AU2007314097A1

AU2007314097A1 - System and process for producing a low-suspended solids solution and uses therefore

Info

Publication number: AU2007314097A1
Application number: AU2007314097A
Authority: AU
Inventors: Roland Leblanc; Farrell Munroe
Original assignee: SCALLOP SHELL POLLUTION SOLUTION Ltd
Current assignee: SCALLOP SHELL POLLUTION SOLUTION Ltd
Priority date: 2006-10-31
Filing date: 2007-08-24
Publication date: 2008-05-08
Also published as: BRPI0718110A2; DK200970014A; MX2009004692A; FI20095600A; FI20095606A; WO2008052302A1; JP2010508142A; RU2009120523A; EP2102111A1; GB2456475A; WO2008052326A1; GB0909297D0; GB0909306D0; CA2667903A1; AU2007314032A1; RU2009120526A; MX2009004690A; GB2456976A; BRPI0718098A2; CA2566562A1

Description

WO 2008/052302 PCT/CA2007/001504 SYSTEM AND PROCESS FOR PRODUCING A LOW-SUSPENDED SOLIDS SOLUTION AND USES THEREFORE FIELD OF THE INVENTION The present invention relates generally to a system and process for producing a low suspended solids solution by filtering a solution through a column comprising crushed shells derived from mollusks. More specifically, the present invention relates to a system and process for manufacturing a low-suspended solids solution having cleaning, disinfecting, and medical treatment properties. Additionally, the present invention relates to a method for preparing an ointment useful for medical treatments in which the ointment comprises in part a composition of crushed shells. BACKGROUND OF THE INVENTION Shells derived from mollusks are generated as industrial waste from fisheries around the world. It is common practice to dump the shell waste into the ocean. However, shells have been efficiently used as a source of calcium and for obtaining antibacterial agents as well as for purifying water. It has been shown that the powder obtained from shells of scallops, oysters, clams, and other mollusks or a solution containing the powder has antibacterial and antiviral properties, as well as use as a water purifying agent. It has also been found that the aforesaid powder has demonstrated useful properties when applied as a deodorant for sterilization as a preservative agent and for selected medicinal use. Antibacterial properties of shell powder are well proven and tested, e.g., the treatment of dermathophytosis (U.S. Patent Application No. 2004/0028748), periodontal diseases (European Patent Application No. 1676583) or for relieving the irritation caused by atopic dermatitis lesions, psoriasis lesions, and for kidney dialysis (Japanese Patent Application No. 2004/256785). Shell powder can also be used in soaps which have been shown to treat tinea pedis (athlete's foot) caused by the breeding of a true fungus. Japanese Patent Application No. 05-267807 (Ueda et al.) describes a method for purifying polluted water as well as the bottoms of rivers, lakes, seas and bays, by spreading a powder of shell fossils across the sea bed to purify the polluted water and the bottoms of rivers.

WO 2008/052302 PCT/CA2007/001504 Japanese Patent Application No. 08-316935 (Suzuki et al.) describes a porous material, made of calcined shells, for purifying water. The material has been shown to effectively purify the water and may be applied effectively for large scale water purification. Japanese Patent Application No. 11-328702 to Sasaya discloses a deodorant obtained by pulverizing the shells of scallops having a crystalline structure consisting of a calcite type structure of calcium carbonate. U.S. Patent Nos. 6,365,193 and 6,488,978 to Sasaki et al. disclose that burned shells can be used as antibacterial agents and water purifying agents. Sasaki et al. disclose heating a shell in an atmosphere of inactive gas and burning the shell. In particular, the antibacterial agent is obtained by burning a powder from the shell of a surf clam in an atmosphere of inactive gas. The powder can be easily dissolved into water, in particular warm water and used as an antibacterial solution. The above uses of shells demonstrate the vast area of applications in which shell properties can be exploited. Further developments directed to new uses of shell material are desired and needed to manage and reduce the great quantity of shell waste produced every year. Most of the above-identified applications require the use of a powder obtained from the shells of mollusks or heat treatment under high temperatures and special conditions, both of which consequently require expensive equipment and complex set-up procedures to practice. In addition, it has been found that when the powder is dissolved in water, the powder tends to lose its active properties over the course of time. SUMMARY OF THE INVENTION It is an object of the present invention to provide a simple process for obtaining a low suspended solids shell extract, containing mainly calcium, that is safe for the human body and environmentally friendly. The low-suspended shell extract inherits the antibacterial properties ofthe shells and as indicated heretofore may effectively be applied as a cleaner and disinfectant or for the treatment of skin diseases. The resultant solution can also be used as a fluid or in mixture with a suitable vehicle to provide a solid or mastic composition. Moreover, the system and process of the present invention are simple and by being economically advantageous can be applied at a larger industrial scale for cleaning and purifying 2 WO 2008/052302 PCT/CA2007/001504 contaminated water. In accordance with an aspect of the present invention, there is provided a process for removing suspended solids from a solution, comprising repeatedly filtering the solution through a filter/extraction column housing crushed mollusk shell particles. In accordance with another aspect of the present invention, there is provided a device for removing suspended solids from a solution, comprising a filter/extraction column; a fluid inlet positioned on one end of the filter/extraction column; and a fluid outlet positioned on the other end thereof, wherein the filter/extraction column houses crushed mollusk shell particles. In accordance with a further aspect of the present invention, there is provided an apparatus for removing suspended solids from a solution. The apparatus may comprise a filter/extraction column; a fluid inlet positioned on one end of the filter/extraction column; and a fluid outlet positioned on the other end thereof, wherein the filter/extraction column houses crushed mollusk shell particles, effectively assembled for removal of said suspended solids. In accordance with a preferred aspect of the present invention, there is provided an apparatus comprising two filter extraction columns arranged in tandem, wherein the first filter/extraction column houses crushed mollusk shell particles and the second filter/extraction column houses crushed mollusk shell particles pre-coated with iron oxide or hematite. In accordance with another aspect ofthe present invention, there is provided a low-suspended solids solution produced by the process described above. In accordance with a further aspect of the present invention, there is provided a use for the low-suspended solids solution for treatment of skin diseases, where the solution has previously been combined with a carrier, such as eucerin or petroleum jelly. Another object of the present invention seeks to provide a cleaner composition comprising the low-suspended solids solution alone or a mix of the solution and sodium hydroxide (NaOH) at a ratio of 0.4 % by weight. This weight factor may vary as may be determined by the man skilled in the art while maintaining cleaning effectiveness. BRIEF DESCRIPTION OF THE DRAWINGS The above and other features of the present invention will become more apparent from the 3 WO 2008/052302 PCT/CA2007/001504 appended drawings, wherein: Fig. 1 shows a cross-sectional view of the extraction column comprising an inlet, an outlet, and a housing member; Fig. 2a is an exploded cross-sectional view of the upper half of the extraction column and illustrates the empty column set-up; Fig. 2b is an exploded cross-sectional view of the upper half of the extraction column and illustrates the column filled with the packing member; Fig. 3 is an exploded cross-sectional view of the lower half of the extraction column and illustrates the empty column set-up; Fig. 4 illustrates a cross-sectional view of the apparatus comprising two extraction columns in a tandem arrangement; Fig. 5 illustrates the measured turbidity of the shell extract with exposure time; and Fig. 6 illustrates the increase of the amount of calcium determined in the shell extract with exposure time. DETAILED DESCRIPTION OF THE INVENTION The following description is directed to a preferred embodiment by way of example of only one of the potential uses of the present invention. Fig. 1, illustrates a filter/extraction column (10) comprising an inlet (11), an outlet (13), two screens (14), and a housing member (12). The housing member (12) defines a passageway (12a) that can be filled with crushed mollusk shells. Fig 2a, illustrates an exploded view of the upper half of the filter/extraction column (10), comprising a top coupling (16), a screw-in stopper (15) and an outlet (13) placed in the stopper (15). A screen (14) may be placed at the top of the housing member (12) in order to contain the crushed mollusk shells in the filter/extraction column (10). The top coupling (16) is fitted with a coupling inside lip (17) in order to attach the screen (14) to the housing member. An interchangeable seal (18), such as silicon can be used to inhibit leaking of the column. Fig. 2b, illustrates an exploded view of the lower half of the extraction column, comprising the bottom coupling (16), stopper (15) and an inlet (11) placed in the stopper (15). The bottom 4 WO 2008/052302 PCT/CA2007/001504 coupling can also be fitted with the coupling inside lip (17) in order to attach the screen (14) to the housing member (12) so as to contain the crushed mollusk shells into the filter/extraction column. The inlet (11) is designed for connection to a plastic valve and a pump used to feed the column with the solvent. An interchangeable silicon seal (18) can be used to avoid leaking of the column. Fig. 3, illustrates the filter/extraction column (10), comprising an inlet (11), an outlet (13), top and bottom identical screens (14), and a housing member (12). The housing member (12) contains crushed mollusk shell particles which may be of equal or different sizes. In one embodiment shown in Fig. 3 the housing member contains at the bottom thereof crushed shell particles of sizes between 0.5 and 1 mm in diameter (20) and crushed shell particles of sizes between 3 and 4 mm in diameter (21). However, the crushed mollusk shells can comprise size particles of about equal and/or of particles distributed along the passageway according to the filter/extraction needs in one or a plurality of zones. A zone is defined as containing crushed shell particles of approximately the same diameter. The packing of the column with crushed shell particles can follow a regular distribution according to a desired gradient or an irregular distribution. Heat treatment can be applied to shells prior to crushing at a temperature of approximately 300 'C for a period of approximately 1.5 min. Fig. 4, illustrates a cross-sectional view of the apparatus (1) according to the present invention and comprises at least two filter/extraction columns (2,3), in a tandem arrangement. In the two-column apparatus (1) the filter/extraction columns are arranged linearly so that the outlet (13) of the first column (2) is connected to the inlet (11) of the second column (3) by a connecting tube (23). The housing member (12) of the first column (2) can contain at the bottom thereof crushed shell particles of sizes between 0.5 and 1 mm in diameter (20), and crushed shell particles of sizes between 3 and 4 mm in diameter (21) thereafter. The housing member (12) of the second column (3) may contain crushed shell particles coated with iron oxide or hematite (24). It is believed that coating the crushed shell particles with iron oxide or hematite may substantially improve the water purifying properties of the filter/extraction columns by reducing the metal content in the water passed through the apparatus (1). Analysis of the water passed through the filter/extraction columns apparatus (1) showed nearly zero content of aluminum and arsenic in contaminated water. In the practice of the present invention, shells are collected directly off the fishing boat and 5 WO 2008/052302 PCT/CA2007/001504 put in tote boxes. The shells are then cleaned by electric drills having a wire brush and throughly washed with water under high pressure to ensure effective cleaning. The cleaning and washing steps may be followed by a cooling step in which the shells are left on a wire rack for an amount of time necessary to cool the shells to the ambient temperature. In the next step the shells are crushed to particles of 1, 2, 3, and 4 mm in diameter. Particles of about the same diameter or a mix of particles with different diameters may be used in the filter/extraction column according to the present invention. The effectiveness of the cleaner will be determined by several factors including the pH of the solvent and the particle size of the crushed shells that form the packing member of the extraction column. By passing distilled water through the filter/extraction column (10) one can control, amongst other parameters, the turbidity, the calcium content, and the suspended solids of the extract. The number of passes and the water flowrate determine the properties of the cleaner, including its cleaning effectiveness. The particle diameter of the crushed shells has been shown to be inversely proportionate to the effectiveness of the cleaner. For example, it is preferred that the particle diameter of the crushed shell be between 0.5 and 4 mm, more preferably between 0.5 and 2 mm to produce a low-suspended solids solution effective as a cleaner. Fig. 5, illustrates the Turbidity vs. Exposure time as determined in Experiment 1 detailed below. It will be noted that the measured turbidity of the solution decreases as it is subject to exposure time to the filter/extraction column. The turbidity was measured after each pass of solvent through the extraction column. After an exposure time of 12 hours the measured turbidity ofthe shell extract was about 2.2 NTU. The above measurements of turbidity are correlated with the measurements of the amount of suspended solids in the shell extract after each pass. Accordingly, as is shown in Table 1 of Experiment 1 as time passes the amount of suspended solids decreases from 6 mg/L after the first pass of solvent through the filter/extraction column to about 0 mg/L after 12 hours. Fig. 6 illustrates the amount of calcium measured after each pass of water through the extraction column versus the exposure time. The final shell extract contains approximately 121 times more calcium than the starting solvent. It is preferred that the calcium content of the shell extract is higher than 14 mg/L and more preferably is higher than 20 mg/L. Other factors that can 6 WO 2008/052302 PCT/CA2007/001504 impact upon the effectiveness of the cleaner are the pH and the turbidity of the shell extract. In order to optimize cleaning results the pH of the shell extract should be between 8.0 and 9.7 and the turbidity should be less than 6 NTU. Experiment 1 An extraction column (10) was constructed with a 6 inch diameter 4 feet long PVC pipe with two couplings closing each end as described in Figure 1. The top coupling had a 90 elbow screw-in with a 3/4 inch plastic tube connected thereto. The top coupling and the plastic tube connected to it represent the outlet (13) according to the present invention. The bottom coupling as constructed had a straight adapter screwed in the coupling stopper and connected to a plastic tube representing the inlet (11) according to the present invention. A 12 V, 360 gallon/hour pump was connected to the inlet of the column and was used to pump distilled water through the column. The top and the bottom of the column were designed in the same way except that the bottom coupling had a 3/4 nipple with a 3/4 plastic tube connected to a plastic valve and the 12 V pump. Two screens (14) as shown in Fig. 1 were used to keep the crushed scallop shells inside the passageway (12a). The composition of the crushed shells was comprised of a mixture of 0.5 and 1 mm diameter scallop shell particles. The mass of the smaller particles was approximately 10 kg and the column was filled to within two inches of the screen (14) of the upper coupling. The rest of the column was filled with larger diameter particles of 3 and 4 mm. After the first pass of distilled water the shell extract had a high suspended solids concentration. The suspended solids concentrations were found to diminish with exposure time. Table 1 shows the suspended solids concentration in the solution as measured by the Hach Company DR- 2400 Spectrometer. This method of determining suspended solids is a simple, direct measurement which does not require the filtration or ignition/weighing steps as do gravimetric procedures. While the USEPA specifies the gravimetric method for solids determinations, this method is often used for checking in-plant processes. Test results are measured at 810 nm. This method is documented in the Hach Water Analysis Handbook, method 8006 page 963. The accuracy of the spectrometric method of measuring the suspended solids concentration 7 WO 2008/052302 PCT/CA2007/001504 cn00 LO 00U iLOV ' 2CO C E0 0 m 1- 'C' C -Ct CO r E o m Lo CD E o r 0 m m m 6 - - R - : - - - coo Ei C) N N N 0) O O ( r- 0 0 =0 Coo Uo *r) v) - -n Fl- - EE -0 LrCO, )C wi U, E >0) 00 Z 0 )L g c ~ a) c 8 WO 2008/052302 PCT/CA2007/001504 was compared against the gravimetric method as described in the Hach Water Analysis Handbook, method 8271 page 947. The mass of the aluminum dish was measured with a Scientech 120 analytical balance to the nearest 1 mg. A 100 ml sample from the solution was taken in situ and placed into the aluminum dish. The dish with sample was placed in a preheated oven and evaporated at 103-105 'C for approximately six hours. The dish was then taken out of the oven and allowed to cool at room temperature in a desiccator. The dish with sample was then taken out of the desiccator and mass measurements were effected to the nearest 0.1 mg with the Scientech 120 analytical balance. This was the first mass measurement of the sample. The dish and sample were put into the preheated oven again for a period of one hour and mass measurements were effected until the results did not differ by more than 0.4 mg. A second measurement of the mass was done in the same manner as above. Table 2 below shows the suspended solids concentration in the solution as measured by the gravimetric method. Total Solids Analysis Table 2 Initial tray 1V dried 2"d dried weight Weight diff Total Solids weight weight (g) 'g) 1S and 2 "d weight ng/L __ 'B) (A) < 0.4 mg Tray 1 8.1982 8.2109 8.2106 0.0003 0.124 Tray 2 8.2245 8.2395 8.2393 0.0002 0.147 Tray 3 8.31 8.3253 8.3250 0.0003 0.15 Tray 4 8.2486 8.2620 8.2620 0.0000 0.144 Tray 5 8.2659 8.2805 8.2806 0.0001 0.147 Total Solids Calculations Equation: mg/L Total solids= ( A - B) X 1000 Sample volume ml Where: A = Weight (mg) of sample + tray B = Weight (mg) of dish % Error of Results %of error = (Dh-D1) x 100= (0.15 m- 0.124mg) x 100 = 0.5 %error 9 WO 2008/052302 PCT/CA2007/001504 # of data points 5 Where: Dh = Highest numerical data results obtained Dl = Lowest numerical data results obtained Experiment 2 Two extraction columns were constructed as indicated above in Experiment 1 (see Fig. 4). The two columns were arranged in tandem with the outlet of the first column directly connected to the inlet of the second column. A 12 V, 360 gallon/hour pump was connected to the inlet of the first column and was used to pump distilled water through the first and second column. The packing member of the first column was made of a mix of smaller 0.5 and 1 mm in diameter scallop shell particles. The mass of the smaller particles was about 10 kg while the column should be filled two inches below the screen (14) of the upper coupling. The rest of the column was filled with larger diameter particles of 3 and 4 mm as described in Experiment 1. The packing member of the second column was made of crushed scallop shell particles coated with iron oxide or hematite (Fe 2 0 3 ). The coating of the crushed shell particles with iron oxide can be effected by any process known to a person skilled in the art. In the present invention the coating of the scallop shells is effected by soaking the shells in iron oxide or hematite for 4 hours, then baking the shells and solution for 4 hours at 200 'C. The shells should then be washed with distilled water and dried in an oven at 200 'C for three hours. Contaminated water with a high content of aluminum and arsenic was passed through the apparatus comprising the two extraction columns arranged in tandem. It has been found in practice that the aluminum and arsenic content of the resulting aqueous solution was reduced to 0 mg/L. INDUSTRIAL APPLICABILITY The invention provides a system and process for producing a low-suspended solids solution by filtering a solution through a column comprising crushed shells derived from mollusks. The result of utilization of the aforementioned system and process is a solution that has numerous properties. In particular, this solution can be effectively implemented as a cleanser and disinfectant, as well as being effective in the treatment of various skin diseases. Further, the present invention provides an application for an industrial waste product, mollusk shells, that are generated in large quantities from fisheries around the world.

Claims

1. A process for removing suspended solids from a solution, comprising repeatedly filtering the solution through a filter/extraction column (10) housing crushed mollusk shell particles (20, 21).

2. A process according to claim 1, wherein the solution is water.

3. A process according to claim 1 or 2, wherein the crushed mollusk shell particles (20, 21) are boiled at a temperature of about 100 'C for a period of about 15 min. prior to placement in the filter/extraction column (10).

4. A process according to any one of claims 1 to 3, wherein the crushed mollusk shell particles (20, 21) are baked at a temperature of about 300 'C for a period of about 1.5 min. prior to placement in the filter/extraction column (10).

5. A device for removing suspended solids from a solution, comprising a filter/extraction column (10); a fluid inlet (11) positioned at one end of the filter/extraction column (10); and a fluid outlet (13) positioned at the other end of the filter/extraction column (10), wherein the filter/extraction column (10) houses crushed mollusk shell particles (20, 21).

6. A device according to claim 5, further comprising a first screen (14) detachably connected at one end of the filter/extraction column (10) near the fluid inlet (11) and a second screen (14) detachably connected at the opposite end of the filter/extraction column (10) near the fluid outlet (13).

7. An apparatus for removing suspended solids from a solution, comprising a plurality of devices according to claim 5 or 6 connected in an operable arrangement effective for the removal of suspended solids from a solution.

8. An apparatus according to claim 7, comprising two filter/extraction columns (10) arranged in tandem wherein the first filter/extraction column (10) houses crushed mollusk shell WO 2008/052302 PCT/CA2007/001504 particles (20, 21) and the second filter/extraction column (10) houses crushed mollusk shell particles pre-coated with iron oxide or hematite (24).

9. A solution made by the process of any one of claims I to 4.

10. The solution according to claim 9, wherein the concentration of calcium is greater than 14 mg/L.

11. The solution according to claim 9 or 10, wherein the concentration of calcium is greater than 20 mg/L.

12. The solution according to any one of claims 9 to 11, wherein the pH of the solution is between 8.0 and 9.7.

13. The solution according to any one of claims 9 to 12, wherein the turbidity of the solution is less than 6 NTU.

14. The solution according to any one of claims 9 to 13, further comprising NaOH in an amount consistent with the effectiveness of said solution.

15. The solution according to claim 14, wherein the ration of NaOH to the solution 0.4 % by weight.

16. The solution according to any one of claims 9 to 13, further comprising a vehicle selected from the group consisting of eucerin and petroleum jelly.

17. Use of the solution according to any one of claims 9 to 15 as a cleaner.

18. Use of the solution according to claim 16 for treatment of skin diseases.