BULLETIN 275 FEBRUARY 1982

ISSN 0043-2326

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THE USE OF QUENCHED AND TEMPERED
2 }4CR-1MO STEEL FOR THICK WALL REACTOR
VESSELS IN PETROLEUM REFINERY PROCESSES:
AN INTERPRETIVE REVIEW OF 25 YEARS OF
RESEARCH AND APPLICATION

W . E. Erwin
J. G. Kerr

These Bulletins contain final Reports from projects sponsored

by the Welding Research Council, important papers presented before
engineering societies and other reports of current interest.

WELDING RESEARCH COUNC IL

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 WRC - The Welding Research Council brings together science and engineering specialists in
developing the solutions to problems in welding and pressure vessel technology. They exchange
knowledge, share perspectives, and execute R and D activities. As needed, the Council organizes
and manages cooperative programs.

MPC – A Council of the WRC, the Materials Properties Council is dedicated to providing
industry with the best technology and the best data that can be obtained on the properties of
materials to help meet today’s most advanced concepts in design and service, life assessment,
fitness-for-service, and reliability and safety.

PVRC – A Council of the WRC, the goal of the Pressure Vessel Research Council is to
encourage, promote and conduct research in the field of pressure vessels and related pressure
equipment technologies, including evaluation of materials, design, fabrication, inspection and
testing.

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WRC Bulletins contain final reports from projects sponsored by the Welding Research Council, important
papers presented before engineering societies and other reports of current interest.

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Copyright © 1982 The Welding Research Council.

All rights, including translations, are reserved by WRC.
Printed in the United States of America.

ISSN 0043-2326
Library of Congress Catalog Number: 85-647116

Welding Research Council

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The Use of Quenched and Tempered 2 ~Cr-1Mo Steel
For Thick Wall Reactor Vessels in Petroleum
Refinery Processes: An Interpretive Review of
25 Years of Research and Application

by W. E. Erwin and J. G. Kerr

CONTENTS
Summary .. . . • . . . . • . . . . . . . . . . • . . . . • • • • • • . 1 D. Embrittlement of Stainless Steel
I. Basic Considerations . . . . . . . . . . . . . . . • 2 W eldmetal . . . . . . . . . . . . . . . . . . . . . . . . . . 39
A. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . 2 III. Reactor Experience . . . . . . . . . . . . . . . . . 40
B. Metallurgical Considerations . . . . . . . . . 3 A. Germany, 1930's-1950's . . . . . . . . . . . . . . . 40
C. Thick Section Properties . . . . . . . . . . . . . 4 B. Chevron Richmond Refinery, 1966 . . . . . 41
1. Historical Development . . . . . . . . . . . 4 C. Japan, 1970's . . . . . . . . . . . . . . . . . . . . . . . . . 44
2. Hardenability of 2 1/ 4Cr-1Mo Steel 6 D. Mexico, 1979 . . . . . . . . . . . . . . . . . . . . . . . . . 45
3. Normalized & Tempered vs.
Quenched & Tempered . . . . . . . . . . . . 6 IV. Future Directions . . . . . . . . . . . . . . . . . . . 45
4. Fracture Toughness . . . . . . . . . . . . . . 7 A. State-of-the-Art . . . . . . . . . . . . . . . . . . . . . 45
D. Hydro processing Reactors-Today . . . . 8 B. Development Needs-Ongoing Research
1. Steelmaking Practice . . . . . . . . . . . . . 9 ..................................... 46
2. Reactor Fabrication . . . . . . . . . . . . . . 10 C. Application to Coal Conversion ...... . 47
II. Research Topics • • . . . . • . . . . . . . . . . . . . . 11 Acknowledgements .....•••.........••••.. 48
A. Tempering Behavior-Carbide References ............•. , ............... . 48
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 Appendix A Data for Chevron 1966 H2
1. Secondary Hardening- Attack (Static Exposure) Study ......•..... 51
Mechanical Properties . . . . . . . . . . . . 11
2. Creep Embrittlement . . . . . . . . . . . . . 12 Appendix B Data for Chevron 1966 H 2
3. Stress Relief Cracking . . . . . . . . . . . . 13 Attack (Stress Rupture) Study ........... . 53
4. Summary-Carbide Reactions . . . . . 14 Appendix C Data for Chevron 1980 H 2
5. Tempering Parameter . . . . . . . . . . . . 15 Attack Study on 2 %Cr-1Mo and 2 1/ 4Cr-%Mo
B. Hydrogen Effects . . . . . . . . . . . . . . . . . . . . 15 Steels ........•....•...................... 54
1. Hydrogen Permeation . . . . . . . . . . . . 16
2. Sulfide Cracking . . . . . . . . . . . . . . . . . 18 Appendix D Data for Chevron 1980 H 2
3. Delayed Hydrogen Cracking . . . . . . 20 Attack Study on Stainless Clad 2 %Cr-1Mo . 55
4. Hydrogen Attack . . . . . . . . . . . . . . . . . 23 Appendix E Data for Chevron 1969 Temper
a. Literature Review-2 1/ 4Cr-1Mo Embrittlement Study-Plate ............. . 56
Steel . . . . . . . . . . . . . . . . . . . . . . . . . 24 Appendix F Data for Chevron 1969 Temper
b. Chevron Study-Static
Exposure ( 1966) . . . . . . . . . . . . . . 25 Embrittlement Study-SMAW ............ . 57
c. Chevron Study-Creep Rupture Appendix G Data for Chevron 1980 Temper
Tests......................... 27 Embrittlement Study .................... . 58
d. Chevron Study-Static
Exposure (1980) . . . . • . . . • . . . . . 27
5. Hydrogen Attack-Stainless
Clad 2 1/4Cr-Mo .. . .. . .. .. .. .. . .. .. 29
a. Chevron Study-Clad 2 %Cr-1Mo Summary
29 Thick wall pressure vessels are the heart of hydro-
C. Temper Embrittlement .............. . 32
1. Application to Hydroprocessing processing units in today's modern petroleum refinery.
Reactors ........................ . 33 These large reactor vessels range up to over 1000 tons
2. Chevron Characterization Studies 34 in weight and some have wall thickness of about 12-in.
3. Temper Embrittlement Control .... 38 Similar reactors, even larger in size, are now being
proposed for processing synthetic fuels derived from
coal, shale, and tar sands.
Low alloy steels are required for resistance to internal
W. E. Erwin and J. G. Kerr are with the Engineering Department Materials
Laboratory of the Standard Oil Company of California, Richmond CA. attack by hydrogen that is absorbed in the hydropro-
Publication of thiR report was sponsored by SO CAL and the Subcommittee cessing reactor shell from the elevated temperature
on Thermal and Mechanical Effects of the Pressure Vessel Research
Committee of the Welding Research Council. process environment. The leanest alloy offering suitable

2 1/4 Cr-1Mo Steel for Vessels 1

resistance in most hydroprocessing environments is the critical part of petroleum refinery hydroprocessing
2 %% chromium 1% molybdenum composition which plants. Generally, these vessels represent about 10% of
also has attractive mechanical properties and responds the capital cost of such a plant. In addition, their func-
to heat treatment in very heavy sections. tion is critical, and any reactor mishap could have severe
Although the first quenched and tempered chrome- consequences. Weights of such vessels built to date
moly reactors were used in Germany nearly 50 years ago, range up to about 1000 tons, and specialized equipment
the evolution of today's hydroprocessing reactor begins is needed in their manufacture, transportation, and
in about 1955. The first large reactors were then de- erection on site. Design, fabrication, and operation of
signed and fabricated from annealed 2 %Cr-1Mo ma- such vessels all require careful consideration. The steel
terial having 60 ksi minimum tensile strength in ac- used almost exclusively throughout the refining in-
cordance with ASME Section VIII rules. At about the dustry for such reactor vessels is a steel of nominal alloy
same time, the Welding Research Council through its composition 2.25% chromium and 1.0% molybdenum,
Pressure Vessel Research Committee began to sponsor which will be referred to hereafter as 21J4 Cr-1Mo
studies at Lehigh University on the heat treatment and steel.
fabrication of heavy section pressure vessel steels. This report is intended to review and summarize
Publication of their research results stimulated wide- approximately 25 years of industry development and
spread interest in the use of quenched and tempered application of 2 %Cr-1Mo steel in hydroprocessing
2 %Cr-1Mo steel at higher strength levels. Use of such reactors. A major part of the research reported herein
steels would not only produce significant savings will be on projects undertaken by Standard Oil Com-
through reduced wall thickness but also simplify process pany of California and its subsidiary Chevron Research
plant design and operation through fabrication of re- Company (hereafter collectively referred to as Chevron)
actors having larger volume. This WRC Bulletin focuses beginning in 1962 and continuing today. Discussion is
on the evolution of modern hydroprocessing reactors also devoted to field experience with reactors, safe-
fabricated from quenched and tempered 2 %Cr-1Mo guards necessary to assure safe operation, and stainless
steel and these important lessons learned from both steel cladding which is important to overall pressure
laboratory research and service experience: vessel integrity. Finally, some discussion of ongoing
1. Tensile strength above about 110 ksi is undesirable
research and needs for future research are identified.
Throughout this report, the term hydroprocessing
because of excessive reductions in fracture
will be used to represent a wide range of refining pro-
toughness and low resistance to hydrogen em-
brittlement cracking. cesses, including hydrocracking, hydrodesulfurization,
2. Temper embrittlement occurs in 2%Cr-1Mo and others which react oil with hydrogen, at high pres-
materials. Increases in the ductile to brittle tran- sures (typically 1500-3000 psig), in the presence of a
sition temperature of as much as 300° F have been catalyst, at temperatures in the range of 650-850° F.
observed. Rigid enforcement of pressure restric- Chemical reactions which occur in these processes are
cracking of large hydrocarbon molecules, conversion of
tions during startup and shutdown, when shell
temperatures are low enough to support brittle nitrogen compounds into ammonia (NH 3 ), and con-
fracture, permits safe operation of temper em- version of sulfur compounds into hydrogen sulfide
(H2S). Such processes are important in production of
brittled reactors. Reactors being fabricated today
have reduced susceptibility to temper embrittle- low sulfur fuels from high sulfur crude oils, and for
ment through better control of chemical compo- conversion of higher boiling point residual oils into
sition. lighter transportation fuels such as gasoline and jet fuel,
3. Thermal stresses at points of structural attach- which is an increasingly important requirement as world
ment to the internal austenitic cladding have production of heavier crude oils increases. In addition,
produced troublesome cracking in many reactors. production and upgrading of synthetic crude oils from
This is effectively avoided by limiting ferrite liquefied coal, oil shale, and tar sands will require many
content of austenitic weldmetals and making at- hydroprocessing reactor vessels.
tachment welds after the final heat treatment To understand the evolution of 2 %Cr-1Mo steel's
during fabrication. use in hydroprocessing reactors, one must go back to
4. Hydrogen charged into a reactor shell during op- Germany in the 1930's. German coal liquefaction plants
eration may have the potential to cause fracture often used forged vessels of quenched and tempered
during or following shutdown depending upon steels alloyed with chromium, molybdenum, vanadium,
operating temperature and wall thickness. Hy- and tungsten for resistance to hydrogen attack. The first
drogen outgassing procedures are recommended American hydrocracker reactors were fabricated from
for those reactors considered to have sensitivity annealed 2 %Cr-1Mo steel in the late 1950's. When
to thermally charged hydrogen. larger hydrocracking plants were considered, the idea
of quenching and tempering 2 %Cr-1Mo to increase
I. Basic Considerations strength of the steel made possible manufacture of
vessels with increased catalyst volume for a given vessel
A. Introduction weight. Large hydroprocessing reactors are ponderous
Thick walled reactor vessels are a significant and vessels, some of which are over 100 ft long, with shells

2 WRC Bulletin 275