Title of Invention

A METALLATE MODIFIED SILICA SOL WITH SOLUBLE IRON ADSORBED ONTO IT

Abstract

The present invention relates to a metal late modified silica sol with soluble iron adsorbed onto it for copious bloom of diatom algae; the said process comprising steps of adsor~ng soluble iron alone or in conjunction with macr micro nutrients onto metallate modified silica sol; use of a metal late modified silica sol with soluble iron alone or in conjunction with macro micro nutrients adsorbed onto it for copious bloom of diatom algae, said process comprising steps of adding said sol to a water body and obtaining the copious bloom of the diatom algae; and a process for reducing global carbon dioxide, said process comprising step of stimulating generation of oceanic photosynthetic phytoplankton's using metallate modified silica sol with soluble iron alone or in conjunction with macro and or micro nutrient(s) adsorbed onto it.

Full Text

SILICA NUTRIENT AND MICRONUTRIENT FOR GROWTH OF DIATOM ALGAE (a)AREA BACKGROUND OF THE INVENTION Man has been trying from time immemorial to duplicate nature's creations and processes and has been quite successful resulting in very large benefits. This invention relates to a process that is happening naturally but has not been successfully duplicated artificially. Algae are the basis of the food chain in the marine world. Diatom algae having silica walls are the most prolific growth and food creators that are responsible for the productivity of the oceans. As compared to other green algae and blue green algae having cellulose cell walls that are not easily digestible, diatoms having silica cell wall is easily absorbed and digested by the starting members of the food chain like zooplankton and fish etc. Analysis and speculation indicate that silica is in the form of monomeric othosilicic acid Si(0H)4 formed by the depolymerisation of solid or colloidal silica. Many textbooks have written volumes on the role of silica, their form and solubility etc on the diatom growth. The deficiency of the silica in the form acceptable for the biological growth of diatoms is the limiting factor in the seas. Sometimes analysis of the seawater indicates that it contains silica but there is no diatom bloom. Another hypothesis was that the seas were lacking in iron and hence algae were not blooming. The SOFEX project was undertaken to test John martin's Iron hypothesis. However the results were indifferent. The burning of fossil fuels resulting in release of carbon dioxide into the atmosphere has enhanced the greenhouse effect leading to global warming. The nations want the extra carbon dioxide to be absorbed by the oceans and converted to food. The productivity of the oceans has been poor due to lack of plankton growth. Adding the appropriate nutrients can fuel diatom growth and then most of the excess carbon dioxide can be absorbed by the growing algae due to photosynthesis and release of oxygen with the manufacture of food. In addition to this the oceans and lakes have been polluted with excess nitrate and phosphate from land run offs and untreated wastes and sewage that toxic species of phytoplankton have started proliferating resulting in problems for the people at large. Examples of" RED TIDES" are well known. The excess nitrate and phosphate have to be converted to food. It is very well known that nutrients like nitrogen, phosphorous, trace minerals and vitamins are required for the growth of all algae. Although iron is the biggest micronutrient required for algal growth there are other very important micronutrients that are required in extremely small quantities but are not readily available in the seawater especially in the alkaline salty conditions. Examples are Manganese, zinc, cobalt and copper. All these micronutrients have to be made available in extremely small quantities for growth of algae. Diatom algae is special in which a silica nutrient is required over and above the other nutrient since the cell walls have silica from 4% to 20% of the dry weight of the cell. Reference for reading: The physiological ecology of phytoplankton "studies in ecology" Vol 7 by I..MORRIS (b) STATUS OF PRIOR ART. What is known of prior art is pretty rudimentary written in textbooks. The addition of silicates with other nutrients coupled with chelating agents like EDTA etc. are known to bring a bloom of diatom algae. The following are some of the US patents that have mentioned about producing diatoms. US Patent Nos. 5567732 Kyle, et all Eicosapentaenoic acid- containing oil and methods US Patent Nos. 5244921 Kyle, et all for its production. In this patent diatoms are grown using Sodium metasilicate in growth medium composition. US patent 6199317 Saiki et all - Materials for growing algae and artificial fishing banks In this diatoms are grown using ferrous ions released into water. US patent 5965117 Howard et all Water buoyant particulate material containing micronutrients for phj1;oplankton. us patent application 20040093785 Markels, Michael JR Method of increasing fish catch in the ocean.. May 20,2004, fc) PROBLEMS WITH PRIOR ART The inorganic silicates used to provide source of silica is by and large useless since they are not absorbed and precipitate out of solution. If you require a sustained and widespread diatom bloom the silica nutrient should be in the solution in an acceptable form for growth and absorption. The earlier US patent 5567732 and US patent 5244921 claiming use of sodium metasilicate for diatom bloom is too elementary and not sustainable for large-scale diatom production. US patent No. 6199317 using ferrous ions may be of help if water contains soluble silica. There is this iron hypothesis theory by J.H.Martin mentioned in "Testing the iron hypothesis in eco systems of the equatorial pacific ocean" Nature Vol: 371, Sept 8, 1998 pp 123-129. The success if any is very limited and does not prove or disprove the theory. If silicic acid or silica sol is used, they will polymerize under the conditions and precipitate out as silica and hence will no longer be available as nutrient. Further there is some truth that iron is required for algal growth but inorganic iron salts precipitates out under seawater conditions and hence cannot help. NOBODY in the prior art have conceived of a comprehensive method of delivering the silica nutrient that will deliver silica with the micronutrient required to the diatoms in the form that the diatoms can absorb, assimilate and grow. (d) HOW THIS INVENTION SEEKS TO SOLVE THE PROBLEM This invention relates to development of a Silica nutrient delivered with the micronutrient required for the growth of diatom algae. The base material for nutrient silica is modified silica sol based on US patent No. 2,892,797 by Guy.B.Alexander and Ralph K.Iler patented on 30^^ June 1959. The details of the preparation of the modified silica sol are mentioned in the patent.. Alumina modified silica sol is the preferred one. The particle size of the sol may vary from 5 to 150 millimicrons. It is preferable to have between 5 and 30 millimicrons. In a typical example a silica sol of 15 nm particles modified in this way with sodium aluminate, the incorporation of only 0.66% by weight of AI2O3 based on silica was sufficient to give stability for the sol in seawater conditions. Alumina modified silica sol based on US Patent 2,892,797 is miscible with seawater in all proportions without gelling or precipitation unlike unmodified silica sol . The alumina modified silica sol is available as a commercial product called LUDOX AM from Du Pont. However this compound by itself is not enough to grow diatoms in the seawater in the absence of iron and other micro and macro nutrients in the seawater. By the process of this invention alumina modified silica sol made as per US patent 2,892,797 is treated with a .limited quantity of a solution of an iron salt such that the iron is adsorbed on the silica sol indicated by the discharge of the colour. The iron salt is adsorbed on to the surface of the silica forming a physical bond. Similarly very small quantities of other micronutrients like Manganese, zinc, cobalt, and copper in a soluble form can be adsorbed on to a alumina modified silica sol. A mixture of iron adsorbed alumina modified sol and the other micronutrient adsorbed alumina modified silica sol is made. This solution can be directly used as a source of silica and micronutrient for growing diatoms in the seawater / fresh water or can be dried to powder, that is redispersible in seawater / fresh water and used as a source of silica nutrient and micronutrients. This iron and other micronutrient adsorbed on alumina modified silica sol is miscible with seawater in all proportions without gelling or precipitation and forms the active silica nutrient that will enable diatoms to grow in large quantities. The preferred iron salt is ferric chloride but other iron salts can be used. The preferred salt for other micronutrients is in the chloride form. Algae require the iron as a micronutrient and hence very small quantity in the region of micrograms is necessary. The other micronutrients are required in still smaller quantities and hence very little need be added to the sol. The quantity of iron salt that can be adsorbed on the silica sol depends on the size of particles and degree of polymerization of the particles in the sol. The smaller the particles size the more quantity of iron salt that it can adsorb. Excessive addition of iron salt can reverse the charge on the particle leading to coagulation and precipitation out from the solution in seawater conditions. In health, nutrition and medicine the compound will find use as a source of iron, other micronutrients and soluble silica. For diatom algae growth it is preferable to restrict iron salt to less than 1% of the silica contents (mole to mole) in order to get a stable sol and that which does not coagulate or precipitate in the presence of seawater. For other micronutrients like manganese less than 0.3% is sufficient, for zinc less than 0.1% is sufficient and for cobalt and copper less than 0.01% is sufficient. However the quantities of micronutrients can be varied depending on individual algal requirements based on detailed study. Example 1 A commercial alumina modified silica sol is available called LUDOX AM from du pont. Other commercially competitive products may also be used. 100 gms. Of this product is taken in a beaker. In another beaker 10 ml of distilled water is taken and 0.3 gm of ferric chloride is dissolved. The solution of ferric chloride is added to the ludox A M with mixing. The brown color is discharged and a faint cream color results indicating the adsorption of iron on to the silica. This solution can be used as such, mixed with example 2 and used as liquid, or dried and used. Example 2. 100 gms of Ludox AM or other commercially competitive products is taken in a beaker. In another beaker 10 ml of distilled water is taken and the following is added, a) 0.1 gm of manganese chloride, b) 0.05 gm of zinc chloride c) 0.01 gm of cobalt chloride d) 0.01 gm of copper chloride. The solution of the various micronutrients is added to the Ludox AM. The micronutrient is adsorbed on the ludox AM. This can be mixed with example 1 and used as such or dried and mixed with example 1 and used. The above quantities are only indicative and it can be changed based on actual requirement. e) WHAT FEATURES ACHIEVE THIS PROBLEM SOLVING Although the alumina modified silica sol has been around from 1959, it has not been used as source for silica nutrient since by itself it cannot favor the growth of diatoms in the absence of soluble iron in the system. Seawater being alkaline in nature and having dissolved salts of sodium, potassium, calcium etc the solubility of iron, zinc, manganese copper etc is negligible, and the solubility and presence of silica as a monomer is very much reduced. In this invention the iron and other micronutrients is adsorbed onto the alumina modified silica sol with the result that the iron and other micronutrients cannot precipitate out from the sea water even though the water is alkaline and dissolved salts are present. Iron plays a crucial role in the bioenergetics of carbon and nitrogen metabolism and is required for the synthesis of chlorophyll and reduction of nitrate. Cobalt is required for synthesis of vitamin B12 and manganese is essential for enzyme activation. When practical tests were done in backwaters, a copious bloom of diatoms was obtained on dosing this iron and micronutrient complexed alumina modified silica sol. (n HOW THE PRESENT INVENTION CONSTITUTES AN IMPROVEMENT The prior art does not describe any product as a silica nutrient that can bring about copious diatom bloom in seawater conditions. The prior art is only suggestive of silicates and other chemicals. This invention provides a product that can directly supply the silica nutrient in conjunction with the required micronutrient for the bloom of diatoms. This invention also identifies the nature and form of the compound that is absorbed for providing the diatom bloom. Use of other chelated nutrients as mentioned in invention US patent application no.20040093785 by Markels assume that silica is available in the water in the form that can be absorbed and only chelated nutrients are lacking. Further no claim has been made for the exact chelating compound. In the other patents, using inorganic silicates will not remain in solution and sustained diatom bloom is not possible. This invention gives a comprehensive solution to the problem of creating a diatom bloom. I CLAIM 1. A product composition in the form of an aqueous sol or redispersible sol particles comprising of an iron adsorbed onto alumina modified silica sol having iron in adsorbed form with alumina modified silica sol with elemental iron varying from 0.01% to 10% of the weight of silica, used alone or in conjunction with other micronutrients adsorbed on alumina modified silica sol, each micronutrient varying in concentration from 0.001% to 10% of the weight of silica and added, ensuring the availability of other necessary macronutrients and vitamins, for the growth of phytoplankton especially DIATOM ALGAE in seawater, fresh water and mixtures thereof, 2. The composition of claim 1 wherein the alumina modified silica sol is made as per the US patent 2,892,797 by Guy .B.Alexander and Ralph K.Iler dated. June 30 1959 3. The composition of claim 1 wherein the source of iron is selected from the group consisting of elemental iron, ferrous sulphate, ferrous ammonium sulphate, ferrous chloride, ferric chloride, ferric nitrate, oxides of iron, mixed metal oxides comprising iron, hydroxides of iron, iron sub oxides, oxyhalides ,mixtures thereof, inorganic compounds of iron, organic forms of iron and chelated iron. 4. The composition of claim 1 wherein the micronutrients is selected from the group consisting of Mn, Co, Zn, Cu, B, Mo 5. The composition of claim 1 wherein the macronutrients is selected from the group consisting of N,P,K,Ca,Mg 6. The composition of claim 1 wherein the vitamins is selected from the group of B complex. 7. The composition of claim 1 wherein the mix of fresh water and sea water can be in any proportion from 0 to 100%. A process for preparing an aqueous sol of a composition comprising of iron adsorbed onto alumina modified silica sol containing 0.1% to 10% of Fe, and a micronutrient adsorbed on alumina modified silica sol consisting of Mn, Zn, Co, Cu, and mixtures thereof in the proportion 0.001% to 10% of the silica surface. The process of claim 8 comprising drying of the aqueous sol of the compositions to provide a free flowing redispersible sol particles. . A process for stimulating photosynthetic phytoplankton growth in ocean, lake, river or a body of water, devoid of, or deficient in, such growth, said process comprising adding of a product composition mentioned in claiml to the said ocean, lake, river or a body of water. , The process of claim 10 wherein said process is performed in an ocean. .The process of claim 10 wherein global carbon dioxide is reduced by stimulated generation of oceanic photosynthetic phytoplankton. using the product composition in claim 1 . The process of claim 10 wherein marine or fresh water food is increased by the stimulated generation of photosjoithetic phytoplankton using the product composition in claim 1. , The process of claim 10 wherein the excess nutrients of N and P are removed from the body of water , The process of claim 10 by which toxic and waste algal species growth is reduced and replaced with !

Documents:

525-che-2004 description (complete) granted.pdf

525-che-2004-abstract.pdf

525-che-2004-claims duplicate.pdf

525-che-2004-claims original.pdf

525-che-2004-correspondnece-others.pdf

525-che-2004-correspondnece-po.pdf

525-che-2004-description(complete) duplicate.pdf

525-che-2004-description(complete) original.pdf

525-che-2004-form 1.pdf

525-che-2004-form 26.pdf

525-che-2004-form 9.pdf