CA2007253C - Method for in-situ repair of solvent dewaxing filter cloths - Google Patents
Method for in-situ repair of solvent dewaxing filter clothsInfo
- Publication number
- CA2007253C CA2007253C CA 2007253 CA2007253A CA2007253C CA 2007253 C CA2007253 C CA 2007253C CA 2007253 CA2007253 CA 2007253 CA 2007253 A CA2007253 A CA 2007253A CA 2007253 C CA2007253 C CA 2007253C
- Authority
- CA
- Canada
- Prior art keywords
- adhesive
- filter cloth
- epoxy resin
- damage area
- area
- 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.)
- Expired - Fee Related
Links
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- 239000002904 solvent Substances 0.000 title claims abstract description 30
- 230000008439 repair process Effects 0.000 title claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 title claims abstract 3
- 239000000853 adhesive Substances 0.000 claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 claims abstract description 81
- 239000004744 fabric Substances 0.000 claims abstract description 81
- 238000005406 washing Methods 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000004848 polyfunctional curative Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical group 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- -1 amido amine Chemical class 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000002415 cerumenolytic agent Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 6
- 229920006332 epoxy adhesive Polymers 0.000 claims 3
- 238000003780 insertion Methods 0.000 claims 2
- 230000037431 insertion Effects 0.000 claims 2
- 230000000694 effects Effects 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 9
- 239000011324 bead Substances 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920003332 Epotuf® Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical group CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 208000034693 Laceration Diseases 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Filtering Materials (AREA)
Abstract
A method is disclosed for the in-situ repair of damaged filter cloths in solvent dewaxing filters.
The damage that can be repaired can be either or both of tears or holes. The method comprises thoroughly washing the filter cloth in the area of the damage to remove wax and oil, applying a quantity of solvent resistant adhesive to the damaged area such that the area of treatment extends beyond the hole or tear and adhesive overlays onto undamaged cloth, inserting pre-cut portions of filter cloth into the damage so as to completely fill the hole or tear but not create a bulge or cloth buildup in the face of the filter cloth where required and, finally, and optimally applying a final coating of adhesive over the repaired area.
The damage that can be repaired can be either or both of tears or holes. The method comprises thoroughly washing the filter cloth in the area of the damage to remove wax and oil, applying a quantity of solvent resistant adhesive to the damaged area such that the area of treatment extends beyond the hole or tear and adhesive overlays onto undamaged cloth, inserting pre-cut portions of filter cloth into the damage so as to completely fill the hole or tear but not create a bulge or cloth buildup in the face of the filter cloth where required and, finally, and optimally applying a final coating of adhesive over the repaired area.
Description
200'?' p 3 ~- 1 -The present invention is a method for repair-ing damaged areas of filter cloths used in solvent dewaxing service. Damage in filter cloths take the form of holes, tears, cuts or rips. Such damage permits the passage of wax through the damaged area and into the filtered solution resulting in the presence of wax in the oil solution which leads to very hazy off specification oil filtrate.
It has been discovered that such damaqed areas can be repaired by the use of a solvent resistant adhesive optionally combined with the use of portions of filter cloth patch material.
The method comprises the steps of carefully and thoroughly cleaning the filter cloth in the area of the damage so as to remove oil and wax from the cloth.
The cleaned area should extend some distance beyond the immediate area of damage, e.g. a six inch radius from .the edge of the damage. A solvent resistant adhesive is than applied to the damage area. The area of application covers the immediate area of damage and additionally extends at least 1/2 inch beyond the edges of the immadiato damage area, and preferably covers the entire previously described cleaned area. Adhesive is applied to the filter cloth so as to thoroughly wet the area to be repaired. In some instances, as when the hole is small or the tear minor (when there has been no loss of filter cloth material) the repair can comprise solely the cleaning of the damage area and the applica-tion of sufficient adhesive to close off the hole or 2~0'~~ ~ 3 tear. In other instances where the damage has been more extensive, involving the loss of filter cloth material in the damage area, it will be necessary to use a quantity of filter cloth as patch material. In those instances, following the application of the adhesive, pieces of filter cloth may be inserted into the damaged area, that is, small pieces of filter cloth are shaped and fitted into the hole, tear, rip or slice to thoroughly fill the damaged area.
Lastly, a final coat of adhesive is applied to the entire damage area and overlaying the aforesaid cleaned area with a final bead of adhesive applied directly to the edges of the damage area to prevent formation of cracks or depressions along such edges.
Alternatively the hole, slice, rip or tear can be repaired by a procedure involving cleaning and application of adhesive, but using a pre-cut portion of filter cloth slightly larger than the hole, etc. This portion of repair cloth can be applied onto the top of the filter cloth creating a patch. The patch material is carefully positioned to overlap the damage area and - smoothed out under the wire commonly used to hold the filter cloth in place on the filter drum, to create a flush patch. The patch material can be applied to the damage area as is or preferably can .first be thoroughly wetted with adhesive. The repaired area can then receive a final coating of adhesive and the sealing bead as previously described.
Solvent dewaxing of waxy hydrocarbon oils involves the direct or indirect chilling of the 200'2 ~ 3 solvent/oil mixture to a temperature low enough to precipitate out the wax in the oil. The precipitated wax is separated from the solvent/oil mix by filtration using rotary vacuum or pressure filters. The filter medium used is a natural or synthetic textile cloth (usually non-woven) which is held in place on the outer surface of the filter drum by means of caulking bars and tightly wrapped with wire. The normal life expec-tancy of the filter cloth ranges from one to four years, after which the well worn cloth is replaced in its entirety.
Filter cloths are also susceptible to damage which is evidenced by a loss in retentive ability indicated by the presence of wax in the filtrate. Such damage takes the form of holes, rips, tears, cuts, gaps etc. and can be caused by any number of things. The wax removal doctor blade in the filter can snag the surface of the cloth, improper installation, minor unobserved defects in the cloth, etc. can lead to localized damage and failure of the cloth.
Such localized damage as compared to a _general wearing out of the cloth, is treated at the site of the damage rather than by total replacement of tha cloth.
The currently practiced site specific filter cloth repair technique involves blanking off the damaged cloth section by sliding a thin metal shim or plate under the hold down wires on the filter drum and onto the face of the filter cloth over the area of damage. This method does not always prove satisfactory because there is no true seal between the cloth and the overlying metal patch and the metal patch cannot be 2~0'~~ ~ 3 effectively used if the damage is near the edges of the drum or adjacent the caulking bars in the drum.
THE PRESENT INVENTION
The present invention constitutes a method for repairing localized damage to filter cloths used in solvent dewaxing process. The method involves the use of a solvent resistant adhesive. When the damage to the filter cloth is accompanied by actual loss of filter cloth matarial in the damage area the repair procedure, in addition to utilizing the adhesive employs pieces of the filter cloth material itself to form smooth) wax impermeable patches, on the filter cloth.
In the process, the filter cloth is carefully and thoroughly cleaned in the area of the damage in the area immediately surrounding the damage, preferably up to six inches from the edges of the damage. This cleaning is practiced so as to remove wax and oil from the filter cloth and facilitate the thorough wetting of the filter cloth with the adhesive so that strong bonds and complete seals will result. This cleaning can involve the use of wax solvents, oil solvents or both and preferably a sequence of each, repeated as often as necessary to remove the wax and oil from the filter cloth. After this treatment the cleaning solvent itsel! is washed from the cloth using a solvent which is allowed to evaporate from the cloth.
Following this evaporation step the cleaned area of filter cloth is coated with a layer of solvent resistant adhesive. Since solvent dewaxing processes involve the use of ketone solvents, aromatic solvents, 200'72 j 3 mixtures of ketone and aromatic solvents, ethers, such as methyl tart-butyl ether etc, and mixtures thereof, the adhesive used must be resistant to the action of such solvents. Other solvents include normally liquid hydrocarbons such as hexane and cyclohexane, alcohols, such as isopropyl alcohol and methanol, fully halogenated hydrocarbons such as carbon tetrachloride, and water, dimethyl fonaamide, and dioxane. It has been discovered that the filter cloth repair technique of the present invention using epoxy resin based adhesives, does not function in a liquified, normally gaseous hydrocarbon autorefrigerative solvent system.
Other solvents which should be avoided include methylene chloride) cresol, acetic acid, chloroform, n-methyl-2-pyrrolidone.
Adhesives which are used in the present invention are epoxy resin formulations comprising the base epoxy resin component and optionally, a hardener component and a catalyst. To insure complete wetting of the cleaned filter cloth it is necessary that the epoxy resin formulation ba used before it becomes too viscous.
Adhesives which can be used comprise those which are (a) single part epoxies and include no hardener or catalyst or (b) two or three part adhesives which may be blended using 0 to 90 parts by wt of hardener together with a portion of catalyst sufficient to react with the portion of epoxy resin used. As there are many catalyst types, the amount is calculated based on the stoichiometric amount required.
It has been discovered that this adhesive stands up to the dewaxing solvent under repeated cycles v of temperature extremes normally encountered in solvent dewaxing filter. The dewaxing filter surfaces are routinely exposed to temperature swings between the temperature of about -10 to -20°C
to 80°C+ (i.e. 90 to 100°C swing) . In the course of a day the filter surface can undergo as many as 6 to 8 temperature cycles when hot ketone is used to wash the filter to remove accumulated wax not otherwise removed by the doctor blade in the filter drum.
The present filter cloth repair technique withstands such wide and repeated temperature swings without deterioration.
The base epoxy resin component is typically a reaction product of bisphenol A and epichlorohydrin, however other epoxy resins can be used so long as it is not an aliphatic epoxy resin as it has been observed that adhesives containing aliphatic epoxy resins do not exhibit good resistance to detone solvents.
Suitable hardeners or curing agents are polyamide or amidoamine low temperature, low exotherm curing agents.
Typical catalysts comprise amines, amides, anhydrides, mercaptans, organic acids, phenols, etc. many of which can be used with Bisphenol A resin to obtain a flexible, stable formulation.
The various components which go to make up the adhesive formulation are available from commercial sources. Suitable reaction products of Bisphenol A and epichlorohydrin are available, for example, from Shell Chemical Company under the designation Epon 828T"", Epon 830TM Epon 825T"~ and Epon 826T""; from Reichold Chemical Company under the designation EpoTuf 37-139T"", EpoTuf 37-140T"~, EpoTuf 37-141T~~; from Ciba Geigy Corporation under the designation AralditeT"' 6005, 6010 and 6020; from Celanese Corporation as Epi-RezTM 508, 509 and 510; and from Dow Chemical Company under the designation D.E.R.T~~ 330, 331, 332, 317 and 337. Suitable low temperature, low exotherm polyamide or _7_ amidoamine curing agents are available, for example from Henkel Corp. under the designation Versamid 140T~" (which has an amine value of about 370-400) , Versamid 115T~", Versamid 125T"" and Versamid 150T"" or Genamid 2000T"" (which has an amine value of about 580-620) and Genamid 250T~"; from Ciba Geigy Corporation under the designation 815T"", 825T~~ and 840T"~ and from Shell Chemical Company under the designation V-15T"", V-25T"" and V-40T"" .
The base epoxy resin component comprises the reaction product of bisphenol-A and epichlorohydrin having a viscosity in the range of about 7000 to 20,000 centipoise preferably 10,000 to 16,000 centipoise at 25°C. (ASTM D445) with a weight per epoxide (WPE) of about 175-210, preferably about 185-195.
As previously stated, the hardener or curing agent is typically a polyamine or amidoamine low temperatures, low exotherm curing agent such as a condensation product of polyamine with fatty acids or dimer acids, and having an amine value of between about 85-620, preferably about 370-620, more preferably about 370-400 or 580-620.
A preferred catalyst is dimethyl amino methyl phenol (DMP).
In practicing the repair of damaged filter cloth, the area to be repaired must be rinsed clean of waxy residue to ensure maximum bonding, since the presence of wax in the filter cloth will inhibit adhesive bonding to the cloth. All material within six inches of the filter damage should be thoroughly cleaned. The following sequence should be used:
1. Locate all cloth lacerations, holes, tears, rips, cuts, gaps, gauges etc;
2. Repeatedly rinse repair area with oil/wax solvents, preferably hot solvent such as hot varsol;
3. Repeatedly rinse area with acetone (to rinse away solvent) _g_ and allow area to dry before adhesive application.
An air purge may be applied to repair area to shorten acetone drying time.
The repair area should look clean (not waxy) after the cleaning procedure. If the area still looks waxy, then the cleaning procedure must be repeated using more hot solvent. If the cleaning procedure is not used or used negligently then good adhesive bonding is not possible.
In preparing the adhesive it is necessary that the components not be used after the shelf life has expired as old components will jeopardize the adhesive quality.
In the following examples the adhesive consisted of 90 parts by weight of the base epoxy resin (a condensation product of bisphenol A and epichlorohydrin) available from Dow Chemical Company and known as DER-331T""; 60 parts by weight of hardener VersamidT"~-140 available from Henkel ChemicalsT"", and 2 parts by weight of catalyst DMP-30T"~ available from Rohm and Haas.
The adhesives are prepared by combining the adhesive components in the suggested ratios and mixing until the paste is evenly constituted (3-4 min). Although the adhesive will remain fluid for up to 12 hours if not cured by heating, the adhesive must be applied to the repair area immediately upon preparation since the working viscosity increases with time and a more viscous adhesive solution will have difficulty penetrating (wetting) the filter cloth resulting in substandard bond strength.
In repairing damaged areas there are two general types of damage which are encountered, holes and cuts or rips.
_g_ Repairing holes is accomplished as follows:
Prepare the adhesive as above and apply directly into the hole and to the area surrounding the hole. The surrounding area application should be no less than ~~~ from the outside edge of the hole. This will aid in the physical entanglement of the adhesive to the filter material.
While this first application is seeping into the filter cloth, the hole should be filled once more with adhesive. The edges of the damage area are then brought together so as to close off the damage an additional layer of adhesive can be applied over the damage area. When the damage is accompanied by loss of filter cloth material, small pre-cut pieces of filter material are inserted into the hole, as many being 2~0'~2 ~3 - to -inserted as can be accommodated without creating a build-up or bulge in the repair area. Pre-cut pieces of spare filter cloth material should be approximately 1/16" x 1/16" x 1/16" in size. Then a second applica-tion of a small amount of adhesive should be made directly to the hole, completely covering and wetting the newly inserted pieces of filter cloth.
Very large holes (greater than 1/2 inch diameter) can be filled using a large shaped piece of filter cloth, with the addition of smaller pieces if necessary. Any large filler piece must be impregnated with adhesive prior to being inserted into the hole.
A final thin coating of adhesive can be spread over the entire repair area and lastly, a small quantity of adhesive ( Nl/16" in height) should be dabbed directly onto the hole. This mound of adhesive will prevent the formation of a small crater in the hole, leaving the repair area flush with the filter cloth.
At this point, the repair should be ready for curing.
Slices, cuts and rips are handled similarly.
It is important to note that if there has been the loss of filter cloth material in the area of the slice in the filter cloth, then this area should be repaired as mentioned for hole repairs whereby filter material chunks are used to help plug the hole or gap.
Using a spatula, force back the sliced edges of the filter material and generously apply adhesive 2~~'~2 ~3 into the slice and under the folded back filter materi-al, especially at the ends of the slice damage. This allows for maximum adhesive contact throughout the entire cross-section of the material repair. Next, a layer of adhesive should be spread on the surrounding repair area. This coating of adhesive should extend outwards at least one inch from the actual slice damage.
All large gaps in the filter material can be filled at this time (per hole repair procedure - using pre-cut pieces of filter cloth). A final thin coating of adhesive can be spread over the entire repair area and lastly, a thin bead of adhesive (nrl/16") can be deposited directly on the slice in the material. This final bead of adhesive will inhibit the formation of a crack or valley along the slice and will leave the repair flush with the filter cloth.
Alternatively) in addition to or instead of forcing small pieces of filter cloth material into the hole or gap, one can usa somewhat larger pieces of material, pieces large enough to cover or patch the entire hole or gap and overlap onto the undamaged surface of the filter cloth. Thia patch is applied over the damaged area of filter cloth but carefully inserted under the wires used to hold the filter cloth tightly to the filter. This patch material can be thoroughly wetted with the adhesive prior to being applied to the face of the filter cloth and carefully inserted under the hold down wires. Alternatively the dry patch material can be applied to the adhesive prepped face of the filter cloth and carefully worked into place, after which it is thoroughly wetted with a layer or layers of adhesive. Rest patch application technique would be to thoroughly wet both the patch and area to be patched with adhesive to ensure that both filter cloth surfaces are wetted. completely.
It has been observed that the adhesive used required 12 hours to cure at 23'C. This cure time however, can be shortened to reduce down time of the filter. Curing with a heat lamp or steam plate suc-cessfully shortened the hardening time and it is preferred that the steam plate cure technique be used. Direct contact to a steam heated aluminum plate will harden (cure) the adhesive in 1 hour. The heat lamp cure time was slightly longer but depends on the distance of the lamp from the adhesive surface and the ease with which the surface of the filter cloth can be approached with the particular heating element.
When using the steam plate curing procedure it is preferred that the repaired area be covered with a protective high temperature plastic sheet coating (e. g. polyparabanic acid) and bring the steam heated aluminum plate into direct contact with the protective coating. The steam heated plate is rested on repair area for 1 hr. after which both the steam plate and plastic sheet are removed after curing.
In a separate demonstration a 3 inch x 3 inch piece of filter cloth was glued to a newly reclothed filter drum employed in propane dewaxing using the same adhesive described above. This piece of filter cloth was not used to repair any damage but just as a demon-stration test. In so far as the filter cloth was new and had not been used for any filtrations it was not rigorously cleaned prior to the application of the adhesive. In the test the adhesive was applied to the ~;L' filter cloth and the 3" x 3" patch placed on top of the adhesive. A bead of adhesive was applied around the perimeter of the patch. The glue was then cured for about 2 weeks in the open atmosphere (about 90~F air temperature). In filtration service, hot kerosine washes were periodically used to clean the filter cloth of accumulated wax not otherwise removed by the doctor blade on the filter drum. After 2 months the patch area was examined and it was seen that one side of the patch had lifted from the surface. The three remaining sides were still holding but with less strength than had been observed in the case of patches exposed to ketone solvent system. Although stronger bonds may be possible if the surface is more rigorously cleaned, it is believed the present system is not well suited for usa in propane systems.
It has been discovered that such damaqed areas can be repaired by the use of a solvent resistant adhesive optionally combined with the use of portions of filter cloth patch material.
The method comprises the steps of carefully and thoroughly cleaning the filter cloth in the area of the damage so as to remove oil and wax from the cloth.
The cleaned area should extend some distance beyond the immediate area of damage, e.g. a six inch radius from .the edge of the damage. A solvent resistant adhesive is than applied to the damage area. The area of application covers the immediate area of damage and additionally extends at least 1/2 inch beyond the edges of the immadiato damage area, and preferably covers the entire previously described cleaned area. Adhesive is applied to the filter cloth so as to thoroughly wet the area to be repaired. In some instances, as when the hole is small or the tear minor (when there has been no loss of filter cloth material) the repair can comprise solely the cleaning of the damage area and the applica-tion of sufficient adhesive to close off the hole or 2~0'~~ ~ 3 tear. In other instances where the damage has been more extensive, involving the loss of filter cloth material in the damage area, it will be necessary to use a quantity of filter cloth as patch material. In those instances, following the application of the adhesive, pieces of filter cloth may be inserted into the damaged area, that is, small pieces of filter cloth are shaped and fitted into the hole, tear, rip or slice to thoroughly fill the damaged area.
Lastly, a final coat of adhesive is applied to the entire damage area and overlaying the aforesaid cleaned area with a final bead of adhesive applied directly to the edges of the damage area to prevent formation of cracks or depressions along such edges.
Alternatively the hole, slice, rip or tear can be repaired by a procedure involving cleaning and application of adhesive, but using a pre-cut portion of filter cloth slightly larger than the hole, etc. This portion of repair cloth can be applied onto the top of the filter cloth creating a patch. The patch material is carefully positioned to overlap the damage area and - smoothed out under the wire commonly used to hold the filter cloth in place on the filter drum, to create a flush patch. The patch material can be applied to the damage area as is or preferably can .first be thoroughly wetted with adhesive. The repaired area can then receive a final coating of adhesive and the sealing bead as previously described.
Solvent dewaxing of waxy hydrocarbon oils involves the direct or indirect chilling of the 200'2 ~ 3 solvent/oil mixture to a temperature low enough to precipitate out the wax in the oil. The precipitated wax is separated from the solvent/oil mix by filtration using rotary vacuum or pressure filters. The filter medium used is a natural or synthetic textile cloth (usually non-woven) which is held in place on the outer surface of the filter drum by means of caulking bars and tightly wrapped with wire. The normal life expec-tancy of the filter cloth ranges from one to four years, after which the well worn cloth is replaced in its entirety.
Filter cloths are also susceptible to damage which is evidenced by a loss in retentive ability indicated by the presence of wax in the filtrate. Such damage takes the form of holes, rips, tears, cuts, gaps etc. and can be caused by any number of things. The wax removal doctor blade in the filter can snag the surface of the cloth, improper installation, minor unobserved defects in the cloth, etc. can lead to localized damage and failure of the cloth.
Such localized damage as compared to a _general wearing out of the cloth, is treated at the site of the damage rather than by total replacement of tha cloth.
The currently practiced site specific filter cloth repair technique involves blanking off the damaged cloth section by sliding a thin metal shim or plate under the hold down wires on the filter drum and onto the face of the filter cloth over the area of damage. This method does not always prove satisfactory because there is no true seal between the cloth and the overlying metal patch and the metal patch cannot be 2~0'~~ ~ 3 effectively used if the damage is near the edges of the drum or adjacent the caulking bars in the drum.
THE PRESENT INVENTION
The present invention constitutes a method for repairing localized damage to filter cloths used in solvent dewaxing process. The method involves the use of a solvent resistant adhesive. When the damage to the filter cloth is accompanied by actual loss of filter cloth matarial in the damage area the repair procedure, in addition to utilizing the adhesive employs pieces of the filter cloth material itself to form smooth) wax impermeable patches, on the filter cloth.
In the process, the filter cloth is carefully and thoroughly cleaned in the area of the damage in the area immediately surrounding the damage, preferably up to six inches from the edges of the damage. This cleaning is practiced so as to remove wax and oil from the filter cloth and facilitate the thorough wetting of the filter cloth with the adhesive so that strong bonds and complete seals will result. This cleaning can involve the use of wax solvents, oil solvents or both and preferably a sequence of each, repeated as often as necessary to remove the wax and oil from the filter cloth. After this treatment the cleaning solvent itsel! is washed from the cloth using a solvent which is allowed to evaporate from the cloth.
Following this evaporation step the cleaned area of filter cloth is coated with a layer of solvent resistant adhesive. Since solvent dewaxing processes involve the use of ketone solvents, aromatic solvents, 200'72 j 3 mixtures of ketone and aromatic solvents, ethers, such as methyl tart-butyl ether etc, and mixtures thereof, the adhesive used must be resistant to the action of such solvents. Other solvents include normally liquid hydrocarbons such as hexane and cyclohexane, alcohols, such as isopropyl alcohol and methanol, fully halogenated hydrocarbons such as carbon tetrachloride, and water, dimethyl fonaamide, and dioxane. It has been discovered that the filter cloth repair technique of the present invention using epoxy resin based adhesives, does not function in a liquified, normally gaseous hydrocarbon autorefrigerative solvent system.
Other solvents which should be avoided include methylene chloride) cresol, acetic acid, chloroform, n-methyl-2-pyrrolidone.
Adhesives which are used in the present invention are epoxy resin formulations comprising the base epoxy resin component and optionally, a hardener component and a catalyst. To insure complete wetting of the cleaned filter cloth it is necessary that the epoxy resin formulation ba used before it becomes too viscous.
Adhesives which can be used comprise those which are (a) single part epoxies and include no hardener or catalyst or (b) two or three part adhesives which may be blended using 0 to 90 parts by wt of hardener together with a portion of catalyst sufficient to react with the portion of epoxy resin used. As there are many catalyst types, the amount is calculated based on the stoichiometric amount required.
It has been discovered that this adhesive stands up to the dewaxing solvent under repeated cycles v of temperature extremes normally encountered in solvent dewaxing filter. The dewaxing filter surfaces are routinely exposed to temperature swings between the temperature of about -10 to -20°C
to 80°C+ (i.e. 90 to 100°C swing) . In the course of a day the filter surface can undergo as many as 6 to 8 temperature cycles when hot ketone is used to wash the filter to remove accumulated wax not otherwise removed by the doctor blade in the filter drum.
The present filter cloth repair technique withstands such wide and repeated temperature swings without deterioration.
The base epoxy resin component is typically a reaction product of bisphenol A and epichlorohydrin, however other epoxy resins can be used so long as it is not an aliphatic epoxy resin as it has been observed that adhesives containing aliphatic epoxy resins do not exhibit good resistance to detone solvents.
Suitable hardeners or curing agents are polyamide or amidoamine low temperature, low exotherm curing agents.
Typical catalysts comprise amines, amides, anhydrides, mercaptans, organic acids, phenols, etc. many of which can be used with Bisphenol A resin to obtain a flexible, stable formulation.
The various components which go to make up the adhesive formulation are available from commercial sources. Suitable reaction products of Bisphenol A and epichlorohydrin are available, for example, from Shell Chemical Company under the designation Epon 828T"", Epon 830TM Epon 825T"~ and Epon 826T""; from Reichold Chemical Company under the designation EpoTuf 37-139T"", EpoTuf 37-140T"~, EpoTuf 37-141T~~; from Ciba Geigy Corporation under the designation AralditeT"' 6005, 6010 and 6020; from Celanese Corporation as Epi-RezTM 508, 509 and 510; and from Dow Chemical Company under the designation D.E.R.T~~ 330, 331, 332, 317 and 337. Suitable low temperature, low exotherm polyamide or _7_ amidoamine curing agents are available, for example from Henkel Corp. under the designation Versamid 140T~" (which has an amine value of about 370-400) , Versamid 115T~", Versamid 125T"" and Versamid 150T"" or Genamid 2000T"" (which has an amine value of about 580-620) and Genamid 250T~"; from Ciba Geigy Corporation under the designation 815T"", 825T~~ and 840T"~ and from Shell Chemical Company under the designation V-15T"", V-25T"" and V-40T"" .
The base epoxy resin component comprises the reaction product of bisphenol-A and epichlorohydrin having a viscosity in the range of about 7000 to 20,000 centipoise preferably 10,000 to 16,000 centipoise at 25°C. (ASTM D445) with a weight per epoxide (WPE) of about 175-210, preferably about 185-195.
As previously stated, the hardener or curing agent is typically a polyamine or amidoamine low temperatures, low exotherm curing agent such as a condensation product of polyamine with fatty acids or dimer acids, and having an amine value of between about 85-620, preferably about 370-620, more preferably about 370-400 or 580-620.
A preferred catalyst is dimethyl amino methyl phenol (DMP).
In practicing the repair of damaged filter cloth, the area to be repaired must be rinsed clean of waxy residue to ensure maximum bonding, since the presence of wax in the filter cloth will inhibit adhesive bonding to the cloth. All material within six inches of the filter damage should be thoroughly cleaned. The following sequence should be used:
1. Locate all cloth lacerations, holes, tears, rips, cuts, gaps, gauges etc;
2. Repeatedly rinse repair area with oil/wax solvents, preferably hot solvent such as hot varsol;
3. Repeatedly rinse area with acetone (to rinse away solvent) _g_ and allow area to dry before adhesive application.
An air purge may be applied to repair area to shorten acetone drying time.
The repair area should look clean (not waxy) after the cleaning procedure. If the area still looks waxy, then the cleaning procedure must be repeated using more hot solvent. If the cleaning procedure is not used or used negligently then good adhesive bonding is not possible.
In preparing the adhesive it is necessary that the components not be used after the shelf life has expired as old components will jeopardize the adhesive quality.
In the following examples the adhesive consisted of 90 parts by weight of the base epoxy resin (a condensation product of bisphenol A and epichlorohydrin) available from Dow Chemical Company and known as DER-331T""; 60 parts by weight of hardener VersamidT"~-140 available from Henkel ChemicalsT"", and 2 parts by weight of catalyst DMP-30T"~ available from Rohm and Haas.
The adhesives are prepared by combining the adhesive components in the suggested ratios and mixing until the paste is evenly constituted (3-4 min). Although the adhesive will remain fluid for up to 12 hours if not cured by heating, the adhesive must be applied to the repair area immediately upon preparation since the working viscosity increases with time and a more viscous adhesive solution will have difficulty penetrating (wetting) the filter cloth resulting in substandard bond strength.
In repairing damaged areas there are two general types of damage which are encountered, holes and cuts or rips.
_g_ Repairing holes is accomplished as follows:
Prepare the adhesive as above and apply directly into the hole and to the area surrounding the hole. The surrounding area application should be no less than ~~~ from the outside edge of the hole. This will aid in the physical entanglement of the adhesive to the filter material.
While this first application is seeping into the filter cloth, the hole should be filled once more with adhesive. The edges of the damage area are then brought together so as to close off the damage an additional layer of adhesive can be applied over the damage area. When the damage is accompanied by loss of filter cloth material, small pre-cut pieces of filter material are inserted into the hole, as many being 2~0'~2 ~3 - to -inserted as can be accommodated without creating a build-up or bulge in the repair area. Pre-cut pieces of spare filter cloth material should be approximately 1/16" x 1/16" x 1/16" in size. Then a second applica-tion of a small amount of adhesive should be made directly to the hole, completely covering and wetting the newly inserted pieces of filter cloth.
Very large holes (greater than 1/2 inch diameter) can be filled using a large shaped piece of filter cloth, with the addition of smaller pieces if necessary. Any large filler piece must be impregnated with adhesive prior to being inserted into the hole.
A final thin coating of adhesive can be spread over the entire repair area and lastly, a small quantity of adhesive ( Nl/16" in height) should be dabbed directly onto the hole. This mound of adhesive will prevent the formation of a small crater in the hole, leaving the repair area flush with the filter cloth.
At this point, the repair should be ready for curing.
Slices, cuts and rips are handled similarly.
It is important to note that if there has been the loss of filter cloth material in the area of the slice in the filter cloth, then this area should be repaired as mentioned for hole repairs whereby filter material chunks are used to help plug the hole or gap.
Using a spatula, force back the sliced edges of the filter material and generously apply adhesive 2~~'~2 ~3 into the slice and under the folded back filter materi-al, especially at the ends of the slice damage. This allows for maximum adhesive contact throughout the entire cross-section of the material repair. Next, a layer of adhesive should be spread on the surrounding repair area. This coating of adhesive should extend outwards at least one inch from the actual slice damage.
All large gaps in the filter material can be filled at this time (per hole repair procedure - using pre-cut pieces of filter cloth). A final thin coating of adhesive can be spread over the entire repair area and lastly, a thin bead of adhesive (nrl/16") can be deposited directly on the slice in the material. This final bead of adhesive will inhibit the formation of a crack or valley along the slice and will leave the repair flush with the filter cloth.
Alternatively) in addition to or instead of forcing small pieces of filter cloth material into the hole or gap, one can usa somewhat larger pieces of material, pieces large enough to cover or patch the entire hole or gap and overlap onto the undamaged surface of the filter cloth. Thia patch is applied over the damaged area of filter cloth but carefully inserted under the wires used to hold the filter cloth tightly to the filter. This patch material can be thoroughly wetted with the adhesive prior to being applied to the face of the filter cloth and carefully inserted under the hold down wires. Alternatively the dry patch material can be applied to the adhesive prepped face of the filter cloth and carefully worked into place, after which it is thoroughly wetted with a layer or layers of adhesive. Rest patch application technique would be to thoroughly wet both the patch and area to be patched with adhesive to ensure that both filter cloth surfaces are wetted. completely.
It has been observed that the adhesive used required 12 hours to cure at 23'C. This cure time however, can be shortened to reduce down time of the filter. Curing with a heat lamp or steam plate suc-cessfully shortened the hardening time and it is preferred that the steam plate cure technique be used. Direct contact to a steam heated aluminum plate will harden (cure) the adhesive in 1 hour. The heat lamp cure time was slightly longer but depends on the distance of the lamp from the adhesive surface and the ease with which the surface of the filter cloth can be approached with the particular heating element.
When using the steam plate curing procedure it is preferred that the repaired area be covered with a protective high temperature plastic sheet coating (e. g. polyparabanic acid) and bring the steam heated aluminum plate into direct contact with the protective coating. The steam heated plate is rested on repair area for 1 hr. after which both the steam plate and plastic sheet are removed after curing.
In a separate demonstration a 3 inch x 3 inch piece of filter cloth was glued to a newly reclothed filter drum employed in propane dewaxing using the same adhesive described above. This piece of filter cloth was not used to repair any damage but just as a demon-stration test. In so far as the filter cloth was new and had not been used for any filtrations it was not rigorously cleaned prior to the application of the adhesive. In the test the adhesive was applied to the ~;L' filter cloth and the 3" x 3" patch placed on top of the adhesive. A bead of adhesive was applied around the perimeter of the patch. The glue was then cured for about 2 weeks in the open atmosphere (about 90~F air temperature). In filtration service, hot kerosine washes were periodically used to clean the filter cloth of accumulated wax not otherwise removed by the doctor blade on the filter drum. After 2 months the patch area was examined and it was seen that one side of the patch had lifted from the surface. The three remaining sides were still holding but with less strength than had been observed in the case of patches exposed to ketone solvent system. Although stronger bonds may be possible if the surface is more rigorously cleaned, it is believed the present system is not well suited for usa in propane systems.
Claims (25)
1. A method for the in-situ repair of damaged filter cloths used in solvent dewaxing filters, said method comprising the steps of:
(a) thoroughly washing the damaged area with oil/wax solvent to remove wax and oil therefrom;
(b) rinsing the washed area with a rinse solvent to remove the oil/wax solvent used in step (a) from the damage area;
(c) drying or evaporating the rinse solvent from the damage area;
(d) applying an epoxy based adhesive to the damage area thoroughly wetting the damage area; and (e) curing the adhesive to effect the complete repair of the damage area
(a) thoroughly washing the damaged area with oil/wax solvent to remove wax and oil therefrom;
(b) rinsing the washed area with a rinse solvent to remove the oil/wax solvent used in step (a) from the damage area;
(c) drying or evaporating the rinse solvent from the damage area;
(d) applying an epoxy based adhesive to the damage area thoroughly wetting the damage area; and (e) curing the adhesive to effect the complete repair of the damage area
2. The method of claim 1 wherein multiple layers of epoxy based adhesive are applied to the damage area prior to effecting the curing step (e).
3. The method of claim 1 or 2 wherein small, pre-cut pieces of filter cloth are inserted into the damage area following the application of adhesive of step (d) but prior to the curing of step (e), the quantity of filter cloth material inserted into the damage area being sufficient to close off the damage without creating a build up or bulge.
4. The method of claim 3 wherein the small, pre-cut pieces of filter cloth are themselves thoroughly wetted with adhesive prior to being inserted into the damage area.
5. The method of claim 1 or 2 wherein a pre-cut piece of filter cloth is overlayed on the damage area to create a patch thereon following the application of adhesive of step (d) but prior to the curing of step (e).
6. The method of claim 5 wherein the pre-cut piece of filter cloth used as a patch is itself thoroughly wetted with adhesive prior to being applied to the damage area.
7. The method of claim 3 wherein a final layer of adhesive is applied to the damage area following insertion of the small pre-cut pieces of filter cloth but prior to the curing step.
8. The method of claim 4 wherein a final layer of adhesive is applied to the damage area following insertion of the adhesive wetted, small pre-cut pieces of filter cloth but prior to the curing step.
9. The method of claim 5 wherein a final layer of adhesive is applied to the damage area following application of the overlay of filter cloth patch material to the damage area but prior to the curing step.
10. The method of claim 6 wherein a final layer of adhesive is applied to the damage area following application of the overlay of the thoroughly adhesive wetted filter cloth patch material to the damage area but prior to the curing step.
11. The method of claim 1 or 2 wherein the epoxy resin adhesive is a single part epoxy containing no hardeners or catalyst.
12. The method of claim 11 wherein the epoxy resin is not aliphatic.
13. The method of claim 1 or 2 wherein the epoxy adhesive is a multi-component adhesive comprising an epoxy resin, a hardener and a catalyst.
14. The method of claim 13 wherein the epoxy resin is not aliphatic.
15. The method of claim 14 wherein the epoxy resin is a reaction product of bisphenol A and epichlorohydrin, the hardener constitutes from 0 to 90 parts by weight of a polyamide or amido amine and the catalyst is selected from amines, amides, anhydrides, mercaptans, organic acids, phenols, and mixtures thereof.
16. The method of claim 3 wherein the epoxy resin adhesive is a single part epoxy containing no hardener or catalyst.
17. The method of claim 16 wherein the epoxy resin is not aliphatic.
18. The method of claim 5 wherein the epoxy resin adhesive is a single part epoxy containing no hardener or catalyst.
19. The method of claim 18 wherein the epoxy resin is not aliphatic.
20. The method of claim 3 wherein the epoxy adhesive is a multi-component adhesive comprising an epoxy resin, a hardener and a catalyst.
21. The method of claim 20 wherein the epoxy resin is not aliphatic.
22. The method of claim 21 wherein the epoxy resin is a reaction product of bisphenol A and epichlorohydrin, the hardener constitutes 0 to 90 parts by weight of a polyamide or amido amine and the catalyst is selected from amines, amides, anhydrides, mercaptans, organic acid, phenols and mixtures thereof.
23. The method of claim 5 wherein the epoxy adhesive is a multi-component adhesive comprising an epoxy resin a hardener and a catalyst.
24. The method of claim 23 wherein the epoxy resin is not aliphatic.
25. The method of claim 24 wherein the epoxy resin is a reaction product of bisphenol A and epichlorohydrin, the hardener constitutes 0 to 90 parts by weight of a polyamide or amido amine and the catalyst is selected from amines, amides, anhydrides, mercaptans, organic acids, phenols and mixtures thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2007253 CA2007253C (en) | 1989-01-13 | 1990-01-05 | Method for in-situ repair of solvent dewaxing filter cloths |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA297,278 | 1989-01-13 | ||
| US07/297,278 US4908082A (en) | 1989-01-13 | 1989-01-13 | Method for in-situ repair of solvent dewaxing filter cloths |
| CA 2007253 CA2007253C (en) | 1989-01-13 | 1990-01-05 | Method for in-situ repair of solvent dewaxing filter cloths |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2007253A1 CA2007253A1 (en) | 1990-07-13 |
| CA2007253C true CA2007253C (en) | 1999-09-14 |
Family
ID=25673868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2007253 Expired - Fee Related CA2007253C (en) | 1989-01-13 | 1990-01-05 | Method for in-situ repair of solvent dewaxing filter cloths |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2007253C (en) |
-
1990
- 1990-01-05 CA CA 2007253 patent/CA2007253C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2007253A1 (en) | 1990-07-13 |
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