WO2012128910A1 - Oxydation avancée d'inhibiteurs d'hydrates cinétiques - Google Patents

Oxydation avancée d'inhibiteurs d'hydrates cinétiques Download PDF

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Publication number
WO2012128910A1
WO2012128910A1 PCT/US2012/027260 US2012027260W WO2012128910A1 WO 2012128910 A1 WO2012128910 A1 WO 2012128910A1 US 2012027260 W US2012027260 W US 2012027260W WO 2012128910 A1 WO2012128910 A1 WO 2012128910A1
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Prior art keywords
khi
ozone
fenton
water
ozonation
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Application number
PCT/US2012/027260
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English (en)
Inventor
Altaf Hussain
Isik Riza TURKMEN
Joel Minier MATAR
Samir GHARFEH
Samer ADHAM
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Conocophillips Company
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Application filed by Conocophillips Company filed Critical Conocophillips Company
Priority claimed from US13/409,553 external-priority patent/US8728325B2/en
Publication of WO2012128910A1 publication Critical patent/WO2012128910A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C02F1/385—Treatment of water, waste water, or sewage by centrifugal separation by centrifuging suspensions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/23—O3
    • C02F2209/235—O3 in the gas phase
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Definitions

  • This invention relates to a process of treating process water, produced water and industrial waste water to remove contaminants including kinetic hydrate inhibitors (KHI).
  • KHI kinetic hydrate inhibitors
  • Hydrates are crystalline solids that can be formed in a fluid whether the fluid is flowing or stationary. Hydrates form crystalline ice-like solids when water under the certain pressures and temperatures in the presence of low molecular weight hydrocarbon gases including methane, ethane, propane, butanes, pentanes, hexanes, H 2 S, C0 2 , and other small gases. Although hydrates are most problematic in fluids that are conveyed through pipe, they may form solid under a variety of conditions and block the surface of the pipe, which can lead to catastrophe. Hydrates can also be abrasive and deteriorate the pipe wall. Changes in pressure and temperature may cause hydrates to expand releasing explosive gases and increasing pressures to dangerous levels. There is a need, therefore, for improved and cost effective methods for inhibiting hydrate formation without permanently contaminating water produced or used during the production and transportation of hydrocarbons, including natural gas, crude oil, bitumen, tar sands, and other hydrocarbon sources.
  • thermodynamic and kinetic inhibitors include water removal, increasing temperature, decreasing pressure, addition of "antifreeze” to the fluid and combinations of these methods.
  • the kinetic approach generally prevents/delays the smaller hydrocarbon hydrate crystals from agglomerating into larger ones (known in the industry as an anti-agglomerate and abbreviated AA), they also may inhibit, retard and prevent initial hydrocarbon hydrate crystal nucleation or crystal growth (known in the industry as a kinetic hydrate inhibitor and abbreviated KHI).
  • films that protect the inside of the pipelines, tubing, valves and such prevent both hydrate crystallization and corrosion of the materials.
  • Thermodynamic inhibitors, kinetic hydrate inhibitors and anti-agglomerate were used to reduce or prevent hydrate formation.
  • Urbans, (2006) describes the use of peroxide as a water treatment method.
  • KHI materials are becoming more complex, KHI concentrations are increasing, and there is a greater volume of produced water, so systems used to process KHI containing water must work more rapidly on a larger scale than previously available. Processes that involve heating, incineration or other attempts simply produce more waste, use more equipment, or are too expensive to be implemented at the variety of hydrocarbon processing locations around the world under a variety of different environmental conditions.
  • An efficient KHI removal process is required not only to remove KHI in production and transportations systems today, but that will allow production from more extreme areas, such as deep water and arctic reservoirs where increased pressures and lower temperatures will contribute to hydrate formation. Improved KHI removal will allow higher concentrations of KHI to be used in these more extreme environments. Additionally, KHIs may be used in systems with other more complex contaminants.
  • An efficient and inexpensive method of KHI removal must be developed to remove kinetic hydrate inhibitors from wastewater and process water that allows the water to be either re-injected into the subterranean formation or further processed without producing solid wastes and/or generating toxic by-products that are difficult to dispose of or damaging to the environment.
  • a robust oxidation system is desired that degrades significant amounts of KHI at lower temperatures, because oxidations reactions improve with increasing temperatures, produced water with KHI will be readily oxidized at higher temperatures if the reaction functions well at low temperatures. Processing the KHI containing solutions at produced water temperature without heating or cooling, reduces the cost of processing, decreases the amount of equipment required, and provides a smaller footprint within the limited confines of the production area.
  • the invention more particularly includes a process for treating kinetic hydrate inhibitor contaminated solutions by mixing one or more kinetic hydrate inhibitor (KHI) containing aqueous solutions with a KHI degrading oxygen containing molecule, including Fenton's Process (adding hydrogen peroxide then adding iron (Fe2+)) and/or bubbling with ozone; separating precipitates from the KHI degraded solution; and obtaining clean water.
  • KHI kinetic hydrate inhibitor
  • a process for treating KHI contaminated solutions where one or more KHI containing aqueous solutions is mixed with Fenton's solution (adding hydrogen peroxide then adding iron (Fe2+)), separating precipitates from the KHI degraded solution; and obtaining clean water.
  • the processes may be conducted in a tank, sediment pond, or other water storage container.
  • the process may use one or more columns in a continuous process.
  • the process may include ozonation and Fenton's process simultaneously.
  • the process may include ozonation followed by Fenton's process.
  • the process may include Fenton's process followed by ozonation.
  • KHIs may include vinyl caprolactam, ester amides, polyester pyroglutamate, N-acylalkylene imines, 2-alkyl-2-oxazolines, PMeOx, PEtOx, PnPrOx, PiBuOx, PnBuOx, N-vinyl-N-methyl acetamide, vinylpyrrolidone, PVP, tetrabutylammonium bromide, PDMAEMA, homopolymers, copolymers, linear, branched, highly branched monomers, polymers and mixed polymers thereof.
  • Oxygenated KHIs may include a highly branched methoxylate, ethoxylate, propoxylate, butoxylate, pentoxylate, hexoxylate, carboxylate, ester, or other oxygenated KHI.
  • FIG. 1 Ozone Bubble column system.
  • FIG. 1A is a diagram of an ozone bubble column for KHI removal
  • FIG. IB is the schematics of the ozone bubble column showing the ozone generator, feed ozone detector, bubble column, dehumidifier, off gas ozone detector and heated catalyst.
  • FIG. 2 Degradation of KHI in field Brine: FIG. 2A demonstrates KHI oxidation of field brine by ozone as function of time. FIG. 2B demonstrates relative KHI concentration of field brine by ozonation as function of time.
  • FIG. 3 Oxidation and Cloud Point of 1.5% KHI solutions in synthetic brine. (1.5%)
  • FIG. 3A demonstrate KHI oxidation and cloud point as function of time.
  • FIG. 3B demonstrates relative KHI concentration of synthetic brine by ozonation as function of time.
  • FIG. 4 Fenton's Process.
  • FIG. 5 Ozone degradation of KHI.
  • FIG. 6 KHI Oxidation at pH 3.5 and pH 9.0.
  • FIG. 6A demonstrates KHI oxidation in synthetic brine by ozone at pH 3.5 and pH 9.0.
  • FIG. 6B demonstrates relative KHI concentration during the ozonation at pH 3.5 and pH 9.0.
  • FIG. 7 Simultaneous ozonation and Fenton process treatment.
  • FIG. 8 Sequential ozonation then Fenton process treatment.
  • FIG. 9 Sequential Fenton process treatment then ozonation.
  • FIG. 10 Ozone contactors including (A) a baffled chamber diffuser, (B) a turbine diffuser contactor, and (C) a side stream ozone system.
  • Abbreviations include: kinetic hydrate inhibitor (KHI); thermal hydrate inhibitor (THI); low dosage hydrate inhibitor (LDHI); normal liters per minute (Nlt/min); grams per normal cubic meter (g/Nm 3 ); parts per million (ppm); monoethylene glycol (MEG), diethylene glycol (DEG), triethylene glycol (TEG), poly(2-methyl-2-oxazoline) (PMeOx); poly(2-ethyl-2-oxazoline) (PEtOx); poly(2-n-propyl-2-oxazoline) (PnPrOx); poly(2-isobutyl-2-oxazoline) (PiBuOx); poly(2-n-butyl-2-oxazoline) (PnBuOx); poly-N- vinylcaprolactam (PVCap); polydimethylaminoethylmethacrylate (PDMAEMA); poly vinylpyrrolidone (PVP); high pressure liquid chromatography (HPLC); advanced
  • hydrocarbons may include natural gas, petroleum, crude oil, bitumen, tarsands, pitch, and other hydrocarbon containing materials as well as processed hydrocarbon materials including methane, ethane, butane, LNG, syngas, gasoline, fuel oil, diesel, kerosene, and the like. Hydrocarbons being recovered, processed and transported may have KHIs added to prevent hydrate formation.
  • Hydrates refers to ice-like structures in which water molecules, under pressure, form structures composed of polyhedral cages surrounding "guest" molecules including salts, methane, ethane or other molecules.
  • KHIs include, but are not limited to: vinyl caprolactam, ester amides, polyester pyroglutamate, N-acylalkylene imines, 2-alkyl-2- oxazolines including PMeOx, PEtOx, PnPrOx, PiBuOx, PnBuOx and the like; N-vinyl- N-methyl acetamide; vinylpyrrolidone; PVP; tetrabutylammonium bromide; PDMAEMA; as well as homopolymers, copolymers, and mixed polymers thereof, including linear, branched and highly branched monomers and polymers.
  • Proprietary KHIs are available from NALCO ® , and include FREEFLOW ® LDHI, among others.
  • Thermodynamic inhibitors include methanol, ethanol, glycol, ethylene glycol, MEG, DEG, TEG, salts, NaCl, CaCl 2 , KC1, and the like.
  • Oxidants for KHI degradation include ozone, Fenton process, OHP ® process, C10 2 , peroxide, and other oxidants weak or strong depending upon the application and concentration of KHI to be removed. Oxidants may be used individually, in series, or during the same oxidation reaction if applicable.
  • Ozone and chlorine dioxide have the highest oxidation potential as shown in Table 1. Ozone and chlorine dioxide produce hydroxyl radicals, whereas Fenton process requires Fe ion to react with hydrogen peroxide at pH 3-5 to produce hydroxyl radicals.
  • Other oxidizers are available that may be adapted to one or more processes. Selection of oxidizing agent will depend upon the kinetic inhibitors used and the concentration of the kinetic inhibitors. Additionally, oxidation can be improved in the presence of electrolysis, sonic cavitation, or other processes. In one example the OZONIX® system which uses cavitation to increase solution temperature during cavitation using electrolysis and sonic cavitation.
  • Brine solution may be any aqueous solution with a mixture of salts, including inorganic salts such as carbonates and sulfates of various metals, i.e. calcium, strontium and barium as well as complex salts of iron such as sulfides, hydrous oxides and carbonates.
  • salt compositions may vary, some typical ions dissolved in brine include sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), iron (Fe), chloride (CI), bromide (Br), sulfate (S0 4 ), bicarbonate (C0 3 ).
  • Brines from a variety of locations, including various production wells and ocean water are shown in Table 2. Brine solution composition will vary greatly dependent upon the reservoir being produced and the treatment being applied to the reservoir, additionally conditions will vary over time.
  • a diffuser is used to ensure contact time between the KHI in solution and the ozone or other gases applied to the solution.
  • Diffusers may include baffled chamber diffusers, turbine diffusers, side stream ozone contactor, and other diffusers some of which are shown in FIG. 10.
  • baffled chamber diffusers are designed to degrade KHI at a rate sufficient to remove all of the KHI even at or above capacity. The number of chambers, the geometry, the diffuser systems, and operation may be adjusted to degrade KHI at an appropriate rate.
  • the ozone contactor has several compartments in series with bubble diffusers at the bottom. In the first compartment the water flows downward against the rising bubbles, and in the second compartment the water flows upward.
  • the chambers are covered to prevent the escape of ozone and to increase the partial pressure of the ozone in the contactor. Additional chambers follow to guarantee a contact time between the ozone and the water.
  • Each of the chambers has sampling ports so that the ozone concentration in each chamber can be determined. This is needed to calculate the product of concentration and retention time required to ensure contact time value.
  • a synthetic brine was prepared by dissolving 1.68 g NaCl, 5.475g CaCl-2H 2 0, 3.120 g MgCl 2 -5H 2 0, 19.5 ml of 0.1 M KC1, 0.111 g Na 2 S0 4 , 0.135 g NH 4 CI, 0.1125 g SrCl 2 -6H 2 0 and 1.2 g NaC 2 H 3 0 2 (Sodium Acetate) per 1.5 liters total of aqueous solution. The solution was adjusted to pH 9.0.
  • commercial brine from ADMA-OPCO is available with the following ionic concentrations: 3,300 mg/L CI " , 350 mg/ml acetate, 50 mg/L S0 4 "2 , 10 mg/L Br “ , 600 mg/L Na + , 50 mg/L K + , 250 mg/L Mg +2 , 1000 mg/L Ca +2 , 30 mg/L NH 4 + , and 25 mg/L Sr +2 .
  • brine solutions may contain only one type of salt, i.e. a sodium chloride brine or potassium sulfate brine for example.
  • the brine concentration varies as the water is produced and may be adjusted to achieve a specific ionic strength by adding de-ionized water, fresh water, or purified water to reduce ionic strength; or by adding recycled water, salts, or other additives to increase ionic strength.
  • the pH may also be monitored as it will fluctuate during production and may be adjusted by adding buffer, acid or base as appropriate.
  • Normal conditions are 0°C and 1 arm pressure unless otherwise stated.
  • the temperature may change during production and processing and may vary depending upon the type of production, the location of the water and the stage of water production.
  • Waste water produced during transportation, i.e. to and from the wellhead or platform may be at 0-4°C.
  • Water produced to and from various LNG processes may be at or below 0°C and may even go down to about -40°C or lower dependent upon the pressures and salt concentrations, while water produced during distillation processes may be at or near boiling.
  • wastewater from a SAGD production may be at or near boiling while wastewater produced from offshore marine platforms may be at or near 0°C.
  • Pressure may also vary and is completely dependent upon the conditions under which the water is produced, although the wastewater or production water can be brought to atmospheric pressure for processing.
  • Ozonation equipment demonstrated in FIG. 1A and as show in detail in FIG. IB includes an oxygen source, an oxygen flow meter (i.e. an MMF oxygen flow meter), an ozone generator (i.e. a BMT ozone generator), an inlet ozone detector (i.e. a BMT 964 2bara ozone detector), a bubble column, a dehumidifier, an outlet ozone detector (i.e. a BMT 964 2bara ozone detector), and a heated catalyst to break down any excess ozone and other by-products.
  • an oxygen flow meter i.e. an MMF oxygen flow meter
  • an ozone generator i.e. a BMT ozone generator
  • an inlet ozone detector i.e. a BMT 964 2bara ozone detector
  • a bubble column i.e. a BMT 964 2bara ozone detector
  • a dehumidifier i.e. a BMT
  • the MMF flow meter described above is available from DWYE ® Instruments, Dakota Mass, PVL, Fox Instruments, and many other commercial suppliers.
  • the oxygen flow meter may measure oxygen content, temperature, flow rate, and other parameters depending upon the model and rate of oxygen flow.
  • the ozone generator is selected to produce above a minimum level of ozone required per hour and ozone generation is monitored using an ozone detector that can measure at a minimum ozone concentration.
  • ozone detector that can measure at a minimum ozone concentration.
  • Numerous ozone generators and detectors are available from BMT Messtechnik GmbH, Berlin, Germany.
  • Ozone generators are also commercially available from Ozone Generator USA, 03 OZONE Generators, DEL® Ozone Generators, PROZONE® Commercial Systems, and other commercial sources.
  • Ozone detectors are available from BMT, ChemLogic, IN USA, Inc., as well as other ozone analyzers including various UV/Vis systems.
  • a bubble column may also be assembled from one or more columns, including mixing columns with filters at the base and/or along the length of the column.
  • a supply tube is placed below a borosilicate frit at the base of a 1 liter column, ozone is bubbled through the frit into the treated solution.
  • a frit at the top of the column prevents foaming solution from escaping the top of the column and entering the gas outlet to the dehumidifier.
  • Mixing may be achieved by bubbling, with paddles or mixers, by pumping, or by aeration with ozone, air, or other gas.
  • the reaction processes described herein may be conducted in a column, mixing column, reactor, tank, mixing tank, storage tank, storage pond, or other means of storage used in the industry for water, wastewater or production water. Where applicable, reactions may be carried out in batch, semi-batch processes, or continuous operations depending upon the amount of aqueous solution, concentration of hydrate inhibitor, and strength of oxidant used.
  • Mixing may be achieved in one or more column and columns may be assembled in series with multiple ozonation columns each with a unique concentration of ozone.
  • Ozonation can remove up to 94% of the KHI present in wastewater (FIG. 5).
  • KHI was removed from a mixed brine solution containing 1.5% KHI by bubbling ozone through the solution.
  • a synthetic brine solution was made with 1.5% KHI, a hyper branched polymer with ethoxy functional group
  • the solution contained 2.2715 g NaCl, 7.3128 g CaCl 2 -2H 2 0, 4.1762 g MgCl 2 -6H 2 0, 26.0295 g of 0.1M KC1 , 0.1493 NaS0 4 , 0.1800 g NH 4 C1; 0.1591 g SrCl 2 -6H 2 0, 1.6081 g NaC 2 H 3 0 2 , and 30.0117 g of hyper branched KHI, pH was adjusted to 8.83 in 2 L aqueous solution.
  • This synthetic brine is similar to brine separated from sludge catcher of crude oil/LNG production at several facilities.
  • Field brine was obtained from a crude oil production.
  • the brine was spiked with KHI to a final concentration of 1.5% KHI.
  • the brine pH with KHI addition was about pH 4.1.
  • 250 ml of KHI spiked brine was bubbled for 3.5 hours with 0.07 Nlt/min oxygen, inlet ozone concentration and ozone mass flow rate werel80 g/Nm 3 and 0.73 g/h respectively.
  • Samples were taken at 15, 30, 45, 60, 90, 120, 150, 180 and 210 minutes (see FIG. 2 A and B).
  • KHI concentration decreased from 16,787 mg/1 initially to 3564 mg/L after ozone treatment.
  • the solution pH decreased from pH 4.1 to 2.2. This demonstrates that ozonation can remove 78% of the KHI from field brine.
  • a solution of 1.5 % KHI in OPCO Brine at a pH of 3.6 was bubbled with ozone for 4 hours. Over 80% of the KHI in solution was degraded and cloud point was reduced dramatically. A total volume of 250 ml of 1.5% KHI was bubbled with ozone at 0.07 Nlt/min. The average inlet ozone concentration after 12 minutes was 180 g/Nm3 (gas phase). The system at this scale was exposed to an ozone dosage of 0.73 g/h. 3 ml samples were taken at 15, 30 and 45 minutes after the start up of the experiment and 10 ml samples were taken at 60, 90, 120, 150, 180, 210 and 240 minutes for cloud point analysis. After 240 minutes, the solution was purged with oxygen to remove the remaining ozone gas.
  • Synthetic brine was mixed with KHI to produce an initial solution with 0.25%KHI (mixed for at least one hour).
  • the pH in two separate brine solutions was adjusted to pH 3.5 and pH 9.0.
  • Ozone was bubbled for one hour with the following parameters: 250 ml of synthetic brine with 0.25% KHI, mixed for greater than one hour, was treated by ozonation with an oxygen flow rate of 0.075 Nlt/min, 4.5 PSI, generating 180 gN/m 3 ozone at the inlet with ozone mass flow rate of 0.78 g/h ozonation. Samples (4 ml) were taken at 5, 10, 20, 30, 45 and 60 minutes. After 60 minutes, the solution was purged with oxygen to remove the remaining ozone gas.
  • the Fenton process was conducted by mixing hydrogen peroxide (H 2 0 2 ) with the KHI solution and adding ammonium ferrous sulfate hexahydrate (NH 4 FeS0 4 -6H 2 0). Mixing the H 2 0 2 with NH 4 FeS0 4 -6H 2 0 releases oxygen radicals producing hydroxyl ions and hydroxyl radicals, that may then react with reactive groups in the KHI (FIG. 4).
  • a 0.25% KHI brine solution was treated using the Fenton Process to remove KHI.
  • 100 ml concentrated 5 fold concentrated synthetic brine was mixed with 100 ml of 12.5 mg/ml KHI for 1 hour.
  • a wastewater stream containing KHI is mixed with concentrated H 2 0 2 and fed into a column (either vertical or horizontal), an iron (Fe 2+ ) containing solution is added either at the top of the column or at intervals along the column then ozone may be added either at the top of the column or along the length of the column, clean water is centrifuged, filtered or otherwise separated from the iron precipitate, to generate purified water for re-injection or other use.
  • KHI containing wastewater mixed with concentrated peroxide may be fed into the top of the column with an iron (Fe 2+ ) containing solution and ozone bubbled from the bottom of the column. After the process is complete, the waste is centrifuged to remove precipitates.
  • the processes may also be run in series where the KHI contaminated brine is treated with ozonation then the Fenton Process.
  • the process may be conducted vertically with the ozone and brine fed at one end of the column and gases removed from the other.
  • the KHI contaminated water is fed into the top of a bubble column and ozone is fed from the bottom.
  • the ozone concentration will increase and the KHI concentration decrease, thus producing treated water at the end of the column.
  • Column flow rate is dictated by the initial concentration of KHI, rate of ozone production, length of the bubble column, and final concentration of KHI desired.
  • the water from the treated column may then mixed with peroxide and fed with iron (Fe2+) into an adjacent column. After sufficient reaction time, the clean water is centrifuged or filtered to remove particulates and the clean water is produced.
  • Fe2+ iron
  • the process may also be run where the KHI contaminated brine is treated by the Fenton process then ozonation. A sequential process is shown in FIG. 9, with Fenton Process and then Ozonation occurring in adjacent columns. Centrifugation may be done after a Fenton process or after ozonation, dependent upon reactor design and the amount of precipitate produced during the Fenton process.
  • columns are used to demonstrate the process these columns may be any diffuser, mixer or contact system including baffle diffusers, turbine diffusers, a side stream contactor with Fenton' s reagents, ozonation, wet oxidation or other AOP fed at the beginning of the diffuser/mixer or along the length of the diffuser/mixer.
  • Fenton' s process and ozonation may be carried out in one or more columns, diffusers, tanks, batch fed tanks, including sedimentation tanks or ponds, to achieve a similar level of water treatment.
  • Fenton' s process is conducted in a sedimentation tank containing KHI contaminated brine.
  • a peroxide solution is added to achieve approximately 7.5: 1 molar ratio of peroxide to KHI.
  • an iron (Fe 2+ ) solution is added to achieve a 1 : 10 ratio for iron to peroxide.
  • the solution is again mixed to achieve a uniform distribution.
  • the solution is allowed to settle before ozone is bubbled in the tank. Once sufficient KHI has been degraded the clean water is removed and the process is repeated. When excess precipitate builds up, the precipitate can be removed and either recycled, sold as raw ferric oxide, or otherwise disposed of.
  • the process may be done at atmospheric pressure and ambient temperature, or the container may be closed and pressurized to prevent bubbling during ozonation. Additionally, an anti-foaming agent may be added to reduce or prevent foaming.
  • the process may be used to process produced water from a subterranean formation. Rates and conditions vary from formation to formation and the oxidation process may be scaled to a variety of production rates as shown in Table 4.
  • scaling may be accomplished by simply increasing contact time with additional ozone, other methods of increasing contact time include increasing the size and length of the diffuser, increasing the number of diffusers, and adding one or more additional oxidizing agents.
  • C10 2 is added prior to ozonation in a diffuser or column.

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

L'invention concerne un procédé d'oxydation avancée, à savoir ozonation et fenton (peroxyde d'hydrogène/Fe:2+) ont été utilisés pour dégrader l'inhibiteur d'hydrate cinétique (KHI). La solution oxydée après piégeage d'oxygène peut être disposée avec succès au puits d'injection. On facilite ainsi l'utilisation de KHI plus fréquemment et à des concentrations plus élevées pour des opérations relatives au pétrole et au gaz de projets futurs. On dispose aussi d'une solution de rechange qui concurrence efficacement l'inhibiteur d'hydrate thermodynamique (THI) ou le complète.
PCT/US2012/027260 2011-03-23 2012-03-01 Oxydation avancée d'inhibiteurs d'hydrates cinétiques WO2012128910A1 (fr)

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US201161466686P 2011-03-23 2011-03-23
US61/466,686 2011-03-23
US13/409,553 2012-03-01
US13/409,553 US8728325B2 (en) 2011-03-23 2012-03-01 Advanced oxidation of kinetic hydrate inhibitors

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WO2013093789A2 (fr) 2011-12-23 2013-06-27 Aker Process Systems As Procédé et système de traitement d'un flux contenant des inhibiteurs d'hydrates à base de glycol et cinétiques
CN103366850A (zh) * 2013-06-28 2013-10-23 清华大学 一种湿式催化氧化法处理放射性阴离子交换树脂的方法
US10131551B2 (en) 2015-06-23 2018-11-20 Conocophillips Company Separation of kinetic hydrate inhibitors from an aqueous solution
CN110040839A (zh) * 2019-05-08 2019-07-23 赵佳妮 处理果蔬垃圾的组合物及其制备方法
US10407611B2 (en) 2016-01-08 2019-09-10 Ecolab Usa Inc. Heavy oil rheology modifiers for flow improvement during production and transportation operations
CN116410015A (zh) * 2021-12-29 2023-07-11 交通运输部天津水运工程科学研究所 一种高含盐量、高有机质涉海淤泥烧制陶粒的方法
WO2024086109A1 (fr) * 2022-10-17 2024-04-25 Saudi Arabian Oil Company Décomposition de produits chimiques de champ gazier

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WO2013093789A2 (fr) 2011-12-23 2013-06-27 Aker Process Systems As Procédé et système de traitement d'un flux contenant des inhibiteurs d'hydrates à base de glycol et cinétiques
US9783436B2 (en) 2011-12-23 2017-10-10 Aker Process Systems As Method and system for processing a stream comprising glycol based and kinetic hydrate inhibitors
CN103366850A (zh) * 2013-06-28 2013-10-23 清华大学 一种湿式催化氧化法处理放射性阴离子交换树脂的方法
US10131551B2 (en) 2015-06-23 2018-11-20 Conocophillips Company Separation of kinetic hydrate inhibitors from an aqueous solution
US10407611B2 (en) 2016-01-08 2019-09-10 Ecolab Usa Inc. Heavy oil rheology modifiers for flow improvement during production and transportation operations
CN110040839A (zh) * 2019-05-08 2019-07-23 赵佳妮 处理果蔬垃圾的组合物及其制备方法
CN110040839B (zh) * 2019-05-08 2022-12-16 山东生态家园环保股份有限公司 处理果蔬垃圾的组合物及其制备方法
CN116410015A (zh) * 2021-12-29 2023-07-11 交通运输部天津水运工程科学研究所 一种高含盐量、高有机质涉海淤泥烧制陶粒的方法
CN116410015B (zh) * 2021-12-29 2024-06-04 交通运输部天津水运工程科学研究所 一种高含盐量、高有机质涉海淤泥烧制陶粒的方法
WO2024086109A1 (fr) * 2022-10-17 2024-04-25 Saudi Arabian Oil Company Décomposition de produits chimiques de champ gazier

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