Nitration. Recent Laboratory and Industrial Developments

287 Pages·1996·25.447 MB·English

by  Lyle F. Albright, Richard V. C. Carr, and Robert J. Schmitt (Eds.)

1 Nitration
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In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
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In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
ACS SYMPOSIUM SERIES 623
Nitration
Recent Laboratory and
Industrial Developments
1
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62 Lyle F. Albright, EDITOR
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6-
99 Purdue University
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10 Richard V. C. Carr, EDITOR
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oi: Air Products and Chemicals, Inc.
s.org 96 | d
bs.ac4, 19 Robert J. Schmitt, EDITOR
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9 | http://pate: April SRI International
0D
20n
22, atio
ber blic Developed from a symposium sponsored
ou
Oct P by the Division of Industrial and Engineering Chemistry, Inc.,

at the 209th National Meeting
of the American Chemical Society
Anaheim, California,
April 2-7, 1995
American Chemical Society, Washington, DC 1996
In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Library of Congress Cataloging-in-Publication Data
Nitration: recent laboratory and industrial developments / Lyle F.
Albright, editor, Richard V. C. Carr, editor, Robert J. Schmitt, editor.
p. cm.—(ACS symposium series, ISSN 0097-6156; 623)
"Developed from a symposium sponsored by the Division of Industrial
and Engineering Chemistry, Inc., at the 209th National Meeting of the
American Chemical Society, Washington, D.C., April 2-7, 1995."
01 Includes bibliographical references and indexes.
0
w
3.f ISBN 0-8412-3393-4
2
6
0 1. Nitration—Congresses.
6-
9
19 I. Albright, Lyle Frederick, 1921- . II. Carr, Richard V. C.,
k- 1947- . III. Schmitt, Robert J., 1952- . IV. American Chemical
1/b Society. Division of Industrial and Engineering Chemistry.
2 V. American Chemical Society. Meeting (209th: 1995: Washington,
0
1 D.C.) VI. Series.
0.
1
oi: QD63.N5N57 1996
s.org 96 | d 547'.26—dc20 96-110C9I6P
bs.ac4, 19
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9 | http://pate: April This book is printed on acid-free, recycled paper.
0D Copyright © 1996
20n
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In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
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In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Foreword
THE ACS SYMPOSIUM SERIES was first published in 1974 to
provide a mechanism for publishing symposia quickly in book
form. The purpose of this series is to publish comprehensive
books developed from symposia, which are usually "snapshots
in time" of the current research being done on a topic, plus
some review material on the topic. For this reason, it is neces
01 sary that the papers be published as quickly as possible.
0
3.fw Before a symposium-based book is put under contract, the
2 proposed table of contents is reviewed for appropriateness to
6
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6- the topic and for comprehensiveness of the collection. Some
9
19 papers are excluded at this point, and others are added to
bk- round out the scope of the volume. In addition, a draft of each
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2 paper is peer-reviewed prior to final acceptance or rejection.
0
1
0. This anonymous review process is supervised by the organiz
1
oi: er^) of the symposium, who become the editor(s) of the book.
bs.acs.org 4, 1996 | d Tmcahemen edaraaut-itrohenoasrd sy o tchf oepbnyo ,tr heav nitsdhe e su thbreemivrii etpw taheprees r fsian naacdl c potarhpdeei nresg d ttiotoo rtthsh,e e perrdeeciptooamrrse ,
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0D
20n tions of previously published papers are not accepted.
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ou
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In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Preface
ALTHOUGH NITRATION IS CONSIDERED to be a "mature" process,
important changes and advances have occurred in the past 20 years. A
comparison of this book with the 1975 ACS Symposium Series book enti
tled Laboratory and Industrial Nitrations, edited by Lyle F. Albright and
Carl Hanson, is just one of the many ways to document these advances.
A summary of these changes and an overview of nitration are
1
0 presented in Chapter 1 of this volume. The more theoretical aspects of
0
3.pr nitration and the production of polynitro compounds are discussed in
2
6 Chapters 2 through 6. The next several chapters discuss NO technol
96-0 ogy, including NO production and use as a nitrating age2nts. Several
9 2 s
k-1 nitrated compounds that are difficult to produce by conventional nitra
1/b tions can be produced rather easily by using NO. Industrial aspects of
2 2 s
0 nitration are discussed in the final chapters of the book. Important pro
1
10. cess improvements are reported.
oi: Several authors and attendees from the 1975 ACS symposium on
org 6 | d nitration were authors or attendees at the 1995 symposium. This book
acs.199 should be of value to all individuals interested in nitration: chemists,
ubs.24, engineers, administrators, experienced scientists, students, industrial
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Beck at Purdue University and Shelia Beltz at Air Products and Chemi
cals, Inc., who worked behind the scenes, having been burdened with
more than normal duties as a result of this book.
LYLE F. ALBRIGHT ROBERT J. SCHMITT
Purdue University SRI International
West Lafayette, IN 47907 Menlo Park, CA 94025
RICHARD V. C. CARR
Air Products and Chemicals, Inc.
Allentown, PA 18195-1501
December 12, 1995
xi
In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
Chapter 1
Nitration: An Overview of Recent
Developments and Processes
Lyle F. Albright1, Richard V. C. Carr2, and Robert J. Schmitt3
1School of Chemical Engineering, Purdue University,
West Lafayette, IN 47907
2Air Products and Chemicals, Inc., 7201 Hamilton Boulevard,
Allentown, PA 18195-1501
1
0
0 3SRI International, 333 Ravenswood Avenue, Menlo Park, CA 94025
h
c
3.
2
06 Although many chemists and chemical engineers consider nitration
96- processes as mature, if not ancient, considerable new information has
9
k-1 been obtained in the last 10-15 years that clarifies the chemistry and
1/b indicates methods to obtain previously unattainable or hard to attain
2
0 nitration products. New and improved nitration processes have also
1
0. been developed that minimize production costs and promise reduced
1
oi: safety hazards. Even more information pertaining to the nitrations can
s.org 96 | d be expected in the near future.
c9
bs.a4, 1 Nitration reactions have been investigated for many years in the laboratory, and
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200n D nitrated products are important high explosives including trinitrotoluene (TNT),
22, atio picric acid, nitroglycerine, nitrocellulose, and RDX. Dinitrotoluene (DNT) is another
ber blic nitrated product of major importance. It is converted to toluene diisocynates that are
ou then used to produce polyurethane foams, elastomers, fibers, and varnishes. Aniline
Oct P is produced from nitrobenzene formed by nitration of benzene. Several nitroparaffins

are produced commercially by the vapor-phase nitration of propane. Although the
term nitration is often restricted to reactions involving organic compounds, the
production of ammonium nitrate from ammonia and nitric acid is an example of the
nitration of an inorganic compound
Chemistry of Nitration
Aromatics, alcohols, glycols, glycerine, and amines are often nitrated by an ionic
mechanism using acid mixtures (containing nitric acid and a strong acid such as
sulfuric acid). Hughes, Ingold, et al. (1) indicated that nitronium ions (NO^'s)
present in the acid mixture attack these organic molecules to form an unstable
complex. When a proton is ejected from this complex, the nitrated hydrocarbon is
0097-6156/96/0623-0001$15.00/0
© 1996 American Chemical Society
In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
2 NITRATION
produced A C-N bond is formed when an aromatic is nitrated, but a O-N bond forms
when an alcohol (or hydrox group) is nitrated In the case of amine nitrations, a N-N
bond is formed. The strong acid in the acid mixture acts as a catalyst when nitric
acid is used and promotes the formation of NOj.
Olah, Malhotra, and Narang (2) have recently reviewed nitration chemistry
with a strong emphasis on nitronium ion salts. These salts, used as a replacement for
mixed acids, are often preferred choices for certain nitrations performed at anhydrous
NO2PF6,
conditions. The two best known salts, NO2BF4 and are effective nitrating
agents for deactivated substrates and for obtaining highly selective nitrations.
Anhydrous N0 (3) is now available, and it too has a wide range of uses, for
2 5
especially the synthesis of nitrocompounds that are unstable in mixed acid media and
for highly selective type nitrations. Anhydrous N2O5 is often prepared by
electrochemical oxidation of N2O4 (or NO2) dissolved in nitric acid (3). Separation
1
0 of N0 from the nitric acid can be performed; Chapters 7, 8, and 9 of this book
h0 2 5
c report recent developments. N2O5 is also readily prepared by oxidizing N2O4
3.
62 dissolved in an aptotic solvent (3,4,5). Suzuki et al. (6,7) have been able to nitrate
0
6- selectively certain aromatics using N2O4/O3/O2 mixtures. (CF3CO)2)0/HN03 can
9
19 be used for selective nitrations of some deactivated substrates, but it is not
bk- recommended since its use has resulted in several explosions.
1/
2
0 When toluene, phenol, or chlorobenzene are nitrated, three isomers of the
1
10. mononitrated product can be produced in each case. Considerable effort has been
oi: expended to develop procedures to produce the more desired isomers. For example,
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bs.a4, 1 nitrotoluene significantly. Recently Kwok and Jayasuriya (9) employed H-2SM-5
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0D positioned in the pores in such a way that nitration occurs mainly at the para position.
20n
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Oct P presence of select ion-exchange resins. An ion-exchange resin with correct pore

structure might become a highly desired catalyst.
The nitrosonium ion (NO+) may be the ion that sometimes attacks easily
nitratable aromatics (11). The attached nitroso group is then oxidized to form a N0
2
group. Much effort has also been given to better identifying by-products including
some which can lead to explosions or other safety problems.
Free-radical reactions are often employed to nitrate paraffins (12). Nitrations
N2O4
using nitric acid or are frequently performed in the gas-phase although on
some occasions liquid-phase processes are used For gas-phase nitrations using nitric
acid, temperatures employed are frequently 380-420°C. Such temperatures cause a
small fraction of the nitric acid to decompose producing the following free radicals:
•NO2
and ΌΗ. Both radicals react with paraffins to produce alkyl radicals. These
latter radicals react with nitric acid to produce nitroparaffins and ΌΗ, and a chain
In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
1. ALBRIGHT ET AL. An Overview of Recent Developments and Processes 3
reaction then occurs. ·Ν0 can also react with an alkyl radical to form a nitroparaffin
2
or an alkyl nitrite. These nitrites are relatively unstable, and when they decompose,
lower molecular weight alkyl radicals and/or oxygenated hydrocarbons are often
produced. When nitric acid is used as the nitrating agent for propane, only 35-40%
of the nitric acid reacts to form nitroparaffins. In this case, l-nitropropane, 2-
nitropropane, nitroethane, and nitromethane are all produced. Oxygenated products
include aldehydes, alcohols, and CO. NO and other oxides of nitrogen are also
produced.
When Ν2Ο4 is used as a nitrating agent, temperatures of 200-250°C are
generally sufficient. Ν2Ο4 decomposes readily producing ·Νθ2, which reacts at
these low temperatures to produce alkyl radicals. The alkyl radicals and ·Νθ2 then
combine to produce nitroparaffins.
1 For free-radical nitrations of paraffins, dinitroparaffins are not produced when
0
h0 the reaction conditions are in the 380-420°C range. 2,2-dinitropropane has, however,
c
3. been produced at lower temperature using a liquid-phase nitration process. At higher
2
06 temperatures, intermediate radicals apparently decompose before dinitroparaffins are
96- produced.
9
1
bk- Although no known attempts have been made to develop a mathematical
21/ model for the free radical nitration of paraffins, sufficient information is probably
0
0.1 available to develop such a model for the vapor-phase nitration of cyclohexane with
oi: 1 N2O4 (13). For this nitration, concentrations of nitrocyclohexane, cyclohexylnitrite,
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c9
bs.a4, 1 however, needed on the side reactions that occur after the nitroparaffins are formed.
u2 Part of these nitroparaffins degrade or are oxidized. Some heavier nitroparaffins may
9 | http://pate: April rceoancvte rftoerdm tion gn itlroowmeert hmanoele.c ular weight nitroparaffins, e.g., a nitropropane may be
200n D Victor Meyer processes, or modifications of them, are also employed to
22, atio produce nitroparaffins. Such processes are of limited industrial importance.
ber blic
ou Physical Steps During Ionic Nitrations
Oct P

During many ionic-type nitrations, two immiscible liquid phases are often present
Using the nitration of benzene with mixed acids as an example, transfer steps are
obviously important in order to contact the reactants. NO$ produced in the acid
phase must be contacted with benzene initially present in the hydrocarbon phase.
The main reactions are generally thought to occur at or at least near the interface
between the two phases (12). A large interfacial area would obviously promote rapid
reactions. Relatively little quantitative information has been found in the literature
on the values of the interfacial area/volume of the dispersions in the reactor or on
which is the preferred continuous phase and which the dispersed phase.
About 30-50 years ago, batch nitrations of benzene or toluene frequently
required 30-60 minutes to complete. In some modern continuous-flow reactors, the
nitration is completed within several seconds or even within one second. Yet the
nitric acid in some of these units is almost completely reacted. The intensity of
In Nitration; Albright, L., el al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.