METHOD OF LASER STIMULATION OF BARIUM AND/OR STRONTIUM COMPLEXION BY DTPA

Abstract

The present invention relates to a Pig laser (10) that is equipped with a heating system to be used in the removal of scaling from subsea production systems (50) such as production lines, manifolds, ANMs and production columns. The induction promoted by the laser radiation is applied to the DTPA solution, heating and accelerating the reaction at the design limit temperature of the equipment to be descaling. At the same time, the laser is capable of maintaining the reaction temperature under control, considering the thermal demand of the reaction and the heat losses by the equipment that is located in ultra-deep waters, where the temperature is below 15 C. The target scaling is barium sulfate or strontium sulfate that are formed due to sulfated water coming from the reservoir that receives the injection of seawater without desulphation treatment. The present invention enables a method for descaling barium and strontium sulfate in the range of 60 to 100 C., with a pH preferably of 12.8, using DTPA composed in a 28.7% v/v solution and a mechanical agitation process.

Claims

1. A method of laser stimulation of barium and/or strontium complexion by DTPA comprising a Pig laser for generating Laser, where the application of Laser radiation generates heating of the DTPA solution preferably in the temperature range 60 to 100 C., with pH preferably 12.8, dissolving Barium Sulfate and/or Strontium Sulfate in DTPA solution, in which the solution is composed of distilled water and a concentration of 28.7% v/v of DTPA; wherein the Laser emission has Nd: YAG (neodymium-doped yttrium aluminium garnet) material, with maximum energy output of approximately 600 mJ and may be 2000 mJ, with a pulse duration of 6 ns, and a wavelength of 1064,532,355 nm, with a power of each pulse of 200 to 600 mJ/pulse; and means in the Pig Laser to promote heating of the solution.

2. A method, according to claim 1, comprising the use of pig laser equipment for generating the laser, which is equipped with batteries, diodes, fiber optic cables, Collimators, temperature sensors, which are part of a minimum structure of the equipment for applying laser radiation.

3. A method, according to claim 1, wherein the laser generated at the end of a device is irradiated on the DTPA solution.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0033] The present invention will be described in more detail below, with reference to the attached figures that, in a schematic manner and not limiting the inventive scope, represent examples of its implementation.

[0034] FIG. 1 illustrates a comparison with the dissolution of Barium with tests using Laser versus Control (without heating).

[0035] FIG. 2 shows the dissolved mass (g/L) during the dissolution of barium sulfate in DTPA. 5K solution, at temperatures of 4, 60 and 90 C., during 4 and 8 hours of testing.

DETAILED DESCRIPTION OF THE CERTIFICATE OF ADDITION OF INVENTION

[0036] The present invention proposes a method of local laser induction in the deep water environment through the application of Laser radiation to promote the complexation reactions of strontium sulfate and barium sulfate with DTPA chelator. This solution will serve to remove these scales in deep and ultra-deep water scenarios, where the cooling of the underwater production lines is caused by the temperature of the seabed, and affects the reduction of the temperature of the fluids used in the removal of saline scales, negatively influencing the yield of the chemical reactions in the removal treatments through this chelator or others. For this purpose, Laser technology was chosen due to its size reduction capacity, and the heat generated by Laser radiation is applied to the reaction medium to photonically promote an increase in heat in the reaction.

[0037] Static test: In this test, on the mixture of 6 g of barium sulfate and 150 ml of DTPA in the beaker, laser radiation is applied to the solution inside the beaker to induce the Ba complexation reaction of BaSO.sub.4. This induction process lasts about 4 hours. Samples are taken every hour for analysis in the MIPOES equipment, where the concentration of barium dissolved by DTPA will be determined every hour of the test.

[0038] Characteristics of the laser used: [0039] Pulsed Nano Laser; [0040] MAX OUTPUT: 600 mJ; [0041] PULSE DURATION: 6 ns; [0042] WAVELENGTH: 1064 nm; [0043] LASER MEDIUM: Nd: YAG;

[0044] The characteristics of the Laser emitter (5) must be through Nd: YAG (neodymium-doped yttrium aluminum garnet) material, with maximum energy output around 600 mJ, with a pulse duration of 6 ns, and wavelength of 1064, 532.35 nm, with power of each pulse of 200 mJ/pulse; and means in the Pig Laser (10) to promote heating of the solution.

[0045] In a DTPA 40 solution at 28.7% v/v with laser thermal induction: On a semi-analytical balance, a mass of 6 grams of the investigated salt or of the mixture of salts is weighed, being 3 grams of BaSO.sub.4+3 grams of SrSO.sub.4 in a 300 ml polypropylene beaker, 150 ml of DTPA 40 at 28.7% is added, and the solution is homogenized. With thermal induction with radiation from the medium Nd: YAG laser with a power of 600 mJ on the solution inside the beaker with stirring by magnet at 600 rpm for 4 hours. Every 1 hour of testing, a 3 ml aliquot was removed with the 5 ml syringe and filtered with a MILEX filter; 0.45 m pore into a 15 ml Falcon vial. Afterwards, 0.5 ml was removed with a pipette with a 0.5 ml tip from the Falcon vial. The dilutions were performed in two stages, the first being a 100-fold dilution, placing the 0.5 ml in a 50 ml Falcon vial with 49.5 ml of distilled water. And the second dilution of 40 times was carried out, removing with a pipette with a 0.5 ml tip the volume of 0.5 ml from the 1st Falcon bottle with 50 ml and placing it in a 2nd Falcon bottle with 19.5 ml of distilled water, totaling a dilution of 4000 times. The objective of this dilution was to protect the MIPOES equipment against the high salinity of the solution in order to avoid damage to it. Since the quantification of the concentration of ions (barium, strontium or the mixture) in the sample is done by the MIPOES technique, the wavelengths used for strontium were 407,771 nm mg/L, barium 455, 403 nm mg/L and potassium 766, 491 nm mg/L. The K analysis was used to monitor the dilution of the aliquots (4000) removed from the dissolution reaction of the salts in relation to the DTPA 5K chelator.

[0046] Static test: In this test, on the mixture of 6 g of barium sulfate and 150 ml of DTPA in the beaker, laser radiation is applied to the solution inside the beaker to induce the complexation reaction of Ba and BaSO.sub.4. This induction process lasts approximately 4 hours. Samples are taken every hour for analysis in the MIPOES equipment, where the concentration of barium dissolved by DTPA will be determined every hour of the test. Table 1 shows the test without the laser and Table 2 shows the test with the use of the laser.

TABLE-US-00001 TABLE 1 Control test without the laser Control Temperature Sample Time (min) (Celsius) Ba (mg/L) T1 60 21.50 188 T2 120 21.50 304 T3 180 21.50 336 T4 240 21.50 376

TABLE-US-00002 TABLE 2 Laser test Laser test Temperature Sample Time (min) (Celsius) Ba (mg/L) T1 60 26. 6 320 T2 120 27.5 408 T3 180 28.0 484 T4 240 27. 9 560

[0047] It can be seen in Table 3 and in the graph in FIG. 1 that the application of laser induction in the dissolution reactions of barium sulfate by complexation in static tests showed a significant increase in yield in relation to the control test, that is, compared to the dissolution test without the application of the laser. The yield is higher than 34% in the worst case.

TABLE-US-00003 TABLE 3 Comparison between Laser versus control tests Comparison of laser induction versus control Control Laser Laser Time Ba Ba Difference gain Sample (min) (mg/L) (mg/L) (mg/L) % T1 60 188 320 132 70.21277 T2 120 304 408 104 34.21053 T3 180 336 484 148 44.04762 T4 240 376 560 184 54.7619

[0048] FIG. 2 shows experimental results considering an increase in the efficiency of dissolving barium sulfate with increasing temperature. The contact time of 4 and 8 h between the remover solution and barium sulfate was not relevant, except for the temperature of 4 C., where the dissolved mass was double after 8 h of reaction (2.1 g/L) compared to the result obtained after 4 h (1.2 g/L) of testing. The literature indicates DTPA as the most efficient complexing agent for dissolving barium sulfate (Lakatos and Szab, 2005; Jordan et al., 2012). It is possible to see that up to 4 h is the time required for the Barium to dissolve in the solution and make it saturated, and after that, waiting up to 8 h, although there is still dissolution, the rate is low and is not viable.

[0049] Therefore, considering the laboratory results, the invention comprises the use of a Pig laser (10) for generating thermal energy through Laser induction, where the application of Laser radiation generates heating of the DTPA solution preferably in the temperature range of 60 to 100 C., with pH preferably at 12.8, dissolving Barium Sulfate and/or Strontium Sulfate in DTPA solution, in which the solution is composed of distilled water and a concentration of 28.7% v/v of DTPA.

[0050] Therefore, it is possible to conclude that the application of laser induction compared to photonic induction performed by laser radiation promotes an increase in the yield of barium sulfate removal in the presence of DTPA.

[0051] The technical and economic advantages are associated with the reduction of the time of the rig and/or stimulation boats to perform the operations of removing saline scales that are normally used to perform the operations of removing barium and strontium sulfate scales in the wells and in the subsea production system. For example, if an operation with a boat costs around US$1,800,000.00 while with the rig having a daily rate ranging from US$153,000/day to US$264,000/day, and the mobilization of the rig to operate in a well takes around 4 to 5 days. The total cost would be US$1,000,000.00 and the reduction would be in 5 days.

REFERENCES

[0052] The application of laser technology as a heating source was suggested due to its adaptability to develop equipment aimed at field application, given the advance in the reduction of the size of devices such as laser diodes in recent years, which allows obtaining power associated with the reduction of the size of the equipment. [0053] [1] FERREIRA DA SILVA MARIO GERMINO [BR], LASER-ENERGIZED HEATING SYSTEM IN CARBONATE ROCK ACIDIFICATION TESTS. Applicants: PETROLEO BRASILEIRO SA PETROBRAS [BR]. Earliest priority: Nov. 6, 2020. Earliest publication: May 6, 2022, BR 102020022705 A2; CN 114441404 A; US2022146486 A1. [0054] [2] GERMINO FERREIRA DA SILVA MARIO [BR]; ALVES FONTES ROSANE [BR]; FERREIRA DO ROSARIO FRANCISCA [BR]; SILVA ALVES DA ROSA KATIA REGINA [BR]; BATISTA ALVIM FELIPE [BR]. LASER RADIATION ARRANGEMENT FOR CATALYSIS IN COMPLEXATION REACTIONS. Applicants: PETROLEO BRASILEIRO SA PETROBRAS [BR]. Earliest priority: Nov. 29, 2019. Earliest publication: Jun. 3, 2021, AR 120569 A1; BR 102019025418 A2; BR 102019025418 B 1; CN 115087510 A; US2022410317 A1; WO 2021102544 A1. [0055] [3] FERREIRA DA SILVA MARIO GERMINO [BR], FERREIRA DO ROSARIO FRANCISCA [BR], EQUIPMENT FOR LASER HEATING OF FLUIDS FOR INJECTION IN WELLS. Applicants: PETROLEO BRASILEIRO SA PETROBRAS [BR]. Earliest priority: Jul. 4, 2019, Earliest publication: Jan. 7, 2021, BR 102019013939 A2; CN 114364937 A; US2022356785 A1; WO 2021000034 A1. [0056] [4] FRANCISCA FERREIRA DO ROSARIO [BR]; MARIO GERMINO FERREIRA DA SILVA [BR], LASER PIG FOR SCALE REMOVAL IN SUBSEA SYSTEMS. Assignee: PETROLEO BRASILEIRO SA PETROBRAS [BR]. Earliest priority: Dec. 10, 2019, Earliest publication: Jun. 22, 2021, BR 102019026153 A2. [0057] [5] GERMINO FERREIRA DA SILVA MARIO [BR], LASER JETTER PIPE TOOL. Applicants: PETROLEO BRASILEIRO SA PETROBRAS [BR]. Earliest priority: Feb. 27, 2020, Earliest publication: Sep. 2, 2021, BR 102020003955 A2; CN 115551666 A; US2023111551 A1; WO 2021168524 A1. [0058] [6] FERREIRA DA SILVA MARIO GERMINO [BR]. LASER MANDREL FOR REMOVAL OF SCALE IN PRODUCTION EQUIPMENT. Applicants: PETROLEO BRASILEIRO SA PETROBRAS [BR]. Earliest priority: Aug. 18, 2021. Earliest publication: Feb. 23, 2023, US2023059801 A1.