QUALITY CONTROL OF HAZARDOUS WASTE FUEL
BY
DAVID G. GOSSMAN
Gossman Consulting, Inc.
Presented at the IEEE Cement Industry Technical Conference - May, 1988
There are three reasons for performing thorough quality control of hazardous waste fuels. It is first necessary to protect the product (cement ) and the process (the kilns) from any negative effects of using hazardous waste fuel. Secondarily, it is necessary to protect the environment and meet any special regulatory needs. Finally, and most important, worker health and safety is critical to the long-term success of using hazardous waste fuels and limiting corporate liabilities.
Worker health and safety can further be enhanced by engineering controls to limit and monitor personal exposure. This approach to quality control and liability limitation can be assured through proper professional management and sophisticated on-site laboratory capabilities designed to triple check each shipment of hazardous waste fuel used.
Introduction
During the last five years, both in the United States and in other countries, the use of hazardous waste fuels in cement kilns has become more and more common.1,2 Numerous tests by government agencies in a number of different countries have proven the ideal nature of cement kilns as thermal treatment devices.3,4,5,6 Little, if any, attention has been paid by these agencies to the risks and liabilities associated with using hazardous waste fuels. Indeed, with a few notable exceptions, many cement manufactures and waste generators do not appear to have examined or may not be aware of the full set of liabilities involved in using and supplying hazardous waste fuels. An examination of these liabilities reveals that proper quality control of hazardous waste fuels can successfully and economically limit the liabilities associated with their use.
There are three basic risks or liabilities associated with using hazardous waste fuels: health and safety, process integrity, and regulatory compliance. The development of hazardous waste fuel specifications which address each of these risks is the first step in limiting liabilities. Subsequently, a system of thorough analytical testing to verify that specifications are always met must be implemented. The goal of such a program is to reduce to near zero the probability of an off-spec fuel entering the plant or the process. One serious mistake can negate many years worth of profitability from a hazardous waste fuel program.
Specification for Protecting Health and Safety
Specifications designed to protect the health and safety of the cement plant personnel are the most often ignored despite their potential for carrying the greatest liability and potential financial exposure. Specifications relative to acutely toxic wastes are a first step in this process. However, the need for a thorough evaluation of worker exposure coupled with a detailed model for evaluating the relative toxicity of hazardous waste fuel components is necessary. Table 1 provides a list of the type of data that might be used in evaluating an individual compound. Waste generators should verify that this type of program exists at facilities they utilize.
These needs imply the necessity of laboratory testing to provide
detailed
information on the volatile and semivolatile organic composition of the
hazardous waste fuels down to approximately 0.1 percent. This
information
can then be used to comply with basic right-to-know guidelines. Through
the use of best available analytical technology, hazardous waste fuel
burners
can place themselves, and generators utilizing their facilities in a
very
defensible position should litigation against the company or
responsible
managers ever occur. Generally, the complex organic composition of
hazardous
waste fuels requires the use of capillary column gas chromatography.
Mass
selective detectors or multiple detectors and/or multiple columns may
be
required to confirm compound identifications. There is certainly risk
in
not knowing and keeping permanent records of every hazardous or
potentially
hazardous responsibility of the generator could eventually affect
individual
generators. Relying on an off-site waste fuel blender to control this
liability
could be difficult. Fuel received from a blender could be fine one day
and the next contain high concentrations of very toxic compounds, since
a fuel blender receives from a large number of different generators.
Thorough
testing at the cement kiln location would appear to be the only
practical
way to minimize this liability without involving a significant conflict
of interest.
Table 1
Compound Health and Safety Evaluation Data
Compound Name
Specification for Process Protection
Specifications to protect the kiln, product quality, and the waste fuel handling system are necessary. This is because, unlike a boiler, in a cement kiln the from the fuel becomes part of the product. These include, but may not be limited to:
It should be noted that among the halogens, chlorine and bromine behave differently in a cement kiln than fluorine. They require different specifications based largely on the chemistry of the particular kiln. In addition, the common test routines for total halogens does not detect fluorine. The effects of adding fluorine to the hot end of a cement kiln is not fully understood, but the potential for brick and coating degradation does exist. The halogens and sulfur can readily be determined in hazardous waste fuels using ion chromatography.7
Specifications for Regulatory Compliance
Because regulatory requirements vary from state to state, specifications set for regulatory compliance will necessarily vary. There are three fairly common concerns which may be worth adding specifications whether or not regulations require them. Publicity on these issues can in some ways cause as much liability as regulatory fines. These public concerns are PCBs, radioactivity, and various volatile heavy metals. There has been a perception for some time that PCB testing was very time consuming and therefore impractical on a truck-by-truck basis. However, methods combining traditional gas chromatography with computerized data handling were published as early as 1938.8 These methods generally allow screening for PCBs at the 50 ppm level in less than 30 minutes for most hazardous waste fuel matrices. Radioactivity is another screen which, however improbable, is inexpensive and easy to perform--good insurance considering the consequences of a mishap. Heavy metals can be determined in hazardous waste fuels using atomic absorption spectroscopy.9
The Application of Statistical Quality Control to the Hazardous Fuel Quality System
It is well known that nay single analytical result has a certain probability of being wrong. Given the number of specifications and therefore, tests needed for hazardous waste fuels, it becomes clear that a single set of tests on hazardous waste fuels during the pre-shipment evaluation process is not enough. Indeed, this approach simply delays the inevitable. Table 2 provides an example of a multi-step analytical testing scheme which can significantly lower the probability of an off-spec fuel entering the plant or process.
The Generator Qualification is performed on a pre-shipment sample sent to the laboratory prior to sending a truck of waste fuel. The Truck Receipt analysis is performed on a sample pulled from the truck after is arrives at the plant, but prior to off loading the shipment. Finally, the Blended Tank analysis is performed prior to burning the fuel.
Table 3 provides a crude statistical analysis regarding the probability of a shipment getting through this system of quality control and causing a potential liability. A typical kiln fuels program utilizes between 1,000 and 4,000 truck annually, thus raising the probability of an improperly analyzed shipment to near certainty within a year unless all checks are performed.
The Role of Proper Analytical Methods, Instrumentation and Trained Personnel
Analytical methods developed by EPA for determining if a waste is hazardous are generally not suitable for screening wastes as hazardous waste fuel candidates. The high-precision, high-accuracy, and time-consuming methods EPA has developed do not fit the fuel screening needs for speed, reasonable accuracy, and lower precision. In addition, the low levels of detection required by EPA methods are generally not required for hazardous waste fuel screening. This is not to say that hazardous waste fuel testing is simple. Indeed, the complex sample matrix of solvents, oils, resins, pigments, etc. requires some of the best instrumentation, computers, and technically qualified personnel available. These complex samples can be quickly and efficiently analyzed to minimize liabilities if the right combination of skilled chemists, sophisticated instrumentation and computer technology is utilized. Waste generators disposing of hazardous waste fuel should make certain that these features are present and used at whatever facility ultimately receives their waste.
Table 2
WASTE ANALYSIS PLAN OUTLINE
Parameter |
Generator
Qualification |
Truck
Receipt |
Blended
Tank |
Burn
Tank* |
| Heat Content | X | X | X | X |
| Ash | X | X | X | X |
| Sulfur | X | X | ||
| Fluoride | X | X | X | X |
| Chloride | X | X | X | X |
| Bromide | X | X | X | X |
| Freeze Point | X | X | ||
| pH (extracted) | X | X | ||
| Viscosity | X | X | ||
| Metals: Lead | X | (Depending upon Qualifications) | X | |
| Zinc | X | X | ||
| Chromium | X | X | ||
| Iron | X | X | ||
| Titanium | X | X | ||
| (other volatile heavy metals) | X | X | ||
| PCBs | X | X | X | |
| Volatile & Semi-Volatile OrganicAnalysis | X | X | ||
| Fingerprint** |
X |
|||
| Radioactivity | X | X | X |
* Weekly, if burn tank is a large separate from blended tanks.
** Note: The fingerprint check can be a computerized overlay of the truck receipt gas chromatography with the original generator qualification gas chromatograph. Only new gas chromatographs peaks then need to be identified.
Table 3
Statistical Analysis of a waste plan for a waste fuel program
Probability of
| Step | Success | Failure |
| 1. Generator qualification | 95% | 5% |
| 2. Truck receipt | 96% | 4% |
| 3. Blended tank | 98% | 2% |
| 1 + 2 | 99.8% | .2% or 1 out of 500 |
| 1 + 3 | 99.9% | .1% or 1 out of 1,000 |
| 2 + 3 | 99.92% | .08% or 1 out of 1,250 |
| 1 + 2 +3 | 99.996% | .004% or 1 out of 25,000 |
ABC CORPORATION MATERIAL SURVEY
| Sample Submitted for:
Fuel__ Waste Recycling__ Other ______________ ABC Sample No. ______ |
ABC Use Only
ABC Control No. _____ Date Recieved _______ |
||||
| A .
Company Name: __________________________________________ Federal EPA ID No.: _______________ County: ____________ Billing Address: Manifest Address__ Facility Address: Manifest Address __ Street: ____________________________________________ Street: ____________________________________________________ City: ________________ State: _______ Zip: ____________ City: ________________________ State: _______ Zip: ____________ Nature of Business: _________________________________________________________________________ SIC No.: ___________ State ID Numbers: State: _______ ID _______________ State: ________ ID _______________ State: ________ ID _____________ |
|||||
| B. Material Description _________________________________________ | D. Material Composition (vol%) | Min | Max | Typical | |
| Process Description ___________________________________________ | |||||
| Volume (gal) ___________________/ Wk_ Mth _Qtr_ Yr_ Once_ | |||||
| Volume on Hand (gal) ________________________ | |||||
| Storage Capacity (gal) __________________ in Drums Bulk | |||||
| Shipping Frequency (gal) __________________ in Drums Bulk | |||||
| C. Physical Description Color _____________ | |||||
| Layers One_ Two _Three_ | Water - | ||||
| Physical State Liquid_ Semisolid_ Solid_ | Non-volatile Material - | ||||
| Liquid Viscosity Low_ Medium _High _ | Settled Solids - | ||||
| E. Attach material safety
data sheets
for components requiring employee communication under OSHA (ref. 29 CFR
1920.1200).
Attach any current analysis of the material. MSDS attached__ Analysis attached__ No attachments__ |
|||||
| F. Check all of the following substances which may be in the material. | Identify if present | Amount | Units | ||
| DOT Corrosives, Poisons, Forbiddens, Radioactives, Explosives, or Gases. | |||||
| TSCA regulated materials (PCBs, PBB, Chlorinated dibenzodioxins or furans). | |||||
| Materials used exclusively as pesticides, herbicides, insecticides, etc.. | |||||
| OSHA carcinogens above exclusive levels (Ref. 29 CFR 1910). | |||||
| Toxic components with OSHA PEL or ACGIH TLV less than 2 ppm or 8 mg/m3. | |||||
| Toxic metals (Antimony, Arsenic, Cadmium, Mercury, Selenium, Thallium). | |||||
| Reactive components (Sulfides, Cyanides, Shock Sensitives, Pyrophorics, etc.). | |||||
| Water reactive components (Isocyanates, Acid Chlorides, Anhydrides, etc.). | |||||
| Biological hazards (Pathogenics, Infectious agents, Etiologic agents, etc.). | |||||
| None of the above__Special Handling Required _______________________________________________________________________ | |||||
| G. DOT Hazardous Material
Description (Ref.
49 CFR 172.101)
Proper Shipping Name _______________________________________________ ___________________________________________________________________ Hazard Class _____________________________ Number _________________ Not a DOT Hazardous Material |
H. EPA Hazardous Waste
Description (Ref.
40 CFR 261)
Waste Number(s) D001_ F001_ F002_F003_F004_ F005 _ ____________ Hazardous Code(s) I T C R E H Not an EPA Hazardous Waste__ |
||||
| I. A sample and a fee is required
for the
qualification of all new material. Purchase Order No.
____________________________
Type of sample: Grab _Tank _Composite _of ______ drums Sample taken by Customer _ABC Representative _ |
|||||
| J. To the best of my knowledge,
this is
an accurate description and the sample submitted is representative of
the
material.
Name _______________________________________________ Title _____________________________________________ Signature _______________________________________________________ Date __________________ Phone (____) __________ Comments _______________________________________________________________________________________________________ |
|||||
| ABC Use Only
Broker _______________________ Salesperson ___________________Territory # _____________ Phone (____) _________________ |
|||||
The Role of Proper QA/QC
In the same way that the hazardous waste fuel must be checked for quality, so too must the product of the laboratory, analytical data, be checked for quality. This is the role of a proper QA/QC (quality assurance/quality control) program. Government agencies may stipulate minimum requirements for such a program. Generally, such a program will incorporate standards, blanks, duplicates, spikes, and round-robin testing along with standard control limits. Table 4 provides an outline of such a program for selected hazardous waste fuel quality control parameters. Again, generators should check to see if the facilities to which they send waste have an active QC/QC program.
Conclusions
Hazardous waste derived fuels present an exciting potential opportunity for cement manufacturers to benefit themselves and at the same time minimize disposal costs for hazardous waste generators. There are, however, significant risks and liabilities associated with the use of hazardous waste fuels. Analytical technology exists to allow economical and thorough quality control to minimize these liabilities and provide for the long-term viability of these projects.
References
1. Lauber, J.D., "Burning Chemical Wastes as Fuels in Cement Kilns," Control Technology News, 32, (7), 771-5 (July 1982).
2. Weitzman, L., "Cement Kilns as Hazardous Waste Incinerators," Environmental Progress, 2 (1), 10-14 (February 1983).
3. Bjorndal, H. and B. Ahling, "Combustion Test with Chlorinate Hydrocarbons in a Cement Kiln at Stora Vika Test Center," report prepared for the Swedish Water and Air Pollution Research Institute (March 16, 1978).
4. Hazelwood, D. L., F. J. Smith, and E. M. Gartner, "Assessment of Waste Fuel Use in Cement Kilns," report prepared for EPA (March 1981) (Number 68-03-2586).
5. Smith, G. E., and J. J. Rom, "Supplemental Fuels Test Burn in Marquette Cement Kiln at Olgesby, Illinois," report prepared for EPA by Systech Corporation (March 31, 1982).
6. McDonald, L. D., D. J. Skinner, F. J. Hopton, and G. H. Thomas, "Burning Waste Chlorinated Hydrocarbons in a Cement Kiln," report prepared for EPA (January, 1978) NTIS Number PB280118).
7. Gossman, D. G., C. Cape, T. Spaits, "The Analysis if Flammable Industrial Wastes Using Ion Chromatography," Pittsburgh Conference and Exposition on Analytical Chemistry and Applied Spectroscopy (1983).
8. Gossman, D. G., "Data Processing as an Alternative to Extensive Cleanup in the Gas Chromatographic Determination of PCBs," Pittsburgh Conference and Exposition on Analytical Chemistry and Applied Spectroscopy (1983).
9. Gossman, D. G., C. Cape, J. Woodford, "The Determination of Metals in Paint and Paint Wastes Using Atomic Absorption and Emission Spectroscopy," Pittsburgh Conference and Exposition on Analytical Chemistry and Applied Spectroscopy (1983).