Document v6pNr5xogob08BB7jovEMdkg6

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I '' ' I i ) U'r A 1 u. /V/^ r~o dmc.Ali &>+*--* -^c ^ La--UAJ2.S , ^19^"/ rtbtwfbj*'y jEsaJt. Ccty^, Xco^is CAI U,LA'i 'OM SH riT - F- lf.Lv CCR ooo0 3S34 \JCVA J- OexV- J ^vpo-vv.siov''--. r/ix 0 . *) 3) ftvre- -Av> Jl\>ou5 ^tjc e^tAot* W)Ctr5' AtjvaJvv 5'Vrju3ayv ' \J>^ JJ^CX^AAA^ \A vc^Wt_ W^- Ou)x- Cvv^te&Sotu- Q-- O VY\or- CAaiU^S-V - aJLQ. Cto-c^OT'S )00`/o -- uaa- srWV't V>o3> . *0 *\H.-3o4 *-^>re-Vfijo&,et" 3-So sA^o/tv-i e^tcN'*" ^S>Ckx\i. ^\ovO *" ow Ia/v%*_< /^p v^vwwfli feu^&Aowv t A u^x^V'-O- *4 UoS-vY-* - Sorvxjl. ^ t) vcu,cir 0 *t>C- "t'voyjcic ( FcCLt. cOdSot **) c*vvyr?,fi>6r -- A<a fccui, Sc*eA-u--- A t-o Ok ~ -io-f 3^ "^sro'bLtvvvJ> - Wvct^Va^ "Vto CawA-ew*^. w^j.4* CA--t_ Ar- Airc^Jr (^Cz. % KJctk- lbv-*cU^JS(vtlni Ao Oxjj. C^O-V/Al * C-^J AorV8_ So\vAs V^CUo^Or-S ! ^ C_<i*~*fKc_ v^cUL&JLS. ........ 4) ^p^pS. ............................................................. . U1 Tw^'wA-irw Etc . j. !._;__[_ _______ 0 'YqjC^s^' !1 -O S\cjO^vvx A.- Cl viw c^rrvAaa.serS < <**3^ -- *? _ . t; H*&c. L.E1. cL A - SoVvAs fc*AV\JC>V)eJ5 (^-prior- A(0 -^fJvvA-S 3 , \)C^ V^JUwc\_ vt- "pre- co^r ^t>C_ - moV `Vojt?>. ^.) h\<iU 6o\vyV 'CMjoi^vC^-S -M M a n t Li y C M LCl X t) -JY ^4jo'l^ e'ctw^s. .* rt-3o3"^ ^ A -304- /3fe*2- ; }A-3*03/310 CQNTIN^Nr*'l. Oil. C'.IV/ASV CALCULATIOM : l-l'/ZT -'-'JNo. .. -------- Tm.r OCR 000038835 [Environmental management < Ozone/UV process effective wastewater treatment Toxic wastes made harmless with commercially developed process certain composite wastes including: glycine, NH3CH2GOOH, the smallest amino acid; ethanol, CH3CII2OH; acetic acid, CH3COOH; glycerol, CH2OHCHOHCH2OH; palmitic acid, CH3(CH2)wGOOH; nitrogen com H. W. Prengle, Jr., C. E. Mauk, R. W, Legan and C. . Hewes, HI, Houston Research, Inc., Houston pounds; potassium cyanide; complexed cyanides, cadmium, copper, nickel, iron; photographic wastes, bleach, fixer; medical wastes; secondary effluent, and others. The most Chemical oxidation of difficult-to-handle impurities in waste-water is practical and economical using an ozone ultraviolet radiation process. The process is particularly effective with toxic and highly refractory compounds such as alcohols, acids, amino acids, fatty acids and polyhy droxy alcohols. Many compounds may be economically difficult to oxidize species are potassium ferricyanide, ethanol and acetic acid; the latter, a product of partial bio and chemical-oxidation of numerous organic materials. In the absence of UV radiation, acetic acid is essentially unoxidized by ozone; however, with UV radiation oxida tion proceeds rapidly at room temperature. oxidized whose reaction rates would otherwise be too REFRACTORIES AND TOXICS CHARACTERIZATION low to be processed in other systems. For purposes of comparison of different refractory and The process can be used in a number of configurations toxic species, a "Refractory Index (RFI)" is defined t Aiepeiiuiug on application. Tv [mail., it is used 10 handle which is a measure of the difficulty of oxidation ot a toxic and/or potentially toxic (when chlorinated) im given molecular species; i.e., the larger RFI, the more purities as a combination secondary and/or tertiary difficult the species is to oxidize. A set of standard run process. Performance unequaled by other systems is conditions are used as follows. i. achievable because of efficient staging of the ozone reactor system with ultraviolet light and results in low capital Ozone is used as the oxidant in a run conducted at room and operating cost. Ultraviolet radiation enhances the temperature (25-27 C). Initial concentration of reactant reaction with ozorie'TfP to 10* fold and drives the reaction is 50-100 mg/1. Reactor is operated in the good to excel to completion to harmless materials such as C02, II20, lent mixing regime. No ultraviolet radiation is used. etc. RFI is calculated by the equations, Much attention has been given to tertiary treatment processes (carbon adsorption, ion exchange, reverse osmosis, chlorination, etc.), which can be added to con ventional wastewater treatment processes to remove diffi cult to oxidize refractory compounds and toxic species and provide effluents which will meet tighter projected discharge standards. However, a number of tertiary pro cesses do not remove all undesirable species some of which RFI (hrs.) = . Bt (TM3/1) (hrs.) A" (mg/1) (la) B t Imp/1) =_ mB (mg/min.) t% (min.) V(l) (lb) where B is the cumulative 03 pumped into the liquid produce highly undesirable species1 when chlorinated in final treatment before discharge or in municipal water TABLE 1--RFI values for various compounds treatment. Now chemical oxidation with ozone is commercially feasible for industrial municipal wastewater treatment for high rate oxidation with improved mass transfer, devel oped through high interfacial area in a continuous stirred reactor and an optimized reactor system to achieve total utilization of the ozone through use of a multistage reactor. UV radiation provides a critical key to enhance reaction rates dramatically. Experimental work prove the process1 ability to oxidize a wide variety of both inorganic and organic species and Compound KCN....................................................... Color fa-'units)................................... Complexed Cd-cyanide................ Phenol.......................... ................. Ammonium ion........................ .... * Simulated medical waste................ Glycine.......................................... .. Palmitic acid (as NH-salt)..... Glycerol.................. .... ^..................... Ethanol................................ Complexed ferricyanide............... Acetic acid......................................... RFI-valuo 0.41 0.66 0.96 4.4 8 13 19.7 27.3 112 246 270 >1.000 Qualitative Beale Slightly refractory (RFI < 1) Refractory (RFI 1 ^ 100) Highly refractory (RFI 100 - 1,000) Very highly refractory (RFI > 1,000) CCR 000038836 82 October 1975 Hydrocarbon- Processing Fig. 1--Typical removal curves for refractory compounds by ozone with UV near 30* C. phase from t ~ 0 to f = f^, per liter of liquid Fig. 2--Ozone oxidation of acetic acid, effect of temperature at low UV intensity. <54 is the time required for 50 percent complete conversion of the reactant component, as mea applied to treatment of many other wastewater species % sured by TOG for organic species and an ap some of which are represented in Fig. 1. Curves of Figs. propriate method for inorganic species 1, 2 and 3 result from experimental studies in a batch, A0 is the initial amount of reactant component continuously sparged and stirred mix reactor. Reactor ms is the Os mass feed rate to the reactor V is the liquid volume in the reactor. design permits direct size scaleup without difficulty.3'4 Acetic acid, which is an important intermediate oxida tion product of most organic materials, is also one of the 'Values of RFI of various compounds studied are shown in Table 1. Potassium cyanide (free cyanide) is least C refractory of all compounds studied; acetic acid is most ' refractory, with complexed ferricyanide, ethanol and glycerol in the highly refractory category. more difficult to oxidize species (Fig. 1). However, a slight elevation in temperature has a marked effect on acetic acid destruction (Fig. 2). The mass transfer limiting line is the theoretical ,,lcidiio:neti'ic 'c-scd --. ll.- rate at with ozone is added to the liquid. Improvement up to this limiting line by elevating temperatures alone is OZONE OXIDATION WITH UV Although the Ozone-UV process was initially developed for treatment of complexed cyanides,2 it is successfully impractical. Ultraviolet light can be used to further improve ozone oxidation of acetic acid (Fig. 3). No reduction of TOC TABLE 2--Photochemical data on refractory compounds Compound/(RFI) Acetic acid (>1,000) Structure O H*C--C \m UV absorption range(nra) Peak:205 180-230 Primary photochemical procease* 1) R + COaH++ (or COa + H) 2) RCOa+* (or R + COj) + II 3) RCO++ (or R + CO) + OH 4) RH + CO. ' Reference `(p. 428 and 431) Ferricyanide (270) Ethanol (345) Glycerol 012) ' Glycine (20) [Fe(CN)rs H A--H.C-- OH 1 H H A--HaC-- CHa Ah Ah bn Ho 1. S HaN--C--C li \ 230 Peak: 182, 152 150-200 Peak: 210. 260 190-280 Peak: 240. 210 190-240 Electron transfer to water of hydration 1) CaHt*+ (or Call. + H) + Oil 2) CHaCHiO** (or CHa + CHaO) + H 35 CaH + HaO 4) CHaCHO + Ha 5) CHi + CHaO Free radical and intramolecular photodissoclative processes *(p. 270) *(p. 442. 444) 1) Add type processes, and 2) Amine type, RNH + H 7*(p. 455 ff) Chloroform f H--C--CI ' ' ^ " Ai - 4 " 1 *1 Peak: 285, 180 - 1) Free radicals 250.240 fv (similarly for CCU) v Peak: 260 150-300 1) OatS.) -4 Oj(Si) -Z) nO,sr(tb,ir) OaOA.) ++O0H(*OD) ) -> ->3) Oa(So) Oa(Ti) Oa(Z:,") + Of*P) <(p. 526. 627) J(p. (207-209) Hydrocarbon Processing October 1975 CCR 000038837 .. 83 \ O PRIMARY PHOTOCHEMICAL PROCESSES INITIAL OXIDATION COj + H:0 + Nj... 1 CO? + HzO... C02 + HjO Fig. 5--Over-all photochemical/oxidation process to produce CCh, ELO, etc. CHEMICAL COAGULATION SEDIMENTATION, CLARIFICATION & EQUALIZATION pH ADJUSTMENT CHEMICAL OXIDATION (I) CHEMICAL OXIDATION (II) OFFGAS Fig. 6--Process flow for mixed cyanides plus organic refractories oxidation. HO I II RC -- C- OH+03 HO HO I H,, RC -- C -- OH -- O -- O -- O- RC-C- OH+ Ot A. (3) The cycle of the chain propagation is then closed by the free radical removing a hydrogen from a neutral mole cule HO HO I II I II RC^C--OH + RH ^ RC -- C--OH + R- O- OH (4) with the unstable molecule immediately rearranging to release C02 Hydrocarbon Processing Octobei 1975 HO H I II I RC--C --OH -> RC -- OH+C02 II OH H (5) In a similar manner, alcohol formed is oxidized to an aldehyde, which is in turn oxidized to an acid. Therefore, for long chain molecules a cycle results, alcohol -- aldehyde -- acid -- alcohol 4- CO2 tI and in the limiting case of a one-carbon-chain, water (not alcohol) is formed on oxidation of the acid. UV radiation produces substantially more free radicals than ozone alone; the radicals initiate many more propa gation chains and cause the over-all reaction to proceed much, much faster. The over-all photochemical process to produce C02, H20, N2, etc., can be represented schemat ically (Fig. 5). The two-step initiation process (primary photomechanical process and initial 03 oxidation) is fol- CCR 000038839 85 i I / alum, activated silica and polyelcctrolyte, followed by sedi mentation, clarification and equalization. The pH is adjusted to 7-8 by acid addition for best results in the chemical oxidation reactors. A single-stage reactor (I) to oxidize front end RFI compounds is followed by a multi stage reactor for final oxidation of high RFI compounds. Multistaging permits more effective oxidation, reduces .u total reactor volume and thereby capital cost. Ozone is supplied by a commercially available ozonator. The unit operates on air. Installed plant cost is $590,000 and operating cost, in cluding amortization, is approximately $500/day. Removal of ammonia, cyanide and organic nitrogen compounds (Fig. 7). Wastewater treatment processing 700 tons/day (117.4 gpm) containing ammonia, cyanide and organic nitrogen compounds -with a total nitrogen content of 1,000 mg/1. The objective of the plant is to reduce the ammonia, cyanide and organic materials to a dischargeable level. The first step is to adjust pH to basic and strip out am monia with steam. Afterward, pH is further adjusted to near neutral for best results in two chemical oxidation reactors. Ozone is provided by generators using recycled oxygen. Installed facility cost is $334,000 and operating cost (including amortization) is approximately $225/day. Tertiary treatment to specifically oxidize refractory organics which would produce toxic compounds if chlo rinated (Fig. 8). Potentially toxic refractory organic compounds remain ing after secondary treatment and carbon adsorption are removed in this facility. A stream of 1 million gallons/day / contains 10 mg/1 of TOC which must be reduced to a conccuttafiou c less than 0.1 mg/1. the influent stream from the previous units is flow controlled to the multistage reaction unit where compounds undergo complete oxida tion to carbon dioxide and water. Ozone is supplied by commercially available ozonation unit operating on air. Ozone concentration is adjusted automatically by an efflu ent monitor. Installed cost of the entire facility is $505,000. OFF GAS Fig. 8--Process flow for oxidation of refractory organics. Fig, g--installed cost of stainless steel reactor, mixer and UV lights. PROCESS ECONOMICS Effective reactor staging results in lower total amortized capital and operating costs (Table 3) where the optimum cost is less than a third of the single-stage treating cost, A similar cost analysis can be prepared for any wastewater species for which reaction rate data are available. Indica tion of the cost contribution for a reactor with mixer and ultraviolet lights is given in Fig. 9. Costs of ozone gener ated from air and from oxygen (Fig, 10) include the cost of oxygen. ACKNOWLEDG M ENT Houston Research, Inc., wishes to acknowledge the U.S. Air Force Con tract (AFSC/AFVVL), F29G01-73-C-0065, and U.S. Army Contract (MERDC), DAAK.02-74-C-0239, under which substantial development of this process was carried out. LITERATURE CITED 1 Bcllar, T. A., Lichtenberg, J. J., and Krongcr, R. C., "The occurrence of organohalidcs in chlorinated drinking water," EPA*670/4-74-008, NERC, Cincinnati, Ohio (November 1974). * Gamon, R. L., Mauk, C. E*. and Prcnglc, H. W., Jr., "Advanced Oa* oxidation system for complcxcd cyanides," First International Symposium on Ozone for Water and Wastewater Ticamtcnt, Washington, D.G., (Dec, 2-5, 1973), International Ozone Institute, Waterbury, Conn. (1975). Barona, N., and Prcngle, II. W. Jr., "Design reactors this way for liquidphase processes," Part 1' and Part 2, Hydrocarbon Processing (March and December 1973). 4 Prcngle, II. W. Jr., Chanslor, F. C.,and Kclada, M., "Power requirements, gas holdup, intcrfacial area and mixing characteristics for a gas-liquid reac tor," Chemical Engineering Department, University of Houston (l`J74). Calvert, J. G., and Pitts, J. N., Jr,, Photochemistry, John Wiley (1906). Fig. 10--Cost of producing ozone, including 10-year amortiza tion. * Dow Chemical Co., Manufacturing Chemists Association Research Project (UV Spectrum No. 57), Texas A&M University (1964). 7 Friedman, L., and Kline, O. L., J, Biol. Chem., 184, 599 (1950). 8 Simons, j. P., and Yarwood, A. J,, Trans Faraday Soc., 57, 2167 (1961). Alder, M, G., and Hill, G. R., /. Am. Ckem. Soc., 72, 1884 (1950). 14 Criegee, R., "Products of ozonation of some olefins," p. 133 ff, Advances in Chemistry Series No. 21', Osone Chemistry and Technology, American Chemical Society (1959). 11 Bailey, P. 5., Bath, S. 3., and Ashton, J, B., "Initial attack of ozone on an uwaturated system," i>. 143, ibid. 13 Schubert C. C. and Pease, R, N., /, rim. Chem. Soc., 78, 2044 (1956). 13 Dilli'fnuth, F. J., Skidmore, D. R.f and Schubert, C. C., /, Phys. Chem., 64, 14% (I960). 14 Bailey, P. S., Potts. F. E., Ill, and Ward, J. W., /. rim. Chem. Soc., 92, 23(1 (1970). ** White, II. M.p and Bailey, P. SM /. Org. Chem., 30, 3037 (1965). Hydrocarbon Processing October 1975 (XR 000038841 87 PURE WATER SYSTEMS, INC 4 EDISON PLACE FAIRFIELD, NEW JERSEY 07006 TEL: (201)575-8750 November 14, 1979 M. McCaulley Conoco P.O. Box 727 Westlake, LA 70669 Mr. McCaulley: In response to your recent request, I am forwarding information about the ultraviolet purification equipment that we produce. Our research has recently resulted in our being able to expand the use of our "thin-film, high-energy" ultraviolet equipment into the arena of destruction of toxic compounds. Qnj--pnQPRB encompasses the injection of an oxidizing compound 2 (AA^'n^:'0 f^-ow stream of the compound being treated followed oy^exposure to our high intensity ultraviolet plasma for approximate ly 200 seconds.This ultraviolet exposure has a multiple reaction in the decomposition of the toxic compound. The H_0 is dissociated photochemically to H, OH, and 02- Additionally, the 184 nanameter ultraviolet will ioni ze the 02 to/'T5TT>The combination o 6h and_0, with the ultraviolet environment ''supply sufficient energy potential for the destruction of not only a very wide range of toxic compounds, but very high concentrations of these compounds. Compounds which we have sucessfully treated to are: cyanides (ferro, sodium, potassium, and complexed cyanides), phenols, PCB's, THM's, DDT, acetic acid, organic contamination of tungsten, and others. Total process time required for the most difficult compounds is two hours. Destruction is to levels beyond detectability (less than 10 ppb). We have laboratory equipment for treating small quanity samples to demonstrate the efficiency of the process and to afford data which is required to scale-up to required volumes. We currently have fullscale toxic destruct equipment with flow capability to 100 GPM. Thank you for your inquiry, and we look forward to serving you further. Very truly yours. PURE WATER SYSTEMS, INC, /uA,' S'' M. Dale Wood President MDW:lvm Ends. Please refer further requests to Wayne Wren. ! OCR 000038842 IA fM*nWn ~4 i mi r-itfiMfeVr"'J WiiriiiitfiSiiifn Ok C1FEC + UV ulVJr Q Scc^oW CHLORINE DIOXIDE GENERATOR United States Patent 3,975,204 THEORY OF OPERATION Because chlorine dioxide is an extremely unstable gas, it cannot be packaged in containers as is chlorine or sulfur dioxide. Therefore it must be generated at the point of use. The most prac tical method is to react an aqueous chlorine solu tion with a sodium chlorite solution producing the following stoichiometric reaction : Cb + 2 NaCIOz --^ 2 CIOi + 2 NaCI (2-1) Therefore, 1.34 lbs of pure sodium chlorite (NaCICb) will react with 0.5 lb chlorine to produce 1.0 lb chlorine dioxide. Most technical grades of sodium chlorite are only about 80 percent pure, so that in practice it requires 1.7 lb of chlorite for the above reaction to be complete. The other important factor in the above reaction is that it must be at a controlled low pH, less than 4.0. SYSTEM DESCRIPTION (see figure 1) The installation consists of a recirculation loop of aqueous chlorine solution under pressure in a Iuvvy !eghlie willed (jieveiHo negative hydrau lic gradient conditions which are detrimental to the process. Recirculation is accomplished by a special corrosion-resistant positive displacement pump (A) This is the secret of the success of the CIFEC " enrichment loop " concept. It insures optimum conditions for the reaction of equation 2-1. There fore the CIFEC system is capable of producting continuously and reliably a chlorine dioxide solution that is 95 to 98 percent pure. This is the only on-site generation system that can make this claim. The current USA methods use an excess of chlorine to insure maximum yield of chlorite to chlorine dioxide. The result is a solution mixture of approximatly 70 percent chlorine and 30 percent chlorine dioxide. This confuses and complicates the measurement of chlorine dioxide residuals in the treated process water. Therefore the French method can be controlled by chlorine dioxide resi duals, but the USA methods must be controlled by the sodium chlorite dosage. which also provides the hydraulic power to operate the chlorinator injector (B). A rotameter assembly and diapinagm valve (C) allow die control and regulation of the make-up water. A sodium chlorite metering pump (E) injects a specified concentration of solution from the so dium chlorite tank (F) into the CIO2 reactor (D). Here the reaction between HOC1 and NaCICh pro duces CIOj. Control equipment (G) contains the controls for the operation of the two pumps and switchgear necessary to automatically stop the system in the event of failure of water supply or chlorine supply. The entire assembly is mounted in a high rigidity PVC chassis reinforced with plastic coated steel for maximum corrosion resistance. SPACE REQUIREMENTS The CIFEC generator can be" located in a small area. The equipment is mounted on a chassis ready to operate with all necessary wiring and piping connections. The sodium chlorite tank and chlorinator and chlorine supply cylinder are usually located outside of, but adjacent to, the generator chassis. The chlorinator can be cylinder mounted. wall mounted or mounted in a separate module. In addition to a clean water supply and electric power, a proper drain must be provided for the usual accumulation of waste overflow which occurs during normal maintenance procedures. Specific dimensions of the generator and chlorite tanks are listed in the technical data section. AUTOMATIC CONTROL Flow proportional control of the CIFEC system can be achieved by the use of a 4-20 ma electric analog signal. This can be expanded to include residual control if desired. CLi'fi) CL-tO ------------------ TECHNICAL DATA -------------- Accuracy 4 % of indicated flow rate. Capacities 10. 25, 50, 100, 200, 500 and 1000 Ib/day chlorine dioxide. Feed range 10.1 for any combination of chlorine and sodium chlorite. operating water supply Must be reasonably clean, operating limits 25-150 psi at 35-70 F. Pressure at point of application Maximum allowable is 6-8 psi depending on maximum flow rate of CICh. Water supply For CICh capacities of 10, 25 and 50 Ib/day is 1-3 gpm, 100 Ib/day is 5 gpm, 200 Ib/day is 10 gpm, 500 Ig/day is 20 gpm, and 1000 Ib/day is 40 gpm. Electrical requirements 220-480 volts A.C. 3 phase 60 Hz current for recirculating pump and 110-V-AC single phase current for controls and alarms. Power requirements This varies from 1-5 HP depending upon size of unit. Sodium chlorite metering pumps Sodium chlorite tank capacity Pumps are furnished in accordance with capacity of the generator; this varies from 30 gpd for the smaller unit up to 1200 gpd for the largest unit. 105 gal, 130 gal, 265 gal and 500 gal depending on size of metering pump. Generator dimensions Up to and including the 200 Ib/day unit: width : 3 ft 7 in, depth : 2 ft 1.5 in, and height: 5 ft 9 in ; the 500 Ib/day unit is : widht: 4 ft 1 in, depth : 2 ft 7.5 in, and height: 6 ft 5 in ; the 1000 Ib/day unit is : width : 5 ft 5 in, depth : 3 ft 1 in, and height: 7 ft 5 in. Sodium chlorite 105 gal = 32 X 33 inches - 130 gal = 34 X 36 inches and tank dimensions 265 gal = 47 X 50 inches. CCR 000038845 ADVANTAGES OF CHLORINE DIOXIDE The most significant chemical properties of chlorine dioxide as they relate to potable water and waste water treatment are as follows : 1/ CIO2 does not react with any natural or man made precursors to form chloroform, which is a known carcinogen - as does chlorine com pounds. 2/ CIO2 does not react with ammonia nitrogen to form germicidal compounds of inferior effi ciency ; PRACTICAL CONSIDERATIONS The most important attribute of chlorine dioxide is that its bactericidal efficiency is equal to that of free chlorine regardless of the presence of ammonia nitrogen. Therefore on a cost-effective basis the use of chlorine dioxide as a disinfectant for high quality secondary effluents and tertiary effluents is of considerable interest. It could easily be the chemical of choice for disinfection require ments of 2.2/100 ml total conforms particularly where virus kill is required. 3/ CIO2 unlike chlorine keeps its germicidal effi ciency in the pH range of 7 to 10. 4/ CIO2 does not give a chlorine taste to water. 5/ CIO2 destroys phenols. 6/ CIO2 has a continuing disinfecting power twice than of chlorine. 7/ CIO2 has a virucidal, bactericidal and algicidal power higher than chlorine. In other situations of potable water and waste water treatment, chlorine dioxide is very effective in removing color and taste and odors resulting from organic compounds. It is specific in its des truction of phenolic compounds. It also is one of the most effective oxidants for the removal of complex organic iron and manganese compounds. In food processing plants where the ammonia nitrogen content of the recycled water is greater thant 2 mg/I, chlorine dioxide kills bacteria on the same order as free chlorine. the new method CIFEC-PALIN for chlorine dioxide analysis With this colorimetric method it is possible to mesure separately chlorine dioxide, free chlorine, mono-, di- and trichloramine, sodium chlorite and ozone in the same sample. CCR 0038846 Cie INDUSTRIELLE DE FILTRATION ET D'tQUIPEMENT CHIMIQUE S. A. 10, civ. de la Porte Molifor, F 75016 PARIS - Tel. 651.52.04 - Telex 611 627 F principle of operation The DC-62 TOC Monitor utilizes ultraviolet promoted chemical oxidation followed by infrared detection to analyze for total organic carbon in water. Inorganic carbon interference is removed by acidification and sparging. The sample is continuously pumped into the instru ment, joined by a phosphoric acid flow, and passes through an inorganic carbon removal sparger and gas- through the quartz reaction coil where organic carbon is oxidized to C02 in the presence of ultraviolet light. This oxidized sample then passes through another sparger and gas-liquid separator where C02 from the oxidation process is transferred to the gas phase. This gas then flows to a C02 specific infrared detector. An integral recorder continuously displays the linearized detector signal which is the TOC level of the sample. PURGE GAS high salt streams Salt solutions have typically been a problem with con ventional TOC monitors utilizing direct injection into a high temperature furnace. The DC-62 overcomes this problem. In the low temperature oxidation pro cess, the salts all remain in solution and are simply discharged through the analyzer waste line. Streams containing salt up to 3% can be handled directly, with out a reduction in oxidation efficiency. Higher salt content streams can be handled after automatic dilu tion to the 3% or lower level. high suspended solids streams The DC-62 is designed to handle particles up to 0.75mm (0.03 iri) in diameter. Streams with larger particles having little organic content should be screened. Streams which have larger particles whose organic content must be measured should be analyzed using the Dohrmann DC-60 TOC monitor. The DC-60 can handle particles up to 2.5mm (0.1 in) and is the preferred instrument for on-line monitoring of high suspended solids streams such as found in municipal waste treatment plants. CCR 0038847 specifications operational Method Mode Options Inorganic Carbon Removal Carbon Range (full scalo, continuously adjustable) performance Linearity Drift data display Local Readout Remote Output Ultraviolet promoted chemical oxidation, infrared detection. Total Organic Carbon (TOC) Total Carbon (TC) >99.5% for low salt* streams >98.0% for high salt* stream* 0-5 mg/I to 0-100 mg/I for low salt* streams O-IOmfl/l to 0-100 mg/I for high salt* streams 0-100 mg/I to 0-1000 mg/I for low and high salt streams, as well as brines* using optional diluter. Higher ranges available upon request. Low salt, <0.1% High salt, >0.1%, <3% Brines , >3%, <30% 2% of full scale 5% of full scale per week, maximum Built-in strip chart recorder Isolated voltage or current. Variable through either 0 to 10V or 0 to 50 mA with variable zero offset. Typical; 4 - 20 mA (1000 max load) alarms TOC Overrange Temp. Overrange Pressure Overrange Liquid Spill Selected as a percent of full scale Reactor region overtemperature Flow system restriction Reactor region leak All alarms feature front panel indicator lamps and contact closures for remote Indication. L for more information, contact sample requirements Flow Rate Suspended Solids Monitor consumes 4 ml/mln Accepts particles up to 0.75 mm (0.03 In) diameter. Oxidation efficiency depends on size and chemical nature of particles. utility and supplies requirements Power IIS VAC, 60 Hz 700 VA Sparge Gas 160 mt/mln, of CO? free nitrogen, oxygen or air, high salt. 240 ml/min. low salt. 1 Low salt application High salt application Persulfate Solution, 5% 7.5 litre/wk (1.65 gal/wk) Phosphoric Acid Solution, 10% 3.2 litre/wk (0.7 gal/wk) Persulfate Solution, 5% 10.8 litre/wk (2.4 gal/wk) Phosphoric Acid Solution, 10% 3.2 lltre/wk (0.7 gal/wk) Hydrazine Sulfete Solution, 3% 3.2 litre/wk (0.7 gal/wk) dimensions Detector Electronics and Readout Module Reaction Module Reagent Module Weight Without Reagents 28cm high, 61cm wide, 61cm deep (11"h x 24"w x 24"d) 46cm high, 61cm wide, 61cm deep (18"h X 24"w x 24"d) 43cm high, 61cm wide, 61cm deep (17"h x 24"w x 24"d) Net: 124kg (272 lb) Shipping: 146kg (322 lb) 3 Specifications subject to change without notice. ENVIROTECH DOHRMANN 3240 Scott Boulevard Santa Clara, California 95050 Telex 346 395 call TOLL-FREE (800) 538-7708 I CCR 000038848 From Alaska, California, Hawaii, Puerto Rico Call Collect (408)249-6000 DOHRMANN, EN VIROTECH and are Trademarks of Envirotech Corporation SM-772--088760 `Printed In U.S.A. Instrumentation/Analyzers Improve tola! organic carbon monitor reliability with ultraviolet converter Top Honors distinction was accorded to a continuously operating process total organic carbon monitor that incorporates a high-intensity, ultraviolet-promoted chem ical oxidation system instead of a hightemperature pyrolysis system. "We judge the TOC analyzer to be a significant entry," one of the judges remarks. "The ultraviolet converter is a definite advantage in the right direction rather than the previously used hightemperature furnaces.1 In developing the award-winning entry, the firm incorporated its highly successful, low-temperature (50C), high-intensity UV-promoted chemical oxidation technol ogy used in an ultra-low-level (part-perbiilioii) labujaioiy TOC into a process monitor. Reliability was maximized and routine maintenance minimized by careful design. The firm was also able to achieve minimum operating cost and purchase price consistent with operational and design parameters. The replacement of the traditional redhot reaction furnace changer with a system that operates at 60C is said to eliminate a possible explosion hazard. If service is required, there is reported to be less hazard presented to maintenance personnel. The low-temperature system eliminates the time-consuming shutdown and exchange problems associated with frequent hightemperature reactor failure due to either Dow stoppage from crystalline salt deposi tion or the "corroded-through" failure due to strong oxidant attack. The low-temperature oxidation system and mechanical features of the monitor minimize the time required to maintain continuous operation. Routine preventative maintenance by semi-skilled personnel is said to run typically about four hours per month. This includes the time needed to check calibration, and return the instru ment to on-line operation. On-line TOC monitors need protection from both their external and internal envi ronments. The instrument's packaging concept provides complete isolation of the electronic module from the chemical oxidation module. Both modules are isolated from the external environment by the use of sealed enclosures. Access to the interior of each module is obtained by (C" t/' pc------co. PURGE GAS Flow schematic illustrates principle of operation of TOC monitor (see text) opening the gasketed front door. All components are readily accessible. The monitor can be wall-mounted if desired. The principle of operation of the instru ment requires using ultraviolet-promoted chemical oxidation followed by infrared detection to analyze for total organic carbon in water (see Dow schematic). Inor ganic carbon interface is removed by acid ification and sparging. The sample is continuously pumped into the instrument, joined by a phosphoric acid Dow, and passes through an inorganic carbon removal sparger and gas-liquid separator. This carbonate-free sample then joins a persulfate solution Dow and the mixture passes through the quartz reaction coil in which organic carbon is oxidized to C03 in the presence of ultraviolet light. This oxidized sample then passes through another sparger ana gas-liquid separator in which C03 from the oxidation process is transferred to the gas phase. This gas then Dows to a C02 specific infrared detector. An integral recorder continuously displays the linearized detector signal which is the TOC level of the sample. An optional diluter can be used to handle carbon levels to 1000 mg/litre and salt brines to 30%. Salt solutions have typically been a prob lem with conventional TOC monitors utilizing direct injection into a hightemperature furnace. The award-winning monitor is said to overcome this problem. In the low-temperature oxidation process, the salts all remain in solution and are simply discharged through the analyzer waste line. Streams containing salt up to 3% can be handled directly, without a reduction in oxidation efficiency. Higher salt content streams can be handled after automatic dilution to the 3% or lower level. Analyzer is designed to handle particles up to 1 mm (0.04") in diameter. Streams with larger particles having little organic content should be screened. (Model DC-62 total organic carbon moni tor -- Envirotcch Corporation, Oohrmann Division, 3240 Scott Blvd., Santa Clara, CA 95050.) Circle 224 opposite last page. 30 MID-NOVEMBER 1978 CHEMICAL PROCESSING CCR 000038849 . .. ULTRA-VIOLET PRODUCTS, INC. PEN-RAY7S0G DATA Stable Ozone Generators i FEATURES: Long term Stability of Light Source Reproducible Ozone Output No Electrical Adjustment Required Simple Sleeving Technique for Varying Ozone Output Light Source of PEN-RAY Lamp Quality Low & High Output Units Available No Heating of Gas Stream by Light Source Quartz Flowtube and Light Source for High 184.9 nm Transmission MAIN APPLICATIONS: Calibration of Field and Laboratory Ozone Analyzers Source of Oxidant for Aging and Oxidation Testing of Materials, Such as Rubber, Polymers, etc. Ozone Source for Instrumentation Development Water Purification Studies Air Pollution Studies 1977 ULTRA;yiOLET^ PRODUCTS. INC. CCR 000038850 ULTRA-VIOLET PRODUCTS, INC.nCT San Gabriel, California 91778Vj/ PEN-RAY7S0G DATA Stable Ozone Generators r OO ^_____________ r------ x--^ Lamp Mounting Flange ^1 1 J-t Exposure Adjusting Sleeve (Uncalibrated) h-------------------------- z------------------------ H fp y 1.125" I --1" 1 L* ----------------------------- '------------------------------- * Quartz Flow Tube 12 MM OD CONSISTS OF: Lamp Power Supply Dimension -- x J z 1 Sleeve Adjustment SOG -1 11SC-1 SCT-1 2" rt // 3" 5.5" Max. of 2" SOG-2 3SC-9 SCT-4 2.125" o// 11.125" 13.5" Max. of 9" The Following Graphs Show Typical Ozone Levels Produced By SOG -1 And SOG - 2 Your Authorized Deo'er / j SP-532L Printed in U.SA LENGTH OF LAMP EXPOSED (IN INCHES) * Above curvet are representative of ozone level* produced by the SOG-J, SQG-2 A We! Ctiemitiry Technique {Kl) was uted to determine otone produced, OCR 000038851 Cat. No. 1108 Effective December 3/, 1976 ULTRA-VIOLET PRODUCTS, INC. 13 HI 5100 WalfHJl Grov* Avenue, San Gabriel, CA 91778 USA. Vv J ListLABORATORY , - . products --Price S* c.hed,ul.e ITEM B-100A B-100A B-100A/R B-100A/R B-100A/X B-100A/X C-61 C-61 C-61 C-62 C-62 C-62 C-70 C-70 C-70 C-71 C-71 C-71 CC-10 CC-15 CC-15 CC-15 CC-20 CC-20 CC-20 G-203 G-275 G-276 G-277 G-278 J-124 J-126 J-129 J-221 J-225 J-236 J-236 DESCRIPTION BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW MINERAUGHT Transilluminator 115V, SW MINERALIGHT Transilluminator 220V, SW MINERALIGHT Transilluminator 250V, SW BLAK-RAY Transilluminator 115V, LW BLAK-RAY Transilluminator 220V, LW BLAK-RAY Transilluminator 250V, LW CHROMATO-VUE Cabinet 115V, SW & LW CHROMATO-VUE Cabinet 220V, SW & LW CHROMATO-VUE Cabinet 250V, SW & LW CHROMATO-VUE Cabinet 115V, LW CHROMATO-VUE Cabinet 220V, LW CHROMATO-VUE Cabinet 250V, LW CHROMATO-VUE Cabinet CHROMATO-VUE Cabinet 115V UL, SW&LW CHROMATO-VUE Cabinet 115VCSA, SW&LW CHROMATO-VUE Cabinet 220V, SW & LW CHROMATO-VUE Cabinet 115V, SW & LW CHROMATO-VUE Cabinet 115V CSA, SW & LW CHROMATO-VUE Cabinet 220V, SE & LW Adapter Filter Assembly Filter Assembly Filter Assembly Filter Assembly Stand Bracket Stand BLAK-RAY Meter, LW BLAK-RAY Meter, SW Certification System 115V, LW Certification System 220V, LW SHPG. WT. 17# 17# 17# 17# 17# 17# 24# 24# 24# 24# 24# 24# 29# 29# 29# 29# 29# 29# 9# 15# 15# 15# 14# 14# 14# 5# 1# 1# 1# 1# 4# 1# 3# 4# 4# 19# 19# LIST $199.00 259.00 259.00 309.00 219.00 279.00 490.00 510.00 525.00 360.00 398.00 398.00 650.00 675.00 675.00 598.00 675.00 675.00 59.95 174.00 179.00 185.00 359.00 379.00 379.00 49.95 22.95 74.95 74.95 33.95 17.95 5.95 29.95 210.00 225.00 598.00 620.00 BLAK-RAY, MINERALIGHT GEM-TEMP PEN-RAY, and CHROMATO-VUE, are regis tered trademarks of ULTRA-VIOLET PRODUCTS. INC. LW=Long wave ultraviolet (365 nm) SW=short wave ultraviolet (254 nm) All prices are F.O.B. San Gabriel, California. Minimum billing $50.00 net Terms: Net 30 days. 'CCR 000038852 m it it 1 ITEM DESCRIPTION J-237 J-237 J-260 J-260 J-2601A J-2602A J-2603A J-330 J-331 J-332 M-14 M-14 M-14 M-15 M-15 M-15 M-16 M-16 M-16 ML-49 MS-47 MSL-48 PCQ-008L PCQ-008PS PCQ-008S PCQ-023 PCQ-023L PCQ-023PS PCQ-024L PCQ-024PS PCQ-024S PCQ9G-1 PCQ9G-1 PCQ9G-1 PCQ9G-1 PCQ9G-1 R-52 R-52 S-68 S-68 S-68A S-68A S-69 S-69 SCT-1 SCT-1 SCT-2 SCT-2 SCT-3 SCT-3 SCT-4 SCT-4 SOG-1 SOG-1 Certification System 115V, SW Certification System 220V, SW Radiometer 115V Radiometer 220V Sensor (254nm) Sensor (365nm) Sensor (297nm) Recharger 115V Recharger`12V~ Recharger 220V MINERALIGHT Lamp 115V, SW MINERALIGHT Lamp 12V, SW MINERALIGHT Lamp 220V, SW MINERALIGHT Lamp 115V, SW & LW MINERALIGHT Lamp 12V, SW.& LW MINERALIGHT Lamp 220V, SW & LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 12V, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp, LW MINERALIGHT Lamp, SW MINERALIGHT Lamp, SW & LW Photochemical Lamp Power Supply Photochemical Lamp Photochemical Lamp Photochemical Lamp Power SuddIu Photochemical Lamp Power Supply Photochemical Lamp Photochemical Lamp, 2xh" Photochemical Lamp, 4" Photochemical Lamp, 6" Photochemical Lamp, 7" or 8" Photochemical Lamp, 10" or 11" MINERALIGHT Lamp 115V, SW MINERALIGHT Lamp 220V, SW MINERALIGHT Lamp 115V, SW MINERALIGHT Lamp 220V, SW MINERALIGHT Lamp 115V, SW MINERALIGHT Lamp 220V, SW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW Power Supply 115V Power Supply 220V Power Supply 115V Power Supply 220V Power Supply 115V Power Supply 220V Power Supply 115V Power Supply 220V Ozone Generator 115V Ozone Generator 220V OCR 000038853 SHPG. WT. 19# 19# 4# 4# 2# 2# 2# 2# 2# 2# 3# 3# 3# 3# 3# 3# 3# 3# 3# 4# 4# 4# 7# 11# 7# 9# 9# 11# 9# - 11# 9# 4# 4# 4# 4# 4# 12# 12# 15# 15# 16# 16# 15# 15# 4# 4# 4# 4# 4# 4# 6# 6# 7# 7# UST $620.00 690.00 785.00 785.00 225.00 225.00 225.00 26.95 26.95 54.95 185.00 185.00 205.00 185.00 185.00 205.00 165.00 165.00 189.00 89.95 110.00 105.00 379.00 175.00 339.00 599.00 775.00 175.00 495.00 175.00 790.00 230.00 235.00 240.00 245.00 249.00 339.00 375.00 549.00 549.00 729.00 819.00 510.00 525.00 79.95 89.95 89.95 99.95 84.95 89.95 84.95 99.95 303.00 325.00 ITEM DESCRIPTION SOG-2 SOG-2 SPR-33 UVC-303 UVC-503 UVL-21 UVL-21 UVL-21 UVL-56 UVL-56 UVL-56 UVS-U USV-11 UVS-11 UVS-54 UVS-54 UVS-54 UVSL-15 UVSL-15 UVSL-15 UVSL-25 UVSL25 UVSL-25 UVSL-55 UVSL-55 UVSL-55 UVSL-58 t nyrt UVSL-58 X15-B X15-B X15-B X-15H X-15H XX-15 XX-15 XX-15 XX-15H XX-40A XX-40A 11SC-1 11SC-1L 11SC-2 22SC-3L 22SC-3S 3SC-9 90-0013-01 90-0014-01 90-0015-01 90-0016-01 90-0017-01 98-0008-01 98-0008-02 90-0008-03 Ozone Generator 115V Ozone Generator 220V Stable PEN-RAY Lamp 115V BLAK-RAY Spectacles BLAK-RAY Safety Goggles BLAK-RAY Lamp 115V UL. LW BLAK-RAY Lamp 115V CSA, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 115V CSA, LW BLAK-RAY Lamp 220V, LW MINERALIGHT Lamp 115V, SW MINERAL1GHT Lamp 115V CSA, SW MINERALIGHT Lamp 220V, SW MINERALIGHT Lamp 115V, SW MINERALIGHT bmp 115V CSA, SW MINERALIGHT bmp 220V, SW MINERALIGHT Lamp 115V, SW & LW MINERALIGHT Lamp 115V CSA, SW & LW MINERALIGHT bmp 220V, SW & LW MINERALIGHT Lamp 115V, SW & LW MINERALIGHT Lamp 115V CSA, SW & LW MINERALIGHT Lamp 220V, SW & LW MINERALIGHT Lamp 115V, SW & LW MINERALIGHT Lamp 115V CSA, SW & LW MINERALIGHT Lamp 220V, SW & LW MINERALIGHT Lamp 115V, SW & LW MINERALIC: IT 115V CSA, SW LW MINERALIGHT bmp 220V, SW & LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 115V CSA, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 115V CSA, LW BLAK-RAY Lamp 220V, LW BLAK-RAY bmp 115V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V PEN-RAY Lamp, SW PEN-RAY Lamp, LW PEN-RAY Ump, SW PEN-RAY bmp, LW PEN-RAY Lamp, SW PEN-RAY Ump', 9" SW PEN-RAY Ump -- Argon Fill PEN-RAY Ump -- Krypton Fill PEN-RAY Ump -- Neon Fill PEN-RAY Ump -- Neon-Mercury Fill PEN-RAY Ump -- Xenon Fill "A" Ump Shield "B" Ump Shield "C" Ump Shield *' CCR OOflni 003Q854 SHPG. WT. UST 13# 13# 46# 1# 1# 3# 3# 3# 4# 4# 4# 1# 3# 3# 4# 4# 4# 3# 3# 3# 3# 3# 3# 4# 4# 4# 4# 4# 4# 7# 7# 7# 7# 7# 8# 8# 8# 8# 20# 20# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# $415.00 435.00 3,475.00 6.00 7.50 44.95 49.95 54.95 64.95 69.95 74.95 64.95 74.95 79.95 109.95 114.95 119.95 64.95 69.95 79.95 79.95 94.95 94.95 99.95 99.95 109.95 114.95 119 95 124.95 84.95 94,95 99.95 99.95 114.95 99.95 99.95 114.95 99.95 124.95 149.95 52.95 78.95 52.95 190.00 119.00 109.95 77.95 77.95 77.95 77.95 77.95 7.95 7.95 7.95 Manufactured by ULTRA-VIOLET PRODUCTS, INC. 59' 5100 Walnut Grove Avenue, San Gabnel, CA 9i77d U.S.A. REPLACEMENT PARTS ITEM BATTERIES J-333 6V Rechargeable J-144 6V Super J-145 45V 12V Rechargeable BULBS 100-watt Spot, LW White, for battery lamps 100-watt Hood, LW FILTERS (254m) for: S-6S, S-63A CC-20 R-52 C-61 UVS-11, UVSL-25 MS-47, MSL.-48, UVS -54, UVSL-55, UVSL-58 M-14, M-15 C-70 UVSL-15 FILTERS (365nm) for: C-70, C-71 UVL-21 CC-20 B-100A C-62 M-16 S-69 FILTERS (365nm) fon. -ttJ K UVSL-15 UVL-56, UVSL-55, MSL-48 FILTERS, Contrast Control for: CC-10, CC-20, C-70, C-71 TUBES. Germicidal (254nm) 4-watt 6-watt 8-watt 15-watt 30-watt TUBES. Black Light Blue (365nm) 4-watt 6-watt 8-watt 15-watt 30-watt 40-watt TUBES, Black Light (365nm) 4-watt 6-watt 8-watt 15-watt 40-watt TUBES, Multiband (254 & 365nm) 4-watt 6-watt 15-watt TUBES. White Light 8-watt For C-70, C-71 TUBES, Quartz For S-68, S-68A For R-52 Cj-57L printed In USA PART NO. 45-0002-01 45-0005-01 45-0006-01 45-0009-01 34-0011-01 34-0014-01 34-0022-01 38-0006-01 38-0004-01 38-0008-01 38-0011-01 38-0012-01 38-0015-01 38-0018-01 38-0031-01 38-0035-01 38-0001-01 38-0002-01 38-0005-01 38.-0009-01 38-0010-01 38-0019-01 38-0032-01 gajYiSd-m 38-0037-01 38-0050-01 38-0013-01 34-0003-01 34-0013-01 34-0007-01 34-0008-01 34-0025-01 34-0010-01 34-0016-01 34-0031-01 34-0017-01 34-0018-01 34-0032-01 SHPG, WT. 2# 6# 6# 1# 2# 1# 2# 1# 1# 2# 4# 2# 2# 1# 2# 2# 2# 2# 1# 2# 4# 1# 1# . lit 2# 2# 1# 1# 1# 1# 2# 5# 1# 1# 1# 2# 5# 8# LIST $ bZ./b 7.75 35.25 8.25 ____ 4U.U0 1.25 50.00 _____ y/.yp 93.95 57.95 197.00 32.95 38.95 18.95 198.00 21.95 36.95 8.y5 30.95 10.95 65.96 5.95 8.95 5.95. 5.95 5.95 20.95 13.25 13.25 13.75 13.75 27.50 11.00 11.00 16.50 16.50 33.00 33.00 34-0005-01 34-0034-01 34-0006-01 34-0009-01 34-0024-01 34-0004-01 34-0015-01 34-0033-01 34-0001-01 34-0002-01 32-0009-01 77-0003-01 1# 5.50 1# 5.50 1# 13.75 2# 13.75 8# 33.00 1# 13.75 1# 13.75 2# 22.00 1# 4.25 1# 3.50 2# 249.00 1# 169.00 CCR 000038855 Cat, No, 175 I AW cit>\iiT\CtitY'tT^ -Ao 4W, Tl 6 S ^>-Veptm ^ifvo yY\ aW, is. IM.ClUX.'&tA. > beCcuAAJL, ArW- \.m^\ W C'O.CLW- ^ vf V e^-cb AW- ew<*A-\A>r. stiAW F wo A.w\^ AW C\VtvJJ.AkWv rP)A- VV\C-UJ2/'5LftS ,, ^ u~~l) Ttes*&. uvw'DT \t> ' fcTk - V^bo-^S VOlo'S - S^ uioa-dT - -------- T\ ortro^S~ -- 3WbT ~W> *>TV- sso'- w M Y-T CCR 000038856 <^% 47cPF m v<AlCi 5^ ^0 Qsy^* A 'fefuO GyN-^ ^ ( W\A ^ lk ) <,s + '^7>] /u <m,7-F Wcc^Wp. l5CcOeF t Ct)01p<AA -ta 4SS T 2.' in ^or X*P -4- t 4SZ.7T *F iSfaoV- ' 550'f t 4^5 54KV yaV^, - 38.?n \V>&.x>es^v- ATu\' "X= 717 <ktoSlv4y 5"45 *F A"T LJV\ !o*S - S3.3 tt><5 S3.* 34-5.3 38.*! C7/7 )" 27,q ^mTSTu/k,^ Cl- a\'S IO "MC^T = 27.7 >*< 'ai^/^ew C? - U J Vv'tAtw^j Ofia^AjljJ 3^1-3 'J,4o"fe ~ VwCASA^ 3+.^ (^loj) ^7n) AT " 17.1 A'TJf(^iStoo * J5^c) C^ >a = I Cp 9*c>)Q#.5*\J t -Zn.9 28.{ IA<V\ (^ '0 (.84*0^ 34-0 -OTU* ^7T C?- ,8^24- 17 eF \aA eA (u) C -7-^-~?3--AT --ZJ&O AT ^ ~~ 3 *5 Cj-^ .8 00 C7/?X 58<?0 * 2^0.7 rnrA ................. .... /)<=W1 y^XL'-UtXUiJu 30.2 - *27.? = 2*S vata 2,8 'rrrrs'^'VKfcT -p,^ \^CC (^20.7j) = X*F f*S4^X34,s^ - loS^f |5(o - \o5io"F -- \&V c>AV*^r "tao ^e*>A -^nvi -To SS F" ft ^Jsco*.elv^. " /V^>|ro)--. IStoO- S4^J) ,&2H4 Cm.Sw) = Z^.sb -- ?_7. 1 M a r. f --------- , 1 * /pish'l rv\^V^. V'_______ ------------ -- J , cj !\o. CCR 000038857 ,.- r / nv,V 0 '^JL ^"/0 V^'U c-wSc c' Cd^jIA W&- V, ^ \4JL/m t '-O 0 tA^- J*A -V ^5^ ^s uUh' "~r>n L\to CCR 000038858 re t MAGNETICALLY INDUCED SEPARATION OF STABLE EMULSIONS } Experiments WRrc FPrfictJ out to rismanstrntp ilia feasibility of recovering oil f Lorn fine, stabls oil-in-v/atcr emulsions by riegrii'lit means. Emulsions in [ f.`,ich the oil pilose was rendered inpinr.ncolly rcsuory.ive by the addition cf a '{frofluid vvctc [uriscd ihrotsjfi packed beds (containing inaaneiie pwiicl-t; nnJ/ I ;r screens) placed "in a magnetic field. The oil conlent uf the effluent stn em t,v, typically two to three outers of m.vjnitirJG Iuupi than the oil conte>;t of -e feed emu Lion. The influence of venous operating pan'mefsts inr/admy \ii height, flow rate, oil msrjnetvatian, end inannnic Held strength were ifstematically evaluated. The results demon1*,tiatad that it i; possible to attain iirtiiBlIy complete 1 unoval of particle? of the ordci of one micron in diameter nitli a static separation device (magnetic demulsifier) using resilience times uf the order of a flection of a minute. Robert Kaiser Clark K. Colton Gabor Miskolczy and Leon Mir The removal of oil from fine oil-in-watcr emulsions is a common problem which has no uni versally applicable solution. Such emulsions ere found in v/nste water effluent streams from nany sources, including chemical processing and manufactureng plants, petroleum refineries, and rolling mills (1). A major source of oil pollution on. the seas occurs from the results of deba1 lasting of vessels, cleaning of oil tanks, and rhe pumping of bilge water which becomes nixed with waste oils. The oil is usually discharged as a dilute emulsion of fine oil droplets in water (2). Many major tanker fleets are now applying improved opera tion methods, such as the load-on-top proce dure, and installing mechanical .shipboard oilimter separators which function by gravita tional sett 1 in)>,. These methods, however, arc not capable of removing the finest particles (2), and the ultimate effluents are generally Li excess of present international standards. All existing methods for breaking oil-inwater emulsions (including chemical, mechani cal, electrical, and thermal treatments) suffer from disadvantages such as high cost technical and practical limitations in ^^Voyment (1_, 3,4), There is need for a more . ^Wi.cienf and economical emulsion breaking System, parti culariy for fine, stable emul - sionc with oil-phase densities close to that ; CorT/jru ion, Lowell, Ibis Such iron t s . Clark loir on is v;i ;!, the ihr.sachuuw 1 in-1 i lute of T. dine 1 o;;y, t.snha id);.., Ihr.x .'n'-lnmc-i. of water and droplet diameters of 10 microns or less. A r.o'/el method of oil-water separation has been developed which utilizes magnetism to separate the two phases.. The basic prin ciple is cs follows: An oil-soluble, waterinsoluhlc- ferrofluid is added to the oil phase, rendering it magnetically re.wonsive. V.'hcn the emulsion is passed through a suit able- device in which a magnetic field, is gen erate1!, a selective magnetic body force is exerted on the oil droplets. This force may bn used to 1) physically separate oil drop lets from the water, and/or 2) retain the cil droplets v.'ithin the device vdiile the water passes through. The retained oil may then be easily recovered in concentrated form hy shutting off the magnetic field. The appli cation of this technique to the problem of removing oil from the surface of the ocean lias been previously described (5) . Tims paper presents thei results of bench-scale cxpe>jmental studies to evaluate the use of magnetic separation techniques for removing and recovering oil from fine, stable cil-invuiter emulsions. The objectives of these studies were to demonstrate the capabilities of the separation technique and to character ize the parameters affecting process operatic: n;ff':o:-i.i;ii) M'O-tttii:s CCR 000038859 "li.ii :tab 1( Vi-1*1 rn*D<ir^- I'Mi^ArtihfiiMl ^tffnvfir'li' i :l~'-*"VthT~ftiM'ii':`r '_l WATER-1971 AlChE SYMPOSIUM SURn s So. 1: retain their liquid characteristics in the presence of a magnetic field and do not settle under gravity or in the presendc of a strong magnetic field. The magnetic response of a ferrofluid results from the coupling of individual magnetic particles with a substan tial volume of the carrier liquid. Coupling is facilitated by a stabilizing agent which adsorbs on the particle surface and is also solvated by the surrounding liquid. Magnetic properties can be selectively conferred on a variety of liquids, including water, hydro carbons, and fluorocarbons, by proper choice of the stabilizing agent. The properties and general applications of ferrofluids, as well as the required physical and chemical charac teristics for oil-water separation processes, have been described elsewhere (5 - 7). PRINCIPLES OF MAGNETIC SEPARATION Magnitude of Forces Involved * When a magnetically responsive fluid oplet is placed in a magnetic field 00 there results an induced magnetization within the droplet (M^.). If, in addition, there is a gradient of the magnetic field, then there is also a magnetic body force (F ) exerted on the droplet. The magnitude of the force is pro portional to the induced magnetization, the magnetic field gradient, and the volume of the droplet (3): 14 F = -- M-VH (-- ttR3) m 477 f 3 CD VH is the local field gradient and R is the droplet radius. The ferrofluid droplet, like all magnetizable objects, is driven toward regions of highest magnetic field intensity. Assuming that a ferrofluid droplet be haves like a solid sphere (i.e., no internal circulation effects), the drag on the droplet at sufficiently low Reynolds numbers is given by Stokes Law: 6uvuR (2) where p is the viscosity of the surrounding fluids and u is the droplet velocity relative 0 the surrounding fluid. By equating the I I agnetic body force with the fluid dynamic drag on the particle, one obtains the equilib rium, steady-state, magnetically-induced velocity of the ferrofluid droplet. 1 M-VHR2 f um 18tt Ji CD OIL WATER OUT OUT t1 - EXTERNALLY IMPOSED TRANSVlrw MAGNETIC FIELD GRADIENT. jjS separat * sagnef I entire \ Study . j are ty; jravit- rath 1 leads reside: A. CONTINUOUS SEPARATION (CONTINUOUS "MAGNETOPHONESIS") WATER OUT PACKED BED (e. 9. SCRFENSI IN UNIFORM MAGNETIC FIELD, H INTERSTICESFC FLUID FLOW / I \ IY^macvt,' "j SCREEN ^ ty EMULSION IN ENLARGEMENT OF EED ElEMENT ARROWS INDICATE DIRECTION OF LOCAL, INTERNALf.Wf.NET 1C FIELD GRADIENT. B. BATCH OR SEMI-CONTINUOUS OPERATION (MAGNETIC ADSORPTION COLUMN) Figure 1 ALTERNATE ARRAN,GEMENTS FOR MAGNETIC DEMULS IF ICATICN Equation (3) is the magnetic analogue of the terminal settling velocity of a particle in a gravitational field resulting from a density difference: 2 ApgR2 g 9V CD where u is the terminal settling velocity, Ap is ^the difference in density between the droplet and the external phase, and g is the acceleration of gravity. A semi-quantitative feel for the magni tude of forces operative in a magnetic separator may be obtained by comparing the equilibrium velocities associated with a magnetic field gradient and with a gravita tional field: CCR 000038860 1 MfVH CD 4tf Apg g Genera T dcmul r, ternaj (e.g. frit.,; separ . cont: , gener mg r. oil at aater; adsor sorpt the r porti, the g; the c. dient for a diene r.ade ' di err: throw This be o'., phase vi ec Cons. core drop 1 tion bed - sore shut i. oil vuinr by b. fluiv Ana 1 For the experiments carried out in this study, typical order of magnitude estimates of these parameters are M- = 10 gauss, II = 106 oe/cm, Ap = 10~l g/cm3, and g c 10 cm/scc2. Substitution into Equation S gives um/ur lO" This shows that a magnetic shov tier that vi'i, ids.- Ct'Lv* - - ?lF- VCrA ~m.sc. eo_s> V plxu^cAcen--S*, ;r -; 'V-1** V_X". v'-a-/A.^> VcL^W^ A ) YVVc^ . \c?30 G^vVQ : 13? ^-caoO ^Co'T 'AL_ 'O CW\. ~V Ao 30 6- - i I ^V^oo^wk J*T ,Va-S>V . 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CTU^d. \, ArvuS VlXcA.-^'C - O^L'jXrcS Utv-*_> ^ U/'~C/wJbdi \ CL- XE- Wciaj~C>X3^ . cAx*^L_,^, tovXk oL- . CX-%, Qoe A- .'ka! SA. 1 ) CJ , - t-~ --* . _.j _. ] __i.__ i-- ;. L. Q- A ckL&v--j2 : u>*S ; V-o^e__ lVA\j .-- ^rW Nje^T. ^ lA\i U^Vk >vv^V<k ^-/Sft_ jP& ^VO^V'C^-A Suvrsj3c\'-'--*\ \>VO fLii- ^ . -V.l . *"? \ ^ , ck Ll^WAcLo ~M5d. ^ i A. 0 .. :J'| \ i - t__ < 1 ' cv>nun:tai. o1: c ~j,.*p;\ CALCULA 1 T Oi\ LH ELT No. CCR 000038861 Vcw\ |<?o h V 1v 1* hKc^, cvA^cv^ fli C Lec^ver- -fr ^eCt^rlv^(^JU^_C^ Xuawwa^ *<A-o sYiXjCV'^'n <> AVvHjOu^\v- c^pod -C`V\cr OC. tE>VA<'2-e''r' cXeo-vutA. , " G-oiaA.^. 0*i^ Xw^jO- cx--<i, Ol AVjujt, \^ fc, \JSk\ju canruA -- OO-OT-. R Va-AVx- e\.vc^t / ciGA <aA^5> .)^r 1 ! ' ; . i _ ; .. I ;___ [ ; Z, ^ p G3: FUaA "to H c Co \ m , ' 1 - 1i' 1' ', 1. 1 , !:1 'i ; _ i i_ _ [ ; ; /\ ^ "^&A- G-X^ A C-VvA'A' d >r~OAoO~tv--A " CjAI \yv^cy%y>r~& d n-cA \ 3. ^Atcrw^- Hc v/o-po" 'Dccl^> o Ytva^r ^octtcjv-w -'V UCVU ^wvn Ao O*-^ W AW V\CX dov-rA'O A d\\^ AVjS-- (A C-Q- o *5*1^ ^6-C uA^cX-C-* ct--cA Stupor ck'row-ooAd' CWv^ua^At SJCyy\ Ci>w Va~ vc-Avnoj^, ^lso Q- uIaA cVjQ^-^2^ l\flA&- a_o---- A,o O)^- , odkvvd\dL- VoOaA'1-' \J CVW *1. 1*^0 \ TfcctaA "&A T&jojc^or. - dcvx-ftop/vvA fc-e^A . (XcAvOO^reA/ ColtAo Crr\ ^ y -eA, <rO As CXbSov d jCa&. C-ViLov'VV-a_ olatvvsu-a^A, <5^ Wo-o id~s> ''y^clm l> \a, v-e-Av^-cp.Ai_ a^)0 AW LAjooJ^s \^L- cdo^Cir^ eA oWr u^_U^- - -\W 1Z.-\DV sUV Va^C. _ . : . ; i j L. .. .: :. _: 5. (P^ -to J2-3o9 sAo^ed i>e. tS^csttOMSlxL -dt> clI/ovJ yv%or<- u>^S <`crv-- /7c^, fi Lzo cM*-l\l- (4 C$ ard d i h &***- > ,, 6. C( k-ejkir U^Lft... 0s- O /iai d rtjj ro ca-db <rnv^ - po^Sib Lc-< ^or Ic4^ tf, &--AfCO {, 1 ' *-t * ;. r i ' : ''v 1' 1 0e. G\Sft>jdVjLr\^ ' TiVLi: . j v fc_ ` j r A L 1 '! L . J'/IPA1'* r IALCUL.ATION SHEET ': J f,> L r * O r iLl,o` . i. i I J. . ICCR 000038862 7. cLCaVnA-C. R^jflLcVoT* . N/o 'Ata^ v^WSt '\\uU* i* . ( lOf\s> Ym3us-- *-- Tw^ ^ ^ ?. 4-U<j&e_ S " Scfl or--^ ec^c.W \**$3bU '- I <^}f3>y>^- jSjL^r^u^c^aj^LtT^- - les*b V/j^Vvfe* iteceoe^ - Vlt^o^. EQC vex-s^M^ ?. /<? //. ^owfii 7ga$ '/tw\^fiiMofcK. *^e ^ *oN;\<>\/ ^,/oe. C-^cJerrvi- . cm>^cI ** dJ- //*C^ *B^ ^4*4A^fiACujS^ sVw.*o^ `fUrtou^W coXfis 4 La. CIjC^wvvw^^^rei3f' st*^*Vwrw c^rww\ . (^^c-.U..yaLa^&_ s s>Ve^~>~- CoxXO^) 4Vjv* Vv\a^^ura^7 ^0 lju~JOi It 4-* f c) ^>OS* /& *v-- "/a^S . \jJj CjOmdbitry*. . u. ^-3oS F.CL^ Ca^aJL^r ww-^re^NflA*.av-- *, u-tefi. $L-)o! (e.V>(L <^XU<k ^ u>-e, vUj^v f?-3c>_5 GxcSs^^j>.4" ~fbVo-Qiij ^CCL*^- (yw.--^T'^^vvoJX'tO "VWoOX <+V^L/'-<- \^o lA\, \^5_ U-v^VL . OU, \*-J0\ Et)C -V ^-^oS Ip S-T ^o'T'rv^o*^ CX-- 6u4'v^3r <4XU*_ ^V&OcNseA . 13. /2-/0| U/&C. 1 ! 14 uc^Cvfi^ y>v1a^*^u/uj" /4*f cx^-- iiA_ \"u^-4d 4W \}Cy\a p Uw^t" lg^-je^|t-xgjP'^k- " ^>Crrr\L. -e^-j^Jr-co/u!^ p&^dtA&A* o^-c. c- )H> 7A tfL C*-A^L~$. &sy^, *_ ^ ..!'!,' ft- UAUL^ Tl^v C-2_ l4<4 w j l^.O, Poi Qs-- d C&And! i/mwc-L "/Ta. Hd / UCyrf flw^xb*sUL~> 4^--*-. fJQj@. (To/il*-'-*-- jZ*df**- ho ]>^n^UC~Sj , ;1 IS. O x AJ< ro duvc.41 (rv*^ -^r ^La*-^ uaa& , TWf (>y Wl/ ^tgk4"j Ca*i>e*\ * ^ &a-@t dcrr*j>< ^c>clc(s * AL>'. .Y ';.m lklo 1 jv - A1 { .. . ' ''"-T ' * 'r' '' A .'!_ i.rr *' Y CALCULATION SHEET joe No -----Fin CCR 000038863 \JC-W\ J Oe.c3<- J- ^s ;' !! o tv^vv^ ftvts- ~L *JUjoOS> ^oc YWNy:^r^- <AvJv\ ^Anijija^vv. ' '*-) \A ^W. CXjJ\- C^nv^Te&Solu ^o-<- O . ^ YAort G^a-L^sA* -- ojlfi. f tttjeJcto'T'S* )00 Vo ^O c r/7% KaAS- .s-WVL *0 "\2.-3oA, ^>re,Vcjs5t`e_ oJ^so sAw**-* e^ex^ot' S) 3oJ3 ^>o^V^\o-o ^u^sAovw OYL* IvVOj xp> ft A.LrjfU> H waS.\K. - So-rvOi- '3?. . lOiLc^T 0 ^t>c "e>^^&s ~?Tby^r (RCL*. Ldsot^WL-) **) c.*^re,t?>6r *- Ac* &ol^s_ St*c^w--- "^CoWjlAWi -- W\Cy^_We~ "^C> CJBw<A'CAa.^_ AWiVV C.'--v_ ^v>v ^4*.^ -V- cAirs^Ar QCi. ^ f-t* f_ i. _ fOeM- Ob~<A.'CAA_S*V>W-5> A 0*vj, 3^ o^o-vaSI ol C^cXovot- SaVvA& Vc^a\o^t>r-S >(0 (S<-\\. ^ C.a**5Lc- v .yv^) k H) ,___ i_. iii- . "FujvjjjVtCkSc^r*-- . j. 0 ?B<W^ \> W.G. CoWftv Co-vAop.&e"s , x^jj E>c_ o-^ L.F.coliw. '*) SA'CjQjvvn <W-_ -" ^n-c - So^vAs 'px^vwjOe^Si (jpTioc- ^ -^r\As } -j:c^5^ci_ *. yrc. IbC ^) ^ecUye. 6o\wv \icoi^vbv^s TUaDI^Ws .* H - 3o3 + ^ (r\ - Mao* rw O '-i' i'Krn r> TIT!H CONTINENTAL OIL C.n..`P^NY C ALCULA TI Of [ C ! I TF LT moV A"QjtS| / 3.^ }A "303/310 Jun CCR 000038864 Environmental Management Ozone/UV process effective wastewater treatment Toxic wastes made harmless with commercially developed process H. W. Prengle, Jr., C. E. Mauk, R. W. Legan and C. G. Hewes, III, Houston Research, Inc., Houston Chemical oxidation of difficult-to-handle impurities in waste-water is practical and economical using an ozone ultraviolet radiation process. The process is particularly effective with toxic and highly refractory compounds such as alcohols, acids, amino acids, fatty acids and polyhy droxy alcohols. Many compounds may be economically oxidized whose reaction rates would otherwise be too low to be processed in other systems. The process can be used in a number of configurations ;ucpeiiuiiig on application. Typically, it is used lo handle toxic and/or potentially toxic (when chlorinated) im purities as a combination secondary and/or tertiary process. Performance unequaled by other systems is achievable because of efficient staging of the ozone reactor system with ultraviolet light and results in low capital and operating cost. Ultraviolet radiation enhances the reaction with ozone lCP- to 10* fold and drives the reaction to completion to harmless materials such as CO., H20, etc. Much attention has been given to tertiary treatment processes (carbon adsorption, ion exchange, reverse osmosis, chlorination, etc.), which can be added to con ventional wastewater treatment processes to remove diffi cult to oxidize refractory compounds and toxic species and provide effluents which will meet tighter projected discharge standards. However, a number of tertiary pro cesses do not remove all undesirable species some of which produce highly undesirable species1 when chlorinated in final treatment before discharge or in municipal water treatment. Now chemical oxidation with ozone is commercially feasible for industrial municipal wastewater treatment for high rate oxidation with improved mass transfer, devel oped through high interfacial area in a continuous stirred reactor and an optimized reactor system to achieve total utilization of the ozone through use of a multistage reactor. UV radiation provides a critical key to enhance reaction rates dramatically. Experimental work prove the process' ability to oxidize a wide variety of both inorganic and organic species and 82 certain composite wastes including: glycine, NH2CH2COOH, the smallest amino acid; ethanol, CH3CH-OH; acetic acid, CIRCOOH; glycerol, CH.OHCIIOHCH,OH; palmitic acid, CH3(CH3)14COOH; nitrogen com pounds; potassium cyanide; complexed cyanides, cadmium, copper, nickel, iron; photographic wastes, bleach, fixer; medical wastes; secondary effluent, and others. The most difficult to oxidize species are potassium ferricyanide, ethanol and acetic acid; the latter, a product of partial bio and chemical-oxidation of numerous organic materials. In the absence of UV radiation, acetic acid is essentially unoxidized, by ozone; however, with UV radiation oxida tion proceeds rapidly at room temperature. REFRACTORIES AND TOXIC5 CHARACTERIZATION For purposes of comparison of different refractory and toxic species, a "Refractory Index (FFI)'' is defined which is a measure of the difficulty of oxidation ot a given molecular species; i.e., the larger RFI, the more difficult the species is to oxidize. A set of standard run conditions are used as follows. Ozone is used as the oxidant in a run conducted at room temperature (25-27 C). Initial concentration of reactant is 50-100 mg/1. Reactor is operated in the good to excel lent mixing regime. No ultraviolet radiation is used. RFI is calculated by the equations, RFI (hrs.) ^ B A [rngj1) (la) R` <W/t) ^ mB (mgfmin.) t* (min.) ff(Z) nb) where B " is the cumulative Os pumped into the liquid TABLE 1--RFI values for various compounds Compound .. RFI-value KCN....................................................... 0.41 Color fa-units)............................ .. Complexed Cd-cyanide................... Phenol............................... .................... 0.60 0.96 4.4 Ammonium ion............................... .. Simulated medical waste............... Glycine................................... .. Palmitic acid (as NIU-salt)......... Glycerol.................. ............................. 8 13 19,7 27.3 112 Ftlianol............................................. Acetic acid................ ............. .. 246 270 >1.000 Qualitative scale Slightly refractory (RFI < 1) Refractory (RFI 1 -> 100) Highly refractory (RFI 100 -> 1,000) Veryhighly refractory (RFI > 1,000; October 1975 CCR 000038865 Hydrocarbon Processing \ y 1 1 1 Fig. 1--Typical removal curves for refractory compounds by ozone with UV near 30* C. phase from t = 0 to t = f^, per liter of liquid Fig. 2--Ozone oxidation of acetic acid, effect of temperature at low UV intensity. t# is the time required for 50 percent complete conversion of the reactant component, as mea applied to treatment of many other wastewater species sured by TOG for organic species and an ap some of which are represented in Fig. 1, Curves of Figs. propriate method for inorganic species A0 is the initial amount of reactant component 1, 2 and 3 result from experimental studies in a batch, continuously sparged and stirred mix reactor. Reactor mB is the 03 mass feed rate to the reactor V is the liquid volume in the reactor. design permits direct size scaleup without difficulty.3'4 Acetic acid, which is an important intermediate oxida tion product of most organic materials, is also one of the more difficult to oxidize species (Fig. 1). However, a Values of RFI of various compounds studied are shown slight elevation in temperature has a marked effect on in Table 1. Potassium cyanide (free cyanide) is least acetic acid destruction (Fig. 2). The mass transfer limiting ( refractory of all compounds studied; acetic acid is most is tll^v.^ u.iCu. l.s.i. on ..... refractory, with complexed ferricyanide, ethanol and rate at with ozone is added to the liquid. Improvement up glycerol in the highly refractory category. to this limiting line by elevating temperatures alone is OZONE OXIDATION WITH UV Although the Ozone-UV process was initially developed impractical. Ultraviolet light can be used to further improve ozone for treatment of complexed cyanides,3 it is successfully oxidation of acetic acid (Fig. 3). No reduction of TOC TABLE 2--Photochemical data on refractory compounds Compound/(RFI) Acetic add (>1,000) Structure O H*C--C \h UV absorption range (nm) Peak: 205 180-230 Primary photochemical processes 1) R + COaH++ (or COj 4- H) 2) RCOat+ (or R + COj) + H 3) RCCC+ (or R + CO) + OH 4) RH + COa Ferricyanide (270) Ethanol (245) Glycerol (112) [Fe(CN)r* H HiC--i--OH k H HsC--A--CHs Ah Ah Ah 230 Peak: 182, 152 150-200 Peak: 210. 260 190-230 Electron transfer to water of hydration 1) (or Call* + H) + OH 2) CHjCHsO++ (or CHj + CHaO) + H 3) Call* + HaO 4) CHiCHO + Ha 5) CH* + CHaO Free radical and intramolecular photodlssociative processes Glycine (20) H0 HaN--c-- c 1\ H OH Peak: 240, 210 190-240 1) Acid type processes, and 2) Amine type, RNH + H Peak: 285.180 ,, Reference *{p. 428 and 431) #(p. 270) *(p. 442, 444) Mp. 455 m ; *(p. 526, 527) c Ozone ` Peak: 200 1) Oa(SJ -> O.i/Si) 150-300 2) Oa(Si) 0,(ix,-) 4- O(iD) (p, (207-209) 3) Oa(So) -> Oa(Ti) - Oa(3,-) + 0(*P) Hydrocarbon Processing October 1975 CCR 000038866 83 1 \ I ,7 ! 1 OZONE/UV PROCESS TABLE 3--Total treatment cost, including amorti zation for a specific applicati n Number of reaction stages 1..................................................................................................... 2..................................................................................................... 3..................................................................................................... fi..................................................................................................... 6..................................................................................................... 8..................................................................................................... Total cost |/lb* COD 0.535 0.234 0.185 0.175 0.162 0.151 0.152 0.104 Fig. 3--Ozone oxidation of acetic acid, effect of UV near 30 C. Fig. 4--Effect of initial pH on oxidation of ozone with UV near 30 C. is. realized in the absence of UV but a low UV intensity starts the reaction going very well. Improvement in re action continues with increased UV. Extrapolation sug gests use of UV of 6 watts/liter would raise the reaction to the mass transfer limiting line. Increasing reaction rate by increasing UV is much more effective than elevating temperature and requires less energy. Although elevated temperature and UV light accelerate ozone reaction rate with all wastewater species, both also accelerate rate of autodecomposition of ozone so that using UV or elevated temperature excessively results in less favorable economics. No generalization of require ments can be made because of the wide variation in re activities of species; for example, free cyanide needs neither UV nor elevated temperature, but iron complexed cyanides need maximum practical temperature and UV. fi4 Favorable economics usually result when sufficient UV and elevated temperature are employed to move the reaction line close to the limiting line. However, this is not necessarily the economic optimum, which must be determined individually for each wastewater being treated. Another controlling variable is pH (Fig. 4). For acetic acid, it is better to treat at naturally occurring pH rather than neutralize, while phenol is not strongly pH depen dent, Since acid is an important intermediate oxidation product from almost all inorganic material, it is concluded that pH control during ozonation with UV is generally not desirable, although this must be determined for each wastewater species. Two distinct aspects of chemistry are involved in the process: Photochemical excitation of molecules by UV radiation Oxidation by ozone. Since the over-all process is reaction rate controlled and oxidation by ozone alone is relatively slow for refrac tory type species, the ozone is not fully utilized. On the other hand, photochemical processes without ozone do not achieve appreciable reaction. Combination of UV and ozone overcor'o thes- Excitation of tn?l??`.t!c: occurs and free radicals are produced which are highly reactive in the presence of ozone. The excited state and free radical species provide more thermodynamically favorable reaction paths as well as increased driving forces for enhancement of reaction rates. Calvert and Pitts5 provide background on primary photochemical processes involved (Table 2). Generally, primary photochemical processes lead to production of free radicals and other smaller neutral molecules including CO and COj. CO is the primary step leading to more rapid subsequent oxidation reactions with ozone. Some smaller neutral molecules are more readily oxidizable (e.g., olefins), and all can in turn absorb UV for further activation. Ozone oxidation reactions have been studied by numer ous investigators: Criegee,10 Bailey and co-workers11-- olefins; Shubert and co-workers1*'15--saturated hydro carbons, and Bailey14,15 and co-workers--free radical formation. Classical chain propagation mechanism of free radical reactions starts with abstraction of a hydrogen atom from a molecule by a second radical, as illustrated for a carboxylic acid. HO HO R -- C -- C -- OH + R - RQ -- C -- OH + RH & "m Ozone additions typically result in the addition of all three oxygen atoms to the radical, followed by rapid release of an oxygen molecule CCR 000038867 October 1975 Hydrocarbon Processing PRIMARY PHOTOCHEMICAL PROCESSES INITIAL OXIDATION COz + HzO + Nz... COz + HzO... COz + HzO Fig. 5--Over-all photochemical/oxidation process to produce COi, HsO, etc. CHEMICAL COAGULATION SEDIMENTATION, CLARIFICATION 1 EQUALIZATION . pH ADJUSTMENT CHEMICAL OXIDATION (I) CHEMICAL OXIDATION (II) -OFFGAS Fig. 6--Process tlow for mixed cyanides plus organic refractories oxidation. HO HO | || | || RC -- C -- OH --* RC -- C -- OH + 03 --> | o -- O -- O- HO RC -- C -- OH + Ot I o- (3) The cycle of the chain propagation is then closed by the free radical removing a hydrogen from a neutral mole cule HO HO I II I II RC -- C -- OH + RH-+RC -- C--OH + R- II O- OH (4) with the unstable molecule immediately rearranging to release C02 HO I 'I RC -- C -- OH I OH H I RC -- OH + C02 I H (5) In a similar manner, alcohol formed is oxidized to an aldehyde, which is in turn oxidized to an acid. Therefore, for long chain molecules a cycle results, alcohol --> aldehyde - acid - alcohol + COz tl - and in the limiting case of a one-carbon-chain, water (not alcohol) is formed on oxidation of the acid. UV radiation produces substantially more free radicals than ozone alone; the radicals initiate many more propa gation chains and cause the over-all reaction to proceed much, much faster. The over-all photochemical process to produce C02, H=0, N2, etc., can be represented schemat ically (Fig. 5). The two-step initiation process (primary photomechanical process and initial 03 oxidation) is fol- Hydrocarbon Processing October 1975 OCR 000038868 85 OZONE/UV PROCESS EQUALIZATION pH ADJUSTMENT AMMONIA STRIPPING pH ADJUSTMENT CHEMICAL OXIOATION III) Fig. 7--Process flow for ammonia, cyanide and organic nitrogen compound oxidation. lowed by propagation chains which produce additional A 4" hv --> R's free radicals, neutral molecules and some C02, H20 R's + 03 -> C03 + Ht0 + by a termination step. (7) The reaction sequence, when the reaction is rate con PROCESS CONFIGURATIONS 5 trolling, may be visualized as follows: Several different applications are presented to illustrate how the process can be used. A + hv^-R-'s R-'s + O3 Fi Removal of mixed cyanides and certain organic refrac P% + hv + 03 -- Pj tory molecules which produce very undesirable organic P, + - halides (Fig. 6). n 1 ! i- o rn _L u ox . . . Over-all: A + hv -\-03 --> C02 + HsO + (6) where R's are the free radicals and Pi, P2, * * are inter mediate species. When the UV input is larger, the reaction becomes mass transferred controlled, and many more smaller free radicals are produced, which go directly to C02, H20, etc., i.e.. A wastewater treatment facility designed to process 500 ,tons/day (83.3 gpm) of wastewater containing 900 mg/1 of total dissolved solids including cyanides and organic components is shown in Fig. b. ivnxed cyaniues include free and complexed cyanide compounds (RFI less than 1 to 300) and refractory organic compounds (RFI approx imately 1 to 1,000). Influent water quality vector is shown on the diagram. Objective of the plant is to reduce total cyanide (TCN) to below detectable limit, less than 0.1 mg/1, and total organic carbon (TOC) to less than 1 mg/1. The first step involves chemical coagulation with About the authors Robert W. Legan manages engineering --i H. William Prengle, Jr., is a process specialist with Houston Research, Inc., professor of Chemical Engineering at the University of Houston and a regis tered professional engineer. He received B.S., M.S. and D.Sc. degrees from Car negie Mellon University. He is a mem ber of AIChE, ACS, WPCF, ARCA and a number of honorary societies. for Houston Research, Inc. He holds B.S. (chemical engineering) and M.S. (nuclear engineering) degrees from Oregon State University and Ph.D. (chemical engineering) from University of Idaho. For 16 years he has been per forming economic evaluations, engineer ing designs and water treatment studies in nuclear, chemical and environmental areas. Charles E, Mauk manages special projects for Houston Research, Inc. He has been principal investigator for over 11 years on a wide variety of environ mental research and development and aerospace projects. A registered profes sional engineer in Texas, he has B.S., M.S. and Ph.D. degrees in chemical en gineering from the University of Hous ton. He is a member of ACS, AIChE, NSPE and Sigma Xi. Cecil G. Hewes, III, is a research scien tist with. Houston Research, Inc. He re ceived B.S., M.S. and Ph.D. degrees in chemical engineering from Texas A&M University. He is a member of AIChE ind Sigma Xi. He has been conducting research in wastewater treatment, par ticularly ozonation, for the past seven CCR 00003886S 86 October 1975 Hydrocarbon Pkooessinq I( alum, activated silica and polyelectrolyte, followed by sedi mentation, clarification and equalization. The pH is adjusted to 7-8 by acid addition for best results in the chemical oxidation reactors. A single-stage reactor (I) to oxidize front end RFI compounds is followed by a multi stage reactor for final oxidation of high RFI compounds. Multistaging permits more effective oxidation, reduces total reactor volume and thereby capital cost. Ozone is supplied by a commercially available ozonator. The unit operates on air. Installed plant cost is $590,000 and operating cost, in cluding amortization, is approximately $500/day. Removal of ammonia, cyanide and organic nitrogen compounds (Fig, 7). Wastewater treatment processing 700 tons/day (117.4 pm) containing ammonia, cyanide and organic nitrogen compounds with a total nitrogen content of 1,000 mg/1. The objective of the plant is to reduce the ammonia, cyanide and organic materials to a dischargeable level. The first step is to adjust pH to basic and strip out am monia with steam. Afterward, pH is further adjusted to near neutral for best results in two chemical oxidation reactors. Ozone is provided by generators using recycled oxygen. Installed facility cost is $334,000 and operating cost (including amortization) is approximately $225/day. Tertiary treatment to specifically oxidize refractory organics which would produce toxic compounds if chlo rinated (Fig. 8). Potentially toxic refractory organic compounds remain ing after secondary treatment and carbon adsorption are removed in this facility. A stream of 1 million gallons/day contains 10 mg/1 of TOC which must be reduced to a concentration of less than 0.1 mg/1. The influent stream from the previous units is flow controlled to the multistage reaction unit where compounds undergo complete oxida tion to carbon dioxide and water. Ozone is supplied by commercially available ozonation unit operating on air. Ozone concentration is adjusted automatically by an efflu ent monitor. Installed cost of the entire facility is $505,000. OFFGAS Fig. 8--Process flow for oxidation of refractory organics. Fig. 9--Installed cost of stainless steel reactor, mixer and UV lights. t> PROCESS ECONOMICS Effective reactor staging results in lower total amortized capital and operating costs (Table 3) where the optimum cost is less than a third of the single-stage treating cost. A similar cost analysis can be prepared for any wastewater species for which reaction rate data are available. Indica tion of the cost contribution for a reactor with mixer and ultraviolet lights is given in Fig. 9. Costs of ozone gener ated from air and from oxygen (Fig. 10) include the cost of oxygen. ACKNOWLEDGMENT Houston Research Inc., wishes to acknowledge the U.S. Air Force Con tract (AFSC/AFWL), F29G01-73-C-0QG5, and U.S, Army Contract (MERDC), DAAKGZ-74-C-0239, under which substantial development of this process was carried out. LITERATURE CITED 1 Bellar, T. A., Lichtcnberg, J. J., and Kronger, R. C., "The occurrence of organohalidcs in chlorinated drinking water," EPA-670/4-74-QQ8, NERC, Cincinnati, Ohio (November 1974). a Gamon, R, L., Mauk, C. E., and Prcnglc, If. W., Jr,, "Advanced Oa oxidation system for complexed cyanides," First International Symposium on Ozone for Water and Wastewater Treatment, Wasliington, D.C., (Dec. 2-5, 1973), International Ozone Institute, Waterbury, Conn. (1975). 1 Barona, N., and Prcngle, H. W. Jr., "Design reactors this way for liquidphase processes," Part P and Fart 2, Hydrocarbon Processing (March and December 1973). 4 Prengle H, W. Jr., Chanslor, F. C., and Kelada, M., "Power requirements, gas holdup, interfacial area and mixing characteristics for a gas-liquid reac tor," Chemical Engineering Department. University of Houston (1974). MWwrt, j* O-r.-ftMl Ffcfer'J*N-*Jz.* tkotmekeamizy^J^iisi Wiley (1906). Hydrocarbon Processing October 1975 Fig, 10--Cost of producing ozone, including 10-year amortiza tion. 4 Dow Chemical Co., Manufacturing Chemists Association Research Project (UV Spectrum No. 57), Texas A&M University (1964). ' Friedman, L., and Kline, O. L., 7. Biol, Chem., 184, 599 (1950). 8 Simons, J. P., and Yarwood, A. J., Trans Faraday $oc., 57, 2167 (1901). Alder, M. G., and Hill, G, R,, J, Am. Chem. Soe., 72, 1884 (1950). 10 Criegee, R., "Products of ozonation of some olefins," p, 133 fT, Advances in Chemistry Series No. 21', Ozone Chemistry and Technologyt American 11 Chemical Society (1959). Bailey, P. S. Bath, S. 5., and Ashton, J. B>, "Initial attack of ozone on an unxaturatcd system," p. 143, ibid. Schubert, C. C,, .and Pease, R. N., /. Am. Chem. Soc,t 78, 2044 (1956). ai DiUemuin, F. J., Skidmore, D. R., and Schubert, C. C., J. Phys. Chem., 64, 14% (I960). 14 Bailey, P, S., Potts, F. E., Ill, and Ward, J. W., J, Am. Chem. Soc.t 92, 230 (1970). White, II. M., and Bailey, P. S-, /. Or*. Chem.t 30, 3037 (1965). CCR 000038870 87 tOa_ SOoVmjv S CIFEC ` CHLORIDE DIOMIDE GENERATOR United States Patent 3,975,284 THEORY OF OPERATION Because chlorine dioxide is an extremely unstable gas, it cannot be packaged in containers as is chlorine or sulfur dioxide. Therefore it must be generated at the point of use. The most prac tical method is to react an aqueous chlorine solu tion with a sodium chlorite solution producing the following stoichiometric reaction : Ch + 2 NaCICh 2 CICb + 2 NaCI (2-1) Therefor^, 1.34 lbs of pure sodium chlorite (NaCICh) will react with 0.5 lb chlorine to produce 1.0 lb chlorine dioxide. Most technical grades of sodium chlorite are only about 80 percent pure, so that in practice it requires 1.7 lb of chlorite for the above reaction to be complete. The other important factor in the above reaction is that it must be at a controlled low pH, less than 4.0. SYSTEM DESCRIPTION (see figure 1) The installation consists of a recirculation loop of aqueous chlorine solution under pressure in a ijiu*j-iTov icyifTie vvinoii prevents iicyaiivt; nyciraulic gradient conditions which are detrimental to the process. Recirculation is accomplished by a special corrosion-resistant positive displacement pump (A) This is the secret of the success of the CIFEC " enrichment loop " concept. It insures optimum conditions for the reaction of equation 2-1. There fore the CIFEC system is capable of producting continuously and reliably a chlorine dioxide solution that is 95 to 98 percent pure. This is the only on-site generation system that can make this claim. The current USA methods use an excess of chlorine to insure maximum yield of chlorite to chlorine dioxide. The result is a solution mixture of ap proximate 70 percent chlorine and 30 percent chlorine dioxide. This confuses and complicates the measurement of chlorine dioxide residuals in the treated process water. Therefore the French method can be controlled by chlorine dioxide resi duals, but the USA methods must be controlled by the sodium chlorite dosage. which also provides the hydraulic power to operate the chlorinator injector (B). A rotameter assembly ami diaphragm vaive (O) aiiow tne control and regulation of the make-up water. ( A sodium chlorite metering pump (E) injects a specified concentration of solution from the so dium chlorite tank (F) into the CIO2 reactor (D). Here the reaction between HOCI and NaCICh pro duces CIO:. Control equipment (G) contains the controls c j for the operation of the two pumps and switchgear necessary to automatically stop the system in the event of failure of water supply or chlorine supply. The entire assembly is mounted in a high rigidity PVC chassis reinforced with plastic coated steel for maximum corrosion resistance. SPACE REQUIREMENTS The CIFEC generator cari.be located in a small area. The equipment is mounted on a chassis ready to operate with all necessary wiring and piping connections. The sodium chlorite tank and chlorinator and chlorine supply cylinder are usually located outside of, but adjacent to, the generator chassis. The chlorinator can be cylinder mounted, wall mounted or mounted in a separate module. In addition to a clean water supply and electric power, a proper drain must be provided for the usual accumulation of waste overflow which occurs during normal maintenance procedures. Specific dimensions of the generator and chlorite tanks are listed in the technical data section. AUTOMATIC CONTROL Flow proportional control of the CIFEC system can be achieved by the use of a 4-20 ma electric analog signal. This can be expanded to include residual control if desired. Accuracy TECHNICAL DATA 4 % of indicated flow rate. Capacities 10, 25, 50, 100, 200, 500 and 1000 Ib/day chlorine dioxide. Feed range 10.1 for any combination of chlorine and sodium chlorite. Ir.jcctcr operating water supply Must be reasonably clean, operating limits 25-150 psi at 35-70 F. Pressure at point of application Maximum allowable is 6-8 psi depending on maximum flow rate of CIO2. Water supply For CIO2 capacities of 10, 25 and 50 Ib/day is 1-3 gpm, 100 Ib/day is 5 gpm, 200 Ib/day is 10 gpm, 500 Ig/day is 20 gpm, and 1000 Ib/day is 40 gpm. Electrical requirements 220-480 volts A.C. 3 phase 60 Hz current for recirculating pump and 110-V-AC single phase current for controls and alarms. Power requirements This varies from 1-5 HP depending upon size of unit. Sodium chlorite Pumps are furnished in accordance with capacity of the generator; this varies metering pumps from 30 gpd for the smaller unit up to 1200 gpd for the largest unit. Sodium chlorite tank capacity 105 gal, 130 gal, 265 gal and 500 gal depending on size of metering pump. Generator dimensions Up to and including the 200 Ib/day unit: width : 3 ft 7 in, depth : 2 ft 1.5 in, and height: 5 ft 9 in ; the 500 Ib/day unit is : widht: 4 ft 1 in, depth : 2 ft 7.5 in, and height: 6 ft 5 in ; the 1000 Ib/day unit is : width : 5 ft 5 in, depth : 3 ft 1 in, and height: 7 ft 5 in, Sodium chlorite 105 gal = 32 x 33 inches - 130 gal = 34 X 36 inches and tank dimensions 265 gal = 47 x 50 inches. ct-- CCR 000038873 ADVANTAGES OF CHLORINE DIOXIDE The most significant chemical properties of chlorine dioxide as they relate to potable water and waste water treatment are as follows : 1/ CIO2 does not react with any natural or man made precursors to form chloroform, which is a known carcinogen - as does chlorine com pounds. 2/ CIO2 does not react with ammonia nitrogen to form germicidal compounds of inferior effi ciency ; PRACTICAL CONSIDERATIONS The most important attribute of chlorine dioxide is that its bactericidal efficiency is equal to that of free chlorine regardless of the presence of ammonia nitrogen. Therefore on a cost-effective basis the use of chlorine dioxide as a disinfectant for high quality secondary effluents and tertiary effluents is of considerable interest. It could easily be the chemical of choice for disinfection require ments of 2.2/100 ml total coliforms particularly where virus kill is required. 3/ CIO2 unlike chlorine keeps its germicidal effi ciency in the pH range of 7 to 10. 4/ CIO2 does not give a chlorine taste to water. 5/ CIO2 destroys phenols. 6/ CIO2 has a continuing disinfecting power twice than of chlorine. 7/ CIO2 has a virucidal, bactericidal and algicidal power higher than chlorine. In other situations of potable water and waste water treatment, chlorine dioxide is very effective in removing color and taste and odors resulting from organic compounds. It is specific in its des truction of phenolic compounds. It also is one of the most effective oxidants for the removal of complex organic iron and manganese compounds. In food processing plants where the ammonia nitrogen content of the recycled water is greater thant 2 mg/I, chlorine dioxide kills bacteria on the same order as free chlorine. the new method CIFEC-PALIN for chlorine dioxide analysis \\' ' With this colorimetric method it is possible to mesure separately chlorine dioxide, free chlorine, mono-, di- and trichloramine, sodium chlorite and ozone in the same sample. CCR 000038874 J Cie INDUSTRIES DE FILTRATION ET D'EQUIPEMENT CHIMI0UE S. A. 10, ov. de la Porte Molitor, F 75016 PARIS - Tel. 651.52.04 - Telex 611 627 F principle of operation The DC-62 TOC Monitor utilizes ultraviolet promoted chemical oxidation followed by infrared detection to analyze for total organic carbon in water. Inorganic carbon interference is removed by acidification and sparging. The sample is continuously pumped into the instru ment, joined by a phosphoric acid flow, and passes through an inorganic carbon removal sparger and gasliquid separator. This carbonate free sample then joins a persulfate solution flow and the mixture passes through the quartz reaction coil where organic carbon is oxidized to C02 in the presence of ultraviolet light. This oxidized sample then passes through another sparger and gas-liquid separator where C02 from the oxidation process is transferred to the gas phase. This gas then flows to a COj specific infrared detector. An integral recorder continuously displays the linearized detector signal which is the TOC level of the sample. An optional diluter can be used to handle high carbon levels and salt brines. . jo..71. DC-62 FLOW SCHEMATIC QC `.t'Wj r -T, ; V'i " -r. -V PURGE GAS high salt streams Salt solutions have typically been a problem with con ventional TOC monitors utilizing direct injection into a high temperature furnace. The DC-62 overcomes this problem. In the low temperature oxidation pro cess, the salts all remain in solution and are simply discharged through the analyzer waste line. Streams containing salt up to 3% can be handled directly, with out a reduction in oxidation efficiency. Higher salt content streams can be handled after automatic dilu tion to the 3% or lower level. high suspended solids streams The DC-62 is designed to handle particles up to 0.75mm (0.03 in) in diameter, Streams with larger particles having little organic content should be screened. Streams which have larger particles whose organic content must be measured should be analyzed using the Dohrmann DC-60 TOC monitor. The DC-60 can handle particles up to 2.5mm (0.1 in) and is the preferred instrument for on-line monitoring of high suspended solids streams such as found in municipal waste treatment plants. 000039875 CCR spocifications operational Method Mode Options Inorganic Carbon Removal Carbon Range (full scale, continuously adjustable) performance Linearity Drift data display Local Readout Remote Output Ultraviolet promoted chemical oxidation, infrared detection. Total Organic Carbon (TOC) Total Carbon (TC) >99.5% for I ow salt* streams >98.0% for high salt* streams 0-5 mg/I to 0-100 mg/I for low salt* streams 0*10 mg/1 to 0-100 mg/I for high salt* streams 0-100 mg/I to 0*1000 mg/l for low and high salt streams, as well as brines* using optional diluter. Higher ranges available upon request. * Low salt, <^0.1% High salt. >0.1%, <3% Brines , >3%, <30% 2% of full scale + 5% of full scale per week, maximum Built-in strip chart recorder Isolated voltage or current. Variable through either 0 to 10V or 0 to 50 mA with variable zero offset. Typical; 4-20 mA (1000 SI max load) alarms TOC Overrange Temp. Overrange Pressure Overrange Liquid Spill Selected as a percent of full scale Reactor region overtemperature Flow system restriction Reactor region leak All alarms feature front panel indicator lamps and contact closures for remote indication. for more information, contact sample requirements Flow Rate Suspended Solids Monitor consumes 4 ml/min Accepts particles up to 0.75 mm (0.03 In) diameter. Oxidation efficiency depend* on size and chemical nature of particles. utility and supplies requirements Power 115 VAC, 60 Hz 700 VA Sparge Gas Reagents Low salt application 160 ml/min, of CO^ free nitrogen, oxygen or air, high salt, 240 ml/min. low salt. Persulfate Solution, 5% 7.5 litre/wk (1,65 gal/wk) Phosphoric Acid Solution, 10% 3.2 litre/wk (0.7 gal/wk) High salt application Persulfate Solution, 5% 10.8 litre/wk (2.4 gal/wk) Phosphoric Acid Solution, 10% 3.2 litre/wk (0.7 gal/wk) Hydrazine Sulfate Solution, 3% 3.2 litre/wk (0.7 gal/wk) dimensions Detector Electronics and Readout Module Reaction Module Reagent Module Weight Without Reagents 28cm high, 01cm wide, 61cm deep (11"h x 24"w x 24"d) 46cm high, 61cm wide, 61cm deep (I8"h x 24"w x 24"d) 43cm high, 61cm wide, 61cm deep (I7f,h x 24"w x 24"d) Net: 124kg (272 lb) Shipping: 146kg (322 lb) 3 Specifications subject to change without notice. i fit i ii ,'iLrr[J UW*ia idi'iitt'il^^ ENVIROTECH DOHRMANN 3240 Scott Boulevard Santa Clara, California 95050 Telex 346 395 call TOLL-FREE (800) 538-7708 CCR 000038876 From Alaska, California, Hawaii, Puerto Rico Q Cali Collect (408)249-6000 DOHRMANN, ENVIROTECH and arc Trademarks of Envirotech Corporation SM--772--088750 Printed in U.S.A. Instrumentation/Analyzers improve total organic carbon monitor reliability with ultraviolet converter Top Honors distinction was accorded to a continuously operating process total organic carbon monitor that incorporates a high-intensity, ultraviolet-promoted chem ical oxidation system instead of a hightemperature pyrolysis system. "We judge the TOC analyzer to be a significant entry," one of the judges remarks. "The ultraviolet converter is a definite advantage in the right direction rather than the previously used hightemperature furnaces." In developing the award-winning entry, the firm incorporated its highly successful, low-temperature (50C), high-intensity UV-promoted chemical oxidation technol ogy used in an ultra-low-level (part-perbiilron) laouialoiy TOC into a process monitor. Reliability was maximized and routine maintenance minimized by careful design. The firm was also able to achieve minimum operating cost and purchase price consistent with operational and design parameters. The replacement of the traditional redhot reaction furnace changer with a system that operates at 60C is said to eliminate a possible explosion hazard. If service is required, there is reported to be less hazard presented to maintenance personnel. The low-temperature system eliminates the time-consuming shutdown and exchange problems associated with frequent high- temperature reactor failure due to either flow stoppage from crystalline salt deposi tion or the "corroded-through" failure due to strong oxidant attack. The low-temperature oxidation system and mechanical features of the monitor minimize the time required to maintain continuous operation. Routine preventative maintenance by semi-skilled personnel is said to run typically about four hours per month. This includes the time needed to check calibration and return the instru ment to on-line operation. On-line TOC monitors neea protection from both their external and internal envi ronments. The instrument's packaging concept provides complete isolation of the electronic module from the chemical oxidation module. Both modules are isolated from the external environment by the use of sealed enclosures. Access to the interior of each module is obtained by C-" OC----------- -CO, fOHGE GAS Flow schematic illustrates principle of operation of TOC monitor (see text) opening the gasketed front door. All components are readily accessible. The monitor can be wall-mounted if desired. The principle of operation of the instru ment requires using ultraviolet-promoted chemical oxidation followed by infrared detection to analyze for total organic carbon in water (see flow schematic). Inor ganic carbon interface is removed by acid ification and sparging. The sample is continuously pumped into the instrument, joined by a phosphoric acid flow, and passes through an inorganic carbon removal sparger and gas-liquid separator. This carbonate-free sample then joins a persulfate solution flow and the mixture passes through the quartz reaction coil in which organic carbon is oxidized to CO, in the presence of ultraviolet light. This oxidized sample then passes tnrough another sparger and gas-nquia separator in which CO, from the oxidation process is transferred to the gas phase. This gas then flows to a CO, specific infrared detector. An integral recorder continuously displays the linearized detector signal which is the TOC level of the sample. An optional diluter can be used to handle carbon levels to 1000 mg/litre and salt brines to 30%. Salt solutions have typically been a prob lem with conventional TOC monitors utilizing direct injection into a hightemperature furnace. The award-winning monitor is said to overcome this problem. In the low-temperature oxidation process, the salts all remain in solution and are simply discharged through the analyzer waste line. Streams containing salt up to 3% can be handled directly, without a reduction in oxidation efficiency. Higher salt content streams can be handled after automatic dilution to the 3% or lower level. Analyzer is designed to handle particles up to 1 mm (0,04") in diameter. Streams with larger particles having little organic content should be screened. (Model DC-62 total organic carbon moni tor-- Envirotcch Corporation, Dohrmann Division, 3240 Scott Blvd., Santa Clara, CA 05050.) Circle 224 opposite last page. 30 MID-NOVEMBER 19/S CHEMICAL PROCESSING Cc 000038877 November 14, 1979 M. McCaulley Conoco P.0. Box 727 Westlake, LA 70669 Mr. McCaulley: In response to your recent request, I am forwarding information about the ultraviolet purification equipment that we produce. Our research has recently resulted in our being able to expand the use of our "thin-film, high-energy" ultraviolet equipment into the arena of destruction of toxic compounds, 0uj=pOess encompasses the injection of an oxidizing compound /'(H2 O^^lnto the flow stream of the compound being treated followed rjy--eJtposure to our high intensity ultraviolet plasma for approximate ly 200 seconds.This ultraviolet exposure has a multiple reaction in the decomposition of the toxic compound. The H-O- is dissociated photochemically to H, OH, and 02- Additionally, the 184 nanameter ultraviolet will ionize the O* fcy^6TT>The combination o OH and-0^ with the ultraviolet environment Supply sufficient energy potential for the destruction of not only a very wide range of toxic compounds, but very high concentrations of these compounds. Compounds which we have sucessfully treated to are: cyanides (ferro, sodium, potassium, and complexed cyanides), phenols, PCB's, THM's, DDT, acetic acid, organic contamination of tungsten, and others. Total process time required for the most difficult compounds is two hours. Destruction is to levels beyond detectability (less than 10 ppb). We have laboratory equipment for treating small quanity samples to demonstrate the efficiency of the process and to afford data which is required to scale-up to required volumes. We currently have fullscale toxic destruct equipment with flow capability to 100 GPM. Thank you for your inquiry, and we look forward to serving you 'further. Very truly yours PURE WATER SYSTEMS, INC. L' President MDW:lvm Ends. Please refer further requests to Wayne Wren CCR 000038878 1 ULTRA-VIOLET PRODUCTS, INC. PEN-RAY7SOG DATA Stable Ozone Generators FEATURES: Long term Stability of Light Source Reproducible Ozone Output No Electrical Adjustment Required Simple Sleeving Technique for Varying Ozone Output Light Source of PEN-RAY Lamp Quality Low & High Output Units Available No Heating of Gas Stream by Light Source Quartz Flowtube and Light Source for High 184.9 nm Transmission MAIN APPLICATIONS: Calibration of Field and Laboratory Ozone Analyzers Source of Oxidant for Aging and Oxidation Testing of Materials, Such as Rubber, Polymers, etc. Ozone Source for Instrumentation Development Water Purification Studies Air Pollution Studies j _ P1977 Ul TRA VIOLET PRODUCTS, INC. CCft 000038879 ULTRA-VIOLET PRODUCTS, INC-RCT San Gabriel, California 9177BVj/ PEN-RAY7S0G DATA Stable Ozone Generators Lamp Mounting Flange ^I Exposure Adjusting Sleeve (Unca/ibraled) ' h-------------------------------z----------------------------- H OT y OI j-t 1.125" --jr cm fp ^j <................................ ... .......................... > -----------------------------------,------------------------------------- \ CONSISTS OF: Lamp Power Supply Dimension -- x z I Sleeve Adjustment SOG -1 11SC-1 SCT-1 2" O// 3" 5.5" Max. of 2" Quartz Flow Tube 12 MM OD SOG-2 3SC-9 SCT - 4 2.125" ?" 11.125" 13.5" Max. of 9" The Following Graphs Show Typical Ozone Levels Produced By SOG - 1 And SOG - 2 Your Authorized Dealer / SP-53M Printed in U.S A. LENGTH OF LAMP EXPOSED (IN INCHES) Above cvrvta art rapresantahra ot ozone (0*9/1 produced by tha SOO-t, SOG'24 Wat C/tamrttry Tactvwiua (Kl) mas utad to detarmina oiono produced. CCR 000038880 Cat. No. 1108 Effective December 31, 1978 - ULTRA-VIOLET PRODUCTS, INC. H Cl ` 5100 Walnut Grove Avenue, San Gabriel. CA 91778 U S A. V V J LABORATORY , . . products List --Pri.ce S_ chedul,e ITEM B-100A B-100A B-100A/R B-100A/R B-100A/X B-100A/X C-61 C-61 C-61 C-62 C-62 C-62 C-70 C-70 C-70 C-71 C-71 C-71 CC-10 CC-15 CC-15 CC-15 CC-20 CC-20 CC-20 G-203 G-275 G-276 G-277 G-278 J-124 J-126 J-129 J-221 J-225 J-236 J-236 DESCRIPTION BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW MINERALIGHT Transilluminator 115V, SW MINERAL1GHT Transilluminator 220V, SW MINERALIGHT Transilluminator 250V, SW BLAK-RAY Transilluminator 115V, LW BLAK-RAY Transilluminator 220V, LW BLAK-RAY Transilluminator 250V, LW CHROMATO-VUE Cabinet 115V, SW & LW CHROMATO-VUE Cabinet 220V, SW & LW CHROMATO-VUE Cabinet 250V, SW & LW CHROMATO-VUE Cabinet 115V, LW CHROMATO-VUE Cabinet 220V, LW CHROMATO-VUE Cabinet 250V, LW CHROMATO-VUE Cabinet CHROMATO-VUE Cabinet 115V UL, SW & LW CHKOMAI'O-VUE Cabinet 115V CSA, SW & LW CHROMATO-VUE Cabinet 220V, SW & LW CHROMATO-VUE Cabinet 115V, SW & LW CHROMATO-VUE Cabinet 115V CSA, SW & LW CHROMATO-VUE Cabinet 220V, SE & LW Adapter Filter Assembly Filter Assembly Filter Assembly Filter Assembly Stand Bracket Stand BLAK-RAY Meter, LW BLAK-RAY Meter, SW Certification System 115V, LW Certification System 220V, LW SHPG.WT. 17# 17# 17# * 17# 17# 17# 24# 24# 24# 24# 24# 24# 29# 29# 29# 29# 29# 29# 9# 15# 15# 15# 14# 14# 14# 5# 1# 1# 1# 1# 4# 1# 3# 4# 4# 19# 19# LIST $199.00 259.00 259.00 309.00 219.00 279.00 490.00 510.00 525.00 360.00 398.00 398.00 650.00 675.00 675.00 598.00 675.00 675.00 59.95 174.00 179.00 185.00 359.00 379.00 379.00 49.95 22.95 74.95 74.95 33.95 17.95 5.95 29.95 210.00 225.00 598.00 620.00 BLAK-RAY, MINERAL1GHT, GEM-TEMP PEN-RAY, and CHROMATO-VUE, are regis tered trademarks of ULTRA-VIOLET PRODUCTS, INC. LW=Long wave ultraviolet (365 nm) SW=short wave ultraviolet (254 nm) All prices are F.O.B. San Gabriel, California. Minimum billing $50.00 net. Terms: Net 30 days. i CCR 000038881 ITEM DESCRIPTION J-237 J-237 J-260 J-260 J-2601A J-2602A J-2603A J-330 J-331 J-332 M-14 M-14 M-14 M-15 M-15 M-15 M-16 M-16 M-16 ML-49 MS-47 MSL-48 PCQ-008L PCQ-008PS PCQ-008S PCQ-023 PCQ-023L PCQ-023PS PCQ-024L PCQ-024PS PCQ-024S PCQ9G-1 PCQ9G-1 PCQ9G-1 PCQ9G-1 PCQ9G-1 R-52 R-52 S-68 S-68 S-68A S-68A S-69 S-69 SCT-1 SCT-1 SCT-2 SCT-2 SCT-3 SCT-3 SCT-4 SCT-4 SOG-1 SOG-1 Certification System 115V1 SW Certification System 220V, SW Radiometer 115V Radiometer 220V Sensor (254nm) Sensor (365nm) Sensor (297nm) Recharger 115V Recharger'12V Recharger 220V MINERALIGHT Lamp 115V, SW MINERALIGHT Lamp 12V, SW MINERALIGHT Lamp 220V, SW MINERALIGHT Lamp 115V, SW & LW MINERALIGHT Lamp 12V, SW & LW MINERALIGHT Lamp 220V, SW & LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 12V, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp, LW MINERALIGHT Lamp, SW MINERALIGHT Lamp, SW & LW Photochemical Lamp Power Supply Photochemical Lamp Photochemical Lamp Photochemical Lamp Power Supply Photochemical Lamp Power Supply Photochemical Lamp Photochemical Lamp, 2Yz" Photochemical Lamp, 4" Photochemical Lamp, 6" Photochemical Lamp, 7" or 8" Photochemical Lamp, 10" or 11" MINERALIGHT Lamp 115V, SW MINERALIGHT Lamp 220V, SW MINERALIGHT Lamp 115V, SW MINERALIGHT Lamp 220V, SW MINERALIGHT Lamp 115V, SW MINERALIGHT Lamp 220V, SW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW Power Supply 115V Power Supply 220V Power Supply 115V Power Supply 220V Power Supply 115V Power Supply 220V Power Supply 115V Power Supply 220V Ozone Generator 115V Ozone Generator 220V SHPG. WT. LIST 19# 19# 4# 4# 2# 2# 2# 2# 2# 2# 3# 3# 3# 3# 3# 3# 3# 3# 3# 4# 4# 4# 7# 11# 7# 9# 9# n# . 9# 11# 9# 4# 4# 4# 4# 4# 12# 12# 15# 15# 16# 16# 15# 15# 4# 4# 4# 4# 4# 4# 6# 6# 7# 7# $620.00 690.00 785.00 785.00 225.00 225.00 225.00 26.95 26.95 54.95 185.00 185.00 205.00 185.00 185.00 205.00 165.00 165.00 189.00 89.95 110.00 105.00 379.00 175.00 339.00 599.00 775.00 175.00 495.00 175.00 790.00 230.00 235.00 240.00 245.00 249.00 339.00 375.00 549.00 549.00 729.00 819.00 510.00 525.00 79.95 89.95 89.95 99.95 84.95 89.95 84.95 99.95 303.00 325.00 CCR 000038882 ITEM DESCRIPTION SOG-2 SOG-2 SPR-33 UVC-303 UVC-503 UVL-21 UVL-21 UVL-21 UVL-56 UVL-56 UVL-56 UVS-11 USV-11 UVS-11 UVS-54 UVS-54 UVS-54 UVSL-15 UVSL-15 UVSL-15 UVSL-25 UVSL-25 UVSL-25 UVSL-55 UVSL-55 UVSL-55 UVSL-58 * ft ipi r n V/ * Ulml UVSL-58 X15-B X15-B X15-B X-15H X-15H XX-15 XX-15 XX-15 XX-15H XX-40A XX-40A 11SC-1 11SC-1L 11SC-2 22SC-3L 22SC-3S 3SC-9 90-0013-01 90-0014-01 90-0015-01 90-0016-01 90-0017-01 98-0008-01 98-0008-02 90-0008-03 Ozone Generator 115V Ozone Generator 220V Stable PEN-RAY Lamp 115V BLAK-RAY Spectacles BLAK-RAY Safety Goggles BLAK-RAY Lamp 115V UL, LW BLAK-RAY Lamp 115V CSA, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 115V CSA, LW BLAK-RAY Lamp 220V, LW MINERAL1GHT Lamp 115V, SW M1NERAL1GHT Lamp 115V CSA, SW MINERALIGHT Lamp 220V, SW M1NERALIGHT Lamp 115V, SW MINERALIGHT Lamp 115V CSA, SW M1NERAUGHT Lamp 220V, SW MINERALIGHT Lamp 115V, SW & LW MINERALIGHT Lamp 115V CSA, SW & LW MINERALIGHT Lamp 220V, SW & LW MINERALIGHT Lamp 115V, SW & LW MINERALIGHT Lamp 115V CSA, SW & LW MINERALIGHT Lamp 220V, SW & LW MINERALIGHT Lamp 115V, SW & LW MINERALIGHT Lamp 115V CSA, SW & LW MINERALIGHT Lamp 220V, SW & LW MINERALIGHT Lamp 115V, SW & LW irtri etfsti-'t-* m . . iimi a cu;pttiii t, u.v W--I. MINERALIGHT Lamp 220V, SW & LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 115V CSA, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 115V CSA, LW BLAK-RAY Lamp 220V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 115V, LW BLAK-RAY Lamp 220V PEN-RAY Lamp, SW PEN-RAY Lamp.LW PEN-RAY Lamp.SW PEN-RAY Lamp, LW PEN-RAY Lamp, SW PEN-RAY Lamp, 9* SW PEN-RAY Lamp -- Argon Fill PEN-RAY Lamp -- Krypton Fill PEN-RAY Lamp -- Neon Fill PEN-RAY Lamp -- Neon-Mercury Fill PEN-RAY Lamp -- Xenon Fill "A" Lamp Shield "B" Lamp Shield "C" Lamp Shield SHPG. WT. LIST 13# 13# 46# 1# 1# 3# 3# 3# 4# 4# 4# 1# 3# 3# 4# 4# 4# 3# 3# 3# 3# 3# 3# 4# 4# 4# 4# 4# 4# 7# 7# 7# 7# 7# 8# 8# 8# 8# 20# 20# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# 1# $415.00 435.00 3,475.00 6.00 7.50 44.95 49,95 54.95 64.95 69.95 74.95 64.95 74.95 79.95 109.95 114.95 119.95 64.95 69.95 79.95 79.95 94.95 94.95 99.95 99.95 109.95 114.95 119 95 124.95 84.95 94.95 99.95 99.95 114.95 99.95 99.95 114.95 99.95 124.95 149.95 52.95 78.95 52.95 190.00 119.00 109.95 77.95 77.95 77.95 77.95 77.95 7.95 7.95 7.95 CCR 00003 8883 Manufactured by ULTRA-VIOLET PRODUCTS, INC. OCp 5100 Walnut Grove Avenue, San Gabriel. CA 9177D U.SA REPLACEMENT PARTS f J ji m ITEM BATTERIES J-333 6V Rechargeable J-144 6V Super J-145 45V 12V Rechargeable BULBS 100-watt Spot, LW White, for battery lamps 100-watt Flood, LW FILTERS (254nm) for: S-68, S-68A CC-20 R-52 C-61 UVS-11, UVSL-25 MS-47, MSL-48, UVS -54, UVSL-55, UVSL-58 M-14, M-15 C-70 UVSL-15 FILTERS (3G5nm) for: C-70, C-71 UVL-21 CC-20 B-100A C-62 M-16 S-69 FILTERS (365nm) for:it - - - UVSL-15 UVL-56, UVSL-55, MSL-48 FILTERS, Contrast Control for: CC-10, CC-20, C-70, C-71 TUBES, Germicidal (254nm) 4-watt 6-watt 8-watt 15-watt 30 watt TUBES, Blade Light Blue (365nm) 4-watt 6-watt 8-watt 15-watt 30-watt 40-watt TUBES, Black Light (365nm) 4-watt 6-watt 8-watt 15-watt 40-watt TUBES. Multiband (254 & 365nm) 4-watt 6-watt 15-watt TUBES, White Light 8-watt For C-70. C-71 TUBES, Quartz For 5-68, S-68A Fot R-52 0 571. fMntcU tn USA PART NO. 45-0002-01 45-0005-01 45-0006-01 45-0009-01 34-0011-01 34-0014-01 34-0022-01 38-0006-01 38-0004-01 38-0008-01 38-0011-01 38-0012-01 38-0015-01 38-0018-01 38-0031-01 38-0035-01 38-0001-01 38-0002-01 38-0005-01 38.-0009-01 38-0010-01 38-0019-01 38-0032-01 '-'38-0034-01 38-0037-01 38-0050-01 38-0013-01 34-0003-01 34-0013-01 34-0007-01 34-0008-01 34-0025-01 34-0010-01 34-0016-01 34-0031-01 34-0017-01 34-0018-01 34-0032-01 SHPG. WT. LIST 2# 6# 6# 1# 2# 1# 2# 1# 1# 2# 4# 2# 2# 1# 2# 2# 2# 2# 1# 2# 4# 1# 1# 1#....... 2# 2# 1# 1# 1# 1# 2# 5# 1# 1# 1# 2# 5# 8# $ 52. lb 7.75 35.25 8.2b 40.00 1.25 50.00 97.95 93.95 57.95 197.00 32.95 38.95 18.95 198.00 21.95 36.95 5.95 30.95 10.95 65.95 5.95 8.95 5.95 5.95 5.95 20.95 13.25 13.25 13.75 13.75 27.50 11.00 11.00 16.50 16.50 33.00 33.00 34-0005-01 34-0034-01 34-0006-01 34-0009-01 34-0024-01 34-0004-01 34-0015-01 34-0033-01 34-0001-01 34-0002-01 32-0009-01 77-0003-01 1# 5.50 1# 5.50 1# 13.75 2# 13.75 8# 33.00 1# 13.75 1# 13.75 2# 22.00 1# 4.25 1# 3.50 2# 249.00 1# 169.00 CCR 000038884