JP2002524651A - Desulfurization process - Google Patents

Abstract

  (57) [Summary] The sulfur-containing carbonaceous material is treated with an oxidizing agent and an oxygenated solvent such as diethyl ether at a temperature in the range of room temperature to about 250 ° F. (121 ° C.) and preferably at a pressure of 1 to 2 atmospheres under alkaline conditions. Desulfurizes by reaction with the mixture. X-rays, infrared, visible, microwave or ultraviolet, alpha, beta or gamma radiation, other atomic emissions from radioactive materials, or ultrasound facilitate desulfurization. The product of the reaction is a sulfur compound separated from the desulfurized carbon material having a sulfur content (for example) of less than about 1%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[Cross Reference with Related Applications]

This application claims priority from provisional application No. 60 / 100,576, filed Sep. 16, 1998. That application is hereby incorporated by reference. Another related application is U.S. patent application Ser. No. 09 / 085,478, filed May 27, 1998, filed by Jeanblanc et al., Which is also incorporated herein by reference.

[0002]

[Federal Sponsored Research or Development Statement. ]

 Not applicable.

[0003]

BACKGROUND OF THE INVENTION

The present invention relates to removing sulfur from sulfur-contaminated carbonaceous materials, generally in the form of sulfur-containing compounds. In one of its more detailed features, the present invention provides:
It relates to a process for significantly reducing the sulfur content of coal. In another aspect, the invention relates to a process for reducing the sulfur content of carbonaceous liquids, such as petroleum and its fractions, distillates, and products.

[0004] Many fossil fuels and other carbonaceous materials contain sulfur compounds as pollutants.
Solid materials such as coal and wax are known to contain varying amounts of sulfur. Certain types of coal contain sulfur to such an extent that its use is banned to combat the environment by burning high sulfur content coal.

[0005] Examples include atmospheric distillation bottoms as well as heavy petroleum fractions and / or vacuum tower bottoms, atmospheric tower bottoms, black oil, heavy cycle stocks, bisbreaker product effluents, asphalt, etc. Petroleum crudes, such as distillates, are often contaminated with high concentrations of sulfur compounds. Sulfur compounds are also present in various processed hydrocarbons such as fuel oils and diesel fuels.

[0006] Sulfur in carbonaceous materials can exist in a variety of combined forms, including heteroaromatic compounds. Desulfurization involves weak sulfur versus sulfur, SS, sulfur
Since it is necessary to break various bonds, including the relatively strong carbon-to-sulfur bond, C--S as well as the to-oxygen, S--O and sulfur--to-hydrogen, S--H, bonds, such Compounds are difficult to desulfurize.

[0007] Removal of these combined forms of sulfur has proven difficult. Sulfur compounds are harmful because burning fuels containing these as pollutants results in emission of smoke or exhaust containing sulfur oxides that is harmful and corrosive and presents significant problems with regard to air pollution. High sulfur petroleum products, such as diesel fuel, other fuel oils, and gasoline, are also subject to sulfur content restrictions based on their atmospheric impact when they are used as fuel.

[0008] In the past, various processes have been performed to remove problematic sulfur-containing compounds from coal and petroleum. Schwa issued on October 22, 1985
No. rzer et al. No. 4,548,708 states that "at least a pressure of about 90 kPa gauge and a decomposition temperature of hydrogen peroxide are reached without the addition of any catalyst or organic compounds or compounds producing them to remove hydrogen sulfide from the organic phase. Reacting natural gas, crude oil or a mixture thereof at a reaction temperature with an aqueous reagent consisting essentially of about 20 to 50% aqueous hydrogen peroxide by reacting the natural gas, crude oil or a mixture thereof. A process for the substantially complete removal of hydrogen sulfide from the organic phase of the mixture. 90 kPa is about 13 psi
It is understood that it is slightly below atmospheric pressure.

[0009] US Patent No. to Pieters. 2,744,054 describes the conversion of mercaptans in hydrocarbons to disulfides in a process with aqueous hydroxide, free oxygen and peroxide. However, Pieters does not describe removing sulfur from hydrocarbons.

Let's look at the following literature. U.S. Patent No. to Levine. 1,950,7
No. 35 describes the use of metal chlorides to remove sulfur. Ke
U.S. Pat. No. 3,964,994 describes the use of hydrogen peroxide to sweeten hydrocarbons. U.S. Patent No. to Burk, Jr, et al. Nos. 4,097,244 and 4,105,416 describe a process for reducing the sulfur content of coal by treating the coal with an iron complexing agent and an oxidizing agent and then heating or treating the coal with hydrogen. Is disclosed. Fr
US patent no. No. 4,121,998 discloses a catalytic process for sweetening sour petroleum distillates. U.S. Patent No. to Urban. No. 4,481,107 discloses oxidizing mercaptans in a hydrocarbon cut using a hydrocarbon-soluble alkali metal compound and a metal chelate catalyst. U.S. Pat. No. 5,310,479 discloses reducing the sulfur content of crude oil by processing the crude oil with hydrogen peroxide and formic acid and then washing the product. U.S. Patent No. to Gillespie et al. 5,
593, 932 discloses a process for sweetening a sour hydrocarbon fraction using a supported metal chelate and a solids based mixture.

In addition, sodium or potassium hydroxide solutions have been used to process crude oil fractions that evaporate in the normal range below about 700 ° F. (370 ° C.).
Extraction with a liquid solvent such as sulfuric acid, sulfur dioxide, or furfural has been used, as well as adsorption on suitable materials such as activated bauxite, charcoal or activated clay. Mercaptans have been converted to disulfides and polysulfides by a plumbite process or a process with hypochlorite or copper salts. Numerous catalytic processes, usually using hydrogen under high temperature and pressure conditions, have also been developed.

In the past, the use of high pressures and temperatures to desulfurize various materials has proven to be somewhat effective. However, the high energy input required the use of special and expensive equipment to achieve this goal, making desulfurization expensive.

[0013] It is desirable to provide an effective process for removing sufficient sulfur from coal, crude oil, or petroleum fractions contaminated by sulfur-containing compounds to obtain products containing, for example, less than about 1% sulfur. Will. Like heavy crude oil, petroleum fractions
It may contain as much as 12% sulfur, and in such a petroleum fraction such a process will remove about 85-95% of the sulfur impurities.

Accordingly, one object of the present invention is to provide a process that is effective in removing a significant portion of sulfur contaminating various carbonaceous materials.

Another object of the present invention is to provide such a process that uses readily available reactants.

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 desulfurizing coal, petroleum products, and other sulfur-contaminated carbonaceous materials in which the process is economical and does not require many special equipment. Is to provide

[0018] Other objects and advantages of the present invention will become apparent from the following series of detailed descriptions and disclosures.

[0019]

SUMMARY OF THE INVENTION

According to the present invention, at least in part or at least one of the above objects is provided by providing a process for removing sulfur from sulfur-containing compounds present in coal, petroleum, petroleum fractions, and other sulfur-containing carbonaceous materials. One is achieved.

One feature of the present invention is a process for removing sulfur from a sulfur-containing carbonaceous material. In this aspect of the invention, the carbonaceous materials requiring desulfurization are processed with an active oxygen source and with an energy source, each of which reduces the sulfur content of the carbonaceous material.

The source of active oxygen used in the process steps is maintained under basic conditions effective to reduce the sulfur content of the carbonaceous material.

The carbonaceous material is exposed to one type of energy source and is effective in further reducing the sulfur content of the carbonaceous material compared to its sulfur content by the same active oxygen process but without the energy process. Under certain conditions.

Another feature of the present invention is also a process for removing sulfur from a sulfur-containing carbonaceous material. In this aspect of the invention, the carbonaceous material requiring desulfurization is processed with a source of active oxygen and a solvent having one of the following structural formulas.

Embedded image Wherein X and Z are independently selected from -O- and C = O; Y is X, it is independently selected from a direct bond between the -OR ₂ O-or R ₁ and R _2; R ₁ is Selected from hydrogen or R ₂ independently selected as described below; R ₂ is a straight or branched alkyl, alkenyl, or alkynyl having 1 to 16 carbon atoms, one or more rings, It is selected from aralkyl having an allyl having 6 to 24 carbon atoms attached to a straight or branched chain alkyl, alkenyl, or alkynyl as defined above.

Yet another feature of the present invention is a low sulfur carbonaceous material made by one of the processes described above.

The present invention is directed to a process for desulfurizing a carbonaceous material containing a compound having sulfur therein. The process provides a means for removing sulfur from coal, petroleum fractions and other organic materials in which sulfur is present as various sulfur-containing organic compounds.

The present invention does not use high temperatures and high pressures for energy input, but only requires low pressures and mild temperatures, and has the advantage of energy generated by the heat generated during the process. The exotherm occurs under basic conditions and requires little, if any, adjustment of temperature and pressure; rather, the reaction is carried out at atmospheric or slightly above atmospheric and vacuum to atmospheric or superatmospheric pressures. Proceeds under relatively mild conditions of pressure. Generally, temperatures in the range of about 32 ° F. (0 ° C.) to about 250 ° F. (121 ° C.) are used. Approximately 120 ° F (49 ° C) to 250 ° F (121 ° C)
Expected temperature. Atmospheric pressure can also be used. In general, pressures range from near zero atmosphere absolute pressure (ie, partial vacuum) to atmospheric pressure or from 2 atmospheres or more (gauge pressure). In particular, sub-atmospheric pressure has been found to be effective to lower the effective boiling point of the solvent and to facilitate removal and removal of the solvent and gaseous sulfur compounds.

[0027] The carbonaceous materials contemplated for use in the present invention include petroleum and its fractions and other products, as described above, bituminous coal, anthracite, coal precursors such as lignites and the aforementioned. There are, but are not limited to, any fractions and other products. More broadly, any fossil fuel containing sulfur would benefit from the present invention. It is contemplated that the present invention can be used with any organic residue containing sulfur in addition to fossil fuels.

The desulfurization reaction is preferably performed in the presence of a solvent. Useful solvents are common solvents for hydrocarbons and water, such as ethers, ketones, aldehydes, alcohols and other relatively polar organic solvents. Suitable solvents have any of the following structures:

Embedded image In these compounds, X and Z are independently selected from C = O (carbonyl bond) and -O- (ether bond). Optionally, X and Z may be more particularly determined as ether linkages. Y is -O -, - it is independently selected from a direct bond between the OR ₂ O-or R ₁ and R _2; R ₁ is selected from R ₂ is independently selected as hydrogen or below; R ₂ is straight-chain or branched alkyl, alkenyl, or alkynyl having 1 to 16 carbon atoms, or aralkyl having a single ring or multiple rings, straight-chain or branched-chain alkyl, alkenyl as defined above, Or allyl having 6 to 24 carbon atoms attached to alkynyl.

Ethers, broadly defined as any of the above structures having one or more ether linkages, are one type of solvent contemplated for use in the process of the present invention.
However, to provide a convenient temperature range in carrying out the process, ethers are relatively low boiling compounds and can be operated under mild conditions of temperature and pressure.
Diethyl ether having a boiling point of 94.1 ° F. (34.5 ° C.);
Isopropyl ether having a boiling point of 3 ° F. (67.5 ° C.) is suitable. Other aliphatic or aromatic ethers can also be used, with appropriate temperature and pressure adjustments. These include butyl ether having a boiling point of 108 ° F. (42 ° C.), ethyl methyl ether having a boiling point of 51.4 ° F. (10.8 ° C.), or ethyl having a boiling point of 198 ° F. (92.2 ° C.). There is n-butyl ether. 1
Cyclic ethers such as tetrahydrofuran having a boiling point of 50.8 ° F (66 ° C) or dioxane having a boiling point of 214.3 ° F (101.3 ° C) can also be used. Other possible ethers include furan and other furans, α-pyran, γ-pyran, other pyrans, 1,3,5-trioxane, s-trioxane, ethylene oxide, propylene oxide, other oxiranes, and others.

Other suitable solvents are, for example, ketones such as dialkyl ketones such as acetone or methyl isobutyl ketone, aldehydes such as formaldehyde or acetaldehyde, alcohols such as methanol or ethanol.

Particularly contemplated solvents used for the present invention are low boiling common solvents, if any, for carbonaceous materials and oxidizing reagents. For example, where the oxidizing agent is aqueous hydrogen peroxide and the carbonaceous material is fuel oil, diethyl ether or acetone are suitable solvents. Coal presents significant solubility problems due to its substantial free carbon content. However, solvents for the soluble part of the coal can be used. again,
Particularly contemplated solvents for coal include acetone and diethyl ether, and any of the above solvents.

As the oxidizing agent or the active oxygen source, a peroxide such as hydrogen peroxide or a peroxide of an alkali metal (for example, sodium) is considered. Organic peroxides such as tertiary butyl hydroperoxide, cyclohexanone peroxide, dicumyl peroxide and the like can also be used as needed. Hydrogen peroxide is, for example, 10
It can be used in the form of an aqueous solution containing from 60% to 60% of hydrogen peroxide. 30% hydrogen peroxide in water is a suitable peroxide source. Another possible oxidizing agent that generates active oxygen is ozone. Ozone is preferably produced where it is used because it is not stable. A normal ozone generator can be used. Free oxygen in gaseous or dissolved form can also be used as part or all of the oxygen. A source of active oxygen that is soluble in water is suitable. Oil-soluble peroxides, especially organic peroxides, can also be used.

To obtain the conditions under which the exothermic reaction takes place, a base, for example a water-soluble base, more particularly a water-soluble hydroxide, is generally used. Sodium or potassium hydroxide is considered for this purpose. Other hydroxides that can be used include ammonium hydroxide and calcium hydroxide. If desired, non-hydroxide basic materials such as sodium carbonate can also be used.

The preferred order of mixing of the reactants is to add the solvent to the coal or petroleum fraction followed by the addition of the base and oxidizer mixture. An exothermic reaction follows and as the temperature rises, the volume of the reaction mixture expands to 3 to 15 times its initial volume, not to limit the invention. When the process is performed at atmospheric conditions, the temperature rises from about 130 ° F. (54 ° C.) to about 150 ° F. (66 ° C.). During the reaction, a significant amount of gaseous product is formed, which is recovered. Following the end of the reaction, any water present can be removed by distillation or other oil / water separation processes.

In another method, the process involves continuously adding reactants and, if necessary,
It can also be said to be performed in a continuous process of heating the reactor. Typically,
During operation of such a continuous process, the temperature in the reaction vessel is about 120 ° F (49 ° C).
Maintained in the range of ~ 250 ° F (121 ° C).

In a preferred embodiment of the present invention, α-radiation which is the product of radioactive decay,
The use of radiation such as beta radiation, gamma radiation, X-rays and other radiation, ultraviolet radiation, visible radiation, infrared radiation, microwave radiation, ultrasonic energy, and combinations thereof enhances sulfur removal. Any type and intensity and method of use of radiation or other energy input can be used to enhance the removal of sulfur from the carbonaceous material.

The effect of radiation is to excite the molecules involved in the reaction to facilitate the breaking of bonds and release sulfur and / or to facilitate the production of sulfur gas once sulfur is released. Thinks. As before fundamental effect of forming the O ₂ molecules bound active oxygen atoms from one another, it would be to form the S-O bonds to accelerate the reaction of sulfur and active oxygen atoms. This theory appears to be a possible explanation for the effects of radiation. However, it is not essential to the present invention and does not limit the scope of the invention. For example, X-rays are used in analytical instruments and are given the wavelength and intensity of X-rays that cause the molecule or atom being analyzed to fluoresce, as well as other types, wavelengths, and intensities of radiation. Can be used for Radiation parameters can be readily determined by those skilled in the art who are aware of the present invention.

The basic products of the reaction are coal, crude oil, refined oil, containing less than about 1% sulfur,
Or a blend of carbonaceous materials such as hydrocarbon fractions, mainly gaseous products containing hydrogen sulfide and salts, but also contains some sulfur dioxide and other sulfur compounds. Gaseous and aqueous products can be easily separated from the carbonaceous material.

If desired, the hydrogen sulfide can be used in a Claus process for converting the hydrogen sulfide component of the gaseous product to elemental sulfur. Sulfur oxide can be recovered from the water recovered after the hydrogen peroxide has been exhausted, as in the conventional process of adding lime to precipitate calcium sulfate. Calcium sulfate is gypsum and can be used to make wallboard, plaster of Paris, and other useful products.
Sulfur oxide is also used to make sulfuric acid. The produced hydrogen sulfide is also converted to sulfur oxide (as by burning it) with oxygen and then processed as described above.

The treatment can be performed initially on carbonaceous materials containing various amounts of sulfur, and to different degrees, so that the amount of residual sulfur in the treated carbonaceous material is Is different. By way of example, according to the US Environmental Protection Agency (EPA) standard of halving the amount that can be present in fuels, which will become generally effective January 2000 (except for deviations allowed), the carbonaceous material supplied Can be classified as a high sulfur fuel, and the processed carbonaceous material can be classified as a low sulfur fuel. In addition, this low sulfur fuel is a fuel that can meet current European standards requiring less than about 0.05% elemental sulfur.

The degree of treatment can also be expressed in terms of initial sulfur versus residual sulfur. For example, the supplied carbonaceous material may have at least about 2% by weight sulfur (expressed as% by weight of elemental sulfur unless otherwise specified), or at least about 3% sulfur, or at least about 4% sulfur, Or at least about 5% sulfur, or at least about 6% sulfur, or at least about 7% sulfur, or at least about 8% sulfur, or at least about 9% sulfur, or at least about 10% sulfur, or at least About 1
It can include 1% sulfur, or at least about 12% sulfur.

After the contacting step, the carbonaceous material may have less than about 1% sulfur by weight, less than about 1% sulfur, or less than about 0.9% sulfur, or less than about 0.8% sulfur. , Or less than about 0.7% by weight sulfur, or less than about 0.6% by weight sulfur, or about 0.5%
Less than about 0.4% by weight sulfur, or less than about 0.3% by weight sulfur, or less than about 0.2% by weight sulfur, or less than about 0.1% by weight sulfur; Or less than about 0.05% by weight sulfur, or less than about 0.05% by weight sulfur, or less than about 0.04% by weight sulfur, or less than about 0.03% by weight sulfur, or about 0.02% by weight % Sulfur, or less than about 0.01% sulfur, or about 0% by weight.
. It can contain less than 005% by weight of sulfur. Those skilled in the art can easily determine within the scope of the present invention how much, or how much, the sulfur content can be reduced. This can be done with optimized process conditions.

In the following description of the process, a crude oil fraction or a basic crude oil is mentioned as an example of the carbonaceous material to be desulfurized. However, it will be appreciated that the process can be applied to coal or coal slurries as well as to other solid or liquid carbonaceous materials. The changes required in the process for processing coal slurries will be apparent to those skilled in the art. For example, it is not necessary to separate water from the coal slurry before transporting the aqueous coal slurry to a burner that uses it directly as a fuel.

Description will be made with reference to the drawings. The tank 10 is used to store petroleum fractions or crude oil (or other carbonaceous materials, preferably fluidized materials such as underwater slurries of coal or airborne coal powder). This carbonaceous material is put into a mixing vessel 16 through a pipe 12 and a pump 14. Diethyl ether or other solvent is introduced into the mixing vessel 16 from the storage tank 18 through tubing 20 and pump 22. The mixture of the carbonaceous material and the solvent from the mixing vessel 16 is introduced into a pump mixer vessel 30 through pipes 24 and 26 and a pump 28. Sodium hydroxide or other base from storage tank 32 is fed into a static mixer 40 through tubing 34 and 36 and pump 38 as a solid form or as a concentrated aqueous solution. Hydrogen peroxide or other oxidizing chemicals, optionally dissolved with water, are passed from storage tank 42 through piping 34 and 44 and pump 46 into static mixer 40.

The mixture of the base and the oxidizing agent from the static mixer 40 is mixed with the mixture of the carbonaceous material and the solvent from the mixing vessel 16 through the pipe 48. The mixture is pumped through a pipe 24 into a pump mixer 30. The mixture of the carbonaceous material, the solvent, the basic sodium hydroxide and the oxidant is introduced into the reaction-separation device 52 through the pipe 50.

Following the reaction, the gas containing gas oil and the low-boiling organic fraction evaporate to form a reaction-separation unit 52.
Exit. These gases and low-boiling fractions are introduced into a reflux condenser 56 through a pipe 54. The non-condensable sulfur gas is passed through line 58 into knockout pot 60 and through line 62 the Claus plant, sulfuric acid production plant, and / or
Or it flows to a lime process plant. The condensate is removed through line 64, recycled to reaction-separation device 52 through line 66, and recycled to mixing vessel 16 through line 68. The gas oil product is passed through the pipe 70 to the reaction separation device 5.
2 and is cooled by a gas oil product cooler 72 and entered into storage via line 74.

The resulting water and the desulfurized high-boiling oil fall to the bottom of the reaction-separation unit 52 where they are removed through line 76 and placed in a crude cooler 78. The cooled product is removed from crude product cooler 78 through line 80 and separated from water and salt in oil-water separator 82. The desulfurized crude product is removed from the oil-water separation device 82 through a pipe 84 and put into a storage device. Water and salt are removed from the oil-water separator 82 through line 86 and fed to a wastewater process unit. Steam heating reboiler 8
8 reheats a portion of the product stream withdrawn from the bottom of the reaction-separator 52 through pipes 90 and 92.

The basic products of the exothermic reaction are desulfurized carbonaceous materials containing less than about 1% sulfur, sulfur-containing gases, and sulfur-containing gases such as hydrogen sulfide, sulfur dioxide, and carbonyl sulfide. Salt.

If radiation is introduced to further remove sulfur, it can be provided at various points in the manufacturing process. For example, in the case shown, the pump mixer 30 can be provided with an X-ray source 90, whereby the reaction mixture is first irradiated when its components are stirred. In the present invention, the reaction mixture can also be irradiated in a suitable device attached to the pipe 50 or the reaction separation device 52 or in a separation vessel adjusted for this purpose.

It is also contemplated that radiation may be introduced after the reaction is still taking place after the mixture of base and oxidant is added to the coal or petroleum fraction dispersed in the solvent. The inventor has found that by introducing radiation in this manner, sulfur can recombine with hydrocarbons or other carbonaceous materials before a secondary bond can occur, and the released oxygen atoms stabilize to form O ₂ molecules. It is theorized that the formation of sulfur gas is facilitated by enhancing the contact of the released sulfur with the oxygen atoms before forming. This theory is considered as a possible explanation for the effects of radiation, but is not essential and does not limit its scope.

The coal can be treated in a similar order using the reactants. As a convenient method, the coal can be used in the form of a submersible slurry, as the coal is often supplied to boilers and other coal-fired combustion units in power plants, in the form of a submersible slurry. In addition, it is expected that the present invention can be used in combination with other physical coal cleaning processes, including but not limited to coal cleaning. Since the first reactant is water-soluble, water can be used in reducing sulfur from coal, reducing the cost of the reactant.

This description of suitable reactors and processes is merely illustrative of the wide range of equipment and processes that can be readily devised and used by those skilled in the field of desulfurization of carbonaceous materials.

Hereinafter, the present invention will be described by way of examples.

[0054]

Example 1 50 mL of heavy California crude was mixed with 10 mL of anhydrous diethyl ether in a 600 mL beaker on a stir plate with stir pellets. The agitated pellet was used throughout the process to agitate the contents in the 600 mL beaker. No heating was done apart from the inherent heat of reaction and dissolution.

[0055] Fifteen pellets of sodium hydroxide (4.49 grams) were added to 15 mL of 30% hydrogen peroxide in a 100 mL beaker. The mixture in a 100 mL beaker was manually swirled until the pellet was completely dissolved.

At the top of the reaction, as it was about to boil, the mixture in a 100 mL beaker was added to the mixture in a 600 mL beaker. There was a vigorous exotherm as the sodium hydroxide pellets dissolved in the hydrogen peroxide (until it was not emptied into a 600 mL beaker without a 100 mL beaker without insulation).

A mixture of hydroxide and hydrogen peroxide was added to a mixture of crude oil and diethyl ether. The combined mixture reacted and expanded, expanding above the top of the 600 mL beaker. And it would have overflowed without a funnel connected to a vacuum attached to the top of the beaker to remove the gas produced. The reaction subsided in less than one minute, but produced relatively large bubbles and continued to release gas. The reaction continued, and at 35 minutes the reaction mixture was placed in two vials. Glass bottle A was capped, while glass bottle B was open.

[0058]

Example 2 A sample was immediately taken from a glass bottle A, and an Oxford Lab X 300 was sampled.
Analysis was performed by X-ray fluorescence using a 0 analyzer. The analysis immediately showed 1.41% sulfur, and in four additional runs to read the average, the sulfur content showed a rapid decrease. In the following four measurements, each measurement dropped until the fifth measurement within 8 minutes showed 0.76% sulfur. A second analysis was performed immediately upon completion of the first analysis. There was a further decrease but at a much lower rate, decreasing from 0.68 to 0.66%. Table 1 shows the results.

[0059]

[Table 1]

[0060]

Example 3 Significant degassing continued in uncovered glass bottle B. It continued until it overflowed into a small pan placed under a glass bottle to catch the overflow. The next morning, about one-third of the amount in the glass bottle was overflowing into the bread. Samples were taken and tested using an Oxford Lab X 3000 analyzer. Table 2 shows the results.

[0061]

[Table 2]

The sulfur content in the first test (after reaction, overnight without analytical irradiation) was 2.22% as shown in the above table. At the end of the five subsequent analyses, the sulfur content was 2
. 13%, resulting in an average of 2.18%. 151 minutes after the introduction of X-rays, starting from the sulfur content in the sample (total elapsed time from the start of the reaction: 1331 minutes)
When tested again, the sulfur content dropped to 0.87%. 174 minutes after the introduction of X-rays to determine the sulfur content in the sample (total elapsed time from the start of the reaction: 1354
Min), the sulfur content dropped to 0.76%. 225 minutes after the introduction of X-rays to determine the sulfur content in the sample (total elapsed time from the start of the reaction: 1405)
Min), the sulfur content dropped to 0.67%.

The crude oils used in Examples 1 and 2 were both taken from the same locality,
And exposed to the same reactants. In Example 2, the sulfur content of the untreated California heavy crude only decreased from 2.69% to 2.22% after 1180 minutes. 0.76% in an additional 174 minutes after exposure to radiation during the analysis
Became.

The inventors have a theory that explains why the sulfur content decreases rapidly when a sample is analyzed. The theory is that irradiation of the sample with X-radiation when analyzing breaks the sulfur bonds already weakened by the hydroxide-peroxide reaction and moves the sulfur atoms and / or the active oxygen of the peroxide, During the transfer of the sulfur-containing reaction product to the aqueous phase. This theory is regarded as a possible explanation for the effects of radiation, but is not essential to the invention and does not limit the scope of the invention.

[0065]

Example 4 In a 600 mL beaker on a stir plate with stirring pellets, 50 mL of a slurry of finely divided coal in water was mixed with 10 mL of diethyl ether. The agitated pellet was used throughout the process to agitate the contents in the 600 mL beaker. No heating was done apart from the inherent heat of reaction and dissolution.

[0066] Fifteen pellets of sodium hydroxide (4.49 grams) were added to 15 mL of 30% hydrogen peroxide in a 100 mL beaker. The mixture in a 100 mL beaker was manually swirled until the pellet was completely dissolved.

When it is about to boil, mix the mixture in a 100 mL beaker with 600
Added to the mixture in the mL beaker. The combined mixture reacted and formed relatively large bubbles, releasing gas. Analysis of the slurry of coal revealed that it contained less sulfur after the reaction than before the reaction. After separating the sulfur gas and ether, the coal slurry was found to be suitable for use as a fuel in a coal slurry fuel burner. Alternatively, process water was separated from the coal slurry by screening out residual salts and additional water was added to obtain a liquid slurry suitable for use as a fuel.

[0068]

Example 5 Basically, except that the solvent used was acetone instead of ether and the ratio of reactants to solvent was varied (all are shown as reactants in Table 3). The process of Example 1 was repeated. The oil sample is heavy California crude oil having an initial sulfur content of 2.67% by weight in each case.
A summary of the results is shown in Table 3.

[0069]

[Table 3]

As shown in Table 3, the introduction of the analytical X-rays with the acetone solvent promotes the desulfurization, but the analysis of the reaction mixture two days after it is produced shows that the sulfur reduction is more pronounced. . This means that the reaction proceeds much more slowly in the case of acetone than in the case of ether, and the sulfur content is less than 0.7% in one day compared to 8 minutes in the case of using ether. This indicates that a slightly shorter time is required. The inventors theorize that the difference between the two solvents is that ethereal solvents provide a lower viscosity reaction mixture and make the reactants more mobile. This theory is
This is considered to be a possible explanation of the effect of the choice of solvent, but is not an essential requirement of the invention and does not limit the scope of the invention.

It should be expressly understood that the above detailed description is given by way of explanation and example only, and that the spirit and scope of the invention is limited only by the appended claims.

[Brief description of the drawings]

The advantages and features of the present invention may be better understood with reference to the following drawings when taken in conjunction with the accompanying drawings. Here, the figure is a conceptual flowchart of a normal process according to the present invention.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] December 5, 2000 (2000.12.5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

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[Claims]

Embedded image Wherein X and Z are independently selected from -O- and C = O; Y is X, it is independently selected from a direct bond between the -OR ₂ O-or R ₁ and R _2; R ₁ is Selected from hydrogen or R ₂ independently selected as described below; R ₂ is a straight or branched alkyl, alkenyl, or alkynyl having 1 to 16 carbon atoms, one or more rings, It is selected from aralkyl having an allyl having 6 to 24 carbon atoms attached to a straight or branched chain alkyl, alkenyl, or alkynyl as defined above.

Embedded image Wherein X and Z are each —O—; Y is independently selected from —O—, —OR ₂ O—, or a direct bond between R ₁ and R ₂ ; R ₁ is hydrogen or independently selected from R ₂ to be decided; R ₂ is decided aralkyl having alkyl having 1 to 16 carbon atoms in straight or branched chain alkenyl or alkynyl, a single or multiple rings, before It is selected from straight chain or branched alkyl, alkenyl, or allyl having 6 to 24 carbon atoms attached to alkynyl.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction contents]

[0001]

[Cross Reference with Related Application] This application claims priority based on provisional application No. 60 / 100,576 filed on September 16, 1998. That application is hereby incorporated by reference. Another related application is U.S. Pat. U.S. patent application Ser. No. 09/08, filed 5,961,820.
No. 5,478, which is also incorporated herein by reference.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10G 27/06 ZAB C10G 27/12 27/12 27/14 27/14 32/00 Z 32/00 C10L 5 / 00 C10L 5/00 B01D 53/34 126 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL , PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, B B, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZWF terms (reference) 4D002 AA03 AC10 BA02 BA05 DA05 DA16 DA35 EA02 FA03 FA07 FA08 4G075 AA13 AA22 BA05 BA06 CA23 CA26 CA32 CA33 CA34 CA38 CA51 CA65 DA01 EB31 4H015 AA10 AA25 AA27 AB01 BA10 BB15 CB01 4H029 DA06 DA07

Claims (37)

[Claims] 1. A. Providing a carbonaceous material containing sulfur; B. Contacting said carbonaceous material with a source of active oxygen in the presence of a base, and using amounts of said active oxygen and said base effective to reduce the sulfur content of said carbonaceous material; and C . Exposing the carbonaceous material to one type of energy source and subjecting the carbonaceous material to conditions effective to further reduce the sulfur content of the carbonaceous material. 2. The method according to claim 1, wherein the carbonaceous material is a fossil fuel.
The process described in. 3. The method according to claim 1, wherein the carbonaceous material is a petroleum product.
The process described in. 4. The process according to claim 1, wherein said carbonaceous material is coal. 5. The method according to claim 1, wherein said active oxygen source is a peroxide.
The process described in. 6. The process of claim 1, wherein said source of active oxygen is an aqueous hydrogen peroxide solution. 7. The process according to claim 1, wherein said source of active oxygen is an ozone generator. 8. The process according to claim 1, wherein said base is added to said active oxygen source. 9. The method according to claim 1, wherein the contacting step is performed by adding a base to the active oxygen source to form a basic active oxygen source, and then combining the basic active oxygen source with the carbonaceous material. Item 2. The process according to Item 1. 10. The method according to claim 9, wherein the contacting step is performed by combining a carbonaceous material, the basic active oxygen source, and a common solvent of the carbonaceous material and the basic active oxygen source. The described process. 11. The process according to claim 1, wherein said contacting step is performed in the presence of a liquid having one of the following structural formulas: Embedded image Wherein X and Z are independently selected from -O- and C = O; Y is X, it is independently selected from a direct bond between the -OR ₂ O-or R ₁ and R _2; R ₁ is Selected from hydrogen or R ₂ independently selected as described below; R ₂ is a straight or branched alkyl, alkenyl, or alkynyl having 1 to 16 carbon atoms, one or more rings, It is selected from aralkyl having an allyl having 6 to 24 carbon atoms attached to a straight or branched chain alkyl, alkenyl, or alkynyl as defined above. 12. The method according to claim 11, wherein X and Z are ether bonds.
The process described in. 13. The method according to claim 13, wherein the contacting step is performed with diethyl ether, isopropyl ether,
Butyl ether, ethyl methyl ether, ethyl n-butyl ether, tetrahydrofuran, dioxane, furan, α-pyran, γ-pyran, s-trioxane,
The process of claim 1, wherein the process is performed in the presence of a liquid selected from the group consisting of ethylene oxide, propylene oxide, acetone, methyl isobutyl ketone, formaldehyde, acetaldehyde, methanol, ethanol, and combinations thereof. 14. The process according to claim 1, wherein said contacting step is performed in the presence of diethyl ether. 15. The process according to claim 1, wherein said base is a hydroxide. 16. The process of claim 1, wherein said base is sodium hydroxide. 17. The energy of the group consisting of α-radiation, β-radiation, γ-radiation, X-radiation, ultraviolet light, visible light, infrared light, microwave, radiation generated from decay of radioactive material, ultrasonic energy, and a combination thereof. The process of claim 1 characterized by being selected. 18. The process according to claim 1, wherein said energy is X-radiation. 19. The process according to claim 1, wherein said energy is ultrasonic energy. 20. The process of claim 1 wherein said source of active oxygen is water-soluble and further comprising the step of separating said carbonaceous material from said source of active oxygen after said contacting step. 21. The process of claim 1, wherein the contacting step includes generating a sulfur-containing gas and further comprising separating the sulfur-containing gas from the carbonaceous material. 22. The process according to claim 21, further comprising the step of extracting elemental sulfur from said sulfur-containing gas. 23. The process of claim 21, further comprising the step of oxidizing said sulfur-containing gas to produce sulfur oxide. 24. The process of claim 23, further comprising the step of reacting said sulfur oxide with lime to form calcium sulfate. 25. The method of claim 1, wherein the provided carbonaceous material is classified as a high sulfur fuel and the carbonaceous material after the contacting step is classified as a low sulfur fuel. process. 26. The carbonaceous material provided contains at least about 2% by weight elemental sulfur and the carbonaceous material after the contacting step contains less than about 1% by weight sulfur. The process of claim 1 comprising: 27. The provided carbonaceous material contains at least about 2% by weight elemental sulfur and the carbonaceous material after the contacting step contains less than about 0.5% by weight sulfur. The process according to claim 1, characterized in that: 28. The carbonaceous material provided contains at least about 1% by weight elemental sulfur and the carbonaceous material after the contacting step contains less than about 0.5% by weight sulfur. The process according to claim 1, characterized in that: 29. The method according to claim 27, wherein the contacting step is performed at about 32 ° F. (0 ° C.) and about 250 ° F. (121 ° C.).
The process according to claim 1, characterized in that it is carried out at a temperature between (° C). 30. The process of claim 1, wherein said contacting step is performed at a pressure of about 0.1 to about 2 atmospheres. 31. A. Providing a carbonaceous material containing sulfur; and B. Contacting the carbonaceous material with an active oxygen source, a base and a solvent under conditions effective to reduce the sulfur content of the carbonaceous material, wherein the solvent has one of the following structural formulas: A process for removing sulfur from characteristic sulfur-containing carbonaceous materials. Embedded image Wherein X and Z are independently selected from -O- and C = O; Y is X, it is independently selected from a direct bond between the -OR ₂ O-or R ₁ and R _2; R ₁ is Selected from hydrogen or R ₂ independently selected as described below; R ₂ is a straight or branched chain alkyl, alkenyl, or alkynyl having 1 to 16 carbon atoms, one or more rings, It is selected from aralkyl having an allyl having 6 to 24 carbon atoms attached to a straight or branched chain alkyl, alkenyl, or alkynyl as defined above. 32. The process according to claim 31, wherein said solvent is an aliphatic ether. 33. The process according to claim 31, wherein said solvent is diethyl ether. 34. A sulfur-reduced carbonaceous material made by the process of claim 1. 35. A sulfur-reduced carbonaceous material made by the process of claim 31. 36. A processed California heavy crude having a sulfur content of less than about 1% by weight. 37. A processed California heavy crude having a sulfur content of less than about 0.5% by weight.