Method and system for removing hydrogen sulfide from sour oil and sour water.

(54) Title: METHOD AND SYSTEM FOR REMOVING HYDROGEN SULFIDE FROM CORROSIVE OIL AND ACID WATER.

(54) Title: METHOD AND SYSTEM FOR REMOVING HYDROGEN SULFIDE FROM SOUR OIL AND SOUR WATER.

(57) Summary

The embodiments of the present invention are generally related to a system and method for removing hydrogen sulfide from acidic water and acidic oil. In particular, hydrogen sulfide is removed from acidic water and acidic oil without the need for special chemicals, such as catalyst chemicals, scrubber chemicals, hydrocarbon sources, or a large-scale installation. The system and method of the present invention are particularly useful in oil and gas exploration fields, where large facilities for removing hydrogen sulfide are probably not accessible. The present invention addresses the need for safe and inexpensive transportation of lethal neurotoxins. The particular modalities involve a system and a method that can be performed both on a small scale and on a large scale in order to sweeten acidic water and acidic oil.

(57) Abstract

Embodiments of the present invention are generally related to a system and method to remove hydrogen sulfide from sour water and sour oil. In particular, hydrogen sulfide is removed from sour water and sour oil without the need for special Chemicals, such as catalyst Chemicals, scavenger Chemicals, hydrocarbon sources, or a large scale facility. The system and method in the present invention is particularly useful in exploratory oil and gas fields, where large facilities to remove hydrogen sulfide may be inaccessible. The present invention addresses the need for safe and cost effective transport of the deadly neurotoxin. Particular performances involve a system and method that can be executed both on a small and large scale to sweeten sour water and sour oil.

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PATENT TITLE No. 357271

Owner (s): ANSCHUTZ EXPLORATION CORPORATION

Address: 555 17th Street Suite 2400, Denver, Colorado, 80202, USA

Name: METHOD AND SYSTEM FOR REMOVING HYDROGEN SULFIDE FROM CORROSIVE OIL AND ACID WATER.

Classification: CIP: C02F1 / 20; C10G21 / 16; C10G21 / 30: C10G31 / 08: B01D19 / 04

CPC: B01D19 / 0005; C02F1 / 20: C02F2101 / 101

Inventor (s): JEFFREY BLAIR MORRIS

REQUEST

Number:

MX / a / 2014/002102

Date of presentation:

February 2014

Hour:

15:14

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Country:

US

Date:

February 2013

Number:

61/768,029

Validity: Twenty years

Expiration Date: February 21, 2034 Issue Date: July 2, 2018

The reference patent is granted based on articles 1, 2 * section V, 6 ° section III, and 59 of the Industrial Property Law, which is valid to keep in force!

In accordance with article 23 of the Industrial Property Law, this patent will start on the filing date of the application and will be subject to the payment of the twenty-year non-renewable rate, counting the rights.

Whoever subscribes to this title does so based on the provisions of articles 6 fractions III and 7 bis 2 of the Industrial Property Law (Official Gazette of the Federation (D.OF.) 06/27/1991, amended on 08/02 (1994, 10/25/1996, 12/26/1997, 05/17Ί999, 01/26/2004, 06/16/2005, 01/25/2006, 06/05/2009, 06/06/01 / 2010, 06/18/2010, 06/28/2010, 01/27/2012 and 04/09/2012), articles 1, 3, section V, a), 4th and 12th fractions I and lll of the Regulations of the Mexican Institute of Industrial Property (DO F 14/12/1999 reformed »on 01, / 07 / 2002.15 / 07/2004, 28/07/2004 and 7/09 / 2007); Articles 1, 3, 4, 5, section V, subsection a), 16 sections I and 11 and 30 of the Organic Statute of the Mexican Institute of Industrial Property (DO F. 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04/2004 and 09/13/2007), 1st, 3rd and 5th paragraph a) of the Agreement that delegates powers to the Deputy Directors General, Coordinator, Divisional Directors, Head of the Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007), i ».

This letter is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3rd of its Regulations, and 1 section III, 2 section V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Electronic Payment and Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.

DIVISIONAL DIRECTOR OF PATENTS NAHANNY CANAL REYES

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MX / 2018/56393

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METHOD AND SYSTEM FOR REMOVING SULFI

CORROSIVE OIL AND AG

Cross Reference with Related Applications Field of the Invention

This application claims the benefit of the Patent Application

Provisional 61 / 768,029, entitled “METHOD AND SYSTEM FOR REMOVING

HYDROFEN SULFIDE FROM SOUR OIL AND SOUR WATER, presented on February 22, 2012, the content of which is incorporated herein by reference in its entirety.

Field of the Invention

The embodiments of the present invention generally relate to a system and method of removing hydrogen sulfide from corrosive oil and acidic water. In particular, hydrogen sulfide is removed from acidic water and corrosive oil without the need for special chemicals, such as catalyst chemicals, scrubbing chemicals, hydrocarbon sources, or a large facility. The system and method in the present invention are particularly useful in oil and gas exploration fields, where large facilities for removing hydrogen sulfide are not accessible. The present invention addresses the need for safe and inexpensive transportation for deadly neurotoxins. The particular modalities involve a system and a method that can be carried out both

<img file="MX357271B_D0008.tif" />

scale as a smaller scale to sweeten acidic water and adWSWor

Background of the Invention

Gas field exploration may involve the discovery of wells containing significant amounts of hydrogen sulfide and other organic and inorganic sulfur compounds. Oil, natural gas, and water with a high concentration of sulfur compounds, such as hydrogen sulfide and sulfur dioxide, are referred to as "acids." Hydrogen sulfide is a colorless, toxic, and flammable gas that is responsible for the foul odor of rotten eggs. It often results when bacteria split organic matter in the absence of oxygen, such as in swamps and drains along with the anaerobic digestion process. It also occurs in volcanic gases, in natural gas, and in certain well waters. Corrosive oil and acidic water are not desirable as acidic products, even though they are useful acidic products, as they are extremely toxic and deadly, due to high levels of sulfur and sulfur by-products. For example, hydrogen sulfide is an extremely toxic deadly gas. The industry considers oil or water containing 100 parts per million (“ppm”) (0.01%) of corrosive oil and acidic sulfur water. Although this is the minimum level, oil and water wells may contain larger quantities. Oil and water can contain hydrogen sulfide up to 300,000 ppm (30%) at the immediate gas / liquid interface, the vapor space in a tank or container, and in the atmosphere surrounding a spill. At higher levels

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IMP

INSTITUTO ftlEXJO of concentration, hydrogen sulfide is highly^Mto® ^

As used here, the term “rnrrr.o._{AND P}”The oil containing levels of hydrogen sulfide is a ratio greater than 100 ppm (0.01%). Corrosive oil can also mean oil that contains 0.5% or more sulfur by weight. The term "acidic water" refers to water that contains hydrogen sulfide in an amount greater than 100 ppm (0.01%). The terms "sweet"; "Sweetened and / or" sweetened "means a product that has low levels of hydrogen sulfide, where the hydrogen sulfide has been removed or refers to the process of removing hydrogen sulfide. The term "stripping" means removing hydrogen sulfide from water and / or oil. The terms "acceptable limits" or "acceptable amounts" or "acceptable levels" refer to the maximum amount of hydrogen sulfide allowed in accordance with any of the relevant standards. For example, the Environmental Protection Agency ("EPA") has certain regulations regarding the concentration of hydrogen sulfide that can be released into the environment. In addition, the Occupational Safety and Health Administration (OSHA) provides certain standards for the amount of hydrogen sulfide to which a person can be exposed without considering it as a fatal risk. There may be other rules that apply, such as state rules. The terms "acceptable limits" or "acceptable amounts" or "acceptable levels" may also refer to the maximum amount of hydrogen sulfide allowed in oil and / or water in order for an installation to accept such materials.

Exploration and development wells with high concentrations

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INSTITUTO MEXICANO BE LA? I «3PKBAD INDUSTIHAI of hydrogen sulfide, far from the hydrogen sulfide removal facilities, present the problem of transporting the acidic water and the corrosive oil. Both liquids can be transported by truck, sometimes over long distances on public and toll roads. In most cases, acidic water, which is a hazardous material to transport, will also not be accepted by many reinjection facilities when they contain more than a trace amount of hydrogen sulfide.

Similarly, corrosive oil, which is also dangerous to transport, will not be accepted by most refineries or in pipeline concentrators when it contains more than one trace of hydrogen sulfide. When a facility is found that wants to accept liquids with a high concentration of hydrogen sulfide, the facility is most likely many kilometers from the exploration well. A truck accident or a simple leak can endanger the transport crew as well as the general public.

There may be other problems related to the transportation of corrosive oil. For example, transportation from the exploration well to the treatment site is generally only the first step in the process. Oil typically has a final destination, which may be another refinery, a distributor, or a consumer. Any hydrogen sulfide contamination along the journey can create safety and environmental risks. An example can be seen in the transportation of oil that is obtained through the fracture or "fracturing" process. Oil extracted through the fracturing process

IMPI

MEXICAN INSTITUTE

OF INDUSTRIAL PROPERTY

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it is typically sweet and contains little hydrogen sulfide. This oil has to be transported from the site to its final destination. Transportation may be impeded, however, when there is upstream hydrogen sulfide contamination in ships or when oils of different grades are mixed for shipment.

Railroad transportation has become a good option for moving oil out of high production areas with little access to pipelines. The railway industry is affected by having to solve the transportation of hydrogen sulfide. The solution to rail safety problems is typically unanticipated costs, including investments in rail cars or new safety protocols governing the transportation of corrosive oil.

For example, an oil freight rail terminal in North Dakota may be forced to suspend operations at the plant unless the hydrogen sulfide in the delivered oil is reduced. The CG Oil Rail Terminal requested the Federal Energy and Regulatory Commission (FERC) to restrict the amount of hydrogen sulfide in oil deliveries, after a high concentration of sulfide was discovered from hydrogen in a tank at a plant. The terminal requested a limit of 5 ppm of hydrogen sulfide. Another company objected to such a request, since it is dedicated to transporting oil to the terminal. In response, the terminal confirmed that without the new hydrogen sulfide limits that govern its plant, employees at the top of railroad tanks that pump oil

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MEXICAN INSTITUTE OF PROPERTY may be exposed to harmful vapors. The WñWal famTóíén argued that if more levels are allowed-alhos tíll and U ends¹other terminals will have to suspend their railway plant.

Even when acidic water and corrosive oil are treated to remove hydrogen sulfide content with conventional methods of using scrubbers or other treatment chemicals, plants will not accept treated water or oil when it contains too many treatment chemicals. This is especially problematic with wells that contain high levels of hydrogen sulfide, which require treatment chemicals to remove concentrations of hydrogen sulfide.

In addition, many regulations are in effect regarding the treatment and disposal of corrosive oil and acidic water. For example, in order to vent undesirable acidic water, less than 10 ppm (0.001%) of hydrogen sulfide vented to open air must be vented in accordance with OSHA standards. Burning corrosive oil quickly reaches emission limits per site. For example, the common limits for sulfur emissions are between 100 tons and

250 tons of sulfur. In order to achieve these lower concentrations, the industry has typically used methods that involve reducing sulfur content with the use of chemical catalysts to remove sulfur. These are typically liquid hydrogen sulfide scrubbers added to water or oil to absorb hydrogen sulfide and prevent it from turning into steam. This solution is feasible and can be achieved when there is a low concentration of sulfur.

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Mexican Institute of Industrial Property

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hydrogen in water or oil. Once the gas product from the well reaches more than 5000 ppm (0.05%), the water and oil will have a hydrogen sulfide content, so that such liquid scrubbers become very expensive. With wells approaching or exceeding 10,000 ppm (1%) of hydrogen sulfide, the cost of using the liquid scrubber on water and petroleum products exceeds the value of the oil itself after transportation costs.

For example, a well with an average of 30,000 ppm (3%) of hydrogen sulfide in its gas product, 40,000 ppm (4%) in the vapor space of its water tanks, and 60,000 ppm (6%) in the Vapor space from your tanks therefore can easily cost $ 20 per barrel of water and $ 40 per barrel of oil to use hydrogen sulfide scrubbers to treat these liquids, to make them safe for transportation. Only then can a special refinery accept oil with high concentrations of scrubber materials.

Furthermore, suitable liquid scrubbers for water and oil are themselves harmful chemicals. Operators working with these chemicals can wear full HAZMAT suits. When there is a spill of scrubbing chemicals at any point during transportation, again, there is a safety risk for transportation personnel and the general public.

Corrosive oil and acidic water with high levels of hydrogen sulfide are extremely toxic and deadly. Hydrogen sulfide is lethal when inhaled at concentrations below 1000 ppm (0.1%) in air, water, or petroleum vapor. With casualties

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^oc merger concentrations, hydrogen sulfide has an aroma^ÜST¿$ Vao similar to the smell of rotten eggs. In concentration, the smell of the rotten egg is lost, since hydrogen sulfide can fatigue the sense of smell.

Hydrogen sulfide is a very toxic gas at normal temperatures. It has a serious risk when inhaled. There is a wealth of information about human exposures. However, in most cases, exposure levels and duration of exposure are unknown and are calculated experimentally. Effects at various levels of exposure are believed to be as follows: 0.001-0.13 ppm - aroma threshold (highly variable); 1.5 ppm, - moderately offensive aroma, possibly with nausea or headache with prolonged exposure; 20-50 ppm irritation of the nose, throat and lungs, digestive condition and loss of appetite, the sense of smell begins to "get tired", the smell cannot be considered as an alert before exposure; 100-200 ppm, severe irritation of nose, throat and lungs, the ability to smell completely disappears; 250-500 ppm - potentially fatal accumulation of fluid in the lungs (pulmonary edema), in the absence of central nervous system effects (headache, nausea, dizziness), especially when exposure is prolonged; 500 ppm - severe lung irritation, excitement, headache, dizziness, staggering, sudden collapse ("paralysis"), unconsciousness and death within 4 to 8 hours, memory loss from exposure period; 500-1000 ppm - respiratory paralysis, tachycardias, collapse and death. It is important to note that the symptoms of pulmonary edema,

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JL - _

DE U P8OPIÍDAD • NDUSTWAt ___ such as chest pain and shortness of breath, may lag up to 48 hours after exposure.

Prolonged exposure (for several hours or days) to concentrations as low as 50-100 ppm can cause a irritated nose, cough, hoarseness, and difficulty breathing. Prolonged exposure to higher concentrations can produce bronchitis, pneumonia, and a potentially fatal accumulation of fluid in the lungs (pulmonary edema). There are several reports of death cases, especially among operators in the petroleum, wastewater treatment and agriculture industries. Many deaths have occurred within confined spaces (for example, sewers, mud tanks, septic tanks, or hydrogen sulfide that accumulates in open pit or buildings). In most cases, multiple deaths have occurred at a single site. Some rescuers trying to save an unconscious worker have entered a confined and / or dangerous area without respiratory protection or safety lines, and have, in turn, been affected by hydrogen sulfide.

Workers who have survived severe hydrogen sulfide exposures for short periods may recover fully or may experience long-term effects. Effects on the nervous system and the respiratory system have been described in human population studies or in case reports. Permanent or persistent effects on the nervous system include fatigue, anxiety, irritability, intellectual impairment, reduced attention span, impaired learning and memory, impaired sense of smell, and motor deficits. Some

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INSTITUTO MBUCanc FX _

D 'THE PROPERTY / + - ..

Effects on the nervous system are due to a lack of oRT ^ ew in brain cells during a p &lt;= ihlftiria, exposure of hydrogen. Respiratory effects include symptoms (difficulty breathing, chest tightness, or wheezing) consistent with airway hypersensitivity (reactive airway dysfunction), permanent damage to the lungs (pulmonary fibrosis), and significant reductions in residual volume. (a measure of lung function).

Although cyanides are well known to the public as highly toxic poisons, hydrogen sulfide is just as deadly. For example, incidents involving the deadly nature of hydrogen sulfide are well documented. One example relates to the deaths of nine people in Texas, who died from gases leaking from an unattended carbon dioxide injection system, which was designed to extract oil from a Texas well. Eight of the victims were in a house 92 meters from the well.

In another example involving the transportation of hydrogen sulfide, two Michigan employees drove a tank truck to a corrosive oil well tank farm to obtain waste brine. When they were unable to capture a stream of brine from a ground-level connection just outside the tank's levee, they advanced toward the brine tank. An employee climbed into the tank, which was 2.6 meters above the ground. He screamed an alert, but was immediately passed out from an escape of hydrogen sulfide-rich gas. Later, he was found lifeless on the platform next to the top of the tank. The other worker, who

ΓΙ i U l'-J Α1 · 1Α1κ · ΛΓΜν&gt; 2 ¡8

OF THE PROPERTY

INDUSTRIAL was waiting near the top of the stairs was reached and collapsed before it could alert. Fortunately, he fell off the stairs, out of the contamination area, and regained consciousness. The hatch that had been opened was closed from the access platform and was approximately 60 cm above it. Clearly, it is a benefit to have a simple, inexpensive, and effective way to reduce the level of hydrogen sulfide in materials in order to improve safety at exploration sites and safety in transporting materials.

In addition to the health risks from exposure to hydrogen sulfide, hydrogen sulfide is a flammable gas that creates additional transportation risks. In recent years, 47 people died when a freight train it was carrying therefore caught fire when it hit. The composition is under investigation, as oil typically does not explode. Contamination of the car with hydrogen sulfide from an upstream source is considered a possible cause for the car to explode. Certain embodiments of the invention address safety concerns with the transportation of oil containing hydrogen sulfide and to prevent contamination of less hazardous oil.

Other current methods of removing hydrogen sulfide involve the use of natural gas to remove sulfur, or the use of special apparatus to use amines to remove sulfur. Most processes to sweeten oil involve the absorption of hydrogen sulfide in an amine solution, the use of a carbonate process, the

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MSXICAN INSTITUTE OF PROPERTY use of solid bed absorbents and physical absorption. 'TPW ^ jem ^ wrTa United States Patent Publication of Amór¡c'd'Nu.ΤΟ'ΤΤΤΟΊΊ 1709 by Hassan et.al., ("Hassan"), incorporated herein in its entirety by reference, describes a method in where the corrosive oil is subjected to high shear and at least one agent to remove sulfur, wherein the sulfur removing agent is selected from the group consisting of bases and inorganic salts to produce a high shear stream and separate the sulfur rich product and sweetened petroleum product from the high shear treated stream. Hassan also describes a system and method that use a shear mechanism in combination with chemicals or other gases to remove sulfur. In accordance with Hassan's system and method, high shear and at least one chemical agent are required to remove sulfur.

United States Patent No. 8,216,520 issued to Choi et. al., and Patent Publications No. 201 1/0147266; No. 2009/0173664 and No. 201 1/0315600 also by Choi et.al., (collectively "Choi"), all incorporated herein by reference in their entirety, involve a system, method and apparatus for refining heavy crude oil. Choi describes a system and method that involves combining heavy oil with supply water in a mixing zone to form a heavy oil / water mixture, where the mixture does not exceed 150 degrees Celsius, the oil mixture is subjected / water to ultrasonic waves to create a sub-microemulsion, pump the submlcroemulslon with the use of a high pressure pump to increase the pressure at or above the critical pressure of the water and heat the sub13

MEXICAN INSTITUTE microemulsion between 150 ° C and 350 ° C. Choi also ÉétáÉSSB &amp; E heated oxidant stream to the oil mixture. heavy / water, where the heated oxidant stream is at a temperature and pressure that exceed the critical temperature and pressure of the water; introducing the mixture into an area essentially free of an externally provided catalyst, where the reaction is subjected to conditions that exceed the supercritical conditions of the water, such that a portion of the hydrocarbons in the reaction mixture undergo the cracking to form a refined mixture. Furthermore, the Choi process requires subjecting the mixture to ultrasonic waves.

The Choi process requires a special apparatus that has a mixing zone to combine the heavy oil with a slightly elevated temperature water supply to create the heavy oil / water mixture, where the mixing zone is a generator of ultrasonic waves; a pre-heating zone that is connected in fluid communication with the mixing zone, which can operate to heat the heavy oil / water mixture to a temperature of up to about 350 ° Celsius, a high pressure pumping medium, which operates to increase the pressure of the heavy oil / water mixture to at least the critical pressure of the water and a reaction zone that is essentially free of an externally supplied catalyst and an externally supplied hydrogen source, connected in fluid communication with the pre-heating zone and with the capacity to withstand the temperature of the critical temperature of the water and which has the capacity to withstand the excessive pressure of the critical pressure

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MEXICAN INSTITUTE of water. The result is a refined oil with exchange ^ Kfi ^ Lre of substances, such as sulfur.

The Choi process, while describing a system and method essentially free of external catalysts or external hydrogen to remove compounds, including sulfur compounds, requires heating of oil and water, mixing the water with an ultrasonic component , a high pressure system to bring the mixture to the critical pressure of the water. Chol also teaches a system and method that can remove sulfur by-products, such as hydrogen sulfide, from corrosive oil without complex equipment and in a highly controlled environment.

United States of America Patent No. 4,253,298, issued to Blytas et.al., ("Blytas") describes an acid water treatment method where acidic water components are removed from the acidic water stream in one step of electrodialysis, where the acid water stream is converted to a dilute stream. The Blytas process submits an acidic water stream to an electrodialysis step, where the acid component and the basic component of the stream migrate from the stream through an anion and cation exchange membrane for one or more concentration currents and stripping the concentration currents with steam in order to remove the volatile acid component and the volatile basic component. Blytas is incorporated herein by reference in its entirety. This method is aimed at a pre-process, upstream of a non-specific steam stripping process. It uses electrodialysis, which

MEXICAN INSTITUTE OF PROPERTY requires complex mechanical parameters and the proc £ § '$ⁱ'ⁿW¿&gt; apVtrpTados for use in the field due to cost and ppit^,ariri^,titta^,il^,'PO'r'mj'eiirptüT Blytas uses a membrane to remove the acidic components from the water. This is a pre-process treatment and does not fix the ventilated hydrogen sulfide in the vapor process with respect to safe breathable concentrations. The present invention does not describe the use of a membrane to remove hydrogen sulfide from acidic water. Furthermore, the present invention does not require a steam stripping process.

Other methods of removing hydrogen sulfide from water involve the use of high-voltage electro-oxidation. United States Patent Publication No. 2012/0273367 to Themy et.al., ("Themy") removes hydrogen sulfide through the use of electro-oxidation. Themy is incorporated herein by reference in its entirety. Hydrogen sulfide is present as part of the typical hydrocarbon streams from oilfield sources. Accordingly, hydrogen sulfide can contaminate various water sources and wastewater streams, including those from hydraulic fracturing operations. Hydrogen sulfide is corrosive and produces certain steel chips, leading to stress cracking of sulfide, which is a concern in many applications, particularly when handling acidic gas and corrosive oil in the oil industry. Thus, removal of hydrogen sulfide is convenient within the art. The primary method used in the technique to remove hydrogen sulfide is the Claus process, which comes from

MEXICAN INSTITUTE v ^^ ewS ^ LA

SAY PROPERTY in accordance with Formula 2H₂S + O₂ -&gt; 2S + 2H₂OR.'^naWH technology is available to remove the hydrogen sulfide l'fTCIU'V'l'á OXly0IIucióri of · high pressure solutions of hydrogen sulfide and oxidations with ozone and hydrogen peroxide. Therefore, water purification systems and methods can also be useful for removing hydrogen sulfide, not only by oxidizing hydrogen sulfide in elemental sulfur or in sulfur-containing anions (eg SO₃, SO₄²'), it also destroys the sulfur-reducing bacteria (SRB), which may be responsible for the production of hydrogen sulfide in certain wastewater sources in the first place. In addition, certain sulfur-containing organic compounds can be oxidized by an electro-oxidation cocktail to reduce their aroma (for example, thioethers oxidized to sulfoxides or sulfones), and other oxidation of the hydrocarbon portion of these molecules can lead to done as Themy states to remove them from the purified waste water.

United States of America Patent Publication No.

2013/0312974 to McCIung IV et.al., ("McCIung) describes treating a well with a material to inhibit bacteria that produce hydrogen sulfide, McCIung describes adding an inhibitor to a treatment fluid. The treatment fluid is added to a source containing bacteria that produce hydrogen sulfide to inhibit the growth of bacteria. McCIung is incorporated by reference in its entirety.

In order to provide additional background and context and to also satisfy the requirements of the written description of 35 USC § 112, the following references are incorporated in their entirety as

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η ηβτιτυτο MEXICAN INDUSTRIAL PROPERTY reference for the express purpose of explaining the nature of the oil and gas industry and of the methods to also describe the different systems, sub-systems, tools and components associated with it. United States Patent No. 4,218,309 issued to Compton, United States Patent No. 4,447,330 and 4,536,293 issued to Babineaux lll, Japanese Patent Publication NO. 200855291, invented by Mashahiko et.al., Chinese Patent No. 101532380, issued by Zhengguo.

The process to remove the sulfur content from acidic water also requires specialized equipment, since acidic water has corrosive properties. The use of air to remove hydrogen sulfide or "aeration" as a unit operation depends on two basic principles: equilibrium conditions and mass transfer considerations. The water to be treated is chemically balanced with its component species and physically in balance with the atmosphere above the water's surface. These equilibrium conditions define the limits of the gas transfer process. Aeration is an effective removal mechanism because hydrogen sulfide exists as a gas dissolved in water. Incidentally, the aeration function is not specifically to oxygenate the water, rather it is stripping the dissolved gas (hydrogen sulfide) out of the water by changing the equilibrium conditions of the water and thus dragging the dissolved gas out.

The removal of hydrogen sulfide by stripping air is defined by the application of Henry's Law. However, Henry's Law,

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it is generally associated with solutions, dilii is related to the concentration of a gas in the water ^ a-Tadel gas in the liquid. It should be remembered that partial pressure is the pressure that a particular gas exerts as it moves toward equilibrium. Balance occurs as gases flow from regions of higher partial pressure to regions of lower pressure. The larger the difference, the faster the flow will be. Hydrogen sulfide exists in equilibrium in three different forms, as shown in the following reactions with their respective pK (dissociation) values:

H₂S = HS * + H + pKa = 7.1

HS * = S₂ + H + pKa = 14

Certain plants prohibit stripping of air, due to the release of potentially combustible gases and costly residual incineration of the air, where current processes in use move away from using air to strip acidic water. It is important that in the traditional processes of using air to strip acidic water, acidic water is mainly used, with very low concentrations of contaminants.

Although it is well known that air can potentially be used to strip water, most current processes use specialized equipment, complicated processes, or use natural gas or other materials to remove high levels of hydrogen sulfide. For example, Japanese Patent No. 2008307475A, issued to Kyoji et.al., ("Kyoji") describes an apparatus and method for removing hydrogen sulfide from groundwater. Kyoji joins here

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IMPI

MEXICAN INSTITUTE as a reference in its entirety. In accordance with^GAVEThe device's preferred R ^ jH $ uses a pump to pump the groundwater into a storage tank. A pipeline applies air to the water in the storage tank, which releases the hydrogen sulfide in the gas phase. The gas phase is then sent to a separate sulfur removal compartment, which contains a sulfur removal agent, such as iron oxide or activated carbon. The air is then vented from the compartment to remove the sulfur. The water is then sent to a separate tank, where the water is processed to remove any matter or precipitate suspended in the remaining water. The water is then discharged after treatment into a separate water treatment tank. Kyoji requires a separate compartment from which air is vented to contain a sulfur-removing agent, such as a chemical catalyst. Although Kyoji mentions that certain modes of the apparatus do not contain a separate sulfur removal compartment, it is unclear whether Kyoji's alternative mode will ventilate air directly from the compartment containing acidic water. Such an alternative modality does not take into account the safety of people or environmental safety. Thus, Kyoji does not describe a separate compartment, nor do catalysts or additional sulfur removal agents, where the hydrogen sulfide concentration is measured before being vented to ensure that the hydrogen sulfide concentration is within limits. acceptable.

European Patent Application Publication No. 2495219 (“EP

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MEXICAN INSTITUTE OF PROPERTY '219 ”) describes a method to remove contaminant¹· DeTSnjua feeding. EP '219 is incorporated here όΟΙΓΙΐ! TgTgTgnfilá' UH YOUR entirety. EP '219 describes a method that includes forming a bubble dispersion of a treatment gas in a continuous phase comprising feed water, where the bubbles have an average diameter of less than about 5 microns and the gas is selected from the air , oxygen and chlorine. Gas bubbles have an average diameter of less than 1 micrometer, or not more than 400 nanometers ("nm"). In the method described in EP '219, the feed water and the treatment gas mixture and the continuous phase are subjected to a shear rate greater than about 20,000s-1. The treatment gas and the continuous phase make contact in a high shear device, where the high shear devices comprise at least one rotor and where the at least one rotor is rotated at a peripheral speed of at least 22.9 meters / second (4,500 ft / minute) during dispersion formation. The high shear device produces a local pressure of at least approximately 150,000 pounds per square inch "psi" (1034.2 MPa) at the extension of a rotor during dispersion formation. The power consumption of high shear devices during dispersion formation can be greater than 1000 W / m³. The dispersion is introduced into the enclosure and the particle containing the water is removed from the enclosure. The water-containing particle is then introduced into the separator. This method uses a specific mechanical device with specific mechanical and process parameters to remove the

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I Mexican Institute of INDUSTRIAL property hydrogen sulfide and other water pollutants. Although its advantages (which may be within a small space, it may be the appropriate water for direct disposal within surface lakes, streams or municipal hydraulic installations, it seems a quick process) seems useful in other work environments, since it is not they need for the transport of produced water or for disposal in distant or near gas and oil production scenarios. Also, the advantages have a higher cost not appropriate for field use since such a method uses a specific mechanical device with the use of very specific mechanical energy and process parameters and ventilates the hydrogen sulfide and when chlorine gas is used there is the possibility of a mixture or breathable, toxic regardless of safe breathable concentrations.

Other known aeration processes to remove hydrogen sulfide from water are not appropriate to remove high levels of hydrogen sulfide, such as those found at exploration sites. For example, certain processes have materials containing hydrogen sulfide exposed to the open environment. This is problematic when materials that have high levels of hydrogen sulfide, as the hydrogen sulfide that escapes into the environment is toxic and dangerous. Certain embodiments of the present invention comprise an enclosed environment for hydrogen sulfide containing materials to prevent high concentrations of hydrogen sulfide from being released into the environment.

Other processes use catalysts to strip acidic water. United States Patent No. 4,784,775 issued for

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Mexican institute Mexican institute; d,

Hardison ("Hardison") describes a system for

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Hydrogen from acidic water with the use of a chelated polyvalent dp motai aqueous solution as the catalyst. The present invention removes hydrogen sulfide from acidic water without the need for a chemical catalyst.

Known acid water treatment processes are complex and have other disadvantages, such as requiring meticulous process parameters. The present invention is novel and improves the prior art because the only parameter that must be accurately monitored is the concentrations of hydrogen sulfide in the open space that is eventually vented to the air. The present invention can be done with minimal parameters. Deviations in the described process can affect the overall process time or its efficiency. However, as those skilled in the art will recognize, deviations will not have much of an impact on the efficacy of the invention. For example, in certain modalities, some perforations in the dispenser bar are located in a tank that contains acidic water and can be 0.63 cm in diameter. In other modalities, the perforations can be 1.27 cm in diameter. In other modalities, the perforations can be 2.54 cm in diameter. The present invention provides a simpler way to remove hydrogen sulfide, so automation is not required. Although automation is not required for the present invention, certain embodiments include automation. Any parameter described in the modalities is not intended to limit the i

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OtLA PROPERTY scope of the Invention in any sense and solarnenteiN8W-pcope? Síe ^^ as an example to illustrate the novelty and Ias m ^^ ar-as · .4c-la.p ^ s ^ nte. invention over the prior art.

The methods present for sweetening oil and stripping acidic water are cost restrictive and only economical when performed on a large scale. Building such facilities is impractical at exploration sites. The present invention can be carried out on a large scale, with the use of no more than items and equipment already on the scan site and other items obtained from equipment stores such as Lowe or Home Depot.

Treatment facilities may not be accessible to those who perform exploration drilling. Furthermore, the equipment and materials required to carry out traditional processes are not economical at exploration sites. People who work at remote exploration sites do not have access to the resources necessary to sweeten corrosive oil or acidic water. For example, many of these typical processes use sweet natural gas to sweeten oil or sweeten water. Often, a source of fresh natural water is not readily available, and it is not economical to sweeten acidic natural gas in order to be used to treat corrosive oil or acidic water.

Due to the remote nature of exploration facilities, toxic and deadly materials must be transported considerable distances to a Treatment Facility. Anyone involved in transportation is subject to the potential risks of hydrogen sulfide as well as an environmental disaster that may occur.

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when something happens far from the remote site of the po ^ yj ^ jt ^ la ^ n¹

M LA INDUSTRIAL WOP1EDAD treatment.

Certain embodiments of the invention provide a system and method for sweetening corrosive oil and water without the need to use hydrocarbons or other catalysts. This is especially useful in the exploration gas industry when corrosive oil to the traditional methods used to sweeten oil and water are not available and are further miles away. Certain modalities include a system and method comprising collecting the corrosive oil in a container, keeping the corrosive oil in an air-free environment, adding water and stirring the mixture. Other embodiments of the present invention include using acidic water to remove hydrogen sulfide from the corrosive oil.

Brief Description of the Invention

The present invention relates to a system and method of removing hydrogen sulfide from petroleum and water. The present invention also reduces the weight content of sulfur. Current ways to remove hydrogen sulfide from water and oil typically use specialized equipment and expensive chemicals. Hydrogen sulfide is a toxic chemical and the transportation of materials containing high levels of hydrogen sulfide present risks for all involved. This is especially for exploration wells, which are often thousands of kilometers from the closest treatment facility. The present invention

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ÜELAWOEsüVAD includes treating oil or water to remove sulfiW⁵^¹ hitfF ^ erfo. The present invention can be used with acidic waterWTTWII dceile loh-o ^ w © 'with high levels of hydrogen sulfide as well as lower levels. Hydrogen sulfide is removed without specialized equipment or expensive chemicals. Sweetened water or sweetened oil can be transported without imposing on those involved in handling and transport any risk of fatal errors and minimizing environmental risks.

In certain embodiments, the invention comprises an air source, a tank, a plurality of lines that distribute air from the air source to the tank, and a ventilation stack, connections that distribute air from the air source into the tank. , a hydrogen sulfide monitor and a ventilation stack connected to the water tank and the air source. Air from the air source is led to a tank filled with acidic water through an air flow line. The air flow line is connected to a pipe with at least one hole. The pipe is located in the water tank. A second line is routed to the vent stack through a second air flow line. In certain modes, air flows into the vent stack at a rate of 120 cubic feet per minute ("scf / m). The air flow is adjusted in increments every hour for twelve hours. The air distribution rate is adjusted every hour until the air flow rate for the water tank line increases to approximately 120 scf / m and the air flow for the vent stack decreases to approximately 20 scf / m. The amount of sulfide in

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INSTITUTO MEXICANO hydrogen is measured near the top of the air plane with acceptable levels of sulfide 4e— ^ idrógoncb— ventila. The plurality of lines that meet from the air source are secured in the manner known to those of skill in the art to connect air lines to the air source. The embodiments of the present invention ensure that any material containing hydrogen sulfide is encompassed within the invention and that it is not exposed to the outside environment. Those skilled in the art will recognize it, the air source can be any air source with the ability to generate air, such as a compressor or a blower.

United States Patent No. 3,547,190, issued to Wilkerson ("Wilkerson) describes an apparatus and method for treating wastewater associated with the production of hydrocarbons. Wilkerson is incorporated herein by reference in its entirety. According to Wilkerson, wastewater from a well is pumped under pressure to a plurality of spray nozzles that are arranged in such a way to spray water into the atmosphere in an essentially vertical direction to open air. The sprayed water is aerated to remove residual hydrogen sulfide from it and to reduce its temperature. The water is then collected in a reservoir, where any excess oil still associated with the water can be skimmed from the surface of the water. The method described in Wilkerson will lose its efficiency as the process water temperature is lowered from the bottle point. In some specific field applications, where the

IMPI

INSTITUTO MEKCANO DE LA IRO5TEDAD INDUSTRIA !.

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water coming from the well itself is very hot, this method can be very useful. For all other applications in the field, there may be problems with this Implementation. For example, it operates over a relatively narrow range of parameters, both mechanical and process. Nozzle size and upstream pumping pressures can be critical. It may result in a mist (as opposed to steam) to be blown over the attached property, namely a spill. Wllkerson requires hot water for its efficiency and may not be suitable for application in cold climates, regardless of the initial process water temperature.

It should be noted that Wilkerson ventilates hydrogen sulfide regardless of safe breathable concentrations. Any non-vented hydrogen sulfide in the initial pass is vented from the open body of water at a rate that is both difficult to measure and difficult to control. This particular method is highly problematic in this regard and those skilled in the art will recognize that the present invention overcomes the safety risks associated with releasing hydrogen sulfide into the environment. Although it is well known in the art that exposing water or oil containing hydrogen sulfide to air will remove hydrogen sulfide, the embodiments of the present invention allow aeration to remove hydrogen sulfide in an enclosed environment to eliminate any risk of safety and environmental risks associated with the release of hydrogen sulfide into the environment.

In other embodiments, the present invention comprises a

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container filled with water, a separate industrial content means to distribute water from the container filled with water to the container filled with oil. The water can be either fresh water or sweet oil. Water travels through corrosive oil since it has a lower specific gravity. This path through the oil creates agitation and the hydrogen sulfide is removed from the oil as the water passes through the oil. Stirring occurs at the oil / water interface. The oil will release hydrogen sulfide into the water each time the water contains a lower concentration of hydrogen sulfide that makes contact with the oil that contains a higher concentration of hydrogen sulfide.

United States Patent No. 3,977,972 issued to Block et.al., ("Bloch") describes a system and method for removing hydrogen sulfide from a seal oil by bubbling a gas such as nitrogen. Bloch is incorporated herein by reference in its entirety. Bloch's preferred embodiment contains a compressor that has an arrow that rotates in a pair of film-liquid seal cartridges that serve as seal retainer seats for the rotary arrow of the compressor. Each of the liquid-film seal cartridges includes a pair of floating, non-rotating sleeve portions that surround the shaft and are interconnected by an intermediate gap portion through which the shaft extends freely. The contaminated oil is then transferred to a cylindrical drum, where the diameter can be within the order of 60 cm, while its height is approximately twice the diameter. The lower inner portion of the

IMPI drum is provided with a deflector in the form of a * «DUSTRUl

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metal extended upwards approximately 60 cm from the bottom of the drum to divide the bottom Inner portion of the drum into a pair of chambers having a cross section of a semi-circle. The contaminated oil seal flows into one of the chambers, where a spraying medium bubbles upward with air or nitrogen through the oil. Oil flows into the second chamber, where the spray medium bubbles air or nitrogen through the oil. Bloch, while possibly appropriate for refined seal and lubrication oils that can be contaminated with higher sulfur fuels, are neither appropriate nor safe with crude oils or any oil that releases fuel into the air. Although the use of pure nitrogen or other inert gas can solve the combustion problem, it is impractical and uneconomical to obtain a source of pure nitrogen at exploration sites and will also create a low oxygen (respirable oxygen) environment in the area near ventilation. It is also not appropriate for higher concentrations (over 10 ppm) of hydrogen sulfide due to its direct, undiluted aeration. As will be appreciated by those skilled in the art, the use of water to remove the hydrogen sulfide content in petroleum reduces the risks associated with adding an outside air source to a combustible material, such as petroleum.

In certain embodiments, nitrogen can be used to keep the oil-water interface cool, where agitation of the water sweetens the oil. Nitrogen is introduced into the bottom of the stripping tank

IMPIAS,

MEXICAN INSTITUTE of oil periodically at low volume, ^DpoÍD¿e ^ BrpMC ^^ Iffa proportion of 19 cubic feet every 15 minutes—^na maHida rlp additional safety to prevent the accumulation of flammable gas.

In certain embodiments, the present invention comprises a tank with a mixture of petroleum and acidic water, a separate tank with acidic water, air distributors that pump air through the tank with acidic water to remove hydrogen sulfide, pump the fresh water inside the tank that contains the oil-water mixture, and allow water from the oil and the water tank to flow into the acid water tank through a gravity feed. As will be appreciated by those skilled in the art, the present invention is an improvement over the prior art requiring the use of catalysts, scrubbers, or other expensive and specialized equipment.

Certain embodiments of the present invention can be implemented with the use of containers typically used in the oil field, such as 500 barrels of "fracturing" tanks and 400 barrels of straight cylindrical tank. In one embodiment, a reduced 185 scf / m air compressor for an elevation of 1500m to 140 scf / m can be used as the air source. A dispenser bar with at least one hole is placed in the water tank. The dispenser bar can be a 2.54 cm or 3.81 cm tube. The ventilation line from the water tank to the ventilation basin is 7.62 cm in diameter.

The equipment described here is only provided as an example and should not be construed as limiting the present invention, as the present invention can be used on almost any scale. For example, the

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL TROHEDAD

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The present invention can be used with samples less than 500 ml of oil or water, as well as in tanks that have an excessive volume of

1000 barrels.

For example, certain modalities include equipment that can be placed on mobile transports, such as a trailer or the back of a cargo truck. Certain tanks, available for sale, are designed to fit in the back of a cargo truck. This modality allows for easy transportation and allows corrosive oil and acidic water to be placed in remote locations, where larger equipment is expensive, impractical or sometimes impossible due to remote area.

In certain embodiments, the equipment can be placed on a trailer trailer, where the invention comprises a configuration having an automation cabinet, an air source, a power source, such as a generator, a water pump, and a concentrations of hose or tubes. Those skilled in the art will appreciate that other variations can be practiced in this embodiment, with other types of tanks that are mobile and can be transported from site to site and are within the scope of the invention. The descriptions provided herein are not intended to limit this

Invention.

In certain embodiments, the invention comprises an air source, a plurality of storage devices, connections that distribute air from the air source into a storage device comprising water, and a connected ventilation stack

Mexican JwsmuTo with the storage device that includes NBfflEeScre air. Air from the air source is led to the storage, which comprises acidic water through the air flow line. The air flow line is connected to a pipe with at least one hole. The pipe is located in the storage device that includes acidic water. A second line is routed to the vent stack through a second air flow line. In certain embodiments, air flows into the vent stack at a rate of approximately 120 scf / m. The air flow is adjusted in increments every hour for twelve hours. The air distribution ratio is adjusted hourly until the air flow ratio to the water tank line increases to approximately 120 scf / m and the air flow to the vent stack decreases to approximately 20 scf / m. The amount of hydrogen sulfide is measured near the top of the vent stack. Air with acceptable concentrations of hydrogen sulfide is then vented. The sweetened water is pumped from the water tank to a second storage device comprising a mixture of acidic water and water through a fitting that couples the water tank to the top of the second storage device comprising the oil. corrosive and water. The storage device comprising a mixture of corrosive oil and acidic water is equalized. Water is pumped from the storage device comprising the acidic water into the storage device comprising the mixture of corrosive oil and water. For example, in modalities that include

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MSXICAN INSTITUTE

400 or 500 barrel tanks, an appropriate ratio will be &amp; M $$ - $ ^ r from the storage device comprising water within the storage device comprising the mixture of corrosive oil and water at a rate of 3 barrels per minute. Other speeds are possible, such as a speed of 75.6 liters to 189 liters per minute. As water passes through oil due to its higher specific gravity, hydrogen sulfide is removed from the oil. The water that is now at the bottom of the storage device comprising oil and water has higher concentrations of hydrogen sulfide. Water from the bottom of the storage device comprising oil and water, flows back from the storage device comprising water due to hydrostatic pressure, ie "gravity feed", through the coupling between the bottom of the storage device, comprising oil and water and the storage device comprising water. The water is then stripped to remove the hydrogen sulfide so that the hydrogen sulfide concentrations reach an acceptable level of venting. The embodiments of the present invention ensure that any material containing hydrogen sulfide is encompassed by the invention and is not exposed to the outside environment.

Certain embodiments of the invention include cavitation ventilation to keep air out of the oil stripping tank.

In certain embodiments of the invention, the water used in the stripping process comprises a pH of about 7.2 or lower. In

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certain modalities, removing all the sulfur is convenient. In embodiments, where it is desired to remove all of the hydrogen sulfide, the hydrogen sulfide can be removed entirely once the ambient temperatures are above 7.2 ° C.

Another embodiment of the invention includes a form for automated regulation of air distribution. In certain embodiments, a loop controller is coupled with a hydrogen sulfide sensor that monitors the concentration of hydrogen sulfide in the vent stack. In this mode, the loop controller is coupled with the vent stack, the air line with the water stripping tank, and the air line with the vent stack. The loop controller is used to keep the ventilated air below 10 ppm. The loop controller is connected with a current to a pressure converter ("I to P converter"). In certain modes, converter I to P converts controller 4 to a 20 ma 0 to 15 psi pneumatic output. As will be appreciated by those skilled in the art, different types of I to P converters can be used in the present invention, and the I to P converter described herein is not intended to limit the present invention.

Certain modes include at least one I to P converter. A specific air line can be regulated by a dedicated I to P converter. In other embodiments, the I to P converter can regulate the plurality of air lines. In preferred embodiments, the use of an I to P converter may be convenient, as it ensures a "safe state" after loss of control signal (either electrical or

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pneumatic), where all the air will be diverted

INDUSTRIAL PROPERTY ventilation and valves will return to their original position.

Based on the information received from the loop controller, the I to P converter or converters will send more air to the air line connected to the ventilation stack and less air to the ventilation line connected to the tank comprising water, that is, the water stripping tank, since the hydrogen sulfide stream exceeds 10 ppm when the hydrogen sulfide monitor reads a concentration that exceeds 10 ppm. When the concentration detected by the hydrogen sulfide sensor drops below 10 ppm, the loop controller sends more air to the air line connected to the water stripping tank. In certain modes, the loop controller can be calibrated, where it can be reset at one-minute intervals, and can also be calibrated for a range of variation of 2 to 3 ppm, where no change will be transmitted to the control to the air lines.

In certain modes, automation can be controlled with an automation control. The automation control allows the measurement of the number of barrels of oil sweetened by the present invention.

In certain embodiments, the automation control comprises a programmable logic controller ("PLC"), a plurality of compartments, an air source, connections that distribute air from the air source to the desired compartments, a pumping medium, sensors , sensor cables and a connected ventilation stack

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with a compartment that contains water. A

Dt the UjewsejP V INDUSTRIAL property is filled with water that may comprise hydrogen sulfide. A second compartment is filled with a mixture comprising the corrosive oil and the acidic water in equal amounts. The sensors are coupled by the sensor cables to the compartments comprising water, corrosive oil and acid water and the ventilation stack. Water from the first compartment is distributed to the second compartment through a connection located at the top of the second compartment. As water passes through oil due to its higher specific gravity, hydrogen sulfide is removed from the oil. The sensor in the second compartment detects the amount of hydrogen sulfide in the second compartment. The water that is now at the bottom of the second compartment has higher concentrations of hydrogen sulfide. Water from the bottom of the second compartment flows back to the first compartment comprising water due to hydrostatic pressure through a coupling between the bottom of the second compartment and the first compartment. The sensor in the first compartment measures the amount of hydrogen sulfide in the first compartment. The sensor in the vent stack also measures the amount of hydrogen sulfide in the vent stack. Air is distributed to the first compartment from the air source through an air flow line. The sensor in the first compartment measures the amount of hydrogen sulfide present in the first compartment. The sensor in the vent stack measures the amount of hydrogen sulfide present in the vent stack.

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Once the sensor detects the amount of níSr ^ gen ^ r ^ ifa sulfur within the desired limit programmed into the PL¿, the air sTTB ^ ra ^ rr automatically. The sweetened water is then pumped from the first compartment to the second compartment. As will be appreciated by those skilled in the art, the sensors monitor the amount of oil sweetened by the process.

In other modalities, data regarding the number of barrels of sweetened oil is transferred remotely to a database, where the number of barrels of sweetened oil can be stored and analyzed. This data transfer can occur with a wireless medium that includes a cellular Internet protocol, Bluetooth, or other wireless data transfers.

Other modalities use a low-volume, high-pressure water pump to circulate the stripped water through a sample to remove the hydrogen sulfide. These modalities include an air compressor or air pump, a container used as a water stripping tank, a low volume, high pressure pump, a pressure regulator, a container filled with a sample of oil pressurized to the sampled psi, a container filled with a water sample and a liquid pressure regulator. The air compressor or air pump pumps the air into the reservoir that contains the water to be stripped. For example, a Coralife SL-381.3 scfm pump can be used. The air is then pumped into the water stripping tank. The water stripping tank is at ambient pressure. An example of a water stripping tank may comprise a

IMPI

INSTITUTO MEXICANO DE U.BSa «SttAD

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plastic or metal material with a capacity of five to ten liters. The water stripping tank is filled to 5/8% of its volume capacity with distilled water. The water from the water stripping tank then travels to the low volume, high pressure pump. The pump can comprise a pneumatic pump or an electric pump. For example, the pump may comprise a Texsteam 5000 series pump. A release regulator is connected to the low volume, high pressure pump and ventilates as needed. As an example, the release regulator can be adjusted in the sample MAOP container, such as 2000 psi. The water from the low-volume, high-pressure pump then travels to a container with an oil sample. For example, certain modalities may use a 100 cubic centimeter ("cc") container, pressurized to 75 psi. Water passes through the oil sample container to a separate container, which contains a water sample. In certain embodiments, the water sample container may comprise a 1000 cc container. The water then passes from the water container back to the water stripping tank. A liquid pressure regulator can be attached to the line that runs from the container with the water sample to the water stripping tank. The liquid pressure regulator can be adjusted to the oil sample pressure, for example 75 psi.

In another embodiment, the present invention comprises a container filled with water, a separate container filled with oil, a distribution means that distributes water from the container filled with water to the container filled with oil.

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FROM the PnoniOAtr

In certain embodiments, the invention includes filling'W'Wnq acid water, aerating the acid water to strip the Trnu úi nim i. fresh water within the separate tank comprising a matched mixture of corrosive oil and acidic water, removing hydrogen sulfide from the corrosive oil, pumping the resulting acidic water into the filled tank with the acidic water.

In certain embodiments, the invention includes components that can be used in remote areas, such as exploration wells. Those skilled in the art will recognize that the invention eliminates the need for expensive and specialized equipment currently used to remove hydrogen sulfide from acidic water and corrosive oil. Furthermore, the invention can be used to strip acidic water and treat corrosive oil containing hydrogen sulfide in any amount, even in excess of 300,000 to saturation a higher amount than the equipment used in the prior art. For example, U.S. Patent No. 5,286,389, issued to Hardlson "The Hardison '389 Patent" Incorporated in its entirety by reference, describes a method and apparatus for stripping hydrogen sulfide from water. The method and apparatus of the Hardison '389 Patent specifically states that the apparatus and method are particularly effective in treating acidic water containing approximately 5 ppm to 500 ppm of hydrogen sulfide. Thus, the Hardison '389 Patent does not teach using such a prior art with water containing higher levels of hydrogen sulfide. Hydrogen sulfide levels do not influence the present invention and therefore, the

MÍMCANO INSTITUTE OF IA PROPERTY

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The present invention can be used with higher hydrogen sulfide coWSWn materials. --—

United States Patent No. 6,444.1 17, issued to Kahn et.al., ("Kahn") describes a process for removing sulfur from sulfur-containing crude oil streams. Kahn is incorporated herein by reference in its entirety. Kahn requires heating the sulfur-containing crude oil to an elevated temperature of at least 149 degrees Celsius to 316 degrees Celsius for an extended period of time, stirring and bubbling an inert gas, such as nitrogen within the crude oil, and adding a scrubber or catalyst within the crude oil stream to generate an exhaust gas, such as hydrogen sulfide. Kahn requires careful monitoring and control of liquid temperature to remain safe. Its maximum efficiency wrap immediately surrounds the flash point of sweetened (unsafe) oil. These parameters must be constantly monitored and controlled and may vary greatly with different types and grades of crude oil. Kahn acknowledges that additional steps are required to reduce the amount of hydrogen sulfide generated by heating the crude to the levels described. Kahn ventilates both hydrogen sulfide and low oxygen mixture without considering safe breathing considerations. As will be appreciated by those skilled in the art, the present invention is a much simpler process that is much safer than was known in the art.

United States of America Patent Application No. 2013/0324397, by Wilson et.al., ("Wilson") describes using an adsorbent of

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WÜUSTRíJU V carbon for the safe removal of hydrogen sulfide, hydrogen sulfide is added to the material that co7itTeñe “hydrogen. Wilson is incorporated by reference in its entirety.

The present invention involves a system and method that removes hydrogen sulfide from water and oil in a low cost manner. In addition, certain modalities allow hydrogen sulfide to be removed on-site at remote locations, such as exploration wells. Certain modalities allow the removal of hydrogen sulfide from water and oil, dilute the concentration to amounts that can be safely vented to the environment, in accordance with current environmental and safety regulations and without endangering anyone in the areas. surrounding, to any animals near the area or environment.

The present invention also reduces sulfur by weight. The typical global definition for corrosive oil is generally approximately 0.5% sulfur by weight. The present invention can be used to sweeten the oil such that the oil is less than 0.5% acceptable.

Other modalities are aimed at improving the price margin, which is the value of sweet oil against corrosive oil, measured in dollars. The price range can vary between $ 5 USD and $ 16 USD per barrel. It is difficult, and usually not feasible, to mix high volumes of hydrogen sulfide in oil. It is not difficult but can be very expensive, mixing high weights of sulfur. A prohibitive amount of 0% hydrogen sulfide would have to be mixed with 10,000 ppm of oil in order to result in a total volume for the limits

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MEXICAN INSTITUTE currently accepted 0.5% or 5 ppm. First as described here, then mix nptmii * ng to a 1: 1 ratio or equal volumes of 0.1 sulfur by weight, which will result in a double-priced oil. Mixing is typically expensive, but by first treating the oils as described here, it provides a low-cost method of minimizing the mixing ratio of downstream processes or eliminates the need to mix oils to increase the price range.

Certain embodiments of the present invention include a plurality of tanks containing different levels of corrosive oil. The oil in one of the tanks can be treated to remove hydrogen sulfide and then mixed with oil from another tank to improve the price range.

Other modalities include an additional chamber, where the removal of hydrogen sulfide from the air can also be stripped, which increases the rate of removal of hydrogen sulfide before venting, once the hydrogen sulfide levels are within acceptable limits.

In another embodiment, the system and method comprises the safe transportation of acidic water and corrosive oil from a remote area, such as an exploration well. High concentrations of hydrogen sulfide are extremely toxic and fatal. Transporting such materials is extremely dangerous and imposes a serious risk on persons handling the material on site, on those involved in loading the transport vehicle, on the transport vehicle driver, on staff

IMPI

INSTITUTO MEXICANO in the treatment plant that discharges the materials ^ B ^ g ^ g ^ of a bad handling risks more people who handle the toxic materials and the greater the distance to travel increases the more personnel at risk. In certain embodiments, the present invention involves a system and method for neutralizing the risk involved in transporting toxic materials, such as acidic water and corrosive oil with high concentrations of hydrogen sulfide. Those skilled in the art will appreciate that the present invention does not so much require the transportation of materials with high concentrations of hydrogen sulfide, which improves safety for those involved in transporting the materials and reduces liability, which could result in a accident during transportation.

The use of the present invention in exploration wells is especially beneficial. For example, when a crew is in the exploration well, they perform tests to see the quality of the wells for hydrogen sulfide. In some wells, levels are extremely high and pose risks to anyone in the area. In order to provide samples for further analysis, personnel are at risk not only from the levels of hydrogen sulfide in corrosive oil and acidic water, but also jeopardize transport samples. In order to transport either the corrosive oil or the acidic water, the staff will have to wear protective suits to load the truck's tanks. Personnel will then have to travel on many routes with corrosive oil or acidic water containing hydrogen sulfide in high concentrations, which will cause

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IMPI iNtmyro mexican Ktxntons (uc MDUSTuC sudden death. Any accident along the way will release such hazardous chemicals, which can kill drivers as well as great harm to the environment. Even when drivers break into the sample or treatment facility , the personnel in these facilities are at risk, any error in the process can be fatal.

The present invention neutralizes this risk. In certain embodiments, there is no need for expensive chemicals, which are dangerous in themselves, and the invention eliminates the need to transport life-threatening toxins over long distances, be it hydrogen sulfide, chemical scrubbers, chemical catalysts, or other chemicals. Other modalities allow water and oil with high concentrations of hydrogen sulfide to be sweetened on site before loading trucks for transport, transporting oil or fresh water, and discharging oil or fresh water at a facility that will undergo another analysis or even for sale.

For example, in certain embodiments, corrosive oil or acidic water can be detected at an exploration site, away from the facility that will treat corrosive oil or acidic water to remove hydrogen sulfide levels. In this embodiment, acidic water and corrosive oil are treated in accordance with the present invention at the exploration site for easy transportation. This includes aerating the acidic water contained in the tank, monitoring the amount of hydrogen sulfide concentration in the water tank, venting air from the steam space of the water tank when hydrogen sulfide is at acceptable levels, pumping the fresh water from the water tank inside a

<img file="MX357271B_D0051.tif" />

separate tank containing the mixture of water and rock ^^ '^^ ta ^^^^ l amount of hydrogen sulfide in the oil is at acceptable levels, return the water from the tank containing the oil and water to a water stripping tank, continue to aerate the water until the hydrogen sulfide levels are acceptable. The oil is then removed from the oil and water tank, loaded into another container for your boat, such as a tank. Oil, which has little or no hydrogen sulfide content, is transported from the exploration site to its destination, where the oil can be further tested or even sold. The water can be reused in the process or can be transported from the exploration site to its destination for further tests or for disposal. Those skilled in the art will appreciate that the risks involved in transporting materials containing hydrogen sulfide are reduced or eliminated, as the materials transported contain little or no hydrogen sulfide. In other embodiments, the invention is directed at an unknown risk, except for persons involved in the transportation of corrosive oil or acidic water. In certain modalities, the method of transportation involves shipping the water or oil through common carriers or private carriers, including via FedEx or UPS. Because there is no hydrogen sulfide in the materials, no additional precautions are needed to ship the materials.

Other embodiments of the present invention include a container that indicates the levels of hydrogen sulfide in the materials within the

<img file="MX357271B_D0052.tif" />

FROM THE CONTAINER HOUSEHOLD. In these modalities, the container propS'rclonáf- ^ eféfra indication that the levels of hydrogen sulfide'eTfTñ ^ pbYTfetraTC-ée` ,, the toxic amounts and can be transported safely. The container and deployment can be calibrated in accordance with relevant standards to indicate when the content of the hydrogen sulfide level is below the required levels. This is particularly useful when samples from a remote well need further analysis at the off-site location. One of the important aspects of the Invention is its flexibility to be used on multiple scales. In this way, hydrogen sulfide can be removed from smaller volumes of corrosive oil or acidic water by the present invention, such as within a specialized container indicating that the materials within the container are safe to transport. In another example, the calibration can be adjusted to indicate that there is no hydrogen sulfide present and that the oil can be sold to a refinery.

Another embodiment of the present invention comprises an indicator that displays a corresponding message or displays the amount of the hydrogen sulfide content in the material to be transported. The indicator can be integrated inside the container or it can be an independent indicator. The indicator displays information on the proper handling of the materials to be transported. With the information, decisions can be made about the safe handling and safe transportation of materials. For example, the decision to ship the materials in trucks, through parcels, through common mail or if the materials are safe to transport, can be made

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OF INDUSTRIAL PROPERTY

<img file="MX357271B_D0053.tif" />

take from the information. For example, when the indicator displays that the hydrogen sulfide level is close to zero, this will indicate that the safe vessel with any transport method will allow the transport of non-hazardous materials similar to those on board.

Although various embodiments of the present invention have been described in detail, it will be apparent that those skilled in the art will be able to envision modifications and alterations. However, it should be understood that such modifications and alterations are within the scope and spirit of the present invention, as set forth in the following claims. Furthermore, the invention described herein has the capacity to support other modalities and to be practiced or carried out in different ways. Furthermore, it should be understood that the phrases and terminology used herein are for the purpose of description and should not be considered as limiting. The use of "including", "comprises" or "adding" and variations thereof are intended to encompass the articles listed here and their equivalents, as well as additional articles.

Brief Description of Drawings

The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate the embodiments of the invention and together with the general description of the invention and the detailed description of the drawings provided below, serve to explain the principles of the invention.

<img file="MX357271B_D0054.tif" />

MEXICAN INSTITUTE OF PROPERTY

It should be understood that in certain cases, the deta¹flW '^orIt was a Trotter necessary for the complete understanding of the nWlri; rünü'l | Ue piinJuteii other difficult to perceive details can be omitted. Furthermore, the system and / or method drawings do not detail all of the system and / or method characteristics, and do not show the complete system and / or method. Of course, it should be understood that this description is not limited to the particular modalities described herein.

Figure 1 illustrates certain embodiments of the invention for removing hydrogen sulfide from petroleum and water.

Figure 2 illustrates certain embodiments of the invention that are mobile.

Figure 3 illustrates certain embodiments of the invention for removing hydrogen sulfide from water.

Figure 4 illustrates certain embodiments of the invention that allow hydrogen sulfide removal on a smaller scale.

Figure 5 illustrates certain embodiments of the invention that comprise a loop controller for regulating air flow.

Detailed Description of the Invention

Figure 1 provides a diagram illustrating certain embodiments of the invention related to a system for removing hydrogen sulfide from water and oil. Element 10 is a container comprising acidic water. Element 11 is a compressor used to distribute air to elements 10 and 16. Element 17 is a line from element 11 to distribute air to element 10,

<img file="MX357271B_D0055.tif" />

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INSTITUTO MWICaw © m la ntornoÁ »sealed with a cover assembly, element 12. The eleffiWftíM line found from element 12 of ensuiilblli Uu lapa-hoota l„ a. air dispenser bar. Element 14 is an air dispenser bar. Element 14 is submerged in the acidic water housed in element 10. Air in the steam space is transferred by element 15 to a ventilation stack, element 16. Element 24 is a second line running from element 11 to element 16, where the air from the air compressor dilutes the air transferred from the steam space to the vent stack. Element 18 is a calibrator that measures the amount of hydrogen sulfide in element 16.

Element 23 is a container comprising acidic water and water. The oil and water in element 23 are equal. Element 19 is a line from element 10 to element 20. Element 20 is a pump that distributes lean water from element 10 to element 23. Element 20 pumps water through element 21, a line is found from element 20 to the top of element 23.

As the water is pumped into element 23, it passes through the corrosive oil due to lower specific gravity. As water travels through the corrosive oil, it gets the hydrogen sulfide from the oil, which removes the hydrogen sulfide from the oil. The water then returns to element 10 through element 22. Element 22 is a line that couples element 23 with element 10. The water is conveyed from element 23 to element 10 through hydrostatic pressure. Hydrogen sulfide is removed from the water returning from the

<img file="MX357271B_D0056.tif" />

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MÍ73CAW J INSTITUTE OF THE FKOPIECAD IIXDlWnuifi.

item 23 as described above. Persons skilled in the art will appreciate that the particular elements in the embodiment illustrated in this Figure are connected with the use of typical connections known to those skilled in the art, such as seals, caps, clamps, tubes, O-rings ( O-rings), well known divider valves, etc. An important aspect of the present invention is that no specialized equipment is needed and that the used items are well known to those skilled in the art.

Figure 2 provides certain embodiments of the Invention that are mobile. Element 26 illustrates a water pump. Element 27 illustrates an automation cabinet. Element 28 illustrates an air source. Item 29 illustrates a shelf where appropriate connections such as pipes and hoses can be stored. Element 20 illustrates a power source, such as a generator. Element 31 illustrates a truck.

Figure 3 provides a diagram illustrating the system for removing hydrogen sulfide from water. Element 10 is a container comprising acidic water. Element 11 is an air compressor used to distribute air to element 10. Element 17 is a line from element 11 to distribute air to element 10, sealed by a cover assembly, element 12. Element 12 is secured with elements 11 and 17 with the use of typical accessories well known to those skilled in the art. Element 13 is a line from cover assembly element 12 to an air dispenser bar, element 14. Elements 12, 13, and 14 are

<img file="MX357271B_D0057.tif" />

^{L, f} LA ΕΑΟΜΕΟλγ coupled with the use of typical known means pW ^ nee experienced in the art. Element 14 is ~ gDm-efekto- £ Jl · the acidic water housed in element 10. The air in the steam space is transferred by element 15 to a ventilation stack, element 16.

Element 24 is a second line running from element 11 to element 16, where the air from the air compressor dilutes the air transferred from the steam space to the vent stack. Element 18 is a gauge that measures the amount of concentration of hydrogen sulfide present in element 16.

Figure 4 illustrates certain embodiments of the invention that allow hydrogen sulfide removal on a smaller scale. Element 41 illustrates a pump. Element 41 is connected to element 45 through element 49. Element 41 pumps water from element 45 through element 42 into element 43. Element 43 is a container filled with corrosive oil and water. Water from element 43 flows through element 44 into element 45. Element 45 illustrates a container filled with water. Element 46 illustrates an air source. Element 46 distributes air through element 47 into element 45. Element 48 illustrates a vent connected to element 45.

Figure 5 provides a diagram illustrating certain embodiments of the invention comprising an I-to-P converter that regulates air flow for a plurality of air lines. The air compressor, item 11 is connected to item 17, an air-conducting line for a tank containing acidic water and item 24,

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MEXICAN INSTITUTE OF INDUSTRY PROPERTY.

<img file="MX357271B_D0058.tif" />

a line that leads air to the ventilation stack. Element 55 is connected to element 53 by element 54. Element 53 converts an electrical signal with element 55 into a pneumatic signal.

The signal from element 53 is transmitted by element 52 to elements 50 and 51. Based on the input signal from element 53, element 50 can increase or decrease the amount of air flowing through element 17. Based on the input signal from element 53, element 51 can increase or decrease the amount that flows through element 24. Although this diagram illustrates a preferred embodiment, other variations for this embodiment, such as using a plurality of I to P converters, can be used and are within the scope of the present invention.

These and other advantages will be apparent from the invention contained herein. The modalities described above, the objectives and the configurations are not complete or exhaustive. As will be appreciated, other embodiments of the invention are possible with the use of one or more features set forth herein when used alone or in combination. Furthermore, this summary is not intended and should not be construed as representative of the entire scope and limit of the present invention. The present invention is set forth in various levels of detail in this summary as well as in the accompanying drawings and the detailed description is not a limitation of the scope of the present invention as it is intended to include or not include elements, components, etc. ., in this summary. Additional aspects of the present invention will become apparent from the detailed description, in particular, when

ΙΜΡϊ ^ mexican institute kSSLsS DS THE PROPERTY taken together with the drawings, and the exemplary claims WSS'ffvas ^^^ provided. '' -ί. »

EXAMPLES

Example 1: To determine the tons of sulfur emitted using an embodiment of the invention, a water tank was filled with approximately 350 barrels of acidic water, acidic water has a concentration of 10,000 (1%) of hydrogen sulfide , as tested through a bottle test described in Example 2, below. Air from an air compressor is distributed at the bottom of the tank at a stable rate of 105 scfm. The air from the vapor space in the tank is then transferred to a ventilation stack. The amount of hydrogen sulfide and sulfur in the vent stack were measured over a twelve hour period. Measurements were taken approximately every thirty minutes. Air in the vent stack measured 11.25 scf of hydrogen sulfide and 1.01 of sulfur. The air flow within the water tank was stable at 105 scfm and the concentration was recorded over time in the ventilated air. This was approximately 350 barrels of water with 1% hydrogen sulfide (in the tank vapor space tested through the bottle test). Although the air flow was manually regulated in this example, certain aspects of the process can be automated. For example, the PID loop and split valve configuration can be used.

Example 2; To determine the amount of hydrogen sulfide present

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<img file="MX357271B_D0059.tif" />

&gt; Mexican wmyro DE LA KOKEDAp) in materials subjected to treatment through certain'ffitSWáftid the Invention, a “bottle test” was conducted. ~ ΈΙ eiissiyu üln liutuHa. It involves filling a container with 50% liquid to be tested, drilling a hole in the top of the container, shaking the container for at least thirty seconds, and measuring the amount of hydrogen sulfide in the steam space with the sulfide meter. hydrogen. In this example, a 1000 ml container was used, but the container size is for illustration purposes only. The 1000 ml container was filled with 500 ml of liquid to be tested, be it oil or water. A small hole was drilled in the lid of the container. The hole in the top of the container was covered. The container was then shaken by moving the container for at least 30 seconds. A longer shaking time does not affect the results. After stirring, the vapor space was measured for the amount of hydrogen sulfide. Hydrogen sulfide can be measured with plunger type, electronic, or similar hydrogen sulfide meters. A bottle test was conducted before removing the hydrogen sulfide in accordance with the present invention, after removing the hydrogen sulfide in accordance with the present invention, but before loading the water and / or oil into the truck for disposal. transport. However, a bottle test was not carried out when there was measurable hydrogen sulfide in the air to be vented, since the hydrogen sulfide will continue to be removed by the present invention until the hydrogen sulfide concentration is below acceptable limits. Acceptable limits may include sulfur levels of

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M5MCMW INSTITUTE οείΛηόηΗΜΏ iNDWniML

<img file="MX357271B_D0060.tif" />

Hydrogen allowed by EPA to be released into the environment, safe limits established by OSHA and / or relevant regulations.

After subjecting the acidic water or the corrosive oil to the treatment with the present invention, it was found that the water or the oil, when the bottle test was carried out, had a reading below 3 ppm of hydrogen sulfide in the vapor space and that the liquids themselves had almost no hydrogen sulfide when tested with the hydrogen sulfide in test strips.

Example 3: The oil at Little Knife Field in North Dakota contained both hydrogen sulfide and sulfur. Hydrogen sulfide from the preprocess in the vapor space was measured at 10.6% or 106,000 ppm. Using a crude oil sulfur analyzer, the sulfur by weight of the pre-process measured 0.66%. After treatment with the present invention, both hydrogen sulfide and sulfur content by weight were reduced, where the hydrogen sulfide was reduced to 0% or less than 1 ppm and the process reduced sulfur by weight to 0.55% in weigh.

Example 4: The Whitney Canyon Field oil in Wyoming contained both hydrogen sulfide and sulfur. Hydrogen sulfide from the preprocess in the vapor space measured 17.4% or 174,000 ppm. Using a crude oil sulfur analyzer, the sulfur by weight of the preprocess measured 0.84%. After treatment with the present invention, both hydrogen sulfide and sulfur by weight were reduced, where the hydrogen sulfide was reduced to 0% or less than 1 ppm and the sulfur by weight was reduced to

0.51% by weight.

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