IE20070425U1 - Ceramic filter - Google Patents

Abstract

ABSTRACT A ceramic filter for filtering liquid, particularly tap water, comprising: (a) from about 75 percent to about 95 percent by weight of diatomaceous earth; (b) from about 10 percent to about 20 percent by weight of a flux; and (c) from about 0.03 percent to about 0.4 percent by weight of metallic compound; the percentages by weight being percentages by weight of the ceramic filter.

Description

Ceramic Filter The present invention relates to a ceramic filter. In particular, it relates to a ceramic filter for filtering liquid, especially tap water so as to remove pathogens or therefrom. ‘ V cram‘. . ‘. L” O Due to the variable quality of many putative drinking water sources (e.g. public utility or group water supply scheme, well water), in general, such water is unpalatable for drinking, and in certain extreme cases may contain pathogens or contaminants, which can lead to serious illness. For example, some drinking water sources may contain harmful protozoa or bacteria such as Crjyptosporidium, Giardia and E. Coli, which can cause illness upon consumption. Thus, there is an increased tendency for water for drinking purposes to be purchased in bottles or other suitable containers, and the purchase of such water can be quite expensive. For example, in the case of athletes who require a regular intake of large volumes of water when training, expenditure on bottled water can be particularly high.

The use ofceramics as a medium in filters is known, including filters for purifying liquid such as tap water. However, such ceramic filters vary in quality, are normally bulky and relatively non-portable, and cannot necessarily be relied on to remove pathogens, such as protozoa from the water. There is therefore a need for a filter which overcomes this problem.

The present invention is directed towards providing a ceramic filter which is capable of removing contaminants including but not limited to harmful protozoa such as C ryptosporidium and Giardia, as well as bacteria and viruses, from liquid such as tap water. The ceramic filter of the present invention has many potential applications. For example, it may be used for purifying mains tap water contained in a container, such as a bottle, as it is being drawn from the container.

According to a first aspect of the invention, there is provided a ceramic filter comprising: (a) from about 75% to about 95% by weight of diatomaceous earth; (b) from about 10% to about 20% by weight of a flux; and (c) from about 0.03% to about 0.4% by weight of a metallic compound; the percentages by weight being percentages by weight of the ceramic filter.

As used herein, the term “flux” is intended to mean a vitrifying agent which reduces the melting temperatures of the ingredients and induces ceramic bonding.

Suitable metallic compounds for use in the invention include Group VI-Xll metallic compounds, excluding silver. Such metallic compounds are preferably selected from chromium, manganese, cobalt, nickel, copper and zinc, more preferably selected from copper and zinc. Copper is particularly preferred. The metallic compound is preferably present in the filter in an amount of from about 0.05% to about 0.3%, preferably from 0.1% to about 0.25%, more preferably from about 0.13% to about 0.23%, most preferably about 0.18% by weight of the ceramic filter.

The ceramic filter is conveniently capable of removing material having a size of 1 5pm or greater in diameter.

The ceramic filter of the invention preferably has a compression ratio of from about 0.30 to about 0.55, more preferably from about 0.35 to about 0.50 or from about 0.37 to about 0.45. A compression ratio of 0.40 is preferred. As used herein, the term “compression ratio” is intended to mean the ratio of the thickness of the ceramic filter in millimetres after firing to the thickness of the ceramic filter in millimetres before firing, wherein the ceramic filter has had a weight applied of approximately 0.08 kg/cmz applied thereto during firing.

The ceramic filter of the invention preferably has a thickness of from about 2.0mm to about 4.5mm, preferably from about 2.5mm to about 4.0mm. A thickness of approximately .2mm is preferred.

The diatomaceous earth preferably has a silica content of at least 70%. A diatomaceous earth comprising silica, sodium, magnesium and ferrite is preferred. A diatomaceous earth sold under the trade name Celatom and comprising at least 70% silica, from about 4% to about 8% sodium, from about 2% to about 4% magnesium and from about 1.5% to 2.5% ferrite is particularly preferred. The diatomaceous earth is preferably a diatomaceous earth sold under the trade name Celatom FW, more preferably a diatomaceous earth sold under the trade name Celatom FW-12 (having an average particle diameter of about 24pm and lEu/0425 capable of removing material having a particle size of about 0.7um), FW-14 (having an average particle diameter of about 28 um and capable of removing material having a particle size of about 0.75 pm), FW-18 (having an average particle diameter of about 3lttm and capable of removing material having a particle size of about 0.8um), FW-20 (having an average particle diameter of about 33pm and capable of removing material having a particle size of about 0.9]J.m), FW-40 (having an average particle diameter of about 40pm and capable of removing material having a particle size of about 1.01.1111), FW—50 (having an average particle diameter of about 42pm and capable of removing material having a particle size of about 1.1 pm), FW-60 (having an average particle diameter of about 48pm and capable of removing material having a particle size of about l.2pm), or FW-80 (having an average particle diameter of about 77 pm and capable of removing material having a particle size of about 1.6um), or mixtures thereof.

The diatomaceous earth may comprise a mixture of two or more diatomaceous earths of different particle diameter, for example a mixture of a diatomaceous earth having an average particle diameter of from about 25 um to about 30pm with one having an average particle diameter of from about 75 pm to about 80pm. A mixture of a diatomaceous earth having an average particle diameter of about 28pm with one having an average particle diameter of from about 77um is preferred. When a mixture of two diatomaceous earths is used, the diatomaceous earth is preferably capable of filtering matter having a particle size of from about 05pm to about 3.0um, preferably from about l.01.tm to about 2.5itm, more preferably from about 1.5 pm to about 2.0um. A mixture of diatomaceous earths sold under the trade names Celatom FW-14 and FW-80 is preferred, preferably a mixture in a ratio of from about 30:70 to about 70:30, more preferably from about 60:40 to about 40:60, most preferably about 50:50, by weight of the diatomaceous earth. A 50:50 mixture of diatomaceous earths sold under the trade names Celatom FW—14 and FW—8O is especially preferred.

The diatomaceous earth is preferably present in an amount of from about 80% to about 90%, preferably from about 81% to about 87%, more preferably from about 83% to about 85%, most preferably about 84% by weight of the ceramic filter.

The flux acts to bind the constituents, namely, the diatomaceous earth and metallic compound during the firing process in the manufacture of the filter, and gives additional strength to the finished ceramic filter. Suitable fluxes for use in the invention include barium carbonate (BaC03), barium (BaSO4), calcite (CaCO3), cha1k(CaC03), comish stone (variable), dolomite (CaC03.MgC03), feldspar (potash) (K2O.A1203.6Si02), feldspar (soda) (Na20.A1203.6Si02), lepidolite (Li2F2.Al203.3Si02), limestone (CaC03), lithium carbonate (Li2C03), magnesium carbonate (MgC03), magnesium carbonate (light) 3MgCO3.Mg(0H) 23H20, manganese carbonate (MnCO3), manganese dioxide (Mn02), nepheline syenite ((K)Na0.A1203.4Si02) (approx)), petalite (Li20.A1203.8SiO2), potassium carbonate (pearl ash) (K2C03), rock powder e.g. basalt or granite, sodium carbonate (soda ash) (Na2CO3), spodumene (Li20.Al203.4Si02), strontium carbonate (SrC03), talc (3Mg0.4Si02.H20), whiting (CaC03), wollastonite (CaO.Si02), wood ash(may contain solubles) (variable, (often high in lime)), zinc oxide (ZnO), and boron- containing compounds.

Boron-containing compounds are particularly preferred, preferably oxides of boron, salts of boron and hydrates of the salts. Suitable salts include alkali metal salts of boron or of boric acid. Sodium borate, also known as sodium tetraborate decahydrate, disodium tetraborate, borax decahydrate or borax (Na2B407-10H20), is preferred.

Suitable oxides of boron include colemanite (2Ca0.3B203.5H20 (variable)), gerstley borate (mixture of colemanite [Ca2B(,01 1'5H2O] and ulexite [N30-2Ca0-5B203~5H20]) and boron oxide having the formula B203. Boron oxide having the formula B203 is preferred, optionally in its amorphous form. A flux comprising boron oxide (B203), aluminium oxide (A1203) and/or silica (Si02) is preferred, particularly a flux comprising from about 10% to about 30% of boron oxide, preferably about 20% of boron oxide; from about 2% to about % of aluminium oxide, preferably about 8% of aluminium oxide; and from about 40% to about 60% of silica, preferably about 50% of silica. A frit comprising boron is preferred, especially a frit comprising an oxide of boron. A frit comprising boron oxide (B203), aluminium oxide (A1203) and/or silica (SiO2) is particularly preferred. A boron frit comprising from about 10% to about 30% of boron oxide, preferably about 20% of boron oxide; from about 2% to about 15% of aluminium oxide, preferably about 8% of aluminium oxide; and from about 40% to about 60% of silica, preferably about 50% of silica is especially preferred.

The flux preferably has a firing temperature from about 300°C to about 1500°C, preferably from about 400°C to about 1300°C, more preferably from about 500°C to about 1200°C.

A firing temperature of approximately 1050°C is preferred. A boron frit having a firing temperature of approximately 1085°C is particularly preferred.

The flux is preferably present in an amount of from about 12% to about 18%, preferably from about 14% to about 16%, more preferably about 15% by weight of the ceramic filter.

A boron frit present in an amount of about 15% is especially preferred.

According to a second aspect of the present invention, there is provided a composition for forming a ceramic filter according to the invention, the composition comprising: (a) from about 10% to about 30% by weight of diatomaceous earth; (b) from about 1% to about 6% by weight of a flux; (c) from about 0.05% to about 1.0% by weight of a metallic compound or a salt thereof or a hydrate of the salt; (d) from about 0.5% to about 6% by weight of a cellulose gum; and (e) from about 2% to about 10% by weight of a bulking agent; and (D from about 50% to about 85% by weight of water; the percentages by weight being percentages by weight of the total composition.

The metallic compound may be a metallic compound as defined above for the ceramic filter and is preferably present in the composition in the form of a salt or a hydrate of the salt. The salt is preferably selected from sulphate, carbonate, chloride and acetate, most preferably sulphate. Copper sulphate or a hydrate thereof is preferred, especially copper sulphate pentahydrate.

The metallic compound or salt thereof or hydrate of the salt is preferably present in the composition in an amount of from about 0.07% to about 0.8%, more preferably from about 0.1% to about 0.5%, even more preferably from about 0.15% to about 0.3%, most preferably about 0.2% by weight of the total composition.

The diatomaceous earth is as defined above for the ceramic filter and is preferably present in the composition in an amount of from about 14% to about 26%, more preferably about IE u'i’046 % to about 24%, even more preferably about 18% to about 22%, most preferably about % by weight of the total composition.

The flux is as defined above for the ceramic filter and is preferably present in the composition in an amount of from about from about 2% to about 5%, more preferably from about 2.5% to about 4.5%, even more preferably from about 3% to about 4%, most preferably about 3.8% by Weight of the total composition.

The cellulose gum in the composition acts to produce a malleable composition.

Suitable cellulose gums include methylcellulose, carboxymethylcellulose. hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and mixtures thereof. Carboxymethylcellulose is preferred. A modified cellulose gum is particularly preferred, preferably a modified carboxymethylcellulose, especially sodium carboxymethylcellulose. Sodium carboxymethylcellulose sold under the trade name Blanose available from Hercules S.A., Alizay, France, is particularly preferred. The cellulose gum is preferably present in an amount of from about 1% to about 5%, preferably from about 1.5% to about 4%, more preferably about 2% to about 3%, most preferably about 2.3% by weight of the total composition. Sodium carboxymethylcellulose in an amount of about 2.3% is especially preferred.

Bulking agents which can be used in the composition include hemp, cotton, flax, silk, wool, cellulose and mixtures thereof. Cellulose is preferred. The bulking agent may be present in an amount of from about 3% to about 7%, preferably from about 3.5% to about 6%, more preferably from about 4% to about 5%, most preferably about 4.3% by weight of the total composition. Cellulose present in an amount of about 4.3% is particularly preferred. The bulking agent is burnt off during the firing process in the manufacture of the ceramic filter, leaving a honeycomb structure within the ceramic. Cellulose is typically burnt off at a temperature of about 300°C.

The water may be present in an amount of from about 55% to about 80%, preferably from about 60% to about 75%, more preferably from about 65% to about 70%, most preferably about 68% by weight of the total composition.

According to a third aspect of the present invention, there is provided a precursor filter for forming a ceramic filter according to the invention, the precursor filter comprising: (a) from about 50% to about 98% by weight of diatomaceous earth; (b) from about 2% to about 20% by weight of a flux; (c) from about 0.1% to about 1.5% by weight of a metallic compound or a salt thereof or a hydrate of the salt; ((1) from about 2% to about 20% by weight of a cellulose gum; and (e) from about 5% to about 35% by weight of a bulking agent; the percentages by weight being percentages by weight of the total precursor filter.

The metallic compound or a salt thereof or a hydrate of the salt, the diatomaceous earth, the flux, the cellulose gum and the bulking agent present in the precursor filter are each as defined above for the composition.

The metallic compound or salt thereof or hydrate of the salt is preferably present in an amount of from about 0.2% to about 1.2%, more preferably from 0.3% to about 1.0%, even more preferably from about 0.4% to about 0.8%, most preferably about 0.5% by weight of the total precursor filter.

The diatomaceous earth is preferably present in an amount of from about 55% to about 90%, preferably from about 60% to about 85%, more preferably from about 62% to about 80%, most preferably about 65% by weight of the total precursor filter.

The flux may be present in an amount of from about 5% to about 15%, preferably from about 8% to about 14%, more preferably about 12% by weight of the total precursor filter.

The cellulose gum is preferably present in an amount of from about 4% to about 15%, preferably from about 5% to about 10%, more preferably about 8% by weight of the total precursor filter.

The bulking agent is preferably present in an amount of from about 8% to about 30%, preferably from about 10% to about 25%, more preferably approximately 13% by weight of the total precursor filter. “/0425 According to the invention, there is also provided a method for preparing a ceramic filter according to the invention, the method comprising the steps of: (A) forming a composition according to the invention by combining the following ingredients: (a) from about 10% to about 30% by weight of diatomaceous earth; (b) from about 1% to about 6% by weight of a flux; (c) from about 0.05% to about 1.0% by weight of a metallic compound or a salt thereof or a hydrate of the salt; (d) from about 0.5% to about 6% by weight of a cellulose gum; and (e) from about 2% to about 10% by weight of a bulking agent; and (i) from about 50% to about 85% by weight of water; the percentages by weight being percentages by weight of the total composition; (B) removing a portion of water from the composition to as to form a Composition having a shaping consistency; (C) drying the composition so as to remove any residual water to form a precursor filter according to the invention; and (D) firing the precursor filter to form the ceramic filter.

In step (A), the ingredients are preferably combined at a temperature of from about 20°C to about 40°C, preferably about 30°C.

In step (A), the ingredients of the composition are preferably combined in the following order of addition: (i) add the metallic compound or salt thereof or hydrate of the salt to water; (ii) add the cellulose gum to the resulting mixture; (iii) add the flux to the resulting mixture; (iv) add the bulking agent to the resulting mixture; and (v) add diatomaceous earth to the resulting mixture.

In step (B), the composition is preferably allowed to rest for from about 30 minutes to about 5 hours, more preferably from about 1 hour to about 3 hours, most preferably about 2 hours, preferably at a temperature of from about 20°C to about 40°C, more preferably about 30°C. The shaping consistency of the composition conveniently allows it to be cut into desired shapes.

E 020430 Following step (B) and prior to step (C), the composition is preferably cut into desired shapes. The desired shapes may take any suitable form, but are preferably substantially circular discs, more preferably discs having a diameter of about 20mm to about 25mm, preferably approximately 22mm.

Step (C) preferably comprises heating for a period of time of about 30 minutes to about 2 hour, preferably about 1 hour, at a temperature of from about 90°C to about 110°C, preferably about 100°C.

In step (D), the firing is preferably carried out at a temperature of from about 800°C to about l200°C, more preferably from about 900°C to about l150°C, even more preferably from about l00O°C to about 1l00°C, most preferably about 1085°C. The precursor filters are preferably fired for a period of from about 4 hours to about 11 hours, preferably from about 6 hours to about 9 hours, most preferably about 8.25 hours.

The method conveniently comprises applying a load to the precursor filters in order to cause compression thereof during firing (step (D)). The load is preferably from about 0.05 kg/C1112 to about 0.1 kg/cmz, preferably about 0.08 kg/cmz.

Advantages of the ceramic filters of the invention include the following: They remove all or substantially all of protozoa, including Crypmsporidium and Giardia from tap water.

When the metallic compound in the filter is copper, it conveniently acts as an anti- bacterial agent.

They have both excellent filtration properties and anti-bacterial properties.

The following examples serve to illustrate the invention but it will be appreciated that the invention is not limited to these examples.

IE W04 EXAMPLE 1 A ceramic filter was prepared from the ingredients listed in Table 1, and prepared according to the steps in Table 2: Table 1 i Ingrecli;1ts—— ii’ M " lVve?gi1.T% (7asJo.Tceram:c l ifilter) f M, ,7 (, W __ Water l —— ——— ———— mmmmmfig c“i @@J““* aznnnm i B@w“‘3gmi }&mE?_”"__i_23—_"_—_( l b@@@fi*af”“”*i ilknm—m- "0 *0 eeeee 0 ioor;" "‘ *‘* * ! 'sodium carboxymcthylcellulose; 27.5% A1303, 13.0% B203, 50.0% S102, 14.0% CaO + Mgo, 10.3% Li3O + Na3O + K30, available from Johnson Mathey Ceramics, Stoke-on-Trent, United Kingdom; 350:50 mixture of diatomaceous eanhs sold under the trade names Celatom FW—14 and F W-80.

Table 2 Step Add 1 g copper sulphate pentahydrateh i _._ . s_ u,__ s,,,, .__. . I i Blend in copper for 20 seconds A Add 15 g Blanose, food grade : i Blend mixture for 60 seconds l Add 22g boron rm lifiiéad rIiiii1“reifori3‘ii(i)isecoI—i-d-sn __Mi ‘\O0O\)O\' Blend mixture for 100 to 140 seconds .lEUfo425 ll 12 1 Add 120g diatomaceous earth Blend mixture for Pour onto plaster bat (slab) to form the composition.

Leave mixture until suitable for shaping (>2 hours), which results in the composition having a shaping consistency.

Use cutter to produce 9 circular discs of required sizes (approximately 22mm diameter).

EXAMPLE 2 A precursor filter produced obtained in step 16 of Table 2 in Example 1 was analysed and Place discs into oven at 100°C and remove when discs have dried out sufficiently to allow compression during firing process, to form precursor filters.

Place discs, evenly spaced, onto clay tile (l50mm X 150mm) and put into kiln Place load onto discs which equates to a load of 0.08 kg/cmz to cause compression during firing process Program temperature settings on kiln as indicated below: (i) 0°C to 300°C, rising at 100°C per hour (total 180 mins); (ii) 300 to l085°C, rising at 150°C per hour (total 314 mins); (iii) falls naturally after 1085°C is reached.

Allow temperature of discs to fall to <700°C below which discs are durable enough to withstand normal handling during T removal from kiln, to form ceramic filters. the results are shown in Table 3: Table 3 . Weight % (based on Ingredlents the precursor filter) Copper sulphate 0.5% Blanosel 8.2% Borax fritz 12.0% Cellulose 13.7% Diatomaceous earth3 65.6% Total 100% ‘sodium carboxymethylcellulose; 27.5% A1203, 18.0% B303, 50.0% SiO2, 14.0% CaO + MgO, 10.3% Li3O + l\'a2O + K30, available from Johnson Mathey Ceramics, Stoke-on—Trent, United Kingdom; 350250 mixture of diatomaceous earths sold under the trade names Celatom FW-14 and FW-80.

EXAMPLE 3 A ceramic filter of the invention obtained in step 20 of Table 2 of Example 1 was analysed and the content shown in Table 4.

Table4 ilngredients E iiiiiii ‘await °/i.__(_bas.e_d. oi1_the—cera-rn_i_cil”1—lt£_:r)__ ‘ Elemental Coppe: 77 E M Diatomaceousiear_t_h_1 z83GA— _ _ u — —__—— 4 __ __ _ _ _ ‘S0250 mixture of diatomaceous earths sold under the trade names Celatom FW-14 and FW—80.

The ceramic filter also comprises frit and other components.

EXAMPLE 4: Six ceramic filters obtained in Example 1 and having a typical content as shown in Example 3 were subjected to a filtration test using de-ionised water, spiked with a quantity of 200 Giardia cysts and 200 Crjyptosporidium oocysts. Prior to testing, the thickness and the compression ratios were determined for each filter. 10 litres of the spiked water was allowed to pass through each ceramic filter at a pressure of l0kPa, flowing at a rate of 1 litre/min. The water was analysed pre-filtration and post—fi1tration for Crfyptosporidizmz and Giardia content. The results obtained are shown in Table 5.

Table 5 Ceramic Giardia Reference Thickness Compression Cryptosporidium Removal no. (mm) Ratio Removal (%) %) 1 3.40 0.49 94.0% 95.0% 2 3.00 0.43 98.0% 99.5% 3 3.00 0.38 90.5% 100.0% 4 2.84 0.36 90.5% 100.0% 3.66 0.52 97.5% 100.0% 6 3.04 0.43 98.0% 100.0% The ceramic filters of the present invention were found to remove up to 98% of (7ryptosp0ridz'um, and up to 100% of Giardia. The best results were obtained using ceramic filter no. 6 having a thickness of 3.04mm and a compression ratio of 0.43.

In summary, the ceramic filters of the invention have been shown to have excellent protazoan filtration properties, and may be used in a wide variety of applications.

Claims (5)

CLAIMS:

1. A ceramic filter comprising: (a) from about 75% to about 95% by weight of diatomaceous earth; (b) from about 10% to about 20% by weight of a flux; and (c) from about 0.03% to about 0.4% by weight of a metallic compound; the percentages by weight being percentages by weight of the ceran1ic filter; and wherein the metallic compound is preferably selected from chromium, manganese, cobalt, nickel, copper and zinc, more preferably selected from copper and zinc, and wherein, most preferably, the metallic compound is copper.

2. A ceramic filter as claimed in claim 1, wherein the metallic compound is present in the filter in an amount of from about 0.05% to about 0.3%, preferably from 0.1% to about 0.25%, more preferably from about 0.13% to about 0.23%, most preferably about 0.18% by weight of the ceramic filter.

3. A composition for forming a ceramic filter as claimed in claim 1 or claim 2, the composition comprising: (a) from about 10% to about 30% by weight of diatomaceous earth; (b) from about 1% to about 6% by weight of a flux; (c) from about 0.05% to about 1.0% by weight of a metallic compound or a salt thereof or a hydrate of the salt; ((1) from about 0.5% to about 6% by weight of a cellulose gum; and (e) from about 2% to about 10% by weight of a bulking agent; and (0 from about 50% to about 85% by weight of water; the percentages by weight being percentages by weight of the total composition; and wherein component (c) is a metallic compound as defined in claim 1, and is present in the composition in the form of a salt or a hydrate of the salt, and wherein the salt is preferably selected from sulphate, carbonate, chloride and acetate, preferably sulphate, and wherein, more preferably, component (c) is copper sulphate or a hydrate thereof, most preferably copper sulphate pentahydrate.

4. A precursor filter for forming a ceramic filter as claimed in claim 1 or claim 2, the precursor filter comprising: (a) from about 50% to about 98% by weight of diatomaceous earth; (b) from about 2% to about 20% by weight of a flux; (c) from about 0.1% to about 1.5% by weight of a metallic compound or a salt thereof or a hydrate of the salt; ((1) from about 2% to about 20% by weight of a cellulose gum; and (e) from about 5% to about 35% by weight of a bulking agent; the percentages by weight being percentages by weight of the total precursor filter, wherein the metallic compound or a salt thereof or a hydrate of the salt is as defined in claim 3.

5. A method for preparing a ceramic filter as claimed in claim 1 or claim 2, the method comprising the steps of: (A) fonning a composition as claimed in claim 3 by combining the following ingredients: (a) from about 10% to about 30% by weight of diatomaceous earth; (b) from about 1% to about 6% by weight of a flux; (c) from about 0.05% to about 1.0% by weight of a metallic compound or a salt thereof or a hydrate of the salt; (cl) from about 0.5% to about 6% by weight of a cellulose gum; and (e) from about 2% to about 10% by weight of a bulking agent; and (t) from about 50% to about 85% by weight of water; the percentages by weight being percentages by weight of the total composition; (B) removing a portion of water from the composition to as to fonn a composition having a shaping consistency; (C) drying the composition so as to remove any residual water to form a precursor filter as claimed in claim 4; and (D) firing the precursor filter to form the ceramic filter.