CN1212890C - Catalyst for preparation of heptanol by hydrogenation of hyptyl aldehyde - Google Patents
Catalyst for preparation of heptanol by hydrogenation of hyptyl aldehyde Download PDFInfo
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- CN1212890C CN1212890C CN 03137025 CN03137025A CN1212890C CN 1212890 C CN1212890 C CN 1212890C CN 03137025 CN03137025 CN 03137025 CN 03137025 A CN03137025 A CN 03137025A CN 1212890 C CN1212890 C CN 1212890C
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- enanthaldehyde
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Abstract
The present invention relates to a catalyst for preparing heptanol from heptaldehyde by the way of hydrogenization. The catalyst comprises 1.0 to 15.0 wt% of Ni-B amorphous alloy and 85.0 to 99.0 wt% of carrier. The catalyst has an application method that the pressure is from 0.5 to 4.0Mpa, the temperature is 100 to 300 DEG C, the air speed of liquid is 0.1 to 4.0h<-1>, and the proportion of hydrogen to aldehyde is from 5 to 80:1. The present invention has the advantages that the selectivity of heptanol can also be as high as 90% or more when the conversion rate of heptaldehyde is more than 95%, and both activity and selectivity of the catalysis are high. The catalyst has low nickel and high efficiency.
Description
Technical field:
The present invention relates to a kind of solid-state carried non-crystal alloy catalyst and application of enanthaldehyde hydrogenation system enanthol.
Background technology:
China is the rich state that produces of world castor-oil plant, and annual production is about about 200,000 tons, occupies the third place in the world.When Viscotrol C deep processing system nylon-11, will produce a large amount of by product enanthaldehyde (accounting for more than 24% of Viscotrol C output), the enanthaldehyde added value is lower, and enanthaldehyde is hydrogenated to enanthol, have the raw material of spices, medicine, organic synthesis and the rubber item etc. of high added value as production, can produce favorable economic benefit and social benefit.Domestic have the investigator to use skeleton nickel as the enanthaldehyde hydrogenation catalyst, adopts the skeletal nickel catalyst cost higher, and environmental pollution is more serious in catalyst preparation process simultaneously.For this reason, research and selection hydrogenation catalyst are absolutely necessary.
At Journal of Molecular Catalysis A:Chemical 169 (2001), once reported among the 295-301 aluminum oxide flooded an amount of nickel chloride solution after, elder generation is slow evaporate to dryness under 70 ℃ of oil baths are stirred, remove residual water-content in 110 ℃ of oven dry then, cooling slowly drips KBH in the ice-water bath of back
4Solution, distilled water wash is used in the back that reacts completely, and obtains a kind of non-crystalline state Ni-B/Al
2O
3Catalyzer.This catalyzer that two step desiccating methods make has improved carrier surface non-crystalline state dispersion degree of active components, and the thermostability of catalyzer and the catalytic activity in benzene hydrogenation thereof all improve greatly.
CN1179358A has disclosed the preparation method of the amorphous alloy catalyst of a kind of nickel and boron, the Ni-B amorphous alloy accounts for the heavy % of 0.1-30.0, solid support material accounts for the heavy % of 70.0-99.9, its preparation method is included in and is higher than solution solidifies o'clock to 100 ℃ temperature range, is the BH that contains of 0.5-10.0 with a kind of nickeliferous solid support material and volumetric molar concentration
4 -The ion solution contact, this method has solved the problem that amorphous alloy is evenly distributed at carrier surface.This catalyzer can be used for the selective hydrogenation of trace acetylene in the ethene, reactions such as toluene hydrogenation system methylcyclohexane, vinylbenzene hydrogenation preparing methylbenzene, adiponitrile preparing hexanediamine.
CN1286140A is incorporated into metal additive in the catalyzer.With a kind of Ni and the metal atomic ratio that feeds intake is the solid support material of 0.1-20.0 and the BH that contains that volumetric molar concentration is 0.5-10.0
4 -Ion solution contacts with (nickel and the metal) atomic ratio that feeds intake by the boron of 1.5-4.The better heat stability of this catalyzer, activity can reach higher.To hydrodesulfurization reaction sulphur content is reduced to below the 15ppm.
The patent that at present relevant amorphous alloy catalyst is applied to enanthaldehyde hydrogenation system enanthol is not appeared in the newspapers as yet.
Summary of the invention:
The purpose of this invention is to provide a kind of amorphous alloy catalyst catalyzer and application method thereof that is used for enanthaldehyde hydrogenation system enanthol.
Catalyzer of the present invention consist of the Ni-B/ carrier, amorphous alloy accounts for 1.0-15.0wt%, carrier accounts for 85.0-99.0wt%.
Nickel and boron atom ratio are 1.0-7.0 in the aforesaid amorphous alloy: 1.0.
Aforesaid carrier is aluminum oxide, silicon oxide or gac, preferred aluminum oxide and gac.
Preparation of catalysts method provided by the invention, concrete steps are as follows:
1. with the above-mentioned carrier of soluble nickel salt solution impregnation, and in 50-150 ℃ of oven dry;
With above-mentioned nickeliferous solid support material with contain BH
4 -Ion solution contacts;
With the distilled water wash solid product to there not being acid group.
In the aforesaid method, the impregnation method that is adopted can use the general dipping method that adopts in the Preparation of Catalyst, preferably adopts saturated pickling process.
In the aforesaid method, used nickel salt solution refers to the aqueous solution or the alcoholic solution of nickel salt, one or more in nickel acetate, nickelous nitrate, nickelous chloride or the solubility nickel carboxylate, preferred nickelous nitrate.
In the aforesaid method, nickeliferous solid support material and contain BH
4 -The ion solution contact is meant and will contains BH
4 -Ion solution slowly is added drop-wise in this solid support material.
The application method that catalyzer of the present invention is used for enanthaldehyde hydrogenation system enanthol is that pressure is 0.5-4.0Mpa, and temperature is 100-300 ℃, and the liquid air speed is 0.1-4.0h
-1, hydrogen-aldehyde rate is 5-80: 1.
The present invention compared with prior art has following advantage:
Catalyzer of the present invention is 95% when above at the enanthaldehyde transformation efficiency, and the enanthol selectivity also can reach more than 90%, catalytic activity and selectivity height; Catalyzer provided by the invention is a kind of low nickel effective catalyst.
Embodiment:
Prepare the Ni-B/ carried catalyst according to method provided by the invention.
Embodiment 1. takes by weighing six water nickelous nitrate 0.5g and adds the 9ml dissolved in distilled water and be configured to nickel nitrate solution, and the oxide impregnation alumina supporter, in 100 ℃ dry nickeliferous carrier; The POTASSIUM BOROHYDRIDE that takes by weighing 0.28g is made into the 12ml aqueous solution, under the room temperature with KBH
4Drips of solution is added in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and does not have acid group with deionized water wash to solid product, the gained catalyzer.
Embodiment 2. takes by weighing six water nickelous nitrate 2.0g adding 9ml dissolved in distilled water and is configured to nickel nitrate solution, and impregnating ratio surface-area 150m
2G
-1Alumina supporter, in 100 ℃ dry nickeliferous carrier; The POTASSIUM BOROHYDRIDE that takes by weighing 1.11g is made into the 12ml aqueous solution, under the room temperature with KBH
4Drips of solution is added in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and does not have acid group with deionized water wash to solid product, the gained catalyzer.
Embodiment 3. takes by weighing six water nickelous nitrate 4.0g and adds the 9ml dissolved in distilled water and be configured to nickel nitrate solution, and the oxide impregnation alumina supporter, in 100 ℃ dry nickeliferous carrier; The POTASSIUM BOROHYDRIDE that takes by weighing 2.23g is made into the 12ml aqueous solution, under the room temperature with KBH
4Drips of solution is added in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and does not have acid group with deionized water wash to solid product, the gained catalyzer.
Embodiment 4. takes by weighing six water nickelous nitrate 2.0g and adds the 9ml dissolved in distilled water and be configured to nickel nitrate solution, and the oxide impregnation alumina supporter, in 100 ℃ dry nickeliferous carrier; The POTASSIUM BOROHYDRIDE that takes by weighing 0.74g is made into the 12ml aqueous solution, under the room temperature with KBH
4Drips of solution is added in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and does not have acid group with deionized water wash to solid product, the gained catalyzer.
Embodiment 5. takes by weighing six water nickelous nitrate 2.0g and adds the 9ml dissolved in distilled water and be configured to nickel nitrate solution, and the impregnated carrier alumina supporter, in 100 ℃ dry nickeliferous carrier; The POTASSIUM BOROHYDRIDE that takes by weighing 1.30g is made into the 12ml aqueous solution, under the room temperature with KBH
4Drips of solution is added in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and does not have acid group with deionized water wash to solid product, the gained catalyzer.
Embodiment 6. takes by weighing six water nickelous nitrate 2.0g adding 9ml dissolved in distilled water and is configured to nickel nitrate solution, and the oxide impregnation silicon carrier; The POTASSIUM BOROHYDRIDE that takes by weighing 1.11g is made into the 12ml aqueous solution, under the room temperature with KBH
4Drips of solution is added in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and does not have acid group with deionized water wash to solid product, the gained catalyzer.
Embodiment 7. takes by weighing six water nickelous nitrate 2.0g and adds the 9ml dissolved in distilled water and be configured to nickel nitrate solution, and the Immesion active carbon carrier, in 100 ℃ dry nickeliferous carrier; The POTASSIUM BOROHYDRIDE that takes by weighing 1.11g is made into the 12ml aqueous solution, under the room temperature with KBH
4Drips of solution is added in the nickeliferous carrier, and reaction is carried out and releasing hydrogen gas immediately, after dripping off, treats that no hydrogen emits, and does not have acid group with deionized water wash to solid product, the gained catalyzer.
The application of the catalyzer of embodiment 1-7 in the enanthaldehyde hydrogenation reaction is as follows.
Hydrogenation reaction is carried out on tubular fixed-bed reaction unit, and catalyzer loading amount 5ml reacts sampling after 2 hours.Reaction conditions and reaction result see Table one.
Table one
| The reaction numbering | The catalyzer numbering | Enanthaldehyde transformation efficiency % | Enanthol selectivity % | Application conditions |
| Pressure, temperature, air speed, hydrogen-aldehyde rate | ||||
| 1 | Embodiment 1 | 91.27 | 89.69 | 1.0Mpa，240℃，3.5h -1，25 |
| 2 | Embodiment 2 | 95.63 | 92.47 | 1.5Mpa，200℃，3.0h -1，20 |
| 3 | Embodiment 2 | 96.56 | 92.06 | 3.0Mpa，120℃，0.5h -1，45 |
| 4 | Embodiment 2 | 97.49 | 91.64 | 0.5Mpa，300℃，1.0h -1，60 |
| 5 | Embodiment 3 | 96.97 | 92.56 | 1.7Mpa，190℃，1.8h -1，35 |
| 6 | Embodiment 4 | 95.24 | 91.67 | 2.5Mpa，180℃，4.0h -1，5.0 |
| 7 | Embodiment 5 | 95.92 | 92.13 | 1.0Mpa，240℃，0.1h -1，80 |
| 8 | Embodiment 6 | 94.87 | 91.32 | 1.5Mpa，220℃，2.0h -1，30 |
| 9 | Embodiment 7 | 96.43 | 94.28 | 2.6Mpa，150℃，0.8h -1，40 |
| 10 | Embodiment 7 | 98.58 | 96.43 | 4.0Mpa，100℃，1.5h -1，15 |
Claims (4)
1. an Application of Catalyst method that is used for enanthaldehyde hydrogenation system enanthol is characterized in that reaction conditions is that pressure is 0.5-4.0Mpa, and temperature is 100-300 ℃, and the liquid air speed is 0.1-4.0h
-1, hydrogen-aldehyde rate is 5-80: 1, and the catalyzer of use consists of the Ni-B/ carrier, and the Ni-B amorphous alloy accounts for 1.0-15.0wt%, and carrier accounts for 85.0-99.0wt%.
2. a kind of Application of Catalyst method that is used for enanthaldehyde hydrogenation system enanthol as claimed in claim 1 is characterized in that nickel and boron atom ratio are 1.0-7.0 in the described Ni-B amorphous alloy: 1.0.
3. a kind of Application of Catalyst method that is used for enanthaldehyde hydrogenation system enanthol as claimed in claim 1 is characterized in that described carrier is aluminum oxide, silicon oxide or gac.
4. a kind of Application of Catalyst method that is used for enanthaldehyde hydrogenation system enanthol as claimed in claim 3 is characterized in that described carrier is aluminum oxide or gac.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137025 CN1212890C (en) | 2003-05-29 | 2003-05-29 | Catalyst for preparation of heptanol by hydrogenation of hyptyl aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137025 CN1212890C (en) | 2003-05-29 | 2003-05-29 | Catalyst for preparation of heptanol by hydrogenation of hyptyl aldehyde |
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| Publication Number | Publication Date |
|---|---|
| CN1456388A CN1456388A (en) | 2003-11-19 |
| CN1212890C true CN1212890C (en) | 2005-08-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03137025 Expired - Lifetime CN1212890C (en) | 2003-05-29 | 2003-05-29 | Catalyst for preparation of heptanol by hydrogenation of hyptyl aldehyde |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2916886A1 (en) * | 2013-07-02 | 2015-01-08 | Basf Se | Process for the preparation of 3-heptanol from a mixture comprising 2-ethylhexanal and 3-heptyl formate |
| CN103952719B (en) * | 2014-03-28 | 2017-05-03 | 中国科学院物理研究所 | Catalyst used for preparation of hydrogen through water electrolysis, and preparation method thereof |
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