Fuel Processing Technology, 37 (1994) 29~305 Elsevier Science B.V.

, Amsterdam

295

Processing of shale oil for potential lubricating oil base stocks

J . F . S t u b i n g t o n * , G.D. S e r g e a n t , D. B a r r e t t , P . T . D . H . D o a n d K . A . R a v a l

Department of Fuel Technology, School of Chemical Engineering and Industrial Chemistry, University of New South Wales, P.O. Box 1, Kensington, N.S.W., 2033 (Australia)
(Received March 12, 1993; accepted in revised form September 20, 1993)

Abstract

Much of the emphasis on shale oil processing research has been towards the production of the transport fuels, diesel oil and gasoline, as an alternative to petroleum crude oil products. This research project was aimed at a broader product range and specifically directed to evaluate the potential for the production of lubricating oil base stocks from the high boiling distillate fraction and residual maltenes of shale oil. The processing steps included vacuum distillation, solvent extraction, alkylation, de-waxing, and hydrogenation of the shale oil from Rundle and Stuart oil shale deposits in Queensland, Australia. Yields of the products were measured at each stage of the process and the elemental compositions determined. The analyses were compared with those of the petroleum-derived lubricating oil base stocks. Significant yields were obtained in the lubricating oil boiling range, but the elemental analysis showed that the products were still lower in hydrogen, compared to the petroleum products. Further investigation of the Rundle distillate is warranted, using more rigorous extraction and hydrogenation conditions.

1. INTRODUCTION O i l s h a l e is p r o c e s s e d b y p y r o l y s i s (i.e. h e a t i n g i n t h e a b s e n c e o f a i r ) i n v a r i o u s d e s i g n s o f r e t o r t t o p r o d u c e s h a l e oil. T h e p r i m a r y o b j e c t i v e o f e a r l i e r research has been towards the production of transport fuels, gasoline and diesel, from oil shale as an alternative source to conventional petroleum crude oil products. Hence, this previous research has concentrated on the determinat i o n o f t h e y i e l d s [1], k i n e t i c s [2] a n d c h e m i c a l c h a r a c t e r i z a t i o n [1, 3, 4] o f t h e shale oils produced by pyrolysis processes. Process development has aimed at t h e d e v e l o p m e n t o f a d v a n c e d r e t o r t i n g t e c h n o l o g y [5, 6], i n c l u d i n g m a t h e m a t i c a l m o d e l l i n g [7], t o m a x i m i s e l i q u i d f u e l y i e l d s . An important factor in helping to establish a shale oil industry in Australia may be the development of a broader product slate that includes bitumen and l u b r i c a t i n g oils. I t w a s s h o w n i n a p r i o r p r o j e c t [8, 9] t h a t b i t u m e n p r o d u c e d from the vacuum residue of Rundle and Stuart shale oils met road grade s p e c i f i c a t i o n s , b a s e d o n s t a n d a r d l a b o r a t o r y t e s t s . T h i s w o r k is n o w b e i n g

* Corresponding author. 0378-3820/94/$07.00 1994 Elsevier Science B.V. SSDI 0378-3820(93) E0100-S

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extended to i n v e s t i g a t e the p o t e n t i a l for l u b r i c a t i n g oil p r o d u c t i o n from the same shale oils.

2. PROCESSING OF SHALE OIL Two different s t a r t i n g m a t e r i a l s from oil shale deposits in Q u e e n s l a n d were available: (a) shale oil from the Rundle deposit, which had been topped at 200C at a t m o s p h e r i c pressure to r e m o v e the gasoline fraction; (b) residue from the h i g h - t e m p e r a t u r e a t m o s p h e r i c distillation of shale oil from the S t u a r t deposit. The Rundle sample was first distilled u n d e r v a c u u m to r e m o v e the r e m a i n i n g gasoline, k e r o s e n e and light/medium diesel fractions to obtain (a) a h e a v y diesel v a c u u m distillate, boiling between 260C and 300C at 13 kPa, for p o t e n t i a l l u b r i c a t i n g oil m a n u f a c t u r e ; this would r e p r e s e n t a low-viscosity l u b r i c a t i n g oil; (b) a v a c u u m residue, to be processed in a m a n n e r similar to the one used for S t u a r t residue. The processing steps adopted in this i n v e s t i g a t i o n are ones which would seem a p p r o p r i a t e for processing in a refinery. The first step was the preparation of a v a c u u m distillate f r a c t i o n and a v a c u u m residual f r a c t i o n from the Rundle shale oil. This Rundle residue and the S t u a r t residue were both solvente x t r a c t e d using n o r m a l pentane, to provide a pentane-soluble e x t r a c t described as a m a l t e n e f r a c t i o n and an asphaltic residue. P e n t a n e e x t r a c t i o n is not n o r m a l l y carried out in refineries; p r o p a n e or b u t a n e are usually the preferred de-asphalting solvents. L a b o r a t o r y limitations were the r e a s o n p e n t a n e was chosen, with the r e a l i s a t i o n t h a t a h i g h e r p r o p o r t i o n of resinous m a t e r i a l would be e x t r a c t e d in the maltSne fraction. Since shale oil is o b t a i n e d by pyrolysis, some t h e r m a l c r a c k i n g of the k e r o g e n occurs, so t h a t some olefinic m a t e r i a l is p r e s e n t [1, 3]. These olefins, being u n s a t u r a t e d , are quite r e a c t i v e and must be removed from any lubricating oil f r a c t i o n to e n s u r e its stability. An a l k y l a t i o n step was t h e r e f o r e introduced to investigate w h e t h e r a l k y l a t i o n could r e d u c e the a m o u n t of olefins present. A n y a l k y l a t i o n o c c u r r i n g should increase the m o l e c u l a r weight, satur a t e aromatics, i n t r o d u c e f u r t h e r side chains to the cyclic s t r u c t u r e s and r e d u c e the a m o u n t of h y d r o g e n r e q u i r e d in the s u b s e q u e n t h y d r o g e n a t i o n step. F o r c o m p a r i s o n purposes, each sample was divided into two; one sample being a l k y l a t e d and one not, as shown in Figs. 1 and 2. F r o m the earlier work on b i t u m e n p r o d u c t i o n [8, 9], it was a p p a r e n t t h a t both shale oil samples c o n t a i n e d a s u b s t a n t i a l a m o u n t of w a x y material. Wax would h a v e to be removed from any l u b r i c a t i n g oil fraction, since wax increases the p o u r point of the product. Such w a x y m a t e r i a l m a y itself be a suitable feedstock for a c r a c k i n g operation. Finally, h y d r o g e n a t i o n was n e c e s s a r y to stabilise any r e m a i n i n g olefins and f u r t h e r r e d u c e the a r o m a t i c content. S c h e m a t i c diagrams of the processing

J.F. Stubington et al./Fuel Processing Technol. 37 (1994) 295 305

297

Distillate (260 - 300 C @ 13 kPa) $ Alkylation

I

BD WBD"-- [ De-waxing DBD

De-waxing I DAD Hydrogenation Lube fraction HDAD

I --"WAD

H~,drogenation Lube fraction HDBD

Fig. 1. Processing steps used to obtain the fractions with possible potential for lubricating oil production from the distillate from Rundle shale oil. Residue ] ] Alkylation AM ] De-waxing DAM [ Hydrogenation Lube fraction HDAM [
I

Maltene extraction

] BM ] ----WAM WBM-,-De-waxing DBM [ Hydrogenation Lube fraction HDBM

Fig. 2. Processing steps used to obtain the fractions with possible potential for lubricating oil production from the distillation residues of Stuart and Rundle shale oils.

used are s h o w n in Figs. 1 and 2, w h e r e the n o m e n c l a t u r e for i d e n t i f i c a t i o n of the s a m p l e s is given.

2.1. M a l t e n e e x t r a c t i o n

A 100 g residue p o r t i o n ( r e m a i n i n g after distillation at 300 C and 13 kPa, for Rundle) was refluxed with 2.41 of n-pentane at 40 C for 12 h and t h e n soaked overnight. This r e p r e s e n t s a higher r a t i o of solvent to residue t h a n used commercially, to m a x i m i s e the e x t r a c t i o n yield of the p o t e n t i a l l u b r i c a t i n g oil m a t e r i a l for this l a b o r a t o r y investigation. P e n t a n e was chosen as the solvent to allow e x t r a c t i o n at a t m o s p h e r i c pressure in the a v a i l a b l e l a b o r a t o r y a p p a r a t u s . The r e a c t i o n m i x t u r e was filtered t h r o u g h a funnel, w a s h e d with n - p e n t a n e and c o n c e n t r a t e d in a r o t a r y v a c u u m e v a p o r a t o r to collect the maltenes. T h e maltene f r a c t i o n was dried in a v a c u u m oven, u n d e r n i t r o g e n a t m o s p h e r e at low v a c u u m and 120 C for 4 5 h. Several b a t c h e s were e x t r a c t e d and t h e n h e a t e d and combined to give a t o t a l weight of a p p r o x i m a t e l y 1000 g of maltenes.

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2.2. A l k y l a t i o n

J.F. Stubington et al./Fuel Processing Technol. 37 (1994) 295 305

A 240g s a m p l e of m a l t e n e was dissolved in 240ml of n - h e p t a n e in a t h r e e - n e c k e d r o u n d - b o t t o m flask u n d e r a n i t r o g e n a t m o s p h e r e . We added 5.4 g of a n h y d r o u s a l u m i n i u m chloride and 1.8 g of m e t a l l i c a l u m i n i u m p o w d e r ( e q u i v a l e n t to 3% of m a l t e n e at a 3:1 r a t i o of a l u m i n i u m chloride to m e t a l l i c a l u m i n i u m ) as a n a l k y l a t i o n c a t a l y s t to the r e a c t i o n mixture, m a i n t a i n e d at 0C by i m m e r s i o n of the flask in a n ice and w a t e r bath. The r e a c t i o n m i x t u r e w a s stirred in a n i t r o g e n a t m o s p h e r e at 0 C for 2 h and at r o o m t e m p e r a t u r e for a f u r t h e r 6 - 8 h before b e i n g allowed to s t a n d for a f u r t h e r 18 h in an i n e r t a t m o s p h e r e . T h e r e a c t i o n m i x t u r e w a s filtered and t h e n distilled in a r o t a r y v a c u u m e v a p o r a t o r to collect a l k y l a t e d p r o d u c t a n d r e c o v e r the n-heptane. The last t r a c e s of s o l v e n t w e r e e v a p o r a t e d in a v a c u u m o v e n u n d e r n i t r o g e n a t m o s p h e r e a n d p a r t i a l v a c u u m at 120 C for 19 h. U n d e r t h e s e conditions, the p r o d u c t h a d a t t a i n e d c o n s t a n t weight, so no re-distillation was n e c e s s a r y .

2.3. De-waxing

B a t c h e s of 30 g of m a l t e n e s w e r e mixed w i t h 450 ml of M I B K a n d the r e a c t i o n m i x t u r e was w a r m e d to a t e m p e r a t u r e of 65 C for 30 min to e n s u r e c o m p l e t e dissolution. T h e r e a c t i o n m i x t u r e was t h e n allowed to cool to r o o m tempera t u r e a n d t h e n to - 17 C in a cold b a t h of m e t h a n o l for 2 h before b e i n g filtered, u s i n g a B u c h n e r funnel t a k e n f r o m the freezer, to s e p a r a t e the w a x w h i c h was t h e n w a s h e d w i t h cold ( - 1 7 C) M I B K to r e m o v e all de-waxed m a t e r i a l . Filt r a t e a n d w a s h i n g s w e r e mixed and c o n c e n t r a t e d in a r o t a r y v a c u u m evapor a t o r to collect the de-waxed fraction. The w a x was dissolved in w a r m M I B K for c o m p l e t e r e c o v e r y , collected in a n o t h e r flask a n d c o n c e n t r a t e d in a r o t a r y v a c u u m e v a p o r a t o r . T h e last t r a c e s of s o l v e n t w e r e r e m o v e d f r o m the de-waxed m a t e r i a l u n d e r a low p a r t i a l p r e s s u r e n i t r o g e n a t m o s p h e r e at 108 C for 19 h, to c o n s t a n t weight.

2.4. Hydrogenation

The h y d r o g e n a t i o n of e a c h of the v a r i o u s f r a c t i o n s of Rundle and S t u a r t shale oil was c a r r i e d o u t in a P a r r - H y d r o g e n a t o r - 4 5 2 2 , at a h y d r o g e n gas p r e s s u r e of 1100-1200 psi and a t e m p e r a t u r e of 300 C, u s i n g a N i / M o c a t a l y s t (5 g N i / M o in 3 ml CS2 per 100 g of sample) for 6 h. The h y d r o g e n a t i n g conditions w e r e v e r y mild to a v o i d c r a c k i n g of the s a m p l e s a n d to s a f e g u a r d the h y d r o g e n a t i o n equipment. A b o u t 30 g of a s a m p l e was t a k e n for e a c h hydrogen a t i o n and dissolved in the m i n i m u m q u a n t i t y of n - h e p t a n e for c o m p l e t e d i s s o l u t i o n ( ~ 50 ml). A f t e r h y d r o g e n a t i o n , the r e a c t i o n m i x t u r e was cooled to r o o m t e m p e r a t u r e and the h y d r o g e n gas p r e s s u r e was released. The a u t o c l a v e was o p e n e d a n d w a s h e d w i t h n-heptane. T h e r e a c t i o n m i x t u r e was filtered to r e m o v e c a t a l y s t a n d t h e n c o n c e n t r a t e d in a r o t a r y v a c u u m e v a p o r a t o r to collect the h y d r o g e n a t e d product. T h e last t r a c e s of s o l v e n t w e r e r e m o v e d by d r y i n g in an o v e n at 110-120 C o v e r n i g h t .

J.F. Stubington et al./Fuel Processing Technol. 37 (1994) 295-305

299

~o~ ~.~ ~.~

~ .~

~~
~"s

..~
0

rl?

300

J.F. Stubington et al./ Fuel Processing Technol. 37 (1994) 295-305

One of the samples (Rundle HDBD) was submitted to a subsequent, longer hydrogenation under the same conditions for a further 12 h, in an effort to obtain significant changes in the product.

3. ANALYSIS For comparison purposes, three lubricating oil base stocks derived from petroleum crude were obtained and analysed in parallel with the proda ~:(s from shale oil processing. The products were analysed for C, H and N on a PerkinElmer-240B elemental analyser. The elemental analysis data for the shale oil samples are shown in Tables 1 and 2 and for the lubricating oil samples in Table 3. The nitrogen analyses were all less than 1.8%, but the nitrogen balances were inconsistent, so these data are not presented. The viscosity of the samples was determined by the method outlined in IP 71/87, in most cases at 60 C and 100 C, since the samples were too viscous at 40C. Only for Rundle de-waxed alkylated distillate could the viscosity be measured at 40 C. For all other samples, the viscosity at 40 C was obtained by extrapolation from determinations made at 60C and 100C, according to ASTM D341-87 using the chart provided, so that the viscosity index could be calculated by the method described in ASTM D2270-86 [10]. Insufficient material was produced to measure the pour points of the samples.

4. DISCUSSION
4.1. Yields

The first yield column in Tables 1 and 2 gives the product recovery data for each of the individual processing steps; whereas the second yield column gives the cumulative yield of the particular product from the starting material, which was topped shale oil in the case of the Rundle and atmospheric distillation residue in the case of Stuart. In view of the losses which inevitably occurred during handling of the small amounts of material in the laboratory, the yield data are only approximate and the final product yields are therefore conservative. Nevertheless, yields of ~13% for the distillate fraction and 23% for the maltenes are significantly greater than the yield of lubricating oil fractions from the Middle Eastern crudes usually used for lubricating oil production.

4.2. E l e m e n t a l a n a l y s i s

The most reliable index of change is provided by the ratio of hydrogen to carbon, calculated from the elemental analysis and shown in Tables I and 2. In general, the elemental analysis was not significantly changed by the alkylation, suggesting that the alkylation step was not effective.

J.F. Stubington et al./ Fuel Processing Technol. 37 (1994) 295-305

301

~o ~
~o

~~ ?

~D

O~

:z

302 TABLE 3

J.F. Stubington et al./Fuel Processing Technol. 37 (1994) 295 305

Elemental analyses and viscosities of the standard lubricating oil base stocks Sample C (wt.%) H (wt.%) C/H (by wt.) H/C (mole ratio) 0.91 0.91 0.90 Measured viscosity at 40 C (cSt) 59.3 91.3 567.5 Measured viscosity at 100 C (cSt) 7.81 10.57 34.8 Viscosity index

ALOR-300SN ALOR-500SN ALOR-160SN

87.2 86.8 87.9

13.2 13.1 13.2

6.60 6.60 6.68

95 98 95

D e - w a x i n g d e c r e a s e d the H/C r a t i o of the Rundle distillate slightly, since the w a x w a s h i g h e r in h y d r o g e n . The w a x e s f r o m the distillate h a d a H/C mole r a t i o of 1.02-1.04, i n d i c a t i n g paraffins ( - C H 2 - for w h i c h H/C ~ 1), highly suitable as a c a t a l y t i c c r a c k i n g f e e d s t o c k or for local i n d u s t r i e s u s i n g p e t r o l e u m wax. H o w e v e r , the w a x e s from the m a l t e n e s w e r e not s t r a i g h t - c h a i n structures, since t h e i r H/C r a t i o s were less t h a n 1. F u r t h e r m o r e , r e m o v a l of the w a x e s f r o m the m a l t e n e s did n o t significantly c h a n g e t h e i r H/C ratios, suggesting t h a t this step did not affect the r a t i o of paraffinic to a r o m a t i c s t r u c t u r e s in the m a l t e n e products. The e l e m e n t a l a n a l y s e s i n d i c a t e d t h a t the initial h y d r o g e n a t i o n step was not effective for the R u n d l e samples, so t h a t m o r e severe o p e r a t i n g c o n d i t i o n s would be n e c e s s a r y for effective h y d r o g e n a t i o n . Small i n c r e a s e s in the H/C r a t i o w e r e o b t a i n e d from the initial h y d r o g e n a t i o n of the S t u a r t m a l t e n e s and f r o m p r o l o n g e d h y d r o g e n a t i o n of the R u n d l e de-waxed distillate sample. T h e H/C r a t i o s for all of the final h y d r o g e n a t e d p r o d u c t s f r o m this shale oil p r o c e s s i n g w e r e significantly l o w e r t h a n for the p e t r o l e u m - d e r i v e d oils (Table 3), s u g g e s t i n g a deficiency of h y d r o g e n e v e n a f t e r h y d r o g e n a t i o n for a longer time.

4.3. Viscosity

M o s t of the shale oil fractions, a l t h o u g h boiling in the s a m e r a n g e as p e t r o l e u m - d e r i v e d l u b r i c a t i o n oils, w e r e too viscous to m e a s u r e t h e i r v i s c o s i t y a t the s t a n d a r d 40 C. Therefore, v i s c o s i t y m e a s u r e m e n t s w e r e m a d e at 60 C a n d 100 C and the v i s c o s i t y at 40 C was e s t i m a t e d by e x t r a p o l a t i o n (except for R u n d l e DAD). T h e v i s c o s i t y at 40C was needed to c a l c u l a t e the v i s c o s i t y index, w h i c h is a m e a s u r e of the effect of c h a n g i n g t e m p e r a t u r e on the viscosity. T h e h i g h e r the v i s c o s i t y index the less is the drop in v i s c o s i t y for a g i v e n t e m p e r a t u r e i n c r e a s e and h e n c e the b e t t e r the p e r f o r m a n c e of the oil. Since v i s c o s i t y index is v e r y s e n s i t i v e to the v a l u e at 40C, this e x t r a p o l a t i o n i n t r o d u c e d significant e r r o r s and the v a l u e s of v i s c o s i t y index g i v e n in T a b l e s 1 and 2 m a y h a v e e r r o r s as h i g h as + 10. A l k y l a t i o n s o m e t i m e s i n c r e a s e d a n d s o m e t i m e s d e c r e a s e d the m e a s u r e d v i s c o s i t y slightly, s u g g e s t i n g t h a t it did c a u s e some r e - a r r a n g e m e n t of the

J.F. Stubington et al./Fuel Processing Technol. 37 (1994) 295 305

303

molecular s t r uc t ur e even though no change in elemental analysis was observed. However, within the accuracy of determination, alkylation did not affect the viscosity index of the final hydrogenated products. Hydrogenation decreased the measured viscosity for all samples, suggesting that it was effective to a small degree in changing the molecular structure, even when no change in elemental composition was detected. For the Rundle distillate products, the measured viscosities were less than those of the petroleum-derived lubricating oil base stocks. However, the physical appearance of these samples at room temperature was of a much more viscous fluid and only one sample (DAD) was fluid enough for its viscosity to be measured at 40C. This phenomenon may be explained by the formation of a suspension of immiscibile microcrystalline components at lower temperatures, forming a slurry-type material. It seems quite possible t hat further separation may be necessary to obtain a potential lubricating oil base stock from the distillate fraction. The yield of distillate product boiling in the lubricating oil range is quite high, so a more rigorous solvent extraction process may still be justified. The estimated viscosity index of 100 for hydrogenated de-waxed Rundle distillate provides further justification for continued work, when compared to the values of 95 98 for the petroleum-derived base stocks. The viscosities of the maltene samples from both Rundle and Stuart shale oils were in the same range as those for the petroleum-derived base stocks. The estimated viscosity indices for hydrogenated residue products from Rundle shale oil (77) were too low for them to be viewed as potential sources of lubricating oil, but the estimated viscosity indices for hydrogenated residue products from Stuart shale oil (89 90) were closer to those of the petroleumderived base stocks.

5. CONCLUSIONS Relatively high yields of potential lubricating oil base stock material were obtained for both the distillate and maltene fractions from Rundle and Stuart shale oils in comparison with yields from crude petroleum. The alkylation step did not significantly change the elemental composition of the samples and would not seem warranted in any scheme to produce lubricating oils. De-waxing removed paraffins from the distillate samples, but removed mixed structures from the residue samples; and only one of the products became liquid at room temperature. In most cases, the initial hydrogenation step was not long enough and/or not severe enough to change significantly the elemental composition. Even after the longer hydrogenation, the H/C ratio was not as high as for the petroleum-derived lubricating oil base stocks and it must be concluded t hat the chemical make-up of the shale oil products is different from the petroleum products. However, the different chemical s t r uct ur e for the shale oil products does not preclude them from consideration as a potential source of lubricating oil.

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Viscosity measurements suggest the Rundle distillate has the potential to produce low-viscosity lubricating oil base stock, but the products from Rundle and S tu ar t residues are less prospective. F u r t h e r separation via solvent extraction of the Rundle distillate may be warranted to remove the presumed microcrystalline phase causing high viscosity at ambient temperature. A detailed structural analysis of the products will be undert aken to identify the structures present.

ACKNOWLEDGEMENT The financial support of the Energy Research and Development Corporation is acknowledged as is the support of Southern Pacific Petroleum N/L, who provided the shale oil samples, and the Australian Lubricating Oil Refinery, who provided the lubricating oil samples. The contribution of Dr. J a c k y Fahy and Dr. Suresh Raj in the experimental program is also acknowledged.

NOMENCLATURE AD ALOR-300SN ALOR-500SN ALOR-160BS AM BD BM DAD DAM DBD DBM HDAD HDAM HDBD HDBM Hyd. HDBD WAD WAM WBD WBM alkylated distillate lubricating oil base stock lubricating oil base stock lubricating oil base stock alkylated maltenes distillate maltenes de-waxed alkylated distillate de-waxed alkylated maltenes de-waxed distillate de-waxed maltenes hydrogenated de-waxed alkylated distillate hydrogenated de-waxed alkylated maltenes hydrogenated de-waxed distillate hydrogenated de-waxed maltenes prolonged hydrogenated de-waxed distillate wax ex alkylated distillate wax ex alkylated maltenes wax ex distillate wax ex maltenes

REFERENCES Nguyen, V.D., 1990. Yields and chemical characteristics of products from fluidized bed steam retorting of Condor and Stuart oil shales; effect of pyrolysis temperature. Fuel, 69: 368-376.

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