This document provides information on chemical treating methods for corrosion control in operating systems. It defines key terms related to treating chemicals and describes common chemicals used for various problems. Corrosion inhibitors are discussed in detail, including how they work and types such as inorganic, organic, anodic, and cathodic inhibitors. Testing methods for evaluating corrosion inhibitors are also summarized.
This document provides information on chemical treating methods for corrosion control in operating systems. It defines key terms related to treating chemicals and describes common chemicals used for various problems. Corrosion inhibitors are discussed in detail, including how they work and types such as inorganic, organic, anodic, and cathodic inhibitors. Testing methods for evaluating corrosion inhibitors are also summarized.
This document provides information on chemical treating methods for corrosion control in operating systems. It defines key terms related to treating chemicals and describes common chemicals used for various problems. Corrosion inhibitors are discussed in detail, including how they work and types such as inorganic, organic, anodic, and cathodic inhibitors. Testing methods for evaluating corrosion inhibitors are also summarized.
participant will be able to select the proper treating chemicals and the best treating methods, given corrosion-related operating systems. ENABLING OBJECTIVE Define chemical treating terms and describe treating chemicals. Describe treatment methods. Describe bacteria monitoring techniques in terms of purpose, methods, and significance of results. Operating Problems and Treating Chemicals Operating Problem Treating Chemical Equipment corrosion Corrosion inhibitor, Oxygen scavenger Microbiologically-influenced Biocide Corrosion Mineral scale deposits Scale inhibitor Suspended solids Coagulant, flocculant Water-in-oil emulsion Emulsion breaker Oil-in-Water emulsion Reverse breaker coagulant, flocculant Chemical Treating Terminology Typical Treating Chemical Composition 1/3 Active Ingredients 2/3 Solvents or additives Treating Chemicals Additives: a treating chemical usually contains an active compound and one or more additives Solvents: are add to most treating chemicals to keep them from separating also lower pour point Solubility: is chemicals ability to dissolve in solution Dispersibility: is chemicals ability to transported by fluids or gases Chemical Treating Terminology Emulsion tendency: a chemicals ability to disperse one liquid phase into another liquid phase Oil Soluble-Water Dispersible Inhibitors : are normally used in oil wells and gas condensate wells Water Soluble Inhibitors : they are soluble in fresh and brine water Chemical Treating Terminology Corrosion Inhibitors They adsorb on metal surfaces They combine with corrosion product film They form precipitates Work by one or more of the following mechanisms: Inhibitor Classifications Corrosion Inhibitors Inorganic Organic Anodic Cathodic Film Forming Chromates Nitrites Molybdates Phosphates Zinc inhibitors Polyphosphates & Phosphonates Amines Amine salts Imidazoilnes Inorganic & Organic inhibitors Inorganic inhibitors are used mainly in boilers, cooling towers, and fractionation units. Organic inhibitors are used mainly in oil field systems. Organic inhibitors are also used to prevent overhead corrosion in some refinery crude units Often used to reduce corrosion in open (aerated) and closed cooling water systems. used alone or in combination with other inhibitors. Not enough anodic inhibitor lead to severe localized pitting. Inorganic Anodic Inhibitors Inorganic Inhibitors Electrochemical Corrosion Reactions in an Open (Aerated) Cooling Water System Precipitation of Black Oxide Hydrolysis and Oxidation Hydrolysis of Dissolved Iron Lowers pH ACIDIC PIT SOLUTION WITH LOWER OXYGEN CONTENT 6 5 3 1 7 2 Precipitation of Red Oxide Iron Dissolves (ANODE) ANODIC AREA Reduction of Oxygen (CATHODE) CATHODIC AREA 4 Evolution of Hydrogen (CATHODE) MAGNETITE MAGNETITE Fe 2 o 3 Fe 3 o 4 RED OXIDE BLACK OXIDE H 2 O 2 OH - Fe e - e - e - e - Fe +2 H + + FeOH + Fe(OH) 2 + FeOH +2 Ferric Iron Deposits as a Gamma Iron Oxide Film Inorganic Anodic Inhibitors 4 Fe 0 + 3 O 2 = 2 Fe 2 O 3 Inorganic Inhibitors Inorganic Anodic Inhibitors Combined Iron Oxide and chromium oxide film on a Metal Surface Inorganic Anodic (Passivating) Inhibitors Shift in Anode Potential Caused by Anodic Inhibitors Before anodic inhibitors After anodic inhibitors Potential Difference More negative More positive Anode Cathode Cathode Anode Inorganic Inhibitors Inorganic Anodic Inhibitors Estimate of Proper Concentration of Sodium Nitrite Weight NaNO 2 (in mg/L) Wt NaCl + Wt Na 2 SO 4 (in mg/L) = 1 Inorganic Inhibitors Not as effective as inorganic anodic inhibitors but safer to use. Inorganic Cathodic Inhibitors O 2 + 4H + + 4e - 2H 2 O O 2 + 2H 2 O + 4e - 4(OH - ) In acidic systems: In neutral or alkaline systems: Reduction Reactions Shift in Cathode Potential Cause by Cathodic Inhibitors Inorganic Cathodic Inhibitors Inorganic Inhibitors Zinc Inhibitors Inorganic Cathodic Inhibitors Zn +2 + 2 OH Zn (OH 2 ) Zinc Ion Hydroxide Ion Zinc Hydroxide Inorganic Cathodic Inhibitors Polyphosphate Structure P NaO O P O O ONa ONa ONa x x = 0 Orthophosphate x = 1 Pyrophosphate x = 2 Tripolyphosphate x = 12-14 Polyphosphate Inorganic Inhibitors Polyphosphates Prevent Reduction Reactions at Cathodic Areas Inorganic Cathodic Inhibitors Polyphosphate inhibitor molecules H + O 2 Metal Fe 2+ O 2 H + e e Polyphosphates reacts with Ca and other divalent ions in water such colloids are attracted to +ve cathode Organic Inhibitors Electrical potential of metal Inhibitor molecule chemical structure Size and shape of inhibitor molecule Complex mixtures of many different molecular compounds Affect both cathodic and anodic sites Their effectiveness depends upon: Representation of an Organic Inhibitor Molecule Using an Aliphatic Amine Organic Inhibitors H C H Electrons available for bonding to metal (chemisorption bond) Polar amine nitrogen group N Hydrocarbon chain Oil soluble and attract crude oil molecules to form oily layer barrier Chemisorption & Physical Adsorption Organic inhibitors molecules attach to metal surfaces by chemisorption and physical adsorption Physical adsorption is weaker than chemisorption Physical adsorption does not involve sharing of electrons Organic Inhibitors Organic Inhibitors Mechanism for Organic Film Forming Inhibitors Inhibitor molecule dispersed in process stream Metal Process Stream H H C N H H H H H H H H H H H H H H H H C C C C C C C C N N N N N N N N N Chemisorption & physical adsorption by polar amine group Hydrocarbon Oil molecule Hydrocarbon chain R H H C Organic Inhibitors Molecular Structure of Common Oil Field Inhibitors Name NH 2 R CONH 2 R C CH 2 N CH 2 N R 1 R N (CH 2 CH 2 O) y H (CH 2 CH 2 O) x H Primary Amine Amine Amine Polyethoxylated Amines Structure R Organic Inhibitors Laboratory Static Test Laboratory Wheel Test Laboratory Electrochemical Test Field Corrosion Test Coupons Field Corrosion Probes Corrosion Inhibitor Testing Corrosion Inhibitor Testing Corrosion Rate Where - W = weight loss in grams A = coupon surfaces area ( in 2 ) d = metal density (g/in 3 ) = g/cm 3 x 16.387 cm 3 /in 3 t = time (days) A x d x t mpy = = 3.9 mpy Weight in grams x 365000 0.037 g x 365000 mpy = 3.875 in 2 x 7.85 g / cm 3 x 16.387 cm 3 / in 3 x 7 days Laboratory Electrochemical Tests LPR Test Apparatus for Continuous Inhibitor Evaluation Corrosion Inhibitor Testing Corrosion Coupons Field Corrosion Test Coupons 0.5 or 1 3 0.0625 or 0.125 Strip coupon Rod coupon Flush-mounted disc Corrosion Inhibitor Testing Field Corrosion Test Coupons Flush-Mounted Corrosion Coupon in an Access Fitting Disc coupon holder assembly Flush disc Retriever Service valve 1 2 3 4 5 Retrieval Procedure 1. Access fitting in service, externals removed. 2. Service valve installed, retriever goes in. 3. Retriever is attached to plug. 4. Retriever extended, plug pass gate, valve closed. 5. Plug removed. Corrosion Inhibitor Testing Field Corrosion Test Coupons Pitting Severity Where - Penetration Rate (mpy) Pitting Severity = Maximum Pit Rate (mpy) Time (days) Maximum Pitting Rate = Maximum Pit Depth x 365 Corrosion Inhibitor Testing Field Corrosion Test Coupons Interpretation of Corrosion Rates and Pitting Rates Corrosion Inhibitor Testing Quality Control of Corrosion Inhibitors Comparison of NMR* Spectra for Two Samples of a Corrosion Inhibitor *NMR = Nuclear Magnetic Resonance Quality Control of Corrosion Inhibitors FT-IR* Spectra of Two Samples of a Corrosion Inhibitor * FT-IR = Fourier-Transform Infrared Oxygen Depolarizes the Cathode Oxygen accepts electrons at the cathode. Electrolyte Cathode Cathode Metal Fe 2+ H + H + H 2 H 2 H 2 H 2 H 2 O 2 e e Anode Oxygen Scavengers O 2 main cause of corrosion in many water systems As low as 0.05 ppm O 2 can cause corrosion in water Arabian seawater contains 5-7 ppm O 2 Sources of O 2 in water systems (open vents, thief hatches on water tanks, suction side of centrifugal pumps, etc) Gas blankets Gas stripping towers Vacuum deaeration Oxygen Scavengers Mechanical techniques: Reduce O 2 to about 1 ppm High-temp scavengers are commonly used in boiler feedwater treatment For boiler: O 2 recommended conc. 7 ppb Sulfite are commonly used in oil field systems In oil field systems: O 2 to be reduced to 50 ppb High-Temperature Oxygen Scavengers Hydrazine N 2 H 4 + O 2 2H 2 O + N 2 Hydrazine Oxygen Water Nitrogen 6Fe 2 O 3 + N 2 H 4 4Fe 3 O 4 + 2H 2 O + N 2 Iron (III) Hydrazine Magnetite Water Nitrogen Oxide Hydrazine will react with iron oxide as follows: Sulfite and Bisulfite Oxygen Scavengers Na 2 SO 3 + 1/2 O 2 Na 2 SO 4 Sodium Sulfite Oxygen Sodium Sulfate NH 4 HSO 3 + 1/2 O 2 NH 4 HSO 4 Ammonium Oxygen Ammonium Bisulfite Bisulfate (Ammonium Acid Sulfate) Are used in most oil field systems Biocides Planktonic and Sessile Bacteria Planktonic Bacteria Metal Surface Sessile Bacteria Biofilm Cause two major operating problems in oil field water systems: declining water quality corrosion Biocide Application Bacteriostats or bactericides. Bacteriostats do not kill bacteria. Bactericides inhibit bacterial growth. Chemicals that control bacteria growth are classified as: Performance is based on success in controlling sessile bacteria. Planktonic counts are used first to screen several biocides. Further testing using sessile counting techniques. Biocide Performance List of Biocides Frequently Used in Oil Field Operations Primary Cocoamine RC NH 2 HOOCH Amine Salts acetate Diamine Cocodiamine RC N C C C NH 2 HOOCH Salts acetate Quarternary Dialkyl-benzyl Ammonium ammonium chloride Salts Aldehydes Glutaraldehyde OCH(CH 2 ) 3 CHO Acrolein CH 2 = CHCHO Oxidizing Chlorine CI 2 Agents Chlorine dioxide CIO 2 R C R C N H C C 6 H 5 CH 2 CI - + H H H H H H H Biocides Biocide Effectiveness ((10,000 - 100) / 10,000) x 100 = 99% Biocides A biocide conc. is consider effective if it kills at least 99% of the bacteria compared to an treated blank sample. Scale can inhibit or promote corrosion Prevent & Remove oil field scale whether or not it protects the metal. Scale can cause operation problems in addition to corrosion Scale deposits are mainly caused by supersaturation: Temp. decrease Temp. increase Press. Decrease Incompatible waters are mixed Water evaporates Saturated waters become stagnant Scale Inhibition Most Common Oil Field Scales NAME FORMULA COLOR WHEN PURE Barium sulfate BaSO 4 White Calcium carbonate CaCO 3 Colorless to white Calcium sulfate Anhydrite CaSO 4 Colorless to white Gypsum CaSO 4 .2H 2 O Colorless to white Iron carbonate FeCO 3 Gray Iron oxide Fe 2 O 3 Redish brown to black Iron sulfite FeS Brown to black Strontium sulfate SrSO 4 Colorless to white Scale Inhibition Ca +2 + 2HCO 3 -
Ca +2 + CO 3 - 2 + CO 2 + H 2 O CaCO 3 + CO 2 + H 2 O Calcium Carbonate Formation Scaling tendency of CaCO 3 as temp Scales Normally produced waters contain Ca +2 , HCO 3 - , and CO 2 Colors of Pure Oil Field Scales NAME FORMULA COLOR WHEN PURE Barium sulfate BaSO 4 White Calcium carbonate CaCO 3 Colorless to white Calcium sulfate Anhydrite CaSO 4 Colorless to white Gypsum CaSO 4 .2H 2 O Colorless to white Iron carbonate FeCO 3 Gray Iron oxide Fe 2 O 3 Redish brown to black Iron sulfite FeS Brown to black Strontium sulfate SrSO 4 Colorless to white Identifying Scales Composition of a Typical Scale Inhibitor 30% Active Ingredients 70% Water Scale Inhibitors Scale Inhibitor Are water based products. Reduce rate of scale deposition. Distort scale micro crystals in solution. Scale Inhibitors Used Most Often in Oil Field Operations NaO O P O ONa O P O ONa O P ON a ONa n R N C C O P N O OH R 1 HOP O CH 2 OH HOP O CH 2 OH N CH 2 CH 2 N HOP CH 2 OH HOP O CH 2 OH O CH2 CH C=O C H + ,Na + n CH 2 CH C=O NH 2 x Inorganic Polyphosphates Organic Phosphates Esters Organic Phosphonates Organic Polymers CLASS STRUCTURE overall effectiveness. Thermal stability Compatibility with water ands solubility in. Scale Inhibitors Selection Most important factors are: Scale Inhibitors Selection Inhibitor Type Solubility* Thermal Stability Phosphate Esters Most soluble Least stable Phosphonates Polymers Least soluble Most stable * Solubility in high-calcium brines. Organic Scale Inhibitor Properties Flocculation process in which water droplets gather into groups Coalescence process in which surfactant film breaks hence water droplets become larger Settling larger droplets settle to the bottom Water Oil Flocculation Coalescence Settling The Oil-Water Separation Process Emulsion Treatments Continuous Chemical Injection Chemical reservoir Injection pump Pipeline Batch Treatments Batch and Fall Application Method Casing Tubing Gas Inhibitor mixture falls down tubing wall Tubing Displacement Treating Method Displacing fluid or nitrogen Inhibitor mixture Oil Perforations Champion Tubing saver Connection for weight bar Gas Wire line tie Nylon brush Knuckle joint Nylon brush Inhibitor mixture Corrosion Inhibitor Squeeze Treatment Casing Displacing Fluid Tubing Inhibitor mixture Parker Perforations Inhibitor Serial Dilution Technique GAB and SRB Broth Media Bottles 9 ml of broth media Nail GAB 9 ml dextrose broth SRB 9 ml lactate broth 9 ml of broth media 28 days incubation period 5 days incubation period Serial Dilution Technique Dilution Ratio 1:10 1:100 1:1,000 1:10,000 1:100,000 1:1,000,000 Dilution Level 10 -1 10 -2 10 -3 10 -4 10 -5 10 -6 Syringe with 1 ml of water sample Triplicate Test for Sulfate Reducing Bacteria Test 1 Test 2 Test 3 10 0 10 1 10 2 10 3 10 4 10 5 10 6 BACTERIA / ML