CN1586717A - Quenched skeleton cobalt base catalyst for cinnamyl aldehyde hydrogenation to prepare cinnamyl alcohol and its preparing method - Google Patents
Quenched skeleton cobalt base catalyst for cinnamyl aldehyde hydrogenation to prepare cinnamyl alcohol and its preparing method Download PDFInfo
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Abstract
The present invention belongs to the field of chemical technology, and especially one kind of quenched skeleton cobalt base catalyst for selective cinnamyl aldehyde hydrogenation to prepare cinnamyl alcohol and its preparation process. The catalyst consists of Co as the active component, Al and metal additive M. The preparation process includes quenching molten alloy at rate over 10E6 K/s in single roller method to obtain quenched Co-Al alloy; alkali extracting quenched Co-Al alloy to eliminate its Al to obtain quenched skeleton Co catalyst; and finally soaking the quenched skeleton Co catalyst in solution of M element to obtain the modified quenched skeleton Co-M catalyst. The quenched skeleton Co-M catalyst is used in cinnamyl aldehyde hydrogenation to prepare cinnamyl alcohol and has much higher hydrogenation activity and selectivity than those of Raney Co catalyst and much higher selectivity than that of Raney Ni catalyst.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of novel sudden cold skeleton cobalt-base catalyst that is used for hydrogenation on cinnamic aldehyde system styryl carbinol and preparation method thereof.
Background technology
Styryl carbinol (COL) is α, in the beta unsaturated alcohol representative one, be a kind of meticulous organic products of high added value, can in organic synthesis, also be widely used as the important source material and the intermediate of spices, medicine and the production of other fine chemical products.The production of styryl carbinol adopts the caustic alkali hot solution to handle natural Soviet Union and sesame oil, Peru Smelling Glue and Oleum Cinnamomi preparation usually, the production cost height, and productive rate is low, and environmental pollution is serious.And selective reduction phenylacrolein (CAL) preparation styryl carbinol is not only with low cost, and helps scale operation.Exist multiple unsaturated functional group in the phenylacrolein molecule, as C=C, C=O and benzene ring structure.In hydrogenation process, can generate one or multiple unsaturated functional group by the product of hydrogenation, so hydrogenation products is quite complicated.Simultaneously, because the bond energy of C=O is higher than the bond energy of C=C, at the easier generation of hydrogenation process C=C key hydrogenation products.So the selective hydration phenylacrolein prepares styryl carbinol and not only has industrial value, and has theoretical investigation value.
Industrially mainly prepare styryl carbinol by pseudoallyl aluminium or benzylalcohol aluminium selective hydration phenylacrolein at present, not only reductive agent costs an arm and a leg, and wants strict control reaction conditions.If reagent is excessive or temperature of reaction is higher, then carbon-to-carbon double bond and carbonyl are reduced simultaneously.No doubt can obtain the styryl carbinol of high yield with tetrahydro-lithium aluminium, sodium borohydride or aluminum isopropylate reductive method, but the separation difficulty of product and reductive agent, solvent etc., the aftertreatment of product is trouble, and the refuse of generation is a lot.Generally, every production 1kg styryl carbinol then will produce the refuse of 20～50kg.If adopt the method for heterogeneous catalytic hydrogenation then can greatly reduce the generation of these refuses, product is easy to separate with catalyzer, if adopt solvent to carry out hydrogenation reaction, as long as product is distilled simply with solvent or underpressure distillation separates, say it is feasible from technological angle, can greatly reduce reaction cost.But because C=C is more active than C=O, therefore, hydrogenation on cinnamic aldehyde often obtains saturated aldehyde (HCAL) or saturated alcohol (HCOL), and is relatively poor to the selectivity of styryl carbinol.One of key that addresses the above problem is the design appropriate catalyst.
Nineteen twenty-five Tuley and Adams reported first on the Pt-Zn-Fe catalyzer the alternative hydrogenation system styryl carbinol (Tuley W.F., Adams R.J.J.Am.Chem.Soc.1925,47,306) of phenylacrolein, people have investigated various catalyzer subsequently.These catalyzer mainly are the precious metal elements of group VIII, and Pt etc. has shown good catalytic effect.Generally speaking, the single-metal reforming catalyst effect does not have the catalyst effect of bimetal or many metals composition good.Cordier finds that the activity of hydrocatalyst of phenylacrolein has following order: Os＞Ir＞Pt＞Ru＞Rh＞Pd, and wherein Pt is the most frequently used.The research of complex catalysis reduction in phenylacrolein selective reduction reaction has also obtained progress preferably.With ruthenium-phosphorus title complex (RuCl
2-TPPTS catalyst system) for catalyzer the synthetic styryl carbinol of phenylacrolein shortening has been shown good selectivity: when transformation efficiency is 83.4%, the selectivity of styryl carbinol is 80.2%, the selectivity of hydrocinnamic aldehyde only is 2.1% (Wang Xiangzhi, Chen Hua, the pears loyal equimolecular catalysis of shining, 1995,9,207).Though these catalyzer have advantages of high catalytic activity and selectivity, cost an arm and a leg; Traditional Ni-catalyst based (as Raney Ni) then is not suitable for styryl carbinol and produces, and its highest yield is less than 50%.
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 skeleton cobalt-base catalyst that the phenylacrolein shortening prepares styryl carbinol, and this Preparation of catalysts method has been proposed.
The catalyzer that is used for hydrogenation on cinnamic aldehyde system styryl carbinol provided by the invention is a kind of sudden cold skeleton catayst that contains cobalt and aluminium.This catalyzer is made up of cobalt Co, aluminium Al and metal additive M, and the weight percentage of Co is 60～95%, and the weight percentage of Al is 5～40%, and the weight percentage of M is 0～20%, and is preferred 0.1～10%, and total amount satisfies 100%.Wherein, Co mainly exists with the form of simple substance, and Al then exists with the form of simple substance and oxidation state, and M is that the form of metallic state, oxidation state or metallic state and oxidation state coexistence exists.
In the catalyzer provided by the invention, metal modifier M can be a kind of in the transition metal in fourth, fifth cycle in the periodic table of elements and the p district metallic element.A kind of in preferred Cr, Mn, Fe, Ni, Cu, Zn, Sn, Mo or its oxide compound.
Catalyzer provided by the invention, specific surface area can reach 5～100m
2/ g has the porous skeleton structure.Its specific activity surface-area is 5～50m
2/ g.
Preparation of catalysts method provided by the invention is: prepare the Co-Al alloy with sudden cold process earlier, obtain sudden cold skeleton Co catalyzer with alkali extracting Co-Al alloy then, use the sudden cold skeleton Co catalyzer of solution soaking of containing metallic additive M element at last, promptly obtain catalyzer of the present invention.
Among the above-mentioned preparation method of the present invention, the preparation of its sudden cold Co-Al alloy is that the cobalt metal of given proportioning and metallic aluminium are added in the silica tube, is heated to the 1573K fusion under argon shield in high frequency furnace, makes its alloying.With the single-roller method cooling, make frangible alloy band again, 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, and obtains the alloy band of thick 2 μ m, wide 5mm.At last banded alloy is ground the back screening in agate mortar, the part of getting a certain size is used for alkali extracting activation.In the consumption of two kinds of metals that add, cobalt accounts for 20～60% of gross weight, and is preferred 30～50%, and all the other are aluminium.
Among the above-mentioned preparation method of the present invention, the alkali extractive process is: will stir adding down to the sudden cold alloy of sizing and be heated in the alkali lye of temperature of reaction, and add the back and continue to stir, and make that aluminium and the alkali lye in the alloy will fully react.Obtain the black solid catalyzer after the reaction.Catalyzer is washed with distilled water to neutral back with washing with alcohol and be kept in the ethanol.The granular size of alloy is 8～400 orders, preferred 80～200 orders; Extraction temperature is 273～373K, preferred 313～363K; The extracting time is 5～600min, preferred 30～120min; Alkali concn is 2～40%, preferred 10～20%; Reactant feeds intake, and is 1 o'clock with weight of cobalt, and the consumption of alkali is 1～10, and preferred 1.5～4.
Among the above-mentioned preparation method of the present invention, the process of the sudden cold skeleton Co catalyzer of metal additive M solution soaking is: the sudden cold skeleton Co catalyzer that will prepare is added in the aqueous solution that contains the M element of specified rate or the ethanolic soln and stirs.Temperature of reaction is 273～373K, preferred 293～323K; Reaction times 5～120min, preferred 50～80min; Concentration 0～0.1mol/L of M, preferred 0～0.05mol/L; With catalyst weight is 1, and the weight of M is 0～1, preferred 0～0.3.
Alkali described in the inventive method is solubility highly basic, as the oxyhydroxide of basic metal and alkaline-earth metal, specifically can be NaOH, KOH, Ca (OH)
2, Ba (OH)
2In a kind of, preferred NaOH or KOH.The immersion process solutions employed is the aqueous solution or the ethanolic soln that contains the M element.Wherein the presoma of Cr is CrCl
3, the presoma of Mn is MnCl
2, the presoma of Fe is FeCl
2, the presoma of Ni is NiCl
2, the presoma of Cu is CuCl
2, the presoma of Zn is ZnCl
2, the presoma of Sn is SnCl
2, the presoma of Mo is Na
2MoO
4
According to catalyzer provided by the invention, the active ingredient cobalt all exists with the nanocrystal form, and forms porous skeleton structure by these nanocrystals, and aluminium exists with the form of metal and oxide compound, plays the support frame effect in catalyzer.At this moment, on the adsorption-desorption thermoisopleth of measuring with the nitrogen physical adsorption at P/P
00.4 a tangible hysteresis loop (as shown in Figure 1) is arranged between～0.9, has tangible vesicular structure.
The catalytic performance of catalyzer provided by the invention can be tested with the following method:
The liquid phase hydrogenation on cinnamic aldehyde reacts the catalytic performance of investigating catalyzer in 220mL stainless steel tank reactor at intermittence.Phenylacrolein, a certain amount of alcohol solvent, 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 the required reaction pressure and in reaction process, remain constant.Turn on agitator is regulated more than the stirring velocity to 1000 rev/min, and is initial as reaction.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 303～373K, preferred 323～353K; Phenylacrolein concentration is 0.1～5.0mol/L, preferred 0.1～2.0mol/L.
Description of drawings
Fig. 1 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 Co-Al alloy
With weight ratio is that 40/60 metal Co and Al add in the silica tube, in high frequency furnace sample is heated to the 1573K fusion, makes its alloying.With argon gas the fused alloy is pressed onto high speed rotating rapidly from silica tube water-cooled copper roller is thrown away, make alloy with～10
6The 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: the preparation of sudden cold skeleton Co catalyzer (RQ Co)
With 100mL concentration is that the NaOH solution of 6.0M is heated to 363K, is adding the sudden cold Co-Al alloy of 10.0g under the magnetic agitation slowly then 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 part characterization result of this catalyzer is shown in table one.
Embodiment 3: the sudden cold skeleton Co-M Preparation of catalysts of modification type (RQ Co-M, M are Cr, Mn, Fe, Ni, Cu, Zn, Sn or Mo)
Under 303K, the sudden cold skeleton Co catalyzer of 10.0g is added to the CrCl of 220mL
3Ethanolic soln, MnCl
2Ethanolic soln, FeCl
2Ethanolic soln, NiCl
2Ethanolic soln, CuCl
2Ethanolic soln, ZnCl
2Ethanolic soln, SnCl
2Ethanolic soln or Na
2MoO
4Stir 60min in the aqueous solution.The reaction back is washed 3 times with ethanol then with distillation washing 3 times, is kept in the ethanol.The add-on of additive is counted 0.10g with the weight of metallic element.The part characterization result of this catalyzer is shown in the table one.
Hydrogenation on cinnamic aldehyde active testing example 1:RQ Co and RQ Co-M catalyzer
Catalyst levels is 0.5g, phenylacrolein 5.0mL, and ethanol 45mL, temperature of reaction 343K, the hydrogen pressure 9atm during reaction, stirring velocity 1000rpm, hydrogenation the results are shown in table two.
Hydrogenation on cinnamic aldehyde active testing example 2: the influence of pressure
Select RQ Co catalyzer for use, the hydrogen pressure when changing reaction, other conditions are with hydrogenation on cinnamic aldehyde active testing example 1, and hydrogenation the results are shown in table three.
Hydrogenation on cinnamic aldehyde active testing example 3: the influence of phenylacrolein concentration
Select RQ Co catalyzer for use, change the concentration of the preceding phenylacrolein of reaction, other conditions are with hydrogenation on cinnamic aldehyde active testing example 1, and hydrogenation the results are shown in table four.
Hydrogenation on cinnamic aldehyde active testing example 4: the influence of temperature of reaction
Select RQ Co catalyzer for use, change temperature of reaction, other conditions are with hydrogenation on cinnamic aldehyde active testing example 1, and hydrogenation the results are shown in table five.
The contrast of hydrogenation on cinnamic aldehyde active testing:
Select Raney Co and Raney Ni catalyzer for use in contrast, its hydrogenation the results are shown in table six.
By table two～table six as seen, adopt sudden cold process obtain skeleton catayst in the selectivity of hydrogenation on cinnamic aldehyde reaction pair styryl carbinol apparently higher than Raney Co and Raney Ni catalyzer.Select for use suitable carriers will further improve activity of such catalysts and selectivity, the yield with styryl carbinol after employing Fe modifies is increased to 92.3%.Select the reaction conditions of low temperature, low pressure and high concentration of feed to help the optionally raising of catalyzer to styryl carbinol.
The part characterization result of table one, RQ Co and RQ Co-M catalyzer
Body phase composite specific surface area pore volume mean pore size
Catalyzer
(atomic ratio) (m
2/ g) (cm
3/ g) (nm)
Raney?Co Co
94.2Al
5.8 29.0 0.138 19.0
RQ?Co Co
93.7Al
6.3 39.8 0.078 7.6
RQ?Co-Cr Co
92.9Cr
0.7Al
6.4 35.6 0.047 5.2
RQ?Co-Mn Co
93.2Mn
0.7Al
6.1 23.1 0.043 7.4
RQ?Co-Fe Co
92.7Fe
1.0Al
6.3 14.2 0.041 11.5
RQ?Co-Ni Co
92.9Ni
1.0Al
6.1 32.1 0.051 6.3
RQ?Co-Cu Co
92.6Cu
0.9Al
6.5 33.9 0.047 5.6
RQ?Co-Zn Co
93.1Zn
0.8Al
6.1 28.2 0.069 9.8
RQ?Co-Sn Co
92.6Sn
0.6Al
6.8 44.9 0.071 6.4
RQ?Co-Mo Co
93.3Mo
0.4Al
6.3 36.9 0.068 7.4
The hydrogenation on cinnamic aldehyde result of table two, RQ Co and RQ Co-M catalyzer
Yield time transformation efficiency selectivity (%)
Catalyzer
(％) (min) (％) HCAL HCOL COL
RQ?Co 71.4 240 94.2 7.3 16.9 75.8
RQ?Co-Cr 75.2 300 95.0 1.6 19.3 79.1
RQ?Co-Mn 91.4 120 97.9 1.3 5.4 93.3
RQ?Co-Fe 92.3 240 97.8 0.5 5.1 94.4
RQ?Co-Ni 35.1 80 89.0 37.2 23.4 39.4
RQ?Co-Cu 89.8 225 98.4 1.1 7.6 91.3
RQ?Co-Zn 85.8 210 96.9 1.8 9.6 88.6
RQ?Co-Sn 87.0 135 95.7 2.3 6.8 90.9
RQ?Co-Mo 77.1 90 95.9 4.2 15.4 80.4
Table three, reaction pressure are to the influence of hydrogenation on cinnamic aldehyde
Reaction pressure yield time transformation efficiency selectivity (%)
(atm) (％) (min) (％) HCAL HCOL COL
5.0 76.8 360 97.7 4.8 16.5 78.7
7.0 74.5 270 95.0 5.1 16.5 78.4
9.0 71.4 240 94.2 7.3 16.9 75.8
11.0 68.5 200 98.6 6.4 24.1 69.5
Table four, phenylacrolein (CAL) concentration are to the influence of hydrogenation on cinnamic aldehyde
CAL concentration yield time transformation efficiency selectivity (%)
(mol/L) (％) (min) (％) HCAL HCOL COL
0.1589 67.5 40 96.7 4.9 25.3 69.8
0.3178 68.3 80 90.2 6.6 17.7 75.7
0.7945 71.4 240 94.2 7.3 16.9 75.8
1.589 73.6 720 98.3 3.8 21.4 74.8
Table five, temperature of reaction are to the influence of hydrogenation on cinnamic aldehyde
Temperature of reaction yield time transformation efficiency selectivity (%)
(K) (％) (min) (％) HCAL HCOL COL
323 73.5 360 96.9 8.1 16.1 75.8
333 72.8 300 92.4 9.1 14.6 76.3
343 71.4 240 94.2 7.3 16.9 75.8
353 69.9 210 93.2 4.6 20.4 75.0
Table six, different catalysts optionally influence hydrogenation on cinnamic aldehyde
Yield time transformation efficiency selectivity (%)
Catalyzer
(％) (min) (％) HCAL HCOL COL
Raney?Ni 2.8 25 97.6 46.2 50.9 2.9
Raney?Co 54.1 240 88.5 7.9 31.0 61.1
RQ?Co 71.4 240 94.2 7.3 16.9 75.8
Claims (10)
1. one kind is used for the sudden cold skeleton cobalt-base catalyst that phenylacrolein is selected hydrogenation system styryl carbinol, it is characterized in that forming by cobalt, aluminium and metal additive M, calculate with metallic element weight, the content of cobalt is 60～95% in skeleton catayst, the content of aluminium is 5～40%, the content of metal additive M is 0～20%, and total amount is 100%; Wherein cobalt mainly is that form with metallic state exists, and aluminium exists with the form of metallic state and oxidation state, and M exists with the form of metallic state, oxidation state or metallic state and oxidation state coexistence.
2. catalyzer according to claim 1, the specific surface area that it is characterized in that catalyzer is 5～100m
2/ g, specific activity surface-area are 5～50m
2/ g.
3. catalyzer according to claim 1 is characterized in that metal additive M is a kind of in the transition metal in fourth, fifth cycle in the periodic table of elements and the p district metallic element.
4. catalyzer according to claim 3 is characterized in that metal additive M is a kind of in Cr, Mn, Fe, Ni, Cu, Zn, Sn, Mo or its oxide compound.
5. one kind as claimed in claim 1ly is used for the preparation method that phenylacrolein is selected the sudden cold skeleton cobalt-base catalyst of hydrogenation system styryl carbinol, it is characterized in that preparing the Co-Al alloy with sudden cold process earlier, obtain sudden cold skeleton Co catalyzer with alkali extracting Co-Al alloy then, use the sudden cold skeleton Co catalyzer of solution soaking of containing metallic additive M element at last, promptly obtain catalyzer of the present invention.
6. Preparation of catalysts method according to claim 5 is characterized in that the preparation process of described sudden cold Co-Al alloy is: with Co and the fusion of Al METAL HEATING PROCESS, make its alloying; With the single-roller method cooling, prepare frangible alloy band; Grind back screening alloy; In the consumption of the two metal, cobalt accounts for 20～60% of gross weight, and remaining is an aluminium.
7. Preparation of catalysts method according to claim 5, it is characterized in that described alkali extractive process is: under agitation add in the alkali lye that has been heated to extraction temperature for the sudden cold alloy of sizing, aluminium and alkali lye in the alloy are fully reacted, obtain the black solid catalyzer; Extraction temperature is 273～373K, and alkali concn is 2～40%, and the extracting time is 5～600min, and the alloying pellet size is 8～400 orders; Reactant feeds intake, and is 1 with weight alloy, and the consumption of alkali is 1～10.
8. Preparation of catalysts method according to claim 5, it is characterized in that described metal additive M solution soaking process is: the sudden cold skeleton Co catalyzer that will prepare is added in the aqueous solution or ethanolic soln that contains M, stir, temperature of reaction 273～373K, reaction times 5～120min, the concentration of M is 0～0.1mol/L; With catalyst weight is 1, and the consumption of M is 0～1.
9. Preparation of catalysts method according to claim 5 is characterized in that the used alkali of extractive process is NaOH, KOH, Ca (OH)
2, Ba (OH)
2In a kind of; The presoma of Co and Al is respectively simple substance Co and Al.
10. Preparation of catalysts method according to claim 5, when it is characterized in that metal additive M is Cr, Mn, Fe, Ni, Cu, Zn, Sn or Mo, its presoma is respectively CrCl
3, MnCl
2, FeCl
2, NiCl
2, CuCl
2, ZnCl
2, SnCl
2, Na
2MoO
4
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| CN102060669A (en) * | 2010-12-07 | 2011-05-18 | 尹华芳 | Method for preparing cinnamyl alcohol |
| CN101164692B (en) * | 2006-10-20 | 2011-06-15 | 中国石油化工股份有限公司 | Cobalt catalyst, preparation method and application thereof |
| CN101164693B (en) * | 2006-10-20 | 2012-01-25 | 中国石油化工股份有限公司 | Iron catalyst, preparation method and its application in synthesizing hydrocarbon reaction |
| CN107537497A (en) * | 2017-07-31 | 2018-01-05 | 常州大学 | A kind of preparation method and application for being used to prepare the catalyst of adjacent methyl cyclohexanol |
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2004
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101164692B (en) * | 2006-10-20 | 2011-06-15 | 中国石油化工股份有限公司 | Cobalt catalyst, preparation method and application thereof |
| CN101164693B (en) * | 2006-10-20 | 2012-01-25 | 中国石油化工股份有限公司 | Iron catalyst, preparation method and its application in synthesizing hydrocarbon reaction |
| CN101199934B (en) * | 2006-12-13 | 2010-09-22 | 中国石油化工股份有限公司 | Process for preparing modified amorphous nickel alloy catalyst |
| CN102060669A (en) * | 2010-12-07 | 2011-05-18 | 尹华芳 | Method for preparing cinnamyl alcohol |
| CN107537497A (en) * | 2017-07-31 | 2018-01-05 | 常州大学 | A kind of preparation method and application for being used to prepare the catalyst of adjacent methyl cyclohexanol |
| CN114250630A (en) * | 2020-09-23 | 2022-03-29 | 湖南博翔新材料有限公司 | Pyrolytic carbonyl iron coating carbon fiber and preparation method thereof |
| CN114250630B (en) * | 2020-09-23 | 2023-08-01 | 湖南博翔新材料有限公司 | Pyrolytic carbonyl iron coating carbon fiber and preparation method thereof |
| CN113786836A (en) * | 2021-09-08 | 2021-12-14 | 天津理工大学 | Metal oxide modified safe porous nickel catalyst |
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| CN1281311C (en) | 2006-10-25 |
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