Document ID: EPA-HQ-RCRA-2002-0002-0110
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2008-01-02T05:00Z

MEMORANDUM

To:           The Record

Subject:  Characterization of Petroleum Refining Waste and Possible
Gasification Scenarios 

In support of the final rule:  Regulation of Oil-Bearing Hazardous
Secondary Materials From the Petroleum Refining Industry Processed in a
Gasification System to Produce Synthesis Gas Fuel (Tier 3,
RIN#2050-AE78) additional analysis was conducted on a proposed condition
requiring gasification residuals to meet the Universal Treatment
Standards for six selected metals (antimony, arsenic, chromium, lead,
nickel, and vanadium).  

Background

In the proposed rule, we requested comment on a condition to the
exclusion that would establish leachate limits (i.e., Universal
Treatment Standards (UTS)) for six toxic metals in the gasification
co-products and residuals prior to any placement on the land.  We
originally considered this condition to ensure that co-products and
residues generated by the gasification process that were to be placed on
the land did not contain toxic metals with a potential for leaching
greater than allowed by the requirements of the Land Disposal
Restrictions (LDR) program.  (See 67 FR at 13691, March 25, 2002.)  In
developing this possible condition, we were influenced by the condition
established for hazardous waste derived products that are used in a
manner constituting disposal (see 40 CFR 266.20).  These materials are
required to meet the appropriate LDR treatment standards prior to use as
products applied to the land (e.g., fertilizers).  We reasoned, in the
proposal, that requiring this same condition for co-products and
residuals would ensure legitimate fuel manufacturing by applying the
same land disposal provisions to the co-products and residuals that
would have existed had the material (i.e., the listed waste) not been
excluded from the definition of solid waste.  Further, we reasoned that
this proposed condition would be needed to assure that the gasification
system is operated for the purpose claimed – conversion of organic
matter in the oil-bearing hazardous secondary material into fuels (or
intermediates), while removing metals from raw synthesis gas and
trapping those metals in an inert matrix.  It was reasoned that the
levels in the proposed condition (UTS levels) would provide a means of
quantifying this premise.  

We received comments that both supported and opposed this condition (See
the Response to Comment Document for a complete presentation and
discussion of all the comments on this condition).  Commenters opposed
to the condition stated that there was no need to impose the UTS
requirements beyond what the regulations (e.g., 40 CFR 261.4(a)(12)(i))
already required for residues generated from the petroleum refining
process (i.e., the characteristic test).  Commenters argued that EPA had
provided no rationale basis for imposing the additional UTS
requirements.

In response to these comments, the Agency set about reexamining the
merits of this condition.  This began with a more detailed analysis of
the characterization data for petroleum refining wastes collected as
part of the LDR program. 

Characterization Data for Listed Wastes Identified as Oil-Bearing
Hazardous Secondary Materials

We reviewed data presented in several Best Demonstrated Available
Technology (BDAT) Background Documents for petroleum refining wastes to
get a better understanding of the total concentration levels of these
metals in different petroleum refining wastes.   Concentration data were
analyzed for nine listed petroleum refining wastes identified as coming
under the category of “oil-bearing hazardous secondary materials”
(Tables 1 and 2).  Next, we look at whether these six metals
constituents were part of the LDR treatment standards for the listed
oil-bearing secondary materials that would be affected by the rule
(Table 3).  

Table 1 – ANALYSIS OF WASTE CHARACTERISTIC DATA

Constituents	K048	K049	K050	K051	K052	K169	K170	K171	K172	F037

K051*	F038

K048*

Water %	81	50	44	70-91.4	18	19.2	11.4	1.3	3.6	---	---

Oil and grease%	12	39	8	4.5-13	13	34.3	29.5	3.6	22	---	---

TOC %	---	---	---	---	---	23	29	4.0	7.0	---	---

Organic liquid %	---	---	---	---	---	31.8	25.7	0.5	1.0	---	---

Solids, dirt, sand %	86	10	47	16	68	54.5	69.7	98.8	97	---	---

BTU content	---	150	1500	---	---	7281	5935	1244	1684	---	---

BDAT constituent %	<1	<1	<1	<1	<1	<1	<1	<1	<1	---	---

Nickel (ppm)

Total concentration	0.025-16	9.2-86	61-170	0.25-150.4	97.2-392	15-380
62-300	66-25,000	8-14,000	12-240	<0.16-95

Nickel (TCLP)	---	---	---	---	---	---	0.2-0.52	0.91-310	0.73-67	---	---

Vanadium (ppm)

Total concentration	0.05-460	2.5-60	0.7-50	1-350	1.0-9.8	5-1,400	91-430
10-33,000	25-31,000	50-<90	50-<90

Vanadium (TCLP)	---	---	---	---	---	---	---	0.25-6.6	0.25-3.3	---	---

Table 2 – CONCENTRATION RANGES OF SELECTED METALS IN PETROLEUM
REFINERY LISTED WASTE (mg/kg) (1.)

	Antimony	Arsenic 	Chromium 	Lead 	Nickel 	Vanadium 

K048	4.4 - 7	0.05 - 10.5	0.04 - 3435	0.05 - 1250	0.025 – 16	0.05 –
460

K049	BDL – 19**	<2.2 – 30***	28.9 - 1400	21.95 - 3900	9.2 – 86	2.5
– 60

K050	---	10.2 -11	11 – 1600	0.5 – 1100	61 – 170	0.7 – 50

K051	9 - 18	0.1 – 32	0.1 - 6790	0.25 - 2480	0.25 - 150.4	1 – 350

K052	111	63 – 525	1.0 - 504	11 - 5800	97.2 – 392	1.0 - 9.8

K169	<6 - 15	5.7 – 32	9.7 - 310	44 - 870	15 – 380	5 – 1400

K170	<6 - 940	<1 - 4.7	8.4 - 34	17 - 47	62 – 300	91 – 430

F037	Not Reported	ND – 61	12 - 2020	22 - 4570	12.4 – 740	Not
Reported

F038	Not Reported	0.34 - 109.4	2.5 - 2990	<1 - 3900	<0.16 – 95	Not
Reported

Composite

Range	4.4 - 940	0.05 – 525	0.04 - 6790	0.05 - 5800	0.025 – 740	0.05
– 1400

Petroleum Coke ****	---	3.53	1.3	1.5	370	1500

1.  USEPA.  Best Demonstrated Available Technology Background Document
for K048, K049, K051, K052.  August 1988; USEPA.  Best demonstrated
Available Technology Background Document for F037 and F038. 1992. 
USEPA.  Best Demonstrated Available Technology Background Document for
K169-K171.  1998.

2.  If ND or BDL was reported, the next largest value was used in
determining the range. 

3.  If the concentration was reported as a “less than” , the
reported value was used without the “less than” designation.  

4.  Nickel and Vanadium concentration values are from: Gasification of
Petcoke Using E-Gas Technology at Wabash River, 2000.  Three
concentration values for petroleum coke were presented, the highest
value was selected for these calculations.

Table 3 – REGULATED BDAT CONSITUTENTS 

	Antimony	Arsenic	Chromium	Lead	Nickel 	Vanadium

TC Levels (mg/L TCLP)	---	5.0 	5.0 	5.0	---	(not a UHC)

UTS(mg/L TCLP)	1.15	5.0	0.60	0.75	11	1.6

K048 - Dissolved air flotation (DAF) float

	X

X

	K049 - Slop oil emulsion solids

	X

X

	K050 - Heat exchange bundle cleaning sludge 

	X

X

	K051 - API separator sludge

	X

X

	K052 - Tank bottoms (leaded)

	X

X

	K169 - Crude oil tank sediment

K170 - Clarified slurry oil sediment

K171 - Spent hydrotreating catalyst

X

	X	X

K172 - Spent hydrorefining catalyst	X	X

	X	X

F037 - Primary oil/water/solids separator sludge

	X

X

	F038 - Secondary oil/water/solids separator sludge

	X

X

	1)  Original treatment standard for Nickel (K048-K052) was calculated
at 0.048 mg/L TCLP based on one data point;

2)  Arsenic treatment standard is the same as TC level; and 

3)  Antimony, Arsenic and Vanadium are regulated in catalysts only
(catalysts may not be suitable gasification feed).

Analysis of Petroleum Coke and Other Gasification Feedstock

We also reviewed chemical characterization data on petroleum coke as
well as other petroleum refining materials that could be used as
feedstock for gasification units (Tables 4, 5, and 6).  Refinery
feedstock suitable for gasification are often off-gas streams and
residual oils such as vacuum resid, visbreaker tar, and deasphalter
pitch.  These residuals are often referred to generically as “heavy
oils”.

The ultimate analysis of petroleum coke showed: 1) Water content ranges
from 7.0% to 12.0%; 2) Carbon content ranges from 77.7% to 81.1%; 3) BTU
value ranges from 13,360 to 14,282; 4) The concentrations of Nickel and
Vanadium (BDAT constituents) in petroleum coke are often in higher
concentrations that in the hazardous waste, except for catalysts K171
and K172.

Table 4 – PETROLEUM COKE CHARACTERIZATION DATA

	1997	1999	2000

Moisture %	7.0	12.0	7.8

Ash %	0.3	0.4	0.6

Volatiles %	12.4	11.2	10.5

Fixed Carbon%	80.4	77.7	81.1

Sulfur %	5.2	5.6	5.7

	Metals in Fuel

	Nickel, ppm	210	290	370

Vanadium, ppm	430	1500	890

Heating value (BTU/lb)	14,282	13,360	14,026

Petroleum Coke Analysis:  (Gasification of Petcoke Using E-Gas
Technology at Wabash River 2000)

Table 5 – CHARACTERIZATION DATA FOR VARIOUS FEEDSTOCK INTENDED FOR
PETROLEUM REFINING GASIFICATION

	Units	Vacuum Resid	Visbreaker Tar	Asphalt	Petcoke

Ultimate Analysis

	C	wt/wt	84.9%	86.1%	85.1%	88.6%

H

10.4%	10.4%	9.1%	2.8%

N

0.5%	0.6%	0.7%	1.1%

S

4.2%	2.4%	5.1%	7.3%

O

	0.5%

0.0%

Ash

0.0%

0.1%	0.2%

Total	wt/wt	100.0%	100.0%	100.0%	100.0%

H2/C ratio	mol/mol	0.727	0.720	0.640	0.188

Density

	Specific Gravity	60/60	1.028	1.008	1.070	0.863

API Gravity	API	6.2	8.88	0.8	---

Heating Values

	HHV(dry)	M BTU/lb	17.72	18.6	17.28	14.85

LHV(dry)	M BTU/lb	16.77	17.6	16.45	14.48

Reference:  Refinery Technology Profiles:  Gasification and Supporting
Technologies, U.S. Department of Energy, National Energy Technology
Laboratory, Energy Information Administration, June 2003

Table 6 – ANALYSIS OF EL DORADO GASIFIER FEEDSTOCK

	Petroleum Coke	Recycled Filter Cake (1.)	Fluxing Additive	Acid Soluble
Oil	API Separator Bottoms	Primary Sludge	Phenolic Residue

D001,D018	K051 (2.)	F037, F038 (3.)	K022 (4.)

Moisture (as received),wt%	5-10	50	5	1.4	20-75	20	0.8

Heating Value (dry), BTU/lb	15,400	13,000	0	18,900	6,300	<1,000	15,700

Ultimate Analysis (dry) Wt%

	Carbon	89.5	88.9	---	86.4	32.8	0-5	82.7

Hydrogen	3.9	0.1	---	12.0	4.3	---	7.4

Nitrogen	1.3	0.7	---	0.02	0.5	---	0.1

Sulfur	4.7	2.4	---	0.3	2.7	---	0.01

Ash	0.4	7.9	100	0.4	57.6	95-100	0.2

1.  This is the unconverted carbon from the gasifier recovered in a
gravity settler and dewatered by rotary vacuum filtration.  It’s
non-hazardous and non-leachable through testing.  Although it has a high
BTU value no buyer has been found, it’s another low value item for the
refinery and recycled back into gasifier.

2.  The refinery’s delayed coker is also capable of processing API
separator bottoms.

3.  The gasifier was not designed to handle the entire refinery
production of primary sludge.  The design intent was to gasify all the
available API separator bottoms and then gasify as much sludge as
possible.  The refinery’s delayed coker is also capable of processing
primary sludge.

4.  Distillation bottom tars from the production of phenol/acetone from
cumene.

Experience with Low Value Feed Gasification at the El Dorado, Kansas
Refinery by Gary DelGrego, Texaco Power and Gasification.  Presented at
the 1999 Gasification Technologies Conference. 

Results of Biennial Report Analysis

Generation Rates

Potential generation rates of oil-bearing hazardous secondary materials
were derived from the 2003 Biennial Report, using the following waste
codes: K048-K052, K169-K172, F037 and F038 representing oil-bearing
hazardous secondary materials.  The BRS reported 324,371 tons of
oil-bearing hazardous secondary materials generated by 153 sites (SIC
2811).  The average generation rate was calculated at 2,314 tons/year,
with a maximum generation rate of 76,582 tons/year and a minimum of less
than 1 ton/year.  Over 82 facilities generate over 10,000 tons/year

Management  

144,012 tons of oil-bearing hazardous material was managed by material
recovery (primarily metal catalysts); 25,457 tons went to energy
recovery (cement kilns, BTU >5000); 92,658 tons to incineration; 17,495
tons to other treatment (sludge treatment, stabilization,
macro-encapsulation); 23,352 tons to disposal (land treatment, landfill,
and deepwell injection); and 21,396 tons went to other management
(unknown management, fuel blending, storage/bulking/transfer).

Possible Gasification Scenarios Utilizing Oil-bearing Hazardous
Secondary Material With Petroleum Coke

Based on all this information, the following possible refining scenarios
utilizing gasification were developed, demonstrating that oil-bearing
hazardous secondary materials (low-value fuels) could supplement the
petroleum coke feed on a very limited basis.  It should be noted
however, that to date, no information has been discovered that would
suggest that this type of activity is being pursued.

As an example, consider a 1000 TPD gasification unit being employed at a
petroleum refinery producing 1000 TPD petroleum coke.  The facility also
produces 2000 TPY of oil-bearing hazardous secondary material.  If the
gasification system is fed the oil-bearing hazardous secondary material
at 10% of the total feed (900 TPD petroleum coke, 100 TPD supplemental
feed).  The supplemental feed will be depleted in 20 days.  If you
reduce the feed to 5%, the supplemental feed is depleted in 40 days, and
1%, the supplemental feed is depleted in 200 days.

As a second example, consider a 2000 TPD gasification unit.  The
petroleum refinery produces 1800 TPD of petroleum coke, and 10,000 TPY
of oil-bearing hazardous secondary material.  If the gasification system
is fed the oil-bearing hazardous secondary material at a rate of 10% of
the total feed (1800 TPD petcoke; 200 TPD supplemental) the supplemental
feed will be depleted in 50 days.  Reduce the feed to 5%, it is depleted
in 100 days; and reduce to 1%, the feed is depleted in 500 days.

These examples suggest that oil-bearing hazardous secondary material can
be introduced, on a limited basis, into a gasification system with
petroleum coke.  

The following table is derived from the Gasification Technology
Council’s website and presents information on various gasification
units operating in the United States.   The information presented on the
future gasifier planned for the BP facility in Carson City, California
was found on the BP website.  

Table 6 – GASIFICATION SYSTEMS USING PETROLEUM COKE AND/OR REFINERY
WASTE AS FEED

Facility	Feed	Status(2004)

Frontier

El Dorado, Kansas	150.60 mt/d petcoke

13.6 mt/d refinery waste

7,000 mm BTU/d 	Operating 

ExxonMobil Chemical

Baytown, Texas	1,000 mt/d deasphalter pitch	Operating

Coffeyville Resources Refining and Marketing

Coffeyville, Kansas	1,100 mt/d petcoke	Operating

Eastman Chemical

Kingsport, Tennessee	1,225 t/d coal	Operating

Wabash

West Terre Haute, Indiana	2,000 mt/d petcoke	Operating

Premcor

Wilmington, Delaware	2,100 mt/d petcoke	Operating

Vanguard

Louisiana	2,700 mt/d petcoke	Startup 2008

BP

Carson, California	4,500 TPD petcoke	Startup 2011

Cost $1 billion

CITGO

Lake Charles, Louisiana	7,000 mt/d petcoke	Startup 2009

Great Plains

Beulah, North Dakota	14,000 t/d coal

50.00 t/d refinery waste	Operating

From:    HYPERLINK "http://www.gasification.org"  www.gasification.org 
and www.bp.com 

Future Trends in Petroleum Refining Gasification

Information from the DOE report, Refinery Technology Profiles:
Gasification and Supporting Technologies. US DOE, National Energy
Technology Laboratory.  June 2003, suggests that growth in petroleum
refinery gasification will most likely be driven by future supply and
demand of petroleum coke.  (Coking capacity has grown by 60% over last
decade, trend is expected to continue but at a slower rate.).  There are
40 refineries (out of 153) within the U.S. (located in California,
Texas, and Louisiana) that produce sufficient quantities of petroleum
coke(>1000 TPD) to be considered candidates for the addition of
petroleum coke gasification at the petroleum refinery.  These 40
facilities account for 98% of total volume of petroleum coke generated
in the U.S.  Simple economic payback estimated at 4-5 years. Market
penetration rate of possibly one plant every two years would not seem
unreasonable.  This would result in 7 to 9 plants by 2010 and as many as
17 plants by 2025.  Gasification plant capacities of 1,000 to 2,000 TPD
typical, however the two planned facilities are over 5,000 TPD
(Louisiana and Texas).  This coincides with the amount of petroleum coke
currently generated at the facilities.  

Both waste characterization data and data on waste generation rates
suggest that industry would probably not build a gasification unit
dedicated to the gasification of oil-bearing hazardous secondary
materials.  However, smaller gasification units are still being explored
for possible application at petroleum refineries, and as part of this
analysis have been evaluated.  Given, existing information and current
gasification patterns, that the most probable gasification scenario,
however, is that a petroleum refinery will build a gasification unit for
petroleum coke gasification with oil-bearing hazardous secondary
material possibly used as a supplemental feed.  As suggested in the DOE
report, gasifiers will most likely be built at petroleum refineries that
generate >1000 TPD of petroleum coke.  There are approximately 40
refineries located in California, Texas, and Louisiana that generate
that quantity of petroleum coke.  Available information on existing
gasification units suggest that if oil-bearing hazardous secondary
material is used as a supplemental feedstock, it could make-up between
0.1 to 10% of the total feed (This range is derived by using the lowest
(Dakota Gasification) input, on a percentage basis of oil-bearing
hazardous secondary material and highest (El Dorado) input of
oil-bearing hazardous secondary material in combination with petroleum
coke or coal to a gasification unit.)  Total BDAT constituents (metals
and organics) in listed refinery wastes account for less than 1% total
composition of the waste. Petroleum coke will dominate residual
composition.  

The DOE report indicates that no new gasification systems will come
on-line until 2008 and possibly only 3 by 2011, and that these
gasification systems will be designed for processing petroleum coke. 
Oil-bearing secondary materials (low value fuels) could supplement the
petroleum coke feed on a very limited basis. However, no information has
been presented to suggest this is what will occur.   (Note:  These
predictions appear to be optimistic based on current information
available to the Agency).

We developed various scenarios for feeding petroleum coke to a
gasification system to estimate TCLP concentrations of selected metals
in the gasification bottoms.  As part of this analysis we made several
assumptions:  1) The concentration of selected metals in the secondary
feed is given as a “composite range” of the listed petroleum
refining wastes K048-K052, K169-K170 and F037-F038;  2)  171 and K172
wastes are catalysts from petroleum refining operations and are not used
as part of the “composite range” because of its low carbon and high
metal content; and 3) 100% of the metals will partition to the
gasification bottoms.  With these assumptions we developed several
gasification scenarios.

  

Scenario 1:  A 2000 MTD gasification system feeding 100% petroleum coke.

Scenario 2:  A 2000 MTD gasification system feeding 90% petroleum coke
and 10% of a refining waste composite using a lower bound and upper
bound analysis for selected metal concentrations in the composite
petroleum refining waste.  This represents a gasification scenario with
a maximum input of oil-bearing hazardous secondary material in
combination with petroleum coke.

Scenario 3:  A 20 MTD gasification system feeding 100% of a refining
waste composite using a lower bound, mean of the composite range and
upper bound analysis for selected metal concentrations.

Scenarios 4 and 5:  A 20 MTD gasification system feeding 100% of a
refining waste composite using a lower bound, mean of the composite
range  and upper bound analysis for selected metal concentrations, where
50% and 80% of the feed partitions to the gasifier bottoms.

Selected Gasification Scenarios:

Scenario 1:

TCLP Concentration Estimates for Selected Metals in Gasifier Bottoms  

2000 MTD Gasifier Feeding 100% Petroleum Coke

	Antimony	Arsenic	Chromium	Lead	Nickel	Vanadium

Characteristic Level (mg/L TCLP)	 ---	5.0	5.0	5.0	---	---

UTS (mg/L TCLP)	1.15	5.0	0.60	0.75	11	1.6

Concentration in Petroleum Coke (mg/kg)	---	3.53	1.3	1.5	370	1500

Total Concentration of Metal in Bottoms (mg/kg)	---	35.3	13	15	3700
15000

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	---	1.76	0.65	0.75	185	750

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by 0.001)	---	0.0353	0.013	0.015	3.7	15

Sample Calculation – Method 1 (Arsenic):

2000 MT (3.53/10E6) = 0.00706 MT of Arsenic

0.00706 MT of Arsenic/200 MT of bottoms = 0.0000353 x 10E6 = 35.3 mg/kg
Arsenic in bottoms

(35.3)(.05) = 1.76 mg/L TCLP

(35.3)(.001) = 0.0353 mg/L TCLP

 

Sample Calculation – Method 2 (Arsenic):

(2000 MT)(1000 kg/MT) = 2,000,000 kg of petroleum coke 

(2,000,000 kg)(3.53mg Arsenic/kg) = 7,060,000 mg Arsenic

7,060,000 mg Arsenic/(200 MT)(1000kg/MT) = 35.3 mg/kg Arsenic in
gasifier bottoms 

(35.3)(.05) = 1.76 mg/L TCLP

(35.3)(.001) = 0.0353 mg/L TCLP

 

Scenario 2:

TCLP Concentration Estimates for Selected Metals in Gasifier Bottoms

2000 MTD Gasifier Feeding 90% Petroleum Coke/10% Petroleum Waste
Composite

LOWER BOUND

	Antimony	Arsenic	Chromium	Lead	Nickel	Vanadium

Characteristic Level (mg/L TCLP)	 ---	5.0	5.0	5.0	---	---

UTS (mg/L TCLP)	1.15	5.0	0.60	0.75	11	1.6

Lower Bound 

Petroleum Waste Composite (mg/kg)	4.4 	0.05  	0.04 	0.05 	0.025	0.05 

Concentration in Petroleum Coke (mg/kg)	---	3.53	1.3	1.5	370	1500

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	---	31.8	11.54
13.55	3330.025	13500

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	---	1.59	0.577	0.6775	166.50	675.0

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by 0.001)	---	0.0318	0.01154	0.01355	3.33	13.5

UPPER BOUND

Upper Bound 

Petroleum Waste Composite(mg/kg)	940	525	6790	5800	740	1400

Concentration in Petroleum Coke (mg/kg)	---	3.53	1.3	1.5	370	1500

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	---	556.77
6801.7	5813.5	4070	14900

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	---	27.84	340.1	290.7	203.5	745

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by 0.001)	---	0.557	6.8	5.81	4.1	14.9

Sample Calculation – Method 1 (Arsenic):

(1800 MT of petcoke)(3.53/10E6) + (200 MT of secondary material)
(0.05/10E6) = 0.006354 + .00000005 = .00635405/200tons x 10E6 = 31.77 =
31.8 mg/kg Arsenic in bottoms

Application of 20:1 ratio from TCLP (multiply by 0.05):  31.77 x .05 =
31.8 x 0.05 = 1.59 mg/L TCLP

Application of 1000:1 ratio from TCLP (multiply by 0.001):  31.77 x .001
= 31.8 x 0.001 = 0.0318 mg/L TCLP   

Sample Calculation – Method 2 (Arsenic)

(1800 MT of petroleum coke)(1000kg/MT) = 1.8 x 10E6 kg petroleum coke   
 (200 MT of secondary material)(1000kg/MT) = 2.0 x 10E5 kg secondary
material.

(1.8 x 10E6 kg petroleum coke)(3.53 mg Arsenic in petroleum coke/kg) =
6.3 54x 10E6 mg Arsenic  

(2.0 x 10E5 kg secondary material)(0.05 mg Arsenic/kg secondary
material) = 1 x 10E4 mg Arsenic 

6.354 x 10E6 mg Arsenic +.01 x 10 E6 mg Arsenic = 6.364 x 10E6 mg
Arsenic

200 MT of gasifier bottoms 

6.364 x 10E6/(200MT)(1000 kg/MT) = 31.8 mg/kg Arsenic in bottoms.

Application of 20:1 ratio from TCLP (multiply by 0.05):  31.8 x .05 =
1.59 mg/L TCLP

Application of 1000:1 ratio from TCLP (multiply by 0.001):  31.8 x 0.001
= 0.0318 mg/L TCLP

Scenario 3:

TCLP Concentration Estimates for Selected Metals in Gasifier Bottoms  

20 MTD Gasifier Feeding 100% Petroleum Waste With 10% of Mass to
Gasifier Bottoms

LOWER BOUND

	Antimony	Arsenic	Chromium	Lead	Nickel	Vanadium

Characteristic Level (mg/L TCLP)	---	5.0	5.0	5.0	---	---

UTS (mg/L TCLP)	1.15	5.0	0.6	0.75	11	1.6

Lower Bound

Waste Composite (mg/kg)	4.4	0.05	0.04	0.05	0.025	0.05

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	44	0.5	0.4	0.5
0.25	0.5

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	2.2	0.025	0.02	0.025	0.0125	0.025

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	0.044	0.0005	0.0004	0.0005	0.00025	0.0005

UPPER BOUND

Upper Bound

Waste Composite (mg/kg)	940	525	6790	5800	740	1400

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	9400	5250	67900
58000	7400	14000

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	470	262.5	3395	2900	370	700

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	9.4	5.25	67.9	58	7.4	14

Sample Calculation (Antimony):

(20 MT)(1000kg/MT) = 20,000 kg waste

(20,000 kg waste)(4.4 mg/kg) =88000 mg Antimony 

In 20 MTD gasifiers 90% mass goes to syngas; 10% to bottoms with 100% of
metals 

Therefore; 2 MTD of bottoms generated.

88000 mg Antimony/(2 MT)(1000kg/MT) = 44 mg/kg of Antimony

Apply 20:1 TCLP ratio (multiply by 0.05) = 2.2 mg/L TCLP

Apply 1000:1 (multiply by 0.001) = 0.044 mg/L TCLP

Scenario 4

TCLP Concentration Estimates for Selected Metals in Gasifier Bottoms  

20 MTD Gasifier Feeding 100% Petroleum Waste With 50% of Mass to
Gasifier Bottoms

LOWER BOUND

	Antimony	Arsenic	Chromium	Lead	Nickel	Vanadium

Characteristic Level (mg/L TCLP)	---	5.0	5.0	5.0	---	---

UTS (mg/L TCLP)	1.15	5.0	0.6	0.75	11	1.6

Lower Bound

Waste Composite (mg/kg)	4.4	0.05	0.04	0.05	0.025	0.05

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	8.8	0.1	0.08
0.1	0.05	0.1

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	0.44	0.005	0.004	0.005	0.0025	0.005

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	0.0088	0.0001	0.00008	0.0001	0.00005	0.0001

MEAN OF THE COMPOSITE RANGE

Mean of the Composite Range (mg/kg)	472.2	262.5	3395	290	370	700

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	944	525	6790
580	740	1400

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	47.22	26.25	339.5	29	37	70

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	0.944	0.525	6.79	0.58	0.74	1.4

UPPER BOUND

Upper Bound

Waste Composite (mg/kg)	940	525	6790	5800	740	1400

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	1880	1050	13580
11600	1480	2800

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	94	52.5	679	580	74	140

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	1.88	1.05	13.58	11.6	1.48	2.8

Sample Calculation (Antimony):

(20 MT)(1000kg/MT) = 20,000 kg waste

(20,000 kg waste)(940 mg/kg) =18,800,000 mg Antimony 

In 20 MTD gasifiers 50% mass goes to syngas; 50% to bottoms with 100% of
metals 

Therefore; 10 MTD of bottoms generated.

18,800,000 mg Antimony/(10 MT)(1000kg/MT) = 1880 mg/kg of Antimony

Apply 20:1 TCLP ratio (multiply by 0.05) = 94 mg/L TCLP;   Apply 1000:1
(multiply by 0.001) =  1.88 mg/L TCLP

Scenario 5

TCLP Concentration Estimates for Selected Metals in Gasifier Bottoms  

20 MTD Gasifier Feeding 100% Petroleum Waste With 80% of Mass to
Gasifier Bottoms

LOWER BOUND

	Antimony	Arsenic	Chromium	Lead	Nickel	Vanadium

Characteristic Level (mg/L TCLP)	---	5.0	5.0	5.0	---	---

UTS (mg/L TCLP)	1.15	5.0	0.6	0.75	11	1.6

Lower Bound

Waste Composite (mg/kg)	4.4	0.05	0.04	0.05	0.025	0.05

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	5.5	0.0625	0.05
0.0625	0.03125	0.0625

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	0.275	0.0031	0.0025	0.0031	0.0016	0.0031

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	0.0055	0.0000625	0.00005	0.0000625	0.000031	0.000625

MEAN OF THE COMPOSITE RANGE

Mean of the Composite Range (mg/kg)	472.2	262.5	3395	290	370	700

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	590.25	328.125
4243.75	362.5	462.5	875

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	29.5	16.4	212.2	18.12	23.12	43.75

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	0.59	0.328	4.24	0.3625	0.462	0.875

UPPER BOUND

Upper Bound

Waste Composite (mg/kg)	940	525	6790	5800	740	1400

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	1175	656.25
8487.5	7250	925	1750

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	58.75	32.81	424.37	362.5	46.25	87.5

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	1.175	0.656	8.48	7.25	0.925	1.750

Sample Calculation (Antimony):

(20 MT)(1000kg/MT) = 20,000 kg waste

(20,000 kg waste)(940 mg/kg) =18,800,000 mg Antimony 

In 20 MTD gasifiers 20% mass goes to syngas; 80% to bottoms with 100% of
metals 

Therefore; 16 MTD of bottoms generated.

18,800,000 mg Antimony/(16 MT)(1000kg/MT) = 1175 mg/kg of Antimony

Apply 20:1 TCLP ratio (multiply by 0.05) = 58.75 mg/L TCLP; Apply 1000:1
(multiply by 0.001) =  1.175 mg/L TCLP

Analysis of Gasification Scenarios

Nickel (370 mg/kg) and Vanadium (1500mg/kg) concentrations found in
petroleum coke will dominate TCLP results in 2000 MTD gasification
scenarios.  The upper bound scenarios for Chromium and Lead are based on
characterization data not reflective of overall reduction in the use of
these metals throughout the refinery industry.   Under LDRs, only
Chromium and Nickel would be regulated as “constituents of concern”
in these wastes.  

Two gasification scenarios were developed that represented
“extremes” for gasification activities that could be conducted at
petroleum refineries.  The first scenario was a large gasification
system ( i.e., 2000 MT/day) utilizing  a feedstock comprised of 90%
petroleum coke and 10% oil-bearing hazardous secondary material (this is
consistent with the largest feedrate for oil-bearing hazardous secondary
material gasified at a petroleum refinery) and a small gasifer dedicated
to processing 100% of oil-bearing hazardous secondary material.  As a
result of this analysis, we concluded, that gasification residuals would
achieve the UTS levels for all metals, except for vanadium in one
scenario (2000 MT/day) and chromium(20 MT/day) in the other.  With
regard to chromium the concentration level was below the characteristic
level, but above the UTS level.  As for vanadium, it was determined that
petroleum coke (a product) contributed most of the vanadium to the
gasifier, and that vanadium concentrations in the gasification residuals
would not be affected when feeding petroleum coke alone or in
combination with oil-bearing hazardous secondary materials. 

TCLP Concentration Estimates for Selected Metals in Gasifier Bottoms  

2000 MTD Gasifier Feeding 90% Petroleum Coke/10% Petroleum Waste
Composite

LOWER BOUND

	Antimony	Arsenic	Chromium	Lead	Nickel	Vanadium

Characteristic Level (mg/L TCLP)	 ---	5.0	5.0	5.0	---	---

UTS (mg/L TCLP)	1.15	5.0	0.60	0.75	11	1.6 

Lower Bound 

Petroleum Waste Composite (mg/kg)	4.4 	0.05  	0.04 	0.05 	0.025	0.05 

Concentration in Petroleum Coke (mg/kg)	---	3.53	1.3	1.5	370	1500

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	---	31.8	11.54
13.55	3330.025	13500

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	---	1.59	0.577	0.6775	166.50	675.0

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by 0.001)	---	0.0318	0.01154	0.01355	3.33	13.5

As generated, the gasifier bottoms will not be characteristic and will
meet the UTS for all metals except vanadium. 

TCLP Concentration Estimates for Selected Metals in Gasifier Bottoms  

20 MTD Gasifier Feeding 100% Petroleum Waste With 80% of Mass to
Gasifier Bottoms

MEAN OF THE COMPOSITE RANGE

	Antimony	Arsenic	Chromium	Lead	Nickel	Vanadium

Characteristic Level (mg/L TCLP)	---	5.0	5.0	5.0	---	---

UTS (mg/L TCLP)	1.15	5.0	0.6	0.75	11	1.6

Mean of the Composite Range (mg/kg)	472.2	262.5	3395	290	370	700

Total Concentration of Metal in Gasifier Bottoms (mg/kg)	590.25	328.125
4243.75	362.5	462.5	875

TCLP Concentration in Gasifier Bottoms Using 20:1 Ratio (mg/L) (multiply
by 0.05)	29.5	16.4	212.2	18.12	23.12	43.75

TCLP Concentration in Gasifier Bottoms Using 1000:1 Ratio (mg/L)
(multiply by .001)	0.59	0.328	4.24	0.3625	0.462	0.875

As generated, the gasifier bottoms will not be characteristic and will
meet the UTS for all metals except chromium. 

Although this analysis showed chromium levels above the UTS in one
scenario, the Agency is convinced that chromium concentrations in
oil-bearing hazardous secondary materials have decreased from the levels
found in our characterization studies, which were written in 1988, 1992,
and 1998, and therefore will be lower than what we used in our analysis
(i. e., the gasification residuals will have concentration levels below
the UTS.)  This is based on information in the preamble for the August
1998 listing rule promulgating the exclusion at 40 CFR 261.4(a)(12)(i)
that indicates that chromium levels in these hazardous secondary
materials will decrease due to a prohibition on chromium-based water
treatment chemicals in industrial cooling towers as a result of Clean
Air Act requirements, see 450 CFR Part Subpart Q (On September 8, 1994
(59 FR 46339), EPA issued a final MACT rule that eliminated the use of
chromium-based treatment chemicals and subsequently chromium compound
emissions from industrial cooling towers.)

   USEPA.  Best Demonstrated Available Technology Background Document
for K048, K049, K051, K052.  August 1988; USEPA.  Best demonstrated
Available Technology Background Document for F037 and F038. 1992. 
USEPA.  Best Demonstrated Available Technology Background Document for
K169-K171.  1998.

 Petroleum Listing (1998):  “EPA also believes that the lead and
chromium in the secondary materials should decline with time.  This is
due to overall reduction in the use of these metals throughout the
refinery (e.g., leaded gasoline is no longer produced on a wide-scale
and chromium-based water treatment chemicals are no longer used in
industrial cooling towers, as a result of Clean Air Act requirements,
see 40 CFR Part 63, Subpart Q).” 

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