CN1546444A - Catalyst for hydrogenation of styrene oxide to beta-phenethyl alcohol, preparation and use thereof - Google Patents
Catalyst for hydrogenation of styrene oxide to beta-phenethyl alcohol, preparation and use thereof Download PDFInfo
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- CN1546444A CN1546444A CNA2003101075187A CN200310107518A CN1546444A CN 1546444 A CN1546444 A CN 1546444A CN A2003101075187 A CNA2003101075187 A CN A2003101075187A CN 200310107518 A CN200310107518 A CN 200310107518A CN 1546444 A CN1546444 A CN 1546444A
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- styrene oxide
- bata
- oxide 98min
- phenethyl alcohol
- catalyzer
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Abstract
The invention discloses the catalyst for preparing beta-phenethylol through styrene oxide hydrogenation, its preparation process and use thereof, wherein the catalyst is loaded Pd-B on NaY, MCM41, beta molecular sieve, metallic oxide gamma-Al2O3, TiO2, MgO by equal volume immersion method, the content of Pd is 0.1wt%-0.15%. The catalyst by the invention exhibits good catalytic activity and high beta-phenethylol selectivity, thus can be applied to mass production.
Description
Technical field
The present invention relates to be used for catalyzer and the preparation and the application of Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol, specifically is the synthetic bata-phenethyl alcohol of metal oxide, the catalysis of molecular sieve carried activeconstituents Pd-B catalyst series.
Background technology
Bata-phenethyl alcohol is a kind of colourless spices with soft and fine and smooth rose scent, is present in rose oil at occurring in nature with the form of free or its ester, and orange flower oil is in the spiceleaf wet goods essential oil.Bata-phenethyl alcohol is because its special fragrance, be widely used in the daily chemical product, as perfume, washing composition, perfumed soap, shampoo, food spice etc., part also is used for other Chemical Manufacture, as synthetic dyestuff intermediate, pharmaceutical intermediate, as Phenylethanolamine sterilizing agent etc., its production status and people's productive life has very close getting in touch.
Industrial synthetic bata-phenethyl alcohol method mainly contains from toluene and begins to prepare bata-phenethyl alcohol, benzene and oxyethane directly synthetic bata-phenethyl alcohol and by Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol under the aluminum chloride katalysis, preceding two synthetic routes, because of its reactions steps many, impurity effect is big, shortcomings such as transportation difficulty are so industrial main employing now is from the method for Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol.
From the method for Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol, homogeneous reaction and inhomogeneous reaction all have bibliographical information.The shortcoming of a maximum of homogeneous reaction is the separation difficulty of product.Various patents all are devoted to improve with heterogeneous catalytic reaction the selectivity of bata-phenethyl alcohol.In heterogeneous catalysis, skeleton nickel is the most frequently used catalyzer.U.S. Pat 2822403 has been introduced under alkaline condition, with skeleton nickel and skeleton nickel-cobalt (platinum, palladium) is catalyzer, water is made solvent, under 20-100 ℃ of temperature of reaction, and hydrogenation preparing bata-phenethyl alcohol technology, but need a large amount of water in this technology, for the 1-5 of Styrene oxide 98min. weight doubly, and need to add emulsifying agent, the distillation of giving aftertreatment has brought difficulty with separating, by product ethylbenzene in this technology, phenylacetic aldehyde amount are many simultaneously, influence quality product.English Patent 760768 has also been introduced similar technology, is to be separately catalyzer with the skeleton nickel, and the shortcoming of existence also is that by product ethylbenzene is too much.It is the technology of catalyzer that U.S. US3579593 and German patent DE 1918852 have been introduced with skeleton nickel, palladium, when being catalyzer with the skeleton nickel, there is 11% ethylbenzene to produce, and when being catalyzer with the palladium, but produce 10% phenylacetic aldehyde, the yield of bata-phenethyl alcohol also has only 85%.In Chinese patent CN1111169A and CN1111228A, though the yield of bata-phenethyl alcohol improves greatly, added toxic organic amine or a large amount of alkaline matters is an auxiliary agent, also used many water to make solvent simultaneously.Japanese kokai publication sho 53-31635 has introduced the technology of making catalyzer in the alkaline condition skeleton nickel, need be 10 ℃ of reaction down, and speed of response is slow, and is unsatisfactory on industrial production.Recently, what U.S. Pat 6166269 was introduced is in the catalyst process with the platinum metals, and the transformation efficiency of Styrene oxide 98min. and bata-phenethyl alcohol be all near 99%, but needs to add a large amount of methyl alcohol in the reaction process as solvent (for 19 times of Styrene oxide 98min.).
In the above-mentioned patent, there is certain shortcoming in varying degrees, the solvent a large amount of as needs, the energy consumption height, separation difficulty, by product is many etc., so the development of effective catalyst has very important significance.
Summary of the invention
The purpose of this invention is to provide a kind of catalyzer and preparation and application of novel Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol, can overcome the shortcoming of prior art, the present invention is the effective catalyst that is used for by Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol, they show good catalytic activity and high bata-phenethyl alcohol selectivity, and the reaction conditions gentleness is easy to industry's enlarging production.
The present invention uses equi-volume impregnating at carrier NaY, MCM41, beta-molecular sieve, metal oxide γ-Al
2O
3, TiO
2Or the last load effective amount of actives Pd-B of MgO, described effective amount of actives Pd/B mol ratio is 1/60, wherein the content of Pd is: 0.1wt%-0.15%.
Above-mentioned Preparation of catalysts method comprises the steps: metering metal oxide or molecular sieve are impregnated into Pd (NH
3)
4Cl
2In the solution, stir 4 hours after-filtration under the room temperature, filter cake dries in air, 120 ℃ of bakings 4 hours, and KBH is used in 500 ℃ of roastings 4 hours
4Solution filters behind 0-35 ℃ of reductase 12 hour, washes neutrality, dries to get final product.
Described Pd (NH
3)
4Cl
2The concentration of solution is 0.0025-0.01mol/L.
Described KBH
4Strength of solution is 0.02mol/L.
The reaction conditions of catalyzer in synthetic bata-phenethyl alcohol reaction by the Styrene oxide 98min. hydrogenation:
The add-on of water is 2.5% of a Styrene oxide 98min.,
The add-on of NaOH is 0.5% of a Styrene oxide 98min..
Styrene oxide 98min.: catalyzer 20: 0.5-1 (weight ratio)
Temperature of reaction: 80 ℃
Hydrogen pressure: 1.0MPa-1.5MPa
Stirring velocity: 400r/min
Reaction times: 4-6.5h
The present invention can overcome the shortcoming of prior art, to good catalytic performance being arranged, Styrene oxide 98min. transformation efficiency height by the synthetic bata-phenethyl alcohol of Styrene oxide 98min. hydrogenation, the bata-phenethyl alcohol selectivity is good, and auxiliary agent, solvent adding amount are few, and reaction conditions is gentle relatively, is easy to suitability for industrialized production.
Substantive distinguishing features of the present invention and unusual effect can be embodied from following embodiment, but they are not that the present invention is imposed any restrictions.
Embodiment
Embodiment 1
Weighing 6.0g NaY molecular sieve joins by 11.3ml water and 6.0ml 5000 μ g/g Pd (NH
3)
4Cl
2In the solution of solution composition, stirring at room dipping is suction filtration after 4 hours, and filter cake dries in air, and 120 ℃ of bakings 4 hours, 500 ℃ of roastings be after 4 hours, and weighing 4.0g joins the 0.02mol/L KBH of 120ml
4In the solution, stirring at room 2 hours, suction filtration is washed neutrality, promptly gets the Pd/NaY catalyzer after drying.The Pd charge capacity is 0.1wt%.
Reaction conditions:
Adopt the autoclave reactor.Each material addition and reaction conditions are as follows:
Styrene oxide 98min.: 40ml
Water: 1.0ml
Sodium hydroxide: 0.2g
Catalyzer: 2.0g
Temperature of reaction: 80 ℃
Hydrogen pressure: 1.0MPa-1.5MPa
Stirring velocity: 400r/min
Reaction times: 4-6.5h
Reaction result sees Table 1.Changing catalyzer as can be seen from Table 1 makes the transformation efficiency of Styrene oxide 98min. and the selectivity of bata-phenethyl alcohol all reach higher level.
Embodiment 2
Change the add-on and the dipping solution concentration of NaY molecular sieve among the embodiment 1, the final charge capacity that makes Pd is 0.15%, KBH
4Amount during solution reduction changes 180ml into, and other condition makes the Pd/NaY catalyzer with embodiment 1.
Reaction conditions is with embodiment 1.Reaction times is 6 hours.Reaction result sees Table 1.As can be seen from Table 1, after the charge capacity of Pd increases, the selectivity of bata-phenethyl alcohol is improved.
Embodiment 3
With KBH among the embodiment 2
4The solution reduction temperature changes 3 ℃ into, and other condition makes the Pd/NaY catalyzer with embodiment 2.
Reaction conditions is with embodiment 1.Reaction times is 4 hours.The catalyzer of preparing under the low temperature has shortened the reaction times as can be seen.
Embodiment 4
Change the NaY molecular sieve among the embodiment 1 into beta-molecular sieve, join by 13.5ml water and 6.0ml 5000 μ g/gPd (NH
3)
4Cl
2In the solution of solution composition, other condition makes the Pd/ beta catalyst with embodiment 1.Reaction conditions is with embodiment 1.Reaction times is 6.5 hours.Reaction result sees Table 1.
Embodiment 5
Change the NaY molecular sieve among the embodiment 1 into the MCM41 mesopore molecular sieve, join by 37.5ml water and 6.0ml5000 μ g/g Pd (NH
3)
4Cl
2In the solution of solution composition, other condition makes the Pd/MCM41 catalyzer with embodiment 1.Reaction conditions is with embodiment 1.Reaction times is 4 hours.Reaction result sees Table 1.
Embodiment 6
Change the NaY molecular sieve among the embodiment 1 into γ-Al
2O
3, join by 49.5ml water and 6.0ml 5000 μ g/gPd (NH
3)
4Cl
2In the solution of solution composition, other condition makes Pd/ γ-Al with embodiment 1
2O
3Catalyzer.Reaction conditions is with embodiment 1.Reaction times is 4 hours.Reaction result sees Table 1.
Embodiment 7
Change the NaY molecular sieve among the embodiment 1 into TiO
2, join by 11.3ml water and 6.0ml 5000 μ g/gPd (NH
3)
4Cl
2In the solution of solution composition, other condition makes Pd/TiO with embodiment 1
2Catalyzer.Reaction conditions is with embodiment 1.Reaction times is 4 hours.Reaction result sees Table 1.
Embodiment 8
Change the NaY molecular sieve among the embodiment 1 into MgO, join by 7.5ml water and 6.0ml 5000 μ g/gPd (NH
3)
4Cl
2In the solution of solution composition, other condition makes the Pd/MgO catalyzer with embodiment 1.Reaction conditions is with embodiment 1.Reaction times is 4 hours.Reaction result sees Table 1.
Embodiment 9
Product after the hydrogenation reaction among the embodiment 1 is taken out, add raw material and auxiliary agent again, carry out hydrogenation reaction, other condition is with embodiment 1,6.5 hours reaction times.Reaction result sees Table 1.As can be seen from Table 1, catalyzer still has very high activity after recycling.
Table 1: the reaction result of different catalysts
| Sequence number | Styrene oxide 98min. transformation efficiency (%) | Bata-phenethyl alcohol selectivity (%) |
| Embodiment 1 | ????99.7 | ????93.8 |
| Embodiment 2 | ????99.8 | ????96.5 |
| Embodiment 3 | ????99.8 | ????97.5 |
| Embodiment 4 | ????98.5 | ????91.8 |
| Embodiment 5 | ????98.7 | ????85.2 |
| Embodiment 6 | ????99.2 | ????91.9 |
| Embodiment 7 | ????99.8 | ????98.0 |
| Embodiment 8 | ????98.9 | ????90.4 |
| Embodiment 9 | ????100 | ????98.5 |
Claims (8)
1, a kind of catalyzer that is used for by Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol is characterized in that they are with equi-volume impregnating load effective amount of actives Pd-B on carrier NaY, MCM41, beta-molecular sieve, metal oxide.
2,, it is characterized in that described metal oxide is γ-Al according to the catalyzer of the described Styrene oxide 98min. hydrogenation preparing of claim 1 bata-phenethyl alcohol
2O
3, TiO
2Or MgO.
3,, it is characterized in that described effective amount of actives Pd/B mol ratio is 1/60 according to the catalyzer of claim 1 or 2 described Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohols.
4,, it is characterized in that the content of described Pd is: 0.1wt%-0.15% according to the catalyzer of each described Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol of claim 1-3.
5, the Preparation of catalysts method of the Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol described in the claim 1 is characterized in that comprising the steps:
1) carrier metal oxide or the molecular sieve with metering is impregnated into Pd (NH
3)
4Cl
2In the solution, stir 4 hours after-filtration under the room temperature;
2) filter cake dries in air, 120 ℃ of bakings 4 hours, 500 ℃ of roastings 4 hours;
3) use KBH
4Solution filters at 0-35 ℃ of reductase 12 hour, washes neutrality, dries.
6,, it is characterized in that described Pd (NH according to the Preparation of catalysts method of the described Styrene oxide 98min. hydrogenation preparing of claim 5 bata-phenethyl alcohol
3)
4Cl
2The concentration of solution is 0.0025-0.01mol/L.
7, according to the Preparation of catalysts method of the described Styrene oxide 98min. hydrogenation preparing of claim 5 bata-phenethyl alcohol, it is characterized in that described KBH
4Strength of solution is 0.02mol/L.
8, the catalyzer of the Styrene oxide 98min. hydrogenation preparing bata-phenethyl alcohol described in the claim 1 using method, it is characterized in that it comprises the steps:
Autoclave reactor, Styrene oxide 98min. are adopted in reaction
Reaction conditions:
Styrene oxide 98min.: catalyzer 20: 0.5-1 weight ratio
The add-on of water is 2.5% of a Styrene oxide 98min.
The add-on of NaOH is 0.5% of a Styrene oxide 98min.
Temperature of reaction: 80 ℃
Hydrogen pressure: 1.0MPa-1.5MPa
Stirring velocity: 400r/min
Reaction times: 4-6.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310107518 CN1226257C (en) | 2003-12-15 | 2003-12-15 | Catalyst for hydrogenation of styrene oxide to beta-phenethyl alcohol, preparation and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310107518 CN1226257C (en) | 2003-12-15 | 2003-12-15 | Catalyst for hydrogenation of styrene oxide to beta-phenethyl alcohol, preparation and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1546444A true CN1546444A (en) | 2004-11-17 |
| CN1226257C CN1226257C (en) | 2005-11-09 |
Family
ID=34334379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310107518 Expired - Fee Related CN1226257C (en) | 2003-12-15 | 2003-12-15 | Catalyst for hydrogenation of styrene oxide to beta-phenethyl alcohol, preparation and use thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342966C (en) * | 2005-09-06 | 2007-10-17 | 南开大学 | Loaded palladium catalyst and preparing method and its use |
| CN101007275B (en) * | 2007-01-25 | 2010-04-07 | 南京工业大学 | Catalyst used in the catalytic hydrogenation of p-nitrophenol and its preparation method |
| CN110776399A (en) * | 2019-10-25 | 2020-02-11 | 万华化学集团股份有限公司 | Method for preparing β -phenethyl alcohol |
| CN112239301A (en) * | 2020-10-09 | 2021-01-19 | 江苏伟恒土壤治理科技有限公司 | Sound-assisted ozone electromagnetic catalytic oxidation sewage treatment equipment |
| CN114950505A (en) * | 2022-03-15 | 2022-08-30 | 浙江大学 | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide and preparation method and application thereof |
-
2003
- 2003-12-15 CN CN 200310107518 patent/CN1226257C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100342966C (en) * | 2005-09-06 | 2007-10-17 | 南开大学 | Loaded palladium catalyst and preparing method and its use |
| CN101007275B (en) * | 2007-01-25 | 2010-04-07 | 南京工业大学 | Catalyst used in the catalytic hydrogenation of p-nitrophenol and its preparation method |
| CN110776399A (en) * | 2019-10-25 | 2020-02-11 | 万华化学集团股份有限公司 | Method for preparing β -phenethyl alcohol |
| CN110776399B (en) * | 2019-10-25 | 2022-08-05 | 万华化学集团股份有限公司 | Method for preparing beta-phenethyl alcohol |
| CN112239301A (en) * | 2020-10-09 | 2021-01-19 | 江苏伟恒土壤治理科技有限公司 | Sound-assisted ozone electromagnetic catalytic oxidation sewage treatment equipment |
| CN112239301B (en) * | 2020-10-09 | 2021-07-06 | 江苏伟恒土壤治理科技有限公司 | Sound-assisted ozone electromagnetic catalytic oxidation sewage treatment equipment |
| CN114950505A (en) * | 2022-03-15 | 2022-08-30 | 浙江大学 | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1226257C (en) | 2005-11-09 |
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