GRANULAR FILTER MEDIUM FOR REMOVING OIL FROM OILY WATER

Abstract: The filter medium comprises smooth surtaced, non-­ porous granular glass or filter sand of which some has been treated with a caustic solution to impart active hydroxyl groups thereto and thereafter treated with a trialkoxysilane. The average concentration of treated medium corresponds to up to 3 to 3.5 grams trialkoxysilane per litre of granular medium in the case of filter sand and up to 1.5 to 1.8 grams trialkoxysilane per litre of medium in the case of granular glass, the desired average concentration being attained either by treating the medium with a corresponding amount of the trialkoxysilane or by treating with a higher amount and diluting the treated medium with untreated medium. The filter medium is backwashable to refresh its lipophilic properties, and does not readily plug or foul when in use.

Description: Granular Filter Medium For Removing Oil From Oily Water This invention relates to a granular filter medium for removing oil from oily water, and more particularly (but not exclusively) pertains to granular media for use in filter beds for cleansing oily water, and still more particularly to granular media for clearing oil-in-water emulsions of their dispersed oil even after several backwashings. Heretofore, filter beds for removing dispersed oils from oil-inwater emulsions utilised a sand or anthracite granular medium to trap the oil in the interstices of the medium. Recent research, however, has shown that a more effective filter ing mechanism would allow the oil to wet and adhere to the medium material in an adsorptive manner. Conventional sand or anthracite materials do not normally have adsorptive characteristics, and their ability to remove and retain oils is therefore limited. After extensive screening of various sand and glass materials for filter bed use, a chemical treatment was developed to enhance the affinity of sand for the oils dispersed in the water. The chemical treatment consisted of treating a 10 to 20 mesh sand with a primary aliphatic amine, as illustrated in U.S. Patent No. 3,901,818 issued August 26, 1975. A filter bed of this treated sand was shown to have superior oil removal ability, but failed to retain this ability after an extended filtering run. After backwashing, this bed of aliphatic amine-treated sand did not regain its former ability to remove the entrained oils. The present invention has developed new and improved chemically treated filter media for removing oil from oil-water emulsions, which media will regain its ability to remove the oils even after many backwashings. The invention uses a chemical treatment which creates a siloxane bond between a lipophilic hydrocarbon and a granulated sand or glass substrate. This chemical treatment binds the lipophilic hydrocarbon to the surface of the medium where it is exposed to the flowing oil-water stream. A similar chemical treatment is shown and described in U.S. Patent No. 4,017,528, issued: April 12, 1977. the above patent teaches the creation of a siloxane-type bond in porous silicon dioxide substrates to improve their absorptive properties for chromatography purposes. The present invention desires to improve the adsorptive properties of a silicon dioxide granulated substrate, but requires that the substrate be one which is substantially non-porous, instead of being porous. The present invention provides a back-washable filter medium for removing oil from oil-in-water emulsions comprising substantially smooth-surfaced, substantially non-porous granular glass or filter sand of which at least some has been treated with a caustic solution to impart active hydroxyl groups thereto and thereafter treated with a trialkoxysilane. The medium may comprise treated filter sand made by treatment first with caustic solution and thereafter with from 3 to 3.5 grams of trialkoxysilane per litre of caustic treated filter sand. The filter medium may comprise a mixture of said treated filter sand and untreated filter sand, e.g. comprising approximately 50 vol % of treated filter sand and approximately 50 vol % of untreated filter sand. In another sense, the indiscriminate treatment with trialkoxy silane when applied to granular substrates for purposes of this invention may not always provide a workable filter medium because the resulting adsorptivity of the filter bed might, in some cases, cause the granular particles to agglomerate. This results in a plugging or general fouling of the bed such that it will not filter properly. In the case where the filter medium comprises substantially smooth-surfaced substantially non-porous granular glass, the risk of plugging or general fouling of the bed is reduced or substantially eliminated when the filter medium comprises treated granular glass made EMI2.1 by treatment first with caustic solution and thereafter with trialkoxysilane so that the average or mean level of trialkoxysilane treatment in the filter medium corresponds to amounts in the range of from 1.5 to 1.8 grams trialkoxysilane per litre of filter medium. The filter medium may comprise a mixture of treated granular glass and untreated granular glass. The filter medium may comprise approximately 50 vol % of treated glass which has been treated with from 3 to 3.5 grams trialkoxysilane per litre of glass and 50 vol % of untreated glass.' It has been found that treated granular glass can be mixed in substantially equal proportions with non-treated glass materials in order to provide substantially uniform flow paths through the cross-section of the filter medium when contained in a filter bed. It is also contemplated that glass granules may be only partially treated with alkoxysilane in order to provide a free flowing filter bed during backwashing. When a mixture of treated and untreated granular material is employed to form the filter medium, the mixture is preferably substantially uniform. Filter sand may be fully treated (i.e. with 3 to 3.5 grams trialkoxysilane per litre of sand) because it has a less adsorptive character than glass granules and a full chemical treatment of the filter sand does not result in an excessively oil-wettable filter bed, generally speaking. The granular glass or filter sand preferably has mesh sizes in the range of from 10 to 30 (U.S. standard sieve size, which is used in the description of the present invention). The or each alkoxy group of the trialkoxysilane preferably has from 1 to 3 carbon atoms. The trialkoxysilane may be selected from at least one of: methyl or vinyl- or gamma-aminopropyl- triethoxysilane or methyl- or Nbeta-aminoethyl, gamma-aminopropyl- trimethoxysilane. Still another procedure which has been found to provide an efficacious filter bed is to fully treat "filter sand" with an alkoxy silane. The filter sand having a less adsorptive character than the glass granules is susceptible to a full chemical treatment without producing an overly oil-wettable filter bed. The aforementioned procedures will provide filter media which not only have superior oil-wetting properties, but which also effectively regain their oil-wettability even after many backwashes. A first embodiment of the invention comprises a mixture of approximately 50 per cent by volume of smooth-surfaced, non-porous granular glass treated with approximately 3 to 3.5 grams/litre granular glass of at least one trialkoxysilane wherein said alkoxy moiety comprises from 1 to 3 e.g. 1 or 2 carbons; and approximately 50 per cent by volume of non-treated smooth-surfaced, nonporous granular glass. A second embodiment comprises smooth-surfaced, non-porous, granular filter sand treated with approximately 3 to 3.5 grams/litre filter sand of at least one trialkoxysilane wherein the alkoxy moiety has from 1 to 3, e.g. 1 or 2 carbons. A third embodiment comprises smooth-surfaced, non-porous, granular glass treated with approximately 1.5 to 1.8 grams/litre granular glass of at least one trialkoxysilane, wherein said alkoxy moiety comprises from 1 to 3, e.g. 1 or 2 carbons. The above granular substrate may have a mesh size (U.S. standard sieve) of either approximately from 10 to 20 or from 20 to 30. The trialkoxysilane may preferably comprise a gammaaminopropyltriethoxysilane. The trialkoxysilane can also be selected from methyl-, vinyl-, ga'nma-aminopropyltriethoxys ilane; methyl- and N-beta-aminoethyl-gamma aminopropyl-trimethoxysilane. It is an object of this invention to provide improved filter media for cleansing an oil-in-water emulsion of dispersed oil; It is another object of the invention to provide filter media which maintain their lipophilic character even after many backwashings. The invention is now further described with reference to some illustrative embodiments thereof, and for comparison, with reference to filter media which are not in accordance with the invention, and with reference to the accompanying diagrammatic drawings, in which: Figure 1 is a schematic diagram of a congealed filter bed of fully treated glass granules; Figure 2 is a schematic diagram of a partially treated filter bed of glass granules; Figure 3 is a schematic diagram of a filter bed containing a mixture of fully treated and untreated glass granules; Figure 4 is a graph of oil removal performance with respect to time (in minutes) of a filter bed containing fully treated filter sand; and Figure 5 is a graph of oil removal performance with respect to time (in minutes) of a filter bed of fully treated glass granules. DETAILED DESCRIPTION OF THE INVENTION Generally speaking, the invention relates to filter media for cleansing oil-in-water emulsions of their dispersed oil. The filter media of this invention are chemically treated granular glass or "filter sand." The granular material is first given a caustic wash with a solution of 10 percent by weight NaOH, in order to impart active hydroxyl groups. These hydroxyl groups allow the material to easily form a siloxane bond with a trialkoxysilane. The trialkoxysilane chemically bonds with the glass or sand material leaving a hydrocarbon group exposed on the surface of the granules, thus imparting adsorptive oil-wettability. The pretreat caustic wash is preferably conducted at higher than ambient temperatures for several hours. More than one wash may be found to be necessary to obtain a properly activated surface for siloxane bonding. After treating the granular material with caustic, the material is washed and dried. Approximately 3 to 3.5 grams/liter of trialkoxysilane is added to the causticly treated granules, and the granules are placed in a 75 to 900C oven until dry. The temperature of the oven is then raised to 1500C for 3 hours. The granules are then allowed to cool to ambient temperature. When glass granules are treated with the trialkoxysilane, as described above, the resulting filter medium is observed to have poor backwashing characteristics. This backwashing problem, and its solution, will be explained hereinafter, with reference to Figures 1-3. The glass granules may be recycled glass of approximately 10 to 20 mesh. Generally speaking, the glass granules are preferred to have a smooth surface, i.e. the granules should not be jagged or contain fissures. Smooth glass granules are preferred to prevent congealing of the granules in the filter bed. Because oil removal is generally accomplished by adsorption of the oil upon the surfaces of the granules, the glass should be of a nonporous variety. Sand of 10 to 20 and 20 to 30 mesh size was also treated with the trialkoxysilane to provide a good filter medium. It was discovered, however, that not all types of sand provide a workable filter medium. Two types of sand were investigated: "filter sand" and "quartz sand." "Quartz sand" is apparently a "loose" term. Such sand is used in casting among other specialty uses, and is sometimes higher in A1203. However, the "quartz sand" purchased from Rudd, Paterson, N.J. (sold as g18 Quartz) was actually whiter than the "filter sand" indicating it was higher in Si02. Rudd cited that it was 99.9% Si02 which is consistent with its appearance. However, the major difference is probably the fact that it is mechanically crushed to obtain the desired mesh size. This increases the surface area, creates fissures and is therefore physically different than uncrushed "filter sand." "Quartz sand" has poor backwashing characteristics. The poor backwashing of "quartz sand" could be due to the increased cohesiveness of the sand particles after they are oil wetted due to possible locking together of the "spines and fissures" of the sand particle surface. "Filter sand" of 10 to 20 mesh and 20 to 30 mesh was purchased from Jessie Morie Co., Mauricetown, N.J. The analysis of this sand by wt% is as follows: Si02 99.39 Fe203 .24 A1203 .19 Ti02 .12 CaO .01 MgO .004 Loss on Ignition .046 (heat 17400F for 2 hours to measure organic content). This sand is not crushed or mechanically worked in any way. The "filter sand" or glass granules are preferably treated with a gamma-aminopropyl triethoxy silane, which can be purchased from Union Carbide, and which is sold with the designation A1100. Other trialkoxysilanes can also be used to treat the granular materials, and have been found to provide the 1filter sand" in particular, with good oil retention capability even after backwashing, as shown below in Table I. TABLE I COMPARISON OF SILANE COUPLING AGENTS OIL RETENTION ON TREATED FILTER SAND AFTER SIMULATED OIL WATER CLARIFICATION AND BACKWASHING UNION OIL RETENTION CARBIDE PPM OIL/GRAM SAND NUMBER NOMENCLATURE 10/20 MESH 20/30 MESH A-162 Methyl Triethoxy Silane 1330 3280 A-163 Methyl Trimethoxy Silane 1370 2180 A-151 Vinyl Triethoxy Silane 870 1600 A-1120 N-Beta-Aminoethyl 1750 2240 Gamma-Aminopropyl Trimethoxy Silane A-1100 Gamma-Aminopropyl 2770 2740 Triethoxy Silane Control No Chemical , 68 57 Filter sand of 10 to 20 mesh size, treated with approximately 3 to 3.5 grams/liter of gamma-aminopropyl triethoxy silane gave consistently good oil removal performance. This was so, even after repeated backwashings of the filter bed, as shown in Figure 4. Very good long term performance was noted even after four backwashes When recycled glass granules were similarly treated, however, the filter medium tended to congeal, i.e. the granules tended to clump together, as illustrated in the filter bed of Figure 1. The congealed granules 10 are believed to result from the fact that the glass when treated with the aforementioned silane, becomes overly effective. That is to say, the glass granules become so oil-wettable that they tend to stick together. Such congealed granules provide a poor filter bed, because channels 11 are formed in the filter bed, thus deteriorating the ability of the filter bed to be cleansed. The effect of cleansing such a bed via backwashing, is shown in Figure 5. In order to resolve this problem, the glass granules were either treated with only 50% by weight of the silane (1.5 to 1.8 grams/liter), or the 100% treated glass granules were mixed with 50% by volume of untreated glass granules, as depicted in the filter beds of Figures 2 and 3, respectively. The aforementioned treated glass granules allow the backwash to flow through the interstices of the beds, as shown by arrows 12. In this way, the beds can be effectively cleansed of their entrained oil, and are thus reusable. The mixed media bed of Figure 3 consisting of a portion of treated granular media and a portion of untreated media prevents congealing of the bed since the oil wettable particles would be separated from one another by untreated particles. The less lipophilic treated bed of Figure 2 has some sites on the particles that are not oil wettable, and hence the congealing effect is reduced. A summary of the performance of the "filter sand" and glass filter beds of this invention are outlined below in Table II. * ** TABLE II SUMMARY OF GRANULAR MEDIA TESTS SYSTEM CONSECUTIVE COMMENTS RUNS 1. 100% Treated * Recycle Glass (Mesb size 4 Poor Backwash : Poor Performanoe range 10/20) 2. 100% Treated white (Quartz) Sand 3 Fair-Poor Parformance (10/20 mesh) 3. 100% Treated Filter Sand (10/20 mesh) 6 Good Backwashing : Very Good Performance 4. 25% Treated ** Filter Sand (10/20 mesh) 3 Fair Performance : Fairly Rapid Breakthrough 5 Mixture of 50 vol % of 100% Treated Filter Sand + 50 vol % Ontreated Filter Sand) 6 Equivalent to 100% Treat Filter Sand Deceaging Effectiveness : Possible 6. Üntreated Filter Sand Additional Runs 7. Mixture of 50 vol % of 100 % Treated) Recycle glass + 50 vol % 3 Fair Parformance Untreabed Recycle Class 3 Good Performance : Better than 100% Treat Glass 8. 25 % Treated ** Recycled Glass "100% treated" means treated with 3 to 3.5 grams trialkoxysilane per litre of granular filter medium. "25% treated" means treated with 25 % of 3 to 3.5 grams trialkoxysilane/litre of granular filter medium.

Claims: CLAIMS 1. A back-washable filter medium for removing oil from oil-in-water emulsions comprising substantially smooth-surfaced, substantially non-porous granular glass or filter sand of which at least some has been treated with a caustic solution to impart active hydroxyl groups thereto and thereafter treated with a trialkoxysilane. 2. The filter medium of claim 1 comprising treated filter sand made by treatment first with caustic solution and thereafter with from 3 to 3.5 grams of trialkoxysilane per litre of caustic treated filter sand. 3. The filter medium of claim 2 comprising a mixture of said treated filter sand and untreated filter sand. The The filter medium of claim 3 comprising approximately 50 vol % of treated filter sand and approximately 50 vol % of untreated filter sand. 5. The filter medium of claim 1 comprising treated granular glass made by treatment first with caustic solution and thereafter with trialkoxy silane so that the average or mean level of trialkoxysilane treatment in the filter medium corresponds to amounts in the range of from 1.5 to 1.8 grams trialkoxysilane per litre of filter medium. 6. The filter medium of claim 5 comprising a mixture of treated granular glass and untreated granular glass. 7. The filter medium of claim 6 comprising approximately 50 vol % treated glass which has been treated with from 3 to 3.5 grams trialkoxysilane per litre of glass and 50 vol % of untreated glass. 8. The filter medium of any one of claims 1 to 7 in which the granular glass or filter sand has mesh sizes in the range of from 10 to 30. 9. The filter medium of any one of claims 1 to 8 in which the or each alkoxy group of the trialkoxysilane has from 1 to 3 carbon atoms. 10. The filter medium of any one of claims 1 to 9 in which the trialkoxy silane is selected from at least one of: methyl- or vinyl- or gamm aminopropyl- triethoxysilane or methyl- or N-beta-aminoethyl, gamma aminopropyl- trimethoxysilane. 11. The use of the filter medium of any one of claims 1 to 10 in removing oil from water.

Inventors: CANEVARI, GERARD PAUL
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1982
Main classification: B01D39
IPC codes: C02F1, B01D39, B01D17, B01J20