CN1605387A - Quenched Ni skeleton catalyst for preparing 3-phenylpropyl aldehyde by cinnamaldehyde hydrogenization and its preparing process - Google Patents
Quenched Ni skeleton catalyst for preparing 3-phenylpropyl aldehyde by cinnamaldehyde hydrogenization and its preparing process Download PDFInfo
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Abstract
本发明属于化工技术领域，是用于肉桂醛加氢制备3－苯丙醛的新型猝冷骨架镍催化剂及其制备方法。该催化剂由镍Ni和铝Al组成，比表面积为5～200m2/g，活性比表面为5～100m2/g。该催化剂通过碱抽提猝冷Ni－Al合金，除去合金中的Al后得到；而猝冷Ni－Al合金采用单辊法使合金以106K/s以上的速率冷却后得到。在肉桂醛加氢制备3－苯丙醛的反应中，该催化剂具有比工业上传统的Raney Ni高得多的3－苯丙醛选择性和得率。The invention belongs to the technical field of chemical industry and relates to a novel quenching framework nickel catalyst for preparing 3-phenylpropanal by hydrogenation of cinnamaldehyde and a preparation method thereof. The catalyst is composed of nickel Ni and aluminum Al, the specific surface area is 5-200m 2 /g, and the active specific surface is 5-100m 2 /g. The catalyst is obtained by extracting and quenching Ni-Al alloy with alkali to remove Al in the alloy; and the quenched Ni-Al alloy is obtained by cooling the alloy at a rate above 10 6 K/s by a single-roll method. In the reaction of preparing 3-phenylpropanal by hydrogenation of cinnamaldehyde, the catalyst has much higher selectivity and yield of 3-phenylpropanal than traditional Raney Ni in industry.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of hydrogenation on cinnamic aldehyde that is used for and prepare novel sudden cold skeletal nickel catalyst of 3-phenylpropyl aldehyde and preparation method thereof.
Background technology
3-phenylpropyl aldehyde (HCAL) has another name called hydrocinnamic aldehyde, is a kind of important chemical product, has a wide range of applications in spices, medicine and other Chemical Manufacture.The 3-phenylpropyl aldehyde has type fragrance such as jacinthe, face cream, because it is more stable in alkaline medium, can be used as the allotment soap compound, also can make corrigent and use in multiple essence.In medicine was synthetic, the 3-phenylpropyl aldehyde was important pharmaceutical intermediate.Recently, find that again the 3-phenylpropyl aldehyde can be as the intermediate of treatment HIV medicine.In all multi-routes of synthetic 3-phenylpropyl aldehyde, (CAL) shortening prepares the 3-phenylpropyl aldehyde and is subjected to extensive concern because of meeting most Atom economy from phenylacrolein.Yet phenylacrolein is a kind of typical α, and beta-unsaturated aldehyde not only has C=O and C=C unsaturated group in its molecule, and also has phenyl ring.In the shortening process, the product that hydrogenation takes place one or more unsaturated functional groups simultaneously may be generated, also hydroformylation product solution can be produced simultaneously.Therefore, be that feedstock production 3-phenylpropyl aldehyde process has economic worth and fundamental research meaning with the phenylacrolein.
Can effectively realize separating of product and catalyzer owing to use heterogeneous catalytic hydrogenation, reduce environmental pollution, reduce production costs, so in the reaction of hydrogenation on cinnamic aldehyde prepared in reaction 3-phenylpropyl aldehyde, based on the existing extensive studies of the heterogeneous catalyst of Pt, Ni and Ru, and obtained certain result.Yet, in catalytic hydrogenation reaction, the C=O hydrogenation often also can take place in the C=C hydrogenation generate styryl carbinol (COL) and 3-phenylpropyl alcohol (HCOL) product, reduced selectivity to the 3-phenylpropyl aldehyde.Simultaneously, expensive Pt and Ru also are not suitable for large-scale commercial production.Raney Ni catalyzer has porous skeleton structure, and its surface adsorption has a large amount of hydrogen, has very high hydrogenation activity, but often generates complete hydrogenation products in catalytic hydrogenation reaction, and is very poor to the selectivity of intermediate.We have developed a kind of sudden cold skeleton Ni catalyzer on the basis of Raney Ni Preparation of Catalyst.Because it has characteristics such as microtexture refinement, homogenization of composition, defect concentration increase, demonstrates high activity and good selectivity in a large amount of catalyzed reactions.Because preparation process is simple, with low cost, be fit to mass preparation, be expected to become the new catalyst that replaces traditional commercial catalysts simultaneously.
Summary of the invention
The objective of the invention is to propose a kind of catalytic efficiency high be used for the novel sudden cold skeletal nickel catalyst that the phenylacrolein shortening prepares the 3-phenylpropyl aldehyde, and this Preparation of catalysts method is proposed.
Provided by the inventionly being used for the catalyzer that the phenylacrolein shortening prepares the 3-phenylpropyl aldehyde, is a kind of sudden cold skeleton catayst of nickeliferous and aluminium.Catalyzer is made up of nickel and aluminium Al, and the weight percentage of Ni is 70-95%, and all the other are Al.Wherein, Ni mainly exists with simple substance form, and Al then exists with simple substance and oxidation state form.
Catalyzer provided by the invention, specific surface area can reach 5～200m
2/ g, the specific activity surface is 5-100%, has the porous skeleton structure.
Preparation of catalysts method provided by the invention is by the sudden cold Ni-Al alloy of alkali extracting, remove to obtain behind the Al in the alloy, and sudden cold Ni-Al alloy prepares by single-roller method.
The preparation of sudden cold alloy provided by the invention is carried out according to the following steps.The metal Ni and the Al of given proportioning are added in the silica tube, in high frequency furnace,, make its alloying sample heating (to 1573K) fusion.With the single-roller method cooling, prepare frangible alloy band, grind back screening alloy.Concrete available argon gas throws away the fused alloy is pressed onto high speed rotating rapidly from silica tube water-cooled copper roller, makes alloy with 10
6The above speed of K/s is cooled off, obtain about 2 μ m thick * the wide alloy strip of 5mm.The speed of rotation of copper roller is that per minute 100-200 changes, and banded alloy is ground the back screening in agate mortar, gets particle diameter and activates for a certain size part is used to take out aluminium.In the metal that adds, the Ni quality accounts for 10～60%, and is preferred 20～60%, and all the other are Al.Wherein, Ni and Al exist with simple substance form.
The alkali extractive process of sudden cold skeleton Ni catalyzer provided by the invention is a certain size sudden cold alloy to be added be heated in the alkali lye of temperature of reaction, adds the back and continues to stir, and makes that aluminium and the alkali lye in the alloy fully reacts.The black solid that obtains after the reaction is catalyzer of the present invention.Extraction temperature is 273～403K, preferred 303～383K.The extracting time is 5～600min, preferred 5～200min.Alkali concn is 2～40%, preferred 10～40%.The granular size of alloy is 8～400 orders, preferred 40～400 orders.The feed ratio of alkali and alloy is 1 with weight alloy, and feed ratio is 1～10, preferred 1.5～3.
Alkali of the present invention is solubility highly basic, is the oxyhydroxide of basic metal and alkaline-earth metal, can be NaOH, KOH, Ca (OH)
2, Ba (OH)
2In a kind of, preferred NaOH or KOH.
According to catalyzer provided by the invention, active component nickel all exists with the nanocrystal form, and forms porous skeleton structure by these nanocrystals.Aluminium exists with the form of metal and oxide compound, plays support frame in catalyzer.At this moment, ° locate the diffraction peak (as shown in Figure 1) of a broadening on the X-ray diffractogram of measuring with Cu K α target in 2 θ=45, show that catalyzer mainly is made up of the nanocrystal of nickel.On absorption-desorption isotherm of measuring with the nitrogen physical adsorption at P/P
00.4 a tangible hysteresis loop (as shown in Figure 2) is arranged between～0.8, has tangible central hole structure.
The catalytic performance of catalyzer provided by the invention can be tested with the following method:
Intermittently react the catalytic performance of investigating catalyzer with the liquid phase hydrogenation on cinnamic aldehyde in the tank reactor at the 220mL stainless steel.Phenylacrolein, certain amount of solvent ethanol, catalyzer are put into still.Autoclave sealing back is with air in the hydrogen exchange still more than 6 times, makes air Ex-all in the still.In water-bath, be heated to temperature of reaction behind the preliminary filling certain pressure hydrogen, charge into hydrogen to reaction pressure and in reaction process, remain constant voltage.Turn on agitator is regulated more than the stirring velocity to 1000 rev/min the reaction beginning.Take out a small amount of reaction solution in the reaction process at regular intervals and use gas chromatographic analysis.Hydrogen pressure is 0.1～4MPa in the hydrogenation reaction, preferred 0.5～1.5MPa; Temperature of reaction is 273～373K, preferred 283～323K; Phenylacrolein concentration is 0.1～5.0M, preferred 0.1～2.0M.
Description of drawings
Fig. 1 is the X-ray diffractogram of catalyzer, and Fig. 2 is the nitrogen physical adsorption-desorption isotherm of catalyzer.
Embodiment
Further specifically describe the present invention below by embodiment.
Embodiment 1: the preparation of sudden cold Ni-Al alloy
4kg metal Ni and 6kg metal A l are mixed in the back adding silica tube, in high frequency furnace, sample is heated to the 1573K fusion, make its alloying.With argon gas the fused alloy is pressed onto high speed rotating from silica tube water-cooled copper roller is thrown away, make alloy with 10
6The above speed of K/s is cooled off, obtain 2 μ m thick * the wide alloy strip of 5mm.Banded alloy is ground the back screening in agate mortar, getting particle diameter is that 100～200 purposes partly are used to take out the aluminium activation.
Embodiment 2: sudden cold skeleton Ni Preparation of catalysts
With 100mL concentration is that 20% NaOH solution is heated to 363K, is adding the sudden cold Ni-Al alloy of 10.0g under the magnetic agitation slowly in batches.After alloy adds, continue under this temperature, to stir 1.0h, so that the aluminium in the alloy is by fully extracting.The black solid powder that obtains is washed till neutrality with a large amount of distilled water, uses ethanol replacing water three times, is stored in the ethanol stand-by.The characterization result of this catalyzer is shown in table one and table two.
Hydrogenation on cinnamic aldehyde active testing example 1: the sudden cold Ni catalyzer for preparing under different cooling, Ni/Al ratio, extracting time, extraction temperature, granular size, the alkali concn
Catalyst levels is 0.5g, phenylacrolein 5.0mL, and ethanol 45mL, temperature of reaction 303K, the hydrogen pressure 0.9MPa during reaction, stirring velocity 1000rpm, hydrogenation the results are shown in table three～table eight.
Hydrogenation on cinnamic aldehyde active testing example 2: the influence of hydrogen pressure
With RQ Ni3 is catalyzer, and other conditions change hydrogen pressure with hydrogenation on cinnamic aldehyde active testing example 1, the results are shown in table nine.
Hydrogenation on cinnamic aldehyde active testing example 3: the influence of temperature of reaction
With RQ Ni3 is catalyzer, and other conditions change temperature of reaction with hydrogenation on cinnamic aldehyde active testing example 1, the results are shown in table ten.
Hydrogenation on cinnamic aldehyde active testing example 4: the influence of phenylacrolein concentration
With RQ Ni3 is catalyzer, and other conditions change phenylacrolein concentration with hydrogenation on cinnamic aldehyde active testing example 1, the results are shown in table ten one.
Comparative Examples 1:Raney Ni catalyzer
Catalyzer is industrial widely used Raney Ni catalyzer, and other are with hydrogenation on cinnamic aldehyde active testing example 1, and hydrogenation the results are shown in table ten two.
By table three～table ten two as seen, adopt sudden cold process to obtain skeleton catayst at the selectivity of hydrogenation on cinnamic aldehyde reaction pair 3-phenylpropyl aldehyde Raney Ni catalyzer apparently higher than industrial widespread use.Select for use suitable preparation condition the highest yield of 3-phenylpropyl aldehyde can be increased to 92.7%.
The composition and the porous of the RQ Ni catalyzer of table one, different cooling
Catalyzer is formed (wt.%) than the long-pending (m of table
2/ g) pore volume (cm
3/ g) aperture (nm)
RQ?Ni1 Ni
82.9Al
17.1 121.5 0.0906 3.002
RQ?Ni2 Ni
82.6Al
17.4 118.8 0.0933 3.142
RQ?Ni3 Ni
81.9Al
18.1 115.7 0.0962 3.325
RQ?Ni4 Ni
81.4Al
18.6 112.2 0.0990 3.532
RQ?Ni5 Ni
80.7Al
19.3 108.2 0.1042 3.690
The composition and the porous of the RQ Ni catalyzer of table two, different Ni/Al ratio
Catalyzer is formed (wt.%) than the long-pending (m of table
2/ g) pore volume (cm
3/ g) aperture (nm)
RQ?Ni3 Ni
81.9Al
18.1 115.7 0.0962 3.325
RQ?Ni6 Ni
90.7Al
9.3 74.2 0.1095 5.900
RQ?Ni7 Ni
91.4Al
8.6 71.1 0.0984 5.535
RQ?Ni8 Ni
92.1Al
7.9 59.1 0.0835 6.162
Hydrogenation on cinnamic aldehyde result on the RQ Ni catalyzer of table three, different cooling
Time HCAL yield transformation efficiency selectivity (mol.%)
Catalyzer
(min) (mol.％) (mol.％) HCAl COL HCOL
RQ?Ni1 90 78.0 98.3 79.3 2.1 18.6
RQ?Ni2 80 80.5 98.0 82.1 1.6 16.3
RQ?Ni3 60 84.4 98.2 85.9 0.8 13.3
RQ?Ni4 50 85.2 97.8 87.1 0.6 12.3
RQ?Ni5 40 88.8 98.4 90.2 0.3 9.5
Hydrogenation on cinnamic aldehyde result on the RQ Ni catalyzer of table four, different Ni/Al ratio
Time HCAL yield transformation efficiency selectivity (mol.%)
Catalyzer
(min) (mol.％) (mol.％) HCAL COL HCOL
RQ?Ni3 60 84.4 98.2 85.9 0.8 13.3
RQ?Ni6 75 85.3 98.0 87.0 0.6 12.4
RQ?Ni7 80 86.3 98.9 87.3 0.5 12.2
RQ?Ni8 135 88.6 98.6 89.9 0.3 9.8
Hydrogenation on cinnamic aldehyde result on the RQ Ni catalyzer of table five, different extracting times
Extracting time time HCAL yield transformation efficiency selectivity (mol.%)
(min) (min) (mol.％) (mol.％) HCAL COL HCOL
5 120 92.7 99.8 92.9 0 7.1
15 85 89.6 98.1 91.3 0.3 8.4
30 70 85.9 100 85.9 0 14.1
60 60 84.4 98.2 85.9 0.8 13.3
120 60 83.2 99.5 83.6 0.4 16.0
180 80 82.3 100 82.3 0 17.7
Hydrogenation on cinnamic aldehyde result on the RQ Ni catalyzer of table six, different extraction temperatures
Extraction temperature time HCAL yield transformation efficiency selectivity (mol.%)
(K) (min) (mol.％) (mol.％) HCAL COL HCOL
303 140 88.9 98.4 90.4 0.4 9.2
323 100 87.1 98.8 88.2 0.3 11.5
343 70 85.4 98.0 87.2 0.7 12.1
363 60 84.4 98.2 85.9 0.8 13.3
383 55 83.9 99.8 84.6 0.5 14.9
Hydrogenation on cinnamic aldehyde result on the RQ Ni catalyzer of table seven, variable grain size
Granular size time HCAL yield transformation efficiency selectivity (mol.%)
(order) be (mol.%) (mol.%) HCAL COL HCOL (min)
40-60 120 79.7 99.2 80.4 0 19.6
60-80 100 80.8 98.8 81.7 0 18.3
80-100 80 83.1 98.6 84.3 0.2 15.5
100-200 60 84.4 98.2 85.9 0.8 13.3
200-400 40 91.2 99.7 91.5 0 8.5
Hydrogenation on cinnamic aldehyde result on the RQ Ni catalyzer of table eight, Different Alkali concentration
The concentration time HCAL yield transformation efficiency selectivity (mol.%) of alkali
(wt.％) (min) (mol.％) (mol.％) HCAL COL HCOL
10 65 86.1 98.6 87.3 0.9 11.8
15 60 84.7 98.9 85.6 0.7 13.7
20 60 84.4 98.2 85.9 0.8 13.3
30 65 83.9 98.4 85.3 0.7 14.0
40 70 83.2 98.7 84.3 0.6 15.1
Table nine, hydrogen pressure are to hydrogenation on cinnamic aldehyde result's influence
Pressure time HCAL yield transformation efficiency selectivity (mol.%)
(MPa) (min) (mol.％) (mol.％) HCAL COL HCOL
0.5 110 80.7 98.1 82.3 0.5 17.2
0.7 75 82.7 99.6 83.0 0.6 16.4
0.9 60 84.4 98.2 85.9 0.8 13.3
1.1 50 85.7 99.5 86.1 1.5 12.4
Table ten, temperature of reaction are to hydrogenation on cinnamic aldehyde result's influence
Temperature-time HCAL yield transformation efficiency selectivity (mol.%)
(K) (min) (mol.％) (mol.％) HCAL COL HCOL
278 210 85.4 98.3 86.9 2.1 11.0
303 60 84.4 98.2 85.9 0.8 13.3
323 35 82.5 98.4 83.9 0.5 15.6
343 15 81.9 96.4 85.0 0.7 14.3
Table ten one, phenylacrolein concentration are to hydrogenation result's influence
Concentration time HCAL yield transformation efficiency selectivity (mol.%)
(M) (min) (mol.％) (mol.％) HCAL COL HCOL
0.3973 35 82.7 98.7 83.8 0.6 15.6
0.7945 60 84.4 98.2 85.9 0.8 13.3
1.192 90 85.6 97.6 87.7 1.2 11.1
1.589 130 85.9 99.1 86.7 1.1 12.2
The hydrogenation on cinnamic aldehyde result of table ten two, Raney Ni and RQ Ni3 catalyzer relatively
Time HCAL yield transformation efficiency selectivity (mol.%)
Catalyzer
(min) (mol.％) (mol.％) HCAL COL HCOL
Raney?Ni 100 57.3 92.0 62.3 7.6 30.1
RQ?Ni3 60 84.4 98.2 85.9 0.8 13.3
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863748A (en) * | 2010-06-29 | 2010-10-20 | 南宁市化工研究设计院 | Method for preparing 3-phenylpropyl aldehyde from cassia oil through direct hydrogenation |
| CN109789399A (en) * | 2016-09-23 | 2019-05-21 | 巴斯夫欧洲公司 | Process for activating a catalyst fixed bed comprising or consisting of monolithic shaped catalyst bodies |
| CN110652985A (en) * | 2019-10-09 | 2020-01-07 | 南京科技职业学院 | A kind of preparation method and application of dimer acid hydrogenation catalyst |
| CN112138666A (en) * | 2020-09-04 | 2020-12-29 | 复旦大学 | Quenching skeleton nickel catalyst for preparing methane by carbon monoxide hydrogenation and preparation method and application thereof |
| CN113786836A (en) * | 2021-09-08 | 2021-12-14 | 天津理工大学 | Metal oxide modified safe porous nickel catalyst |
| CN115193443A (en) * | 2022-06-21 | 2022-10-18 | 苏州彼定新材料科技有限公司 | A kind of highly active nickel-aluminum alloy hydrogenation catalyst and preparation method thereof |
-
2004
- 2004-09-01 CN CN 200410054195 patent/CN1605387A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863748A (en) * | 2010-06-29 | 2010-10-20 | 南宁市化工研究设计院 | Method for preparing 3-phenylpropyl aldehyde from cassia oil through direct hydrogenation |
| CN101863748B (en) * | 2010-06-29 | 2013-06-05 | 南宁市化工研究设计院 | Method for preparing 3-phenylpropyl aldehyde from cassia oil through direct hydrogenation |
| CN109789399A (en) * | 2016-09-23 | 2019-05-21 | 巴斯夫欧洲公司 | Process for activating a catalyst fixed bed comprising or consisting of monolithic shaped catalyst bodies |
| CN110652985A (en) * | 2019-10-09 | 2020-01-07 | 南京科技职业学院 | A kind of preparation method and application of dimer acid hydrogenation catalyst |
| CN112138666A (en) * | 2020-09-04 | 2020-12-29 | 复旦大学 | Quenching skeleton nickel catalyst for preparing methane by carbon monoxide hydrogenation and preparation method and application thereof |
| CN113786836A (en) * | 2021-09-08 | 2021-12-14 | 天津理工大学 | Metal oxide modified safe porous nickel catalyst |
| CN115193443A (en) * | 2022-06-21 | 2022-10-18 | 苏州彼定新材料科技有限公司 | A kind of highly active nickel-aluminum alloy hydrogenation catalyst and preparation method thereof |
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