CA1323943C - Process for the treatment of waste - Google Patents

Process for the treatment of waste

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Publication number
CA1323943C
CA1323943C CA 557451 CA557451A CA1323943C CA 1323943 C CA1323943 C CA 1323943C CA 557451 CA557451 CA 557451 CA 557451 A CA557451 A CA 557451A CA 1323943 C CA1323943 C CA 1323943C
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Prior art keywords
liquid
waste
organic waste
stream
ash
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Expired - Fee Related
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CA 557451
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French (fr)
Inventor
Hermann W. Peterscheck
William L. Schwoyer
Larry S. Jaycox
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Waste Treatment Patents & Research Nv
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WASTE TREATMENT PATENTS & RESEARCH N.V.
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/38Treatment of water, waste water, or sewage by centrifugal separation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/586Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/02Biological treatment
    • C02F11/04Anaerobic treatment; Production of methane by such processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/06Treatment of sludge; Devices therefor by oxidation
    • C02F11/08Wet air oxidation
    • C02F11/083Wet air oxidation using deep well reactors
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/18Treatment of sludge; Devices therefor by thermal conditioning
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/12Halogens or halogen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/28Anaerobic digestion processes
    • C02F3/286Anaerobic digestion processes including two or more steps
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124Water desalination
    • Y02A20/131Reverse-osmosis
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/20Sludge processing

Abstract

PROCESS FOR THE TREATMENT OF WASTE
ABSTRACT OF THE DISCLOSURE

A method of treating organic waste is provided which includes separating the liquid portion of the waste from the solid portion prior to reacting said solid portion in an accelerated wet oxidation reaction. The method includes using an internally-derived ash from the wet oxidation reaction to weight the organic waste, thereby increasing the rate at which the liquid phase can be separated from the solid phase. By first removing the liquid portion of the waste, the oxygen demand of the waste to be processed by wet oxidation is substantially lowered. ammonia is removed from the liquid portion of the waste in a de-ammoniating step which is followed by biological decomposition to form a liquid stream having a greatly reduced oxygen demand. In one embodiment, the method includes further treating the liquid steam to substantially remove salts and using the resulting deionized stream as a diluent to dilute the solid portion of the waste prior to wet oxidation. The present invention also provides a method of treating organic waste which includes reacting said waste in accelerated wet oxidation reaction apparatus to produce a low-volume sterile ash, a liquid effluent portion and a mixture of reaction off gases. The liquid effluent portion is de-ammoniated then decomposed biologically lo form a liquid stream having a greatly reduced oxygen demand. The liquid stream is then desalinated and used as a diluent to dilute the organic waste prior to its introduction into the wet oxidation reaction apparatus.

Description

1 3 2 3 9 4 3 B27û75010 ~0~6.108 PROCES5 FOR THE TREAT~ENT OF WASTE

FIELD OF INVENTI()N

..
The present invention rel~tes gener~lly to methods ~or treatis~g organic waste ~nd wastewater. More specifically the present invention relates to integrated processes which utilize physical, biological and chemica~ operaffons for the tre~trnent o~ animal waste.

BACKGROUND OF THE lNVENTlON

It is estimated that in the United ~ates 810ne, over 1.5 b~llion tons oî anim~I waste are produced annually. While a portion of this w~ste is generated on f~r~ where disposal n~y consist of on-site rn~nure spreading, large unts are ~lso produced in feedlots, many of which are located near urban areas.
~or a number OI reasons, manure spreading, incineration and other traditional waste disposal alternatives may be undesirable or impraetical. Hence, econor~cal animal waste processing methods which prodllce enviro~nentally desirable products are needed.

Modern animal feedstuffs are ~omplex mixtures of protein, fiber, VitQn~ins, minerals, salts ~nd ol~er con~onents, balanced to provide opthT~n nutrition at nlinimum cost. Sodium, c~l~i~n, phosphorous, r~gnesimn, potassi~, and other n~nerQls are present in most feedstuf~s. In addition, large am~unts of ~hlorides ~re ingested by li~estock, o~ten iEran s~lt blocks and the like. The inge~tion o~ sallt is knoHm to increase the thirst snd ~ppetite of animEIls which incre~es body weight. Although nutrient-enriched diets Rre designed to produ~e healthier, mDre ~T~rketable livestock, the high concentrations o~ ~hlorides, sn~Dia, ~nd minerals whi~h these highly nutritious feedstuffs produce in anin~l waste are of particulllr concern in waste processing systems.

J

1 3239~3 ~086.108 G~nerally, livestock wQste c~ntains fPom about 8 percent to ~bout 11 percent by weight carbonaceous m~teriQl, ~lthough concentrations outside this rsnge are not uncomnon, depending on the amount of wash~down water present.
Unprocessed or raw anim~l wastes typic~lly have ~ chemical oxygen demand (COD) of ~rom about 80,000 mg/l to ~bout 120,000 mg/l. The ehernical oxygen delTand is ~ measure of the quEmtity of shemically oxidizable components present in the waste. Anirn~l wastes also genera~ly have a biochemical oxygen delTsnd (BOD) of from about 40,000 mg/l to sbout 30,000 rng/l. The biochemical oxygen demand is the quantity of oxygen required during decomposition of the organic waste matter by aerobic biochen~ical action. The BOD is usually determined by measuring oxygen conswTption of dec~ly microorganislT6 in a waste sample during a five-day period at 20 C. As will be appreciated by ~hose skilled in the art, one irr~ortant objective of waste treatment processing is the reduction of the oxygen dem~nd of the waste effluent. Oxygen depletion or deoxygenation o~ receiving waters due to the discharge of waste effluents having high oxygen den~nds is ~ significant environmental concern and is the subject of consider~ble governrnental regulation.

Waste processing system; are designed to provide the m~st environmentally compa~ible waste effluent a~ the lowest co~t, with n~ximum utilization of process by-products. Thus, processing schembs which require a relatively low initial capital expenditure and which have low oper~tional and mRintenance costs ~re highly desirable. Those conYentional w~ste pro~essing systenE; which are adaptubl~ to processing anin~l wRstes lack efficient, ~omprehensive methods for ~ubstantially reducing the oxygen demand of the wastes ~ile also remvving harmful chlorid~s and t31e like which cause corrosion of the waste processing squipmen~. Further, eonYentional processes do not ~dequately inhibit the fcIlT~tion or transfer of enviror~ntally wldesirable products. The present inventi~n provides an integrated waste treatment system particularly suited for the processing of animsl sv~stes ~ h ~olves mEmy of the problems associated with conventional waste pro~essing systerrs.

20~6.108 SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided Q
total, integrated system for processing waste, which ~ p~rffcul~rly suitable for processing animal w~ste. In os~e errbodin~nt, the rnethod includes adding an Lnternally-derived ~sh as a weighting agent to animal waste, then dewatering the weighted waste to form a liquid stream which n~y contain ~s much as half of the biochemical oxygen demand of the initial w~ste. This liquid stream also contains a substantial portion of the chlorides and amnDnia present in the waste. The li~uid stream is then de-asrmoniated, preferably by ar~onia stripping, and the resulting alTmonia conpounds are reclnim~d for use as fertilizer or the like. The de-~nnnoniated liquid strea3n is ~owed directly to a biological po~shing unit where suspended solids and dissolved organic matter are deconposed efficiently. The preferred biological processing step is an~erobic polishing in which carbon~eous s~uterial is converted to metharle and other gases which can then be used as ~uel, preferably on-site. The biological sludge or biomass produced during biological polishing is recornbined with the dewatered waste which undergoes the~
treatment (aerobic or anaerobic). Preferably, anions such as phosphate, sulf~te, earbonate and oxalate ions are removed from the liquid stream during the de-~niating process. By adding calciwn hydroxide or another suitable precipit~nt to the liquid stre~n in the present invention, th~se anions are precipitated out of ~olution. Simultaneously, the addition of calcium hydroxide raises the pH of the liquid stre~m so that amnor,ia c~n be renved in an arr~nia stripper. The precipit~tes are separated from the stre~n ~nd added to the ash derived from thermal tre~ nt o the earbonaceous ~olids, and then dewatered for disposal or recovery.

The present invention ~lso cvntem~>lates the u~e of inte~lly-derived gaseous ~rbon dioxide to carbon~te ehe liquid stream ~ollowing the ~ion remDval/arn~nia stripping step. ~hi achieved in one aspect by bubbling biogas generated during biological polishing or during R subsequer;t wet oxidation stage ~rough the de-a~noniated liquid stream to preeipitate scale-~orming cations su~h i ~ : :

1 323q~3 086.10~
as c~lcium Qnd m~gnesium which m~y otherwise fo~n scale on the re~ction app0ratus during subsequent waste treatment. The resulting c~rbonate precipit~ltes are ~enadded to the ash to be dewatered and undergo disposal as described herein.

.
The liquid effluent strearn, after biological polishing, is the preferably further treated by aerobic polishing, evaporation/~ondensation or mDst preferably by ultrafiltration and reverse osmosis. me substantially deionized liquid stre~n is then preferably used ~s a feed diluent for di.luting ~he dewatered waste which also conhins the aforementioned ash and biom~ss. Alternatively, externally-derived, low-~hlol ide water may be used as the feed diluent. The diluted liquid waste is then :flowed islto a wet oxidation reHction app~ratus where the waste is heated and n~ixed with o2~ygen as it is ~ubs~ntiPlly, completely oxidized in an accelerated wet oxidation reaction. The exothe~nic wet oxidation reaction takes place at about 420-600 F, preferably between 530 and 550 F.
lhe heat generAted by the reaction m~y be recovered as ste~n o~ 150-lOûO psig, preferably 300-600 psig, to be used along with the aforementioned internally-derived methane to generate electricity, superheated steam or hot water. The influent liquid mny ~Iso be preheated &s may be required. l`he effluent from the wet oxidation re~ction is then processed in gas/liquid and 3~quidlsolids sep~rating equipment which preferably includes the steps of clarification, thiekening and dewatering. A porffon of the resulting low-volume, sterile ~sh is used as the weighting agent which is co~ined w~th the waste during the initial waste dewatering process. The rem~ining ssh may be reused as an snin~l food supplement or soil conditioner. The liquid stream fronn the wet oxidation reaction effluent is flowed to the biological polishing unit to be processed along with the de~ ni~ted liquid s~ream.

By first 32par~ting the soluble U)D from the wast~ before the dewatered waste is oxidized through wet oxidation, a greater concentraffon of w~ste ~fin be processed in the wet oxidation app~atus. ~ er, rean~ving the highly amnDniated liquid îrom ~e waste before ~e w~ste is oxidized through wet oxidation facilitates rena~val of a~rmonia to levels that do not ir~ibit biological --"" 1 3239~3 086.108 po:lishing ~nd reduces the production o undesirable nitrates. By using the internally-derived ash from the wet oxidation reaction as a weighting sgent which is added to the waste ~or the initial dewateringJ the sediment~tion rate of the waste is enhanced considerably. Also, since the ash derived ~rom the wet oxid~tion reaction generally retains some COD, by u~ing it as a weighting agent which then passes once agQin through the wet oxidation ~eaction apparltus, thisremQining COD is further reduced.

In another embodirrænt, live stock or other organic waste is diluted and fed directly into n wet oxidation reaction apparatus along with a source of oxygen. At an elevsted temperature and uJader pressure, the waste is oxidized through a wet oxidation reac~ion whereby ~he chemical oxygen demEmd OI
the waste is substanîially reduced. The reaction products or effb~ent ere then dewatered and the liguid portion so produced is processed by the method previously described which in~ludes ~e~ niating the liquid por~on, precipitatinK out seale-fo~ning ions, polishing the liguid porffon in a biological unit and, optionally, treating the liquid portion by ultrafiltration and reverse osmosis. This treatment substantially eliminates any Pemaining CODo The substantially deionized liquid strearn is then preferably used as a feed diluent for the waste which is flowed into the wet oxidation rea~ffon apparatus.

BRIEE DESCRIPTION OF THE DRAWlNGS

Figure 1 is a block diagram of the method o~ the pressnt invention.

Figure 2 is ~ block diagram o~ ~ por~don of tl~e present invention illustrating an alternative processing step.

Figure 3 is a blo~k diagram of an alternQtive embodin~nt of the present invention.

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, .

1 323q~3 2086.10~
DESCRIPTION OF THE PREFERRED EMBODIMEN~S

Referring now to Figure 1, the w&ste 2~ to be processed, preferably anirnal waste such Qs swine m~nure is ~olT bined with an internally-derived ~sh 22 ~t mixer 23, ~nd the mixture 2~ is dewatered by liquidtsolids separation 26. The ash acts ~s a weighting ~gent or body feed to enhance the sedimentetion of the raw waste during liquid/solids separa~ion. Other benefits o~
the present invention may be realized without the ~ddition of ~ weighting agent ~lthough it is preferred that a weightin~ a~ent be used~ Raw wAste does not sçttle rapidly. By combining it with ash, a heevier m~ss is creAted which settles m~re qui~kly, thus facilitating separa~ion. It is believed p~rticles of &sh serve as nuclei for the fom~tion of flocculent solids which then settle more rapidly. lBy using an internally~erived ~sh, no additional aolids ~re added to the system. Ash 2a is preferably mixed with waste 20 to evenly distribute it in waste 20. Other advantages of using this internally-derived nsh 22 as a weighting agent will be described m~re fully hereinafter. The weighted waste mixture 24 is suitably dewatered by centrifugation, vacuwn filtration, belt filtration or simply by ~llowing the weighted waste to settle in response to grevity. Other wa~te dewatering te~hniques including the: use of ~ coagulant aid mQy be suit~ble or desir~ble in parffcular ~pplic~tion.

Dewatering produces liquid stre~n 28 ~nd dewatered wsste 2~.
Liquid streun 28 may contain up to 50 percerlt of the chemical o2~gen dem~nd of the initial waste ao. Typical ~n~l waste rn~y have a COD of ~om about 80,0û0 mg/l to ~bout la0,û00 mg/l. Liquid streDm 28 cont~ins the dis~lved COD ~i~h ~y be fr~n sbout 30,000 mg/l to about 60,000 m~/l. In ~ddition, liquid stre~ 28 m~y contain most of the phosphorous eo~ounds (q0-400 mg/l) which were present in the hitial waste, from ~bout 3,000 to ~bout 6,000 mgtl of ~nia co~ pounds and considerable qu~ntities of ~oluble salts including chlorides. Liquid ~tream 28 is then de-~mnoniated, preferably by ~n amr~nia-stripping procedure 30 which n~y include raising the pH of the ~iquid stre~rn to drive off the amnDnia in the form OI
a v~por. This ~por ~an then be condensed ~s arm~onium hydro~cide ~ieh is ~086.108 preferably reclaimed for use RS El fertilizer 32. 1~ ~y be possible to de-arrrr~niate liquid stream ~8 using a biological reactor; however, conventional rrucrobes will generally not tolerate the high concentrEltion of arnnonia present in the liquid stre~n and, thus, substanti~l dilution of liquid stre~n 28 would be required. The ~Tmonia vapors c~n bP readily collected using a scrubbing stre~
although other methods mEIy be scceptable. While substantially a~l of the ammoni~
is removed from liquid stre~T 28, a sufficient quantity is left to act ns a nutrient for subsequent bivlogic~l processing.

lt is most preferred that precipitate-fo~ing anions such as phosphate, sulfate, carbonate end oxalate ions be removed from liquid stream 28 during the dç-arrn~niating process. This is achieved by adding calcium hydroxide or another suitsble precipitant to the liquid stream 28 to raise the pH, thereby vapori7ing the elTn~nia, flnd to precipitate these ions out of solution. The precipitates 31 are then directed to Ash liquid/solids sep~rator 64 where they are dewatered with the weighted ash. Following urm~nia stripping/anion removal, liquid strearn 34 is preferably treated to remove potentially scale-folming cations such as calcium and m~gnesium ions. By precipitating these cations with ~
precipitant which forn~ relatively insoluble precipitQtes, the potential to ~o~n scele during ~ubsequent wet oxidation is elimin~ted. In the present invention, these cations are removed by canbining liquid stream 34 with c~rbon dioxide in precipitator 35 to form carbon~te precipitates 135 which are then directed to ash liquid/solids sep~rator 64 to be dew~tered. The 2 used in this ~tep is preferably derived as biogas 38 fr~n biological polishing w~it 36 during a subsequent step.

The de~ Enoniated liquid stream 34, whi~h is subst~ntially deiorlized ~nd which contains enough phosphorous to meet biological nutrient requirerrænts, is then flowed to a biologic~l polishing unit 36 where suspended and dissolved c~rbonaceous mstter, remE~ining sul~ates and nitrates are ~ubst~ntially decorrQosed by mi~robes, preîerably ~n~erobic n~croorganisn~ such as EmHerobic bacteria. Although aerobic microbes could be used, this alternative would Peguire ,, ~ ,.

--"` 1 323943 2086.10~
th&t oxygen be supplied to biolo~ical polishing unit 36 Qnd, re irnport~ntly, that liquid stream 34 be substanti~lly diluted. This is due to the f~ct that ~erobic microbes cannot toler~e high COD concentrQtions Rt re~sonable hydr~ulic retention tirnes. During an~erobic polishing, biog~s 38 is evolved, princip~lly con~prising n~thane and carbon dioxide. Smaller amounts of c~rbon monoxide 8nd hydrogen sulfide mRy also be gener~ted. Biogas 38 is prefer~bly recovered, ~nd in some ~pplications it may be practicnl to separAte the constituent g~ses. Biogas 38 is preferably used on-site to generate heAt.

While liquid stream 34 may hsYe a COD as high QS 60,000 mg/l, ~fter processing in anaerobic polishing unit 36, the resulting liquid stre~n 40 has a ~)D of about 1,000 to 29000 mg/L There iS also produced a biornass or biologic&l sludge 39 during biological polishing ~onsisting of microbes which may represent Irom ~bout .1 to about 2.û pereent by weight of the COD of liquid stream 34 where the polishing is c~rried out by an~erobic microbes~ lhe percentsge of biomass 39 is much greater when aerobic microbes are used in aerobic polishing. Bio~ss 39 is recon~ined with the initial dewatered WASte 29 which undergoes fur~her processing ~s will be expl~ined herein.

Depending upon how stringent the effluent oriteri~ are in R
p~rticul~r setting, liquid stream 40 may then be tre~ted by aerobic polishing (not ~hown), provided the prior biologic 91 polishing step ~onsisted of an~erobic polishing. lhis further reduces the COD in rn~y instances to as low ~s 20 to 30 mg/l. Alternatively, and prefer~bly for use in the present invention, liquid stre~n 4û receives f~ther total solids rem~val. The preferred filtration process includes ultrafiltr~tion 42, ~ollowed by reverse ~mosis unit 4~. If necess~ry, co~gul~tion and media filtraffon (not ~hown) m~y precede ultrafiltr~tion. Both techniques are rane rlltration processes. IJltrafiltr~tion is a "Lqrge screen" process whlch ren~ves particulste matter having a diameter greater than ~bout .45 mi~rometer.
After 1:he particulate matter has been reved by filtration unit 42, llguid stre~n 46 is flowed to a reverse o~nosis wlit 44 ~ere substantislly all of the d~ssolved salts, including chlorides, are r~ved. After ultrafiltration 42 And reverse .

,, 1 32~q~3 D86.10û
osnosis 44, liquid ~tream 48 is substantiaLly pure, deionized water. In a modification of the present invention shown in Figure 2"~1trafDtrstion 42 and reverse osmosis treatment 44 are replaced by an evaporation step 50 in which w~ter is driven off to be condensed into ~ fluid s~ream 52, leaving any salts and very fine particulate mat~er behind in the form of ~ brine or cake. EvaporatiOn 50 is not necessarily preferred for use herein, however, because volatile orgsnics n~y be evaporated with the w~ter during condense,tion9 causing contamination. Itis in~ortant to note that either ultrafiltration 42 ~nd reverse o~mosis 44, or evaporation 50 produces a liquid stream which is substan~dally free of ~hlorides, magnesium, c~lciu n, and other such substances which are generRlly considered corrosive when brought in contact with metal surfaces. The deioni2ed or demineralized liquid stream 48 is then dischsrged or reused, prefer~bly as a ~eed diluent to dilute the initial dewatered waste 29 at mixer 54 to form diluted wsste 56. An external source of low-chloride water ~ould be used as the feed diluent.

If total desalination OI the discharge stream is not required, split stream trea'anent may he employed to meet the desired ef~luent dissolved ~olids ~ontent. In split stream ltreatment, only part o the biological polishing unit effluent 40 is des~linated by m0mbrane filtration or evapor~tion. lhe desalinated ~tream is then recombined with thQt portion of the stream which is not des~linated by membr~ne or ~vapolation resulting in a net reduction of dissolved solids.

The diluted waste 56 is then preier~bly treated by wet oxidation in wet oxidation reaction apparstus 58. lt is to be ~derstood that one of the ~portant adv~ntages of the present invention is the substantial reduction of the oxygen dem~nd of the waste by ~irst ~ rating and ~en di~/erting lhe liq~id portion ~ntaining the dissolved o~cygen demE!nd through th~ aforemention~d treabment steps. By r~ving the dissolved COI) fraTI ~e w~ste befo-e it iæ
~ubjected to an sccelerated wet oxidation reaction, 3everal benefits are achieved.
A greater ~oncelltration of waste ~an be flowed into lthe oxid~tion unit since lile waste has a substanti~lly reduced COD. This all~ws ~or b2tter ut~lization of the we$ oxidaffon reaction appsratus to convert l~e ~olid COD to liquid which is ml~>re 1 323~43 ,6.108 r~pidly digested by the biologieal polis~ing unit. ..~.lso, by first separating ~he liquid ~treQm from the waste, corrosion of Ule wet oxid~ion r~action ~ppar~tus i~s ~ubst~nti~lly reduced by virtue of the reduced chloride content.

Particul6rly ~vlth anim~l weste, dur~n~ wet oxidation, substantial ~orrasion of e~en high grade stsi~ess steel re~ction vessels nuy occur due to the high eoncentraffon of chlorides n the w~ste. allorides, ~ulfstes, phosphate, ~arbonates as well as calci~n ~nd other ions whjch ~.re ~ubstan~ y ren~ed by the method of the presene 3nvention, ~orm Insoluble compounds wh~ch m~y produce ~cale on the netsl w~lls of the re~c~ion ~pparatus vr c~use orevice and stress ~orrosion, resulting in oracking, spalling and ultimRtely eatastrophic fa~ure of the reaction ~pparatus. 8y remDyin~ these corr~sive and scAle-produofng con~nents ~rom ~e waste before wet oxidation, 1es5 expensive met~Ls n~y be ~ed oonstruct wet oxid~tion reaction ~ppsratus 58 ~nd less ~requent cle~ning of the walls o~ re~ction appsrstus 58 is needed. Oorrosion is fur~her redu~d in the present ~nvention by using ~ 10~N chloride feed diluent whieh is pre~erably derived intern~lly in the m~nner described. ~s ~tated, calc~n and other met~ onnlng ~oluble c&rbonates mEly also be roved by treQting the effluent 22 with e~flu~nt g~s. Ihe decreases se~ling even fiarther.

~ he met~d of we~ idati~ a~l ~e preferred wet ~idatio~ apparat;ls 58 used in *le ~ent inve~tion U5~ ~e principles disclosed in l~hited states Paterst No. 4, 272, 383 to I~I;rew ~ich assigned to ~e assi~nee of ~e present i~ ticn. ~e wet c~idatia~

dis~d c~ric bibes ne~d to form an influerlt waste passage and an efflu~t wa~te a~ulus. ~e reactian vessel e~ snds ~ertically a~ imately c~e mile bel~w ~ an~ is gen~rally kr~ as a do~hole we~ ~dati~ r~actic$l E;y~nO Dilut~ lig~id waste 56 is fl~d i~ the influ~t passage as an influ~nt waste ~;tre~. Dilut~ liq!lid waste 56 is heated b~ a a~ter a~nt heat e~ar~er as it ~l~rs into ~e wet oxidatian reactiQn a~ara~s 58, an~l a sauroe of cx~en 60, ~h as air ,. `i, --10--' ~ . '.

-` 1 3239~3 2086.108 flow inside reaction ~pparatus 58 provides good eont~cting and mixing between liquid wQste 56 ~nd oxygen 60. In the most preferred errbod~ent of the present invention, liquid waste stream 5B is he~ted u~ing waste heat recovered in the energy recovery unit including biogas 3g derived from the biolc~gical polishing unit 36 QS fuel. The oxygenated liquid waste forrns a hydrostatic colur~ of considerdble fluid pressure in the influent was~e p~sage where the exothe~ic wetoxidation reaction continues, generating substantial heat. Between 1, 000 and 6,000 feet below ground surface, a resction zone is establLshed where the ternperature of the liquid w~st~ reaches approximately 530-550 F, pro~ucing a self-sustaining, greatly accelerated wet oxid~tion reaction. Boiling of the r~terial at this high temperature is inhibited by the hydrost~tic fluid pressure of the ~olumn.

Although in our E~referred method diluted waste 56 is treQted by wet oxidation to oxidize the co~mbustible waste cornporlents, the wet oxidation step of the present invention may be repl~ced ~nth son# type of anoxic ~em~l oonditioning process ~nd may include hydrolysis or the like. As set forth in the aforen~ntioned McGrew patent, substantial heat ~an be recovered fro}n the wet oxidation reaction of the pref~rred method of the present invention which can be advant~geously used to heat the liguid influent waste stream.

Next, the effluent ~2 from ~e wet oxidstion reaction apparatus 58 is flowed to ash solids/liquid separation equipment 64 to fusther concentrate the ash solids. This solids/liquid separ~tion step preferably includes clarification, thickening, by ~ plate sepflrator and then dewatering to form sterile ash 22 and liquid stream 66. A gravity settler or dissolved air flotation unit could be used in lieu of the pl&te ~eparator. As ststed, at lea3t Q portion of the result;ng sterile ~ 2a ~ used as a body eed or weighting agent to pranote sedirnentation of the raw waste 20. In addition to its ability to pr~n3te settling of raw waste 20 during the initial dewaterirlg step 269 ~ny COD remEIining in ash 22 is further reduced in Its seoond trip through the wet oxidatIon app~r~tus 58. Liquid stre~n ~6 is flowed to the biological polishing unit 36 for further treab~nt in the described m~nner.

; , - ., ~; ~

1 3~39~3 20~6.108 ~t m~y be suitable ~nd necessary in some instHnces to first strip liquid e~fluent stre~rn 66 of alTmonia. However, as stated, the concen~ration of amnonia is very low at this stage due to the initial dewatering step of the present invention. Of courseJ as stated, this inili~l dewaterirlg step substantially reduces the amo~t of monia which passes through the wet oxidation re~ction Rpparatus~ thus reducing the prcduction of undesired nitrogen-containing efnuent products such ~s pyridenes and other nitrogen-containing organic ~ompounds.

lt is to be understood that in its broadest scope, the present invention cornprehends separating ~ subs~antially untrented waste to fo~n Q liquid portion and a solid portion using an internally~erived ~sh ~s a weigh~ing ~gent as previously described. It is preferred thRt the liquid portion so isol~$ed then be processed by the preferred method of the present invention.

Referring now to Figure 3 of the drawings, in ~nother ~nbodiment of the preserlt invention, raw subst~ntially unprocessed waste 100 is diluted preferflbly with an internally-derived diluent 102 which h~s been ~ubstantia~ desalinated. It may be possible to use a desalin~ted exte~ally derived diluent alone or in co~T~ination with internally-derived diluent 102. W~ste 100 is diluted with diluent 102 in mixer 104, ~nd the resulting diluted waste 106 ~s flowed directly to wet o~cidation app~r~tus 108 wbere it is corrbined with g~seous oxygen or an oxygen-rich gas 110. Diluted waste 106 pre~er~bly is diluted ~uch that solids ~re present in a COncentrQtiOn of about 5% by weight. In wet oxidation reaction apparatus 108, corrbustible waste present in diluted w~ste 106 is ~ubstantially oxidized. Ag~in, the preferred n#thod and apparatus for carrying out the wet oxidation reaction uses the principles disclosed in the McGrew patent, which w~s previously described. The reaction products or effluent 112, produ~d during the ~et oxidation reaction, ~re then 1Owed to 9ep8ragion equipment 114 where ef~luent 112 is deg~ssed when the liquid por~on is sep~rated ~om the solids.
me off gases llB include ¢arbon dioxide. Solids portion 117 comprises a low-vol~e sterile ash. The liquid effluent portion 118 is then pre~erably filrther processed beginning with the remDval of ar~nia and certain Qnions including -la-" 1 3239~3 086.10~
phosphate, sulfate, carbonate and oxalate ions. A part of liquid portion 118 r~yalso be flowed directly back to mixer 104 to be used in diluting wQste 100. It is preferred, however, that the liquid portion 118 receive fur~er treatment in the nnanner to be described.

Liquid por'don 118 is flowed into al7monia stripper/precipitntor 120 where it is con~ined with precipitants such as calcium carbonate 121. As previously ~escribed, the addition of calcium car~onatç! is controlled such ~at phosphate, sulfate, carbonate arsd oxalate ions are precipitated out of soluffon ~nd the pH of liquid portion 118 as sufficiently raised such that amr;onia is driven off as a vspor to be condensed for use as a fertilizer 122. ~ liquid stre~rn 124 B
lthus produced which has a subs$an~dally redueed amnonia content and fro~n which the ~oregoing anions have been substan~ially removed. ~ufficient nitrogen c3mpounds sre left, however, in liquid stream 124 to facilitate ~ubsequent biological polishing.

Liquid stream 124 is then flowed into preclpitator 126 where it is mixed with carbon dioxide from the off gases 116 derived during the degassin~ o~
the wet oxidation effluent 112. Any poten~cial scale-forrning ions remEIining in liquid stream 124, such as calcium and mEIgnesium ions~ are ~ereby carbonated The resulting de-ar~oniated, deionized stresm 128 is then nowed into biological polishing unit 130 where anaerobic n~crobes decorr~ose n~ch of ffle dissolved Rnd suspended organic Ir~tter. Biological polishing 130 mQy include a $equerlce of ~naerobic polishing followed by aerobic polishing if desired in ~ particular application. Biogas 131 is evolved AS aL byproduct of the biological p~lishing process and includes methane snd carbon d~oxide. It mE-y be appropriate, as in the pre~iously des~ribed elTbodirnent9 to use biogas 131 to c~rbonate liquid strea~n 12~
to r~3ve magnesium And calci~n ions By stripp~ng out the c~rbon dioxide in this n~nner, the fuel value of biogas 131 is incrsased due to the re~lsltant inere~se in the percentage o~ methane. Sludge or bi~s 132, which is also generated during the biological polishing step, is coTrbined with the diluted waste in mixer lOJ. to be oxidized in wet oaddation appar~tus 108.

1 323q~3 20~6.10~

Liquid stream 134, resulting after biologic~.l polishing 130, h~s a substanti~lly reduced COD. Prefer~bly, liquid stre~m 134 receives filrther processing by Iiltration unit 136, which is prefer~bly an ultr~filtrQtion system.
The filtered stre~rn 138 is 'chen treated by reverse osmosis ~re~ent 140, vthic~
produ~es diluent liquid stream ~02 th~t is substantially free of ~hlorides, msgnesium, c~lcium, phosphate, sulf~te, carbona~e and oxalate. me removal of chlorides, rnRgnesium, and calcium are particul~rly significant due to their tendency to corrode met~l surf~ces ~s previously indicated. lhe deionized or deminera~ized liquid strearn 102 is therl pre~erably used ~s a diluent for waste 100 as described.
As in the previous embodimen~, filtration 136 and reverse asmosis 140 m~y be replaced by evaporation me~ns (not shown). Of course, r~ther ~an using liquid s'¢eam lD2 as ~ diluent, it mEly be sirnply discharged into receiving waters.

HAving described the preferred method of the present invention, it is to be understood that various m~difications m~y be made to the invention disclosed herein within the purview OI the appended claims.

Claims (19)

1. A method of treating organic waste having a liquid component and a solid component, comprising the steps of:
weighting the organic waste with ash to accelerate sedimentation of said weighted organic waste;
separating the weighted organic waste to isolate said liquid component from said solid component;
chemically reacting said solid component to substantially lower the oxygen demand of said solid component and to produce a liquid effluent and an ash, a portion of said ash being used in said weighting step to weight said organic waste;
de-ammoniating said liquid component to form a de-ammoniated liquid stream;
combining said liquid effluent with said de-ammoniated liquid stream to form a combined liquid stream;
and contacting said combined liquid stream with biologically active microbes to lower the oxygen demand of said combined liquid stream.
2. The method for treating organic waste recited in claim 1, wherein said separating step includes allowing said weighted organic waste to settle in response to gravity to separate said liquid component from said solid component.
3. The method for treating organic waste recited in claim 1, wherein said chemically reacting step includes diluting said solid component with substantially deionized water, adding oxygen to said diluted solid component, and elevating the temperature of said diluted solid component to produce a wet oxidation reaction.
4. The method for treating organic waste recited in claim 3, wherein said chemically reacting step is carried out in a vertical, down-hole wet oxidation reaction apparatus.
5. The method for treating organic waste recited in claim 1, wherein said de-ammoniating step includes ammonia stripping.
6. The method for treating organic waste recited in claim 1, wherein said biologically active microbes include anaerobic microorganisms which convert organic waste to methane, carbon dioxide and other compounds.
7. The method for treating organic waste recited in claim 1, wherein said chemically reacting step includes anoxic thermal conditioning of said solid component.
8. A method for continuous processing of organic waste having a liquid component and a solid component, comprising the steps of:
adding ash to said organic waste, said ash serving to weight said organic waste;
separating said weighted organic waste to isolate said liquid component from said solid component;
oxidizing said solid component of said organic waste in an accelerated wet oxidation reaction to lower the oxygen demand of said solid component and to form a liquid effluent and an ash, said ash being used in said ash-adding step;
de-ammoniating said liquid component to form a de-ammoniated liquid stream;
adding said liquid effluent to said de-ammoniated liquid stream to form a combined liquid stream; and contacting said combined liquid stream with biologically active microbes to reduce the oxygen demand of said combined liquid stream and to form a low oxygen demand stream.
9. The method for treating organic waste recited in claim 8, further including the step of filtering said low oxygen demand stream to remove substantially all suspended organic matter and substantially all salts to form a deionized stream.
10. The method for treating organic waste recited in claim 9, wherein said oxidizing step includes diluting said solid portion with said deionized stream to form a liquid influent, flowing said liquid influent into a vertical, subterranean wet oxidation reaction apparatus, adding oxygen to said liquid influent, raising the temperature of said liquid influent to produce an accelerated wet oxidation reaction, whereby said solid portion of said organic waste is substantially oxidized.
11. The method for treating organic waste recited in claim 9, wherein said step of filtering said low oxygen demand stream includes ultrafiltration followed by reverse osmosis.
12. A process for treating organic waste having an oxygen demand, comprising the steps of:
weighting said organic waste with an internally-derived ash, said weighting step including combining said organic waste with said internally-derived ash to form a weighted organic waste and mixing aid weighted organic waste to substantially, evenly distribute said internally-derived ash in said organic waste;
separating said weighted organic waste into a solid component and a liquid component, said liquid component having at least a portion of said oxygen demand of said organic waste;
oxidizing said solid component in a wet oxidation reaction in a vertical, down-hole wet oxidation reaction apparatus to form said internally derived ash for use in said weighting step and to form a liquid effluent;
de-ammoniating said liquid component to form a de-ammoniated liquid stream;
combining said de-ammoniated liquid stream with said liquid effluent to form a combined stream;
contacting said combined stream with biologically active microbes to reduce the oxygen demand of said combined stream and to produce a low oxygen demand stream;
and filtering said low oxygen demand steam to form a deionized stream.
13. The process for treating organic waste recited in claim 12, wherein said oxidizing step includes diluting said solid component with said deionized stream.
14. The process for treating organic waste recited in claim 12, wherein said de-ammoniating step includes ammonia stripping.
15. A method for processing waste containing organic matter which includes the wet oxidization of said waste to produce an ash having a first COD level, said method comprising the steps of:
combining said ash with said waste to form an ash-weighted waste;
separating said ash-weighted waste into a liquid portion and a solid portion; and oxidizing said solid portion in a wet oxidization reaction such that said first COD level of said ash is reduced to a second COD level.
16. A method for treating waste containing organic matter comprising the steps of:
diluting said waste with a substantially de-ammoniated, deionized diluent;
chemically reacting said diluted waste in a wet oxidization reaction apparatus to substantially lower the oxygen demand of said waste and to produce a liquid effluent, an ash, and a mixture of gases;
separating said liquid effluent, said ash and said gas mixture;
de-ammoniating said liquid effluent to form a de-ammoniated liquid stream;
contacting said de-ammoniated liquid stream with biologically active microbes to lower the oxygen demand of said liquid stream; and treating said liquid stream after said microbe contacting step by ultrafiltration followed by reverse osmosis to produce said de-ammoniated, deionized diluent.
17. The method for treating waste containing organic matter as recited in claim 16, further including the step of removing anions from said liquid effluent during said de-ammoniating step.
18. The method for treating waste containing organic matter as recited in claim 17, further including removing cations from said de-ammoniated liquid stream by combining said de-ammoniated liquid stream with carbon dioxide.
19. The method for treating waste containing organic matter as recited in claim 18, wherein said carbon dioxide is derived from said gas mixture.
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DE3873112T2 (en) 1992-12-03
DE3873112D1 (en) 1992-09-03
EP0278745A2 (en) 1988-08-17
US4765900A (en) 1988-08-23
DK63688D0 (en) 1988-02-08
EP0278745B1 (en) 1992-07-29
EP0278745A3 (en) 1988-10-19

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