepares Cu/SiO used by Acetaldehyde at present2Catalyst is asked there are selectivity of product is low
Topic.Zhang Yue [master thesis, University Of Tianjin, China, 2007] is prepared for 5wt%Cu/SiO by infusion process2Catalyst,
280 DEG C of catalysis ethanol dehydrogenations, conversion ratio 48.6%, acetaldehyde are selectively 68.7%.Shin-ichiro Fujita etc.
[React.Kinet.Catal.Lett.2001,73:367] is prepared for 30wt%Cu/SiO using infusion process2Catalyst, 220
DEG C catalysis ethanol dehydrogenation, conversion ratio 76%, acetaldehyde are selectively only 21.6%.Chinese patent CN103880661A report with
Mesoporous SBA-15 molecular sieve (SiO2) be carrier Cu base catalyst, for ethyl alcohol convert, be in 260 DEG C of ethanol conversions
45%, acetaldehyde is selectively 21%, and ethyl acetate is selectively 66%.Chinese patent CN103880660A, which is reported, loads Cu
In micropore MCM-41 molecular sieve (SiO2), it is converted for ethyl alcohol, is 40.6% in 260 DEG C of ethanol conversions, acetaldehyde selectivity is only
It is 18.6%.
The selectively low reason of acetaldehyde is since silica support surface silicone hydroxyl abundant (Si-OH) can be catalyzed target
The secondary responses such as aldol condensation occur for product acetaldehyde or catalysis ethanol dehydration generates ethylene or ether, reduce acetaldehyde selectivity.
In order to improve acetaldehyde selectivity, many researchers are in Cu/SiO2Doped alkali metal or alkaline-earth metal in catalyst
[Zhang Yue, master thesis, University Of Tianjin, China, 2007；Ind.Eng.Chem.Res., 1998,37:2618], Huo Zheti
The air speed of height reaction, is reduced residence time [Appl.Catal.A:General, 2006,304:30], however alkali (soil) metal
Introducing can cover active sites, reduce the utilization rate and reactivity of Ni metal.Chinese patent CN103127945A describe with
SiO2、ZrO2、Al2O3At least one is carrier, and Cu is active component, and addition P is auxiliary agent, and prepared catalyst is de- for ethyl alcohol
Hydrogen acetaldehyde, ethanol conversion are greater than 55%, and acetaldehyde is selectively greater than 93%.International monopoly PCT/EP2007/056940 (China
Publication number CN101489967A) it is reported between 270-300 DEG C, ethyl alcohol can be by ZnO, CoxOyOr Cr2O3The Cu of modification is catalyzed
Dehydrogenation generates acetaldehyde in agent, and ethanol conversion 30-50%, acetaldehyde is selectively 90-95%.However above method cannot be from this
Solve the problems, such as that acetaldehyde is selectively low in the reaction process in matter.
Summary of the invention
It is an object of the invention in view of the deficienciess of the prior art, providing a kind of for ethyl alcohol direct dehydrogenation preparation second
The catalyst of aldehyde, the carrier are the oxide coated (Al of charcoal2O3、SiO2、ZrO2, ZnO, MgO etc.), catalyst is urged for support type
Agent.Catalyst precursor is first prepared using equi-volume impregnating, the presoma is then handled under an atmosphere of hydrogen and catalysis is made
Agent.Since copper can generate methane with catalytic carbon and hydrogen reaction, so the copper nano-particle formed " can penetrate " layer of charcoal, with oxygen
Compound surface contacts and forms chemical interactions.Wherein, the innovation of catalyst includes the preparation innovation and catalyst preparation of carrier
Two aspect of innovation.Compared with traditional catalyst, prepared catalyst acetaldehyde selectivity with higher, excellent catalysis is stablized
Property, there is good prospects for commercial application.
Technical solution of the present invention:
A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, and the active component of the catalyst is Cu, the carrier of catalyst
For the oxide coated compound of charcoal；The component for including in catalyst by percentage to the quality,
Using Cu as active component, active component is 0.1~30wt% of catalyst quality；
Using the oxide coated compound of charcoal as carrier, carrier is 70~99.9wt% of catalyst quality；Wherein, charcoal is
0.5~50wt% of carrier quality, remaining is oxide.
The charcoal source can be any forms such as unformed, graphitization；May further choose ethylene glycol, glucose,
Sucrose, furfuryl alcohol, ethylene, the one of which in acetylene, but it is not limited only to these charcoal sources.
The oxide carrier can be Al2O3、SiO2、ZrO2, ZnO, MgO etc., preferred embodiment SiO2, include SBA-
15, unformed SiO2Etc. different pattern and aperture size.
When the oxide coated compound of charcoal is that charcoal coats SiO2Compound when, active component be catalyst quality 5
~30wt%, charcoal are 10~40wt% of carrier quality, remaining is oxide.
A kind of ethyl alcohol direct dehydrogenation prepares the method for preparing catalyst of acetaldehyde, including preparation catalyst carrier method and preparation
Catalyst method, the specific steps are as follows:
The first step, preparation catalyst carrier method include using liquid charcoal source as the method for charcoal source preparation catalyst carrier
Method with using gas charcoal source as charcoal source preparation catalyst carrier
The first, uses liquid charcoal source as the method for charcoal source preparation catalyst carrier
1. dose volume score is the charcoal source solution of 5~80vol%, while oxalic acid is added as catalyst；
2. charcoal source solution incipient impregnation oxide carrier 1~3 time 1. prepared with step, it is stored at room temperature 0.5~10h,
It is dry；
3. the product 2. step is dried after is in an inert atmosphere in 600~850 DEG C of 0.5~10h of stops to get to charcoal bag
Cover the compound of oxide.
It is the mixing of one or more of methanol, ethyl alcohol, benzene, trimethylbenzene with solvent needed for the solution of charcoal processing source, it is excellent
Select trimethylbenzene；
Second, method of the using gas charcoal source as charcoal source preparation catalyst carrier
1. oxide carrier is placed in flat-temperature zone, lazy using chemical vapor deposition method for preparing carbon/carbon oxide coated compound
Property atmosphere purging；
2. the product 1. step is dried after is warming up to 500~900 DEG C of 0.5~10h of stop in an inert atmosphere；It is then logical
Enter the mixed gas of gas charcoal source and inert gas, wherein in mixed gas the volume fraction in gas charcoal source be 0.1~
99.9vol%；The 0.1-5h compound oxide coated to get charcoal is stopped in 500~900 DEG C；Gas charcoal source is closed, is changed into lazy
Property gas, after continuing 1~10h of purging, is down to room temperature.
Inert gas can be He, Ar, N2At least one of.
Second step prepares catalyst method
1. preparing copper salt solution and/or mantoquita alcoholic solution, the oxide coated compound of charcoal prepared by the first step is carried
Body is impregnated in copper salt solution and/or mantoquita alcoholic solution 1~3 time, is stored at room temperature 0.5~2h, dry；
2. by step 1. dry after product in 350~450 DEG C through hydrogen atmosphere restore 1~5h to get arrive the load
Type composite catalyst.
The concentration of the copper salt solution is 0.075g/mL~0.75g/mL, and the concentration of mantoquita alcoholic solution is 0.075g/
ML~0.225g/mL.
The mantoquita is selected from least one of chloride, nitrate or acetate.
Alcoholic solvent can choose at least one of methanol, ethyl alcohol.
The original content of going back of hydrogen atmosphere is 5~20vol%H2/N2、H2/He、H2One of/Ar.
A kind of method that alcohol dehydrogenase prepares acetaldehyde, in 140~350 DEG C of reaction temperature and reaction pressure 0.1MPa condition
Under, ethyl alcohol is passed through in the reactor for being loaded with above-mentioned catalyst, direct dehydrogenation produces acetaldehyde.
Beneficial effects of the present invention: catalyst provided by the invention has very high acetaldehyde selectivity, and acetaldehyde selectivity is high
In 92.1%；The catalyst has excellent stability simultaneously, substantially without inactivation (Cu/10C/SiO in test 40h2For).
This is mainly due to charcoal material surface inertia, have a small amount of oxygen-containing functional group, promote the desorption of acetaldehyde, and then inhibit acetaldehyde
Occur secondary response (as shown in Figure 5)；Cu and oxide surface, which pass through chemical bonding, simultaneously has chemical interaction, guarantees
The stability of copper at reaction conditions.Further, the application preparation method is simple, does not need to add any auxiliary agent.
Detailed description of the invention
Fig. 1 is the 10Cu/C/SiO of embodiment 32XRD spectrum after furfuryl alcohol reduction.
Fig. 2 is the residence time of embodiment 7 to 10Cu/9C/SiO2The map that furfuryl alcohol sample products selectively influence.
Fig. 3 is the residence time of embodiment 7 to 10Cu/9C/SiO2The map that furfuryl alcohol sample ethanol conversion influences.
Fig. 4 is the residence time of embodiment 7 to 10Cu/SiO2The map that sample products selectively influence.
Fig. 5 is the residence time of embodiment 7 to 10Cu/SiO2The map that sample ethanol conversion influences.
Fig. 6 is the 10Cu/9C/SiO of embodiment 82Variation diagram of the conversion ratio and selectivity of furfuryl alcohol sample in 40h.
Specific embodiment
Detailed statement is made to the present invention below by way of some embodiments, but the invention is not limited to these embodiments.
Carrier nC/MOxCarbon source indicates, in which:
The quality of n=cladding layer of charcoal accounts for percentage composition × 100 of total weight of carrier；Charcoal source-representation uses ethylene glycol, grape
Sugar, sucrose, furfuryl alcohol, ethylene, the one of which in acetylene.
Catalyst is indicated with mCu/ carrier, in which:
M=Cu load capacity accounts for percentage composition × 100 of total catalyst weight.
Embodiment 1
SiO2Coat the preparation process of high-area carbon:
(1) using trimethylbenzene as solvent, furfuryl alcohol/front three benzole soln of 10 and 40vol% is prepared, while Microamounts of Oxalic Acid work is added
For catalyst；
(2) furfuryl alcohol solution incipient impregnation carrier 1 time prepared with step (1)；0.5~2h is stored at room temperature after having impregnated；
(3) mixture after standing step (2) places dry 12h respectively at 60 DEG C and 80 DEG C of baking ovens；
(4) product by step (3) after dry under Ar atmosphere in 150 DEG C of dry 3h, then at 850 DEG C of stop 2h to get
SiO is coated on to the C2The C/SiO on surface2Compound.
(5) 10 and 40vol% furfuryl alcohol/front three benzole soln, SiO are used2The thickness of surface layer of charcoal is respectively 0.5 and 1.5nm,
Carbon content is respectively 9 and 24wt%, and resulting vehicle is denoted as 9C/SiO respectively2Furfuryl alcohol and 24C/SiO2Furfuryl alcohol.
Embodiment 2
Al2O3Coat the preparation process of high-area carbon:
(1) using acetylene as charcoal source, using the C/Al of the method preparation layer of charcoal clad surface of chemical vapor deposition2O3Compound load
Body；
2. chemical vapor deposition stove is horizontal positioned, the porcelain boat for being loaded with 1.0g sample is placed on to the flat-temperature zone of stove, Ar is blown
Sweep 30min；
3. 2. Al that step is placed2O3In lower 150 DEG C of Ar inert atmosphere dry 2h, the impurity such as surface adsorption water are removed；
4. the product 3. step is dried after is warming up to 600 DEG C of stop 1h under Ar inert atmosphere；It is subsequently passed 100mL/
The 10vol%C of min2H2/ Ar gas is coated on Al then at 600 DEG C of stop 0.1h to get to the C2O3The C/Al on surface2O3It is multiple
Close object.It is then turned off C2H2/ Ar gas, changes Ar gas into, continues after purging 1h, is down to room temperature.Carbon content is after tested
8.6wt%, theoretical carbon layer~1.6nm, is denoted as 8.6C/Al2O3-C2H2。
Embodiment 3
9C/SiO2Furfuryl alcohol and 24C/SiO2The preparation process of furfuryl alcohol loaded Cu catalyst:
(1) 9C/SiO is taken2Furfuryl alcohol, the dry 2h in 120 DEG C of air flow ovens, removes surface physics and adsorbs water；
(2) at 25 DEG C, the Cu (NO prepared by number 3 in table 1 is taken3)2·3H2O aqueous solution incipient impregnation step (1)
The 9C/SiO being dried to obtain2On furfuryl alcohol charcoal, 2h is stood；
(3) mixture after standing step (2) obtains catalyst precursor in 50 DEG C of dry 10h；
(4) catalyst precursor for obtaining step (3) is in 140 DEG C of dry 0.5h, subsequent 450 DEG C of hydrogen reduction 2h
(10vol%H2/N2), 10Cu/9C/SiO is made2Furfuryl alcohol (number 3 in table 1) catalyst.
(5)24C/SiO2Furfuryl alcohol copper-loading catalyst process is identical as above-mentioned steps, number 7 in corresponding table 1.
The XRD spectrum of gained catalyst is as shown in Figure 1.
The preparation condition process of other catalyst is same as Example 3.The corresponding relationship of sample number into spectrum and preparation condition is such as
Shown in table 1.
The sample number into spectrum of 1 embodiment 3 of table and the corresponding relationship of preparation condition
Embodiment 4
8.6C/Al2O3-C2H2The preparation process of loaded Cu catalyst:
(1) 8.6C/Al is taken2O3-C2H2, the dry 2h in 120 DEG C of air flow ovens, removing surface physics absorption water；
(2) at 25 DEG C, the Cu (NO prepared by number 3 in table 1 is taken3)2·3H2O ethanol solution incipient impregnation step
(1) 8.6C/Al being dried to obtain2O3-C2H2On charcoal, 2h is stood；
(3) mixture after standing step (2) obtains catalyst precursor in 50 DEG C of dry 10h；
(4) catalyst precursor for obtaining step (3) is in 140 DEG C of dry 0.5h, subsequent 450 DEG C of hydrogen reduction 2h
(10vol%H2/N2), 3Cu/8.6C/Al is made2O3-C2H2(number 13 in table 1) catalyst.
Embodiment 5
The experiment of the composite carrier load Cu catalyst alcohol dehydrogenase of different oxides and charcoal.
Using ethyl alcohol as raw material, carry out Dehydrogenating reaction of alcohol in fixed bed reactors.Reaction condition is as follows: being in internal diameter
Loading catalyst in the fixed bed reactors of 8mm, normal pressure, 260 DEG C of reaction temperature, ethanol phase flow rate is 0.3mL/h.Reaction is steady
After fixed, reaction raw materials and the analysis of product utilization on-line chromatograph.Sample number into spectrum and the active corresponding relationship of alcohol dehydrogenase such as 2 institute of table
Show.
The sample number into spectrum and the active corresponding relationship of alcohol dehydrogenase of 2 embodiment 5 of table
Embodiment 6
10Cu/9C/SiO at different temperatures2Furfuryl alcohol catalysis ethanol dehydrogenation reaction.
Using ethyl alcohol as raw material, carry out Dehydrogenating reaction of alcohol in fixed bed reactors.Reaction condition is as follows: being in internal diameter
Load 0.1g catalyst in the fixed bed reactors of 8mm, normal pressure, 160~300 DEG C of reaction temperature, ethanol phase flow rate is
0.3mL/h, GHSV=26,000h-1.After stable reaction, reaction raw materials and the analysis of product utilization on-line chromatograph.Reaction result such as table
Shown in 3.
The reaction temperature and 10Cu/9C/SiO of 3 embodiment 6 of table2The corresponding relationship of furfuryl alcohol catalysis ethanol dehydrogenation activity
Embodiment 7
10Cu/9C/SiO2Furfuryl alcohol and 10Cu/SiO2The product of the catalysis ethanol dehydrogenation under the different residence times is distributed real
It tests.Using ethyl alcohol as raw material, carry out Dehydrogenating reaction of alcohol in fixed bed reactors.Reaction condition is as follows: being consolidating for 8mm in internal diameter
The different amounts of catalyst of filling in fixed bed reactor, normal pressure, 260 DEG C of reaction temperature, ethanol phase flow rate is 0.3mL/h.Reaction
After stabilization, reaction raw materials and the analysis of product utilization on-line chromatograph.The gained residence time is to selectivity of product and ethanol conversion shadow
Loud map is as shown in Fig. 2,3,4,5.
Embodiment 8
10Cu/9C/SiO2The stability test of furfuryl alcohol catalysis ethanol dehydrogenation is tested.
Using ethyl alcohol as raw material, carry out Dehydrogenating reaction of alcohol in fixed bed reactors.Reaction condition is as follows: being in internal diameter
The different amounts of catalyst of filling in the fixed bed reactors of 8mm, normal pressure, 260 DEG C of reaction temperature, ethanol phase flow rate is 0.3mL/
h.After stable reaction, reaction raw materials and the analysis of product utilization on-line chromatograph.Conversion ratio and selectivity are within the reaction time of 40h
Variation diagram is as shown in Figure 6.
Claims (8)
1. the preparation method that a kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, which is characterized in that the active group of the catalyst
It is divided into Cu, catalyst carries the oxide coated compound of charcoal；The component for including in catalyst is by percentage to the quality, with Cu
Active component, active component are 0.1~30wt% of catalyst quality；Using the oxide coated compound of charcoal as carrier, carrier
For 70~99.9wt% of catalyst quality；Wherein, charcoal is 0.5~50wt% of carrier quality, remaining is oxide；The preparation
Method includes preparation catalyst carrier method and prepares catalyst method, the specific steps are as follows:
The first step, preparation catalyst carrier method include using liquid charcoal source as the method for charcoal source preparation catalyst carrier and making
Use gas charcoal source as the method for charcoal source preparation catalyst carrier
The first, uses liquid charcoal source as the method for charcoal source preparation catalyst carrier
1. dose volume score is the charcoal source solution of 5~80vol%, while oxalic acid is added as catalyst；
2. charcoal source solution incipient impregnation oxide carrier 1~3 time 1. prepared with step, it is stored at room temperature 0.5~10h, it is dry；
3. the product 2. step is dried after coats oxygen in 600~850 DEG C of 0.5~10h of stop in an inert atmosphere to get to charcoal
The compound of compound；
Second, method of the using gas charcoal source as charcoal source preparation catalyst carrier
1. using the oxide coated compound of chemical vapor deposition method for preparing carbon/carbon, oxide carrier is placed in flat-temperature zone, inertia atmosphere
Enclose purging；
2. the product 1. step is dried after is warming up to 500~900 DEG C of 0.5~10h of stop in an inert atmosphere；It is subsequently passed gas
The mixed gas in body charcoal source and inert gas, wherein the volume fraction in gas charcoal source is 0.1~99.9vol% in mixed gas；
The 0.1-5h compound oxide coated to get charcoal is stopped in 500~900 DEG C；Gas charcoal source is closed, changes inert gas into, after
After 1~10h of continuous purging, it is down to room temperature；
Second step prepares catalyst method
1. preparing copper salt solution and/or mantoquita alcoholic solution, the oxide coated complexes carrier of charcoal prepared by the first step soaks
Stain is stored at room temperature 0.5~2h 1~3 time in copper salt solution and/or mantoquita alcoholic solution, dry；
2. the product 1. step is dried after restores 1~5h through hydrogen atmosphere in 350~450 DEG C and answers to get to the support type
Close catalyst.
2. the preparation method that ethyl alcohol direct dehydrogenation according to claim 1 prepares the catalyst of acetaldehyde, which is characterized in that institute
The oxide carrier stated is Al2O3、SiO2、ZrO2, ZnO or MgO.
3. the preparation method that ethyl alcohol direct dehydrogenation according to claim 2 prepares the catalyst of acetaldehyde, which is characterized in that when
The oxide coated compound of charcoal is that charcoal coats SiO2Compound when, active component be catalyst quality 5~30wt%, charcoal
For 10~40wt% of carrier quality, remaining is oxide.
4. preparation method according to claim 1, which is characterized in that be with solvent needed for the solution of charcoal processing source in the first step
The mixing of one or more of methanol, ethyl alcohol, benzene, trimethylbenzene.
5. preparation method according to claim 1 or 4, which is characterized in that the mantoquita be selected from chloride, nitrate or
The concentration of at least one of acetate, copper salt solution is 0.075g/mL~0.75g/mL, and the concentration of mantoquita alcoholic solution is
0.075g/mL~0.225g/mL.
6. preparation method according to claim 1 or 4, which is characterized in that wherein, hydrogen atmosphere go back original content be 5~
20vol%H2/N2、H2/He、H2One of/Ar.
7. preparation method according to claim 5, which is characterized in that wherein, hydrogen atmosphere go back original content be 5~
20vol%H2/N2、H2/He、H2One of/Ar.
8. a kind of catalyst that the preparation method described in claim 1-3 is made carries out the method that alcohol dehydrogenase prepares acetaldehyde,
It is characterized in that, under the conditions of 140~350 DEG C of reaction temperature and reaction pressure 0.1MPa, ethyl alcohol is passed through and is loaded with above-mentioned catalyst
Reactor in, direct dehydrogenation produce acetaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611118124.5A CN106673977B (en) | 2016-12-07 | 2016-12-07 | A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611118124.5A CN106673977B (en) | 2016-12-07 | 2016-12-07 | A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, preparation method and applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106673977A CN106673977A (en) | 2017-05-17 |
| CN106673977B true CN106673977B (en) | 2019-06-07 |
Family
ID=58869167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611118124.5A Active CN106673977B (en) | 2016-12-07 | 2016-12-07 | A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106673977B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109894110B (en) * | 2017-12-07 | 2020-10-09 | 中国科学院大连化学物理研究所 | Catalyst and preparation method thereof, and method for preparing acetaldehyde by ethanol dehydrogenation |
| CN108620095B (en) * | 2018-05-16 | 2020-09-29 | 扬州工业职业技术学院 | Composite catalyst and application thereof in synthesis of glyceraldehyde |
| CN110385139B (en) * | 2019-08-20 | 2022-05-17 | 大连理工大学 | Catalyst for preparing acetaldehyde by directly dehydrogenating ethanol, preparation method and application |
| RU2752678C1 (en) * | 2019-09-25 | 2021-07-29 | федеральное государственное автономное образовательное учреждение высшего образования "Российский университет дружбы народов" (РУДН) | Method for preparing ethanol dehydrogenation catalysts |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013484A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Carbon-alumina supported copper oxide catalyst, preparation method and applications thereof |
| CN105148911A (en) * | 2015-05-28 | 2015-12-16 | 大连理工大学 | Catalyst for preparing acetaldehyde by ethanol dehydrogenation and its preparation method and use |
-
2016
- 2016-12-07 CN CN201611118124.5A patent/CN106673977B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013484A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Carbon-alumina supported copper oxide catalyst, preparation method and applications thereof |
| CN105148911A (en) * | 2015-05-28 | 2015-12-16 | 大连理工大学 | Catalyst for preparing acetaldehyde by ethanol dehydrogenation and its preparation method and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106673977A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106673977B (en) | A kind of ethyl alcohol direct dehydrogenation prepares the catalyst of acetaldehyde, preparation method and applications | |
| US20230096172A1 (en) | A catalyst for propane dehydrogenation to propylene and its preparation method and application | |
| CN105727980B (en) | A kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane | |
| CN106944147B (en) | Heteropoly acid ammonium type catalyst and preparation method thereof | |
| CN105148911B (en) | The catalyst, its preparation method and application of acetaldehyde are prepared for alcohol dehydrogenase | |
| CN105013484A (en) | Carbon-alumina supported copper oxide catalyst, preparation method and applications thereof | |
| CN105435779A (en) | A catalyst for gas-phase synthesis of oxalate from carbon monoxide | |
| CN104722301B (en) | A kind of selective glycerol aoxidizes the preparation method and applications method of the catalyst of dihydroxy acetone processed | |
| CN106944087A (en) | A kind of preparation method of producing isobutene from oxidative dehydrogenation of isobutane catalyst | |
| CN103880661B (en) | A kind of catalysis ethanol direct dehydrogenation is prepared the method for ethyl acetate | |
| CN103130625B (en) | Method for preparing acetaldehyde and co-producing acetal by using ethanol | |
| CN106944143B (en) | Heteropoly acid ammonium type catalyst and its preparation method | |
| CN102173977B (en) | Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol | |
| CN106281526B (en) | A kind of method that two-step method prepares liquefied petroleum gas | |
| CN105642351A (en) | Heteropolyacid ammonium salt catalyst and preparation method thereof | |
| CN102153446A (en) | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis | |
| CN110026191B (en) | Catalyst and method for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol | |
| CN106944136B (en) | A kind of heteropoly acid ammonium salt form catalyst and its preparation method | |
| CN110385139A (en) | Ethyl alcohol direct dehydrogenation prepares catalyst, preparation method and the application of acetaldehyde | |
| CN110075910A (en) | A kind of method of modifying for ethyl alcohol and benzene alkylation reaction IM-5 molecular sieve catalyst | |
| CN104672058A (en) | Method of preparing 1, 3-propanediol by virtue of hydrogenation of glycerol | |
| CN1364655A (en) | Carbon nanometer tube copper-base dmethanol synthesis promoting catalyst and its preparing method | |
| KR20220069110A (en) | Catalyst for production of isopropylbenzene, and method and use thereof | |
| Neramittagapong et al. | Acetaldehyde production from ethanol over Ni-based catalysts | |
| CN106944148B (en) | A kind of preparation method of heteropoly acid ammonium catalyst |
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 |