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Corrosion by Hazardous Chemicals Otto Drescher, P.E. Discuss Uses & Some Properties Case History Materials Selection Guidelines. Summary. Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl. HF Organic Acids Caustic Ammonia & Amines. Specific Chemicals.
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Corrosion by Hazardous Chemicals Otto Drescher, P.E.
Discuss Uses & Some Properties Case History Materials Selection Guidelines Summary
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Largest Tonnage of Inorganic Chemicals Major Use in Petroleum Refining, Fertilizers, Paints, Pigments, Dyes, Explosives, and pH Control Powerful Oxidizing Agent Sulfuric Acid
Conc. Acid is 70% to 100% Oleum (Fuming) – 100% + excess SO3 Dilute Acid - < 25% Contaminants Greatly Effect Corrosion Sulfuric Acid
Erosion-corrosion in 93% H2SO4Carbon Steel Nozzle 4 - 6 fps (1.2 – 1.8 m/s) at RT Design Velocity Limit is <2 fps (0.6 m/s)
Sulfuric Acid – GuidelinesMaterials Selection °F °C Tantalum Glass Si-Iron Boiling Point Curve Alloy B-2, B-3, B-4 316 825 20Cb-3 904L 316 Steel Concentration, Wt.%
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Nitric Acid • Major Use in Ammonium Nitrate and Phosphate Fertilizers, Nitro Explosives, Plastics, and Dyes • Always an Oxidizing Acid
Nitric Acid • Concentrated Acid is 67% to 95% • Fuming Grades are > 99% • HF Addition Makes It Reducing • Cl- Contaminantion Releases Nascent Cl2
Nitric-HF Acid Pickling LineAlloy 33 (33Cr-32Fe-31Ni-1.6Mo) Tank
Nitric Acid – GuidelinesMaterials Selection ° C °F Boiling Point Curve Tantalum Si-Iron 1815 LC Si 304L 310 LCN Titanium 67% Aluminum Concentration, Wt.%
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Phosphoric Acid • Major Use in Phosphate Fertilizers, Food & Beverages, Drying Agents, Plasticizers, Oil Additives, Fire Retardants, and Insecticides • Is a Reducing Acid, More So When Contaminated With Cl- and F-
Phosphoric Acid • Two Types of Pure Acid (85%): • C. P. Grade • Food Grade • Superphosphoric Acid - > 105% • Industrial Grades May Be Contaminated With Cl-, F-, and Fe+++
Preferential Attack in H3PO4Ambient Temperature, Steam Traced 304 Compare Thickness 316
Phosphoric Acid – GuidelinesMaterials Selection °F °C C-276 G-3 G-30 G-35 Alloy 28, 31 Boiling Point Curve 825/904L 317L 316L Concentration, Wt.%
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Chlorine • Uses - Organic • Drugs • Plastics • Solvents • Insecticides • PVC • Deodorants Uses - Inorganic • Chlorides Salts • Bleaching • Chlorination • Dyes • Rockets • Explosives
Chlorine • Poisonous, greenish-yellow gas • Does Not Attack Metals < 400 °F (204 °C), Except Ti • Moisture aggravates corrosivity • HOCl is a Powerful Oxidizing Acid
Chlorine – GuidelinesMaterials Selection • Liquid Cl2 – Carbon Steel ( Dry! ) • Cl2 Gas • Carbon Steel to 250 °F (121 °C) Wall Temp • Caution! Carbon Steel May Ignite • Alloy 400 to 570 °F (299 °C) Wall Temp
Chlorine – GuidelinesMaterials Selection • Chlorinated Organics • Carbon Steel to 200 °F (93 °C) Wall Temp • Alloys 400 & 200 to B.P. • Chlorinated Waters – Titanium, C-276
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Hydrochloric Acid • 2nd in Importance to Sulfuric Acid • Major Use in Pickling Steels, Oil Well pH, Chemical Cleaning, Ore Reduction, Food Processing, Synthetic Rubber, and Regeneration of Ion Exchange Resins
Hydrochloric Acid • Anhydrous is Non-corrosive, Very Hygroscopic • Strong, Reducing Acid • Attacks Most Metals Below H2 in EMF Series • Forms Metal Chlorides and Liberates H2
Hydrochloric Acid • Attacks Noble Metals Only If DO or Oxidizing Contaminants Are Present (Fe+++) • Water Solution is 28% – 35% • Commercial Grade is Muriatic Acid • Constant Boiling Mixture is 20.2%
HCl Pitting CorrosionAlloy 825 Pickling Hook in Heated Acid Contaminated With Fe+++
Hydrochloric Acid – GuidelinesMaterials Selection °C °F Boiling Point Curve B-2, B-3 Zirconium Tantalum 400 Air Free C-Family 200, 400 825 Concentration, Wt.%
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Hydrofluoric Acid • Major Uses are Refrigerants, Fluorocarbons, Etch/Polish Glass, Pickling, Ore Processing Acidification of Oil Wells • Is a Weak, Reducing Acid • Anhydrous HF and HF Acid are Very Hazardous • Commercial Grades are 48% & 70% • Fluoride Ions Less Aggressive Than Chloride
HF Acid – GuidelinesMaterials Selection °C °F Boiling Point Curve 400 200, 400, C-276, C-22, 686 Concentration, Wt.%
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Organic Acids • Major Uses are Dyeing, Pigments, Pesticides, Tanning, Esters, Alcohols, Organic Chemicals • Are Weak, Reducing Acids • Less Corrosive as Carbon Chain Lengthens (or as Molecular Weight Increases)
Organic Acids • Rank in Corrosivity: Formic > Acetic > Propionic > Butyric • Aeration & Temperature Increase Corrosion • Contaminants (e.g. Cl-) Increase Corrosion
Crevice CorrosionAcetic Acid-Acetic AnhydrideDistillation Column at 248 °F (120 °C) 316 Bubble Cap Attack Due to Oxygen-Concentration Cell
Selective CorrosionBoiling Acetic Acid Weld Metal Corroded More Than Base Metal Base Metal Corroded More Than Weld Metal
Organic Acids – GuidelinesMaterials Selection • IGA Probable, if Low C Not Used • SCC Possible, if Chlorides Present • 304L For Storage and Low Temperatures • 316L For Higher Temperatures • 6% Mo Alloys if Crevices & Cl- Present • May Need 6% or Higher Mo Alloy Welds
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Sodium HydroxideCaustic Soda • Major Uses are Sodium Compounds, Metallurgical (Aluminum), Glass, Rayon Fibers, Cellophane, Paper Industry, Detergents, Bleaching, Whitening Products, Soaps, Cleaning (Dissolves Organics), pH Control • Strong Alkali • KOH Is Very Similar to NaOH
Caustic Cracking of SteelHeating Coil in 50% NaOH General Corrosion Stress Corrosion Cracking
Caustic SodaCorrosion Rates for 304 °C °F >30 mpy (0.76 mm/y) Boiling Point Curve 1 - 30 mpy (0.03 – 0.76 mm/y) < 1 mpy (0.03 mm/y) Freezing Point Curve Concentration, Wt.%
Caustic SodaStress Corrosion Cracking Zones °C °F 304 Boiling Point Curve C Steel Freezing Point Curve Concentration, Wt.%
Caustic Soda – Chlorate FreeCorrosion Rates for Alloy 200 °C °F >5 mpy (0.13 mm/y) Boiling Point Curve 1 - 5 mpy (0.03 – 0.13 mm/y) 0.1 - 1 mpy (0.003 – 0.03 mm/y) < 0.1 mpy (0.003 mm/y) Freezing Point Curve Concentration, Wt.%
Sulfuric Acid Nitric Acid Phosphoric Acid Chlorine HCl HF Organic Acids Caustic Ammonia & Amines Specific Chemicals
Ammonia • Major Uses are Organic Compounds, Drugs, Plastics, Dyes, Fertilizers, Explosives, Production of Nitric Acid, Ammonium Salts, Refrigerant, Cleaning Agents • 4th Most Important Chemical
Ammonia – GuidelinesMaterials Selection • Anhydrous Ammonia Is Non-corrosive Except for SCC of Steel • NH3 + H2O NH4OH Water Dilution Forms Ammonium Hydroxide - Inhibits SCC of Steel • Ingress of Water and O2 Corrosive to Cu and Cr-free Ni Alloys (Even ppm)
Ammonia – GuidelinesMaterials Selection • Corrosion of Steels Through Stainless Steels May Be Caused By CO2 Contamination (Ammonium Carbamate) • Chloride Contamination Can Reduce Life of Stainless Steel Equipment
Discussed Specific Chemicals Reviewed Use & Some Properties Presented Materials Selection Guidelines for Each Chemical Summary
The End Questions?