CN109876745A - The palladium copper composite film material of load TS -1 molecular sieve and preparation and application - Google Patents
The palladium copper composite film material of load TS -1 molecular sieve and preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of palladium copper composite film material for loading TS -1 molecular sieve.The present invention plates one layer of palladium-copper alloy film using the method for the film forming of plating on cellular ceramic substrate, prepares one layer of loose porous TS -1 molecular sieve layer by the method for hydrothermal synthesis in alloy film surface later.While ensure that alloy film hydrogen permeability energy, the H of composite membrane is improved2/N2Selectivity, in addition the addition of TS -1 molecular sieve promotes the utilization of film surface active hydrogen, can be applied to, the fabricated in situ and propylene ring oxidation reaction of hydrogen peroxide.The present invention breaks through the limitation of traditional fixed bed reaction technique, will have low-temperature stability and high H2/N2The palladium-copper alloy film of selectivity, combines with TS -1 molecular sieve catalyst, is applied to have simple process, equipment investment few in membrane reactor, operates convenient advantage.
Description
Technical field
The present invention relates to a kind of technologies of preparing of difunctional palladium copper composite film material for loading TS -1 molecular sieve, construct porous
Ceramic monolith skeleton, the compound system of dense palladium tin-copper alloy film main body and loose porous TS -1 molecular screen membrane reaction center.Three
Person cooperates, and has collectively constituted membrane reactor structure.The method for being in particular in the film forming using plating is carried in porous ceramics
One layer of palladium-copper alloy film is plated on body, later in alloy film surface, by the method for hydrothermal synthesis, one layer of preparation is loose porous
TS -1 molecular sieve layer.On the one hand, it ensure that the stronger hydrogen permeability energy of alloy film, on the other hand, improve the H of composite membrane2/N2Choosing
Selecting property, meanwhile, the addition of TS -1 molecular sieve promotes the utilization of film surface active hydrogen, improves hydrogen in propylene ring oxidation reaction
Utilization efficiency, also increase the equilibrium conversion of reaction.
Background technique
Film is widely used in the fields such as food, weaving, medicine, chemical industry as a kind of cleaning, efficient material.Film reaction,
Membrane separation technique is purified as a kind of low-carbon, the technology of energy-saving and environmental protection in chemicals production, capture separation of pernicious gas etc.
Every aspect plays vital effect.With the development of industrial technology, the membrane material of simple function, increasingly cannot
Meet the growing production requirement of people.So exploring a kind of difunctional composite film material, and it is applied to traditional
In industrial production, for pushing production efficiency, improves production level and be of great significance to.With the epoxidation reaction of propylene
For, in traditional production technology, chlorohydrination, due to needing a large amount of chlorine in reaction process, and it is useless containing chlorine to react generation
Water causes certain environmental pollution, affects the process of sustainable development.Indirect oxidation method, scale of investment is big, and process flow is multiple
Miscellaneous, product economy is influenced by many factors such as joint product markets.Catalytic oxidation of hydrogen peroxide method, in the fortune of hydrogen peroxide
During defeated, there are certain risks, and inevitably have the decomposition of hydrogen peroxide, reduce the utilization rate of raw material,
Add somewhat to production cost.
The present invention, for deficiency present in traditional handicraft, comprehensive utilization compact metal palladium film selection hydrogen permeability and
While the catalytic activity of porous molecular sieve membrane, it is prepared for a kind of difunctional palladium copper composite film material for loading TS -1 molecular sieve,
The efficient progress of the partial oxidation reactions such as epoxidation of propylene may be implemented.Copper is wherein added in palladium film and forms palladium-copper alloy
Film can not only reduce the dosage of precious metal palladium, but also the solubility and diffusion coefficient of changeable hydrogen, and it is therefore possible to modulation hairs
The temperature of raw hydrogen embrittlement can be applied in low-temp reaction, and its hydrogen permeability can determine the input rate of active hydrogen atom,
And then the progress of subsequent reactions is ensured.To realize that efficient, cleaning, the design of energy-efficient epoxidation of propylene catalytic process provide one
New approaches and scientific guidance.
Composite film material mentioned in the present invention, the membrane reactor being assembled into can be applied to gas-phase propene epoxidation reaction.
It is embodied in, hydrogen selective permeable palladium copper film, and forms active hydrogen atom in film surface, active hydrogen atom is anti-with oxygen
It answers, the active oxygen species of generation, the propylene as unstripped gas is reacted life with active oxygen species on TS-1 molecular screen membrane surface
At target product, propylene oxide.This is a completely new exploration, which is not necessarily to solvent, without the extraction of intermediate product, is reduced
Chemical engineering unit operation process, it is more environment-friendly.The generation of product and separation are coupled by the present invention by film, can be into one
Step improves the utilization efficiency of hydrogen and the selectivity of reaction.
Summary of the invention
The object of the present invention is to provide it is a kind of load TS -1 molecular sieve difunctional palladium copper composite film material preparation method,
It solves in actual experiment production process, Hydrogen Separation and purification, the utilization of active hydrogen and the epoxidation reaction in membrane reactor
Equal process flows, to the needs of high-performance supported type bifunctional molecule sieve membrane.To achieve the above object, inventor constructs porous pottery
Ceramic carrier, dense palladium tin-copper alloy film, loose porous TS -1 molecular screen membrane compound system, using cellular ceramic substrate be film group
The skeleton of part, fine and close palladium-copper alloy film provides the main body of reactive hydrogen atom as separation hydrogen, after TS -1 molecular screen membrane is used as
The center of continuous reaction.Three cooperates, and has collectively constituted membrane reactor structure, and the partial oxidation for being applied to hydro carbons is anti-
Ying Zhong, the very high utilization efficiency of hydrogen, increases reaction conversion ratio.
To achieve the goals above, this patent provides a kind of difunctional palladium copper composite film material for loading TS -1 molecular sieve
Preparation method.Concrete technology flow process is as follows:
1. the selection and surface preparation of carrier
Cellular ceramic substrate main component is γ-Al2O3And ZrO2Without electric conductivity, so will be in advance in carrier surface
One layer of palladium core of kind, increases its electric conductivity.Concrete operations are as follows: (can refer to patent [Xu Hengyong, Tang Chunhua, Li Chunlin, Ge Qingjie,
A kind of preparation method of high hydrogen permeation selectivity metal palladium-based composite membrane, CN 101670245A]).
2. fine and close palladium-copper alloy film is electroplated
Three-electrode system is constructed, wherein working electrode connects pretreated cellular ceramic substrate, and reference electrode is connected as
Saturated calomel electrode, model (217), to electrode connection a gauze platinum electrode (effective long 90mm, diameter 40mm), applied to palladium
Electrochemical deposition；B copper post electrode (effective length 150mm, diameter 40mm), the electrochemical deposition applied to copper.Adjust electrification
Parameter is learned, suitable operation interval is selected.Cyclic voltammetry (CV) is selected to carry out electrochemical plating film reaction.According to required palladium copper
Composition (the X of two kinds of metals in alloy filmCu, XPd) and film thickness (d), determine the quality of required Metal Palladium and metallic copper
(mCu, mPd), the amount (n of substanceCu, nPd), according to Faraday law: Q=zFn, (wherein Q is total quantity of electric charge, and z is electrochemistry
The stoichiometric coefficient of electronics transfer in reaction, works as palladium, and copper participates in z=2 when reaction；F is Faraday constant, about 96500C/mol；
N is the amount for participating in the substance of metal of electrode reaction) determine the quantity of electric charge total needed for electrode reaction.
The preparation of 3.TS-1 molecular screen membrane
(1) molecular sieve seed nucleus is carried out on the dense palladium tin-copper alloy film surface prepared.
(2) polyethyleneimine (PEI) is added, the polymer such as polydimethyl diallyl ammonium chloride (PDADMAC) promote kind
Core.
(3) the colloidal sol containing silicon source and titanium source is prepared, main component has: tetrapropylammonium hydroxide (TPAOH), orthosilicic acid four
Butyl ester (TEOS), butyl titanate (TNBT), hydrogen peroxide (H2O2)。
(4) by the complete membrane material of seed nucleus, it is placed in autoclave, 200 DEG C are reacted 24 hours.
(5) after the reaction was completed, membrane material is taken out, 150 DEG C of drying in baking oven.
So far, loose porous TS-1 zeolite membrane material completes preparation.
The advantage of difunctional composite film material prepared by the present invention is:
1. can control the component and thickness of intermediate palladium-copper alloy layer by electric plating method.
2. TS-1 molecular sieve is directly supported on compact metal film surface in the form of loose more empty films, formed a kind of novel
Structure, during reducing traditional fixed bed reaction, the dosage of TS-1 molecular sieve, while reducing the mass transfer resistance of reaction gas
Power.
3. this difunctional composite film material is applied in membrane reactor, conjunctival separation and purification function can be with
The utilization efficiency of reactant is improved, while membrane reactor is lightly easy, be convenient for assembly and disassembly, is applied in actual production, can subtract
Few equipment investment capital.
While ensure that alloy film hydrogen permeability energy, the H of composite membrane is improved2/N2Selectivity, in addition TS -1 molecular sieve
Addition promote the utilization of film surface active hydrogen, can be applied to, the fabricated in situ and epoxidation of propylene of hydrogen peroxide are anti-
It answers.The present invention breaks through the limitation of traditional fixed bed reaction technique, will have low-temperature stability and high H2/N2The palladium copper of selectivity closes
Golden film is combined with TS -1 molecular sieve catalyst, is applied to have simple process, equipment investment few in membrane reactor, operation is just
Prompt advantage.
Detailed description of the invention:
Fig. 1 is the structural schematic diagram of zeolite membrane material.
Fig. 2 be zeolite membrane material SEM scheme, (a), (c) be palladium-copper alloy film surface microscopic appearance, (b), (d) be
The microstructure of dual functional film material after having loaded TS-1 molecular sieve.
Specific embodiment
The technology of the present invention details is subject to detailed description by following embodiments, its effect of illustrated embodiment only further illustrates
Technical characteristic of the invention, rather than limit the present invention.
Embodiment 1
1 μm of TS-1 is molecular sieve carried on 4 μ m-thick PdCu alloy films
1. Vehicle element
Cellular ceramic substrate pipe range 50mm, outer diameter 14.05mm.First in the NaCO of dehydrated alcohol (99.7%)3Solution
(NaCO3Concentration is 0.05mol/L) in impregnate 30min, remove the greasy dirt on surface, carrier pipe surface ash point removes.It is going later
It is impregnated in ionized water and washes 15min, remove remaining alcoholic solution, the pure white light of support tube.Finally 150 DEG C of drying are standby in an oven
With program setting are as follows:
More empty ceramic tube carriers of drying and processing are sensitized, by porous stainless steel carrier, immerse reducing agent (diformazan ammonia
Base monoborane) in, restore 5min, support tube is rinsed well with distilled water, then immerse 0.05mol/L palladium sulfate and
In the borax mixed liquor of 0.02mol/L, activation kind palladium core.Iterative cycles 3 times, until carrier film surface, color are become from white
Until black gray expandable.So far, palladium kernel covering is uniform, and cellular ceramic substrate pretreatment is completed.
2. PdCu alloy film is electroplated
(1) preparation of electroplate liquid
1. the preparation of copper electrolyte
With HFA2004 assay balance, 30gNa is weighed2EDTA is dissolved in 40 DEG C -50 DEG C of 400ml of warm water, is denoted as
SolutionA is spare.Weigh 10g CuSO4·5H2O is dissolved in 40 DEG C of 100ml of warm water, is denoted as solution B.A is slow
Ground is added with stirring in B, in blue-tinted transparent solution, is generated blue precipitate, is become cloudy.Reaction equation are as follows:
Weigh 23g Na2CO3It is dissolved in 40 DEG C of 100ml of warm water.It is denoted as solution C, C is slowly stirred, B is added
In, the blue precipitate previously generated fades away, and solution becomes clarification again.Ultrasonic 5min keeps solution mixing more uniform.Claim
Take 40mg C10H8O2It is dissolved in 40ml distilled water, is denoted as solution D, weighs 60mgK4[Fe(CN)6]·3H2O is dissolved in 50ml
In distilled water, it is denoted as solution E, under stirring, slowly D, E are added in B, is settled to 1L, adjusts pH to 9.0~10.0.
So far, the copper electrolyte of blue-tinted transparent is obtained.
2. the preparation of palladium plating solution
1.7g PdCl is weighed with HFA2004 assay balance2, it is dissolved in 65 DEG C 10% of 3mL of HCl, generates peony
H2PdCl4Solution.Reaction equation are as follows:
PdCl2After being completely dissolved, it is 0.89g/cm that 3mL~5mL relative density is slowly added under stirring3NH3H2O, with depth
Red solution reaction generates pink gelatinous precipitate, adds excessive ammonium hydroxide, until the red precipitate generated is completely dissolved, and
Generate [Pd (the NH of grass green3)4]Cl2Until solution.Reaction equation are as follows:
H2PdCl4+6NH4OH→[Pd(NH3)4]Cl2+2NH4Cl+6H2O
Undesired impurities are filtered off, the HCl of 40mL-50mL10% is slowly added in clear liquid, until being settled out completely in solution bright
Yellow [Pd (NH3)2]Cl2Until precipitating.It is depressurized with Buchner funnel and filters precipitating, and precipitating is cleaned with distilled water, until being formed
Until the thick precipitating of glassy yellow.[Pd (the NH that will be filtered and clean up3)2]Cl2Being dissolved in 50mL relative density is 0.89g/
cm3NH3H2In O, the NH of the 1mol/L prepared in advance is added4Cl solution regulation system pH to 8.5-9.5 is micro- green to get arriving
Bright palladium plating solution.
(2) palladium plating tin-copper alloy film
It selects cyclic voltammetry (CV), relevant parameter (High E=-0.65V~-0.75V, Low E=-0.75V is set
~-0.85V；Scan Rate=0.01V/s；Sweep Segments=1000；Sensitivity=0.001A/V).Setting
The total amount of electric charge Q=35.89C of copper plate.Control work volume current density is 0.25A/dm3~0.45A/dm3, current efficiency is
90%.After 10min, the brick-red copper film of surface-brightening is obtained.The quantity of electric charge Q=28.82C of plating palladium layers is set.Control volume electric current
Density is 0.15A/dm3~0.45A/dm3, current efficiency 90%.After 8min, obtaining surface-brightening has silvery white non-ferrous metal light
The palladium film in pool.Circulation plating Pd metal layer and Cu metal layer realize that Cu-Pd-Cu-Pd metal layer alternately increases.Finally add up plating
Tetra- layers of Cu, tetra- layers of Pd.About 0.5 μm of every layer of metal layer thickness, totally 4 μm, component is controlled in Pd50Cu50.The alloy that preparation is completed
Film, the N in tube furnace2Alloying 1000min under atmosphere.The preparation of palladium-copper alloy film layer is completed, and microstructure is shown in (a) of Fig. 2
(c).
3. hydrothermal synthesis TS-1 molecular screen membrane
(1) seed nucleus
0.3g TS-1 nanocrystal is dissolved in 60ml distilled water, ultrasonic 30min, is uniformly mixed.It will be prepared in step 2
Good PdCu alloy film, impregnates 10min in the solution, later dry 20min under the conditions of 60 DEG C.Repetitive operation 3 times.
(2) polymer promotes seed nucleus
It is that PEI (polyethyleneimine) promotes seed nucleus first.0.2g TS-1 nanocrystal is dissolved in 40ml distilled water, is added
Enter 0.8g PEI, ultrasonic 30min, is uniformly mixed.PdCu alloy film is impregnated into 10min in the solution, is done at 60 DEG C later
Dry 20min.Repetitive operation 3 times.
It is that PDADMAC (polydimethyl diallyl ammonium chloride) promotes seed nucleus later.0.2g TS-1 nanocrystal is dissolved in
In 40ml distilled water, the NH of 0.1mol/L is added3·H2O adjusts the ultrasound of pH to 10.0 30min, is uniformly mixed, is denoted as solution A.It will
6.75g NaCl and 12.5g PDADMAC are dissolved in 250g water, and ultrasonic 10min is uniformly mixed, and are denoted as solution B.By PdCu alloy
Film impregnates 15min in solution B, impregnates 10min in solution A later, later 60 DEG C of dry 10min.Repeat aforesaid operations 3
It is secondary.
(3) TS-1 molecular sieve forms a film
It is the preparation of synthesis of molecular sieve colloidal sol first.2g, 25% TPAOH (tetrapropylammonium hydroxide) is claimed to be dissolved in 36.8g
H2In O, 2.8g TEOS (four butyl ester of orthosilicic acid) is added dropwise, gentle agitation 30min is denoted as solution C.In addition 0.13g is taken
TNBT (butyl titanate), 0.43g, 30% H2O2, it is dissolved in 2.43g deionized water, is uniformly mixed, is denoted as solution D.It will be molten
Liquid D is added dropwise in solution C, is vigorously stirred 30min, obtains solution E.Wherein butyl titanate is colloidal liquid, viscosity ratio
It is larger, H is added2O2Later, yellow is presented, is gradually dissolved in distilled water after ultrasound.
Later, by the method for hydrothermal synthesis, molecular screen membrane is grown on PdCu alloy membrane carrier.By step (1) and (2)
In, the carrier that seed nucleus is completed is placed in autoclave, 50ml solution D is added, the setting program of homogeneous reactor is 200 DEG C
Reaction 24 hours, wherein revolving speed is 30r/min.The molecular screen membrane that reaction is completed, it is 10 hours dry under the conditions of 100 DEG C.
So far, 1 μm of TS-1 molecular sieve layer, the dual functional film material of the PdCu alloy-layer of 4 μ m-thicks are loaded, preparation is completed.Its
Microstructure is shown in (b) and (d) of Fig. 2.
The material is before use, need in N2Under atmosphere, 400 DEG C of activation 2000min.
Embodiment 2
1 μm of TS-1 is molecular sieve carried on 5 μ m-thick PdCu alloy films
1. Vehicle element
Processing method is the same as embodiment 1.
2. PdCu alloy film is electroplated
(1) preparation of electroplate liquid
Preparation method is the same as embodiment 1.
(2) palladium plating tin-copper alloy film
Relevant parameter is arranged with embodiment 1, it should be noted that the charge of copper plate in same selection cyclic voltammetry (CV)
Total amount Q=47.55C.Plate the quantity of electric charge Q=28.23C of palladium layers.The film plating process for equally taking circulation to be superimposed finally adds up plating Cu
Five layers, five layers of Pd.About 0.5 μm of every layer of metal layer thickness, totally 5 μm, component is controlled in Pd47Cu53.The alloy film that preparation is completed,
The N in tube furnace2Alloying 1000min under atmosphere.
3. hydrothermal synthesis TS-1 molecular screen membrane
(1) seed nucleus
Operating method is the same as embodiment 1.
(2) polymer promotes seed nucleus
Operating method is the same as embodiment 1.
(3) TS-1 molecular sieve forms a film
Operating method is the same as embodiment 1.
So far, 1 μm of TS-1 molecular sieve layer, the dual functional film material of the PdCu alloy-layer of 5 μ m-thicks are loaded, preparation is completed.
The material is before use, need in N2Under atmosphere, 400 DEG C of activation 2000min.
Embodiment 3
2 μm of TS-1 are molecular sieve carried on 3 μ m-thick PdCu alloy films
1. Vehicle element
Processing method is the same as embodiment 1.
2. PdCu alloy film is electroplated
(1) preparation of electroplate liquid
Preparation method is the same as embodiment 1.
(2) palladium plating tin-copper alloy film
Relevant parameter is arranged with embodiment 1, it should be noted that the charge of copper plate in same selection cyclic voltammetry (CV)
Total amount Q=27.99C.Plate the quantity of electric charge Q=20.75C of palladium layers.The film plating process for equally taking circulation to be superimposed finally adds up plating Cu
Five layers, five layers of Pd.About 0.3 μm of every layer of metal layer thickness, totally 3 μm, component is controlled in Pd48Cu52.The alloy film that preparation is completed,
The N in tube furnace2Alloying 1000min under atmosphere.
3. hydrothermal synthesis TS-1 molecular screen membrane
(1) seed nucleus
Operating method is the same as embodiment 1.
(2) polymer promotes seed nucleus
Operating method is the same as embodiment 1.
(3) TS-1 molecular sieve forms a film
It is the preparation of synthesis of molecular sieve colloidal sol first.4g, 25% TPAOH (tetrapropylammonium hydroxide) is claimed to be dissolved in 73.6g
H2In O, 5.6g TEOS (four butyl ester of orthosilicic acid) is added dropwise, gentle agitation 30min is denoted as solution C.In addition 0.26g is taken
TNBT (butyl titanate), 0.86g, 30% H2O2, it is dissolved in 4.86g deionized water, is uniformly mixed, is denoted as solution D.It will be molten
Liquid D is added dropwise in solution C, is vigorously stirred 30min, obtains solution E.Wherein butyl titanate is colloidal liquid, viscosity ratio
It is larger, H is added2O2Later, yellow is presented, is gradually dissolved in distilled water after ultrasound.
Later, by the method for hydrothermal synthesis, molecular screen membrane is grown on PdCu alloy membrane carrier.By step (1) and (2)
In, the carrier that seed nucleus is completed is placed in autoclave, 100ml solution D is added, the setting program of homogeneous reactor is 200 DEG C
Reaction 24 hours, wherein revolving speed is 30r/min.The molecular screen membrane that reaction is completed, it is 10 hours dry under the conditions of 100 DEG C.
So far, 2 μm of TS-1 molecular sieve layers, the dual functional film material of the PdCu alloy-layer of 3 μ m-thicks are loaded, preparation is completed.
The material is before use, need in N2Under atmosphere, 400 DEG C of activation 2000min.
Embodiment 4
2 μm of TS-1 are molecular sieve carried on 4 μ m-thick PdCu alloy films
1. Vehicle element
Processing method is the same as embodiment 1.
2. PdCu alloy film is electroplated
(1) preparation of electroplate liquid
Preparation method is the same as embodiment 1.
(2) palladium plating tin-copper alloy film
Relevant parameter is arranged with embodiment 1, it should be noted that the charge of copper plate in same selection cyclic voltammetry (CV)
Total amount Q=39.48C.Plate the quantity of electric charge Q=25.94C of palladium layers.The film plating process for equally taking circulation to be superimposed finally adds up plating Cu
Five layers, five layers of Pd.About 0.4 μm of every layer of metal layer thickness, totally 4 μm, component is controlled in Pd46Cu54.The alloy film that preparation is completed,
The N in tube furnace2Alloying 1000min under atmosphere.
3. hydrothermal synthesis TS-1 molecular screen membrane
(1) seed nucleus
Operating method is the same as embodiment 1.
(2) polymer promotes seed nucleus
Operating method is the same as embodiment 1.
(3) TS-1 molecular sieve forms a film
It is the preparation of synthesis of molecular sieve colloidal sol first.4g, 25% TPAOH (tetrapropylammonium hydroxide) is claimed to be dissolved in 73.6g
H2In O, 5.6g TEOS (four butyl ester of orthosilicic acid) is added dropwise, gentle agitation 30min is denoted as solution C.In addition 0.26g is taken
TNBT (butyl titanate), 0.86g, 30% H2O2, it is dissolved in 4.86g deionized water, is uniformly mixed, is denoted as solution D.It will be molten
Liquid D is added dropwise in solution C, is vigorously stirred 30min, obtains solution E.Wherein butyl titanate is colloidal liquid, viscosity ratio
It is larger, H is added2O2Later, yellow is presented, is gradually dissolved in distilled water after ultrasound.
Later, by the method for hydrothermal synthesis, molecular screen membrane is grown on PdCu alloy membrane carrier.By step (1) and (2)
In, the carrier that seed nucleus is completed is placed in autoclave, 100ml solution D is added, the setting program of homogeneous reactor is 200 DEG C
Reaction 24 hours, wherein revolving speed is 30r/min.The molecular screen membrane that reaction is completed, it is 10 hours dry under the conditions of 100 DEG C.
So far, 2 μm of TS-1 molecular sieve layers, the dual functional film material of the PdCu alloy-layer of 4 μ m-thicks are loaded, preparation is completed.
The material is before use, need in N2Under atmosphere, 400 DEG C of activation 2000min.
Comparative example 1
4 μm of TS-1 are molecular sieve carried on cellular ceramic substrate
1. Vehicle element
Cellular ceramic substrate pipe range 50mm, outer diameter 14.05mm.First in the NaCO of dehydrated alcohol (99.7%)3Solution
(NaCO3Concentration is 0.05mol/L) in impregnate 30min, remove the greasy dirt on surface, carrier pipe surface ash point removes.It is going later
It is impregnated in ionized water and washes 15min, remove remaining alcoholic solution, the pure white light of support tube.Finally 150 DEG C of drying are standby in an oven
With program setting are as follows:
2. hydrothermal synthesis TS-1 molecular screen membrane
(1) seed nucleus
Operating method is the same as embodiment 1.
(2) polymer promotes seed nucleus
Operating method is the same as embodiment 1.
(3) TS-1 molecular sieve forms a film
It is the preparation of synthesis of molecular sieve colloidal sol first.8g, 25% TPAOH (tetrapropylammonium hydroxide) is claimed to be dissolved in 147.2g
H2In O, 11.2g TEOS (four butyl ester of orthosilicic acid) is added dropwise, gentle agitation 30min is denoted as solution C.In addition 0.52g is taken
TNBT (butyl titanate), 1.72g, 30% H2O2, it is dissolved in 9.72g deionized water, is uniformly mixed, is denoted as solution D.It will be molten
Liquid D is added dropwise in solution C, is vigorously stirred 30min, obtains solution E.Wherein butyl titanate is colloidal liquid, viscosity ratio
It is larger, H is added2O2Later, yellow is presented, is gradually dissolved in distilled water after ultrasound.
Later, by the method for hydrothermal synthesis, molecular screen membrane is grown on PdCu alloy membrane carrier.By step (1) and (2)
In, the carrier that seed nucleus is completed is placed in autoclave, 100ml solution D is added, the setting program of homogeneous reactor is 200 DEG C
Reaction 48 hours, wherein revolving speed is 30r/min.The molecular screen membrane that reaction is completed, it is 10 hours dry under the conditions of 100 DEG C.
So far, 2 μm of TS-1 molecular sieve layers, the dual functional film material of the PdCu alloy-layer of 4 μ m-thicks are loaded, preparation is completed.
The material is before use, need in N2Under atmosphere, 400 DEG C of activation 2000min.
Comparative example 2
4 μ m-thick PdCu alloy films are supported on cellular ceramic substrate
1. Vehicle element
Processing method is the same as embodiment 1.
2. PdCu alloy film is electroplated
(1) preparation of electroplate liquid
Preparation method is the same as embodiment 1.
(2) palladium plating tin-copper alloy film
Relevant parameter is arranged with embodiment 1, it should be noted that the charge of copper plate in same selection cyclic voltammetry (CV)
Total amount Q=39.48C.Plate the quantity of electric charge Q=25.94C of palladium layers.The film plating process for equally taking circulation to be superimposed finally adds up plating Cu
Five layers, five layers of Pd.About 0.4 μm of every layer of metal layer thickness, totally 4 μm, component is controlled in Pd45Cu55.The alloy film that preparation is completed,
The N in tube furnace2Alloying 1000min under atmosphere.
The material is before use, need in N2Under atmosphere, 400 DEG C of activation 2000min.
The basic experiment parameter of embodiment and comparative example, summarize in table 1.
The basic performance comparison of the different membrane materials of table 1.
The present invention breaks through the limitation of traditional fixed bed reaction technique, will have low-temperature stability and high H2/N2The palladium of selectivity
Tin-copper alloy film is combined with TS -1 molecular sieve catalyst, is applied to have simple process, equipment investment few in membrane reactor, behaviour
Make convenient advantage.
Claims (8)
1. a kind of difunctional palladium copper composite film material for loading TS -1 molecular sieve, it is characterised in that: in cellular ceramic substrate side
Or two side surface set gradually dense palladium tin-copper alloy film, loose porous TS -1 molecular screen membrane, constitute compound system, utilization is porous
Ceramic monolith is the skeleton of membrane module, and fine and close palladium-copper alloy film provides the main body of reactive hydrogen atom, TS -1 as separation hydrogen
Center of the molecular screen membrane as subsequent reactions；Three cooperates, and has collectively constituted membrane reactor structure.
2. composite film material according to claim 1, it is characterised in that: the matrix carrier material is porous ceramics
γ–Al2O3, porosity is 40% -55%, and pore size distribution is 70mm -100mm, and wherein volume ratio shared by the hole of 70mm -80mm is
Volume shared by the hole of 50% -75%, 80mm -100mm is 20% -35%；Middle layer is compact metal palladium-copper alloy film；Surface layer is
TS -1 molecular sieve, porosity 50% -75%, pore size distribution are 25mm -55mm, and wherein volume ratio shared by the aperture of 25mm -40mm is
Volume ratio shared by the aperture of 70% -95%, 40mm -55mm is 10% -35%.
3. composite film material according to claim 1, it is characterised in that: dense palladium tin-copper alloy film is dredged with a thickness of 3 μm -5 μm
Loose porous molecular screen layer is with a thickness of 1 μm -2 μm.
4. the preparation method of a kind of claim 1,2 or 3 composite film materials, it is characterised in that:
1) densified metal layer is obtained by Alloying Treatment after preparation palladium layers and layers of copper are electroplated respectively；
It takes water as a solvent, in the ingredient of the palladium plating solution, main salt: [Pd (NH3)2]Cl2, auxiliary salt: NH4Cl, KCl, complexing agent: quality
The NH of score 20%~25%3·H2O；In the ingredient of copper electrolyte, main salt: EDTA-Cu, auxiliary salt: KNO3, K4[Fe(CN)6]·
H2O, brightener: 2-2 bipyridyl (C10H8N2)；
Palladium plating solution: [Pd (NH3)2]Cl2Mass concentration be 5g/L~10g/L, NH4The mass concentration of Cl is 5g/L~10g/L,
The mass concentration of KCl is 0.5g/L~2g/L, and amount of complex is 10mL/L~20ml/L in water；
Copper electrolyte: the mass concentration of EDTA-Cu is 10g/L~15g/L, KNO3Mass concentration be 2g/L~5g/L, K4[Fe
(CN)6]·H2The mass concentration of O is 1g/L~3g/L, 2-2 bipyridyl (C10H8N2) it is 50mg/L；The pH of palladium plating solution be 8.0~
9.5, the pH of copper electrolyte is 8.5~10.0；
2) loose porous TS -1 molecular sieve layer is prepared by hydrothermal synthesis method；The difference of reagent needed for synthesis of molecular sieve
It is:
Tetrapropylammonium hydroxide (TPAOH), polyethyleneimine (PEI), polydimethyl diallyl ammonium chloride (PDADMAC), matter
Measure the ammonium hydroxide (NH that score is 20%~25%3·H2O), four butyl ester of orthosilicic acid (TEOS), butyl titanate (TNBT), peroxidating
Hydrogen (H2O2)；
Take water as a solvent, the mass concentration that dosage is respectively as follows: TPAOH is 7g/L~14g/L, the mass concentration of PEI be 10g/L~
The mass concentration of 35g/L, PDADMAC are 25g/L~75g/L, and the mass concentration of TEOS is 45g/L~85g/L, the quality of TNBT
Concentration is 1g/L~5g/L, H2O2Mass concentration be 2g/L~8g/L.
5. the preparation method according to claim 4, it is characterised in that:
(1) plating conditions: 30 DEG C -50 DEG C, normal pressure, stirring rate is 25r/s -60r/s；
(2) Alloying Treatment condition: 400 DEG C -650 DEG C, 1000min.
6. the preparation method according to claim 4, it is characterised in that: hydrothermal synthesis molecular sieve, temperature of reaction kettle 200
DEG C, the reaction time is 24 hours.
7. condition according to claim 4, it is characterised in that: the composite membrane prepared, it will be in N before2Under atmosphere, 200
DEG C -400 DEG C of activation 2000min -3000min.
8. a kind of application of claim 1,2 or 3 composite film materials in propylene ring oxidation reaction.
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| CN107029720A (en) * | 2017-04-28 | 2017-08-11 | 四川大学 | Support type high grade oxidation catalytic material and preparation method thereof |
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