KR101378610B1 - Ammoxidation catalyst of xylene and method for preparing dicyanobenzene by using the same - Google Patents

Abstract

The present invention relates to a catalyst for the dark oxidization reaction useful for the dark oxidization of xylene and to a process for producing dicyanobenzene from xylene using the same, the catalyst for dark oxidization reaction is (a) vanadium (V ); Chromium (Cr); Molybdenum (Mo), tungsten (W) or both; At least one element selected from alkali metals and alkaline earth metals; And an oxide consisting of manganese (Mn), or (b) vanadium (V); Chromium (Cr); Molybdenum (Mo), tungsten (W) or both; At least one element selected from alkali metals and alkaline earth metals; Manganese (Mn); A catalytically active component containing an oxide composed of at least one element selected from the group consisting of zinc (Zn), tin (Sn), bismuth (Bi), indium (In), lead (Pb) and antimony (Sb), and TiO ₂ and a carrier component containing a metal borate.
By using the catalyst for dark oxidation reaction of the present invention, even if the dark oxidation of xylene is carried out in a fixed bed reactor, the heat of reaction can be easily controlled to ensure the reaction safety.

Description

Catalyst for amoxylation reaction of xylene and method for preparing dicyanobenzene using the same {AMMOXIDATION CATALYST OF XYLENE AND METHOD FOR PREPARING DICYANOBENZENE BY USING THE SAME}

The present invention relates to a catalyst for the dark oxidization reaction of xylene which can be used in a fixed bed reactor and a method for producing dicyanobenzene from xylene using the same.

In general, dicyanobenzene (m-dicyanobenzene, isophthalonitrile) prepared from m-xylene, and para-dicyanobenzene (p-xylene) prepared from (p-xylene) -dicyanobenzene), which is used as a raw material for synthetic resins, medicines, pesticides, dyes and pigments.

Methods of preparing dicyanobenzene have been known for a long time in the art, and various proposals have been made for catalysts used therein. On the other hand, the ammoxidation reaction in which the aromatic compound substituted with an alkyl group is gas phase reacted with ammonia and oxygen or an oxygen-containing gas in the presence of a catalyst is an exothermic reaction process with a high heat of reaction. In particular, in the case of dark oxidization reaction in which two alkyl groups such as dicyano benzene must be converted to a nitrile group at the same time, the calorific value is so large that it is difficult to control the reaction heat. For this reason, the fluidized-bed reaction process which is easy to control reaction heat industrially is performed. Accordingly, catalysts used for the dark oxidization reaction, most of which are suitable for the fluidized bed reaction process have been developed and proposed.

For example, KR 10-364920 and JP 9-71561 disclose fluidized bed dark oxidation catalysts based on vanadium and antimony oxides.

In addition, as an example of another fluidized bed dark oxidization catalyst, GB 1351523 proposes a VCrBO _x / SiO ₂ catalyst consisting of vanadium, chromium and boron oxide, and US 4,985,581 with vanadium oxide, chromium oxide, boron oxide and molybdenum oxide. EP 052367 proposes a catalyst consisting of, and in the VCrBMoPO _x / SiO ₂ catalyst system further comprising phosphorus in vanadium, chromium, boron and molybdenum oxide, the molybdenum oxide and phosphorus are phosphorus molybdic acid or phosphrous molybdate compounds. It is proposed about a catalyst which is produced from. In addition, in US Pat. No. 6,107,510, alkali metals or alkaline earth metals are added to the catalyst system proposed in EP 0525367, oxides of molybdenum (Mo) or tungsten (W) are made from heteropolyacids of Mo or W, and phosphates are heteropolyacids. A VCrBMo (or W) PKO _x / SiO ₂ based catalyst, which is prepared from In addition, CN 1500775 proposes a VCrBTiPMo (or W) MO _x catalyst, where M = alkali metal or alkaline earth metal.

However, in order to carry out the dark oxidization reaction in a fluidized bed reactor, the catalyst used requires excellent fluidity, wear resistance and heat transfer ability. In particular, fluidized bed catalysts are required to be abrasion resistant in order to alleviate process problems in subsequent steps due to wear of the catalyst. In order to satisfy this problem, a catalyst having improved particle strength by using a large amount of inorganic binders such as silica and alumina has been proposed. However, fluidized bed catalysts with improved particle strength have limitations in improving catalyst performance due to interactions between the catalytically active components and the large amounts of inorganic binders used to improve wear resistance.

On the other hand, in addition to the fluidized bed catalyst described above, VSbMo (or W) / Support catalyst as an example of a catalyst (hereinafter referred to as a 'fixed catalyst') used in performing the dark oxidization reaction in a fixed-bed reactor (WO 2007/009921). However, by using the catalyst, the occurrence of abnormal reactions such as run-away due to the heat of reaction generated in the dark oxidation of xylene should be suppressed, and the reaction safety should be ensured. For this purpose, low concentrations of xylene and excess ammonia compared to xylene were used, and also nitrogen gas was used as the diluent gas, and the dark oxidation reaction of xylene under reaction conditions having a very high gas hourly space velocity (GHSV) Was performed. However, the conventional stationary phase as described above has to be recovered and reused, and excessive energy costs are incurred due to the hydrolysis of the product with ammonia, the use of nitrogen and the performance of dark oxidization reactions under high GHSV reaction conditions. The use of catalysts is not satisfactory from an industrial point of view. In addition, US Pat. No. 4,018,713 proposes a VNbMO _x / α-Al ₂ O ₃ based catalyst in which V ₂ O ₅ / Al ₂ O ₃ is converted to Nb ₂ O ₅ and an alkali metal, but the yield of dicyano benzene is low. There is. On the other hand, US Pat. No. 5,183,793 proposes a VBiSbFeOx / TiO ₂ -based catalyst, but this has a problem in that the conversion of xylene and the yield of dicyanobenzene are low even though the concentration of the reactants is performed.

The present inventors can secure the reaction safety even under the reaction conditions having high productivity without excessively using ammonia when preparing dicyanobenzene from xylene through a dark oxidization reaction in a fixed bed reactor, and furthermore, high selectivity and It is an object of the present invention to provide a fixed bed catalyst for dark oxidation of xylene, which can produce dicyanobenzene in yield.

In addition, the present invention provides a method for efficiently preparing dicyanobenzene from xylene using the catalyst for dark oxidization reaction, and a dicyanobenzene prepared thereby.

The present invention provides a catalyst for dark oxidation reaction of xylene, the catalyst for dark oxidation reaction

at least one element selected from (a) (iii) vanadium (V), (ii) chromium (Cr), (iii) molybdenum (Mo) and / or tungsten (W), (iii) alkali metals and alkaline earth metals, and (Iii) an oxide consisting of manganese (Mn), or

(b) at least one element selected from (iii) vanadium (V), (ii) chromium (Cr), (iii) molybdenum (Mo) and / or tungsten (W), (iii) alkali metals and alkaline earth metals, ( Iii) one or more elements selected from the group consisting of manganese (Mn), (S) zinc (Zn), tin (Sn), bismuth (Bi), indium (In), lead (Pb) and antimony (Sb) oxide

A catalytically active ingredient containing

Carrier components containing TiO ₂ and metal borate.

In addition, the present invention in the presence of the catalyst for the dark oxidization reaction in the reactor, a method of producing dicyanobenzene by dark oxidizing xylene (xylene) with oxygen-containing gas and ammonia, and the method prepared by Provide dicyanobenzene.

The present invention is selected from (i) vanadium (V), (ii) chromium (Cr), (iii) molybdenum (Mo) and / or tungsten (W), (iii) alkali metals and alkaline earth metals in the preparation of dicyanobenzene. In addition to one or more elements, oxides composed of (i) manganese (Mn) are included as catalytically active components, or (i) zinc (Zn), tin together with (i) manganese, in addition to (i) to (i). (Sn), bismuth (Bi), indium (In), lead (Pb) and antimony (Sb) comprising an oxide consisting of at least one element selected from the group consisting of a catalytically active ingredient, wherein the catalytically active ingredient is TiO ₂ And by using the catalyst for the dark oxidization reaction supported on a carrier component consisting of a metal borate, even if the dark oxidization reaction of xylene is carried out in a fixed bed reactor can be easily controlled heat reaction can be secured reaction safety.

In addition, the present invention uses the catalyst for the dark oxidization reaction, even if the dark oxidization reaction is carried out under the condition that the concentration of ammonia compared to xylene compared to the case of using the conventional dark oxidization catalyst, selectivity of dicyanobenzene Since there is almost no reduction and the reaction safety is excellent and the dark oxidization reaction can be performed at a low space velocity, it is unnecessary to use a dilution gas unlike the case of using the conventional dark oxidization catalyst.

In addition, since the present invention uses a small amount of ammonia as described above, unlike the case where the dark oxidization reaction is carried out using excessive ammonia, the process load and energy cost for the recovery and reuse of unreacted ammonia after the reaction are reduced. In addition, the hydrolysis reaction of the intermediate or final product by ammonia can be suppressed to improve the selectivity and yield of dicyanobenzene.

In addition, the present invention by using the catalyst for the dark oxidization reaction, the dark oxidization in a fixed bed reactor under the same feed conditions (LHSV = about 0.1 ~ 0.14 hr ^-1 ) of xylene in a general fluidized bed reactor The reaction can be performed stably to ensure high productivity.

Hereinafter, the present invention will be described in detail.

In general, the biggest problem in carrying out the dark oxidization reaction in the presence of xylene, ammonia and oxygen in a tubular fixed bed reactor is that run-away occurs easily due to the high heat of reaction, which can ensure reaction safety. It is not. The heat of reaction is not only an amoxylation reaction for producing dicyanobenzene from xylene, but also a non-selective reaction to a complete oxidation reaction such as CO ₂ , CO and an autooxidation reaction of ammonia used at least about 5 mole times compared to xylene. It is also caused by

Accordingly, the present invention provides a catalyst capable of securing the stability of the reaction by providing a catalyst of high selectivity capable of suppressing the self-oxidation of ammonia and the complete oxidation of xylene to CO and CO ₂ , and the dish from xylene using the same. Provided are methods for preparing anobenzene.

<Catalyst for Catalyst of Ammoxidation of Xylene and Manufacturing Method Thereof>

The present invention is a catalyst for dark oxidation reaction that can be used in a fixed bed reactor, (i) vanadium (V), (ii) chromium (Cr), (iii) molybdenum (Mo) and / or tungsten (W), and ( (Iii) in addition to at least one element selected from alkali metals and alkaline earth metals, (iii) comprising oxides of manganese (Mn) as catalytically active ingredients, or (b) in addition to (v) to (v) together with (b) Iii) Oxides comprising at least one element selected from the group consisting of zinc (Zn), tin (Sn), bismuth (Bi), indium (In), lead (Pb) and antimony (Sb) as catalytically active components And supporting the catalytically active component on a carrier component comprising TiO ₂ and a metal borate.

Accordingly, the present invention lowers the catalytic activity per unit weight of the catalyst, but increases the reaction selectivity, the change in the activity of the catalyst with the change in the reaction temperature can be controlled gently, and the free active vanadium catalyst at high temperature Decomposition into an oxide is suppressed, thereby improving the reaction safety.

In addition, when the catalyst for the dark oxidization reaction of the present invention is used, the reaction safety during the dark oxidization reaction of xylene is significantly increased and the selectivity of the catalyst is increased, so that dicyanobenzene can be produced in high selectivity and high yield. In addition, when the catalyst for the dark oxidization reaction, the liquid hourly space velocity (LHSV) can be safely operated even under the supply conditions of the reactants having a suitable productivity of about 0.1 hr ^-1 or more.

In addition, the catalyst of the present invention has little change in activity before and after the runaway reaction, and can be operated under the reaction conditions set at the beginning of the reaction even after the runaway reaction, so that the reaction conditions need not be set again. Considering that a typical commercial fixed bed reactor is made of multi-tubular, aberrant reactions in one or several tubes affect the operating conditions of the entire reactor. It is advantageous.

In the catalyst for dark oxidation reaction of xylene of this invention, it is preferable to include the said catalyst active component in the range of about 0.2 to 30 weight% based on the total weight of the catalyst for dark oxidation reaction. If the content of the catalytically active component is less than the lower limit, the activity of the catalyst is low, while if the content of the catalytically active component exceeds the upper limit, the activity of the catalyst per unit weight (or volume) is too high. It is difficult to secure reaction safety. At this time, it is preferable that the content of the carrier component is as much as the remaining amount adjusted so that the total weight of the catalyst for dark oxidization reaction is 100% by weight.

The carrier component supporting the catalytically active component is characterized by comprising TiO ₂ and a metal borate. The carrier provides stability of the catalyst during the reaction by controlling the calorific value, and when applied to the multilayer catalyst layer, TiO ₂ having a different surface area for each catalyst layer may be used to control the reaction activity for each catalyst layer. In addition, due to the metal borate it is possible to suppress the runaway reaction even when the reaction temperature changes can ensure the stability of the reaction.

The TiO ₂ and the metal borate are preferably included in a weight ratio of 40:60 to 95: 5. If the carrier component contains an excessive amount of metal borate, the catalytic activity is low and uneconomical. On the other hand, if the metal borate is contained too small, the reaction safety may be lowered.

On the other hand, in the present invention, the smaller the particle size of TiO ₂ (or the larger the specific surface area), the higher the activity of the catalyst, so that the BET specific surface area ranges from about 5 to 100 m 2 / g in order to secure the catalyst selectivity and reaction safety at the same time. It is appropriate to use TiO ₂ . In addition, the crystal structure of TiO ₂ may be in the form of anatase, rutile, or a mixture thereof.

In addition, the metal borate metal usable in the present invention is selected from the group consisting of aluminum (Al), calcium (Ca), barium (Ba), bismuth (Bi), tin (Sn) and zinc (Zn). It may be one component or two or more components, but is not limited thereto. Specifically, examples of the metal borate include aluminum borate, calcium borate, barium borate, bismuth borate, tin borate, zinc borate, calcium aluminum borate, calcium tin borate and the like. to be.

The catalyst for dark oxidation reaction according to the present invention may be a catalyst for dark oxidation reaction represented by the following formula (1).

In Formula 1,

Cr _a Mn _b V ₁ M ¹ _c M ² _d M ³ _e O _x is a catalytically active component,

Cr is chromium,

Mn is manganese,

V is vanadium,

M ¹ is one or more elements selected from molybdenum (Mo) and tungsten (W),

M ² is at least one element selected from alkali metals and alkaline earth metals on the periodic table, preferably M ² may be K, Cs, Rb, Mg, Ca.

M ³ is at least one element selected from the group consisting of zinc (Zn), tin (Sn), bismuth (Bi), indium (In), lead (Pb), and antimony (Sb),

O is oxygen,

a, b, c, d, e and x represent the atomic ratios of Cr, Mn, M ¹ , M ² , M ³ and O to V, respectively,

0.1 ≦ a ≦ 2, 0.01 ≦ b ≦ 2, 0.01 ≦ c ≦ 0.5, 0.001 ≦ d ≦ 0.2, and 0 ≦ e ≦ 1, respectively, and x is a number determined by the oxidation state of each component,

TiO ₂ -M ⁴ BO _y is a carrier component for supporting the catalytically active portion,

TiO ₂ is titanium dioxide, preferably from ₂ BET specific surface area of from about 5 to 100 ㎡ / g TiO range,

M ⁴ BO _y represents a metal borate such as aluminum borate, calcium borate, barium borate, bismuth borate, tin borate, zinc borate, calcium aluminum borate, calcium tin borate, and M ⁴ is A compound formed by combining one or more elements selected from the group consisting of aluminum (Al), calcium (Ca), barium (Ba), bismuth (Bi), tin (Zn), and zinc (Zn), and y is It is a number determined according to the components of M ⁴ , the atomic ratio of B and the oxidation state of each component.

In addition, in Formula 1, the value of a + b + d + e is about 0.5 or more and about 3 or less, preferably about 0.8 or more and about 2 or less, based on when the composition of V is 1. When the value of a + b + d + e is about 0.5 or more and about 3 or less, the catalytic activity and dicyanobenzene selectivity and reaction safety are generally good. If the value of a + b + d + e in Chemical Formula 1 exceeds 3, the activity of the catalyst is too low, while the value of a + b + d + e in Chemical Formula 1 is less than 0.5, While the activity is high, the selectivity of dicyanobenzene is low, and reaction safety may be lowered.

On the other hand, the catalyst for the dark oxidization reaction of the present invention can be used by molding the composition powder itself through a molding method such as pelletizing.

In addition, the catalyst for the dark oxidization reaction of the present invention can be used by being supported and coated on a preformed inert support having a certain size and shape, in addition to molding the composition powder itself.

The inert support usable in the present invention is made of alumina, silica, silica-alumina, silicon carbide (SiC), etc., and has a large pore and a BET specific surface area of about 1 m ² / g or less And preferably in the range of about 0.01 to 1 m ² / g.

The shape of the inert support is not particularly limited, such as spherical, cylindrical or hollow.

In addition, the size of the inert support is not particularly limited, but it is appropriate that the particle diameter and length range from about 3 to 15 mm. For example, when the shape of the inert support is cylindrical, the particle diameter may range from about 3 to 15 mm, the length may range from about 3 to 15 mm, and when the shape of the inert support is hollow, the outer diameter (OD) ) May range from about 5 to 15 mm, inner diameter (ID) ranges from about 3 to 12 mm, and length may range from about 5 to 15 mm.

In addition, in order to support the catalyst for dark oxidation reaction of this invention, it is suitable that the porosity of a support is about 20 to 70%, Preferably it is about 30 to 60%.

The above-mentioned inert support may be prepared and used according to the purpose of the present invention, but a commercially available support may be selected and used. For example, AL-family of FUJIMI, SA-family of NORTON CHEM., MA-family of TIPTON CORP., Etc. are mentioned.

The amount of the catalyst supported on the inert support may range from about 5 to 30 wt%, preferably about 10 to 25 wt%, based on the total weight of the inert support and the catalyst supported thereon. If the supported amount of the catalyst is too small, the catalyst activity is too low, and if the supported amount of the catalyst is too large, the catalyst particles may peel off from the support.

On the other hand, the catalyst for the dark oxidization reaction of the present invention can be prepared through the following manufacturing method, but is not limited thereto.

According to an example of the present invention, the catalyst for dark oxidation reaction

A first step of dispersing TiO ₂ and metal borate in deionized water to provide a first suspension;

A first suspension obtained by dissolving a vanadium-containing precursor and an M ¹ -containing precursor, wherein M ¹ is molybdenum (Mo), tungsten (W) or both) in deionized water, is mixed with the first suspension to form a second suspension. Providing a second step;

A second solution obtained by dissolving a chromium-containing precursor, a manganese-containing precursor, and an M ² -containing precursor (wherein M ² is at least one element selected from alkali metals and alkaline earth metals on the periodic table) in deionized water is used as the second suspension. A third step of mixing to provide a slurry liquid;

Adjusting the pH of the slurry solution to about 7 and hydrothermally aging for about 2 to 12 hours at a temperature of about 70 to 90 ° C .;

Spray drying the slurry solution and drying at a temperature of about 90 to 150 ° C. to provide a powder of the catalyst composition; And

A sixth step of compressing the powder of the catalyst composition and calcining under an air atmosphere having a temperature of about 400 to 700 ° C.

&Lt; / RTI &gt;

According to another example of the present invention, when forming the second solution in the third step, M ³ containing precursor (wherein M ³ is zinc (Zn), tin (Sn), bismuth (Bi), indium (In) And at least one element selected from the group consisting of lead (Pb) can be dissolved in deionized water together with the chromium-containing precursor, the manganese-containing precursor, and the M ² -containing precursor to obtain a second solution.

Further, according to another example of the present invention, the third step is a second solution obtained by dissolving the chromium-containing precursor, the manganese-containing precursor and the M ² -containing precursor in deionized water and the second suspension of the second step M ³ containing precursor (wherein M ³ is an antimony (Sb) element) is added to the slurry liquid formed by mixing.

Further, according to another example of the present invention, the catalyst for the dark oxidization reaction is carried out by coating and coating the powder of the catalyst composition obtained in the fifth step on an inert support, under an air atmosphere having a temperature of about 400 to 700 ℃ It can be obtained by baking.

Hereinafter, a step-by-step description of the method for producing a catalyst for the dark xylation reaction of xylene according to the present invention.

The first step is to obtain a first suspension in which TiO ₂ and metal borate are uniformly dispersed in deionized water.

As described above, it is appropriate to use the TiO ₂ having a BET specific surface area in the range of about 5 to 100 m 2 / g.

In addition, the metal of the metal borate is Al, Ca, Ba, Bi, Sn, Zn and the like, but is not limited thereto.

The TiO ₂ and the metal borate are appropriately mixed in a weight ratio of 40:60 to 95: 5 in order to secure catalyst activity and reaction safety at the same time.

The second step is a step of mixing the first solution obtained by dissolving the vanadium-containing precursor and the M ¹ -containing precursor in deionized water with the first suspension obtained in the above-described first step to obtain a second suspension.

An example of the vanadium containing precursor is ammonium metavanadate. The M ¹ -containing precursor may be a tungsten (W) -containing precursor, a molybdenum (Mo) -containing precursor, or a mixture thereof. For example, ammonium tungstate, ammonium molybdate, ammonium heptamolybdate, and the like.

In forming the first solution, it is preferable to dissolve the vanadium-containing precursor and the M ¹ -containing precursor in deionized water such that the M ¹ -containing precursor is in a range of about 0.01 to 0.5 equivalents based on 1 equivalent of vanadium (V). If the amount of the M ¹ component exceeds about 0.5 equivalents based on 1 equivalent of vanadium, the catalytic activity is lowered. If the amount of the M ¹ component is less than about 0.01 equivalent based on 1 equivalent of vanadium, the reactivity control and selectivity The improvement may be insignificant.

When dissolving the vanadium-containing precursor and the M ¹ -containing precursor, it can be dissolved while heating to a temperature of about 30 to about 90 ℃. In this case, the monoethanolamine may be added to the first solution to increase the solubility of the vanadium-containing precursor and the M ^1- containing precursor, and the amount thereof is suitably used in a range of about 0.5 to about 2 moles relative to vanadium. .

The third step is a second solution obtained by dissolving a chromium-containing precursor, a manganese-containing precursor, and an M ² -containing precursor (wherein M ² is at least one element selected from alkali metals and alkaline earth metals on the periodic table) in deionized water. , A step of obtaining a slurry liquid by mixing with the second suspension obtained in the second step. Optionally, M ³ containing precursor in the formation of the second solution, wherein M ³ is at least one member selected from zinc (Zn), tin (Sn), bismuth (Bi), indium (In) and lead (Pb) Bovine) can also be added and dissolved, or an M ³ -containing precursor (wherein M ³ is an Sb element) can be added to the slurry.

Examples of chromium-containing precursors, manganese-containing precursors and M ² -containing precursors in which M ² is at least one element selected from alkali metals and alkaline earth metals on the periodic table are used as examples of nitrates or acetates containing respective components. Etc., but is not limited thereto.

In addition, the said M ³ containing precursor contains each said component, when (m) M <^3> component is 1 or more types chosen from zinc (Zn), bismuth (Bi), indium (In), and lead (Pb). If nitrate is one suitable and, (ⅱ) M ^third component is tin (Sn) components, Sn-containing chloride is suitable and, (ⅲ) M when the ^third component is antimony (Sb) component, antimony oxide (Sb ₂ O _3, or Sb-containing oxides such as Sb ₂ O ₅ ) are suitable.

In preparing the second solution, the chromium-containing precursor, the manganese-containing precursor, and the M ² -containing precursor each range from about 0.1 to 1 equivalents, about 0.01 to 2 equivalents, and about 0.001 based on 1 equivalent of the vanadium (V) component. It is suitably used in the range of -0.2 equivalent, and the M ³ containing precursor is suitably used in the range of about 0-1 equivalent based on 1 equivalent of the vanadium (V) component.

At this time, in order to increase the activity and selectivity of the catalyst and the range of adjustment of operating variables to increase the utility as an industrial catalyst, the sum of the composition ratios of chromium, manganese, M ² component and M ³ component is based on the composition 1 of vanadium (V). It is desirable to adjust the range to about 0.5 to 3, preferably about 0.8 to 2.

The fourth step is to drop the base solution to the slurry solution obtained in the third step described above to neutralize the pH to about 7, and then the neutralized slurry solution is hydrothermally aged for about 2 to 12 hours at a temperature of about 70 to 90 ℃ As a step of making, by performing this step, all components except the M ² component can be obtained in a precipitated state.

Here, it is preferable to use ammonia water as the base solution in that the post-treatment process can be simplified.

On the other hand, the second, third and fourth step described above, by adjusting the pH by dropping the first solution, the second solution, and ammonia water in advance to the suspension obtained in the first step described above in one step, May be performed.

The fifth step is spray drying the slurry liquid obtained in the fourth step using a conventional spray drying apparatus, and then dried at a temperature of about 90 to 150 ℃ for about 4 to 14 hours to obtain a catalyst composition powder Step.

On the other hand, in order to decompose and remove unnecessary ammonium nitrate, ammonium chloride and the like in the catalyst composition powder, the composition powder may optionally be calcined after the spray drying step at a temperature of about 250 to 400 ° C.

The sixth step is a step of sintering the catalyst composition powder obtained in the fifth step and calcining in an air atmosphere of about 400 to 700 ℃. In the tablet forming, the tablet for dark oxidization reaction of the present invention can be obtained by adding a tableting aid such as graphite and tableting. Alternatively, the catalyst composition for the dark oxidization reaction of the present invention may be obtained by baking the catalyst composition powder on an inert support instead of the tableting and then baking under an air atmosphere at about 400 to 700 ° C.

<Production of Dicyanobenzene>

The present invention provides a method for producing dicyanobenzene from xylene using the catalyst for dark oxidization reaction described above. Specifically, dicyanobenzene may be obtained by subjecting xylene to an oxygen-containing gas and ammonia in the presence of the catalyst for dark oxidation reaction in the fixed bed reactor.

Preferably, two or more layers of the catalyst for dark oxidization reaction having different activity per unit volume are charged to the fixed bed reactor in a two-stage stacking manner so that the heat of reaction generated during the dark oxidization reaction can be more easily controlled, resulting in more stable reaction safety. Can be improved.

Two or more kinds of catalysts for dark oxidation reactions having different activities can be obtained by using TiO ₂ having different catalytic active components and / or particle sizes (or BET specific surface areas) with different weight ratios.

Specifically, it is preferable to charge the catalyst to the reactor so that the weight ratio of the catalytically active component and / or the BET specific surface area (or particle size) of TiO ₂ is sequentially increased from the inlet side to the outlet side of the fixed bed reactor. Do.

For example, when two or more kinds of catalysts having different activities are charged to the fixed bed reactor, it is preferable to charge a catalyst having a low catalytic activity at the top of the fixed bed reactor and a catalyst having a high catalytic activity at the bottom of the fixed bed reactor.

In one example, the catalyst charged to the inlet side of the fixed bed reactor, ie the top catalyst, can be prepared using a BET specific surface area of TiO _{2 in} the range of about 5-20 m 2 / g, and / or the weight ratio of catalytically active component It can be used in the range of about 0.2 to 10% by weight, preferably in the range of about 0.3 to 5% by weight based on the total weight of the catalyst for the dark oxidization reaction.

In this case, it is preferable to use the catalyst charged at the outlet of the fixed bed reactor, that is, the lower catalyst, by adjusting the weight ratio of the catalytically active component and / or the BET specific surface area of TiO ₂ to have higher catalytic activity than the upper catalyst. For example, the catalyst may be prepared using a BET specific surface area of TiO _{2 in} the range of about 10 to 100 m 2 / g, and / or the weight ratio of the catalytically active component is about 0.4 to 30 based on the total weight of the catalyst for the dark oxidation reaction. It is appropriate that it is in the weight percent range, preferably in the range of about 0.5 to 15 weight percent.

The fixed-bed reactor filled with the catalyst for the dark oxidization reaction is supplied with xylene, oxygen-containing gas and ammonia, which can be supplied to the reactor as follows, but not limited to:

a) feed rate of xylene: liquid hourly space velocity (LHSV) of about 0.01 to 0.5 hr ⁻¹ , preferably LHSV of about 0.07 to 0.25 hr ⁻¹ ;

b) Supply of oxygen-containing gas: oxygen-containing gas (x ₂ / xylene) = about 3/1 to about 7/1 (m / m), preferably O ₂ / xylene = about 4/1 To about 5.5 / 1 (m / m); And

c) Supply of ammonia: ammonia to xylene (NH ₃ / xylene) = about 3/1 to about 10/1 (m / m), preferably NH ₃ / xylene = about 4/1 to about 8 / 1 (m / m).

The ammoxidation reaction of xylene, oxygen-containing gas and ammonia thus supplied is a gas hourly gas of about 500 to 2000 hr ⁻¹ at a temperature in the range from about 300 to 500 ° C., preferably at a temperature in the range from about 350 to 420 ° C. space velocity), preferably GHSV of about 550 to 1000 hr ⁻¹ , but is not limited thereto.

In addition, the present invention may optionally use steam to enhance reaction safety in dark oxidization reactions. However, when the excess amount of steam, the selectivity of dicyano benzene can be reduced, the amount of steam used is about 0.01 to 10 vol%, more preferably about 0.05 to 6 based on the total volume in the gaseous state of the total reactants Adjusting to the vol% range is appropriate.

When dicyanobenzene is produced by the above-mentioned preparation method, the conversion of xylene can be increased to about 95% or more, and dicyanobenzene can be obtained with a selectivity of about 85% or more.

Hereinafter, the present invention will be described in more detail by way of examples. However, the examples are provided to illustrate the present invention, and the present invention is not limited thereto.

Example 1

[Example 1-1]

Catalyst A Cr _{One .One} Mn _{0 .2} V _One Mo _{0 .02} W _{0 .02} K _{0 .025} Cs _{0 .025} O _x (3.2) / TiO ₂ (86.8) Al ₁₈ B ₄ O ₃₃ (10)] Manufacturing>

86.8 g of TiO ₂ (Anatase, Aldrich, BET specific surface area: 14.6 m 2 / g) and 10 g of Aluminum Borate (SHIKOKU Kaseico, Alborex YS4, Al ₁₈ B ₄ O ₃₃ ) were added to 400 g of deionized water and stirred To uniformly disperse to form a first suspension.

Subsequently, 1.908 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.083 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], 0.058 g Ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] and 1.1 g of monoethanolamine were added, and the first solution obtained by dissolving them at a temperature of 80 ° C. was added to the first suspension. To form a second suspension.

Subsequently, 7.178 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.819 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], and 0.040 g of potassium acetate (KOAc) in 100 g of deionized water. ) And 0.078 g of cesium acetate (CsOAc) were added to the second suspension to obtain a slurry solution. Thereafter, the pH of the slurry solution was adjusted to 7 using aqueous ammonia and then hydrothermally aged at 80 ° C. for 5 hours. Thereafter, the slurry solution was spray dried to produce fine particles, which were dried at a temperature of 120 ° C. for about 12 hours and then calcined in an air atmosphere having a temperature of about 350 ° C. to obtain a catalyst A powder.

<Catalyst B [ Cr _{One .One} Mn _{0 .2} V _One Mo _{0 .04} K _{0 .02} Cs _{0 .02} O _x (5.4) / TiO ₂ (84.6) Al ₁₈ B ₄ O ₃₃ (10)] Manufacturing>

In preparing the catalyst A powder, (iii) 84.6 g of the same TiO ₂ is used instead of 86.8 g of TiO ₂ used in the formation of the first suspension; (Ii) 1.908 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.083 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], 0.058 g used in the formation of the first solution. 3.248 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.196 g Ammonium heptamolybdate, and 1.70 g instead of Ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], and 1.1 g monoethanolamine. Monoethanolamine of; (Iii) 7.178 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.819 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], 0.040 g used in the formation of the second solution. 12.222 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 1.394 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ instead of potassium acetate (KOAc) and 0.078 g cesium acetate (CsOAc) O], 0.054 g of potassium acetate (KOAc) and 0.107 g of cesium acetate (CsOAc) were used in the same manner as in the preparation of Catalyst A to obtain a catalyst B powder.

<Catalyst C [ Cr _{One .0} Mn _{0 .One} V _One W _{0 .04} K _{0 .015} Cs _{0 .015} O _x (10) / TiO ₂ (80) Al ₁₈ B ₄ O ₃₃ (10)] Manufacture>

In the preparation of the catalyst A powder, (iii) 80 g of TiO ₂ (P-25, Degussa, average particle diameter of primary particles: 21 nm, BET instead of 86.8 g of TiO ₂ used in forming the first suspension) Specific surface area: 52.4 m 2 / g); (Ii) 1.908 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.083 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], 0.058 g used in the formation of the first solution. 6.382 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.554 g Ammonium metatungstate [(NH ₄ ) instead of Ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], and 1.1 g monoethanolamine. ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], and 3.34 g of monoethanolamine; (Iii) 7.178 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.819 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], 0.040 g used in the formation of the second solution. 21.830 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 1.369 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ instead of potassium acetate (KOAc) and 0.078 g cesium acetate (CsOAc) O], 0.080 g of potassium acetate (KOAc) and 0.157 g of cesium acetate (CsOAc) were used in the same manner as in the preparation of Catalyst A to obtain a catalyst C powder.

[Example 1-2]

<Production of Catalyst 1>

52 g of the catalyst A powder prepared in Example 1-1 was added to 60 g of deionized water, followed by ball milling to prepare a slurry liquid. The slurry solution was added to 235 g of alumina support AL-S73 (manufactured by FUJIMI, porosity: 47.5%, specific surface area: <1 m ² / g, spherical, average particle diameter: 5 mm), and then supported by a coating pen. Coated. Thereafter, the catalyst A-supported and coated alumina support was dried at a temperature of about 120 ° C. for 12 hours, and then calcined under an air atmosphere at 550 ° C. for 5 hours to obtain catalyst 1. The supported amount of the obtained catalyst 1 was 17.1 wt% based on the total weight of the catalyst, and the bulk density of the catalyst 1 was 1.21 g / cc.

<Production of Catalyst 2>

46.8 g of the catalyst B powder and 5.2 g of the catalyst C powder prepared in Example 1-1 were added to 65 g of deionized water, followed by ball milling to prepare a slurry liquid. The slurry solution was added to 235 g of alumina support AL-S73, which was then supported and coated in a coating pen. After drying for 12 hours at a temperature of 120 ℃, and calcined for 5 hours in an air atmosphere of 550 ℃ to obtain a catalyst 2. The supported amount of the obtained catalyst 2 was 16.8 wt% based on the total weight of the catalyst, and the bulk density of the catalyst 2 was 1.18 g / cc.

<Production of Catalyst 3>

26 g of the catalyst B powder and 26 g of the catalyst C powder prepared in Example 1-1 were added to 80 g of deionized water, followed by ball milling to prepare a slurry liquid. The slurry solution was added to 235 g of alumina support AL-S73, which was then supported and coated in a coating pen. After drying for 12 hours at a temperature of 120 ℃, and calcined for 5 hours in an air atmosphere of 550 ℃ to obtain a catalyst 3. The supported amount of the obtained catalyst 3 was 16.0 wt% based on the total weight of the catalyst, and the bulk density of the catalyst 3 was 1.13 g / cc.

Example 1-3 Amoxylation Reaction

In a reactor using an molten salt as a heat medium (inner diameter: 22 mm, length: 120 cm) After stacking 70 cc of catalyst 3, 80 cc of catalyst 2, and 90 cc of catalyst 1, which were prepared as the lower, middle and upper catalysts, respectively, the ammoxidation reaction was performed under the following reaction conditions. .

<Reaction Conditions>

-Reaction temperature = 392 ° C

Feed rate of metaxylene = 0.4 ml / min (LHSV = 0.1 hr ^-1 )

NH ₃ / metaxylene = 7/1 m / m

-O ₂ / metaxylene = 5/1 m / m

-Steam supply = 4 vol% based on the total volume of reactants in the gas phase

SV (space velocity) = 635 hr ^-1

As a result, the conversion of metaxylene was 98.7%, the selectivity of isophthalonitrile was 88.5%, and the selectivity of monotoluonitrile (MTN) was 4.5%.

The selectivity was calculated by the following Equation 1, respectively.

[Example 2]

Amoxylation reaction was carried out in the same manner as in Example 1-3, except that the reaction was performed under the following reaction conditions instead of the reaction conditions set in Example 1-3.

<Reaction Conditions>

-Reaction temperature = 392 ° C

Feed rate of metaxylene = 0.4 ml / min (LHSV = 0.1 hr ^-1 )

NH ₃ / metaxylene = 4/1 m / m

-O ₂ / metaxylene = 5/1 m / m

-Steam supply = 4 vol% based on the total volume of reactants in the gas phase

SV (space velocity) = 635 hr ^-1 (except nitrogen gas (N ₂ ) supply)

As a result of the reaction, the conversion of metaxylene was 98.8%, the selectivity of isophthalonitrile was 88.1%, and the selectivity of monotoluonitrile was 4.8%.

[Example 3]

Amoxylation reaction was carried out in the same manner as in Example 1-3, except that the reaction was carried out in the following reaction conditions instead of the reaction conditions set in Example 1-3.

<Reaction Conditions>

-Reaction temperature = 392.7 ° C

Feed rate of metaxylene = 0.48 ml / min (LHSV = 0.12 hr ^-1 )

NH ₃ / metaxylene = 5.5 / 1 m / m

-O ₂ / metaxylene = 5/1 m / m

-Steam supply = 4 vol% based on the total volume of reactants in the gas phase

SV (space velocity) = 730 hr ^-1

As a result, the conversion of metaxylene was 98.6%, the selectivity of isophthalonitrile was 87.3%, and the selectivity of monotoluonitrile was 5.9%.

Example 4

(1) A dark oxidation reaction was carried out in the same manner as in Example 1-3, except that the reaction was performed under the following reaction conditions instead of the reaction conditions set in Example 1-3. At this time, the maximum temperature of the local high temperature portion of the upper catalyst layer was 429.1 ° C. As a result of the reaction, the conversion rate of metaxylene was 98.9%, the selectivity of isophthalonitrile was 88.5%, and the selectivity of monotoluonitrile was 5.2%.

<Reaction Conditions>

-Reaction temperature = 392.6 ° C

Feed rate of metaxylene = 0.42 ml / min (LHSV = 0.105 hr ^-1 )

NH ₃ / metaxylene = 5.5 / 1 m / m

-O ₂ / metaxylene = 5/1 m / m

-Steam supply = 4 vol% based on the total volume of reactants in the gas phase

SV (space velocity) = 635 hr ^-1

(2) After that, the reaction temperature was raised from 392.6 ° C. to 400 ° C. to continue the dark oxidization reaction. As a result, the temperature of the highest local high temperature portion of the upper catalyst layer rose to 460 ° C., but the runaway reaction did not proceed and was safely performed. Could drive. As a result of the reaction, the conversion rate of metaxylene was 99.0%, the selectivity of isophthalonitrile was 89.0%, and the selectivity of monotoluonitrile was 3.8%.

Comparative Example 1

[Comparative Example 1-1]

<Catalyst D [ Cr _One V _One W _{0 .04} K _{0 .02} Cs _{0 .02} O _x (4.5) / TiO ₂ (95.5)]

In the preparation of Catalyst A of Example 1-1, (iii) only 95.5 g of TiO ₂ (Anatase, Aldrich) was used instead of 86.8 g of TiO ₂ and 10 g of Aluminum Borate used in the formation of the first suspension. and; (Ii) 1.908 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.083 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], 0.058 g used in the formation of the first solution. 2.987 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.259 g Ammonium metatungstate [(NH ₄ ) instead of Ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], and 1.1 g of monoethanolamine. ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], and 1.56 g of monoethanolamine; (Iii) 7.178 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.819 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], 0.040 g used in the formation of the second solution. 10.219 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.050 g of potassium acetate (KOAc) and 0.098 g of cesium acetate instead of 0.078 g of potassium acetate (KOAc) and 0.078 g of cesium acetate (CsOAc) CsOAc) A catalyst D powder was obtained in the same manner as in the preparation of Catalyst A of Example 1-1, except that it was used.

[Comparative Example 1-2]

<Production of Catalyst 4>

55 g of the catalyst D powder prepared in Comparative Example 1-1 was added to 68 g of deionized water, followed by ball milling to prepare a slurry liquid. The slurry solution was added to 250 g of alumina support AL-S73, and then supported and coated by a coating pen. Thereafter, the mixture was dried at a temperature of 120 ° C. for 12 hours, and then calcined for 5 hours under an air atmosphere of 550 ° C. to obtain a catalyst 4. The supported amount of the obtained catalyst 4 was 18.0 wt% based on the total weight of the catalyst.

[Comparative Example 1-3]-Dark Oxidation Reaction

(1) 240 cc of the catalyst 4 prepared in Comparative Example 1-2 was charged into a reactor (inner diameter: 22 mm, length: 120 cm) using a molten salt as the heat medium, and then subjected to the dark oxidization reaction under the following reaction conditions. Was performed.

<Reaction Conditions>

-Reaction temperature = 376.5 ℃

Feed rate of metaxylene = 0.4 ml / min (LHSV = 0.1 hr ^-1 )

NH ₃ / metaxylene = 7/1 m / m

-O ₂ / metaxylene = 5/1 m / m

-Steam supply = 4 vol% based on the total volume of reactants in the gas phase

SV (space velocity) = 635 hr ^-1

As a result, the conversion of metaxylene was 79.0%, the selectivity of isophthalonitrile was 49.4%, the selectivity of monotoluonitrile was 44.8%, and the maximum temperature of the local high temperature portion of the catalyst layer was about 415 ° C.

(2) Thereafter, the reaction temperature was raised from 376.5 ° C. to 379.2 ° C. to continuously carry out the dark oxidization reaction. As a result of continuing the dark-oxygenation reaction, the runaway reaction advanced.

(3) Then, after stopping and stabilizing the amoxylation reaction, the conditions for supplying oxygen to metaxylene and for supplying ammonia to metaxylene at the reaction temperature of 379.2 ° C. were adjusted to be the same as the initial reaction conditions. The reaction safety was investigated by increasing gradually to the state. As a result, it was possible to operate until the supply amount of metaxylene was LHSV = 0.075 hr ⁻¹ at the reaction temperature of 379.2 ° C., but when the supply amount of metaxylene was increased to 0.08 hr ⁻¹ , the runaway reaction proceeded to operate. This was impossible.

[Example 5]

[Example 5-1]

<Catalyst E [ Cr _{One .One} Mn _{0 .2} V _One W _{0 .04} K _{0 .02} Cs _{0 .02} O _x (3.2) / TiO ₂ (76.8) Al ₁₈ B ₄ O ₃₃ (20)]

In the preparation of Catalyst A of Example 1-1, (iii) 76.8 g of TiO ₂ (Anatase, Aldrich) and 20 g instead of 86.8 g of TiO ₂ and 10 g of Aluminum Borate used in the formation of the first suspension Aluminum Borate (Alborex YS4) is used; (Ii) 1.908 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.083 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], 0.058 g used in the formation of the first solution. 1.891 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.164 g Ammonium metatungstate [(NH ₄ ) instead of Ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], and 1.1 g monoethanolamine. ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], and 0.99 g of monoethanolamine; (Iii) 7.178 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.819 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], 0.040 g used in the formation of the second solution. 7.114 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.811 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ instead of potassium acetate (KOAc) and 0.078 g of cesium acetate (CsOAc) O], 0.032 g of potassium acetate (KOAc) and 0.062 g of cesium acetate (CsOAc) were used in the same manner as in the preparation of Catalyst A of Example 1-1, to obtain a catalyst E powder.

Example 5-2

<Production of Catalyst 5>

55 g of the catalyst E powder prepared in Example 5-1 was added to 68 g of deionized water, followed by ball milling to prepare a slurry liquid. The slurry solution was added to 250 g of alumina support AL-S73, which was then supported and coated in a coating pen. Thereafter, the mixture was dried at a temperature of 120 ° C. for 12 hours, and then calcined for 5 hours under an air atmosphere of 550 ° C. to obtain a catalyst 5.

The supported amount of the obtained catalyst 5 was 17.2 wt% based on the total weight of the catalyst.

Example 5-3 Amoxylation Reaction

(1) Instead of 240 cc of catalyst 4 used in Comparative Example 1-3, 240 cc of the catalyst 5 obtained in Example 5-2 was charged to the reactor and the reaction temperature of the reactor was changed to 397.5 ° C instead of 376.5 ° C. Except for adjusting, the dark oxidization reaction was performed under the same reaction conditions as in Comparative Examples 1-3.

As a result of the reaction, the conversion of metaxylene was 67.4%, the selectivity of isophthalonitrile was 57.6%, the selectivity of monotoluonitrile was 36.4%, and the maximum temperature of the local high temperature portion of the catalyst layer was about 432 ° C.

(2) Thereafter, the reaction temperature was raised from 397.5 ° C. to 404 ° C. to perform the dark oxidization reaction. As a result, the local high temperature portion of the catalyst layer was heated up to 490 ° C., but the runaway reaction did not proceed.

[Example 6]

Amoxy was used under the same reaction conditions as in Example 1-3, except that paraxylene was used instead of the metaxylene used in Example 1-3, and the reaction temperature of the reactor was adjusted to 385.4 ° C. The reaction was carried out.

As a result of the reaction, the conversion of paraxylene was 99.7%, the selectivity of paradicyanobenzene was 94.9%, and the selectivity of monotoluonitrile was 0.3%.

[Example 7]

[ Example  7-1]

<Catalyst F [ Cr _One Mn _{0 .One} Zn _{0 .One} V _One W _{0 .04} K _{0 .02} Cs _{0 .02} O _x (2.5) / TiO ₂ (87.5) Al ₁₈ B ₄ O ₃₃ (10)] Manufacturing>

In the preparation of Catalyst A of Example 1-1, (iii) 437.5 g of TiO ₂ (Anatase, Aldrich) and 50 instead of 86.8 g of TiO ₂ and 10 g of Aluminum Borate used in the formation of the first suspension g of Aluminum Borate (Alborex YS4) was used; (Ii) 1.908 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.083 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], 0.058 g used in the formation of the first solution. 7.638 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.663 g Ammonium metatungstate [(NH ₄ ) instead of Ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], and 1.1 g of monoethanolamine. ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], and 3.99 g of monoethanolamine; (Iii) 7.178 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.819 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], 0.040 g used in the formation of the second solution. 26.128 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 1.639 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ instead of potassium acetate (KOAc) and 0.078 g cesium acetate (CsOAc) O], 1.942 g of zinc nitrate [Zn (NO ₃ ) ₂ .6H ₂ O], 0.128 potassium acetate (KOAc) and 0.251 g of cesium acetate (CsOAc), except that Catalyst F powder was obtained by the same method as in the preparation of Catalyst A.

[Example 7-2]

<Production of Catalyst 6>

To 300 g of the catalyst F powder prepared in Example 7-1, 10 g of graphite powder was added and mixed. Thereafter, the mixture was molded by molding into a hollow cylinder type (outer diameter x inner diameter x length = 8 mm x 3 mm x 3.5 mm), and then calcined under an air atmosphere at 550 ° C. for 5 hours to obtain a catalyst 6. . The bulk density of catalyst 6 was 0.80 g / cc.

Example 7-3

In Example 1-3, except that the catalyst 6 prepared in Example 7-2 was charged to the 70 cc reactor in place of the 70 cc of the catalyst 3 used as the lower catalyst in Example 1-3, Amoxylation reaction was performed under the same conditions.

As a result, the conversion of metaxylene was 99.2%, the selectivity of isophthalonitrile was 86.8%, and the selectivity of monotoluonitriryl (MTN) was 3.5%.

[Example 8]

[Example 8-1]

<Catalyst G [ Cr _One Mn _{0 .One} V _One W _{0 .04} K _{0 .02} Cs _{0 .02} Bi _{0 .One} O _x (2.5) / TiO ₂ (87.5) Al ₁₈ B ₄ O ₃₃ (10)] Manufacturing>

In the preparation of Catalyst A of Example 1-1, (iii) 437.5 g TiO ₂ (Anatase, Aldrich) and 50 g instead of 86.8 g TiO ₂ and 10 g Aluminum Borate used in the formation of the first suspension Aluminum Borate (Alborex YS4), and (ii) 1.908 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.083 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ used in the formation of the first solution. O ₄₀ .5H ₂ O], 0.058 g of Ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O], and 1.1 g of monoethanolamine instead of 7.078 g of Ammonium metavanadate (NH ₄ VO ₃ ), 0.614 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], and 3.696 g of monoethanolamine, and (iii) 7.178 g used in the formation of the second solution. Chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.819 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], 0.040 g of potassium acetate (KOAc) and 0.078 g of cesium acetate (CsOAc Instead of 24.210 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 1.519 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], and is the embodiment except for the use of nitric acid 1.467g bismuth _{[Bi (NO 3) 3 ·} 5H 2 O], of the potassium acetate (KOAc) and 0.232g 0.119g of cesium acetate (CsOAc) Catalyst G powder was obtained by the same method as the preparation of catalyst A of 1-1.

[Example 8-2]

<Production of Catalyst 7>

In the same manner as in Example 7-2, except that 300 g of Catalyst G powder prepared in Example 8-1 was used instead of 300 g of Catalyst F powder used in Example 7-2. Catalyst 7 was obtained. The bulk density of the catalyst 7 was 0.79 g / cc.

[Example 8-3]

In Example 1-3, except that the catalyst 7 prepared in Example 8-2 was charged to the 70 cc reactor instead of the 70 cc of the catalyst 3 used as the lower catalyst in Example 1-3, Amoxylation reaction was performed under the same conditions.

As a result, the conversion of metaxylene was 99.2%, the selectivity of isophthalonitrile was 87.0%, and the selectivity of monotoluonitriryl (MTN) was 4.1%.

[Example 9]

[Example 9-1]

<Catalyst H [ Cr _One Mn _{0 .One} V _One W _{0 .04} K _{0 .015} Cs _{0 .015} Sb _{0 .One} O _x (10) / TiO ₂ (80) Al ₁₈ B ₄ O ₃₃ (10)] Manufacturing>

80 g of TiO ₂ (P-25, Degussa Co., Ltd.) and 10 g of Aluminum Borate (Alborex YS4) were added to 400 g of deionized water, and then uniformly dispersed to prepare a first suspension.

5.864 g of Ammonium metavanadate (NH ₄ VO ₃ ), 0.509 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O] and 3.1 g of monoethanolamine were dissolved in 100 g of deionized water. A first solution was prepared, and 20.060 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 1.258 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], 0.811 g of antimony oxide ( Sb ₂ O ₅ ), 0.074 g of potassium acetate (KOAc) and 0.144 g of cesium acetate (CsOAc) were dissolved in 100 g of deionized water to prepare a second solution, and 5% diluted ammonia water was also prepared.

Thereafter, while stirring the prepared first suspension vigorously, the first solution, the second solution, and the diluted ammonia water, respectively prepared thereto, were simultaneously added dropwise to obtain a slurry solution. At this time, the dropwise addition of the diluted ammonia water was adjusted to pH 7 of the slurry solution. After completion of the dropwise addition, 0.811 g of antimony oxide (Sb ₂ O ₅ ) powder was carefully added to the slurry solution, followed by continued stirring. Subsequently, the slurry solution was hydrothermally aged and aged at a temperature of 80 ° C. for 5 hours, followed by spray drying to obtain a catalyst composition powder. The catalyst composition powder was dried at a temperature of 120 ° C. for about 12 hours and then calcined in an air atmosphere having a temperature of about 350 ° C. to obtain a catalyst H powder.

[Example 9-2]

<Production of Catalyst 8>

26 g of the catalyst H powder prepared in Example 9-1 and 26 g of the catalyst B powder prepared in Example 1-1 were placed in 80 g of deionized water, followed by ball milling to prepare a slurry solution. The slurry solution was added to 235 g of alumina support AL-S73, which was then supported and coated in a coating pen. Thereafter, the mixture was dried at a temperature of 120 ° C. for 12 hours, and then calcined under an air atmosphere of 550 ° C. for 5 hours to obtain a catalyst 8.

The supported amount of the obtained catalyst 8 was 17.0 wt% based on the total weight of the catalyst 8, and the bulk density of the catalyst 8 was 1.21 g / cc.

Example 9-3 Amoxylation Reaction

In Example 1-3 except that the catalyst 8 prepared in Example 9-2 was charged to the 70 cc reactor instead of the 70 cc of the catalyst 3 used as the lower catalyst in Example 1-3, Amoxylation reaction was carried out under the same conditions.

As a result of the reaction, the conversion rate of metaxylene was 99.0%, the selectivity of isophthalonitrile was 87.1%, and the selectivity of monotoluonitriryl (MTN) was 4.9%.

[Comparative Example 2]

[Comparative Example 2-1]

<Catalyst I [ Cr _One Mn _{0 .One} V _One W _{0 .04} Cs _{0 .02} O _x 10 / TiO ₂ (90)]

In the preparation of Catalyst A of Example 1-1, (iii) only 90 g of TiO ₂ (Anatase, Aldrich) instead of 86.8 g of TiO ₂ and 10 g of Aluminum Borate used as a carrier in the formation of the first suspension Use; (Ii) 1.908 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.083 g Ammonium metatungstate [(NH ₄ ) ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], 0.058 g Ammonium used in the formation of the first solution 6.38 g Ammonium metavanadate (NH ₄ VO ₃ ), 0.534 g Ammonium metatungstate [(NH ₄ ) instead of heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], and 1.1 g monoethanolamine ₆ H ₂ W ₁₂ O ₄₀ .5H ₂ O], and 4.5 g of monoethanolamine; (Iii) 7.178 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 0.819 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ O], 0.040 g used in the formation of the second solution. 21.83 g of chromium nitrate [Cr (NO ₃ ) ₃ .9H ₂ O], 1.37 g of manganese nitrate [Mn (NO ₃ ) ₂ .4H ₂ instead of potassium acetate (KOAc) and 0.078 g cesium acetate (CsOAc) O], and 0.21 g of potassium acetate (KOAc) A catalyst I powder was obtained in the same manner as in the preparation of catalyst A of Example 1-1, except that it was used.

[ Comparative Example  2-2]

<Production of Catalyst 9>

The catalyst I powder prepared in Comparative Example 2-1 was dried at a temperature of 120 ° C. for 12 hours, calcined under an air atmosphere of 550 ° C. for 5 hours, and then molded into a size of 20 to 40 mesh to obtain a catalyst 9. .

Comparative Example 2-3-Amoxylation Reaction

The microreactor (inner diameter: 12 mm, length: 30 cm) was charged with 4 g of the catalyst 9 prepared in Comparative Example 2-2, and then subjected to an dark oxidization reaction under the following reaction conditions.

<Reaction Conditions>

-Reaction temperature = 383 ℃

Feed rate of metaxylene = 0.01 ml / min (LHSV = 0.1 hr ^-1 )

NH ₃ / metaxylene = 7/1 m / m

-O ₂ / metaxylene = 7/1 m / m

As a result of the reaction, the conversion of metaxylene was 98.5%, the selectivity of isophthalonitrile was 80%, the selectivity of monotoluonitrile was 4%, and the selectivity of CO ₂ was 8%.

Thereafter, the reaction temperature was raised from 383 ° C. to 388 ° C. to continue the dark oxidization reaction. As a result, the runaway reaction proceeded.

[Comparative Example 3]

[ Comparative Example  3-1]

<Catalyst J [ Cr _One Mn _{0 .One} V _One W _{0 .04} Cs _{0 .02} O _x (10) / TiO ₂ (70) Al ₁₈ B ₄ O ₃₃ (20)]

70g TiO ₂ (Anatase, Aldrich) and 20g Aluminum Borate (SHIKOKU Kaseico, Alborex) instead of 90g TiO ₂ (Anatase, Aldrich) used as a carrier in the formation of the first suspension in the preparation method of the catalyst I YS4, Al ₁₈ B ₄ O ₃₃ ) was used in the same manner as in the preparation of Catalyst I, except that Catalyst J powder was obtained.

[ Comparative Example  3-2]

<Production of Catalyst 10>

Catalyst 10 was obtained in the same manner as in the preparation of Catalyst 9, except that Catalyst J powder was used instead of Catalyst I powder.

[Comparative Example 3-3]-Dark Oxidation Reaction

The microreactor (inner diameter: 12 mm, length: 30 cm) was charged with 4 g of the catalyst 10 prepared in Comparative Example 3-2, and then the dark oxidization reaction was carried out under the same reaction conditions as described above.

<Reaction Conditions>

-Reaction temperature = 383 ℃

Feed rate of metaxylene = 0.01 ml / min (LHSV = 0.1 hr ^-1 )

NH ₃ / metaxylene = 7/1 m / m

-O ₂ / metaxylene = 7/1 m / m

As a result of the reaction, the conversion of metaxylene was 99%, the selectivity of isophthalonitrile was 83%, the selectivity of monotoluonitrile was 7.8%, and the selectivity of CO ₂ was 6%.

Thereafter, the reaction temperature was raised from 383 ° C. to 388 ° C. to continue the dark oxidization reaction, but no runaway reaction occurred.

Claims (19)

(a) (iii) vanadium (V), (ii) chromium (Cr), (iii) molybdenum (Mo), tungsten (W) or both, (iii) at least one element selected from alkali metals and alkaline earth metals, And (iii) an oxide consisting of manganese (Mn), or
(b) (iii) vanadium (V), (ii) chromium (Cr), (iii) molybdenum (Mo), tungsten (W) or both, (iii) at least one element selected from alkali metals and alkaline earth metals, (Iii) manganese (Mn) and (iii) one or more elements selected from the group consisting of zinc (Zn), tin (Sn), bismuth (Bi), indium (In), lead (Pb), and antimony (Sb) Oxide
A catalytically active ingredient containing
Carrier Component Containing TiO ₂ and Metal Borate
A catalyst for dark oxidization reaction comprising a. The catalyst for dark oxidization reaction according to claim 1, which is represented by the following Chemical Formula 1.
[Chemical Formula 1]

(In the formula 1,
Cr _a Mn _b V ₁ M ¹ _c M ² _d M ³ _e O _x is a catalytically active component,
Cr is chromium,
Mn is manganese,
V is vanadium,
M ¹ is one or more elements selected from Mo and W,
M ² is one or more elements selected from alkali metals and alkaline earth metals on the periodic table,
M ³ is at least one element selected from the group consisting of zinc (Zn), tin (Sn), bismuth (Bi), indium (In), lead (Pb), and antimony (Sb),
O is oxygen,
a, b, c, d, e and x represent the atomic ratios of Cr, Mn, M ¹ , M ² , M ³ and O to V, respectively,
0.1 ≦ a ≦ 2, 0.01 ≦ b ≦ 2, 0.01 ≦ c ≦ 0.5, 0.001 ≦ d ≦ 0.2, and 0 ≦ e ≦ 1, respectively, and x is a number determined by the oxidation state of each component,
TiO ₂ -M ⁴ BO _y is a carrier component for supporting the catalytically active portion,
TiO ₂ is titanium dioxide, M ⁴ BO _y represents a metal borate (metal borate),
M ⁴ is a compound in which one or more elements are selected from the group consisting of aluminum (Al), calcium (Ca), barium (Ba), bismuth (Bi), tin (Zn), and zinc (Zn). , y is a number determined by the components of M ⁴ , the atomic ratio of B and the oxidation state of each component). The catalyst for dark oxidization reaction according to claim 2, wherein in the general formula (1), 0.5 ≦ a + b + d + e ≦ 3.0. The catalyst for dark oxidization reaction according to claim 1, wherein the content of the catalytically active component is in the range of 0.2 to 30 wt% based on the total weight of the dark oxidization catalyst. The catalyst for dark oxidization reaction according to claim 1, wherein TiO ₂ and metal borate in the carrier component are included in a weight ratio of 40:60 to 95: 5. According to claim 1, wherein the BET surface area of the TiO ₂ is a catalyst for dark oxidization reaction, characterized in that in the range of 5 to 100 m 2 / g. The catalyst for dark oxidization reaction according to claim 1, wherein the metal borate comprises aluminum borate. The catalyst for dark oxidization reaction according to claim 1, wherein the catalyst for dark oxidization reaction is additionally supported on an inert support. The catalyst for dark oxidization reaction according to claim 8, wherein the specific surface area of the inert support is in the range of 0.01 to 1 m 2 / g. A method for producing dicyanobenzene by xylene reacting with the oxygen-containing gas and ammonia in the presence of the catalyst for dark oxidation reaction according to any one of claims 1 to 9. The catalyst according to claim 10, wherein the catalyst for dark oxidation reaction is two or more catalysts having different activities per unit volume,
At least two catalysts having different activities are different in weight ratio of the catalytically active component, BET specific surface area of TiO ₂ , or both of them. 12. The method of claim 11, wherein the production process occurs in a fixed bed reactor, and the weight ratio of the catalytically active component in the catalyst increases sequentially from the inlet to the outlet toward the outlet of the fixed bed reactor. How to. 12. The method of claim 11, wherein the BET specific surface area of TiO ₂ increases sequentially with the number of packed stages from the inlet side to the outlet side of the fixed bed reactor. The method of claim 11, wherein the catalyst at the inlet side of the reactor among the two or more catalysts having different activity,
The BET specific surface area of TiO ₂ is in the range of 5 to 20 m 2 / g, and the weight ratio of the catalytically active component is in the range of 0.2 to 10% by weight based on the total weight of the catalyst for the dark oxidization reaction,
The catalyst on the outlet side of the reactor,
Method The BET specific surface area of the weight ratio of the catalytically active component and TiO ₂ is for producing dicyano benzene, characterized in that each larger than the weight ratio of the catalytically active component of the inlet-side catalyst, and a BET specific surface area of TiO _2. The method of claim 14, wherein the catalyst on the outlet side of the reactor,
Dicyano benzene is produced, characterized in that the BET specific surface area of TiO ₂ is in the range of 10 to 100 m 2 / g, and the weight ratio of the catalytically active component is in the range of 0.4 to 30% by weight based on the total weight of the catalyst for dark oxidization reaction. How to. The method of claim 10, wherein the xylene is supplied at a liquid hourly space velocity (LHSV) of 0.01 to 0.5 hr ⁻¹ . The method of claim 10, wherein the oxygen-containing gas is oxygen-containing gas (O ₂ / xylene) is supplied to 3/1 ~ 7/1 (m / m) compared to xylene, the ammonia is ammonia (NH compared to xylene) ₃ / xylene) is supplied to 3/1 ~ 10/1 (m / m) method for producing a dicyanobenzene. The method of claim 10, wherein the dark oxidization reaction is performed at a gas hourly space velocity (GHSV) of 500 to 2000 hr ⁻¹ at a temperature of 300 to 500 ° C. ¹² . The method according to claim 10, wherein in the dark oxygenation reaction, the steam is based on the total volume in the gaseous state of the total reactants Method for producing dicyanobenzene, characterized in that it is additionally used in the range of 0.01 to 10 vol%.