Catalytic Upgrading of SRC-II Syncrude - American Chemical Society

3 Catalytic Upgrading of SRC-II Syncrude H A R R Y A. FRUMKIN, RICHARD F. SULLIVAN, and BRUCE E. STANGELAND Chevron Research Company, 576 Standard Avenue, Richmond, CA 94802

Chevron Research Company, under a contract sponsored by the U.S. Department of Energy (DOE), is conducting a program to determine the feasibility and estimate the costs of using modern petroleum processing technology to produce distillate fuels, such as high octane gasoline, jet fuel, and diesel, from a number of synthetic crude feedstocks. Pilot plant tests for the key processing steps are being conducted to the extent needed to make reasonable estimates of commercial plant performance. The first feedstock studied under this contract was Paraho shale o i l . In a series of recent papers (1-4) and a DOE report (5), three basic shale oil processing routes for the production of transportation fuels were studied: hydrotreating followed by hydrocracking, hydrotreating followed by fluid catalytic cracking (FCC), and severe coking followed by hydrotreating. It was concluded that shale oil can be refined to high quality transportation fuels via modern state-of-the-art refining technology and that it can serve as a substitute for crude oil in a refinery equipped with modern hydrotreating facilities. The key to successful shale oil refining is the initial hydrotreating step which removes contaminants (nitrogen, sulfur, oxygen, olefins, and metallic contaminants) and permits the use of conventional conversion and refining processes to make finished products. This chapter reports results of a similar study to determine the feasibility of converting solvent refined coal (SRC) to transportation fuels. The next chapter discusses upgrading of H-Coal process products. The SRC process, in its two forms, is one of the major processes under current study in programs sponsored by the DOE for conversion of coal to either (1) a solid deashed low sulfur product or (2) a low boiling liquid. In the original SRC process (6), now designated as SRC-I, coal is dissolved under moderate hydrogen pressure in an 0097-6156/81/0156-0075$10.00/0 © 1981 American Chemical Society

76

UPGRADING COAL LIQUIDS

i n t e r n a l l y generated heavy aromatic solvent to y i e l d a product from which most of the m i n e r a l matter i s removed by f i l t r a t i o n . Solvent i s recovered f o r reuse by vacuum d i s t i l l a t i o n . The d i s t i l l a t i o n r e s i d u e (known as SRC or SRC-I) i s a s o l i d under ambient c o n d i t i o n s . Research on the upgrading of SRC-I i s reported i n other chapters of t h i s book. In an a l t e r n a t e v e r s i o n of the process ( 7 ) , designated SRC-II, a p o r t i o n of the c o a l s o l u t i o n i s r e c y c l e d as solvent i n place of the d i s t i l l a t e solvent of the SRC-I process. The f i l t r a t i o n step i s e l i m i n a t e d ; and, t y p i c a l l y , the process operates a t a higher pressure, higher temperature, and longer residence time than the SRC-I process. Hydrogen consumption and the conversion of d i s s o l v e d c o a l i s i n c r e a s e d , and the primary product i s a l i q u i d r a t h e r than the s o l i d product of the SRC-I process. The l i q u i d product of the SRC-II process i s the feedstock that i s the subject of the work described i n t h i s chapter. In a previous paper (_8) , we presented r e s u l t s of hydrot r e a t i n g SRC-II process product at s e v e r a l s e v e r i t i e s , and p r e l i m i n a r y cost estimates were given. In the present chapter, previous r e s u l t s are summarized; and r e s u l t s of f u r t h e r downstream processing p i l o t p l a n t s t u d i e s are presented, together w i t h process engineering s t u d i e s and updated cost estimates. More d e t a i l s of t h i s study a r e given i n a DOE r e p o r t . (_9) Feeds The P i t t s b u r g and Midway Coal Mining Company provided the SRC-II process products that were used as feeds i n these s t u d i e s . They were produced i n the F o r t Lewis, Washington, p i l o t plant from a West V i r g i n i a c o a l ( P i t t s b u r g Seam, B l a c k s v i l l e No. 2 Mine of the Consolidated Coal Company). Three f r a c t i o n s of SRC-II were provided. These were reblended i n a r a t i o recommended by the DOE t o c o n s t i t u t e the net whole l i q u i d process product from " t y p i c a l " SRC-II o p e r a t i o n as best could be estimated at the time t h i s p r o j e c t was s t a r t e d ( A p r i l 1978). Table I shows the i n s p e c t i o n s of the r e c o n s t i t u t e d SRC-II process product. C h l o r i d e was not removed from the samples before hydroprocessing. However, i t was shown t h a t water washi n g can remove most of the c h l o r i d e . I t i s our understanding that t h i s would t y p i c a l l y be done at the upstream (SRC) proc e s s i n g f a c i l i t y i n a commercial s i t u a t i o n . P r o c e s s i n g of SRC-II P i l o t plant t e s t s were made to hydrotreat the whole SRC-II process product blends to remove n i t r o g e n , s u l f u r , oxygen, and metals using f i x e d c a t a l y s t beds.

FRUMKIN ET AL.

SRC-II Syncrude

TABLE I PROPERTIES OF SRC-II PROCESS PRODUCT Inspections G r a v i t y , °API A n i l i n e P o i n t , °F S u l f u r , Wt % T o t a l Nitrogen, Wt % Basic Nitrogen, Wt % Oxygen, Wt % Hydrogen, Wt % Hydrogen/Carbon Atom R a t i o C h l o r i d e , ppm Pour P o i n t , °F Ramsbottom Carbon, Wt % Hot Heptane I n s o l u b l e s , Wt % Benzene I n s o l u b l e s , Wt % Ash, Wt % Molecular Weight TBP D i s t i l l a t i o n , °F St/5 10/30 50 70/90 95/99

18.6 Steam reforming feeding gas and naphtha in Cases 3A and 3B, 6A and 6B.

F

Refinery

•

Whole SRC-11 Oil

Refining Units

Sour Water from

Gas

Refinery Gas

Light Ends

Gas to Refinery Fuel

Hydrocracking

H,S

Heavy Naphtha

2

Gas

Figure 7.

Heavy Naphtha

SRC-II Oil

Sulfur Plant

.1

Catalytic Reforming

L

Gas

I

Hydrogen Plant*

Refinery Fuel

Motor Gasoline

Ammonia

Sulfur

Hydrogen to Hydrotreaters

Flow diagram: refining of SRC-II oil by hydrotreating and hydrocracking, case 4

J

To Hydrogen Plant Hydrogen

Light Naphtha

Naphtha Hydrotreating Hydrogen

H,S

H S Recovery

• Steam reforming feeding gas and naphtha in Cases 4A, 4B, and 4D. Partial oxidation feeding SRC-II oil in Case4C.

Hydrogen .

Hydrogen

Whole SRC-II Oil Intermediate Severity Hydrotreating

Recycled Water to Refining Units

Sour Water from Refining Units Waste Water Treating

Gas

Refinery Gas

^a^JoJRe^inery Fuel

r ο g θ

8

g δ ο

C Ο >

00

Hydrotreating

Severity

Moderate

to Refining Units

Recycled Water

Treating

Waste Water

2

HS

ι

Gas

2

H S

Heavy Naphtha

Figure 8.

ι m

Hydrogen

Reforming

Catalytic

Gas

Gas Oil

t 1

Plant

t

To Hydrogen Gas

Sulfur Plant

J

r

Hydrogen to Hydrotreating

and Refinery Fuel

No. 2 Furnace Oil

Motor Gasoline

Ammonia

Sulfur

Gas to Refinery Fuel

Plant*

Hydrogen

Simplifiedflowdiagram: refining of SRC-II oil by moderate severity hydrotreating, case 5

Partial oxidation feeding SRC-II oil in Case 5C.

I

Light Naphtha

Naphtha Hydrotreating

Hydrogen

2

HS

Recovery

* Steam reforming feeding gas and naphtha in Cases 5A, 5B, and 5D.

Hydrogen

Whole SRC-II Oil

Refining Units

from

Sour Water

Refinery Gas

_N aphtha

_S R£- I K W

100


e f f e c t on r e f i n e r y cost of r e l a x i n g the ground r u l e to make only t r a n s p o r t a t i o n f u e l s . The appendix shows y i e l d s and product p r o p e r t i e s from each of the h y d r o t r e a t e r s and hydrocrackers estimated f o r the studies. Stock Balances - Tables XII-XVI show d e t a i l e d stock b a l ances f o r each of the f i v e cases. Y i e l d s are based d i r e c t l y on p i l o t plant r e s u l t s and general petroleum processing c o r r e l a t i o n s where a p p r o p r i a t e . The primary b a s i s i s to make a cons t a n t 50,000 BPCD of d e s i r e d products i n each case. This c a p a c i t y was s e l e c t e d f o r the f i r s t s e r i e s of s t u d i e s because i t matches the maximum f e a s i b l e throughput f o r a s i n g l e SRC-II plant as p r e s e n t l y conceived. The r e f i n e r i e s are stand-alone grass roots f a c i l i t i e s , that i s , complete new i n s t a l l a t i o n s , i n c l u d i n g a l l necessary supporting f a c i l i t i e s , such as u t i l i t y p l a n t s , tankage, and r e q u i r e d environmental c o n t r o l equipment. Another o b j e c t i v e f o r t h i s s e r i e s was to meet r e f i n e r y furnace f u e l and hydrogen p l a n t feed requirements w i t h i n t e r n a l l y s u p p l i e d clean f u e l s , ensuring minimum a i r emissions. B o i l e r p l a n t s , however, were assumed to be c o a l f i r e d i n comp l i a n c e with present DOE r e g u l a t i o n s . Other options f o r f u e l and hydrogen plant feed are examined i n the complete DOE r e p o r t . (9) Estimates of f i n i s h e d g a s o l i n e production were made by using c o r r e l a t i o n s f o r c a t a l y t i c reforming of naphtha and blending of g a s o l i n e components. C o r r e l a t i o n s could be used i n t h i s case because the p r o p e r t i e s of the reformer feeds d i s t i l l e d from the p i l o t plant h y d r o t r e a t e r products were w e l l w i t h i n Chevron's range of experience on petroleum s t o c k s . Gasoline blending o b j e c t i v e s were to make a s i n g l e unleaded pool meeting accepted i n d u s t r y s p e c i f i c a t i o n s f o r q u a l i t y w i t h minimum octane numbers of 93 (Research + Motor)/2. These octane numbers are t y p i c a l of those projected f o r the e a r l y 1980 s. Table XVII l i s t s the r e f i n e r y product i n s p e c t i o n s . Each plan represents a completely f e a s i b l e and reasonably e f f i c i e n t r e f i n i n g arrangement. A more d e t a i l e d o p t i m i z a t i o n of c o n d i t i o n s , cut p o i n t s , and other f a c t o r s , while not w i t h i n the scope of t h i s study, would be c a r r i e d out i n the course of a normal r e f i n e r y design. Cost Estimates - P l a n t investment costs were developed using cost c o r r e l a t i o n s based on a c t u a l plants constructed by Standard O i l Company of C a l i f o r n i a . The important bases f o r these estimates are summarized i n Table X V I I I . Costs f o r the o v e r a l l Case 1 r e f i n e r y are broken down and d e t a i l e d i n Table XIX. Investments are c a t e g o r i z e d as "onplot," those d i r e c t l y concerned w i t h the i n d i v i d u a l r e f i n e r y process p l a n t s , and " o f f p l o t , " f o r a u x i l i a r y or supporting f a c i l i t i e s , such as u t i l i t y p l a n t s , tankage, e t c . The e s t i m a t i n g allowances shown f

Day

+

Sulfide

Day

• I n c l u d i n g 4.6 LV % B u t a n e s Note: P a r e n t h e s e s () D e n o t e

Hydrogen Sulfur Ammonia

Tons P e r C a l e n d a r

a Negative Quantity,

i.e.,

96

29.1

(174.9)

7, 505

Hydrogen, M i l l i o n s o f Standard Cubic Feet Per C a l e n d a r Day

(Loss) (625)

Gain

67,365 (59,860)

Fuel

Liquid

Product Feed

(97.5 F - l C l e a r )

Liquid Liquid

Total Total

Reformate

6

38,370 3,000

5

300-550°F Kerosene 5 5 0 ° F Bottoms

795 1, 380 1,410

(59,860)

High S e v e r i t y Hydrotreating

3, 795 18,615

59,860 1, 870

Refinery Input

C /C Light Gasoline 180-300°F Heavy G a s o l i n e

Fuel O i l

SRC I I O i l * Equivalent Fuel O i l

F u e l Gas, E q u i v a l e n t Isobutane Normal Butane

Whole Coal,

per Calendar

Feeds and P r o d u c t s ,

Barrels

TABLE X I I

Consumption

17.0

(545)

(990)

9,080 (10,070)

8, 940

(10,070)

115 15 10

Catalytic Reforming

157.9

(5,525)

(9,575)

(9,575)

(8,545)

(510) (520)

Hydrogen Manufacture

Processing

(29.1) 26.2

2

H S Recovery and Sulfur Plant

(1,870)

Offplot Boiler Plant

STOCK BALANCE - CASE 1A REFINING S R C - I I O I L BY HIGH SEVERITY HYDROTREATING TO PRODUCE 50,000 BARRELS PER CALENDAR DAY OF MOTOR GASOLINE PLUS J E T FUEL DOE CONTRACT E F - 7 6 - C - 0 1 - 2 3 1 5

6,695

(105)

6,800

2, 570 3, 000

910 160 160

Refinery Fuel

14,200

8, 940

3,795

725 740

Motor Gasoline

35,800

35,800

Kerosene Jet Fuel

Products

26.2 96

Byproducts


(97 F - l C l e a r )

• I n c l u d i n g 4.6 LV % Butanes Note: Parentheses () Denote a N e g a t i v e Q u a n t i t y ,

Hydrogen S u l f i d e Sulfur Ammonia

Tons Per C a l e n d a r Day

i . e . , Consumption

96

28.7

(41.5)

18

140.9

(4,940)

(117.1)

(770)

Hydrogen, M i l l i o n s o f Standard C u b i c F e e t Per Calendar Day

(8,395)

(1,010)

(250)

2,285

4, 590

(530)

(Loss)

(8,395)

11,900

(6,930)

(735) (730)

12,09Q (13,100)

33,025

(13,100)

145 25 20


36,400 (34,115)

Fuel

L i q u i d Gain

T o t a l L i q u i d Product T o t a l L i q u i d Feed

Reformate

H y d r o t r e a t e d Kerosene

(34,115)

3,170

205

Middle Distillate Hydrotreating

Processing Naphtha Hydrotreating and C a t a l y t i c Reforming

63,616 (59,620)

35,075 4, 535

+

300-550°F Kerosene 5 5 0 ° F Bottoms

645 1, 360 1, 360

(59,020)

Intermediate Severity Hydrotreating

3,775 16,860

59,020 1,250

Refinery Input

Cj/Cg L i g h t G a s o l i n e 180-300°F Heavy G a s o l i n e

F u e l Gas, E q u i v a l e n t F u e l O i l Isobutane Normal Butane

Whole SRC I I O i l * Coal, Equivalent Fuel O i l

B a r r e l s per C a l e n d a r Day

TABLE X I I I

(28.7) 26

2

HS Recovery and S u l f u r Plant (1,250)


STOCK BALANCE - CASE 2A REFINING OF SRC-II OIL BY INTERMEDIATE SEVERITY HYDROTREATING TO PRODUCE 50,000 BARRELS PER CALENDAR DAY OF MOTOR GASOLINE PLUS JET FUEL DOE CONTRACT EF-76-C-01-2315

6, 490

6,490

960 4, 535

995

Refinery Fuel

16,975

11,900

3,775

650 650

Motor Gasoline

33,025

33,025

Kerosene Jet Fuel

Products

26 96

Byproducts

Refinery Input

59,130 1,890



• I n c l u d i n g 4.6 LV % Butane Note: P a r e n t h e s e s () Denote a N e g a t i v e Q u a n t i t y ,

Hydrogen S u l f i d e Sulfur Ammonia

Tons Per C a l e n d a r Day

i.e.,

96

28.8

(172.7)

Hydrogen, M i l l i o n s o f Standard C u b i c F e e t per C a l e n d a r Day

Consumption

(385) 47.0

(1,470)

(2,570)

(1,640)

1, 905

7,415

(625)

(Loss)

24,660 (27,230)

24,055

(27,230)

60

220 65

260

Catalytic Reforming

4,270 (5,910)

1,910 (1,515) (1,130) (1,800)/1,300 (745)/535 (720)/525

L i g h t Ends Recovery

Processing

27,595 (25,690)

-

(25,690) 3,415

11,665 6,295

310 1, 575 1,130 1, 800 745 720

Fluid Catalytic Cracking

66,545 (59,130)

-

Fuel

L i q u i d Gain


Reformate

(98.5 F - l C l e a r )

25,690

+

4 0 0 ° F Bottoms FCC C y c l e O i l

6

3, 750 33,560

1, 395

1,365

785

(59,130)

High S e v e r i t y Hydrotreating

C5/C L i g h t G a s o l i n e 180-400°F Heavy G a s o l i n e FCC L i g h t G a s o l i n e FCC Heavy G a s o l i n e

F u e l Gas, E q u i v a l e n t F u e l O i l Propylene Propane Isobutane Butylène Normal Butane

B a r r e l s per C a l e n d a r Day

TABLE XIV

125.7)

(4,400)

(7,560)

(7,560)

(6,330)

(510)

(220) (500)

Hydrogen Mfg.

(28.8) 25.9

2

HS Recovery and Sulfur Plant

STOCK BALANCE - CASE 3A REFINING SRC-II OIL BY HIGH SEVERITY HYDROTREATING AND FLUID CATALYTIC CRACKING TO PRODUCE 50,000 BARRELS PER CALENDAR DAY OF MOTOR GASOLINE DOE CONTRACT EF-76-Ç-01-2315

(1,890)


6,680

6,680

3,415

3,265

Refinery Fuel

50,000

24,055

11,665 6,295

3,750

2,230 535 1,470

Motor Gasoline

Products

25.9 96

Byproducts

6

+

Sulfide

• I n c l u d i n g 4.6 LV % Butanes. Note: Parentheses () Denote a Negative


Day

Quantity,

(52.5)


92

27.7

(142.0)

Tons Per C a l e n d a r

(570) 49.0

145. 5

(5,015)

(9,190)

(2,795) (1,880)

6,965

6,195 (230)

(9,910)

31,060

(4,325)

(3,325) (1,546)

31,720 (34,515)

(32,625)

38,615

(34,515)

475 100 85


39,590 (32,625)

10,795 21,755

3,700 17,085


62,715 (56,520)

470 5,235 1,335

Hydrocracking

675 1, 320 1, 320

(56,520)

Intermediate Severity Hydrotreating

Hydrogen, M i l l i o n s o f Standard c u b i c F e e t Per Calendar Day

(Loss)

56,520 1,110

Refinery Input

Fuel

L i q u i d Gain


(96 F - l C l e a r )

Bottoms

Reformate

300°F

5

C /C Light Gasoline 180-300°F Heavy G a s o l i n e

F u e l Gas, E q u i v a l e n t F u e l O i l Isobutane Normal Butane


Day

Products,

B a r r e l s per C a l e n d a r

Feeds and

TABLE XV

?

(27.7) 25

HS Recovery and Sulfur Plant

STOCK BALANCE - CASE 4A REFINING OF SRC-II OIL BY INTERMEDIATE SEVERITY HYDROTREATING AND SINGLE-STAGE ISOCRACKING TO PRODUCE 50,000 BARRELS PER CALENDAR DAY OF MOTOR GASOLINE DOE CONTRACT EF-76-C-01-2315

(1,110)


7,695

7,695

5,990

1,620 85

Refinery Fuel

50,000

31,060

14,494

3,245 1,200

Motor Gasoline

Products

25 92

Byproducts

p e r C a l e n d a r Day

Feed O i l

+

Note:

4.6 LV % B u t a n e s

Sulfide

P a r e n t h e s e s () D e n o t e

•Including


T o n s P e r C a l e n d a r Day

a Negative Quantity,

17.0

84.1

(2,945)

(5,125)

(930) (740)

(5,125)

(4,605)

(260) (260)

11,870 (10,800)

11,590

(12,800)

215 35 30




88

26.7

(101.1)

3,085

Hydrogen, M i l l i o n s o f Standard Cubic Feet Per C a l e n d a r Day

(Loss)

60,285 (57,200)

36,585

3,165 17,405

490 1, 320 1, 320

(57,200)

Moderate Severity Hydrotreating

Fuel

Gain

Liquid

Product Feed

56,200 8C0

Refinery Input

(410)

Liquid Liquid

Total Total

(96.5 F - l C l e a r )

Bottoms

Reformate

300°F

6

Cs/C Light Gasoline 1 8 0 - 3 0 0 ° F Heavy G a s o l i n e

F u e l Gas, E q u i v a l e n t Isobutane Normal Butane

W h o l e SRC I I O i l * Coal, Equivalent Fuel O i l

Barrels

Feeds and P r o d u c t s

TABLE XVI

(26.7) 24 .0

2

H S Recovery and Sulfur Plant

(860)


4,095

(145)

4,230

3,090

705 220 215

Refinery Fuel

STOCK BALANCE - CASE 5A REFINING S R C - I I O I L BY MODERATE SEVERITY HYDROTREATING TO PRODUCE 50,000 BARRELS PER CALENDAR DAY OF MOTOR GASOLINE PLUS NUMBER TWO HEATING O I L DOE CONTRACT E F - 7 6 - Ç - 0 1 - 2 3 1 5

16,505

11,590

3,165

875 875

Motor Gasoline

33,495

33,495

Number Two Oil

Products

24.0 88

Byproducts

106


REFINERY PRODUCT INSPECTIONS REFINING OF SRC-II OIL DOE CONTRACT EF-76-C-01-2315

Case

I n s p e c t i o n s of Motor

1978 Specifications

1

2

3

4

5

D 323 D 484 D 1266

Negative 0.0 3 Max

10 Negat i v *

Catalytic Upgrading of SRC-II Syncrude - American Chemical Society

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