Investigations leading to a specification for aviation turbine fuel produced from whole crude shale oil are described. Refining methods involving hydrocracking, hydrotreating, and extraction processes are briefly examined and their production capabilities are assessed

Coppola, E. N.

English

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MILITARY JET FUEL FROM SHALE O I L  
Edward N. Coppola 
Aero Propulsion Laboratory 
Wright-Patterson Air Force B a s e  
M i l i t a r y  j e t  f u e l  accounts for 60% of the to ta l  f u e l  requirement of the 
Department of Defense (DOD) as shown i n  Table 1. Because of the  need t o  
obtain a secure domestic source f o r  mi l i ta ry  f u e l  and because it is evident 
t h a t  the  DOD must be i n  the posi t ion t o  u t i l i z e  f u e l  produced from domestic 
non-petroleum sources, the  Air Force has embarked on an Aviation Turbine Fuel 
Technology Program. As p a r t  of t h i s  Air Force Program "A Program Leading t o  
Specification f o r  Aviation Turbine Fuel Produced from Whole Crude Shale O i l "  
w a s  i n i t i a t e d .  Past s tud ies  have shown t h a t  o i l  from shale i s  the most prom- 
i s ing  a l t e rna te  source of je t  fuel .  
commercialization than coal l iquefact ion and shale  o i l  i s  m o r e  amenable t o  con- 
version i n t o  j e t  f u e l  than are coal  l iqu ids  (Ref. 1, 2 ,  3 ) .  The shale  o i l  pro- 
gram i s  invest igat ing j e t  f u e l  qua l i t i e s ,  y ie lds  and economics f o r  novel pro- 
cesses capable of producing high yields  of j e t  fue l .  Shale derived f u e l  pro- 
pe r t i e s  of spec ia l  i n t e r e s t  include boiling range, freeze point ,  combustion 
charac te r i s t ics ,  and thermal and storage s t a b i l i t y  as affected by hydrocarbon 
type, and nitrogen and trace m e t a l  content. Contracts w e r e  awarded by the  
A i r  Force t o  three companies i n  January 1979 to  carry out  t h i s  28 month, four 
phase program. Ashland Research and Development - Ashland Petroleum Co., 
Suntech Inc. - Sun Company, and UOP Process Division - UOP, Inc. have completed 
the preliminary process designs and economic evaluations const i tut ing Phase I 
of t h i s  program. 
preliminary r e s u l t s  from Phase I follow. 
The o i l  shale industry is closer to  
A br ief  descr ipt ion of the  processes investigated and the  
The Ashland program is  based upon a ref ining method cal led the "Fxtracta- 
cracking" process. This process is  spec i f ica l ly  designed €or the conversion of 
nonconventional feedstocks i n t o  f inished conventional products. A simple block 
diagram of t h i s  process i s  shown i n  Figure 1. Whole crude shale  o i l  is con- 
verted by a combination of hydrotreating, extract ion,  and f l u i d  cracking s teps  
i n t o  a material su i t ab le  f o r  f inished fue l  production. F ina l  product t r ea t ing  
s teps  are provided as necessary f o r  the  production of specif icat ion qua l i ty  
fue ls .  In general t h i s  process uses low pressure processing equipment and has 
r e l a t ive ly  low hydrogen consumption f o r  a process optimizing je t  fue l .  
The Suntech program is  studying the technical f e a s i b i l i t y  of three d i f f e r -  
e n t  processing schemes. 
crude shale  o i l  would be hydrotreated, washed with 80% su l fu r i c  acid,  and 
fract ionated t o  y ie ld  s t r a i g h t  run products. A second scheme, shown i n  Figure 
2 ,  involves t r ea t ing  with anhydrous hydrogen chloride i n  conjunction with hydro- 
t r ea t ing  and hydrocracking. A t h i r d  scheme i s  similar t o  the  HC1 scheme, how- 
ever, it u t i l i z e s  a l i qu id  extract ion solvent. The solvent,  N,N-dimethylforma- 
mide (DMF),  w a s  screened from several other candidates based on the  se lec t ive  
removal of polyaromatics and nitrogen compounds. In  general, the  Suntech 
extract ion processes o f f e r  f l e x i b i l i t y  i n  product slate with the capabi l i ty  to  
produce high y ie lds  of j e t  f u e l  and essent ia l ly  eliminate res idual  fue l  pro- 
duction. 
A base case w a s  defined as a process i n  which the  
49 
https://ntrs.nasa.gov/search.jsp?R=19800020807 2020-03-21T03:23:34+00:00Z
The UOP program is  studying var ia t ions of two basic flow schemes, one f o r  
JP-4 and one f o r  JP-8. 
cracking, u t i l i z i n g  a proprietary modified flow hydrocracking scheme. The UOP 
process f o r  the production of JP-8 is  shown i n  Figure 3.  The only m a j o r  d i f -  
ference between t h i s  scheme and t h e  one t o  produce JP-4 i s  the  addition of 
naphtha hydrotreating and platforming un i t s  f o r  processing and gasoline fract ion.  
Each of these two schemes w a s  evaluated with three d i f f e ren t  product slates, 
one slate with the maximum j e t  f u e l  y ie ld  a t ta inable  and two slates with reduced 
j e t  f u e l  y ie lds .  The UOP scheme o f fe r s  e s sen t i a l ly  proven operational tech- 
nology t o  produce high y ie lds  of aviat ion turbine fue l  from shale o i l .  
The UOP process i s  composed of hydrotreating and hydro- 
The shale  o i l  crudes being studied i n  the  Air Force program are Occidental 
modified in-s i tu  re tor ted  material and Paraho surface re tor ted  material. These 
w e r e  se lected primarily because of ava i l ab i l i t y  and because they are repre- 
sen ta t ive  of a range of propert ies  t h a t  could be expected i n  o i l  produced from 
western o i l  shale  by various r e to r t ing  methods. 
The r e s u l t s  t h a t  follow are f rom scliemes maximizing JP-4 and JP-8 pro- 
duction. 
derived from r e s u l t s  presented by Ashland, Suntech, and UOP i n  Phase Z reports 
submitted t o  the  Air Force. 
A l l  information presented here w a s  e i t h e r  d i r ec t ly  extracted or 
Yield and product information is  presented i n  Tables 2 and 3 .  The product 
yield i s  based on the  volume of a l l  l i qu id  feed material, including shale o i l  
crude and f u e l  used f o r  process heat  and hydrogen production, divided i n t o  the 
volume of a l l  l i qu id  products. 
It is  ant ic ipated t h a t  a l l  product q u a l i t i e s  w i l l  m e e t  or exceed the  cur- 
r e n t  mi l i ta ry  specif icat ions.  However, the  projected j e t  f u e l  q u a l i t i e s  shown 
i n  Table 4 do show variance depending upon the processing method. 
rea l ized  t h a t  f o r  processes maximizing j e t  f u e l  some fue l  propert ies  w i l l  have 
t o  be pushed t o  the spec i f ica t ion  l i m i t  by def ini t ion.  
turbine f u e l  propert ies  and on quality/yield/economic trade-offs w i l l  be gen- 
erated later i n  these programs. 
It should be 
Experimental da ta  on 
The overa l l  economics are based on a nominal 100,000 bar re l  per day grass  
The economic r e su l t s  i n  
roots  re f inery  located i n  the  midwest adjacent t o  an ex is t ing  refinery; some of 
the major economic bases are shown i n  Tables 5 and 6. 
September 1978 do l l a r s  are shown i n  Tables 7 and 8 f o r  JP-4 and SP-8 respective- 
l y .  The bottom l i n e  product pr ices  are a l l  between 80 and 84$/gallon a t  the  
re f inery  . 
The economic r e su l t s  generated i n  Phase I are based on preliminary process 
These process designs w e r e  developed without the  da ta  t o  be generated designs. 
i n  bench and p i l o t  p l an t  scale tests which are scheduled t o  be accomplished i n  
Phase I1 and I11 of the Ashlnad, Suntech and UOP programs. D a t a  generated i n  
Phases I1 and 111 w i l l  r e s u l t  i n  a be t t e r  understanding of t he  yields ,  the pro- 
p e r t i e s ,  and the cos t s  of j e t  f u e l  produced from whole crude shale o i l .  From 
t h i s  data,  an updated overa l l  economic evaluation w i l l  be accomplished i n  
Phase I V  of the  programs. 
50 
Up t o  1000 gallons of var iable  qua l i ty  f u e l  samples w i l l  r e s u l t  from the  
Ashland and Suntech programs with less being generated i n  the UOP e f f o r t .  
l a rger  quantity of specif icat ion ded f o r  a Fuel Mainburner/ 
Turbine Effects program being ca Electric and P r a t t  & 
Whitney as part of the Air Force Aviation Turbine Fuel Technology program. 
This test fue l  w a s  procured through the Suntech program with Hydrocarbon 
Research Inc. ( H R I )  par t ic ipa t ing  as a subcontractor. A total  of 11,300 
gallons of spec i f ica t ion  qua l i ty  JP-4 w a s  produced by HRI from Geokinetics 
crude shale  o i l  i n  a s ingle  s tage severe hydrogenation process. The JP-4 
y ie ld  f r o m  t h i s  process w a s  33%. The properties of the JP-4 and residual  
material produced are shown i n  Table 9. A l s o  shown i n  Table 9 are the  average 
propert ies  of the JP-4 procured by the Air Force i n  1978. 
A 
REFERENCES 
1. Angello, L.C.,  Churchill,  A.V., Delaney, C.L., Lander, H.R., "Shale O i l  - 
The Answer t o  the  Jet  Fuel Avai labi l i ty  Question," Paper 781027 presented a t  
SAE Aerospace Meeting i n  San Diego, CA, November 1978. 
2 .  Shaw, H . ,  Kalfadelis, E .D . ,  "Evaluation of Methods t o  Produce Aviation 
Turbine Fuels from Synthetic Crude O i l s  - Phases I - 11," Air Force Aero 
Propulsion Laboratory, AFAPL-TR-75-10, Volumes I - If;, 1975, 1976, 1977. 
3. Sullivan, R.F.,  Strangeland, B.F., Rudy, C.E., Green, D.C., Frumkin, H.A., 
"Refining and Upgrading of Synfuels from Coal and O i l  Shale by Advanced 
Catalyt ic  Processes, F i r s t  Interim Report, Processing of Paraho Shale O i l , "  
United States Department of Energy, HCP/T2315-25, 1978. 
51 
TABLE 1 
DOD FUEL PROCUREME~TS FY78 
220 MILLION BARRELS 
yo OF TOTAL 
41% 
12% 
FUEL 
IP-4 
IP-5 
OTHER JET FUELS 
DIESEL FUEL MARINE (OFM) 
RESIDUAL, DIESEL AND OTHER FUEL OILS 
GASOLINE 
- 
TOTAL 
1% 
14% 
21 % 
5% - 
100% 
TABLE 2 
YIELD DATA FOR PROCESSES MAXIMIZING JP-4 
ASHLAND SUNTECH UOP 
HCI EXTRACTION MAX 1P-4 IP-4'OFM 
PRODUCT YIELD 
(VOL Yo OF FEED) 86.8 94.1 95.5 95.3 
PRODUCT SLATE 
(VOL % OF PRODUCTS) 
1P-4 54.3 100.0 100.0 70 4 
__ 29 6 OFM/(OF-2) (22.9) -___ 
BURNER FUEL 5.8 -- 
GASOLINE 17.0 __ -- _- 
52 
TABLE 3 
YIELD DATA FOR PROCESSES MAXIMIZING JP-8 
ASHLANO SUNTECH ll0P 
HCI EXTRACTION MAX IP-8 IP-I/DFM 
PROOLCT YIELD 
(VOL Yo OF FEED) 87.4 93.1 93.3 93.8 
PRODUCT SLATE 
(VOL % OF PRODUCTS) 
IP-8 62.3 63.1 86.9 14.2 
-- 15.1 OFM - - 
BURNER FUEL 5.7 
GASOLINE 32.0 36.9 13.1 10.7 
__ - -_ 
TABLE 4 
PROJECTED QUALITIES OF SHALE OIL DERIVED JP-4 
MIL SPEC ASHLAND SUNTECH UOP 
GRAVITY (OAPI) 
AROMATICS (VOL Yo) 
FREEZING POINT (OF) 
SMOKE POINT (MM) 
SULFUR (PPM) 
NITROGEN (PPM) 
HYDROGEN (Wr %) 
RVP (PSI) 
45-57 
25 MAX 
-12 MAX 
20 MIN 
(4000) 
NO SPEC 
13.6 MIN 
2-3 
45 50.5 
25 11 
- 72 - 75 
20 > 20 
< 1  < 5  
1 10 
13.6 14.0 
3 2.5 
52.6 
6 
- 72 
35 
< 1  
< 5  
14.5 
1.9 
53 
TABLE 5 
ECONOMIC BASIS 
CAPITAL RECOVERY 
COST BASE: SEPTEMBER 78 
EfiUITY FINANCING: 100% 
RETURN ON INVESTMENT: 15% DISCOUNTED CASH FLOW AFFER TAXES 
WORKING CAPITAL: 30 DAYS CRUDE INVENTORY AT $16.00/BARREL 
30 DAYS PRODUCT INVENTORY AT $21 .OWBARREL 
DEBT FINANCED AT 10% ANNUAL INTEREST RATE 
TABLE 6 
ECONOMIC BASIS 
OPERATING COST 
CRUDE SHALE OIL: $25.00 PER BARREL AT PLANT 
FUEL: EOUAL TO SHALE OIL CRUDE COST 
PROOUCT VALUES: FUELS EQUAL ($21.00 FOR WORKING CAPITAL) 
BY-PRODLICTS - AMONIA - $120/SHORT TON 
SULFUR - '53/LONG TON 
54 
TABLE 7 
ECONOMIC RESULTS FOR PROCESSES MAXIMIZING IP-4 
ASHLAND SUNTECH UOP 
HCI EXTRACTION MAX JP-4 JP4/DFM 
MANUFACTURING COSTS 
$/BEL PRODUCT 5.33 8.55 8.69 7.84 
ADJUSTED CRUDE COST 
$/BEL PRODUCT 28.80 26.57 26.21 26.23 
TOTAL COST 
$/BEL PRODLCT 34.13 35.12 34.90 34.07 
C/GAL PRODUCT 81 84 . 83 81 
TABLE 8 
ECONOMIC RESULTS FOR PROCESSES MAXIMIZING JP-8 
ASHLAND SUNTECH UOP 
HCI EXTRACTION MAX IP-8 JP-E/OFM 
MANUFACTURING COSTS 
S/BBl PROOUCT) 
ADJUSTED CRUDE COST 
S/BBL PRODUCT) 
TOTAL COST 
WBBL PRODUCT 
C/GAL PRODUCT 
5.20 8.55 8.39 7.56 
28.60 26.85 26.80 26.65 
33.80 35.40 35.19 34.21 
80 84 84 a i  
55 
TABLE 9 
PROPERTIES OF SUNTECH/HRI PRODUCTS 
1978 HRI HRI 
lP-4 JP4 RESIDUAL 
GRAVITY (OAPI) 53.9 50.2 37.4 
AROMATJCS MIL%) 11.4 8.9 
FREEZING POINT (OF) -76 
SULFUR (W%) 0.04 < 0.01 < 0.01 
NITROGEN (PPM) < 1  4 
HYDROGEN (W%) 14.36 14.39 
RVP (PSI) 2.6 I 2.5 
F E E D  
NAPHTHA 1-1
SHALE 011 
I 
GUARDCASE 
HYOROTREATER 
1 
1 
GASOLINE 
REFORMER * 
I 
Figure 1. - Ashland Petroleum Co. - extractacracking process. 
56 
f- 
T 
I 
0 
N 
- 
450 - 1000°F 
- JET FUEL 
OIESEL 
1 1  - 
-.. 
F 
R 
A 
C 
T 
I 
0 
N 
A 
T 
0 
R 
T I RECYCLE 1 
TO EXTINCTION 
TPO TEXACO PARTIAL 
EXTRACT RE C 0 V E R OXIDATION PROCESS 
Figure 2. - Sun Technology - HCI extractionlmax JP-4. 
s H ~ ~ ~ o o l ~  HYOROTREATER FEED 
TO I 
HYDROTREATING 
HY OROCRACKING 
4 
I 
IOGEN 
RECYCLE 
BUTANES 
.t 
R 
A LIGHT NAPTHA PRODUCTION 
C I  I J  c 
PRODUCTION 
Figure 3. - UOP Process Division - modified flow hydrocracking JP-8. 
57 


Military jet fuel from shale oil

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