KR20140006409A - Manufacturing method of w-containing oxidative desulfurization catalyst - Google Patents

Abstract

The present invention relates to a tungsten-containing selective and oxidative desulfurization catalyst, more specifically to a selective and oxidative desulfurization catalyst obtained by making Keggin structure heteropoly acid including tungsten in the structure react with ammonium salt. The selective and oxidative desulfurization catalyst of the present invention has strong chemical affinity against petroleum-based sulfur compounds and has high desulfurization activity for transforming the non-degradable petroleum-based sulfur compounds into sulfone compounds using selective partial oxidation reaction, and removing the non-degradable petroleum-based sulfur compounds.

Description

Technical Field [0001] The present invention relates to a selective oxidation desulfurization catalyst containing tungsten,

The present invention relates to a selective oxidation desulfurization catalyst containing tungsten, and more particularly, to a catalyst capable of converting a petroleum sulfur compound obtained by reacting a tungsten-containing heteropoly acid with an ammonium salt into a sulfone compound by selective partial oxidation, And a manufacturing method thereof.

Crude oil has different composition ratios according to its production area, but its main component is hydrocarbons bound with different sizes of carbon and hydrogen, and consists of hydrocarbon mixture such as paraffin, naphthene and aromatic. Sulfur, oxygen, nitrogen, and metals. These impurities are very small in content but they have a great effect on the properties of petroleum. In particular, sulfur compounds, which are contained in 1 ~ 3% in most crude oil, burn out to produce sulfur dioxide (SO _x ) And it is a main cause of air pollution including acid rain. It causes corrosion of the catalyst for purification of exhaust gas of automobile, which obstructs the decomposition of sulfur dioxide.

Recently, the preference for low-sulfur crude oil products has increased, while low-sulfur crude oil (crude oil with a sulfur content of 0.5% or less) has been depleted, and the demand for petroleum hydrocarbons has increased sharply and the need for light oil has increased, , Residue fluid catalytic cracking (RFCC) and fluid catalytic cracking (FCC) processes are indispensable. However, in the light cycle oil (LCO) and heavy cat naphtha (HCN), which are by-products of these processes, a large amount of sulfur compounds are contained, and these mainly contain aromatic sulfur compounds such as dibenzothiophene derivatives .

When hydrodesulfurization is carried out to remove sulfur compounds, the hydrodesulfurization reactivity is lowered due to steric hindrance, hydrogen consumption is increased, cetane number and octane number are decreased due to olefin saturation reaction, and the disadvantage is not economical have. As an alternative to the above problems, a selective oxidation desulfurization process has been developed. Oxidative desulfurization (ODS) converts an oil-based sulfur compound to a sulfone compound by using an oxidizing agent together with a catalyst. Since the sulfone compound has a high polarity, it can be extracted and adsorbed It can be easily removed. In addition, the reactivity of the selective oxidative desulfurization reaction is stronger the higher the electron density of sulfur, especially the reactivity of methylphenyl sulfide, diphenyl sulfide, thiophenol, methyl benzothiophene, 4,6-methylbenzothiophene and dibenzothiophene strong. Therefore, a selective oxidation desulfurization process has been attracting attention because a sulfur compound, which has not reacted well due to hydrogen desulfurization, can be easily oxidized through a selective oxidation reaction.

The selective oxidation desulfurization technique can be roughly classified into a method using a homogeneous catalyst and a method using a heterogeneous catalyst. U.S. Patent No. 5,310,479 issued to Mobil Oil Company using a homogeneous catalyst discloses a method for removing sulfur compounds using hydrogen peroxide as an oxidizing agent and formic acid as a catalyst, and U.S. Patent Nos. 6,402,940 and 6,406,616 Discloses a method of performing an oxidative desulfurization reaction using hydrogen peroxide as an oxidizing agent and formic acid as a catalyst and removing the residual acid with calcium oxide. US Patent Nos. 6,402,939 and 6,500,219 of Surfco disclose a method of removing hydrogen peroxide or tert - Oxidation desulfurization reaction was carried out using butylhydroperoxide as an oxidizing agent and a chain-like hydrocarbon having 15 to 20 carbon atoms as a surface active material which promotes the emulsion formation of the organic layer and the water layer as a catalyst and a homogeneous transition metal as a catalyst. Methods are difficult to separate and remove catalysts, and the catalysts used as catalysts in petroleum- If the left there is a disadvantage that the problem of color and phase separation has occurred.

U.S. Patent Nos. 7,144,499 and 7,314,545 of Liondel using non-homogeneous systems were subjected to an oxidative desulfurization process using tert-butyl hydroperoxide as the oxidizing agent and a TiO ₂ / SiO ₂ catalyst, and the remaining oxidizing agent was Cr / SiO ₂ catalyst. UOP has carried out oxidative desulfurization using a heterogeneous catalyst and tert-butyl hydroperoxide and reacted hydrocarbons with oxygen to produce an organic hydroperoxide oxidizing agent In addition, various techniques for oxidative desulfurization using a Mo / Al203 catalyst as a catalyst have been developed. However, since the ratio of the oxidizer to the sulfur source is high and the two-phase reaction is difficult, a continuous reaction is difficult [Applied Catalysis A: General 279 2005 27], the consumption of oxidizing agents is high [Applied Catalysis A: General 305 2006 15] The molybdenum component elutes and the reaction activity drops rapidly [Journal of Catalysis 242 2006 299]. In addition, the currently reported oxidation desulfurization process using heterogeneous catalysts for oxidative desulfurization is applied to catalytic cracking distillates having a sulfur compound content of up to 1,000 ppmw, an aromatic content of 70% or more, and a sulfur compound content of 4,000 ppmw or more And there is a problem that the catalyst life is also lowered even in a conventional oil fraction.

1. US 5310479 2. US 6402940 3. US 6406616 4. US 6402939 5. US 6500219 6. US 7144499 7. US 7314545

1. Applied Catalysis A: General 279 2005 27 2. Applied Catalysis A: General 305 2006 15 3. Journal of Catalysis 242 2006 299

Therefore, a first problem to be solved by the present invention is to provide a selective oxidation desulfurization catalyst containing highly active tungsten which can be applied to selective oxidation desulfurization of catalytic cracked oil having a high content of a refractory sulfur compound.

A second problem to be solved by the present invention is to provide a method for preparing the catalyst for selective oxidation desulfurization containing tungsten.

In order to achieve the first object of the present invention,

Characterized in that the non-degradable petroleum sulfur compound is converted into a sulfone compound by a selective partial oxidation reaction with a heteropoly compound composed of a Keggin structure heteropoly acid and an ammonium salt containing tungsten in the structure and having the following formula (1) A catalyst for selective oxidation desulfurization is provided:

[Formula 1]

(NR ₁ R ₂ R ₃ R ₄ ) _n (P _x W _{y - p} M _p O _Z )

In Formula 1,

R ₁ , R ₂ , and R ₃ may be the same or different from each other, and each independently may be an alkyl group containing hydrogen, a straight chain or branched chain carbon chain having 1 to 3 carbon atoms,

R ₄ may be a linear or branched alkyl group having 1 to 6 carbon atoms, an alkyl group having 7 to 12 carbon atoms, a linear, branched or cyclic carbon chain-containing alkyl group,

n is an integer between 1 and 10,

x is 1 to 2,

when x is 1, y is from 9 to 12, z is from 34 to 40,

when x is 2, y is from 18 to 21, z is from 62 to 71,

p is an integer of 0 to 3;

According to one embodiment of the present invention, the heteropoly acid used for the synthesis of the ketene-type heteropoly compound may be a compound represented by the following formula (2)

(2)

[P _x W _yp M _p O _Z ] ^n-

In Formula 2,

n is an integer between 1 and 10,

x is 1 to 2,

when x is 1, y is from 9 to 12, z is from 34 to 40,

when x is 2, y is from 18 to 21, z is from 62 to 71,

p is an integer between 0 and 3,

M is any one selected from the group consisting of tungsten, molybdenum, and vanadium.

According to another embodiment of the present invention, the heteropolyacid is [PW ₁₂ O ₄₀ ] ^3- , [PW ₁₁ MoO ₄₀ ] 0 ^3- , [PW ₁₀ Mo ₂ O ₄₀ ] 0 ^3- , [PW ₉ Mo ₃ O ₄₀ ] 0 ^3- , [PW ₁₁ VO ₄₀ ] 0 ^3- , [PW ₁₀ V ₂ O ₄₀ ] 0 ^3- , [PW ₉ V ₃ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , _{[P 2 W 21 O 71]} 6-, [PW 11 O 39] 7-, [PW 9 O 34] 9-, [P 2 W 19 O 67] which are selected one is selected from the group consisting of ^10- It may be abnormal.

According to another embodiment of the present invention, the ammonium salt may be any one selected from the group consisting of hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride and tetramethylammonium chloride.

According to another embodiment of the present invention, the hardly decomposable petroleum sulfur compound is methylphenyl sulfide, diphenylsulfide, thiophenol, methylbenzothiophene, 4,6-methylbenzothiophene and dibenzothiophene in the group consisting of It may be one or more selected.

According to another aspect of the present invention,

(1) dissolving heteropoly acid and an ammonium salt in an organic solvent;

(2) heating and stabilizing the dissolved heteropoly acid in a temperature range of 50 to 70 캜;

(3) adding the ammonium salt dissolved in the step (1) to the heteropoly acid solution of step (2) and refluxing the mixture at a temperature ranging from 50 to 70 ° C for 30 minutes to 120 minutes;

(4) collecting the product produced in the step (3), filtering, and drying the product. The present invention further provides a method for preparing a catalyst for selective oxidation desulfurization comprising tungsten in the structure do.

According to one embodiment of the present invention, the content of the heteropoly acid may be 1 to 3 molar ratio based on 1 mol of the ammonium salt.

The catalyst for selective oxidation desulfurization according to the present invention has a strong affinity for petroleum-based sulfur compounds and exhibits a high desulfurization activity because heteropoly acid containing tungsten and ammonium salt substituted with an alkyl group are coordinated to select a refractory petroleum sulfur compound It shows an excellent effect of converting to a sulfone compound by partial oxidation reaction and removing it.

FIG. 1 is a graph showing the sulfur shift ratio of the selective oxidation desulfurization catalyst prepared using molybdenum-containing heteropoly acid and ammonium salt prepared according to the comparative example of the present invention and the petroleum sulfur compound according to the reaction time.
FIG. 2 is a graph showing a sulfur shift ratio of a selective oxidation desulfurization catalyst prepared using a tungsten-containing heteropoly acid and an ammonium salt produced according to an embodiment of the present invention and a petroleum sulfur compound according to a reaction time.
3 is a gas chromatography (GC-PFPD) analysis before and after the reaction of selective oxidation desulfurization catalyst containing tungsten produced according to an embodiment of the present invention and catalytic cracking oil. (3a: before the reaction, 3b: after the reaction)

Hereinafter, the present invention will be described in more detail.

The present invention relates to a heteropoly compound composed of a Keggin structure heteropoly acid and an ammonium salt, which contains tungsten in the structure, and has the following formula (1), and a refractory petroleum sulfur compound is converted into a sulfone compound by selective partial oxidation And a catalyst for selective oxidation desulfurization.

[Formula 1]

(NR ₁ R ₂ R ₃ R ₄ ) _n (P _x W _{y - p} M _p O _Z )

In Formula 1,

R ₁ , R ₂ , and R ₃ may be the same or different from each other, and each independently may be an alkyl group containing hydrogen, a straight chain or branched chain carbon chain having 1 to 3 carbon atoms,

R ₄ may be a linear or branched alkyl group having 1 to 6 carbon atoms, an alkyl group having 7 to 12 carbon atoms, a linear, branched or cyclic carbon chain-containing alkyl group,

n is an integer between 1 and 10,

x is 1 to 2,

when x is 1, y is from 9 to 12, z is from 34 to 40,

when x is 2, y is from 18 to 21, z is from 62 to 71,

p is an integer between 0 and 3,

M is any one selected from the group consisting of tungsten, molybdenum, and vanadium.

The molecular structure of [AM ₁₂ O ₄₀ ] ^3- , which is an anion of the quasic catalyst, is shown in the following structural formula 1. AO ₄ tetrahedron based on central element A, three MO ₆ octahedrons sharing three corners form one group, four of these groups share edges or sides, and share vertices with AO ₄ tetrahedron in the center While a heteropoly acid anion having a size of about 11 Å is formed.

[Structural formula 1]

It is known that the redox potential of the heteropoly acid varies depending on the cation, the central element, and the coordination element. As a central element of the heteropoly acid, phosphorus, silicon, boron, etc. can be used. As a coordination element, molybdenum, tungsten and vanadium can be used, and a heteropoly acid is reacted with various cations. As a result, The present invention has been accomplished based on this finding.

In the catalyst for selective oxidation desulfurization according to the present invention, the heteropoly acid used for the synthesis of the ketone type heteropoly compound may be a compound represented by the following formula (2).

(2)

[P _x W _yp M _p O _Z ] ^n-

In Formula 2,

n is an integer between 1 and 10,

x is 1 to 2,

when x is 1, y is from 9 to 12, z is from 34 to 40,

when x is 2, y is from 18 to 21, z is from 62 to 71,

p is an integer between 0 and 3,

M is any one selected from the group consisting of tungsten, molybdenum, and vanadium.

In addition, the heteropolyacid may be [PW ₁₂ O ₄₀ ] ^3- , [PW ₁₁ MoO ₄₀ ] 0 ^3- , [PW ₁₀ Mo ₂ O ₄₀ ] 0 ^3- , [PW ₉ Mo ₃ O ₄₀ ] 0 ^3- , [PW ₁₁ VO ₄₀ ] 0 ^3- , [PW ₁₀ V ₂ O ₄₀ ] 0 ^3- , [PW ₉ V ₃ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [P ₂ W ₂₁ O ₇₁ ] ^6- , [PW ₁₁ O ₃₉ ] ^7- , [PW ₉ O ₃₄ ] ^9- , and [P ₂ W ₁₉ O ₆₇ ] ^10- .

In addition, the ammonium salt may be any one selected from the group consisting of hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride and tetramethylammonium chloride. When the number of carbon atoms in the alkyl chain of the ammonium salt is 11 or more Dibenzothiophene. When the number of carbon atoms in the alkyl chain of the ammonium salt is 8 or less, the ability to remove sulfur compounds is lowered due to the lowering of the solubility (dispersibility).

On the other hand, the hardly decomposable petroleum sulfur compounds effective for the selective oxidation desulfurization catalyst according to the present invention is a group consisting of methylphenylsulfide, diphenylsulfide, thiophenol, methylbenzothiophene, 4,6-methylbenzothiophene and dibenzothiophene. It may be any one or more selected from.

In order to achieve the second object of the present invention,

(1) dissolving heteropoly acid and an ammonium salt in an organic solvent;

(2) heating and stabilizing the dissolved heteropoly acid in a temperature range of 50 to 70 캜;

(3) adding the ammonium salt dissolved in the step (1) to the heteropoly acid solution of step (2) and refluxing the mixture at a temperature ranging from 50 to 70 ° C for 30 minutes to 120 minutes;

(4) collecting the product produced in the step (3), filtering, and drying the product. The present invention further provides a method for preparing a catalyst for selective oxidation desulfurization comprising tungsten in the structure do.

In the process according to the present invention, the heteropoly acid and the ammonium salt are the same as described above. In the step (1), the organic solvent may be any one selected from the group consisting of methanol, ethanol, propanol, acetonitrile, and tetrahydrofuran. The use of ethanol enhances the dispersion effect in an aqueous solution Which is more preferable for reacting the catalyst with the ammonium salt.

In the method according to the present invention, the content of the heteropoly acid may be 1 to 3 molar equivalents based on 1 mol of the ammonium salt. When the content of the heteropoly acid is less than 1 mol, the content of the heteropoly acid is lowered, However, when the molar ratio exceeds 3, there is a problem that the solubility (dispersity) of the heteropoly acid is lowered.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments for better understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

< Example >

Manufacturing example  One.

Selective Oxidative Desulfurization  Preparation of the catalyst

H ₃ PW ₁₂ O ₄₀ and 1 mmol of hexadecyltrimethylammonium chloride were dissolved in 10 ml of ethanol. Then, heteropoly acid dissolved in a 100 ml three-necked flask equipped with a condenser was added and stirred at 60 ° C. at a rate of 5 ° C./min The temperature was raised. When the temperature of the aqueous solution was stabilized at 60 ° C, hexadecyltrimethylammonium chloride dissolved in ethanol was added and stirred for 1 hour. The product was collected and filtered for 1 hour in an aspirator apparatus. The solid product obtained through filtration was dried at 80 DEG C for 10 hours, and the dried product was pulverized to prepare a powdery form.

Experimental Example  One.

Benzothiopene (BT), Dibenzothiopene (DBT), 4-methylbenzothiophene (4-Methyl Dibenzothiopene; 4MDBT), 4,6-dimethyl dibenzothiophene (4,6) 30 g of a solution of -Dimethyl Dibenzothiopene (46DMDBT) dissolved in tridecane at a concentration of 200 ppm each, 0.2 g of a catalyst for selective oxidation and desulfurization prepared in Preparation Example 1 and 0.6 ml of hydrogen peroxide were added and reacted at 80 ° C. The sulfur variation rate was measured.

Experimental Example  2.

1 g of the catalyst for selective oxidation desulfurization prepared in Preparation Example 1 and 4 ml of hydrogen peroxide were placed in a three-necked flask, and the mixture was heated at 80 DEG C for 3 hours After the reaction, the change was analyzed by gas chromatography equipped with a pulsed flame photometric detector (PFPD). The physical properties of the catalytic cracking oil used in the experiment are shown in Table 1 below.

Physical properties LCO API 13.5 S, ppm 3600 N, ppm 550 Color (ASTM) L2.5 Aromatics, wt.% Total 74.3 Mono 14.3 Di 40.6 Tri + 19.4 Cetane Index 24.9 Distillation, ^o C IBP / 5/10
30/40/50
60/90/95
EP 225/256/262
284/292/308
325/398 / -
-

Comparative Example  One.

Comparative Example 1 was prepared in the same manner as in Production Example 1, except that 3 mmol of heteropoly acid H ₃ PMo ₁₂ O ₄₀ and 1 mmol of hexadecyltrimethylammonium chloride were used.

Comparative Example  2.

Using the catalyst prepared in Comparative Example 1, the sulfur transition ratio according to the reaction time was measured in the same manner as in Experimental Example 1.

1 is a catalyst for selective oxidation desulfurization prepared using a molybdenum-containing heteropolyacid and an ammonium salt prepared according to a comparative example of the present invention, and a petroleum-based sulfur compound, benzothiophene (BT), dibenzothiophene (DBT), 4- Methylbenzothiophene (4MDBT) and 4,6-dimethyl dibenzothiophene (46DMDBT) were reacted, and the sulfur variation rate of sulfur component was converted to sulfone compound by partial oxidation reaction and removed according to reaction time. When the reaction time was 10 minutes after the start of the reaction, the conversion rate of sulfur compounds to sulfone compounds was lower than 20% for all four sulfur compounds, and the time required for conversion to sulfone compounds to 50% was dibenzothiophene ( DBT) was 30 minutes, 4-methylbenzothiophene (4MDBT) was about 35 minutes, 4,6-dimethyl dibenzothiophene (46DMDBT) was about 50 minutes, and 100 minutes for benzothiophene (BT). It was measured to take longer.

On the other hand, Figure 2 is a catalyst for selective oxidation desulfurization and petroleum-based sulfur compounds benzothiophene (BT), dibenzothiophene (DBT), 4 prepared using the tungsten-containing heteropoly acid and ammonium salt prepared by the above-described method -Graph showing the sulfur variability of methyl benzothiophene (4MDBT) and 4,6-dimethyl dibenzothiophene (46DMDBT) in which the sulfur component is converted into a sulfone compound by partial oxidation and removed according to the reaction time. 5 minutes after the start of the reaction, the conversion rate to the sulfur compound sulfone compound was more than 20%, and the sulfur variation rate after 10 minutes was about 47% for dibenzothiophene (DBT) and 4-methyl. Benzothiophene (4MDBT) was about 42%, 4,6-dimethyl dibenzothiophene (46DMDBT) was about 34%, and benzothiophene (BT) was about 30%. The ratio of sulfur compounds to sulfone compounds This time is 50% dibenzothiophene (DBT) 15 minutes, 4-methylbenzo It took about 18 minutes for thiophene (4MDBT), about 26 minutes for 4,6-dimethyl dibenzothiophene (46DMDBT), and about 50 minutes for benzothiophene (BT). This supports the fact that the selective oxidation desulfurization catalyst prepared using the tungsten-containing heteropoly acid and the ammonium salt prepared according to the present invention is effective in removing the poorly decomposable sulfur compounds.

FIG. 3 is a graph showing the results of gas chromatography (GC-PFPD) analysis before and after the reaction of the catalyst for selective oxidation desulfurization produced using tungsten-containing heteropoly acid and ammonium salt produced according to an embodiment of the present invention FIG. 3A is a gas chromatograph (GC-PFPD) for catalytic cracking oil, and FIG. 3B is a graph showing the results of gas chromatography (GC-PFPD) after reacting catalytic cracking oil and a catalyst for selective oxidation desulfurization produced according to the present invention for 3 hours Chromatography (GC-PFPD). As shown in Figs. 3A to 3B, the sulfur-specific peaks were observed in the vicinity of 5 to 25 minutes in the pre-reaction catalytic cracking oil, but the catalytic cracking oil was reacted with the catalyst for selective oxidation desulfurization prepared according to the present invention Showed that the peak of the sulfur component in the vicinity of 5 to 25 minutes was reduced and the specific peak in the sulfone compound was detected in the vicinity of 25 to 30 minutes so that the sulfur component of the catalytic cracking oil was effectively converted into a sulfone compound have.

Claims (7)

A heteropoly compound consisting of an ammonium salt of a Keggin structure heteropolyanion containing tungsten in a structure and having the following general formula (1), wherein the hardly decomposable petroleum sulfur compound is converted into a sulfone compound by a selective partial oxidation reaction to be removed. Selective Oxidation Desulfurization Catalyst:
[Chemical Formula 1]
(NR ₁ R ₂ R ₃ R ₄ ) _n (P _x W _{y - p} M _p O _Z )
In Formula 1,
R ₁ , R ₂ , and R ₃ may be the same or different from each other, and each independently may be an alkyl group containing hydrogen, a straight chain or branched chain carbon chain having 1 to 3 carbon atoms,
R ₄ may be a linear or branched alkyl group having 1 to 6 carbon atoms, an alkyl group having 7 to 12 carbon atoms, a linear, branched or cyclic carbon chain-containing alkyl group,
n is an integer between 1 and 10,
x is 1 to 2,
when x is 1, y is 9 to 12, z is 34 to 40,
when x is 2, y is 18 to 21, z is 62 to 71,
p is an integer between 0 and 3,
M is any one selected from the group consisting of tungsten, molybdenum, and vanadium. The method of claim 1,
Heteropoly acid used for the synthesis of the kegin-type heteropoly compound is a catalyst for selective oxidation desulfurization, characterized in that the compound represented by the following formula (2):
(2)
[P _x W _{y - p} M _p O _Z ] ^n-
In Formula 2,
n is an integer between 1 and 10,
x is 1 to 2,
when x is 1, y is 9 to 12, z is 34 to 40,
when x is 2, y is 18 to 21, z is 62 to 71,
p is an integer between 0 and 3,
M is any one selected from the group consisting of tungsten, molybdenum, and vanadium. 3. The method of claim 2,
The heteropolyacid is [PW ₁₂ O ₄₀ ] ^3- , [PW ₁₁ MoO ₄₀ ] 0 ^3- , [PW ₁₀ Mo ₂ O ₄₀ ] 0 ^3- , [PW ₉ Mo ₃ O ₄₀ ] 0 ^3- , [PW ₁₁ VO ₄₀ ] 0 ^3- , [PW ₁₀ V ₂ O ₄₀ ] 0 ^3- , [PW ₉ V ₃ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [P ₂ W ₂₁ O ₇₁ ] ^6- , [PW ₁₁ O ₃₉ ] ^7- , [PW ₉ O ₃₄ ] ^9- and [P ₂ W ₁₉ O ₆₇ ] ^10- any one or more selected from the group consisting of a catalyst for oxidative desulfurization. The method of claim 1,
The ammonium salt is a catalyst for selective oxidative desulfurization, characterized in that any one selected from the group consisting of hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetramethyl ammonium chloride. The method of claim 1, wherein the hardly decomposable petroleum sulfur compound is any one or more selected from the group consisting of methylphenylsulfide, diphenylsulfide, thiophenol, methylbenzothiophene, 4,6-methylbenzothiophene and dibenzothiophene Selective oxidation desulfurization catalyst, characterized in that. (1) dissolving heteropoly acid and an ammonium salt in an organic solvent;
(2) heating and stabilizing the dissolved heteropoly acid in a temperature range of 50 to 70 캜;
(3) adding the ammonium salt dissolved in the step (1) to the heteropoly acid solution of step (2) and refluxing the mixture at a temperature ranging from 50 to 70 ° C for 30 minutes to 120 minutes;
(4) a method for producing a catalyst for selective oxidative desulfurization comprising tungsten in a structure which is prepared by a method comprising the step of collecting, filtering and drying the product produced in step (3). 6. The method of claim 5,
The content of the heteropoly acid is a method for producing a catalyst for selective oxidation desulfurization, characterized in that it is contained in a 1 to 3 molar ratio based on 1 mole of ammonium salt.

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