Академический Документы
Профессиональный Документы
Культура Документы
Nickel-Containing Alloys
in Organic Acids
and Related Compounds
Table of Contents
PART I.
INTRODUCTION
A. The Organic Acids
4
B. Scope
4
C. Corrosion Testing in Organic Acid Media
4
PART II. ACETIC ACID
A. General
5
B. Austenitic Stainless Steels
5
1. General
5
2. Effect of Alloy Composition
6
3. Effect of Contaminants
10
4. Effect of Temperature
12
5. Effect of Microstructure
14
6. Quality Control
15
C. Martensitic & Ferritic Stainless Steels
15
D. Duplex Austenitic-Ferritic and Precipitation
Hardening Stainless Steels
15
E. Iron-Base Nickel-Chromium-Copper
Molybdenum Alloys
16
F. Nickel-Base Chromium-Iron-MolybdenumCopper Alloys
17
G. Iron-Base Nickel-Chromium-Molybdenum Alloys18
H. Nickel-Base Molybdenum-Chromium-Iron Alloys 18
I.
Nickel-Copper Alloys
20
J. Copper-Nickel Alloys
21
K. Nickel-Chromium Alloys
23
L. Iron-Nickel-Chromium Alloys
23
M. Nickel-Base Molybdenum Alloys
24
N. Nickel
24
O. Process and Plant Corrosion Data
25
l. Acetic Acid Production
25
a. Oxidation of Acetaldehyde
25
b. Liquid Phase Oxidation of
Straight-Chain Hydrocarbons
26
c. Methanol-Carbon Monoxide Synthesis
28
2. Acetic Acid Storage and Shipping
28
3. Vinegar Production and Storage
29
P. Acetic Anhydride
29
PART III. OTHER ORGANIC ACIDS
A. Formic Acid
31
B. Acrylic Acid
36
C. C3 Through C8 Acids
38
(Propionic, Butyric and Higher Acids)
D. Fatty Acids
44
(Lauric, Oleic, Linoleic, Stearic, Tall Oil Acids)
E. Di and Tricarboxylic Acids
46
(Oxalic, Maleic, Phthalic, Terephthalic,
Adipic, Glutaric and Pimelic Acids)
F. Naphthenic Acids
52
G. Organic Acids with Other Functional Groups
53
1. Glycolic Acid
53
2. Lactic Acid
53
3. Tartaric Acid
54
4. Citric Acid
54
5. Chloroacetic Acids
56
6. Amino Acids
57
7. Sulfoacetic Acid
57
PART IV ESTER PREPARATIONS
A. Acetic Esters
58
B. Phthalate Esters
60
C. Esterification of Fatty Acids
60
D. Acrylate Esters
60
References
Trademarks
Page 1
64
Inside Back Cover
Ni
Fe
Cr
Mo
Cu
Si
Mn
Other
WROUGHT ALLOYS
Stainless SteelsAustenitic
AISI Type 201
AISI Type 202
AISI Type 204
AISI Type 204L
AISI Type 216
AISI Type 216L
AISI Type 304
AISI Type 304L
AISI Type 309
AISI Type 310
AISI Type 316
AISI Type 316L
AISI Type 317
AISI Type 317L
AISI Type 318
AISI Type 321
AISI Type 330
AISI Type 347
4.5
5.0
5.0
6.0
6.0
6.0
9.5
10.0
13.5
20.0
13.0
13.0
14.0
14.0
14.0
11.0
35.0
11.0
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
17.0
18.0
18.0
18.0
19.5
19.5
18.5
18.5
23.0
25.0
17.0
17.0
19.0
19.0
18.0
18.0
15.0
18.0
2.25
2.25
3.25
3.25
3.25
NITRONIC alloy 50
12.5
Balance
22.0
6.5
4.5
4.0
7.0
7.0
Balance
Balance
Balance
Balance
Balance
Balance
29.0
34.0
0.15 Max
0.15 Max
0.08 Max
0.03 Max
0.08 Max
0.03 Max
0.08 Max
0.03 Max
0.20 Max
0.25 Max
0.08 Max
0.03 Max
0.08 Max
0.03 Max
0.08 Max
0.08 Max
0.25 Max
0.08 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
6.5
8.0
8.0
8.0
8.0
8.0
1.5
1.3
2.0 Max
2.0 Max
1.7
1.8
2.0 Max
2.0 Max
2.5 Max
2.0 Max
2.0 Max
2.0 Max
N 0.25 Max
N 0.25 Max
N 0.25 Max
N 0.25 Max
N 0.25-0.50
N 0.25-0.50
1.53.0
0.06 Max
1.0 Max
5.0
N 0.2-0.4, Cb 0.1-0.3
26.0
27.5
16.0
16.5
17.0
15.0
1.02.0
0.4
2.5
1.0
4.0
0.06 Max
0.10 Max
0.03 Max
0.07 Max
0.09 Max
0.09 Max
0.40
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
0.40
2.0 Max
12.0
1.0 Max
1.0 Max
1.0 Max
N 0.3
Cb + Ta 0.3
Al 1.1
Al 1.1
43.0
20.0
2.0 Min
3.0 Min
0.07 Max
1.0
0.8
39.0
20.0
2.5
3.3
0.07 Max
0.6
0.8
Cb + Ta 0.6
0.03
0.03
0.35
0.35
0.65
1.3
AI 0.15, Ti 0.9
W 0.5. Cb + Ta 2.12
Cb + Ta 10XC Min
Ti 5XC Min
Cb + Ta 10XC Min
Nickel-Base Chromium-Iron
Molybdenum-Copper Alloys
INCOLOY alloy 825
HASTELLOY alloy G
Iron-Base Nickel-Chromium
Molybdenum Alloys
ALLEGHENY alloy AL-6X
HAYNES alloy 20 Mod
JESSOP alloy JS-700
MULTIMET alloy
41.8
45.0
30.0
19.5
21.5
22.2
3.0
6.5
1.8
2.0
24.0
26.0
25.0
20.0
46.0
42.0
46.0
29.0
20.0
22.0
21.0
21.0
6.5
5.0
4.5
3.0
0.025 Max
0.05 Max
0.03
0.12
0.5 Max
1.0 Max
0.5
1.0 Max
1.5 Max
2.5 Max
1.7
1.5
Nickel-Base Molybdenum
Chromium-Iron Alloys
HASTELLOY alloy C(2)
HASTELLOY alloy C-276
HASTELLOY alloy C-4
HASTELLOY alloy N
INCONEL alloy 625
54.0
54.0
61 ..0
69.0
60.0
5.0
5.0
3.0 Max
5.0
5.0 Max
15.5
15.5
16.0
7.0
21.5
16.0
16.0
15.5
16.5
9.0
0.08 Max
0.02 Max
0.015 Max
0.06
0.1 Max
1.0 Max
0.05 Max
0.08 Max
0.3
0.5 Max
1.0 Max
1.0 Max
1.0 Max
0.3
0.5 Max
Nickel-Copper Alloys
MONEL alloy 4OO
MONEL alloy K-500
66.0
65.0
1.35
1.0
31.5
29.5
0.12
0.15
0.15
0.15
0.9
0.6
AI 2.8, Ti 0.5
10.0
20.0
30.0
1.25
0.75
0.55
88.0
78.0
67.0
76.0
80.0
7.2
15.8
20.0
0.1
0.04
Ti 4XC Min
Cb 0.30
Co 20.0, W 2.5, N
0.15,Cb + Ta1.0
Copper-Nickel Alloys
Copper-Nickel alloy C70600
Copper-Nickel alloy C71000
Copper-Nickel alloy C71500
0.3
0.4
0.5
Nickel-Chromium Alloys
INCONEL alloy 600
NICHROME V
Page 2
0.2
0.2
Alloys
Ni
Fe
Cr
Mo
Cu
Si
Mn
Other
Iron-Nickel-Chromium Alloys
INCOLOV alloy 800
INCOLOY alloy 804
32.0
41.0
46.0
25.4
20.5
29.5
0.3
0.25
0.04
0.05
0.35
0,38
0.75
0,75
61.0
5.0
1.0 Max
28.0
67.0
28.0
68.0
35.0
15.0
10.0
7.0
15.0
3.0 Max
15.0
20,0
20A
20.0
3.0
10.0
7.0
0.06
0.15
0.10
1.0 Max
2.0
1.5
Stainless Steels
ACI CD-4MCu
ACI CF-3
ACI CF-3M
ACI CF-8
ACI CF-8M
ACI CG-8M
ACI HK
5.5
10.0
11.0
9.0
10.0
11.0
20.0
61.0
66.0
63.0
67.0
64.0
62.0
49.0
26.0
19.0
19.0
19.0
19.0
19.0
26.0
2.0
2.5
2.5
3.5
3.0
0.04 Max
0.03 Max
0.03 Max
0.08 Max
0.08 Max
0.08 Max
0.4
1.0 Max
2.0 Max
1.5 Max
2.0 Max
2.0 Max
1.5 Max
2.0 Max
1.0 Max
1.5 Max
1.5 Max
1.5 Max
1.5 Max
1.5 Max
2.0 Max
29.0
24.0
44.0
48.0
20.0
20.0
1.0
3.3
1.5 Max
0.6
8.0
58.0
28.0
2.0
3.0
0.75
0.75
24.0
20.0
44.0
50.0
21.0
16.0
5.0
2.0
5.0
57.0
26.0
2.0
0.5 Max
0.08
1.0 Max
58.0
5.0
22.0
6.0
6.0
0.2
0.2
58.0
57.0
6.0
3.0 Max
16.5
18.5
17.0
18.5
1.0 Max
1.0 Max
60.0
62.0
5.0
1.0 Max
3.0 Max 1.0 Max
28.0
31.5
80.0
75.0
70.0
55.0
49.0
3.0 Max
0.4
5.0
1.0
3.0
3.0 Max
12.5
28.0
28.0
31.0
3.0
8.0
8.0
5.0
5.0
3.0 Max
3.0 Max
3.0 Max
3.0 Max
30.0
29.0
1.5 Max
1.5 Max
20.0
30.5
70.0
55.0
2.2
5.0
WROUGHT ALLOYS
AI 0.3, Ti 0.6
CAST ALLOYS
0.20
0.07 Max
0.8
0.04
2.0 Max
0.5
9.5
1.25 Max
(1)
(2)
(3)
(4)
2.5
Sn 8.0, Zn 7.0, Ag 6.0
0.05 Max
Sn 4.0, Bi 3.75
0.05
0.7 Max 1.25 Max
0.05
4.5
1.25 Max B 0.05-0.55
2.35
1.0 Max 1.0 Max W 12.5, Others 1.0 Max,
Bal Co
1.0 Max 1.5 Max 1.0 Max W 14.0, Bal Co
1.1
1.5 Max 1.0 Max W 4.5, Bal Co
1.9
5.5
1.2
0.6
(5) Includes alloys such as CHLORIMET alloy 3, ILLIUM alloy W2, etc.
(6) Includes alloys such as cast HASTELLOY alloy B, ILLIUM alloy M1,etc.
(7) Includes alloys such as CHLORIMET alloy 2, ILLIUM alloy M2, etc.
(8) STELLITE alloys 3 and 4 are cast wear resistant alloys that are no longer
produced by Cabot Corporation.
* An improved version of this alloy, HASTELLOY alloy B-2 has
replaced HASTELLOY B.
Page 3
PART I. INTRODUCTION
B. Scope
This bulletin attempts to characterize the corrosion resistance of alloys in the wide range of exposure conditions
employed today in the production and handling of the
organic acids. Space does not allow the complete coverage
of alloy use in all organic acid processes, or even full
treatment of such a large subject as acetic acid production.
However, once the basic properties of the alloys in such
media are established, along with adequate warning of
problems to be avoided, the judicious choice of an alloy for
a similar application can usually be made. The major pitfall
in such use of data is assurance that the recorded conditions
of exposure are indeed the same as those existing in the
proposed application. Only parts per million of certain
contaminants in an organic acid process stream can have a
profound effect on the corrosion rate of an alloy. Thus, it is
critical to learn the details of proposed operating conditions,
as well as the possibilities for inadvertent changes in stream
composition.
Corrosion data reported throughout this bulletin must be
interpreted as providing valuable information regarding the
relative corrosion resistance of the various alloys in specific
environments and modes of testing. Retesting of the alloys,
particularly those containing chromium, under the same
apparent conditions may provide variations in corrosion
rates of two to three times. However. the relative resistance
of the various alloys normally remains the same.
Corrosion data for alloys in all of the many organic acids
are reported when they are available. Extensive data for the
more common acids encountered are reported. In addition,
data for representative homologues of the various types of
organic acids are reported. With this information as a guide,
the interested party should be able to select candidate
materials for an organic acid exposure of any type.
The nominal composition of alloys cited in the tables and
text are shown in the table on pages 2 and 3. An attempt has
been made to provide as comprehensive a listing of alloys as
possible to achieve the maximum utility from these data.
Some of the proprietary alloys have been improved by
compositional modifications. Where data exist for the newer
modification they are included; however, some data on the
obsolete alloys are included. Corrosion rates on the newer,
improved alloys may be assumed to be approximately
equivalent. Trademarks of proprietary alloys have been used
in the text and are listed on the inside back cover. All
materials are assumed to be in the mill annealed condition
unless notations to the contrary are shown.
Type 316L stainless steel tanks and piping and cast ACI CF-8M pumps
and valves are utilized in this plant handling organic acids. Courtesy
Walworth Company-Aloyco Valves.
Page 4
A. General
Acetic acid and its derivatives are produced in large quantities as commercial products. Perhaps of even greater
interest from a corrosion standpoint is the fact that in
industries processing many other organic chemicals, acetic
acid is a common impurity in process streams as a result of
the oxidation of lower compounds or the degradation of
larger molecules. Consequently, a knowledge of the corrosive potential of the acid is necessary to assure the
economic life of equipment or to prevent contamination of
process streams with metallic corrosion products.
Although acetic acid has a low ionization constant compared with many other acids, the effective acidity of
aqueous streams contaminated with the acid increases
rapidly with concentration. Table I shows change of pH
with concentration of acetic acid.
A wide range of alloys can be used in acetic acid
exposures. Those alloys renowned for resistance to oxidizing conditions are often a first choice for a specific exposure
while in a remarkably similar application the wisest choice
will be alloys used to combat reducing conditions. In some
process areas, both can be equally resistant and an economic
comparison is necessary before making a choice. However,
a thorough appraisal of each exposure must be made to
identify the optimum material of construction.
Page 5
pH
0.0006
0.006
0.06
0.6
6.0
60.0 (6%)
5.2
4.4
3.9
3.4
2.7
2.4
Reference 43
Cast ACI CF-8M valves and pumps in finished acetic acid storage
service. Piping and tanks are constructed of Type 316L stainless steel.
Courtesy Walworth Company-Aloyco Valves.
Page 6
TABLE II
Comparison of Cast Stainless Steels with Wrought
Type 316 Stainless Steel in Organic Acid Media
Test Conditions: All tests at boiling temperature for approximately 150 hours in laboratory.
Each result shown represents duplicate specimens.
Corrosion Rate
ACI CF-8M
Annealed
Temperature
Solution
Glacial Acetic Acid
50% Acetic Acid
10% Acetic Acid
85% Acetic-15% Formic
50% Acetic-15% Formic
85% Formic-15% Acetic
88% Formic Acid
50% Formic Acid
10% Formic Acid
5%*
Sensitized
10%*
5%*
mm/y mpy
117
102
100.5
109
106.5
104.5
104.5
102
100
242
216
213
228
224
220
220
216
212
.05
.03
<.03
.15
.30
.84
48
.64
.38
.05
.03
<.03
.18
33
.89
43
76
36
2
1
<1
6
12
33
19
25
15
2
1
<1
7
13
35
17
30
14
.03
.03
.03
.13
.18
.23
.28
.61
.46
10%*
Wrought
Type 316
Stainless
Steel
Annealed
.03
03
01
.15
.20
.25
.28
.66
.46
1
1
0.5
6
8
10
11
26
18
.05
Nil
Nil
.08
.25
.13
.33
.51
.43
CD-4MCu
mpy mm/y
2
Nil
Nil
3
10
5
13
20
17
Type 329
Stainless
Steel
ACI
Nil
Nil
Nil
<.03
08
15
18
.15
<.03
WORTHITE**
mpy mm/y
Nil
Nil
Nil
<1
3
6
7
6
<1
ALLOYCO
20***
03
Nil
Nil
<.03
<.03
03
05
.15
08
1
Nil
Nil
<1
<1
1
2
6
3
<.03
.03
<.03
<.03
<.03
.03
.03
.10
.10
<1
1
<1
<1
<1
1
1
4
4
mm/y
mpy
<.03
<.03
.64
1.35
1.65
8.38
<1
<1
25
53
65
330
*% Ferrite in alloy
**Trademark of Worthington Corp.
***Trademark of Aloyco, Inc.
TABLE III
Field Tests in Acetic Acid Distillation Columns
Location in Column
Test Duration (Days)
Temperature C (F)
Per Cent Acetic Acid
Alloy
Type 316 stainless steel
Type 304 stainless steel
Type 309 stainless steel
Type 329 stainless steel
Type 216 stainless steel
Type 410 stainless steel
Type 430 stainless steel
1
CARPENTER alloy 20Cb-3
2
JESSOP alloy JS-700
3
INCOLOY alloy 825
4
HASTELLOY alloy C*
5
CHLORIMET alloy 2
HASTELLOY alloy B
3
INCONEL alloy 600
3
MONEL alloy 400
C 10300 (Copper)
Nickel 200
Top
11
120 (248)
99.5+
mm/y
<.03
.30
.89
.03
<.03
Top
40
106 (223)
99.9+
mpy
<1
12
35
1
<1
mm/y
< .03
Mid
375
100 (212)
20
mpy
<1
>12.7
>12.7
<.03
.15
.08
.15
.08
6
3
6
3
<1
<1
.08
Corrosion Rate
mm/y
mpy
.05
2
>500
>500
<1
<.03
<.03
Bottom
62
121 (250)
99.9+
Page 7
.13
.03
5
1
mm/y
< .03
.05
mpy
<1
2
<.03
<.03
<.03
<1
<1
<1
Bottom
30
119 (246)
90
mm/y
.15
mpy
6
.05
<.03
.05
.13
.25
28
2
<1
2
5
10
11
41
16
TABLE IV
Comparison of Nickel and Manganese Austenitic
Steels in Organic Acid Exposures
Conditions: Duplicate specimens tested in the boiling
solution (temperatures shown) for 48 hours
or longer. Air not excluded or added.
Corrosion Rate
Temperature
Test Medium
Acetic acid, 100%
Acetic acid, 75%
Acetic acid, 50%
Acetic acid, 25%
Acetic acid 99%;
Acetic anhydride 1%
Acetic acid 90%;
Formic acid 10%
Formic acid, 20%
2-Ethyl butyric
acid, 100%
Esterification
1
mixture
Type 304
Stainless Steel
mpy
.18
160
275
280
CRUCIBLE*
alloy 223
C
117
104
102
100
F
242
219
216
212
mm/y
.46
4.06
6.98
7.11
mm/y
.18
.05
Nil
<.008
117
242
.33
13
2.26
109
102
228
216
.23
1.75
9
69
185
365
.53
86
187
.41
Type 316
Stainless Steel
mpy
7
2
<0.1
0.3
mm/y
.01
.01
.08
Nil
mpy
0.4
0.3
3
Nil
89
.22
8.5
.08
4.75
3.1
187
.17
.56
6.5
22
21
.04
1.5
.04
1.4
16
2.79
110
.02
0.7
(1) Synthetic mixture of 75% butyl acetate, 11% butanol,10% acetic acid, 4% water, 0.3% sulfuric acid.
*Trademark of Colt Industries, Inc.
Page 8
TABLE V
Corrosion of Alloys in Acetic-Hydroxy Acid Solution
Conditions:
Alloy
Type 304 Stainless Steel
Type 316 Stainless Steel
(annealed)
Type 316 Stainless Steel
(sensitized)
Type 216 Stainless Steel
Type 317 Stainless Steel
Type 326 Stainless
Steel (IN-744)
CARPENTER alloy 20Cb-3
INCOLOY alloy 825
JESSOP alloy JS-700
HASTELLOY alloy G
mm/y
mpy
.01
0.4
mm/y
1.12
mpy
44
Nil
<0.1
.09
3.7
.01
Nil
Nil
0.3
<0.1
<0.1
.11
.05
.08
4.2
2.0
3.2
Nil
.00
.01
Nil
Nil
<0.1
0.1
0.2
<0.1
<0.1
2.84
.05
.03
.01
.01
112
1.8
1.2
0.3
0.4
TABLE VI
Effect of Thermal Treatments on Molybdenum-Containing
Stainless Steels
Corrosive medium: Acetic acid 35%, formic acid 1.0%, water 64%.
Conditions
: Process liquid at 131 C (268 F) (boiling) for 84 days, air free.
Corrosion Rate
mm/y
mpy
Alloy
Condition of Specimen
Annealed
1 hr 677 C (1250 F) AC
4 hr 871 C (1600 F) AC, 1 hr 677 C (1250 F) AC
As-welded (316L rod)
Welded, 1 hr 704 C (1300 F) AC
Welded, 1 hr 871 C (1600 F) AC
As-welded (310 Mo rod)
Welded (310 rod) 1 hr 871 C (1600 F) AC
Annealed
2 hr 621 C (1150 F) AC
1 hr 677 C (1250 F) AC
As-welded (316 rod)
Welded, 1 hr 871 C (1600 F) AC
Annealed
4 hr 593 C (1100 F) AC
1 hr 677 C (1250 F) AC
As-welded (317 rod)
Welded, 1 hr 704 C (1300 F) AC
Annealed
1 hr 677 C (1250 F) AC
1 hr 1316 C (2400 F) AC + 1 hr 677 C (1250 F) AC
As-welded (318 rod)
Welded + 1 hr 704 C (1300 F) AC
Welded + 1 hr 871 C (1600 F) AC
.06
.06
.04*
.08
.08
.07
.06
.06
.39
.39
.65
.40
.71
.05
.16*
.68*
.04
.55*
.07
.07
.64*
.06
.07
.30
2.5
2.5
1.4*
3.2
3.0
2.6
2.3
2.4
15.5
15.3
25.5
15.9
27.7
2.0
6.3*
26.9*
1.73
21.5*
2.6
2.6
25.1*
2.4
2.6
12.0
Reference 11
TABLE VII
Corrosion of Alloys in Acetic-Formic Acid Process Mixtures
Corrosion Rate
Stream
Composition
Test
Temperature Period
Type 316
Stainless
Steel
Type 317
Stainless
Steel
CARPENTER
alloy 20
INCOLOY
alloy 825
HASTELLOY HASTELLOY
alloy C
alloy B
INCONEL
alloy 600
Nickel
200
MONEL
alloy 400
Arsenical
Admiralty
EVERDUR*
1010
100
212
452
03
.03
05
.61
24
.25
10
08
.05
91
196
55
.08
.05
.05
.03
<.03
<1
.10
6% Acetic Acid
10% Formic Acid
3% Water
81% Organics
81
178
55
15
.13
.08
.08
<.03
<1
.10
121
250
355
05
<.03
<1
.05
.08
.03
106
223
99
.51
20
.28
11
38
15
.18
.51
20
.03
days mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
Page 9
TABLE VIII
Corrosion of Metals in Acetic Acid Residue Still
Test Conditions: Test assembly installed in liquid and in
vapor space of still at temperatures of
80 to 100 C (176 to 212 F) for 2000
hours. Residues contain acetic acid,
anhydride, acetates, tar.
Corrosion Rate
Liquid
Alloy
Vapor
mm/y
mm/y
mpy
2.13
.97
2.01
2.01
1.22
.18
Nil
.05
.18
.76
.03
.03
Cast iron
Ni-Resist Type 11
Mild steel
Type 501 chrome steel
Type 430 stainless steel
INCONEL alloy 600
HASTELLOY alloy C
DURIMET* 20
Type 329 stainless steel
Type 304 stainless steel
Type 316 stainless steel
Type 317 stainless steel
mpy
84
38
79
79
48
7
Nil
2
7
30
1
1
1.32
.30
2.51
1.47
.36
.13
Nil
.13
.30
.36
.18
.05
52
12
99
58
14
5
Nil
5
12
14
7
2
3. Effect of Contaminants
Although pure acetic acid can be handled readily in many
alloys, the presence of only parts per million of other
chemical agents can render an alloy useless as a material of
construction.
Acetic anhydride is produced as a co-product in the
older acetaldehyde oxidation process for acetic acid, and
the anhydride can often be found in other acetic acid
process streams. When small quantities of the anhydride
exist in a glacial acid, a greatly accelerated attack on the
stainless steels can be anticipated. Tables IV, IX and X
incorporate data substantiating the adverse effect of
5
anhydride in acetic acid as reported by Elder and others.
The difference in the two commercial, glacial acids shown
in Table XI can probably be attributed to the presence of
anhydride in the product of Plant B. As the amount of
anhydride in the acid is increased, the rate of attack rapidly
drops to an acceptable level, and high concentrations of
anhydride are innocuous. (See section on Acetic
Anhydride.) However, the presence of small amounts of
anhydride sufficient to dehydrate the acid produces in6
creased attack on all alloys.
Oxygen may influence corrosion rates in acetic acid, and
other organic acids as well. Even though process streams
have been stripped of gaseous components in distillation
systems, the possibility of oxygen pickup from air leaks
into the system is present. The use of stainless steels as
materials of construction assures that no accelerated attack
will occur under such circumstances. Indeed, when corrosion of the stainless steels in a process system is higher than
desired, the rate of attack can often be reduced by
introducing oxygen into the system. Table XLIII shows
the effect of adding oxygen to a distillation column during
the processing of propionic acid. A hundred-fold reduction in the corrosion rate is evident as the oxygen provided
TABLE IX
Corrosion of Type 316 Stainless Steel in Acetic
Acid Solutions Containing Chlorides
Conditions: Duplicate 48-hour tests conducted at the
boiling temperature in glacial acetic acid with
additions made as shown.
Corrosion Rate
Diluent addition
to acid
None
0.2% Acetic Anhydride
0.1 % Water
0.3% Water
0.33% Water
0.50% Water
0.67% Water
1.0% Water
0
mm/y
1.98
.03
.03
.03
mpy
78
1
1
mm/y
.05
1.27**
.08
.03
.18
3
.33
1
.66
7
.41
Page 10
61
mpy
17
48**
13
26
16
mm/y
2.10
1.19**
.71
.38
.36
mpy
81
75*
28
15
14
TABLE X
Corrosion of Alloys in Contaminated Acetic Acid
Condition: Duplicate tests of 120 hours conducted at
the boiling temperature with additions made
as shown.
Corrosion Rate
Test
No.
1
2
Type 316
CARPENTER
HASTELLOY
Stainless Steel alloy 20Cb-3
alloy C
Test Medium
mm/y mpy
mm/y mpy mm/y mpy
Glacial acetic acid
.08
3
<.03
<1
Nil
Nil
(1) + 0.1 % Acetic
.94
37
.84
33
.03
1
Anhydride
1.32
52
1.07
42
.03
1.73
68
1.47
58
.03
.03
.03
.03
TABLE XI
Corrosion of Type 316 Stainless Steel in
Acetic Acid Solutions
Conditions: Coupons exposed in hot wall tester to
glacial acetic acid from Plant A and Plant B
with the additions shown.
Acid
Tested
Addition
Exposure
Period
Specimen
Wall
Temperature
hr
Plant A
(None)
Plant A
1%water
Plant A
Plant A
Plant B
0.5% formic
1.0% formic
(None)
Plant B
1 % water
48
96
68
92
48
48
68
96
48
136
146
132
131
137
141
149
152
140
277
295
270
268
278
286
300
306
284
Corrosion
Rate
mm/y
.23
.10
.03
.03
.03
<.03
7.80
12.55
.03
mpy
9
4
1
1
1
<1
307
494
1
TABLE XII
Corrosion of Type 316 Stainless Steel in Acetic Acid with
Additives at Higher Temperatures
Conditions: Laboratory tests in glacial acetic acid contained in pressure autoclaves at temperature
shown for multiple runs of 48 hours each. Data
averaged. Additions to the acetic acid made as
shown.
Corrosion Rate
Additive
None
1500 ppm
hydrogen peroxide
3000 ppm
hydrogen peroxide
3000 ppm H 2O2 +
1500 ppm
Fe +++ (a)
1500 ppm Fe+++ (a)
1500 ppm
hydrogen peroxide
*650 C ( 1202 F) for one hour
a = Added as FeOH(C 2H 3 O 2 ) 2
Page 11
Temperature
C
F
190
374
Annealed
Sensitized*
mm/y mpy mm/y mpy
.20
8
190
374
.23
190
374
.08
190
190
374
374
.69
.56
27
22
240
464
.61
24
.89
35
until excessive rates of attack are obtained. However, CF8M resists the effect of increased temperature quite well
and has potential for use at the 200 C (392 F) temperature.
Field applications utilizing CF-8M pumps in acid near this
temperature confirm the utility of the alloy for handling hot
acid when oxidizing conditions exist.
Table XII shows other data obtained in the upper
temperature region of Figure 1. Note the lower corrosion
rate for a Type 316 stainless steel at 190 C (374 F),
although the test period is longer. Sufficient peroxide
appears to be effective in reducing corrosion, even at these
high temperatures. The presence of ferric ion was detrimental at these temperatures as opposed to the beneficial
effect noted at lower temperatures.
Vapors of the acid at higher temperatures are not
aggressive in the absence of condensation (Tables VIII and
XIV). However, condensation or drippage of liquid on a hot
metal surface can produce excessive attack. In addition,
pitting of the austenitic stainless steels in acetic acid
exposures at the higher temperatures is possible.
It is obvious that careful assessment of the stability of the
300 series stainless steels in an acetic acid environment
must be made before discounting their use at even the
higher temperatures.
TABLE XIII
Corrosion of Nickel-Containing Alloys in Buffered
Acetic Acid at High Temperature
Test Conditions: Specimens exposed in a high pressure
autoclave at temperature of 200 C
(392 F) for 8 days to the following
solution without aeration or agitation:
15% acetic acid plus 19% ammonium
acetate aqueous solution at 250 psi.
Corrosion Rate
Alloy
4. Effect of Temperature
It has been shown that Types 316 and 316L stainless
steels are satisfactorily resistant to attack by all
concentrations of acetic acid to the boiling point and that
Type 304 stainless steel is acceptable for use in all
concentrations of acid less than approximately 90 per cent
to the boiling point. As the temperature is increased
beyond these points, the rate of attack on the stainless
steels in the liquid acid increases, but certainly not as
rapidly as the Arrhenius equation would indicate.
Laboratory and field data presented in Tables V and XI
through XIII show that for both wrought and cast alloys
the stainless steels remain useful at temperatures well
above the atmospheric boiling point. Various techniques
of testing can produce significantly different results and
ingenuity is required to establish stable conditions for the
desired test environment.
Figure 1 condenses considerable data generated by
Ohio State University personnel when exploring the
corrosion resistance of the cast alloys in acetic acid up to
9
200 C (392 F). The cast CF-8 alloy corrodes at increasingly greater rates as the temperature is increased
Page 12
mm/y
mpy
02
0.6
02
0.7
02
03
04
05
0.8
1.0
1.5
1.8
13*
5.2*
04*
1.5*
*Incipient pitting
TABLE XIV
Corrosion of Stainless Steels in Vapors Over 52 Per
Cent Aqueous Acetic Acid at High Temperature
Temperature
System
Pressure
psig
Corrosion
Rate
Alloy
142
288
35
mm/y
.03
153
308
55
.10
142
288
35
<.03
<1
153
306
55
.05
mpy
1
TABLE XV
Corrosion by Acetic Acid Under Heat Transfer Conditions
Temperature
Without
Heat Transfer
Test Medium
Acetic Acid
10%
50%
99.6%
Corrosion Rate
With Heat*
Transfer
Type 304
Stainless
Steel
Type 316
Stainless
Steel
CARPENTER
alloy 20 Cb-3
HASTELLOY
alloy B
INCONEL
alloy 600
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
101
102
118
214
216
244
110
125
140
110
125
140
110
125
140
230
257
284
230
257
284
230
257
284
<.03
<.03
<.03
<.03
3.30
5.33
5.59
6.35
1.75
6.60
8.64
51
<1
<1
<1
<1
130
210
220
250
69
260
340
20
<.03
<.03
<.03
<.03
<.03
<.03
<.03
<.03
<.03
<.03
33
.25
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
13
10
<.03
<.03
<.03
<.03
<.03
.05
.08
<.03
.18
.13
.05
2.54
<1
<1
<1
<1
<1
2
3
<1
7
5
2
100
.08
.18
.15
.10
.13
.13
.05
.05
<.03
.18
.18
.08
3
7
6
4
5
5
2
2
<1
7
7
3
.51
.71
.69
.20
1.24
1.12
.79
36
.56
.91
1.14
.36
20
28
27
8
49
44
31
14
22
36
45
14
MONEL
alloy 400
mm/y
mpy
51
1.30
580
14.73
>25.40 >1000
>25.40 >1000
76
1.93
120
3.05
145
3.68
130
3.30
1
.03
120
3.05
68
1.73
220
5.59
*Metal temperature
Reference 10. See that publication for apparatus and technique used.
TABLE XVI
Corrosion with Heat Exchange in Aqueous Acetic Acid Containing Additives
Test Conditions: Apparatus and procedure same as described in Reference 10. Metal temperature 110 C (230 F) with bulk liquid temperature of 100 C (212 F). Test periods
of 4 to 96 hours used. All results
represent duplicate specimens.
Corrosion Rate
Type 304
Stainless
Steel
Type 310
Stainless
Steel
Type 316
Stainless
Steel
Type 329
Stainless
Steel
CARPENTER HASTELLOY
alloy 20 Cb-3 alloy C-276
AMBRALOY*
901
MONEL
alloy 400
Test Medium
Acetic
Acid Additive
56% 1% H 2 SO 4
mm/y
36.07
mpy
1420
mm/y
Nil
mpy
Nil
mm/y
5.8415.24
mpy
230600
mm/y
Nil80
mpy
Nil30
mm/y
64
mpy
25
mm/y
mpy
mm/y
mpy
mm/y
.23
mpy
9
56%
5% H 2 SO 4
22.35
880
Nil61.57
Nil24 24
76.63
3017
5.72
225
17.93
706
36.58
1440
.91
36
25%
4% Formic
Acid
28.83
1135
50.8
200
.71
28
Nil
Nil
Nil
Nil
Nil
Nil
1.17
46
Page 13
TABLE XVII
Corrosion in Acetic Acid Vaporizer
Field Test: 312 hr, 140 C (284 F) mass temperature.
Chlorides present
Corrosion Rate
Alloy
Type 316 stainless steel, annealed
sensitized
Type 304 stainless steel
CARPENTER alloy 20Cb-3
INCONEL alloy 600
Titanium
HASTELLOY alloy C-276
*Dissolved
**Pitting
mm/y
mpy
8.13
320
6.86
270
33.02 min* 1300 min*
6.35
250
6.60
260
.08**
3**
.08
3
Page 14
Page 15
TABLE XVIII
Corrosion of Alloys in Acetic Acid
Corrosion Rate
Per Cent
Acetic Acid
5
5
10
20
20
20
25
25
25
30
40
50
50
60
75
75
75
95
95
99.9
99.9
99.9
100
100
100
100
100
Temperature
C
F
25
99
25
25
100
116
25
104
116
116
116
25
116
110
25
65
116
25
116
25
116
90
25
35
50
100
116
77
210
77
77
212
241
77
219
241
241
241
77
241
230
77
149
241
77
241
77
241
194
77
95
122
212
241
Cast Iron
mm/y
mpy
254
27.69
2.03
20.07
Type 410
Stainless Steel
mm/y
mpy
Carbon Steel
mm/y
mpy
.25*
10,000
57.15
.20*
127
.20*
1,090
7.62
1.02
16.51
.76
12.7
6.86
1.65
80
1.70
1.7811.18
790
10*
2250
8*
5000
8*
300
40
650
30
500
270
65
67
70440
1.274.86
.01
50585
0.3
Type 430
Stainless Steel
mm/y
mpy
<.03
<.03
<.03
3.05
4.27
.38
.25
<.03
<.03
<.03
1.027.62
1.02
1.27
6.86
Nil
1.27
.645.08
<1
<1
<1
120
168
15
10
<1
<1
<1
40300
40
50
270
Nil
50
25200
Ni-Resist
Type 2
mm/y mpy
.91
.53
.58
1.96
1.68
.53
36
21
23
77
66
21
alloy is particularly critical and must be thoroughly understood when appraising the alloy for acid services.
Duplex stainless steels can also exhibit good corrosion
resistance in acetic and other organic acid environments.
Type 329 stainless steel and cast ACI CD-4MCu are
examples. Tables II, III, VIII, XVI and XXVIII show the
excellent corrosion resistance evidenced by these alloys in
certain specific exposures. These alloys are also more
sensitive to changes in environment than are the austenitic stainless steels. However, in the proper application,
the alloy can exhibit good stability while providing resistance to stress-corrosion cracking. It is for this latter
reason that the duplex alloys are sometimes appraised for
organic acid use.
Page 16
TABLE XIX
75%
50%
25%
Corrosion Rate
Alloy
Type 430
Type 304
PH15-7Mo (as received)b
PH15-7Mo (Al 750)
PH15-7Mo (TH1050)
PH15-7Mo (RH950)
17-7PH* (as received)
17-7PH (A1750)
17-7PH (TH1050)
17-7PH (RH950)
17-4PH* (as received)
17-4PH (H900)
17-4PH (H1025)
17-4PH (H1150)
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
4.90
.43
<.03
08
08
08
30
38
28
25
25
28
33
23
193
17
<1
3
3
3
12
15
11
10
10
11
13
9
1.32
2.21
.05
<.03
30
18
46
10
03
05
15
03
25
05
52
87
2
<1
12
7
18
4
1
2
6
1
10
2
7.67
<.03
03
<.03
71
56
28
28
<.03
08
<.03
<.03
<.03
<.03
302
<1
1
<1
28
22
11
11
<1
3
<1
<1
<1
<1
4.27
<.03
<.03
<.03
76
51
<.03
<.03
<.03
.05
<.03
<.03
<.03
<.03
168
<1
<1
<1
30
20
<1
<1
<1
2
<1
<1
<1
<1
a. Average of duplicate specimens for three 48-hour exposure periods in boiling acid.
b. Heat Treatment A = Annealed
T = Transformation near 760 C (1400 F)
H = Hardening between 482-593 C (900-1100 F) of T or R material
R = Refrigerate treated to 73 C (100 F)
*Trademark of Armco Steel Corporation
Page 17
TABLE XX
25 C (77 F)
mm/y
Medium
10% Acetic Acid
HASTELLoy alloy B
HASTELLoy alloy C
HASTELLoy alloy D
HASTELLoy alloy N
HAYNES* alloy No. 25
MULTIMET* alloy
50% Acetic Acid
HASTELLOY alloy B
HASTELLOY alloy C
HASTELLOY alloy D
HASTELLOY alloy N
HAYNES alloy No. 25
MULTIMET alloy
99% Acetic Acid (Glacial)
HASTELLOY alloy B
HASTELLOY alloy C
HASTELLOY alloy D
HASTELLOY alloy N
HAYNES alloy No. 25
MULTIMET alloy
mpy
Corrosion Rate
66 C (151 F)
mm/y
mpy
Boiling
mm/y
mpy
.01
.01
.02
.03
Nil
Nil
0.5
0.2
0.6
1
Nil
Nil
.15
.01
.23
.07
Nil
Nil
6
0.2
9
2.7
Nil
Nil
.02
.01
.05
.03
.00
.00
0.7
0.4
2
1.2
0.1
0.1
.03
.00
.08
.03
Nil
Nil
1
0.1
3
1
Nil
Nil
.10
.00
.46
.06
Nil
Nil
4
0.1
18
2.5
Nil
Nil
.01
.00
.08
.04
.00
.00
0.4
0.1
3
1.7
0.1
0.1
.00
.01
.01
02
Nil
Nil
0.1
0.2
0.5
0.7
Nil
Nil
.01
.00
.13
.02
Nil
Nil
0.5
0.1
5
0.7
Nil
Nil
.01
.00
.02
.02
Nil
.00
0.2
0.1
0.9
0.8
Nil
0.1
Reference 45
Page 18
TABLE XXI
Comparison of Corrosion of Various Proprietary
Alloys in Acetic Acid Solutions
Conditions: Duplicate specimens tested in the boiling solution for 48 hours or longer. Air not excluded or added.
Corrosion Rate
Acetic
Acid,
glacial
Alloy
Type 316
Stainless Steel
INCOLOY alloy 825
IN alloy 102 (A)2
IN alloy 102 (HT)3
50%
10%
30%
Acetic Acid
Acetic Acid
Aqueous
50% Acetic
2%
Acetic Acid
Anhydride
Formic Acid
Esterification
1
Mixture
mpy
99%
90%
90%
Acetic Acid Acetic Acid Acetic Acid Acetic Acid
1% Acetic
10%
70%
10% Acetic
Anhydride Formic Acid
Anhydride
mm/y mpy mm/y mpy
.01
0.4
1.07
42
.03
<.03
<1
9.12
359
.23
.17
6.5
1.70
<.03
.03
<.03
67
<1
1.1
<1
20.24
.69
.71
.08
797
27
28
3
.36
.15
.10
.03
14
6
4
1
3.66
.18
.18
.28
144
7
7
11
<.03
<1
.08
.03
.28
11
HASTELLOY
<.03
<1
.38
15
.04
1.5
.28
11
alloy C-276
Titanium
<.03
.05
<1
<1
30
25
44
7
1.83
.69
1.19
.91
2.46
.03
.03
<.03
72
27
47
36
97
1
1
<1
6.12
.71
1.14
.05
4.09
.66
.36
241
28
45
2
161
26
14
<.03
.41
<1
16
<.03
.15
.76
.28
.08
<1
6
30
11
3
.05
1.45
.61
.56
57
24
22
1.47
58
.43
.69
17
27
5.84
230
10.67
1.50
420
59
INCONEL
<.03
HASTELLOY alloy D
.76
WAUKESHA * No. 23
.64
WAUKESHA No. 54
1.12
WAUKESHA No. 88
.18
KROMARC ** 55
JESSOP JS-700
4
CARPENTER alloy 20
Multiphase
MP35N***
CROLOY***** 16-1
Chromium Carbide
with 12%
nickel binder
1.
2.
3.
4.
Synthetic mixture of 75% butyl acetate, 11% butanol, 10% acetic acid, 4% water, 0.3% sulfuric acid
Annealed
840 C (1544 F) for one-half hour and furnace cooled
CARPENTER alloy 20 has been superseded by an improved alloy CARPENTER alloy 20Cb-3
*
**
***
*****
Trademark
Trademark
Trademark
Trademark
of
of
of
of
Page 19
TABLE XXII
Corrosion of High Nickel Alloys in Acetic Acid
Corrosion Rate
%
Acetic Acid
Temperature
C
MONEL alloy
Nickel
200
400
F
mm/y
B
mpy
mm/y
30
86
2
2
5
6
70
116
116
26-30
158
241
241
79-86
.03
A
B
.30 ,.05
1
A
B
12 ,2
.28
A
B
1.19 ,.10
11
A
B
47 , 4
10
26-30
79-86
.33A,.08B
13A,3B
.10B
4B
10
10
20
25
30
30
50
50
50
70
70
116
70
26-30
26-30
60
26-30
80
116
116
158
241
158
79-86
79-86
140
79-86
176
241
241
75
26-30
99.9
99.9
mpy
54
.10
.01
.08
4
0.2
3
.02
0.8
13
.36
.05
.33
1.37
600
mm/y
99.9
.03
mpy
INCONEL alloy
14
3.05
120
1.30
A
B
.41 ,.08
51
B
16A,3
3.30
.46
.74A,.10B
18
29A,4B
.05
76-86
.36A,.05B
79-86
.23A,.08B
9A,3B
80
176
130
14A,2B
26-30
116
241
100
26-30
116
241
170A, 10B
66B
19
.15
.13B
5B
.61B
79-86
100
4.32A,.25B
1.68B
.48
24B
.36
14
.10
.30
12
.99
39
A = Aerated
B = Unaerated
Reference 46 primarily.
There are process conditions which require that essentially no corrosion of the material of construction occur.
Critical items of equipment required to operate with close
tolerances such as orifice plates or control valve trim are
examples. Another possibility is that the catalyst system
used in the reactor of the process will not tolerate
contamination with foreign metallic ions. In these cases, the
maximum in corrosion resistance is demanded of an alloy,
and only the nickel-base Mo-Cr-Fe, the nickel-base
molybdenum, zirconium, titanium and tantalum alloys are
potential candidates as solid or clad materials of
construction.
Although the organic acids are less aggressive than
mineral acids in detecting sensitization of this class of alloy,
prolonged exposure of the sensitized alloy in hot acetic acid
can produce intergranular attack. The newer wrought
12
materials, such as HASTELLOY alloys C-276, C-4 and
INCONEL alloy 625 are stabilized to forestall such attack
on fabricated items of equipment. Castings of this type of
alloy should be purchased in the fully solution-annealed
condition. A test for susceptibility to intergranular attack is
defined in reference 13.
These alloys usually provide the ultimate in corrosion
resistance to hot organic acid streams. If the environmental
Page 20
TABLE XXIII
Effect of Aeration on Corrosion of Nickel, Copper and
Their Alloys in Acetic Acid
Conditions: Laboratory tests in 6% acetic acid at 30 C
(86 F)
Corrosion Rate
Without Aeration
J. Copper-Nickel Alloys
Alloy
All of the copper alloys excepting those with high (> 15%)
zinc are resistant to acetic acid in the absence of air and
other oxidants. Until the advent of the stainless steels,
copper was used almost exclusively for the handling of
acetic acid.
With Aeration
mm/y
mpy
mm/y
mpy
.08
.05
.08
.08
3
2
3
3
.28
.20
.81
.48
11
8
32
19
Nickel 200
MONEL alloy 400
C 71500 (70-30 Cupro-nickel)
Copper C 10300
Reference 47
TABLE XXIV
Effect of Velocity on Corrosion of MONEL
Alloy 400 in Acetic Acid
Temperature
Medium
30
86
Test
Period, hr
48
Aeration
100 cc/min
Velocity
ft/sec
Corrosion Rate
mm/y
mpy
.38
15
.41
.43
16
17
8.7
.41
16
12.5
Page 21
0
1.8
3.8
.46
18
TABLE XXV
Corrosion of Copper-Nickel Alloys in Acetic Acid Solutions
Conditions: Quadruplicate specimens exposed in pure aqueous acid solutions for 120 hours at the
boiling temperature except tests without air sparging were extended to 336 hours.
Additives added as shown.
Corrosion Rate
Per Cent
Acetic Acid
Per Cent
Nickel in Alloy
No
Air Sparge
mm/y
mpy
100
0
10
20
30
67
100
.01
.02
.01
.01
Nil
.04
0.4
0.7
0.3
0.2
0.1
1.4
75
0
10
20
30
67
100
.03
.03
.03
.03
.05
.01
0
10
20
30
67
100
.03
.03
.03
.03
.03
.08
1
1
1
1
1
3
25
0
10
20
30
67
100
.05
.03
.03
.03
.03
.15
Air
Sparged
mm/y
mpy
.08
.08
.08
.08
.05
.03
3
3
3
3
2
1
7.87
5.41
4.95
4.78
2.13
1.60
310
213
195
188
84
63
2900 ppm
Fe+++
Added as
Fe(OH)(OAc)2
mm/y
mpy
2100 ppm
Fe+++
Added as
FeCl 3 6H 2 0
mm/y
mpy
mm/y
mpy
51
1.32
2.87
6.15
2.97
81
20
52
113
242
117
32
.25
.30
.28
.25
.18
.13
10
12
11
10
7
5
.76
.76
.74
.74
1.30
5.21
30
30
29
29
51
205
19
31
34
33
36
28
3.28
2.64
2.69
2.36
1.83
1.98
129
104
106
93
72
78
3.00
2.59
2.06
2.46
2.82
4.39
118
102
81
97
111
173
1
1
1
1
2
0.4
50
3200 ppm
Cu++
Added as
Cu(OAc)2
2
1
1
1
1
6
.48
.79
.86
.84
.91
.71
Page 22
This 15,000 pound capacity reactor kettle of INCONEL alloy 600 was used
for over 27 years for the dehydration or polymerization of castor, linseed
and soybean oils. Alloy 600 was chosen to withstand the corrosive effects
of vegetable oil acids and C 18 fatty acids at a temperature of 600 F.
L. Iron-Nickel-Chromium Alloys
Alloy 800 has fair resistance to hot acetic acid solutions.
The iron and chromium of the alloy dictate that conditions
should be slightly oxidizing to realize the best resistance
from the alloy. However, the alloy cannot compete with
Alloy 825 or other metals containing molybdenum as a
prime candidate for process use.
The good chloride stress-corrosion cracking resistance
of the alloy makes use of the material attractive for small,
specialty applications, but the corrosion rate must be
determined closely to assure that adequate life will be
obtained. As a general statement, the better solution to a
problem involving acetic acid corrosion and chloride stresscorrosion cracking is the use of the type 20 alloys, or the
nickel-base iron-chromium-molybdenum-copper alloys.
TABLE XXVI
Effect of Sodium Chloride in a Mixed Acid Medium on
the Corrosion of Copper-Nickel Alloys
Conditions: Duplicate specimens immersed in a boiling 116 C
(241 F) solution of 60% acetic acid, 10% formic
acid, 10% heavy organic acids and 20% water for
100 hours.
Corrosion Rate
C70600
(90-10
Cupro-Nickel)
Copper
C71500
(70-30
Cupro-Nickel)
mpy
Type 316
Stainless Steel
mm/y
mpy
mm/y
mm/y
mpy
mm/y
mpy
0.05
.01
0.4
.01
0.3
.01
0.3
.38
15
0.10
1.0
.01
.08
0.3
3
.01
.05
0.3
2
.01
.08
0.5
3
.56
12.27
22
483
2.0
.10
.08
.10
22.66
892
Page 23
N. Nickel
Commercial nickel is less resistant to attack by acetic acid
at any temperature than are the nickel-copper alloys, the
cupro-nickel alloys, or the austenitic stainless steels.
Consequently, nickel as a basic material of construction is
not generally used. The material is used as the underbead
in the welding of copper-clad steel, being compatible with
both the copper and the steel backing.
Data showing the resistance of wrought Nickel 200 to
acetic acid under varying conditions are contained in
Tables III, VII, XIII, XXII, XXIIL XXV, XXVII, XXIX
and XXX.
The presence of air accentuates the corrosion of nickel.
For example, Uhlig reports a rate of attack of .02 mm/y
(0.9 mpy) for nickel in a 6% acetic acid solution charged
with nitrogen at room temperature, but a rate of .28 mm/y
19
(11 mpy) when air is introduced.
TABLE XXVII
Corrosion of Metals and Alloys in Acetaldehyde Oxidation
Process for Acetic Acid
Corrosion Rate
Exposure*
Alloy
10
mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
ACI CF-8
0.38
15
ACI CF-8M
.03
ACI CN-7M
Nil
0.1
.13
Nil
0.1
.02
0.6
.01
0.4
.01
0.5
.19
7.5
.06
2.5
2.54
100 1.70
67
.09
3.5
1.78
.06
2.4 2.34
.02
0.7
CARPENTER alloy 20
.01
0.5
70 1.22
48
2.16
85
.18
.13
.08
.03
.25
10
92
.33
13
.43
17
.05
.03
.03
Nil
Nil
Nil
Nil
.01
0.4
.01
0.5
.01
0.5
.03
Nil
Nil
Nil
Nil
Nil
0.2
.89
35
.18
.20
.05
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
.03
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
HASTELLOY alloy C
Nil
Nil
.03
.03
.03
.03
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
HASTELLOY alloy B
01
0.5
.28
11
.23
.03
.05
.18
.25
10
HASTELLOY alloy D
.1 5
.12
4.6
.36
14
.23
Nickel 200
.10
4.1
.86
34
.81
32
.11
4.4
1.12
44 1.07
42
.94
37
.01
0.3
.03
Nil
Nil
Nil
Nil
.10
3.9
Copper
.28
11
<.03
<1
DURIRON **
*Exposure
1-Product flash kettle base liquid at 95-100 C (203-212 F) for 737 days. Approx. 58% acetic acid, 40% anhydride, 2% residue with peroxides present.
2-Stripping still kettle liquid at 148-150 C (298-302 F) for 56 days. Approx. 65% acetic acid, 36% anhydride, residues, peroxides and catalyst salts.
3-Liquid of stripping still base section at 120 C (248 F).
4-Vapor of stripping still base section at 120 C (248 F).
5-Liquid of stripping still mid-section.
6-Anhydride still kettle liquid at 145 C (293 F). Essentially anhydride.
7-Anhydride still kettle vapor at 145 C (293 F).
8-Acetic acid refining still base liquid at 145 C (293 F). Mostly anhydride.
9-Acetic acid refining still base vapor at 145 C (293 F).
10-Acetic acid refining still overhead at 120 C (248 F).
**Trademark of The Duriron Company, Inc.
Page 24
TABLE XXVIII
Corrosion of Alloys in a Hydrocarbon Oxidation
Unit for Acetic Acid
Corrosion Rate
Location *
Alloy
Type 304 Stainless Steel
Type 202 Stainless Steel
Type 316 Stainless Steel
Type 317 Stainless Steel
Type 329 Stainless Steel
CARPENTER alloy 20Cb-3
HASTELLOY alloy G
HASTELLOY alloy C
HASTELLOY alloy B
INCONEL alloy 600
IN alloy 102
MONEL alloy 400
STELLITE alloy No. 3**
STELLITE alloy No. 4
STELLITE alloy No. 6
HAYNES alloy No. 93**
HAYNES alloy 25
ILLIUM B***
ILLIUM P
ILLIUM PD
ILLIUM 98
DURICHLOR****
Titanium
Zirconium
Copper
C70600
(90-10Cupro-Nickel)
mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
mm/y
mpy
.05
.05
<.03
.10
.13
.05
<.03
2
<1
5
2
<1
.05
<.03
<.03
<.03
.08
Nil
Nil
<1
<1
<1
3
Nil
Nil
.05
.05
<.03
.10
Nil
2
<1
Nil
.03
1
.25
<.03 < 1
.05
<.03 <1
.05
2
<.03
<.03
.10
4
.18
7
.46
18
>2.54 >100
.03
1
<.03 < 1
<.03 <1
<.03 <1
.10
4
.56
Page 25
.05
10
<1
<1
22
.03
<.03
.05
.03
<.03
Nil
.69
.10
<1
Nil
27
.05
Nil
.08
Nil
28
.30
<.03
.03
<.03
5.59
3.56
11
12
<1
1
<1
220
140
<1
.05
.10
b.
TABLE XXIX
Corrosion of Allays in Laboratory Equivalents of the Methanol-Carbon Monoxide Reaction Medium
Conditions: Small autoclave tests for 48 hours using 50%
acetic acid at autogenous pressure without
and with catalyst (7 grams cobalt acetate
Corrosion Rate
Without
Catalyst
Temperature
With
Catalyst
Alloy
mm/y
mpy
250
300
250
300
300
250
260
300
250
260
280
260
230
280
260
230
260
230
260
260
260
260
482
572
482
572
572
482
500
572
482
500
536
500
446
536
500
446
500
446
500
500
500
500
>25.4*
>25.4
9.14*
5.08
1.63
3.81
.36
<.03
>1000*
> 1000
360*
200
64
150
14
<1
CARPENTER alloy
INCOLOY
20
alloy 825
alloy C
HASTELLOY
HASTELLOY
Nickel 200
Silver
DURIRON
Titanium
Zirconium
Tantalum
alloy B
*Pitting
mm/y
mpy
2.03
10.16
22.35
5.08
1.78
5.08
.36
71
5.84
3.05
2.67
<.03
<.03
<.03
80
400
880
200
70
200
14
28
230
120
105
<1
<1
<1
Reference 17
Page 26
TABLE XXX
Corrosion of Alloys in Synthetic Reactor Product from
Methanol-Carbon Monoxide Process for Acetic Acid
Conditions: Aqueous 70% acetic acid at the boiling temperature 107 C (243 F) without and with
catalyst (ca. 6% cobalt acetate hydrate and
6% potassium iodide). Purged with CO.
Corrosion Rate
Without
Catalyst
Alloy
Type 304 Stainless Steel
Type 321 Stainless Steel
Type 347 Stainless Steel
Type 316 Stainless Steel
24Cr-20Ni-Mo-Cu**
CARPENTER alloy 20
INCOLOY alloy 825
INCOLOY alloy 800
HASTELLOY alloy C
HASTELLOY alloy B
INCONEL alloy 600
Nickel 200
MONEL alloy 400
C71500 (70-30 Cupro-Nickel)
C70600 (90-10 Cupro-Nickel)
Aluminum Bronze
Titanium
DURIRON
With
Catalyst
mm/y
mpy
mm/y ,
mpy
41
.51
1.91
.15
<.03
15
<.03
.48
.53
.18
Nil
Nil
16
20
75
6
<1
6
<1
19
21
7
Nil
Nil
15*
.25*
.33*
.08*
.03*
.23*
.05
.13*
.10*
.20
.38
.33
.41
.94
1.14
2.34
Nil
Nil
6*
10*
13*
3*
1*
9*
2
5*
4*
8
15
13
16
37
45
92
Nil
Nil
Page 27
Page 28
The forward tanks in this double-skinned barge are clad with Type 316
stainless steel, capable of transporting organic acids as well as other
liquid cargo.
Page 29
TABLE XXXI
Corrosion of Stainless Steels in
Vinegar Production
Corrosion Rate
Test 1
Alloy
Test 2
Test 3
Test 4
mm/y
mm/y
mpy
mm/y
mpy
mm/y
mpy
Nil*
Nil
Nil
mpy
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
*No detectable attack in the form of general corrosion, pitting or crevice corrosion.
Location
Vinegar Concentration
(Grain)
Temperature Range C
F
Test Duration
Test 1
Storage
Tank
Test 2
Test 3
Accumulator
Test 4
Storage
Tank
Freezer
40-66
80-122
50-300
80-320
21-35
70-95
27-34
80-93
17 to 2
2-28
0-16
32-60
TABLE XXXII
Deterioration of Alloys in Glacial Acetic Acid Vapors at
750 C (1382 F)
Average Penetration
Initial Exposure
200 hours
Metal
Second Exposure
100 hours
mm/y
mpy
mm/y
mpy
.48
19
1.22
48
.91
36
.18
.41
16
ACI HK Alloy
Type 304L stainless steel equipment and piping and ACI CF-8M valves
for metering acetic anhydride to process kettles. Courtesy Walworth
Company-Aloyco Valves.
Page 30
TABLE XXXIII
Corrosion of Type 316 Stainless Steel in
Boiling Formic Acid Solutions
Test Conditions: Specimens exposed in liquid of boiling,
aqueous formic acid solutions under anaerobic conditions for 72 hours.
Corrosion Rate
Liquid
Vapor
Condensate*
Concentration of
Formic Acid, %
mm/y
mpy
mm/y
mpy
mm/y
mpy
50
70
78
90
97
100
.38
.33
.36
.15
.15
.11
15
13
14
6
6
4
.41
.48
.51
.46
.13
.08
16
19
20
18
5
3
.46
.89
.38
.61
.25
.25
18
35
15
24
10
10
Page 31
TABLE XXXIV
Corrosion of Five Alloys in Boiling Aqueous
Formic Acid Solutions
Test Conditions: Average rate of duplicate specimens exposed in boiling 100-107 C (212-223 F)
solutions for 96 hours except as noted.
No aeration or deaeration.
Corrosion Rate
Type 304
Stainless Steel
Test A
Test B*
Formic Acid
Type 316
Stainless Steel
Test A
Test B*
mm/y
mm/y
mpy
mm/y
mpy
mm/y
.18
.79
1.34
1.93
3.45
4.24**
3.45**
4.04**
4.29**
3.28**
1
5
10
20
40
50
60
70
80
90
mpy
7
31
53
76
136
167**
136**
159**
169**
129**
.36
1.07
1.52
1.75
2.39
2.11
2.11
2.31
2.13
2.11
14
42
60
69
94
83
83
91
84
83
.08
.05
25
.28
.10
.51**
.46**
.48**
.48**
.28**
3
2
10
11
4
20**
18**
19**
19**
11**
<.03
.20
.20
.20
.25
.28
.23
.25
.25
.28
C70600
(90-10
Cupro-Nickel)
Copper
mpy
Titanium
mm/y
mpy
mm/y
mpy
mm/y
.03
.03
.03
.20
.12
.25
.05
.76
.20
.23
1
1
1
8
5
10
2
30
8
9
.03
03
.03
41
.33
.53
.03
.71
13
.18
1
1
1
16
13
21
1
28
5
7
13
2.41
3.05
<.03
<1
8
8
8
10
11
9
10
10
11
mpy
5
95
120
<1
TABLE XXXV
Corrosion of Alloys in Boiling Formic Acid Solutions
Test Conditions: Laboratory test results averaged from three separate 48-hour test periods in most cases.
Tests conducted with and without aeration in acid concentrations noted.
Corrosion Rate
10%
50%
Unaerated*
Liquid
Alloy
90%
Unaerated*
Vapor
Liquid
Aerated
Vapor
Liquid
99%
Unaerated*
Vapor
Liquid
Aerated
Vapor
Liquid
Unaerated
Vapor
Liquid
Vapor
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
Mild steel
24.13
950
Type 430
stainless steel
Type 304
stainless steel
Type 310
stainless steel
Type 316
stainless steel
Type 317
stainless steel
CARPENTER
alloy 20
HASTELLOY
alloy C
HASTELLOY
alloy B
INCONEL
alloy 600
MONEL
alloy 400
Nickel 200
11.26
444
.89
35
10.41
410
1.52
60
Copper
mpy
10.21
402
.61
24
.18
.23
.23
.53
21
<.03
<1
74
29
.36
14
.18
< 03
<1
.79
31
.13
.10
.13
.13
<.03
<1
30
12
.05
03
<1
.66
26
.10
03
.05
10
<.03
<1
.51
20
10
.08
08
.03
.76
30
.64
25
1.24
45
.20
<.03
<.1
.08
.23
.08
.03
.03
7.62
300
.23
.15
.15
.36
14
.43
17
.84
33
2.24
88
.61
24
.28
11
69
27
.41
16
.08
.18
.13
.28
11
.25
10
.15
14.30
563
37.80
93
EVERDUR 1010
.18
.23
3.30
130
.69
27
Aluminum 3003
31.09
1224
21.89
862
31.70
1248
10.16
400
7.62
300
10
<.03
<1
Titanium
.13
2.92
115
<.03
<1
Chromium
carbide with 12%
nickel binder
.51
20
Page 32
alloys at temperatures above those obtained at one atmosphere of pressure. Consequently, the effect of
increasing the temperature on the corrosion rate of the
common alloys must be determined. Table XXXVIII
presents a composite of the data contained in the report
of Miller and Wachter on corrosion by acids at high
24
temperatures. Of greatest interest is the information for
the Type 316 stainless steel. The rates are higher for this
alloy than would be expected for a test of longer
duration. The important inference to be made is that the
rate of attack approximately doubles for each 15C
(27F) increase in temperature. (It should be recognized
that this is a very rough approximation that does not
always hold true.) Corrosion tests in many other media
show a similar relationship rather than one conforming to
the ideal Arrhenius equation.
Figure 5 and isocorrosion charts (Figures 6 through
25
11), originally published by the NACE, indicate the
corrosion behavior of several alloys in formic acid.
Isocorrosion charts are intended only as guides; there are
conditions where higher or lower rates can prevail. In
fact, Figure 5 shows much lower rates for Type 316
stainless steel in boiling formic acid than is shown in the
isocorrosion chart, Figure 6. It is believed that Figure 5 is
more representative of pure formic acid and that the
higher rates shown by the isocorrosion chart must reflect
the presence of unidentified impurities.
TABLE XXXVI
Corrosion of HASTELLOYS and Related Alloys
in Formic Acid Solutions
Laboratory data obtained without aeration or deaeration using five 24-hour test periods.
(Courtesy of the Cabot Corporation, Stellite Division.)
Corrosion Rate
%
Formic Acid
Temperature
C
F
HASTELLOY
alloy B
HASTELLOY
alloy C-276
HAYNES
alloy No. 25
MULTIMET
alloy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
10
26
66
Boiling
78.8
150
.03
.23
.08
1
9
3
<.03
<.03
.13
<1
<1
5
Nil
Nil
.20
Nil
Nil
8
Nil
Nil
.10
Nil
Nil
4
20
26
66
Boiling
78.8
150
.05
.25
.10
2
10
4
< .03
<.03
.18
<1
<1
7
<.03
<.03
.25
<1
<1
10
<.03
<.03
.15
<1
<1
6
30
26
66
Boiling
78.8
150
08
.30
.08
3
12
3
<.03
<.03
.20
<1
<1
8
40
26
66
Boiling
78.8
150
.08
.28
.05
3
11
2
<.03
<.03
.13
<1
<1
5
<.03
Nil
.38
<1
Nil
15
<.03
Nil
.20
<1
Nil
8
60
26
66
Boiling
78.8
150
.05
.25
.03
2
10
1
< .03
<.03
.18
<1
<1
7
<.03
Nil
.51
<1
Nil
20
<.03
<.03
.15
<1
<1
6
90
26
66
Boiling
78.8
150
<.03
.03
<.03
<1
1
<1
<.03
<.03
.05
<1
<1
2
<.03
<.03
.15
<1
<1
6
Nil
Nil
.08
Nil
Nil
3
Page 33
TABLE XXXVII
Corrosion by Formic Acid Under Heat Transfer Conditions
Temperature
Formic Acid
Test Medium
Without
Heat Transfer
Corrosion Rate
With Heat
Transfer*
Type 304
Stainless Steel
C
10% aqueous
50% aqueous
89% aqueous
mm/y
mpy
101
103
103
214
217
217
110
125
140
110
125
140
110
125
140
230
257
284
230
257
284
230
257
284
18.85
>25.4
14.48
14.48
>25.4
>25.4
>25.4
>25.4
18.19
13.72
12.7
13.21
Type 316
Stainless Steel
742
>1000
570
570
>1000
>1000
>1000
>1000
716
540
500
520
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
10
16
62
73
39
58
60
84
10
48
40
48
.25
.41
1.57
1.85
.99
1.47
1.52
2.13
.25
1.22
1.02
1.22
HASTELLOY
alloy B
mpy
mm/y
CARPENTER
alloy 20Cb-3
INCONEL
alloy 600
MONEL
alloy 400
<.03
.05
.20
.69
.15
.23
.33
.31
.13
.10
.15
.25
<1
2
8
27
6
9
13
12
5
4
6
10
.25
1.27
1.42
2.03
.28
.23
.13
113
<.03
.13
.08
.18
10
50
56
80
11
9
5
5
<1
5
3
7
.89
1.85
1.68
1.52
1.55
1.93
3.30
2.92
1.02
1.27
1.93
1.42
35
73
66
60
61
76
130
115
40
50
76
56
3.38
16.26
>25.4
>25.4
2.21
1.93
1.22
2.54
.03
.56
.84
1.27
133
640
>1000
>1000
87
76
48
100
1
22
33
50
*Metal temperature.
Reference 10. See that publication for apparatus and technique used
TABLE XXXVIII
Corrosion of Alloys in Formic Acid at High Temperatures
(Tests conducted in sealed pressure tubes)
% Formic Acid
Test Period, days
1
1
2*
27
Test Temperature
4.6
1
Corrosion Rate
Alloy
mm/y
mpy
mm/y
mpy
170
170
170
150
170
170
100
150
170
200
150
170
170
170
150
170
150
170
150
170
150
150
170
170
170
170
338
338
338
302
338
338
212
302
338
392
302
338
338
338
302
338
302
338
302
338
302
302
338
338
338
338
.13
.20
.89
5
8
35
.46
.10
.05
.08
.03
.03
.03
.03
18
1
1
24
1
mm/y
mpy
mm/y
mpy
16.26
10.41
.66
3.56
2.36
.58
1.52
1.83
1.68
1.60
.10
.23
3.30
2.34
.89
.20
.15
10.16
7.37
640
410
26
140
93
23
60
72
66
63
4
9
130
92
35
8
6
400
290
1.04
3.05
3.30
41
120
130
Reference 24
Page 34
FIG 7Isocorrosion Chart for Type 304 Stainless Steel in Formic Acid
Page 35
B. Acrylic Acid
Acrylic acid is the most common 3-carbon acid encountered in industry. The great reactivity of this unsaturated
acid makes the material and its esters useful in the
preparation of a wide variety of resinous products used in
manufacturing plastics, paints, textiles, paper and polishes. There are probably some one billion pounds of the
esters produced in the USA today, of which 75% is ethyl
acrylate.
The significant fact about handling acrylic acid is that
temperatures are maintained as low as possible to prevent
homopolymerization of the acid. Distillation in vacuum
stills, dilution with innocuous solvents, storage of the
product at the lowest convenient temperatures and reaction
of the acid in polymerization processes at low temperatures
are common process conditions. Consequently, exposure
conditions in most acrylic acid applications are less severe
than in the saturated acid processes.
As with propionic acid, the acrylic acid can be considered as equivalent to acetic acid in aggressiveness at a
given temperature. However, the contaminants in acrylic
acid process streams can be different from those found in
This HASTELLOY alloy C-276 tube bundle is used in the reboiler in the
manufacture of acrylic monomers. It was found to be the most
economical material of construction for this severely corrosive service.
Courtesy Stellite Division, Cabot Corporation.
Page 36
TABLE XXXIX
Corrosion of Alloys in a Nitrile-Type Acrylic Acid Process
Corrosion Rate
Exposure*
3A
38
Alloy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
Type 304
Stainless Steel
>7.62
>300
2.24
88
10.16
> 400
.03
<.03
<1
08
03
<.03
<1
Type 316
Stainless Steel
Type 201
Stainless Steel
CARPENTER
alloy 20
INCONEL
alloy 600
INCONEL
alloy 625
HASTELLOY
alloy C
HASTELLOY
alloy B
MONEL
alloy 400
C70600 (90-10
Cupro-nickel)
Copper
Lead,
chemical
Aluminum 3003
Titanium
Zirconium
Tantalum
>7.62
>300
2.11
83
10.16
400
Nil
Nil
<.03
<1
<.03
<1
<.03
<1
<.03
<1
3.00
118
Nil
Nil
Nil
Nil
13
<.03
<1
>7.62
>300
64
25
4.98
196
Nil
Nil
<.03
<1
Nil
Nil
<.03
<1
>7.62
> 300
4.57
180
03
20
<.03
<1
.89
35
<.03
<1
7.11
280
2.95
116
74
29
<.03
<1
1.35
53
74
29
25
10
>7.62
>300
2.54
100
2.64
104
.05
03
15
.20
> 7.62
> 300
1.14
45
6.09
>7.62
240
>300
6.35
250
2.95
5.28
116
208
1.17
46
.05
05
25
2
10
23
30
9
12
76
> 5.08
30
> 200
>7.62
> 300
>7.62
.86
.03
>300
34
1
10. 16
1.35
<.03
> 400
53
<1
13
<.03
<.03
5
<1
<1
.03
38
15
33
<.03
13
<1
> 7.62
> 300
<.03
<1
*1
2
3A
3B
4
5
6
7
8
TABLE XL
Corrosion of Alloys in Propylene Oxidation
Process for Acrylic Acid
Corrosion Rate
Exposure*
Alloy
Type 304
Stainless Steel
Type 316
Stainless Steel
CARPENTER
alloy 20
HASTELLOY
alloy C
INCONEL
alloy 625
INCONEL
alloy 600
MONEL
alloy 400
Copper
Nickel 200
1
2
3
4
5
6
7
8
9
10
11
12
mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
<.03 <1
<.03
<1 <.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1 <.03
<1
<.03
<1
<.03
<1 <.03 <1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
.25
10
.25
10
.03
.13
.48
19
.97
.28
38
11
.81
<.03
32
<1
.20
.03
8
1
.05
.05
2
2
.13
.08
.53
21
.91
36
Page 37
TABLE XLI
Corrosion of Stainless Steels During the Preparation
of -Methacrylic Acid
Corrosion Rate
Exposure
Type 304
Type 316
CARPENTER HASTELLOY HASTELLOY
Stainless Steel Stainless Steel
alloy 20
alloy C
alloy B
mpy
DURIRON
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
.03
.03
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
.03
.05
Nil
Nil
.51
20
<.03
<1
<.03
<1
<.03
<1
<.03
<1
.38
15
1.88
74
<.03
<1
.23
TABLE XLII
Corrosion of Alloys in Dimethyl Acrylic
(Seneceoic) Acid
Field test obtained by exposure of alloys in the
overhead stream of a refining column at 145C (293F)
for three days.
Corrosion Rate
Alloy
mm/y
mpy
1.83
.18
.18
<.03
.05
.46
1.45
72
7
7
<1
2
18
57
mpy mm/y
Aluminum
3003
mm/y
Oxidation of the acid by
air blowing of the
aldehyde at 40 C (104 F)
Distillation of the crude
oxidation product at ca.
55 C (131 F) (liquid
exposure)
As above (vapor exposure)
mm/y
Silicon
Bronze
pylene-acrolein process. The oxidation product of the methacrylic aldehyde would contain some oxidized decomposition compounds such as formic and acetic acids.
However, the reasonable low temperatures at which the
product must be handled, combined with the low concentration of such contaminants, does not produce an
aggressive medium for the stainless steels. The data of
Table XLI show results obtained in oxidation and primary
distillation steps of the process.
Further information relating to the acrylic acids is
contained in Table XLII. In processing the more stable
dimethyl acrylic acid at the higher temperatures, it is
apparent that a Type 316 stainless steel is required. The
temperature of the operation exceeds the point where the
Type 304 stainless steel is adequately resistant.
C. C3 Through C8 Acids
The major commercial approach to acrylic acid production today is the direct oxidation of propylene to acrolein
with subsequent oxidation to acrylic acid or a one-step
oxidation with only the acid recovered. One advantage of
the process is the milder corrosive conditions existing
throughout the unit. Steel and the austenitic stainless
steels may be used for all equipment except where
chloride stress-corrosion cracking of the stainless steels
requires the use of Alloy 600, Alloy 400, or other crackresistant alloys. Table XL provides data regarding the
corrosion of a number of alloys in significant portions of a
propylene oxidation process. Although the austenitic
stainless steels are resistant to the primary corrosive
agents throughout the process, the use of INCONEL alloy
600 and other high alloys have been used in the process
for the reason cited.
Similar data were obtained by the exposure of alloys in
a plant preparing -methyl acrylic (crotonic, 2-buteneoic)
acid. Types 304L and 316L stainless steels and CARPENTER alloy 20Cb-3 were unattacked in process handling of
the acid up to 90 C (194 F) in a process similar to that
described for the production of acrylic acid by the pro-
Page 38
HASTELLOY alloy C-276 replaced silver in this primary cooler for propionic
acid. The alloy was found to have better resistance to thermal cycling than the
precious metal. Courtesy of Stellite Division, Cabot Corporation.
Page 39
TABLE XLIII
Effect of Oxygen on Corrosion of Stainless Steel in Propionic Acid
Conditions: 95% propionic acid containing 2% water, alcohol, ketone and higher acids
used in laboratory tests and processed in field.
Corrosion Rate
Type of Test
Additive
Temperature
Exposure
Type 316
Stainless Steel
Type 304
Stainless Steel
Type 202
Stainless Steel
mm/y
mpy
mm/y
mpy
mm/y
mpy
Laboratory
None
122
to
135
252
to
275
Liquid
Vapor
Condensate
.15
.20
.05
6
8
2
.30
.28
.36
12
11
14
Laboratory
Air Sparged
122
to
135
252
to
275
Liquid
Vapor
Condensate
Nil
Nil
Nil
Nil
Nil
Nil
1.63
.15
Nil
64
6
01
Laboratory
9 ppm H 2 0 2
122
to
135
252
to
275
Liquid
Vapor
Condensate
01
01
Nil
0.3
0.2
0.1
.04
.02
Nil
1.5
0.6
0.1
Laboratory
1 ppm H 2 O 2 +
air sparged
122
to
135
252
to
275
Liquid
Vapor
Condensate
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Laboratory
122
to
135
252
to
275
Liquid
Vapor
Condensate
Nil
Nil
Nil
<0.1
<0.1
<0.1
Nil
Nil
Nil
<0.1
<0.1
<0.1
Air and H 2 O 2
injected
in feed stream
110
to
137
230
to
279
Kettle
Based on column
Feed line
Middle of column
Top of column
Nil
Nil
Nil
Nil
Nil
<0.1
<0.1-0.1
0.1
0.1
<0.1
Nil
Nil
Nil
Nii
Nil
<0.1
<0.1-0.1
0.1
<0.1
<0.1
Field Column
processing the acid*
Nil
Nil-.03
Nil
Nil
01
<0.1
<0.1-1
0.1
0.1
0.3
Page 40
TABLE XLIV
Corrosion of Stainless Steels in Propionic Acid
Below the Boiling Temperature
Conditions: Duplicate tests in various concentrations of
propionic acid at 75 and 50 C (167 and 122 F)
without aeration or deaeration.
Corrosion Rate
% Propionic
Acid
Type 420
Stainless Steel
75 C (167 F)
Type 304
Stainless Steel
50 C (122 F)
mm/y
99
80
67
50
33
20
mpy
mm/y
mpy
2.54
52.32
90.93
79.76
39.88
42.67
100
2060
3580
3140
1570
1680
.03
6.09
9.27
1.65
4.83
1.57
1
240
365
65
190
62
75 C (167 F)
mm/y
Nil
.05
.03
<.03
<.03
<.03
mpy
Nil
2
1
<1
<1
<1
Type 316
Stainless Steel
50 C (122 F)
75 C (167 F)
50 C (122 F)
mm/y
mpy
mm/y
mpy
mm/y
mpy
Nil
.05
.05
<.03
Nil
Nil
Nil
2
2
<1
Nil
Nil
Nil
<.03
Nil
Nil
<.03
<.03
Nil
<1
Nil
Nil
<1
<1
Nil
.03
Nil
<.03
<.03
Nil
Nil
1
Nil
<1
<1
Nil
Corrosion Rate
% Proponic
Acid
Type 318
Stainless Steel
75 C (167 F)
mm/y
99
80
67
50
33
20
<.03
<.03
Nil
Nil
<.03
<.03
HASTELLOY
alloy C
50 C (122 F)
mpy
mm/y
<1
<1
Nil
Nil
<1
<1
Nil
.03
Nil
Nil
Nil
Nil
75 C (167 F)
mpy
mm/y
mpy
Nil
1
Nil
Nil
Nil
Nil
Nil
Nil
.03
<.03
Nil
Nil
HASTELLOY
alloy B
50 C (122 F)
mm/y
Nil
Nil
1
<1
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
mpy
Nil
Nil
Nil
Nil
Nil
Nil
75 C (167 F)
50 C (122 F)
mm/y
mpy
mm/y
mpy
.64
.30
.28
.10
.08
.05
25
12
11
4
3
2
.15
.61
.30
.38
.20
<.03
6
24
12
15
8
<1
Corrosion Rate
% Propionic
Acid
INCONEL
alloy 600
75 C (167 F)
mm/y
99
80
67
50
33
20
.38
.48
.18
.10
.10
.13
MONEL
alloy 400
50 C (122 F)
75 C (167 F)
mpy
mm/y
mpy
mm/y
mpy
15
19
7
4
4
5
<.03
.41
.36
.20
.18
.13
<1
16
14
8
7
5
1.19
.15
.13
.13
.10
.13
47
6
5
5
4
5
Page 41
Copper
50 C (122 F)
mm/y
.48
.41
.23
.28
.05
.18
mpy
19
16
9
11
2
7
75 C (167 F)
mm/y
>1.27
.23
.28
.25
.28
.05
mpy
>50
9
11
10
11
2
50 C (122 F)
mm/y
mpy
1.02
1.09
.41
.38
<.03
.13
40
43
16
15
<1
5
TABLE XLV
TABLE XLVII
Liquid
mm/y
Type 430 Stainless Steel
129.41
Type 304 Stainless Steel
141.86
Type 347 Stainless Steel
3.63
Type 316 Stainless Steel
9.91
Type 316 Stainless Steel (Sen.)
12.01
Type 317 Stainless Steel
4.55
Type 318 Stainless Steel
7.95
CARPENTER alloy 20
7.26
Vapor
mpy
5095
5585
143
390
475
179
313
286
mm/y
80,01
78.10
116.84
7,09
4.01
2.44
7.65
8.36
mpy
3150
3075
4600
279
158
96
301
329
Corrosion Rate
Alloy
mm/y
mpy
.03
.05
<.03
.89
.18
.28
.03
<.03
.03
5.33
<.03
1
2
<1
35
7
11
1
<1
1
210
<1
TABLE XLVI
Corrosion of Alloys in Higher Organic Acids
Conditions: Laboratory tests for 48 hours at temperatures
shown in refined (99.9+) acids.
Corrosion Rate
Acid (Approximate
boiling point)
Test
Carbon Steel
Temperature
C
26
116
26
Propionic (140 C or 284 F)
110
26
Butyric (163 C or 325 F)
163
26
Valeric (185 C or 365 F)
140
26
2-Ethylbutyric (190 C or 374 F)
150
2-Methylpentanoic
26
(195 C or 383 F)
150
2-Ethylhexanoic
26
(220 C or 428 F)
190
26
Iso-octanoic (240 C or 464 F)
190
26
Iso-decanoic (265 C or 509 F)
190
Acetic (116 C or 240 F)
Copper
mpy
Silicon
Bronze
Type 304
Type 316
Stainless Steel Stainless Steel
mm/y
mpy
mm/y
mm/y
mpy
mm/y
78.8
240
78.8
240
78.8
325
78.8
284
78.8
302
2.79
5.33
.71
1.98
.15
.05
1.37
.18
.86
110
210
28
78
6
2
54
7
34
.28
.08
.05
2.13
Nil
.05
2.06
.03
.41
11
3
3
84
Nil
2
27
1
16
.41
.08
.15
3.40
.05
.05
.13
.03
.23
16
3
6
134
2
2
5
1
9
<.03
.25
<.03
.13
<.03
1.14
<.03
<.03
<.03
.53
mpy
<1
10
<1
5
<1
45
<1
<1
<1
21
<.03
.08
<.03
<.03
<.03
.10
<.03
<.03
<.03
<.03
mm/y
mpy
<1
3
<1
<1
<1
4
<1
<1
<1
<1
78.8
302
.03
.53
1
21
.08
.30
3
12
.10
.08
4
3
<.03
<.03
<1
<1
<.03
<.03
<1
<1
78.8
374
78.8
374
78.8
374
.03
1.27
.03
.89
.03
.84
1
50
1
35
<1
33
<.03
<.03
05
<.03
<.03
<.03
<1
<1
2
<1
<1
<1
<.03
<.03
.03
<.03
<.03
<.03
<1
<1
1
<1
<1
<1
<.03
.20
<.03
.43
<.03
.20
<1
8
<1
17
<1
8
<.03
<.03
<.03
<.03
<.03
<.03
<1
<1
<1
<1
<1
<1
Reference 5
Page 42
TABLE XLVIII
Corrosion of Alloys in Higher Organic Acids
(Laboratory Tests)
Corrosion Rate
Temp.
Acid
2- Ethyl butyric acid
Crude acid (60%)
Crude acid
Refined acid
2- Ethyl hexanoic acid
Refined acid
Refined acid
n- Butyric acid
+5% Acetic Acid
agitated
Type 304
Stainless
Steel
Time
days mm/y
26
115
125
78.8
239
257
10
10
1
125
150
130
257
302
266
1
5
60
Type 316
Stainless
Steel
CARPENTER
INCOLOY
HASTELLOY
alloy 20
alloy 825
alloy C
mm/y mpy
mm/y
Copper
mpy
mm/y
mpy mm/y
Nil
.08
Nil
Nil
3
Nil
Nil
.08
Nil
Nil
3
Nil
Nil
61
Nil
24
<.03
05
<1
2
.03
.03
.01
0.3
Steel
mpy
mm/y
mpy
<.03
1.52
<1
60
.89
35
TABLE XLIX
Corrosion of Alloys During Preparation
of n-Octanoic Acid
Corrosion Rate
Temp.
Type 304
Stainless
Steel
Time
Type 316
Stainless
Steel
CARPENTER
HASTELLOY
alloy 20
alloy C
Exposure
days
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
Preparation of the
acid by carbonylation
of the appropriate
olefin
175
347
13
<.03
<1
<.03
<1
<.03
<1
Distillation of the
octanoic acid from
above preparation
230
446
2.54
100
<.03
<1
<.03
<1
<.03
<1
TABLE L
Corrosion of Alloys in 2-Ethyl Hexanoic Acid
Corrosion Rate
Test No.
Alloy
mm/y
08
.15
.10
.03
<.03
05
15
2
mpy
mm/y
3
6
4
1
<1
2
6
05
13
.05
<.03
<.03
05
.15
3
mpy
2
5
2
<1
<1
2
6
mm/y
mpy
mm/y
08
08
.20
1.12
3
3
8
44
36
46
.08
.05
<.03
.18
.18
5
mpy
14
18
3
2
<1
7
7
mm/y
05
15
.08
.03
.03
08
.23
6
mpy
2
6
3
1
1
3
9
mm/y
mpy
.08
13
56
.66
3
5
22
26
a Test 11% of 98% H SO added to commercial grade 2-ethyl hexanoic acid. Solution at 90 C (194 F) at atmospheric pressure for
2
4
7 days with agitation.
Test 21% of 98% H 2 SO 4 added as before. Solution at 120 C (248 F) at atmospheric pressure for 7 days with agitation.
Test 31% of 98% H 2 SO 4 added as before. Solution averaged 143 C (290 F) at 200 mm pressure for 3 days with agitation.
Test 4Same as Test 1 except 2% H 2 SO 4 added.
Test 5Same as Test 2 except 2% H 2 SO 4 added.
Test 62% H 2 SO 4 added; average temperature of 142 C (288 F) at 300 mm pressure for 3 days.
Page 43
D. Fatty Acids
The fatty acids comprise those organic acids exceeding
four carbons in length according to some chemical text
definitions. However, the term as used industrially and in
this text refers to the higher acids of six or more carbons.
These are characterized by lauric, oleic, linoleic, stearic,
tall oil and rosin acids as produced for commerical use
from products of the meat, agricultural and paper industry.
The large volume product of industry is not a pure
compound, but a mixture of two or more of the compounds meeting certain chemical specifications.
At the lower temperatures, the acids may be considered
as harmless polar oils. However, when the products are
heated to the high temperatures necessary for processing
and production, significant corrosion of steel can result.
Fortunately, there is a wide variety of alloys which have
excellent resistance to the conditions of production and
subsequent use of the acids. A proper economic analysis
of the use of the alternative materials is necessary to
achieve an optimum selection.
TABLE LI
Corrosion of Alloys in Tall Oil Fractions
Corrosion Rate
Conditionsa
Temperature C (F)
Time, days
Exposure
100(212)
30
Vapor
Alloy
275(527)
195
Liquid
Vapor
mpy
mpy
10
11
12
13
14
15
25(77)
19
Liquid
265(509)
54
Liquid
265(509)
134
Liquid
265(509)
100
Liquid
220(128)
242
Vapor
250(482)
66
LiqVap.
240(464)
50
LiqVap.
265(509)
73
Liquid
247(477)
66
Vapor
247(477)
66
LiqVap.
220(428)
66
Vapor
260(500)
63
Vapor
mpy
.09
.06
3.4
2.5
.02
.02
.03
Nil
0.9
07
1
0.1
.77
.38
.20
.25
30
15
8
10
.25
.08
.09
.09
Nil*
01
>.76
>30
>7.6
Nil
0.1
.36
14
<.03
<1
.05
Nil
0.1
>.76
>30
>7.6
Nil
0.1
>.76
>30
.46
Nil
0.1
<.03
<1
.08
>7.6
>30
Consumed
>6.35 >250
mm/y
mm/y
Steel
Cast Iron
NiResist
Type 2
Nickel 200
MONEL alloy 400
INCONEL alloy 600
Type 304
Stainless Steel
Type 316
Stainless Steel
Type 31 7
Stainless Steel
CG8M Casting
Type 310
Stainless Steel
Type 330
Stainless Steel
INCOLOY alloy 825
INCOLOY alloy 800
INCOLOY alloy 804
HASTELLOY
alloy C
HASTELLOY
alloy B
Copper
CN7M Casting
Titanium
mm/y
300(572)
3
Liquid
260(500)
mm/y
Consumed
mpy
mm/y
mpy
mm/y
mpy
mpy
Consumed
mm/y
mpy
.43
17
mpy
mm/y
mpy
.15
.28
6
11
.43
17
.79
31
.91
1.60
36
83
.43*
17
.61*
24*
.15
.79
31
3*
.03*
.10
Nil
Nil
Nil
Nil
Nil
.02
0.8
Nil
Nil
Nil
NII
Nil
Nil
Nil
Nil
Nil
Nil
Nil
0.3
_
41
Nil
Nil
Nil
Nil
Nil*
NII
.08
Nil
Nil
mpy
mm/y
mpy
mm/y
mm/y
.13
.20
.05
5
8
2
0.9
0.1
0.1
3.5
0.5
0.2
.17
6.6
.23
>30 1.57
62
Nil
0.1
4.70
185
Consumed
Nil
0.1
.86
34
.84
33
.20
.08
3I
.05
1.78*
70
08*
Nil
NII
.23
.08
.10
3
4
.03
Nil
Nil
Nil
0.1
Nil
0.1
.99*
39
Nil
>30
.15
18
.05
Nil
NII
.02
2.67
86
0.7
105
34
.61*
>2.13
>2.29
24*
>84
>90
<.03
<1
.03
Nil
Nil
Nil
Nil
Nil
Nil
.01
.05
Nil
>7.6
> 30
.25
10
Nil
Nil
.01
Nil
Nil
.71
28
.03
Nil
1
Nil
Nil
Nil
Nil
Nil
.02
.06
1.04
*Pitted
aConditions
mm/y
10
31
3.6
3.7
Consumed
mm/y
440
mpy
of the exposures:
1 Field test in vapor of light-odor tall oil fraction during distillation in vacuum column. Water present.
2 Field test in bottom and top of tall oil vacuum distillation column. Oil (presumably crude) from southern kraft pulp mill.
3 Laboratory test in crude tall oil acids from kraft pulp mill distilled under vacuum with agitation of 300 rpm in kettle.52
4 Laboratory test in crude and semi-refined oil with velocity of 0.3 fps provided in liquid.
5 Field test in base of tall oil distillation column (20% oleic acids, 60% rosin acids and 20% pitch).30
6 Field test in base of tall oil distillation column (65% fatty acids and 35% rosin acids).30
7 Field distillation of 65% fatty acid35 % rosin acids. 31
8 Field distillation of 93% fatty acids5% rosin acids.31
9 Field distillation of 90-93% oleic acids with <1% rosin acids with steam injected. Velocity of 62 fps.31
10 Field test six inches above the outlet of a reboiler on 97% fatty acids,1.5% rosin acids and 1.7% residues with high velocity.31
11 Field test in heat exchanger head handling 85% fatty acids and 15% rosin acids with steam present.
12 Field test in reboiler nozzle at base of distillation column handling 90-93% oleic acids and 1% rosin acids with steam injected.
13 Field test on distillation column tray near bottom while processing 90% oleic acids, 2% stearic acid, 0.4% rosin acids, 0.5 light ends and 6.4% higher
acids with steam present.
14 Field test in top of distillation column handling analysis of No. 13 above.
15 Field test near bottom of distillation column handling 30-32% rosin acids, 8-20% oleic acids and 62-48% higher boiling acids with steam present.
Page 44
mm/y
mpy
mm/y
mpy
mm/y
mpy
TABLE LII
Effect of Temperature on Corrosion in Refined Tall Oil
Conditions: Laboratory tests conducted in liquid of
same oil at various temperatures.
Corrosion Rate
285 C (545 F) 300 C (572 F) 315 C (599 F) 330 C (626 F)
Material
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
Type 302
4.57
180
12.7
500
20.32
800
Type 316
.10
.10
1.35
53
12.7
500
Stainless Steel
Type 317
.03
.03
.53
21
.28
11
Stainless Steel
Stainless Steel
HASTELLOY alloy C
.10
.13
.10
.25
10
.25
1 0
.33
13
Note that Types 316 and 316L stainless steels are useful
for many tall oil processing requirements but, in some
instances, either an excess of light ends or an exceptionally high temperature causes high rates with this alloy.
In these cases, the use of Types 317 or 317L stainless
steels or alloys with a higher molybdenum content should
be investigated in the search for an economical material of
construction. If these alloys are inadequate, the use of
more highly alloyed materials can be considered. The
nickel-base molybdenum-chromium-iron alloys show essentially a nil corrosion rate in all such exposures.
Alloy 600 is a contender for use in a number of applications and should not be overlooked. The use of nickelcopper alloys or copper-nickel alloys varies depending on
the oxidizing capacity of the solution, as would be
expected. In the absence of oxidants, the rate of attack on
these alloys is acceptably low.
It has been stated that streams containing a higher
proportion of the straight chain fatty acid produced more
corrosion than those containing a higher ratio of rosin
(cyclic) acids. This does not appear to be invariably true.
The presence or absence of steam has a significant
effect on the corrosion to be expected, particularly as
observed for the stainless steels. The oxidizing capacity of
the water reduces corrosion rates on the stainless steels
appreciably while accentuating attack on the nickel-copper
and/or copper-base alloys.
As with any other corrosive environment, the effect of
temperature must be carefully defined. Table LII shows
data for five alloys exposed to the same refined tall oil
TABLE Llll
Corrosion of Metals in Vegetable Fatty Acids
Conditionsa
Temp. C (F)
Time, days
Exposure
1
370 (698)
45
Liq-vap.
2
370 (698)
3
Vapor
3
190 (374)
30
Liquid
4
190 (374)
23
Liq-vap.
5
277 (530)
50
Vapor
6
116(240)
32
Vapor
7
255(491)
42
Vapor
Corrosion Rate
Alloy
mm/y
Carbon Steel
Cast Iron
Ni-Resist Type 2
Type 304 Stainless Steel
Type 309 Stainless Steel
Type 316 Stainless Steel
Type 317 Stainless Steel
INCONEL alloy 600
Nickel 200
MONEL alloy 400
C71500 (70-30 Cupro-nickel)
HASTELLOY alloy C
mpy
01
Nil
Nil
08
.08
0.2
0.1
0.1
3
3
mm/y
Nil
25
.18
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
0.1
10
7
38
48
03
Nil
Nil
Nil
Nil
Nil
10
.05
01
15
19
1
Nil
Nil
Nil
Nil
Nil
4
2
0.4
1.04
20
Nil
Nil
Nil
10
.13
41
8
0.1
0.1
0.1
4
5
3.05
10.92
43
97
Nil
0.3
30
.25
120
430
17
38
0.1
1
12
10
25
01
Nil
Nil
Nil
03
.02
10
05
0.1
0.1
0.1
1
0.9
12.45
86
25
05
Nil
Nil
20
.20
Nil
49
0
34
a Conditions:
1Field
2Field
3Field
4Field
5Field
6Field
7Field
test
test
test
test
test
test
test
in
in
in
in
in
in
in
Page 45
10
2
Nil
0.1
8
8
Nil_
TABLE LIV
Corrosion of Alloys in Animal Fatty Acids
a
Conditions
Temp. C (F)
Time, days
Exposure
1
100 (212)
130
Liquid
2
250 (482)
147
Liquid
3
250 (482)
210
Vapor
4
250 (482)
84
Vapor
Corrosion Rate
Alloy
Mild Steel
Cast Iron
Ni-Resist Type 2
Type 304 Stainless Steel
Type 316 Stainless Steel
INCONEL alloy 600
Nickel 200
MONEL alloy 400
Copper
mm/y
.18
1.63
.23
Nil
Nil
Nil
.08
.05
mpy
7
64
9
Nil
Nil
Nil
3
2
mm/y
.36*
Nil
.01
.41
.58
*Pitted
a Conditions:
1Field
2Field
3Field
4Field
test
test
test
test
mpy
14*
0.1
0.3
16
23
mm/y
mpy
Consumed
Consumed
>3.46
.33
.05*
.01*
.01
.13
.15
>140
13
2*
0.2*
0.3
5
6
mm/y
mpy
Consumed
Consumed
.79
.20
Nil
.05
.08
.10
.13
31
8
Nil
2
3
4
5
References 28,49
in storage tank for mixed acids from fish oils.
in outlet of preheater to distillation column processing animal tatty acids.
in overhead vapor of column distilling acids from fish oils.
on feed tray of distillation column handling crude fatty acids from tallow.
Page 46
TABLE LV
Corrosion of Annealed and Heat Treated Alloys
in Dicarboxylic Acids
Laboratory test in 10% boiling dibasic acid stated for 5 days without aeration or deaeration. Acetic
acid added for comparison.
Corrosion Rate
Oxalic
Acid
Alloy
Maleic
Acid
Phthalic
Acid
Acetic
Acid
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
.94
37
.01
0.2
.01
0.2
.01
mpy
0.3
.66
26
.01
0.2
.01
0.3
Nil
<0.1
.58
23
.01
0.2
Nil
<0.1
Nil
<0.1
.23
Nil
<0.1
Nil
0.1
Nil
0.1
.51
.38
20
15
Nil
.02
0.1
0.7
Nil
Nil
<0.1
0.1
Nil
.05
<0.1
1.8
(Heat treated)*
(Heat treated)*
INCOLOY alloy 825 (annealed)
INCOLOY alloy 825
(Heat treated)
*650 C (1200 F) for one hour, water-quenched.
TABLE LVI
Corrosion of Alloys by Oxalic Acid
Laboratory tests without aeration or deaeration except as noted
% Oxalic Acid
Temp. C
F
Test Period (days)
1
Boiling
Boiling
1.5
10
25
77
7
10
35
95
6
10
50
122
6
10
80
176
0.1-10
10
Boiling
Boiling
2-10
30
60
140
11
Corrosion Rate
Alloy
Type 430 stainless steel
Type 304 stainless steel
Type 316 stainless steel
Type 216 stainless steel
ALLEGHENY alloy AL-6X*
Act CN-7M
HASTELLOY alloy C-276
HASTELLOY alloy B
ELGILOY**
Titanium
Vanadium
C71500 (70-30 Cupro-nickel)
WAUKESHA No. 23
WAUKESHA No. 54
WAUKESHA No. 88
KROMARC 55
Multiphase MP35N
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
.81
32
(1)
.03
.03
(1)
1
.03
(2)
.41
1
(2)
4
(1)
.81
11.68
(2)
.25
(1)
32
460
(2)
10
(1)
1.52
(1)
60
63.5
(1)
21614.48
.18 2.44
1.52
.28
.18
.25
.13
.10
24.173.7
(2)
5.46
.63
.48
.05
.23
.10
(1) Type 304L material heat treated at 675 C (1250 F) for 1 hour
(2) Aerated.
Page 47
mpy
2500
(1)
85570
796
60
11
7
10
5
4
950
(2)
215
25
19
2
9
4
mm/y
mpy
.20
TABLE LVII
Corrosion of Alloys in Aqueous
Maleic Acid Solutions
Corrosion Rate
2%*
Alloy
mm/y
5%*
mpy
mm/y
10%*
30%**
mpy
mm/y
mpy
40%*
mm/y
mpy
59%**
mm/y
mpy
mm/y
mpy
.03
.03
4.06
160
4.06
160
3.71
146
5.33
210
Nil
Nil
Nil
Nil
Nil
Nil
<.03
<.03
<1
<1
Nil
Nil
<.03
<.03
<1
<1
.08
<.03
<1
Nickel 200
.91
36
Copper (C10200)
Silver (fine)
.10
.03
Nil
2
Nil
HASTELLOY
HASTELLOY
alloy C
alloy B
TABLE LVllI
Field Exposure of Alloys in a Phthalic Anhydride Plant
Corrosion Rate
Exposure
Alloy
10
11
12
13
14
mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
1
2
1
<0.
1
<0.
1
<0.
1
<0.
1
0.1
0.2
7
.05
.05
.03
.01
.01
.01
Nil
Nil
Nil
.01
Nil
.01
.13
.02
2
2 1.22
1 .56
0.2 .10
0.4 .03
0.2 .03
<0. .03
<0.
<0.
1
.03
.08
0.4 .08
0.1 1.14
0.2
5 .03
39
19
0.3
0.1
<0.
1
<0.
1
33
74
44
39
48
0.7
0.1
<0.
1
0.1
0.8
22
51
22
1.93
Nil
<0.1 .01
Nil
<0.1 .01
Nil
Nil
Nil
<0.1
.01
01
>5.0 0.2 Nil
8 >200 .01
01 0.4 Nil
>5.0 >200 .01
8 160 .01
4.06
< 0.1
Nil
3.02 119
38
.97
11
0.2
.28
2.21 87
0.2
.99 39 .02 0.6
0.1
.28 11 Nil <0.1
0.1
.86 34
0.2
.51 20
Nil
Nil <0.1
0.3
6
0.1 1.22 48 .15
27
3
.69
5
2
51 20 .13
18
.46
.56
22
Mild Steel
Cast lron (gray)
Ni-Resist Type IV
Type 304 Stainless Steel
Type 309 Stainless Steel
Type 316 Stainless Steel
Type311 Stainless Steel
CARPENTER alloy 20
ACI CN-7M
INCOLOY alloy 825
HASTELLOY alloy C
HASTELLOY alloy B
INCONEL alloy 600
Nickel 200
MONEL alloy 400
Copper
Titanium
Aluminum 3003
.03
.05
.03
Nil
Nil
Nil
Nil
Nil
.05
.18
Mel
*Pitting
48 .01* 0.4*
22 .01 0.3
4 .01 0.2
1
Nil <0.1 .99
1
Nil <0.1 .48
1
Nil <0.1 .01
Nil
Nil
Nil
1
Nil <0.1 .84
3
Nil <0.1 1.88
3
Nil <0.1 1.12
45 .69 27
1 .05*
2
.41
.02
16 .99
1.22
0.6 .02
Nil
Nil
Nil
.02
.56
1.55
.56
Page 48
.56
.01
Nil
Nil
22 5.08 200
Nil
Nil
Nil
.01
Nil
0.1
.18
.20
0.1
<0.1
<0.1
0.2
0.1
0.3
7
8
TABLE LIX
Corrosion of Alloys in
Phthalic Acid and Phthalic Anhydride
Conditions: Laboratory test of duplicate specimens at
150 C (302 F) for 13 days without aeration
ordeaeration.
Corrosion Rate
Phthalic
Anhydride
Alloy
1:1 Phthalic
Anhydride:
Phthalic Acid
Mixture
Phthalic
Acid
mm/y
mpy
mm/y
mpy
mm/y
mpy
<.03
<1
<.03
<1
.03
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
Mild Steel
Type 304
Stainless Steel
Type 316
Stainless Steel
TABLE LX
Corrosion of Alloys in Terephthalic Acid Media
Laboratory Test
6% Terephthalic
Acid in Water
Laboratory Test
6% Terephthalic Acid
84.6% Acetic Acid
9.4% Water
Field Test
TPA Leach Feed
Slurry (TPA +
Acetic Acid)
Field Test
Leach Crystallizer
Liquid (14.1 % TPA,
82.7% Acetic Acid,
2.7 % water)
232
450
24
232
450
24
260
500
14
177
351
523
Temperature, C
Temperature, F
Test Period, days
Corrosion Rate
Alloy
Type 304 Stainless Steel
Type 316 Stainless Steel
Type 216 Stainless Steel
Type 317 Stainless Steel
CARPENTER alloy 20Cb-3
INCOLOY alloy 800
HASTELLOY alloy C- 276
Titanium
mm/y
.01
.01
Nil
Nil
mpy
0.4
0.3
0.1
<0.1
mm/y
mpy
mm/y
mpy
mm/y
.06
.02
Nil
Nil
2.4
0.8
0.1
0.1
.19
.04
Nil
7.3
1.5
0.1
.03
.01
.02
.35
.03
Nil
Page 49
mpy
1.0
0.2
0.7
13.8
1.1
<0.1
TABLE LXI
Corrosion of Alloys in Adipic Acid Process
Low temperature, 100 C (212 F), reaction with ammonium vanadate and cupric ion, process involved
oxidation of cyclohexanone and cyclohexanol (KA oil)
in strong nitric acid. In addition to the desired adipic
acid, succinic, glutaric and lighter acids were formed in
the process.
Corrosion Rate
Reactor
Scrubber
Separation
Still
Absorber
mpy mm/y
mpy mm/y
Crystallizer
mpy mm/y
Lower
Acids
Stripper
mpy mm/y
Crystallizer
mpy mm/y
Centrifuge
mpy mm/y
Product
Washing
and
Drying
Equip.
Alloy
Type 304
Stainless Steel
Type 316
Stainless Steel
.23
.30
12
.23
.91
36
.18*
7*
.41
16
.03
.13
Nil
Nil
.36
14
.05
.05
.30
12
.08*
3*
.05
.03
.05
Nil
Nil
CARPENTER
.10
.05
.03
.13
Nil
Nil
.03
Nil
Nil
.03
Nil
Nil
HASTELLOY
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
alloy C-276
Titanium
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil*
Nil*
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
alloy 20Cb-3
*Pitting indicated
TABLE LXII
Laboratory Tests for Corrosion of Alloys
in Molten Adipic Acid at 170 C (338 F)
Corrosion Rate
Alloy
mm/y
mpy
1.30
51
.43
17
Page 50
TABLE LXIII
Corrosion of Alloys in Glutaric Acid
Glutaric Anhydride Mixtures
Conditions:
Temperature, C
Temperature, F
Exposure, days
40-90
104-194
1
(oxidation)
7
210
410
1
(distillation)
9
260
500
210
410
13.5
Corrosion Rate
Alloy
mm/y
mpy
mm/y
<.03
Nil
03
3.56
<1
Nil
140
1.58
.28
.15
.56
66
<.03
Nil
30
Copper
MONEL alloy 400
mpy
62
11
6
22
26
<1
Nil
12
mm/y
.94
.20
.86
<.03
Nil
Nil
mpy
mm/y
mpy
37
8
34
<1
Nil
.69
41
23
18
.20
27
16
9
7
8
Page 51
F. Naphthenic Acids
TABLE LXIV
Corrosion of Stainless Steels in Molten
Pimelic (Heptanedioic) Acid
Conditions: Metal specimens completely immersed in
molten acid under quiescent conditions at
225 C (437 F). Unreported contaminant
suspected to be present. Results shown
are averages of duplicate tests.
Corrosion Rate
Initial 117 hr
Alloy
Second 73 hr
mm/y
mpy
mm/y
mpy
9.36
5.89
369
232
12.89
7.26
508
286
1.65
65
2.77
109
Fig 13 Corrosion Isotherms for Various Steels and MONEL alloy 400 in
White Oil/Naphthenic Acid Blends at 235 C (455 F) Temperature
Page 52
TABLE LXV
Corrosion of Alloys in Various Concentrations
of Aqueous Lactic Acid
Conditions:
% Lactic Acid
Temperature, C
Temperature, F
Test Period, days
Other
0.5
100
212
1
1
65
149
1
2
100
212
1
1%
2%
5
26
79
21
45
26
79
14
Aerated;
agitated
10-50
54
129
15
Field Test
in vacuum
evap.
Corrosion Rate
0.5%
Alloy
Type 304 Stainless Steel
INCONEL alloy 600
C71000
(Cupro- nickel 80- 20)
C71500
(Cupro-nickel 70-30)
5%
45%
10-50%
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
.03
Nil
Nil
.03
Nil
0.1
.20
.02
0.9
1.4
57
References 19, 49
Page 53
TABLE LXVI
High Temperature Exposure of Cast
Stainless Steels in
Aqueous 50% Lactic Acid
(Laboratory tests in autoclaves for 18-22
hours at temperatures shown)
Corrosion Rate
107 C (225 F) 151 C (304 F) 157 C (315 F) 162 C (324 F)
Alloy
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
Nil
Nil
Nil
Nil
2.29
Nil
Nil
Nil
Nil
90
44.20
Nil
2.03
1740
Nil
80
27.94
39.88
1100
1570
.99
1.65
39
65
CF-8
CF-8*
CF-8M
CF-8M*
Copper
Reference 9
TABLE LXVII
Corrosion of Alloys in Boiling Aqueous Lactic Acid
Solutions During Five-Day Laboratory Tests
Corrosion Rate
Alloy
Type 304
mm/y
mpy
mm/y
.0854.61 32150
mpy
mm/y
mpy
56.64
2230
7.21
284
Stainless Steel
Type 309
3.30
130
<.03.38
<115
.03
.08.33 313
<.03
<1
.03
.18
<.03
<1
.05
.03
.03
.10
.05
.43
17
.38
15
.13.33
513
.15
.15
Stainless Steel
Type 316
Stainless Steel
CARPENTER
alloy 20Cb-3
INCOLOY
alloy 825
HASTELLOY
alloy C-276
HASTELLOY
alloy B
INCONEL
alloy 600
MONEL
alloy 400
Copper
.33
13
.05
.08
Zirconium
Nil
Nil
Nil
Nil
Nil
Nil
Titanium
.03
.03
<.03
<1
Tantalum
Nil
Nil
Nil
Nil
Nil
Nil
<.03
<1
<.03
<1
Columbium
3. Tartaric Acid
Tartaric acid (dihydroxybutanedioic acid) is one of the
more innocuous acids produced in large quantity. As
indicated by Table LXVIII, the product is not aggressive in
aqueous solution up to the boiling point. Any of the
austenitic stainless steels maintain purity in the product and
prevent undesired contamination when storing or
processing the tartaric acid solutions. Higher alloys are not
indicated to be required for such service.
4. Citric Acid
Citric acid (hydroxypropane tricarboxylic acid) is a more
aggressive compound. This tart-tasting constituent of
citrus products can be handled well by the austenitic
stainless steels. Data for many of the other alloys are
shown in Table LXIX. Here it will be noted that Alloy 400
is a candidate for use in many of the food product services.
Others have described the use of MONEL alloy 400 and
14, 41, 42
other nickel-base alloys for such use.
As with the
other organic acids, the presence of air will determine the
rate of corrosion on Alloy 400 in these solutions. Alloy
600 and other alloys of chromium and nickel have good
resistance to the acid and can be used when desired.
References 49, 51
Page 54
TABLE LXVIII
Corrosion of Metals by Aqueous Tartaric Acid Solutions
Conditions: Laboratory tests without aeration or deaeration except as noted.
Corrosion Rate
%Tartaric Acid
Temperature C (F)
Test Period, days
Other
Alloy
2
26 (79)
21
5
26(79)
21
10
35(95)
6
Aerated
60(140)
6
Aerated
100(212)
6
Aerated
103(217)
2
35(95)
6
Aerated
25
60(140)
6
Aerated
30
100 (212)
6
Aerated
26(79)
11
60(140)
11
50
60(140)
6
Aerated
35(95)
6
Aerated
100(212)
6
Aerated
57
54(129)
10
Field lead.
yacuum
yap.
mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
Nil
Nil
Nil
.01
Nil
Nil
Nil
0.4
.01
Nil
Nil
.04
.4
.1
Nil
1.5
.01
Nil
Nil
.48
Nil
.03
0.2
Nil
0.1
<0.1
19
.02
0.8
.04
1.6
Nil
11
Nil
Nil
Nil
Nil
Nil
Nil
Nil
.01
Nil
Nil
.02
0.1
Nil
Nil
Nil
Nil
0.1
Nil
<0.1
Nil
Nil
Nil
Nil
Nil
Nil
.01
Nil
Nil
0.4
Nil
Nil
.05
.01
Nil
2.1
0.5
Nil
.06
2.4
.03
1.2
.05
1.8
TABLE LXIX
Corrosion of Metals by Citric Acid
Corrosion Rate
%
Citric
Acid
Temperature
Test
Period
Type 316
Stainless
Steel
INCOLOY
INCONEL
alloy 825
alloy 600
MONEL
Nickel 200
Days
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
78.8
78.8
78.8
60.8
86
140
216
212
150.8
212
61
60-78*
26
26
26
16
30
60
102
100
66
100
Boiling
100
26
60
Boiling
20
100
Boiling
26
90
Boiling
60
42-64
44
7
21
30
7
7
3
6
3
2
45
6
11
11
7
1
6
6
7
2
1
30
37
Nil
Nil
09
53
02
06
3.5
21
0.6
2.4
.01
.06
.16
.02
.12
.13
.10
.11
.22
Nil
.43
.01
65
Boiling
30
.21
8.1
.12
4.8
.79
31
.19
1
2
5
7
10
15
20
25
30
50
58
212
78.8
140
68
212
78.8
194
140
107.6147.2
Page 55
mpy
alloy 400
C71500 (70-30
Cupro-nickel)
CARPENTER
Copper
alloy 20Cb-3
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
2
2.2
6.2
.9
4.9
5
4.1
4.2
8.8
.1
16.8
.5
Nil
.03
.07
.04
.19
.21
.53
Nil
.16
.02
Nil
1.1
2.7
1.5
7.4
8.4
2.1
.1
6.2
.9
.06
.02
2.5
.8
.07
2.8
.01
Nil
Nil
.14
.2
.1
Nil
5.5
7.3
.11
4.2
TABLE LXX
Corrosion of Stainless Steels by Citric
Acid Containing Chlorides
Corrosion Rate
Solution
No Chloride
Metal
Type 304
Stainless Steel
Type 316
Stainless Steel
No Chloride
85 (185)
Temperature, C (F)
Specimen 1 Specimen 2
Specimen 1 Specimen 2
Specimen 1 Specimen 2
Specimen 1 Specimen 2
<.03
<1
<.03
<1
.10
.08
<.03
<1
<.03
<1
.03
.03
<.03
<1
<.03
<1
Nil
Nil
Nil
Nil
<.03
<1
<.03
<1
<.03
<1
<.03
<1
5. Chloroacetic Acids
The chloroacetic acids are a most important product for
the preparation of drugs, dyes, agricultural chemicals and
as intermediates for the preparation of other organic
compounds. Monochloroacetic acid and dichloroacetic
acid are normally produced simultaneously and separated
as desired. Trichloroacetic acid may be produced by an
additional process step.
TABLE LXXI
Corrosion of Alloys in Monochloroacetic Acid (MCA)
a
Test
Temperature C (F)
Test Period, days
1
25 (77)
2
25 (77)
3
60 (140)
4
18 (64)
28
5
55 (131)
17
6
170 (338)
22
Corrosion Rate
Alloy
MONEL alloy 400
Nickel 200
INCONEL alloy 600
Copper
HASTELLOY alloy B
HASTELLOY alloy C
HASTELLOY alloy D
CARPENTER alloy 20
Type 316 Stainless
Type 317 Stainless
DURICHLOR
Lead
Silver
30% Nickel Cast Iron
NICHROME V*
mm/y
.18
.51
.03
.10
.03
.20
.66
mpy
7
20
1
4
1
26
mm/y
.28
.56
.33
.97
2.03
.94
mpy
11
22
13
38
80
37
a 1Laboratory
mm/y
.18
.18
.51
.94
.79
2.16
2.21
mpy
7
7
20
37
31
85
87
mm/y
.43
.69
.61
.48
.15
<.03
<.03
<.03
<.03
<.03
.05
mpy
17
27
24
19
6
<1
<1
<1
<1
<1
mm/y
.05
.03
.03
.08
.03
<.03
.05
.08
.05
<.03
.33
.03
mpy
2
1
1
3
1
<1
2
3
2
<1
13
1
mm/y mpy
.10
4
.08
3
3.56 140
.18
7
.36
14
.70
28
20.32 800
1.27
50
.53
21
1.50
59
test in 60% monochloroacetic acid liquor from a process containing 1.5% acetyl chloride, 0.5% hydrogen chloride and the
remainder acetic acid. Light agitation.
2Same as No. 1 with high agitation.
3Field test in MCA liquor comparable to that of Test No. 1
4Field test in tank containing 78% MCA in water with moderate aeration
5Field test in same solution as Test No. 3, but with no aeration.
6Field test in refined MCA in storage tank.
Page 56
solution would be nickel-copper Alloy 400 or the nickelbased molybdenum-chromium-iron alloy. The use of
Alloy 400 is contingent again on the removal of oxidizing
species from the aqueous systems; residual chlorine, air or
other oxidants, can greatly increase the rate of attack.
For the reaction area in chloroacetic acid production
equipment, where chlorine is reacted with acetic acid,
glass-lined steels, TEFLON-lined, or other fluorocarbon
plastic-lined equipment is often used. HASTELLOY alloy
C-276 appears to be acceptable for many of these exposures, but the conventional process utilizes lined equipment for the reaction area. Other metals such as tantalum
or titanium may also be used if available.
Trichloroacetic acid is perhaps even more corrosive than
monochloroacetic acid. Glass-lined equipment, titanium,
HASTELLOY alloy B-2, DURICHLOR and certain other
specific alloys selected after extensive testing may be used
for handling the material at lower temperatures. None of
the chloroacetic acids should be stored or processed in any
quantity without a thorough understanding of the corrosive
nature of these materials and the judicious choice of the
materials of construction for tankage or process
equipment. Although the nickel-based alloys are prime
candidates for use in these solutions once the free chlorine
is removed, all alloys may show evidence of pitting or
crevice corrosion in the halogenated acids, and a thorough
exploration of corrosion resistance of the various alloys in
a specific stream should be conducted.
6. Amino Acids
The aminocarboxylic acids are an important group of
chemicals used for the preparation of drugs, agricultural
chemicals and as precursors for numerous other organic
compounds. As a group, the compounds are not excessively corrosive. The basic material glycine (aminoacetic
acid) provides essentially the same corrosive characteristics as acetic acid at the lower temperatures and is less
corrosive than its counterpart at the higher temperatures.
As the molecule is lengthened, the amino acids become
less corrosive, and those above approximately four carbons in length can be considered as inhibitors in aqueous
INCOLOY alloy 825 tanks for the storage of monochloracetic acid resin
solution. This alloy was required to maintain product purity.
Page 57
A. Acetic Esters
One major use of acetic acid is as a precursor of the various
esters that become important solvents for paints and other
chemical products. In the production of acetic esters, the
acid is combined with other organic compounds containing a hydroxyl group. The more common esters are ethyl
acetate, butyl acetate, isopropyl acetate and Cellosolve
acetate.
Corrosion to be expected in the preparation of these
esters can vary greatly depending on the operation. If
acetic acid were the only corrosive contaminant present,
the data provided previously for acetic acid could be used
as a guide. Unfortunately, a catalyst is necessary to
improve the efficiency of the process, and in most
instances, the presence of this catalyst determines the
corrosion to be expected. Temperatures required for the
production of these esters will range from 60 to 150 C
(140-302 F), depending on the boiling point of the ester.
Sulfuric acid has long been used as the catalyst for
synthesis of the esters. This is added as concentrated
sulfuric acid in small quantities of only 0.5 to 2.0% of the
total charge. In anhydrous medium, this would not be
excessively corrosive. However, water is produced by the
reaction between the alcohol and acid which can serve as a
temporary diluent for the sulfuric acid. The water formed
TABLE LXXII
Corrosion of Alloys in Batch Acetic Ester Preparations
Conditions: Exposure of racks in same kettle during the preparation of esters
using sulfuric acid catalyst. Temperature varies with ester prepared.
Cupric ion present. Liquid (L) and vapor (V) exposures.
Test 1Ethyl and isopropyl acetate alternately for 50 days @ 110 C (230 F).
Test 2Isopropyl acetate for 14 days @ 110 C (230 F).
Test 3Amyl acetate for 11 days @ 115 C (239 F).
Test 4Ethyl and isopropyl acetate alternately for 81 days @ 110 C (230 F).
Test 5Butyl and methyl Cellosolve acetate alternately for 29 days @ 115 C(239 F) and 150 C (302 F).
Corrosion Rate
1
L
Alloy
mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
Type 304
Stainless Steel
.05
.56
22
.15
.28
11
.05
.43
17
.05
.30
12
Type 329
Stainless Steel
Type 316
Stainless Steel
Type 216
Stainless Steel
CARPENTER
alloy 20 Cb-3
JESSOP
alloy JS-700
HASTELLOY
alloy G
<.03
<1
.15
.28
11
.03
.03
.18
.10
<.03
<1
.23
.18
.23
.08
.10
.03
<.03
<1
.23
.41
16
.23
.08
.13
.13
.03
.03
.03
.03
.08
.08
.05
.05
.86
34
.15
.13
.08
.03
1.65
65
.10
4.57
180
.05
1.42
56
.08
2.72
107
.43
17
.13
.03
MONEL
alloy 400
Copper
Page 58
TABLE LXXIII
Effect of Sulfuric Acid Concentration on Corrosion of
Type 316 Stainless Steel in an Esterification Reaction
Conditions: Solution of 25% acetic acid, 59% butyl
acetate, 10% water and 6% butanol prepared
and sulfuric acid added as indicated. Tests
conducted at the boiling point.
Corrosion Rate
% Sulfuric Acid
Added (as 95% H2SO4)
mm/y
mpy
0.0
0.1
0.5
Nil
.48
5.92
Nil
19
233
1.0
17.53
690
TABLE LXXIV
Hot Wall Tests of Alloys in a Synthetic
Esterification Mixture
Conditions: Laboratory tests using hot wall apparatus for three days (<3 days for alloys showing
high corrosion rates) in a mixture of 83% acetic acid9.3% formic acid3.8% H2S04
3.9% water. Comparison with conventional immersion test at boiling temperature 112 C
(234 F) provided.
Hot Wall
Solution
Temperature
Alloy
E-BRITS 26-1
HASTELLOY alloy G
HASTELLOY alloy C-276
MONEL alloy 400
Copper (C10200)
Zirconium
Type 316 Stainless Steel
Hot Wall
Specimen
Temperature
Hot Wall
Corrosion
Rate
Immersion
Test Corrosion
Rate
mm/y
mpy
mm/y
mpy
120
112
118
118
118
118
248
234
244
244
244
244
150
155
140
137
135
142
302
311
284
277
275
288
3.94
.99
.48
.41
1.42
.03
155
39
19
16
56
1
1.88
.20
3.63
74
8
143
Page 59
TABLE LXXV
D. Acrylate Esters
The acrylate esters comprise one of the newer, more
reactive group of chemicals available for the synthesis of a
TABLE LXXVI
Comparison of Esterification Catalysts on
Corrosion of Alloys
Corrosion Rate
Test 1
Test 2
Alloy
mm/y
mpy
11.18
.25
440
10
8.38
330
.33
13
1.14
45
.43
17
.36
1.27
.58
14
50
23
HASTELLOY alloy C
.20
HASTELLOY alloy B
.58
.23
23
9
Nickel 200
.51
.99
20
39
.18
.43
7
17
Copper
.51
20
.18
CARPENTER alloy 20
INCOLOY alloy 825
ILLIUM alloy G
mm/y
mpy
Conditions: Preparation of a higher acetic ester in semiworks equipment using 1.5 per cent sulfuric
acid at 75-110 C (167-230 F) during 32
days for Test 1 and 0.32 per cent boron
trifluoride at 75-85 C (167-185 F) for 5
days in Test 2.
Corrosion Rate
Test 1
Alloy
Type 304 Stainless Steel
Type 316 Stainless Steel
E-BRITE 26-1
mm/y
.03
.03
.05
Copper (C10200)
Page 60
Test 2
mpy
1
1
2
mm/y
.43
.05
2.49
mpy
17
2
98
.03
.03
Nil
.18
Nil
7
Nil
.30
Nil
12
TABLE LXXVII
Corrosion Generated in Phthalic Anhydride Esterifications
Exposure 1Octyl phthalate batch preparation using 0.15% H2SO4 with trace chloride
present in some batches. Exposure of 83 days on 84 rpm agitator shaft in
kettle liquid at average of 149 C (300 F).
Exposure 2Higher alcohols and phthalic anhydride plus 0.5% toluene sulfonic acid
and 0.25% H2SO4 at 140 C (284 F) average for 135 days in kettle liquid.
Exposure 3Toluene sulfonic acid catalyzed reaction of phthalic anhydride and higher
alcohols at 174 C (345 F) for 10 days in glass laboratory kettle.
Corrosion Rate
1
Alloy
Type 304 Stainless Steel
Type 202 Stainless Steel
Type 316 Stainless Steel
Type 317 Stainless Steel
CARPENTER alloy 20
ACI CN-7M Casting
HASTELLOY alloy C
HASTELLLOY alloy B
INCOLOY alloy 825
INCONEL alloy 600
MONEL alloy 400
Nickel 200
Ni-Resist Type2
Copper
Titanium
mm/y
mpy
mm/y
mpy
mm/y
mpy
.25
.30
.15
.08
.03
<.03
.03*
.08*
.03
.10
.18
.08*
10
12
6
3
1
<1
1*
3*
1
4
3*
>1.27
1.60
1.04
.03
<.03
.03
.33
.08
.20
.15
>50
63
41
1
<1
1
13
3
8
6
.05
.05
.03
.13
.18
Page 61
TABLE LXXVIII
Field Exposure of Alloys in
Fatty Acid Esterifications
Exposure 1On agitator shaft in liquid of kettle during esterification of C12-C18 fatty acids with
alcohols + 0.25% H2SO4 at 100 C (212 F) for 33 days.
Exposure 2In liquid of kettle near head during esterification of fatty acids (myristic present) with
alcohols (isopropanol present) with sulfuric acid at approximately 110 C (230 F) for 82
days.
Exposure 3Liquid and vapor phase of a kettle (liquid velocity ca. 16 ft/sec) for 18 days during
glyceryl esterification, amidation and sulfurization of tall oil.
Corrosion Rate
1
Alloy
Type 304 Stainless Steel
Type 216 Stainless Steel
Type 316 Stainless Steel
Type 317Stainless Steel
CARPENTER alloy 20Cb-3
ACI CN-7M Cast Alloy
NITRONIC** 50
INCOLOY alloy 825
INCONEL alloy 600
INCONEL alloy 625
HASTELLOY alloy G
HASTELLOY alloy C-276
HASTELLOY alloy B
JESSOP JS-700
MONEL alloy 400
Nickel 200
Copper
Titanium
30% Nickel Cast Iron
Ni-Resist Type 1
Liquid
Liquid
3*
Liquid
Vapor
mm/y
mpy
mm/y
mpy
mm/y
mpy
mm/y
mpy
.51
.51
.10
.25
.10
.15
20
20
10
.16
.03
.15
.08
.01
.02
.01
.02
.01
.01
.09
.05
.01
6.2
1.1
5.8
3.1
0.4
0.9
0.4
0.7
0.4
0.5
3.7
2.0
_
0.3
.23
.05
<.03
.13
<.03
.18
.56
.97
.33
.15
<1
<1
7
22
38
13
6
<.03
<.03
<.03
<.03
<.03
.15
.30
.36
.15
.30
<1
<1
<1
<1
<1
6
12
14
16
12
*Reference 30
**Trademark of Armco Steel Corporation
Page 62
TABLE LXXIX
TABLE LXXXI
Base of Reactor
Alloy
mm/y
mpy
mm/y
mpy
.89
.25
.13
.13
.08
.03
.05
.08
.03
.03
.53
<.03
35
10
5
5
3
1
2
3
1
1
21
<1
5.08
>10.16
.33
.20
.51
.91
.58
.63
1.14
200
>400
13
8
20
36
23
25
45
Corrosion Rate
Alloy
mm/y
mpy
1.27
.33
.08
.05
.25
2.03
3.30
50
13
3
2
10
80
130
TABLE LXXX
Corrosion of Alloys in Higher Acrylate Esters Production
Conditions: Exposure in base of reactor processing higher
acrylates at 110-160 C (230-320 F) for times
shown. Sulfuric acid catalyst used.
Butyl
67 days
Octyl
11 days
Decyl
11 days
Corrosion Rate
Alloy
Type 316 Stainless Steel
CARPENTER alloy 20
INCOLOY alloy 825
HASTELLOY alloy G
HASTELLOY alloy C
HASTELLOY alloy B
HASTELLOY alloy D
INCONEL alloy 600
MONEL alloy 400
DURIRON
Titanium
Zirconium
mm/y
mpy
mm/y
mpy
mm/y
mpy
3.63-5.49
.13-.58
.61
.10
.08-.61
.15-.28
.08
.66-1.24
.18-.25
.03
.08-.13
.03-.05
143-216
5-23
24
4
3-24
6-11
3
26-49
7-10
1
3- 5
1- 2
10.16
1.78
1.02
2.79
400
70
40
110
>38.1
1.27
.76
1.90
<.03
>1500
50
30
75
<1
Page 63
REFERENCES
l. Tsinman, A. L, et al., Corrosion-Electrochemical Behavior of
Metals in Organic Media, Elecktrokhimiya, 11, No. 1, 1975, p.
127.
2. Flowers, J. W, Beck, E H. and Fontana, M. G., Corrosion and
Age Hardening Studies of Some Cast Stainless Alloys Containing
Ferrite, Corrosion, 19, No. 5. 1963, p. 186t.
3. Dillon, C. P, Compositional Effects in the Corrosion of Type 347
and 316 Stainless Steel in Chemical Environments, Corrosion, 16,
No. 9, 1960, p. 433t.
4. Hamstead, A. C. and VanDelinder, L. S., Comparative Corrosion
Resistance of 200 and 300 Series Stainless Steels in Chemical
Manufacturing Processes, Corrosion, 15, No. 3, 1959, p. 147t.
5. Elder, G. B., Corrosion by Organic Acid, Process Industries
Corrosion, Published by the National Association of Corrosion
Engineers, 1975, p. 247.
6. Shimose, T, et al., Corrosion Behavior of Various Metals and
Alloys in Acetic Acid Environments, Boshoku Gijutsu, 15, 2,
1966, pp. 49-55.
7. NACE Technical Committee Report, Corrosion by Acetic Acid,
Corrosion, 13, No. 11, 1957, pp. 757t-766t.
8. Rabald, E., The Influence of Oxygen on the Corrosion of Metals
in Organic Acids, International Symposium on Stainless Steels
and Alloys with Special Regard to the Chemical Industry, Prague,
No. 16, 11-13, September 1961, 10 pp.
9. Ohio State University Research Foundation, Corrosion at
Elevated Temperatures and Pressures, Report to the Alloy
Casting Institute, May 1, 1951.
10. Groves, N. D., et al., Corrosion of Metals by Weak Acids Under
Heat Transfer Conditions. Corrosion, 17, No. 4, 1961, p. 173t.
11. Intergranular Corrosion of Chromium-Nickel Stainless Steel,
Progress Report No. 1, Welding Research Council Bulletin No.
93, January, 1964.
12. Leonard, R. B., Thermal Stability of Hastelloy Alloy C-276,
Corrosion, 25, No. 5, 1969, pp. 222-228.
13. ASTM Standards, Detecting Susceptibility to Intergranular
Attack in Wrought Nickel-Rich, Chromium-Bearing Alloys, Part
10, Standard G 28-72.
14. Mason, J. E, Jr., The Resistance of Alloys to Corrosion During
the Processing of Some Foods, Corrosion, 4, No. 7, 1948, p. 305.
15. Guidelines for Selection of Marine Materials, Publication A404, The International Nickel Company, Inc., New York, 1971.
16. Togano, H., et al., Corrosion Tests on Materials Used in the
Synthesis of Acetic Acid from Methanol and Carbon Dioxide. I.
Examination in Acetic Acid Solutions at Increased Temperatures,
Tokyo Kogyo Shikenso Hokoku, 57, 1962, pp. 342-50.
17. Togano, H., et al., Corrosion Test on the Construction Materials
for Acetic Acid Synthesis from Methanol and Carbon Monoxide
(1) Corrosion Tests by Acetic Acid Solutions at Elevated
Temperatures, Boshoku Gijutsu, 10, 1961, pp.529-33.
18. Togano, H., et al., Corrosion Tests on the Materials of
Construction for Acetic Acid Synthesis from Carbon Monoxide
and Methanol (II) Tests in Acetic Acid Solutions at Temperatures
Below Boiling Points, Tokyo Kogyo Shikensho Hokoku, 60, 6,
1965, pp. 221-31.
19. Uhlig, H. H., Corrosion Handbook, John Wiley and Sons, New
York, 1958, pp. 89, 154, 156, 260, 274, 275, 289, 290, 298, 760.
20. Volokhova, V. 1., et al., Study of the Corrosion Resistance of
Electroless Nickel-Phosphorus Coatings, Prot. Met., 11, No. 3,
1975, p. 370.
21. Anon., Acetic Acid, Chemical and Process Engineering, 47, No.
10, 1966, p. 51.
22. Kirk-Othmer, Encyclopedia of Chemical Technology; 2nd Edition,
Vol. 8, John Wiley and Sons, New York, 1965, p. 386.
23. Loveless, L. W. J., The Catalytic Cracking of Acetic Acid for the
Production of Acetic Anhydride, Trans. of the Am. Inst. of
Chem. Engrs., 27, 1949, p. 7.
24. Miller, R. E, et al., Corrosion by Acids at High Temperatures,
Corrosion, 10, No. 1, 1954, p. 7.
Page 64
TRADEMARKS
ALLEGHENY
ALOYCO
AMBRALOY
CARPENTER
CHLORIMET
CROLOY
CRUCIBLE
DURALOY
DURICHLOR
DURIMET
DURIRON
E-BRITE
ELGILOY
EVERDUR
HASTELLOY
HAYNES
ILLIUM
INCOLOY
INCONEL
JESSOP
KROMARC
MONEL
MULTIMET
MP35N
NICHROME
NITRONIC
STELLITE
TEFLON
WAUKESHA
WORTHITE
PH 15-7Mo
17-7PH
17-4PH
PRODUCT OF
Allegheny Ludlum Steel Corporation
Aloyco Inc.
Anaconda American Brass Co.
Carpenter Technology Corporation
The Duriron Company, Inc.
Babcock & Wilcox Co.
Colt Industries Inc.
The Duraloy Co.
The Duriron Company, Inc.
The Duriron Company, Inc.
The Duriron Company, Inc.
Allegheny Ludlum Steel Corporation
Elgiloy Co.
Anaconda American Brass Co.
Cabot Corporation
Cabot Corporation
Stainless Foundry & Engineering, Inc.
INCO family of companies
INCO family of companies
Jessup Steel Company
Westinghouse Electric Corporation
INCO family of companies
Cabot Corporation
Standard Pressed Steel Co.
Driver-Harris Company
Armco Steel Corporation
Cabot Corporation
E. I. duPont de Nemours & Co.
Waukesha Foundry Company
Worthington Corporation
Armco Steel Corporation
Armco Steel Corporation
Armco Steel Corporation