Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
  • C23C18/1208—Oxides, e.g. ceramics
  • C23C18/1212—Zeolites, glasses
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/165—Natural alumino-silicates, e.g. zeolites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
  • B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3204—Inorganic carriers, supports or substrates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3234—Inorganic material layers
  • B01J20/3238—Inorganic material layers containing any type of zeolite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/082—X-type faujasite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/084—Y-type faujasite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/7003—A-type
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/391—Physical properties of the active metal ingredient
  • B01J35/395—Thickness of the active catalytic layer
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1229—Composition of the substrate
  • C23C18/1241—Metallic substrates
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
  • C23C22/66—Treatment of aluminium or alloys based thereon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/60—Synthesis on support
  • B01J2229/66—Synthesis on support on metal supports
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/05—Nuclear magnetic resonance [NMR]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency
  • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

• the present invention relates to a method for forming a aluminosilicate zeolite layer on an aluminum-containing metallic substrate of metallic aluminum or an aluminum alloy, which is converted into an aqueous reaction dispersion in which the network-forming elements are silicon and optionally aluminum, wherein the molar ratio between aluminum in the aqueous reaction dispersion to the sum of the network forming elements contained in the aqueous reaction dispersion is less than 0.5, which heats the aluminum containing metallic substrate containing aqueous reaction dispersion, the aluminum-containing metallic substrate for the aluminosilicate zeolite-forming aluminum removed and the layer of an aluminosilicate - Zeolite is formed on the metallic substrate by in situ crystallization.
• Zeolites are in the narrow mineralogical sense silicate minerals and in particular alumo-silicates of complex chemical structure, which are characterized by the formation of porous tetrahedral networks (T-networks).
• T-networks porous tetrahedral networks
• IZA International Zeolite Association
• zeolites are understood to mean those materials which have T-networks of a network density of ⁇ 19 T atoms per 1000 ⁇ 3 . They show a structure with internal cavities, which can accept molecular sizes. This results in the property of zeolites to be able to absorb foreign atoms or foreign molecules into their porous structure.
• zeolites can store large amounts of water and release them when heated. Zeolites are particularly suitable for heat transformation when in contact with a heat exchanger.
• beds of shaped zeolites or zeolites are used, which are introduced into open-pore solids, which are in thermal contact with a heat exchanger.
• Such a prior art results, for example, from DE 101 59 652 C2.
• zeolites are used in the chemical industry for a variety of other applications. These are z. As ion exchange processes, usually synthetic zeolites are used in powder form a crystal size of a few micrometers. In addition, zeolites are used as molecular sieves, wherein the zeolites can be introduced as a loose bed of Krista llen or molded materials in a filter system.
• US 2003/0091872 A1 describes a method for producing a zeolite layer on a metal, such as aluminum, nickel, steel or titanium.
• a metal such as aluminum, nickel, steel or titanium.
• classical aluminum silicate layers are formed in an aqueous reaction dispersion having a pH of from neutral to 12.
• the reaction dispersion also contains aluminum.
• Direct growth of the zeolites onto the substrate improves the adhesion of the zeolite layer to the substrate.
• the Si and Al sources in the solution provide the building blocks for the aluminosilicate zeolites to be formed on the substrate.
• some aluminum atoms of the substrate may also be incorporated into the aluminosilicate-zeolite network.
• the initially described prior art which is based on WO 2010/099919, is already satisfactory.
• the aluminosilicate-zeolite-coated metallic substrate obtained by the known process technology is accessible to a wide variety of possible uses, preferably in sorption-based application areas.
• This technology has many advantages, which can be represented as follows: 1. There are thin, hydrophilic aluminosilicate zeolite layers on aluminum-containing metallic substrates, in particular Al-rich aluminosilicates present, accessible. These carry a higher lattice charge and are therefore much more hydrophilic than low-AI zeolites. 2.
• Classic adsorbents, such as FAU can be produced for the first time as compact layers with fixed, direct bonding to metallic aluminum (very good heat conduction).
• the known method is a single-step synthesis, whereby no foreign zeolite layer is necessary as a binding matrix. 4. Many of the aluminosilicate zeolites contemplated are available without a template and therefore without calcination. 5. A layer of aluminum-rich aluminosilicate zeolite is formed very firmly on a metallic Al support. It has been shown that optimizations could be sought in individual cases. In these individual cases, the following, by no means distinct, drawbacks have emerged: low layer yield, unwanted poorly soluble alumina hydrate (eg gibbsite) occasionally occurs as an interfering precipitate on the support Al (negative shielding of the surface).
• gibbsite unwanted poorly soluble alumina hydrate
• the object of the invention is based on the following object of the invention: This relates to a process for forming an aluminosilicate zeolite layer on an aluminum-containing metallic substrate made of metallic aluminum or an aluminum alloy which is introduced into an aqueous reaction dispersion adjusted in an alkaline manner which contain, as the network-forming elements, silicon and, if appropriate, aluminum, the molar ratio between the aluminum in the aqueous reaction dispersion and the sum of the network-forming elements contained in the aqueous reaction dispersion, regardless of whether aluminum is present in the aqueous reaction dispersion or the excess ratio, is less than 0.5, more preferably less than 0.4, and when aluminum is not present in the aqueous reaction solution, the inferior molar ratio is 0, and the alkaline metal
• these aluminum complexing agents have no structure-directing templating effect, such as many amines and ammonium salts. It is expedient to choose the reaction conditions so that the synthesis windows for the desired Al-containing zeolites are not left. This is especially true for the content of Alkalionenionen- and to be adjusted basic pH. It should be noted here that the targeted introduction of zeolite layers onto an aluminum-containing metallic carrier can be improved by the additional incorporation of zeolite crystallization seeds. These germs are expediently applied as a porous coating in layer form to the aluminum-containing metallic support to be coated and thus also fulfill the function of a kind of protective layer.
• the gist of the invention consists in the use of aluminum complexing compounds (chelating agents). Particularly suitable are organic polyacids and their salts and similar chelating agents with 0 as the anchor atom in the complex. Various chelating agents with coordination numbers from 2 to 8 (in brackets) are listed below: oxalate (2), dimercaptum succinic acid (2), acetylacetone (2), tartrate (2) and citrate (3).
• the mentioned aluminum complexing agent with O-anchor atoms is an organic multiple acid or a salt thereof, in particular in the form of a sodium and / or potassium salt.
• Preferred ligands here are organic di- and tri-acids, in particular oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, tartaric acid, malic acid, glutamic acid and / or citric acid, in particular in the form of the sodium and / or potassium salts.
• acetylacetone it is also possible to specify acetylacetone here.
• the concentration of the complexing agent used according to the invention in the aqueous reaction dispersion is preferably greater than 8.5.
• an excess of alkali hydroxide which is not neutralized by the organic acid should be present.
• the minimum amount of the complexing agent salt with respect to Na 2 O could be given as 0.15 mol for the dianion and 0.1 mol for the trianion. This is a suitable guideline for the person skilled in the art Carrying out the method according to the invention taking into account the other parameters relevant to the invention successfully proceed.
• the organic complexing agents are removed by washing from the product or decomposed at lower temperatures than amines, which then no amines, acrylic compounds, (iso) cyanides or (iso) cyanates and nitrogen oxides arise as in the calcination of amines.
• a layer of aluminum-rich aluminosilicate zeolite is formed on an aluminum-containing metallic substrate, then this is to be understood as far as possible.
• the following aluminum-rich aluminosilicate zeolites are to be highlighted: FAU (zeolite X and Y), LTA, CHA, MOR and GIS.
• zeolites are distinguished by a water sorption capacity at 25 ° C. of at least 12% or more, based on the pure mass of the zeolite, and by IU-PAC type I equilibrium isotherms for water vapor (see Sing et al, Pure Appl Chem. 57 (1985) p. 603) and are described by Rodrizez-Reinoso et al. (seeRatricez-Reinoso et al., Studies in Surface Science and Catalysis 62 (1991), pp. 685-692) assign adsorbents to the hydrophilic "Group 1." A higher proportion of aluminum generally leads to a stronger adhesion of the adsorbents formed zeolite layer on the aluminum-containing substrate.
• the aim of the invention is also, as shown, to form a layer of aluminum-rich aluminosilicate zeolite of the specified requirements on an aluminum-containing metallic substrate.
• it may be a substrate made of metallic aluminum.
• Other elements may be included to form an alloy.
• Typical aluminum alloys are, for example, AlFe 1.5 Mn 0.5 or AIMg3.
• special alloying constituents may be included in view of a beneficial effect for the particular application, such as silicon.
• the aluminum is not present either in the aqueous reaction dispersion, wherein the mentioned inferior molar ratio is then 0, or only in such amounts that the corresponding value is at least less than 0.5, in particular less than 0.4 lies.
• the deficit refers to the present in the produced zeolite Si / Al ratio and this ratio can vary, in particular for the aluminum-rich aluminosilicate zeolites of 1 to 10, a graded indication of the deficit quotient AI / (AI + Si) is useful.
• AI / (AI + Si) the deficit quotient quotient
• Table 1 corresponding statements, resulting in a relationship between the aluminum deficiency (AI / (AI + Si)) in the reaction dispersion and the zeolite composition (rounded data) results.
• the mentioned molar ratio is below 0.05, in particular below 0.02. It may be particularly preferred if the deficient molar ratio is 0 if the aqueous reaction dispersion does not directly contain any AI source.
• This undershoot requirement is technologically explained as follows. As a result, in situ crystallization of said layer occurs on the aluminum-containing metallic substrate. This recrystallization is a major reason why the process product exhibits desirable properties, in particular good adhesion of the formed zeolite layer to the surface of the aluminum-containing metallic substrate. For example, if this deficiency is 0, it means that the network-forming aluminum alone is removed from the aluminum-containing metallic substrate to form the crystallized zeolite layer.
• the elemental aluminum is oxidized to Al 3+ and formed in the aqueous reaction medium while equivalent hydrogen.
• the Al 3+ is then primarily (OH) " or complexed according to the invention as a counterion in the region of the substrate surface and can continue to react there, resulting in a particularly good anchoring between the surface of the aluminum-containing substrate and the formed aluminosilicate zeolite WO 2006/084211 A deals with the afore-mentioned inferior molar ratio which has already been mentioned above. was spoken and referred to.
• the aqueous reaction dispersion used contains a Si source.
• a Si source is silicic acid, silicates and / or silicic acid esters.
• an Al source is added to the practical embodiment of the process according to the invention in the aqueous reaction dispersion, taking into account the aforementioned requirements, it is advantageous if it is an aluminum oxide hydrate, in particular pseudoboehmite, and / or aluminum aluminate .
• the existing aqueous reaction dispersion is made alkaline, since otherwise the layer of an aluminum-rich metallic aluminosilicate zeolite does not form.
• the pH of the aqueous reaction dispersion may in particular be sodium hydroxide, potassium hydroxide, amines, basic Na salts and / or sodium aluminate. It is preferred that the pH of the aqueous reaction dispersion is set to more than 9 and / or less than 13.8, in particular for Al alloys with an Al content of more than 90%.
• colloidal sources of silicon and / or aluminum are used. It may be expedient to add fluoride salts or hydrofluoric acid to the mineralization thereof, wherein it must be considered that the aqueous reaction dispersion must have a pH of more than 7.
• the aqueous reaction dispersion may comprise an organic template or an organic structure-directing agent, in particular amines or ammonium salts or crown ethers. The function of such substances is known. They are mentioned in the literature et al. also referred to as “Template Molecule” and “Template Molecule” (see Stephen G. Wilson, "Templating in Molecular Seed Synthesis” (by Elesivier Science P.V.)).
• an aged gel is a reaction dispersion capable of forming the respective zeolite zeolite of the layer in powder form and, after several hours at room temperature, is already in the nucleation phase of zeolite development, but without entering the zeolite growth phase.
• the high viscosity of the gel additionally allows the crystallization nuclei to be applied directly to the aluminiu m-containing metallic substrate.
• the process according to the invention is preferably carried out at elevated temperature. It is expedient that the aqueous reaction dispersion and the aluminum-containing metallic substrate contained therein are heated to a temperature of 50 to 200 ° C, in particular from 70 to 130 ° C. In the event that the temperature of 100 ° C is exceeded, it may be necessary to carry out the reaction in a closed system, thus in an autoclave.
• the inventors have recognized that, for an advantageous embodiment of the method according to the invention, it is particularly expedient to pay attention to the ratio of the surface of the aluminum-containing substrate to the volume of the aqueous reaction dispersion (in cm 2 / cm 3 ). It proves to be preferred if this ratio is adjusted to 0.03 to 20, in particular to 0, 1 to 15 and most preferably to 1 to 8. If it is less than 0.1, in particular less than 0.03, then too much aqueous reaction dispersion is available, which can have a destructive effect on the aluminum-containing metallic substrate. In addition, it was found that too high a volume over the aluminum-containing substrate reduces the layer growth in favor of the unwanted crystal growth in the reaction dispersion. If the value of 15, in particular of 20, exceeded, then are in the reaction solution is not enough reactants for a sufficient coverage of aluminum aluminum substrate with aluminosilicate zeolite crystals available.
• the layer thickness can be set desirable and preferably at about 5 ⁇ to 200 ⁇ , in particular 5 ⁇ to 100 ⁇ , lie.
• the method according to the invention uses an organic structure-directing agent or an organic template, it is possible to further remove this agent or template, optionally after washing, by calcination.
• the aluminosilicate zeolite-coated aluminum-containing metallic substrates obtained in accordance with the invention are accessible to a wide variety of applications, preferably in sorption-based fields of application, in particular for heterogeneous catalysis, in separation and purification processes, in sorption heat pumps, in connection with immobilized catalysts and in microreaction technology. This list is not limiting.
• the invention can be in their practical realization various advantages in appearance. Unwanted extraneous phases do not arise, the partial reaction of the aluminum dissolution is greatly reduced and easily controllable.
• An advantageous zeolite is formed as a layer on the metallic carrier. A particular advantage is the fact that almost all technically relevant zeolites have become accessible. The mentioned gibbsite formation is strongly suppressed. By and large, all the optimization objectives are achieved, which are mentioned above with regard to the optimization of the teaching of WO 2010/099919 A2.
• the invention proves to be particularly advantageous as follows: aluminum ions form complexes with ligands with N as the anchor atom (amines, ammonium salts), although these complexes are complexed reacting in a subsequent reaction to an inert aluminum oxide hydrate (gibbsite). This precipitates immediately and thus stands for the desired zeolite formation not available as aluminum source.
• complexing agents with O as anchor atoms especially organic polyacids and their salts
• form complexes which subsequently react further to the reactive Al pseudoboehmite Al oxide hydrate (a common aluminum source in classical zeolite syntheses).
• the suitable aluminum complexing according to the invention also has a positive effect for the recrystallization on aluminum-containing metallic substrate.
• the reactive metal is less dissolved, which is always critical at the high necessary pH values.
• the reason may be the increased presence of the aluminum ions (as a complex) in the solution, shifting the dissolution balance more towards the side of the metallic aluminum.
• Table 1 Examples of the dependence of the aluminum deficit AI / (AI + Si) in the reaction dispersion of the zeolite composition (data rounded)
• Example 1 A reaction mixture of the composition 1.65 Na 2 O: 1.0 Si0 2 : 0.5 trisodium citrate: 140 H 2 O with sodium metasilicate as silicon source is prepared.
• a partial solution 1 a 25% strength NaOH solution with the required citric acid and half of the water is stirred at 600 rpm for 1 h.
• the silicon source (98%) is stirred with the rest of the water also at 600 U / min for lh.
• partial solution 2 is added to partial solution 1 and the mixture is stirred for 2 h at 800 rpm.
• the containers are cooled with water (5-10 min).
• the coated aluminum samples are removed and washed thoroughly with water.
• the samples are then dried at 75 ° C.
• a reaction mixture of composition 0.9 Na 2 O: 1.0 SiO 2 : 0.5 di-sodium tartrate: 140 H 2 O with sodium metasilicate as silicon source is prepared according to Example 1.
• the containers are cooled with water (5-10 min).
• the coated aluminum samples are removed and washed thoroughly with water.
• the samples are then dried at 75 ° C.
• FIG. 1 dissolution of aluminum in the NaOH solution without additions at pH 12.5 to form disadvantageous gibbsite
• FIG. 2 aluminum dissolution in the NaOH solution with Na tartrate (complexing agent according to the invention) at pH 12, FIG. 5th There is no formation of gibbsite

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Analytical Chemistry (AREA)
• Metallurgy (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Thermal Sciences (AREA)
• Physics & Mathematics (AREA)
• Ceramic Engineering (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)
• Chemical Treatment Of Metals (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=57485494

Family Applications (1)

Country Status (9)

Families Citing this family (1)

Citations (7)

Family Cites Families (12)

• 2015
  • 2015-12-18 DE DE102015122301.5A patent/DE102015122301B4/de not_active Expired - Fee Related
• 2016
  • 2016-12-06 EP EP16806107.5A patent/EP3390689B1/de active Active
  • 2016-12-06 US US16/063,420 patent/US20180371616A1/en not_active Abandoned
  • 2016-12-06 BR BR112018012421-4A patent/BR112018012421A2/pt not_active Application Discontinuation
  • 2016-12-06 KR KR1020187019332A patent/KR102221016B1/ko not_active Expired - Fee Related
  • 2016-12-06 ES ES16806107T patent/ES2827504T3/es active Active
  • 2016-12-06 CN CN201680073837.6A patent/CN108474117B/zh not_active Expired - Fee Related
  • 2016-12-06 WO PCT/EP2016/079905 patent/WO2017102442A1/de not_active Ceased
  • 2016-12-06 JP JP2018532076A patent/JP7022435B2/ja not_active Expired - Fee Related

Patent Citations (7)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events