Ceramic membrane having a catalytic membrane-material coating
A porously coated, densely sintered ceramic membrane, which can be produced from a green membrane and subsequent sintering. The membrane is coated with ceramic material, which contains noble metals, which can be produced by application and subsequent thermal treatment. The noble metals are contained at a concentration of 2.5 to 5 mass percent.
1. Porously coated, densely sintered ceramic membrane producible from a green membrane and submitted to subsequent sintering, the said membrane being coated with a ceramic material containing precious metals, producible by application and subsequent thermal treatment,
characterised in that
the precious metals are contained in the coating in a concentration of 0.2 to 5% by mass.
2. Porously coated, densely sintered ceramic membrane according to claim 1 , characterised in that the precious metals are contained in the porous coating in a concentration of 2.5 to 5% by mass and preferably of 3.8 to 4.5% by mass.
3. Porously coated, densely sintered ceramic membrane according to claim 1 or 2 , characterised in that the precious metals contained in the porous coating are selected from a group containing silver, ruthenium, platinum and palladium or the porous coating contains a mixture of these precious metals.
4. Porously coated, densely sintered ceramic membrane according to claim 3 , characterised in that the porous coating contains palladium.
5. Porously coated, densely sintered ceramic membrane according to one of claims 1 to 4 , characterised in that the porous coating has a thickness of 3 to 10 μm.
6. Porously coated, densely sintered ceramic membrane according to one of claims 1 to 5 , characterised in that the membrane is formed by an oxide ceramics with a perovskite structure or a brownmillerite structure or an Aurivillius structure.
7. Porously coated, densely sintered ceramic membrane according to claim 6 , characterised in that the oxide ceramics preferably has a perovskite structure ABO 3-δ , A implying bivalent cations and B implying trivalent or higher-valent cations, the ionic radius of A being larger than the ionic radius of B and δ being a number between 0.01 and 0.9, preferably between 0.7 and 0.9, in which A and/or B may be mixtures of different cations.
8. Porously coated, densely sintered ceramic membrane according to claim 7 , characterised in that the cations of type A are selected from chemical elements of group 2, group 11, group 12 of the periodic table or the group of lanthanides or are mixtures of these cations, preferably from Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cu 2+ , Ag 2+ , Zn 2+ , Cd 2+ and/or the lanthanides and the cations of type B are selected from elements of groups 3 to 10 of the periodic table and/or the group of lanthanides, the metals of group 15 or are mixtures of these cations, preferably from Fe 3+ , Fe 4+ , Ti 3+ , Ti 4+ , Zr 3+ , Zr 4+ , Ce 3+ , Ce 4+ , Mn 3+ , Mn 4+ , Co 2+ , Co 3+ , Nd 3+ , Nd 4+ , Gd 3+ , Gd 4+ , Sm 3+ , Sm 4+ , Dy 3+ , Dy 4+ , Ga 3+ , Yb 3+ , Al 3+ , Bi 4+ or are mixtures of these cations.
9. Porously coated, densely sintered ceramic membrane according to claim 7 , characterised in that the oxide ceramics consists of BaCo a Fe b Zr c O 3-δ , wherein a+b+c=1 and δ is a number between 0.01 and 0.9, preferably between 0.7 and 0.9.
10. Porously coated, densely sintered ceramic membrane according to claim 6 , characterised in that the oxide ceramics of the porous coating is different from the oxide ceramics of the densely sintered ceramic membrane.
11. Porously coated, densely sintered ceramic membrane according to claim 7 , characterised in that the oxide ceramics of the porous coating consists of BaCo a Fe b Zr c N d O 3-δ , wherein a+b+c+d=1 with d=0.01 to 0.5 and δ is a number between 0.01 and 0.9, preferably between 0.7 and 0.9 and N stands for a precious metal.
12. Porously coated, densely sintered ceramic membrane according to one of claims 1 to 11 , characterised in that the membrane used is of the hollow-fibre type which in sintered state is of a non-linear, arched or bent form of preference, the said hollow fibre being porously coated with ceramic material containing precious metals.
13. Porously coated, densely sintered ceramic hollow fibre according to claim 12 , characterised in that the hollow fibre of a round cross-sectional geometry has an outside diameter of 0.1 mm to 5 mm and an inside diameter of 0.01 mm to 4.5 mm.
14. Production process for porously coated, densely sintered ceramic membranes according to one of claims 1 to 13 , including the following steps:
a) dissolving the constituents of the ceramic material in water and mixing them with EDTA acid and citric acid in a ratio of EDTA acid:citric acid:metal cations of 1:1.5:1, the pH value being adjusted to 9,
b) condensation under supplied heat in a temperature range between 100° C. and 200° C., a gel being formed,
c) thermal treatment of the gel at a temperature of up to 700° C. for 1-2 h, an amorphous powder being formed,
d) calcination of the amorphous powder in a temperature range between 800° C. and 1100° C. for 8-10 h at a continuous temperature rise of 2° C. to 5 K/min.,
e) pressing the powder at 100-200 kN for 10-25 minutes and subsequent extrusion to form green membranes,
f) pressureless sintering for 8-16 h at 1000° C. to 1400° C. in an air atmosphere at a continuous temperature rise or drop of 2 to 5 K/min, a ceramic membrane being formed,
g) dissolving a ceramic material containing precious metals and treated according to steps a) to d) in citric acid and subsequent grinding, an aqueous mass being formed,
h) application of the aqueous mass onto the ceramic membrane produced according to f),
i) thermal treatment at 1000° C. to 1100° C. for 0.5-1.5 h, the precious metals of the porous coating being admixed in a concentration of 1 to 5% by mass.
15. Membrane reactor for selective gas separation, consisting of at least a porously coated, densely sintered ceramic membrane according to claims 1 to 13 , which subdivides the membrane reactor into at least one permeate chamber and at least one substrate chamber; of at least one feed line for a feed gas containing oxygen and/or an oxygen-releasing compound, the feed line being connected to the substrate chamber; of at least one discharge line for a feed gas depleted of oxygen and/or of at least an oxygen-releasing compound, the discharge line being connected to the substrate chamber; of at least, if required, one feed line for a purge gas containing, if required, at least one reactant; this feed line being connected to the permeate chamber; and at least one discharge line for oxygen, for a gas mixture containing oxygen and/or a purge gas containing oxidised reactant, this feed line being connected to the permeate chamber.
16. A process a membrane reactor according to claim 15 , wherein gas constituents, preferably oxygen, are separated from gas mixtures, particularly air.
17. A process according to claim 16 , wherein the separated oxygen is provided to the subsequent performance of an oxidation reaction in the gas phase.
18. A process according to claim 17 , wherein the separated oxygen is provided to a partial oxidation of a hydrocarbonaceous gas mixture for the production of synthesis gas.
19. A process according to claim 17 , wherein the separated oxygen is provided to an oxidative dehydrogenation of hydrocarbons.
20. A process according to claim 17 , wherein the separated oxygen is provided to an oxidative coupling of methane.