Investigation of the Corrosion and Passive Behavior of HP-13Cr Stainless Steel in Formate Annulus Protection Fluid

doi:10.1007/s40195-024-01689-x

Abstract

Abstract:

The corrosion and passive behavior of HP-13Cr stainless steel (HP-13Cr SS) in formate annulus protection fluid was investigated. HP-13Cr SS exhibited good passive behavior in clean formate annulus protection fluid, which was attributed to a thinner and more dense passive film mainly composed of Cr₂O₃. In the formation water solution, the passive film was composed of metastable Cr(OH)₃, which was explained by the isoelectric point theory, resulting in the deterioration of the passive behavior of HP-13Cr SS. When the formation water penetrated the formate annulus protection fluid, a large number of loose FeCO₃ particles formed in the corrosion scales, thus HP-13Cr SS suffered severe corrosion. Therefore, avoiding formation water penetrating the formate annulus protection fluid is conducive to improving the service life of HP-13Cr SS oil tubes in extremely aggressive environment.

Key words: HP-13Cr SS, Passive behavior, Formate annulus protection fluid, Isoelectric point

Jidong Wang, Tengfei Yin, Wenlong Qi, Xuanpeng Li, Yang Zhao, Tao Zhang, Fuhui Wang. Investigation of the Corrosion and Passive Behavior of HP-13Cr Stainless Steel in Formate Annulus Protection Fluid[J]. Acta Metallurgica Sinica (English Letters), 2024, 37(6): 1087-1103.

Figures/Tables 19

Fig. 1 Schematic diagram of super-deep well

Table 1 Chemical composition of FW, SF, and FW/SF (1:1) solution (mg/L)

	HCO₃⁻	Cl⁻	SO₄²⁻	Ca²⁺	Mg²⁺	K⁺	Na⁺	HCOO⁻
FW	189	128,000	430	8310	561	6620	76,500	-
SF	20,000	-	-	-	-	-	707,300	687,300
FW/SF (1:1)	10,095	6400	215	4155	281	3310	391,900	343,650

Fig. 2 Corrosion rate of HP-13Cr SS in various extremely aggressive environments

Fig. 3 Potentiodynamic polarization curves for HP-13 Cr SS in various extremely aggressive environments at different temperatures and pressures

Table 2 Electrochemical parameters obtained by polarization curves in the extremely aggressive environment at different temperatures/pressures

Condition	Sample	E_corr (mV)	E_pit (mV)	E_pit-E_corr (mV)	i_p (μA/cm²)
95 ℃/2.8 MPa	SW	− 245.62	− 3.41	242.21	11.69
	SF	− 440.79	30.99	471.78	2.09
	FW/SF (1:1)	− 359.35	-	-	-
120 ℃/3.2 MPa	SW	− 253.69	− 11.49	242.2	15.53
	SF	− 456.94	− 23.77	433.17	2.07
	FW/SF (1:1)	− 383.92	-	-	-
150 ℃/3.6 MPa	SW	− 316.88	− 100.99	215.89	27.62
	SF	− 514.15	− 119.25	394.9	11.11
	FW/SF (1:1)	− 396.21	-	-	-
180 ℃/3.8 MPa	SW	− 343.2	− 125.57	217.63	44.46
	SF	− 601.56	− 330.92	270.64	16.12
	FW/SF (1:1)	− 453.07	-	-	-

Fig. 4 Surface SEM images of the corrosion scales formed on HP-13Cr SS in various extremely aggressive environments: a FW (CO2), b SF (N2), c FW:SF = 1:1 (CO2); (1) 95 °C/2.8 MPa, (2) 120 °C/3.2 MPa, (3) 150 °C/3.6 MPa, (4) 180 °C/3.8 MPa

Fig. 5 Cross-sectional SEM images of the corrosion scales formed on HP-13Cr SS in various extremely aggressive environments: a FW (CO2), b SF (N2), c FW:SF = 1:1 (CO2); (1) 95 °C/2.8 MPa, (2) 120 °C/3.2 MPa, (3) 150 °C/3.6 MPa, (4) 180 °C/3.8 MPa

Fig. 6 SEM images and the corresponding EDS maps of the corrosion scales formed on HP-13 Cr SS in various extremely aggressive environments at 180 ℃/3.8 MPa: a FW (CO2), b SF (N2), c FW:SF = 1:1 (CO2)

Fig. 7 XRD patterns of the corrosion scales formed on HP-13 Cr SS in various extremely aggressive environments: a FW (CO2), b SF (N2), c FW:SF = 1:1 (CO2)

Fig. 8 STEM bright-field images and the selected area diffraction patterns from the region indicated of the corrosion scales formed on HP-13Cr SS in various extremely aggressive environments at 150 °C/3.6 MPa: a FW (CO2), b SF (N2), c outer corrosion scales with FW:SF = 1:1 (CO2), d inner corrosion scales with FW:SF = 1:1 (CO2)

Fig. 9 STEM images and the corresponding EDS maps of the corrosion scales formed on HP-13Cr SS in various extremely aggressive environments at 150 °C/3.6 MPa: a FW (CO2), b SF (N2), c outer corrosion scales with FW:SF = 1:1 (CO2), d inner corrosion scales with FW:SF = 1:1 (CO2)

Fig. 10 XPS spectra of the corrosion scales formed on HP-13 Cr SS in various extremely aggressive environments at 95 °C/2.8 MPa; a the wide XPS spectra, b Cr 2p3/2 peaks, c Fe 2p3/2 peaks, d Mo 3d peaks

Fig. 11 XPS spectra of the corrosion scales formed on HP-13 Cr SS in various extremely aggressive environments at 120 °C/3.2 MPa; a the wide XPS spectra, b Cr 2p3/2 peaks, c Fe 2p3/2 peaks, d Mo 3d peaks

Fig. 12 XPS spectra of the corrosion scales formed on HP-13 Cr SS in various extremely aggressive environments at 150 °C/3.6 MPa; a the wide XPS spectra, b Cr 2p3/2 peaks, c Fe 2p3/2 peaks, d Mo 3d peaks

Fig. 13 XPS spectra of the corrosion scales formed on HP-13 Cr SS in various extremely aggressive environments at 180 °C/3.8 MPa; a the wide XPS spectra, b Cr 2p3/2 peaks, c Fe 2p3/2 peaks, d Mo 3d peaks

Table 3 Equilibrium constant at the different temperatures/pressures

T (°C)	${K}_{1}$ (×10^–3)	K₂ (×10^-3)	K₃ (×10^-5)	K₄ (×10^-10)	K₅ (×10^-6)	K_w (×10^-13)
95	4.15	2.58	9.44	4.23	11.66	4.25
120	3.37	2.58	5.40	3.82	8.88	11.20
150	2.90	2.58	2.48	2.86	6.03	27.00
180	2.77	2.58	1.02	1.79	3.90	47.60

Table 4 Ion concentrations (mol·L−1) in various extremely aggressive environments

		${C}_{{{\text{CO}}}_{2}}$	${C}_{{{\text{H}}}_{2}{{\text{CO}}}_{3}}$	${C}_{{{\text{HCO}}}_{3}^{-}}$	${C}_{{{\text{CO}}}_{3}^{2-}}$	${C}_{{\text{HCOOH}}}$	${C}_{{{\text{HCOO}}}^{-}}$	${C}_{{{\text{OH}}}^{-}}$	${C}_{{{\text{H}}}^{+}}$	pH
SF (N₂)	95 ℃/2.8 MPa	3.74 × 10^-4	1.55 × 10^-6	0.161	0.079	1.11 × 10^-3	14.8488	11.2 × 10^-4	0.87 × 10^-9	9.06
	120 ℃/3.2 MPa	12.9 × 10^-4	4.30 × 10^-6	0.182	0.056	2.07 × 10^-3	14.8479	20.8 × 10^-4	1.24 × 10^-9	8.91
	150 ℃/3.6 MPa	43.8 × 10^-4	12.7 × 10^-6	0.200	0.036	3.90 × 10^-3	14.8461	39.0 × 10^-4	1.59 × 10^-9	8.80
	180 ℃/3.8 MPa	123 × 10^-4	34.1 × 10^-6	0.206	0.022	6.44 × 10^-3	14.8436	64.6 × 10^-4	1.69 × 10^-9	8.77
FW (CO₂)	95 ℃/2.8 MPa	0.166	4.27 × 10^-4	3.11 × 10^-4	9.62 × 10^-10	-	-	3.11 × 10^-9	3.12 × 10^-4	3.51
	120 ℃/3.2 MPa	0.154	3.97 × 10^-4	2.27 × 10^-4	8.70 × 10^-10	-	-	11.26 × 10^-9	2.27 × 10^-4	3.64
	150 ℃/3.6 MPa	0.149	3.84 × 10^-4	1.51 × 10^-4	6.51 × 10^-10	-	-	40.58 × 10^-9	1.52 × 10^-4	3.82
	180 ℃/3.8 MPa	0.151	3.89 × 10^-4	0.97 × 10^-4	4.08 × 10^-10	-	-	111.3 × 10^-9	9.76 × 10^-4	4.01
FW:SF (CO₂)=1:1	95 ℃/2.8 MPa	0.116	2.98 × 10^-4	8.31	0.68	4.32 × 10^-3	14.8402	0.83 × 10^-4	7.74 × 10^-9	8.11
	120 ℃/3.2 MPa	0.107	2.77 × 10^-4	7.65	0.98	3.27 × 10^-3	14.8425	3.79 × 10^-4	4.46 × 10^-9	8.35
	150 ℃/3.6 MPa	0.104	2.68 × 10^-4	6.91	1.36	2.37 × 10^-3	14.8446	18.53 × 10^-4	2.19 × 10^-9	8.66
	180 ℃/3.8 MPa	0.105	2.72 × 10^-4	6.26	1.68	1.68 × 10^-3	14.8462	71.45 × 10^-4	1.00 × 10^-9	9.00

Fig. 14 Calibrate the trajectory of Fe2+, Cr3+, pH of HP-13Cr SS in the aggressive oilfield environment at the criterion line for deposition diagram of Fe(OH)3, FeCO3, Cr2O3, Cr(OH)3 with the increasing of immersion time at 150 °C/3.6 MPa

Fig. 15 Zeta potentials of FeCO3, Cr2O3, Fe2O3 materials

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