MXPA99001729A - Process and composition for increasing the reactivity of sulfur scavenging iron oxides - Google Patents

Abstract

In ridding fluids, including hydrocarbon fluids, both gaseous and liquid, of sulfur compounds including hydrogen sulfide, oxides of sulfur, and thiols, the present invention uses a small quantity of an activator, generally a noble metal oxide, preferably a copper oxide, along with a known oxide product such as iron oxide to thoroughly remove sulfur contaminants in a short amount of time. The activator allows for the use of smaller reactor vessels and the production of hydrocarbon fluids substantially free of sulfur products.

Description

PROCEDURE AND COMPOSITION TO INCREASE THE REACTIVITY OF IRON OXIDES SULFUR WIPERS This application claims the benefit of the provisional application of E.U.A. No. 60 / 024,239, filed on August 20, 1996.

FIELD OF THE INVENTION This invention relates to the activation of "Oxide products which are reactive with sulfur compounds, wherein the activated oxide products desulfurize fluids, both gases and liquids, contaminated with sulfur-containing compounds, such as hydrogen sulphide and thiols (mercaptans). Preferably, this invention relates to improving the removal of sulfur compounds from hydrocarbon streams by adding an activator to an iron oxide product that increases the rate of reactivation of the iron oxide product with the sulfur compounds present in hydrocarbon streams. .

BACKGROUND OF THE INVENTION Oxides, particularly iron oxides, supported on inert particulate matter, have been used for a long time in packed flow bed processes to react with, and sweep, hydrogen sulfide and thiols (mercaptans) present in natural gases. liquid hydrocarbons. Reactions between oxides and sulfides have traditionally been relatively slow, in comparison with other systems of sulfur removal or gas desulphurisation. Due to the slow reaction rate, large beds of iron oxide contained in large reactor vessels have been required to adequately remove hydrogen sulphide and thiols from the hydrocarbon fluids. The larger reaction vessels allow for longer contact times between the oxides and the sulfur compounds, with longer contact times being necessary to adequately remove the sulfur compounds. An advantage that somewhat compensates for the slowness and size requirements of iron oxide beds, is that the iron oxide bed material that was reacted can be discarded as a nontoxic waste, unlike some other water treatment methods. Sulfur removal that requires toxic waste disposal systems. Common products based on iron oxide designed to remove sulfur compounds from gas or steam streams have performance limitations. An example of such performance limitation refers to the minimum residence time of the gas or hydrocarbon fluid in the vessel of a reactor, since the residence time required by the gas in the vessel limits the space and the practical size of the vessel in the vessel. some cases. The minimum time of exposure or retention of gas in low pressure iron oxide beds typically ranges from about 1 to about 1.3 minutes, based on the amount of unoccupied bed space and the actual gas volume. Thus, large diameter beds and containers are commonly required for efficient design common in low pressure iron oxide bed applications. Large diameter containers are also required in high pressure oxide processes and, like low pressure iron oxide beds, are • very expensive. Due to the prolonged gas retention time, it is difficult to adapt container sizes in applications of "small footprint", such as limited space plant facilities or offshore drilling. Consequently, there is a problem because small vessel sizes can not be used to desulfurize hydrocarbon fluids, which means that certain facilities do not have access to packed bed iron oxide processes. Due to the limited space, it would be convenient to have an iron oxide bed that requires less space and still has the capacity to desulfurize hydrocarbon fluids. Unforeseen increases in gas volumes and incoming hydrogen sulfide levels, beyond the design capacity of normal iron beds, cause underutilization of iron oxide product and excessive costs. Iron oxide systems that are appropriately designed from the outset may experience increased gas flow and / or higher levels of hydrogen sulfide that significantly exceed the normal design conditions, resulting in inefficient utilization of the products of the product. type of iron oxide, and substantially higher operating costs. Because unforeseen increases in volume often occur, it is convenient to have a product and procedure that allows handling volume increases without discarding the iron oxide product. An additional problem involves fluids, gas and liquid * of hydrocarbons that are less than fully saturated with water, since unsaturated hydrocarbon fluids require long contact times to effectively remove hydrogen sulfide. Likewise, systems designed for water-saturated conditions operate inefficiently when the fluid is not saturated with water. Natural gas and steam, as well as liquid hydrocarbon streams that are less than fully saturated with water, will result in a reduced removal efficiency of hydrogen sulfide through the iron oxide product, and higher operating costs. Thus, there is a problem because the common iron oxide products are commercially efficient only in the removal of dissolved hydrogen sulfide or other sulfur compounds in hydrocarbon fluids if there is sufficient contact time and the hydrocarbon fluids are saturated. . However, it is often not practical to inject water to completely saturate the hydrocarbon fluid to achieve the normal removal of hydrogen sulphide. Consequently, it is convenient to have a system for 'Desulfurizing hydrocarbon fluids that do not require the hydrocarbon fluids to be completely saturated with water. Systems designed to control odors in vapors from wastewater treatment systems and ventilation in oil tankers, often use bellows and pressure boosters that create unsaturated gas or vapor currents, changing the physical properties 'of the hydrocarbon fluids. These operating practices can reduce the efficiency of iron oxide products that remove hydrogen sulphide and other sulfur compounds from fluids. Thus, it is convenient to have a system that can remove hydrogen sulphide and other sulfur compounds from gas and vapor streams that have constantly changing physical properties. Additionally, some systems can inject air into the hydrocarbon fluid. The injection of air, which includes oxygen, causes greater corrosion and safety problems despite the improved capacity for the removal of hydrogen sulphide. It has long been seen that the intentional and unintentional inclusion of air, including oxygen, in natural gas or steam streams increases the capacity of wood chips and other oxide products impregnated with iron oxide to react with sulfur of hydrogen. However, corrosion and safety problems increase greatly due to the presence of oxygen, which will react with the container containing the oxide product. Likewise, many natural gas agreements specifically limit the amount of oxygen in the gas, and some agreements prohibit the intentional injection of air due to problems caused downstream in gas transportation systems. The inclusion of a "non-oxidizing" stimulant or activator in the iron oxide product that improves the sulfur removal capacity, without the associated problems of organic or inorganic oxidants, such as air, would increase the use of oxide products in sulfur removal procedures. Liquid hydrocarbons commonly include dissolved hydrogen sulfide and other sulfur compounds. In some cases, the removal of hydrogen sulphide sufficiently satisfies the quality required in the product for sale for pipes and conveyors. However, often, other sulfur compounds, such as mercaptans, carbonyl sulphides and carbon disulfide, need to be removed to meet the sulfur limits and the required product quality tests before the hydrocarbons can be marketed. An improved iron oxide product that effectively removes hydrogen sulphide and other sulfur compounds to meet the sulfur limitations required in hydrocarbon fluids, would significantly increase the commercial utility of the sulfur removal procedures by iron oxide. Thus, it is convenient to have an iron oxide bed process and compositions that work in a small reactor vessel, remove sulfur compounds in a short time, remove sulfur compounds from unsaturated fluids, do not require air injection, and remove most, if not all, of the sulfur compounds in a fluid, particularly a hydrocarbon fluid. As will be seen, the present invention activates the process and oxide bed composition to meet the above criteria.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to the use of an activator in an oxide product that reacts with sulfur compounds. The activator increases the reactivity rate of the oxide product with sulfur compounds contained in fluids. Preferably, the activator will have an electropotential greater than the oxide product, so that when the activator is coupled with the oxide product, the coupling will result in an increase in the reactivity of the oxide product with sulfur compounds contained in fluids. Additionally, when the oxide product and the activator are coupled, the oxide product can remove sulfur compounds, including sulfur oxides, hydrogen sulfide and thiols, from fluids including saturated and unsaturated fluids, as well as liquids, gases, or 'a combination of these, and not just hydrocarbon fluids. Typically, the activator is a noble metal oxide, and the oxide product is an iron oxide product. One of the most preferred embodiments of the activator includes the use of small amounts of copper oxide, either cuprous or cupric, added to a conventionally made sulphide reactive oxide bed, such as an iron oxide bed. An example of said iron oxide bed used for the removal of hydrogen sulfide is found in the patent of E.U.A. 5,320,992. The copper oxide activator reacts with the iron oxide product in the iron oxide bed to increase the reactivity rate of the iron oxide product with sulfur compounds present in fluids, including hydrocarbon fluids. The increased reactivity of the iron oxide product caused by the copper oxide activator results in the completion of the removal reaction of the sulfur compound in less than half the time of a normal sulfur removal reaction, making it feasible the use of iron oxide beds equal to half, or less, in volume, than conventional beds. It is thought that this unexpected result is due to the substantially higher electropotential of the copper oxides, compared to that of the iron oxides. Additionally, the use of limited quantities of copper oxide activator will prevent the spent bed from being considered a hazardous waste by standards promulgated by the Evironmental Protection Agency. In accordance with another aspect of the present invention, even when fluids contaminated with hydrogen sulfide include thiols, mercaptans in particular, offensive odors are completely eliminated along with a • reduction of the total sulfur content to acceptable levels by commercial buyers. Another aspect of the invention is that the hydrocarbon fluids do not have to be saturated so that the oxide product, coupled with an activator, has to adequately remove thiols (mercaptans). Because the activator of the invention effectively increases the rate of reactivity of oxide products, this invention results in the improvement in the use of disposable oxide products for the removal of sulfur compounds from natural gas and vapors and others. hydrocarbon liquids. Thus, the present invention is convenient because it allows an oxide product to be contained in a small reactor vessel, as well as the removal of sulfur compounds in a short time, the removal of sulfur compounds from fluids of unsaturated hydrocarbons, the non-inclusion of air, and the complete removal of sulfur compounds from fluids.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an X-ray diffraction reading showing the presence of copper oxide after hydrogen sulfide has passed through an iron oxide product.

DESCRIPTION OF THE PREFERRED MODALITIES In accordance with the present invention, an activation method and composition are provided to increase the reactivity of oxide products, preferably iron oxide products, with sulfur compounds in contaminated fluids, including gases, liquids, or a combination thereof, resulting in removal of the sulfur compounds of the fluids. Oxide products that react with sulfur compounds are also known as sulphide reactive oxides. The process is initiated by adding an activator composition, preferably a noble metal oxide, to the iron oxide product, preferably a packed bed iron oxide product. The noble metal oxide activator will react with the iron oxide product to increase the reactivity of the iron oxide product with sulfur compounds. The reaction between the activator and the iron oxide product causes the iron oxide product to react more readily with sulfur compounds, such as thiols, sulfur oxides and hydrogen sulfide (H2S), resulting in the removal of the sulfur compounds of various fluids. Preferably, the sulfur compounds are removed from the hydrocarbon fluids, so that after the removal of said compounds, the hydrocarbon fluids can be used for commercial purposes. The process, as already noted, involves the addition of an activator to an iron oxide product reactive with sulfur compounds, wherein the activator reacts with, and activates, the iron oxide product. The activator increases the reactivity of the iron oxide product with sulfur compounds that may be present in hydrocarbon fluids. The activator can be selected from noble metal oxides, which include, but are not limited to, platinum oxide, gold oxide, silver oxide, copper oxide, cadmium oxide, nickel oxide, palladium oxide, lead oxide, mercury oxide, tin oxide and cobalt oxide. In addition to the noble metal oxides, alloys made of noble metals can also be used. The most preferred noble metal oxide is copper oxide, whether cuprous or cupric oxide. In the same way, a combination of cuprous oxide and cupric oxide can be used. Regardless of the selected noble metal oxide, the activator is designed to increase the efficiency of fluid treatment with known iron oxide products. The activator causes a greater reactivity in the iron oxide product because it has a higher electropotential than the iron oxide product, the different electropotential causing bimetallic coupling between the activator, copper oxide for example, and the oxide product of iron. This bimetallic coupling results in an increased reaction rate between the iron oxide product and the sulfur compounds - present in fluids, in particular hydrocarbon fluids. The activator makes the iron oxide more reactive by increasing the corrosion rate of the iron oxide, which causes a greater reactivity between the iron oxide product and the sulfur compounds. Essentially, the activator causes the iron oxide to react with the sulfur compounds before the activator reacts with said compounds. More specifically, although it is known that copper oxide reacts rapidly with hydrogen sulfide, this reaction occurs after the reaction of activated iron oxide with hydrogen sulfide, and the reaction between copper oxide and hydrogen sulfide. It continues for much longer than the activator concentration can allow. This is demonstrated in Figure 1, which shows the presence of copper oxide in an iron oxide, after the sulfur compounds have passed through, and reacted with, the iron oxide bed. The presence of copper oxide is shown in Figure 1 by line 6, with Figure 1 being an X-ray diffraction reading taken after the "activated iron oxide" product had removed the hydrogen sulfide from the gaseous hydrocarbon. In particular, Figure 1 shows that copper oxide activated the iron oxide to react first, since the amount of hydrogen sulfide that was passed through the iron oxide bed was equal to eight (8) times more hydrogen sulfide than would be necessary to exhaust the copper oxide present in the - bed of iron oxide. Because copper oxide did not react completely with hydrogen sulfide, this indicates that iron oxide reacted with hydrogen sulfide before copper oxide. In addition to coupling with iron oxides and activating them, the activator can be used to activate other oxides. The other oxides, besides iron oxide, are oxides that have a lower electropotential than the activator. An amount of activator equal to less than 1% by total weight of the iron oxide product is sufficient to increase the reactivity of the iron oxide product with the sulfur thickened. Thus, the addition of a small amount of activator, such as copper oxide, in combination with an iron oxide product, results in a faster reaction with hydrogen sulphide, thiols (mercaptans) and other sulfur compounds, including carbonyl sulfide and carbon disulfides. In addition to increasing the reactivity of the iron oxide product, copper oxides are preferred because they can be easily obtained and meet the current environmental standards promulgated by the Environmental Protection Agency. Finally, the dependence of gas or steam streams fully saturated with water for the efficient removal of sulfur is not necessary, due to the higher reaction rates caused by the activator of this invention. The use of copper oxide as an activator is also - convenient because it does not generally corrode the reactor vessel. When unprotected mild steel equipment, such as reactor vessels that house iron oxide beds, is exposed to copper ions, corrosion of the steel may occur. However, because a relatively small amount of noble metal oxide, preferably copper oxide, is used, the reactor vessel is not significantly corroded. The corrosion rates of the reactor vessel are not significantly higher than the common iron oxide products due to the minimal presence of copper ions that cause high corrosion rates. The oxide product that reacts with the sulfur is also known as sulfur reactive oxide, and is selected from a group of metal oxide having a lower electropotential than the activator. Typically, the oxide product is a. iron oxide product which may be Fe2? 3, Fe3? 4, or a combination thereof. An alternative to the iron oxide product is a zinc oxide * product. Normally, the iron oxide product is combined with an inert bed material to form an iron oxide bed which is housed in a reactor vessel.; however, it is not necessary to combine the iron oxide product with the material of the inert bed or to make some other variant. When the iron oxide bed is made of an inert vehicle material, the iron oxide product is • fixed to the inert vehicle material that holds the iron oxide product in place when it comes into contact with hydrocarbon fluids. Preferably, the inert carrier is a calcined montmorillonite vehicle which is convenient because it is not hazardous, and is stable, reliable and easy to clean. Instead of an inert vehicle, the iron oxide product can be combined with other vehicles such as water. After the iron oxide product and the vehicle have been reacted with sulfur compounds, the reactive iron oxide product remains stable and is non-hazardous, in accordance with currently enacted State and Environmental Protection Agency standards. When activated, the iron oxide product reacts with sulfur compounds to remove sulfur compounds from fluids, including gases, liquids, vapors, and combinations thereof, as well as fluids not fully saturated. The activated iron oxide product can remove sulfur compounds from fluids including air streams, carbon dioxide streams, gas 'nitrogen, and gaseous hydrocarbons, liquids, and combinations thereof. Sulfur compounds that are removed from fluids include, but are not limited to, thiols (mercaptans) of C ?. to C3, hydrogen sulfide, carbon disulfides, carbonyl sulphide and other sulfur oxides. The preferred composition of the iron oxide bed containing the activator is formed from a carrier of from about 0% to about 77% by weight of the total composition of the iron oxide bed, and more preferably about 59% by weight. about 76.8% by weight. An iron oxide product amount is added to the iron oxide bed composition equal to from about 3% to about 30% by weight of the total composition of the iron oxide bed, and more preferably equal to about 5% to about 22% by weight of the total composition of the iron oxide bed. An amount of water can be added to the iron oxide bed composition ranging from about 0% to about 80% by weight of the total composition of the iron oxide bed, and more preferably about 18% by weight of the total composition of the iron oxide bed. Finally, an activator, preferably copper oxide, is added to the composition of the iron oxide bed in an equal amount of from about 125% to about 5% by weight of the total composition of the iron oxide bed. Preferably, the activator is used in an amount equal to about .25% to about 2% by weight of the total composition of the iron oxide bed. Larger amounts of the activator, greater than 5% by weight, can be used; however, it is more preferable to use an amount of activator equal to about 1% by weight of the total composition of the iron oxide bed. An alternative embodiment would include an amount of iron oxide product equal to about 95% to about 99.875% by weight of the • total composition of the iron oxide bed in combination with an amount of activator equal to about .125% to about 2% by weight of the total composition of the iron oxide bed. Another embodiment will include the use of water as the primary carrier, the water being added in an amount equal to about 50% to about 80% by weight of the total composition of the iron oxide bed, an amount of iron oxide product added. water in an amount equal to about 5% to about 22% by weight of the composition of the iron oxide bed, and an activator added to the water and to the iron oxide product equal to about .125% to about 5%. % by weight of the total composition of the iron oxide bed. The preferred combination of activator: iron oxide product is equal to about 1 part by weight of activator: from about 10 to about 50 parts by weight of iron oxide product. It should be mentioned that the amount of activator required is comparatively small when analyzed in view of the oxide product. This is because a comparatively small amount of activator is required to increase the reactivity of the iron oxide product or other oxide products. It should further be noted that the presence of oxygen in the fluid containing sulfur compounds further increases the electropotential difference between the oxide product and the activator. A) YesEven smaller containers with dramatically shorter contact times are possible to control the applications and systems for removing hydrogen sulphide with naturally occurring vapors, or with the deliberate addition of air, which may include oxygen. To better illustrate the present invention, the following examples are given. However, it should be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

EXAMPLE 1 As will be shown in the following example, smaller reactor vessels can be used for the removal of hydrogen sulphide and other sulfur species, including thiols (mercaptans), from gaseous and liquid hydrocarbons, by the addition of a small amount of copper oxide activator to a reaction bed based on iron oxide contained in a steel reactor vessel. Gaseous hydrocarbon samples were filtered in a reactor vessel that was 2.44 m in length and 5.08 cm in diameter. The vessel contained 4.54 kg of an experimental iron oxide mixture, which contained approximately 2.68 kg of an inert carrier, the vehicle being a calcined montmorillonite vehicle, an amount of iron oxide powder equal to approximately .97 kg, and an amount of water equal to approximately 0.86 kg. Five (5) batches of the iron oxide mixture were obtained, so that five (5) different tests could be carried out in the reactor vessel. Each of the five tests started by passing nitrogen / gaseous carbon dioxide contaminated with hydrogen sulphide, followed by the amount of hydrogen sulfide contained in the contaminated gas, through the mixture of iron oxide contained in the container of reactor. In three of the tests, copper oxide was added to the iron oxide mixture, the amount of which is given below. In two of the tests no copper oxide was added to the iron oxide mixture. Similarly, the tests were carried out in different amounts of hydrogen sulfide (H2S) contaminating nitrogen content / gaseous carbon dioxide. Additionally, some nitrogen / gaseous carbon dioxide samples contained oxygen, the amount of which is given below. Thus, the nitrogen / carbon dioxide samples that were tested included samples with and without oxygen. The amount of copper oxide activator added to the iron oxide bed was equal to about 1% or less by weight of the total bed composition. The actual amount of copper oxide added was about 1% by weight, or an amount equal to about 0.45 kg and about .25% by weight or about 0.011 kg. The specific parameters for each test are given below in the following table. The conditions in the reactor vessel in which the tests were carried out are the following: Test Conditions; Temperature 21.1 ° C Flow velocity of natural gas containing H2S 5.41 liters / min Pressure 0.035 kg / cm2 Bed height 2.40 m The gas was saturated with water The contact time for the gas in the test unit was approximately 50 seconds at the pressure, temperature and flow rate given above. The gas was filtered through the reactor vessel containing the iron oxide mixture. As can be seen below, a comparison was made between the removal efficiency of the iron oxide mixture without an activator, and the mixture of iron oxide with it, that is, copper oxide. The tests were also divided into nitrogen / carbon dioxide gas samples containing moderate amounts and extreme amounts of H2S. Nitrogen / gaseous carbon dioxide extremely contaminated with H2S was filtered through a mixture of iron oxide without activator, a mixture of iron oxide containing 1% by weight of activator, and a mixture of iron oxide containing. 25% by weight thereof.

The measurements were carried out by means of Sensidyne dye tubes for total mercaptans and hydrogen sulfide, manufactured by the company Sensidyne. As can be seen, in the moderately contaminated gas, the addition of a small amount of activator, i.e., copper oxide, substantially decreased the depth of the iron oxide bed required for the complete removal of the hydrogen sulfide. The iron oxide bed with an activator required .97 m less to remove the sulfur compounds, that the bed of iron oxide without it. In the extremely contaminated gas, the bed of activated iron oxide required less than half the amount of material, 1.12 m, comparatively with 2.40 m, to remove the sulfur compounds. In addition, as can be seen, a greater amount of activator increases the reactivity of iron oxide. The mixture of iron oxide • having 1% by weight of an activator added thereto required only .82 m to remove the hydrogen sulfide; while the iron oxide mixture containing .25% by weight of an activator added thereto, required less than 1.12 m to remove the hydrogen sulfide. A smaller amount of iron oxide mixture was required to remove the hydrogen sulfide from the gas extremely contaminated with H2S, compared to gas moderately contaminated with it. The reason that there was a better removal of the gas with extreme contamination by hydrogen sulfide, comparatively with the gas with moderate contamination by it, was the addition of oxygen to the gas. This shows that oxygen further increases the reactivity of the iron oxide product when an activator is added thereto. It should be noted that the addition of oxygen did not increase the reactivity of the iron oxide product without activator.

Thus, the above examples demonstrate that the use of an activator results in the possibility of using a smaller bed and container. The examples also demonstrate that the iron oxide product has increased activity when exposed to an amount of oxygen in combination with an activator.

EXAMPLE 2 The following experiment was carried out to "determine the amount of dissolved hydrogen sulphide and mercaptans removed from natural gas liquids (NGL) by an iron oxide product composition containing an activator.The removal of hydrogen sulfide and mercaptans from the gas liquid Natural is indicated by the reduction of concentrations of hydrogen sulfide and mercaptans measured in the vapor or "main space" adjacent to the liquid.Two tests were carried out on two (2) reactor vessels that were 1.22 m high. For each test, each reactor vessel contained approximately 18.16 kg of reaction material, including approximately 10.75 kg of solid inert carrier, a montmorillonite carrier, approximately 3.45 kg of water, and approximately 3.90 kg of iron oxide powder. test, approximately 0.18 kg of copper oxide was added to the reaction material, while in another test the same was not added to the reaction material.

The test conditions were the following: Natural gas liquids (NGL), 72 API (density) at 21.1 ° C. H2S untreated in the main space = > 4,000 ppm. Untreated mercaptans in the main space - the mercaptan content could not be determined due to the high levels of H2S.

Flow rate adjusted to the increasing speed in the unoccupied bed equivalent to 5.80 cm.

The measurements were carried out by means of Sensidyne dye tubes for total mercaptans and hydrogen sulfide, manufactured by the company Sensidyne. The test results, indicated by the measurements of the concentration in the main space, were the following: * The test was concluded due to the high amount of hydrogen sulfide, greater than 400 ppm, that remained in the main space of the liquid hydrocarbon. ** The negligible increase in mercaptan levels indicates that the maximum concentration has been reached.

The quality of the liquid hydrocarbon was excellent (light yellow NGL) leaving the units charged with the copper oxide activator and the iron oxide product without the need for further processing. Conversely, the iron oxide product that did not have an activator did not result in sufficient removal of hydrogen sulphide or mercaptans. Additionally, it should be noted that the iron oxide bed at the 2.44 m level did not contain any detectable sulfur compound. This means that the sulfur compounds were removed from the hydrocarbon fluid before coming into contact with the iron oxide product at the 2.44 m level. Accordingly, the use of the present invention has at least these significant advantages: the increased reactivity rate allows the use of beds of much smaller reactive materials; and, when mercaptans and / or hydrogen sulfide are present in liquid hydrocarbons, the products of the reaction are odor free and are no longer contaminated with these sulfur compounds.

EXAMPLE 3 Two reactor vessels that were 4.57 m in length were prepared, and each reactor vessel contained approximately 13.62 kg of iron oxide mixture. The iron oxide mixture contained approximately 8.06 kg of vehicle, approximately 2.58 kg of water, approximately 292.83 kg of iron oxide product, and approximately 0.0394 kg of copper oxide. The reactor vessel was connected to a source of gaseous carbon dioxide. The gaseous carbon dioxide, before passing through the reactor, was saturated with water through a continuous stream and filtered in the reactor under the following conditions: Flow rate 849.48 1 / h Temperature 21.1 ° C Pressure 28.12 kg Bed height 9.15 m H2S input 25 ppm Input mercaptans 20 ppm The incoming gas contained several other species of sulfur, in addition to mercaptans and hydrogen sulfide, sulfur compounds being more abundant methyl and ethyl sulfides and disulfides. Three samples of gaseous carbon dioxide were tested, one sample per day for 3 consecutive days, each sample passing through the iron oxide mixture in the same reactor. The sulfur components, apart from hydrogen sulphide and the mercaptans, were not removed by the iron oxide mixture. Hydrogen sulfide (H2S) and mercaptans were removed in approximately 1.52 m of the iron oxide mixture, of 9.15 m possible. The following table shows the amount of hydrogen sulphide and mercaptans entering the reactor, as well as the conditions in the reactor vessel. The following table shows the data that were collected and formulated with measurements taken by Sensidyne dye tubes for total mercaptans and hydrogen sulfide, manufactured by the Sensydine company, as well as test meters.

EXAMPLE 3 (CONTINUED) The samples tested revealed that the mixture of activated iron oxide removed the contaminants, with 1.52 m of iron oxide mixture, from the contaminated carbon dioxide streams. Specifically, it should be noted that no contaminants were detected in the second orifice or 3. 05 m. The tests showed that neither hydrogen sulfide (H2S) nor the mercaptans passed the first 4.57 m of the reactor. Thus, the mixture of iron oxide with an activator had the ability to remove hydrogen sulphide and mercaptans from carbon dioxide streams saturated with water.

EXAMPLE 4 Two reactor vessels each having 4.57 m in length were prepared, and each reactor vessel contained approximately 13.62 kg of iron oxide mixture. The iron oxide mixture contained approximately 8.06 kg of vehicle, approximately 2.58 kg of water, approximately 292.83 kg of iron oxide product, and approximately 0.0394 kg of copper oxide. The reactor vessel was connected to a gaseous carbon dioxide well. The gaseous carbon dioxide was saturated with water by 20%, and run in the reactor under the following conditions: Flow rate 849.48 1 / h Temperature 21.1 ° C Pressure 28.12 kg Bed height 9.76 m Input H2S 25 ppm Input mercaptans 20 ppm Input carbonyl sulphide .025 ppm The incoming gas contained several other species of sulfur, in addition to mercaptans, hydrogen sulfide and carbonyl sulphide, the most abundant sulfur compounds being methyl and ethyl sulfides and disulfides. Three samples of gaseous carbon dioxide were tested, one sample per day for 3 consecutive days, each sample passing through the iron oxide mixture in the same reactor. Hydrogen sulfide and mercaptans were put to the test, in addition to carbonyl sulphide. Other sulfur compounds were not removed by the iron oxide mixture, nor were they tested. The following table shows the amount of hydrogen sulphide, mercaptans and carbonyl sulfide entering the reactor, as well as the conditions in the reactor vessel. The following table shows the data that were collected and formulated with measurements taken by Sensidyne dye tubes for total mercaptans and hydrogen sulfide, manufactured by the Sensydine company, as well as test meters.

EXAMPLE 4 (CONTINUED) As can be seen, the activated iron oxide product did not remove the sulfur compounds from the gaseous carbon dioxide unsaturated with water as effectively as the sulfur compounds did from the gaseous carbon dioxide saturated with water. However, the activated iron oxide product still removed the sulfur compounds from the gaseous carbon dioxide unsaturated. Thus, a novel method and composition for the activation of oxides reactive with sulfur compounds to remove sulfur compounds from fluids has been shown and described, which will satisfy all the objectives and advantages previously sought. However, it will be apparent to those skilled in the art that many changes, variations, modifications, and other uses and applications of the method and composition are possible, and that said changes, variations, modifications, and other uses and applications are also considered. do not depart from the spirit and scope of the invention, are covered by it, which is limited only by the following claims.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. - A method for increasing the removal efficiency of sulfur compounds from fluids, characterized in that it comprises passing the fluids through a reactive oxide product with sulfur with an effective amount of an activator added to the oxide product, said activator having a electropotential greater than the oxide product, and said activator increasing the reactivity rate of the oxide product with the sulfur compounds present in the fluid.

2. - The method according to claim 1, further characterized in that said activator is selected from the group consisting of noble metal oxides.

3. - The procedure in accordance with the • claim 2, further characterized in that said noble metal oxides are selected from the group consisting of platinum oxide, gold oxide, silver oxide, copper oxide, cadmium oxide, nickel oxide, palladium oxide, lead oxide , mercury oxide, tin oxide and cobalt oxide.

4. - The method according to claim 1, further characterized in that said activator is selected from the group consisting of alloys of noble metals.

5. - The process according to claim 3, further characterized in that said copper oxides are selected from the group consisting of cupric oxide and cuprous oxide.

6. - The method according to claim 1, further characterized in that said activator is added to the oxide product in an equal amount of about 0.125% by weight to about 5% by weight of the total composition.

7. - The procedure in accordance with the - claim 1, further characterized in that said activator is added to the oxide product in a ratio equal to 1 part by weight of said activator: from about 10 to about 50 parts by weight of the oxide product.

8. A composition designed to sweep sulfur compounds in fluids, characterized in that said composition comprises an oxide product reactive with sulfur compounds, and an activation composition equal to about .125% to about 5% by weight of the composition , said activation composition having an electropotential greater than the sulfur reactive oxide product, said activation composition being selected from the group consisting of oxides of noble metals and noble metal alloys, and said activator composition increased the reactivity of the product of oxide with sulfur compounds.

9. - The composition designed to sweep sulfur compounds in fluids according to claim 8, further characterized by said noble metal oxides are selected from the group consisting of platinum oxide, gold oxide, silver oxide, copper, cadmium oxide, nickel oxide, palladium oxide, lead oxide, mercury oxide, tin oxide and cobalt oxide.

10. The composition designed to sweep sulfur compounds in fluids according to claim 9, further characterized in that said copper oxides are selected from the group consisting of cupric oxide and oxide. - Cuprous

11. An improved composition of iron oxide designed to sweep sulfur compounds present in fluids, further characterized in that said iron oxide composition comprises an iron oxide product reactive with sulfur compounds, wherein the improvement comprises adding to the iron oxide composition an activation composition in an amount equal to about .125% to about 5% by weight of the total iron oxide composition, said activation composition having an electropotential greater than the iron oxide product, said activating composition being selected from the group consisting of oxides of noble metals and noble metal alloys, and said activation composition resulting in the iron oxide composition having greater reactivity with the sulfur compounds in the fluids.

12. - A composition for activating a permeable bed made of vehicles and a reactive iron oxide, characterized in that said activation composition is selected from the group consisting of noble metal oxides and noble metal alloys, said group having an electropotential greater than the oxide of iron.

13. - A process for removing hydrogen sulfide from hydrocarbon fluids, characterized in that it involves adding an activator to an oxide, wherein said activator is coupled to the oxide to increase the speed of "Oxide reaction with sulfur.