Corrosion inhibitor for iron-containing materials

Abstract: An organic salt, 2,4 Diamino-6-mercapto pyrimidine sulfate, together with an oxysalt of Group IVB or VB of the Periodic Table provides an inhibitor formulation having corrosion resistant characteristics; for example in a sulfur-containing environment.

Description: This invention relates to a corrosion inhibitor for iron-containing materials, more especially for such materials when in a sulfur-containing environment. The production and transportation of predominantly hydrocarbon gases and oils involve the use of iron containing materials which are subject to severe corrosion in sulfur containing atmospheres, particularly at production conditions which may involve temperatures of about 40 to 205°C (about 100°F to 400°F). Japanese Patent Publication (Kokai) No. 55-158278 describes a 2-mercaptopyrimidine derivative as a principal component in the prevention of metal corrosion. The compound is added to a medium corrosive to metal optionally in combination with a variety of known anticorrosives. According to a first aspect, the present invention provides a corrosion inhibitor for an iron-containing material which comprises a mixture of (A) 2,4-diamino-6-mercapto pyrimidine sulfate (DAMPS), and (B) a Group IVB (preferably Ti, Zr, Hf) or Group VB (preferably V, Nb, Ta) oxy salt. The metal salt and its use are fully described in U.S. Patent 4,763,729 and is incorporated herein by reference. In a second aspect the present invention provides a method for inhibiting corrosion of an iron-containing material comprising treating the material with a corrosion inhibitor as defined above. The iron-containing material is usually an iron alloy, for example steel. Recent evidence suggests that corrosion occurs by the rapid migration of iron atoms through an iron sulfide surface film. To control this phenomenon the invention provides a mixed inorganic/ organic inhibitor, to change the bulk chemistry of the sulfide film by suppressing iron migration and providing inhibition by adsorptions on the sulfide surface. We believe that the refractory metal oxy salt is incorporated into the iron sulfide scale formed on the iron alloy and inhibits growth of the scale, while the nitrogen atoms of DAMPS reacts at the surface of the scale, thereby further preventing the migration of iron atoms to the surface and inhibiting the formation of additional iron sulfide scale. The figure shows relative corrosion rates, plotted in mils/year, in the ordinate v. hours in the abscissa, for an uninhibited iron alloy, carbon steel (A), inhibited with DAMPS only (B), inhibited with an oxy salt only (C), and inhibited with a combination of DAMPS and an oxysalt (D). 1 mil is 25.4 micrometres. Both the DAMPS, a commercially available chemical, and the metal oxy salt are used in amounts that are effective for inhibiting corrosion, e.g., at least about 10-50 ppm DAMPS, at least about 10-50 ppm of the oxy salt. A solution, preferably an aqueous solution containing appropriate amounts of DAMPS and the oxy salt is easily prepared and applied in known manner to the iron containing alloy to be inhibited. Preferably, DAMPS in an amount of 50-150 ppm, the oxy salt in amounts of about 50-100 ppm are used. Particularly effective oxy salts are the meta-, ortho-, and pyrovanadates (e.g. NaVO 3 , Na 3 VO 4 , and Na 4 V 2 O 7 ). EXAMPLE Corrosion rates in mils per year for a 4130 series carbon steel were determined by immersing a small example of the material in 3 wt% aqueous sodium chloride solution contained in a pyrex flask fitted with probes for electrochemical corrosion rate measurements. A gas mixture containing 20% hydrogen sulfide in argon was continuously bubbled through the aqueous solution, thus providing the corrosive medium. The results are shown graphically in Figure 1. The measurements were made at a temperature of 95°C. The 4130 steel is typically comprised of, in wt%, 0.28-0.33 C, 0.4-0.6 Mn, 0.035 max S, 0.15-0.35 Si, 0.8-1.1% Cr, and 0.15-1.25% Mo, the balance being iron. Curve A shows corrosion rates in mils per year (mpy) for an uninhibited steel, curve B for steel inhibited with 80 ppm DAMPS, and curve C for steel inhibited with 50 ppm of sodium meta vanadate. It is observed that both DAMPS and sodium meta vanadate have inhibiting properties, the former providing protection at a level of 58% while the latter provides 70% corrosion protection under conditions used in the experiment described. Curve D represents the corrosion rate measurement where 80 ppm DAMPS have been combined with 50 ppm sodium meta vanadate. In this experiment, the corrosion rate is seen to be suppressed by 95%. The most interesting point of these examples is that DAMPS and the meta vanadate by themselves are but fair corrosion inhibitors. However, when combining the two, rather than obtaining an average of the two for corrosion inhibition, a substantially enhanced corrosion protection of 95% is achieved.

Claims: A corrosion inhibitor for an iron-containing material which comprises a mixture of (A) 2,4 diamino-6-mercapto pyrimidine sulfate and (B) a Group IVB or Group VB oxy salt. The inhibitor of claim 1 wherein (A) and (B) are in an aqueous solution. The inhibitor of claim 1 or 2 wherein the oxy salt is selected from metavanadate, orthovanadate, and pyrovanadate. The inhibitor of claim 3 wherein the oxy salt is the metavanadate A method for inhibiting corrosion of an iron-containing material comprising treating the material with a corrosion inhibitor as claimed in any preceding claim. The method of claim 5 wherein the iron-containing material is an iron alloy. The method of claim 6 wherein the iron alloy is steel. The method of claim 7 wherein the steel is carbon steel.

Inventors: RAMANARAYANAN TRIKUR ANANTHARA, VEDAGE HYACINTH LORNA, RAMANARAYANAN, TRIKUR ANANTHARAMAN, VEDAGE, HYACINTH LORNA
Applicants: EXXON RESEARCH ENGINEERING CO, EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1993
Main classification: C23F11
IPC codes: C23F11