Abstract:
Process for preparing a two layer metal palladium or palladium alloy composite membrane consisting of a porous substrate support and a palladium or palladium alloy membrane by rinsing/washing and drying the porous substrate support, treating the porous substrate support with a pore filler in order to decorate the pores of the support and the disfigurements of the substrate surface, sensitizing and activating with a palladium solution the decorated substrate support, and plating the resulting support with a palladium solution to form the two layer composite membrane, drying. The resulting composite membrane is subjected to a post-processing where the pore fillers residing in the pore-channels of the porous substrate are partly removed or reduced in volume through heating.

Description:
This application is the U.S. National Phase of International Application PCT/GB2005/000041, filed 7 Jan. 2005, which designated the U.S. PCT/GB2005/000041 claims priority to Chinese Application No. 200410021025.6 filed 9 Jan. 2004. The entire content of these applications are incorporated herein by reference. 
     BACKGROUND OF THE INVENTION 
     The present invention relates to a metal palladium—or alloy palladium—composite membrane which exhibits a high permeable hydrogen flux and high hydrogen selectivity for separation or purification. The present invention further relates to a preparation method for producing these said metal or alloy palladium composite membranes. 
     The increased demand for hydrogen in recent years in many sectors such as petroleum refining, petrochemical and semi-conductor processing and in new energy-related applications such as clean fuel for fuel cells and vehicles has led to a high interest in methods for separation and purification of hydrogen from gas mixtures. Palladium membranes or alloy palladium membranes have been the subject of many studies, due largely to their unmatched potential as hydrogen selective membranes for separation or purification and membrane reactors for hydrogenation/dehydrogenation reactions. However, these studies show that improvement regarding hydrogen permeability in pure and composite membranes is necessary, as the measured hydrogen permeation flux throughout the studies remained very low. 
     Another significant problem found in membrane studies is, under 275° C., pure palladium membrane is susceptible to cracking during the phase transformation due to the amount of hydrogen absorbed. This phenomenon is often termed ‘hydrogen embrittlement’. It is known however that hydrogen embrittlement can be dramatically reduced, even at room temperature, by the formation of an alloy palladium membrane such as Pd—Ag alloy membrane, Pd—Cu alloy membrane or Pd—Au alloy membrane. 
     Membranes can either exist as a pure or as a composite membrane. A pure palladium membrane, that is an unsupported palladium membrane, is well known in the public domain. The corresponding thickness of the membrane must be greater than 200 microns in order to ensure enough mechanical strength to sustain the reaction; consequently this specified membrane thickness results in a low hydrogen permeable flux and a very high production cost. Therefore composite membranes are preferred, that is a supported palladium membrane where the palladium membrane layer is connected to a porous substrate support, hence reducing the required thickness of the palladium membrane layer and consequently reducing the expense and improving the hydrogen permeation flux, whilst still maintaining the mechanical strength of the whole membrane. 
     As shown in the prior art, conventional composite membranes exist in three defined layers; palladium/palladium alloy membrane layer, the surface substrate support and an intermediate layer interconnecting the previous two layers. Indeed, in order to obtain a thin palladium/palladium alloy membrane layer on porous substrates, an intermediate layer is usually introduced in the prior art, which results in a three-layer composite membrane. However this three layer formation again presents the major problem of a low hydrogen permeation flux. 
     SUMMARY OF THE INVENTION 
     The present invention concentrates on the aforementioned problems, of the low hydrogen permeable flux and high production costs and proposes a technique for forming a palladium composite membrane directly onto the surface of a porous substrate support without use of an intermediate layer between the membrane and the support. This technique will create a two layer composite membrane as opposed to the conventional three layer composite membrane. 
     The present invention concentrates on a simple and easy to operate method to modify the porous substrate by preoccupying the pore channels or disfigurements of the substrate surface. Then it becomes possible to produce a thin dense palladium membrane using an electroless plating preparation method. 
     The known preparation method for the conventional three layer palladium/palladium alloy composite membrane comprises of a method wherein the porous substrate support is first subjected to ‘Surface decoration’ in order to overcome the problems associated with the existence of large pores and disfigurement at the surface. These said defects arise due to the non-homogeneous nature of both the surface and of the pore distribution of the support and as a result make it difficult to form a dense palladium membrane on the surface of the support which consequently reduces the membranes&#39; permeable hydrogen selectivity. Surface decoration is used to avoid the existence of the large pores and defects and can be performed by either:
         a) Using a porous surface modifier such as γ-Al 2 O 3 , to coat a thin layer over the substrate surface through coating or moulding in order to produce an intermediate layer.   b) Using a porous material, which has a smaller pore-diameter than the pore channels of the substrate support, such as γ-Al 2 O 3 , ZrO 2 , SiO 2  or CeO 2  to fill in the large pore channels or disfigurements of the substrate surface.       

     There are however some serious problems associated with these two conventional ‘surface decoration’ methods. For the first ‘surface decoration’ method mentioned above, porous materials such as γ-Al 2 O 3  were used to coat a thin intermediate layer over the channels of substrate surface through coating or moulding. Unfortunately upon membrane formation the palladium plating solution enters into the pore channels, resulting in palladium deposition in the channels of the substrate, thus effectively causing a second resistance to hydrogen permeation and lowering the hydrogen permeation flux. 
     In the second decoration method, porous materials, which have a smaller pore-diameter than the pore channels of the substrate support, such as γ-Al 2 O 3 , ZrO 2 , SiO 2  or CeO 2  are used to fill in the large pore channels or disfigurements of the substrate surface before electroless plating. This method presents problems for the same reason as the first method. The electroless plating solution inevitably enters into the pore channels of the chosen substrate. Thus, the porous materials filled in the substrate pore channels will again form a second resistance to hydrogen permeation and thus the hydrogen permeation flux is again considerably low. 
     Therefore the objective of this present invention is to provide a new efficient surface decoration method of the porous substrate support, for preparation of a two layer palladium or palladium alloy composite membrane that exhibits a high hydrogen permeable flux. 
     To achieve the above objective, the present invention is essentially a two layer metal palladium composite membrane consisting of a porous substrate support and a palladium membrane. The metal palladium composite membrane is characterized in that the palladium metal substantially exists on the outer surface of the porous substrate support with little or no presence in the pore channels of the substrate. 
     This invention also includes a two layer palladium alloy composite membrane, consisting of a porous substrate support and a palladium alloy membrane. The palladium alloy composite membrane is characterized in that the palladium alloy membrane substantially exists on the outer surface of the porous substrate support with little or no presence in the pore channels of the substrate. 
     According to the preparation procedure of present invention there is ‘little or no presence’ of palladium in the pore channels of the support because our pore filler preoccupies the pore channels of porous substrate which prevents the palladium plating solution from entering the substrate. 
     According to a preferred embodiment of the present invention, ‘little or no presence’ of palladium in the pore channels of the support is defined as the porous substrate support containing less than 5% of the total palladium weight present in the whole of the composite membrane and in particular less than 2% of the total palladium weight present in the whole of the composite membrane. 
     The present invention relates to both of these aforementioned two layer composite membranes which are both obtainable by the following preparation process. According to a preferred embodiment of the present invention the process proceeds by the following consecutive steps;
         1. The porous substrate support is rinsed with a dilute solution of hydrochloric acid, washed, rinsed with a dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with a solvent like CCl 4 , and dried under ambient conditions.   2. The porous substrate support prepared as above is then immersed in a solution of pore filler under vacuum conditions for 20 min. The excess pore filler residing on the substrate surface is preferably removed by mechanical cleaning e.g. wiping the substrate surface, and then washed with distilled water. According to a preferred embodiment of the present invention this method of decoration is repeated 5˜6 times.   3. After surface decoration the porous substrate support is sensitized in SnCl 2  solution and activated in PdCl 2  solution, respectively. According to a preferred embodiment of the invention this process is repeated 4 times. The Pd 0  atoms, formed in the reduction of Pd 2+  by Sn 2+  adsorb over the substrate surface and form nuclei for further Pd growth.   4. The porous substrate is then immersed in a chemical plating solution (electroless plating) with a typical composition of [Pd(NH 3 ) 2 ]Cl 2  (4 g/l), EDTA 2Na (65 g/l), NH 2 —NH 2 .H 2 O (0.6 g/l), NH 3 .H 2 O (28%) (300 ml/l), pH=˜10, 50° C. In the formation of Pd 0 , Pd 2+  existed in the chemical plating solution as metastable metal complex ion continuously being reduced to Pd 0  by reducing agent hydrazine. Pd nuclei gradually become large to form the dense palladium membrane.   5. The porous substrate is then subjected to post-processing where the pore fillers residing in the pore-channels of the porous substrate are removed or reduced in volume through either heating or physical/chemical dissolving. The Pd membrane is then dried at 200° C. in nitrogen for 60 min, and then calcined at 500° C. for 120 min.       

    
    
     
       BRIEF DESCRIPTION OF THE DRAWING 
         FIG. 1  represents a schematic description of the preparation steps procedure and of the resulting membrane. The four corresponding preparation steps are as follows; 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     
         
         
           
             (1) Substrate modification—The modification of porous support involves preoccupying the channels of the porous substrate by pore fillers, for example Al(OH) 3 , which can be removed or partly removed by post-processing. 
             (2) Palladium nuclei formation—Palladium nuclei will be formed by the sensitization and activation technique. 
             (3) Membrane formation—Palladium or palladium alloy membrane are formed by electroless plating method. 
             (4) Modifier decomposition—The pore fillers, for example Al(OH) 3  are decomposed to porous Al 2 O 3  which will keep the channels of the substrate open, which form free passages for H 2  permeation.
 
As indicated hereabove, the pore fillers are substances that
 
             are capable of preoccupying the channels of the porous substrate and optionally the disfigurements of the substrate surface during the decoration technique step, and 
             prevent palladium ingress inside the pores during the preparation. 
           
         
       
    
     Preferably, the said pore fillers are then removed or partly removed by post-processing, e.g. heat treatment (preferably pyrolysis) and/or physical dissolution. 
     The said pore fillers can preferably be gels sols, colloids or precipitates. 
     They are preferably chosen amongst Al-sol, Si-sol, Ti-sol, Zr-sol and/or Ce-sol. They can also be preferably chosen amongst hydroxide-colloid, alkali carbonate colloid and/or carbonate colloid. 
     They can also be preferably chosen amongst hydroxide-precipitates, alkali carbonate precipitates and/or carbonate precipitates. 
     Most preferably, the pore fillers used according to the present invention are characterised by a particle size lower than 0.2 micron, preferably lower than 0.1 micron, most preferably lower than 0.05 micron. 
     In the technique scenario of this invention, the chemical particles which could be processed (such as pyrolysis) to porous tiny particles as pore fillers, or which could evidently shrink its volume by pyrolysis process such as gel, sol, colloid, precipitate (Al-sol, Si-sol, Ti-sol, hydroxide colloid, alkali carbonate colloid, carbonate precipitate, et al.), are considered as pore filler. Under the vacuum conditions, porous substrate membrane was suspended in the sol, colloid, or precipitates solution of said pore fillers, the tiny particles of pore fillers entered the pore channel of porous substrate, especially the big channel or the disfigurement, such will decorate the substrate surface and will benefit the formation of dense palladium membrane. Due to the pyrolysis process after palladium membrane formation made the pore fillers shrink its volume and decomposed to porous materials, which provide the free passages for hydrogen permeating the membrane, metal palladium composite membrane derived from modified porous substrate will have high hydrogen permeable flux. 
     According to a preferred embodiment of the invention the material used for the porous substrate support of the metal palladium composite membrane or alloy palladium composite membrane is selected from one of the following porous materials; porous stainless steel, porous nickel, porous glass or porous ceramics. According to a preferred embodiment of the invention the preferred materials used for the support are porous stainless steel and porous ceramics. 
     The characteristics of the present invention are as follows;
         i. Simple technology. In this invention, vacuum is the only condition needed for pore filler particles entering the pore channels of porous substrate. Both the operation and technology are very simple.   ii. Wide application. This invention is not limited to the substrate membrane decoration for metal palladium/palladium alloy composite membrane preparation; it can also be applied for the decoration of any porous substrates for other metal membranes. However, the pore fillers are those which do not react with the plating solution.   iii. Low production cost. In this invention, cheap pore fillers, which could be decomposed by pyrolysis, are used such as sol, colloid, or precipitate. The raw materials used are inexpensive, the preparation technology is simple, and easy to perform, therefore the production cost of the process is low.       

     EXAMPLES 
     The details of this invention will be described in the following examples. In the following examples, hydrogen permeable flux and permeable selectivity are measured at 500° C. 
     Example 1 
     Colloid preparation: the solution of aluminium nitrate and the solution of sodium carbonate are simultaneously dropped in one beaker at 55° C., pH=8 to obtain an alkali alumina carbonate colloid. The colloid was washed 6 times with distilled water. If the above solution of sodium carbonate is replaced by the solution of potassium carbonate, ammonia, sodium hydroxide and/or potassium hydroxide as precipitator, the corresponding colloid or precipitates will be obtained. 
     Porous substrate surface decoration: substrate is alumina porous ceramic tube. Porous substrate was first rinsed with the dilute solution of hydrochloric acid and the dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with CCl 4 , and then dried. The rinsed alumina porous ceramic tube were immerged in the above colloid solution at vacuum condition, colloid particles will enter the pore channels and the surface disfigurements of alumina porous ceramic tube. The excess surface pore filler residing on the surface of the support was then removed by mechanical cleaning. 
     Palladium composite membrane preparation: Porous substrates after decoration were sensitized in SnCl 2  solution and activated in PdCl 2  solution, respectively. The above steps were repeatedly 4 times. Pd 0  atoms, formed in the reduction of Pd 2+  by Sn 2+  adsorbed over the substrate surface. 
     Immerging the porous substrate into the electroless plating solution, whose typical composition is [Pd(NH 3 ) 2 ]Cl 2  (4 g/l), EDTA.2Na (65 g/l), NH 2 —NH 2 .H 2 O (0.6 g/l), NH 3 .H 2 O (28%) (300 ml/l), pH=10, 50° C. In the catalysis of Pd nuclei, Pd 2+  existed in the electroless plating solution as metastable metal complex ion continuously being reduced to Pd 0  by reducing agent hydrazine. Pd 0  gradually became large enough to form a dense palladium membrane. 
     Post processing: The palladium composite membrane was then subjected to drying at 200° C. and calcining at 500° C. in order to decompose the pore fillers of alkali alumina carbonate colloid which resides in the pore-channels of the porous substrate. 
     Table 1 gives the hydrogen permeable performances of palladium composite membrane prepared with Al(NO 3 ) 3  and different precipitators which modified the porous alumina ceramic tube. 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Hydrogen permeable performances of metal palladium composite 
               
               
                 membranes 
               
             
          
           
               
                   
                   
                 Hydrogen flux 
                 Hydrogen selectivity 
               
               
                   
                 Precipitator 
                 m 3  · m −2  · h −1  · bar −1   
                 H 2 /N 2   
               
               
                   
                   
               
               
                   
                 Na 2 CO 3   
                 74 
                 8800 
               
               
                   
                 K 2 CO 3   
                 69 
                 5800 
               
               
                   
                 NH 3 •H 2 O 
                 67 
                 7200 
               
               
                   
                 NaOH 
                 56 
                 4200 
               
               
                   
                 KOH 
                 70 
                 5900 
               
               
                   
                   
               
             
          
         
       
     
     Example 2 
     Colloid preparation: it is the same as that in example 1. 
     Porous substrate surface decoration: substrate is porous stainless steel tube. Decoration method is the same as that in example 1. Post processing method is the same as that in example 1. 
     Table 2 gives the hydrogen permeable performances of palladium composite membrane prepared with Al(NO 3 ) 3  and different precipitators which modified the porous stainless steel tube. 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Hydrogen permeable performances of metal palladium composite 
               
               
                 membranes 
               
             
          
           
               
                   
                   
                 Hydrogen flux 
                 Hydrogen selectivity 
               
               
                   
                 Precipitator 
                 m 3  · m −2  · h −1  · bar −1   
                 H 2 /N 2   
               
               
                   
                   
               
               
                   
                 Na 2 CO 3   
                 38 
                 4400 
               
               
                   
                 K 2 CO 3   
                 34 
                 5100 
               
               
                   
                 NH 3 •H 2 O 
                 29 
                 3500 
               
               
                   
                 NaOH 
                 33 
                 3900 
               
               
                   
                 KOH 
                 34 
                 4100 
               
               
                   
                   
               
             
          
         
       
     
     Example 3 
     Colloid preparation: the solution of cerium nitrate and the solution of sodium carbonate are simultaneously dropped in one beaker at 55° C., PH=9 to obtain an alkali cerium carbonate colloid. The colloid was washed 5 times with distilled water. If the above solution of sodium carbonate is replaced by the solution of potassium carbonate, ammonia, sodium hydroxide and/or potassium hydroxide as precipitator, the corresponding colloid or precipitates will be obtained. 
     Porous substrate surface decoration: substrate is alumina porous ceramic tube. Porous substrate was first rinsed with the dilute solution of hydrochloric acid and the dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with CCl 4 , and then dried. The rinsed alumina porous ceramic tube were immerged in the above colloid solution at vacuum condition, colloid particles will enter the pore channel channels and the surface disfigurements of alumina porous ceramic tube. The excess surface pore filler residing on the surface of the support was then removed by mechanical cleaning. 
     Palladium composite membrane preparation: the procedures are the same as those in example 1. 
     Post processing method is the same as that in example 1. 
     Table 3 gives the hydrogen permeable performances of palladium composite membrane prepared with Ce(NO 3 ) 3  and different precipitators which modified the porous alumina ceramic tube. 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Hydrogen permeable performances of metal palladium composite 
               
               
                 membranes 
               
             
          
           
               
                   
                   
                 Hydrogen flux 
                 Hydrogen selectivity 
               
               
                   
                 Precipitator 
                 m 3  · m −2  · h −1  · bar −1   
                 H 2 /N 2   
               
               
                   
                   
               
               
                   
                 Na 2 CO 3   
                 72 
                 7600 
               
               
                   
                 K 2 CO 3   
                 70 
                 4800 
               
               
                   
                 NH 3 •H 2 O 
                 69 
                 6200 
               
               
                   
                 NaOH 
                 62 
                 3100 
               
               
                   
                 KOH 
                 56 
                 4100 
               
               
                   
                   
               
             
          
         
       
     
     Example 4 
     Colloid preparation: CO 2  is injected into the Ca(OH) 2  solution to form CaCO 3  precipitate, which were rinsed 5 times with distilled water. 
     Porous substrate surface decoration: substrate is alumina porous ceramic tube. Porous substrate was first rinsed with the dilute solution of hydrochloric acid and the dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with CCl 4 , and then dried. The rinsed alumina porous ceramic tube were immerged in the above CaCO 3  precipitate suspending liquid at vacuum condition, CaCO 3  precipitate particles will enter the pore channels and the surface disfigurements of alumina porous ceramic tube. The excess surface pore filler residing on the surface of the support was then removed by mechanical cleaning. 
     Palladium composite membrane preparation: the procedures are the same as those in example 1. 
     Post processing method is the same as that in example 1. 
     Palladium composite membrane, prepared by chemical plating method and porous alumina ceramic substrate modified by CaCO 3  precipitate, exhibit a 66 m 3 ·m −2 ·h −1 ·bar −1  of hydrogen permeable flux and a 3800 of hydrogen permeation selectivity (H 2 /N 2 ). 
     Example 5 
     Porous substrate surface decoration: γ-AlOOH sol, derived from SB powder, is being as surface pore filler, substrate is alumina porous ceramic tube. Porous substrate was first rinsed with the dilute solution of hydrochloric acid and the dilute solution of sodium hydroxide, and then washed with distilled water, rinsed with CCl 4 , and then dried. The rinsed alumina porous ceramic tube were immerged in the above Al-sol solution at vacuum condition, AlOOH particles will enter the pore channels and the surface disfigurements of alumina porous ceramic tube under the vacuum conditions. The excess surface pore filler residing on the surface of the support was then removed by mechanical cleaning. 
     Palladium composite membrane preparation: the procedures are the same as those in example 1. 
     Post processing method is the same as that in example 1. 
     Palladium composite membrane, prepared by chemical plating method and porous alumina ceramic substrate modified by γ-AlOOH sol, exhibit a 58 m 3 ·m −2 ·h −1 ·bar −1  of hydrogen permeable flux and a 3800 of hydrogen permeation selectivity (H 2 /N 2 ). 
     Example 6 
     Colloid preparation: the procedure is the same as those in example 3. Porous substrate surface decoration: the procedure is the same as those in example 3. Palladium-silver alloy composite membrane preparation: First, the procedures are the same as those in example 1. Then, palladium composite membrane obtained is immerged into the chemical plating solution containing silver which component is AgNO 3  (9 g/l), sodium citrate (6.5 μl), formaldehyde (37 wt %) (18 ml/l), buffer solution (PH=10) (90 ml/l). Pd—Ag alloy membrane was formed after 4 h calcinations at 450° C. of composite membrane obtained. 
     Post processing method is the same as that in example 1. 
     Table 6 lists the hydrogen permeable performances of palladium-silver alloy composite membrane prepared with Ce(NO 3 ) 3  and different precipitators which modified the porous alumina ceramic tube. 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Hydrogen permeable performances of Pd—Ag alloy 
               
               
                 composite membranes 
               
             
          
           
               
                   
                   
                 Hydrogen flux 
                 Hydrogen selectivity 
               
               
                   
                 Precipitator 
                 M 3  · m −2  · h −1  · bar −1   
                 H 2 /N 2   
               
               
                   
                   
               
               
                   
                 Na 2 CO 3   
                 72 
                 6900 
               
               
                   
                 K 2 CO 3   
                 62 
                 5200 
               
               
                   
                 NH 3 •H 2 O 
                 53 
                 4800 
               
               
                   
                 NaOH 
                 51 
                 5800 
               
               
                   
                 KOH 
                 54 
                 6200 
               
               
                   
                   
               
             
          
         
       
     
     Example 7 
     For Comparison 
     Porous substrate surface decoration: porous γ-Al 2 O 3  is suspended in distilled water, substrate is alumina porous ceramic tube. Porous alumina porous ceramic tube were immerged in the above suspending liquid at vacuum condition, porous γ-Al 2 O 3  particles will enter the pore channels and the surface disfigurements of alumina porous ceramic tube under the vacuum conditions. Such decorates the substrate. It is the same surface decoration with CeO 2 , TiO 2 , and ZrO2 instead of γ-Al 2 O 3 . 
     Palladium composite membrane preparation: the procedures are the same as those in example 1. 
     Table 7 lists the hydrogen permeability of palladium composite membrane prepared with different pore fillers (γ-Al 2 O 3 , CeO 2 , TiO 2 , ZrO 2 ) which modified the porous alumina ceramic tube. 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Hydrogen permeable performances of composite palladium membranes 
               
             
          
           
               
                   
                   
                 Hydrogen flux 
                 Hydrogen selectivity 
               
               
                   
                 Pore fillers 
                 M 3  · m −2  · h −1  · bar −1   
                 H 2 /N 2   
               
               
                   
                   
               
               
                   
                 γ-Al 2 O 3   
                 12.8 
                 2300 
               
               
                   
                 CeO 2   
                 14.4 
                 1800 
               
               
                   
                 TiO 2   
                 13.7 
                 1900 
               
               
                   
                 ZrO 2   
                 10.8 
                 2400 
               
               
                   
                   
               
             
          
         
       
     
     It is seen from table 7 that the conventional γ-Al 2 O 3 , CeO 2 , TiO 2 , ZrO 2  modified the surface of porous alumina ceramic tube will result in palladium deposit in the channel of γ-Al 2 O 3 , CeO 2 , TiO 2 , ZrO 2  during membrane formation, and further result the lower hydrogen permeable flux of palladium composite membrane obtained. 
     Example 8 
     For Comparison 
     Porous substrate surface decoration: substrate is porous stainless steel tube. Surface decoration method is the same as that shown in example 7. 
     Palladium composite membrane preparation: the procedure is the same as that in example 1. 
     Table 8 lists the hydrogen permeability of palladium composite membrane prepared with different pore fillers (γ-Al 2 O 3 , CeO 2 , TiO 2 , ZrO 2 ) which modified the porous stainless steel tube. 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 8 
               
             
             
               
                   
               
               
                 Hydrogen permeable performances of composite palladium membranes 
               
             
          
           
               
                   
                   
                 Hydrogen flux 
                 Hydrogen selectivity 
               
               
                   
                 Pore fillers 
                 M 3  · m −2  · h −1  · bar −1   
                 H 2 /N 2   
               
               
                   
                   
               
               
                   
                 γ-Al 2 O 3   
                 6.2 
                 3100 
               
               
                   
                 CeO 2   
                 9.8 
                 3200 
               
               
                   
                 TiO 2   
                 3.2 
                 2200 
               
               
                   
                 ZrO 2   
                 5.1 
                 1800 
               
               
                   
                   
               
             
          
         
       
     
     It is seen from table 8 that the conventional γ-Al 2 O 3 , CeO 2 , TiO 2 , ZrO 2  modified the surface of porous stainless steel tube will result in palladium deposit in the channel of γ-Al 2 O 3 , CeO 2 , TiO 2 , ZrO 2  during membrane formation, and further result the lower hydrogen permeable flux of palladium composite membrane obtained.