CN103706377A - Method for preparing platinum-based catalyst for producing isopropanol through acetone hydrogenation - Google Patents
Method for preparing platinum-based catalyst for producing isopropanol through acetone hydrogenation Download PDFInfo
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- CN103706377A CN103706377A CN201310714229.7A CN201310714229A CN103706377A CN 103706377 A CN103706377 A CN 103706377A CN 201310714229 A CN201310714229 A CN 201310714229A CN 103706377 A CN103706377 A CN 103706377A
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- platinum
- based catalyst
- isopropyl alcohol
- catalyst
- acetone hydrogenation
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Abstract
The invention discloses a method for preparing a platinum-based catalyst for producing isopropanol through acetone hydrogenation. The method comprises the following steps: dissolving octadecylamine, adding a carrier, so as to enable the octadecylamine and the carrier to be uniformly mixed; raising the temperature to a reaction temperature, injecting acetyl acetone platinum and a transition metal salt dissolved in oleylamine under rapid stirring, continuously stirring for a period of time, cooling, adding ethanol for settling, pouring supernatant liquid, washing for a plurality of times by using absolute ethyl alcohol, drying to obtain a supported platinum-based catalyst for producing the isopropanol through the acetone hydrogenation. The catalyst is easy to prepare and simple in operation, an original catalyst is replaced by the platinum-based catalyst, and the problems of production of Cr-containing toxic catalysts and subsequent environmental pollution can be solved. Moreover, the catalyst is used for acetone hydrogenation reaction, and an isopropanol product is high in yield and high in selectivity.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst of producing isopropyl alcohol for acetone hydrogenation, belong to technical field of chemical material preparation.
Background technology
Industrial isopropyl alcohol is produced the general method of propylene hydration that adopts and is obtained, esterification process as indirect in sulfuric acid, solid acid catalyst or cation exchange resin catalyst direct hydration method.
Industrial acetone is mainly obtained by isopropylbenzene peroxidating method, and in phenol coproduction.Due to the increase of phenol demand, produce a large amount of acetone, there is the imbalance of demand, the situation that causes acetone surplus, and H2 low price easily obtains, so just making becomes an economically feasible route by preparing isopropyl alcohol by acetone hydrogenation, also meets Atom economy.
At present, the available Ni-based or copper-based catalysts of prior art acetone hydrogenation reaction or adopt the catalysis such as precious metals pt, Pd, Ru, Rh.Reaction unit mainly adopts fixed bed reactors, and acetone and hydrogen enter the reactor that catalyst is housed continuously with gas phase form with certain proportioning, under proper temperature and hydrogen pressure, be hydrogenated into isopropyl alcohol.
Nickel-base catalyst be take Raney Ni as best, and the flat 3-141235 of Japanese Patent Laid discloses acetone, and on raney nickel catalyst, Hydrogenation is for the reaction of isopropyl alcohol, and acetone conversion and isopropyl alcohol are selectively up to 99.9%.But raney nickel catalyst price is relatively high, and more complicated when Catalyst packing, operation.
The advantage of copper-based catalysts is that preparation is simple, low price and easy operating are used.Copper-based catalysts is generally carried on carrier, or compound as catalyst with other metal oxide.Improved copper-based catalysts can reach the catalytic effect same good with nickel-base catalyst, but can cause some other side reactions, causes isopropyl alcohol selectively not high.In addition, adopt some poisonous oxides as Cr
2o
3as auxiliary agent is compound, can produce problem of environmental pollution (Russian Patent SU1051055A, SU1118632A, the flat 3-41038 of Japan Patent).
, although activity and selectivity is higher, price is more expensive for noble metal catalyst (as Pt, Pd, Ru, Rh).In addition, hydrogenation technique condition is harsh, and reaction pressure is too high.The flat 2-279643 of Japan Patent discloses Ru/Al
2o
3catalysis acetone hydrogenation technique, under the pressure of 9MPa, reaches as high as 99.9% conversion ratio, and isopropyl alcohol is selectively also up to 99.9%.
Summary of the invention
The object of the invention is to for shortcomings and deficiencies of the prior art, provide a kind of acetone hydrogenation to produce the platinum based catalyst preparation method of isopropyl alcohol.
Technical scheme of the present invention is as follows:
A platinum based catalyst preparation method for isopropyl alcohol is produced in acetone hydrogenation, it is characterized in that the method carries out as follows:
1) by octadecylamine in 80 ℃～100 ℃ dissolvings, add carrier that it is mixed;
2) be then warming up to 240 ℃～280 ℃, under vigorous stirring, by being dissolved in the acetylacetone,2,4-pentanedione platinum of oleyl amine and the salt of transition metal M, inject, continue to stir 15min～30min; Described Pt and the mol ratio of transition metal M are 1:3～3:1;
3) reaction finishes to be cooled to 70 ℃～80 ℃, adds absolute ethyl alcohol sedimentation, topples over supernatant liquor, then with after absolute ethanol washing several, the dry platinum based catalyst that obtains described acetone hydrogenation production isopropyl alcohol.
Carrier of the present invention is active carbon, Al
2o
3, ZrO
2and TiO
2in a kind of; The load capacity of platinum in described acetylacetone,2,4-pentanedione platinum on carrier is 1wt%～5wt% by weight; Described transition metal M is a kind of in Fe, Co and Sn; The salt of described transition metal M adopts acetylacetonate, chloride or nitrate.
The present invention has the following advantages and the technique effect of high-lighting: this catalyst is preparation and simple to operate easily, with the original catalyst of this catalyst replaced, can avoid containing poisonous Catalyst Production and follow-up problem of environmental pollutions such as Cr simultaneously, adopt catalyst of the present invention, in dirty hydrogenation reaction, reaction temperature is 60～150 ℃, and pressure is normal pressure; In autoclave reaction, reaction temperature is 100～150 ℃, and pressure is 2MPa, under above-mentioned reaction condition, can obtain high acetone conversion and isopropyl alcohol selective.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram that embodiment 1 makes sample.
The specific embodiment
Below by embodiment, the invention will be further described, and its object is only better to understand research contents of the present invention but not limits the scope of the invention.
The platinum based catalyst preparation method of isopropyl alcohol is produced in a kind of acetone hydrogenation provided by the invention, and the method concrete steps are as follows:
First by octadecylamine in 80 ℃～100 ℃ dissolvings, add carrier that it is mixed; Then be warming up to 240 ℃～280 ℃, under vigorous stirring, by being dissolved in the acetylacetone,2,4-pentanedione platinum of oleyl amine and the salt of transition metal M, inject, continue to stir 15min～30min; The mol ratio of Pt and transition metal M is 1:3～3:1; Reaction finishes to be cooled to 70 ℃～80 ℃, adds absolute ethyl alcohol sedimentation, topples over supernatant liquor, then with after absolute ethanol washing several, the dry platinum based catalyst that obtains described acetone hydrogenation production isopropyl alcohol.The load capacity of described platinum on carrier is 1wt%～5wt% by weight; Carrier is active carbon, Al
2o
3, ZrO
2and TiO
2in a kind of, the salt of transition metal M preferably adopts acetylacetonate, chloride or nitrate, transition metal M is preferably a kind of in Fe, Co and Sn;
Embodiment 1
By 5g octadecylamine in 80 ℃ of dissolvings, add 0.2g active carbon that it is mixed, then be warming up to 240 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0035g ferric acetyl acetonade are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 15min, reaction finishes to be cooled to 70 ℃, adds ethanol sedimentation, topples over supernatant liquor, with after absolute ethanol washing several, 70 ℃ are dried the support type Pt that obtain described acetone hydrogenation production isopropyl alcohol again
3fe/C alloy catalyst.
Embodiment 2
By 5g octadecylamine in 100 ℃ of dissolvings, add 0.2138g active carbon that it is mixed, then be warming up to 260 ℃, 0.0039g acetylacetone,2,4-pentanedione platinum and 0.0035g ferric acetyl acetonade are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 30min, reaction finishes to be cooled to 70 ℃, adds ethanol sedimentation, topples over supernatant liquor, with after absolute ethanol washing several, 80 ℃ are dried the support type PtFe/C alloy catalysts that obtain described acetone hydrogenation production isopropyl alcohol again.
Embodiment 3
By 5g octadecylamine in 80 ℃ of dissolvings, add 0.2138g active carbon that it is mixed, then be warming up to 280 ℃, 0.0196g acetylacetone,2,4-pentanedione platinum and 0.053g ferric acetyl acetonade are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 30min, reaction finishes to be cooled to 70 ℃, adds ethanol sedimentation, topples over supernatant liquor, with after absolute ethanol washing several, 80 ℃ are dried the support type PtFe that obtain described acetone hydrogenation production isopropyl alcohol again
3/ C alloy catalyst.
Embodiment 4
5g octadecylamine, in 100 ℃ of dissolvings, is added to 0.2g Al
2o
3it is mixed, then be warming up to 260 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0035g ferric acetyl acetonade are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 15min, reaction finishes to be cooled to 70 ℃, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ of dry support type Pt that obtain described acetone hydrogenation production isopropyl alcohol
3fe/Al
2o
3alloy catalyst.
Embodiment 5
5g octadecylamine, in 80 ℃ of dissolvings, is added to 0.2g ZrO
2it is mixed, then be warming up to 260 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0035g ferric acetyl acetonade are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 15min, reaction finishes to be cooled to 70 ℃, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ of dry support type Pt that obtain described acetone hydrogenation production isopropyl alcohol
3fe/ZrO
2alloy catalyst.
Embodiment 6
5g octadecylamine, in 80 ℃ of dissolvings, is added to 0.2g ZrO
2it is mixed, then be warming up to 260 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0087g cabaltous nitrate hexahydrate are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 15min, reaction finishes to be cooled to 70 ℃, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ of dry support type Pt that obtain described acetone hydrogenation production isopropyl alcohol
3co/C alloy catalyst.
Embodiment 7
5g octadecylamine, in 80 ℃ of dissolvings, is added to 0.2g ZrO
2it is mixed, be then warming up to 260 ℃, by 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0057g SnCl
22H
2o is dissolved in ultrasonic 5min in 2.5mL oleyl amine, injects above-mentioned system under vigorous stirring, continues to stir 15min, reaction finishes to be cooled to 70 ℃, adds ethanol sedimentation, topples over supernatant liquor, with after absolute ethanol washing several, 70 ℃ are dried the support type Pt that obtain described acetone hydrogenation production isopropyl alcohol again
3sn/C alloy catalyst.
Embodiment 8
The explanation of this example generates in isopropanol reaction at acetone hydrogenation, and catalyst provided by the invention is for the catalytic reaction result of fixed bed.
Reaction unit is normal pressure continuous-flow fixed bed, and reactor inside diameter is 7mm, and the loadings of catalyst is 0.1g, and catalyst grain size is 20～40 orders.
Acetone sample rate is 1.8mL/h, and nitrogen flow is 30mL/min, and hydrogen flowing quantity is 30mL/min, and reaction temperature is 100 ℃, and reaction pressure is normal pressure, and the reaction time is 1h.
Before catalyst reaction, need at 300 ℃ at N
2(30mL/min) and H
2(30mL/min) in mixed atmosphere, activate 2h.
Reactant acetone and hydrogen enter beds continuously with gas phase, and product is passed through capillary gas chromatography online, flame ionization ditector, and testing result is as table 1.
Table 1
| Catalyst | Acetone conversion (%) | Isopropyl alcohol selective (%) |
| Embodiment 1 | 80.9 | 100 |
| Embodiment 2 | 81.5 | 100 |
| Embodiment 3 | 82..8 | 100 |
| Embodiment 4 | 72..6 | 100 |
| Embodiment 5 | 66.7 | 100 |
| Embodiment 6 | 78.5 | 100 |
| Embodiment 7 | 73.5 | 100 |
Embodiment 9
The explanation of this example generates in isopropanol reaction at acetone hydrogenation, and catalyst provided by the invention is for the catalytic reaction result of autoclave.
Reaction unit is autoclave, and the consumption of catalyst is 0.1g, the feeding intake as 5mmol of acetone, and cyclohexane is 15mL, and reaction temperature is 150 ℃, and reaction pressure is 2MPa, and the reaction time is 4h.
Product is passed through capillary gas chromatography, flame ionization ditector, and measurement result is as table 2.
Table 2
| Catalyst | Acetone conversion (%) | Isopropyl alcohol selective (%) |
| Embodiment 1 | 81.5 | 100 |
| Embodiment 2 | 84.5 | 100 |
| Embodiment 3 | 87.8 | 100 |
| Embodiment 4 | 75.5 | 100 |
| Embodiment 5 | 70.4 | 100 |
| Embodiment 6 | 75.2 | 100 |
| Embodiment 7 | 76.7 | 100 |
Experimental result shows, adopts catalyst provided by the invention to preparing isopropyl alcohol by acetone hydrogenation, and product yield is high, selectively good.
Claims (5)
1. a platinum based catalyst preparation method for isopropyl alcohol is produced in acetone hydrogenation, it is characterized in that the method carries out as follows:
1) by octadecylamine in 80 ℃～100 ℃ dissolvings, add carrier that it is mixed;
2) be then warming up to 240 ℃～280 ℃, under vigorous stirring, by being dissolved in the acetylacetone,2,4-pentanedione platinum of oleyl amine and the salt of transition metal M, inject, continue to stir 15min～30min; Described Pt is 1:3～3:1 with the mol ratio of crossing metal M;
3) reaction finishes to be cooled to 70 ℃～80 ℃, adds absolute ethyl alcohol sedimentation, topples over supernatant liquor, then with after absolute ethanol washing several, the dry platinum based catalyst that obtains described acetone hydrogenation production isopropyl alcohol.
2. the platinum based catalyst preparation method who produces isopropyl alcohol according to a kind of acetone hydrogenation claimed in claim 1, is characterized in that: the carrier described in step 1) is active carbon, Al
2o
3, ZrO
2and TiO
2in a kind of.
3. according to a kind of acetone hydrogenation described in claim 1 or 2, produce the platinum based catalyst preparation method of isopropyl alcohol, it is characterized in that: step 2) described in acetylacetone,2,4-pentanedione platinum in the load capacity of platinum on carrier be 1wt%～5wt% by weight.
4. according to a kind of acetone hydrogenation claimed in claim 1, produce the platinum based catalyst preparation method of isopropyl alcohol, it is characterized in that: step 2) described in the salt of transition metal M adopt acetylacetonate, chloride or nitrate.
5. according to a kind of acetone hydrogenation described in claim 1 or 4, produce the platinum based catalyst preparation method of isopropyl alcohol, it is characterized in that: step 2) described in transition metal M be Fe, Co or Sn.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693989A (en) * | 2016-12-23 | 2017-05-24 | 清华大学 | Wire mesh loaded nano composite catalyst, preparation method thereof, and application of wire mesh loaded nano composite catalyst in alcoholic preparation of aldehyde ketone |
| CN111841610A (en) * | 2020-08-04 | 2020-10-30 | 西北工业大学 | Electron-rich single-atom Pt alloy intermetallic compound catalyst and preparation method thereof |
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2013
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693989A (en) * | 2016-12-23 | 2017-05-24 | 清华大学 | Wire mesh loaded nano composite catalyst, preparation method thereof, and application of wire mesh loaded nano composite catalyst in alcoholic preparation of aldehyde ketone |
| CN106693989B (en) * | 2016-12-23 | 2020-01-31 | 清华大学 | Metal wire mesh loaded nano composite catalyst, preparation method thereof and application thereof in preparation of aldehyde and ketone from alcohol |
| CN111841610A (en) * | 2020-08-04 | 2020-10-30 | 西北工业大学 | Electron-rich single-atom Pt alloy intermetallic compound catalyst and preparation method thereof |
| CN111841610B (en) * | 2020-08-04 | 2022-11-08 | 西北工业大学 | Electron-rich single-atom Pt alloy intermetallic compound catalyst and preparation method thereof |
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