CN108126696B - A kind of ethyl alcohol synthesis of acetic acid catalyst and preparation method and acetic acid - Google Patents
A kind of ethyl alcohol synthesis of acetic acid catalyst and preparation method and acetic acid Download PDFInfo
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- CN108126696B CN108126696B CN201810078381.3A CN201810078381A CN108126696B CN 108126696 B CN108126696 B CN 108126696B CN 201810078381 A CN201810078381 A CN 201810078381A CN 108126696 B CN108126696 B CN 108126696B
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- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
Abstract
The present invention relates to a kind of preparation methods of ethyl alcohol synthesis of acetic acid catalyst, comprising: S1: carbon nanotube is pre-processed, and obtains pretreatment carbon nanotube；S2: pretreatment carbon nanotube is handled with aqueous hydrogen peroxide solution, obtains hydrogen peroxide treatment carbon nanotube；S3: H is prepared2PtCl6·6H2O and PdCl2Mixed aqueous solution, hydrogen peroxide treatment carbon nanotube is added in mixture aqueous solution, is ultrasonically treated, it is sufficiently dry, obtain catalyst precursor；S4: catalyst precursor is subjected to two sections of temperature programming calcination processings of staged in reducing atmosphere and inert atmosphere respectively to get the catalyst.The preparation method passes through multiple unique preparation steps, and the selection and determination of multiple unique technology features in each step, so as to obtain the ethyl alcohol synthesis of acetic acid catalyst with excellent properties, so that preparing acetic acid for ethyl alcohol provides catalyst completely new, with superperformance.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof and its application, relate more particularly to a kind of ethyl alcohol synthesis of acetic acid
Catalyst (i.e. the catalyst as used in ethyl alcohol synthesis of acetic acid is referred to as " ethyl alcohol synthesis of acetic acid catalyst " below) and preparation
Method and acetic acid belong to catalyst technology and acetic acid preparation technical field.
Background technique
In chemical technology field, acetic acid is a kind of very important Organic Chemicals, and purposes is very extensive, can be used for
A variety of subsequent chemical industry substances such as vinyl acetate monomer, aceticanhydride, terephthalic acid (TPA), acetates, cellulose acetate are produced, spy is standby to be
With the fast development of terephthalic acid (TPA) and acetic acid downstream product, ethylene production has become the one of chemical field and national economy
A important component.
Currently, acetic acid production mainly include catalytic oxidation technique (ethyl alcohol-acetaldehyde oxidation, ethylene-acetaldehyde oxidation) and
Methyl alcohol carbonyl synthetic technique etc..Consider that methyl alcohol carbonyl synthetic technique is using coal tar, natural gas, heavy oil as base from production technology angle
This raw material especially can be used cheap natural gas and coal instead of petroleum as raw material, be very suitable for coal in China deposit
The fundamental realities of the country that more, petroleum resources lack, therefore the technique occupies leading position in the commercial acetic acid production in China.
But on the other hand, with the rapid development of society, either catalytic oxidation technique or methyl alcohol carbonyl synthetic work
Skill, all refers to fossil resource in corresponding reaction process raw material, and this kind of fossil resource can not reproducibility keep it increasingly withered
It exhausts, corresponding energy crisis also forces people to seek new renewable and clean energy resource to substitute conventional fossil resource.In addition, the energy
Diversification and the sustainable development of production also have a very important significance, this energy safeguard and safety to China
With urgent realistic meaning.
Ethyl alcohol is also a kind of important basic chemical industry raw material, and especially it can be the fermented system of raw material by biomass
It obtains (namely bio-ethanol).In China, large-scale industry has been realized using agricultural crop straw fiber matter raw material production ethyl alcohol
Metaplasia produces.In view of the reproducibility of biomass resource, bio-ethanol is produced with this technique, overcomes the office of traditional fossil resources
The sustainability of production may be implemented in limit.
With the further investigation to oxidation of ethanol technology, had already research achievement [such as
Angew.Chem.Int.Ed.2006,45,4648] [J.Catal.2007,251,332 etc.] shows load type gold, platinum, palladium base
There is catalyst certain Catalytic oxidation of ethanol performance, especially Au-based catalyst to show high catalytic reaction activity, thus
It can be used for oxidation of ethanol and prepare acetic acid.
But it is generally speaking, still fewer for the research of catalyst used in oxidation of ethanol acetic acid, in a few studies
Also there are still certain defects in the reaction, such as catalyst amount is excessive, catalytic activity is not high, acetic acid producing rate is excessively low, this
There is still a need for it is further studied and improved.Therefore, for novel ethyl alcohol synthesis of acetic acid catalyst and its preparation and
There are still necessity and demand for continuing research for application method, this is also exactly the power place and starting point that the present invention is accomplished.
Summary of the invention
It is being paid to research and develop novel ethyl alcohol synthesis of acetic acid catalyst and its preparation method and application method, the present inventor
After a large amount of creative experiments are explored, the ethyl alcohol synthesis of acetic acid catalyst is invented by further investigation, and then complete
The present invention.Specifically, the present invention relates to following aspects.
First aspect, the present invention provides a kind of preparation method of ethyl alcohol synthesis of acetic acid catalyst, the preparation methods
Include the following steps:
S1: carbon nanotube is pre-processed, and obtains pretreatment carbon nanotube；
S2: the pretreatment carbon nanotube is handled with aqueous hydrogen peroxide solution, hydrogen peroxide treatment carbon is obtained and receives
Mitron；
S3: H is prepared2PtCl6·6H2O and PdCl2Mixed aqueous solution, by the hydrogen peroxide treatment carbon nanotube be added
Into the mixture aqueous solution, ultrasonic treatment is then sufficiently dry, obtains catalyst precursor；
S4: the catalyst precursor is carried out to two sections of program liters of staged in reducing atmosphere and inert atmosphere respectively
Warm calcination processing is to get the ethyl alcohol synthesis of acetic acid catalyst.
In the preparation method of the ethyl alcohol synthesis of acetic acid catalyst of the invention, the step S1 is specific as follows: by carbon
Nanotube is placed in the concentrated nitric acid that mass percent concentration is 66-70%, is sufficiently stirred 50-60 minutes at 25 DEG C at room temperature,
It then heats to 120 DEG C and flows back 6 hours at such a temperature, filtering sufficiently washs much filtrate with deionized water, until eluate
For neutrality, then it is dried in vacuo completely to get the pretreatment carbon nanotube at 80 DEG C.
Wherein, there is no stringent restrictions for the dosage of the concentrated nitric acid, as long as carbon nanotube sufficiently can be impregnated,
Those skilled in the art can carry out suitable determination and selection, no longer be described in detail herein.
Wherein, the carbon nanotube is preferably multi-walled carbon nanotube, for example, the outer diameter of the multi-walled carbon nanotube can be
20-40nm, length can be 5-15 μm, and specific surface area can be 80-140m2/g.Multi-walled carbon nanotube is a kind of commercially available
Known carbon nanotube, can be commercially available by multiple channel, is no longer described in detail herein.
In the preparation method of the ethyl alcohol synthesis of acetic acid catalyst of the invention, the step S2 is specific as follows: room temperature
Under, the pretreatment carbon nanotube is placed in the aqueous hydrogen peroxide solution that mass percent concentration is 35-45%, magnetic agitation
10-14 hours, filtering sufficiently washed much filtrate with deionized water, until eluate is neutrality, had then been dried in vacuo at 80 DEG C
Entirely to get the hydrogen peroxide treatment carbon nanotube.
Wherein, there is no stringent restrictions for the dosage of the aqueous hydrogen peroxide solution, as long as can be by the pretreatment carbon
Nanotube sufficiently impregnates, and those skilled in the art can carry out suitable determination and selection, is no longer described in detail herein.
In the preparation method of the ethyl alcohol synthesis of acetic acid catalyst of the invention, the step S3 includes the following steps:
S3-1: H is weighed according to the molar ratio of 1:0.3-32PtCl6·6H2O and PdCl2, by both substances be added to for
In the deionized water of 180-220 times of its gross mass, and dissolution is sufficiently stirred, obtains dipping solution；
S3-2: it weighs as H2PtCl6·6H2O and PdCl2At the hydrogen peroxide of both 10-20 times of substance gross masses
Carbon nanotube is managed, and is added in the dipping solution, is ultrasonically treated at room temperature, ultrasonic power density is 0.35-0.55W/
cm2, 80 DEG C are then heated to, solvent volatilization completely, and residue is sufficiently dried to get the catalyst precursor.
Wherein, in the step S3-1, H2PtCl6·6H2O and PdCl2Molar ratio be 1:0.3-3, may be, for example, 1:
0.3,1:0.6,1:0.9,1:1.2,1:1.5,1:1.8,1:2.1,1:2.4,1:2.7 or 1:3, most preferably 1:1.
Wherein, in the step S3-2, the ultrasonic time of the ultrasonic treatment should make in finally obtained ethyl alcohol
In catalyst for preparing acetic acid, the two gross mass counted using simple substance Pt and simple substance Pd is the 0.5- of ethyl alcohol catalyst for preparing acetic acid quality
1.5% (namely the total load amount of both simple substance Pt and simple substance Pd be 0.5-1.5wt%), may be, for example, 0.5%, 0.7%,
0.9%, 1.1%, 1.3% or 1.5%, most preferably 1%.
Wherein, in the step S3-2, the ultrasonic power density of the ultrasonic treatment is 0.35-0.55W/cm2, such as
It can be 0.35W/cm2、0.4W/cm2、0.45W/cm2、0.5W/cm2Or 0.55W/cm2, most preferably 0.45W/cm2。
In the preparation method of the ethyl alcohol synthesis of acetic acid catalyst of the invention, the step S4 includes the following steps:
S4-1: the catalyst precursor is placed in the hydrogen atmosphere of reproducibility, at room temperature with 3 DEG C/min of liter
Warm rate is warming up to temperature T1, heat preservation calcining 180-220 minutes at temperature T1；
After the completion of S4-2: step S4-1 heat preservation calcining, the hydrogen atmosphere of reproducibility is replaced as inert nitrogen atmosphere,
Continue to be warming up to temperature T2 by T1 with 5 DEG C/min of heating rate, heat preservation calcining 100-120 minutes, heat preservation at temperature T2
After the completion of calcining, continue to remain nitrogen atmosphere, and cooled to room temperature is to get the ethyl alcohol synthesis of acetic acid catalyst.
Wherein, in the step S4-1, the temperature T1 is 200 ± 10 DEG C, may be, for example, 190 DEG C, 200 DEG C or 210
℃。
Wherein, in the step S4-2, the temperature T2 is 300 ± 10 DEG C, may be, for example, 290 DEG C, 300 DEG C or 310
℃。
As described above, the preparation method is logical the present invention provides a kind of preparation method of ethyl alcohol synthesis of acetic acid catalyst
The selection and determination of multiple unique technology features in multiple unique preparation steps and each step are crossed, so as to
To a kind of ethyl alcohol synthesis of acetic acid catalyst with excellent properties, to be provided completely newly for the preparation that oxidation of ethanol obtains acetic acid
Catalyst, and have good catalytic performance.
The second aspect, the present invention relates to the ethyl alcohol synthesis of acetic acid catalyst according to obtained by above-mentioned preparation method.
By the study found that the ethyl alcohol synthesis of acetic acid catalyst obtained such as the method has excellent catalytic activity, such as
Ethanol conversion, acetic acid selectivity and cyclical stability etc., to have a good application prospect in ethyl alcohol synthesis of acetic acid field
And industrial production potential.
In terms of third, the present invention provides a kind of method that ethyl alcohol prepares acetic acid, this method is synthesized using the ethyl alcohol
Acetic acid catalyst.
More specifically, the method specifically: the ethyl alcohol synthesis of acetic acid catalyst is placed in autoclave, is added
Entering ethyl alcohol or ethanol water, is passed through air until pressure is 3-4MPa, sealing is reacted 3-6 hours at 140-180 DEG C, thus
Obtain acetic acid.
Ethyl alcohol in the acetic acid, in the ethyl alcohol synthesis of acetic acid catalyst and ethyl alcohol or ethanol water
Mass ratio be 1:5-15 (mass ratio of the ethyl alcohol synthesis of acetic acid catalyst and ethyl alcohol be 1:5-15 or the ethyl alcohol close
Mass ratio at ethyl alcohol contained in acetic acid catalyst and ethanol water is 1:5-15), it may be, for example, 1:5,1:10 or 1:
1.5。
In the acetic acid, air is passed through until pressure is 3-4MPa, the volume for being passed through air is (i.e. high
Spatial volume in pressure reaction kettle in addition to liquid) it should be able to make oxygen contained therein that all ethyl alcohol are all at least up to oxidized to second
1.5 times of required amounts of acid, those skilled in the art can carry out suitably selecting and determining, no longer be described in detail herein.
As described above, the present invention provides a kind of ethyl alcohol synthesis of acetic acid catalyst and preparation method thereof and acetic acid preparation side
Method, the ethyl alcohol synthesis of acetic acid catalyst have excellent catalytic properties, to have in acetic acid preparation technical field good
Application prospect and industrialized production and application potential.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used to enumerate the present invention, not constitutes any type of any restriction to real protection scope of the invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
Embodiment 1: the preparation of oxidation of ethanol catalyst for preparing acetic acid
S1: carbon nanotube is pre-processed, and obtains pretreatment carbon nanotube；The step is specific as follows:
By multi-walled carbon nanotube (be purchased from Nanometer Port Co., Ltd., Shenzhen, outer diameter 20-40nm, length be 5-15 μm, than
Surface area is 80-140m2/ g) it is placed in the concentrated nitric acid that appropriate mass percent concentration is 66%, at room temperature at 25 DEG C sufficiently
Stirring 60 minutes then heats to 120 DEG C and flows back 6 hours at such a temperature, and filtering is sufficiently washed with deionized water and filtered out
Then object is dried in vacuo completely to get the pretreatment carbon nanotube at 80 DEG C until eluate is neutrality；
S2: the pretreatment carbon nanotube is handled with aqueous hydrogen peroxide solution, hydrogen peroxide treatment carbon is obtained and receives
Mitron；The step is specific as follows:
At room temperature, by it is described pretreatment carbon nanotube be placed in appropriate mass percent concentration be 35% hydrogen peroxide it is water-soluble
In liquid, magnetic agitation 14 hours, filtering sufficiently washed much filtrate with deionized water, until eluate is neutrality, then at 80 DEG C
Vacuum drying is completely to get the hydrogen peroxide treatment carbon nanotube；
S3: H is prepared2PtCl6·6H2O and PdCl2Mixed aqueous solution, by the hydrogen peroxide treatment carbon nanotube be added
Into the mixture aqueous solution, ultrasonic treatment is then sufficiently dry, obtains catalyst precursor；Specifically comprise the following steps:
S3-1: H is weighed according to the molar ratio of 1:12PtCl6·6H2O and PdCl2, both substances are added to as it always
In the deionized water that 180 times of quality, and dissolution is sufficiently stirred, obtains dipping solution；
S3-2: it weighs as H2PtCl6·6H2O and PdCl2The hydrogen peroxide treatment of 10 times of both substance gross masses
Carbon nanotube, and be added in the dipping solution, (ultrasonic time of ultrasonic treatment should make final institute to ultrasonic treatment at room temperature
In obtained ethyl alcohol catalyst for preparing acetic acid, the two gross mass counted using simple substance Pt and simple substance Pd is ethyl alcohol catalyst for preparing acetic acid quality
1%), ultrasonic power density be 0.45W/cm2, 80 DEG C are then heated to, solvent volatilization is complete and residue is sufficiently dry
It is dry to get the catalyst precursor；
S4: the catalyst precursor is carried out to two sections of program liters of staged in reducing atmosphere and inert atmosphere respectively
Warm calcination processing is to get the ethyl alcohol synthesis of acetic acid catalyst；Specifically comprise the following steps:
S4-1: the catalyst precursor is placed in the hydrogen atmosphere of reproducibility, at room temperature with 3 DEG C/min of liter
Warm rate is warming up to temperature T1 (for 190 DEG C), heat preservation calcining 220 minutes at temperature T1；
After the completion of S4-2: step S4-1 heat preservation calcining, the hydrogen atmosphere of reproducibility is replaced as inert nitrogen atmosphere,
Continue to be warming up to temperature T2 (for 290 DEG C) by T1 (i.e. 190 DEG C) with 5 DEG C/min of heating rate, keeps the temperature and forge at temperature T2
It burns 120 minutes, after the completion of heat preservation calcining, continues to remain nitrogen atmosphere, and cooled to room temperature is to get ethyl alcohol synthesis of acetic acid
Catalyst is named as C1.
Embodiment 2: the preparation of oxidation of ethanol catalyst for preparing acetic acid
S1: carbon nanotube is pre-processed, and obtains pretreatment carbon nanotube；The step is specific as follows:
By multi-walled carbon nanotube (be purchased from Nanometer Port Co., Ltd., Shenzhen, outer diameter 20-40nm, length be 5-15 μm, than
Surface area is 80-140m2/ g) it is placed in the concentrated nitric acid that appropriate mass percent concentration is 70%, at room temperature at 25 DEG C sufficiently
Stirring 50 minutes then heats to 120 DEG C and flows back 6 hours at such a temperature, and filtering is sufficiently washed with deionized water and filtered out
Then object is dried in vacuo completely to get the pretreatment carbon nanotube at 80 DEG C until eluate is neutrality；
S2: the pretreatment carbon nanotube is handled with aqueous hydrogen peroxide solution, hydrogen peroxide treatment carbon is obtained and receives
Mitron；The step is specific as follows:
At room temperature, by it is described pretreatment carbon nanotube be placed in appropriate mass percent concentration be 45% hydrogen peroxide it is water-soluble
In liquid, magnetic agitation 10 hours, filtering sufficiently washed much filtrate with deionized water, until eluate is neutrality, then at 80 DEG C
Vacuum drying is completely to get the hydrogen peroxide treatment carbon nanotube；
S3: H is prepared2PtCl6·6H2O and PdCl2Mixed aqueous solution, by the hydrogen peroxide treatment carbon nanotube be added
Into the mixture aqueous solution, ultrasonic treatment is then sufficiently dry, obtains catalyst precursor；Specifically comprise the following steps:
S3-1: H is weighed according to the molar ratio of 1:12PtCl6·6H2O and PdCl2, both substances are added to as it always
In the deionized water that 220 times of quality, and dissolution is sufficiently stirred, obtains dipping solution；
S3-2: it weighs as H2PtCl6·6H2O and PdCl2The hydrogen peroxide treatment of 20 times of both substance gross masses
Carbon nanotube, and be added in the dipping solution, (ultrasonic time of ultrasonic treatment should make final institute to ultrasonic treatment at room temperature
In obtained ethyl alcohol catalyst for preparing acetic acid, the two gross mass counted using simple substance Pt and simple substance Pd is ethyl alcohol catalyst for preparing acetic acid quality
1%), ultrasonic power density be 0.45W/cm2, 80 DEG C are then heated to, solvent volatilization is complete and residue is sufficiently dry
It is dry to get the catalyst precursor；
S4: the catalyst precursor is carried out to two sections of program liters of staged in reducing atmosphere and inert atmosphere respectively
Warm calcination processing is to get the ethyl alcohol synthesis of acetic acid catalyst；Specifically comprise the following steps:
S4-1: the catalyst precursor is placed in the hydrogen atmosphere of reproducibility, at room temperature with 3 DEG C/min of liter
Warm rate is warming up to temperature T1 (for 210 DEG C), heat preservation calcining 180 minutes at temperature T1；
After the completion of S4-2: step S4-1 heat preservation calcining, the hydrogen atmosphere of reproducibility is replaced as inert nitrogen atmosphere,
Continue to be warming up to temperature T2 (for 310 DEG C) by T1 (i.e. 210 DEG C) with 5 DEG C/min of heating rate, keeps the temperature and forge at temperature T2
It burns 100 minutes, after the completion of heat preservation calcining, continues to remain nitrogen atmosphere, and cooled to room temperature is to get ethyl alcohol synthesis of acetic acid
Catalyst is named as C2.
Embodiment 3: the preparation of oxidation of ethanol catalyst for preparing acetic acid
S1: carbon nanotube is pre-processed, and obtains pretreatment carbon nanotube；The step is specific as follows:
By multi-walled carbon nanotube (be purchased from Nanometer Port Co., Ltd., Shenzhen, outer diameter 20-40nm, length be 5-15 μm, than
Surface area is 80-140m2/ g) it is placed in the concentrated nitric acid that appropriate mass percent concentration is 68%, at room temperature at 25 DEG C sufficiently
Stirring 55 minutes then heats to 120 DEG C and flows back 6 hours at such a temperature, and filtering is sufficiently washed with deionized water and filtered out
Then object is dried in vacuo completely to get the pretreatment carbon nanotube at 80 DEG C until eluate is neutrality；
S2: the pretreatment carbon nanotube is handled with aqueous hydrogen peroxide solution, hydrogen peroxide treatment carbon is obtained and receives
Mitron；The step is specific as follows:
At room temperature, by it is described pretreatment carbon nanotube be placed in appropriate mass percent concentration be 40% hydrogen peroxide it is water-soluble
In liquid, magnetic agitation 12 hours, filtering sufficiently washed much filtrate with deionized water, until eluate is neutrality, then at 80 DEG C
Vacuum drying is completely to get the hydrogen peroxide treatment carbon nanotube；
S3: H is prepared2PtCl6·6H2O and PdCl2Mixed aqueous solution, by the hydrogen peroxide treatment carbon nanotube be added
Into the mixture aqueous solution, ultrasonic treatment is then sufficiently dry, obtains catalyst precursor；Specifically comprise the following steps:
S3-1: H is weighed according to the molar ratio of 1:12PtCl6·6H2O and PdCl2, both substances are added to as it always
In the deionized water that 200 times of quality, and dissolution is sufficiently stirred, obtains dipping solution；
S3-2: it weighs as H2PtCl6·6H2O and PdCl2The hydrogen peroxide treatment of 15 times of both substance gross masses
Carbon nanotube, and be added in the dipping solution, (ultrasonic time of ultrasonic treatment should make final institute to ultrasonic treatment at room temperature
In obtained ethyl alcohol catalyst for preparing acetic acid, the two gross mass counted using simple substance Pt and simple substance Pd is ethyl alcohol catalyst for preparing acetic acid quality
1%), ultrasonic power density be 0.45W/cm2, 80 DEG C are then heated to, solvent volatilization is complete and residue is sufficiently dry
It is dry to get the catalyst precursor；
S4: the catalyst precursor is carried out to two sections of program liters of staged in reducing atmosphere and inert atmosphere respectively
Warm calcination processing is to get the ethyl alcohol synthesis of acetic acid catalyst；Specifically comprise the following steps:
S4-1: the catalyst precursor is placed in the hydrogen atmosphere of reproducibility, at room temperature with 3 DEG C/min of liter
Warm rate is warming up to temperature T1 (for 200 DEG C), heat preservation calcining 200 minutes at temperature T1；
After the completion of S4-2: step S4-1 heat preservation calcining, the hydrogen atmosphere of reproducibility is replaced as inert nitrogen atmosphere,
Continue to be warming up to temperature T2 (for 300 DEG C) by T1 (i.e. 200 DEG C) with 5 DEG C/min of heating rate, keeps the temperature and forge at temperature T2
It burns 110 minutes, after the completion of heat preservation calcining, continues to remain nitrogen atmosphere, and cooled to room temperature is to get ethyl alcohol synthesis of acetic acid
Catalyst is named as C3.
In the following, detailed investigation has been carried out to each technical characteristic, it is specific as follows.
Embodiment 4-10:H2PtCl6·6H2O and PdCl2Molar ratio investigation
Except respectively by H in step S3-12PtCl6·6H2O and PdCl2Molar ratio replace with outside the molar ratio in the following table 1,
Other operations are identical, thus repetitive operation embodiment 1-3.The molar ratio of the two, corresponding embodiment and gained are urged
Agent name is specifically shown in shown in the following table 1.
Table 1
Embodiment 11-16: the investigation of active metal load capacity
Except respectively by the two gross mass counted in step S3-2 using simple substance Pt and simple substance Pd as ethyl alcohol catalyst for preparing acetic acid matter
Amount 1% replaces with outside following load capacity, other operations are identical, thus repetitive operation embodiment 1-3.The two
Load capacity, corresponding embodiment and the name of gained catalyst are specifically shown in shown in the following table 2.
Table 2
Embodiment 17-20: the investigation of ultrasonic power density
Except respectively by the ultrasonic power density 0.45W/cm in step S3-22It replaces with outside following ultrasonic power density,
Other operations are identical, thus repetitive operation embodiment 1-3.Ultrasonic power density, corresponding embodiment and gained are urged
Agent name is specifically shown in shown in the following table 3.
Table 3
Comparative example 1-3: the investigation of aqueous hydrogen peroxide solution processing
In addition to respectively being omitted step S2 (do not carry out hydrogen peroxide treatment, and directly by the pretreatment of step S1
The operation of carbon nanotube progress step S3), other operations are identical, to distinguish repetitive operation embodiment 1-3, sequentially
Comparative example 1-3 is obtained, gained catalyst is sequentially named as D1, D2 and D3.
Comparative example 4-6: the investigation of ultrasonication
In addition to being revised as the ultrasonic treatment in step S3-2 to stand impregnation, other operations are identical, thus
Distinguish repetitive operation embodiment 1-3, sequentially obtains comparative example 4-6, gained catalyst is sequentially named as D4, D5 and D6.
Comparative example 7-12: the investigation of calcination atmosphere
Comparative example 7-9: (reproducibility hydrogen is used always in addition to the nitrogen atmosphere in step S4-2 is replaced with hydrogen atmosphere
The all operationss of gas atmosphere progress S4-1 and S4-2), other operations are identical, to distinguish repetitive operation embodiment 1-
3, comparative example 7-9 is sequentially obtained, gained catalyst is sequentially named as D7, D8 and D9.
Comparative example 10-12: (inertia nitrogen is used always in addition to the hydrogen atmosphere in step S4-1 is replaced with nitrogen atmosphere
The all operationss of gas atmosphere progress S4-1 and S4-2), other operations are identical, to distinguish repetitive operation embodiment 1-
3, comparative example 10-12 is sequentially obtained, gained catalyst is sequentially named as D10, D11 and D12.
Comparative example 13-18: the investigation of two-part calcining
Comparative example 13-15: in addition to being omitted step S4-2, other operations are identical, to repeat to grasp respectively
Embodiment 1-3 is made, has sequentially obtained comparative example 13-15, gained catalyst is sequentially named as D13, D14 and D15.
Comparative example 16-18: (the i.e. arrival temperature T1 in addition to not carrying out heat preservation calcining in step S4-1 at corresponding temperature T1
Afterwards, no longer heat preservation calcining, but the operation of step S4-2 is carried out at once), other operations are identical, to repeat to grasp respectively
Embodiment 1-3 is made, has sequentially obtained comparative example 16-18, gained catalyst is sequentially named as D16, D17 and D18.
The method that ethyl alcohol prepares acetic acid
Acetic acid preparation test, tool are carried out respectively to the ethyl alcohol catalyst for preparing acetic acid that above-described embodiment and multiple comparative examples obtain
Gymnastics is made as follows: ethyl alcohol catalyst for preparing acetic acid being placed in autoclave, the ethyl alcohol that mass percent concentration is 40% is added
Aqueous solution, wherein the mass ratio of ethyl alcohol contained in the ethyl alcohol catalyst for preparing acetic acid and the ethanol water is 1:10, is led to
Enter enough air until pressure is 3.5MPa, sealing is reacted 4.5 hours at 160 DEG C, to obtain acetic acid.
Acetic acid preparation test is carried out to different ethyl alcohol catalyst for preparing acetic acid, after reaction, measures and calculates ethyl alcohol turn
Rate (%) and acetic acid selectivity (%):
Ethanol conversion (%)=(amount of ethyl alcohol after amount-reaction of ethyl alcohol before reacting)/amount of the preceding ethyl alcohol of reaction ×
100%；
Acetic acid selectivity (%)=(amount that acetic acid product changes into reactant ethyl alcohol into)/(before reacting after amount-reaction of ethyl alcohol
The amount of ethyl alcohol) × 100%；
The catalyst performance data of embodiment and all comparative examples synthesis is listed in the following table 4.
Table 4
Wherein, " C1/C2/C3 " indicates the numerical order corresponding to it, such as with ethanol conversion (%) " 99.8/99.7/
For 99.9 ", the ethanol conversion (%) for indicating that the ethanol conversion (%) of C1 is 99.8, C2 is 99.7, and the ethyl alcohol of C3 turns
Rate (%) is 99.9, and other similar expression also have identical corresponding relationship, and this is no longer going to repeat them.
It is to be noted that " C4/C5/ (C7-C10) " also illustrates that the numerical order corresponding to it, but " C7-C10 " institute is right
The numerical tabular answered is indicated with the section that wherein minimum value and maximum value are constituted, such as ethanol conversion (%) corresponding to it
For " 85.9-92.1 ", then it represents that in this four catalyst of C7-C10, minimum ethanol conversion (%) is 85.9%, and highest
Alcohol conversion (%) be 92.1%, the ethanol conversion (%) of remaining two kinds of catalyst then between the two numerical value,
Its similar expression also has identical meaning relationship, and this is no longer going to repeat them.
From the data of upper table 4:
1, H in step S3-12PtCl6·6H2O and PdCl2Molar ratio it is extremely important, when the two be 1:1 when can obtain
Best catalytic effect, this should can obtain Pt and Pd in catalyst under the molar ratio can play optimum synergistic catalysis
Effect, and it is bigger to deviate the value, then effect reduction is more obvious；
H in 2 but even rapid S3-12PtCl6·6H2O and PdCl2Molar ratio be most preferred 1:1 when, with simple substance Pt
Final catalytic effect is equally significantly affected with the total load amount of Pd meter, best effect can be obtained for the 1wt% moment, excessively
Or very few ethanol conversion and acetic acid selectivity is caused to decrease；It can also be seen that the identical deviation relative to 1wt%
Amount, when effect when lower than 1wt% is better than higher than 1wt% effect (such as the bias relative to same 0.3wt%,
But the effect of C13 is better than C14)；
3, the ultrasonic power density in ultrasonic treatment is extremely important, when for 0.45W/cm2When, best catalysis can be obtained
Effect, this should be due under the ultrasonic treatment of the power density, active metal can cross in nanotube duct generate it is best
Be uniformly distributed, thus have most excellent active site distribution, and then have best catalytic performance (C17-C18 reduce it is non-
Chang Xianzhu)；
4, when carbon nanotube does not carry out hydrogen peroxide treatment, then catalytic performance decreases, this is because hydrogen peroxide
Processing thoroughly handle with complete removal of impurities to carbon nanotube, obtains clean nanotube duct, is subsequent active metal
Absorption and sinter molding provide the foundation.
5, ultrasonication can significantly improve the catalytic performance of catalyst, this is because can be made by ultrasonication
Active metal is completely into duct inside and is uniformly distributed, and impregnation is then unable to reach the effect.
6, calcination atmosphere is first most preferably hydrogen atmosphere, is afterwards inert atmosphere.And works as and be all hydrogen atmosphere or inert atmosphere
When, cause catalytic performance to have significant decrease (when being especially all inert atmosphere, reducing the most significant), this is because of reducing atmosphere
It handles and high-temperature process, the two ensure that the activity of metallic compound is kept, be produced by the high-temperature calcination of subsequent second stage
Sinter molding provide high activity site.
7, two-part calcination processing can significantly affect the high-temperature calcination of catalytic effect, especially second stage (see D13-
D15), this proves the sinter molding that active site metal can be further stabilized by the high-temperature calcination of second stage and improvement
Its catalytic activity.
In conclusion passing through many skills in multiple steps in the preparation method of ethyl alcohol catalyst for preparing acetic acid of the invention
The mutual collaboration and combination of art feature, so as to the catalyst being had excellent performance.
The cyclical stability of ethyl alcohol catalyst for preparing acetic acid is tested
By taking the best C3 of performance as an example, the cyclical stability of its ethyl alcohol acetic acid ability is investigated, that is, has been repeated above-mentioned
Identical ethyl alcohol acetic acid test, respectively be recycled 20 times, 50 times and 100 times after, measure its each performance data, as a result
It see the table below 5, in order to more directly compare, the performance data (the C3 data i.e. in table 4) of first time also listed together.
Table 5
By upper table 5 as it can be seen that catalyst of the invention has excellent cyclical stability, after being recycled 100 times, still have
There are very high ethanol conversion and acetic acid selectivity；Although ethanol conversion is reduced to 92.9% recycling 100 hereafter,
The reduction very little of acetic acid selectivity, still up to 96.2%, show the cyclical stability of excellent acetic acid selectivity.
In conclusion the preparation method that the present invention is mutually cooperateed with by unique multiple technical characteristics, and obtain having excellent
The ethyl alcohol catalyst for preparing acetic acid of anisotropic energy has a good application prospect latent with industrialized production in acetic acid preparation technical field
Power can be used among the large-scale production of acetic acid.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within guarantor defined by the application the appended claims
Within the scope of shield.
Claims (8)
1. a kind of preparation method of ethyl alcohol synthesis of acetic acid catalyst, the preparation method include the following steps:
S1: carbon nanotube is pre-processed, and obtains pretreatment carbon nanotube；
S2: the pretreatment carbon nanotube is handled with aqueous hydrogen peroxide solution, obtains hydrogen peroxide treatment carbon nanotube；
S3: H is prepared2PtCl6·6H2O and PdCl2Mixed aqueous solution, the hydrogen peroxide treatment carbon nanotube is added to institute
It states in mixture aqueous solution, is ultrasonically treated, it is then sufficiently dry, obtain catalyst precursor；
S4: the catalyst precursor is subjected to two sections of temperature programmings of staged respectively in reducing atmosphere and inert atmosphere and is forged
Processing is burnt to get the ethyl alcohol synthesis of acetic acid catalyst；
The step S1 is specific as follows: carbon nanotube being placed in the concentrated nitric acid that mass percent concentration is 66-70%, in room temperature
It is sufficiently stirred at lower 25 DEG C 50-60 minutes, then heats to 120 DEG C and flows back 6 hours at such a temperature, deionization is used in filtering
Water sufficiently washs much filtrate, until eluate is neutrality, is then dried in vacuo completely to get the pretreatment carbon nanometer at 80 DEG C
Pipe.
2. preparation method according to claim 1, it is characterised in that: the step S2 is specific as follows: at room temperature, will be described
Pretreatment carbon nanotube is placed in the aqueous hydrogen peroxide solution that mass percent concentration is 35-45%, and magnetic agitation 10-14 is small
When, filtering sufficiently washs much filtrate with deionized water, until eluate is neutrality, be then dried in vacuo at 80 DEG C completely to get
The hydrogen peroxide treatment carbon nanotube.
3. preparation method according to claim 1, it is characterised in that: the step S3 includes the following steps:
S3-1: H is weighed according to the molar ratio of 1:0.3-32PtCl6·6H2O and PdCl2, both substances are added to as its total matter
In the deionized water of 180-220 times of amount, and dissolution is sufficiently stirred, obtains dipping solution；
S3-2: it weighs as H2PtCl6·6H2O and PdCl2The hydrogen peroxide treatment carbon of both 50-60 times of substance gross masses
Nanotube, and be added in the dipping solution, it is ultrasonically treated at room temperature, ultrasonic power density is 0.35-0.55W/cm2, so
After be warming up to 80 DEG C, solvent volatilization completely, and residue is sufficiently dried to get the catalyst precursor.
4. preparation method according to claim 3, it is characterised in that: in the step S3-2, the ultrasonic treatment
Ultrasonic power density is 0.45W/cm2。
5. preparation method according to claim 1-4, it is characterised in that: the step S4 includes the following steps:
S4-1: the catalyst precursor is placed in the hydrogen atmosphere of reproducibility, at room temperature with 3 DEG C/min of heating speed
Rate is warming up to temperature T1, heat preservation calcining 180-220 minutes at temperature T1；
After the completion of S4-2: step S4-1 heat preservation calcining, the hydrogen atmosphere of reproducibility is replaced as inert nitrogen atmosphere, is continued
Temperature T2 is warming up to by T1 with 5 DEG C/min of heating rate, heat preservation calcining 100-120 minutes at temperature T2, heat preservation calcining
After the completion, continue to remain nitrogen atmosphere, and cooled to room temperature is to get the ethyl alcohol synthesis of acetic acid catalyst；
Wherein, in the step S4-1, the temperature T1 is 200 ± 10 DEG C；
Wherein, in the step S4-2, the temperature T2 is 300 ± 10 DEG C.
6. the ethyl alcohol synthesis of acetic acid catalyst that any one of -5 preparation methods are prepared according to claim 1.
7. a kind of method that ethyl alcohol prepares acetic acid, the method uses ethyl alcohol synthesis of acetic acid catalyst as claimed in claim 6.
8. according to the method described in claim 7, it is characterized by: the method specifically: urge the ethyl alcohol synthesis of acetic acid
Agent is placed in autoclave, and ethyl alcohol or ethanol water is added, and is passed through air until pressure is 3-4MPa, in 140-180
Sealing reaction 3-6 hours at DEG C, to obtain acetic acid.
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