KR20130134064A - Zsm-5 catalyst with micropores and mesopores, preparation method thereof and production method of light olefins through catalytic cracking of hydrocarbons using the catalyst - Google Patents

Abstract

The present invention relates to a manufacturing method for a ZSM-5 catalyst with micropores and mesopores used for producing light olefins containing ethylene and propylene by the catalyst cracking of hydrocarbons of C4-C7 produced after a naphtha cracking process. The manufacturing method for the ZSM-5 catalyst with micropores and mesopores comprises: (a) a step of forming gel by aging a mixed solution containing silica precursors and aluminum precursors; (b) a step of adding carbon powers in the gel, mixing them and aging them; (c) a step of forming a solid product by crystallizing a mixture aged in the step of (b); (d) a step of heat-treating the solid product in order to remove carbons; and (e) a step of bringing a phosphorus precursor in the heat-treated solid product with impregnation or an ion exchange method. The present invention can produce the catalyst with micropore properties and mesopore properties and can improve the production yield of light olefins containing ethylene and propylene from hydrocarbons of C4-C7 since the properties of the catalyst improves the diffusion of reactants and intermediate products, minimizes pore blockage phenomena due to the phosphorous and metal and prevents activity degradation. [Reference numerals] (AA) Light olefin yield (%);(BB) Example 1;(CC) Example 2;(DD) Example 3;(EE) Example 4;(FF) Example 5;(GG) La/P atom ratio

Description

Fine and medium porosity PSSM-5 catalyst, its preparation method and method for producing light olefins by catalytic catalytic cracking of hydrocarbon mixture using the catalyst {SHM-5 CATALYST WITH MICROPORES AND MESOPORES CATALYTIC CRACKING OF HYDROCARBONS USING THE CATALYST}

The present invention relates to a fine and medium-porous ZSM-5 catalyst, a method for preparing the same, and a method for preparing light olefins through catalytic catalytic cracking of a hydrocarbon mixture using the catalyst, and more specifically, 4 to 7 carbon atoms generated after naphtha cracking. The present invention relates to the efficient preparation of light olefins through catalytic catalytic cracking of a hydrocarbon mixture of ZSM-5, which improves the physical properties of the ZSM-5 catalyst used in the production of light olefins including ethylene and propylene.

Ethylene and propylene are important raw materials for petrochemical products and are used for the synthesis of polyethylene, polypropylene, acrylonitrile, polyvinyl chloride, and the like. Until now, most of light olefins such as ethylene and propylene are produced by pyrolysis of naphtha as a raw material at a high temperature of 800 ° C or higher. Since the production of light olefins through pyrolysis of naphtha consumes about 40% of the energy consumed by the petrochemical industry, the proportion of energy consumption is very large and causes a problem of environmental pollution due to the generation of a large amount of carbon dioxide.

Therefore, a catalytic cracking technique using a catalyst has been attracting attention as a method of reducing energy consumption due to high temperature pyrolysis. Catalytic catalytic cracking is performed at a reaction temperature as low as about 50 to 200 ° C compared to the conventional pyrolysis process, so energy consumption is low and the generation of coke on the inner wall of the tube is suppressed, thereby extending the cycle and lifetime of the plant. In addition, it is expected that the supply and demand imbalance of ethylene and propylene can be solved because it is possible to minimize the environmental pollution by reducing the generation of carbon dioxide and to control the composition of the produced olefin according to demand.

A typical catalyst system used for producing light olefins through catalytic catalytic cracking is a catalytic cracking process using an acid catalyst. Among various acid catalysts, zeolite is most widely used because zeolite is easy to control acidity through chemical composition change and has shape selectivity so that conversion of reactant and yield of light olefin can be easily controlled This is because. ZSM-5, USY, REY, β-zeolite and the like are used as typical zeolites for catalytic catalytic cracking.

The ZSM-5 catalyst is a zeolite A having an 8-membered ring pore size and erionite and a 12-membered ring, Unlike the faujasite with super-cage, the mordenite with zeolite X and Y or the two-dimensional pore structure, the pore size of the medium-sized 10-membered ring And has a uniform pore size and structure due to a pore structure formed by a three-dimensional intersection of a straight channel of 5.4 × 5.6 Å and a sinusoidal channel of 5.1 × 5.5 Å, (H. Krannila et al., J. Catal., Vol.135, p115, 1992), which is excellent in selectivity, low in inertness, and excellent in thermal stability due to high Si / Al ratio.

As described above, the ZSM-5 catalyst is used in various reactions including catalytic catalytic decomposition reaction, isomerization reaction and esterification reaction due to its unique structure and excellent acid characteristics. However, when the reaction proceeds under high temperature and high humidity conditions, There is a problem in that the structure is collapsed and the acid sites are reduced and the activity of the catalyst is reduced. Therefore, attempts have been made to introduce various materials to improve the instability of the catalyst, which occurs under high temperature and high humidity reaction conditions. A method for improving the thermal stability of representative catalysts is to add manganese and phosphorus to the zeolite (T. Blasco et al., J. Catal., Vol. 237, p. 267, 2006). When the zeolite such as ZSM-5 is modified with phosphate ion, the Si-OH-Al moiety serving as the Bronsted acid point in the zeolite is modified by the phosphate ion (PO4 ^{3 -} ) to stabilize the unstable P = O group Thereby minimizing dealumination. However, the method of simply modifying phosphorus in zeolite can contribute to suppressing catalyst deactivation for a long time by improving the hydrothermal stability of the catalyst, but it is inadequate to improve the production of light olefins.

In addition to the efforts to improve the thermal stability of the catalyst, the important thing is to control the product distribution after reaction. In order to maximize the production of light olefins, the production of paraffins and aromatic compounds should be suppressed and the production of olefins should be maximized. This requires an improvement in the reaction process, such as lowering the reaction pressure, raising the reaction temperature, lowering the residence time of the reactants, and appropriately controlling the ratio of the reactants to the catalyst (MA Den Hollander et al., Appl. Catal. A, vol.223, p85, 2002), along with efforts to improve the production of light olefins through the development of new catalysts. As a part of this effort, a method of preparing a catalyst by adding a transition metal or a rare earth metal to a ZSM-5 catalyst has been carried out (N. Rahimi et al., Appl. Catal. A, vol.398, p1, 2011). In this document, it is reported that when a transition metal such as iron or chromium is added to ZSM-5, the reactant hydrocarbon is dehydrogenated to induce a decomposition reaction more easily, thereby producing more light olefins. It has been reported that the addition of rare earth metals such as neodymium, cerium, and lanthanum to ZSM-5 improves the selectivity of light olefins. However, the effect of rare earth metals on the selectivity of light olefins Opinion is divided. When a metal such as a transition metal or a rare earth metal is used, large metal atoms are located at the pore openings of the zeolite, which may cause a problem of lowering the reaction activity when the pores are closed. Therefore, it can be said that there is a limitation in modifying the metal to pure ZSM-5 showing microporous characteristics. To overcome this, it is required to prepare ZSM-5 having micro and medium porosity characteristics.

U.S. Patent No. 6,835,863 discloses a process for the catalytic cracking of naphtha using a shaped catalyst comprising 5 to 75% by weight of ZSM-5 and ZSM-11, 25 to 95% by weight of silica or kaolin, and 0.5 to 10% by weight of phosphorus. However, there is no mention of hydrothermal stability of specific starting materials of phosphorus and shaped catalysts, and no catalyst having mesoporous characteristics is used.

US Patent Publication No. 20060011513 discloses a technique for selecting one of lanthanide, Sc, Y, La, Fe and Ca to zeolites such as ZSM-5, β, mordenite and ferrierite, There is no mention of the specific chemical structure of the phosphate and its description of its role is lacking, and no technology for improving the olefin yield is specified.

U.S. Patent No. 7,531,706 discloses a method for producing light olefins using a pentasil-type zeolite modified with a rare-earth metal, manganese or zirconium with phosphorus, wherein the modified metal has a hydrothermal stability of the catalyst and a yield of light olefin However, it is not enough to interpret the specific role of the metals, and it is only aimed at improving the durability of the zeolite.

Non-Patent Document 1 (G. Zhao et al., J. Catal. Vol. 48, p29, 2007) was intended to improve hydrothermal stability by introducing phosphorus into HZSM-5. As a result, the introduction of phosphorus contributed to improvement of hydrothermal stability. However, the introduction of phosphorus resulted in a drastic decrease in surface area and pore volume due to blocking of the inlet of micropores, and the limitation that phosphorus does not play a role in improving light olefin production have.

Non-Patent Document 2 (J. Lu et al., Catal. Commun., Vol. 7, p199, 2006) studied the preparation of light olefins by catalytic catalytic cracking of isobutane. As a result of preparing a catalyst modified with iron on the basis of ZSM-5 catalyst, it has been reported that the modification of iron makes it possible to produce more light olefins by improving the acid property of the catalyst. However, , The activity was decreased rapidly. This can be attributed to the microporosity of ZSM-5, which is caused by aggregation between iron atoms. Further, the hydrothermal stability of the catalyst is not mentioned.

In a non-patent document 3 (W. Xiaoning et al., J. Rare Earths, vol.25, p321, 2007), while conducting a study to produce light olefins from butane using a ZSM-5 catalyst containing a rare earth metal, The effect of the acid on the acid property of the catalyst is discussed and the effect of the acid property change of the catalyst on the reaction activity is discussed. However, the effect of the rare earth metal on the base property is not considered, The effect of the properties on the mechanism of the degradation reaction is not mentioned.

On the other hand, natural gas crackers for obtaining ethylene from natural gas, which is comparatively less expensive than naphtha due to rising oil prices and heavy crude oil, have been added. However, since ethylene can be selectively produced, it is unbalanced in the supply and demand of propylene Unlike in the case of natural gas-rich European countries, crude oil importing countries such as Korea depend on naphtha cracking, which is a disadvantage in terms of reducing greenhouse gas emissions. In Korea, the amount of ethylene obtained from the naphtha cracking process reaches 5 million tons per year, and the amount of C5 oil discharged as a by-product reaches 700 thousand tons, but it can not be used effectively. Therefore, the necessity of the development of ethylene / propylene supply and demand control technology is high, for this purpose a light olefin restructuring technology is required, the utilization of C5 fraction as a raw material for light olefin restructuring will also be important.

Accordingly, the present invention has been made to solve the above problems, in the production of ZSM-5 catalyst for producing a light olefin containing ethylene and propylene by catalytic catalytic cracking of a hydrocarbon mixture of 4 to 7 carbon atoms produced after naphtha cracking In addition, the present invention provides a method for preparing a ZSM-5 catalyst which can improve the yield of light olefins while maintaining physical and chemical properties of the existing catalyst and exhibiting excellent pore characteristics.

In addition, the present invention provides a method for preparing a ZSM-5 catalyst having optimum conditions for maximizing the yield of ethylene and propylene, a catalyst prepared by the method, and a method for preparing light olefins including ethylene and propylene using the catalyst.

In order to solve the above problems, the present invention, by catalytic catalytic cracking of a hydrocarbon mixture of 4 to 7 carbon atoms generated after naphtha cracking process, fine and medium-porous ZSM-5 used to prepare light olefins including ethylene and propylene A method of preparing a catalyst, comprising: (a) aging a mixed solution comprising a silica precursor and an aluminum precursor to form a gel; (b) adding carbon powder to the gel to mature after stirring; (c) crystallizing the mixture aged in step (b) to form a solid product; (d) heat treating the solid product to remove the carbon; And (e) introducing a phosphorus precursor into the heat-treated solid product by impregnation or ion exchange. The method provides a method for preparing a fine and medium porosity ZSM-5 catalyst comprising a.

In addition, (f) introducing a rare earth metal precursor or an alkali metal precursor into the solid product into which the phosphorus precursor is introduced, by impregnation or ion exchange method; micro and medium porosity ZSM-5 catalyst preparation further comprising Provide a method.

In addition, the mixed solution of step (a), (a-1) dissolving monovalent metal hydroxide and tetrapropylammonium halide (ditrapropylammonium halide) in distilled water; (a-2) adding the silica precursor to form a homogeneous mixture; And (a-3) dropping the liquid aluminum precursor onto the homogeneous mixture. The method provides a method for preparing a fine and medium porosity ZSM-5 catalyst, comprising the step of dropping the aluminum precursor in a liquid state.

In addition, the silica precursor is colloidal silica, the aluminum precursor is sodium aluminate (NaAlO ₂ ), aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum secondary-butoxide (aluminum sec-butoxide), Aluminum tert-butoxide, aluminum tri-sec-butoxide, aluminum tri-tert-butoxide, aluminum ethoxide ( It provides a method for producing fine and medium porosity ZSM-5 catalyst, characterized in that at least one selected from the group consisting of aluminum ethoxide) and aluminum isopropoxide.

In addition, the carbon powder provides a method for producing fine and medium porosity ZSM-5 catalyst, characterized in that the particle size is at least one selected from the group consisting of spherical, square, rectangular and cylindrical with a diameter of 2 ~ 50nm.

In addition, the carbon powder provides a fine and medium porosity ZSM-5 catalyst production method characterized in that 5 to 80 parts by weight based on 100 parts by weight of the silica precursor.

In addition, the fine and medium porosity ZSM-5 catalyst provides a method for producing a fine and medium porosity ZSM-5 catalyst, characterized in that the Si / Al atomic ratio of 5 ~ 300.

In addition, the heat treatment of step (d) provides a fine and medium porosity ZSM-5 catalyst production method characterized in that performed for 3 to 10 hours at 300 ~ 750 ℃.

In addition, the method of impregnating the phosphorus precursor in the step (e), (e-1) hydrating the phosphorus precursor in water; (e-2) impregnating by adding the solid product heat-treated in step (d) to a solution in which the phosphorus precursor is hydrated; And (e-3) drying and heat-treating the impregnated solid product. The method provides a method for preparing a fine and medium porosity ZSM-5 catalyst comprising a.

Further, the phosphorus precursor is phosphoric acid (H ₃ PO ₄ ), ammonium phosphate ((NH ₄ ) H ₂ PO ₄ ), diammonium phosphate ((NH ₄ ) ₂ HPO ₄ ) and triammonium phosphate ((NH ₄ ) ₃ PO _It provides a method for producing a fine and medium porosity ZSM-5 catalyst, characterized in that at least one selected from the group consisting of ₄ ).

In addition, the phosphorus precursor provides a fine and medium porosity ZSM-5 catalyst production method, characterized in that 0.01 to 10 parts by weight based on 100 parts by weight of the prepared fine and medium porosity ZSM-5 catalyst.

In addition, the heat treatment of the step (e-3) provides a method for producing fine and medium porosity ZSM-5 catalyst, characterized in that performed for 1 to 10 hours at 500 ~ 750 ℃.

In addition, the method of impregnating the rare earth metal precursor or the alkali metal precursor in the step (f) comprises: (f-1) hydrating the rare earth metal precursor or the alkali metal precursor in water; (f-2) impregnating the rare earth metal precursor or the alkali metal precursor by adding a solid product having phosphorus introduced thereinto in step (e); And (f-3) drying and heat-treating the impregnated solid product.

In addition, the rare earth metal is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb) , Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thorium (Tm), Ytterbium (Yb) and Lutetium (Lu) fine and medium porosity ZSM-5 It provides a method for producing a catalyst.

In addition, the alkali metal is fine and medium-porous ZSM-5, characterized in that at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs). It provides a method for producing a catalyst.

In addition, the rare earth metal or alkali metal content provides a fine and medium porosity ZSM-5 catalyst production method characterized in that the atomic ratio to the phosphorus.

In addition, the heat treatment of the step (f-3) provides a fine and medium porosity ZSM-5 catalyst manufacturing method characterized in that performed for 1 to 10 hours at 500 ~ 750 ℃.

In addition, between the step (d) and (e), (d-1) cation substitution of the heat-treated solid product; And (d-2) heat-treating the cation-substituted solid product. It provides a method for preparing a fine and medium porosity ZSM-5 catalyst further comprising a.

In addition, the cation substitution is one selected from the group consisting of ammonium nitrate (NH ₄ NO ₃ ), ammonium chloride (NH ₄ Cl), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ) and ammonium fluoride (NH ₄ F) It provides a method for producing a fine and medium porosity ZSM-5 catalyst, characterized in that performed using a solution containing the above.

In addition, the heat treatment of the step (d-2) provides a fine and medium porosity ZSM-5 catalyst manufacturing method characterized in that performed for 3 to 10 hours at 400 ~ 700 ℃.

In addition, the hydrocarbon mixture provides a fine and medium porosity ZSM-5 catalyst production method, characterized in that consisting of C5 fraction.

In order to solve the above another problem, the present invention, the catalytic contact cracking of the hydrocarbon mixture having 4 to 7 carbon atoms generated after naphtha cracking process to produce a fine and medium-porous ZSM-5 used to prepare a light olefin containing ethylene and propylene In the catalyst, the catalyst is prepared using carbon as a template material, and provides a fine and medium porosity ZSM-5 catalyst characterized in that it comprises phosphorus.

In addition, the catalyst provides a fine and medium porosity ZSM-5 catalyst, characterized in that it further comprises a rare earth metal or alkali metal.

In addition, the phosphorus content provides a fine and medium porosity ZSM-5 catalyst, characterized in that 0.01 to 10 parts by weight based on 100 parts by weight of the fine and medium porosity ZSM-5 catalyst on a phosphorus precursor basis.

In addition, the rare earth metal or alkali metal content to provide a fine and medium porosity ZSM-5 catalyst, characterized in that the atomic ratio to the phosphorus.

In addition, the catalyst has a specific surface area of 300 to 400 m 2 / g, micropore volume of 0.1 nm or less in diameter of 0.1 ~ 0.14 cm 3 / g, medium pore volume of 0.09 to 0.11 cm 3 / g of 2 nm or more in diameter, ammonia elevated temperature desorption experiment The weak acid point according to the acid content is 75 ~ 88μmol-NH ₃ / g-catalyst, the strong acid point is 24 ~ 38μmol-NH ₃ / g-catalyst and the base amount is 5 ~ 30μmol-CO ₂ / g-catalyst It provides a fine and medium porosity ZSM-5 catalyst.

In addition, the hydrocarbon mixture provides a fine and medium porosity ZSM-5 catalyst, characterized in that consisting of C5 fraction.

In order to solve the above another problem, the present invention, in the method for producing a light olefin comprising catalytic ethylene by ethylene and propylene by catalytic catalytic decomposition of a hydrocarbon mixture having 4 to 7 carbon after the naphtha cracking process, the fine and medium-porous ZSM- It provides a method for producing light olefin, characterized in that for reacting the hydrocarbon mixture in the presence of a catalyst at a reaction temperature of 300 ~ 700 ℃ at a weight space velocity (WHSV) 1 ~ 20h ^-1 conditions.

In addition, the hydrocarbon mixture provides a process for producing light olefins, characterized in that consisting of C5 fraction.

According to the present invention, a ZSM-5 catalyst can be prepared using carbon as a template, and a catalyst having both fine and medium porosity characteristics can be prepared. The catalyst properties can be introduced by improving the diffusion of reactants and intermediate products. It is possible to improve the production yield of light olefins including ethylene and propylene from C4 to C7 hydrocarbon mixtures by minimizing pore blockage by metals to inhibit activity degradation.

In addition, by introducing phosphorus and rare earth metals or alkali metals into the ZSM-5 catalyst having the characteristics of fine and medium pores, it is possible to control the acid and base properties of the catalyst and to prepare a catalyst having an optimum atomic ratio, C4 to C7 hydrocarbon When used in the preparation of light olefins comprising ethylene and propylene from the mixture, it is possible to provide a fine and medium pore ZSM-5 catalyst with stable and good activity over a long period of time while improving the production of light olefins.

1 is a flow chart illustrating a method for preparing a fine and medium porosity ZSM-5 catalyst according to an embodiment of the present invention;
2 is a flowchart illustrating an example of a process of preparing a mixed solution of step (a) in the method for preparing a fine and medium porosity ZSM-5 catalyst according to the present invention;
Figure 3 is a flow chart illustrating an example of the process of impregnating the phosphorus precursor in the method for producing fine and medium porosity ZSM-5 catalyst of the present invention,
4 is a flowchart illustrating an example of a process of impregnating a rare earth metal precursor or an alkali metal precursor in the method of preparing the micro and medium porosity ZSM-5 catalyst according to the present invention;
FIG. 5 is a flowchart illustrating a process of cation-substituting a solid product heat-treated in the method for preparing a fine and medium porosity ZSM-5 catalyst according to the present invention;
6 is a graph showing the results of X-ray diffraction analysis of the ZSM-5 catalyst prepared according to Examples 1 to 5,
7 is a graph showing the results of X-ray diffraction analysis of the ZSM-5 catalyst prepared according to Examples 6 to 8,
8 is a graph showing the results of nitrogen adsorption and desorption experiments of the ZSM-5 catalyst prepared according to Examples 1 to 5;
9 is a graph showing the results of an ammonia elevated desorption experiment of the ZSM-5 catalyst prepared according to Examples 1 to 5;
10 is a graph showing the results of ammonia elevated desorption experiment of ZSM-5 catalyst prepared according to Examples 6 to 8;
11 is a graph showing the results of carbon dioxide elevated desorption experiment of the ZSM-5 catalyst prepared according to Examples 1 to 5;
12 is a graph showing the relationship between the basic properties of the catalyst and the hydrogen transfer activity of the ZSM-5 catalyst prepared according to Examples 1 to 5,
13 is a graph showing the effect on the reaction activity of the acid and base properties of the ZSM-5 catalyst prepared according to Examples 1 to 5,
FIG. 14 is a graph showing the relationship between lanthanum / phosphorus atomic ratio and light olefin yield for ZSM-5 catalysts prepared according to Examples 1-5.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims and their equivalents. It is to be understood that various equivalents and modifications may be substituted for those at the time of the present application.

1 is a flow chart illustrating a method for preparing a fine and medium porosity ZSM-5 catalyst according to an embodiment of the present invention, Figure 2 is a method for producing a fine and medium porosity ZSM-5 catalyst of the present invention (a) 3 is a flowchart illustrating an example of a process of preparing a mixed solution of the step, and FIG. 3 is a flowchart illustrating an example of a process of impregnating phosphorus precursors in the method of preparing a micro and medium porosity ZSM-5 catalyst according to the present invention. 4 is a flowchart illustrating an example of the impregnation of the rare earth metal precursor or the alkali metal precursor in the method for preparing the fine and medium porosity ZSM-5 catalyst of the present invention, and FIG. 5 is the fine and medium porosity ZSM- of the present invention. 5 is a flowchart illustrating an example of a process of cation substitution of a solid product heat-treated in a catalyst production method.

First, referring to FIG. 1, the present invention provides a method for preparing a fine and medium-porous ZSM-5 catalyst, comprising: (a) aging a mixed solution containing a silica precursor and an aluminum precursor to form a gel (S100) ); (b) adding carbon powder to the gel (gel) to stir after stirring (S200); (c) crystallizing the mixture aged in step (b) to form a solid product (S300); (d) heat treating the solid product to remove the carbon (S400); And (e) introducing a phosphorus precursor into the heat-treated solid product by impregnation or ion exchange (S510). A method of preparing a fine and medium porosity ZSM-5 catalyst comprising a;

In addition, (f) introducing a rare earth metal precursor or an alkali metal precursor into the solid product to which the phosphorus precursor is introduced by impregnation or ion exchange (S520); micro and mesoporous ZSM- further comprising a 5 A method for preparing a catalyst is disclosed.

In the present invention, the term "microporous" refers to a characteristic having a pore size (diameter) of 1 nm or less in consideration of the general ZSM-5 catalyst having fine pores of about 1 nm or less, and referred to as "medium porosity". By means the characteristic that the pore size (diameter) has a pore size of at least 1 nm or more, preferably 2 nm or more. However, the pore size value is not a strict meaning and may mean a relative value according to the catalyst production conditions. However, hereinafter, the "medium sized pores" according to the present invention will be described as pores having a pore size (diameter) of 2 nm or more.

The fine and medium porosity ZSM-5 catalyst prepared according to the present invention is used to produce light olefins including ethylene and propylene by catalytic catalytic cracking of hydrocarbon mixtures of C4 to C7 produced after naphtha cracking process. Preferably, the catalytically cracked C5 fraction generated after the naphtha cracking process may be used to prepare light olefins including ethylene and propylene.

In general, the ZSM-5 catalyst may be hydrothermally synthesized in an alkaline silicate-aluminate reaction mother liquor using an organic cation as a template, and according to the method for preparing the micro and mesoporous ZSM-5 catalyst of the present invention, steps (a) and ( As in step b), a mixed solution including a silica precursor and an aluminum precursor is first formed to form a gel, and then carbon powder is added to the gel. The added carbon powder is then removed by firing through a heat treatment operation to form not only fine pores but also medium pores, which will be described later.

The step (a) (S100) is a gel for forming the gel (gel) in order to form a solid product to be easily stirred and homogeneously crystallized with a mixture of the gel (gel) to be formed thereafter added carbon powder Optimal mixed solution preparation is required. 2, in the present invention, the mixed solution of step (a) comprises (a-1) dissolving monovalent metal hydroxide and tetrapropylammonium halide in distilled water (S110); (a-2) adding a silica precursor to form a homogeneous mixture (S120); And (a-3) dropping the aluminum precursor in a liquid phase into the homogeneous mixture (S130).

Here, as the monovalent metal hydroxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), and the like may be used, and the tetrapropylammonium halide may be tetrapropylammonium bromide, tetrapropylammonium chloride. And the like can be used.

Referring to the process of preparing the mixed solution of step (a) in more detail, first completely dissolving the monovalent metal hydroxide and tetrapropylammonium halide in distilled water (S110) and then adding a silica precursor to form a mixture (S120) do. At this time, the mixture should be mixed in a homogeneous state. Colloidal silica may be used as the silica precursor, and specifically, at least one selected from the group consisting of Ludox ^® HS-40, Ludox ^® AS-40, and Ludox ^® HS-30. Thereafter, an aluminum precursor is added to the homogeneous mixture (S130). At this time, the aluminum precursor is preferably added slowly to the homogeneous mixture. That is, a liquid aluminum precursor can be added by the method of dropwise addition to the homogeneous mixture. The aluminum precursors include sodium aluminate (NaAlO ₂ ), aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum secondary-butoxide, aluminum tert-butoxide, aluminum With tri-second-butoxide, aluminum tri-tert-butoxide, aluminum ethoxide and aluminum isopropoxide It may be one or more selected from the group consisting of.

The mixed solution thus prepared is appropriately stirred and then aged to form a gel-like mixture (S100). Such a gel-like mixture may be formed by stirring the mixed solution at room temperature for 1 to 3 hours and then ripening at room temperature for 2 to 10 hours.

Thereafter, as in step (b), carbon powder is added to the mixture on the gel (gel) as a mold material (S200). The carbon is not limited as long as it is a shape capable of forming medium pores, and may be, for example, spherical, square, rectangular, or cylindrical. However, the size is preferably 2 to 50 nm in consideration of the smooth adsorption and desorption of the hydrocarbon mixture of C4 to C7, which is the catalytic catalytic cracking reaction, to the catalyst active point.

In addition, the carbon allows the medium pore to be better developed in proportion to the amount added. And the content thereof may be 5 to 80 parts by weight based on 100 parts by weight of the silica precursor. When the carbon content is less than 5 parts by weight, the formed medium pore volume may not be satisfactory. When the carbon content exceeds 80 parts by weight, the catalytic activity point may decrease, and thus the catalytic activity may decrease. However, even if the medium pore characteristics are improved by adding a large amount of carbon and subsequent firing removal, the reaction activity of the catalyst due to the relaxation of molecular diffusion restriction is improved due to the adsorption and desorption space size of hydrocarbon mixtures and reaction products of C4 to C7. Will not always be proportional to. That is, the present inventors have carefully observed the added carbon content, but the reaction activity of the catalyst increases up to 80 parts by weight with respect to 100 parts by weight of the silica precursor, but when it exceeds 80 parts by weight, the degree of improvement of the reaction activity of the catalyst is increased. It was found to be inconspicuous.

The carbon powder is added in advance by drying for 1 to 5 hours at 100 ~ 150 ℃ and the mixture is stirred for 1 to 5 hours at room temperature and then aged at room temperature for 1 to 5 hours to prepare a crystallization step.

On the other hand, it may be considered to add the carbon powder together in the gel-forming mixture forming step, but the carbon content added as a template material has to increase relatively, so that selective zeolite crystallization occurs afterwards. It is not desirable to have very precise chemical control in order to produce ZSM-5 catalysts having better reaction activity in a simple process by quantitative addition to the gel phase mixture according to the present invention, followed by stirring and aging. It was confirmed that it was possible.

It is preferable to select a Si / Al atomic ratio (molar ratio) of 5 to 300 in the fine and medium porosity ZSM-5 catalyst prepared through the addition of carbon powder under the above conditions. When the Si / Al atomic ratio is less than 5, there is no significant effect on the change in catalyst activity, but the acid amount of the catalyst may cause deactivation due to coking or the like. It is not satisfactory and the conversion of the catalytic catalytic cracking reaction of the C4 to C7 hydrocarbon mixture can be lowered.

The mixture prepared by adding, stirring and aging the carbon powder to the gel is then crystallized to form a solid product (S300). The crystallization may be generally used methods such as hydrothermal synthesis, microwave synthesis, dry-gel synthesis, and the like. Through this crystallization, the zeolite grows into a large single crystal around the carbon particles, which are template materials.

Thereafter, the solid product is heat-treated to remove carbon to form medium pores (S400). At this time, the solid product produced by the crystallization in the pretreatment process may be washed several times with filtration and distilled water and dried for 5 to 15 hours at about 100 ~ 120 ℃. Thereafter, the heat treatment may be performed by crushing the solid product produced through drying and calcining at 300 to 750 ° C. for 3 to 10 hours. Preferred firing conditions for the complete firing of the carbon is to perform 4-6 hours at 500 ~ 600 ℃. Through such heat treatment, the zeolite single crystal structure can retain medium pores formed from carbon.

Thereafter, a phosphorus precursor is introduced into the heat-treated solid product to prepare a ZSM-5 catalyst modified with phosphorus.

An impregnation or ion exchange method is used as the phosphorus precursor introduction method, but in the present invention, it is preferable to use an impregnation method that is easy to control acid points, particularly strong acid points.

Referring to FIG. 3, the method of impregnating the phosphorus precursor with a ZSM-5 catalyst may include, for example, hydrating the phosphorus precursor in water (S511), and adding the solid product heat-treated in the step (d) to the hydrated solution. After impregnation (S512) by addition and drying and heat treatment (S513) it can be used.

Specifically, after dissolving the phosphorus precursor in water (distilled water) in an amount capable of completely dissolving the phosphorus precursor (S511), the mixture is stirred for 5 to 15 minutes at 70 ~ 90 ℃, 70 ~ 90 by adding the heat treated solid product After the solution is sufficiently impregnated at ℃ (S512) and all the water evaporates it can be prepared by drying for 10 to 15 hours in an oven at 90 ~ 110 ℃ and then baked (500) (S513) for 1 to 10 hours at 500 ~ 750 ℃. Here, the above-mentioned impregnation is carried out at a temperature of 70 to 90 ° C in order to make the framework of the ZSM-5 catalyst and the phosphorus component be more advantageous than to perform at room temperature. If the calcination temperature is less than 500 ° C, the organic and inorganic materials contained in the phosphorus precursor may not be completely removed. If the calcination temperature is higher than 750 ° C, the phosphorus is not preferable from the viewpoint of energy efficiency and is deteriorated. The organic and inorganic removal performance may be deteriorated.

At this time, it is important that the phosphorus precursor introduction content is set in an optimal range with respect to the amount of carbon deposited according to the acid amount and the catalytic reaction of the final ZSM-5 catalyst. Therefore, in the present invention, the phosphorus precursor introduction content is preferably added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the fine and medium porosity ZSM-5 catalyst prepared in the range of addition of the above-described carbon powder, 0.05 to 3 It is more preferable to introduce a weight part, It is still more preferable to introduce | transduce 0.1-1.5 weight part, It is most preferable to introduce 0.1-1 weight part.

To the precursor, for example, phosphoric acid (H ₃ PO _4), ammonium phosphate ((NH ₄₎ H ₂ PO _4), phosphoric acid ammonium ((NH _{4) 2} HPO _4), tricalcium phosphate, ammonium ((NH ₄ ) ₃ PO ₄ ) and the like can be used.

Thereafter, a rare earth metal precursor or an alkali metal precursor may be introduced into the solid product having the phosphorus precursor introduced therein to prepare a ZSM-5 catalyst capable of controlling acid and base properties of the catalyst. The introduction of the rare earth metal precursor and the alkali metal precursor may be performed separately, or may be performed together to simultaneously express catalytic properties according to the introduction of each metal.

The impregnation or ion exchange method is used by the rare earth metal precursor or alkali metal precursor introduction method, but in the present invention, it is preferable to use an impregnation method which is easy to control acid and base properties.

Referring to FIG. 4, the method of impregnating the rare earth metal precursor or the alkali metal precursor to the ZSM-5 catalyst may be performed in a manner similar to the introduction of the phosphorus precursor, that is, hydration of the rare earth metal precursor or the alkali metal precursor in water (S521). In addition, a method of impregnating (S522) by adding a solid product having phosphorus introduced in step (e) to the hydrated solution may be dried and heat treated (S523).

Specifically, after dissolving the phosphorus precursor in water (distilled water) in an amount capable of completely dissolving the rare earth metal precursor or the alkali metal precursor (S521), the mixture is stirred at 70 to 90 ° C. for 5 to 15 minutes, and the heat treated solid product is After input and stirred to be sufficiently impregnated (S522) at 70 ~ 90 ℃ and then evaporated all the water is dried for 10 to 15 hours in an oven of 90 ~ 110 ℃ and then fired (S523) for 1 to 10 hours at 500 ~ 750 ℃ Can be.

At this time, it is important that the rare earth metal precursor or alkali metal precursor introduction content is set in an optimum range with respect to the acid amount, base amount and carbon deposition amount according to the catalytic reaction of the final ZSM-5 catalyst. Therefore, in the present invention, the rare earth metal precursor or the alkali metal precursor introduction content is preferably introduced at an atomic ratio of 2 or less in the above-described carbon powder addition range, more preferably at an atomic ratio of 0.1 to 1.5. It is preferable to introduce | transduce at the atomic ratio of 0.5-0.9.

As the rare earth metal contained in the rare earth metal precursor, lanthanum (La), Ce, Pr, Ne, Prommium, Sm, At least one member selected from the group consisting of terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thorium (Tm), ytterbium (Yb) and lutetium (Lu) Lanthanum may be selected. The alkali metal contained in the alkali metal precursor may include at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs) Preferably potassium, rubidium, and cesium, and more preferably, cesium can be selected. For example, when lanthanum is selected as the rare earth metal, lanthanum nitrate (La (NO ₃ ) ₃ .6H ₂ O) can be introduced in the form of a precursor. When lithium is selected as the alkali metal, lithium nitrate (LiCO ₃ ) .

Referring to FIG. 5, in the method for preparing the micro and medium porosity ZSM-5 catalyst of the present invention, it is preferable to further perform a cation substitution of the heat treated solid product (S410) before the phosphorus precursor is introduced. The cation substitution is for exchanging zeolite generally substituted with sodium ion (Na ⁺ ) with a proton (H ⁺ ), and the zeolite catalyst substituted with a proton is more effective in cracking reaction because acid strength is increased compared to other cations. The cation substitution may be carried out by specifically adding the solid product to a solution for cation substitution at 70 to 90 ° C. and stirring for 2 to 4 hours at the same temperature conditions, and further filtering and washing the cation-substituted aqueous solution. The cation substitution process may be repeated one to three times. The solution used in such cation exchange, the ammonium nitrate (NH ₄ NO _3), ammonium chloride (NH ₄ Cl), the group consisting of ammonium carbonate _{((NH 4) 2 CO 3} ) and ammonium fluoride (NH ₄ F) 1 < / RTI >

In addition, the step (S420) of the heat treatment of the cation-substituted solid product may be further performed. The heat treatment may be performed by firing at 400 to 700 ° C for 3 to 10 hours. If the heat treatment temperature is less than 400 ° C, the ammonium salt that is primarily substituted in the zeolite catalyst may not be sufficiently removed, so that the acid strength of the zeolite may decrease. If the temperature exceeds 700 ° C, the catalyst collapse and the Bronsted acid point . If the heat treatment temperature is less than 3 hours, it may be difficult to remove sufficient ammonium salt, and if it exceeds 10 hours, power loss may occur. Here, it is preferable that the cation-substituted solid product is dried at 100 to 120 ° C for 5 to 15 hours before the heat treatment, and then the heat treatment is performed.

The micro and mesoporous ZSM-5 catalysts prepared according to the present invention have both micro and mesoporous properties simultaneously, and these catalyst properties enhance the diffusion of reactants and intermediate products to improve the diffusion of reactants and intermediate products from ethylene and propylene from C4 to C7 hydrocarbon mixtures. It is possible to improve the production yield of a light olefin comprising a. In addition, the fine and medium porosity ZSM-5 catalyst prepared in accordance with the present invention by introducing an optimal content of rare earth metal or alkali metal with phosphorus, to provide a ZSM-5 catalyst having an optimal acid amount and base amount, which is C4 to When used in the preparation of light olefins comprising ethylene and propylene from C7 hydrocarbon mixtures it is possible to provide fine and medium pore ZSM-5 catalysts which are stable over a long time and have good activity.

That is, the fine and medium pore ZSM-5 catalyst prepared according to the present invention contains 0.01 to 10 parts by weight of phosphorus precursor with respect to 100 parts by weight of the fine and medium porosity ZSM-5 catalyst, and contains rare earth metal or alkali metal. Including the atomic ratio to phosphorus 2 or less, the specific surface area of 300 ~ 400㎡ / g, the micropore volume of 0.1 nm or less, 0.1 ~ 0.14 cm 3 / g, the medium pore volume of 2 nm or more 0.09 ~ 0.11 cm 3 / g, weak acid point acidity 75-88μmol-NH ₃ / g-catalyst, ammonia 24-38μmol-NH ₃ / g-catalyst and base amount 5-30μmol-NH ₃ It will provide a fine and medium porosity ZSM-5 catalyst / g-catalyst.

The fine and medium porosity ZSM-5 catalyst prepared according to the present invention can be used for the production of light olefins including ethylene and propylene by catalytic catalytic cracking of hydrocarbon mixtures of C4 to C7 produced after naphtha cracking process. At this time, the hydrocarbon mixture is reacted at a reaction temperature of 300 to 700 ° C. in the presence of the fine and medium porosity ZSM-5 catalyst at a weight space velocity (WHSV) of 1 to 20 h ⁻¹ to prepare light olefins. If the weight-space velocity is less than 1h ^-1 is possible to increase the conversion rate, but may reduce the selectivity due to side reaction, 20h ^- if more than ¹ may reduce the conversion rate and lead to decreased catalyst life.

Example  One

1.6 g of sodium hydroxide (NaOH, Samchun Chem.) Was added and dissolved in 150 ml of distilled water, and then TPABr was added to the aqueous solution by adding 2.28 g of tetrapropylammonium bromide (TPABr, Sigma-Aldrich) as a ZSM-5 structural inducer. Stir until completely dissolved. Then, colloidal silica (Ludox HS-40, Sigma-Aldrich) was slowly added dropwise to an aqueous solution containing sodium hydroxide and TPABr, and stirred at room temperature until a uniform mixture was formed. Meanwhile, 0.78 g of sodium aluminate (NaAlO ₂ , Junsei) was dissolved in another 30 ml of distilled water, and then a solution was stirred for 1 hour and slowly added dropwise to a solution containing a silica precursor (colloidal silica) at room temperature. Stirred for 1 hour to form a gel. Carbon powder to be used as a template (BP2000, Cabot Corporation) was dried in an oven at 110 ℃ for 3 hours, added to the gel at a rate of 30 parts by weight based on 100 parts by weight of the silica precursor, and then 3 hours Was stirred. Thereafter, the stirred solution was placed in an autoclave and hydrothermally synthesized at 160 ° C. for 48 hours. After the hydrothermal synthesis, the resulting product was filtered, washed several times with distilled water, and the washed solid sample was dried at 110 ° C for 10 hours. The solid product produced after drying was crushed and calcined at 650 ° C. for 10 hours to remove carbon as a template material. After firing, 100 ml of a 1 molar concentration of ammonium nitrate (NH ₄ NO ₃ , Junsei Co.) was prepared and maintained at 80 ° C., and 4 g of solid product was added thereto and stirred at 80 ° C. for 3 hours. . The cation-exchanged aqueous solution was subjected to filtration and washing, and an additional two cation exchange procedures were carried out. The solid product having completed cation substitution was dried at 110 ° C. for 10 hours and calcined at 650 ° C. for 5 hours. Thereafter, the phosphorus precursor quantified to be contained 0.3 parts by weight based on 100 parts by weight of the final ZSM-5 catalyst was impregnated by the impregnation method. To this end, the quantified phosphoric acid (85%, H ₃ PO ₄ , Sigma-Aldrich) was dissolved in 10 ml of distilled water, stirred at 60 ° C. for 10 minutes, and then 1 g of the cationic substituted and calcined solid product was added thereto, followed by sufficient impregnation. Stirring at 60 ° C. was continued to occur. After all the distilled water was evaporated, it was dried in an oven at 100 ° C for 12 hours and then calcined at 650 ° C for 3 hours to prepare a fine and mesoporous ZSM-5 catalyst.

Example  2

In the catalyst prepared in Example 1, lanthanum (La) in the rare earth metal was selected to introduce a lanthanum precursor quantified to have a lanthanum / phosphorus atomic ratio of 0.3 by impregnation. To this end, lanthanum nitrate (La (NO ₃ ) ₃ · 6H ₂ O, Sigma-Aldrich) was dissolved in 10 ml of distilled water, stirred at 60 ° C. for 10 minutes, and then 1 g of the catalyst prepared in Example 1 was added thereto. And stirring was continued at 60 ° C. to ensure sufficient impregnation. After all the distilled water was evaporated, it was dried in an oven at 100 ° C for 12 hours and then calcined at 650 ° C for 3 hours to prepare a fine and mesoporous ZSM-5 catalyst.

Example  3

A fine and medium porosity ZSM-5 catalyst was prepared in the same manner as in Example 2, except that the lanthanum precursor was quantified and impregnated so that the lanthanum / phosphorus atomic ratio was 0.7 in Example 2.

Example  4

A fine and medium porosity ZSM-5 catalyst was prepared in the same manner as in Example 2, except that the lanthanum precursor was quantified and impregnated so that the lanthanum / phosphorus atomic ratio was 0.9 in Example 2.

Example  5

A fine and medium porosity ZSM-5 catalyst was prepared in the same manner as in Example 2 except that the lanthanum precursor was quantified and impregnated so that the lanthanum / phosphorus atomic ratio was 1.2 in Example 2.

Example  6

Lithium (Li) in the alkali metal was selected to the catalyst prepared in Example 1, and a lithium precursor quantified to have a lithium / phosphorus atomic ratio of 0.7 was introduced by the impregnation method. To this end, dissolved lithium nitrate (LiNO ₃ , Sigma-Aldrich) was dissolved in 10 ml of distilled water, stirred at 60 ° C. for 10 minutes, and then 1 g of the catalyst prepared in Example 1 was added thereto, and 60 ° C. was sufficient to impregnate. Stirring continued at. After all the distilled water was evaporated, it was dried in an oven at 100 ° C for 12 hours and then calcined at 650 ° C for 3 hours to prepare a fine and mesoporous ZSM-5 catalyst.

Example  7

A potassium precursor quantified to select potassium (K) in the alkali metal and have a potassium / phosphorus atomic ratio of 0.7 was introduced to the catalyst prepared in Example 1 by impregnation. To this end, potassium nitrate (KNO ₃ , Sigma-Aldrich) dissolved in 10 ml of distilled water was dissolved, stirred at 60 ° C. for 10 minutes, and then 1 g of the catalyst prepared in Example 1 was added thereto, and 60 ° C. was sufficient to impregnate. Stirring continued at. After all the distilled water was evaporated, it was dried in an oven at 100 ° C for 12 hours and then calcined at 650 ° C for 3 hours to prepare a fine and mesoporous ZSM-5 catalyst.

Example  8

In the catalyst prepared in Example 1, cesium (Cs) in the alkali metal was selected and the cesium precursor quantified to have a cesium / phosphorus atomic ratio of 0.7 was introduced by the impregnation method. To this end, dissolve cesium nitrate (CsNO ₃ , Sigma-Aldrich) in 10 ml of distilled water, stir at 60 ° C. for 10 minutes, and then add 1 g of the catalyst prepared in Example 1 to 60 ° C. so that sufficient impregnation occurs. Stirring continued at. After all the distilled water was evaporated, it was dried in an oven at 100 ° C for 12 hours and then calcined at 650 ° C for 3 hours to prepare a fine and mesoporous ZSM-5 catalyst.

Experimental Example  1: fine and Medium porosity ZSM Characterization of --5 Catalyst

(1) Effect on ZSM-5 Catalytic Crystal Structure of Phosphorus, Rare Earth Metals and Alkali Metals

X-rays of ZSM-5 catalysts prepared according to Examples 1-8 to investigate the effects of phosphorus, rare earth metals and alkali metals on the crystal structure of the fine and medium porosity ZSM-5 catalysts prepared according to the present invention Diffraction analysis (D-MAX2500-PC, Rigaku Co., Ltd.) was carried out and the results are shown in FIGS. 6 and 7.

Referring to FIG. 6, it can be seen that the characteristic peak of ZSM-5 is well developed in the catalyst according to Example 1 having phosphorus introduced and the catalysts according to Examples 2 to 5 having phosphorus and lanthanum introduced therein. However, below 10 degrees, it can be observed that the relative sensitivity of the peak decreases as the amount of lanthanum introduced is increased. In general, it is reported that the ZSM-5 characteristic peak at low angles in the XRD pattern of ZSM-5 varies greatly depending on the species present in the channel (L. Zhang et al., Catal. Lett., vol. 130, p355, 2009). Therefore, the decrease in the relative sensitivity at the lower angle of the lanthanum-introduced catalyst can be judged because the lanthanum species are present in the channel of the prepared ZSM-5 catalyst and the characteristic peaks of the lanthanum and lanthanum oxide in the X-ray diffraction analysis. It can be seen that the size is so small that it is not detected by the X-ray diffractometer.

Referring to FIG. 7, it can be seen that the characteristic peaks of ZSM-5 are well developed in all catalysts into which alkali metals are introduced, as in Examples 6 to 8. From this, it can be seen that the introduction of alkali metals does not affect the structural change of ZSM-5, and since no additional peaks were observed in addition to the characteristic peaks of ZSM-5, the introduced alkali metal particle size was analyzed by X-ray diffraction analysis. It can be seen that the size is small enough not to be detected by the device.

(2) Analysis of fine and medium pore formation of ZSM-5 catalyst

Nitrogen adsorption and desorption experiments of the ZSM-5 catalysts prepared according to Examples 1 to 5 were carried out to confirm the formation of micropores and mesopores of the micro and mesoporous ZSM-5 catalysts prepared according to the present invention. And pore volume. Figure 8 is a graph showing the nitrogen adsorption and desorption curves of the ZSM-5 catalyst measured using BET (ASAP-2010, Micrometrics Instrument, Inc.), Table 1 below shows the specific surface area and pores of the ZSM-5 catalyst The result of measuring a volume is shown.

catalyst Specific surface area
(M < 2 > / g) Pore volume (cm 3 / g) Micropore Mesopore Example 1 387.8 0.148 0.114 Example 2 384.2 0.131 0.109 Example 3 368.7 0.123 0.108 Example 4 360.3 0.115 0.102 Example 5 312.2 0.111 0.097

First, referring to FIG. 8, it can be seen that adsorption and desorption curves of type IV-type in which the adsorption amount gradually increases as the relative pressure (P / P ₀ ) increases in all catalysts prepared using carbon as a template material, It can be seen that the isotherm measured in the adsorption process and the isotherm measured in the desorption process show a hysteresis that is inconsistent. From this, it can be confirmed that the ZSM-5 catalyst prepared according to the present invention using carbon as a template material has a medium pore in accordance with the intention of the present invention.

In addition, referring to Table 1 above, ZSM-5 catalysts (Examples 2 to 5) in which both phosphorus and lanthanum are introduced, compared to phosphorus-only ZSM-5 catalysts (Example 1), have a smaller specific surface area, micropores, and It can be seen that it has a medium pore volume, and as the lanthanum content is introduced, it can be seen that the micropore volume is greatly reduced. This may be due to pore blocking of micropores due to the introduction of lanthanum. On the other hand, the medium pore volume did not appear to decrease significantly with increasing lanthanum content. From this, when the medium pore characteristics are imparted to the ZSM-5 catalyst, it can be judged that the pore blocking phenomenon of the catalyst can be suppressed compared to the ZSM-5 having only the fine pore characteristics.

(3) Acid Characterization of ZSM-5 Catalyst

Investigation of the Effect of Phosphorus, Rare Earth Metals and Alkali Metals on Acid Properties of the Fine and Medium Porosity ZSM-5 Catalysts Prepared According to the Present Invention Ammonia Temperature Desorption of ZSM-5 Catalysts Prepared According to Examples 1-8 The experiment (BELCAT-B, BEL Japan Co., Ltd.) was carried out and the results are shown in FIGS. 9 and 10. The acidity of each catalyst was calculated from the peak areas of FIGS. 9 and 10. Shown in Here, FIG. 10 and Table 3 together show the results of Example 3 for comparison. As shown in FIG. 9 and FIG. 10, it can be seen that the main desorption peaks were observed at 100 to 150 ° C. and 370 to 420 ° C. positions in all catalysts, and the peaks at 100 to 150 ° C. were defined as weak acid points. Peaks appearing at 370-420 ° C. were defined as strong acid points.

division Acidity (μmol-NH ₃ / g-catalyst) Weak acid Strong acid Total acid Example 1 84.5 40.8 125.3 Example 2 84.7 37.8 122.5 Example 3 83.4 36.2 119.6 Example 4 78.8 33.3 112.1 Example 5 75.2 31.6 106.8

division Acidity (μmol-NH ₃ / g-catalyst) Weak acid Strong acid Total acid Example 3 83.4 36.2 119.6 Example 6 78.2 33.1 111.3 Example 7 87.4 27.6 112.4 Example 8 77.2 24.6 101.8

First, referring to Table 2, as the content of the introduced lanthanum increases, no change in acid strength was observed, but it can be seen that the weak acid point acidity and the strong acid point acidity both showed a tendency to decrease. This may be due to the fact that the lanthanum introduced is associated with some acid sites (L. Zhang et al., Catal. Lett., Vol. 130, p355, 2009). Therefore, the higher the amount of lanthanum introduced, the lower the acid content of the catalyst. Can be observed.

In addition, referring to Table 3, the acid amount of the catalyst showed a tendency to decrease in the order of lanthanum, cesium, potassium, lithium based on the same content of the introduced metal, and it is noteworthy that the weak acid point acid content in all catalysts has a big difference Although not seen, the acidity of strong acid points decreased significantly. This can be judged because the degree of bonding with the acid point of the catalyst, particularly the strong acid point, varies depending on the nature of the alkali metal introduced.

(4) Base Characterization of ZSM-5 Catalyst

Carbon dioxide elevated temperature desorption experiment of ZSM-5 catalyst prepared according to Examples 1 to 5 to investigate the effect of phosphorus and rare earth metals on the basic properties of the fine and medium porosity ZSM-5 catalyst prepared according to the present invention (BELCAT -B, BEL Japan Co., Ltd.) and the results are shown in FIG. 11, and the basicity of each catalyst was calculated from the peak area of FIG. 11 and shown in Table 4 below. As shown in FIG. 11, it can be seen that all catalysts had one characteristic peak observed around 100 to 200 ° C.

division Basicity (μmol-CO ₂ / g-catalyst) Example 1 4.3 Example 2 7.3 Example 3 11.7 Example 4 14.7 Example 5 24.5

Referring to Table 4, it can be seen that the base amount increases as the lanthanum content is increased, which may be because the base point is generated on the surface of the ZSM-5 with the introduction of the lanthanum (Y. Zhang et al., Appl. Catal. A, vol. 333, p202, 2007).

On the other hand, hydrocarbon decomposition is known to proceed largely by two mechanisms, monomolecular cracking and bimolecular cracking (H. Krannila et al., J. Catal., Vol. 135, p115, 1992). ). Monomolecular decomposition results in the immediate decomposition of hydrocarbons by β-scission at the acidic point of the catalyst or by high reaction temperatures to produce mainly olefin-like products, whereas bimolecular decomposition involves carbenium ions adsorbed on paraffins and acidic sites. Larger carbenium ions are formed by hydride transfer between them, followed by decomposition reactions by β-scission, or aromatic compounds by cyclization, and isomerization. Isomers are also produced by D. Mier et al., Ind. Eng. Chem. Res. Vol. 49, p8415, 2010. Therefore, in order to maximize the production of light olefins, it is necessary to suppress the mechanisms proceeding by bimolecular decomposition and activate the reaction mechanisms proceeding by monomolecular decomposition. Hydrogen transfer activity is an indicator used to determine which of these two mechanisms dominate the reaction pathway. Hydrogen transfer activity can be determined by the ratio of paraffin / olefin of a specific hydrocarbon in the product produced at the beginning of the reaction. In the case of high hydrogen transfer activity, that is, in the case of high hydride ion capacity, the reaction according to the bimolecular mechanism is predominant, resulting in the generation of aromatic compounds and paraffins, while in the case of low hydrogen transfer activity, that is, hydride ions. In the case of low capacity, monomolecular decomposition is predominantly generated by direct β-scission of carbenium ions, and more light olefins are produced.

In order to determine how the base properties of the ZSM-5 catalyst prepared according to the present invention affect the hydrogen transfer activity, the hydrogen transfer activity of the ZSM-5 catalyst prepared according to Examples 1 to 5 was measured. The relationship with the base characteristic of the catalyst is shown in FIG. Hydrogen transfer activity was expressed as a ratio of (i-butane + n-butane) / butene.

Referring to FIG. 12, it can be seen that as the base amount of the catalyst increases, that is, the hydrogen transfer activity tends to decrease as the amount of lanthanum introduced increases. From this, the introduction of a metal exhibiting basic properties to the ZSM-5 catalyst can control the hydrogen transfer activity, it can be judged that the light olefin can be more efficiently prepared using these properties.

Experimental Example  2: fine and phosphorus and rare earth metals introduced Medium porosity ZSM Light Olefin Production Yield and Catalytic Activity Analysis by Catalytic Catalytic Decomposition of Hydrocarbon Mixtures with -5 Catalyst

Preparation of light olefins, in particular ethylene and propylene, by the catalytic catalytic cracking of hydrocarbon mixtures using fine and medium porosity ZSM-5 catalysts with phosphorus and rare earth metals prepared according to the invention The reaction was carried out. The hydrocarbon mixture used as the reactant used a C5 fraction and its composition is shown in Table 5 below.

Chemical name Composition ratio (mol%) Pentane 33.4 Isopentane 25.0 Pentene 8.3 Isopenpentene 25.0 Cyclopentane 8.3

[Manufacturing reaction example]

For the catalytic catalytic cracking reaction of the C5 fraction, the ZSM-5 catalysts prepared according to Examples 1 to 5 were each charged in a reactor, and the catalyst was activated at 600 ° C. for 1 hour with nitrogen gas (40 mL) before the reaction. After the catalytic activation, the reaction proceeded as the reactants passed through the catalyst bed in the reactor continuously. The weight hourly space velocity (WHSV) of the reactant was maintained at 3.5 h ^-1 and the catalytic catalytic cracking reaction temperature of the C5 oil was 600 ° C. The product produced after the reaction was analyzed by gas chromatography, and the conversion of C5 fraction, selectivity and yield of light olefin (ethylene + propylene) according to the reaction time of each catalyst were calculated, and reaction of the acid and base properties of the catalyst was performed. The effect on activity is shown in FIG. 13 and the relationship between lanthanum / phosphorus atomic ratio and light olefin yield is shown in FIG. 14. Here, the conversion rate, light olefin selectivity, and light olefin (ethylene + propylene) yield of the C5 hydrocarbon mixture were calculated according to the following equations (1) to (4). In addition, the reaction result of FIG. 13 was based on the result obtained after 20 hours passed after the start of reaction.

First, as a result of the experiment, no deterioration of the reaction activity was observed during the reaction time of 20 hours, and it can be seen that the phosphorus component introduced suitably played a role of suppressing deactivation of the catalyst by preventing dealumination.

Referring to Figure 13 (a), it can be seen that the base properties of the catalyst has a great effect on the distribution of the product produced after the reaction. As the base amount of the catalyst increases, that is, as the amount of lanthanum introduced increases, the selectivity of light olefins is greatly improved, while the selectivity of aromatic compounds (benzene, toluene, xylene, etc.) tends to decrease. Can be. This tendency is because, as described above, the hydrogen transfer activity decreased as the base characteristics of the catalyst were improved (see FIG. 12). While the hydrogen transfer activity of the catalyst is reduced, bimolecular decomposition is suppressed, whereas monomolecular decomposition is promoted, thus direct β-scission is more likely to occur than cyclization and isomerization of carbenium ions, resulting in light olefin selectivity. While the production of aromatic compounds is inhibited.

On the other hand, referring to Figure 13 (b), it can be seen that the introduction of lanthanum did not play a positive role in improving the conversion rate of the C5 fraction. As mentioned above, the introduction of lanthanum reduces the acid properties of the catalyst (see FIG. 9), and the decrease in acid properties of the catalyst leads to a decrease in decomposition activity, thereby reducing the reaction activity. In other words, the introduced lanthanum is partially combined with the acid point of the catalyst to reduce the acid amount of the catalyst, and as a result, the conversion rate of the C5 fraction decreases as the amount of introduced lanthanum increases because the degradation activity is weakened.

However, as shown in FIG. 14, the light olefin yield shows a volcanic distribution with respect to the lanthanum / phosphorus atomic ratio. In other words, the increase in the lanthanum content has the disadvantage of reducing the conversion of the C5 fraction by reducing the acid amount of the catalyst, while increasing the selectivity of the light olefins by improving the base properties of the catalyst to weaken the hydrogen transfer activity. As in Example 3, a catalyst having an appropriate lanthanum / phosphorus atomic ratio can be prepared to optimally control the acid and base properties of the catalyst, thereby inhibiting catalyst deactivation and maximizing light olefin yield.

Experimental Example  3: fine and phosphorus and alkali metal introduced Medium porosity ZSM Light Olefin Production Yield and Catalytic Activity Analysis by Catalytic Catalytic Decomposition of Hydrocarbon Mixtures with -5 Catalyst

ZSM prepared according to Examples 6-8 for the production yield analysis of light olefins by catalytic catalytic cracking of hydrocarbon mixtures using fine and medium porosity ZSM-5 catalysts having phosphorus and alkali metals prepared according to the invention For the -5 catalyst, the preparation reaction was carried out under the same conditions as in Experimental Example 2, and the results are shown in Table 6 below. Here, the results using the ZSM-5 catalyst prepared according to Examples 1 and 3 for comparison are also shown.

division
Conversion Rate (%)
Selectivity (%) yield(%)
Ethylene Propylene Aromatic compounds Example 1 95.3 30.9 28.2 12.4 56.3 Example 3 93.5 30.7 31.2 7.2 57.9 Example 6 32.7 16.2 24.9 1.2 13.4 Example 7 86.6 30.2 33.6 4.6 55.2 Example 8 90.6 31.0 33.7 5.3 58.7

Referring to Table 6, in the case of the catalyst (Examples 6 and 7) introduced by selecting lithium or potassium as the alkali metal, the catalyst having phosphorus introduced (Example 1) or the catalyst having phosphorus and lanthanum introduced (Example 3) Reaction activity was slightly lower than that of), but the catalyst of Cesium (Example 8) showed a slightly lower conversion rate of C5 fraction, but showed better yield due to improved selectivity of light olefins. have. In addition, all of the catalysts into which alkali metal is introduced show a lower selectivity of aromatic compounds than those in which a phosphorus or rare earth metal is introduced, indicating that the introduction of alkali metals is progressed by bispecific decomposition as compared with the introduction of phosphorus or rare earth metals It can be judged that it inhibits the mechanism and activates the reaction mechanism which proceeds by monomolecular decomposition. From these results, when selective alkali metals are selectively introduced into the ZSM-5 catalyst with phosphorus, light olefins are prepared by catalytic catalytic cracking of the C5 fraction as compared to the catalyst with rare earth metal into the ZSM-5 catalyst with phosphorus. It can be seen that can be performed more effectively.

While the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, Such modifications and changes are to be considered as falling within the scope of the following claims.

Claims (29)

In the method for producing a fine and medium porosity ZSM-5 catalyst used for catalytic light cracking the hydrocarbon mixture of 4 to 7 produced after the naphtha cracking process to produce a light olefin comprising ethylene and propylene,
(a) aging a mixed solution comprising a silica precursor and an aluminum precursor to form a gel;
(b) adding carbon powder to the gel to mature after stirring;
(c) crystallizing the mixture aged in step (b) to form a solid product;
(d) heat treating the solid product to remove the carbon; And
(e) introducing a phosphorus precursor into the heat treated solid product by impregnation or ion exchange;
Method for producing a fine and medium porosity ZSM-5 catalyst comprising a. The method of claim 1,
(f) introducing a rare earth metal precursor or an alkali metal precursor into the solid product into which the phosphorus precursor has been introduced by impregnation or ion exchange;
Method for producing a fine and medium porosity ZSM-5 catalyst further comprising a. 3. The method according to claim 1 or 2,
The mixed solution of step (a),
(a-1) dissolving monovalent metal hydroxide and tetrapropylammonium halide in distilled water;
(a-2) adding the silica precursor to form a homogeneous mixture; And
(a-3) dropping the liquid aluminum precursor onto the homogeneous mixture;
Method for producing a fine and medium porosity ZSM-5 catalyst, characterized in that it is prepared, including. The method of claim 3,
The silica precursor is colloidal silica, and the aluminum precursor is sodium aluminate (NaAlO ₂ ), aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum secondary-butoxide, aluminum terminator. Aluminum tert-butoxide, aluminum tri-sec-butoxide, aluminum tri-tert-butoxide, aluminum ethoxide ) And aluminum isopropoxide (aluminum isopropoxide) is one or more selected from the group consisting of fine and medium porosity ZSM-5 catalyst production method. 3. The method according to claim 1 or 2,
The carbon powder is a fine and medium porosity ZSM-5 catalyst production method, characterized in that the particle size is at least one selected from the group consisting of spherical, square, rectangular and cylindrical with a diameter of 2 ~ 50nm. 3. The method according to claim 1 or 2,
The carbon powder is a fine and medium porosity ZSM-5 catalyst production method, characterized in that 5 to 80 parts by weight based on 100 parts by weight of the silica precursor. 3. The method according to claim 1 or 2,
The fine and medium porosity ZSM-5 catalyst is a method for producing a fine and medium porosity ZSM-5 catalyst, characterized in that the Si / Al atomic ratio of 5 ~ 300. 3. The method according to claim 1 or 2,
The heat treatment of step (d) is a fine and medium porosity ZSM-5 catalyst production method, characterized in that performed for 3 to 10 hours at 300 ~ 750 ℃. 3. The method according to claim 1 or 2,
The method of impregnating the phosphorus precursor in the step (e),
(e-1) hydrating the phosphorus precursor in water;
(e-2) impregnating by adding the solid product heat-treated in step (d) to a solution in which the phosphorus precursor is hydrated; And
(e-3) drying and heat treating the impregnated solid product;
Method for producing a fine and medium porosity ZSM-5 catalyst comprising a. 10. The method of claim 9,
The phosphorus precursors include phosphoric acid (H ₃ PO ₄ ), ammonium phosphate ((NH ₄ ) H ₂ PO ₄ ), diammonium phosphate ((NH ₄ ) ₂ HPO ₄ ) and triammonium phosphate ((NH ₄ ) ₃ PO ₄ ) Method for producing a fine and medium porosity ZSM-5 catalyst, characterized in that at least one selected from the group consisting of. 10. The method of claim 9,
The phosphorus precursor is a method for producing fine and medium porosity ZSM-5 catalyst, characterized in that 0.01 to 10 parts by weight based on 100 parts by weight of the prepared fine and medium porosity ZSM-5 catalyst. 10. The method of claim 9,
The heat treatment of the step (e-3) is a method for producing fine and medium porosity ZSM-5 catalyst, characterized in that performed for 1 to 10 hours at 500 ~ 750 ℃. 3. The method of claim 2,
The method of impregnating the rare earth metal precursor or alkali metal precursor in the step (f),
(f-1) hydrating the rare earth metal precursor or alkali metal precursor in water;
(f-2) impregnating the rare earth metal precursor or the alkali metal precursor by adding a solid product having phosphorus introduced thereinto in step (e); And
(f-3) drying and heat treating the impregnated solid product;
Method for producing a fine and medium porosity ZSM-5 catalyst comprising a. The method of claim 13,
The rare earth metal is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thorium (Tm), ytterbium (Yb) and lutetium (Lu) at least one member selected from the group consisting of fine and medium porosity ZSM-5 catalyst Way. The method of claim 13,
The alkali metal is a fine and medium porosity ZSM-5 catalyst production, characterized in that at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs). Way. The method of claim 13,
The rare earth metal or alkali metal content of the fine and medium porosity ZSM-5 catalyst production method characterized in that the atomic ratio to the phosphorus. The method of claim 13,
The heat treatment of the step (f-3) is a method for producing fine and medium porosity ZSM-5 catalyst, characterized in that performed for 1 to 10 hours at 500 ~ 750 ℃. 3. The method according to claim 1 or 2,
Between steps (d) and (e),
(d-1) cationic substitution of the heat treated solid product; And
(d-2) heat treating the cationic substituted solid product;
Method for producing a fine and medium porosity ZSM-5 catalyst further comprising a. 19. The method of claim 18,
The cation substitution is one or more selected from the group consisting of ammonium nitrate (NH ₄ NO ₃ ), ammonium chloride (NH ₄ Cl), ammonium carbonate ((NH ₄ ) ₂ CO ₃ ) and ammonium fluoride (NH ₄ F) Method for producing a fine and medium porosity ZSM-5 catalyst, characterized in that performed using a solution containing. 19. The method of claim 18,
The heat treatment of the step (d-2) is a fine and medium porosity ZSM-5 catalyst manufacturing method, characterized in that performed for 3 to 10 hours at 400 ~ 700 ℃. 3. The method according to claim 1 or 2,
The hydrocarbon mixture is a method for producing a fine and medium porosity ZSM-5 catalyst, characterized in that consisting of C5 fraction. In the fine and medium pore ZSM-5 catalyst used for catalytic light cracking of a hydrocarbon mixture having 4 to 7 carbon atoms produced after naphtha cracking process to produce light olefins including ethylene and propylene,
The catalyst is prepared using carbon as a template material, fine and medium porosity ZSM-5 catalyst comprising a phosphorus. The method of claim 22,
The catalyst is a fine and medium porosity ZSM-5 catalyst characterized in that it further comprises a rare earth metal or alkali metal. 24. The method according to claim 22 or 23,
The phosphorus content is fine and medium porosity ZSM-5 catalyst, characterized in that 0.01 to 10 parts by weight based on 100 parts by weight of the fine and medium porosity ZSM-5 catalyst based on the phosphorus precursor. 24. The method of claim 23,
The rare earth metal or alkali metal content is fine and medium porosity ZSM-5 catalyst, characterized in that the atomic ratio to the phosphorus. 24. The method of claim 23,
The catalyst has a specific surface area of 300 to 400 m 2 / g, a micropore volume of 1 nm or less in diameter of 0.1 ~ 0.14 cm 3 / g, a medium pore volume of more than 2 nm in diameter of 0.09 ~ 0.11 cm 3 / g, ammonia temperature desorption experiment The weak acidic acid content is 75 ~ 88μmol-NH ₃ / g-catalyst, the strong acidic acid content is 24 ~ 38μmol-NH ₃ / g-catalyst and the base amount is 5 ~ 30μmol-CO ₂ / g-catalyst Micro and Mesoporous ZSM-5 Catalysts. 24. The method according to claim 22 or 23,
The hydrocarbon mixture is fine and medium porosity ZSM-5 catalyst, characterized in that consisting of C5 fraction. In the method of producing a light olefin comprising ethylene and propylene by catalytic catalytic cracking of a hydrocarbon mixture having 4 to 7 carbon atoms generated after naphtha cracking process,
Hard characterized in that the hydrocarbon mixture in the presence of the fine and medium porosity ZSM-5 catalyst of claim 22 or 23 at a reaction temperature of 300 ~ 700 ℃ at a weight space velocity (WHSV) 1 ~ 20h ^-1 conditions Olefin production method. 29. The method of claim 28,
The method of producing a light olefin, characterized in that the hydrocarbon mixture consists of C5 fraction.

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