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Metals
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H. 0. TEEPLE and
R. M. FULLER
International Nickel Co., 67 Wall St., New ‘fork
Equip=/
5, N. Y. I I
New Chemical Products and High Nickel Alloys Nickel and high nickel alloys are used in environments to which they are particularly resistant, yet the manufacture of new chemical products involves some of the reagents most commonly used in the chemical and process industries
N I C K E L and high nickel alloys have been used in substantial quantities since the turn of the century in the production of “new” chemical products. Their extensive application has been based on one or more important favorable factors such as resistance to corrosion by chemicals, good mechanical properties, rather unique physical properties, good fabricability, and the many useful forms in which the alloys are produced. I t is not claimed that the production of new chemical products over the years could only have been accomplished through the use of nickel or high nickel alloys, but a great many of these products have been possible because of economies directly related to the suitability of these materials. The alloys discussed in this article are listed in Table I, with their nominal chemical composition. These materials fall into several alloy groups : Nickel Commercially rolled nickel Low-carbon nickel Duranickel, wrought age hardenable alloy Nickel-copper Monel, nickel copper alloy
K-Monel, wrought age hardenable alloy H-Monel, silicon-containing cast allov S-Monel, silicon-containing age hardenable cast alloy Nickel-chromium Inconel Inconel X, wrought age hardenable allov Nickel-molybdenum Hastelloy alloy B Chlorimet 2 Nickel chromium - molybdenum tungsten Hastelloy alloy C Chlorimet 3 Nickel-silicon Hastelloy alloy D
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-
Experience has shown that the individual alloys included in each group will perform in much the same fashion corrosionwise, although the addition of certain alloying elements produces profound differences in mechanical and physical properties. Thus, upon occasion, it is possible to secure the advantages of the high tensile strength properties of the wrought age hardenable alloys with the assurance of no loss of corrosion resistance. Although nickel has useful resistance
to corrosion by a large number of chemicals and chemical solutions, the economic applications of nickel over the years have been, and are, based on particular resistance to the following corrosives: Caustic alkalies a t all concentrations and temperatures Commercially dried chlorine and hydrogen chloride to elevated temperatures Hydrochloric acid solutions within certain limiting concentrations and ternpera tures Hot wet organic chlorides and chlorinated organic solvents Fluorine and hydrogen fluoride a t elevated temperatures Hot aqueous solutions of inorganic neutral and acid chloride salts, except oxidizing salts Molten salts, such as sodium and potassium chlorides and sodium nitrate Molten alkali metals, such as sodium and potassium but not lithium Monel, by virtue of its high nickel content, is somewhat similar to nickel in its resistance to these corrosives, except molten salts and molten alkali metals. However, the appreciable copper content enables Monel to resist V O l . 48, NO. 1 1
NOVEMBER 1956
1971
Table 1.
Nominal Composition of High Nickel Alloys Chromium,
Molybdenum,
Iron,
Silicon,
Manganese,
%
%
%
%
%
%
0.05
0.2 0.2 0.30 1 0.75 0.75 0.75 0.25 0.5 1 1 1 1 1
0.1 0.02 max. 0.17 0.15 0.15 0.1 0.1 0.08
NateriaE
... ... ... ... ... ...
Nickel" Low-carbon nickel" Duranickel Momla
K-Monel H-Mone16
... 15.5
S-Monelb Inconel" Inconel X Hastelloy alloy B Hastelloy alloy C Hastelloy alloy D6 Chlorimet Z b Chlorimet 3b a
15.0
...
17
...
. I .
18
Also available in form of clad steel.
Test A :
8
.
.
28 17
... 32
18
0.35 1.4 0.9 2.0 2.0 7.5 7.0 6.0 6.0
...
3 max. 3 max.
0.15 0.50 0.1 0.50 3 4
0.25 0.40 1
1 10 1 1
strong hypochlorites, ferric chloride, and cupric chloride at moderate temperatures. I t is relatively unique in this respect, as it is one of a very limited number of wrought materials available for such aggressive service. Chlorimet 3 is a somewhat similar alloy available only in cast forms. The Hastelloy nickel-silicon alloy D is usefully resistant to boiling sulfuric acid at most concentrations and is used extensively even though it is available only in cast forms with rather limited mechanical properties. There are a number of other high nickel alloys commercially available which are useful in a large number of aggressively corrosive environments. However, a discussion of the applications of the more widel>- used types will include typical performances of many of these other special alloys. Many of the corrosives described in this article are commonly encountered in the chemical and process industries and are frequently involved in the production of many of the new chemicals currently being manufactured. Nickel or high nickel alloys are employed to obtain
Corrosion Resistance of Nickel Alloys to Chlorinated Organic Compounds Field test, 19 days in chlorination o f phenol at 125' F., specimens exposed in vapor phase S a m e a s A except specimens exposed i n liquid phase Field test, 21 days in distillation of crude 2,4-dichlorophenol at 280' F. Field test, 52 days in vapors in reactor producing 2,4-dichlorophenoxyaceticacid, at 248' F. S a m e a s test D, except specimens exposed 29 days in liquid phase Field test, 128 days in vapor phase in reactor producing tetraalkyl thiuram disulfide at 68' F. S a m e a s test F, except specimens exposed in liquid phase
Test B : Test C : Test D : Test E : Test F : Test G :
Xaterzal
Test A
Monel Nickel Inconel Hastelloy B Hastelloy C Chlorimet 3 Carbon steel
0.0024
7 972
... ... ...
0.15 0.05
0.0010 0.0012 0.0020 0.0011 0.0015 0.034
Indicated Corrosion Rates, Inch Penetrataon,'Year Test B Test C Test D Test E Test F 0.0068 0.0065 0.0094
0.0067 0.0007 0.0008 0.030
0.04
0.12 max. 0.12 max. 0.12 max. 0.10 0.07
yo Other Elements
... . . e
... ...
Al,4.4
Ti, 0.5
Al, 2.75
Ti, 0.5
...
... ...
...
Al, 0.90
... ... AI, 1 ... ...
I . .
...
Ti, 2.5
...
w, 4.5
... ... ...
Available only i n cast form.
more effectively attack by nonoxidizing acids such as sulfuric, hydrochloric, hydrofluoric, phosphoric, and these acid salts. I n addition, Monel has superior resistance to nonoxidizing salt solutions such as sodium, calcium, and magnesium chlorides. Inconel, a high nickel alloy containing about 15% chromium is more resistant to oxidizing solutions than is nickel or Monel. However, because of its high nickel content, Inconel also is resistant to many of the same corrosives as are nickel and Monel. including hot caustic alkalies. chlorine, and hydrogen chloride at elevated temperatures. In many of these instances, the advantage of the greater strength of Inconel at high temperatures is an important factor in its use. The Hastelloy nickel-molybdenum alloy B is particularly resistant to attack by hot concentrated solutions of hydrochloric. sulfuric, and phosphoric acids. Chlorimet 2 is a somewhat similar alloy available only in cast forms. The Hastelloy nickel-chromiummolybdenum-tungsten alloy C finds economical application in wet chlorine,
Table II.
... ... ... ... . a .
Carbon,
Test G
0.0034
0.027
0.034
...
0.0042
0.0058 0.0065
...
0.0043
0.057
0.163
0.0023
0.0053
0.0002
0.0002
0.14
0.36
... ... ...
0.020
INDUSTRlAL AND ENGINEERING CHEMISTRY
...
... ...
*..
...
...
... ... ...
... . . I
0 * 0001
... ...
economical corrosion resistance, or for protection against product contarnination.
Chlorine and Organic Chlorinations Nickel and Monel are resistant to commercially dried chlorine, Hastelloy alloy B to wet hydrogen chloride and hydrochloric acid: and Hastelloy alloy C to wet chlorine. In many organic chlorination reactions a t moderate temperatures these several situations arc encountered. These are opportunities for the economical application of onr or more of these materials of construction. Among new chemical products involving chlorination reactions are those comprising a group of modern insecticides, pesticides, and herbicides. In this group are 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyaceticacid, chlorophenol, benzene hexachloride, and tetraalkyl thiuram disulfide. In Table I1 are presented corrosion data pertinent to several of these compounds. In the production of 2,4-dichlorophenoxyacetic acid, nickel is used for the dichlorophenol still, steam coils, fractionating tower, condenser, and storage tanks. The weigh tank for the pure dichlorophenol is made of Monel, as is much of the equipment for making the 2>4-D such as the reactor, stripping column, centrifuge, and dryer. Monel also is used for the reactor in which the sodium salt is made. Hastelloy alloy C is used as a lining in a vessel operating at 175 pounds per square inch and 300' F, in the recovery of benzene hexachloride. Kickel is used for cooling coils. Inconel \vas specified for the reactor material of construction in the manufacture of tetraalkyl thiuram disulfide and has performed satisfactorily. Other organic chlorinations involving the use of nickel and nickel alloys are in the manufacture of vinyl chloride, vinylidene chloride, and poly(viny1 chloride), a plastic material which is finding much
SPEC IA L METALS- E Q U IPMENT - P R O DUCTS commercial application in handling aggressive corrosive solutions a t moderate temperatures. Duranickel is commonly employed as dies in the extrusion of these chlorinated plastic materials. I n the transporting of organic chlorides such as benzyl chloride, nickel is used for shipping drums and for tank trucks to maintain product purity. Benzyl chloride finds use in the manufacture of dyestuffs, plasticizers, germicides, and pharmaceuticals. Nickel is used for reaction vessels, distillation columns, and storage tanks in the production of phosphorus trichloride and phosphorus oxychloride. Nickel also is used for shipping drums and as clad steel for tank cars. Table I11 presents corrosion data showing the suitability of nickel for these applications. Phosphorus trichloride finds use as a plasticizer and as an intermediate in the production of tricresyl phosphate. Tricresyl phosphate, or TCP, is employed as a gasoline additive to reduce undesirable carbon build-up on spark plugs and in the engine. Nickel is used for the reactors employed in the manufacture of tricresyl phosphate. Corrosion data fer the in-service performance of nickel alloys are presented in Table IV. A new chemical product is chlorine trifluoride, and one of its uses is as an oxidant in rocket fuel systems. Nickel is used for the reactor, which operates at 700' F., for thermocouple wells, and for run-off lines.
Much interest has developed in the use of chlorine dioxide for paper pulp bleaching. The corrosive conditions prevailing in the generation of chlorine dioxide are very severe and much use is made of nonmetallic materials. Studies disclosed that Hastelloy alloy C and its equivalent, Chlorimet 3, have substantial application in bleaching process. Hastelloy alloy C is used for linings in the mixers where the chlorine dioxide is mixed with the pulp. I n other parts of the bleaching process, Hastelloy alloy C is used as the feed pipe for admitting chlorine to the unbleached pulp. In high temperature chlorination reactions, such as the production of titanium tetrachloride, Inconel is especially suitable because of its resistance to corrosion combined with good strength a t high temperature. Some of the more interesting new chemical products are the organic isocyanates. These include such products as ( u ) highly abrasion resistant elastomers, (6) a variety of rigid or semirigid foamed materials, (c) adhesives that are particularly effective in bonding dissimilar materials such as fabrics to rubber, plastics, and rubbers to metals, and (d) monomers for polymers for synthetic fibers, bristles, and filaments. A process for making isocyanates is based on the reaction of phosgene with a n amine or amine salt such as amine hydrochloride in a suitable solvent, such as dichlorobenzene. In these reactions the use of nickel is dictated for process equipment
Corrosion Resistance of Nickel Alloys to Phosphorus Trichloride and Phosphorus Oxychloride
Table 111.
Test A : Field test, 30 days in mixture of phosphorus trichloride, organic solvent, and trace of water at 293' F. Test B : Field test, 20 days in vapor phase of phosphorus oxychloride head fractions at reflux temperature Test C : Same as test B, except specimens exposed in liquid phase Tegt D : Field test, 153 hours in reaction kettle in mixture of hydrochloric acid, phosphorus oxychloride, and cresylic acid used in manufacture of tricresyl phosphate
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Material Monel Nickel Inconel Castiron
Table IV.
Indicated Corrosion Rates, I n c h Penetration/ Y e a r Test B Test C Test D Test A 0.0024 0.0008 0.0006 0.0055 0.0018 0.0010 0.0004 0.0035 0.0014 0.0007 0.0008 0.0043
...
...
...
0.96
Table V. Corrosion Data in Iodide Process for Zirconium Production (24-hour tests in iodine vapor) Corrosion R a t e , I n c h PenetrationlPer Y e a r Material 572' F . 842" F. Platinum 0 0.0002 Tungsten 0 0.0003 Gold 0 0.0009 Molybdenum 0.0001 0.0013 Tantalum 0.0002 0.035 Hastelloy B 0.002 0.018 Hastelloy C 0.002 Inconel 0.004 0.021 Nickel 0.011 0.047 Monel 0.022 0.10 Silver Completely Completely reacted reacted a B. Lustman and F. Kerze, Jr., "Metallurgy of Zirconium," Natl. Nuclear Energy Ser., Div. VII, p. 143, McGraw-Hill, New York, 1955.
...
by the need for resistance to attack by hydrogen chloride and by dilute hydrochloric acid that may be formed by the hydrolysis of the reactants.
Iodine There is today much interest in the metal zirconium. I n the iodide process for zirconium production it became necessary to find a material of construction resistant to attack under the prevailing conditions. A number of tests were carried out, and the results are shown in Table V. As a consequence, Hastelloy alloy B was selected for the reactor. Molybdenum was utilized for internal parts subject to especially severe corrosive conditions. Gold proved to be an excellent high temperature gasket material. Inconel is being used for the reactor in which zirconium tetraiodide is formed. The use of nickel to resist attack by chlorine in the Kroll process has been reported. Inconel is being used to handle the zirconium chloride during the reduction process.
Fluorine, Hydrogen Fluoride, and Hydrofluoric Acid
Plant Corrosion Tests of Nickel Alloys in Tricresyl Phosphate
Test A : 80-day exposure in bottom of cresol distillation colum at 250-300' F. Test B : 90-day exposure in crude tricresyl phosp4ato distillation column at 570" F. Test C : 33-day exposure in SS-QO% tricresyl phosphate, 5% cresylic acid, 5% thiophenols, traces of HCl and organic chlorides at 580° F. Test D : 43-dag exposure in 88-90% tricresyl phosphate, 5% cresylic acid, 570 thiophenols, traces of HCl and organic chlorides at 300' F. Material Nickel Monel Hastelloy B Hastelloy C Carbon steel
Indicated Corrosion R a t e , I n c h PenetrationlYear Test A Test B Test C Test D 0.00,08 0.005 0.008 0.0002 0.0014 0.007 0.013 0.0020 0.0001 0.0002 0.012 0.029 0.044 0.063
......
...
... ...
...
Nickel and Monel are useful for handling fluorine, hydrogen fluoride, and hydrofluoric acid in many industrial applications. Their resistance to attack a t high temperatures has been noted. Other applications are the use of nickel in handling hexafluoride and the extensive use of Monel in the production of isooctane by hydrofluoric acid alkylation and in the construction of improved fluorine cells. Both Monel and nickel are used in the production of stannous fluoride, a n additive to dentifrices. VOL. 48, NO. 11
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Bromine Monel and nickel are used as shipping containers for commercially dried bromine and they also find use in the manufacture of chlorobromomethane, a new fire extinguisher fluid.
AI kalies While it is known that nickel has excellent resistance to corrosion by the fixed alkalies. a new application is the use of low-carbon nickel in Dolvtherm heated evaporators for the continuous production of rayon-grade anhydrous caustic soda. Much space is conserved Over the old-fashioned caustic pot method. Low-carbon nickel and I n conel are used in organic caustic fusion reactions producing such compounds as phenol and resorcinol. The choice of nickel or Inconel is predicated upon the absence or presence of sulfur compounds and, also, the operating temperatures. If sulfur compounds are present. or if the metal wall temperature is substantially above 600’ F.. Inconel is the preferred material, since nickel and Inconel are suitable for use in contact with sodium and nickel is used in the manufacture of this metal. I n alkaline pulping Inconel has proved itself to be suitable for digester linings because of its economical resistance to corrosion by the alkaline liquors and its freedom from stress corrosion cracking in the environment. I n the manufacture of caustic-base dyestuffs, nickel and nickel-clad steel are used for autoclaves operating at 410’ F. and at 250 pounds per square inch. Of dual concern are the maintenance of product purity and resistance to corrosion by the environment.
Pharmaceuticals In the manufacture of pharmaceuticals it is important to use materials of construction that combine adequate protection against product contamination and resistance to corrosion by the process conditions. Such alloys are Inconel and Hastelloy alloys for Chloromycetin and penicillin. Hastelloy alloy B is used in the production of Aureomycin (chlorotetracycline) and Achromycin (tetracycline). Hydrochloric acid is used in the process, and the alloy provides adequate resistance to corrosion as well as protection for product purity. An interesting use of these new tetracyclines is in combination with streptomycin and vitamin B12 in soluble fertilizers for foliar feeding of plants.
Synthetic Detergents I n the production of synthetic detergents such as alkyl aryl sulfonates, Monel is used to provide resistance to attack by dilute hydrochloric acid present in the alkylate produced by a FriedelCrafts reaction. After sulfonation, Monel
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again is used to protect product purity since even small traces of iron in the detergent may accelerate unwelcome chemical reactions. A large number of synthetic detergents such as anionic, cationic, and nonionic detergents are finding much commercial application. Xickel and nickel alloys are commonly employed in the production of fatty acids of a high degree of purity. Inconel is used for the continuous hydrolysis of fats and oils. Nickel and Inconel are used in continuous soap-making processes, and nickel is commonly employed in the deodorization of fats and oils to avoid oxidation of the fats, as it has been found that nickel is free of any pro-oxidant effect on the fat.
Acids
ALLOY CORROSION RESISTANCE Ni
Am. SOC.Metals, “Metals Handbook,” 1948. Atomic Energy Commission, Washington, D. C. “Liquid Metals Handbook,” 1950. (Molten alkali metals) Brown, M . H., D e Long, T.V. B., Auld, J. R., IND.Eso. CHEM. 39, 839-44 (1947). (Dry C12 and HC1 to elevated temperatures) International Nickel Go. Inc., Tech. Bull. T-29 (1945). (HC1 within limited concentrations and temperatures; hot wet organic chlorides and chlorinated organic solvents) Ibid., T-13 (1948). (Hot, aqueous inorganic neutral and acid chloride salts, except oxidizing salts) Ibid., T-6 (1949). (Caustic alkalies) Meyers, W.R . , D e Long, W.B., Chem. Eng. Progr. 44, 359-62 (1948). (F and HF a t elevated temperatures) Uhlig, H. H., “Corrosion Handbook,” IViley, New York, 1948. Ni-Cu
There are, of course, a wide variety of applications of nickel alloys in acid service. Monel is used for a neutralizer column, a reboiler, vaporizer bundles, and vessels in the handling of diisopropyl sulfate used in the manufacture of isopropyl alcohol. Monel is used to resist corrosion by dilute sulfuric acid at 170’ F. and for the neutralizer where residual acids in the isopropyl alcohol are neutralized by caustic soda. Monel is commonly employed in many instances in hydrofluoric acid alkylation to produce high octane gasoline. Inconel is used for pectin evaporators to withstand the hydrochloric acid added to aid the hydrolysis of insoluble protopectin to soluble pectin. Inconel was chosen to protect product purity and, at the same time, to resist stress corrosion cracking by the environment. Hastelloy alloy B is used in the handling of hydrogen chloride gas at 1000’ F. in the production of tetraethyllead. Kickel is used as domes on the sodium cells to withstand the corrosive attack of chlorine a t 1100’ F. Hastelloy alloy B also is used in the petroleum industry in the isomerization of butane and butylene employing an aluminum chloride-hydrogen chloride catalyst. This alloy also is used for pumps for recycling the corrosive catalyst and for valves in the catalyst recovery operation. I n the manufacture of a particular dye intermediate, the Hastelloy nickel-silicon alloy D is used for agitator shafts, propellers, and thermometer wells in a kettle in which concentrated sulfuric acid is heated to a temperature of 392’ F. During the process certain organic compounds containing chlorine are added and the hydrogen chloride gas formed a t the high temperature causes severely corrosive conditions.
BIBLIOGRAPHY
International Nickel Co., Inc., Tech. Bull. T-29 (1945). (Hot salt solutions) Ibzd., T-3(1948). (HzSOa) Ibrd.. T-29 11945). IHC1) Friend, T.V. Z., Teeple, H.’O., Oil and Gas .I. 44, 87-101 (March 16, 1946). (HF) Friend, W.Z., Chem. and .Met. Eng., No. 9, 203-6 (1946). (HsPOh) Ni-Cr
International Nickel Co. Inc., Tech. Bull. T-13 (1948). (Hot salt solutions, Cl2, HCl) Nickel-Mo
Haynes Stellite Division, “Hastelloy High Strength, Nickel-Base Corrosion-Resistant Alloys,” 1950. (Hot HCI, HzSO4, H3P04) Fontana, M. G., Chem. Eng. 53, No. 10, 114-15 (1 946). Ni-Cr-Mo-W
Haynes Stellite Division, “Hastelloy High Strength, Xickel Base Corrosion Resistant Alloys,” 1950. (’iYet Cl2, strong hypochlorites, FeC13, CuC12) HALOGEN ACTION
Friend, W.Z., Teeple, H . O., Oil and Gas J. 44, 87-101 (March 16, 1946). (HF alkylation) Haines, G. S . , I N D . END. CHEIII.41, 2792-7 (1949). (Br) International Nickel Co., Process Inds. Quart. 14, No. 4 (1953). (Bleaching) Lustman, B., Kerze, F., Jr., “Metallurgy of Zirconium,” National Nuclear Energy Series Div. VII, p. 143, McGraw-Hill, New York, 1935. (I2) Miles, P. T., Wiswall, R. H., Heus, R . J., Hatch, L. P. ATucucleonics 12, No. 7, 26-9 (1954). (UFs) Miller, G. L., “Zirconium,” Academic Press, New York, 1954. Raynor, W. M., “Zirconium and Zirconium Alloys,” Am. Soc. Metals, Cleveland, Ohio, 1953. (12) PHARMACEUTICALS
Lee, J. A , , “Materials of Construction for Chemical Process Industries,” McGraw-Hill, New York, 1950. (Penicillin) Olive, T. R., Chem. Eng. 56, No. 10, 107-12 (1949). (Chloromycerin) SYNTHETIC DETERGENTS
International Nickel Co., Process Inds. Quart. 14, No. 4 11953). Ziels, N. W., Schmidt, W.H., Orl and SO@ 22, No. 12, 327 (1945). \
ALKALIES
Badger, W. L., Standiford, F. C., Chem. Eng. 61, KO. 2, p. 183-7 (1954). (Anhydrous NaOH) Teeple, H. O., Southern Pulp Paper M f g . 16, No. 8, 62, 64, 66 (1953).
INDUSTRIAL A N D ENGINEERING CHEMISTRY
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RECEIVED for review A p r i l 21, 1956 AccEPTEr) September 12, 1956
