CN103566930A - Pd/SiO2 catalyst and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a Pd/SiO2 catalyst and a preparation method and application thereof. The Pd/SiO2 catalyst comprises the following components: 98-99.99% of silicon dioxide carrier, 0.01-1% of palladium metal component, and 0-1% of promoter, wherein the silicon dioxide carrier is a spheroidal or block silica gel particle, the specific surface area is 150-300m<2>/g, the most probable pore diameter is 15-30nm, the pore volume is 0.8-1.2ml/g, the particle size is 4-18 mesh, the average value of particle strength is greater than 1kg per particle, and the promoter is selected from one or a few of alkali metal, alkaline-earth metal, transition metal and rear earth metal. The catalyst not only has high catalytic activity, but also can be used for solving the problem of excessive hydrogenation of the reaction product caused by internal diffusion limitation, and is especially suitable for continuous liquid phase selective hydrogenation of 6,10,14-trimethyl-13-alkene-2-pentadecanone with large molecular weight in a fixed bed reactor.
Description
Technical field
The invention belongs to catalytic hydrogenation field, be specifically related to a kind of Pd/SiO
2catalysts and its preparation method and application.
Background technology
Hexahydrofarnesyl acetone (6,10,14-trimethyl-2-pentadecanone, PA) micro-sweet, blurt out, be a kind of for the preparation of pohytol and different vegetable alcohol, and then prepare the important chemical intermediate of vitamin E.In the synthetic route of industrial several PA, finally all need just can obtain PA(course of reaction as shown in Figure 1 through the selective catalytic hydrogenation process of 6,10,14-trimethyl-13-alkene-2-pentadecanone (FA-4H) at present).
As seen from Figure 1, the two key generation selective hydrogenations of C=C in FA-4H generate product P A, C=O double-bond hydrogenation in while PA, and react (2) generate accessory substance 6,10,14-trimethyl-2-pentadecanol (PA-alcohol); The two keys of C=O in a small amount of FA-4H also can be prior to the two key generation hydrogenation of C=C, react (3) obtain accessory substance 6,10,14-trimethyl-13-alkene-2-pentadecanol (FA-alcohol), the two keys of C=C in FA-alcohol continue to occur hydrogenation reaction and also finally generate PA-alcohol.In the industrial chain of vitamin E, FA-4H is main intermediate, and it is carried out to selective hydrogenation generation PA is committed step wherein.When in Fig. 1, reaction (1) is carried out, the frequency higher accessory substance FA-alcohol of reaction (2), (3) and (4) generation and the growing amount of PA-alcohol are more, the impurity generating in vitamin E is just more, thereby its quality is impacted.
In existing liquid-phase hydrogenatin at intermittence reaction process, under the effect of Powdered palladium carbon catalyst, FA-4H selective hydrogenation generates the conversion ratio >99.7% that selectively approaches 100%, FA of PA.But intermittent reaction automation technolo degree is low, troublesome poeration, comprising: the multistep production operation processes such as 1) charging (raw material, hydrogen and catalyst), reaction (needs are mended hydrogen continuously), separated (hydrogen is emptying, filtering recovering catalyst).Therefore, not only production operation is dangerous for intermittent reaction technique, labour intensity is large, and the reaction of every still finishes a large amount of hydrogen of rear waste.In addition, intermittently the production technology in tank reactor also needs special filtering catalyst device, and this certainly will cause the loss of catalyst again.Adopt fixed bed (trickle bed, bubbling bed) continuous catalytic hydrogenation technique can effectively overcome some problems that exist in liquid-phase hydrogenatin at intermittence technique.The fixed bed continously hydrogen adding reaction of participating in for the larger FA of molecular weight, inner diffusional limitation is one of principal element affecting its reaction rate.And active carbon mainly be take micropore as main, mesoporous negligible amounts, thereby while using active carbon for carrier, be difficult to obtain higher reactivity; " limited reaction " occurs while FA in less catalyst granules duct may make PA be easier to excessive hydrogenation generation by-product alcohol.In addition, fixed bed reactors have special requirement to the granular size of catalyst and intensity.Therefore the Powdered Pd/C catalyst, using in liquid-phase hydrogenatin at intermittence technique under normal conditions can not be for the fixed bed Continuous Liquid Phase hydrogenation of FA.
Summary of the invention
The invention provides a kind of Pd/SiO
2catalysts and its preparation method and application, this Pd/SiO
2catalyst is applied to the fixed bed Continuous Liquid Phase selective catalytic hydrogenation of 6,10,14-trimethyl-13-alkene-2-pentadecanone (FA-4H), has higher activity and selectivity.
A kind of Pd/SiO
2catalyst, is comprised of the component of following percentage by weight:
Silica supports 98～99.99%
Palladium metal component 0.01～1%
Co-catalyst 0～1%
Described silica supports is ball-type or block silica gel particle, and specific surface is 150～300m
2/ g, most probable aperture is 15～30nm, and pore volume is 0.8～1.2ml/g, and granularity is 4～18 orders, granule strength: mean value is greater than 1kg/;
Described cocatalyst component is selected from one or more in alkali metal, alkaline-earth metal, transition metal and rare earth metal.
Described alkali metal comprises Li and Na, described alkaline-earth metal comprises Mg and Ba etc., described transition metal comprises Ti and Zr etc., described rare earth metal comprises La, Ce and Sm etc., and above-mentioned cocatalyst component can be present in the form of metal simple-substance, slaine or metal oxide described Pd/SiO
2in catalyst.As further preferred, described co-catalyst is one or more in rare earth metal.
Being take in large aperture, particle silica gel in the present invention is carrier, at the surfaces externally and internally of silica gel, has adsorbed Pd, has made large aperture, graininess Pd/SiO
2catalyst.Its larger pore is convenient to FA-4H and the product 6 that molecular weight is larger, 10,14-trimethyl-2-pentadecanone (PA) is in the diffusion of catalyst granules inside, this can not only improve the activity of catalyst, and reduced the time that product P A stops in catalyst duct, avoid FA-4H and PA that " limited reaction " occurs in less duct, thereby reduced Main By product 6, the generation of 10,14-trimethyl-13-alkene-2-pentadecanol (FA-alcohol).Experimental result shows, when silica supports aperture is greater than 15nm, can significantly improve the selective of principal product.Thereby catalyst of the present invention both retained the good hydrogenation characteristic of conventional powder shape palladium carbon catalyst, again applicable to fixed bed continuous reactor, be specially adapted to the fixed bed Continuous Liquid Phase selective hydrogenation of FA-4H.And when silica supports is greater than 30nm, its specific area is relatively little, thereby the decentralization of active component is reduced, Pd/SiO
2the hydrogenation activity of catalyst is lower.
As preferably, described Pd/SiO
2catalyst, is comprised of the component of following percentage by weight:
Silica supports 98.5～99.988%
Palladium metal component 0.01～1%
Co-catalyst 0.002～0.5%;
Described co-catalyst is selected from one or more in the metals such as Li, Mg, Ti, La and Ce; Adding of co-catalyst is conducive to hydrogenation reaction conversion ratio and optionally further improves.
The present invention also provides described Pd/SiO
2the preparation method of catalyst, comprising:
(1) dried silica supports is immersed in palladium presoma-hydrochloric acid solution, places 1～4 hour, stir and obtain mixture;
Described palladium presoma is palladium chloride;
Stirring frequency is to stir once every 20～40 minutes;
(2) by the moisture evaporate to dryness in said mixture, make palladium presoma uniform load to the surfaces externally and internally of described silica supports, obtain dry catalyst;
(3) dried catalyst is put into Muffle furnace 110-700 ℃ of roasting 1-6 hour, obtained described Pd/SiO after cooling
2catalyst.
As preferably, in step (1), in described palladium presoma-hydrochloric acid solution, further add the soluble-salt of described co-catalyst, the cation of described soluble-salt is that transition metal ions is (as Ti
3+, Zr
4+), rare earth ion is (as La
3+, Ce
3+, Sm
3+), alkali metal ion is (as Li
+, Na
+) or alkaline-earth metal ions (as Mg
2+, Ba
2+) etc. one or more in metal, the anion of described soluble-salt is generally selected NO
3 -or Cl
-deng, wherein the concentration of hydrochloric acid is without strict especially requirement.
As preferably, in step (1), in described palladium presoma-hydrochloric acid solution, add complexant; General micromolecular carboxylic acid and the aminated compounds selected of described complexant, for Pd
2+there is coordination, improve the stability of Pd presoma, thereby play, prevent that Pd presoma from the effect of reuniting occurring in dry, roasting process subsequently.As further preferably, in step (1), described complexant is ammoniacal liquor, ethylenediamine, ethylenediamine tetra-acetic acid or citric acid etc., and the mol ratio of described complexant and described palladium presoma is 1～40:1.
In step (1), described palladium presoma-hydrochloric acid solution is preferably palladium chloride-hydrochloric acid solution, described palladium chloride-hydrochloric acid solution is mixed and is formed by C.P level palladium chloride and C.P level concentrated hydrochloric acid, the weight ratio of concentrated hydrochloric acid and palladium chloride is 15～20:1, after palladium chloride dissolves, then be 0.01～0.15g/ml by the concentration that deionized water is diluted to palladium chloride.
In step (2), described mixture evaporate to dryness on Rotary Evaporators, the rotating speed of Rotary Evaporators motor is 10～50 revs/min, the vacuum in its cavity is 0.08～0.1MPa, the heating schedule of heating water bath is: 30～60 ℃ keep 1～4 hour, then keep 1～4 hour in 70～90 ℃.
The present invention also provides a kind of described Pd/SiO
2the application of catalyst in the selective hydrogenation of 6,10,14-trimethyl-13-alkene-2-pentadecanone (FA-4H), described selective hydrogenation carries out continuously in fixed bed reactors;
Described Pd/SiO
2catalyst shows higher than 99.7% FA-4H conversion ratio and selective higher than 99.0% hexahydrofarnesyl acetone (PA) in the selective hydrogenation of FA-4H.As shown in Figure 2, this reaction unit is an existing apparatus to FA-4H Continuous Liquid Phase selective hydrogenation fixed-bed reactor.
Catalyst need to carry out reduction pretreatment before using in mobile hydrogen.Pretreatment condition is: hydrogen gas space velocity is 0.5～3.0h
-1, reduction temperature is 200～350 ℃.
As preferably, the temperature of described hydrogenation reaction is 25～200 ℃, and reaction pressure is 1.0～4.0MPa, and liquid air speed is 0.5～3.0h
-1, now, the yield of described hexahydrofarnesyl acetone or selectively the highest.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) large aperture being made by said method, graininess Pd/SiO
2catalyst most probable aperture is 15～30nm, when this pore diameter range makes the hydrogenation reaction of its application and FA-4H, has higher reactivity and selective simultaneously, has improved the yield of hexahydrofarnesyl acetone;
(2) described Pd/SiO
2the granularity of catalyst is 4～18 orders, granule strength: mean value is greater than 1kg/, this size and intensity make this catalyst can be applicable to the fixed bed Continuous Liquid Phase selective hydrogenation of FA-4H, thereby have overcome the series of problems such as liquid-phase hydrogenatin at the intermittence explained hereafter operation of the Powdered palladium carbon catalyst of current use is dangerous, labour intensity large, hydrogen expends seriously, catalyst separation trouble.
Accompanying drawing explanation
Fig. 1 is the course of reaction of the catalytic hydrogenation reaction of 6,10,14-trimethyl-13-alkene-2-pentadecanone;
Fig. 2 is the schematic diagram of FA-4H Continuous Liquid Phase selective hydrogenation fixed bed device; In Fig. 2,1-measuring pump, 2-fixed bed reactors, 3-beds, 4-point for measuring temperature, 5-condenser, the import of A-liquid charging stock, B-hydrogen inlet, C-reactor bottom, D-reactor head, E-products export.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
0.52ml palladium bichloride-hydrochloric acid solution (palladium bichloride concentration is 0.08g/ml) is joined in 50ml deionized water, add again 1.5g citric acid, treat that it dissolves, and after mixing, pours 25g6～8 object spherical silica gel particle wherein to flood 2 hours into palladium bichloride-hydrochloric acid solution.Said mixture is first at 50 ℃ on Rotary Evaporators, under the condition of 0.09MPa, be dried 3 hours, then in 80 ℃, the dry 2h of 0.09MPa.Dried catalyst is placed in to 400 ℃ of roastings of Muffle furnace and within 3 hours, obtains catalyst A.The weight content of its metal Pd is 0.1%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object spheric granules, and particle mean intensity is 8.3Kg/; Its specific area is 213.5m
2/ g, most probable aperture is 19.6nm, pore volume is 1.01ml/g.
Embodiment 2
The preparation method of catalyst B is with embodiment 1, but carrier used is 6～8 object block silica gel particles.The weight content of its metal Pd is 0.1%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object blocky-shaped particles, and particle mean intensity is 3.1Kg/; Its specific area is 166.2m
2/ g, most probable aperture is 23.4nm, pore volume is 0.98ml/g.
1.56ml palladium bichloride-hydrochloric acid solution (palladium bichloride concentration is 0.08g/ml) is joined in 50ml deionized water, add again 1.5g ethylenediamine, treat that it dissolves, and after mixing, pours 25g6～8 object block silica gel particle wherein to flood 2 hours into palladium bichloride-hydrochloric acid solution.Said mixture is first at 50 ℃ on Rotary Evaporators, under the condition of 0.09MPa, be dried 1 hour, then in 80 ℃, the dry 2h of 0.09MPa.Dried catalyst is placed in to 400 ℃ of roastings of Muffle furnace and within 3 hours, obtains catalyst C.The weight content of its metal Pd is 0.5%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object spheric granules, and particle mean intensity is 4.0Kg/; Its specific area is 220.1m
2/ g, most probable aperture is 18.6nm, pore volume is 0.97ml/g.
By 1.56ml palladium bichloride-hydrochloric acid solution (palladium bichloride concentration is 0.08g/ml) and 0.0779g lanthanum nitrate (La (NO
3)
36H
2o) join in 50ml deionized water, then add 2.0g citric acid, treat that it dissolves, and after mixing, pours 25g block silica gel particle wherein to flood 2 hours into palladium bichloride-hydrochloric acid solution.Said mixture is first at 50 ℃ on Rotary Evaporators, under the condition of 0.09MPa, be dried 2 hours, then in 80 ℃, the dry 2h of 0.09MPa.The 400 ℃ of roastings in Muffle furnace of dried catalyst are obtained to catalyst D for 3 hours.The weight content of its metal Pd is 0.5%, and the weight content of metal La is 0.1%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object blocky-shaped particles, and particle mean intensity is 3.5Kg/; Its specific area is 216.4m
2/ g, most probable aperture is 18.7nm, pore volume is 1.01ml/g.This embodiment shows, rare earth metal co-catalyst add the further conversion ratio that has improved reaction and selective.Lanthanum nitrate in the present embodiment can also be used Ti (NO
3)
4or MgCl
2replace, also can further improve the conversion ratio of reaction with selective.
Comparative example 1
The preparation method of catalyst E is with embodiment 1, and carrier used is also 6～8 object spherical silica gel particles, but its most probable aperture is less.The weight content of its metal Pd is 0.1%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object spheric granules, and particle mean intensity is 10.6Kg/; Its specific area is 390.0m
2/ g, most probable aperture is 9.6nm, pore volume is 1.01ml/g.
Comparative example 2
The preparation method of catalyst F is with embodiment 1, and carrier used is also 6～8 object spherical silica gel particles, but its most probable aperture is larger.The weight content of its metal Pd is 0.1%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object spheric granules, and particle mean intensity is 5.4Kg/; Its specific area is 110.2m
2/ g, most probable aperture is 44nm, pore volume is 1.05ml/g.
Comparative example 3
The preparation method of catalyst G is with embodiment 3, but carrier used is 6～8 object granular active carbons.The weight content of its metal Pd is 0.5%, and all the other are absorbent charcoal carrier; Gained catalyst is 6～8 object spherical particles, and particle mean intensity is 1.4Kg/; Its specific area is 1295.2m
2/ g, most probable aperture is 2.2nm, pore volume is 0.68ml/g.
Comparative example 4
The preparation method of catalyst H is with embodiment 3, but in dipping solution, there is no adding citric acid as Pd
2+complexant.The weight content of its metal Pd is 0.5%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object blocky-shaped particles, and particle mean intensity is 3.8Kg/; Its specific area is 214.3m
2/ g, most probable aperture is 19.0nm, pore volume is 0.98ml/g.
Comparative example 5
The preparation method of catalyst I, with embodiment 4, has still wherein added metal Ru as co-catalyst.The weight content of its metal Pd is 0.5%, and the weight content of metal Ru is 0.1%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object blocky-shaped particles, and particle mean intensity is 3.6Kg/; Its specific area is 222.2m
2/ g, most probable aperture is 18.5nm, pore volume is 1.01ml/g.
Comparative example 6
The preparation method of catalyst J is with embodiment 4, and carrier used is also 6～8 object block silica gel particles, but its most probable aperture is less.The weight content of its metal Pd is 0.5%, and the weight content of metal La is 0.1%, and all the other are silica-gel carrier; Gained catalyst is 6～8 object blocky-shaped particles, and particle mean intensity is 11.2Kg/; Its specific area is 385.0m
2/ g, most probable aperture is 9.3nm, pore volume is 0.99ml/g.
Catalyst A, B, C, D, E, F, G, H, I and J and on fixing bubbling bed reactor reaction condition and the result of FA-4H Continuous Liquid Phase selective hydrogenation as shown in the table.
Table 1
Result by table 1 can be known, compares with catalyst A, and the most probable aperture of catalyst E is decreased to after 9.6nm, accessory substance PA-alcohol showed increased; After the most probable aperture of catalyst F increases, the yield of principal product obviously reduces.
Claims (8)
1. a Pd/SiO
2catalyst, is characterized in that, the component of following percentage by weight, consists of:
Silica supports 98～99.99%
Palladium metal component 0.01～1%
Co-catalyst 0～1%
Described silica supports is ball-type or block silica gel particle, and specific surface is 150～300m
2/ g, most probable aperture is 15～30nm, and pore volume is 0.8～1.2ml/g, and granularity is 4～18 orders, granule strength: mean value is greater than 1kg/;
Described cocatalyst component is selected from one or more in alkali metal, alkaline-earth metal, transition metal and rare earth metal.
2. Pd/SiO according to claim 1
2catalyst, is characterized in that, the component of following percentage by weight, consists of:
Silica supports 98.5～99.988%
Palladium metal component 0.01～1%
Co-catalyst 0.002～0.5%;
Described co-catalyst is selected from one or more in Li, Mg, Ti, La and Ce.
3. the Pd/SiO described in a claim 1 or 2
2the preparation method of catalyst, is characterized in that, comprising:
(1) dried silica supports is immersed in palladium presoma-hydrochloric acid solution, places 1～4 hour, stir and obtain mixture;
Described palladium presoma is palladium chloride;
(2) by the moisture evaporate to dryness in said mixture, make palladium presoma uniform load to the surfaces externally and internally of described silica supports, obtain dry catalyst;
(3) dried catalyst is put into Muffle furnace 110-700 ℃ of roasting 1-6 hour, obtained described Pd/SiO after cooling
2catalyst.
4. Pd/SiO according to claim 3
2the preparation method of catalyst, is characterized in that, in step (1), further adds the soluble-salt of described co-catalyst in described palladium presoma-hydrochloric acid solution.
5. according to the Pd/SiO described in claim 3 or 4
2the preparation method of catalyst, is characterized in that, in step (1), in described palladium presoma-hydrochloric acid solution, adds complexant.
6. Pd/SiO according to claim 5
2the preparation method of catalyst, is characterized in that, in step (1), described complexant is ammoniacal liquor, ethylenediamine, ethylenediamine tetra-acetic acid or citric acid, and the mol ratio of described complexant and described palladium presoma is 1～40:1.
7. the Pd/SiO described in a claim 1 or 2
2catalyst is applied in the selective hydrogenation of 6,10,14-trimethyl-13-alkene-2-pentadecanone (FA-4H), it is characterized in that, described hydrogenation reaction is carried out continuously in fixed bed reactors;
The product of described selective hydrogenation is hexahydrofarnesyl acetone, selectively higher than 99.0%.
8. Pd/SiO according to claim 7
2the application of catalyst in FA-4H selective hydrogenation, is characterized in that, the temperature of described hydrogenation reaction is 25～200 ℃, and reaction pressure is 1.0～4.0MPa, and liquid air speed is 0.5～3.0h
-1.
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