WO2024095167A1 - Ultrasound-assisted oxidative desulfurization of fuel oil using metal oxide catalysts - Google Patents
Ultrasound-assisted oxidative desulfurization of fuel oil using metal oxide catalysts Download PDFInfo
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- WO2024095167A1 WO2024095167A1 PCT/IB2023/060989 IB2023060989W WO2024095167A1 WO 2024095167 A1 WO2024095167 A1 WO 2024095167A1 IB 2023060989 W IB2023060989 W IB 2023060989W WO 2024095167 A1 WO2024095167 A1 WO 2024095167A1
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- Prior art keywords
- oxide
- fuel oil
- catalysts
- accordance
- ultrasound
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 239000000295 fuel oil Substances 0.000 title claims abstract description 18
- 238000002604 ultrasonography Methods 0.000 title claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 5
- 150000004706 metal oxides Chemical class 0.000 title claims description 5
- 238000006477 desulfuration reaction Methods 0.000 title description 17
- 230000023556 desulfurization Effects 0.000 title description 17
- 230000001590 oxidative effect Effects 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 2
- -1 sulfone compounds Chemical class 0.000 abstract description 2
- 150000003462 sulfoxides Chemical class 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910003439 heavy metal oxide Inorganic materials 0.000 abstract 1
- 239000003209 petroleum derivative Substances 0.000 abstract 1
- 238000000638 solvent extraction Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 239000000446 fuel Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YDULQTLSFNLWCO-UHFFFAOYSA-N 4,6-dimethyl-1-benzothiophene Chemical compound CC1=CC(C)=C2C=CSC2=C1 YDULQTLSFNLWCO-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/08—Inorganic compounds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/16—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Definitions
- This invention is directed to the removal of sulfur compounds from Heavy fuel such as Fuel Oil etc. Also more particularly, their removal by a combination of four steps: ultrasound, catalysts, oxidation and extraction.
- Major fuel oil produced in the world has a sulfur content of more than 0.5% wt and industrial desulfurization methods such as hydrotreating methods are not able to remove sulfur in fuel oil effectively and economically due to the molecular nature of these compounds.
- Compounds such as benzothiophene, dibenzothiophene and other cyclic sulfur-containing compounds are not changed under hydrotreating methods and remain in the fuel. Therefore, relatively extensive studies are being conducted in this regard, and this invention provides a new method to reduce the sulfur content of heavy fuels, especially fuel oil, in an effective and economical way.
- one aspect of this disclosure is directed to a method of mixing-assisted oxidative desulfurization of fossil fuels in which the fossil fuel is combined with an aqueous oxidizer Solution including hydrogen peroxide having at least one carbon chain of 8 or more carbon atoms as a phase transfer catalyst to achieve improved conversion of sulfides to sulfoxides with higher yield and without the unwanted formation of side products.
- the mixing-assisted oxidative desulfurization process of this disclosure is also advantageous over the conventional Sono-reactor or ultrasonic desulfurization process with fixed bed catalyst, for example, with respect to have much fewer problems relating to scale up to mass production because of the lack of the accompanying corresponding function generator and RF amplifier that are found in Sono-reactors, and not presenting long term detriment to possible chain cracking of long chain hydrocarbons.
- the evaporative tower is coupled to one decanter and to one mixing tank So as to produce Sulfones, the decanter yields an organic phase that is Substantially Sulfone-free.
- FIG. 1 is a schematic diagram of a portable continuous desulfurization device in accordance with a first embodiment of the present disclosure.
- the aqueous solution is mixed with the fuel oil and the oxidizer aqueous solution including hydrogen peroxide or other organic peroxide and carboxylic acid such as formic acid or acetic acid.
- the ratio of the fuel oil and oxidizer aqueous solution may vary from about 3:1 to about 1:3, and preferably about 3:1.25.
- the concentration of hydrogen peroxide in the oxidizer aqueous solution is substantially in the range of 20% to 30%. And although they may affect the efficiency of the process or the ease of handling the fluids, the ratio is critical to this invention.
- H2O2 hydroperoxide
- H2O2 con centration within the range from about 20% to about 30% by Volume (as H2O2) of the combined aqueous and organic phases, and preferably from about 3%.
- H2O2 con centration within the range from about 20% to about 30% by Volume (as H2O2) of the combined aqueous and organic phases, and preferably from about 3%.
- the preferred relative volumes will be those of equivalent molar amounts.
- the mixture passes through the reactor bed and it is subjected to ultrasound.
- the residence time in the invention varies from 2 minutes to 20 minutes and depends on the ultrasonic power (250 to 2000 watts), ultrasonic intensity (5 to 50 watts per square centimeter), ultrasonic frequency (16000 to 32000 Hz), the amount of catalyst in the reactor, also depends on the type of catalyst (molybdenum oxide (MoO2), vanadium oxide (V2O5), Iron(III) oxide (Fe2O3), Titanium oxide (TiCh), Magnesium oxide (MgO), Alumina (AI2O3)).
- the output material is mixed with a polar solvent such as distilled water, ethanol, acetonitrile, acetone, etc. Moreover, separated into aqueous and organic phases in a decanter. There is very little sulfur in the organic phase of fuel oil.
- the solvent and oxidizer are sent to a stripping tower for recovery, and sulfonic and sulfoxide compounds are separated from the oxidizer solvent and returned to the storage tank.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
In this innovation, sulfur compounds in heavy petroleum products are converted into sulfoxide and sulfone compounds using a combined process consisting of oxidants, ultrasound, heavy metal oxides catalysts such as molybdenum oxide (MoO2), vanadium oxide (V2O5), Iron(III) oxide (Fe2O3), Titanium oxide (TiO2), Magnesium oxide (MgO), Alumina (Al2O3) and solvent extraction. This process is removed sulfur from the fuel oil, and the process performance evaluated in a continuous pilot system. The results are shown the sulfur content change from 3.5 to 0.5% wt.
Description
Ultrasound-assisted oxidative desulfurization of Fuel Oil using metal oxide catalysts
Background of the Invention
This invention is directed to the removal of sulfur compounds from Heavy fuel such as Fuel Oil etc. Also more particularly, their removal by a combination of four steps: ultrasound, catalysts, oxidation and extraction.
One of the main concerns of today's world is the environment, the reduction and management of environmental pollutants. Environmental pollution management will be the recovery, conversion and decomposing of existing pollutants. But for a significant change, it is necessary to identify the sources of pollution and act to prevent the spread of pollution. One of the sources of air pollution is the compounds in the gases resulting from the combustion of fossil fuels. One of these special compounds was sulfur, which in the past decades, these gases had an increasing trend. With the identification of the problems caused by the emission of these gases, appropriate international standards and requirements for the quality of fuel consumption and the performance of vehicle engines reduced these gases. In 2020, the International Maritime Organization set a requirement in relation to the oil Tankers, which reduced the allowed amount of sulfur content from 3.5% to 0.5% wt.
Major fuel oil produced in the world has a sulfur content of more than 0.5% wt and industrial desulfurization methods such as hydrotreating methods are not able to remove sulfur in fuel oil effectively and economically due to the molecular nature of these compounds. Compounds such as benzothiophene, dibenzothiophene and other cyclic sulfur-containing compounds are not changed under hydrotreating methods and remain in the fuel. Therefore, relatively extensive studies are being conducted in this regard, and this invention provides a new method to reduce the sulfur content of heavy fuels, especially fuel oil, in an effective and economical way.
Sulfur removal from the fuel oil has been a challenging operation even after petroleum refining, and the issue remains critical to petrochemical industries. Thiols, thiophenes, benzothiophenes, dibenzothiophenes, and 4,6-dimethylbenzothiophene are examples of sulfur-containing compounds present in liquid fuels . Owing to the damaging impact of the sulfur compounds, most countries set stringent regulations on the needed amount of sulfur in fuel toward achieving a sustainable environment. The European Union and other developed countries like Japan and the USA set the highest permissible sulfur content limit for gasoline at 10 ppm and diesel at 15 ppm . The need to develop an efficient desulfurization technology that will remove sulfur compounds from fuel based on the recent strict environmental regulations is therefore necessary. Technologies such as hydrodesulfurization, biodesulfurization, extractive distillation, selective adsorption, and
oxidative desulfurization have been proposed for fuel oil desulfurization. A summary of the effect of sulfur emission due to the S -compounds in the surrounding environment, the consequence of regulatory bodies to push researchers in the study for sustainable alternatives. Green technology of ODS employed a suitable catalyst that is considered to increase the activity of oxidants for rapid sulfur removal from oil under mild reaction conditions of temperature and pressure.
Indeed, numerous catalysts such as MOFs based and their composites with, titanate nanotubes, materials with hexagonal 2D structure, supported metal oxides, and phase transfer materials, have been previously studied as a catalyst for desulfurization of fuel oil. Among the recent used of the catalysts for ODS application, the newly emerging class of advanced materials, are one of the most commonly used catalysts for deep oil desulfurization. There is rapid progress in desulfurization studies involving fuel oil worldwide to tackle industrial and environmental concerns.
Advances in the development of new techniques and materials have offered exciting research opportunities to revolutionize the desulfurization processes toward increasing the standards of producing green oil fuel. Although research on desulfurization has been reported in the recent past, a focused review on oxidative desulfurization of fuel oil using advanced materials is significantly lacking. Noteworthy, there are many reports to boost the quality of fuel oil by employing advanced materials for deep desulfurization, and have been reviewed by researchers. In addition, the catalytic ODS performance over various types of catalysts is compared and discussed from a scientific point of view.
Summary of The Invention
In order to overcome the above-mentioned problems, one aspect of this disclosure is directed to a method of mixing-assisted oxidative desulfurization of fossil fuels in which the fossil fuel is combined with an aqueous oxidizer Solution including hydrogen peroxide having at least one carbon chain of 8 or more carbon atoms as a phase transfer catalyst to achieve improved conversion of sulfides to sulfoxides with higher yield and without the unwanted formation of side products. The mixing-assisted oxidative desulfurization process of this disclosure is also advantageous over the conventional Sono-reactor or ultrasonic desulfurization process with fixed bed catalyst, for example, with respect to have much fewer problems relating to scale up to mass production because of the lack of the accompanying corresponding function generator and RF amplifier that are found in Sono-reactors, and not presenting long term detriment to possible chain cracking of long chain hydrocarbons. The evaporative tower is coupled to one decanter and to one mixing tank So as to produce Sulfones, the decanter yields an organic phase that is Substantially Sulfone-free.
Brief Description of The Drawing
The drawing is included to provide a further understanding of the invention also it is incorporated in and constitute a part of this specification. The drawing illustrates embodiments of the invention together with the description, explain the principles of the invention.
FIG. 1 is a schematic diagram of a portable continuous desulfurization device in accordance with a first embodiment of the present disclosure.
Description of Innovation
The aqueous solution is mixed with the fuel oil and the oxidizer aqueous solution including hydrogen peroxide or other organic peroxide and carboxylic acid such as formic acid or acetic acid. The ratio of the fuel oil and oxidizer aqueous solution may vary from about 3:1 to about 1:3, and preferably about 3:1.25. The concentration of hydrogen peroxide in the oxidizer aqueous solution is substantially in the range of 20% to 30%. And although they may affect the efficiency of the process or the ease of handling the fluids, the ratio is critical to this invention.
In most cases, however, improved results will be achieved when using metal oxide catalyst into the Sono-reactor. When the hydroperoxide is H2O2, improved results are generally achieved in most systems with an H2O2 con centration within the range from about 20% to about 30% by Volume (as H2O2) of the combined aqueous and organic phases, and preferably from about 3%. For hydroperoxides other than H2O2, the preferred relative volumes will be those of equivalent molar amounts.
The mixture passes through the reactor bed and it is subjected to ultrasound. The residence time in the invention varies from 2 minutes to 20 minutes and depends on the ultrasonic power (250 to 2000 watts), ultrasonic intensity (5 to 50 watts per square centimeter), ultrasonic frequency (16000 to 32000 Hz), the amount of catalyst in the reactor, also depends on the type of catalyst (molybdenum oxide (MoO2), vanadium oxide (V2O5), Iron(III) oxide (Fe2O3), Titanium oxide (TiCh), Magnesium oxide (MgO), Alumina (AI2O3)).
After the Sono-reactor stage, the output material is mixed with a polar solvent such as distilled water, ethanol, acetonitrile, acetone, etc. Moreover, separated into aqueous and organic phases in a decanter. There is very little sulfur in the organic phase of fuel oil. The solvent and oxidizer are sent to a stripping tower for recovery, and sulfonic and sulfoxide compounds are separated from the oxidizer solvent and returned to the storage tank.
The foregoing is offered primarily for illustrative purposes. The present disclosure is not limited to the above-described embodiments, various variations and modifications might be possible without departing from the scope of the present invention.
Claims
1. A method for sulfur removal from a fuel oil, comprising:
(a) Mixing a fuel oil with an oxidizer Solution, a carboxylic acid (b) Sono-reactor or ultrasonic reactor with fixed bed metal oxide catalyst
(c) mixing a reactor outlet and polar solvent
(d) separating an oil phase from an aqueous phase using a decanter,
(d) solvent and oxidizer recovery into a second stripper.
2. The method in accordance with claim 1, wherein the catalysts are molybdenum oxide (MoO2), vanadium oxide (V2O5), Iron(III) oxide (Fe2O3), Titanium oxide (TiCh), Magnesium oxide
(MgO), Alumina (AI2O3).
3. The method in accordance with claim 2, wherein the catalysts are fixed in reactor.
4. The method in accordance with claim 3, wherein the average catalysts size are 1.2 mm and specific area of catalysts are 500 m2 gr 1.
5. The method in accordance with claim 1, wherein the power of ultrasonic machine is 2000 W.
6. The method in accordance with claim 5, wherein the frequency of ultrasound is 16000 to 32000
Hz.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202263422036P | 2022-11-03 | 2022-11-03 | |
| US63/422,036 | 2022-11-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024095167A1 true WO2024095167A1 (en) | 2024-05-10 |
Family
ID=90929901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2023/060989 WO2024095167A1 (en) | 2022-11-03 | 2023-11-01 | Ultrasound-assisted oxidative desulfurization of fuel oil using metal oxide catalysts |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024095167A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020189975A1 (en) * | 2001-05-16 | 2002-12-19 | Petroleo Brasileiro S.A. - Petrobras | Process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from hydrocarbon streams |
| US20090236266A1 (en) * | 2008-03-20 | 2009-09-24 | Shun-Sheng Cheng | Diesel desulfurization method |
| US20120018350A1 (en) * | 2010-07-20 | 2012-01-26 | Hsin Tung Lin | Mixing-assisted oxidative desulfurization of diesel fuel using quaternary ammonium salt and portable unit thereof |
| US20160046878A1 (en) * | 2014-08-12 | 2016-02-18 | Roger K. Lott | Ultrasonic cavitation reactor for processing hydrocarbons and methods of use thereof |
| US20210002562A1 (en) * | 2018-03-23 | 2021-01-07 | International Ultrasonic Technologies Inc. | Ultrasonic oxidative desulfurization of heavy fuel oils |
-
2023
- 2023-11-01 WO PCT/IB2023/060989 patent/WO2024095167A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020189975A1 (en) * | 2001-05-16 | 2002-12-19 | Petroleo Brasileiro S.A. - Petrobras | Process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from hydrocarbon streams |
| US20090236266A1 (en) * | 2008-03-20 | 2009-09-24 | Shun-Sheng Cheng | Diesel desulfurization method |
| US20120018350A1 (en) * | 2010-07-20 | 2012-01-26 | Hsin Tung Lin | Mixing-assisted oxidative desulfurization of diesel fuel using quaternary ammonium salt and portable unit thereof |
| US20160046878A1 (en) * | 2014-08-12 | 2016-02-18 | Roger K. Lott | Ultrasonic cavitation reactor for processing hydrocarbons and methods of use thereof |
| US20210002562A1 (en) * | 2018-03-23 | 2021-01-07 | International Ultrasonic Technologies Inc. | Ultrasonic oxidative desulfurization of heavy fuel oils |
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