Paper No.

01343

CORROSION

2001

CORROSION BY ORGANIC ACIDS

L. A. Scribner, Jr. Union Carbide Technical Center P.O. Box 8361 South Charleston, WV 25314

ABSTRACT The corrosion of materials by organic acids is complicated by the virtually unlimited number of possible compounds. The corrosion of metals by organic acid is often confounded by trace impurities such as oxygen and metallic salts. This paper concentrates on corrosion by acetic, formic and propionic acids and gives some information on longer chain organic acids. Keywords: Organic acids, acetic, formic, propionic, corrosion, impurities, manufacture INTRODUCTION A key group of industrial chemicals is organic acids. They are often used in their pure form and they are used as an intermediate in a wide variety chemical reactions to make products ranging from polyester clothing to amino acids used in vitamins. Acetic acid is synthetically produced in the largest volume of all of the carboxylic or organic acids and is best known by the general public as the weak aqueous solution, 'Vinegar'. The simple, straight chain aliphatic acids are discussed in this paper. They are often called "fatty acids" because those containing an even number of carbon atoms (four or greater) exist in a combined form with glycerol as fats and oils. l Since there are almost an unlimited number of organic acids possible, the subject is complicated. Often the acids are not handled as pure products but as mixtures with inorganic acids, salts, a wide variety of organic solvents, and in mixtures with other organic acids. They have odors that vary from sharp like formic and acetic acid, to rancid like butyric acid (butter) or even worse, smell like sweaty goats - caproic acid.
Copyright 2001 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper are solely those of the author(s) and not necessarily endorsed by the Association. Printed in U.S.A.
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CORROSION CHARACTERISTICS Organic acids are weak acids when compared to the common inorganic acids like HC1 or H2SO4 but still hydrolyze well enough to act as true acids toward most metals. Aliphatic organic acids are usually considered to be slightly reducing. They are often handled in copper which does not directly displace hydrogen from acids. The 400 series stainless steels exhibit borderline passivity and are thus are seldom selected whereas the 300 series stainless steels are today's work-horse. The 300 grade of stainless steels require oxidizing conditions to maintain their passivity, especially at high temperatures. The reversal of corrosion resistance as the environment changes from oxidizing to reducing characteristics make contaminants extremely important because they tend to shift the oxidizing capacity of the acid mixture. Aeration (i.e. dissolved oxygen or DO), ferric ions, peracids or peroxides will cause rapid attack of copper and copper alloys while the presence of chlorides, which are reducing, can have disastrous effects on stainless steels. 2 Corrosion testing in organic acid media can be either difficult or misleading, mainly because of the effect of impurities. Electrochemical measurements are used almost exclusively in the dilute aqueous solutions of organic acids, wherein hydrolysis effects improve conductivity. Electrical conductivity is very low in high concentrations of organic acids and in solutions in non-aqueous solvents like benzene. The addition of sodium or chloride salts is reported to allow electrochemical measurements in these types of solutions. 3 Electrochemical data obtained in strong acetic acid, acetic acid-anhydride and formic acid solutions showed active-passive behavior for stainless steels and nickel containing alloys. This is consistent with field experience.4 Laboratory data from by immersion tests often show erroneous results unless the atmosphere is carefully controlled. Short tests of metals, especially those that exhibit active-passive behavior, can be misleading because the metal may remain passive during the initial exposure only to corrode in an active state at a rapid rate after longer exposure. Without atmospheric control, the solution will be saturated with air at the beginning of the test but will lose dissolved oxygen as the temperature is increased until at boiling conditions almost all of the oxygen will be removed. Testing with other metals that are corroding will contaminate the testing solution and also give erroneous results. These situations can lead to results that vary widely, depending on the duration of the test. Truly anhydrous organic acids are usually much more corrosive to stainless steels than acid containing even traces of water. Corrosion rates reported for "glacial" acids can vary because the acids may be truly anhydrous or may contain trace amounts of water.

CORROSION PREDICTION The electrochemical corrosion of non-passive metals in simple organic acids (those that do not complex or form chelates like citric acid) can generally be predicted from a basic understanding of the oxidation-reduction or emf series. Rule: In order f o r an electrochemical corrosion reaction to proceed, the potential (measured in volts) of the anodic or oxidation reaction must be more negative than the corresponding cathodic or reduction reaction 5. Oxidation reactions generated electrons whereas the reduction reactions consume electrons. Both reactions are required before electrochemical corrosion can occur.

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18 to 0 .+-~ Fe ++ Cu ~ Cu ÷+ + 2e2 H + + 2e. 2 H ÷ + 2eFe ~+ Fe ++ <--+ H2 + 2e0.337 Corrosion possible (7) (8) Tingyue Gu . This corresponds to a concentration of 1 to 10 PPM and 10 to 100 PPM of dissolved metal.R e d u c t i o n Potentials.56 Potential at 1 x 10 6 molar concentration o f ions.Invoice INV-475575-QJVHQQ. the effect o f impurities like metal ions in solution and d i s s o l v e d o x y g e n can also b e understood.0. +1. 1 6 0 to +0.56 +0.000 -0.45 +0. 2. respectively. the corrosion o f iron b y h y d r o g e n reduction to f o r m h y d r o g e n gas will result in corrosion b e c a u s e .337 0.62 A g <---> A g + + eFe +++ + e .12 -0.771 +0. 3) When molar concentrations of ions are at 1 x 10.771 volts Cu +--r C u ++ + 2e+0. 4H + + 02 + 4e <--+ 2 H 2 0 Cu ~ C u ++ + 2e+l.Single-user license only. copying and networking prohibited. Fe ÷++ + e.337 (5) Corrosion possible (6) The effect o f impurities like oxidizing metal ions can also b e d e m o n s t r a t e d .3 +1.~ H2 Fe ~ Fe +÷ + 2e- Notes: 1) The standard state is 1 molar concentration of dissolved ions and a partial pressure of one atmosphere. Concentration of H ÷ ions always held at one molar. volts.799 +0.17 +0.440 (3) (4) Corrosion possible B y using the s a m e logic. 2.337 volts .14 +0.3 +1.TABLE 1 Standard O x i d a t i o n . volts.440 Potential at 1 x 1 0 -4 m o l a r concentration o f ions. the corresponding H2 and 02 partial pressure is 1 x 10 -4 and 1 x l 0 -6 atmospheres. the c o r r o s i o n reaction is m o r e negative than its c o r r e s p o n d i n g reduction reaction. volts.4 and 1 x 10 -6 molar.22 +0. downloaded on 8/24/2011 4:13:18 PM .18 -0. in this case.16 +0. B y the s a m e logic. F o r e x a m p l e .0. W h i l e referring to T a b l e 1. 2) Potential calculated at metal ion concentration of 1 x 10.~ Fe +÷ +0. if d i s s o l v e d o x y g e n is not p r e c l u d e d f r o m the acidic solution. c o r r o s i o n c a n n o t p r o c e e d since the c h o s e n oxidation or corrosion reaction is m o r e e l e c t r o c h e m i c a l l y positive than the c o r r e s p o n d i n g cathodic reaction and breaks the rule given above. notice that the e l e c t r o c h e m i c a l potentials o f c o p p e r are a l w a y s m o r e positive or a b o v e those o f h y d r o g e n reduction: Cu <--+ Cu ++ + 2 H + + 2e~ 2eH2 + 0 .4 and 1 x 10 -6 molar.228volts +0. 0 0 0 No corrosion (1) (2) In this case. .228 +0. 25°C 4H + + 02 + 4e<---) 2 H 2 0 Potential at Standard State o f ions. c o p p e r can be c o r r o d e d b e c a u s e a o x y g e n / h y d r o n i u m ion reduction reaction exists that is m o r e e l e c t r o c h e m i c a l l y positive than the c o p p e r corrosion reaction.000 .

It is also important to point out that just the tendency to corrode is forecast. . Since no oxygen is present in the first reaction steps. the practical application to organic acid streams is often valid. if carried down-stream in sufficient quantities. the best known being Butane Oxidation and the Monsanto Low-Pressure processes. hydrolysis [which for the organic acids is quite low and 1. using the more conventional materials only to handle the acid after the halide has been removed. MANUFACTURE OF ORGANIC ACIDS Acetic acid is made by a variety of processes.Single-user license only. certainly has the potential to pit.000 to 100. The methyl formate is made by the reaction of steam with carbon monoxide (probably in methanol) and the formic acid is recovered from a dilute process stream and concentrated.The above discussion is of course not at all rigorously valid since the effect of the specific acid. has the notorious habit of generating a variable but small quantity of peroxide compounds in the reaction cycle and these are forever changing the corrosion in the downstream equipment from reducing to oxidizing conditions. downloaded on 8/24/2011 4:13:18 PM . Various patents have been filed to overcome the corrosion caused by the halogens that are in the reaction cycle. copying and networking prohibited. in which butane is partially combusted to acetic acid. This process has all but replaced the now antiquated Wacker Process. reports excellent corrosion resistance of commercially pure zirconium in the reaction system 8 The Butane Oxidation process. zirconium and tantalum for this high-pressure. Data derived directly from the field exposure of alloys is not available. The Monsanto process is based upon the carbonylation of methanol (with carbon monoxide) using a rhodium catalyst and an alkyl halide such as methyl iodide. but the problem facing the corrosion engineer who selects materials for these processes has been outlined by Togano and others. These have varied from the use of silver compounds to form insoluble silver salts to ingenious distillation schemes to minimize carrying bromides into other parts of the plant. This further complicates the recovery and purification of the reaction products. Yau. As can be surmised. the addition of the halogen reaction promoter to the reaction cycle requires the use of very corrosion resistant alloys and spreads trace halides throughout the rest of the plant. acetic acid was produced by fermentation of grain and then by oxidation of acetaldehyde. its concentration. Secondly. He considers nickel-molybdenum and nickel-copper alloys attractive for the recovery system that still contains the halide. Historically. activity. crack and corrode the stainless steel used in the downstream equipment.Invoice INV-475575-QJVHQQ. in the Outlook Journal. high temperature system. Nevertheless. the rate of corrosion being determined by other important reaction variables such as the concentration and diffusion of ions. 6 The Monsanto process (and its various improvements thereof) is the most popular method for the production of acetic acid. the formic acid produced is very reducing often requiring the use of zirconium in the distillation train. The bromide addition. such a formic and propionic. the Butane oxidation process produces a variety of other organic acids. Tingyue Gu . Formic acid is produced as a by-product of butane oxidation and by the hydrolysis of methyl formate in the Leonard/Kemira process. and combinations of copper and stainless steel equipment were used for acetaldehyde oxidation. 7 The reaction system contains the halogen promoter and Togano suggests that Alloy B should be tested along with titanium. The fermentation process was usually carried out in copper equipment or wooden tanks. along with a wide variety or organic solvents like ketones.000 times less than a corresponding inorganic acid like hydrochloric] have been conveniently ignored.

The data is for aluminum 1100 but similar rates would be expected for alloys such as 3003. as well as other organic acids. It is rapidly attacked below about 95% acetic acid at the boiling point and is again attacked very rapidly in concentrations near 100 percent or in those mixtures containing excess acetic anhydride. The aldehyde is then simply oxidized to form the corresponding acid .6063 (A96063). C4 acids.The dominant processes for the production C3 acids. It is based upon the hydroformylation of olefins with syngas (H2/CO) in the presence of rhodium/phosphorous catalysts or cobalt catalysts to produce the required aldehyde. . The Low Pressure process is so mild that ordinary type 316L stainless steel has been found to be satisfactory. The copper bearing "2000" series. A92000. uncontaminated acetic acid. although it causes contamination of the anhydride due to formation of a white crystalline solid. This good performance is predicted by the elementary discussion in Section 3 on the electrochemical stability of copper in organic acids. The corrosion resistance of aluminum is strongly affected by contaminants in acetic acid. aluminum triacetate. With the exception of the alloys that contain more than 15% zinc. downloaded on 8/24/2011 4:13:18 PM . C5 acids and C8 acids (2ethylhexanoic) is the Low Pressure OXO process of Union Carbide/Kvaerner. Aluminum again becomes resistant to pure acetic anhydride. Copper and Copper Alloys. alloys of aluminum are not suitable for acetic acid service because of high corrosion caused by the copper rich precipitates. at concentrations stronger than 1 molar. Steel is attacked quite rapidly.25 mm/y. propionaldehyde to propionic acid. The higher aldehydes. Copper was used almost exclusively to handle acetic acid until the advent of the stainless steels.Invoice INV-475575-QJVHQQ. 3003 (A93003) and the 5000 series like 5052 (A95052) are used for storage and shipment of the acid. Laboratory tests that introduced oxygen into room temperature 50% acetic acid gave corrosion rates of 1. which precipitates in the liquid.9 mm/y compared to only 0. copper (C12000) and all of its alloys show good resistance to all concentrations of acetic acid up to and even above the atmospheric boiling temperature in the absence of oxygen or other oxidants.58 mm/y.g. today Type 316L ($31603) stainless steel and higher alloys are often used.75 to 1. and aluminum can corrode in almost any concentration of acetic acid at any temperature if the acid is contaminated with the proper species.i.e. or 5086. McKee and Binger have written an excellent summary of the use of aluminum in acetic acid and anhydride. Similar data in 6% acetic acid showed a corrosion rate of only 0. the rate rose to 0. Grades 1100 (A91100).Single-user license only. Steel is therefore normally unacceptable for use in acetic acid service. Tingyue Gu . x 10 -3 Aluminum. copying and networking prohibited.9 Figures 1 and 2 show the resistance of aluminum in acetic acid and acetic anhydride.08 mm/y in nitrogen blanketed tests. used to produce to produce linear C7 and C9 aldehydes are also made by a similar low pressure OXO process using Celanese technology. with hydrogen evolution. Glacial acetic acid at room temperature is less aggressive than weaker acid but still corrodes at a rate of 0. ALLOYS USED TO HANDLE ACETIC ACID Steel. Aluminum shows good resistance to nearly all concentrations of acetic acid at temperatures up to 50 ° C. The absence of oxidizing agents is a requirement for copper to be useable acetic acid solutions. Slight contamination of acetic acid with air through storage under an air atmosphere or by ingress of air through a vacuum leak can increase the corrosion to rates that are unsuitable whereas copper is nearly immune to attack by pure. even at room temperature. e.03 mm/y when passing hydrogen over the solution whereas when oxygen is passed over the solution.

Single-user license only. 38.FIGURE 1 .5 .5 • I ~ I I I .1 25. ACETIC -~ I ~ I 60 ~ I *'-' I 20 ACID 80 - 100 ANHYDRIDE I 100 I 0 80 60 PERCENT.8 -- • BOILING TEMP. .M E T A L LOSS FOR 1100-H14 (A91100) A L U M I N U M A L L O Y IN ACETIC ACIDACETIC A N H Y D R I D E SOLUTIONS AT ATMOSPHERIC BOILING T E M P E R A T U R E 9 is o >. o ROOM TEMP.u knz 0 (/) 0 E 0 o 63. " ~-- 0. E E I. The nickel addition also increased the resistance to the effect of oxidants.-. Tests in air sparged 50 percent aqueous acetic acid at the boiling point gave rates of 7.5" z ~ 2.1.1 ~2.Invoice INV-475575-QJVHQQ. copying and networking prohibited.7 mm/y for copper containing 30 percent nickel and 2.7 ~ A .4 20.4- 0 1 2 3 10 30 50 70 90 97 PERCENT.3 15. o. downloaded on 8/24/2011 4:13:18 PM .0 0.2 % _ • BOILING TEMP.EFFECT OF C O N C E N T R A T I O N A N D T E M P E R A T U R E ON C O R R O S I O N OF 1100H14 (A91100) A L U M I N U M A L L O Y IN ACETIC ACID 9 25. ACETIC ACID 98 99 100 FIGURE 2 . E E 5. 40 ACETIC Copper alloyed with increasing quantities of nickel showed increased corrosion resistance to acetic acid.0 0 ~ 1. C.2 ~ 10. C. Similar reductions in corrosion rates with increasing nickel content were noted when ferric ion was added to the Tingyue Gu .1 mm/y for copper containing 70% nickel.4 1 2.5 0 1.51 -- ~.~~-- o 0 ~'~ 20 40 PERCENT.~ 50. 4. A 50 DEG.75 mm/y for copper. A50 DEG.

Previously published data ~ show that glacial acetic acid can be handled in Type 304 to a temperature of about 80°C (175°F). Low corrosion rates for the straight chromium 400 series stainless steels in dilute acetic acid solutions can often be shown in laboratory tests. The effect of oxidizing impurities cannot be overlooked when using type 304 stainless steel. acetic acid because of the lower metal pick-up from corrosion.Single-user license only. Type 316L. from leaking condensers) results in contamination of the acid with sodium chloride. slightly less than 20 PPM of chloride in the organic acid stream can be tolerated. Figure 3 illustrates the reduction in corrosion rate as more acetic anhydride is added. An exception is high purity chromium-molybdenum stainless steel. Type 304L ($30403) stainless steel is the lowest grade commonly used. with subsequent formation of hydrochloric acid by the following reaction: NaC1 + CH3COOH ---) CH3COONa + HC1 ~ (9) The hydrochloric acid moves through the system causing its own problems. However.again pointing out the harmful effects of oxidizing impurities. The hotter the solution. as in heat exchangers. the rates still are still too high for economical use even though the nickel addition was beneficial .g. but higher concentrations are likely to cause rapid equipment failure. Type 316L ($31603) stainless steel is the alloy most commonly used in equipment processing acetic acid. e. copying and networking prohibited. rapid corrosion can ensue. very tenuous passivity is exhibited by these alloys and field experience with these materials indicates a susceptibility to high corrosion rates and pitting attack. Corrosion of stainless steel equipment by the hydrochloric acid. If acetic acid only contains small quantities of acetic anhydride or if the acid is truly anhydrous. Stainless Steel. the rate of attack on Type 316L is very high. a condition of accelerated corrosion and pitting results from chloride contamination. because of its volatility and strong oxidizing nature. However. Reportedly. P. A method to test metals under heat-transfer conditions has been described by Groves. Even glacial acid at temperatures above the atmospheric boiling point can be handled if the impurities are held within proper levels. and it has been satisfactory for lower concentrations to the boiling point of the acid. can alter the corrosion mechanism and rate of corrosion. rather than type 304L is most often the required alloy for tankers shipping C.solution. If oxidizing conditions are lost.g. Alloy 26-1 ($44627) which shows good resistance. is particularly pernicious. To prevent this intergranular attack.Invoice INV-475575-QJVHQQ.. Intergranular corrosion of sensitized Type 304 stainless steel will occur in 60°C and hotter acetic acid. Leakage of chloride-bearing water to acetic acid process streams (e. downloaded on 8/24/2011 4:13:18 PM . Besides SCC. The old acetaldehyde oxidation process for manufacturing acetic acid also produced acetic anhydride as a co-product in and is often found in acetic acid streams. The introduction of just a few tenths percent of water will reduce the corrosion back to normal rates. because it is a strong oxidant. Type 304 ($30408) stainless steel finds wide use in dilute acetic acid solutions and in the shipment and storage of concentrated acetic acid. and he has Tingyue Gu . al. . The volatility of ferric chloride allows it to move freely through a processing system and. produces ferric chloride (along with chromium and nickel chlorides) which. it promotes stress-corrosion cracking (SCC). et. for example. the more critical for the presence of adequate quantities oxygen or other oxidizing impurities. the use of the low carbon grade 304L is recommended for welded construction. 12 Heat transfer. The low-carbon grade 316L is required for the higher temperature applications where welding is required.

Titanium.25 RATE.g. Titanium is resistant to all concentrations of acetic acid up to the atmospheric boiling point. I 0. 15 Laboratory tests confirmed hydrogen absorption in 95% acid at 210 ° C with 1000 ppm hydrobromic acid.. However.51 CORROSION than does Type 316 stainless steel .developed data on stainless steels and some nickel alloys under heat transfer conditions. Alloy 2205 exceeded 1 mm/y whereas Alloy 2507 ($39275) corroded at less than 0. In 80% acid containing 2000 PPM chlorides at 90°C.IJ n>.38 rnm per year I 0. copying and networking prohibited. greater than 1 mm/y for Type 316L. in evaporators.13 I 0. some failures of titanium in hot strong acetic acid have been reported with most failures associated with hydrogen embrittlement.14 The anomalous behavior of the type 304 in the 40% acetic acid / 55% water / 5% glycol diacetate is probably the result of too short an exposure time..05 mm/y vs. Among the duplex grades. . e. The older duplex stainless steels like type 329 ($32900) also exhibited this improvement in corrosion resistance to acetic acid mixtures as shown in Table 2.ACETIC ANHYDRIDE MIXTURES 11 l. Alloy 2205 offers an advantage over Type 316L only in the presence of chlorides. which preserved the passivity temporarily. W i .02 mm/y. Alloy 20Cb3 weld overlay has been used successfully to combat crevice corrosion of Type 316 stainless steel in areas such as flange faces. Tingyue Gu .r z <[ I- 100 8O 60 40 n. However. Electrochemical corrosion studies in acetic acid solutions suggest that it is possible to attack titanium in anhydrous acetic acid although titanium has been successfully used in commercial practice. downloaded on 8/24/2011 4:13:18 PM . The high-strength titanium alloys should not be used because of their propensity for stress corrosion cracking. 825 (N08825) and 904L(N08904) show better resistance to acetic acid FIGURE 3 - LABORATORY CORROSION OF TYPE 316 STAINLESS STEEL ($31600) IN ACETIC ACID . 13 Higher alloys such as Alloys 20Cb3. The expected rate would be much higher and would undoubtedly have been encountered in a longer test exposure or under operating plant conditions.Single-user license only.especially when being used to heat the acid. in boiling 99.5% acid with 200 PPM chlorides.03 Z I11 n I 0. it showed a rate of less than 0.-- 20 _a 1 0 0 80 w " 60 " q 40 20 " ~ 0 0.Invoice INV-475575-QJVHQQ.

02%acetaldehyde 87. degree of aeration. silver has found very little use in the United States. Because of the high electrochemical potential (see Section 3.01 0. such as with combinations of acetic acid and sulfuric acid. and it is quite resistant to all concentrations at normal temperatures. Room temperature stagnate dilute acetic acid corrodes lead at rate at rates exceeding 1 mm/y. Other Alloys.09 Lab 115 Type 329 Type 304 Type 329 Type 316 <0. while Alloy C-276 is commonly used in acetic acid solutions which are highly oxidizing in nature. . Zirconium (R60702) has found good use in the Monsanto Process for the production of acetic acid. perhaps caused by ordering reactions within improperly heat treated plate.5% acetic acid 6% water 0.08 <0. 0. mm/yr. which limits the use of stainless steel or copper alloys. copying and networking prohibited. and velocity was low. °C 102 Corrosion Rate.Invoice INV-475575-QJVHQQ. In the food industry. downloaded on 8/24/2011 4:13:18 PM . Lead has been used to store glacial acetic acid where temperature. Non-Metallic Materials.1% water <0. stainless steel tanks are now widely used with the exception of pickle production. Zirconium.TABLE 214 Stainless Alloy Type 329 Type 316 Type of Test Plant Corrosive Medium 99. wherein copious amounts of salt are dissolved in the weak acid. Alloy B-2 is used under reducing conditions. Tingyue Gu .02 0.5% formic acid 4% acetaldehyde 40% acetic acid 55% water 5% glycol diacetate 25% acetic acid 4% formic Temperature.01% formic acid O. Because of cost considerations. wooden stave storage tanks have been used for the storage of dilute acetic acid and many years of service are common with wood tanks in 3 to 4% acid. Alloy B-2 has been used in similar environments with good corrosion resistance but with occasional cracking.Single-user license only. Alloys C-276 (N10276) and B-2 (N10665) are resistant to acetic acid solutions at all normal concentrations and temperatures.03 0. 16 Zirconium withstands all concentrations of acetic acid with or without oxidizing conditions or halogen impurities but does not perform well in the presence of copper ions if the acetic acid also contains acetic anhydride. Silver has been used frequently in European practice to handle acetic acid.08 Lab 110 Nickel Alloys. but is generally not considered to be a suitable metal. Alloy C276 has been used for glacial acetic acid evaporators.01 Lab 126 Type 329 Type 347 0.9% acetic acid <0. Table 1) silver will be much more resistant to acids contaminated with metals ions like iron and copper since it is more electrochemically positive than these metals in the reduced form.01 1. These materials are sometimes used where the acetic acid is mixed with inorganic acids and salts. It is able to withstand the very corrosive conditions that are encountered in the reaction cycle where both acetic acid and very corrosive concentrations of iodide ions are present. However.

The shipping of 95 to 99 percent formic acid can be done in aluminum tanks but it is important to prevent the loading of hot acid. they can fail by hydrogen-assisted cracking (HAC) when exposed to corrosion by strongly ionized acids. The maximum temperature normally encountered during transportation is 45°C. Of the thermosetting resins. it becomes porous and fades from a dark blue to a pale blue via ion exchange. No attack on borosilicate glass is reported below about 149 to 177°C. FRP construction using a bisphenol polyester and vinyl esters has been successfully employed. as the concentration of water goes up in the acid. Soft rubbers tend to swell. Stressed 18% nickel maraging steel cracked when exposed to 10 percent aqueous formic acid but did not crack in 91 percent formic or in either glacial or 10 percent acetic acid. EPDM is satisfactory above 5% concentration at room temperature.4°C. and it boils at 100. Many plastics tend to be susceptible to solvent action by the acid. decomposing to carbon monoxide and water. Steel is not normally not considered for formic acid service because it is attacked quite rapidly at all concentrations and temperatures. When the glass is attacked. Carbon and graphite are resistant to the boiling point and impervious graphite heat exchangers have been used in many demanding acetic acid services. Tingyue Gu .Successful use of both hard and soft rubber linings has been experienced in the storage of acetic acid. Formic acid is soluble in water. glacial acetic acid. . Its corrosion reactions with copper are predictable in solutions that contain substantial concentrations of water. At this temperature. Its specific gravity is 1.Single-user license only. chlorinated polyethers and furanes have been used to about 100°C. aluminum exhibits fair resistance at any concentration while at ambient temperatures (Figure 4). it melts at 8. downloaded on 8/24/2011 4:13:18 PM . Therefore. in conformance with Section 3. heavy metal salts. most often in the form of very aggressive pitting..g.the haze of aluminum salts making the acid unmarketable. As long as there is no contamination of the formic acid. the rate of attack increases rapidly. can cause severe corrosion of aluminum. contamination with a wide variety of materials. e. Butyl rubber will withstand glacial acetic acid to about 80°C. Typical rates of corrosion on grade 5086 aluminum in formic acid are shown in Figure 5. aluminum is seldom used for formic acid containment.~8 However. Glass linings have been used to handle acetic acid. polyethylene drums are used to handle C. its dissociation constant being about ten times greater than that of acetic acid. It is very reducing.P. except for concentrations exceeding 90%. Of the plastic materials. provided that discolorization of the product is not objectionable. alcohol and ether. ALLOYS USED TO HANDLE FORMIC ACID Formic acid is the most highly ionized of the common organic acids and thus the most corrosive. copying and networking prohibited. acid stored in aluminum becomes turbid . 17 Aluminum. If alloy steels are heat treated to high strengths and placed under stress. The fluorinated plastics are completely resistant to their normal temperature limits. It reacts readily with many oxidizing and reducing compounds and is somewhat unstable as the concentration approaches 100 percent.Invoice INV-475575-QJVHQQ.8°C at one atmosphere. Reinforced phenolics are suitable to about 120°C. Steel. This is easily detected by simple wetting of the surface to detect a color change.220. Additionally.

El 50°C. although some increase in the rate of corrosion in intermediate acid strengths is to be expected because of maximum ionization at these concentrations. FIGURE 4 . respond in approximately the same manner to exposure to formic acid.RATE OF CORROSION FOR 1100-H1 (A91100) ALUMINUM IN AQUEOUS REAGENT GRADE FORMIC ACID 18 t 63. Tingyue Gu .03 1.Copper and Copper Alloys. Stainless Steels.Single-user license only. o-To0 20 40 60 80 PERCENT. . Resistance is maintained in all concentrations of formic to the atmospheric boiling point and above. Table 3 shows typical corrosion rates for copper (C10300) and 90-10 copper nickel (C70600) in various concentrations of formic acid. showed rates of less than 0. Copper and its alloys used to be the most widely used materials for handling formic acid but have been supplanted by the many grades of molybdenum-bearing containing stainless steels and high-nickel alloys.10 12. except yellow brasses which can dezincify.BOILING O E E 2. the exposure of copper to formic acid is dependent on having a short residence time to prevent the build-up of sufficient cupric ions which increase the corrosion rate over and above that which would normally occur. Ampco 8 (C61900). FORMIC ACID 100 Copper and copper-based alloys (other than high-zinc brasses) can be successfully employed in formic acid. type 15-7Mo (S 15700) would be a candidate based upon its similarity to type 316L. Thus. such as the higher rate of attack in 50 and 70 percent formic acid. if a PH grade were needed. However. oxygen.50 38.05 mm/y at 90C. a proprietary aluminum bronze. Corrosion of these alloys is autocatalytic because of the buildup in the solution of cupric ions (Cu ++ ). downloaded on 8/24/2011 4:13:18 PM . This is in good agreement with the Section 3 electrochemical prediction information. copying and networking prohibited. The 400 series and precipitation hardening stainless steels are usually not resistant to formic acid and they are seldom used. providing oxidizing species are absent and no accumulation of copper corrosion products can occur. Type 304L stainless steel exhibits nil corrosion rates at all concentrations of formic at ambient temperatures and is therefore the preferred material of construction for the storage of the acid. ~'. However. In laboratory tests. which are themselves an oxidizing species.02 . are probably caused by incomplete deaeration during laboratory tests. or other oxidizing species. Copper and all of its alloys.Invoice INV-475575-QJVHQQ. The successful use of copper and its alloys is contingent on the absence of air.54 A O ROOM TEMP.70 2.x'-c----vo------v~ . The anomalies in the data shown in Table 1.

Table 4 shows typical rates of attack on various stainless steels in several concentrations of formic acid at the atmospheric boiling temperature. Type 304L will not be acceptable unless oxidizing contaminants stronger than oxygen are present. 0.64 0.02 <0.02 0.38 D. downloaded on 8/24/2011 4:13:18 PM . Type 304L stainless steel is resistant to only 1 or 2 percent formic acid where it will corrode at rates of about 0. % 1.Invoice INV-475575-QJVHQQ.76 0.51 >.54 0. E E 0. For process streams.39 0. copying and networking prohibited.13 0.19 Tingyue Gu .0 10.0 5.02 <0.C O R R O S I O N OF 5086 (A95086) A L U M I N U M IN F O R M I C ACID AT 45°C ~8 0.20 0. 0 90 95 1 O0 PERCENT FORMIC ACID T A B L E 3 . F I G U R E 5 .22 90-10 Copper Nickel mm/yr.25 O -- O O 0. It is doubtful that Type 304L stainless will prove to be suitable in any process and it should not be considered. actual corrosion tests are advisable anytime that Type 304L stainless steel is considered for handling formic acid at elevated temperatures.02 0.0 Copper mm/yr.02 0.0 40.0 70.Single-user license only.C O R R O S I O N OF C O P P E R A N D 90-10 C O P P E R N I C K E L BY F O R M I C ACID ( L A B O R A T O R Y TESTS.33 0.05 0.02 0.o.2 m m / y .25 0.19 0. . A T M O S P H E R I C BOILING T E M P E R A T U R E .0 20. For formic acid concentrations above 5% and below about 95%.0 60.75 0.0 80.at the atmospheric boiling point.13 -- o .03 0. 0. @ 0.14 0. 96 H O U R S E X P O S U R E DEAERATED) l] Acid Concentration.0 50.75 0.0 90.

and molybdenum contents higher than Type 316 stainless steel. 3. MM/Y 19 20% Formic Acid 0.77 0.0 0.25 Note: 1. 316 1 mm/yr. the low carbon grades are generally selected if any elevated temperatures are expected.Single-user license only. Alloy 2507 reportedly resist all concentrations at or slightly below the atmospheric boiling point.04 10. 48 Hour exposure 304 1 mm/yr.20 50.025 40% Formic Acid 0.40 0.09 0.50 0.Type 316L stainless steel is the preferred material. the super duplex alloys are subject to higher rates when the acid concentration goes above 90% and can corrode at higher rates in the acid reflux than in the liquid in the kettle.03 <0. 316 z Alloy 20-Cb3 3 mm/yr.46 70. such as Alloys 28 (N08028) and 904L.025 Type 317L I Alloy 2205 ($31803) Alloy 255 ($32550) Tingyue Gu . and corrosion tests are advisable in any given situation.0 0. Table 5 shows that the newer duplex alloys such as Alloy 2205 and Alloy 255 ($32550) are superior to Type 316 stainless steel and even Type 317L ($31703) stainless steel.l M o 1 mm/yr.10 Alloy 20Cb3.41 0. <0.0 3.02 0.23 <0.40 0.0 4. TABLE 5 CORROSION OF 317L AND DUPLEX STAINLESS STEEL IN BOILING FORMIC ACID.Invoice INV-475575-QJVHQQ. 1.0 1. downloaded on 8/24/2011 4:13:18 PM . Since intergranular corrosion is common in acetic acid service.0 0. the corrosion rate for Type 304 was about 8 times more than for Type 316 under the same conditions.20 0. .26 20.23 0. especially by intermediate strengths of formic acid at higher temperatures. ATMOSPHERIC BOILING TEMPERATURE.27 40.97 0. TABLE 4 . showing excellent resistance to formic acid in all concentrations at ambient temperatures and being resistant to at least 5 percent formic acid at the atmospheric boiling temperature.0 1. ~9 Even then. copying and networking prohibited.02 0. In the corrosion data reported in Table 4.46 60.0 3. Type 316L stainless steel can be seriously attacked.0 3.61 100.0 4. 26 C r . Deaerated.33 0.025 0.CORROSION OF STAINLESS STEEL BY FORMIC ACID (LABORATORY TESTS.17 5.64 80.47 90.43 -<0.0 3. nickel.48 0.20 0. also show superior resistance to mixtures of formic and acetic acid and would be expected to be better in formic acid itself. Oxygen not controlled 2. Other alloys with chromium. 96 HOUR EXPOSURE) II Acid Concentration mm/yr.89 0. is more resistant to formic acid than Type 316 stainless steel. However. and its use should be considered in higher concentrations at higher temperatures. coupons exposed to the refluxed condensate.

plastics are not normally considered for this service. like Alloy 26-1. Therefore. downloaded on 8/24/2011 4:13:18 PM . such as sulfuric acid catalyzed esterification reactions.Invoice INV-475575-QJVHQQ. This suggests that zirconium is a good candidate material for the distillation portions of formic acid plants. in which the acid concentration and the temperatures are both high. C-276 and C-4 (N06455) have shown outstanding resistance to formic acid in process equipment and are reported to have very good resistance even at temperatures above the atmospheric boiling point.. As is to be expected. even when the acid is contaminated with metal salts or iodine. Alloy 29-4-2 ($44800) which contains 4% Mo did not corrode in boiling 45% formic acid. Alloy 625 (N 10625) contains only 9% Mo and should be expected to be somewhat less corrosion resistant than Alloy C-276 but is so similar in resistance as to be useable in all but the most severe of services. the Alloy B is not better than the Alloy C types when strongly oxidizing conditions prevail.g. even slightly. because Alloy B usually costs more. While titanium will resist acetic acid under almost all conditions to the boiling point. High-Nickel Alloys. Weld overlays of Alloy 20Cb3 have proven partially successful for solving this problem. in those services that are very reducing. When the titanium does corrode. Notice that Figure 5 also shows a zone of higher corrosion for Alloy B-2. copying and networking prohibited. Titanium. In laboratory tests.Single-user license only. the Alloy B should be superior to the Alloy C . threaded connections). The super ferritics. Alloy 6XN. Several of the high nickel alloys such as Alloys B-2. approaching the anhydrous state. hydriding of the metal occurs and loss of ductility results. Alloy B (N 10001) sometimes exhibits lesser corrosion resistance in intermediate strengths than Alloy C but. Alloy 20Mo-6 (N08026). which is good with all concentrations to about 35 ° C The fluorocarbon plastics are resistant to their normal temperature limitations. pure formic will corrode titanium at the boiling point in all concentrations above 10%. Alloy B is often the better choice. N08367) should be even better than the Alloy 20Cb3 which contains only 2-3% Mo. The chromium-molybdenum-nickel alloys are all similar to the Alloy C and B alloys. which have a temperature limitation of about 93°C. except as coatings.02 mm/y.Under gaskets and in other occluded areas (e. Corrosion data for Alloy C (N10002) are shown in Figure 52°. 22 Non Metallics. . Commercially pure zirconium exhibits very good resistance to boiling formic acid with rates below 0. However. A 6% Mo version of the 20-type alloy is now available. Zirconium. The superaustenitic alloys containing 6% molybdenum (e. it will resist formic acid only under strongly oxidizing conditions. appear to have exceptional corrosion resistance to formic acid in preliminary laboratory studies and plant usage. is not often selected. 21 A titanium heat exchanger disappeared in less than one day when strong conditions. Tingyue Gu . which makes it very destructive to most organic materials and coatings. had been encountered in a distillation system. Titanium exhibits borderline passivity in formic acid and under normal conditions. An exception is polyethylene. Formic acid is an excellent solvent.g. and it should definitely be considered for tubing for heat exchangers handling formic acid. In services where contamination from sodium chloride or other halogens is possible. Type 316L stainless steel sometimes undergoes crevice corrosion.

6 mm/y in pure propionic acid at room temperature and at much higher rates in aqueous solutions of the acid. kU I-- 20 I 0 20 40 I 60 PERCENT. FORMIC ACID I 80 I 100 ALLOYS USED TO HANDLE PROPIONIC ACID Propionic acid or methyl acetic acid boils at 141.20 mm per year / /- BOIUNG POINT CURVE 100 d t/) 144 uJ 60 u~ uJ D. As with formic and acetic acid.ALLOY C-276 (N10276) AND ALLOY B-2 (N10665) IN FORMIC ACID 2° 0. Copper and Copper Alloys. Steel. copying and networking prohibited. neoprene and butyl rubbers are resistant at ambient temperatures and fluoroelastomers to about 50°C. Copper and copper alloys containing not more than 15% zinc will handle propionic acid in all concentrations.4°C and is water-soluble. FIGURE 5 . Therefore. but this is believed to be an anomaly caused by incomplete deaeration of the solution since propionic acid been routinely handled in copper lined equipment. high rates are possible. .. downloaded on 8/24/2011 4:13:18 PM .Hard rubber. The data shown in Figure 7 indicates attack on copper in boiling 100 percent propionic acid. copper and its alloys are satisfactory only if the solutions are completely deaerated and do not contain other oxidizing agents. Rubber linings can be used for storage if discoloration of the acid is not a matter of concern. Tingyue Gu . Aluminum will resist 100% propionic acid at room temperature but becomes unacceptable at about 80°C. steel has very limited usefulness in this service. It is a weaker acid than acetic but otherwise very similar to acetic acid.Single-user license only. Like acetic acid. if the propionic acid is contaminated with anhydride or heavy metal ions. Aluminum. Steel is attacked at rates of about 0.Invoice INV-475575-QJVHQQ. The corrosion diagram displayed in Figure 6 23 shows that the attack is very similar acetic acid.

The 400 series stainless steels will pit in propionic acid solutions. the rate of corrosion of copper is shown to increase rapidly. • 50DEG. probably because of borderline passivity.TEMp. These were short term tests in which the gaseous atmosphere above the boiling solutions was not FIGURE 6 .5 O O 1. The low -carbon grade should be utilized to avoid possible intergranular attack. to boiling propionic acid solutions. ROOMG BOILIN A-_ ui ~10. Above 65 percent acid.. including type 316 stainless. Type 304 stainless steel shows good resistance to propionic acid at room temperature and to aqueous solutions up to about 50 percent concentration at the atmospheric boiling point. Figure 7 shows the resistance of various materials. It is likely that this resulted in two erroneous results.5 0 ~ 0 1 2 3 10 PERCENT. In process equipment.RESISTANCE TO CORROSION OF 1100-H14 (A91100) ALUMINUM ALLOY IN PROPIONIC ACID SOLUTIONS AT VARIOUS TEMPERATURES 23 25.4 20. This would be true if air were present but not in its absence. respectively. downloaded on 8/24/2011 4:13:18 PM .2 >. Other nickel alloys of similar Tingyue Gu .Single-user license only.C. field experience has been that the alloy demonstrates borderline passivity above 80% and in not suitable for such service. .Stainless Steel.0 0.PROPIONIC ACID 30 50 70 9 0 97 98 99 100 controlled.Invoice INV-475575-QJVHQQ. Alloys B-2 and C-276 show excellent resistance to propionic acid solutions under reducing and oxidizing conditions. It is quite suitable for all ranges of concentration noting that oxidizing conditions are beneficial and that the rate can be somewhat high around 65% concentration as show in Figure 7. They should not be used unless they are tested in the exact environment.3 15. and are therefore unreliable. copying and networking prohibited. High-Nickel Alloys.0 o~ 0 m 1. Although Type 304L stainless steel has shown decreasing corrosion rates in laboratory tests between 80 and 100% propionic acid. providing air or other oxidants are absent.2.TEMP" I 114"0ram@99"8% •. copper has shown to have low rates of corrosion in all concentrations of acid. Type 316L stainless steel is the preferred material for handling hot concentrated solutions of propionic acid.1 - ¢z: z ----.2 E E 5.

This critical temperature is usually close to the atmospheric boiling point. Steel.U._ 0 10 20 30 40 50 60 70 80 90 100 ACID. Aluminum. maleic..___.~.I < nU.U U. PERCENT IN W A T E R It is possible to make some generalized statements concerning the higher molecular weight acids. butyric. Steel is usable at ambient temperatures in the higher molecular weight acids.02 < I.g. copying and networking prohibited.27 E E Z 0 I- 1. .76 / .__f..I 0. Such acids are usually non-corrosive to Type 304L.I Z I.).CORROSION OF METALS IN BOILING PROPIONIC ACID 23 G} L_ t~ 1. Table 7 shows data on the corrosion of some less familiar alloys in various organic acids. a sampling of corrosion rates of various metals in several of the longer chain aliphatic acids. 0. etc.. providing iron contamination is not a matter of concern. Aluminum shows good resistance to such acids at room temperature and is widely used for their shipment and storage.31~6304 . Good summaries of the corrosion characteristics of di. at which temperature Type 316L is usually required. OTHER ORGANIC ACIDS The solubility in water decreases with increasing molecular weight of the aliphatic monobasic acids (e. " " - J soo 0... ..). until the temperature becomes high enough to promote dissociation.and tricarboxylic acids (oxalic. °~=~" ....~- A L LO y C. It is impossible to cover here the corrosion characteristics of the many different organic acids. " . and it is used occasionally to store many of the much heavier acids and their corresponding anhydrides. . . -'------------~ I " ~.composition show similar good resistance to propionic acid but are not normally used since type 3 16L is suitable for most concentrations at high temperatures. Some of the higher molecular weight acids cause severe attack of Tingyue Gu .Invoice INV-475575-QJVHQQ. However.~.i=.4 FIGURE 7 . downloaded on 8/24/2011 4:13:18 PM .50 ~"-t . pentanoic.25 • .~ ___.Single-user license only. naphthenic acids and multifunctional acids have been published. aromatic acids and some dicarboxylic acids is shown in Table 6 and 7 24._. etc. for example.

in the absence of oxidants.02 <0.02 1.07 0/13 <0. copying and networking prohibited.68 0.05 <0.02 <0.02 <0.02 0. 50% in an ether.07 0.88 <0.85 0.02 <0.02 <0.40 Acid Acrylic.05 0.02 0.02 0.25 0.40 <0.05 0.02 <0.aluminum at highly elevated temperatures.20 0.02 0.07 1. the dissolved oxygen may remain in solution and not be boiled out at atmospheric pressure. 150°C Pentanedioic (Glutaric) 210°C Pentanoic (Valeric) 26°C.02 <0.83 0.02 0.18 <0.10 0. 90% 138°C Butyric 26°C.02 <0.02 0.02 <0.02 <0.02 0.02 <0. Room Temp. 150°C 2-Ethyl hexoic 26°C.20 <1 0. Room Temp 190°C 2-Methyl pentanoic 26°C.15 0.38 0.53 <0. Room Temp. Copper and copper alloys show good resistance to all of the higher molecular weight acids and can be used quite widely to handle the acids. Room Temp. 190°C Heptanedienoic (Pimelic) 225°C Iso-Octanoic 26°C.02 0. 88°C Benzoic.Single-user license only.35 0.02 Copper and Copper Alloys.53 <0. so the use of aluminum must be considered for the specific acid and temperature desired. Room Temp.CORROSION OF METALS IN REFINED ORGANIC ACIDS II Steel mm/y Copper mm/y Silicon Bronze mm/).02 <0.02 <0.02 <0. even at elevated temperatures. Room Temp. . The problem with copper is that the long chain fatty acids can contain dissolved oxygen over and above that of the simple acids like acetic.05 0. 190°C Iso-decanoic 26°C.02 0.02 <0. 2-Ethylbutyric acid will exhibit this property and cannot be handled in c o p p e r y Tingyue Gu .20 <0.02 <0. Room Temp.02 0.02 <0.93 <0.02 0.02 0.07 <0. TABLE 6 .02 0.02 <0.02 <0.13 <0.05 1. Even worse. downloaded on 8/24/2011 4:13:18 PM .02 0.Invoice INV-475575-QJVHQQ.02 <0.02 0.18 0. 115°C 163°C (Boiling) 2-Ethyl butyric 26°C.02 0.02 0.23 <0. 114°C 316SS mm/y ($31608) <0.02 0.30 <0.13 <0.02 <0. 304SS mm/y ($30408) <0.02 <0.68 0.

even at elevated temperatures. Tingyue Gu .02 0.10 Stainless Steel.02 <0.02 <0. With the concentrated acids.02 4. downloaded on 8/24/2011 4:13:18 PM . ATMOSPHERE: NOT CONTROLLED) 11 [ Test Medium Acetic Acid.02 0.58 Type 329 SS <0. Aqueous 2-Ethylbutyric Acid 10% Oxalic Acid. Type 316L stainless steel is then required and is usable in almost all of the acids. .02 <0.02 <0. have found usage for processing the higher molecular weight acids at elevated temperatures.02 <0.02 Corrosion Rate mm/y Tantalum Nil Nil Titanium <0.13 <0. Aqueous 20% Formic Acid. such as inorganic acids. Type 304L stainless steel has excellent resistance to the higher molecular weight organic acids at room temperature and at lower concentrations at high temperatures.68 <0. Type 304L stainless steel is sometimes severely corroded.02 <0. The nickel-molybdenum and nickel-ruolybdenum-chromium alloys show excellent resistance to the higher molecular weight acids.CORROSION OF MISCELLANEOUS ALLOYS BY ORGANIC ACIDS (EXPOSURE: 48 HOURS. particularly nickel-copper Alloy 400 (N04400).Invoice INV-475575-QJVHQQ.Single-user license only. are also present.20 <0.13 1.02 0.02 Nil 0.02 0.58 <0.02 0.02 0. Nickel Alloys. copying and networking prohibited.25 <0.35 0.02 Crucible 223 7 22. The nickel-based alloys.70 Nil <0.02 Nil Nil <0. but the expense of these alloys is rarely justified unless other contaminants.02 Zirconium Nil <0.18 <0.50 Alloy 26-1 <1 ] MP35N (R30035) Nil <0.02 <0. Glacial 99% Acetic Acid: 1% Acetic Anhydride 90% Acetic Acid: 10% Acetic Anhydride 50% Acetic Acid: 50% Acetic Anhydride 90% Acetic Acid: 10% Formic Acid 70% Formic Acid.35 0.02 <0.TABLE 7 .02 0. They can be particularly useful when contamination of such acid prohibits the use of 316L stainless steel. TEMPERATURE: ATMOSPHERIC BOILING. Aqueous 0.

Materials Performance 21. p. 2 Dillon.. P. 1157. MS 2: Formic. (Lexington." The Organometallic HyperTextBook. 1967) p. (Metals Park: American Society for Metals. ACKNOWLEDGEMENT The author extends his appreciation and thanks for the review and comments of C. 1 (1954) p. W. p. 19 Dillon.Invoice INV-475575-QJVHQQ. 4 "Corrosion Resistance of Nickel Containing Alloys in Organic Acids and Related Compounds. P. P. Part II in 60.Single-user license only. 13 Groves.173t. M. (Metals Park. ~8T-5A-7c Work Group Report. Ontario. P. 8 Yau.ilpi. 5 Fontana. N. 253.. 598 ~1 Elder. G. W.CONCLUSIONS The corrosion of common materials in the more common. 1 (1995) p. 221-231. (St. . ibid. T. 259.77." Tokyo Kogyo Shikensho Hokoku. Metals Handbook Ninth Edition. 1 (1975): p.. The Corrosion of Light Metals (New York. 14 Debold. 12 Dillon. 338 22 Yau. 6 "The Monsanto Acetic Acid Process. 16. 4 3 Tsinman. G. 6 (1965) p. B. 4. TX: National Association Engineers 1975) p. 17 Elder. Canada: Nickel Development Institute. ibid. mentor and friend." Toronto. Dillon pre-eminent corrosion expert.. Organic Chemistry. Theory of Corrosion and Protection of Metals. Corrosion 17. Corrosion. NY: John Wiley and Sons 1967) p. E. Te-Lin. 15 Yau.3. B. Outlook. A. Heath. 15. p 13. (New York. Although a lot of data has been presented. et al. ibid. B. Louis. The effect of process impurities and how to predict their roles in the corrosion of some of the metals was proposed. Te-Lin. ibid. Materials Selector for Hazardous Chemicals. 786t. C. Volume 13. NY: McGraw-Hill. Te-Lin. P. Corrosion Engineering. Tingyue Gu . et al. G. N. C." Duplex Stainless Steels. ibid.. p. NY: Macmillan Company 1966) p. 127. 127. 177. Corrosion Engineering Bulletin CEB-6. et al. et al. D. p. 10. et al. No. OH: American Society for Metals 1983) p. 304.. D. Te-Lin. A. 251. 24. G. et al. laboratory tests of candidate materials is always suggested because of the deleterious effect of impurities and the ability to predict their presence. C. simple organic acids has been presented. 4 (1961) p. Vol. Materials Performance 13. 1987)p.7 (1974). Examination in Acetic Acid solutions at Increased Temperature. 23 Elder. B. MA: D. C. C.com/organomet/monsanto. (Houston. et al... "Duplex Stainless Offers Strength and Corrosion Resistance. 20 T-5A-7c Work Group Report. p. 10 Tomashov. et al. P. H. 1 (1995) p.html. Electrokhimya II. copying and networking prohibited. 57 (1962) p. 21 Godard.. H. I. 16. downloaded on 8/24/2011 4:13:18 PM . 9 McKee A. "Corrosion Tests on Materials Used in the Synthesis of Acetic Acid from Methanol and Carbon Dioxide.. www. G. (New York. 24 Elder. 16 Yau. 1970) p.. REFERENCES i Linstromberg. 342-50. Process Industries Corrosion.. 252. Acetic and Other Organic Acids. ibid. Outlook. ibid. B. 9 (1965): p. 7 Togano. MO: Materials Technology Institute 1997) p. 25 Dillon.

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