Petroleum Derived Carbons

1. I200*F ε. S ε ν ε. 900·-. R. 1000· F. I. L. Τ. 0. Y w. 800·-. 900#F. THERMAL ..... 30LC C-12A. Applied pressure ... Voltage drop, bus to lo...
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2 Petroleum Based Carbon CHARLES L. M A N T E L L

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447 Ryder Rd., Manhasset, N.Y., 11030

Petroleum-derived carbon is a huge industry, based on the heavy residual oils from vacuum fractionation or solvent extraction. These oils are feed stock for electrode coke or fuel for steam and power generation. Figure 1 shows the pyrolysis of residual hydrocarbons with severity of cracking. Table I shows transformations during coking. Table II shows commercial coke processes. Figure 2 shows a flowchart for delayed coking operations. Figure 3 shows interrelated petroleum coke quality variables. Table III shows typical analyses of petroleum coke. Figure 4 shows industrial utilization of pet coke. Table IV shows typical properties of calcinated petroleum coke. Figure 5 shows outlets for calcined petroleum coke. Table V gives analyses of calcined petroleum coke. A generalized flow sheet of electrode manufacture where petroleum coke is the preferred and almost exclusive raw material, is calcined, ground, mixed with binders, shaped, baked into amorphous forms and later graphitized, is shown in Figure 6. Petroleum coke is the life blood of the electro-process i n dustries. Coking is practiced by the petroleum industry to i m prove yields. The electro-process industries consume more than a quarter of our annual power production. Petroleum coke is preferred in its low volatile, low sulfur, low metal content for electrolytic anodes, electrodes for aluminum and magnesium, pastes for linings of fused salt electrolysis cells and self-baking units, electric furnace electrodes for copper, steel, cast iron melting; preparation of ferro alloys of wide variety, manufacture of calcium carbide and synthetic abrasives, refractories for blast furnaces, dies for continuous casting of metals; lumber and vessel linings, chemically resistant equip-

18

Deviney and O'Grady; Petroleum Derived Carbons ACS Symposium Series; American Chemical Society: Washington, DC, 1976.

2.

MANTELL

Petroleum Based Carbon OVER 2000»F

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D ε G R Ε ε 0 F C R A C Κ 1 Ν v>

S ε ν ε R I Τ Y

H 1 G H

1 Ν τ ε R M ε D I A Τ 1

ε

1800·· 2000T

THERMAL

HYDROGEN GAS THERMAL CARBON BLACK

DECOMPOSITION

400 8TU/CU FT GAS HEAVY AROMATIC 0 « S T « L I ATES PITCH COKE

HIGH TEMPERATURE COKING

700 BTU/CU.FT.OIL GAS

LOW 8TU

1600·I600 F

AROMATIC LIGHT OILS

OIL GAS

#

AROMATIC OIL GAS TAR

PRODUCTION

1300·* 1600· F

LAMPBLACK

HIGH BTU

1000 BTU/CUFT S HIGHER OIL GAS

OIL GAS

LIGHT OILS OIL GAS TAR

PRODUCTION

900·I200*F

REFINERY OAS

LOW

GASOLINE

TEMPERATURE

GAS OIL

COKING

#

REFINERY GAS GASOLINE GAS OIL

CRACKING

L 0 w 800·900 F

PETROLEUM COKE

THtNMAL

900·1000· F

19

THERMAL TAR

REFINERY GAS GASOLINE

VIS8REAKING

FUEL OIL

Figure 1. Pyrolysis of residual hydrocarbons with severity of cracking

TABLE I Transformations During Coking Product Characteristics Volatile matter, % Solubility in trichlorethylene, % Carbon-hydrogen ratio

Asphalt — 45 100 10-14

P i t c h -- S e m i pitch

A s p h a l t i c — Carboid coke coke

30-45

20-30

7-20

Less than 7

60-100

40-60

2-40

Less than 2

18-24

Greater than 24

Deviney and O'Grady; Petroleum Derived Carbons ACS Symposium Series; American Chemical Society: Washington, DC, 1976.

PETROLEUM DERIVED CARBONS

20

TABLEII Commercial Coking Processes Coking temperatures Type

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Method

Range, ° F

Type

Atmospheric still coker

Batch

Low

900-1000

Delayed coker

Semicontinuous

Low

900-935

Broad-oven coker

Batch

High

Greater than 1600

Contact coker

Continuous

Low

900-9C0

Fluid coker

Continuous

Low

900-950

6.700 LBS/HR

Ι 2 Ι · Α Ρ Ι MIO-CONTINENT 30% RE0UCED CRUDE |6% C0NRA0S0N CARBON DRUM 0VERHEA0

CAS COMPRESSOR

PRODUCT FUEL GAS 50 MM BTU/Hft [ACCUMULATOR C3-C4 PR00UCT 200 BS0

GASOLINE NO 2 FUEL OIL HEAVY FUEL OIL BLENDING

Figure 2.

Delayed coking operations

Deviney and O'Grady; Petroleum Derived Carbons ACS Symposium Series; American Chemical Society: Washington, DC, 1976.

Deviney and O'Grady; Petroleum Derived Carbons ACS Symposium Series; American Chemical Society: Washington, DC, 1976.

^Moisture-free basis. determinations made in accordance with Great Lakes Carbon Corp. analytical methods.

0.01

0.008

(35) 0.014

0.021 0.02

0.05

0.3

1.2

7.2

Fluid

West Coast

(34) 0.02 0.01

0.04

0.7

7.0

5.0

Fluid

Hawkins

(34) 0.17 0.06

(32) 0.0009

0.08

0.7

6.4

5.3

Fluid

Elk Basin

0.008

0.071

(34)

0.066

0.01

2.8

1.4

Fluid

South Louisiana

0.031

(32) 0.0006

0.01

0.37

0.21

13-18

1.8

Delayed

American Gilsonite Co.

0.0001

0.0004

(32)

0.11

0.14

0.10

9.2

7.8

0.0010

0.0284

0.040

0.0283

0.054

0.025

0.40

1.15

10.2

6.0

Delayed

Batch

2

(32) 0.0021 0.0006

0.0042

0.055

0.053

0.166

0.51

4.51

12.9

5.5

Delayed

(32) 0.0019 0.0003

0.0007

0.0060

0.021

0.012

0.11

1.08

12.8

6.0

Delayed

0.0031

0.0088

0.014

0.008

0.13

1.49

12.3

3.2

(32) 0.027

0.0002

Delayed

(32) 0.0038

0.0003

0.0086

0.020

0.0097

0.011

0.14

0.77

11.0

7.0

Delayed

(32)

0.011

0.0003

0.0041

0.0084

0.013

0.038

0.15

1.3

11.7

0.14

Delayed

(32)

l

Vanadium, Reference wt % 0.019

0.0003

0.0094

0.020

0.026

0.043

0.30

2.9

Titanium,

13.5

l

Nickel, wt %

0.81

i

Delayed

l

Silicon, Calcium, wt% wt %

Iron. wt%*

1

Ash. wt%

Sulfur, wt%l

Type

Pennsylvania2

California

2

2

Mid-Continent

Arkansas

2

Mid-Continent

2

2

Middle West

Ohio

2

Middle West

Source

Volatile matter, wt %1

Moisture, wt%

TABLE H I Typical Analyses of Petroleum Cokes

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to

Ο

r ι



PETROLEUM DERIVED CARBONS

• CHARACTERIZATION FACTOR OEGREE Of REDUCTION FEEDSTOCK VARIABLES

CONRADSON CAROON SULFUR CONTENT • METALLIC CONSTITUENTS

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PETROLEUM COKE QUALITY

PROCESSING VARIABLES

TIME -TEMPERATURE - PRCSSURE CRACKING INTERRELATIONSHIPS • RECYCLE TO FEEOSTOCK RATIO COKE REMOVAL FACTORS BATCH, SEMI-CONTINUOUS, OR CONTINUOUS

ENGINEERING

VARIABLE

• CAPACITY ANO SIZE FACTORS •COKE REMOVAL EQUIPMENT COKE HANDLING, STORAGE, AND TRANSPORTATION

Figure 3. Interrelated petroleum-coke quality variables

LOW ASH FUEL

HIGH PURITY REACTANT

FERROUS METALLURGY

CALCINATION

• POWER PLANTS • DOMESTIC FUEL CEMENT KILNS

• CALCIUM CARBIDE • SILICON CARBIDE -MISCELLANEOUS CARBIDES -HIGH OENSITY FOUNORY COKE -BLAST FURNACE COKE CALCINED PETROLEUM COKE

Figure 4. Utilization of raw petroleum coke

Deviney and O'Grady; Petroleum Derived Carbons ACS Symposium Series; American Chemical Society: Washington, DC, 1976.

2.

MANTELL

23

Petroleum Based Carbon

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T A B L E IV Typical Properties of Petroleum Coke Used in Carbon and Graphite Manufacture Property

Raw coke

Coke calcined to 1300°C

15-100

15-100

Ash, %

0.1-1.0

0.2-1.5

Boron, ppm

0.1-0.5

0.2-0.7

25-500

25-500

Aluminum, ppm*

Calcium, ppm Fixed carbon, % Hydrogen, % Iron, ppm Manganese, ppm Magnesium, ppm Moisture, %

97-99

87-97