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    AlloySelectionforCausticSodaService 10019 PDF

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    AlloySelectionforCausticSodaService 10019 PDF

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    Michael Walters
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    AlloySelectionforCausticSodaService 10019 PDF

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    Michael Walters

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    © All Rights Reserved
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    NiDI Need Pert cud resis Alloy selection for caustic Pyele rea (er) ret eo ae Ree La) The material presented in this publication has been prepared for the general information of the reader and should not be used or relied on for specific applications without first securing competent advice. ‘The Nickel Development Institute, its members, staff and consultants do not represent or warrant its suitablity for any general or specific use and assume no liability or responsibilty of any kind in connection with the information herein. Alloy selection for caustic soda service by C.M. Schillmoller* Caustic soda (ie., sodium hydroxide, NaOH) and chlo- rine are co-produced by the electrolysis ofa sodium chloride solution. Both chemicals find world-wide application in the chemical and related process industries. (Alloy selection for Chlorine is discussed in the NiDI publication #10020, “Alloys to Resist Chlorine, Hydrogen Chloride and Hydrochloric Acid.”) Caustic soda ranks third in tonnage production among the inorganic chemicals; some 13.2 million tons were used in the USA alone in’ 1986. Roughly half of all caustic produced is used in the ‘manufacture of other chemicals. Another 16% is consumed by the pulp and paper industry. Other important uses are in the production of rayon, cellulose, textiles, petroleum products, soaps and the refining of Bauxite ore in the production of aluminum. CRITERIA FOR MATERIALS SELECTION A number of materials of construction may be used to produce and handle caustic solutions. Their suitability for specific applications will depend upon factors associated With the concentration and use of the caustic and the process variables involved In general, factors to be considered in materials selec tion include practicality, availability, mechanical properties, corrosion resstance, risk/benefit considerations and eco- nomics. Critical factors in caustic service include: 1. The concentration of the caustic solution, 2. The temperatures to be encountered (including pos- sible excursions) 3. The presence of other chemicals which may be present in the caustic, as contaminants or additives. 4, Tolerance limits for metallic ion contamination of the caustic itself (or of the process end-product) 5. Residual or applied tensile stresses, which may affect corrosion resistance. 66. The economics of costlife considerations. Metals and alloys most frequently considered for use in caustic soda are carbon steel, stainless steels, nickel and high-nickel alloys. Some alloys, with their generic names, common trade-names, UNS numbers and nominal com- positions are given in Table 1 Table 1 ‘Alloys commonly used in caustic soda systems | Reterence Nominal Composition, 9 AST | UNS |Most Common Mater intext” [Wr] Cr] Fe] Mo| [7 B) | Numbers | ‘Tradenames. Nickel Nickel ‘oy 200 | 99. 161-165 | 102200 | Nickel 200 Lomearbon Nickel ‘iy 201 | 99. eictes_| No2201_| Nickel 201 Nickel Copper Alloys Nickel-copper alloy ‘Alley 400 | 67 15 3i 163-165 | 1o4s00 | Monel 400 ‘Nicke-Cromiumon Alloys Nicketehwomium alloy Atoy 600 | 76 | 15] 8 169-168 | 106600. | Incone 600 Niekeliron-chromium alloy ‘Ay 600 | 32 | 21) 46 4es.407 | Noee00 | incoley” 600 Nekeron-chromium- ‘molycopper alloy Mloy 2s | a2 | 21] so] 9 | 23 163.423 | Noee25 | Incoloy* 825 Nicketiren chromium ‘molycopper alloy aey20 | 36 | 20] 39 | 25 | 39 484-468 | NoB020 | Carpenter: 20.003" ‘Siaiiess Steels ‘Chromiumnicksl stainless type 304 | 10 | 19) 72 s20400 | Type 204 Ghromiumnicketmoly staniess | Typo set | 12 | 18) 70 531003. | Type ste. Ghromium stanioss ‘Type 490 17] 83 543000 | Type 430 Ghromium-moly stains 26.4 as| 73| 4 5626-1 Titanium Tianium, grade 2 Tanium Gre +) 398 Tianium G2 "Mana acre! and Tas are Padarames othe inaratoal Mekal Ga "*Carpente’and 20 C23 are vadenames of CARTECH *Schitimoller Associates, Houston, TX; Consultant to NiDI As these represent a considerable variation in first costs, the final choice for a specific service will depend on an anal- ysis of all of the above factors. MATERIALS OF CONSTRUCTION ‘Steel and Cast Irons Carbon steel is useful for handling sodium hydroxide up to about 50% concentration, where iron contamination is not_a problem, to moderate temperatures, eg., 85°C (185°F). However, steels are subject to an anodic form of environmental cracking [ie.,. stresscorrosion cracking {SCC}, often called “caustic embrittlement,” in hot caustic. ‘The relation of temperature and concentration in promoting cracking is shown in Figure 1. Because ofthe effect of residual stress in promoting this type of attack, both welded and cold-worked (je, flared, bent) fabricated steel equipment must be thermally stress. relieved to extend its life in caustic ser For services where iron pick-up is undesired, stee! tanks are frequently coated with an organic paint system to ‘minimize iron contamination. Cast iron is not usually used in caustic service, because of the safety problems caused by its inherent brittleness. However, ductile cast iron is permissible, and the high- nickel cast irons, such as Ni-Resists (UNS* F41NNN and F43NNN series) are even more corrosion-resistant. Austenitic Stainless Steels ‘The “18-8"ype stainless steels, exemplified by Types 304 ($30400) and 316 ($31600), have a usefully low corrosion rate in caustic at up to 50% concentration to about 70°C (160°F). Note that Figure 2, based on Copson’s work (5) on SOC of stainless steels, is somewhat more optimistic, showing less than 1 mpy up to about 93°C (200°F). This is prob- ably due to dissolved oxygen or traces of oxidizing species, because itis known that Type 304 can go active in 40% caustic at about 80°C (175%F) and in 50% caustic at 70°C (160°F). In the active state, the 18:8 alloys corrode faster than carbon steel Table 2 shows the results of a study by NACE Task Group TSA-3D (4) to assess the relative corrosivity of diaphragm-cell caustic vs. mercury-cell caustic. The results indicate nc significant difference between Types 304 (30400) ard 316 ($31600) in 50% caustic, nor in 73% ‘concentration in which both materials suffered active cor- rosion as well as some pitting attack. It seems probable that these products contained unknown amounts of chlorates, as produced. 150 600} “s T T T T T T hing por Ganve je ass Cracking Zone (250}— oot Oe 125, 500;— G 9 eso SSS ee RRS 4 eSing Bosnd 200} CRRA, }100 400 be Cracking jary N 1 Atmospheric ° NS racking Not . soins $50 Boe, 2 ~ 5 3 i. Brook SN Dame: zo jo] a E Dre £ ‘Cracking Reported’ ~. 50 100 ol. Re Cave i 4s 0 100 4 Titing Pont ° Gino 40 ol 1 1 1 1 L 1 1 1 70 2 30 40 «5060 Sodium Hydroxide, wt °% Figure 1 Relation of temperature and concentration of sodium hhydroxide to cause stress cracking of carbon steel tpn Ua Nein Sem ON hb 20 40 60 30 Sodium Hydroxide, wt % Figure 2 Isocorrosion chart for AISI 304 and 316 stainless steels in sodium hydroxide, with stress cracking boundary ‘superimposed Table 2 “Round Robin’ test program by four caustic soda producers—comparison of corrosiveness of diaphragm cell vs. ‘mercury cell caustic (conducted by NACE Committee TSA-3D) ‘Company, ‘Company 1 2 2 ‘ 1 2 a4 ‘average Temperature [Corrosion ate, mpy Matera Corrodent voce | oc | cc oF Nike! 200, 50% NaOH Diaphragm Con | 95. 95 | 29. 05 os feoa [cox 508 NaOH Diaphragm Col | 40 108 | — = S01 50% NaOH Mareuy Cal | 38 100 | 105 221 l

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