MXPA01002772A - Desulfurization process - Google Patents

Abstract

Sulfur-containing carbonaceous materials are desulfurized by reaction with a mixture of an oxidizing agent and an oxygenated solvent such as diethyl ether under alkaline conditions at a temperature preferably ranging from ambient temperature to about 250°F (121°C) and a preferred pressure of about 1 atmosphere to 2 atmospheres. The use of radiation - such as X-ray, infrared, visible, microwave, or ultraviolet radiation, alpha, beta, or gamma radiation, other atomic radiation emanating from a radioactive material, or ultrasound - facilitates desulfurization. The products of the reaction are a desulfurized carbonaceous material in which the sulfur content is (for example) less than about 1%and separated sulfur compounds.

Description

DESULFURIZATION PROCESS Field of the Invention The present invention relates generally to the removal of sulfur from carbonaceous materials contaminated with sulfur in the form of sulfur-containing compounds. In one of its more particular aspects, the present invention relates to a process for substantially reducing the sulfur content of the mineral coal. In another aspect, the present invention relates to a process for reducing the sulfur content of carbonaceous fluids such as oils and their fractions, distillates and products.

Background of the invention Many fossil fuels and other carbonaceous materials contain sulfur compounds as a contaminant. It is known that solid materials such as mineral coal and waxes contain varying amounts of sulfur. Some mineral carbons contain sulfur to such an extent that their use is contraindicated due to the polluting effect that the burning of said mineral coal with high sulfur content can have on the environment.

Crude oil oils, for example, such as crude or reduced crude residues, as well as other heavy fractions of petroleum and / or distillates, including vacuum tower bottoms, atmospheric tower bottoms, black oils, heavy cycle materials, Spills of mixed products, bitumens, and the like, are frequently contaminated by excessive concentrations of sulfur compounds. Sulfur compounds are also present in various processed hydrocarbons such as fuel oils and diesel fuels. The sulfur in the carbonaceous materials may be present in several combined forms including heteroaromatic compounds. Such compounds are difficult to desulfurize because disulfurization requires the breakage of several bonds including the relatively long bond of carbon to sulfur, CS, as well as the weakest bonds of sulfur to sulfur, SS, sulfur to oxygen, S- 0 and from sulfur to hydrogen SH. The removal of these combined forms of sulfur has proven difficult. Sulfur compounds are objectionable because the combustion of fuels containing them as contaminants results in the release of an exhaust gas or stream containing sulfur oxides, which are noxious and corrosive and present a serious problem with respect to sulfur oxides. to the pollution of the atmosphere. High sulfur oil products such as diesel fuel, other fuel oils and gasoline are also subject to the restrictions due to sulfur content, based on their impact on the environment when they are used as fuels. Several processes have been used in the past to remove objectionable sulfur-containing compounds from mineral coal and oil. U.S. Patent No. 4,548,708 issued to Schuarzer et al. On October 22, 1985, claims: "A process for the substantially complete removal of hydrogen sulfide from the organic phase of natural gas, crude oil and mixtures thereof, consisting essentially of the step of reacting, by mixing, the natural gas, the crude oil or the mixture thereof with an aqueous reagent consisting essentially of about 20 to 50% aqueous nitrogen peroxide, without the addition of catalysts or organic compounds some or compounds that produce them at an addition of at least about 90 kPa gauge, and a reaction temperature up to the decomposition temperature of hydrogen peroxide to remove w? the hydrogen sulfide from the organic phase. " HE understands that 90 kPa is approximately 0.91403. kg / cm2, which is slightly lower than atmospheric pressure. U.S. Patent 2,744,054 issued to Pieters, describes the conversion of mercaptans to disulfides in a hydrocarbon, by treatment with an aqueous hydroxide, free of oxygen and a peroxide. However, Pieters does not describe the removal of sulfur from the hydrocarbon. See also the following references. The patent North American No. 1,950,735, issued to Levine, explains the use of metallic chloride to remove sulfur. US Patent No. 3,964,994, issued to Kelly, describes the use of hydrogen peroxide to sweeten hydrocarbons. The US Patent Nos. 4,097,244 and 4,105,416, issued to Burk, Jr. and associates, describe methods to reduce the sulfur content of the mineral coal by treating it with an agent generating iron complexes and an oxidant, then heating the coal mineral and treating it with hydrogen. US Patent No. 4,121,998, issued to Frame, describes a catalytic process for sweetening a sulfur oil distillate. U.S. Patent No. 4,481,107, issued to Urban discloses the oxidation of mercaptans in a hydrocarbon fraction using an alkali metal soluble in the hydrocarbon and a metal chelating catalyst. U.S. Patent No. 5,310,479 describes the reduction of the sulfur content of crude oil by treating it with hydrogen peroxide and formic acid, and then washing the product. U.S. Patent No. 5,593,932, issued to Gillespie et al., Describes a process for sweetening a sulfurous hydrocarbon fraction using a mixture of a supported metal chelator and a solid base. In addition, solutions of sodium hydroxide or potassium hydroxide have been used to treat the boiling of petroleum fractions in a general range of less than about 700 ° F (370 ° C). Extraction has also been used with a liquid solvent, such as sulfuric acid, sulfur dioxide or ureturaldehyde, which has absorption in suitable materials, such as activated bauxite, charcoal or clay. Mercaptans have been converted into disulfides and polysulfides by treatment with plumbite or treatment with hypochlorite or copper metals. Many catalytic processes that generally use hydrogen under high pressure and temperature conditions have also been developed. The use of high pressures and temperatures to desulfurize various materials has proven to be successful to some extent in the past. But the high energy input required has required the use of specialized and costly apparatus for this purpose and has made desulfurization very expensive. It would be desirable to provide a process which is effective in removing sufficient sulfur from the mineral coal, crude oil, or petroleum fractions contaminated with sulfur-containing compounds to result in a product containing, for example, less than about 1% sulfur. Because petroleum fractions, such as heavy crudes, can contain as much as approximately 12 to 18% sulfur, this process would represent the removal of approximately 85-95% of the sulfur contaminant in said petroleum fractions. Accordingly, it is an object of the present invention to provide a process that is effective to remove a substantial proportion of the sulfur contaminating various carbonaceous materials. It is another object of the present invention to provide said process using readily available reagents. Another object of the present invention is to provide a process that can be operated at moderate temperatures and pressures. It is a further object of the present invention to provide a process for desulphurizing mineral coal, petroleum products, and other carbonaceous materials contaminated with sulfur, which process is economical to operate and requires a minimum of specialized equipment. Other objects and advantages of the present invention may be appreciated during the course of the following detailed description of the invention. • SUMMARY OF THE INVENTION The present invention performs at least one of the objects described above in whole or in part, providing a process for the removal of the sulfur from sulfur-containing compounds present in the mineral coal, petroleum, petroleum fractions. and other carbonaceous materials containing sulfur.

One aspect of the present invention is a process for removing sulfur from carbonaceous materials containing sulfur. In this aspect of the present invention, the carbonaceous material which requires the disulfurization is treated with an activated oxygen source, and with an energy source, which each reduce the sulfur content of the carbonaceous material. The source of active oxygen used in the treatment step is maintained under basic conditions effective to reduce the sulfur content of the carbonaceous material. The carbonaceous material is exposed to an energy source of a type and under effective conditions to further reduce the sulfur content of the carbonaceous material, compared to its sulfur content with the same activated oxygen treatment, but without the energy treatment. Another aspect of the present invention is also a process for removing the sulfur from carbonaceous materials containing sulfur. In this aspect of the present invention, a carbonaceous material that requires desulfurization is treated with an activated oxygen source and with a solvent having one of the following structures: (Insert formula on page 4). Where X and Z are each -O-; Y is independently selected from -0-, -0R20- or a direct link between Ri and R2; R2 is selected from oxygen or an independently selected R2 as defined below; R2 is selected from straight-chained or branched alkyl, alkenyl, or alkynyl, from 1 to 16 carbon atoms, aralkyl having a single ring or multiple-ring aryl having from 6 to 24 carbon atoms attached to an alkyl, alkenyl or straight or branched chain alkynyl as defined above; under effective basic conditions to reduce the sulfur content of the carbonaceous material. Yet another aspect of the present invention is a carbonaceous material with low sulfur content made in accordance with one of the processes described above.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention will be better understood by the following description when considered in conjunction with the accompanying drawing, in which the figure is a schematic flow diagram of a typical process according to with the present invention.

Detailed Description of the Invention The present invention relates to a process for the desulfurization of carbonaceous materials which contain compounds in which sulfur is present. The process provides means to remove the sulfur from the mineral coal, petroleum fractions, and other organic materials in which the sulfur is present in the form of various organic compounds containing sulfur. The present invention, instead of using high temperatures and pressures for the introduction of energy, requires only moderate temperatures and low pressures and takes advantage of the energy produced by an exotherm that occurs during the process. Exothermia takes place under basic conditions and requires few, if any, adjustments of temperature and pressure; rather, the reaction proceeds under relatively moderate conditions, including ambient or slightly elevated temperatures and a pressure which may be in a range of ambient or higher vacuum. In general, temperatures are used in a range of approximately 32 ° F (0 ° C) approximately 250 ° F (121 ° C). Temperatures of approximately 120 ° F (49 ° C) to 250 ° F (121 ° C) are contemplated. You can also use the room temperature. The pressures generally in a range of 5 near an absolute pressure of zero atmospheres (for example, a partial vacuum) at an ambient pressure to two atmospheres or more (gauge pressure). It has been found that an internal pressure to the environment is useful, particularly to decrease the point of (?) Effective boiling of the solvent and facilitating the extraction and removal of the solvent and the gaseous sulfur compounds The carbonaceous materials contemplated for the use of the present invention include, but are not limited to, petroleum and subtractions and other products, as identified above; ^^ bituminous mineral coal, anthracite coal, mineral coal precursors such as lignite, and fractions and other products of any of the above. More broadly, it is contemplated that any easy fuel containing sulfur can be benefited by the treatment of the present invention. In addition to fossil fuels, any organic sulfur-containing waste for use in the process of the present invention is contemplated. The desulfurization reaction is carried out • preferably in the presence of a solvent. Useful solvents include mutual hydrocarbon and water solvents, such as ethers, ketones, aldehydes, alcohols, and other relatively polar organic solvents. Suitable solvents have any of the following structures: • 10 X / \ Y R.-Z-Ra In these compounds, X and Z are independently selected from C = 0 (a carbonyl bond) and -O-, (an ether bond). Optionally, X and Z can be more specifically defined as ether bonds. And it is independently selected from -O-, -OR20- or a direct link between Ri and R2. R2 is selected from hydrogen or an independently selected R2 as defined below. R2 is selected from Straight branched alkyl, alkenyl, or alkynyl having 1 to 16 carbon atoms, for alkyl having 1 single ring or multiple rings, aryl having 6 to 24 carbon atoms attached B to the branched straight chain alkyl, alkenyl, or alkynyl as defined above. The ethers, broadly defined as any of the structures mentioned above that include one or more ether linkages, are a type of solvent contemplated for use in the process of present invention. However, to produce a convenient temperature range for the operation of the process, the ether can be a compound with a relatively low boiling point to operate under moderate conditions of temperature and pressure. The diethyl ether having a boiling point of 94.1 ° F (34.5 ° C), or isopropyl ether having a ^ Boiling point of 153.3 ° F (67.5 ° C). Other aliphatic or aromatic ethers can also be used with appropriate temperature and pressure settings. These include butyl ether, which has a boiling point of 108 ° F (42 ° C), ethyl methyl ether, which has a boiling point of 51.4 ° F (10.8 ° C), or ethyl n-butyl ether, which has a boiling point of 198 ° F (92.2 ° C). Cyclic ethers such as tetrahydrofuran, having a boiling point of 150.8 ° F (66 ° C) or dioxane having a boiling point of 214.3 ° F (101.3 ° C) can also be used. Other contemplated ethers include furan and other furans, α-pyran, β-pyran and other pyranos, 1,3,5-trioxane, s-trioxane, ethylene oxide, propylene oxide, other oxiranes and others. Suitable solvents are acetones, for example dialkyl ketones such as acetone or methyl isolutylacetone, aldehydes such as formaldehyde or acetaldehyde and alcohols such as methanol or ethanol. A solvent contemplated specifically for use in the present invention is a low boiling point mutual solvent for the carbonaceous material and the oxidation agent where it exists. For example, if the oxidizing agent is an aqueous hydrogen peroxide, and the carbonaceous material is a combustible oil, the suitable solvents are diethyl ether or acetone. The mineral carbon presents a greater problem of solubility, due to its content of substantially free carbon. However, a solvent can be used for the soluble portions of the carbon. Again, the specific solvents contemplated for the mineral coal include any of the above solvents, including acetone and diethyl ether.

As oxidation agents or active oxygen source, a peroxide such as hydrogen peroxide, or an alkali metal peroxide (eg, sodium) is contemplated. Organic peroxides such as hydroperoxide, tertiary butyl, cyclohexanone peroxide, dicumyl peroxide and the like may be used if desired. The hydrogen peroxide can be used in the form of an aqueous solution containing, for example, from about 10% to 60% hydrogen peroxide. 30% hydrogen peroxide in water is a convenient source of peroxide. Another contemplated oxidation agent that provides the active oxygen is ozone. Ozone is conventionally generated at the point of use since it is not stable. A common ozone generation equipment can be used. Free oxygen in its gaseous or dissolved form can also be used as part of or all of the oxygen. A water soluble source of active oxygen is adequate. Oil-soluble peroxides, particularly organic peroxides, can also be used. To achieve the basic conditions for the exothermic reaction to occur, a base, for example a water-soluble base, more particularly a water-soluble hydroxide, is generally used.

For this purpose, sodium hydroxide or potassium hydroxide are contemplated. Other hydroxides that may be used include ammonium hydroxide and calcium hydroxide. Basic materials that are not hydroxics such as sodium carbonate can also be used if desired. The preferred order of mixing the reagents is to add the solvent to the mineral coal or petroleum fraction, followed by the addition of a mixture of the base and an oxidizing agent. An exothermic reaction is caused and the volume of the reaction mixture expands to, as a non-limiting example, 3 to 15 times its original volume while increasing the temperature. When the process is performed under ambient conditions, the temperature increases from approximately 130 ° F (54 ° C) to approximately 150 ° F (66 ° C). During the reaction a substantial amount of gaseous product was formed, which can be recovered. After finishing the reaction, any water present can be removed by distillation or by any other oil / water separation process. Alternatively, the process can be performed with a continuous process in which reagents are continuously introduced and, if desired, heat is added to the reaction vessel. In the reaction temperatures are generally maintained in a range of about 120 ° F (49 ° C) to 250 ° F (121 ° C) during the operation of said continuous process. In a preferred embodiment of the present invention, the removal of sulfur is enhanced by the use of radiation, such as alpha radiation, beta radiation, gamma radiation, X radiation, other radiation that is the product of radioactive progressive decay, ultraviolet radiation, radiation of visible light, infrared radiation, microwave radiation, ultrasonic energy and combinations thereof. Any type and intensity and manner of application of radiation or other energy input that is effective to increase the removal of sulfur from the carbonaceous material can be used. The inventor contemplates that the effect of the radiation is to excite the molecules involved in the reaction and to facilitate the breaking of bonds to release the sulfur and / or facilitate the formation of sulfur gases, once the sulfur has been released. Its main effect may be to promote the reaction of sulfur and the activated oxygen atoms to form S-0 bonds before the activated oxygen atoms combine with one another to form 02 molecules. This theory is considered as a possible explanation for the effect of the radiation, however, and not as a requirement of the invention or any limitation of its scope. For example, x-rays having a wavelength and intensity of x-rays used in the analytical equipment can be provided to cause fluorescence of the molecules or atoms being analyzed. Other types can also be used, wavelengths and radiation intensities. The parameters of the radiation can be easily determined by one skilled in the art who knows the present invention. The main products of the reaction are a carbonaceous material, such as mineral coal, crude oil, refined petroleum or a hydrocarbon fraction, which contains less than about 1% sulfur and a mixture of gaseous products and salts that predominantly include sulfur hydrogen, but they also contain some sulfur dioxide, as well as other sulfur compounds. The gaseous and aqueous products can be easily separated from the carbonaceous material. If desired, hydrogen sulphide can be used in a Claus process for the conversion of the hydrogen sulfide content of the gaseous product to an elemental sulfur. The sulfur oxides can be recovered from the water recovered after the consumption of hydrogen peroxide, as happens by means of conventional processes of adding lime to the precipitated calcium sulfate. Calcium sulfate is gypsum, and can be used to make wallboard, plaster of Paris, and other useful products. Sulfur oxides can also be used to make sulfuric acid. The hydrogen sulfide producan also be converted into sulfur oxides by reaction with oxygen (as by burning) and then further treated as described above. The treatment can be carried out on the carbonaceous materials initially containing various amounts of sulfur, and can be carried out in different degrees, resulting in different amounts of residual sulfur in the treated carbonaceous material. As an example, the elemental carbonaceous material can be classified as a high sulfur content fuel, and the carbonaceous material treated can be classified as a fuel with a low sulfur content, in accordance with the standards of the Environmental Protection Agency of the EU (EPA). Generally effective as of January 2000 (except where deviations are allowed), reducing by half the amount of sulfur that fuels can contain. Alternatively, the fuel with low sulfur content may be a fuel that meets current European standards that require that the fuel not contain more than about 0.05% elemental sulfur. The degree of treatment can also be expressed in terms of the initial sulfur against the residual sulfur. For example, the carbonaceous material as provided may contain at least about 2% by weight of sulfur (expressed as a weight percentage of elemental sulfur unless otherwise indicated in this description); alternatively, at least about 3% sulfur; alternatively, at least about 4% sulfur; alternatively, at least about 5% sulfur; alternatively, at least about 6% sulfur; alternatively, at least about 7% sulfur; alternatively, at least about 8% sulfur; alternatively, at least about 9% sulfur; alternatively, at least about 10% sulfur; alternatively, at least about 11% sulfur; alternatively, at least about 12% sulfur. The carbonaceous material after the contacting step may contain less than about 1% by weight of sulfur; alternatively less than about 0.9% by weight of sulfur; alternatively less than about 0.8% by weight of sulfur; alternatively less than about 0.7% by weight of sulfur; alternatively less than about 0.6% by weight of sulfur; alternatively less than about 0.5% by weight of sulfur; alternatively less than about 0.4% by weight of sulfur; alternatively less than about 0.3% by weight of sulfur; alternatively less than about 0.2% by weight of sulfur; alternatively less than about 0.1% by weight of sulfur; alternatively no more than about 0.05% sulfur; alternatively less than about 0.05% sulfur; alternatively less than about 0.04% sulfur; alternatively less than about 0.03% sulfur; alternatively less than about 0.02% sulfur; alternatively less than about 0.01% sulfur; alternatively less than about 0.005% sulfur. A person skilled in the art can easily determine how much to reduce the sulfur content, or how much can be reduced within the scope of the present invention. This can be done by optimizing the process conditions. In the following description of the process of the carbonaceous material to be desulfurized it will be exemplified as a fraction of petroleum, or basic crude oil. However, it should be understood that the process is applicable in a manner similar to mineral coal, or carbon pastes as well as other solid and liquid carbonaceous materials. The modifications necessary for the process to process the mineral carbon pastes will be obvious to a person skilled in the art. For example, water does not need to be separated from the mineral coal paste before it is transported to a burner that uses an aqueous mineral coal paste directly as fuel.

Returning now to the drawing, a tank identified by the reference number 10 is used to store the fraction of petroleum or crude oil (or alternatively another carbonaceous material, preferably a liquid material such as a mineral coal paste in water, or a powder of mineral coal transported through the air). This carbonaceous material is introduced into a mixing vessel 16 through a conduit 12 and a pump 14. A diethylether or other solvent from a storage tank 18 is introduced into the mixing vessel 16 through the conduit 20 and a pump 22 A mixture of the carbonaceous material and the solvent of the mixing vessel 16 is introduced into a pump mixer vessel 30 through the conduits 24 and 26 and a pump 28. Sodium hydroxide or other base of the storage tank is introduced. 32, either in solid form or as a concentrated aqueous solution within a non-moving mixer 40 through conduits 34, 36 and a pump 38. Hydrogen peroxide or other oxidizing agent, optionally dissolved in water from a tank, is introduced. of storage 42 within the non-moving mixer 40 through the conduits 34, 44 and a pump 46.

A mixture of the base and the oxidizing agent of the non-moving mixer 40 is mixed with a mixture of the carbonaceous material and the solvent of the mixing vessel 16 through a conduit 48. The mixture is introduced into the pump mixer 30 through of a conduit 24. The mixture of the carbonaceous material, the solvent, the sodium hydroxide, the base and the oxidizing agent is introduced into a reactor-separator 52 through the conduit 50. After the reaction, the gases and the organic fractions low boiling point, including the light oils, are vaporized and leave the reactor-separator 52. These gases and low-boiling fractions are introduced into a reflux condenser 56 through a duct 54. The sulfur gases can not be condensed are introduced into a dehydrating container 60 through the conduit 58 and flow to a Claus plant, a sulfuric acid production plant and / or a processing plant lime through a conduit 62. The condenser is removed through conduit 64, recycled to reactor-separator 52 through conduit 66, and recycled to mixing vessel 16 through conduit 68. The light oil product is removed from the reactor-separator 52 through a duct 70, cooled in a light oil product cooler 72 and passed to storage through a duct 74. The resulting water, and the higher desulphurized boiling oils descend to the bottom of the separator reactor 52, where they are removed through a conduit 76 and introduced into a crude product cooler 78. The cooled product is removed from the raw product cooler 78 through a conduit 80 and separated from the water and the salt in an oil-water separator 82. The desulfurized crude product is removed from the oil-water separator 82 through a conduit 84 and passed to storage. The water and salt are removed from the oil-water separator 82 through a conduit 86 and passed to the waste water treatment. A steam-heated reboiler 88 reheats a portion of the product stream from the bottom of the reactor-separator 52 expelled through conduits 90 and 92. The main products of the exothermic reaction are desulfurized carbonaceous materials containing less than about 1. % sulfur, sulfur-containing gases, sulfur-containing salts, for example, hydrogen sulfide, sulfur dioxide and carbonyl sulfide. If radiation is going to be introduced to further remove sulfur, it can be provided in several points in the production process. For example, with reference to the figure, the pump mixer 30 can be provided with an x-ray source 90, so that the reaction mixture is irradiated as the components are mixed together initially. The inventor contemplates that the reaction mixture can also be irradiated by means of suitable equipment associated with the conduit 50 or the reactor-separator 52, or in a separate container adapted for that purpose. The inventor contemplates that the radiation can be introduced while the reaction is still occurring after the addition of the mixture of a base and an oxidizing agent to the • mineral coal loaded with solvent or petroleum fraction. The inventor has a theory that this The way to supply the radiation will facilitate the formation and release of the sulfur gases by improving the contact of the sulfur released with the oxygen atoms before the sulfur can have a secondary reaction and re-attacking the sulfur gases. hydrocarbon or other carbonaceous material, and before the sulfur atom released stabilizes to form molecules 02. This theory is considered a possible explanation of the effect of radiation, however, it is not a requirement of the invention or any limitation of its reach. The mineral coal can be treated using the reagents in a similar order. Conveniently, the mineral coal can be used in the form of a paste in water, and is often supplied to the boilers of electric power plants and other combustors operated by coal. In addition, it is anticipated that the present invention can be used in combination with other processes of physical cleaning of the mineral coal including, but not limited to the washing of the mineral coal. As the initial reagent is soluble in water, water can be used to lower the reagent's costs in the reduction of sulfur from the mineral coal. This description of a suitable apparatus and reaction process is only an example of the wide range of apparatuses and processes that can be easily conceived and used by a person skilled in the technique of desulfurization of the carbonaceous material.

The present invention is exemplified as follows: EXAMPLE 1 50 ml were mixed. of heavy California crude oil with 10 ml. of anhydrous diethyl ether in a 600 ml beaker. on a stirring plate with a remover button, which was used throughout the process to remove the contents of the 600 ml beaker. No heat was added, apart from the inherent heat of the reaction and dissolution. 15 buttons of sodium hydroxide were added (4.49 grams) to 15 ml. of 30% hydrogen peroxide in a 100 ml beaker. This mixture in the 100 ml beaker was swirled by hand until the buttons were completely dissolved. At the height of this reaction, when it was easy to boil, mix the beaker of 100 ml. was added to the 600 ml beaker mixture. There was extreme exothermia in the dissolution of the sodium hydroxide buttons in the hydrogen peroxide, (to the point that the 100 ml beaker could not be maintained without isolation, and could not be emptied into the beaker. 600 ml precipitation).

The mixture of hydroxide and peroxide was added to the crude oil plus the mixture of diethyl ether. The combined mixture was reacted to expand it beyond the top of the glass of precipitation of 600 ml. and would have spilled except for a funnel attached to a vacuum which was placed on top of the beaker to remove the gases that were formed. In a period of less than one minute, the reaction decreased in size but continued to release gases with the formation of relatively large gas bubbles. The reaction continued and at 35 minutes the reaction mixture was poured into two vials. The vial A was capped while the vial B was left open.

EXAMPLE 2: A sample was immediately packaged from vial A and analyzed by x-ray fluorescence using a Oxford Lab X 3000 analyzer. The analysis immediately showed 1.41% sulfur, and then showed rapid decreases in sulfur content in four additional analyzes used to create an average reading. The four subsequent measurements each decreased until the fifth showed a content of 0.76% sulfur after less than 8 minutes. A second analysis was carried out immediately after finishing the first one and showed an additional decrease, but at a much slower rate, decreasing from 0.68% to 0.66%. The results are illustrated in table 1.

TABLE 1 RESULTS OF THE ANALYSIS-VIAL 1 (B 10 Time of treatment elapsed, minutes% Sulfur 0 (before the reaction or radiation) 2.69 35 (reaction and radiation) 1.41 42 (reaction and radiation) 0.66 15 1089 (reaction and radiation) (-18 hours) 0.72 1403 (reaction and radiation) (~ 23 hours) 0.67 • EXAMPLE 3 Substantial degassing continued in vial 20 B, which was left uncovered. It continued to the point of overflow in a small tray that had been placed below the vial to capture the overflow. The next morning, about a third of the amount contained in the vial had been spilled on the tray. A sample was taken and tested on the Oxford Lab X 3000 analyzer. The results are illustrated in Table 2.

TABLE 2 RESULTS OF THE ANALYSIS-VIAL B Elapsed time, minutes% Sulfur 0 (before the reaction or radiation) 2.69 1180 (zero radiation time) 2.22 1331 0.87 1354 0.76 1405 0.67 The sulfur content of the initial test (after reacting overnight without radiation analysis) was 2.22%, as illustrated in the Table above. The sulfur content decreased to 2.13% by the end of five consecutive analyzes, resulting in an average of 2.18%. When the sulfur content in the sample was tested again 151 minutes after the first introduction of x-rays (total elapsed time since the start of the reaction: 1331 minutes), the sulfur content had dropped to 0.87%. When tested 174 minutes after the first introduction of x-rays, (total time elapsed since the start of the reaction: 1354 minutes), the sulfur content had decreased to 0.76%. When tested 225 minutes after the first introduction of x-rays (total time 5 elapsed since the start of the reaction: 1405 minutes), the sulfur content had fallen to 0.67%. The crude oil used in Example 1 and Example 2, has been obtained in both cases from the same source, and was exposed to the same reagents. He Example 2 had decreased only the sulfur content of the untreated California heavy crude from 2.69% to 2.22% after 1180 minutes. After exposure to radiation during the analysis, it decreased to 0.76% in an additional period of 174 minutes . The inventor has a theory to explain why the decrease in sulfur content quickly when the sample was analyzed. The theory is that irradiation of the sample with x-radiation in the course of the analysis broke the sulfur bonds already weakened by the hydroxide-peroxide reaction and mobilized the sulfur atoms and / or activated oxygen of the peroxide, to induce an additional reaction between them, mobilized the transfer of the reaction products containing sulfur to the aqueous phase of the system. This theory is considered as a possible explanation of the effect of radiation, however, it is not considered as a requirement flB of the present invention or any limitation of its reach.

EXAMPLE 4 50 mL of finely divided mineral coal in water are mixed with 10 mL of diethyl ether in a β-cup? 10 of precipitation of 600 mL in a stir plate with a stirrer button, which is used throughout the process to stir the contents of the 600 mL beaker. No heat was added apart from the inherent heat of the reaction and dissolution. 15 15 sodium hydroxide buttons were added (4.49 grams) at 15 mL of hydrogen peroxide % in a 100 mL beaker. This mixture • in the 100 mL beaker is shaken by hand until the buttons have dissolved completely. When ready to boil, the 100 L beaker mix is added to the 600 mL beaker mix. The combined mixture reacts, releasing gases with the formation of relatively large gas bubbles. The mineral coal paste is analyzed and found to contain less sulfur after the reaction. After the sulphurous gases and the ether are separated, the mineral coal paste was found to be suitable for use as fuel in a burner supplied with pulp mineral coal. Alternatively, the process water is separated from the mineral coal paste, slurried to remove residual salts, and then additional water is added to form a fluid paste suitable for use as fuel.

EXAMPLE 5 The process of Example 1 was essentially repeated, except that the solvent used was acetone instead of ether, and the proportions of the reactants and the solvent (all of which we refer to as reactants in Table 3) were changed. The oil sample was heavy California crude having an initial sulfur content of 2.67% by weight in each case. The results are summarized in Table 3.

Test and Sample Container Experiment Time% Sulfur Test Description Open or Closed to Remaining Analysis 1a: Nominal Reagents open 2 days 1.76% 1b: same as 1a closed 2 days 1.52% 2a: Reagent increase 1 1 day 0.70% 2b: same as 2a 2 days 0.25% 3a: Reagent increase 2 closed 2 days 1.13% 3b: same as 3a open 2 days 0.98% 4a: Reagent increase 3 closed 2 days 1.48% 4b: same as 4a open 2 days 3.85% 5a: Decrease of reagent 1 closed 2 days 2.46% 5b: same as 5a open 2 days 2.28% As illustrated in Table 3, the acetone solvent allowed desulfurization to proceed with the introduction of analytical X-rays, but the sulfur reduction was much more pronounced when the reaction mixture was analyzed two days after it was formed. This indicates that the reaction proceeded much more slowly in acetone than in ether, requiring somewhat less than a day for the sulfur content to be reduced by a percentage lower than 0.7%, compared to eight minutes using ether. The inventor has the theory that the difference between the two solvents is due to the fact that the ether-based solvent produces a less viscous reaction mixture, allowing more mobility of the reactants. This theory is considered as a possible explanation for the effects of the selection of the solvent, however, it is not considered as a requirement of the present invention or any limitation of its scope.

The above detailed description can be clearly understood since it is provided by way of illustration and example only, the spirit and scope of the present invention being limited only by the appended claims.

Claims (41)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and therefore, property is claimed as contained in the following: CLAIMS 1. A process for removing the sulfur from carbonaceous materials containing sulfur, which comprises: A provide a carbonaceous material containing sulfur; B. contacting said carbonaceous material with an active oxygen source in the presence of a base, using amounts of said active oxygen and said base effective to reduce the sulfur content of said carbonaceous material; and C. exposing said carbonaceous material to a source of energy of a type and under effective conditions to further reduce the sulfur content of said carbonaceous material.
2. 2. The process according to claim 1, wherein said carbonaceous material is a fossil fuel.
3. 3. The process according to claim 1, wherein said carbonaceous material is a petroleum product.
4. 4. The process according to claim 1, wherein said carbonaceous material is mineral coal.
5. 5. The process according to claim 1, wherein said source of active oxygen is a peroxide.
6. 6. The process according to claim 1, wherein said active oxygen source is an aqueous solution of hydrogen peroxide.
7. 7. The process according to claim 1, wherein said active oxygen source is an ozone generator.
8. 8. The process according to claim 1, wherein said base is added to said source of active oxygen.
9. 9. The process according to claim 1, wherein said contacting step is carried out by adding a base to said source of active oxygen to form a source of basic active oxygen, then combining said source of basic active oxygen with said carbonaceous material.
10. 10. The process according to claim 9, wherein said contact step is carried out combined said carbonaceous material, said basic active oxygen source, and a mutual solvent for said carbonaceous material and said basic active oxygen source.
11. 11. The process according to claim 1, wherein said contact step is carried out in the presence of a fluid having one of the following structures: X / \ * »« »\ / Y wherein X and Z are independently selected from C = 0 and -0-; Y is independently selected from X, -OR20- or a direct link between Ri and R2; Ri is selected from hydrogen or R2 independently selected as defined below; R2 is selected from straight or branched chain alkyl, alkenyl or alkynyl having from 1 to 16 carbon atoms, aralkyl having a single ring or multiple ring aryl having from 6 to 24 carbon atoms attached to alkyl, alkenyl or straight or branched chain alkynyl as defined above.
12. 12. The process according to claim 11, wherein X and Z are ether linkages.
13. 13. The process according to claim 1, wherein said contact step is carried out in the presence of a fluid selected from the group consisting of: diethyl ether, isopropyl ether, butyl ether, ethyl methyl ether, ethyl n-butyl ether, tetrahydrofuran , dioxane, furan, V-pyran, (-piran, β-trioxane, ethylene oxide, propylene oxide, acetone, methyl isobutyl ketone, formaldehyde, acetaldehyde, methanol ethanol, and combinations thereof.
14. 14. The process according to claim 1, wherein said contact step is carried out in the presence of diethyl ether.
15. 15. The process according to claim 1, wherein said base is a hydroxide.
16. 16. The process according to claim 1, wherein said base is sodium hydroxide.
17. 17. The process according to claim 1, wherein said energy is selected from the group consisting of alpha radiation, beta radiation, gamma radiation, X radiation, ultraviolet radiation, visible light radiation, infrared radiation, microwave radiation, radiation resulting from radioactive progressive disintegration, ultrasonic energy and combinations thereof.
18. 18. The process according to claim 1, wherein said energy comprises X-radiation.
19. 19. The process according to claim 1, wherein said energy comprises ultrasonic energy.
20. 20. The process according to claim 1, wherein said source of active oxygen is soluble in water, the step further comprising separating said carbonaceous material from said active oxygen source after the contacting step.
21. 21. The process according to claim 1, wherein said contacting step generates a gas containing sulfur, further comprising the separation step of said sulfur-containing gas from said carbonaceous material.
22. 22. The process according to claim 21, which further comprises the step of extracting the elemental sulfur from said sulfur-containing gas.
23. 23. The process according to claim 21, which additionally comprises the step of oxidation of said sulfur-containing gas to form sulfur oxides.
24. 24. The process according to claim 23, which additionally comprises the passage of the reaction of said sulfur oxides with lime, forming calcium sulfate.
25. 25. The process in accordance with the ^. Claim 1, wherein said carbonaceous material as provided is classified as a fuel with high sulfur content, and said carbonaceous material after said contacting step is classified as a fuel with low sulfur content.
26. 26. The process according to claim 1, wherein said carbonaceous material as it is provided contains at least 20 about 2% by weight of elemental sulfur, and said carbonaceous material after said contact step contains less than about 1% by weight of sulfur.
27. 27. The process according to claim 1, wherein said carbonaceous material as provided contains at least about 2% by weight of elemental sulfur, and said carbonaceous material after said contacting step contains less than about 0.5. % by weight of sulfur.
28. 28. The process according to claim 1, wherein said carbonaceous material as provided contains at least about 1% by weight of elemental sulfur, and said carbonaceous material after said contacting step contains less than about 0.5% in weight of sulfur.
29. 29. The process according to claim 1, wherein said contacting step is carried out at a temperature between about 32 ° F (0 ° C) and about 250 ° F (121 ° C).
30. 30. The process according to claim 1, wherein said contacting step is carried out at a pressure of about 0.1 atmospheres to about 2 atmospheres.
31. 31. A process for removing sulfur from carbonaceous materials containing sulfur, which comprises: A. providing a carbonaceous material containing sulfur; and B. contacting said carbonaceous material with an active oxygen source, a base, and a solvent under conditions effective to reduce the sulfur content of said carbonaceous material; said solvent having one of the following structures: X / \ RiRa \ / Y and wherein X and Z are each -0-; And it is independently selected from -O-, -OR20-, or a direct link between Ri and R2; Ri is selected from hydrogen or an independently selected R2 as defined below; R2 is selected from alkyl, alkenyl 0 alkynyl straight or branched chain that has 1 to 16 carbon atoms, aralkyl having a single ring or multiple ring aryl having from 6 to 24 carbon atoms attached to straight or branched chain alkyl, alkenyl or alkynyl as defined above.
32. 32. The process according to claim 31, wherein said solvent is an aliphatic ether.
33. 33. The process according to claim 31, wherein said solvent is diethyl ether.
34. 34. A carbonaceous material with reduced sulfur produced by means of the process according to claim 1.
35. 35. A carbonaceous material with reduced sulfur content made by the process according to claim 31.
36. 36. A treated heavy California crude oil having a sulfur content of less than about 1% by weight.
37. 37. A treated heavy California crude oil having a sulfur content of less than about 0.5% by weight.
38. 38. The process according to claim 1, wherein said energy comprises ultraviolet radiation.
39. 39. The process according to claim 1, wherein said energy comprises a visible light radiation.
40. 40. The process according to claim 1, wherein said energy comprises microwave radiation.
41. 41. The process according to claim 1, wherein said energy comprises the radiation resulting from the radioactive progressive disintegration.