KR100885497B1 - Process for the reduction of sulfur- or nitrogen-containing compounds and the produciton of useful oxygenates from hydrocarbon materials via selective oxidation in a single step - Google Patents

Abstract

The present invention relates to a method for the selective oxidation of a hydrocarbon substrate, and more specifically, the present invention is a homogeneous catalyst represented by a mixed catalyst of M ^{n +} / first solvent or M ₁ ^{n +} / second solvent and M ₂ ^{m +} / third solvent And by oxidizing the hydrocarbon substrate in the presence of an oxidizing agent, in addition to producing a large amount or controlled amount of useful oxygen-containing compounds that act as cetane or octane enhancers in hydrocarbon substrates including transport fuel oils such as gasoline or diesel. At the same time it relates to a process for the selective oxidation of hydrocarbon substrates which can be carried out directly at denitrification and desulfurization or at least converted into sulfur or nitrogen containing precursors which are easy to remove.

Desulfurization, denitrification, oxygenated compounds, cetane number, octane number, homogeneous catalyst, oxidant, selective oxidation

Description

Process for the reduction of sulfur- or nitrogen-containing compounds and the produciton of useful oxygenates from hydrocarbon materials via selective oxidation in a single step}

FIG. 1 shows 4,6-dimethyldibenzothiophene (4,6-DMDBT), dibenzothiophene (DBT), and benzothiophene (BT), respectively, using Mo (oxirane) catalyst solution and TBHP. Oxidation treatment is a graph showing the degree of oxidation over time (ㅁ: 4,6-DMDBT, ο: DBT, Δ: BT).

The present invention relates to a method for the selective oxidation of a hydrocarbon substrate, and more specifically, the present invention is a homogeneous catalyst represented by a mixed catalyst of M ^{n +} / first solvent or M ₁ ^{n +} / second solvent and M ₂ ^{m +} / third solvent And by oxidizing the hydrocarbon substrate in the presence of an oxidizing agent, in addition to producing a large amount or controlled amount of useful oxygen-containing compounds that act as cetane or octane enhancers in hydrocarbon substrates including transport fuel oils such as gasoline or diesel. At the same time it relates to a process for the selective oxidation of hydrocarbon substrates which can be carried out directly at denitrification and desulfurization or at least converted into sulfur or nitrogen containing precursors which are easy to remove.

In hydrocarbon substrates such as petroleum, stable compounds, commonly referred to as refractory sulfur compounds, such as thiols, sulfides and disulfides, are surprisingly unstable and sulfur compounds such as simple sulfur and aliphatic organic sulfur that are easily removed by heat treatment or conventional hydrotreating processes. This exists.

Conventionally used techniques for removing such sulfur compounds are hydrodesulfurization or hydrodesulfurization (HDS), which is a fierce competition among oil companies around the world. Or, it has been markedly developed by academic research, and has become the most important process for oil refineries to remove sulfur in compliance with stringent air pollution control regulations in Europe, the United States, and Japan.

As already led by EU countries, some European countries are already aiming to reduce sulfur levels to near zero (10 ppm S) in automotive fuels, especially gasoline. To achieve this goal, very advanced desulfurization techniques are required. As shown below, regulations in Korea are accelerating towards lowering sulfur content in automotive fuels.

2006's In 2008 2010's Gasoline, ppm S 130 50 10 Diesel oil, ppm S 430 30 10

However, the sulfur-containing compounds present in petroleum are not only compounds that are easy to remove, but include compounds that are very difficult or impossible to remove, such as a series of thiophene-based compounds and their condensed thiophene derivatives.

Specifically, among the condensed thiophene derivatives, more condensed sulfur compounds such as benzothiophene, dibenzothiophene, 4-methyldibenzothiophene, and especially 4,6-dimethylbenzothiophene are used for gasoline and diesel fuels. fuel, HDS middle distillates, heavier fractions and residual bottoms of petroleum crudes. This dibenzothiophene or its alkyl derivatives are called so-called refractory sulfur compounds because they are thermally stable even at high temperatures (650 ° C.) and are very difficult to be removed by conventional HDS purification processes.

For this reason, the goal of reducing the sulfur content to near zero is almost impossible to achieve even with the most advanced HDS catalyst technology at present, which is inherently difficult to overcome by the fundamental chemical principles involved in the current HDS process, as described above. Because there is a problem.

In order to solve this problem, many HDS catalysts have been reported experimentally, but even these techniques require an excessively harsh HDS process, so essential hydrocarbon components such as aromatic compounds including olefins, paraffins and multi-ring compounds This excessively hydrogenated resulted in another problem: the consumption of enormous amounts of expensive hydrogen.

In addition to the economic problems of expensive hydrogen consumption, this results in the production of large amounts of gaseous products and excess hydrogenated products and a significant reduction in the amount of HDS products, which is a significant amount of octane (gasoline) or cetane (diesel). This results in loss. As a result, cracking reactions and specific oxygenated compounds to meet the desired physical and chemical properties (e.g. to recover octane numbers for gasoline and to meet the oxygen content required by reformed gasoline and future oxygenated diesel, respectively). Additional processes, such as mixing with, have to be carried out separately, which leads to another serious problem that can no longer be a practical vehicle fuel.

In order to overcome the problems of the conventional HDS technology, the present invention is innovative removal of the conventional refractory sulfur compounds to achieve the ultra-desulfurization of almost sulfur-free desulfurization, and at the same time the selective oxidation showing the effect of performing denitrification Here's how. Furthermore, unlike the conventional HDS technique causing octane or cetane loss, the selective oxidation process according to the present invention simultaneously shows a synergistic effect of selectively oxidizing allyllic or benzylic hydrocarbon substrates to enhance the octane or cetane number. There is great significance in this regard.

According to an aspect of the present invention, by selectively oxidizing a hydrocarbon substrate in the presence of a homogeneous catalyst and an oxidant represented by a mixed catalyst of M ^{n +} / first solvent or M ₁ ^{n +} / second solvent and M ₂ ^{m +} / thi solvent And converting a sulfur or nitrogen containing compound into a sulfur or nitrogen containing precursor which is easy to desulfurize and denitrate, and simultaneously converting a benzylic or allyl compound to an oxygenated compound.

This selective oxidation step not only produces a large amount or a desired amount of oxygenated compound which acts to promote gasoline octane number and diesel cetane number, but also converts into a sulfur or nitrogen containing precursor which is relatively easy to remove. Therefore, by performing the post-treatment step for desulfurization and denitrification sequentially after the above selective oxidation process, super-depth desulfurization and denitrification can be easily achieved.

In order for sulfur-containing compounds to be effectively removed, dealkylation and / or isomerization reactions, ie, transfer of methyl groups from the 4- and 6-positions to other positions, must be preceded in order to bypass the steric effects that interfere with oxidation. However, sulfur compounds, such as 4,6-dimethyldibenzothiaphene, which are problematic in the conventional HDS technology, are largely influenced by two methyl groups in the 4- and 6-positions structurally surrounding sulfur atoms and thus desulfurized. This is the most difficult compound, and the fundamental problem of the conventional HDS technology can be said to be due to this fundamental chemical principle. In short, the conventional HDS technology is economically and technically fatal in that the most advanced form of HDS catalyst does not provide a practical process for lowering the sulfur content to almost zero. It will be said to have a limit.

On the other hand, in contrast to the steric effect of the 4,6-dimethyldibenzothiophene structure in the HDS process, the electron donating function of the two methyl groups in the 4- and 6-positions of the substrate molecule is sulfur atom as shown below. The electron density increases, so the sulfur atom becomes even more functional to undergo an electrophilic attack, for example an oxidation reaction.

Electron density of sulfur atoms (Energy & Fuels 2000, 14, 1232-1239) Sulfur compounds rescue Electron density K (L / mol X minutes) Methylphenyl sulfide

5.915 0.295 Thiophenol

5.902 0.270 Diphenyl sulfide

5.860 0.156 4,6-DMDBT

5.760 0.0767 4-MDBT

5.759 0.0627 Dibenzothiophene

5.758 0.0460 1-benzothiophene

5.739 0.00574 2,5-dimethylthiophene

5.716 - 2-methylthiophene

5.706 - Thiophene

5.696 -

Thus, sulfur compounds, DBTs and their alkyl derivatives, which are difficult to remove, exhibit reactivity tendencies opposite to those observed in traditional HDS reactions for selective sulfoxidation processes. In other words, sulfur compounds, such as 4,6-dimethyldibenzothiophene, which are stable even at high temperatures (460 ° C.) and are difficult to remove even under severe conditions by conventional HDS technology, are oxidative desulfurization (ODS) processes. Desulfurization is the easiest substrate, and is shown schematically below.

More specifically, in the case of non-thiophene-based compounds, the electron density of sulfur compounds increases in the order of diphenylsulfide <thiophenol <methyl phenyl sulfide as shown above, and consequently, Electronic attack proceeds in the same direction as seen in the electron density of sulfur atoms in oxirane-soluble Mo-catalysts. A series of thiophene derivatives, particularly dibenzothiophene (DBT), 4-alkyldibenzothiophene (4-MDBT) and 4, which are difficult to remove in a desulfurization process in similar homogeneous catalyst systems containing transition metal ions The same chemical principle can also be applied to the selective oxidation of 6-dialkyldibenzothiophene (4,6-DMDBT) as follows.

In addition, unlike oxygen atoms, S atoms generally readily expand their oxidation state to produce various oxides, for example DBT derivatives are first partially oxidized and converted to sulfoxides as shown below. In turn, it is switched to sulfone continuously. Depending on the degree of oxidation, physical and chemical properties, such as boiling point, molecular polarity, and solubility in solvents, are greatly changed. By using these points, simple physical treatment methods, filtration separation, fractionation, pyrolysis, solvent selective extraction, and adsorption are used. The method allows for easy separation and removal of the oxidized product. On the other hand, desulfurization may be performed by chemical decomposition using a catalyst such as a base, which is shown schematically below.

Desulfurization Mechanism by 4,6-DMDBT Sulfone Pyrolysis and Base Catalyst

The sulfur or nitrogen-containing precursor thus converted can be easily desulfurized or denitrified by sequentially performing the various methods presented in the present invention, and thus, the purpose or effect of improving the cetane number or octane number through desulfurization, denitrification, and oxygenated compound generation may be achieved. The significance of the present invention is that it can be achieved.

That is, the selective oxidation process of the present invention is a non-hydrogen process in order to solve the problem of the conventional HDS process that requires the use of expensive H ₂ in a large amount of characteristics of the oxidative desulfurization (ODS) process As the eco-friendly regulations have already defined 2.0-2.7% oxygen content in gasoline, and the regulation of oxygen content in diesel is also very fast, it is rather controlled to replace the concept of indiscriminate oxidation of hydrocarbons. The most significant aspect of the present invention is that it can simultaneously produce superoxide desulfurization and denitrification, while generating an oxygen compound that can selectively enhance the oxidation of gasoline and the cetane number of gasoline while selectively achieving oxidation. will be.

In addition, as described above, the steps of desulfurization and denitrification can be performed not only sequentially with the selective oxidation step but also simultaneously with the oxidation treatment of the hydrocarbon substrate, and in particular hydrocarbon substrates, this simultaneous treatment method is relatively better. It was also confirmed that it shows an effect.

Therefore, according to another aspect of the present invention, by selectively oxidizing the hydrocarbon substrate in a biphasic reaction system in the presence of the homogeneous catalyst and the oxidizing agent of the present invention, the desulfation and denitrification of the hydrocarbon substrate and the benzylic or allyl compound It relates to a method for the selective oxidation of a hydrocarbon substrate comprising the step of converting to an oxygenated compound.

Specifically, DBT, indole and tetralin are selected as representative model compounds of sulfur-containing hydrocarbons, nitrogen-containing hydrocarbons, allyllic or benzylic hydrocarbons, respectively, to select biphasic (non-polar / polar) selective oxidation. As the reaction is carried out, the resulting S or N-containing precursors and oxygenated products are transferred to a polar solvent layer such as an aqueous solution or vinegar-water, which can be relatively easily separated or removed. Schematically shown in.

Selective Extraction in a Dual Phase Reaction System

On the other hand, if there is more than a certain amount of nitrogen-containing compounds in the hydrocarbon substrate may act as an element that interferes with the selective oxidation reaction, and according to a preferred embodiment of the present invention, according to the preferred embodiment of the present invention, A pretreatment step may be performed that partially removes the nitrogen-containing precursor before. This pretreatment step can be performed using an adsorbent. In addition, instead of being separately employed as an adsorbent, a part of the homogeneous catalyst according to the present invention may be used as an adsorbent for adsorbing the nitrogen-containing precursor, and the remaining part may act as a catalyst for selective oxidation.

As the homogeneous catalyst which can be used in the present invention, a homogeneous catalyst represented by the mixed catalyst of the M ^{n +} / first solvent or M ₁ ^{n +} / second solvent and M ₂ ^{m +} / third solvent can be used.

Above, wherein M ^{+ n} is ^{3 +} Co, Mo ^{+ 6, 2 +} MoO _2, MoO ^{4 +,} MoO ₄ ^{2 -,} V ^{5 +, +} VO ^3, VO ₂ ^{+ 3,} W ^{+ 6,} ₄ ² WO ^-, Cr ^{+ 3,} Ti ^{+ 4,} Fe ^{+ 3,} Ni ^2+, Zr ^{4 +, +} ZrO ^2, Hf ^{+ 4,} Ta ^{+ 6, 5 +} Nb, Ce ^{4 +} and Ce ^{3 +} selected from Become;

M ₁ ^{n +} is selected from Co ³⁺ , Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ and MoO ₄ ^2- ;

M ₂ ^{m +} is Fe ³⁺ , Ni ²⁺ , Cu ²⁺ , V ⁵⁺ , VO ³⁺ , VO ₂ ³⁺ , Cr ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , ZrO ²⁺ , Hf ⁴⁺ , Ta ⁶⁺ , Nb ⁵⁺ , Re ⁴⁺ , Ru ⁴⁺ , May be selected from Sm ⁴⁺ , Pr ³⁺ and Ce ³⁺ .

Among them, M ^{n +} and M ₁ ^{n +} are Mo series such as Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ , MoO ₄ ^2- , and M ^{n +} and M ₂ ^{m +} are V ⁵⁺ , VO ³⁺ , VO ₂ ³ It is preferable to select from the V series such as ^{+ in terms} of the activity, conversion, yield, selectivity, etc. of the catalyst; In particular, M ^{n +} is most preferably Mo series.

The first solvent, the second solvent and the third solvent may be the same or different from each other, and water, alcohols, CH ₃ CN, DMF, N-pyrrolodon, formic acid, acetic acid, octanoic acid, Trifluoroacetic acid, acetic acid-water mixture, aliphatic or aromatic C ₆ -C ₁₆ hydrocarbon, H-donor solvent, diesel, gasoline, LCO and mixtures thereof, especially second solvent And the use of alcohols such as TBA as the third solvent are preferred in many respects such as catalyst activity, conversion, yield, and selectivity.

Herein, a solvent pair in which the second solvent / third solvent lacks compatibility with each other such as, for example, TBA / benzene is not preferable, and a solvent pair having polarity / polarity or nonpolarity / nonpolarity and high miscibility with each other is preferable. Although highly compatible solvent pairs are not listed in the present invention, it will be apparent to those skilled in the art that they can be easily selected and used based on the disclosure of the present invention and the following experimental results. I will say.
In addition, the gasoline and light cycle oil of the first to third solvent components are the same components as the starting substrate of the hydrocarbon substrate and can perform the role of the reaction raw material at the same time as the solvent component of the catalyst, which is generally reacted in the field of catalytic reaction It is more effective considering the compatibility between the components used in the.

In the present invention, the selective oxidation system of "homogeneous catalyst + oxidant" or the "oxidant" used at this time serves to selectively partially oxidize the hydrocarbon substrate not excessively, and examples of oxidants usable in the present invention include O ₂ / CO ₂ mixed gas, H ₂ O ₂ , t-butylhydroperoxide (TBHP), H ₂ O ₂ / HCOOH, H ₂ O ₂ / CF ₃ COOH, ethylbenzenehydroperoxide, cumylhydroper Lockside, cyclohexylperoxodicarbonate (C ₆ H ₁₁ ) ₂ C ₂ O ₆₎ , H ₂ O ₂ / heteropolyacid (H ₃ PMo ₁₂ O ₄₀ , H ₃ PW ₁₂ O _40, H _0.5 Cs _2.5 PMo ₁₂ O ₄₀ ), H ₂ O ₂ / Mo (CO) ₆ , TBHP / Heteropolyacid (H ₃ PMo ₁₂ O ₄₀ , H ₃ PW ₁₂ O _40, H _0.5 Cs _2.5 PMo ₁₂ O ₄₀ ), TBHP / Mo (CO) ₆ , TBHP / M (acac) ₂ (where M = Mo or V), H ₂ O ₂ / metal naphthenate (where M = Mo, V, Cr, Mn, Ti, Co, Fe, Ni, Ta, Re, Nb, Ri, Re, Rh and W), TBHP / VOC ₂ O ₄ , TBHP / M ¹ ₂ M ^IV O (C ₂ O ₄ ) ₂ , TBHP / M ¹ ₂ M ^IV O (C ₂ O ₄ ) ₃ , TBHP / M ¹ ₂ M ^IV O ₂ (C ₂ O ₄ ) ₂ , H ₂ O ₂ / metal octoate (where M = Mo, V, Co, Fe, Ni, Ti, Cr, Mn, Selected from W, Ce and Ru), TBHP / metal octoate, provided that M = Mo, V, Co, Fe, Ni, Ti, Cr, Mn, W, Ce and Ru, or mixtures thereof Included, but not limited to.

Among them, a mixed gas of O ₂ / CO ₂ , TBHP, H ₂ O ₂ , t-butylhydroperoxide (TBHP), H ₂ O ₂ / HCOOH, H ₂ O ₂ / CF ₃ COOH, ethylbenzene hydroperlock Said, cumyl hydroperoxide, cyclohexyl peroxodicarbonate ((C ₆ H ₁₁ ) ₂ C ₂ O ₆ ) and the like are preferred as the oxidizing agent in the present invention.

In particular, in the case of using a mixed gas of O ₂ / CO ₂ as the oxidizing agent that can be used in the present invention, 5-100% by volume of CO ₂ may be included in the mixed gas, and preferably 7-80% by volume of CO. It is advantageous to include ₂ , more preferably 10-60% by volume of CO ₂ .

In addition, the O ₂ / CO ₂ mixed gas, which is an oxidizing agent, may further contain helium, argon, nitrogen, and the like, which may be advantageous in that it may serve as an inert diluent gas that does not participate in the oxidation reaction. The helium or argon is O ₂ / CO ₂ can be used in addition to 5 to 30 vol.% Relative to the mixed gas by volume, nitrogen, so also is a problem that the paper to cause the oxidation reaction can participate in the oxidation reaction O ₂ / CO It is advantageous to make it less than 20% by volume, preferably less than 10% by volume, more preferably less than 5% by volume, based on ₂ volumes. In this case, it is advantageous that nitrogen is ultimately 0% by volume as additional components used.

When O ₂ / CO ₂ or O ₂ / CO ₂ / Ar (N ₂ ) oxidizing gas is used together with the homogeneous catalyst according to the present invention, it is possible to obtain peroxide, hydroperoxide and peroxocarbonate in the liquid oxidation reactor itself. Oxidatively active intermediates are produced in-situ in the oxidation reactor, and by performing such selective oxidation reactions, it is possible to replace expensive conventional oxidants that have been used conventionally. .

 Anticipated Oxidation Tendency Based on Coordination Bond Formation

The present invention aims to produce an oxygen compound that can improve the cetane number or octane number at the same time as removing sulfur or nitrogen. Therefore, in view of this purpose, there is no need to remove sulfur or nitrogen contained therein. It is applicable to the present invention as long as it is a hydrocarbon substrate which also needs to generate an oxygen compound. Examples of such hydrocarbon substrates include, but are not limited to, the following hydrocarbon substrates.

(i) FCC (fluid phase) selected from gasoline, light cycle naphtha (LCN), heavy cycle naphtha (HCN), middle distillate, light cycle oil (LCO), heavy cycle oil (HCO), and cladified oil (CLO) Crude oil and its products (ii) Hydrocarbon substrate of (i) after hydrogenation (HDS and HDN) (iii) Heavy oil, bunker seed oil or residue oil from atmospheric or vacuum distillation process (iv) Aspoltin Isolated from Crude Oil (v) Whole crude oil without refinery (vi) Tar sands, oil sands or peat (vii) Hydrogenated Coal and H-Coal (viii) Chemically Deashed, Desulfurized, Denitrified Coal (ix) cokes

Among these hydrocarbon substrates, (i) a gasoline modified to include an oxygen compound by desulfurization and denitrification through selective hydrogenation, and (ii) a light cycle oil, a heavy cycle oil, a heavy oil fraction, and the like, which have been hydrogenated. Mixtures, and (iii) diesel that has been desulfurized, denitrified through a hydrogenation process, and modified to include an oxygen compound by selective oxidation, are examples of preferred hydrocarbon substrates to which the present invention is applicable.

In the present invention, "benzylic or allylic compound" is a concept that includes all compounds that can act as a starting material for producing an oxygenated substance that can improve the cetane number or octane number in the hydrocarbon substrate, representative examples thereof Tetralin; Alkyltetraline derivatives; Partially hydrogenated naphthalene and naphthene; Alkylbenzene derivatives such as xylene, cumene, isopropylbenzene, mesitylene, psuedocuemene, durene; And mixtures thereof, but is not limited thereto.

In the present invention, the "oxygen compound" is a concept including all oxygen-containing compounds that act to improve the cetane number or octane number in the hydrocarbon substrate, and representative examples thereof include α-tetralol and 1- (2-naphthyl). Alcohols such as ethanol; ketones such as α-tetralone, 1,4-naphthoquinone and fluorenone; aldehydes such as α-tetralene aldehyde; Organic acid esters such as methyl oleate, propyl linoleate, butyl stearate and methyl soyate; Aromatic or aliphatic organic acids such as dibutyl merate, terephthalic acid, 2,6-diphthalic acid and stearic acid; Ethers such as glyme, diglyme, triglyme and tripropylene glycol methyl ether; And mixtures thereof, but is not limited thereto.

In the present invention, examples of the "sulfur-containing compound" include dialkyldibenzothiophene (4,6-DMDBT, 2,5-DMDBT), 4-alkyldibenzothiophene (4-MDBT), dibenzothiophene (DBT), alkylbenzothiophene, benzothiophene (BT), dialkylthiophene, thiophene, diphenylsulfide, thiophenol, methylphenylsulfide, alkyldisulfide and mixtures thereof. In addition, in the present invention, “sulfur-containing precursor” means an oxygen-containing sulfur compound in the form of sulfoxide or sulfone of such sulfur-containing compound.

In the present invention, examples of "nitrogen-containing compounds" include, but are not limited to, pyridine, quinoline, pyrrole, indole, carbazole, and alkyl derivatives thereof, aromatic and aliphatic amines, and mixtures thereof. In the present invention, "nitrogen-containing precursor" means an oxygen-containing nitrogen compound in the form of N-oxide, oxime, nitron, nitrosobenzene, nitrobenzene or indigo of such nitrogen-containing compound.

In the present invention, "biphasic reaction system" means a nonpolar / polar reaction system, and examples of such a bipolar reaction system include oil / acetonitrile, oil / DMF, oil / acetic acid, oil / pyrrolidone, oil / NaOH Aqueous solutions, oil / NaHCO ₃ aqueous solutions, oil / Na ₂ CO ₃ aqueous solutions, oil / acetic acid-water mixtures, oil / t-BuOH and oil / MeOH.

In the present invention, the term "oil" narrowly means a hydrocarbon substrate to which the method of the present invention can be applied, such as TGO, and broadly, benzene which can be used as a simulated fraction experimentally in addition to a hydrocarbon substrate that may be applied commercially in practice. Or a nonpolar solvent such as n-octane.

Preferred "oxidizing agents" or "monocatalyst-oxidizing systems" which can be used in such biphasic reaction systems include O ₂ (10-40%)-CO ₂ / heteropolyacid, O, among the oxidizing agents or oxidation systems described above. ₂ (10-40%)-CO ₂ / Mo ⁶⁺ (blue oxirane catalyst solution), O ₂ (10-40%)-CO ₂ / Mo ⁶⁺ -M ^{n +} catalyst solution (M = Fe, Co, Ru , Selected from Cu, Zr, Hf, Ni and Zn), hydroperoxide / heteropolyacid, and hydrotalcite, it is preferable in practical terms to use.

In the present invention, the selective oxidation is preferably treated at 1-30 atm, more preferably at 5-20 atm, most preferably at 10-15 atm, and at the lower end of the pressure range. If the upper limit is exceeded, problems with sluggish oxidation reactions and problems with performance and stability under excessive pressure may occur.

In addition, the temperature of the selective oxidation is preferably 80-210 ° C, more preferably 130-190 ° C, most preferably 140-180 ° C, if the deviation from the lower and upper limits of the temperature range In each case, a desired oxidation reaction may be sluggish or excessively performed.

In the present invention, the desulfurization and denitrification post-treatment steps include filtration separation, fractionation, selective adsorption, solvent extraction, catalytic destruction, and selective oxidation. And pyrolysis.

Among them, the filtration separation method generates the sulfur or nitrogen-containing precursor generated in the selective oxidation step and precipitated in the polar solvent layer by a filtration device or a centrifuge.

In addition, selective adsorption methods include active carbon fibers, carbon nanotubes, carbon molecular sieves; M / activated carbon fiber, M / carbon nanotube, M / carbon molecular sieve (M = Pd, Zn, Cu, Ni, Fe, Mn, Ti, Mg, Sr, Ba, Na and K); Mesoporous alumina, silica gel, zeolite; Mesoporous alumina activated by metal treatment, silica gel activated by metal treatment, zeolite activated by metal treatment; M / Al ₂ O ₃ , SiO ₂ , MCM-41 (M = Y, La, Ni, Mo, Cr, W, V, Co and Cu selected), perovskite, Y ³⁺ addition Metal oxide stabilized with; ZrO ₂ , CeO ₂ -ZrO ₂ , and PrO ₂ -ZrO ₂ , MgO-MgAl ₂ O ₄ , MgAl ₂ O ₄ .xMgO, MgAl ₂ O _4. .yAl ₂ O ₃ , Cs / ZSM-5, Ba / MCM -41, Zn-Al double layered hydroxide (DLH), hydrotalcite, AlGaPON, ZrGAPON, Mg _0.819 Ga _0.181 (OH) ₂ (CO ₃ ) can be performed using one or more adsorbents. .

Solvent extraction methods include N, N'dimethylformamide (DMF), CH ₃ CN, DMF, DMSO, MeOH, t-BuOH, methyl ethyl ketone (MEK), CH ₃ COOH, dimethylpyrrolidone, dioxane, sulfolane (sulfolane), alkali metal and sodium carbonate (NaHCO ₃ , Na ₂ CO ₃ ) It can be carried out using a solvent selected from aqueous solution.

In addition, the catalyst removal method is t-BuONA, NAOH, NaOH-KOH, CH ₃ CO ₂ Na, eutectic mixture of Li ₂ CO ₃ -NaCO ₃ -K ₂ CO ₃ (Raney Ni), Raney iron (raney Fe), Na / K, Na / Al ₂ O ₃ , K / Al ₂ O ₃ , Li / MgO, Cs / SiO ₂ , MgFe ₂ O ₄ , [Ni (COD) ₂ Bipy], commercial HDS catalyst, One selected from a commercial HDN catalyst, hydrotalcite, Ce / V / MgO.MgAl ₂ O ₄ (commercial DeSOx catalyst), MgO.MgAl ₂ O ₄ (solid solution) and Zn-Al double layer hydroxides, or It is carried out in the presence of one or more base catalysts.

The pyrolysis method comprises dihydronaphthalene, tetralin, decalin, hydrogenated LCN, LCO and HCO, and among them H-doner solvents and / or MgO.MgAl ₂ O ₄ , xAl ₂ O _3. yMgAl ₂ O ₄ (Soluble), Cs / ZSM-5, Ba / MCM-41, Cs / SiO ₂ , Zn-Al double layered hydroxide, hydrotalcite, and Li / MgO, Li / MgO-CaO, Na / Al ₂ O ₃ , K / Al ₂ O ₃ , AlGaPON, ZrGaPON, Mg _1-x Ga _x (OH) ₂ CO _{3 It} will be carried out in the presence of a base catalyst.

In this case, the MgO MgAl ₂ O ₄ , the xAl ₂ O ₃ yMgAl ₂ O ₄ (solid solution), the Ce / V / MgO MgAl ₂ O ₄ , the Cs / ZSM-5, the Na / Al ₂ O ₃ , the K / Al ₂ O ₃ , the Cs / SiO ₂ , the Ba / MCM-41, NaOH-KOH, NaOH, CVD Fe / Mo / DBH, FCC catalyst, spent FCC catalyst, spent RFCC spent catalyst, zeolite ( ZSM-5, MCM-41, etc.), a commercial HDS catalyst (a catalyst or waste catalyst), a commercial HDN catalyst (a catalyst or a waste catalyst), and various other waste solid acid catalysts can be recycled and used.

In the present invention, desulfurization and denitrification are preferably made practically to remove sulfur-containing compounds and nitrogen-containing compounds at less than 20 ppm and less than 10 ppm, respectively, more preferably less than 10 ppm and less than 5 ppm, most preferably. Preferably it is advantageous to desulfurize and denitrify at less than 5 ppm and less than 2.5 ppm, ultimately 0 ppm, respectively.

In addition, in order to satisfy the oxygen content regulation value of the reformed gasoline, the oxygen-containing compound is preferably produced at 2.0-5.0 wt% based on oxygen, more preferably 2.2-3.0 wt%, most preferably 2.2- It is advantageous in terms of octane number or cetane number enhancement, PM reduction, NOx and SOx reduction, which produce oxygen compounds at 2.7% by weight (oxygen content environment regulation). In the case of diesel, the regulation of oxygen content has not yet been established, but it is only necessary to comply with future figures.

Meanwhile, the method of the present invention may also be applied to a transport oil selected from reformed gasoline or hydrogenated diesel, through which the octane number or cetane number of gasoline or diesel that has been desulfurized and denitrated by a conventional hydrotreating process is used. This is because there is an advantage that can be greatly improved.

Example

Hereinafter, the content of the present invention will be described in detail through examples. However, the following examples are provided to explain the contents of the present invention and do not limit the scope of the present invention.

Example 1

(1) Preparation of a "single phase" selective oxidation system of "single component homogeneous catalyst" + "TBHP oxidant"

Hydrogenated LCN, HCN, LCO, HCO and S-, N-compounds in clarified oils and benzylic hydrocarbons such as tetralin can optionally be oxidized in one reactor Homogeneous catalyst solution was prepared as follows.

M-naphthenate, M-stearate, M (CO) ₆ , MO ₂ (acac) ₂ (acac: acetylacetonate), M-octoate (M: Mo, V, Te, Re M-complex salts dissolved in hydrocarbons such as, selected from Ta and Nb) or insoluble such as various metal powders (selected from Mo, V, Te, Re, Ta and Nb), MoO ₃ and molybdic acid The precursor was reacted with TBHP incorporated in t-butyl alcohol (TBA) to make a homogeneous catalyst.

Among them, the Mo (oxirane) homogeneous catalyst having a particularly high oxidation activity is first dissolved by dissolving 1.48 g of Mo powder (<200 mesh size) in a TBHP: TBA: ethylene glycol mixed solvent (2: 4: 1 weight ratio). mL of blue catalyst solution was made. A small amount of formic acid, t-butylformate, t-butylacetate, etc. could be added to this mixed solvent to make the catalyst solution much easier.

In order to further improve the economics in the production of such a catalyst, a commercial catalyst solution could be prepared by directly using the residue waste liquid discharged from the propylene oxide commercial process instead of the mixed solvent. This homogeneous waste catalyst is treated with 1% NaOH or NH ₄ OH aqueous solution after the desired selective oxidation reaction, and then, the aqueous phase and the organic phase generated are separated, and the separated aqueous solution is precipitated by basic treatment such as CaO. It could be recovered.

(2) Confirmation of oxidation activity of "single phase" selective oxidation system of "single component homogeneous catalyst" + "TBHP oxidant"

The activity was verified by performing a liquid phase oxidation reaction in a benzene solvent at 80 ° C. for 2 hours using a single component homogeneous catalyst of various metals prepared in the following composition. The results of this experiment are summarized in Table 4 (activity verification experiment of single metal homogeneous catalyst).

Mixture substrate

Diethylsulfide 1 / 3x10 ^-2 mol

Benzothiophene 1.3x10 ^-2 mol

t-BuOOH (TBHP) 0.03 mol

Benzene 52 mL

0.100 g (100 ppm Mo) of Mo (oxirane) catalyst solution

(3) Preparation of "Single Phase" Selective Oxidation System of "Single-Component Homogeneous Catalyst" + "Oxidants Other than TBHP"

Mo-catalyst solutions and V-catalyst solutions with superior effects are used, but instead of TBHP, pseudocumene hydroperoxide, ethylbenzene hydroperoxide, H ₂ O ₂ / HCOOH, H ₂ O ₂ By using / CH ₃ COOH, CX ₃ COOH (X = F, Cl), a selective oxidation system of "homogeneous catalyst" + "oxidant other than TBHP" was prepared. In addition, the oxidative activity was confirmed, and as a result, an equivalent oxidative activity (conversion rate and oxidation selectivity) was observed when TBHP was used.

In addition, the oxidizers are expensive, so instead of using synthesized hydroperoxides, peroxides, H ₂ O ₂ , or peracids, the oxidants can be selected directly by using known processes in oxidation reactors. The oxidation reaction could be carried out at low cost. For example, if H ₂ O ₂ from H ₂ and _{O 2 Pd (1%) t} -Pt (0.1%) / TS-1 [P. Albert et al., J. Mol. Catal. 58, 115 (1990); R. Meiers et al., Catal. Lett., 59, 161 (1999)], anthraquinone using Pd catalyst [kirch-Othmer Encyclopedia of Chem. Tech., 13, 4th Ed., 1995, p.961], zeolite catalysts such as Pt-Au catalyst and TS-1 with MFI structure and TS-2 with MEL structure, water, H ₂ O + MeOH, acetone , CH ₃ and in the oxidation reactor from CN the solvent by immediately organic oxidation (in situ oxidation) reaction by creating a H ₂ O ₂ attempt to improve the process economy by using the oxidation desired H ₂ O ₂ - and achieve selective oxidation The economics of the whole process could be improved [B. Notari et al., Advances in Catalysis, Vol 41, p.253, 1996, Academic Press; RN Cochran et al., US 5,039,508 (1991).

Furthermore, while using monocomponent Mo- and V-catalyst solutions that perform well above, the gas is pre-mixed with O ₂ / CO ₂ (O ₂ and CO ₂ in a suitable formulation instead of using the expensive oxidizers above. ) Was added to the oxidizing gas to perform selective oxidation. As a result, it was confirmed that peroxocarbonate was formed in-situ of an active intermediate, and it was also confirmed that DBT sulfone was produced with high selectivity and high conversion rate. In this case, selective oxidation was carried out under a pressure of 5-15 atm using a reactor such as an autoclave, thereby achieving a high level of DBT sulfone production yield that is equivalent to or better than that of TBHP above.

Example 2

(1) Preparation of a "single phase" selective oxidation system of "two-component homogeneous catalyst" + "TBHP oxidant"

Metal and organometallic compounds capable of promoting the selective oxidation of allylic and benzylic hydrocarbons to a second metal compound, particularly as shown in Table 4, on a blue Mo (oxirane) catalyst made by dissolving Mo powder in TBA and TBHP. The selective oxidation system of various "two-component homogeneous catalysts" + "TBHP oxidants" was prepared by blending.

(2) Confirmation of selective oxidation activity of "single phase" selective oxidation system of "two-component homogeneous catalyst" + "TBHP oxidant"

Selective oxidation of DBT was carried out at 80 ° C. and atmospheric pressure for 2 hours using a selective oxidation system of “two-component homogeneous catalyst” + “TBHP oxidant” prepared above. The results are summarized in Table 5 (verification experiment of a two-component catalyst system for DBT oxidation).

In experiment 1 or 2 in the above table, a benzene solution of Co (acac) ₂ or Mn (acac) ₃ was combined with Mo (oxirane) (solution catalyst dissolved in TBA / TBHP), whereby Co or Mn It was inactivated because it existed in a completely separated precipitation state, and thus the DBT was not properly oxidized.

On the other hand, in experiment 3-7, two types of metals were independently present in the homogeneous phase as metal ions, thereby showing activity in DBT oxidation reaction to produce DBT sulfone. In particular, as can be observed in the seventh experiment, the two-component catalyst system made by dissolving the two metal powders in TBA / TBHP medium was excellent in activity and was confirmed as a very excellent catalyst system for the preparation of DBT sulfone.

(3) Preparation of "single phase" selective oxidation system of "two-component homogeneous catalyst" + "oxidant other than TBHP" and confirmation of selective oxidation activity

A two-component selective oxidation system was prepared by using an oxidizing gas of O ₂ / CO ₂ (30/70) instead of TBHP, and the selective oxidation of DBT was carried out under a pressure of 5-15 atmospheres using an autoclave. As a result, it was confirmed that DBT sulfone was synthesized in a very good yield without using a hydroperoxide such as TBHP.

In addition, the selective oxidation of benzylic hydrocarbons, such as tetralin, also showed that ketones, alcohols, and aldehydes, such as tetranone, known as cetane number enhancers, were synthesized in high yields. Could be confirmed.

Example 3

Representative thiophene compounds that are difficult to remove, such as dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), are each represented by Mo ( Oxirane) was oxidized to TBHP with a catalyst solution (a blue solution catalyst made by dissolving Mo metal powder), and the degree of oxidation was traced over time, and is shown in FIG. 1 (ㅁ: 4,6-DMDBT, ο: DBT , Δ: BT).

The figure shows that the removal order tendency of the conventional HDS process and the difficulty tendency of oxidation due to electrophilic attack are opposite directions. In other words, due to steric hindrance in the HDS process, compounds such as 4,6-DMDBT tend to be extremely difficult to oxidize, whereas in selective oxidation, 4,6-DMDBT is most easily oxidized in a very short time to completely form sulfones. Shows the switch.

As a result of this, various serious weaknesses of the conventional HDS process, that is, the complete elimination of sulfur (S-free) or the fact that depth or super depth desulfurization are virtually impossible, are overcome by the selective oxidation method of the present invention. It can be said clearly that it can be.

Example 4

(1) Preparation of a "bi-phase" selective oxidation system of "two-component homogeneous catalyst" + "TBHP oxidant" and identification of selective oxidation activity for "sulfur-containing compound"

A catalyst solution (2.5 μmol Mo + 2.5 μmol W) prepared by dissolving Mo and W metal powder (<200 mesh) in a mixed solvent of TBHP: TBA: EG (2: 4: 1) was mixed with 50 mL of CH ₃ CN. It was. A biphasic mixture was prepared by adding CH ₃ CN solution prepared above to a solution of 10 mmol DBT and 10 mmol 4,6-DMDBT in n-octane.

While performing vigorous stirring at 60 ° C. using TBHP as the biphasic reaction system and oxidant thus produced, the amount of migration and disappearance of the two substrates on the octane into the CH ₃ CN layer was followed by HPLC. In addition, the rate of migration of the two substrates from the octane layer to the CH ₃ CN layer was measured without performing a selective oxidation reaction.

As a result, it was confirmed that under the selective oxidation conditions, DBTO ₂ (sulfone) and 4,6-DMDBTO ₂ (sulfone) were rapidly transferred from the octane layer to the CH ₃ CN layer in amounts corresponding to 99% and 100%, respectively. On the other hand, in the absence of selective oxidation, 65% of DBT and 56% of 4,6-DMDBT were found to migrate to the CH ₃ CN layer.

In other words, the above results show that refractory thiophenes can be almost eliminated by selective oxidation in a dual-phase solvent system, while a significant level of removal is not accompanied by oxidation. Suggests that possible. However, if the above operation is repeated 2-3 times without performing a selective oxidation reaction, however, a considerable amount of sulfur-containing compounds which are difficult to oxidize can be separated and removed. Selective oxidation is still essential, in which case the dual phase selective oxidation system has been shown to be a very useful means.

In addition, it was confirmed that the selectivity, yield, etc. can be controlled by changing the composition of the appropriate solvent and the dual phase system, and in certain hydrocarbon substrates, the dual phase selective oxidation system is more effective than the single phase in terms of desulfurization, denitrification, and oxygenated compound generation. It was also confirmed that excellent results can be shown.

(2) Preparation of a "bi-phase" selective oxidation system of "two-component homogeneous catalyst" + "TBHP oxidant" and identification of selective oxidation activity for "nitrogen-containing compounds" and "allylic or benzylic hydrocarbons"

Using the dual phase selective oxidation system prepared above, selective oxidation was carried out under the same conditions for the nitrogen component and the allyllic or benzylic hydrocarbon component in addition to the sulfur component, and as a result showed excellent denitrification performance, and each corresponding oxidation product, That is, it was confirmed that the selective oxidation to the oxygen compound.

(3) Preparation of "bi-phase" selective oxidation system of "two-component homogeneous catalyst" + "oxidant other than TBHP" and confirmation of selective oxidation activity

A dual phase selective oxidation system was prepared using H ₂ O ₂ or O ₂ (20-40%) / CO ₂ (balance) in place of the TBHP oxidant, to perform the selective oxidation reaction. In particular, in the case of O ₂ (20-40%) / CO ₂ (balance), selective oxidation was performed at 5-15 atmospheres using an autoclave.

As a result, it was confirmed that the sulfur-containing compound, the nitrogen-containing compound and the allyllic or benzylic compound were each selectively oxidized with excellent efficiency, and furthermore, this selective oxidized product could be effectively separated or removed by quickly moving to a polar solvent. Confirmed.

Example 5

(1) In-situ Preparation of "Active Oxygen Oxidizers"

Among hydrotreated HDS fuel oils, an oil having a boiling point of 205-232 ° C. was cut, the components of which were paraffin 43.8%, cycloparaffin 36.3%, alkylbenzene 10.1% and tetralin It was analyzed at 5.5%. Of these components, alkylbenzenes and tetralins are representative benzylic hydrocarbons in many hydrotreated fractions.

For this fraction, attempts have been made to generate strong oxidants directly in the reactor itself using a Co-catalyst solution to use them as in-situ oxidants. This selective oxidation was carried out using a glass apparatus under an oxygen pressure of 1,000 mmHg and a temperature of 120 ° C. for 1 hour, and the results are summarized in Table 6 below (hydroperoxide in-situ preparation experiment).

(2) Confirmation of selective oxidation activity using "active oxygen oxidant"

Under the conditions of Experiment 5 above, where significant production of free radicals was confirmed, pickling oxidation for DBT was performed using Mo-solution (blue oxirane) catalyst and active oxygen generated in-situ directly in Experiment No. 5. It was. Selective oxidation was carried out in a liquid phase at 60 ℃ and atmospheric pressure, and it was confirmed that DBTO (sulfoxide) and DBTO ₂ (sulfone) were converted to high yield (> 95%) within a short time within 1 hour.

In addition, the same experiment was performed using a solution catalyst of V, Ti, W, Re in addition to the Mo-solution catalyst, and in this case, a high yield conversion was also confirmed.

From these results, organic hydroperoxides, although relatively strong oxidants, can generally be oxidized only to the sulfoxide stage in the reaction system in which no transition metal is present, no matter how much is consumed, but Mo, V, Ti, W As the presence of transition metal ion catalysts such as Re and Co, this sulfoxide was quantitatively oxidized to sulfone.

(3) Selective oxidation using "oxidants other than active oxygen oxidants" Of air oxidation in the presence of alkali  Check active

In addition to the catalytic reaction of the transition metals described above, it was confirmed that the sulfoxide was smoothly converted to sulfone at room temperature in the presence of NaOH. In addition to NaOH, the activity of various bases showed the following tendency. t-BuONa> NaOH (NaOH-KOH)> Na ₂ CO ₃ , CH ₃ CO ₂ Na >> Li ₂ CO ₃ -Na ₂ CO ₃ -K ₂ CO ₃ (eutectic mixture)

On the other hand, it was confirmed that dimethyl sulfoxide was oxidized to sulfone at room temperature with EtOH solvent by cumene hydroperoxide. On the other hand, when water coexisted, the reaction was stopped.

Example 6

(1) selective oxidation treatment

For heavy cyclic naphtha (HCN) containing 0.12% S component and 45 ppm N component, a blue Mo (oxirane) catalyst system was used and the O ₂ (26%) / CO ₂ (74%) Liquid phase oxidation was carried out at 80 ° C. for 2 hours using each of the systems.

(2) Filtration after treatment

The oxide produced in the above (1) was filtered under reduced pressure using a glass filter and an aspirator. As a result of analyzing the S and N components remaining in the filtrate, it was confirmed that the S component was detected at less than 25 ppm, and the N component was not detected at all.

In other words, sulfon, which is an oxide of DBT, and indigo, which is an oxide of indole, which is one of the N-compounds, were precipitated and existed in the solid state in the oxidation reaction system, so they could be easily separated by filtration to achieve a very high desulfurization rate. It was also confirmed that the removal was almost completely impossible to detect.

(3) HDS post-treatment

The oxide produced in (1) was hydrogenated on Ni (6%)-Mo (18%) / γ-Al ₂ O ₃ (M = Ti, Zr, B, P), a conventional commercial HDS catalyst. . Analysis of the product obtained after the treatment confirmed that the S component was detected at less than 20 ppm, and the N component was not detected at all.

That is, by selective selective oxidation of the oily substrate, the major S-components in the oil, which are refractory condensed thiophenes, are converted to sulfones, making removal much easier than condensed thiophenes. Very high desulfurization rate was achieved and the N-component was almost completely removed so that it could not be detected.

(4) FCC Waste Catalyst Cracking Post Treatment

For the oxide produced in (1), hydro-cracking and normal cracking were performed using FCC waste catalyst loaded with Ni, V, and Fe. Analysis of the product obtained after the treatment confirmed that the S component was detected at less than 10 ppm, and the N component was not detected at all.

From these results, the catalysts already used and discarded in FCC and residual fluid catalytic cracking (RFCC) exhibited excellent desulfurization (<10 ppm) performance using waste catalysts containing large amounts of V, Ni, and Fe. It was confirmed that the N-component was also almost completely removed so that it could not be detected.

Example 7

(1) "peroxophosphotungstate oxidant" and "oil / CH ₃ Selective Oxidation Using CN Dual-Phase System

60 ° C. in a dual phase system (oil / CH ₃ CN) using peroxosophosphotungstate (30% H ₂ O ₂ / tungstophosphoric acid) for light diesel containing HDS treatment and relatively low sulfur (330 ppm) Desulfurization via selective oxidation was carried out for 3 hours while maintaining the temperature of. The results are summarized in the following table.

(2) peroxophosphotungstate oxidizer and " oil / CH ₃ Selective Oxidation Using a Dual-Phase System Other Than CN

Apply the same reaction conditions as above except for oil / MeOH, oil / DMF, oil / acetic acid, oil / pyrrolidone, oil / p-dioxane, benzene / MeOH instead of oil / CH ₃ CN used above as a dual phase medium. The selective oxidation reaction was carried out using an oil / NaOH aqueous solution, respectively. As a result, the result of excellent depth desulfurization and denitrification was confirmed as in oil / CH ₃ CN.

(3) "oxidants other than peroxophosphotungstate" and oils / CH ₃ Selective Oxidation Using a Dual-Phase System Other Than CN

The same reaction conditions as above were applied except that the selective oxidation reaction was carried out using the oxidizing agent described below instead of the peroxophosphotungstate used above as the oxidizing agent.

As a result, materials containing organic peroxides or hydroperoxides, such as heteropolyacids, Mg-Al layered double hydroxide; Mg-Al hydrotalcite; Rh / Mg ₆ Al ₂ (OH) _16.4 H ₂ O), Zn-Al layered double hydroxide (Zn-Al layered double hydroxide; Zn-Al hydrotalcite material) was found that the results of excellent depth desulfurization and denitrification, In particular, the hydrotalcite material containing anion pillars shown in Table 8 yielded very good results.

(4) "monometal homogeneous catalyst" or "bimetal homogeneous catalyst" and "O ₂ / CO ₂  Selective Oxidation in a Dual-Phase System Using an Oxidizer

Monometallic solution catalysts and bimetallic solution catalysts were prepared by dissolving the metal powder in a suitable solvent, as indicated above, and using this, at atmospheric pressure or under an oxidizing gas of air and O ₂ (30%) / CO ₂ (70%). The selective oxidation reaction was carried out in the Ti-autoclave (15 atm) in the above-listed dual phase system for 1-4 hours, and as a result, it was confirmed that the desulfurization to a good degree.

Example 8

(1) Selective oxidation of LCO using "Mo (oxirane) homogeneous catalyst" and "TBHP oxidant"

For light cycle oil (LCO) containing 0.07% S-component and 40 ppm N-component, lightly hydrotreated, in a 1 L three-necked flask using blue Mo (oxirane) solution catalyst and TBHP Selective oxidation was performed under controlled conditions (160 ° C., 3 hours, atmospheric pressure, 150 rpm stirring) to oxidize S- and N-compounds as well as allyl or benzylic hydrocarbons.

(2) Select oxidation  Through S- or N-component precursors and Oxygen  Confirmation of Formation of Compound

IR analysis of the oxidized product obtained in the above experiments showed that the S-component was converted to sulfone at nearly 100%, and the N-component was also converted into an easy-to-remove precursor, as well as a significant amount of "carbonyl". It was confirmed that the product was produced.

(3) Post-treatment by pyrolysis

For an aliquot portion (40 mL) of the oxide obtained in the above experiment, pyrolysis was carried out in a pyrolysis unit for 3 hours at 450 ° C with H-donor solvent. As a result, a desulfurization rate of about 92-97% was achieved as shown in the following table, and the N-component could not be detected at all. On the other hand, in the case of coexistence of naphthalene and not H-donor, the desulfurization rate was 83%.

(4) Post-Pyrolysis Treatment in the Presence of Base Catalyst

For some other portion (40 mL) of the oxide obtained above, bases such as hydrotalcite, Na / Al ₂ O ₃ , Na / K / activated carbon, Cs / ZSM-5, Cs / SiO ₂ , Ba / MCM-41 5 g of the catalyst was added and then heat treated in a pyrolysis unit at 450 ° C. for 1 hour.

As a result, desulfurization rate (> 98%) and denitrification rate (~ 100%) were achieved, and at the same time, the excellent effect of removing almost all metals (> 95%) including Mo used as a catalyst was found to be excellent. .

(5) post-treatment with adsorbent

Some other portion (40 mL) of the oxide obtained above was pre-filtered, and then sulfur or nitrogen containing precursors were separated and removed using activated carbon fibers, silica gel and carbon molecular sieves (10 mL / g adsorbent). It was confirmed that the S and N-components were not detected at all in the final filtrate by treating the adsorbent once or twice.

In addition to the conventional adsorbents above, Pd / Al ₂ O ₃ , Pt / Al ₂ O ₃ , Pd / Activated Carbon, Pt / Activated Carbon, PdBaTiO ₃ , Pt / BaTiO ₃ , Pt / Mg ₂ Al ₂ O ₅ , Pd / MgAl ₂ O ₄ , V / Ce / MgAl ₂ O ₄ , V / Ce / MAl ₂ O ₄ (M = selected from Fe, Cr, Co, Ni, Cu, Cd, Hg, Zn and Zr), V / Ce / MgAl ₂ O ₄ .xAl ₂ O ₃ , M / MgAl ₂ O ₄ (M = selected from Fe, V, Cr, Ta, Nb, Ti, Mo, Zr and Mn), M / zeolite, M / active carbon, Post-treatment using new adsorbents such as M / active carbon fibers, M / carbon molecular sieves, M / carbon nanotubes (M = Fe, V, Cr, Ta, Nb, Ti, Mo, Zr and Mn) The results were also confirmed to show an excellent degree of desulfurization, denitrification effect.

(6) Post-treatment by Selective Extraction of Polar Solvents

Some other portion of the oxide obtained above (40 mL) was pre-filtered to remove any possible solid deposits, and the filtrate was then selectively extracted using polar solvents such as DMF (dimethyl formamide), CH ₃ CN and organic acids. Was performed.

The sulfur and nitrogen components remaining after the selective extraction from the above were measured, and when compared with the contents existing in the original substrate, it can be seen that excellent desulfurization and denitrification were made as shown in the following table.

(7) Post-treatment by fractionation

For some other portion (200 mL) of the oxide obtained above, fractional distillation was performed after filtration in advance. As a result, it was confirmed that more than 90% of desulfurization and almost complete denitrification could be realized in the oil obtained by distillation at the highest boiling point of the oil which did not undergo oxidation reaction.

(8) Component Analysis for Selective Oxidation Products

For the oxidation product of the hydrotreated LCO obtained by performing the liquid phase oxidation reaction in the above experiment, the component analysis was performed.

The chromatography is classified into aliphatic, aromatic, and polar substances according to polarity, and then subjected to Fourier-converted IR spectroscopy and high resolution gas chromatography-mass spectrometric technique. A detailed analysis was performed.

As a result, it was confirmed that the aliphatic compound was mainly paraffin and remained in its original state without being oxidized without any change, except that only monocycloalkane was completely oxidized. In addition, the aromatic compounds consisted mainly of ketones and lactones which are cyclic esters, with the polar part being composed of DBT sulfone and oxidized N-compounds, such as N-oxides, oximes, indigo, aromatic alcohols, anhydrides, aldehydes and carboxyls. It was confirmed that the acid, ester, ketones such as α-tetralone.

It is confirmed that the selective oxidation method according to the present invention converts sulfur or nitrogen-containing precursors which are easily desulfurized and denitrified into excellent yields, and at the same time, a large amount of oxygen-containing compounds capable of enhancing cetane number or octane number are also produced. will be.

Example 9 Selective Oxidative Desulfurization of Coal

(1) coal cleaning process

Selective oxidative desulfurization experiments were performed by selecting bituminous coal from the United States as feed coal. First, the sample is crushed to a suitable size using a homomoloid hammer mill, and the pulverized sample is changed to a hydrophilic surface by using an ash conditioning agent. Demineralization was performed by (oil agglomeration) method. At this stage, all experimental procedures were carried out in an atmosphere of nitrogen to prevent unwanted natural oxidation of the sample generated by air.

(2) selective oxidation reaction

The deash sample of the first step was mixed with distilled water and then heated with stirring vigorously (~ 1500 rpm) to make a 20% by weight slurry in a 300 cc autoclave. It took about 40 minutes to reach the reaction temperature (90 ^° C.).

As soon as the reaction system is stable at this reaction temperature, a concentrated Na ₂ C ₂ O ₄ solution containing Fe ³⁺ is pumped into the reactor, and the [Fe (C ₂ O ₄ ) ₃ ] ^3- complex catalyst is immediately added. Produced and the pH of the reaction medium slurry was adjusted to 4.0-5.5. Of course, some Fe ⁺³ ions may be produced by the reaction of pyrite in coal with an excess of [C ₂ O ₄ ] ^2- ions.

A small amount of the reaction solution sample was drawn at regular intervals through an outlet tube connected to a metal filter tip at the end to keep track of the pH of the reaction medium during the reaction.

Analysis of Cleaned Coal Samples Raw coal Deash sample (one step treatment) Ash 12.7 wt% 7.98 wt% Sulfur total 3.30 wt% 1.29 wt% Pyritic 1.96 wt% 0.45 wt% Sulfate 0.32 wt% 0.01 wt% Organic sulfur 1.02 wt% 0.83 wt%

Another U.S. bituminous coal sample containing air containing large amounts of organic sulfur as a sample using clean coal as a pretreatment described above, and air and O ₂ / CO ₂ oxide gas in the same Fe ^{3 +} / [C ₂ O ₄ ] ^2- medium. Oxidation reaction was carried out by selective oxidation under an atmosphere, and then desulfurized by base treatment. The desulfurization results were summarized in Table 12 (Fe ^{3 +} / [C ₂ O ₄ ] ^2- (mainly [Fe (C ₂ O ₄ )). ₃ ] ^3- ) Desulfurization by selective oxidation and base treatment under an atmosphere of air (O ₂ / N ₂ ) and O ₂ / CO ₂ oxidizing gas under a catalyst).

Oxidation gas was prepared by mixing air and O ₂ (20-30%) / CO ₂ (balance) in advance, and the oxidation was performed under a constant pressure. The slight rise in temperature was observed by the addition of this oxidizing gas, and the pyrite (FeS ₂ ) was completely extinguished and a considerable amount of organic matter was allowed to proceed to complete the oxidation reaction by severe stirring in a pH-controlled buffer medium. The reaction was maintained to achieve sulfur removal. Na ₂ C ₂ O ₄ solution was supplemented if necessary during the course of the reaction for pH control of the reaction medium.

Immediately after the desired oxidation reaction was completed, the cold water was passed through the autoclave cooling coil to cool rapidly. Upon cooling, an excess amount of oxidizing gas was immediately released to the outside, and the cooled reaction mixture was recovered. The oxidized coal was separated from the yellow-green filtrate, washed thoroughly with warm water, and washed until no [C ₂ O ₄ ] ^2- ions were detected in the filtrate. The coal product thus separated was dried and analyzed in a high vacuum at 120 ℃.

(3) base treatment deoxidation

Organic sulfur contained in coal macerol was optionally oxidized to sulfoxide, sulfone, sulfonate under the above conditions. These oxidized organosulfurs, especially sulfur that is difficult to remove, and yellowish blue, which may remain in trace, were removed by treatment at high temperature with an aqueous solution of base such as Na ₂ CO ₃ , NaOH-KOH.

A 20 g sample of this oxidized coal was placed in a 300 cc Monel autoclave with 100 mL aqueous solution of base. The reactor was subjected to a base desulfurization treatment at 625-650 ° C. for 0.5-1.0 hours with air passing through a nitrogen stream to remove air and vigorously stirring. The water / coal weight ratio was 3/1, the Na ₂ CO ₃ / coal weight ratio was 0.3, and in general, the weight ratio of base / coal depends on organic sulfur, but about 2 mol of base per mol of organic sulfur is required. .

The results are shown in Table 12 above. From these results, Fe ³⁺ / [C ₂ O ₄ ] ^2- (mainly O ₂ / CO ₂ oxidation in the catalytic oxidation of [Fe (C ₂ O ₄ ) ₃ ] ^3- ) In the case of gas, it was confirmed that the desulfurization rate of inorganic and especially organic sulfur increased from 12% to 89% compared to general air oxidation.

Example 10 "Dual Metal Powders" and "O ₂ / CO ₂  Selective Oxidation with "Oxidant"

n-decane (99%, Aldrich), n-hexadecane (99%, Aldrich), benzene (99%, Aldrich), t-butylbenzene (99%, Aldrich) was used as the simulated oil, and DBT (dibenzo Thiophene, 98%, Aldrich), 4,6-DMDBT (4,6-dimethyl dibenzothiophene, 97%, Aldrich) and the like were used as model compounds to prepare simulated substrates having the composition shown in the table below. .

DBT 5,000 ppm 4,6-DMDBT 5,000 ppm n-decane 34.3 g n-hexadecane 34.3 g benzene 14.7 g t-butylbenzene 14.7 g

Liquid oxidation was carried out in 200 mL of Ti-autoclave using 0.142 g of the same substrate and FeMoO ₄ powder. The reaction was performed under conditions of 10 atm, 150 ° C., reaction time 3 hours, and 350 rpm while flowing O ₂ / CO ₂ (30% / 70%) oxidizing gas. The final material after oxidation was analyzed using GC-MS (Agilent 5973I), GC-FID (Agilent 6890N), PFPD (OI model 5380). As a result of this experiment, it was confirmed that other components were not oxidized at all and sulfur compounds DBT and 4,6-DMDBT were selectively oxidized to DBT-O ₂ (52%) and 4,6-DMDBT-O (45%), respectively. .

From the experimental results, it was confirmed that when the FeMoO ₄ powder was uniformly dispersed in the reaction medium, the FeMoO ₄ powder had almost the same effect as the dual metal homocatalyst system of Fe and Mo according to the following formula. In other words, the monometallic component and the bicomponent or multicomponent homogeneous catalyst reactions are substantially the same as when the pure homogeneous solution catalyst is used even if the solid catalyst is pulverized into fine powder and uniformly dispersed in an appropriate medium to perform the oxidation reaction in a high liquid phase. It can be said that there is another technical meaning of the present invention in that the oxidation can be carried out in the same reactor.

For reference, although the catalyst used is a FeMoO ₄ solid catalyst, in fact it is converted into a mixed oxide component of Fe ₂ (MoO ₄ ) ₃ and Fe ₂ O ₃ according to the following reaction equation when contacted with an oxidizing gas of O ₂ / CO ₂ . ₂ (MoO ₄ ) ₃ as the main catalyst component can maintain the oxidation effect that simulates the two-component homogeneous solvent catalyst system of Fe ^{3 +} and Mo ^{6 +} .

As described above, the present invention shows the effect of performing one-step liquid phase selective oxidation in one reactor to remove sulfur and nitrogen-containing compounds from various hydrocarbon substrates and to synthesize useful oxygen compounds at the same time. . In particular, the process of the present invention is a process that performs depth or super-depth desulfurization and denitrification, and simultaneously satisfies the oxygen content, octane number and cetane number regulation required for future transport oils.

Hydrocarbon substrates to which the present invention is applicable include petroleum derived FCC products, transport fuels (petrol and diesel), middle distillates, heavy oils and residues. It can also be applied to the cleanliness of coal, all fossil-derived products, solid fossil fuels such as shale oil and tar sand.

According to the present invention, a non-MC type homogeneous catalyst represented by a mixed catalyst of M ^{n +} / first solvent or M ₁ ^{n +} / second solvent and M ₂ ^{m +} / third solvent is used for gasoline, light oil and heavy oil in naphtha. Sulfur in various petroleum products, such as residues, in particular refractory thiophene derivatives, benzthiophene (BT), dibenzothiophene (DBT) 46-dimethyl-dibenzothiophene (4 , 6-DMDBT), N-compounds (amine, pyrrole-based, pyridine-based), and benzyl acid and allyl hydrocarbon are selected by oxidation reactions, respectively, corresponding sulfoxide / sulfone, N-oxide / indigo / oxime and cetane number of diesel, Useful oxides (ketones, alcohols, aldehydes, ethers), which are gasoline octane enhancers, can be synthesized in one reactor in one reactor.

The sulfoxides / sulfones and N-oxides / indigo / oximes produced in this selective oxidation process are separated / removed into the polar solvent phase in the dual phase (polar / non-polar solvent) oxidation reactor or simple pyrolysis (H-provided in the second step). Solvent-free, non-catalyst), contact desulfurization / denitrification using conventional catalysts and new base catalysts, or using conventional simple known separation methods (solvent selective extraction, selective adsorbents, fractionation, oxidation or non-oxidation double phase separation). Desulfurization and denitrification are carried out to produce fractions of sulfur or nitrogen at ultra-low or no (S-free and N-free) fractions, as well as to synthesize useful oxygenates (oxygenates) for future oxygen. It is a petroleum oil clean process that can cope with the strengthening of environmental regulations regarding contents.

Claims (18)

By oxidizing the hydrocarbon substrate in the presence of a homogeneous catalyst and an oxidant, converting the sulfur or nitrogen containing compound to a sulfur or nitrogen containing precursor that is easy to desulfurize and denitrate, while simultaneously converting the benzylic or allyl compound to an oxygenated compound As a selective oxidation method of a hydrocarbon substrate comprising; The homogeneous catalyst is selected from a mixed catalyst of M ^{n +} / first solvent, M ₁ ^{n +} / second solvent and M ₂ ^{m +} / third solvent; M ^{n +} is Co ³⁺ , Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ , MoO ₄ ^2- , V ⁵⁺ , VO ³⁺ , VO ₂ ³⁺ , W ⁶⁺ , Selected from WO ₄ ^2- , Cr ³⁺ , Ti ⁴⁺ , Fe ³⁺ , Ni ²⁺ , Zr ⁴⁺ , ZrO ²⁺ , Hf ⁴⁺ , Ta ⁶⁺ , Nb ⁵⁺ , Ce ⁴⁺ and Ce ³⁺ Become; M ₁ ^{n +} is Co ³⁺ , Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ and MoO ₄ ^2- Is selected from; M ₂ ^{m +} is Fe ³⁺ , Ni ²⁺ , Cu ²⁺ , V ⁵⁺ , VO ³⁺ , VO ₂ ³⁺ , Cr ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , ZrO ²⁺ , Hf ⁴⁺ , Ta ⁶⁺ , Nb ⁵⁺ , Re ⁴⁺ , Ru ⁴⁺ , Sm ⁴⁺ , Pr ³⁺ and Ce ³⁺ ; The first solvent, the second solvent, and the third solvent are the same or different from each other, and water, alcohols, CH ₃ CN, DMF, N-pyrrolodon, formic acid, acetic acid, octanoic acid, and trifluorine, respectively. Process for selective oxidation of hydrocarbon substrates, characterized in that selected from roacetic acid, acetic acid-water mixtures, aliphatic or aromatic C ₆ -C ₁₆ hydrocarbons, H-donor solvents, diesel, gasoline, LCO and mixtures thereof . (a) oxidizing the hydrocarbon substrate in the presence of a homogeneous catalyst and an oxidizing agent to convert the sulfur or nitrogen containing compound into a sulfur or nitrogen containing precursor that is easy to desulfurize and denitrate, while simultaneously converting the benzylic or allyl compound into an oxygenated compound Selective oxidation step of conversion; And (b) desulfurizing and denitrifying the hydrocarbon substrate by removing the sulfur or nitrogen containing precursor, the method of selective oxidation of the hydrocarbon substrate, The homogeneous catalyst is selected from a mixed catalyst of M ^{n +} / first solvent, M ₁ ^{n +} / second solvent and M ₂ ^{m +} / third solvent; M ^{n +} is Co ³⁺ , Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ , MoO ₄ ^2- , V ⁵⁺ , VO ³⁺ , VO ₂ ³⁺ , W ⁶⁺ , WO ₄ ^2- , Cr ³⁺ , Ti ⁴⁺ , Fe ³⁺ , Ni ²⁺ , Zr ⁴⁺ , ZrO ²⁺ , Hf ⁴⁺ , Ta ⁶⁺ , Nb ⁵⁺ , Ce ⁴⁺ and Ce ³⁺ ; M ₁ ^{n +} is Co ³⁺ , Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ and MoO ₄ ^2- Is selected from; M ₂ ^{m +} is Fe ³⁺ , Ni ²⁺ , Cu ²⁺ , V ⁵⁺ , VO ³⁺ , VO ₂ ³⁺ , Cr ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , ZrO ²⁺ , Hf ⁴⁺ , Ta ⁶⁺ , Nb ⁵⁺ , Re ⁴⁺ , Ru ⁴⁺ , Sm ⁴⁺ , Pr ³⁺ and Ce ³⁺ ; The first solvent, the second solvent, and the third solvent are water, alcohols, CH ₃ CN, DMF, N-pyrrolodon, formic acid, acetic acid, octanoic acid, trifluoroacetic acid, acetic acid-water mixture , Aliphatic or aromatic C ₆ -C ₁₆ hydrocarbons, H-donor solvent, diesel, gasoline, LCO selected process for the oxidation of a hydrocarbon substrate, characterized in that selected from. By oxidizing the hydrocarbon substrate in a biphasic reaction system in the presence of a homogeneous catalyst and an oxidizing agent, the benzylic or allylic compound is converted while converting the sulfur or nitrogen containing compound into a sulfur or nitrogen containing precursor which is easy to desulfurize and denitrate. A method of selective oxidation of a hydrocarbon substrate comprising the step of converting to an oxygenated compound; The homogeneous catalyst is selected from a mixed catalyst of M ^{n +} / first solvent, M ₁ ^{n +} / second solvent and M ₂ ^{m +} / third solvent; M ^{n +} is Co ³⁺ , Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ , MoO ₄ ^2- , V ⁵⁺ , VO ³⁺ , VO ₂ ³⁺ , W ⁶⁺ , Selected from WO ₄ ^2- , Cr ³⁺ , Ti ⁴⁺ , Fe ³⁺ , Ni ²⁺ , Zr ⁴⁺ , ZrO ²⁺ , Hf ⁴⁺ , Ta ⁶⁺ , Nb ⁵⁺ , Ce ⁴⁺ and Ce ³⁺ Become; M ₁ ^{n +} is Co ³⁺ , Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ and MoO ₄ ^2- Is selected from; M ₂ ^{m +} is Fe ³⁺ , Ni ²⁺ , Cu ²⁺ , V ⁵⁺ , VO ³⁺ , VO ₂ ³⁺ , Cr ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , ZrO ²⁺ , Hf ⁴⁺ , Ta ⁶⁺ , Nb ⁵⁺ , Re ⁴⁺ , Ru ⁴⁺ , Sm ⁴⁺ , Pr ³⁺ and Ce ³⁺ ; The solvent is water, alcohols, CH ₃ CN, DMF, N-pyrrolodon, formic acid, acetic acid, octanoic acid, trifluoroacetic acid, acetic acid-water mixture, aliphatic or aromatic C ₆ -C ₁₆ hydrocarbons Selective oxidation method of a hydrocarbon substrate, characterized in that selected from H-donor solvent, diesel, gasoline, LCO. The method according to any one of claims 1 to 3, wherein M ^{n +} and M ₁ ^{n +} are the same or different from each other and are selected from Mo ⁶⁺ , MoO ₂ ²⁺ , MoO ⁴⁺ and MoO ₄ ^2- ; M ^{n +} and M ₂ ^{m +} are the same or different from each other and are selected from V ⁵⁺ , VO ³⁺ and VO ₂ ³⁺ Selective oxidation method of the hydrocarbon substrate, characterized in that. The method according to any one of claims 1 to 3, wherein the oxidizing agent Mixed gas of O ₂ / CO ₂ , O ₂ / CO ₂ / He mixture gas, O ₂ / CO ₂ / Ar mixture gas, H ₂ O ₂ , t-butylhydroperoxide (TBHP), H ₂ O ₂ / HCOOH, H ₂ O ₂ / CF ₃ COOH, Ethylbenzene hydroperoxide, Cumyl hydroperoxide, and Method for the selective oxidation of a hydrocarbon substrate, characterized in that at least one selected from cyclohexyl peroxodicarbonate ((C ₆ H ₁₁ ) ₂ C ₂ O ₆ ). The method of claim 5, wherein the mixed gas of O ₂ / CO ₂ comprises 7-80% by volume of CO ₂ . The method of claim 6, wherein the mixed gas of O ₂ / CO ₂ comprises 10-60% by volume of CO ₂ . 6. The method of claim 5, wherein the mixed gas of O ₂ / CO ₂ further comprises 5-30% by volume of helium or argon. The method of claim 5, wherein the O ₂ / CO ₂ mixed gas further comprises a nitrogen of 0 to less than 20% by volume of the selective oxidation of the hydrocarbon substrate. The method of claim 1, wherein the hydrocarbon substrate is (i) FCC selected from gasoline, light cycle naphtha (LCN), heavy cycle naphtha (HCN), middle distillate, light cycle oil (LCO), heavy cycle oil (HCO), and clade oil (CLO) Crude oil and products thereof (fluidic contact cracking); (ii) the hydrocarbon substrate of (i), which has been subjected to a hydrogenation process (HDS and HDN); (iii) heavy oil, bunker seed oil or residue oil from atmospheric or vacuum distillation processes; (iv) aspoltin isolated from crude oil; (v) whole crude oil without refinery process; (vi) Tar sands, oil sands or peat; (vii) hydrogenated liquefied coal and H-coal; (viii) clean coal that has been chemically deashed / desulfurized / denitrified; And (ix) A method of selective oxidation of a hydrocarbon substrate, characterized in that it is at least one hydrocarbon substrate selected from coke. The method of claim 10, wherein the hydrocarbon substrate is coal that has been chemically deashed and desulfurized inorganic sulfur; The homogeneous catalyst is Fe ³⁺ / [C ₂ O ₄ ] ^2- and has the form of [Fe (C ₂ O ₄ ) ₃ ] ^3- ; Wherein the oxidant is an O ₂ / CO ₂ mixed gas. 4. The hydrocarbon substrate according to any one of claims 1 to 3, wherein the hydrocarbon substrate is subjected to (i) desulfurization and denitrification through a hydrogenation process and gasoline modified to include an oxygen compound by selective oxidation, and (ii) a hydrogenation process. Selected from coarse light cycle oils, heavy cycle oils, heavy oils and mixtures thereof, and (iii) diesel oils which are desulfurized and denitrified through a hydrogenation process and modified to include oxygenated compounds by selective oxidation. A method of selective oxidation of a hydrocarbon substrate, characterized by the above-mentioned. The process of claim 1, wherein the hydrocarbon substrate is a transport oil selected from modified gasoline or hydrotreated diesel; The reformed gasoline or hydrotreated diesel is a selective oxidation method of a hydrocarbon substrate, characterized in that the desulfurization and denitrification by a hydrogenation process. The method of claim 1, wherein the benzylic or allyl compound is tetralin; Alkyltetraline derivatives; Partially hydrogenated naphthalene and naphthene; Alkylbenzene derivatives selected from xylene, cumene, isopropylbenzene, mesitylene, psuedocuemene, durene; And mixtures thereof; The oxygen compound is selected from alcohols, ketones, aldehydes, organic acid esters, aromatic or aliphatic organic acids, ethers and mixtures thereof; The sulfur-containing compound is dialkyldibenzothiophene (4,6-DMDBT, 2,5-DMDBT), 4-alkyldibenzothiophene (4-MDBT), dibenzothiophene (DBT), alkylbenzothiophene , Benzothiophene (BT), dialkylthiophene, thiophene, diphenylsulfide, thiophenol, methylphenylsulfide, alkyldisulfide and mixtures thereof; The sulfur-containing precursor is an oxygen-containing sulfur compound in the form of sulfoxide or sulfone of the sulfur-containing compound; The nitrogen-containing compound is selected from pyridine, quinoline, pyrrole, indole, carbazole, and alkyl derivatives thereof, aromatic and aliphatic amines and mixtures thereof; The nitrogen-containing precursor is a method for the selective oxidation of a hydrocarbon substrate, characterized in that the nitrogen-containing compound N-oxide, oxime, nitron, nitrosobenzene, nitrobenzene or indigo oxygenated nitrogen compound. The biphasic reaction system according to claim 3, wherein the biphasic reaction system is oil / acetonitrile, oil / DMF, oil / acetic acid, oil / pyrrolidone, oil / NaOH aqueous solution, oil / NaHCO ₃ aqueous solution, oil / Na ₂ CO ₃ A nonpolar / polar reaction system selected from aqueous solution, oil / acetic acid-water mixture, oil / t-BuOH and oil / MeOH; The oxidizing agent in the biphasic reaction system was O ₂ (10-40%)-CO ₂ / heteropoly acid, O ₂ (10-40%)-CO ₂ / Mo ⁶⁺ (blue oxirane catalyst solution), O ₂ In (10-40%)-CO ₂ / Mo ⁶⁺ -M ^{n +} catalyst solution (M = Fe, Co, Ru, Cu, Zr, Hf, Ni, Zn), hydroperoxide / heteropolyacid, and hydrotalcite The method of selective oxidation of a hydrocarbon substrate, characterized in that it is selected. The method of any one of claims 1 to 3, wherein the oxidation is carried out under a pressure condition of 1-20 atm and a temperature condition of 80-190 ° C. The method of claim 2, wherein (b) the desulfurization and denitrification step is performed by filtration separation, fractionation, selective adsorption, solvent extraction, catalytic destruction, selective oxidation. ) And pyrolysis is carried out by at least one method selected from the group consisting of. The process according to claim 1, wherein the desulfurization and denitrification is made to remove sulfur-containing compounds and nitrogen-containing compounds at 0 or more and less than 20 ppm and 0 or more and less than 10 ppm, respectively; The oxygen compound is a selective oxidation method of a hydrocarbon substrate, characterized in that produced in the range of 2.0 to 5.0% by weight based on oxygen.

Images