CN103447030B - The preparation method of the plumbous bimetallic catalyst of a kind of " eggshell " structure Pd - Google Patents

The preparation method of the plumbous bimetallic catalyst of a kind of " eggshell " structure Pd Download PDF

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CN103447030B
CN103447030B CN201310378970.0A CN201310378970A CN103447030B CN 103447030 B CN103447030 B CN 103447030B CN 201310378970 A CN201310378970 A CN 201310378970A CN 103447030 B CN103447030 B CN 103447030B
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catalyst
alumina
palladium
alumina support
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CN103447030A (en
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韩军兴
闫瑞一
刁琰琰
王蕾
公茂明
张锁江
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Institute of Process Engineering of CAS
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester

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Abstract

The present invention relates to the preparation method of the plumbous bimetallic catalyst of one " eggshell " structure Pd, the method adopts first load P b presoma, improves the method for Pb load capacity to alumina support introducing Pb species, then obtains Pd-Pb bimetallic catalyst through liquid-phase reduction; In gained catalysis, Pd-Pb bimetal nano particles is distributed in " eggshell " region of below carrying alumina external surface 20 μm.This catalyst is prepared in the reaction of methyl methacrylate (MMA) at alcohol aldehyde oxidation and esterification and is had high catalytic activity, selectivity of product and stability.Compared with conventional P d-Pb bimetallic catalyst, novel " eggshell " structure Pd-Pb bimetallic catalyst has that preparation method is simple, Pd decentralization is high, catalyst composition is easy to the advantages such as control, therefore precious metals pd load capacity can reduce about 150%, and catalyst cost of investment significantly reduces.

Description

The preparation method of the plumbous bimetallic catalyst of a kind of " eggshell " structure Pd
Technical field
The present invention relates to the preparation method of one " eggshell " structure bimetallic catalyst, refer to the preparation method of the plumbous bimetallic catalyst of a kind of efficient, low load capacity palladium especially, the direct oxidation esterification of this method gained catalyst to unsaturated aldehyde and lower aliphatic alcohols has high catalytic activity, selectivity of product and stability, belongs to field of catalyst preparation.
Background technology
Carboxylate is the important compound of a class, is widely used in fields such as medicine, agricultural chemicals, spices, additives.Corresponding therewith, the research about ester type compound synthetic method has the history more than more than 100 years.Up to the present, chemists have established the method for multiple efficient synthesizing ester compound.Such as: carboxylic acid or carboxylic acid derivates and alcohol generation esterification be synthesizing ester compound the earliest, most effective method; Carboxylic acid and aldehyde compound are the effective ways set up in bio oil grading process through an one-step hydrogenation esterification reaction synthesizing ester compound; First aldehyde compound is obtained carboxylic acid through oxidation reaction, and carboxylic acid reacts obtained carboxylate again with alcohol compound be using aldehyde compound as one of raw material method preparing ester type compound; Alcohol aldehyde direct oxidation esterification is the method preparing ester type compound recently developed.Wherein, using molecular oxygen as oxidant, alcohol aldehyde direct oxidation esterification is a kind of green, the method preparing ester type compound efficiently.Take particularly isobutene as raw material substitution traditional acetone cyanalcohol legal system in two-step method (see the reaction scheme below) process of methyl methacrylate (MMA) at petroleum base route, alcohol aldehyde (methyl alcohol and MAL) direct oxidation esterification process is the technological core of this process route.
According to the literature, alcohol aldehyde direct oxidation esterification system mainly comprises two classes: a class be using molecular oxygen as oxidant, transition metal (as Ag, Au, Ir, Pd, Rh, Ru etc.) is as the reaction system of catalyst; Another kind of is that oxide is stoichiometrically (as KMnO 4, CrO 3, V 2o 5, KHSO 5deng) as the reaction system of oxidant.In above-mentioned two kinds of reaction systems, palladium-based catalyst using molecular oxygen as oxidant, high, the process of catalytic efficiency is green clean, therefore in the commercial process of MMA, obtains application.Used catalyst mainly Pd in the reaction of MMA is produced at present at MAL (MAL) and methyl alcohol direct oxidation esterification 5pb 5/ MgO-Al 2o 3and Pd 5pb 5/ CaCO 3(Pd 5pb 5in expression catalyst, the load capacity of Pd is the load capacity of 5wt%, Pb is 5wt%).
Palladium belongs to rare precious metals, the abundance in the earth's crust lower (being about 6.3ppb) and annual production limited (annual production is about 24 tons).Current two-step method is prepared Pd load capacity in the catalyst of MMA and is about 5wt%, this load capacity is higher, thus cause that catalyst is expensive, proportion is comparatively large (to produce the process units of 10,000 tons of MMA per year in cost of investment, its required investment is about 100,000,000 yuan, and wherein only buying one, metal just needs cost 1,000 ten thousand yuan.), this limits the popularization of two-step process route to a certain extent.The load capacity of raising palladium-based catalyst catalytic efficiency, reduction precious metal palladium has important theory significance and application prospect.
Aluminium oxide has excellent mechanical strength, large specific area and abundant pore passage structure, is therefore widely applied as catalyst carrier.Comprise a large amount of micropore canals in common alumina support, reactant and the product diffusional resistance in duct is comparatively large, makes the catalyst activity position being positioned at micropore canals be difficult to be utilized effectively.For improving mass-transfer efficiency and utilization rate of inner surface, researcher have developed the alumina support with ordered mesoporous pore canals structure.Mesoporous alumina carrier appear at the utilization ratio that improve load type metal nano particle to a certain extent, but mesoporous alumina carrier mechanical strength is low, heat endurance (particularly hydrothermal stability) is poor, is therefore difficult to be applied in industrial catalyst.
Controlling active component distribution is on the alumina support the another kind of method improving catalyst efficiency.Make it form " eggshell " structure distribution can to reduce reactant resistance to mass tranfer, improve the collision probability of active sites and reactant by active component Pd being enriched in the certain thickness space of below aluminum oxide micro-sphere outer surface, thus realize the raising of catalytic efficiency.Compared with non-porous support (as calcium carbonate), " eggshell " structure catalyst inhibits reunion and the loss of metal nanoparticle by pore passage structure, thus ensure that the stability that catalyst is high.Japan Asahi Kasei Corporation researcher using aluminum oxide micro-sphere as carrier, K +, Mg 2+, Al 3+as competitive adsorbate, successfully obtained the Pd-Pb bimetallic catalyst with " eggshell " structure, the thickness of " eggshell " part is about 20 microns (US6228800B1), but in the catalyst synthesized by this method, Pd load capacity is still up to 5wt%.There is the shortcomings such as preparation process is loaded down with trivial details, severe reaction conditions, alkali and alkaline earth metal ions ion easily run off in this method simultaneously.
Summary of the invention
The object of the invention is to overcome the shortcoming that existing Pd-Pb Catalyzed by Pt/M Bimetallic Nano efficiency is low, noble-metal-supported amount is high, preparation process is loaded down with trivial details, provide one to prepare the preparation method of " eggshell " structure Pd-Pb bimetallic catalyst.This preparation method is simple to operate, and catalyst composition is easy to control, and catalytic efficiency is high, and noble-metal-supported amount can reduce about 150%.
The present invention take Woelm Alumina as carrier, with acetylacetone,2,4-pentanedione lead, plumbi nitras, lead chloride, lead sulfate or lead acetate for Pb presoma, the acid of palladium bichloride, palladium nitrate, palladium, chlorine palladium, chlorine palladium acid sodium or dichloro two ammino palladium are Pd presoma, are regulated distribution and the catalytic activity of active component in catalyst by the parameter such as Mo-Co catalyst, load capacity, sintering temperature, reducing agent kind, reduction temperature, recovery time changing Pd, Pb.In catalyst, Pd, Pb distribution on carrier characterizes with electron probe after being embedded by catalyst granules, cutting into slices.
In the present invention, alumina support used can be the one in spherical, powder or column.
In the present invention, the Mo-Co catalyst of Pd, Pb is first to load P b presoma on alumina support, then load P d presoma.
In the present invention, Pd load capacity is 0.5-5%, Pb load capacity is 1-10%.
In the present invention, Pb can adopt the one in equi-volume impregnating, excessive infusion process or chemical vapour deposition technique to the load on alumina support.
To need after alumina support load P b presoma in the present invention under air atmosphere or oxygen atmosphere through high-temperature roasting process to reach decomposed P b presoma, to strengthen Pb species and the interactional object of alumina support.The temperature of high-temperature roasting is 300-700 DEG C, and roasting time is 0.5-10h.
The present invention adopts liquid phase reduction to obtain Pd-Pb bimetallic catalyst, and reducing agent used can be hydrazine hydrate, formalin, higher alcohol or NaBH 4, reduction temperature is 25-100 DEG C, and the recovery time is 0.5-10h.
The present invention prepares methyl methacrylate (MMA) for the activity of model reaction to catalyst with MAL (MAL) and methyl alcohol direct oxidation esterification and evaluates.
Accompanying drawing explanation
Fig. 1 is Pd 2pb 8/ Al 2o 3the distribution of Pd on aluminum oxide micro-sphere section in catalyst, scale represents 20 μm.
Fig. 2 is Pd 5pb 5/ MgO-Al 2o 3the distribution of Pd on aluminum oxide micro-sphere section in catalyst, scale represents 20 μm.
Detailed description of the invention
The present invention's following examples illustrate, but are not limited to following embodiment, and in the scope not departing from the described aim in front and back, change is included within technical scope of the present invention.
Embodiment 1
5g spherical alumina support is added in 500mL beaker, adds deionized water, put into water-bath, under mechanical agitation, add 4.0mLH 2pdCl 4solution, is warming up to 60 DEG C.Drip 20mL n-butanol, after 0.5h, stop reaction.Be chilled to room temperature, suction filtration, massive laundering, dry 12h in 40 DEG C of vacuum drying chambers.Gained catalyst gauge is done: Pd 2/ Al 2o 3.In catalyst, Pd and Pb content ICP-AES records, in table 1.Embodiment 2
Add in alumina support after 0.16g acetylacetone,2,4-pentanedione lead deionized water dissolving, leave standstill, then put into the dry 12h of vacuum drying chamber.300 DEG C of roasting 0.5h in air atmosphere.Leaded alumina support after dipping-roasting is added in 500mL beaker, adds deionized water, put into water-bath, under mechanical agitation, add 4.6mL palladium solution, be warming up to 60 DEG C.Drip 25mL37wt% formalin, after 6h, stop reaction.Be chilled to room temperature, suction filtration, massive laundering, dry 12h in 80 DEG C of vacuum drying chambers.Gained catalyst gauge is done: Pd 1pb 1/ Al 2o 3.In catalyst, Pd and Pb content ICP-AES records, in table 1.
Embodiment 3
2.56gPbCl 2with adding in alumina support after deionized water dissolving, leaving standstill, then putting into the dry 12h of vacuum drying chamber.500 DEG C of roasting 3h in air atmosphere.Leaded alumina support after dipping-roasting is added in 500mL beaker, adds deionized water, under mechanical agitation, add 9.0mLH 2pdCl 4solution.Under 25 DEG C of conditions, drip 30mLNaBH 4solution, stops reaction after 10h.Suction filtration, massive laundering, dry 12h in 80 DEG C of vacuum drying chambers.Gained catalyst gauge is done: Pd 2pb 8/ Al 2o 3.Fig. 1 is shown in Pd distribution on the alumina support, can find out that in the catalyst adopting new method to prepare, Pd is enriched in " eggshell " region of below aluminum oxide micro-sphere outer surface 20 μm.In catalyst, Pd and Pb content ICP-AES records, in table 1.
Embodiment 4
0.64gPb (NO 3) 2with adding in alumina support after deionized water dissolving, leaving standstill, then putting into the dry 12h of vacuum drying chamber.600 DEG C of roasting 8h in air atmosphere.Leaded alumina support after dipping-roasting is added in 500mL beaker, adds deionized water, put into water-bath, under mechanical agitation, add 9.0mL palladium nitrate solution, be warming up to 100 DEG C.Drip 35mL80wt% hydrazine hydrate, after 5.5h, stop reaction.Be chilled to room temperature, suction filtration, massive laundering, dry 12h in 80 DEG C of vacuum drying chambers.Gained catalyst gauge is done: Pd 2pb 2/ Al 2o 3.In catalyst, Pd and Pb content ICP-AES records, in table 1.
Embodiment 5
Add in alumina support after 1.60g acetylacetone,2,4-pentanedione lead deionized water dissolving, leave standstill, then put into the dry 12h of vacuum drying chamber.450 DEG C of roasting 10h in air atmosphere.Leaded alumina support after dipping-roasting is added in 500mL beaker, adds deionized water, put into water-bath, under mechanical agitation, add 7.2mL palladium acetylacetonate solution, be warming up to 80 DEG C.Drip 40mL37wt% formalin, after 4.5h, stop reaction.Be chilled to room temperature, suction filtration, massive laundering, dry 12h in 80 DEG C of vacuum drying chambers.Gained catalyst gauge is done: Pd 2pb 10/ Al 2o 3.In catalyst, Pd and Pb content ICP-AES records, in table 1.
Embodiment 6
0.8gPbSO 4with adding in alumina support after deionized water dissolving, leaving standstill, then putting into the dry 12h of vacuum drying chamber.650 DEG C of roasting 4.5h in air atmosphere.Leaded alumina support after dipping-roasting is added in 500mL beaker, adds deionized water, put into water-bath, under mechanical agitation, add 9.0mLNa 2pdCl 4solution, is warming up to 75 DEG C.Drip 20mLNaBH 4solution, stops reaction after 9h.Be chilled to room temperature, suction filtration, massive laundering, dry 12h in 80 DEG C of vacuum drying chambers.Gained catalyst gauge is done: Pd 2pb 5/ Al 2o 3.In catalyst, Pd and Pb content ICP-AES records, in table 1.
Embodiment 7
0.16gPbCl 2with adding in alumina support after deionized water dissolving, leaving standstill, then putting into the dry 12h of vacuum drying chamber.700 DEG C of roasting 4h in air atmosphere.Leaded alumina support after dipping-roasting is added in 500mL beaker, adds deionized water, put into water-bath, add 7.2mL dichloro two ammino palladium solution under mechanical agitation, be warming up to 55 DEG C.Drip 25mL80wt% hydrazine hydrate, after 5h, stop reaction.Be chilled to room temperature, suction filtration, massive laundering, dry 12h in 80 DEG C of vacuum drying chambers.Gained catalyst gauge is done: Pd 2pb 1/ Al 2o 3.In catalyst, Pd and Pb content ICP-AES records, in table 1.
Embodiment 8
4.28gMgCl 2with being warming up to 80 DEG C after deionized water dissolving.In above-mentioned solution, add alumina support, be stirred to dry, then put into the dry 12h of vacuum drying chamber.In air atmosphere, 500 DEG C of roasting 6h, obtain MgO-Al 2o 3complex carrier.By 10gMgO-Al 2o 3complex carrier add in deionized water be warming up to 80 DEG C after add 12mL palladium acetylacetonate solution, stir 8h, filter, washing, obtain Pd 5/ MgO-Al 2o 3presoma.
0.39g lead chloride deionized water dissolving, is warming up to 85 DEG C.Add gained Pd 5/ MgO-Al 2o 3presoma, stirs 3h, drips 40mL80wt% hydrazine hydrate, stops reaction after 6.5h.Be chilled to room temperature, suction filtration, massive laundering, dry 12h in 80 DEG C of vacuum drying chambers.Gained catalyst gauge is done: Pd 5pb 5/ MgO-Al 2o 3.Fig. 2 is shown in Pd distribution on the alumina support, can find out and adopt Pd in the obtained catalyst of traditional preparation methods not form significantly " eggshell " type distribution, but more trend towards being uniformly distributed in alumina support.In catalyst, Pd and Pb content ICP-AES records, in table 1.
Embodiment 9
In the batch tank reactor of 100mL jacketed, add catalyst prepared in 2.0g embodiment 1-8, then add 3.5g MAL and 30g absolute methanol successively, with the NaOH-CH of 5% 3oH solution regulates reactant pH value to 10, to be mixed evenly after, pass into oxygen, oxygen flow is set as 40mLmin -1.With 80 DEG C of thermostatic circulation baths, reactor is heated, reaction time 2h.Feed stock conversion and product yield gas chromatogram fixative calculate, and experimental result is in table 1.
Table 1. catalyst composition and active testing result

Claims (8)

1. a preparation method for the plumbous bimetallic catalyst of alumina load palladium, is characterized in that:
(1) carrier of catalyst is activated alumina;
(2) active component of catalyst is palladium;
(3) catalyst activity component palladium is on the alumina support in " eggshell " structure distribution;
(4) auxiliary agent of catalyst is plumbous;
(5) leaded solution impregnation of alumina carrier is first used in catalyst preparation process, again leaded for gained alumina support is used containing palladium solution impregnation after drying, roasting, finally by the palladium lead bimetallic catalyst obtaining alumina load after reducing agent reduction, filtration, washing, drying.
2. method according to claim 1, active aluminum oxide carrier is spherical.
3. method according to claim 1, leaded solution impregnation of alumina carrier adopts equi-volume impregnating or excessive infusion process.
4. method according to claim 1, the baking temperature through the alumina support of leaded solution impregnation is 60-120 DEG C, and drying time is 6-12 hour.
5. method according to claim 1, the sintering temperature through the alumina support of leaded solution impregnation is 300-700 DEG C, and roasting time is 3-10 hour.
6. method according to claim 1, adopts equi-volume impregnating or excessive infusion process containing the leaded alumina support of palladium solution impregnation.
7. method according to claim 1, reducing agent adopts hydrazine hydrate, formaldehyde or NaBH 4in one.
8. method according to claim 1, reduction temperature is 50-100 DEG C, and the recovery time is 1-10 hour.
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