Document kmXBOQZ91X092MOEq0kKEOBDy

PPG INDUSTRIES, INC. ~ INDUSTRIAL CHEMICAL DIVISION LAKE CHARLES, LOUISIANA ........ LD 2206 12-15-1981 JOBE, J D QADIR, S CLASSIFIER BOTTOM EVALUATION FOR BAFV WTOKFICATIO* AND DISPOSAL Dlatrlbutiom 1. 2. 3. 4. 5. 6. 7. 8.-11. 12.-13. 14. 15. 16. J. E. Pike H. J. Romm, Jr. C. P. Lellanc Richard Millar Moatafa Kasai M. U. Wood Central Fllaa - C.O. Technical Fllaa Technical Information Center Author - J. D. Jobe Author - Sped Qadir Laboratory File ism* Ear Words Sottome Sludge NCI Ferric Chloride Partlculatee Organlca Detoxification Pre-treatment Pyrolyala Reaidue Analyala EP-Toxlelty Teat SL 085453 LABORATORY DEPARTMENT J. D. JOBE SYED QADIR TECHNICAL REPORT DECQ1BER 15, 1981 CLASSIFIER BOTTOMS EVALUATION FOR SAFE DETOXIFICATION AND DISPOSAL LD-2206 INTRODUCTION The recent accelerating emphasis on protection of the environment has necessitated the need of rapid development In technology to eld in pollu tion control. The proper management of hazardous waste Is now clearly recognized as one of the major tasks the chemical industry will have to accomplish in the coming decades. As environmental laws and regulation are becoming stricter in the near future. Industry's waste disposal options have become increasingly limited and costly. Recently, the Resource Conservation Recovery Act (RCRA) has helped to promote environmental safeguards, but also has required more costly waste management practices to deal with hazardous waste. The cost of putting a hazardous waste into a secure landfill in bulk form Is about $0.45/gallon; whereas, in dnms, the cost is higher and the practice will soon be ruled out by EPA. PPG Industries Chemical Division at Lake Charles is paying over $67,000 annually for the disposal of Its Bottoms Plant solids and liquid hazardous waste alone. The future prospect for ouch disposal is not promising. The ever increasing high cost and possible future restriction on transportation, as well as the limitation of secure landfill facilities are quite unpredictable. Concerned with all these problems, a need was recognized to have an alternate solution. A project was jointly originated by Process Engineering and the Laboratory to look into such possibilities. The objective of this project is to present specific information pertinent to the possible in-plant alternate to dispose of such hasardous waste. The laboratory responsibility was considered to provide those dealfn parameters of the unit process which are Involved in physical--chemical treatment of the raw waste for detoxlfication, as well as the analytical data to determine the best suited design criteria in selection of the candidate process. The approach should be envlroneentally and legally safe, technologically feasible, a* well as economically desirable. Also, if possible, this method should be adaptable to our other similar solid waste problems which would be generated bv various other operating units. Classified bottoms sludge contains mostly residue of dopp kettles and those heavies which can neither be incinerated In our existing facilities, nor separated In API Separators. A general characterization and analyaea are summarized in Table Nos. I, II snd III to show the solid and vaporizable contenta and other chemical and physical characteristics. SL 085454 LD-2206/3 Table I. General Characteristics of Classifier Bottoms (Untreated) Physical Characteristics State Semi-viscous sludge. Color Greenish black with brown specks. Odor Pungent and chlorinated organics. Solids and Vaporizable Contents 8-10Z solids and 90-92X vaporizable components. Chemical Characteristics BTU/lb (gross) tesidoe 350*C 3376 7.5X Organic Contents (volatiles) 52Z (See Table II) Inorganic Contents (metals) pH 6Z (See Table III) Less than one (highly acidic) SL 085455 LD-2206/4 Table II. Analysis of Total Organics (weight Z volatiles) Present In Classifier Bottoms Component, wt Z Vinyl Chloride 11/21/80 Trace 11/24/80 - 12/02/80 - 6/16/81 - Average Ethyl Chloride 8.53 0.94 1.01 0.34 2.7 1,1-Dichloroethane 21.21 7.00 5.52 7.99 10.38 cis-1,2-Dichloroethylene 0.13 0.12 0.11 0.16 0.13 Chloroform 0.37 0.22 0.20 1.33 2.12 1,2-Dichloroethane 6.06 6.12 6.50 9.04 6.92 Methylchloroform 0.63 2.96 1.41 0.69 1.42 Carbon Tetrachloride 0.41 0.38 0.35 0.30 0.36 Trichloroethylene 6.43 7.46 7.01 5.61 6.62 1,1,2-Trichloroethane 9.10 2.95 3.34 3.16 4.63 Toluene 0.04 - - - 0.04 Perchloroethylene 8.03 8.75 9.53 10.42 8.93 unsym-Tetrachloroethane 4.01 1.26 1.34 1.68 2.06 aym-Tetrachloroethane 3.33 1.09 0.88 3.46 2.19 Pentachloroethane 4.73 1.66 1.80 1.74 2.48 Hexachloroethane 1.64 0.34 0.39 0.79 0.75 Hexachlorobutadlene 0.03 0.69 0.90 1.39 0.75 Total Volatiles Average 52.571 Method of Analysis: Cas Chromatography methylene chloride extraction. SL 085456 LD-2206/5 Table III. Total Inorganic (weight Z metals) Present In Classifier Bottom (Raw Sludge) Metals Fe Cr Cu Pb Ni Hg Ca Total 1st Composite 4.9 Z < 0.0001 Z 0.02 X < 0.0001 z 0.01 z 0.05 pp 2nd Composite 5.4 Z 0.003 Z 0.023 Z 0.001 Z 0.005 Z 0.3 pp 0.117 z 3rd Composite 4.8 Z 0.004 z 0.033 z 0.002 z 0.015 z 0.5 ppm 3.20 Z Average 5.03 Z 0.002 z 0.025 z 0.0010 z 0.01 z 0.43 ppm 1.10 z 6.17 z SL 085457 LD-2206/6 ABSTRACT Laboratory studies were conducted to develop a means to detoxify bottom material from the Plant B Classifier. A two step process involving pre treatment with lime followed by pyrolysis was found to decompose the toxic components of the waste, rendering the resulting solid suitable for landfill. A continuous pilot plant to verify this treatment process is recommended. EXPERIMENTAL A. Sampling The classified bottoms holding tank is a 38' x 10' x 8' rectangular pond where the tar buggies dump the material from various dopp kettles and vacuum trucks discharge organic waste from other operating units. The solids are separated from organics and water and settle down to the bottom by gravity as well as by the precipitating action of ferric chloride present as the spent catalyst from the dopp kettles. The sampling scheme (Figure No. 1) was devised to ensure collection of a representative portion of the classified bottoms material. The surface area of the pond was divided into an imaginary grid system and a total of 12 cored samples were taken (using EPA's COLIWASA method) with a 2-1/2" x 5' spun fiberglass pipe operated by two men. The twelve core samples were composited and equal portions were transferred into three one-gallon plastic containers holding about 10 pounds each of sampled material for laboratory experimentation. The sampling was performed in compliance with existing regulations promulgated by the regulatory agencies (EPA 600/2-80-018, January 1980. Samplers and Sampling Procedures for Hazardous Waste Streams, Analytical Operating Procedures Manual, Department of Natural Resources, Office of Environmental Affairs, Hazardous Waste Management Division, Baton Rouge, Louisiana, August 1980). B. Equipment and Apparatus The initial laboratory pyrolysis experiment was performed in a platinum crucible using an electric heater to study the weight loss relationship to heat and total time period (Table IV). Later, for pilot studies, the apparatus for pyrolyzing the classified bottoms was designed for comparative batch incinerations, ranging from 100-500 grams. The system (Figure No. 2 and Photograph No. 1 of the pilot plant) consisted of a one-liter borosilicate reactor vessel and a trio of Creenberg-Smith 500 mL water scrubbers. An air filter of 0.45 urn particle retention (C,elman-089~844 8" x 10" size) was installed after these scrubbers to verify that all the particulates of interest were trapped. To collect this sample. Research Appliance Company's particulate Air Sampler (Model CMWL-2000) was used. This air sampling equipment served a dual purpose: first, for collection of the said particulate, and second, as the source of induction air needed for oxidation during the pyrolysis. The entire assembly was a closed system except for an air inlet, provided by a glass tube opening into the reactor vessel. The exhaust was connected to the three water scrubbers followed by the particulate sample equipment. A 750 watt, variable control, electric distillation furnace was used to provide the necessary heat. A digital SL 085458 k. Study of Thermal Duco^waltlon ud Orgemlea Weight Loee of Cleoolflod lotto Sula Caperimeetatloe) Weight loot it rtht ft .t n iu.tw wimt ut t x> m--m w*ut u.t t *3 wuw %ie **t w* te_ ^ ii*T i TounmM Ofctirwi foMntiri OtoinM To*for4tre Ob#*md T^tmton noorvod Taunton BN t*~100*C ' ' 12^130*C 2*3-320"C 270*C Loiii weight Weight loMlolog ttetght WilfkC laaUlil Weight Weight lalilW Weight no-no'staalAlU woight Weight Volfhr. | Lost, g Loot* t Wolfit, g Loot* 1 U. 1 Weight, * Loot* | Loot* S Weight* | Loot, g Lcei , 1 Val*bt, * Lott, | El t) L> 7*37 15.7 17*45 42. 70.43 3*44 2.0* 21.44 21. fl 4.1* *1.44 2.03 12.97 91.4* 1.9* l.M 23.02 23.0* *1.12 92.24 l.H 1.93 23.04 23.07 92.14 92.21 Sft 9.11 i's 4.40 13.92 17.1J 43-4* a.*7 4.2 1.77 20.03 22.44 *3.35 *.1 2.04 l.4 23.19 13.3* 91.9 92.72 l.M 1.** 13.*3 11.3* 92.44 92.74 1.77 1.44 23.44 23.54 92.94 92.71 U ifriohi loo* SL 085460 LD-2206/9 B. pyrometer was used to study the temperature within the reactor, and another pyrometer was attached to the heat source to monitor the heat differentials during the pyrolysis (Figure No. 2). The entire systan was mounted in a hood and all experimentation performed with the hood door closed and hood exhaust on. C. Procedure Weighed samples of the material to be pyrolyzed were placed in the reactor vessel along with the thermocouple. Another thermocouple was placed between the heat source arxi the reactor vessel bottom. The reactor vessel, scrubbing units, and air sampling equipment were connected to each other. The flow of air into the system was adjusted by a bypass valve. The heating of the reactor vessel was controlled manually by monitoring both the sludge and the heat source temperatures. Temperature readings were recorded every two to five minutes depending on the temperature differential. The three scrubbers were charged with ISO mL water to retain any sublimates and water soluble gases coming out of the reactor. This was followed by the 0.45 urn filter assembly of the sir sampling equip ment. This unit retains all the particulates not trapped by the scrubbing units. DISCUSSION AND RESULTS The major constituents of the sludge are: spent ferric chloride cetalyst, muriatic acid, sand, chlorinated organics, water, and tar-like heavy sludge. Pyrolysis of these materials offers the opportunity to reduce the Tolimt as well as the toxic components to levels qualifying for disposal at a non-hazardous, sterile landfill. The results of the preliminary experiments show that the sludge saeple contains approximately 92* volatile constituents with 8* eollds (Table XV). The spectrographic analysis of the residue indicated that the major constituents were Pe0* end sand with minor quantities of Hg and Ca (Table V). The vaporizable constituents were largely composed of organics, muriatic acid (HC1), FeClj and water. Although volume reduction of the bulky waste was achieved, as well as detoxification, the resultant particulate emissions, chiefly iron, were highly undesirable (Photograph No. 2). Strict sir pollution regulations and highly corrosive gaseous emissions (HC1) prevent such prsctices. The evolved HC1 formed Indigenously by hydrolysis of FeCl, and thermal decomposi tion of chlorinated organics would have s significant effect on the performance and life of the reactor and its hardware. Therefore, It was necessary to select an agent that would neutralize existing HC1 and that formed by the decomposition of chlorinated organics. SL 085461 LD-2206/10 /c'sS" O'^/SrH r/iJJGC *: V'. ry/. SL 085462 085463 LD-2206/12 Table V. Metal Analysis of Pyroly2ed Sludge (dntreated Pyrolyred Residue Of Raw Sludge) Metals Fe Cr Cu pb Ni Hg Ca Total 1st Composite 35.9 1 0.24 0.19 0.004 0.10 < 0.10 ppm 0.24 2nd Composite 39.5 Z < 0.0001 (0.18 ppm) 0.15 < 0.0001 (0.04 ppm) 0.04 0.5 ppm 0.25 Averagi 37.5 0.120 0.170 0.002 0.070 0.30 0.245 38.11 gL 085464 Lr'-22n^/i4 ^sveral neutralizing agents vere rnr'iHerid including cal-iur car'"^nar.e, _nlcium oxide (quick line'' arc! slaked line. .Slaked line *as selected '-ecause it is readilv available and safe to use. Ouick line releases !tree quantities of beat upon contacting vater vhicb could result in a Mr" or release "f organic? in air. Calcium carbonate is not efficient for neutralizing and more expensive. The typical dose was considered to be 20 g/100 g of waste, but it may range from 18 g-22 g/100 g depending upon the nature of the waste. The 1:5 mix ratio was successfully used for our pilot plant experiments. A pH range of 9.8 to 10.5 was considered a good indication of thorough mixing and complete neutralization of lime and waste. The slight excess alkalinity serves as a reserve for any other HC1 produced during the pyrolysis. The treated waste (20 g/100 g) was heated. At temperatures of 1 3 * ` - ! '" ` 0 , the charred remains of organics reached the auto ignition point and warned with a slight glow. The pyrolysis was completed without if particulate emissions at 350'C. ^Photograph No. 3'. The residues and scrubbing waters and leachate testings 'Tables VI, the air sampling unit was weighed were negative. were analvg.cd for organics, inor'-inics, VII, and VIII t. The filter paper from and checked for anv retention. Results * f Sabine 'clear well' River Water was used in the scrubbers for one incinera tion of treated sludge for comparison to the total suspended solids formation when scrubbing with distilled water. Results did not show anv difference. Scrubber efficiency was determined by comparing total suspendeds'-i'd-; retained in each scrubbing unit to the total of the three. The- rus-'er efficiencies were: No. 1 scrubber retained 87.91 of the total parti -clue. No. 2 scrubber retained 12.57 and No. 3 scrubber collected '"'.l*. scrubber waters were s t ep-f 111 er cd through a range of filter rare`hr .1 t_ d i --1 r 1 u t I o n a na 1 v s i s ( 7 a b 1 c V I I I j , I I |\; ; 1 s ] p, : in results of several tests proved that the lime treatment wa . c:;v effective for t he neutralization of waste prior to the f rfucv controlled verv efficiently the problem, of paniculate and comsiv, _ i-, emissions. 1 he quantity of final residue resulting from, lime treatment w t . L e u i d e r a 1 ! creator but it is offset by the lack of atmosphericemission- and-..hi i loading of the scrubber water hv this nr'cess. 1 - ve ! : - -n r i: r - tv -iur i r c : > - i \ i n c - ' ! 11 , - ' , ' * f i ' ` vi > .i 1 ' : - ` t t' idui i nd t c a t ar, ; 1 \ no ' - v.-rn 1 i - ' i : i t at i - . The hi' tnieitv test for heavv metals -'able VII 1 was negative for toxic metals. Residues were analvzed for high molecular we i giit organics such as PCB, and results were negative. A detailed ana 1 vs is and comparative results of treated and untreated pyrolvzed residues are given in Table VIII. LD-2206/15 - "" " i.!gr;- ' r " i.' - - , 1 ;'s '`iy.'' Table VI. Metal Analytes of Treated and Pyrolyaed Botteas Sludge ' -> Metals Pe Cr Cu Pb HI Hg Ca T tal 1st Coaooslts 19.3 X 0.00005 0.17 0.00005 X X X 0.01 X 0.2 20.0 ppa X 2nd Coanoslte 20.8 Z 0.009 z 0.094 z 0.004 X 0.05 X 0.1 ppa 16.50 z 3rd Coaooslts 12.2 0.018 0.083 0.004 0.035 0.2 19.6 ppa Z Averate 17.43 X 0.009'' X 0.115 z 0.0027 "x 0.0416 X 0.17 ppa 18.7 X 36.47 X Table VII. EP Toxicity Analysis for Bmrioo* sad Toxic Natal tvalvatlm (lasMust of Treated and Fyrolyxad Sludge) Toxic jfrartp ^t.<^pofU ftlfki 3m_cqqkih lSilra Ca - CKo ppa^i 0.733 PPa 5.0 ag/L HI - Al Pfg| ** PPeqff* 0.80 ppa - Cr 1.0 PP 0042 ppag ^&9 ppa0^ 0.70 ppa 5.0 ag/L Pb 1.0 nm *06 ppa0t 0.80 ppa 5.0 ag/L C4 < g ppa 0^2 ppa pf%^t&l ppa |3pf' 0.1 ppa 1.0 ag/L As < 5.0 ppa - - 5*0 ag/L Ba 100.0 ag/L Hg 0.005 PP < 0.002 ppa < 0.002 ppa < 0.003 ppa 0.2 ag/L SL 085467 ID-2206/16 Table VIII. Comparative Study of Chemical and Physical Characteristics of Pyrolyzed, Treated and Untreated Sludge Characteristics Sludge Treated (With Lime) Sludge (Untreated) State 9nu.ll granular, lumpy and Medlta to fine grain and hydroscopic. powder. Color Rust brown. Brownish black. Odor Residue, Z None 25-35 None 10-15 Residue pH 10.4 5.8 Volatiles and Sublimates 75-65Z 90-85X Pyrolysls-optlma 350*C 480*C Temperature T.D.S. (Scrubber Water) T.S.S. (Scrubber Water) 0.0063X 10 ppm N/A 500 ppm Distribution of Particulate f- Sire (Scrubber Water) 30-60 us 10-20 us - 8 ys 2 2 1 112 111 110 5 ys 3 54 3 urn 1 50 1.2 un 0 36 0.8 ura 1 2 0.45 um 0 25 pH of Scrubber Waters Scrubber No. 1 3.7 0.8 Scrubber No. 2 5.0 1.6 Scrubber No. 3 5.2 2.7 SL 085468 RECOMMENDATIONS LD-2206/17 There are a few important factors which should be observed for an efficient pyrolysis and detoxification of thiB waste. Complete neutralization of waste is necessary, since the majority of pyrolysis problems are caused by HC1. Neutralization is greatly simplified if the lime is added in the ,'orm of a thick slurry. This serves two functions: first, water promotes the hydiolysis of FeCls and second, water provides an effective medium for the homogeneous acid neutralisation. The lime mixing ratio (1:5 based on the acidity of sludge) is also an important factor in this process. Exceeding the optimum neutralization level may cause higher pH in the residue. A pH of 12.5 or above classifies any waste as hazardous. Calcium chloride converts into a porous, hygroscopic, amorphous mass above 200"C. It fuses and begins to decompose at 500*-710* into oxy-chlorlde, calcium chloride, calcium oxide, and chlorine in the presence of air. Upon rapid cooling, it solidifies into a glass-like crypto-crystalline mass which sticks to the reactor vessel. The safe range was considered to be between 350-400*C to prevent glass formation. Therefore, most experiments were performed up to the range of 350-400*C, although a few of the experiments reached 500*C. Finally, a larger scale continuous pilot plant is recommended for further analytical testing of emissions to verify the complete detoxification of waste material that was achieved in laboratory scale experiments. Author: Author: Approved: Mark W. Wood Approved: C. P. LeBlanc >b -r> Date A Date Date Date Date rv SL 085469 * ' LD-2206/18 Bibliography 1. "Air Pollution Aspects of Sludge Incineration", EPA Technology Transfer Seminar Publication, June 1975. 2. "Oxygen Activated Sludge Waste Water Treatment System, Design Criteria and Operating Experience", EPA Technology Transfer Seminar Publication - 1973. 1 3. "Hazardous Waste", Editorial . Industrial Waste . A Scranton Gillet Publication. July/August 1980 - 380 NW Highway, Desplalnes, ILL. 4. "Hazardous Waste Landfills", Environmental Science and Technology; Volume 15, No. 3, March 1981. 5. "Waste Disposal Chemistry", ES&T, Volume 14, Ho. 5, May 1980. .6 "EPA Regulates Hazardous Waste", ES&T, Volmae 14, No. 7, July 1980. 7. "Hazardous Waste Here and There", ES&T, Voltae 14, Ho. 8, August 1980. 8. "Incinerator Research A Building", ES&T, Volume 14, No. 19, September 1980. 9. Lynch, J. W., "The New Hazardous Waste Regulations", Chemical Engineering, 87, 15, 55 (1980). . t SL 085470