CA1134966A - Method and apparatus for processing waste - Google Patents

Abstract

Abstract of the Disclosure A method and apparatus for processing biodegradable organic waste in an aqueous medium, which method comprises serially passing an organic waste-containing aqueous medium through a first, hydrolytic redox bioreactor and a second, anaerobic bioreactor, with each bioreactor containing immobilized microbes. The apparatus comprises the two bioreactors which are serially connected. The disclosure also provides an apparatus and process for determining the biochemical oxygen demand of an organic waste in an aqueous medium.

Description

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~3~66 8ackgrount o~ th~ Snventlon Th~s al~closure ?ert~ln~ to organic waste ~roce~sl~q.
Moro particularly, ~hl~ dlsclo3ure p~rtain~ to n ~ethod and app~ratus for processing hiodogr~t~ble org~nio wasta in an ~qu~ou~ ~ediu~. The disclosure al~o pert~ins to fi~ appara-tus ~nd proces6 ~or deterslning the ~iochemical ox~gen ~em~nd ~OD) of ~n organlc waste ~n ~n aqu~ou~ mediu~.
A vsriety o~ wethods ~or ~he di3rosal oi org~nic w~e, ~lther industrl 1 or agricultural. Are av~l~a~le.
Some of the~e ~etho~s, such as buri~ d-flll, ~uwplng at se~, and the lik~, h~Ye 3 n~gatlve ~nvi~Dn~en~al ~pa~t ~nd ar~ 30t deslr~ble. On the other h~nt, ~e~ho~s ase ~vail~ble or convertinS orgrnic w~t- to a:30urc~ o~ en~rgy and/o~ a usnbl- produ~t and lnclude, ~ong othe:s, biologio~l a~robic ferment~tion, biological ~naero3:ie ~erment~tion, thcr~ophilie aor~7ic ~iS1gl:~tlon, dest:u ti~ dlsit1llhtio~, (inolu~ing hy~_o-carboni2ntlon ~1 pyroly~ n elr.er~t~on. ~. J. J~well et al., "Methar.e Gen~r~tlon ~ m Ag:rieultusal W~t~s~QVi~W
o~ Concept and ~utu~ ppl:Lestlon~, P~p~r . ~74-107, pr~ n:e~ A'C t~- 1974 ~orth~e~t ~gional ~-et.~ng o~

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American Society of Agricultural Engineers, West Virginia University, Morgantown, West Virginia, August 18-21, 1974.
Of this latter group, biological anaerobic fermentation appears to be the most promising and has received consider-able attention in recent years.
Current interest Ln blological anaerobic fermentation appears to be due, at least in part, to the development of the anaerobic ilter. See, for example, J. C. Young et al., Jour. Water Poll. Control Fed., 41, R160 (19691; P. L.
~cCarty, "Anaerobic Processes", a paper presented at the 3irmingham Short Course on Design Aspects of siological Treatment, International Associatlon of Water Pollution Research, 3irmingham, England, September 18, 1974; and J. C.
Jennett et al., ~our. Water Poll. Control Fed., 47, 104 (1975).
The anaerobic filter basically is a rock-filled bed similar to an aerobic trickling filter. In the anaerobic filter, however, the waste is distributed across the bottom or the . filter. The flow of waste is upward through the bed of rocks so that the bed is completely submerged. Anaerobic micro-organisms accumulate in the void spaces between the rocks and provide a large, active biological mass. The effluent typically is essentially free of biological solids. See J. C. Young et al., supra at R160.
The anaerobic filter, however, is best suited for the treatment of water-soluble organic waste. J. C. Young et al., supra at R160 and R171. Furthermore, verv long reten-tion times of the waste in the filter are required in arder to achieve hlgh reductions in the chemical oxygen demand (COD) of the waste to be treated. That is, depending upon the COD of the waste stream, reductions in such COD oi' from 36.7 percent to 93.4 ercent requircd retention times of

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, from 4.5 hours to 72 hours. J. C~ Young at al., supra at R167. In addition, such results were achieved tith optimized synthetic wastes which were balanced in carbon, nitrogen, and phosphorus content and which had carefully adjusted pH values Accordingly, there remains a great need for a waste pro-! cessing method which can tolerate the presence of solids in the waste stream and which can more rapidly process the waste on an "as is" basis, Summary of the Invention In accordance with the prssent invention, there is pro-vided a method for processing biodegradable organic waste in an aqueous medium which comprises serially passir.g an organic waste-containing aqueous medium through a first immobilized microbe bioreactor and a second immobilized microbe bioreactor, in which:
A. the first bioreactor is a hydrolytic redox bio-. re~ctor containing a porous inorganic support which is suit-able for the accumulation of a biomass, and ~. the second bioreactor is an anaerobic bioreactor containing a porous inorganic support ~hich is suitable for the accumulation of a biomass.
If desired, however, the second bioreactor can be an anaerobic bioreactor comprising a controlled-pore, hydro phobic inorganic membrane which contains a parous inorganic support which is suitab}e for the accumulatian of a biomass.
Also in accordance with the present invention, there is provided an apparatus for processing biodegradable organic waste in an aqueous medium which comprises a first immobilized microbe bioreactor sexially connected to a second immobilized microbe bloreactor, in which:

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A the first bioreactor i~ a hydrolytic redox blo-re~ctor containing a porous inorganic 3upport whlch is suit-able for th~ accumulation of a biom~ss, Rnd ~ the ~econd bior~acto~ is an an~ero~lc kioreactor co~taining a porous inorglmic support which ls s~itdble for the accw~ulation of ~ biol~ss Again, if de3ired, the ~econd bior~actor can be an an~erobic bioreactor comprlsing ~ controlled-pore, hydro-phobic inoryanic ~embrane which contain3 a porous inorganic ~upport whlch 18 suitable ~or the accumulntion of a biomass Thc present invention al~o provldes an apparatus for the det-rmination o~ the biochemical oxygen d~mand o~ an organic waste in an ~queous medlum which csmpri~es a sampling and/or sensing means serially connected to an immobilized mi~robe bioraactor which ln ~urn is serlally connected to a s~mpling and/or sens~ng means, ln which the bioreac~or is an ~ero~ic ~ioreactor containlng a porous inorganic support which iQ ~uita~le for th~ ~ccu~ulatlon of a ~io~a e, The present i~vcntlon ~urther provides ~ method for the determination of the biochemical oxygen demand of an organic wnste in ~n asu~ous medium whLch comprises s~-ially passing a~ organic waste-containing aqueous ~edlu~ through a fi~st ~ampling ~nd/or s~nsin~ means, an immobiliz2d mlcrobe bio-ra~ctor, ~nd a second 3a~plins L~djor ~en~ing m~ans, in which the bioroactor is n aeroblc bior~acto; cont~ininS a porou- inorganic ~upport which ~3 ~uitable ~or the accumu-l tion of a biom ~3.
3rief DescrlPtion o~ the Drawings : . The drawings :(Fig. 1 & Fig. 2) illustrate two embodi- :
: ments of the present invention as described by Examples 1 and 2, and E~amples : - 4 -, 1`:'-- "'`
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4-7, respectively, which embodiments comprise treating sewage or other waste to give an effluent having a signi-ficantly reduced oxygen demand and methane as a gaseous pro-duct.

Detailed Description of the Invention As used herein, the term "biodegradable" meang only that at least some of tha organlc waste to be treated must be capable of being degraded by microorganisms. As a practical matter, at least about 50 percent by weight of the organic waste usually will be biodegradable. It may be necessary or desirable, however, to utiliza in the processinq method of the present invention waste having substantially lowsr levels of biodegradable organic matter.
Thus, the organic waste or the aqueous medium containing such waste can contain non-biodegradable organic matter and inorganic materials, provided that the organic waste and .aqueous medium are essentially free of compounds having signi-ficant toxicity toward the microbes present in aither reactor.
In general, the nature of the aqueous medium is not cri-tical. In most instances, water will constitute at least about50 percent by weight of the medium. Preferably, water will constitute ~rom about 80 to about 98 percent by weight of the aqueous medium.
Frequently, the waste stream to be treated by the ~ro-cessing method of the present lnvention can be used without any pretreatment. Occaslonally, i' may be desirable or necessarv to dilute the waste stream with water, to separate ;~ ~from the waste stre~m excessive amounts of solids or excessivaly coarse sollds which might interfere with the pumplng equlpment necessary to move ~- a~ueous medlum through the processlng .~ _5_ : ., ; ~ , : .
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. . ~.3~ ;6 apparatus of the present Lnvention, or to increase the pH of the a~ueous medium by, for example, the additlon of an inorganic or organic base, such as potassium carbonate, sodium hydroxide, triethylamine, and the like. Alternativel~, 801id or es3entially nonaqueous organic waste can ba diluted ! with water as desired.
The term "bioreactor'', as used herein, is a contraction of "biochemical reactor" and, thersfore, means that the chemical transformations or conversions taking placa therein are carried out by living organisms. ~he term "immobilized microbe bioreactor" is used to identify such living organlsms as microbes which are in an immobilized state ~as that term is used by those having ordinary s~ill in the art).
As already indicated, both the first and second bio-reactors of the processing method and apparatus of the pre-sent invention contain a porous inorganic support which is suitable for the accumulation of a biomass. In the case o~
. the second bioreactor, the inorganic support optionally is contained within a controlled-pore, hydrophobic inorganic membrans.
As a matter of conveniencaj ths lnorganic support in the two bioreactors will be of the same ty2e, although such is not required. Preferably, the inorganic support in each bioreactor is a porous, high surface area inorganic support which is suitable for the accumulation of a high biomass sur-face within a relatively 3mall volume. More preferably, at least 70 percent of the pores of the inorganic support will have diameters at least as large as the smallest major dimen-sion, but less than about five times the largest major dimen-~ion, of the microbes present in the bioreactor. Most . :.
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~L3~66 pre~erably, the average dlameter ot the pores of the inorganic support is Ln the range of ~rom about 0.3 to about 220~.
As used herein, the expression "high sur~ace area inor-ganic support" means an inorganic support having a surface area greater than about 0.01 m2 per gram of support. In gen-eral, surface aroa is determined by lnert gas adsorption or the 8.E.T. method; see, e.g., S.J. Gregg and K.S.W. Sing, "Adsorption, Surface Area, and Porosity", Academic Pre5s, Inc., New York, 1967. Pore diameter~, on the other hand, are most readily determined by mercury intrusion porosimetr~l; see, e.g., N.M. Winslow and J.J. Shapiro, "An ~nstrument for the Measure-ment of Pore-Size Distribution by Mercury Penetration'', ASTM
Bulletin NQ. 236, Feb. 1959.
The inorganic support in general can be either sLliceous or nonsiliceous metal oxides and can be either amorphous or crystalline. Examples of siliceous materials include, among others, glass, silica, halloysite, ~aolinite, cordierite, wollastonite, bentonite, and the like. Examples of nonsili-ceous metal oxides include, among others, alumina, spinel, apatite, nickel oxide, titania, and the like. The inorganic support also can be composed of a mixture o~ siliceous and nonsiliceous materials, such as alumina-cordierite. Cordierite and clay (i,e., halloysite and/or kaolinite) materials such as those employed in the examples are preferred.
For a more complete description of the inorganic support, see application Serial No. 833,278, filed September 14, 1977, in the names of Ralph A. Messing and Robert A. Oppermann, now U.S. Patent No. 4,153,510.
As already indicated, the inorganic support in each bio-reactor provides a locus for the acoumulation of microbes.~ha ~orQu9 n~ure o~ :ha support not only permits the .

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'~13~6 accumulation o~ a relatively high biomass per unit volume of bioreactor but also aids ln the retention of the biomass within each bioreactor.
As used herein, the term "nticrobe" (and derivatlons thereof) Ls meant to include any microorganism which degrades organic materials, e.g., utilizes organic materials as nutri-ents. This ~erminology, then, also lncludes microorgani9ms which utilize as nutrients one or more metabolites of one or more other microorganisms. Thus, the term "microbe", by way of illustration only, includes algae, bacteria, molds, and yeasts. The preferred microbes are bacteria, molds, and yeasts, with bacteria being most preferred.
In general, the nature of the microbes present in each bioreactor is not critical. It is only necessary that the biomass in each bioreactor be selected to achieve the desired results. Thus, such biomass can consist of a single microbe species or several species, which species can be known or unknown (unidentified). Furthermore, the biomass in each bio-reactor need not be strictly aerobic or strictly anaerobic, provided that the primary functions of the two bioreactors are consistent with their designations as hydrolytic redox and anaerobic bioreactors, respectively. The term "primary func-tion" as used herein means that at least 50 percent of the - biomass in each bioreactor functions in accordance with the reactor designation.
Stated differen-tly, the demarcation line or zone between a hydrolytic redox function and an anaerobio function is not critical and need not always lie between the two reactors.
In practice, such demarcation line or zone can vary from the midpoint of the first bioreactor to the midpoint of the second bioreactor and to some extent can be controlled by regulating the amount of oxygen dissolved in the waste stream.
As used herein, the term "hydrolytlc redox'' refers to the function of the first bloreactor which i9 to break down any macromolecules present lnto smaller units, e.g. monomers and oligomers, by hydrolysis and oxldation-reduction reactions.
In so doing, the first bioreaator also serves to deplete the aqueous medium of dissolved oxyqen.
It should be apparent, therefore, that the first bio-reactor is not an aerobic bioreactor as the term "aerobic"is used in the prior art. The aqueous medium is no-t aerated continuously or even saturated with air or oxygen. 3ecause residual oxygen in the medium i9 depleted, however, at least some oxidation-reduction occurs aerobically.
Examples of microbes ~hich can be employed in the hydro-lytic redox bioreactor include, among others, strict aerobic bacteria such as Pseudomonas Eluorescens, Acinetobacter -calcoaceticus, and the like; facultative anaerobic bacteria such as Escherichia coli, Bacillus subtilis, Stre~tococcus faecalis, Staphylococcus aureus, Salmonella typhimurium, Klebsiella pneumoniae, Enterobacter cloacae, Proteus vulqaris, and the like; anaerobic bacteria such as Clo~t~idium butyricum, Bacteroides fra2ilis, Fusobacterium necroohorum, Leptotrichia buccalis, Veillonella parvula, Methanobacterium _ _ , formicicum, ethanococcus mazei, ?Nethanosarcina bar~eri, Peptococcus anaerobi~s, Sarcina ventriculi, and the like;
molds such as Trichoderma viride, .~s~irqillus niger, and the liXe; and yeasts suoh as SaccharomYces cerevisiae, Saccharomyces ellipsoideus, and the like. Obviously, the hydrolytic redox bioreactor should not contain either strict aerobes or strict anaerobes only.

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Examples of mlcrobe3 which can be utilized in the anaerobic bioreactor lnclude, among others, ~acultatLve anaerobic bacteria, anaeroblc bacteria, and yeasts such aq those listed above. Of course, the anaerobic bioreactor should not contain strict aerobes only, although the presence of such microbes usually is not harmful.
As already pointed out, the microbes employed ln each bioreactor are selected on the basis of the results desired.
I~ a particular product is not recuired, the choice of microbes can be made on the basis o~ wa9te converqion e~iciency, operatlng parameters such as temperature, flow rate, and the like, microbe availability, microbe stablllty, or the like.
I~, on the other hand, a particular produot i9 desired, the microbes typically are selected to maximize production ol that product. By way of illustration only, the table below indicates some suitable combinations oi miorobes whioh will yield the indicated produot.

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o 1~34~66 In general, the microbes are Lntroduced lnto each bio-reactor in accordance wlth aonventional procedures. For exampla, the bioreactor can be seeded with the desired microbes, typically by circulating an aqueous microbial suspension through the bioreactor. Alternatively, the microbes can be added to the waste stream at any desired point. }n cases where the waste stream already contains the approprlate types of mlcrobes, the passage of such waste through the t~/o bioreactors will in due course establish the requisite microbe colonies therein. Of course, the bioreactors can be a~sembled using inorganic support having microbes immobllized thereon.
~ he second bioreaator optionally contains a controlled-pore, hydrophobic inorganic membrane. As used herein, the term "membrane" refers to a continuous, formed article, the shape and dimensions of which are adapted to process requirements. Thus, the membrane can be a flat or curved sheet, a three-dimensional article such as a rectangular or cylindrical tube, ox a complex monolith having alternating channels for gas and aqueous medium.
A9 a practical matter, the membrane most often will consist of a cylinder, open at both ends to provide passage of aqueous mediu~ through its length. Wall thiakness is not critical, but must be suf~icient to permit the membrane to withstand process conditions without deformation or breakage. In gen-eral, a wall thickness of at least about 1.0 mm is desired.
The membrane can be either siliceous or nonsiliceous metal oxides. Examples of siliceous~materlals include, among others, glass, silica, wollastonite, bentonite, and the like.
Examples of nonsiliceous metal oxides include, among others, alumina, spinel, apatite, nickel oxide, titania, and the like.
Siliceous materials are preferred, with glass and silica being ,.

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most preferred. Of the nonslliceous metal oxides, alumlna is preferred.
The membrane mu9t ha~e a controlled poro91ty such that at least about 90 percent of the pores have diameters of from about 1O0A to about 10,000A. Preferably, the pore diameter range will be from about 900A to about 9,000A, and most pre-ferably from about 1,500 to about 6,000R.
Methods of preparing inorganic membranes having controlled porosity as described above are well known to those ha~ing ordinary skill in the art and neèd not bs discu8sed in detail here. See, e.g., U.S. Patent Nos. 2,106,764, 3,485,687, 3,549,524, 3,673,144, 3,782,982, 3,827,893, 3,850,849, and 4,001,144, British Patent Specification No. 1,392,220, and Canadian Patent No. 952,289. In addition, variou3 porous inorganic materials are commercially available which can be formed into shaped articles by known methods. Among suppliers of such porous inorganic materials are the following:
Alcoa, Catalytic Chemical Co. Ltd., Coors, Corning Glass Works, Davison Chemical, Fuji Davison Co. Ltd., ~arriscns &
Crosfield (Paci~ic) Inc., Xaiser Chemicals, Mizusawa Kagaku Co. Ltd., (Chemical Division), and Shokubai Xasei Co. Ltd.
As a second recuirement, in addition to controlled 2or sity, the inorganic membrane must be hydrophobic. Since the inorganic materials of which the membrane usually is composed are not inherently hydrophobic, the property of hydrophobicity normally must be imparted to the membrane by treating it either before or after the membrane is shaped or formed. As a ~ractical matter, such treatment Will be a post-formation treatment. The nature~o.^ the treatment is not critical, and essentially any treatment can be employed which will render the membrane hydrophobic. The property of hydrophobicity, ~-13-- ' ' ~
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~3~66 however, must be imparted throughout the entire void volume o~ the membrane, and not just to the external surface areas.
~ydrophoboclty i3 most conveniently lmparted to the shaped or ~ormed membrane by immersing the membrane in an organic solvent which oontains dissolved therein a suitable hydrophobic reagent, removing the membrane from the solvent, and allowing it to air dry. Although the concentration o~ the reagent is not critical, an especially useful concentration range has been found to be from about 3 to about 25 percent, weight per volume of solvent. A most convenient concentration is 10 percent. Essentially any solvent in which the hydro-phobio reagent is soluble can be employed. Examples of suit-able solvents inolude, among others, hexane, cyclohexane, diethyl ether, acetone, methyl ethyl ketone, benzene, toluene, the xylenes, nitrobenzene, chlorobenzena, bromobenzene, chloro-form, carbon tetrachloride, and the like. Examples of suitable hydrophobic reagents include, among others, natural waxes such as spermaceti, beeswax, Chinese wax, carnauba wax, and the like; synthetic waxes such as cetyl palmitate, cerotic acld, myricyl palmitate, ceryl cerotate, and the liXe; aliphatic hydrocarbons such as octadecane, eicosane, docosane, tetraco-sane, hexacosane, octacosane, triacontane, pentatriacontane, and the like; polycyclio aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, chrysene, pyrene, and the like; polybasic acids such as Empol Dimer Acid and Empol ~rimer Acid (Emery Industries, Inc.); polyamide resins such as the Emerex Polyamide Resins ~Emery Industries, Inc.);
water-insoluble polymeric isocyanates such as poly(methylene-phenylisocyanate) which is commercially available as PAPI
(Upjohn Company); alkylhalosilanes such as octadecylt~ichloro- `
silane, di(dodecyl)difluorosilane, and the like; and similar -14- ~

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materials. The alkyhalosilanes are preferred, with octadecyl-trichlorosilane being most preferred.
~ rom the foregoing, it should be apparent to one having ordinary skill in the art that essentially any hydrophobLc reagent which wlll adhere to the inorganic membrane with a reasonable degree of permanence can be employed. Such adherence can be by purely physical means, such as van der Waalq attraction, by chemical means, such as ionic or covalent bonding, or by a combination of physical and chemical means.
It also should be apparent to one having ordinary skill in the art that the configurati.ons of the two bioreactors are not critical to either the processing method or the apparatus of the present invention. Thus, the present invention comprehends any confLguration which i9 not lnconsistent with the instant disclosure. ~ost often, each bioreaator will be a conventional cylindrical or tubular plug flow-type reactor, such as those described in the examples. ~ccordingly, each bioreactor typically comprises a cylinder or tube open at both ends which contains the inorganic support. Typically, such cylinder is composed of any suitable material which is imper-vious to both gases and liquids. Suitable materials include, among others, glass, stainless steel, glass-coated steel, poly(tetrafluoroethylene), and the like. Each bioreactor optionally is jacketed. The jacket, if present, can be con-structed from any of the usual materials, such as those listed for the bioreactcrs.
It will be appreciated by thcse having ordinary skill in the art that when evolved gaseous products are tc be contained or otherwise handled, the configuration of the second bLo-reactor must be appropriately designed. Such design require-ments, however, are well ~md~r~tood by those having ordinary .
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In the ca9e o~ the 3econd bloreactor, the bloreactor or cylinder optionally compri3es the controlled-pore, hydro-phobic inorganic membrane. The bioreactor still can be, and pre~erably is, jacketed, especially when it ls either neces-3ary or desirable to contain, lsolate, analyze, utilize, or otherwise handle gaseous products evolved during the processing method of the present invention.
In more general terms, each bioreactor normally will be shaped in such a manner as to provide one or more channels for the passage of a fluid. Where multiple channel3 are pro-vided, such channels can provid~ independent flow of the fluid through such channels or they can be serially connected. The aqueous medium can flow through such channels or around such channels. Thus, the inorganic support can be contained in such channels or located around such channels. For example, given the cylindrical bioreactor already described, the inor-ganic support can be contained within the cylinder or tube.
Alternatively, the cylinder or tube can be jacketed and the inorganic support can be located between the ~acket and the cylinder or tube. Hence, the aqueous medium can flow either through or around the cylinder or tube.
When the inorganic membrane i9 used in the second bio-reactor, gaseous products will pass from or into the cylin-drical membrane, depending upon whether the aqueous medium passes through or around the cylindrical memorane. When the inorganic membrane i9 not used, gaseous products simply pass from the bioreaotor liquid phase to a vapor or gas phase.
Gaseous product removal, of course, i9 readily achieved by the various means ~nown to those having ordinary skill in ; 30 the art. Typically, the gaseous products are simply pumped away from the second bioreactor. Th:t isj the gas space of , . ,. . ,. i, . , . . . ;. .:, .: .: . : : -~ . : - ; .~ ; :

:. " ' :, ' : ~; ~ ' ' .''. :, , ';'' ' j.'. ' ,:,. :., ': ' "': ' ~L134$~;6 the second reactor i9 connected to a gas collection means via a means for maintaining the gas collectlon maans at a pressure which i~ les9 than that of the second reactor gas space. Alternatively, when the inorganic membrane is employed-in the 3econd bloreactor, a liquid 301vent having a high affinity for the gaseous products (i.e., in which the gaseous product3 have a high degree of solubility) can be circulated about or through the membrane in what normally would be the gag side of the membrane. Sultable solvent3 for many gase3 include silicone~ and fluorocarbon~, among others. The use of such a gas solvent usually ls neither nece33ary nor desired and, therefore, i9 not preferred.
Since the proce33ing method and apparatu3 of the pre3ent invention are well-suited for the production of u3able gase3, it is preferred that the second bioreactor have a gas removal means attached thereto. When an inorganlc membrane i3 employed, it i3 pre~erred that the second bioreactor is sealably enclosed within a ~acket having a gas removal means attached thereto.
While proces3 temperatures are critical only to the extent that the microbe3 present in each reactor remain viable, as a practical matter the proces3 of the present invention will be carried out at a temperature of from about 10C. to about 60C. Under normal circumstances when the inorganio membrane is used in the second reactor, both reactors are maintained at ambient temperature. '~hen the inorganic membrane is not employed, the first reactor pre-ferably is maintained at an elevated temperature, i.e., a temperature above ambient temp-rature. The prsferred tem-perature range for the first reaotor under such circumstance3 is irom about 30C. to about 40C.
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' ~ ' 1~34~66 As already indicat~d, the waste stream to be treated by the processing method of the present invention ~requently can be used without any pretreatment. Whether or not pretreat-ment i9 required is determined largely by the results expected.
3y way of illustration only, various of the examples describe the treatment of sewage or other waste to give an affluent having a significantly reduced chemical oxygen demand and methane as a principal product. Because the methane thus produced can be employed as a euel, Lt is desLred to minimize the production of non-euel gaseous by-product~, such as carbon dioxide. Accordingly, no pretreatment of, e.g., sew-age is necessary when the anaerobic bioreactor utilizes an inorganic me~rane. ~hat is, the use of the membrane ~re-quently results in the production of methane with less than five percent carbon dioxide content. In order to keep car-bon dioxide in the methane at acceptably low levels when the membrane is not used, however, it is necassary to ad~ust the pH of the sewage to about 8 or above. ~his pH ad~ustment serves primarily to keep the carbon dioxide, produced by the microbes, in solution. ~hus, various of the examples illustrate two preferred embodiments of the process of the present invention, one cf which utilizes an inorganic membrane in the anaerobic bioreactor, and the other of which does not.
~he present invention also provides an apparatus eor the determination of the biochemical oxygen demand (BOD) of a bio-degradable organic waste in an aqueous medium. Such apparatus comprises a sampling and/or sensing means serially connected to an aerobic bioreactor, which bioreactor in turn is serially connected to a sampling and/or sensing means.
As used hereln, the term "sampling and/or sensing means"
is meant to include a sampling means, a sensing means, and a sampling and sensing means.

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1~34~66 Accordingly, the sampllng and/or 3ensing means can be nothing more than a port, fitted wlth, for example, a stopcock or rubber septum, to provide a means for the manual withdrawal of a sample from the waste stream. Alternatively, such 3ampl-ing means can be an automated sampling device which automatic-ally removes samples o~ a precise si~e at predetermined inter-vals and stores such samples for iuture handling or analysis.
Examples of suitable sensing means include, among o-thers, dissolved oxygen sensor, conductivity sensor, ammonium ion sensor, p~ electrode, and the li~e. Actually, any sensing means can be used which will detect measurable di~erences in the organic waste-containing aqueous medium which are the result oi the biochemical conversions taking place in the apparatus ior determining 30D.
As contemplated by the pre~ent invention, a sampling and sensing means can be any combination oi' a sampling means and a sensing means. For example, an automated sampling device can be serially connected to an automated device i'or determining COD by a chromic acid oxidation procedure. Other variations and combinations, however, will be readily apparent to one having ordinary skill in the art.
Finally, the two sampling and/or sensing means need not be physically discrete or separate. That is, with appropriate connecting and waste stream directing means, a single sampling and/or sensing means can be employed in the BOD apparatus o~
the present invention, and such use is within the scope oi .
the instant disclosure. Thus, when using a single sampling and/or sensing means, the waste stream or a portion thereof ~irst is passed through the sampling and/or sensing means.
The waste stream then enters the aerobic bioreactor. Upon exiting the aerobic bioreactor, the waste stream or a portion -19- , -, :

~L~3~966 thereof i5 directed to the sampling and/or sensing means by appropriate connecting and directing means which are ~"ell known to those having ordinary sklll ln the art.
A9 a practical matter, it is advisable to avold the use of a sampling means which can only add to the complexity and cost of the BOD apparatus. Thus, the use of a sensing means only is preferred, and the use of a dlssolved oxygen sensor is most preferred.
Whether or not the sensing means measures di3solved oxygen, excess oxygen must be present in the aqueous medlum since the apparatus depends upon aerobic mlcroblal conver-slons for the determination of BOD. Thus, the bioreactor is an aerobic bioreactor and requires microbes capable of functloning aerobically. Thus, the bioraactor cannot con-taln only strlct anaerobes. Accordlngly, sultable microbes include those llsted for the flrst bloreactor of the ~aste processlng apparatus, strlct anaerobes excluded. Otherwlse, the descrlptlon of such first bioreactor applies equally to the aerohic bioreactor of the BOD apparatus.
The present invention further provides a process for the determination of the biochemical oxygen demand of an organic waste in an aqueous medium which o~omprises serlally passing an organic waste-containing aqueous medium through a first sampling and/or sensing means, an immobilized microbe bio-reactor, and a second sampling and/or sensing means, in whlch the bloreactor ls an aeroblc bioreactor containing a porous lnorganic support which is suitable for the accumu-lation of a blomass.
In general, the process can be carried out at any tem-perature at which the microbes remain viable and functional.
Practically, the process will be carried out at a temperature .

~3~;6 of irom about 10C. to about 60C., wlth amblent tempera-ture being preferred.
As already indicated, the aqueous medium must contain excess oxygen. That i9, the aqueous medium emerging from the aerobic bioreac-tor must contain at least some dissclved oxygen. The need for excess dissolved oxygen, however, does not require aeration of the aqueous medium. Normal dis301ved oxygen levels can be adequate i3 bioreactor size and medium residence times (flow rates) are appropriately adjusted.
sioreactor size and medium residence times are not crltlcal and are readlly optlmized by one having ordinary sklll in the art. While medlul~ 30D levels normally are not critical, it should be apparent that (1~ higher BOD levels may require serlal dllution in order to maintaln accuracy and precision, and (2) bioreactor size and medium residence tlmes are variables which must be considered for any given BOD values. 8y way of lllustration, the BO~ apparatus described in the examples in general works well for the determination of actual media BOD lettels of from about 1 to about 10 ppm (or mg/l) oxygen. ~ith such apparatus, residence times greater than about one hour seldom are required.
The present inventlon ls further descrlbed, but not limlted, by the followlng examples whlch lllustrate the use of the processlng method and apparatus of the present invention in the treatment of sewage. Unless otherwise stated, all temperatures are in degrees Celsius.
The process employed ln Examples l and 2 is descrlbed below, with reference to Figure l.
Sewage 1 is pumped from container 2 by pump 3 to ; 30 hydrolytic redox bloreactor 4 via rubber tubing ; sealably connected to the pump and the hydrolytlc redox bloreactor.

, ~L3~66 The hydroLytic redox bloreactor consl3ts of lnner glas~ tube 6 sealably enclosed wlthin glass ~acket 7. The inner glass tube contains inorganic carrier 8 such as that described in U.S. Patent No. 4,153,510, whlch is suitable for the accumu-lation o~ a biomass. Sewage leaving the hydrolytic redox bioreactor is transported to anaerobic bioreactor 9 via ~ rubber tubing l0 sealably connected to both bioreactors.
The anaeroblc bloreactor consists of inorganlc membrane 11 and glass jacket 12 having exlt port 13. The inorganic membrane ls fllled wlth addltional lnorganlc carrier 8 and is sealably enclcsed within the glass jacket. Rubber tublng lg, sealably connected to the exit port of the jacket, lead~
to pump 15 which removes gas (methane) from air space 16 enclosed by the jacket. Such gas in turn is aollected by any suitable means such as by the dlsplacement of water in an inverted vessel (not shown). Sewage effluent 17 then is transported via rubber tubing 18 sealably connected to the anaerobic bioreactor, to receiving vessel 19.
The sewage employed in each of the examples was obtained from the inlet pipe to the Corning, New Yor~, ~unicipal Sewage Waste Treatment Plant. The sewage was stored at 4-6C. Prior to use, the sewage was filtered through cheesecloth and glass wool to remove coarse particulate matter. Sewage was collec-ted either weekly or biweekly.

~xample l Pump 3 consisted o~ a Fluid ~etering pump, ~PlG6CSC
(Fluid ~etering, Inc., Oyster 3ay, ~.Y.), which was connected ; to hydrolytic redox bioreactor 4 with~a 14-inch length of rubber tubing. A 20-inch length of rubber tubing was attached to the intake side of the pump and led from a flask con-taining sewage.

1~3~166 The hydrolytic redox bloroactor consisted of a Pharmacia A16/20 column (Pharmacia Fin& Chemlczls, Uppqala, Sweden) with water jacket; the water ~acket was le~t vented to the atmos-phere. The column was charg~ with 24 g. o~ cordierlte (CGZ) carrier havlng a por~ diameter distributlon o,8 2-9~ and an ~verage pore diameter o~ 4.S~. The carrler w~ seeded with Jewage microbes by flowing through the bloreactor sludge obtained pr~viou~ly ~rom a ~unlcipal anaerobic ~lgestor.
The inorg~nic membrane 11 o~ ~n~erobic ~ior~actor 9 was a slllca membrane, prep~red in accordance wlth know~ procedures;
s~e, ~or exa~ple, V.S. Patent Nos. 3,678,144, 3,7a2,982, and 3,a27,893. ~he membrane was approximAtely 18 cm. long wlth cross-~ectional dimenslons o~ 10.5 mm. l.d. and 15.5 ~m. o.d.
The average pore ~iameter o~ the membrane w~s 3500~ with a pore di~meter di~tribution o~ 2000-3600A. Wall por~sity was 60 percent and pore volume was 0.99 cc/y. The me~brane was randered hydrophobic by placiug it in 75 ml. o~ ten percent soIution of octadecyl~rlchlorosllane in acetone and allowing it to soak overnight. The me~brane th~n was removed from the solution, wa3hed with 500 ml. o~ acetone, and ~ir-tried.
~ he membr ne was mounted ln a Ph~macia R16/20 water jacket by means of the ~tAndard rubber sealing ring and Uh eaded locking ring and was charyed with ten g. of the CGZ
carrier. Both ~loreactors together had a total void or 81uid volume of ~bout 30 ml.
The two ~ioreactor~ were coupled with about ou~ inches of rubber tubing. One of the port3 o~ the anaerobic bioreact~r jack~t was ealed hy attaching ~ ~hort pioce of Iygon tubinj ther~to and clo~lng the tubing by means of a cl~mp. The othe~ port was attached to e ~uchler Polystalti~ Pu~p (Buc~ler Inst~ents, In~., Fort ~e~, ~.J.J with a length oi thick-walled `:~
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~34~;6 Tygon tublng. Gas evolved and passed through the me~brane W~iJ collected by the dlsplacement of water ln a callbr~ted cylinder inverted ~ni wat2r~illed, large, ~h~llow ve3sel. ~he rats of gas evolution was ob3~r~ed and the ooll~cted ga3 was analyzed ~it ~east dally by ma33 speetroJcopy. ~n addition, the ~hemlcal oxygen demaind (COD) o~ the sewage u~ed ~is feed and the e~luent emerglng ~ro~ the nnaerobic bloreactor were deter~lned perlodically by standard, well-known colorimetric dlchromate oxidation procedures.
~he process wa5 ru~ ~or a perlod o~ about nine months.
Although data wer~ generated on a ~ally ba~iq, except ~or COD ant~ly~es, weekly averages o~ the data are preaented ln Table It ln the table, COD analyses ~re averaged where more than one analysis w~s o~tained per week.
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3L~3~6 Example 2 The procedure of E~ample 1 was repeated, except that the hydrolytLc redox bioreactor was charged with 19 g. of CGZ
carrier, the carrier in the hydrolytic redox bloreactor was not 3eeded, the lnorganic membrane of the anaerobic bioreactor was an alumina membrane, and the anaerobic bioreactor was charged with 18.4 g. of the CGZ carrier.
The alumina membrane was prepared in accordance with well-known procedures. 3rlefly, 300 g. of SA alumina contalning three percent by weight of carbowax was isostatically pressed at 1,758 kg./cm.2 (25,000 psi) in a mold which consisted of a cylindrical mandrel having a diameter of 1.9 cm. and a cylinder with rubber sleeve having an inner diameter of 3.65 cm. The resulting cylindrical tube had the following cross-sectional dimensions: i.d., 1.9 cm., and o.d., 2.62 cm.
The tube was turned on a lathe to an o.d. of 2,4 cm. The tube was about 36 cm. in length. The tube then was fired in a furnace as follows: The furnace was heated -to ;00 (from ambient temperature) at 50 per hour and held at 500 for two hours. The temperature then was increased to l;iO at a first rate o~ ;0 per hour to 950 and a second rate of 100 per hour to 1550 , at which temperature the furnace was held for five hours. The furnace then was cooled at 100 per hour to 950, and at SO per hour to ambient temperature.
The resulting ~lumina controlled-pore membrane had an i.d.
of 1.43 cm., an o.d. of 1.75 cm., and a wall thickness of 2.Q mm. Pore diameter distribution was from 3500~ to 4500~, with an average pore diameter o~ 4000~. Wall porosity was 46.8 percent and pore volume was 0.22 cc./g. The membrane was rendered hydrophobic by placing it in ;0 ml. of acetone ' ., ~13~66 containlng ten percent octadecyltrichlorosllane and allowing it to react overnlght at ambient temperature. The membrane then was removed ~rom the acetone solutlon and wa3hed ~our times with 50-ml. portions o~ ac~tone. The membrane was air-dried ~or ~our hours, and then was heated at 120 ~or 1.5 hours.
The data obtalned from this example are summarized in Table II, again as weekly averages.

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Example 3 The procedure of Example 1 was repeated with some changes in equipment. The hydrolytic redox bLoreactor consi3ted of a Lab-Crest column, without jacket, 400 x 15 mm. The bioreactor was charged with 50 g. of CGZ carrier. The anaerobic bioreactor consisted of an outer ~acket 31.1 cm. in length and a fritted glass membrane 30.5 cm. in length and 1.6 cmO in diameter. The membrane, which was fused to the outer jacket, consisted of three sections of fritted glass tubing of equal length which had been fused together. The total length of the anaerobic reactor was 40.6 cm. The membrane had a pore diameter distri-bution of 3-6~ and an average pore diameter of 4.5~. Ths mem-brane was made hydrophobic by allowing it to react with 130 ml.
of ten percent octadeayltrichlorosilane in acetone at ambient temperature for about three days. The membrane then was removed from the acetone solution and washed successively with two 130-ml. portions of acetone, two 130-ml. portions of methanol, and a 130-ml. portion of acetone. The membrane was air-dried by aspiration. The anaerobic bioreactor was charged with 23 g. of CGZ carrier. The gas pump was a Cole-Parmer Masterflex peristaltic pump.
The results are summarized in Table III. The membrane, however, passed liquid water during the time the process was in operation, demonstrating that the pore diameters of the fritted glass membrane in general were too large.

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Example 3 also lllustrate3 a preferred embodiment of the process of the present invention, which embodiment comprises establishing an additional microbe colony on the gas-space side of the inorganic membrane of the anaerobic bioreactor.
Most preferably, such microbes will be photosynthetlc microbes, examples of which include, among others Rhodospirillum rubrum, ChromatLum Sp., Chlorobium thiosuliatophilum, ChloroPseudomonas ethylica, Chorella Sp. Scenedesmus So., Chlamydomonas Sp., Ankistrodesmus Sp., Chondrus S2., Corallina ~e~ Callilhamnion Sp., and the like.
The process employed Ln Examples 4-7 is descrlbed below, with reference to ~igure 2.
5ewage (or other waste) 1 is pumped from container 2 by pump 3 via rubber tubing 5 sealably connected to the pump.
The discharge from the pump ls led to hydrolytic redox bLo-reactor 4 via rubber tubing 7 having inserted thexein prassure gauge 6, the rubber tubing being sealably connected to the pump, gauge, and bioreactor. The hydrolytic redox bloreactor conslsts of inner glass tuba 8 sealably enclosed wlthin glass jacket 9. The inner glass tube contains inorganic carrier 10 such as that described in U.S. Patent Mo. 4,153, 510, which is suitable for the accumula-tion of a biomass. The glass jacket is sealably connected via rubher t~lbing 11 to constant-tempera-ture water-bath 12. Sewage (or other waste) leaving the hydrolytic redox bioreactor is transported to anaerobic bioreactor 13 via rubber tubing 14 sealably connected to both bioreactors. The anaerobic bioreactor consists of glass jacket 15 having exit port 16. The glass ~acket is partially filled with additional inorganic carrier 10 and is sealably closed at each end. Rubber tubing 17, sealably connected to the exit port of the ~acket, leads to pump 18 : ~ ' 3~

which removes gas (methane) from air ~pace 19 enclosed by the jacket. Such gas ln turn is collected by any 3uitable means such as by the displacement of water in an inverted vessel (not shown). The glass ~acXet of the anaerobLc bioreactor i3 fitted with liquid level sensing means 20 which i9 connected electrically to liquid level controller 21. The controller in turn ls electrically connected to pump 18. Sewage effluent 22 then is transported, vla rubber tubing 23 sealably connected to the anaerobic bioreactor and fitted with check valve 24, to receiving vessel 25.

Example 4 The procedure of Example 1 was repeated, except ~or -the following modifications. The hydrolytic redox bloreactor was charged with 24.5 g. of cordlerite carrler having an average pore diameter of 3~ and a pore diameter distribution o~ 2-9~.
~he anaerobic bioreactor was a 250 x 15 mm. Lab-Crest jacketed column havlng about 125 mm. of the lnner coIumn or cylinder removed. Thus, the jacket became the bioreactor, with the end pieces of the inner column serving only to seal the ends of the bioreactor. The anaerobic bioreactor then was charged with 51 g. of the cordierite carrier and the bioreactor was mounted in a substantially horizontal position. a presgure gauge was inserted in the tubing connecting pump 3 to the inlet of the hydrolytic redox bioreactcr. The water ~acket -~
of the hydrolytic redox bioreactor was connected to a constant-temperature water-bath. The total fluid volume of the pump, tubing, and bioreactors was 120 ml.
The apparatus was seeded as follows: The tubing leading~
from the pres3ure gauge was disconnected from the inlet of the hydrolytic redox bioreactor. To such inlet then was ' ~ - " , :: :
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attached the tubing leadlng ~rom the anaeroblc bloreactor of the operatlonal apparatus o~ Examp]e 1. U31ng sewaqe a~
feed, the two apparatuses were malntained in the coupled configuration and operated essentially as described in Example l for 13 days. During thi3 period, apparatus per~ormance was monitored as summarized ln ~able IV.

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-4;- -~34'~6 Example 5 The procedure of ~xample 4 was repeated, except that the carrier employed was Duralite Rouge (F. Guery, Ramber-villers, France) having a pore diameter distribution of 0.4~
6u, an average pore diameter of 4.5~, a pore volume of 0.4 cc./g., and a porosity of 51.5%; the amounts of carrier employed in the hydrolytic redox bioreactor and the anaerobic bioreactor were 22 g. and 52.5 g., respectively.
The apparatus was seeded as descrLbed in Example 4, except that the water-bath temperature was adjusted to 31 and opera-tion in a coupled configuration was maintained for about 9iX
days. Additionally, a one psi check valve was inserted in the end of the effluent tubing leading from the anaerobic blo-reactor. Although the performance of the apparatus was moni-tored over the next 33 days, satisfactory per~ormance was not observed until the fortieth day of operation tincluding the six days of operation in the coupled oonfiguration). On the twentieth day of operation, the one psi check valve was replaced with a three psi check valve. Table VII summarizes the operating parameters and gas composition from the fortieth day of operation and Table VIII similarly summarizes apparatus performance and carbon balance calculations.

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The apparatus was set up and see~ded ~or ten days as described in ~xample 5. Appreciable reduc:tions in COD were not observed until the 34th day of operation; consequently, the tabular summaries begin with the 34th day. Table IX summarizes operating parameters and gas composition and Table X summarizes appaxatus performance and carbon balanoe calculations.

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:' ' L3~66 Exam~le 7 The procedure of EXample 4 was repeated, except that the carrier employed was Johns-Manvi11e Insulating Firebrick JM-23 (Johns-Manville Corp./ Denver, Colorado) having a pore diameter distribution o~ 2-lS~, an average pore diameter o~
9~, a pore volume o~ 1.0 cc./g., and a porosity O~c 68%. The amounts of carrier employed in the hydrolytic redox and anaerobic bioreactors were ten g. and 15 g., respectively.
Again, the apparatus was set up and seeded Cor seven days as described in Example 5. Although satis~actory per~ormance was observed on the 29th day, periodic leaks were a problem until the 37th day of operation. Beglnning with the 29th day, Tables XI and XII summarize operating parameters and gas composition, and apparatus per~ormance and carbon balance calculations, respectively.

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~; , ! 1 ~ 3 ~ 6 The example~ which lc\llow illustrate one e~odiment of the B4~ ~pparAtus ol' the E~resent invention.
Ex~mple 8 A two-liter reagent bottle with a side ~r~ at the ~ottom W35 connected, via a l~ngl~ of mygon tubing ~ttached to the ~ide arm, to the inlet port ol' a Pluid Metering, Inc. Model ~P G-6 pump (Fluid Metering, Inc., Oy~ter Bay, Naw York). ~he outlet port of the pu~p was attached, aga~n via ~ygon tubing, to th~ bot'om o~ A vertically-mounted 9 x lSO mm. Fisher and Porter chromatographic colu~n (obt2in~d l'rom Arthur ~. Thom~s Co., Philadelphia, PA.). m~he column was charged wlth 6.5 g.
of the CGZ carrier described ln Ex~mple 1. ~he top oi' the column was con~ected by Tygon tubins te the inlet port o~' a cell having sealably mounted therein the dissolved oxygen sensor of a Dif1'usion Oxygen Analyzer (International Bio-physics, Corp., Irvine, Cal.). The outlet port of the cell was connected with Iygon tu~ing to a r~ceiving vessel.
~nother di-~solved oxygen ~ensor was pl~ced in the reagent bottle which ~erved as waste stre~m reservoir. ~ach tis-,~olved oxygen sensor was standardized against air-saturated ~ater nt 21.9~ saturati~n.
~he column W~5 secded by continuously recir~ulating a volume of sewage through the column at ~ ~low rate of 1 ml./min. ior iive days. A ~ter~le, stand rd BOD solution cont~inlng l50 mg/liter each o~ glut~mic acid and ~lucos~ was passed tbrough ~e column at 0.37 ml/min~ ~'or 24 hours as a preconditioning to insure adequate bioaccu~ulation priox to collectlng oxyge~ uptak~ data. The standard BOD ~olution then was pa~sed through the oolumn or immobili2ed aerobic mlcrobe bioreactor. The e~fluent percent saturation was :
~;Trade Mark.

: ~:

: . ,.. ~ ~ : , - ~L3~3~
, ; measured at three different flow rates. In each case, the percent saturation of the feed in the reservoir was 21.9%
and the effluent percent saturation reading stabilized within 20-60 min. aiter changing the flow rate. The results are summarized in Table XIII.
:
TABLE XIII
Oxygcn Uptake in an Aerobic Bioreactor BOD A?~paratus Flow Rate (ml./min ) Effluent ~ Saturation 10 0.19 7a 2.07 18.5 aDecreased to 4.5 after an additional 12 hours.
From Table XIII, it is apparent that oxygen uptake is inversely proportional to the flow rate. Oxygen uptake, . expressed as the percentage of dissolved oxvgen consumed, is summarized in Table XIV and was calculated in accordance with the following formula:

% 2 consumed = Feed % Sat nd- ESft,~ Sat n x 100 TABL~ XIV
Percentage of Dissolved Oxygen Consumed In An Aerobic Bioreactor BOD A??~aratus Flow Rate, ml.~min. ~ 2 Consumed 0.19 68a 0.37 54 2.07 16 Increased to 79~ after an additional 12 hours.
.

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~39~ 6 Example 9 The procedure of Example 8 was repeated, except that the column was seeded with 200 ml. of an overnight tryptic soy broth culture of Escherichia coli (109 cells/ml.) and the standard BOD solution was replaced with sterile broth.
After the 24-hour preconditioning period, the effluent percent saturation was measured and found to be 0~; the broth percent saturation originally was 21.9%. Thus, 100%
of the dissolved oxygen was consumed.
Examples 8 and 9 clearly demonstrate the feasibility of measuring a difference in an organic waste-containing aqueous medium, which difference is the result of biochemical conver-sions (oxidations) taking place in the BOD apparatus aerobic bioreactor.
Such a measurable difference then is readily correlated to BOD by known procedures. For one example of such a correlation, see I. Xarube et al., Biotechnol. Bioenq., 19, 1535 (1977). Thus, for a given aerobic bioreactor, passing standard solutions having varying concentrations of organic material at a given flow rate will yield a set of, for example, oxygen uptake data. The BOD values of such standard solutions can be determined by conventional methods to give a set of conventional BOD values. The two sets of data then can be combined in graph form to give a standard curve for each flow rate employed. The BOD of any organic waste in an aqueous medium then is determined quickly and simply by passing such aqueous medium through the BOD apparatus and comparing the data obtained with the appropriate standa~d curve.

:
,: ~

Claims (58)

I CLAIM:

1. A method for processing biodegradable organic waste in an aqueous medium which comprises serially passing an organic waste-containing aqueous medium through a first immobilized microbe bioreactor and a second immobilized microbe bioreac-tor, in which:
A. the first bioreactor is a hydrolytic redox bio-reactor containing a porous inorganic support which is suit-able for the accumulation of a biomass, and B. the second bioreactor is an anaerobic bioreactor containing a porous inorganic support which is suitable for the accumulation of a biomass.

2. The method of claim 1 in which the anaerobic bioreactor has a gas removal means attached thereto.

3. The method of claim 1 in which the hydrolytic redox bioreactor is maintained at a temperature of from about 10°C. to about 60°C.

4. The method of claim 3 in which the temperature is from about 30°C. to about 40°C.

5. The method of claim 1 in which the inorganic support of the hydrolytic redox bioreactor is a porous, high surface area inorganic support which is suitable for the accumulation of a high biomass surface within a relatively small volume.

6. The method of claim 5 in which at least 70 percent of the pores of the inorganic support have diameters at least as large as the smallest major dimension, but less than about five times the largest major dimension, of the microbes present in the hydrolytic redox bioreactor.

7. The method of claim 5 in which the average diameter of the pores of the inorganic support is in the range of from about 0.8 to about 220µ.

8. The method of claim 7 in which the inorganic support is a cordierite material.

9. The method of claim 8 in which the cordierite inorganic support has a pore diameter distribution of from about 2 to about 9µ, and an average pore diameter of about 4.5µ.

10. The method of claim 7 in which the inorganic support is a halloysite or kaolinite material.

11. The method of claim 10 in which the inorganic support has a pore diameter distribution of from about 0.4 to about 6µ and an average pore diameter of about 4.5µ.

12. The method of claim 10 in which the inorganic support has a pore diameter distribution of from about 0.8 to about 30µ and an average pore diameter of about 6µ.

13. The method of claim 10 in which the inorganic support has a pore diameter distribution of from about 2 to about 15µ and an average pore diameter of about 9µ.

14. The method of claim 1 in which the inorganic support of the anaerobic bioreactor is a porous, high surface area inorganic support which is suitable for the accumulation of a high biomass surface within a relatively small volume.

15. The method of claim 14 in which at least 70 percent of the pores of the inorganic support have diameters at least as large as the smallest major dimension, but less than about five times the largest major dimension, of the microbes pre-sent in the anaerobic bioreactor.

16. The method of claim 14 in which the average diameter of the pores of the inorganic support is in the range of from about 0.8 to about 220µ.

17. The method of claim 16 in which the inorganic support is a cordierite material.

18. The method of claim 17 in which the cordierite inorganic support has a pore diameter distribution of from about 2 to about 9µ, and an average pore diameter of about 4.5µ.

19. The method of claim 14 in which the inorganic support is a halloysite or kaolinite material.

20. The method of claim 19 in which the inorganic support has a pore diameter distribution of from about 0.4 to about 6µ and an average pore diameter of about 4.5µ.

21. The method of claim 19 in which the inorganic support has a pore diameter distribution of from about 0.8 to about 30µ and an average pore diameter of about 6µ.

22. The method of claim 19 in which the inorganic support has a pore diameter distribution of from about 2 to about 15µ and an average pore diameter of about 9µ.

23. The method of claim 1 in which the principal product is ethanol which is a constituent of the liquid effluent emerging from the anaerobic bioreactor.

24. An apparatus for processing organic waste in an aqueous medium which comprises a first immobilized microbe bioreactor serially connected to a second immobilized microbe bioreactor, in which:
A. the first bioreactor is a hydrolytic redox bio-reactor containing a porous inorganic support which is suitable for the accumulation of a biomass, and B. the second bioreactor is an anaerobic bioreactor containing a porous inorganic support which is suitable for the accumulation of a biomass.

25. The apparatus of claim 24 in which the anaerobic bio-reactor has a gas removal means attached thereto.

26. A method for processing biodegradable organic waste in an aqueous medium which comprises serially passing an organic waste-containing aqueous medium through a first immobilized microbe bioreactor and a second immobilized microbe bioreac-tor, in which:
A. the first bioreactor is a hydrolytic redox bioreac-tor containing a porous inorganic support which is suitable for the accumulation of a biomass, and B. the second bioreactor is an anaerobic bioreactor com-prising a controlled-pore, hydrophobic inorganic membrane which contains a porous inorganic support which is suitable for the accumulation of a biomass, in which at least about 90 percent of the pores of the inorganic membrane have dia-meters of from about 100.ANG. to about 10,000.ANG..

27. The method of claim 26 in which the anaerobic bioreactor is sealably enclosed within a jacket having a gas removal means attached thereto.

28. The method of claim 26 in which the hydrolytic redox bioreactor is maintained at a temperature of from about 10°C.
to about 60°C.

29. The method of claim 28 in which the temperature is ambient temperature.

30. The method of claim 28 in which the temperature is from about 30°C. to about 35°C.

31. The method of claim 26 in which the inorganic support of the hydrolytic redox bioreactor is a porous, high surface area inorganic support which is suitable for the accumulation of a high biomass surface within a relatively small volume.

32. The method of claim 31 in which at least 70 percent of the pores of the inorganic support have diameters at least as large as the smallest major dimension, but less than about five times the largest major dimension, of the microbes pre-sent in the hydrolytic redox bioreactor.

33. The method of claim 31 in which the average diameter of the pores of the inorganic support is in the range of from about 0.8 to about 220µ,

34. The method of claim 33 in which the inorganic support is a cordierite material.

35. The method of claim 34 in which the cordierite inorganic support has a pore diameter distribution of from about 2 to about 9µ, and an average pore diameter of about 4.5µ.

36. The method of claim 26 in which the inorganic support of the anaerobic bioreactor is a porous, high surface area inorganic support which is suitable for the accumulation of a high bio-mass surface within a relatively small volume.

37. The method of claim 36 in which at least 70 percent of the pores of the inorganic support have dimensions at least as large as the smallest major dimension, but less than about.
five times the largest major dimension, of the microbes present in the anaerobic reactor.

38. The method of claim 36 in which the average diameter of the pores of the inorganic support is in the range of from about 0.8 to about 220µ.

39. The method of claim 38 in which the inorganic support is a cordierite material.

40. The method of claim 39 in which the cordierite inorganic support has a pore diameter distribution of from about 2 to about 9µ, and an average pore diameter of about 4.5µ.

41. The method of claim 26 in which the pore diameter range of the pores of the inorganic membrane of the anaerobic bio-reactor is from about 1,500.ANG. to about 6,000.ANG..

42. The method of claim 41 in which the inorganic membrane is composed of a material which is selected from the group consisting of glass, spinel, silica, and alumina.

43. The method of claim 41 in which the membrane is rendered hydrophobic by a post-formation treatment with octadecyltri-chlorosilane.

44. The method of claim 26 in which an additional microbe colony is established on the gas-space side of the inorganic membrane of the anaerobic bioreactor.

45. The method of claim 26 in which a principal product is methane which is passed through the controlled-pore, hydro-phobic inorganic membrane of the anaerobic bioreactor.

46. An apparatus for processing organic waste in an aqueous medium which comprises a first immobilized microbe bioreactor serially connected to a second immobilized microbe bioreactor, in which:
A. the first bioreactor is a hydrolytic redox bioreac-tor containing a porous inorganic support which is suitable for the accumulation of a biomass, and B. the second bioreactor is an anaerobic bioreactor comprising a controlled-pore, hydrophobic inorganic membrane which contains a porous inorganic support which is suitable for the accumulation of a biomass, in which at least about 90 percent of the pores of the inorganic membrane have diameters of from about 100.ANG. to about 10,000.ANG..

47. The apparatus of claim 46 in which the anaerobic bio-reactor is sealably enclosed within a jacket having a gas removal means attached thereto.

48. System for processing biodegradable organic waste in an aqueous medium which comprises serially passing an organic waste containing aqueous medium through a first immobilized microbe bioreactor and a second immobilized microbe bioreactor, charac-terized in the first bioreactor is a hydrolytic redox bioreactor containing a porous inorganic support which is suitable for the accumulation of a biomass, and the second bioreactor is an aner-obic bioreactor containing a porous inorganic support which is suitable for the accumulation of a biomass.

49. System of claim 48 in which the anaerobic bioreactor has a gas removal means attached thereto.

50. System of claim 48 in which the inorganic support of the hydroliytic redox bioreactor and/or the anaerobic bioreactor is a porous, high surface area inorganic support which is suitable for the accumulation of a high biomass surface within a reala-tively small volume.

51. System of claim 50 in which at least 70 percent of the pores of the inorganic support have diameters at least as large as the smallest major dimension, but less than about five times the largest major dimension, of the microbes present in the hydrolytic redox bioreactor and/or the anaerobic bioreactor.

52. System of claim 50 in which the average diameter of the pores of the inorganic support is in the range of from 0.8 to 220µ.

53. System of claim 52 in which the inorganic support is a cordierite material.

54. System of claim 53 in which the cordierite inorganic support has a port diameter distribution of from 2 to 9µ and an average pore diameter of 4.5µ.

55. System of claim 52 in which the inorganic support is a halloysite or kaolinite material.

56. System of claim 55 in which the inorganic support has a pore diameter distribution of from 0.4 to 6µ and an average pore diameter of 4.5µ, or from 0.8 - 30µ, average 6µ, or from 2- 15µ, average 9µ.

57. System of claim 48 wherein the principal constituent of the liquid effluent from the anaerobic bioreactor is ethanol.

58. System of claim 48 wherein the bioreactors are con-nected in series.