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1.
The basis of most of our study of industrial chemicals thus far has been
the top 50. These chemicals are produced utilizing some fascinating
processes on a large scale, and an understanding and appreciation of these
chemicals, their manufacture and uses, provides the student with a solid
background in industrial chemicals. We might ask ourselves what comes
next? What are some other important large-scale chemicals that, though not
made quite at the volume of the top 50, nevertheless in their own right make
important contributions to the chemical industry?
In 1988 we made the first attempt at developing a list of the second 50
chemicals arranged by approximate U.S. production. This list and the
manufacture and uses of the chemicals were discussed in two papers. The
list contains very interesting chemistry and can bring out many instructive
features on the day-to-day importance of chemistry. The list was revised and
incorporated into the text on industrial chemistry in 1992. We have again
updated this list for this book to see what trends have occurred over a tenyear period. This is a valuable reference to those interested in studying
commodity chemicals in greater detail than what the top 50 list offers.
Indeed in previous chapters we have included some of these chemicals in our
discussions, especially those that are monomers for important polymers to be
mentioned later. Nearly half of the second 50 have been noted already in
passing. This chapter will present these compounds as a unit, discuss the
second 50 list in general terms, and summarize briefly each of the 50
chemicals in regard to manufacturing methods and use. The list of
1999
1992
1988
Chemical
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
51
53
54
84
51
53
66
59
60
57
55
~
65
60
57
69
64
63
99
91
58
69
71
94
56
63
73
82
52
61
90
62
89
58
66
71
Phosgene
Acetic anhydride
Linear alpha olefms
Tall oil
Calcium chloride
Caprolactam
Isopropyl alcohol
Acrylic acid
Hexamethylenediamine
Hydrogen cyanide
-Butyl alcohol
Borates
Aniline
Sodium sulfate
Hydrogen peroxide
Ethanol (synthetic)
Methyl methacrylate
Methylene diphenyl diisocy.
Phthalic anhydride
Methyl chloride
Acetone cyanohydrin
Cyclohexanone
o-Xylene
Sodium bicarbonate
Potassium sulfates
Propylene glycol
Butyl acrylate
Toluene diisocyanate
Linear alkylbenzenes
Ethanolamines
Diethylene glycol
Sulfur dioxide
2-Ethylhexanol
Acetaldehyde
^-Paraffins
72
93
75
81
84
96
98
85
77
74
85
91
75
78
81
83
80
73
70
Prod.
Bill.
Ib
2.60
2.10
2.00
.94
.80
.60
.48
.47
.45
.44
.40
.39
.34
.28
.26
.22
.18
.14
.13
.12
.10
.10
.09
.08
.05
.05
1.00
0.90
0.85
0.85
0.78
0.78
0.77
0.73
0.71
Ave. %
Ann.
Growth
4.0
1.5
4.4
1.0
1.5
2.3
0.5
7.0
4.5
3.0
2.5
0.5
5.4
-2.0
9.0
2.0
2.0
7.0
3.5
2.5
3.7
8.3
2.0
3.5
5.0
3.0
5.5
2.7
1.5
2.5
2.5
2.0
1.0
4.0
0.5
Ave.
Price
C/Ib
74
50
60
5
11
93
34
87
116
60
51
25
49
6
42
32
70
115
42
39
73
13
46
9
67
82
100
58
58
39
12
56
46
21
Ave. %
Ave.
Prod.
1988
1992
Ann.
Bill.
Chemical
1999
Price
Growth
C/lb
Ib
68
79
1.2
Phosphorus
86
125
0.70
0.64
Nonene
96
89
87
8.2
22
0.64
79
-0.5
46
Methyl
ethyl
ketone
88
~
95
0.62
1,4-Butanediol
89
4.6
116
88
3.2
186
87
90
0.58
Potassium hydroxide
Maleic anhydride
98
2.5
53
0.56
91
92
37
0.52
Sorbitol
3.5
65
45
0.52
Sodium tripolyphosphate
93
-5.0
Chloroform
95
94
30
0.52
2.0
Bromine
56
95
5.0
0.50
Isobutane
68
8
0.49
96
-1.9
87
Hydrofluoric acid
97
-2.0
65
0.49
1-Butene
48
100
90
7.0
0.48
98
93
Glycerol
99
3.0
60
0.46
__
__
54
0.45
Ferric chloride
100
5.0
Source: Chemical Profiles and Chemical Prices in Chemical Marketing Reporter, Facts
and Figures in Chemical and Engineering News, and Chemical and Economics
Handbook
chemicals with their rank, production, growth, and prices is given in Table
13.1.
Production figures are sometimes very difficult to obtain for chemicals.
A number of sources have been examined in detail and recent production
amounts were found for most chemicals in an attempt to generate the second
50. Generally, the guidelines for selection of the chemicals are similar to
those for the top 50 list. A single chemical, or a commercially useful,
closely related family of chemicals, is included. No polymers are listed.
Some chemicals do not appear on the list, or are lower than what they might
be due to a large captive use and unofficially reported production. We make
no claim that the exact ranking is correct. Nevertheless we feel the list as
developed is quite functional. Literature to 1999 is covered.
2.
C4 Fraction
Benzene
Acetaldehyde
Acetic anhydride
Diethylene glycol
Ethanol
Ethanolamines
Linear alpha olefms
Acetic anhydride
Hexamethylenediamine
Isobutane
1-Butene
Maleic anhydride
Methyl ethyl ketone
Aniline
Caprolactam
Cyclohexanone
Linear alkylbenzenes
Methylene diphenyl diisocy.
Propylene
Methane
Acetone cyanohydrin
Acrylic acid
Butyl acrylate
rc-Butyl alcohol
2-Ethylhexanol
Glycerol
Hexamethylenediamine
Hydrogen cyanide
Isopropyl alcohol
Methyl methacrylate
Propylene glycol
Acetic anhydride
1,4-Butanediol
Butyl acrylate
-Butyl alcohol
Chloroform
2-Ethylhexanol
Hydrogen cyanide
Methyl chloride
Methylene diphenyl diisocy.
Methyl methacrylate
Phosgene
Toluene diisocyanate
Xylene
Toluene
Phthalic anhydride
o-Xylene
Other Sources
1 ,4-Butanediol
Glycerol
Linear alpha oleflns
Linear alkylbenzenes
Nonene
^-Paraffins
Sodium bicarbonate
Sorbitol
Tall oil
Toluene diisocyanate
3.
4.
Derivative
Acetic anhydride
Methyl methacrylate
Butyl acrylate
Methylene diphenyl diisocyanate
Methyl ethyl ketone
Butyl acrylate
Acetone cyanohydrin
Linear alkylbenzenes
Linear alkylbenzenes
Linear alpha olefms
Nonene
Methylene diphenyl diisocyanate
Toluene diisocyanate
Phthalic anhydride
5.
The following sections briefly mention the one or two processes used to
make the chemical on a large scale. Then the chemical's uses are given with
approximate percentages. A close study of this chemistry uncovers many
interesting relationships among all 100 top chemicals in the U.S. The
section numbers below correspond to the ranking of chemicals from 51-100
in Table 13.1.
51. Phosgene
Phosgene is manufactured by reacting chlorine gas and carbon monoxide
in the presence of activated carbon. Much of the market is captive. The
merchant market is small.
^CH3(CH2)nCH=CH2
n = 3 to 15
* Na2SO4 + 2RCOOH
56. Caprolactam
Caprolactam is discussed more completely in Chapter 11, Section 5. It is
made from cyclohexane by oxidation to cyclohexanone-cyclohexanol
mixture, formation of cyclohexanone oxime, and acid-catalyzed
rearrangement.
cyclohexane
or
phenol
Acrylic acid and its salts are raw materials for an important range of
esters, including methyl, ethyl, butyl, and 2-ethylhexyl acrylates. The acid
and its esters are used in polyacrylic acid and salts (32%, including
superabsorbent polymers, detergents, water treatment chemicals, and
dispersants), surface coatings (18%), adhesives and sealants (15%), textiles
and non-wovens (12%), plastic modifiers (5%), and paper coating (3%).
^ 2HCN + 6H2O
O)
(2)
H-Butyl alcohol is used for butyl aery late and methacrylate (36%), glycol
ethers (31%), solvent (13%), butyl acetate (12%), and plasticizers (4%).
62. Borates
The principal chemicals that make up this general category are borax
pentahydrate (Na2B4O7^SH2O), anhydrous borax (Na2B4O7), borax
decahydrate (Na2B4O7MOH2O), and boric acid (H3BO3 and HBO2). These
chemicals all begin with boron minerals from brines. The metal borates such
as borax react with strong mineral acids to form boric acid. A large sodium
borate deposit was discovered in California in 1913 and this has become the
principal world source of sodium borates and boric acid.
Glass fiber insulation (30%) is the primary use of borates. Other uses
include textile glass fiber (18%), soaps, detergents, and bleaches (10%),
glass (10%), agriculture (7%), and flame retardants (6%).
63. Aniline
Aniline is discussed further in Chapter 11, Section 6. It is made by the
reduction of nitrobenzene (83%) by either catalytic hydrogenation or acidic
catalyst
** Na2SO4 + 2H2O
* CH3-CH2-OH
MDI
Rigid polyurethane foams account for 80% of MDI use, especially for
construction (about half of this use), refrigeration, packaging, and tank and
pipe insulation.
Other uses are reaction-injection molding (RIM)
applications (13%) and cast elastomers (2%).
^CH 3 Cl + H2O
^ CH3Cl + HCl
72. Cyclohexanol/Cyclohexanone
Cyclohexanol and cyclohexanone are made by the air oxidation of
cyclohexane (81%) with a cobalt(II) naphthenate or acetate or benzoyl
peroxide catalyst at 125-16O0C and 50-250 psi. Also used in the
manufacture of this mixture is the hydrogenation of phenol at elevated
temperatures and pressures, in either the liquid or vapor phase (19%). The
ratio of alcohol to ketone varies with the conditions and catalysts.
mixed oil
"Mixed oil" is used for the manufacture of caprolactam (53%, for nylon
6) and adipic acid (44%, for nylon 6,6). Cyclohexanol is favored if the use
is for adipic acid; cyclohexanone is favored if the mixture is to be made into
caprolactam.
73. 0-Xylene
There are two methods of manufacture of the xylenes. The major one is
from petroleum by catalytic reforming with a platinum-alumina catalyst.
The second method (which has been developed recently) is by processes
involving the disproportionation of toluene or the transalkylation of toluene
with trimethylbenzenes The ortho isomer is separated from the meta and
para isomer by fractional distillation.
o-Xylene is used almost exclusively as feedstock for phthalic anhydride
manufacture.
74. Sodium Bicarbonate
Sodium bicarbonate can be made by treating soda ash with carbon
dioxide and water. Sodium bicarbonate is called bicarbonate of soda or
baking soda. It is also mined from certain ores called nahcolite.
Na2CO3 H- CO2 + H2O
^ 2NaHCO3
The uses of sodium bicarbonate include food (32%), animal feed (24%),
cleaning products (9%), pharmaceuticals and personal care (9%), chemicals
(8%), water treatment (6%), and fire extinguishers (2%).
75. Potassium Sulfates
Potassium sulfate (K2SO4) is produced from mixed minerals or brines
such as langbenite ore, K2SO4 2MgSO4, found in Mexico. Reaction with
potassium chloride gives pure potassium sulfate. In the Mannheim process
potassium chloride reacts with sulfuric acid to give the sulfate.
(1) K2SO4 -2MgSO4 + 4KCl
(2) KCl + H2SO4
KCl + KHSO4
^ KHSO4 + HCl
* K2SO4 + HCl
Ni(CO)4
* CH2-CH-COOR
HCl
2 CH2=CH-COOH
^ CH2=CH-COOR
Acrylates find major use in coatings (45%), textiles (25%), and fibers,
polishes, paper, and leather (15% collectively).
78. Toluene Diisocyanate (TDI)
Toluene diisocyanate (TDI) is made from the reaction of 2,4toluenediamine and phosgene. The diamine is made by reduction of
dinitrotoluene, which in turn is manufactured by nitration of toluene. See
Chapter 11, Section 7.
80. Ethanolamines
Ethanolamines are made by reacting ethylene oxide and excess ammonia,
followed by separation of unreacted ammonia and the three ethanolamines.
The proportion of the three products depends on reaction conditions.
monoethanolamine (MEA)
diethanolamine (DEA)
(HO- CH2-CH2)2NH
triethanolamine (TEA)
(HOCH2- CH2)3N
^ SO2
Uses include chemicals (40%), pulp and paper (23%), food and
agriculture (14%), water and waste water treatment (9%), metal and ore
refining (6%), and oil recovery and refining (4%).
83. 2-Ethylhexanol
2-Ethylhexanol is produced by aldol condensation of butyraldehyde
followed by reduction. It can also be made in one step from propylene and
synthesis gas converted to butanols and 2-ethylhexanol without isolating the
butyraldehydes. See Chapter 10, Section 6.
87. Nonene
Originally made by the trimerization of propylene to give a branched
nonene, this product now has limited use for detergents because of
nonbiodegradability. Cracking and dehydrogenation of w-paraffms is now
the preferred method, giving very linear chains. With good linear wax, an
olefin product containing as much as 90% linear alpha olefins can be
prepared.
89. 1,4-Butanediol
1,4-Butanediol, also known as tetramethylene glycol, is produced by the
hydrogenation of butynediol (made from acetylene and formaldehyde).
HC=CH + 2HCHO
^ HO-CH2-C=C-CH2-OH
2 2
HO(CH 2 ) 4 OH
92. Sorbitol
D-glucose
D-sorbitol
94. Chloroform
Chloroform is produced by the chlorination of methylene chloride, which
in turn is made by the chlorination of methyl chloride and methane.
CH4 + Cl2
CH3Cl + Cl2
^ CH2Cl2 + HCl
CH2Cl2 + Cl2
95. Bromine
Bromine is present in brines as sodium bromide. The brines are heated to
about 9O0C and treated with chlorine to oxidize the bromide ions. The
elemental bromine is then separated from the brine solution by blowing out
with steam or air. The crude brominecontaining water, chlorine and
organic matteris purified, typically by a distillation process, and then dried
with concentrated sulfuric acid. About 95% of the bromine is recovered
from the brine.
2NaBr + Cl2
** Br2 + 2NaCl
96. Isobutane
Isobutane can be isolated from the petroleum 4 fraction or from natural
gas by extraction and distillation.
extraction
distillation
There are two major uses of isobutane. Dehydrogenation to isobutylene
is a large use. The isobutylene is then converted into the gasoline additive
methyl /-butyl ether. Isobutane is also oxidized to the hydroperoxide and
then reacted with propylene to give propylene oxide and /-butyl alcohol.
The /-butyl alcohol can be used as a gasoline additive, or dehydrated to
isobutylene. See Chapter 8, Section 5.
98. 1-Butene
The steam-cracking of naphtha and catalytic cracking in the refinery
produce the 4 stream, which includes butane, 1-butene (butylene), cis- and
/r<ms-2-butene, isobutylene, and butadiene. 1-Butene can be separated by
extracting the isobutylene with sulfuric acid and distilling the 1-butene away
from butane and butadiene. About 54% is made this way. See Chapter 8,
Section 4.1. It is also made by Ziegler ethylene oligomerization with other
longer linear alpha olefins (25%). Shell uses a proprietary non-Ziegler
oligomerization (21%).
CnH2n+2
> CH3-CH2-CH=CH2 + H2
99. Glycerol
Approximately 27% of glycerol (glycerin) comes from a synthetic
process, the hydrolysis of epichlorohydrin. The remaining 73% is made
from fats as a by-product of soap manufacture.
Glycerol is used for drugs, personal care (including toothpaste), skin, and
hair care products (42%), food and beverages (18%), tobacco (13%),
polyether polyols for urethanes (11%), and alkyd resins (6%).
^ 2FeCl3
Suggested Readings
Chemical Economics Handbook gives production, uses, and prices for
chemicals.
Chemical Profiles and Chemical Prices series in Chemical Marketing
Reporter provide many production estimates, use patterns, and
prices for chemicals.
Chenier, P.J.; Artibee, D.S. J. Chem. Educ. 1988, 65, 244-250.
Chenier, P.J.; Artibee, D.S. J. Chem. Educ. 1988, 65, 433-436.
Facts and Figures, an annual series in Chemical and Engineering News,
gives production for some chemicals.