EP0824369A1 - A method for manufacturing a support material for catalysis - Google Patents
A method for manufacturing a support material for catalysisInfo
- Publication number
- EP0824369A1 EP0824369A1 EP97906399A EP97906399A EP0824369A1 EP 0824369 A1 EP0824369 A1 EP 0824369A1 EP 97906399 A EP97906399 A EP 97906399A EP 97906399 A EP97906399 A EP 97906399A EP 0824369 A1 EP0824369 A1 EP 0824369A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- medium
- gelating
- chloride
- sol
- sulphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000006555 catalytic reaction Methods 0.000 title description 2
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 5
- 239000011707 mineral Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims abstract 2
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 238000001879 gelation Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 239000001166 ammonium sulphate Substances 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000002657 fibrous material Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000001132 aluminium potassium sulphate Substances 0.000 claims description 2
- 235000011126 aluminium potassium sulphate Nutrition 0.000 claims description 2
- 239000001164 aluminium sulphate Substances 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 235000011127 sodium aluminium sulphate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 238000007664 blowing Methods 0.000 claims 1
- 239000002612 dispersion medium Substances 0.000 abstract 1
- 239000002609 medium Substances 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 11
- 210000005056 cell body Anatomy 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 241000575946 Ione Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003915 air pollution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
Definitions
- the present invention relates to a method for manufacturing a support material for catalysts, here a paper of mineral fibres, such as a paper of glass fibres is formed to a body with fine through channels, whereafter a gel is provided on the body.
- the main object of the invention is to achieve a support material for catalysts providing these desired qualities.
- a block, a rotor or any other body is manufactured in that two tracks or bands of a paper of mineral fibres, one of which is folded or corrugated, is connected to a so-called single well in using any convenient adhesive.
- the paper contains artificial, e.g. spun or extruded fibres of various minerals, here glass fibres.
- the folded or corrugated paper track has a wave height of 1 to 7 mm.
- the single well produced in such a way is placed into blocks to form a stationary body with the desired shape and the desired dimensions or are wound into a cylindric rotor with a desired size.
- Various body shapes are depending on the application possible such as square, rectangular or even triangular or similar forms.
- the produced structure is from one end surface of the body to the corresponding opposite end surface provided with parallel through channels, laterally separated from each other by contact points between the plane and the folded layers.
- the cell body of glass fibre paper been manufactured in this way an impreganation of the body is provided in that a dispersion of a filling substance, a silica so and a dispersing medium is applied to it.
- the application might be provided by means of dipping, the body then being placed into the dispersion for a certain period.
- the dispersion can be mixed in a mixer before it is transferred to an impregnating bucket where the dipping is provided.
- the dispersion has a tendency to form a skin when remaining untouched for some period, but this problem can be avoided by means of some kind of circulation in the impregnating bucket.
- Another alternative is that this part of the process is performed with a flushing of the cell body by means of a so-called liquid curtain.
- the silica sol is as previously mentioned mixed with a filling substance to a dispersion. This procedure is made to increase the dry content of the impregnating sol over 50 % being considered to present the upper limit for a silica sol. Together with a dispersing medium a dry content of 60 to 65 % can be achieved for the entire dispersion. This is necessary, as the glass fibre paper to be impregnated is very porous and usually has blanks of 90 to 95 %. An alternative method could be to impregnate several times in a sol and gelate it. Besides that the process costs would increase the sol is in most cases more expensive than a filler substance, this also increasing the costs for the raw materials.
- a non fibrous filler medium is according to the invention used and examples of such preferred filler media are kaolin and other clay materials, silica, mica, talcum, felspar.
- a gutting of the cell body can be performed with e.g. air to clean the channels from the dispersion sol.
- the sol being a silica sol consists of small particles of silicic acid not sedimenting in water.
- the silicic acid is thus not solved in the water but so to say finely distributed.
- the particles can be 5 to 150 n large. With such small particles and contents of about 15 to 50 % their total area will be extremely large.
- the system will physically decrease its boundary, i.e. the particles will converge to fewer and essentially larger aggregates. Thus, a minor boundary is obtained.
- the sol is generally stabilized by means of sodium hydroxide.
- the negative hydroxide iones settle on the particles surface and make these repellant to each other thus preventing any aggregation. If the sol is dried, i.e. the water is removed, the particles will finally approach each other so much that the stabilising effect is partly overcome and a gelation is performed.
- a gel medium is instead provided, e.g. a salt.
- the effect of the hydroxide iones on the sol particle area will be abolished due to a higher charging density in the sol.
- the effect of the hydroxide iones is overcome and the silicic acid particles are approaching each other sufficiently so that the whole sol is polymerized (gelated), i.e. obtains the minor boundary to be achievable between the silicic acid and the water. In practice however, the water will be locked into the structure and is there bound capillarily.
- Most soluble salts can perform as a gelating medium.
- chlorides might thus be used such as sodium chloride, calcium chloride, magnesium chloride, aluminium chloride, zinc chloride and litium chloride, sulphates such as ammoniumsulphate, sodium sulphate, aluminium sulphate and aluminium-potassium sulphate, nitrates such as ammonium nitrate, aluminium nitrate and potassium nitrate and acetates such as ammonium acetate, calcium acetate and sodium acetate.
- sulphates such as ammoniumsulphate, sodium sulphate, aluminium sulphate and aluminium-potassium sulphate
- nitrates such as ammonium nitrate, aluminium nitrate and potassium nitrate
- acetates such as ammonium acetate, calcium acetate and sodium acetate.
- a flushing or a washing of the cell body is thereafter performed to remove residues of the gelating medium from the cell body surfaces.
- residues might possibly form dangerous gases during a following calcination of the cell body.
- the cell body is therefore washed under e.g. a water curtain.
- the cristallized gelating medium is solved and can be returned to a recovering system to recover the gelating medium.
- a calcination of the body can be performed at a high temperature to achieve a body form stability for a further treatment. In cases where organic materials exist in it this material will be burned off.
- a final treatment is then performed, in which the the supporting body is coated (by means of an already known technology) with a Si0 ⁇ *- ⁇ surface or a y-AU ___>O, surface.
- a cell body manufactured from glass fibre paper according to the procedure described in the beginning is impregnated e.g. by means of dipping or flushing with a dispersion of 25 to 35 % kaolin or any other filling material of the kind mentioned above, 65 to 75 % silica sol with a concentration (dry content) above 40 % (a silica sol with various particle size can be mixed) and a small amount, e.g. 0.5 % of a dispersing medium. Before any gelating is performed the body is gutted with air to clean the channels from any excess of dispersing sol.
- the gutted body is then provided with a gelating medium, here a sol with 10 % ammonium sulphate up to a saturated sol or a combination of the salts (NH ⁇ SC and Na ⁇ SC , performed by means of dipping during about 30 minutes.
- a gelating medium here a sol with 10 % ammonium sulphate up to a saturated sol or a combination of the salts (NH ⁇ SC and Na ⁇ SC , performed by means of dipping during about 30 minutes.
- a gelating medium here a sol with 10 % ammonium sulphate up to a saturated sol or a combination of the salts (NH ⁇ SC and Na ⁇ SC , performed by means of dipping during about 30 minutes.
- the body is dried to remove capillarily bound water in an air stream with a temperature below 100 ° C until the body is completely dry.
- a washing or flushing av the body is performed to remove residues of the ammonium sulphate formed on the body surfaces during the gelation and the drying. These residues would during a following burning or calcination disintigrate into NH and SO-, these gases performing as air pollutions during the burning.
- the washing is provided in that the body is e.g. flushed under a water curtain.
- a drying by means of air is performed at maximum 140 ° C and thereafter the temperature is raised either for a burning or a calcination at a temperature of about 240 to 300 C and with a dwelling period of 30 to 60 minutes to achieve a proper burning of possibly existing organic material and/or a raising of the temperature to e.g. 550 to 600 C at the end of the burning to achieve a good form stability of the body for a following treatment.
- Another impregnation of the body is thereafter provided with a sol with a dry content of 5 to 15 % and with an inner specific surface depending on the application, whereafter a drying is performed at a temperature below 100 C.
- This method provides a SiC surface.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A mineral fibre paper is formed to a body with fine through channels, the body being impregnated with a dispersion of a filling material, a sol and a dispersion medium. A gelating medium is provided to the body to gelate the sol so that the whole sol is polymerized or gelated.
Description
A METHOD FOR MANUFACTURING A SUPPORT MATERIAL FOR CATALYSIS
The present invention relates to a method for manufacturing a support material for catalysts, here a paper of mineral fibres, such as a paper of glass fibres is formed to a body with fine through channels, whereafter a gel is provided on the body.
It is already known to use bodies manufactured in this way in form of blocks, rotors or similar as a support material for catalysts. In such methods to manufacture the support material the body is impregnated with a dispersion of a filling material and a silica sol. By means of drying the impregnated body at a low temperature a gelating of the sol is achieved. This implies a tideous process being very critical as to achieve the right deposition of the gel. Thus it is usual that the channels are clogged by the sol accumulated at the ends of the channels. This provides a far too high temperature during the following calcination of the body possibly resulting in burned-out portions of the body. The already known methods for manufacturing a support material are therfore providing a large rejection in manufacturing.
To handle the stresses created on the cell body and the gel properties such as a strong, even and non-cracking gel are aimed at. The main object of the invention is to achieve a support material for catalysts providing these desired qualities.
This object is according to the invention achieved in a way as stated in the claims to follow.
The method according to the invention will be described more in detail here below.
A block, a rotor or any other body is manufactured in that two tracks or bands of a paper of mineral fibres, one of which is folded or corrugated, is connected to a so-called single well in using any convenient adhesive. The paper contains artificial, e.g. spun or extruded fibres of various minerals, here glass fibres. The folded or corrugated paper track has a wave height of 1 to 7 mm. The single well produced in such a way is placed into blocks to form a stationary body with the desired shape and the desired dimensions or are wound into a cylindric rotor with a desired size. Various body shapes are depending on the application possible such as square, rectangular or even triangular or similar forms. The produced structure is from one end surface of the body to the corresponding opposite end surface provided with parallel through channels, laterally separated from each other by contact points between the plane and the folded layers.
The cell body of glass fibre paper been manufactured in this way an impreganation of the body is provided in that a dispersion of a filling substance, a silica so and a dispersing medium is applied to it. The application might be provided by means of dipping, the body
then being placed into the dispersion for a certain period. The dispersion can be mixed in a mixer before it is transferred to an impregnating bucket where the dipping is provided. The dispersion has a tendency to form a skin when remaining untouched for some period, but this problem can be avoided by means of some kind of circulation in the impregnating bucket. Another alternative is that this part of the process is performed with a flushing of the cell body by means of a so-called liquid curtain.
When manufacturing the catalysts support according to the invention the silica sol is as previously mentioned mixed with a filling substance to a dispersion. This procedure is made to increase the dry content of the impregnating sol over 50 % being considered to present the upper limit for a silica sol. Together with a dispersing medium a dry content of 60 to 65 % can be achieved for the entire dispersion. This is necessary, as the glass fibre paper to be impregnated is very porous and usually has blanks of 90 to 95 %. An alternative method could be to impregnate several times in a sol and gelate it. Besides that the process costs would increase the sol is in most cases more expensive than a filler substance, this also increasing the costs for the raw materials. During gelation also a shrinking is performed. If the distances then are comparatively large as they are in a glass fibre paper the stresses on the gel become very large and weakening crack formations are obtained. To have a filling medium dispersed in the sol is a way to decrease these distances and thereby any crack formations. The support will thus be stronger, tougher and have increased form stability than without any filler medium. Moreover, if a temperature resistent filling medium is used the support will with preserved properties resist higher temperatures.
Preferably a non fibrous filler medium is according to the invention used and examples of such preferred filler media are kaolin and other clay materials, silica, mica, talcum, felspar.
After the impregnation a gutting of the cell body can be performed with e.g. air to clean the channels from the dispersion sol.
The sol being a silica sol consists of small particles of silicic acid not sedimenting in water. The silicic acid is thus not solved in the water but so to say finely distributed. The particles can be 5 to 150 n large. With such small particles and contents of about 15 to 50 % their total area will be extremely large. The system will physically decrease its boundary, i.e. the particles will converge to fewer and essentially larger aggregates. Thus, a minor boundary is obtained. To prevent this the sol is generally stabilized by means of sodium hydroxide. The negative hydroxide iones settle on the particles surface and make these repellant to each other
thus preventing any aggregation. If the sol is dried, i.e. the water is removed, the particles will finally approach each other so much that the stabilising effect is partly overcome and a gelation is performed.
As described in the beginning such a drying procedure is however a tedious and sensitive process resulting in a large rejection of the manufactured support material due to clogged channels, as the impregnating sol will accumulate after some time due to gravitation.
According to the present invention a gel medium is instead provided, e.g. a salt. The effect of the hydroxide iones on the sol particle area will be abolished due to a higher charging density in the sol. The effect of the hydroxide iones is overcome and the silicic acid particles are approaching each other sufficiently so that the whole sol is polymerized (gelated), i.e. obtains the minor boundary to be achievable between the silicic acid and the water. In practice however, the water will be locked into the structure and is there bound capillarily. Most soluble salts can perform as a gelating medium. According to the invention chlorides might thus be used such as sodium chloride, calcium chloride, magnesium chloride, aluminium chloride, zinc chloride and litium chloride, sulphates such as ammoniumsulphate, sodium sulphate, aluminium sulphate and aluminium-potassium sulphate, nitrates such as ammonium nitrate, aluminium nitrate and potassium nitrate and acetates such as ammonium acetate, calcium acetate and sodium acetate.
Even other gelating media might be used such as e.g. acids, bases and alcolhols. Like salts they can disturb the fine balance existing in a stabilized silica sol and provide a strong gel structure. The stronger gel structure provides the possibility to manufacture a stronger support inspite of that fibrous materials are not used as a filler material. Previously such metarials have been used to achieve some kind of reinforcement. These material are however questionable in respect to health considerations. Examples of such fibrous materials now being avoided are: attapulgite, halloysite, sepiolite and wollastonite.
Thereafter a drying of the body is performed at a temperature below 100 °C to remove capillarily bound water without creating any crack formations. The cautious drying achieves that the excess salt leaves the structure and is deposited on the surface, where it is easily flushed off.
A flushing or a washing of the cell body is thereafter performed to remove residues of the gelating medium from the cell body surfaces. These residues might possibly form dangerous gases during a following calcination of the cell body. To avoid such gases as an air
pollution the cell body is therefore washed under e.g. a water curtain. Thus, even the cristallized gelating medium is solved and can be returned to a recovering system to recover the gelating medium.
After the flushing and another drying of the body a calcination of the body can be performed at a high temperature to achieve a body form stability for a further treatment. In cases where organic materials exist in it this material will be burned off.
To achieve the right structure for the supporting body surface depending on the application a final treatment is then performed, in which the the supporting body is coated (by means of an already known technology) with a Si0 ■*-< surface or a y-AU ___>O, surface.
Here below an example of a method for manufacturing a support material for catalysts will be described. A cell body manufactured from glass fibre paper according to the procedure described in the beginning is impregnated e.g. by means of dipping or flushing with a dispersion of 25 to 35 % kaolin or any other filling material of the kind mentioned above, 65 to 75 % silica sol with a concentration (dry content) above 40 % (a silica sol with various particle size can be mixed) and a small amount, e.g. 0.5 % of a dispersing medium. Before any gelating is performed the body is gutted with air to clean the channels from any excess of dispersing sol.
The gutted body is then provided with a gelating medium, here a sol with 10 % ammonium sulphate up to a saturated sol or a combination of the salts (NHΛ^SC and Na^SC , performed by means of dipping during about 30 minutes. At the end of the gelation the body is dried to remove capillarily bound water in an air stream with a temperature below 100 °C until the body is completely dry.
Thereafter, a washing or flushing av the body is performed to remove residues of the ammonium sulphate formed on the body surfaces during the gelation and the drying. These residues would during a following burning or calcination disintigrate into NH and SO-,, these gases performing as air pollutions during the burning. The washing is provided in that the body is e.g. flushed under a water curtain.
During the following step a drying by means of air is performed at maximum 140 °C and thereafter the temperature is raised either for a burning or a calcination at a temperature of about 240 to 300 C and with a dwelling period of 30 to 60 minutes to achieve a proper burning of possibly existing organic material and/or a raising of the temperature to e.g. 550 to
600 C at the end of the burning to achieve a good form stability of the body for a following treatment.
Another impregnation of the body is thereafter provided with a sol with a dry content of 5 to 15 % and with an inner specific surface depending on the application, whereafter a drying is performed at a temperature below 100 C. This method provides a SiC surface.
After a possible cutting of the body to obtain the desired dimensions and/or clean end surfaces on the body a catalyst supporting material has been obtained with the good properties indicated in the beginning.
The invention is obviously not limited to the embodiment here described but can be modified within the scope of the claims to follow.
Claims
1. A method for manufacturing a support material for catalysts, in which a mineral fibre paper is formed to a body with fine through channels and where the body is impregnated with a dispersion of a filling material, a sol and a dispersing medium, characterized in that a gelating medium is applied to the body to gelate the sol so that the complete sol is polymerized or gelated.
2. A method according to claim 1, characterized in that a non fibrous material is used such as kaolin or other clay materials, silica, mica, talcum, felspar.
3. A method according to claim 1 or 2, characterized in that the gelating medium is a salt such as a chloride, a sulphate, a nitrate or an acid, a base or an alcohol.
4. A method according to anyone of the claims 1 to 3, characterized in that the body is dried at a temperature below 100 °C to remove capillarily bound water and to force any excess of salt to protrude to the surface.
5. A method according to claim 4, characterized in that a washing or a flushing of the body is performed after the gelation and the drying to remove any possible excess of gelating medium.
6. A method according to anyone of the claims 1 to 5, characterized in that after the gelation a drying with air up to 140 C is performed and that the temperature thereafter is raised for burning off possibly existing organic material as well as a further raise of the temperature to about 550 to 600 °C to bum the body to achieve a good form stability for it.
7. A method according to claim 3, characterized in that as a gelating medium is used a chloride such as sodium chloride, calcium chloride, magnesium chloride, aluminium chloride, zinc chloride and litium chloride.
8. A method according to claim 3, characterized in that as a gelating medium is used a sulphate such as ammonium sulphate, sodium sulphate, aluminium sulphate and aluminium- potassium sulphate.
9. A method according to claim 3, characterized in that as a gelating medium is used a nitrate such as ammonium nitrate, aluminium nitrate and potassium nitrate.
10. A method according to claim 3, characterized in that as a gelating medium is used an acetate such as ammonium acetate, calcium acetate or sodium acetate.
11. A method according to claim 3, characterized in that as a gelating medium is used an acid, a base or an alcohol.
12. A method according to anyone of the claims 1 to 11, characterized in that a blowing of the body channels is performed after the impregnation to clean the channels from the dispersing sol.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9600818A SE506498C2 (en) | 1996-03-01 | 1996-03-01 | Process for preparing a catalyst support material |
SE9600818 | 1996-03-01 | ||
PCT/SE1997/000338 WO1997031710A1 (en) | 1996-03-01 | 1997-02-26 | A method for manufacturing a support material for catalysis |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0824369A1 true EP0824369A1 (en) | 1998-02-25 |
Family
ID=20401640
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97906399A Withdrawn EP0824369A1 (en) | 1996-03-01 | 1997-02-26 | A method for manufacturing a support material for catalysis |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0824369A1 (en) |
JP (1) | JPH11504568A (en) |
AU (1) | AU2110097A (en) |
SE (1) | SE506498C2 (en) |
WO (1) | WO1997031710A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1195197B1 (en) * | 2000-10-06 | 2015-07-08 | Akzo Nobel N.V. | Catalyst carrier comprising a fibre paper impregnated with micro fibres, process for its production and its uses |
US6787497B2 (en) | 2000-10-06 | 2004-09-07 | Akzo Nobel N.V. | Chemical product and process |
EP1195196A1 (en) * | 2000-10-06 | 2002-04-10 | Akzo Nobel N.V. | Catalyst carrier comprising a fibre paper impregnated with micro fibres, process for its production and its uses |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5254195A (en) * | 1992-05-08 | 1993-10-19 | Industrial Technology Research Institute | Process for manufacturing moisture exchange element |
US5468558A (en) * | 1992-05-22 | 1995-11-21 | Solvay Catalysts Gmbh | Process for preparing fracture-resistant sol/gel particles |
-
1996
- 1996-03-01 SE SE9600818A patent/SE506498C2/en not_active IP Right Cessation
-
1997
- 1997-02-26 WO PCT/SE1997/000338 patent/WO1997031710A1/en not_active Application Discontinuation
- 1997-02-26 EP EP97906399A patent/EP0824369A1/en not_active Withdrawn
- 1997-02-26 AU AU21100/97A patent/AU2110097A/en not_active Abandoned
- 1997-02-26 JP JP9530876A patent/JPH11504568A/en active Pending
Non-Patent Citations (1)
Title |
---|
See references of WO9731710A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU2110097A (en) | 1997-09-16 |
SE506498C2 (en) | 1997-12-22 |
SE9600818L (en) | 1997-09-02 |
SE9600818D0 (en) | 1996-03-01 |
WO1997031710A1 (en) | 1997-09-04 |
JPH11504568A (en) | 1999-04-27 |
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