KR20100025428A - Long-time catalyst for mto reaction and preparing method thereof - Google Patents

Abstract

PURPOSE: A long-time MTO reactive catalyst and a method for manufacturing the catalyst are provided to control a damage and abrasion caused by thermomechanical fatigue of the catalyst by recycling the catalyst at low temperature. CONSTITUTION: A method for manufacturing a long-time MTO(Methanol-To-Olefin) reactive catalyst comprises: a first step which ion-exchanges zeolite into a transition metal of one species or more which are selected among copper(Cu), nickel(Ni), and cobalt(Co); a second step plasticizing the zeolite at 350°C ~ 700°C after drying the ion-exchanged zeolite of the first step; and a third step stabilizing the plasticized zeolite of the second step by processing the zeolite with nitrogen dioxide at 100°C ~ 400°C.

Description

Long-life catalyst for MTO reaction and preparation method thereof Long-time catalyst for MTO reaction and Preparing method

The present invention relates to a catalyst for MTO reaction prepared by stabilizing ion-exchanged transition metals present in the zeolite pores by ion-exchanging zeolites with ion-exchanged zeolites, followed by nitrogen dioxide treatment. It can be used in a chemical process for preparing lower olefins from methanol, and the catalyst for MTO reaction of the present invention can prevent catalyst deterioration and also regenerate the catalyst at a much lower temperature than before. Even if used, the activity of the catalyst and the selectivity to the lower olefins are continuously maintained.

Polyolefins such as polyethylene and polypropylene and lower olefins such as ethylene, propylene and butene, which are the most important starting materials for the petrochemical industry, are produced by pyrolysis of naphtha. Recently, some of the lower olefins are also produced in the pyrolysis process of ethanol and the fluidized bed catalytic cracking process, but the production scale is much smaller than that of naphtha. The naphtha pyrolysis process uses a lot of energy to use about 40% of the energy used in petrochemical plants, but it is widely used because of its simple process and easy operation. However, due to the sharp rise in the price of crude oil, the price of naphtha, a raw material, has risen, and the cost burden of energy required in the pyrolysis process increases, and various alternative processes are being developed. The development of a process that uses less energy and produces lower olefins is very urgent.

The process for producing lower olefins from methanol (methanol-to-olefin (MTO)) is derived from the process for producing gasoline from methanol (methanol-to-gasoline). A brief description of the MTO reaction is that methanol is dehydrated in an acid catalyst to dimethyl ether, followed by conversion to lower olefins such as ethylene, propylene, butene {CD Chang, "Methanol conversion to light olefins", Catal. Rev. -Sci. Eng ., 26 , 323 (1984) and G. Seo, "Conversion of methanol to chemical feedstock and fuel", Prog. Ind. Chem ., 27 (1), 15 (1987)}, the converted lower olefins become saturated hydrocarbons and aromatic hydrocarbons which have undergone various reactions such as polymerization, cyclization and dehydrogenation. In addition, in the MTO reaction, a catalyst having a maximum selectivity for lower olefins is generally used by promoting the production of lower olefins and suppressing further olefins. Since the catalyst has eight pore inlets, bears a paraffin or W aromatic hydrocarbons prevent passage, SAPO-34 molecular sieve, or the two of these generated is inherently suppressed and because neutralize the strong acid sites to partially generally the MFI zeolite to suppress the further reaction of a lower olefin with a catalyst use. In particular, the Ni-SAPO-34 catalyst, in which nickel is introduced into the skeleton, has excellent selectivity to lower olefins and thus is used as a catalyst in a test plant of a UOP / Hydro process (DR Dubois, DL Obrzut, J. Liu, J. Thundimadathil). , PM Adekkanattu, JA Guin, A. Punnoose, MS Seehra, "Conversion of methanol to olefins over cobalt-, manganese- and nickel-incorporated SAPO-34 molecular sieves", " Fuel Process. Technol ., 83 , 203 (2003) }.

Methanol is alkylated with hexamethylbenzene formed in the pores of SAPO-34 molecular sieves with CHA (chabazite) framework and then converted to lower olefins through side-chain alkylation or paring reactions. do. Hexamethylbenzene produced in the pore is the reactive active material, the time required for the active material to be produced is the induction period, and the concentration in the pore of the material determines the reaction rate. In other words, the number and reactivity of hexamethylbenzene in SAPO-34 pores that can react with methanol determines the catalytic activity. However, when hexamethylbenzene is converted into a polycyclic aromatic hydrocarbon (PAH) having a plurality of rings such as naphthalene, anthracene, and phenanthrene through an additional cyclization reaction, the catalytic active point is reduced and the pores are occupied by PAH, thus blocking the inlet, There is a problem that it can not react and gradually loses its function as a catalyst. {JQ Chen, A. Bozzano, B. Glover, T. Fuglerud, S. Kvisle, "Recent advancements in ethylene and propylene production using the UOP / Hydro MTO process ", Catal. Today , 106 , 103 (2005)}. If the reaction temperature is high or the concentration of methanol is low, the cyclization reaction is slowed and the decomposition reaction is accelerated, and the activity decrease is significantly suppressed. However, the adjustment of the reaction conditions alone does not sufficiently suppress the activity decrease of the SAPO-34 molecular sieve itself. There is. In the MTO reaction, since the deactivation of the catalyst is inevitable, a process using a SAPO-34 molecular sieve as a catalyst is operated by installing a regenerator in a fluidized bed reactor. The regeneration method is a method in which a degraded catalyst is collected by a cyclone and sent to a regenerator to burn and remove the deposited PAH to reuse the catalyst. The pore inlet of the SAPO-34 molecular sieve is a slightly inclined ellipse of 0.38 8 0.38 nm consisting of eight oxygen atoms. The selectivity for lower olefins is very good because the inlet is small enough to pass through only the lower olefin molecules, but the pore inlet is small in the regeneration step of burning PAH deposited in the pores, resulting in slow removal of PAH. In addition, there is a problem in that the pore structure of the catalyst is broken due to the heat generated in the process of burning the deposited PAH, and the physical properties such as mechanical strength are degraded.

Therefore, the present inventors have studied and tried to solve the problem of deactivation of the catalyst for the conventional MTO reaction, chemically stabilize the hexamethylbenzene intermediate of the MTO reaction or fill a part of the catalyst pores with other materials to generate PAH In addition to suppressing the present invention, it was found that the present invention can increase the regeneration cycle of the catalyst for MTO reaction. That is, an object of the present invention is to provide a catalyst for MTO reaction having a long regeneration cycle and a high catalyst activity for a long time, and a long lifetime of the catalyst itself, and a method for preparing the same.

A method for preparing a catalyst for long-life MTO reaction of the present invention for solving the above problems is a first step of ion-exchanging a zeolite with a discontinuous or at least two transition metals selected from among copper (Cu), nickel (Ni) and cobalt (Co) ;

A second step of drying the ion exchanged zeolite of the first step and then calcining at 350 ° C to 700 ° C; And

And a third step of stabilizing the calcined zeolite of the second step by treating with nitrogen dioxide at 100 ° C. to 400 ° C .;

In addition, the present invention relates to a catalyst for long-life MTO reaction, characterized in that produced by the above method.

The catalyst for long life MTO reaction of the present invention can increase the regeneration cycle and catalyst activity of the catalyst by minimizing or preventing the generation of PAH in the pores of the catalyst, and regeneration at a low temperature even in the regeneration process of the catalyst. Since it is possible to suppress the wear and breakage due to the thermal mechanical fatigue of the catalyst due to the regeneration process performed in the existing high temperature atmosphere, it is possible to relatively increase the life of the catalyst. And the fall of the yield of lower olefin resulting from the acidic fall of a catalyst can also be prevented.

The long-life MTO reaction catalyst and the preparation method thereof of the present invention described above will be described in detail.

[Method of producing catalyst for long life MTO reaction]

The long life MTO (Methanol-To-Olefin) reaction method of the present invention will be described in detail.

In the present invention, in order to provide a method for preparing a catalyst having a high selectivity for lower olefins but a slow activity deterioration in a MTO reaction, Cu, a single or two paper type zeolite selected from CHA zeolite, LTA zeolite, MOR zeolite and BEA zeolite Ions were exchanged using a transition metal compound containing Ni or Co. At this time, a transition metal ion solution having a weak acidity was used at a temperature as low as possible to exchange ions in a solution state without breaking the pore structure of the zeolite. In addition, in the solid state ion exchange, the amount of the transition metal compound was controlled and the treatment temperature was lowered to minimize damage to the crystal structure. The exchanged transition metal ions may migrate out of the pores under MTO reaction conditions and may move out of the particles to agglomerate. In particular, in reducing conditions, they move out of the pores to form agglomerates, so the exchange effect may be lost. Therefore, the treatment with nitrogen dioxide to stabilize the transition metal ions in the pores of the zeolite, to minimize the movement by a stable fixation to the skeleton in the transition metal oxide state.

Referring to the step-by-step description of the production method of the catalyst for long-life MTO reaction to be provided by the present invention,

A first step of ionizing the zeolite with a discontinuous or at least two transition metals selected from copper (Cu), nickel (Ni) and cobalt (Co);

A second step of drying the ion exchanged zeolite of the first step and then calcining at 350 ° C to 700 ° C; And

And a third step of stabilizing the calcined zeolite of the second step by treating with nitrogen dioxide at 100 ° C. to 400 ° C .;

In the first step, the zeolite is selected from CHA (chabazite) zeolite, LTA (Linde Type A) zeolite, MOR (Mordenite) zeolite or BEA (beta polymorph A) zeolite or at least two or more. When the zeolite is ion exchanged with a transition metal, the transition metal is supported on the inside or the surface of the zeolite in the form of a transition metal oxide such as CuO.

Next, with reference to the second step, the second step is a step of firing the catalyst ion-exchanged with a transition metal, the firing temperature is preferably carried out at a temperature of 350 ℃ to 700 ℃, if the firing temperature is 350 If the temperature is less than 0 ° C., the metal may not be sufficiently calcined, and thus the transition metal may not be stabilized. If the temperature exceeds 700 ° C., some structures may collapse.

The third step is the step of treating the ion-exchanged transition metal with a strong oxidizing agent nitrogen dioxide to stabilize it and fix it in the pores of the catalyst. Nitrogen dioxide having a concentration of 100 ppm to 5,000 ppm at a temperature of 100 ° C. to 400 ° C. Can be processed with At this time, if the nitrogen dioxide treatment temperature is less than 100 ℃ does not oxidize sufficiently, the structure is collapsed if it exceeds 400 ℃, the oxidation reaction is too slow if the concentration of nitrogen dioxide is less than 100 ppm, the problem of precipitation as an oxide if more than 5,000 ppm It is desirable to remain within this range as it may occur. As such, after the first to third steps, the transition metal oxide ion-exchanged inside the pores of the zeolite catalyst is stably fixed.

Whether copper ions were exchanged in the pores of the catalyst for MTO reaction prepared by the preparation method of the present invention was determined by electron spin resonance (ESR) and xenon (nuclear magnetic resonance) spectroscopy (NMR). You can check it.

[Catalyst for Long Life MTO Reaction]

In addition, the catalyst for long-life MTO reaction of the present invention is characterized by being prepared by the method described above. The catalyst for long life MTO reaction of the present invention

It is characterized by containing 0.5-5% by weight of the transition metal oxide with respect to the total weight of the catalyst by ion-exchanging one or two or more transition metals selected from Cu ²⁺ , Ni ²⁺ and Co ²⁺ to the zeolite. Here, the transition metal oxide includes CuO, NiO, CoO and the like.

The zeolite contained in the catalyst for MTO reaction of the present invention described above is selected from CHA (chabazite) zeolite, LTA (Linde Type A) zeolite, MOR (Mordenite) zeolite or BEA (beta polymorph A) zeolite You can use this, but if you describe it in different ways,

Silicoaluminophosphate-34 having a chabazite zeolite skeleton structure (hereinafter defined as "SAPO-34"); Zeolites having an LTA framework structure; Zeolites having a MOR skeleton; Or zeolites having a BEA skeleton; You can use the selected one.

In the present invention, a transition metal oxide can be selectively used depending on the type of zeolite used.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited thereto .

Preparation of SAPO-34 Molecular Sieve with CHA Zeolite Structure

SAPO-34 molecular sieves were synthesized using tetraethylammonium hydroxide (TEAOH, Aldrich, 35%) as a template. 138 g of aluminum isopropoxide (Junsei Chemical, 98%) and 182 g of tetraethylammonium hydroxide were mixed and stirred for 1 hour 30 minutes. The solution was stirred well by dropping a solution of 77 g of phosphoric acid (Merck, 85%) and 80 g of water. To this homogeneously mixed solution, 6 g of fume silica (SiO ₂ , Aldrich, 95%) and 7 g of water were mixed and stirred well. The solution was mixed with 2 TEAOH: 0.3 SiO ₂ : 1 Al ₂ O ₃ : 1 P ₂ O ₅ : 52 H ₂ O into a high pressure reactor and subjected to hydrothermal reaction at 175 ° C for 48 hours. The resulting solid material was filtered, washed with deionized water and heated at 100 ° C. for 12 hours. This was calcined at 600 ° C. for 5 hours to prepare an H-type SAPO-34 molecular sieve (hereinafter referred to as “CHA'-H”) having a CHA zeolite structure. The mass of the CHA-H synthesized after firing was 70 g, and the yield calculated based on aluminum isopropoxide, phosphoric acid, and product silica was 50%. In the X-ray diffraction pattern of the prepared CHA-H, the diffraction peak of the chabazite structure was clearly seen, the diffraction peak of other impurities was not observed, and the BET equation was applied to the nitrogen adsorption isotherm obtained at the liquid nitrogen temperature. The calculated surface area was very large (620 m ² / g), and the crystallinity of the synthesized CHA-H was excellent.

Preparation of Catalyst for MTO Reaction Using SAPO-34 Catalyst

Example 1

To 50 g of a SAPO-34 molecular sieve having a CHA zeolite structure purchased from Zeolith, 1 L of 0.1 M copper nitrate (as opposed to 97%) was added, stirred at 60 ° C. for one day, and then filtered. It was washed with deionized water to remove precursors in the non-ion exchanged transition gold. After drying at 100 ° C., calcining was carried out in an air stream at 400 ° C., and at 24 ° C. for 24 hours with 1,000 ppm nitrogen dioxide (Dukyang Energen) to form a SAPO-34 molecular sieve containing CuO (hereinafter referred to as “CHA-Cu”). It is prepared. The composition of the catalyst prepared in Table 1 was summarized by the energy dispersive X-ray (EDX) method of the scanning electron microscope (SEM, Hitachi, S-4700).

Example 2

In the same manner as in Example 1, 1L of a 0.15M copper nitrate (as opposed to 97%) solution was added to the CHA-H zeolite prepared directly, and the SAPO-34 molecular sieve containing higher copper oxide than Example 1 ( Hereinafter, "CHA'-CuA" was prepared.) Example 2 was carried out, and the composition thereof is shown in Table 1 below.

Comparative Examples 1 and 2

SAPO-34 molecular sieve having a CHA zeolite structure purchased from Zeolite, which was not ion-exchanged with a transition metal, was designated as CHA-H and carried out in Comparative Example 1.

      Directly prepared CHA-H (hereinafter referred to as "CHA'-H") which was not ion-exchanged with a transition metal was carried out in Comparative Example 2, and its composition is shown in Table 1 below.

Classification (Unit: wt%) Al ₂ O ₃ P ₂ O ₅ SiO ₂ CuO Example 1 33.2 55.3 9.2 2.3 Example 2 57.4 33.3 6.5 2.9 Comparative Example 1 33.2 57.5 9.3 - Comparative Example 2 59.5 33.6 6.9 -

Experimental Example 1

Catalytic Activity Test of Catalyst for MTO Reaction Using CHA Zeolite

In order to test the performance of the catalysts prepared in Examples and Comparative Examples, the conversion of methanol to lower olefins and the yield of lower olefins were measured by a typical atmospheric flow reaction apparatus, and the results are shown in FIGS. 1 and 2. In FIG. 1, the reaction temperature was 350 ° C., and the mass reference space velocity (WHSV) was 0.7 h ⁻¹ . In FIG. 2, the reaction temperature was 350 ° C., and the mass reference space velocity (WHSV) was 2.9 h ⁻¹ . After pretreatment at 550 ° C. for 2 hours, methanol was supplied. The conversion fed methanol was defined as the percentage consumed due to the reaction, and the yield was defined as the methanol used to produce the lower olefins in the fed methanol.

Referring to the experimental results of FIG. 1, the initial conversion rate is 100% in any SAPO-34 catalyst regardless of ion exchange, but the conversion rate decreases as the reaction time elapses. After the start of the reaction in the CHA-H catalyst of Comparative Example 1 At 90 minutes, the conversion rate begins to drop slightly, and after 300 minutes, the conversion rate drops to 70%. In contrast, in the CHA-Cu catalyst of Example 1, activity started to decrease after 130 minutes, and the conversion was high as 80% even after 300 minutes.

In the experimental results of FIG. 2, the initial conversion rate is high as 100% in any SAPO-34 catalyst regardless of ion exchange, but the conversion rate decreases as the reaction time elapses. In the CHA'-H catalyst of Comparative Example 2, the conversion began to decrease little by little from 90 minutes after the start of the reaction, and then to 30% after 300 minutes. On the other hand, in the CHA'-CuA catalyst of Example 2, activity started to deteriorate after 130 minutes, and the conversion rate was high as 60% after 300 minutes.

In the catalysts of Examples 1 and 2, further reaction of hexamethylbenzene is suppressed due to the mechanical effect of reducing the pore volume due to the presence of copper ions in the pores and the chemical effect of hexamethylbenzene interacting with the copper ions to stabilize. It can be seen that the deactivation of the catalyst is considerably slower.

Preparation of LTA Zeolite

LTA zeolite was synthesized by using tetraethylammonium hydroxide (TEAOH, Aldrich, 35%) and tetramethylammonium chloride (TMACl, Acros Organics, 98%) as a template.

After mixing 337 g of tetraammonium hydroxide solution and 208 g of water, the mixture was stirred well. Then, 2 g of sodium hydride (a tablet, 98%) was added to the solution, and 5.6 g of tetramethylammonium chloride was added to the solution. 20.8 g of aluminum isopropoxide (Junsei Chemicalm, 98%) was added to this solution, and the mixture was stirred well for 30 minutes. Then, 170 g of tetraethyl orthosilicate (Aldrich, 98%) was added to this uniformly mixed solution. After dropping, aged at room temperature for 12 hours. A mixed solution having a composition of 8 TEAOH: 0.5 TMACl: 0.25 Na ₂ O: 0.5 Al ₂ O ₃ : 8 SiO ₂ : 240 H ₂ O was placed in a high pressure reactor and hydrothermally reacted at 98 ° C. for 14 days. The resulting solid material was filtered, washed with deionized water and heated at 100 ° C. for 12 hours. This was calcined at 550 ° C. for 5 hours to prepare a Na-type LTA zeolite. The mass of the synthesized LTA after firing was 20 g, and the yield calculated based on aluminum isopropoxide and tetraethyl orthosilicate was 20%. 50 g of the Na-type LTA zeolite was added with 1 L of a 0.5 M ammonium nitrate (stable, 98%) solution and stirred at 60 ° C. for 12 hours to exchange ammonium ions, followed by filtration and washing with deionized water at 100 ° C. Dried. After drying, firing was carried out for 4 hours at 550 ° C. with an air stream to prepare an H-type LTA zeolite (hereinafter referred to as “LTA-H”).

In the X-ray diffraction pattern of the prepared LTA-H zeolite, the diffraction peaks of the LTA-H structure were apparent at 2θ = 7.31, 10.42, 12.70, 22.08, 24.43, 26.57, 27.67, 30.50, and no diffraction peaks of other impurities were found. . The surface area calculated by applying the BET equation to the nitrogen adsorption isotherm obtained at the liquid nitrogen temperature was 640 m ² / g, which was very large, and thus the crystallinity of the synthesized LTA zeolite was judged to be excellent.

Preparation of Catalyst for MTO Reaction Using LTA Zeolite

Example 3

To 50 g of the LTA_H zeolite prepared above, 1 L of 0.1 M copper nitrate solution (coated, 99%) was added thereto, stirred at 60 ° C. for 24 hours to exchange copper ions, and then filtered and washed sufficiently with deionized water. Dried at ° C. The dried LTA-H was calcined with air at 400 ° C. and then treated with 1,000 ppm nitrogen dioxide (Dukyang Energen) for 24 hours to prepare LTA zeolite containing CuO (hereinafter referred to as “LTA-Cu”). The composition is shown in Table 2 below.

Examples 4-5

LTA zeolite catalyst containing 1.1 wt% of CoO as shown in Table 2, using 1 L of 0.1 M cobalt nitrate (as opposed to 97%) instead of 0.1 M copper nitrate Hereafter, "LTA-Co" is manufactured.

Comparative Example 3

The LTA-H prepared directly without ion exchange with a transition metal was carried out in Comparative Example 3, the composition of which is shown in Table 2 below.

Classification (Unit: wt%) Al ₂ O ₃ SiO ₂ CuO NiO CoO Example 3 21.73 75.9 2.4 - - Example 4 22.6 76.3 - - 1.1 Comparative Example 3 23.3 76.7 - - -

Experimental Example 2

Catalytic Activity Test of Catalyst for MTO Reaction Using LTA Zeolite

In the same manner as in Experimental Example 1, the catalytic activity of the catalyst for MTO reaction prepared in Examples 3 to 5 and Comparative Example 3 was carried out, and the results are shown in FIG. The reaction temperature was 350 ° C. and the mass reference space velocity (WHSV) was 0.7 h ⁻¹ .

As in Examples 3 and 4, LTA-Cu and LTA-Co containing appropriate amounts of transition metal oxides remained active after 240 minutes.

Preparation of MOR Zeolite

MOR zeolite was synthesized in a manner not using a template material. Stir well with 19 g sodium hydroxide (balanced, 98%) and 40 g of water. To this solution was added 14.3 g of sodium aluminate (NaAlO ₂ , Kanto, Al ₂ O ₃ : 35%, Na ₂ O: 31%) and 645 g of water, followed by stirring for 30 minutes. 98.2 g of silica was added to this homogeneously mixed solution, followed by stirring for 30 minutes. A solution having a composition of 6 Na ₂ O: 1 Al ₂ O ₃ : 30 SiO ₂ : 780 H ₂ O was placed in a high pressure reactor and hydrothermally reacted at 170 ° C. for 24 hours. The resulting solid material was filtered, washed with deionized water and heated at 100 ° C. for 12 hours to prepare a Na-type MOR zeolite. The mass of the synthesized Na-type MOR zeolite was 68 g, and the yield calculated based on sodium aluminate and product silica was 60%.

50 g of the Na-type MOR zeolite was added with 1 L of a 0.5 M ammonium nitrate solution (stable, 98%) and stirred at 60 ° C. for 12 hours to exchange ammonium ions. The mixture was filtered and washed sufficiently with deionized water at 100 ° C. Dried. After drying, firing was carried out for 4 hours at 550 ° C. with an air stream to prepare an H-type MOR zeolite (hereinafter referred to as “MOR-H”). The zeolite has a Si / Al molar ratio of about 10, which is quite high in aluminum.

Preparation of Catalyst for MTO Reaction Using MOR Zeolite

Example 5 and Comparative Example 4

1 g of 0.001 M copper acetate (Aldrich, 98%) solution was added to 50 g of the MOR-H synthesized above, stirred at 60 ° C. for 1 day, and then washed with deionized water while filtering to remove copper salts that were not ion exchanged. Was removed and dried at 100 ° C. Thereafter, the mixture was calcined with an air stream at 400 ° C. and then treated with 1,000 ppm nitrogen dioxide (Dukyang Energen) at 120 ° C. for 24 hours to contain 1.1 wt% CuO and nitrogen dioxide-treated MOR zeolite catalyst (hereinafter referred to as “MOR-Cu”). Was prepared. The composition is shown in Table 3 below.

The MOR-H prepared directly without ion exchange with a transition metal was carried out in Comparative Example 4, and its composition is shown in Table 3 below.

division Al ₂ O ₃ SiO ₂ CuO Example 5 8.9 90 1.1 Comparative Example 4 8.9 91.1 -

Experimental Example 4

Catalytic Activity Test of Catalyst for MTO Reaction Using MOR Zeolite

The catalytic activity experiments of the catalysts for the MTO reaction of Example 5 and Comparative Example 4 were carried out in the same manner as in Experiment 1, the results are shown in FIG. Reaction conditions were 350 degreeC and WHSV was 0.70 h <^-1> .

Referring to FIG. 4, the MOR-H catalyst of Comparative Example 4 rapidly deactivated from the beginning of the reaction, and after 240 minutes, the conversion was very low, at 30%. On the other hand, the MOR-Cu catalyst of Example 6 initially had a slightly low activity, but maintained the initial value without decreasing the conversion even after the reaction time had elapsed.

Preparation of Catalyst for MTO Reaction Using BEA Zeolite

Example 6 and Comparative Example 5

To 50 g of H-BEA zeolite having a Si / Al molar ratio of 100 (hereinafter referred to as "BEA-H") purchased from SENECA, 1 L of 0.005 M copper acetate (Aldrich, 98%) solution was added to 60 ° C. Stirred for one day. It was then washed with deionized water while filtering to remove copper salts that were not ion exchanged. After drying at 100 ° C., the MOR zeolite catalyst containing 1.5% by weight of CuO and nitrogen dioxide (hereinafter referred to as “BEA-Cu”) was treated with 120 ppm of 1,000 ppm nitrogen dioxide (Dukyang Energen) for 24 hours. Preparation was carried out in Example 6, the composition is shown in Table 4 below.

BEA-H not ion-exchanged with a transition metal was carried out in Comparative Example 4, the composition thereof is shown in Table 4 below.

division Al ₂ O ₃ SiO ₂ CuO Example 6 1.0 97.5 1.5 Comparative Example 5 1.3 98.7 -

Experimental Example 5

Catalytic Activity Test of Catalyst for MTO Reaction Using BEA Zeolite

The catalytic activity experiments of the catalysts for the MTO reaction of Example 6 and Comparative Example 5 were conducted in the same manner as in Experimental Example 1, and the results are shown in FIG. 5. Reaction conditions were 350 degreeC and WHSV was 2.7 h- ¹ .

In Fig. Referring to Figure 5, Comparative Example 5, the H-BEA catalyst is the conversion rate is slowly decreased. It is presumed that the degradation of activity is slow due to the large bent pores of the BEA zeolite. On the other hand, in the BEA-Cu catalyst of Example 6 , the conversion rate was not lowered and was maintained as it was, and the decrease in activity of BEA zeolite was suppressed by copper ion exchange. The choice for lower olefins is also quite different with the exchange of copper ions.

In the BEA-H catalyst of Comparative Example 5, the yield of the lower olefins in the initial state was about 55% higher than that of the BEA-Cu catalyst of Example 6. Furthermore, in the BEA-H catalysts, the selectivity for lower olefins increases slightly as the reaction proceeds. In contrast, the BEA-Cu catalyst of Example 10 showed a constant selectivity for lower olefins.

As described above, the catalyst for MTO reaction of the present invention can not only prevent deactivation of the catalyst but also prolong the life of the catalyst.

1 is a catalytic activity test result of the catalyst for MTO reaction using the SAPO-34 molecular sieve having a CHA zeolite structure carried out in Experimental Example 1.

2 is a catalytic activity test result of the catalyst for MTO reaction using the SAPO-34 molecular sieve having a CHA zeolite structure carried out in Experimental Example 2.

3 is a catalytic activity test result of the catalyst for MTO reaction using LTA zeolite carried out in Experimental Example 3.

4 is a catalytic activity test result of the catalyst for MTO reaction using the MOR zeolite carried out in Experimental Example 4.

5 is a catalytic activity test result of the catalyst for MTO reaction using BEA zeolite carried out in Experimental Example 5.

Claims (4)

A first step of ionizing the zeolite with a discontinuous or at least two transition metals selected from among copper (Cu), nickel (Ni) and cobalt (Co); A second step of drying the ion exchanged zeolite of the first step and then calcining at 350 ° C to 700 ° C; And And a third step of stabilizing the calcined zeolite of the second step by treating with nitrogen dioxide at 100 ° C. to 400 ° C .; MTO (Methanol-To-Olefin) reaction catalyst for a long life. The long life MTO reaction according to claim 1, wherein the zeolite is one or more selected from CHA (chabazite) zeolite, LTA (Linde Type A) zeolite, MOR (Mordenite) zeolite and BEA (beta polymorph A) zeolite. Catalyst. The method of claim 1, wherein the nitrogen dioxide is 100 ppm to 5,000 ppm. Catalyst for long life MTO reaction, characterized in that prepared by the method of claim 1 or 3.

Images