Title of Invention

A PROCESS FOR PRODUCING ACETIC ACID

Abstract A process for producing acetic acid, or a salt thereof, comprising the steps of: (a) providing a continuous flow of gas selected from the group consisting of: (i) a gas comprising carbon monoxide; (ii) a gas comprising carbon monoxide and hydrogen; and (iii) a gas comprising hydrogen and carbon dioxide; into a bioreactor; said bioreactor comprising an aqueous nutrient medium and anaerobic, acetogenic bacterium C. 1jungdahlii ERI-2; (b) directing a continuous flow of said aqueous nutrient medium into said bioreactor; (c) fermenting said gas ad said nutrient medium using said anaerobic, acetogenic C. 1jungdahlii ERI-2 bacterium at a pH of less than 5.1; wherein at least 2 g/L of said acetic acid is produced in free acid form in said bioreactor in a liquid effluent-
Full Text BIOLOGICAL PRODUCTION OP ACETIC ACID FROM
WASTE GASES
The present invention is directed to biological methods, processes, microorganisms, and apparatus for producing products, materials, intermediates, and the like such as organic acids, single cell protein ("SCP"), hydrogen, alcohols, and organic acid salts from the waste gas streams of certain industrial processes and more particularly concerns a process utilizing continuous gaseous substrate fermentation under anaerobic conditions to accomplish this conversion.
The conventional procedure far producing organic acids, alcohols, hydrogen and organic acid salts is chemical synthesis of petroleum-derived feedstocks . The rapidly escalating cost of petroleum has generated considerable interest in producing these valuable commodities by fermentative processes that utilize renewable or waste materials as the feedstock. Single cell protein is produced as a by-product of the fermentations to be used as an animal feed supplement.
There is also growing concern over the massive amounts of atmospheric pollutants and greenhouse gases produced by conventional industrial processes. The

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Environmental Protection Agency recently estimated that over aix million metric tons of carbon monoxide and nearly four million metric tons of hydrogen were discharged annually by the industrial complex. A substantial portion of this waste carbon monoxide and hydrogen is the result of carbon black manufacture and coke production, roughly 2.6 million metric tone of CO and 0.5 million metric tons of H2. Large amounts of carbon monoxide or hydrogen are also produced by the ammonia industry (125, 144 metric tone of CO in 1991), petroleum refining (8 metric tons per thousand barrels), steel mills {152 pounds per metric ton of steel produced) , and sulfate pulping of wood (286 pounds per ton of pulp) . In 1351, the adipic acid industry generated 40,773 metric tons of carbon monoxide that was burned for fuel value or. flared. In many cases, these gases are discharged directly to the atmosphere, placing a heavy pollution burden on the environment.
Typically, the waste gases from the manufacture of industrial products are released at low pressures and temperatures. Current technology cannot utilize these dilute gases under such conditions. Adapting

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existing technology to separate and recover hydrogen or carbon monoxide from these waste streams would be expensive and impractical.
In light of the foregoing, there is a need for a cost effective and practical method, microorganism, and apparatus for utilizing the above-described waste gases and for producing products, materials, intermediates and the like such as organic acids, alcohols, hydrogen and organic acid sales by other than chemical synthesis of petroleum derived feedstocks.
SUMMARY OF THE INVENTION
In accordance with the Present invention, products, materials, intermediates, and the like such as oxganic acids, alcohols, hydrogen, single cell protein and/or organic acid salts are produced from the waste carbon monoxide., hydrogen, and/or carbon dioxide of industrial processes, thereby reducing environmental pollution while at the same time saving energy and chemical feedstocks.
In accordance with an exemplary process of the present invention, the desired components of the

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dilute gas mixtures are introduced into a bioreactor containing one or more cultured strains of anaerobic bacteria that utilize the waste gaa components by a direct pathway to produce a desired compound. The compound is recovered from the aqueous phase in a separate vessel or vessels, utilizing a suitable recovery process for the compound produced. Examples of recovery processes include extraction, distillation or combinations thereof, or other efficient recovery processes. The bacteria are removed from the aqueous phase and recycled to avoid toxicity and maintain high cell concentrations, thus maximizing reaction rates. Cell separation, if desired., is accomplished by centrifugation, membranous ultrafiitration, or other techniques.
The principal object of the present invention is the provision of a process and/or microorganism for the production of products, intermediates, materials, and the like such as organic acids, hydrogen, single cell protein, alcohols, and/or organic acid salts from carbon monoxide, hydrogen, and/or carbon dioxide.
Another object of the present invention is the provision of methods, microorganisms and apparatus for



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the production of items such as organic acids, alcohols, hydrogen, single cell protein and/or salts from the waste gas streams of industrial processes such as oil refining, carbon black, coke, ammonia, and methanol production.
A still further object of the present invention is the provision of a process for producing acetic acid and/or ethanol from a waste gas stream of identical composition to that found in the manufacture of carbon black.
Yet another and more particular object of the present invention is the provision of a method, microorganism and apparatus involving continuous gaseous substrate fermentation under anaerobic conditions to accomplish the conversion of waste gas streams of certain industrial processes into useful products such as organic acids including acetic acid, alcohols, hydrogen, single cell protein and organic acid salts.
Other objects and further scope of the applicability of the present invention will become apparent from the detailed description to follow, taken in conjunction with the accompanying drawings

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wherein like parts are designated by like reference
numerals.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS Fig. I is a schematic diagram of a process for
the production of acetic acid from waste gas.
Fig. 2 is a schematic diagram of a process for the production of CMA from waste gas.
Fig. 3 is a schematic diagram of a process for the production of ethanol from waste gas.
Fig. 4 is a schematic representation of a continuous fermentation system in accordance with an embodiment of the present invention.
Fig. 5 is a graphical illuscration of cell concentration (OD) versus time.
Fig. 6 is a graphical representation of acetic
acid (HAC) versus time.
DETAILED DESCRIPTION OF THE INVENTION
The term 'waste gas" or "waste gas streams" as used herein means carbon" monoxide and hydrogen mixed with other elements ox compounds, including carbon dioxide, nitrogen and methane, in a gaseous state and which are typically released or exhausted to the atmosphere either directly or through combustion. Normally, release taxes place under standard smokestack temperatures and pressures. Accordingly,

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the processes of the present invention are suitable for converting these atmospheric pollutants into useful products such as organic acids, alcohols and organic acid salts. These products include, but are not limited to acetic, propionic, and butyric acids; methanol, ethanol, propanol, and n-butanol; plus salts, such as calcium magnesium acetate (CMA) and potassium acetate (KA).
Anaerobic bacteria which are known to convert carbon monoxide and water or hydrogen and carbon dioxide into alcohols and acids and acid salts include Acetobacterium kiwi, A. woodii, Clostridium aceticum, Butyribacterium methylotrophicum, C. acetobutylicum, C. formicaceticum, C. kluyveri, C. thermoaceticum, C. thermocellum, C. thermohydrosulfuricum, C. thermosaccharolyticum, Eubacterium limosum, C. ljungdahlii PETC and peptostreptococcus productus. Anaerobic bacteria known to produce hydrogen from carbon monoxide and water include Rhodospirillum rubrum and Rhodopseudomonas gelatinosa.
More specifically, bacterial species such as Acetogrenium kivui, Peptostreptococcus productus,

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Acetobacterium woodii, Clostridium thermoaceticum and Eubacterium limosum produce acetate by the reaction: 4CO + 2H2O ? CH3COOH + 2CO2 dG = -39 kcal/reac. (1)
Many anaerobic bacteria are also known to produce acetic acid from H2 and CO2. These bacterial isolates include A. kivui, P. productus, and Acetobacterium sp. , which utilize homoacetic fermentation by anaerobically oxidizing hydrogen and CO2 according to the equation;
4H2 + 2CO2 ? CH3COOH + 2H2 dG = -25 kJ/reac. (2)
Acetobacterium woodii and Acetoanaerobium noterae produce acetate from H2 and CO2 according to the above reaction, but in addition no acetate, A. noterae produces some propionate and butryrate. Another chemolithotrophic bacteria, Clastridium aceticum, produces acetate from CO, using a glycine decarboxylase pathway.
Same bacteria, like A kivni, P. productus, and A woodii, produce acetate from either CO and H2O or H2 and CO2. P. productus gives particularly fast rates of conversion and demonstrates high tolerance to CO; however, this organism shows a preference to follow Equation (1) over Equation (2).

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In addition to these listed bacteria, two strains of an additional clostridia which produce acetic acid or ethanol from CO and H2O or H2 and CO2 have been isolated. One is a Clostridium ljungdahlii ERI2 rod-shaped, gram positive, non-thermophilic anaerobe which gives superior acetic acid yields and operates at a low pH, which greatly enhances the recovery of the product, C. ljungdahlii ERI2 carries out a vigorous acetogenic fermentation of glucose. It also infrequently forms spores and carries out a primarily acetogenic fermentation of hexose or H2:CO2. It is motile with peritrichous flagellation. This new strain of C. ljungdahlii, referred to as ERI2, was isolated from a natural water source and was deposited, on December 8, 1992, with the American Type Culture Collection (ATCC) , Rockville, Maryland, accession no. 55380.
In preparing the products of the present invention, "mixed strains" of the bacteria enumerated hereinabove may be utilized. By mixed strains, it is meant a mixed culture of two or more anaerobic bacteria. This mixed strain, when utilized in the process described herein, produces organic acids (such as acetic acid and the like) or salts thereof, alcohols, hydrogen, SCP, etc.

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In the development of the present invention, new strains of anaerobic bacteria have been isolated which enact this conversion with high efficiency. In addition, modifications to the fermentation conditions can result in the production of ethanol instead of acetic acid in some strains. Depending on the specific microorganism(s) utilized, variables which must be considered in forming products from waste gases include nutrient constituents and concentrations, medium, pressure, temperature, gas flow rate, liquid flow rate, reaction pH, agitation rate (if utilising a Continuously Stirred Tank Reactor), inoculum level. maximum substrate (introduced gas) concent rations to avcid inhibition, and maximum product concentrations to avoid inhibition. In accordance with an exemplary embodiment of the present invention and as shown in Figure 1 of the drawings, a first step in the conversion process is the preparation of nutrient media (10) for the anaerobic bacteria. The content of the nutrient media will vary based on the type of anaerobe utilized and the desired product. The nutrients are constantly fed to a bioreactor or fermenter (12), consisting of one or more vessels and/or towers of a type which includes

-li-
the Continuously Stirred (CSTR), Immobilized Cell (ICR), Trickle Bed (TBR), Bubble Column, Gas Lift
Fermentere, or other suitable fermentation reactor.
the Within/bioreactor (12) resides the culture, either
single or mixed species, of anaerobic bacteria utilized in the gas conversion process. For the CSTRS, TBRs, Bubble Columns and Gas Lift Fermenters, these bacteria live dispersed throughout the liquid phase of the reactor, but for ICRs, the bacteria adhere to an internal packing medium. This packing medium must provide maximal surface area, high mass transfer rate, low pressure drop, even gas and liquid distribution, and must minimize plugging, fouling, nesting and wall channeling. Examples of such medium materials axe ceramic Berl saddles, Raschig rings or other high performance packings.
The waste gases (14) are continuously introduced into the bioreactor (12). The gas is retained in the bioreactor (12) for the period of time which maximizes efficiency of the process. Exhaust gases (16), containing inert and unreacted substrate gases, are then released. The liquid effluent (18) is passed to a centrifuge, hollow fiber membrane, or other

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filtration device (20) to separate out microorganisms that are entrained. These microorganisms (22) are returned to the bioreactor (12) to maintain a high cell concentration which yields a faster reaction rate (cell recycle).
A next step in the process is separation of the desired biologically produced product(s) from the permeate or centrifugate (24) . In the embodiment depicted in Figure 1, the permeate or centrifugate (24) is passed to an extraction chamber (26) where it is contacted with a solvent (28). The solvent (28) should have a high distribution coefficient for the desired end product, a high recovery factor, low toxicity to humans, low toxicity to the barteria, immiecibility with water, appropriately high boiling point, and form no emulsion with the bioreactor constituents. The distribution of solute between solvent and aqueous phase will determine the thermodynamic feasibility and the amount of solvent required to remove the end product- Typical solvents include secondary and tertiary amines in a suitable solvent, tributyl phosphate, ethyl acetate, tri-octyl phosphine oxide and related compounds in a suitable

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co-solvent, long chain alcohols, hexane, cyclohexane, chloroform, and tetrachloroethylene.
The nutrients and materials in the aqueous phase (30) pass back to the bioreactor (12) and the solvent/acid/water solution (32) passes to a distillation column (34) , where it is heated to a sufficient temperature to separate the solvent (28) from the acid and water (36). The solvent (28) passes from the distillation column (34) through a cooling chamber (38) to lower the temperature to the optimum temperature for extraction, then back to the extraction chamber (26) for reuse. The acid and water solution (36) passes to a final distillation column (40) where the desired end product {42/ is separated from the water and removed. The water (44) is recirculated for nutrient preparation.
Figure 2 shows a process for the production of the road deicer calcium magnesium acetate (CMA) (46) , from waste gas (48) . The process is identical to the acetic acid process of Figure 1 through solvent extraction. That is, identical organisms, nutrients and process conditions are used in continuous fermentation, including the reaction vessels.

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Similarly, cell recycle by hollow fiber membrane, centrifugation or other filtration device is identically employed in the process. Finally, the extraction of acetic acid in an extraction chamber, followed by recycle of the acid-free medium, is employed.
After extraction, the process for producing CMA differs greatly from the acetic acid production process of Figure 1. In the CMA process the solvent (50) containing acetic acid and a small amount of water is sent to a reaction vessel {52} for CMA production. The water content of the solvent stream is dependent upon the solvent used for acetic acid extraction. Again, solvents such as secondary and tertiary amines in a suitable co-solvent, tributyl phosphate, ethyl acetate, tri-octyl phosphine oxide and related compounds in a suitable co-solvent, long chain alcohols, hexane, cyclohexane,- chloroform and tetrachloroethylene may be employed with varying success. The reaction vessel (52) for CMA is most suitably a Continuous Stirred Tank Reactor (CSTR) , although other reactor systems may be employed. A mixture (54) of dolomitic lime and magnesium oxide in

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water is added to the solvent containing acetic acid and water. Reaction occurs to produce CMA in aqueous solution at or below the saturation level.
The CMA, water and solvent (56) are then sent to a settling device (58) to separate the aqueous and solvent phases. The solvent phase (60) is returned to the extraction chamber for recycle. The CMA/water (62) is sent to drying/pelletizing (64) to produce a pelletized CMA product.
Potassium acetate (KA) can be produced as an alternative product by substituting caustic potash (or potassium oxide) for the dolomitic lime. Since KA is produced as a 50 percent aqueous solution, drying and , pelletizing are not required.
Figure 3 shows a process for the production of ethanol from waste gas. As in Figure 1, waste gas (66) and nutrients (68) are fed into a reactor (70) containing a culture of microorganisms. The reactor may be any of the types described above in the narrative of Figure 1. The organism used in the ethanol production process must be capable of producing ethanol in place of acetic acid/acetate. In

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general, a low fermentation pH of 4.0 - 5.5 is required, coupled with a nutrient limitation. The bacteria listed hereinabove which are capable of operating at these reduced pH levels can be used in this process of ethanol production.
Waste gas is fed into the reactor containing the culture of organisms capable of ethanol production along with the required nutrients. Ethanol is produced as the product in a similar fashion as in Figure 1. Cell recycle (72) may be used to enhance the cell concentration in the reactor, but this operation is not required to make the process work. The permeate (74) from the cell recycle apparatus containing dilute ethanol in medium is sent to distillation (76), where the water (78) and ethanol (80) are separated. 95 percent ethanol exits the top of the distillation column and water (spent medium) exits the bottom of the column. The spent medium is sent back to the reactor as water recycle. The 95 percent ethanol is sent to a molecular sieve system (82) to produce anhydrous ethanol (84).

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Thus in accordance with the present invention it is now possible to produce valuable organic acids, alcohols, or organic acid salts by a gaseous substrate fermentation, not only reducing consumption of valuable chemical feedstocks, but also removing hazardous atmospheric pollutants from the waste gas streams of many industries. Previous processes to derive these chemicals biologically were based on fermentation of sugars.
In the processes described hereinabove, it is preferred that the process is conducted at higher than 1 atmosphere. Preferably, it is preferred that it be conducted at pressures up to 3 0 atmospheres and more preferably up to 20 atmospheres and most preferably up to 15 atmospheres.
The following specific examples are submitted to illustrate but not to limit the present invention. Unless otherwise indicated, all parts and percentages in the specification and claims are based upon volume.

EXAMPLE 1
PRODUCTION OF ACETIC ACID FROM CARBON BLACK WASTE GASES
This example is directed to a process utilized to convert waste gas of a composition which matches that of the furnace exhaust of carbon black manufacture to acetic acid. The waste gas has a composition of about 13 percent carbon monoxide, 14 percent hydrogen, and 5 percent carbon dioxide, with the remaining 68 percent largely nitrogen with traces of oxygen and sulfur compounds. The waste gases are produced as the result of partial oxidation of gaa or oil with insufficient air to form amorphous carbon, with about 1.2 pounds of carbon monoxide produced per pound of elemental carbon. These waste gases form a serious atmospheric contamination problem and also represent a valuable chemical feedstock resource not presently being recovered.
In the development of the present process, two distinct routes to produce acetic acid from carbon black waste gases were studied. The direct route converts CO and H2O or H2 and CO2, directly into acetic acid according to Equations (1) and (2), respectively.

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An indirect route involves the conversion of CO and H2O into H3 and CO2 by the water gas shift reaction, followed by production of acetic acid from H2 and CO2. This indirect route was found to be a less efficient utilization of the technology.
The acetogens tested are summarized in Table l. Among these bacteria that produce acetic acid directly from CO, A. kivui and the newly isolated strain, C. Ijungdahlii ERI2, show far superior rates for both CO and H2 utilization. Further experimentation proceeded using these two anaerobic bacteria.
There are obvious advantages to the bacteria utilizing carbon monoxide and hydrogen simultaneously. This would afford the most efficient use of the waste gases and remove the greatest amount of atmospheric pollutants.
Bench Scale Operation of the Described Process
to Produce Acetic Acid
As shown in Figure 4 of the drawings and in accordance with one embodiment of the present invention, a bench scale continuous conversion system is shown to include a BioFlo IIC fermentor (150) from New Brunswick Scientific Co., Inc.. Edison, NJ. The

fermentor (150) is equipped with an agitation motor, pH controller, foam controller, thermostat, dissolved oxygen probe, nutrient pump, and 2.5 L culture vessel. The working volume is variable (1.5-2.0 L). Other variable operational parameters include medium feeding rate (Dilution rate), gas flow rate {Gas retention time), agitation (rpm). The vented or exhaust gases exit the fermentor (150) through a condenser fixed to a vented hood via a water trap and a sampling port. The culture broth (152) is recycled through a cross-flow hollow fiber module (154) by a peristaltic pump (from Cole Parmer). The recycling rate is about 80-100 mli/min. The hollow fiber module (154) has the following characteristies; the surfacs area is 0.3 5 ft2, the pore size is 0.2 µm and the lumen diameter is 1 mm. The permeate (156) is pumped to a storage tank (158) (Feed storage). The culture cells are returned to the fermenter along line (155).
A counter-current acetic acid extraction system, including two stage mixer and settler components includes first and second mixers (160) and (162) and first and second settling tanks (164) and (166). The permeate (168) from storage (158) is pumped to mixer

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(160) through a flow controller (170) . The solvent (172) is pumped to mixer (162) from solvent storage (174) through a flow controller (176). Both mixer (160) and mixer (162) are equipped with a stirring mechanism to achieve good mixing of aqueous phase and solvent phase. The mixture of both phases from the mixers (160) and (162) is led to settlers (164) and (166), respectively. The phase separation is accomplished in the settlers. The aqueous phase (178) from settler (164) is pumped to mixer (162), the solvent phase (180) from settler (164) is pumped to a separator (182), the aqueous phase (184) from settler (166) is pumped to raffinate storage (156), and the solvent phase (188) from settler (166) is pumped to mixer (160) . The raffinate is recycled to the CSTR 50 along a line (190). This recycle line (190) is partially bled at (192) to remove inhbiting factors.
The solvent (180) loaded with acetic acid is pumped to a distillation flask (134) through a preheater (196) . The distillartion flask (194) is equipped with two thermocouples (196) and (198) to monitor and control temperature in the liquid phase and gas phase. The heating temperature for

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distlllation is aet to achieve maximum vaporization of the acetic acid. The acetic acid vapors are condensed in a condenser (100) and collected in a flask (102). The stripped solvent (104) is pumped through a cooling coil (106) to solvent storage (174) .
A bench scale operation of the described process as diagrammed in Figure 4 was fabricated in the laboratory to determine quantitative yields under optimized conditions. The nutrient mixture fed to the culture was as follows:
1. ao.O ml of a salt, composed of
KH2PO4 3-00 g/L
KaHPO4 3.00 g/L (NH4)2SO4, 6.00 g/L NaCl 6.00 g/L MgSO4.2H2O 1.25 g/L
2. l.0 g of yeast extract
3. 1.0 g of trypticase
4. 3.0 ml of PFN (Pfenning) trace metal
solution
FeCl2 * 4HaO 1500 mg ZnSO4 * 7H2O 100 mg MnCl2 * 4H2O 30 mg

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H3BO3 3 00 mg CoCl3 * 6H20 200 mg CuCl3 * H20 10 mg NiCl2 * 6H2O 20mg NaMoO4 * 2H2O 30mg Na3SeO3, 10 mg Distilled water 1000 ml 5. 10.0 ml of B vitamins
Pyridoxal HCl 10 mg Riboflavin 50 mg Thiamine HCl 50 mg Nicotinic acid 50 mg Ca-D-Pantotheinate 5C mg lapoic Acid 60 mg P-arainobenzoic acid 50 mg Folic acid 20 mg Biotin 20 mg Cyanocobalamin 50 mg Distilled water 1000 ml 6. 0.5 g of Cysteine HCl 7. 0.06 g of CaCl3.2H2O B. 2.0 g of NaHCO, 9. 1.0 ml of Resazurin (0.01%)

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10. 920.0 ml of distilled water
For use with A kivui, the nutrient solution was pH adjusted to 6.6, whereas for the new strain, C. ljungdahlii ERI2, the pH was adjusted to 4.9. The ability to operate at a lower pH is a great advantage in acetic acid recovery. The solution was then sparged for 20 minutes with a 20% CO2 and 80% N2 atmosphere, then transferred anaerobically and autoclaved for 15 minutes.
Numerous experiments were carried out with both Continuous Stirred Reactors (CSTR) and Immobilized Cell Reactors (ICR)- The results obtained are exemplified in the following data.
CSTR Experiments Utilizing the bacterial Strains A. kivui and C. ljungdahlii ERX2
The bench scale system operating with the CSTR and the anaerobic bacteria, C. ljungdahlii ERI2 and A. kivui, consisted of a New Brunswick Scientific Bioflo IIe fermenter, a hollow fiber membrane unit for cell recycle, and extraction and distillation columns.. Nutrient mixture was fed into the bioreactor at a rate of 3.2 cubic centimeters per minute. Capacity of the

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reactor was 2.5 liters, within which a constant fluid level of 1.5 liters was maintained. The fluid was agitated at variable rates of up to 1000 revolutions per minute with gas introduced at a rate of approximately 500 cubic centimeters per minute. Optimal gas retention times were in the range of three minutes. The gas feed varied with its uptake by the bacteria, which was in turn a function of the cell density.
The liquid from the bioreactor was passed to the hollow fiber membrane at a rate of 55 to 70 milliliters per minute. From the hollow fiber membrane, permeate was gathered at a rate of 1.5 milliliters per minute. Analysis of this permeate indicates the acetic acid/acetate concentration at this stage to range in excess of 20 grams per liter. Operating at a pH of 4.9, 42 percent of this product was in the acid form using C. ljnngdahlii ERI2. For A. Kivui, the acid yield was only 1.4 percent. Results of various runs for the two bacteria, including conversion rates and product yields are summarized in Tables 2 and 3.

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ICR Experiments Utilizing the Bacterial Strain u. ljungdahlii ERI2
An Immobilized Cell Reactor (ICR) , consisting of a 2 inch outside diameter by 24 inch tall glass tube packed with fabric to support the cells and Enkamat 7020 as an immobilizing medium was also tested in the acetic acid production process. With C. ljungdahlii ERI2 as the acetogenic anaerobe, 100 percent of the carbon monoxide and 79 percent of the hydrogen were converted at a gas retention time of 20 minutes. Acetic acid concentrations in the removed liquid were approximately 6.0 grams per liter. Results of the ICR studies are summarized in Table 4.
The ICR has a certain attractiveness on an industrial scale in that the energy costs to operate the reactor are reduced significantly. The proper selection of packing materials, solution phases, and pressures may yield production approaching that of the CSTR. Acetic Acid Recovery
Various solvents were tested for recovering acetic acid from the permeate, the results are summarized in Table 5. Tributyl phosphate was

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identified as having both a high distribution coefficient and a high boiling point. The solvent and permeate from the cell separator were commingled in a two stage extraction process. Alternatively, an extraction column could be used. Permeate was introduced into a 3 liter flask where it was mixed with incoming solvent. A ratio of 1 part solvent to 1 part permeate worked well and gave high recovery rates. The combined fluids were passed from the mixer to a 4 liter settling chamber where the solvent/acetic acid mixture separate as a lower density phase from the water and nutrients. Retention times of approximately 15 minutes were used in the settling tanks. The lower density phase was extracted and fed to a distillation flask. Tbe raffinate was passed from the first settler to a second mixer where it was contacted again with solvent, then removed to a second settling chamber. This allowed for more complete extraction of the acetic acid; acid recovery increased from 82 percent to greater than 96 percent using tributyl phosphate. The solvent/acetic acid mixture from this settler was returned to the first mixer,

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while the raffinate of water and organica was passed back to the bioreactor.
The distillation unit was a 5 liter flask with a boiling mantle. A common distillation column, with reflux, could be used for complete acid recovery. Because of the high boiling point of tributyl phosphate, nearly complete recovery is accomplished in one step. The solvent/acetic acid mixture was heated to 120 degrees C. with the acetic acid collected overhead in a condensing coil. In this single stage system, distillation efficiencies of 70 percent were achieved.
Solvent mixtures were also tried and distribution coefficients of mixed solvents are summarized in Table 6.
EXAMPLE 2
PRODUCTION OP ACETIC ACID FROM CARBON BLACK WASTE GASBS
AT HIGHER PRESSORES
Mass transport in the cellular reactions can be further enhanced by operating the system at increased pressures. Simple batch experiments were carried out to test the dynamics of this system. It was found that

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reaction rates increased in linear proportion to the pressure, with a corresponding reduction in effective retention time. Another advantage to operating at increased pressure is that reactor volume can also be reduced in linear fashion, i.e. operation at 10 atmospheres pressure requires a reactor with one tenth the volume of a reactor operating at 1 atmosphere. Figures 5 and 6 show the increase in cell density and acetic acid concentration, respectively, with the increased pressure. This acetic acid concentration far exceeds typical batch concentrations for a batch reactor at atmospheric pressure.
EXAMPLE 3 PRODUCTION OP ACETIC ACID FROM CARBON BLACK WASTE
GASES WITH SURFACTANTS
Mass transport is also increased by the use of surfactants. Table 7 presents the results of carbon monoxide uptake tests performed on C. ljungdahlii ERI2 in the pressure of various commercial surfactants. In each case, the control value of 100 (percent) represents CO uptake in batch fermentation, and the sample value, the percentage of the control in batch fermentation in the presence of the surfactant.

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TABLE 1
ACETOGENIC BACTERIA TESTED FOR CO, H2, AND CO2
CONVERSION
Bacterial Route Simultaneous Consumption of CO and H2
Direct Route
P. productus No
E. limosum No
A. noterae No
C. aceticum No
C. thermoaceticum No
S. sphaeroides No
A. woodii Yes
A. kivui Yes
C. ljungdahlii ERI2 Yes
Indirect Route
R. gelatinosa No
R. rubrum No

Table 2, Summary of ERI2 Experiments in the CSTR with Cell Recycle







9.30
0.056
730
80.75
74.5
2.3
9.7
0.07
0.
43
0.13
9.28
0.055
750
82.1
72.0
3.32
9.55
0.094
0.
52
0.15
6.14
0.061
750
73.6
46.5
4.11
12.78
0.125
0.
78
0.19
6.4
0.08
750
74.8
49.6
5.02
12.98
0.125
1.
05
0.19
4.?4
0.087
750
66.5 .
37.2

12.38
0.125
1.
08
0.23
4.91
0.10
750
66.5
50.2
4.53
10.73
0.05
1.
OB
0.24
6.05
0.102
750
65.5
58.1
3,27
11.49
0.076
1.
17
0.22
3.96
0.103
900
74.3
67.9
6.17
12.73
0.1
1.
31
0.21
2.89
0,117
900
64.1
33.9
5.91
11.69
0.04
1.
38
0.23
3.28
0.105
1000
74.6
51.3
7.30
12.83
0.13
1.
35
0.18
3.22
0.125
1000
73.1
54.0
10.25
13.57
0.08
1.
71
0.17
2.65
0.13
1000
68.9
44.0
11.0
l4. 63
0.12
1.
90
0.17
2.3
0.134
1000
66.0
38.7
11.1
20.59
0.113
2.
77
0.25
2.7
0.11
1000
72.7
67.7
8.37
25.62
0.27
2.
.88
0.34
2.4
0.11
1000
63.6
63.3
9.88
25.62
0.36.
2.
.95
0.30
2.55
0.122
1000
72.1
87.4
9.82
25.62
0.72
3
.12
0.32
3.0
0.13
1000
76.6
73.3
12.4
22.33
0.52
2
.90
0.23

table 3. summary of A, Kivui Experiments in the CSTR with Cell Recycle





5.0
0.03a
750
67.0
44.2
4.00
16.15
0.9o
0.24
4.4
0.958
750
S3.7
38.5
4.8
16.63
0.54
0.19
4.3
0.038
900
71.3
40.7
4.5
17.03
0.99
0.21
3.72
0.038
900
69.0
37.3
5.14
19,16
1.13
0.22
3.72
0.076
900
70.3
41.1
5.28
16.17
1.21
0.23
3.2
0.076
900
63.&
41.4
5.71
16. 85
1.23
0.23
2.8
0.076
900
61.5
29.1
5. DO
16. 15
1.22
0.23
2.8
0.076
1000
69.5
36.3
5.8
18.58
1.62
0.29
2.8
0.11
1D0O
70.2
41.6
5.9
18.4
1.84
0. 36
2.2
0.11
1000
64.0
28.0
7.2
16.5
2.1
0.3

Table 4. Fabric ICR Performance vith ERI2






Table 5. Acatic ACid Distribution Coefficient Study





Equilibrium Aqueous
Acetic Acid

Acetic Acid
Distribution
Solvent
Concentration z/L.
Coefficients
Kexane
6.559
0.0
Dacane
5.968
0.08
Chloroform
5.128
0.09
Kerosene
4.648
0.11
Hexaoecane
5.866
0.13
Dodecane
4.654
0.13
Dodecyl acetate
5.787
0.15
Dibutyl phosphate
4.615
0.18
Oleyl alcohol
5.114
0.28
Trioctylamine
3.765
0.31
Undeeyl alcohol
4.528
0.40
Ethyl acetate
4.550
0.41
Ethyl butyrate
4.665
0.42
Descyl alcohol
3.890
0.42
Octanol
4.358
0.45
Nonyl alftohol
3,470
0.55
2-ethyl-1-hexanol
3.308
0.77
3-methylcyclohexanol
2.110
1.26
Cyclohexanone
2.702
1.66
Tributyl Phosphate
1.657
2.38



o

ro

ro o



Ul

Table 6. Distribution Coefficients of Mixed Solvents




Solvent Mix


Distribution Coefficiencs
Percent Increase
Oleyl Alcohol Oleyl Alcohol Oleyl Alcohol
(10cc) (lOcc) + Cyc (lOec) + TBP
(1cc)
(1cc)
0.17 0.31 0.29
72 61
Oleyl Alcohol Oleyl Alcohol
(lOcc) + Cyc (lOcc) + TBP
(2cc) (2cc)
0.45 0.42
150 133
Oleyl Alcohol Oleyl Alcohol
(10ce) + Cyc (lOcc) + TBP
(3cc) (3cc)
0.36 0.42
100 133
Oleyl Alcohol Oleyl Alcohol
(lOcc) + Cyc
(lOcc) + TBP
(4cc) (Acc)
0.35 0.4 0
94 122
Oleyl Alcohol oleyl Alcohol
(lOcc) + Cya (10ne) + TBP
(6cc) (6cc)
0.52 0.65
188 261
Oleyl Alcohpl Oleyl Alcohbl
(lOcc) + Cyc (lOec) + TBP
(7cc) (7cc)
0.69 0.74
283 311

-36-
TABLE 7. CO CONSUMPTION BY ER12 IN THE PRESENCE OF SURFACTANTS


Control*
With Surfactant
DNAP (0.1%, v/v
100
0
Nondiet P-40 (0.1%, v/v)
100
0
Tergitol NP-10 (0.1%, v/v)
300
0
Tergitol Min Foam IX (0.1%, v/v)
100
0
Tergitol TMN-10 (0.1%, v/v)
100
0
Triton X-15 (0.1%, v/v)
100
0
Triton X-100 (0.1%, v/v)
100
0
Triton X-114 (0.1%, v/v)
100
0
Triton N-101 (0.1%, v/v)
i An
J- V M
5.83
Triton X-405 (0.1%, v/v)
100
7.82
Tergitol 8 {0.1%, v/v)
100
12.15
Triton N-42 (0.1%, v/v)
100 42.90
Witconol NS-500K (0.01%, w/v)
100
79.08
Tween 8S (0.1%, v/v)
100
62.16
Witconol H-33 (0.1%, v/v)
10G
90.12
Witconol 6903 (0.1%, v/v)
100
92.39
Tween 80 (0.1%, v/v)
100
97.15
Arlacel 83 (0.1%, v/v)
100
97.43
Span SO (0.1%, v/v)
100
99.12
Tyloxapol (0.1%, v/v)
100
104.86
Witconol 5906 (0.1%, v/v)
100
108.42
Span 85 (0.1%, v/v)
100
124.85
W-1 (O.001%, w/v) First time Second time regas
100 100
105.89 0
Brij 96 (0.004%, w/v) Firat time Second time regas
100
100

107.98
0

-37-
EXAMPLE 4
PRODUCTION OF CMA FROM CARBON BLACK WASTE GAS
Carbon black waste gas containing about 14 percent CO, 17 percent H2 and 4 percent CO2, as the major components in N2 is sparged into a 160L continuous stirred tank reactor, maintained at 6 atm 37°C, and containing Clostirxdium ljungdahlii isolate ER12 ATCC deposit 55380. The waste gases axe produced as the result of partial oxidation of hydrocarbons with insufficient air to form amorphous carbon, with about 1.2 pounds of carbon monoxide produced per pound of elemental carbon. These waste gases form a serious atmospheric contamination problem and also represent a valuable chemical feedstock resource net: presently being recovered. The gas retention time (defined as the ratio of the reactor volume to the gas flow rate an standard conditions) is maintained at 0.52 min. An aqueous liquid medium containing water, base salts, B-vitamins, a nitrogen source and a sulfide source is fed to the reactor at a liquid dilution rate (defined as the ratio of the liquid flow rate to the reactor volume) of 1.05 hr-1. The agitation rate in this reactor is 322 rpm, the temperature is 37°C and the

-38-
operating pH is 5.03. Under these conditions, the conversion of CO was 83 percent and the conversion of H2 was 54 percent. A hollow fiber membrane cell recycle unit is used to maintain a cell concentration of 10.5 g/L inside the reactor. The dilute acetic acid/acetate product stream from the reactor containing 13.2 g/L acetic acid/acetate is sent to a three stage countercurrent extraction device, where it is extracted with solvent. The solvent to feed ratio is 1 to 4. The acetic acid in the acetic acid/acetate product stream is 3.7 g/L. The acetic acid concentration in the solvent leaving the extractor is 16.7 g/L. Water (medium) from extraction is sent back to the fermenter as recycle.
Dolomitic lime/MgO is added to the acetic acid directly in the solvent phase to form CMA. After reaction the saturated CMA solution is sent to drying and pelletizing 1.15 lb of CMA containing a Ca2+/Mg2+ molar ratio of 3/7 is formed per pound of acetic acid.

EXAMPLE 5
PRODUCTION OF ACETIC ACID FROM CARBON BLACK WASTE GAS
Carbon black waste gaa containing about 14 percent CO, 17 percent H2 and 4 percent CO2 in N2 is sparged into a 144 L trickle bed reactor operating at 1.58 atm, 37°C and containing Clostridium Ijungdahlii isolate ER12 ATCC deposit 55380. A trickle bed reactor is a column packed with a commercial packing such as Raschig ringa or Berl saddles in which liquid and gas are contacted with each other due to flow through the column. In the present example, the liquid and gas both enter the column from the top in a cocurrent fashion, although countercurrent flow (gas entering the bottom, liquid entering the top) is possible. The gas retention time is maintained at 0.46 min and the liquid medium dilution rate is 0.57 hr-1. The liquid medium contains the same constituents as in Example l. Agitation in the reactor is provided by liquid recirculation, using a recirculation rate of 6.0 gpm. The operating pH in the reactor is 5.05. Under these conditions, the CO conversion is 57 percent and the H2 conversion is 58 percent. A hollow

-40-
fiber unit is used to maintain a cell concentration of 13.6 g/L inside the reactor.
The dilute acetic acid/acetate product stream containing 6.4 g/L combined acetic acid/acetate and 2 g/L acetic acid is sent to a three stage countercurrent extraction column. The solvent to feed ratio is 1:4. The acetic acid in the solvent leaving the extractor is 10 g/L. Water (medium) from the extraction unit is sent back as recycle to the reactor.
The solvent containing the acetic acid is sent to distillation to recover the acid and solvent. A vacuum solvent distillation column and an acetic acid distillation column axe used in the sepsration. Glacial acetic acid is produced as the final product. EXAMPLE 6
PRODUCTION OF POTASSIUM ACETATE PROM CARBON BLACK WASTE GAS
The carbon black waste gas of Example 4 is used to make potassium acetate instead of CMA. All fermentation and solvent extraction conditions remain the same. Caustic potash (potassium oxide) is used to react with the acetic acid to form a 50 percent



-41-
solution of potassium acetate directly in the solvent phase. EXAMPLE 7
PRODUCTION OF SCP FROM COKE OVEN WASTE GAS A coke oven waste gas containing about 6 percent CO, 2 percent CO2, 57 percent H2, 5 percent N2, and 27 percent gaseous hydrocarbon is fed to a continuous stirred tank reactor with cell recycle as described previously in Example 4. The reactor is used to produce a product such as dilute acetic acid or ethanol. In addition, the cell concentration inside the reactor is 13.6 g/L. These cells (microorganisms) can be harvested to produce bacterial single cell protein as an animal feed. A purge stream from the reactor containing cells is sent to a dryer to process dry single cell protein. EXAMPLE 8
PRODUCTION OF H2 FROM REFINERY WASTE GAS Refinery waste gas containing about 45 percent CO, 50 percent H2 and 5 percent CH4 is sparged into a 1L CSTR operating at 50°C and a few inches of water pressure containing Bacillus emithii isolate ERIH2 which was deposited on March 18, 1993 with the

-42-
American Type Culture Collection, Rockville, Maryland and given deposit accession no. 55404. The medium to the reactor is 1.0 g/L corn steep liquor. CO in the waste gas is converted along with water to CO2 and H2. With a 90 percent conversion, the exit gas stream contains 3.2 percent CO, 64.4 percent H2, 2 8.8 percent C02 and 3.6 percent CH4. The CO, CO., and CH4 are removed from the gas stream by solvent extraction. EXAMPLE 9
PRODUCTION OF OTHER CHEMICALS FROM CARBON BLACK WASTE GAS
Carbon black waste gas containing about 14 percent CO, 17 percent H2 and 4 percent CH4 in N2 is sparged into a 1L CSTR operating at 37oc and a few inches of water pressure. The medium in the reactor is a basal salts mixture containing water, B~vitamins, salts and minerals. The single or mixed culture in the reactor produces a liquid phase product of methanol, propanol, butanol, propionic acid, butyric acid or other desirable product. The system is set up essentially the same as in Example 6. Following dilute product formation, the product is recovered in a suitable product recovery system consisting of

-43-
extraction, distillation or other well-known product recovery techniques. If multiple products are produced, a stagewise product recovery system is employed.
Thus, it will be appreciated that as a result of the present invention, a highly effective improved process for converting waste gases to acids, including organic acids, e.g., acetic acid, alcohols, hydrogen, SCP or organic acid salts is provided by which the principle objective, among others, is completely fulfilled. It is contemplated and will be apparent to those skilled in the art from the preceeding description and accompanying drawings that modifications and/or changes may be made in the illustrated embodiments without departure from the present invention. Accordingly, it is expressly intended that the foregoing description and accompanying drawings are illustrative of preferred embodiments only, and are not limiting, and that the true spirit and scope of the present invention be determined by reference to the appended claims.

-44-WE CLAIM:
1- A process for producing acetic acid, or a salt thereof,
comprising the steps of:
(a) providing a continuous flow of gas selected from the
group consisting of:
(i) a gas comprising carbon monoxide;
(i i) a gas comprising carbon monoxide and hydrogen; 5 and (iii) a gas comprising hydrogen and carbon dioxide; into a bioreactor;
said bioreactor comprising an aqueous nutrient medium and anaerobic, acetogenic bacterium C- ljungdahlii ERI-2;
(b) directing a continuous flow of said aqueous nutrient
medium into said bioreactor;
(c) fermenting said gas ad said nutrient medium using said
anaerobic, acetogenic C. ljungdahlii ERI-2 bacterium at a pH of
less than 5.1;
wherein at least 2 g/L of said acetic acid is produced in free acid form in said bioreactor in a liquid effluent -
2- The process as claimed in claim 1 wherein the gas
comprises carbon monoxide.
3. The process as claimed in claim 1 wherein the gas
comprises carbon dioxide and hydrogen.
4- The process as claimed in claim 1 wherein said gas further
comprises nitrogen or methane.
5. The process as claimed in claim 1 wherein said gas (i) or
(ii) further comprises carbon dioxide.

- 45 -
6. The process as claimed in claim 1 wherein the gas is produced by an industrial process selected from the group consisting of the manufacture of carbon black, the production of ammonia, the production of methanol, the production of coke, and the refining of petroleum.
7. The process as claimed in claim i wherein said bioreactor
is a continuously stirred tank reactor, an immobilized microbial
cell bioreactor, a trickle bed bioreactor, a bubble column
bioreactor, or a gas lift bioreactor.
8. The process as claimed in claim 1 wherein said bioreactor
is maintained at a pressure of greater than one atmosphere.
9. The process as claimed in claim 1, wherein said process is
performed at up to 15 atmospheres of pressure.

10. The process as claimed in claim 1 further comprising:
isolating said acetic acid from said liquid effluent.
11. The process as claimed in claim 10, further comprising:
distilling said isolated acetic acid.
12. The process as claimed in claim 1 wherein said bioreactor
comprises a mixed culture of two or more anaerobic acetogenic
bacteria, wherein one of said bacteria is C. 1jungdahlii ERI-2 and
another bacteria is selected from the group consisting of Aceto-
bacterium kivui, A, woodii, Butyribacterium methylotrophicum,
Clostridium aceticum, C. acetobutylicum, C.formicaceticum,
C.kluyveri, C- thermoaceticum, C. thermocellum, C.thermohydrosul-
furicum, C.thermosaccharolyticum, Eubacterium limosum, and Pepto-
streotococcus products.
13. The process as claimed in claim 1, wherein the pH in said
bioreactor is about 4.9.
10.
15. The process as claimed in claim 11, wherein said acetic
acid is contacted with dolomitic lime and magnesium oxide and
dried, thereby producing calcium magnesium acetate.
16. The process as claimed in claim 11, wherein said acetic
acid is contacted with potassium hydroxide, thereby producing
potassium acetate.
16. The process as claimed in claim 1, wherein said
bioreactar comprises a mixed culture of two or more anaerobic
acetogenic bacteria, wherein one of said bacterium is C.
ljungdahlii ERI-2 and another bacterium is C.ljungdahlii PETC,
17. The process as claimed in claim 1, wherein said acetic
acid and said anaerobic, acetogenic C. ljungdahlii ERI-2
bacterium are separated by passing the product of step c) through
a filtration device, returning the anaerobic, acetogenic C.
ljungdahlii ERI-2 bacterium to the bioreactor to maintain a high
anaerobic, acetogenic C- ljungdahlii bacterium concentration and
producing a C- ljungdahlii ERI-2 bacteria-free acetic acid-
comprising stream.
18. The process as claimed in claim 18, wherein said
separating is accomplished by a step selected from the group
consisting of centrifugation, filtration, settling, and ultra-
filtration .

19. The process as claimed in claim 1 wherein said bioreactor
further comprises a surfactant.
20. The process as claimed in claim 1, wherein said gas (i i)
comprises less than 15% carbon monoxide or less than 15%
hydrogen.
21. The process as claimed in claim 1, wherein said acetic
acid is farmed according to the reactions.

- 47 -
4C0 + 2H O => CH COOH + 2C0
2 3 2
4H + 2C0 => CH COOH + 2H O 2 2 3 2
22. The process as claimed in claim 1, wherein the unreacted
gaseous components are vented from said bioreactor.
23. The process as claimed in claim I, wherein said anaerobic
acetogenic C. ljungdahlii ERI-2 bacterium is removed from said
liquid effluent to form a permeate comprising acetic acid and
nutrient medium.
24. The process as claimed in claim 24, wherein said removed
anaerobic, acetogenic C.ljungdahlii ERI-2 bacterium is returned to
said bioreactor.
25. The process as claimed in claim 24, wherein said permeate
is contacted with a solvent in an extraction chamber to form a
solvent phase comprising acetic acid and an aqueous phase
depleted in acetic acid.
26. The process as claimed in claim 26, wherein said aqueous
phase comprising nutrient medium, acetate and some acetic acid is
returned to said bioreactor.
27. The process as claimed in claim 26, wherein said solvent
phase is distilled at an elevated temperature to separate said
acetic acid and water from said solvent.
28. The process as claimed in claim 27, wherein said solvent
is returned to said extraction chamber.
29. The process as claimed in claim 28, wherein said acetic
acid is separated from said water in a final distillation column
and said water is recycled to said bioreactor.
30. The process as claimed in claim 29, further comprising:
adding dolomitic lime/MgO to said solvent phase to form a
saturated calcium magnesium acetate solution;

- 48 -
removing said solvent from said saturated calcium magnesium
acetate solution in a settling device and returning said solvent
to said extraction chamber; and
drying said calcium magnesium acetate solution and pelleting it
in a settling tank, whereby pelleted calcium magnesium acetate is
formed from processing of said gas.
31. The process as claimed in claim 30, further comprising:
adding potassium oxide to said solvent phase to form a saturated
potassium acetate solution; and
removing said solvent from said saturated potassium acetate
solution in a settling tank and returning said solvent phase to
said extraction chamber,
drying potassium acetate solution farmed from processing of said
gas.
Dated this 30th day of September 2002

A process for producing acetic acid, or a salt thereof,
comprising the steps of:
(a) providing a continuous flow of gas selected from the group consisting of:
(i) a gas comprising carbon monoxide;
(ii) a gas comprising carbon monoxide and hydrogen; and
(iii) a gas comprising hydrogen and carbon dioxide;
into a bioreactor;
said bioreactor comprising an aqueous nutrient medium and anaerobic, acetogenic bacterium C. 1jungdahlii ERI-2;
(b) directing a continuous flow of said aqueous nutrient medium into said bioreactor;
(c) fermenting said gas ad said nutrient medium using said anaerobic, acetogenic C. 1jungdahlii ERI-2 bacterium at a pH of less than 5.1;
wherein at least 2 g/L of said acetic acid is produced in free acid form in said bioreactor in a liquid effluent-


Documents:

00566-cal-2002 abstract.pdf

00566-cal-2002 claims.pdf

00566-cal-2002 correspondence.pdf

00566-cal-2002 description(complete).pdf

00566-cal-2002 form-1.pdf

00566-cal-2002 form-2.pdf

00566-cal-2002 form-3.pdf

566-CAL-2002-ASSIGNMENT.pdf

566-CAL-2002-CORRESPONDENCE 1.1.pdf

566-CAL-2002-CORRESPONDENCE 1.2.pdf

566-CAL-2002-CORRESPONDENCE.pdf

566-CAL-2002-FORM 13.pdf

566-CAL-2002-FORM-27.pdf

566-CAL-2002-OTHERS.pdf

566-CAL-2002-PA.pdf


Patent Number 194084
Indian Patent Application Number 566/CAL/2002
PG Journal Number 30/2009
Publication Date 24-Jul-2009
Grant Date 06-May-2005
Date of Filing 30-Sep-2002
Name of Patentee BIOENGINEERING RESOURCES INC.
Applicant Address 1650, EMMAUS ROAD, FAYETTE VILLE, ARKANSAS
Inventors:
# Inventor's Name Inventor's Address
1 GADDY JAMES L. 2207 TALL OAKA ROAD DRIVE, FAYETTEVILLE, ARKANSAS
PCT International Classification Number C12P07/06,C12P 07/40
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA