CN103030528B - Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde - Google Patents
Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde Download PDFInfo
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- CN103030528B CN103030528B CN201110293321.1A CN201110293321A CN103030528B CN 103030528 B CN103030528 B CN 103030528B CN 201110293321 A CN201110293321 A CN 201110293321A CN 103030528 B CN103030528 B CN 103030528B
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Abstract
The present invention relates to a kind of method of Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde, mainly solve that existing catalysis technique activity is low, the problem of poor selectivity.The present invention take apolar substance as reaction solvent, with phenyl aldehyde and hydrogen for raw material, it is 60 ~ 160 DEG C in temperature of reaction, reaction pressure is at 1.0 ~ 5.0MPa, raw material and catalyst exposure, reaction generates phenylcarbinol, and wherein catalyst comprises following component: a) 5.0 ~ 20.0%NiO; B) 5.0 ~ 15.0%P
2o
5; D) 45.0 ~ 75.0%Al
2o
3; E) 3.0 ~ 15.0% MgO, BaO, ZrO is selected from
2, the technical scheme of at least one solves this problem well in CaO, can be used for Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde.
Description
Technical field
The present invention relates to a kind of preparation method of phenylcarbinol, particularly a kind of method of Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde.
Background technology
Phenylcarbinol is the important intermediate of synthetic perfume, medicine, can be used for making spices and seasonings, has and applies very widely, also can be used as the solvent of gelatin, shellac, casein and cellulose acetate etc. in fields such as dyeing and finishing, photosensitive, makeup.The main production process of current phenylcarbinol is Benzyl Chloride with soda ash batch hydrolysis and continuous hydrolysis process, toluene oxidation method, methyl benzoate liquid phase reduction, adopts tandem reactor gas-solid hydrogenation method and phenyl aldehyde By Liquid-phase Hydrogenation Process continuously mutually.In the hydrogenation process of phenylformic acid and derivative thereof, toluene becomes main side components, is the product of phenylcarbinol excessive hydrogenation, but to how effectively to suppress the generation of toluene to rarely have report with the research improving benzyl alcohol selective by catalyst modification.
(chemical journal, 2007,10, (65): the Cu/SiO 877 ~ 880) adopting Na to modify such as Xu Hualong
2catalyzer carries out phenyl aldehyde Hydrogenation for phenylcarbinol on micro fixed-bed reactor.When temperature of reaction is 225 DEG C, air speed is 5.5h
-1time, phenyl aldehyde transformation efficiency can reach 76.5, and the selectivity now generating phenylcarbinol reaches 96.6.
It is low to there is catalytic activity in the method, generates the problem that benzyl alcohol selective is low.
Summary of the invention
Technical problem to be solved by this invention is that catalyst application prepared by prior art exists the problem that activity is low, generation benzyl alcohol selective is low in phenyl aldehyde Hydrogenation is for phenylcarbinol process, provides a kind of method of new Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde.The method adopt catalyzer to have active high, advantage that selectivity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: with phenyl aldehyde and hydrogen for raw material, it is 60 ~ 160 DEG C in temperature of reaction, reaction pressure is at 1.0 ~ 5.0MPa, raw material and catalyst exposure, reaction generates phenylcarbinol, and wherein catalyst comprises following component: a) 5.0 ~ 20.0%NiO; B) 5.0 ~ 15.0%P
2o
5; D) 45.0 ~ 75.0%Al
2o
3; E) 3.0 ~ 15.0% MgO, BaO, ZrO is selected from
2, at least one in CaO.
In technique scheme, by weight percentage for phenyl aldehyde is 5 ~ 100% in the mixture of raw material and solvent, solvent is 0 ~ 95%; MgO, BaO, ZrO by weight percentage
2or at least one consumption is 5.0 ~ 10.0% in CaO; Temperature of reaction preferable range is 80 ~ 120 DEG C; Reaction pressure preferable range is 2.0 ~ 4.0MPa.
This catalyst preparing comprises the following steps: 1) with SiO
2for carrier; 2) a certain amount of Ni (NO is taken
3)
26H
2o is dissolved in distilled water, then adds a certain amount of (NH
4)
2hPO
4, drip dense HNO wherein
3by resolution of precipitate, and adjust pH value between 4 ~ 5, form solution I; 3) calculate by weight percentage, in solution I, add citric acid, keep its concentration 2 ~ 5%, form solution II; 4) solution II is heated to 70 DEG C, equal-volume is added drop-wise to SiO while hot
2on carrier; 5) sample after dipping, roasting 12 hours at 400 ~ 700 DEG C after drying; 6) catalyzer reduces 12 hours in 450 ~ 700 DEG C before using under H2.
Generate in the process of phenylcarbinol alcohol at phenyl aldehyde hydrogenation, phenylcarbinol is easy to further hydrogenation and generates toluene, also has the generation of part ether material simultaneously.Increasing of the acidic site of catalyzer, can increase the generation of toluene, therefore needs to select acid more weak SiO
2for carrier; The too high raising being also unfavorable for benzyl alcohol selective of catalyst hydrogenation activity, is controlled the hydrogenation activity of catalyzer, thus makes the Ni based metal catalysts of preparation keep good activity and selectivity by the content of reasonably control Ni, P.
Adopt method provided by the invention, at catalyzer after reduction, be 60 ~ 160 DEG C in temperature of reaction, be applied to phenyl aldehyde hydrogenation under the condition of reaction pressure 1.0 ~ 5.0MPa, phenyl aldehyde transformation efficiency generates benzyl alcohol selective when reaching 93% can be greater than 94%, this catalyst activity selectivity is high, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Take 10.0g Ni (NO
3)
26H
2o, 8.0g Mg (NO
3)
26H
2o is dissolved in 12.0g distilled water, adds a certain amount of 2.5g NH
4h
2pO
4or 3.6g (NH
4)
2h
2pO
4, drip dense HNO wherein
3by resolution of precipitate, and adjust pH value between 4 ~ 5, form solution I; Solution I is heated to 70 DEG C, is added drop-wise to 15.0g SiO while hot
2on carrier, roasting 8 hours at 550 DEG C after drying at 120 DEG C.Catalyzer consists of: 13.0%NiO-6.2%MgO-7.5%POx-73.3%SiO
2.Get this catalyzer 3.0g in 300ml autoclave, add phenyl aldehyde 5.0g, hexanaphthene 120g, at 120 DEG C, hydrogen pressure is evaluate under 3.0MPa reaction conditions, and evaluation result is in table 2.
[embodiment 2 ~ 8]
Method for preparing catalyst and appreciation condition are with embodiment 1, and catalyzer composition is in table 1, and evaluation result is in table 2.
[comparative example]
With reference to chemical journal, 2007,10, (65): 877 ~ 880, preparation Cu/SiO
2, get catalyzer 3.0g, 4h after 250 DEG C of reduction, for subsequent use after passivation.
The composition of table 1 catalyzer and preparation condition
| Catalyzer | Catalyzer composition (weight percent %) |
| 2 | 13.0％NiO-6.2％CaO-7.5％P 2O 5-73.3％SiO 2 |
| 3 | 13.0％NiO-6.2％ZrO 2-7.5％P 2O 5-73.3％SiO 2 |
| 4 | 13.0％NiO-6.2％BaO-7.5％P 2O 5-73.3％SiO 2 |
| 5 | 15.0％NiO-3％MgO-3％CaO-7.5％P 2O 5-71.5％SiO 2 |
| 6 | 10.0％NiO-3％MgO-3％CeO 2-6％P 2O 5-78％SiO 2 |
| 7 | 10.0％NiO-6％P 2O 5-84％SiO 2 |
| 8 | 20.0％NiO-3％MgO-12％P 2O 5-65％SiO 2 |
| 9 | 5.0％NiO-3％MgO-12％P 2O 5-80％SiO 2 |
| 10 | 15.0％NiO-10％MgO-12％P 2O 5-63％SiO 2 |
| Comparative example | 20％CuO-80％SiO 2 |
The phenyl aldehyde hydrogenation reaction performance of table 2 catalyzer 1 ~ 10
As can be seen from Table 2, under identical reaction conditions, catalyzer 5,10 have good stability and selection, and selecting catalyst 5 investigates temperature and pressure on catalytic activity with optionally affect.Reaction times is all fixed on 4.0h.
Phenyl aldehyde hydrogenation catalyst evaluation result under table 3 differential responses condition
From table 2,3 can find out, this technology is applied to be prepared phenylcarbinol and achieves good reaction result, the activity of temperature of reaction 60 ~ 160 DEG C, reaction pressure 2.0 ~ 4.0Mpa, catalyzer and selectivity substantially good, compared with catalyst based with Cu, this catalyst activity selectivity is high, achieves good technique effect.
Claims (5)
1. the method for a Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde, with phenyl aldehyde and hydrogen for raw material, it is 60 ~ 160 DEG C in temperature of reaction, reaction pressure is at 1.0 ~ 5.0MPa, raw material and catalyst exposure, reaction generates phenylcarbinol, and wherein catalyst comprises following component: a) 5.0 ~ 20.0%NiO; B) 5.0 ~ 15.0%P
2o
5; D) 45.0 ~ 75.0%Al
2o
3; E) 3.0 ~ 15.0% MgO, BaO, ZrO is selected from
2, at least one in CaO;
Described catalyst preparing comprises the following steps: 1) with SiO
2for carrier; 2) a certain amount of Ni (NO is taken
3)
26H
2o is dissolved in distilled water, then adds a certain amount of (NH
4)
2hPO
4, drip dense HNO wherein
3by resolution of precipitate, and adjusted to ph is between 4 ~ 5, forms solution Ι; 3) calculate by weight percentage, in solution Ι, add citric acid, keep its concentration 2 ~ 5%, form solution Ι Ι; 4) solution Ι Ι is heated to 70 DEG C, equal-volume is added drop-wise to SiO while hot
2on carrier; 5) sample after dipping, roasting 12 hours at 400 ~ 700 DEG C after drying; 6) catalyzer uses front at H
2under in 450 ~ 700 DEG C reduction 12 hours.
2. the method for a kind of Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde according to claim 1, is characterized in that solvent is 0 ~ 95% by weight percentage for phenyl aldehyde is 5 ~ 100% in the mixture of described raw material and solvent.
3. the method for a kind of Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde according to claim 1, is characterized in that MgO, BaO, ZrO by weight percentage
2or at least one consumption is 5.0 ~ 10.0% in CaO.
4. the method for a kind of Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde according to claim 1, is characterized in that described temperature of reaction is 80 ~ 120 DEG C.
5. the method for a kind of Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde according to claim 1, is characterized in that described reaction pressure is 2.0 ~ 4.0MPa.
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| CN201110293321.1A CN103030528B (en) | 2011-09-29 | 2011-09-29 | Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde |
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| CN103030528B true CN103030528B (en) | 2015-08-12 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442149A (en) * | 2016-05-31 | 2017-12-08 | 中国科学院金属研究所 | The foaming structure catalyst reacted for benzaldehyde Hydrogenation for phenmethylol and preparation |
| CN111215081A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Catalyst for preparing alcohols by aldehyde hydrogenation and preparation method thereof |
| CN109824484A (en) * | 2019-03-21 | 2019-05-31 | 合肥学院 | A kind of method of Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde under temperate condition |
| CN111450836A (en) * | 2020-04-12 | 2020-07-28 | 浙江师范大学 | Method for synthesizing p-hydroxybenzyl alcohol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173394A (en) * | 1997-02-27 | 1998-02-18 | 大连理工大学 | Prepn. and application of heteropolyacid salt modified skeletal nickel catalyst |
| CN1379747A (en) * | 1999-10-20 | 2002-11-13 | 沙特基础工业公司 | Liquid phase catalytic hydrogenation process to convert aldehydes to corresponding alcohols |
| CN101376104A (en) * | 2007-08-31 | 2009-03-04 | 赢创奥克森诺有限责任公司 | Hydrogenation catalyst and method for the production of alcohols by hydrogenating carbonyl compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5867637A (en) * | 1981-10-20 | 1983-04-22 | Nippon Kayaku Co Ltd | Preparation of hydroxybenzyl alcohol compound |
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2011
- 2011-09-29 CN CN201110293321.1A patent/CN103030528B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1173394A (en) * | 1997-02-27 | 1998-02-18 | 大连理工大学 | Prepn. and application of heteropolyacid salt modified skeletal nickel catalyst |
| CN1379747A (en) * | 1999-10-20 | 2002-11-13 | 沙特基础工业公司 | Liquid phase catalytic hydrogenation process to convert aldehydes to corresponding alcohols |
| CN101376104A (en) * | 2007-08-31 | 2009-03-04 | 赢创奥克森诺有限责任公司 | Hydrogenation catalyst and method for the production of alcohols by hydrogenating carbonyl compounds |
Non-Patent Citations (1)
| Title |
|---|
| 钠对苯甲醛加氢合成苯甲醇催化剂Cu/SiO2 的修饰作用影响活性;徐华龙等;《化学学报》;20071231;第65卷;第877～880页 * |
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