METHOD AND APPARATUS FOR SEQUESTERING CARBON DIOXIDE IN THE DEEP OCEAN OR AQUIFERS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a method and apparatus for removing carbon dioxide from power plant emissions or from the general atmospheric environment and sequestering it in the deep ocean. More particularly, the invention relates to a method and apparatus for producing carbon dioxide clathrates which can be deposited in the deep ocean thereby sequestering the carbon dioxide for 500 years or more. 2. Description of Related Art There is presently a growing concern that continued unabated emissions of carbon dioxide may lead to a global temperature rise or other climatic change. One o the methods to control carbon dioxide emissions is to separate the carbon dioxide fro power plant or other flue gases and pump the carbon dioxide at a high pressure into the ocean below the thermocline. This has been shown to be a very energy-intensive and cosdy process due to the large gas compression energy losses. An alternate approach is to dispose of carbon dioxide in the oceans by liquefying the carbon dioxide and pumping it to depths greater than 1000 meters. Thi is also very energy-intensive and costiy. Still others have discussed the formation of carbon dioxide clathrates at ambient sea-water temperatures and pressures greater than 40 atmospheres, and/or as high as 100 atmospheres by combining sea water with liquid carbon dioxide at temperatures of 5 ^e to 10 ^C C. Again, this is a very energy- intensive approach and economically unaπractive. Therefore, it is apparent that what is needed is a simple and energy efficient method of sequestering carbon dioxide in the deep ocean. SUMMARY OF THE INVENTION WITH OBJECTS One object of the present invention is to provide an energy efficient method and apparatus to sequester carbon dioxide in the deep ocean. Another object of the present invention is to provide a cycle for carbon dioxide sequestration which utilizes the cold of deep ocean waters to promote carbon dioxide

clathrate formation. Still another object of the present invention is to form carbon dioxide clathrates for sequestration without having to use refrigeration for all of the suh-cooling of the carbon dioxide and thereby saving a significant portion of the refrigeration energy which would odierwise be required to accomplish said clathrate formation. Yet one more object of the present invention is to form carbon dioxide clathrates for sequestration without having to compress said carbon dioxide to high pressures and thereby expend the energy necessary for said compression. These and other objects are accomplished in a system which uses sub-cooled carbon dioxide gas phase and liquid water (fresh or salt) in a reactor to form carbon dioxide clathrates in a continuous process at pressures from 3 to 20 atmospheres. The seawater feed for the clathrate reactor is pumped to the surface from a deptii of approximately 500 to 1000 meters. A shp stream of the reactor feed water is used to pre-cool the carbon dioxide gases. The pre-cooled gaseous, or liquid, carbon dioxide and the reaαor surfaces are then sub-cooled by refrigeration to temperatures of -40°C to 0°C, which is typically only 5° to 45°C below ambient sea water temperatures at depths of 500 to 1000 meters. Forming clathrates in this manner is considerably less energy-intensive than CO ₂ compression and liquefaction at high pressures. The reactor may either be submerged in me ocean at some depth less than 1000 meters or operated on die surface of the ocean by pumping deep ocean water (from 500 meters to 1000 meters or so) into the reactor and returning clathrates direcdy or newly (partially) dissolved clathrates to depth with unreacted sea water. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the overall cycle for the carbon dioxide cooling and conditioning, and the clathrate formation, removal, and sequestration system. Fig. 2 is a section view of the clathrate reactor used in practicing the present invention.. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Clathrate compounds are combinations of compounds in which one compound is caged within the lattice structure of another compound. Carbon dioxide clathrates

may be formed from a water "lattice" of 46 H ₂ 0 molecules at pressures greater than 4 atmospheres and temperatures below 10°C. The number of carbon dioxide molecules enclosed in this lattice may vary from 1 to 8 depending on die formation conditions. Most data indicate that the number of carbon dioxide molecules trapped in the lattice depends primarily on the operating pressures, higher pressures increasing the number of molecules trapped. The primary determinant of the amount of carbon dioxide trapped in either fresh or sea water will be both the ambient temperature and pressure (T, P) conditions and relative mole fractions of carbon dioxide and water present. CO ₂ clathrates of various levels of stability and volume fractions of crystals or granules have been produced with mole fractions of CO ₂ varying from 0.05 to 0.52 in batch tests conducted at high pressure by admixing water with gaseous C at approximately 6°C These have been produced with various levels of agitation provided by a glass rod which is enclosed in the reaction section. From the phase diagram for CO ₂ , water, and hydrate, similar clathrate formation conditions exist for a sub-cooled mixture of CO ₂ (gas) and water at pressures as low as 3 atmospheres, with temperatures of -30°C If liquid water and sub-cooled gaseous CO ₂ are simultaneously sprayed into a sub- cooled low pressure reactor, stable solid CO ₂ clathrates will form and be deposited in the reactor. Formation of clathrates under these conditions allows for sequestration of carbon dioxide in the deep ocean regions for long periods of time. Referring now to Fig. 1. a flow diagram for the present invention is depicted.

can be of any conventional design including positive displacement or centrifugal compressors capable of compressing the gas to pressures between 3 and 20 atmospheres. The compressed carbon dioxide gas is men routed to heat exchanger 102. Heat exchanger 102 is of the conventional shell and tube, or plate type and receives cooling water from deep pipe 104. Deep pipe 104 draws suction from fresh or sea water from a depth of approximately 500 to 1000 meters. Pump 106 delivers water from deep pipe 104 to'heat exchanger 102. In a parallel manner, pump 106

supplies water to the refrigeration unit 110. Water further cooled by the refrigeration unit 110 in this manner is later useα as feed water for a clathrate reactor. Sea water brought from a depth of 500 to 1000 meters is generally at a temperature of about 0°C to 10°C, and more typically is approximately 5°C. Heat transfer from the compressed carbon dioxide to die sea water results in the carbon dioxide being cooled to approximately 10°C. At this point, the cooled carbon dioxide gas is fed to refrigeration unit 110. Refrigeration unit 110 can be a typical vapor compression or adsorption type unit. The refrigeration unit cools both the compressed carbon dioxide and the sea water deUvered to the refrigeration unit from the deep pipe 104. The carbon dioxide gas temperature is reduced to between 0°C and -30°C by the refrigeration unit 110. At the same time, Λe feed water is cooled to approximately 0°C. Both the carbon dioxide gas and the feed water are routed to clathrate reactor 120. Turning now to Hg. 2, a cross section view of the clathrate reactor is depicted. The clathrate reactor 120 is a pressurized cylinder 122 suitable for mixing the sub- cooled carbon dioxide gas and sea water under the necessary conditions to form clathrates. Although the reactor 120 is depicted as a cylinder, it is readily understood that its overall dimensions can take on other shapes such as a sphere or rectangular box. Sub-cooled carbon dioxide is fed to d e reactor 120 by pipe 124 which connects to diffuser 126 mounted internal to vessel 122. Diffuser 126 contains a plurality of holes (not shown) which serve to distribute the carbon dioxide gas evenly within the reactor 120. Sub-cooled sea water is brought to die reactor 120 by pipe 128. Pipe 128 feeds a plurality of spray nozzles 130 which direct a sea water spray across the carbon dioxide gas being released by diffuser 126. Although the nozzle orientation depicted in this figure is cross-flow . counter-flow nozzles can be used to advantage. As die carbon dioxide and sea water react under the favorable pressure and temperature conditions maintained ir. the reactor 120, clathrates 140 are formed and accumulate in a mound 142 in hopper 150. To further promote the formation of clathrates, reactor 120 can be coole by refrigeration unit 110. Cooling of reactor 120

assists in maintaining a stable operating condition for continuous clathrate formation. The clathrates are removed from reactor 120 through nozzle 152. When valve 160 is opened, clathrates from mound 142 flow into mixing chamber 162. Sea water fed to chamber 162 by pipe 164 flushes the clathrates through discharge pipe 166 to die deep ocean. The deposited material may be removed with a cycling pressure let- down system such as a pressure lock system which is known in the an. The clathrates will either be released as solids into the ocean at a specified depth to ensure carbon dioxide sequestration or pumped and dissolved in deep ocean water which has been upwelled to form the clathrates and acts as a carrier to return the clathrates or partially dissolved clathrates to deptiis between 500 and 1000 meters. Although the system described sequesters carbon dioxide in the ocean, the same system can be used to sequester CO ₂ in cold, underground fresh water aquifers in a similar manner, as clathrates form equally well in fresh or salt water. The clathrate formation conditions are also dependent on d e rotational orientation of the carbon dioxide molecules relative to the 46 water molecules with which they interact Various methods are available to optimize rotational orientation and diereby improve the packing density of carbon dioxide. Referring back to Fig. 1, options to improve molecular interaction such as sonic or infrared preconditioning of the carbon dioxide gas are shown in box 250. The reactor may include other methods to catalyze or enhance die reaction rates of the carbon dioxide water reaction including swirl or co-axial nozzles to enhance contact between the low-pressure gaseous carbon dioxide and water, clathrate crystal recycle to "seed ^" the clathrate formation, or selected metallic surfaces to further catalyze the reactions. The packing density of CO ₂ into the water matrix; i.e.. the optimum CO ₂ mole fraction fixed in the lattice, is important to the longevity of the sequestration of the carbon dioxide. This increased packing density increases the specific gravity of the clathrates to levels greater than that of sea water; i.e.. 1.1 gm/cc. Once these highly packed clathrates are formed and returned to the ocean at significant depth, they will sink by gravity toward the ocean floor. Of course, dissolution of the clatfirates in the open ocean or in fresh-water systems will occur at some rate. Thus, final

sequestration in the oceans or deep water aquifers may either be in the form of cladirates (which form naturally on the ocean floor) or as dissolved clathrates, which increase the bicarbonate concentration of cold sea water. In either case, once the carbon dioxide is "deposited" below 1000 meters, it has greater than a 500-year lifetime in the ocean, and is considered to be sequestered. Therefore, the overall invention is this entire system for carbon dioxide sub- cooling, clathrate formation, transfer, and discharge at depth in the ocean or in cold- water aquifer systems. The invention focuses on the continuous reactor for reacting gaseous carbon dioxide and water to form solid CO ₂ clathrates, as well as the use of deep ocean water to form and transport die clathrates to depth. Having thus described an exemplary embodiment of die invention, it is understood that those skilled in die art may modify or change the details of implementing the invention without departing from the spirit and scope of the invention as defined in the following claims.