JP5094506B2 - Production method of light olefin - Google Patents

Description

  The present invention relates to a method for producing light olefins, and more particularly to a method for producing light olefins capable of obtaining propylene in a high yield.

  Ethylene and propylene (hereinafter referred to as “light olefins”), which are important as basic raw materials for various chemicals, are mainly made from gaseous hydrocarbons such as ethane, propane, and butane or liquid hydrocarbons such as naphtha. It is manufactured by a method in which it is thermally decomposed in a steam atmosphere in a thermal tubular furnace. However, this method has an economical disadvantage in that it requires a high temperature of 800 ° C. or higher in order to increase the olefin yield, and thus expensive equipment materials must be used. There is also a problem that the amount of propylene produced is smaller than that of ethylene. For this reason, various methods for catalytic conversion of hydrocarbons using zeolite catalysts have been studied as methods for obtaining more light olefins, particularly propylene.

As the zeolite catalyst, there are the most reports using a pentasil type zeolite such as ZSM-5 type. For example, Patent Document 1 discloses an alkali metal ion and / or alkaline earth metal ion type ZSM-5 type zeolite. And a method for producing ethylene, propylene, and the like by performing a naphtha reaction using a catalyst containing a group IB element (such as silver) in the periodic table.
In this catalyst, “it is important to prepare so as to have substantially no acidic sites” (see paragraph [0013]). According to the patent document, the yield of propylene is lower than the yield of ethylene.
Patent Document 2 discloses a method for producing ethylene and propylene by reacting butene using a catalyst that is substantially free of protons and contains a group IB element (such as silver) in the periodic table. Has been. As for this catalyst, there is a description that "group IB metal is contained in a corresponding cation state" (see paragraph [0031]). This catalyst is characterized in that the amount of protons (acid amount) in the zeolite is 0.02 mmol or less per gram of zeolite and is “substantially free of protons” (see paragraph [0027]). The propylene yield described in the patent document is about 20% by mass.

On the other hand, an example is also disclosed in which ZSM-5 type zeolite modified with rare earth or phosphorus is used instead of modification with elements of group IB of the periodic table (such as silver) as in the above-mentioned patent document. For example, Patent Document 3 describes an example in which the reaction of n-butane was performed using a catalyst in which ZSM-5 type zeolite was modified with rare earth and phosphorus, but the yield of propylene was about 20% by mass. Yes, lower than the yield of ethylene (see Example 4). Further, Patent Document 4 describes an example in which a reaction of n-butane was performed using ZSM-5 type zeolite modified with manganese and / or zirconium in addition to rare earth and phosphorus as a catalyst. The yield is about 20% by mass or less (see Example 8).
Patent Document 4 and Patent Document 5 disclose propylene by a catalytic reaction of hydrocarbons mainly composed of paraffins having 3 to 10 carbon atoms using silver or copper and ZSM-5 type zeolite modified with phosphorus as a catalyst. Although it is described that it can be obtained in a high yield (30 to 60% by mass), it is a result of a pulse reaction highly diluted with helium gas, and the propylene is continuously high under industrially practicable reaction conditions. No yields have been reported.
In addition, as the description of the “periodic table”, in the above description of the prior art, the description of the periodic table described in Non-Patent Document 1 is described according to the cited patent document, but in the following description, It is described in accordance with the periodic table “IUPAC Periodic Table of the Elements, October 3th, 2005” of the International Union of Pure and Applied Chemistry (IUPAC: The International Union of Pure and Applied Chemistry). Therefore, for example, “Group IB” such as the above-mentioned silver becomes “Group 11” in the periodic table of IUPAC.

JP-A-8-126844 JP 2007-106738 A Japanese Patent Laid-Open No. 11-180902 JP 2004-143373 A JP-A-2-1413 Japanese Patent Laid-Open No. 2-184638 CRC Handbook of Chemistry and Physics, 75th edition (David R. Lide et al., CRC Press Inc., 1994-1995, pp. 1-15)

  An object of this invention is to provide the manufacturing method of the light olefin which can obtain propylene industrially with a high yield from a hydrocarbon as a raw material.

  As a result of diligent research to solve the above problems, the present inventors have used a zeolite catalyst containing a specific element, and using the zeolite catalyst in which the particle size of the specific element is selected. We found that the problem could be solved. The present invention has been completed based on such findings. That is, the present invention

[1] In a method for producing a light olefin by catalytic conversion of a hydrocarbon raw material, using a zeolite containing phosphorus and a rare earth element and containing at least one element of Groups 10 to 12 of the periodic table as a catalyst; and A method for producing a light olefin, wherein the particle size of the group 10-12 element supported on the zeolite is 1 nm or less;
[2] The method for producing a light olefin according to the above [1], wherein the group 10-12 element of the periodic table is at least one element selected from silver, zinc, and palladium,
[3] The method for producing a light olefin according to [1] or [2], wherein the zeolite is a pentasil-type zeolite,
[4] The method for producing a light olefin according to any one of [1] to [3], wherein the zeolite is a zeolite having an MFI type structure,
[5] The method for producing a light olefin according to any one of [1] to [4], wherein the hydrocarbon raw material contains 10% by mass or more of hydrocarbons having 4 or more carbon atoms,
[6] The method for producing a light olefin according to any one of [1] to [5] above, wherein the hydrocarbon raw material is butenes, and [7] the light olefin contains propylene as a main component. The method for producing a light olefin according to any one of [1] to [6],
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the light olefin which can use a hydrocarbon raw material as a raw material and can obtain propylene industrially with a high yield can be provided.

  The present invention provides a method for producing a light olefin by catalytic conversion of a hydrocarbon raw material, using phosphorus and a rare earth element as well as a zeolite containing at least one element of Groups 10 to 12 of the periodic table, and A method for producing a light olefin, wherein the particle size of the group 10-12 element supported on the zeolite is 1 nm or less.

  As the hydrocarbon raw material used in the present invention, gaseous or liquid hydrocarbons at normal temperature and normal pressure can be used. Generally, hydrocarbon raw materials having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms are used. Examples of such hydrocarbon raw materials include paraffins such as ethane, propane, butane, pentane and hexane, olefins such as butenes, pentenes and hexene, naphthenes such as cyclohexane, or naphtha and light oil. A light hydrocarbon fraction can be mentioned. Among these, as a raw material suitable for producing more propylene, a raw material containing 10% by mass or more of hydrocarbons having 4 or more carbon atoms is preferable. In addition, raw materials having an unsaturated bond such as butenes, pentenes, and hexenes are preferable, and in particular, raw materials containing 10% by mass or more, preferably 20% by mass or more of butenes are suitable. Butenes are 1-butene, 2-butene, and isobutene, and these can be used in the state of a mixture.

The catalyst of the present invention contains, as a main component of the catalyst, a zeolite containing a rare earth element and phosphorus and containing at least one element of Group 10-12 of the periodic table. As the zeolite, a pentasil type zeolite is preferable, and an MFI type structure is particularly preferable. “MFI” is one of the structural codes given to a zeolite species having a specific crystal structure by the International Zeolite Association. A typical example of MFI type zeolite is ZSM. -5 and / or ZSM-11.
The zeolite has a SiO ₂ / Al ₂ O ₃ ratio of 25 to 800, preferably 40 to 600, and more preferably 60 to 300.

  Any element can be used as the rare earth element, and preferred examples include lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium and the like. The rare earth elements may be used alone or in combination of two or more. Rare earth modification to the catalyst uses various salts such as acetate, nitrate, halide, sulfate, carbonate, alkoxide, acetylacetonate, etc., ion exchange method, impregnation method or hydrothermal synthesis method, etc. It can be done by the method.

  In order to develop the performance of the present catalyst, it is essential that the catalyst contains phosphorus and at least one element of Groups 10 to 12 of the periodic table in addition to the rare earth element. There is no particular limitation on the order of modification with rare earth elements, phosphorus, and elements of Group 10-12 of the periodic table, and they may be modified simultaneously, but in the order of elements of Group 10-12 of the periodic table, phosphorus, rare earth elements. It is more preferable to modify. As an element of periodic table group 10-12, silver, zinc, and palladium are preferable, and silver is more preferable. The introduction into the zeolite can be performed by an ion exchange method, an impregnation method, a hydrothermal synthesis method, or other methods using various compounds. Phosphorus can be supported by impregnating zeolite in an aqueous solution such as phosphoric acid and / or ammonium salt of phosphoric acid, or by spraying these aqueous solutions on zeolite. The amount of phosphorus supported is preferably 0.2 to 10% by mass, more preferably 1 to 5% by mass.

It is important that rare earth elements, phosphorus, and elements of Groups 10 to 12 in the periodic table are supported or contained on the zeolite, and the physical properties of the catalyst can be obtained only by physically mixing the zeolite and these modifiers. There is no effect.
In the catalyst of the present invention, the rare earth element content is 0.4 to 20, preferably 0.6 to 5, and more preferably 1 to 3 in terms of atomic ratio with respect to aluminum in the zeolite. When the amount is small, heavy coke and aromatics, which are by-products, increase, and when the content is too large, the catalytic activity is lowered and the propylene yield is reduced. On the other hand, the content of the elements of Group 10-12 of the periodic table is such that the total number of moles is 0.1-20, preferably 0.5-10, more preferably 1 with respect to the number of moles of aluminum in the zeolite. When the content is less than these values, the amount of propylene produced is low, and when the content is too high, the catalytic activity is low. At this time, it is necessary to control the supported elements of Groups 10 to 12 of the periodic table so that the particle diameter on zeolite is 1 nm or less. When these particle diameters after loading are larger than 1 nm, the catalytic activity is remarkably lowered. The particle diameter of these metals can be measured with a transmission electron microscope (TEM), powder X-ray diffraction analysis, or the like.

The shape of the catalyst of the present invention is not particularly limited, and may be any shape such as powder or molded product. In addition, these catalysts may contain other components other than zeolite and rare earth elements, phosphorus, and elements of Groups 10 to 12 of the periodic table, such as alkali elements, alkaline earth elements, various binders, and the like. It is also possible to use a mixture with a filler such as silica, alumina, magnesia or quartz sand.
The mode of the catalytic conversion reaction of the present invention is not particularly limited, but it is performed by supplying a hydrocarbon raw material to the catalyst bed filled with the above catalyst using a reactor of a fixed bed, moving bed, fluidized bed or the like. Is called. At this time, the hydrocarbon raw material may be diluted with nitrogen, hydrogen, helium, steam or the like. The reaction temperature ranges from 350 to 780 ° C, preferably from 450 to 650 ° C, more preferably from 500 to 600 ° C. Although it can be carried out at temperatures above 780 ° C., the production of methane and coke increases rapidly. Moreover, since sufficient activity cannot be obtained at 350 ° C. or lower, the yield of propylene per pass is reduced. The reaction pressure can be any of normal pressure, reduced pressure, or increased pressure. Usually, normal pressure or slightly increased pressure is employed.
When the method of the present invention is carried out under the above conditions, light olefins, particularly propylene, can be selectively produced from hydrocarbon raw materials.

  Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

Example 1
[Preparation of zeolite catalyst]
As zeolite, 100 parts by weight of powdered proton type ZSM-5 zeolite (SiO ₂ / Al ₂ O ₃ ratio measured by fluorescent X-ray analysis = 60, specific surface area 350 m ² / g, particle diameter 150 μm or less), silver nitrate An aqueous solution (1.575 parts by weight of silver nitrate dissolved in 1000 parts by weight of deionized water) was impregnated and stirred at 40 ° C. for 2 hours. While the resulting slurry was stirred at 40-60 ° C. under reduced pressure, water was evaporated over about 2 hours to obtain a white powder. The obtained powder was dried in air at 120 ° C. for 8 hours, then heated to 600 ° C. over 4 hours in a muffle furnace, and calcined at 600 ° C. for 5 hours. The obtained solid was pulverized and further impregnated with an aqueous lanthanum chloride solution (26.7 parts by mass of lanthanum chloride heptahydrate dissolved in 1000 parts by mass of deionized water), and the same as when impregnated with an aqueous silver nitrate solution. The white solid was obtained by drying and calcination by various operations. It is pulverized in a mortar, impregnated in an aqueous diammonium hydrogen phosphate solution (17.1 parts by mass of diammonium hydrogen phosphate dissolved in 1000 parts by mass of deionized water), dried and fired in the same manner, A white solid was obtained. This was pulverized in a mortar, kneaded after adding 25 parts by mass of an alumina binder, and extruded to form a cylindrical molded body having a diameter of 1.6 mm and a length of about 2 cm (referred to as “catalyst A”).
The obtained molded body (catalyst A) contained lanthanum: 6.4% by mass, phosphorus: 3.0% by mass, and silver: 0.6% by mass (quantitatively determined by X-ray fluorescence analysis, the same applies hereinafter). .

The catalyst prepared as described above was observed with an HF2200 transmission electron microscope (acceleration voltage 200 kV) manufactured by Hitachi High-Technologies Corporation (the observation sample was a dispersion liquid after the catalyst was pulverized in a mortar and dispersed in a heptane solvent. Was dripped onto a copper mesh with a microgrit support film and prepared by drying heptane at room temperature).
As a result of observation, no clear particles based on silver were observed, and no peak based on silver particles was observed in X-ray powder diffraction analysis (X-ray powder diffraction analysis was performed using a RINT Ultimate III X-ray diffractometer manufactured by Rigaku). And measured with Cu-Kα ray under the conditions of measuring range 2θ = 5 to 80 °, X-ray output 40 kV, 40 mA).
From these facts, it was confirmed that the particle diameter of the supported silver was 1 nm or less.

On the other hand, when infrared spectroscopic analysis of the catalyst A was performed by Fourier transform infrared spectroscopy, absorption based on acidic protons (3605 cm ⁻¹ ) was observed, and it was confirmed that the catalyst had acidic protons. Further, when the amount of acid sites was measured by ammonia TPD analysis, it was found to have an acid amount of 0.12 mmol / g.
The Fourier transform infrared spectroscopic analysis is performed using a Fourier transform infrared spectrophotometer FT / IR-550 type manufactured by JASCO Corporation according to the method described in Non-Patent Document 2, and the ammonia TPD analysis is performed. According to the method described in Non-Patent Document 3, measurement was performed using a TPD-1-AT type manufactured by Nippon Bell Co., Ltd.

Non-Patent Document 2: Trends in Physical Chemistry, Vol. 1, page 133 (T. Sano et al., 1990)
Non-Patent Document 3: Zeolite, Vol. 21, No. 2, pp. 45-52 (Naoto Katada, Miki Niwa, 2004)

[Light olefin production experiment]
1 g of this catalyst was packed into a stainless steel reaction tube having an inner diameter of 10 mm (with an inner tube for thermocouple having an outer diameter of 3 mm). The upper and lower sides of the catalyst layer were filled with quartz sand. The temperature of the catalyst layer was raised to 600 ° C. while flowing air at 40 cm ³ / min (0 ° C., converted to 1 atm, the same applies hereinafter) into this reactor, and pretreatment was performed for 1 hour. After completion of pretreatment, the temperature of the catalyst layer was held at 550 ° C., of 1-butene 6 cm ³ / min, nitrogen and steam was continuously supplied at a flow rate of each 20cm ³ /min,1.0g/h as a raw material Then, the catalytic conversion reaction of 1-butene was performed.
Three hours after starting the feed of the raw material, when the activity was stabilized, the product at the outlet of the reactor was analyzed by gas chromatography, and the product yield and the raw material conversion rate were calculated by the following equations.
Product yield (mass%) = (weight of each component / feed weight) × 100 (Formula 1)
Raw material conversion (%) = (1-unreacted raw material weight / feed raw material weight) × 100 (Formula 2)
The propylene yield calculated by the formula (1) was 36.7% by mass, and the raw material conversion calculated by the formula (2) was 72.0%.
The analysis results of the reaction product are shown in Table 1.

Comparative Example 1
[Preparation of zeolite catalyst]
A zeolite catalyst (catalyst B) containing rare earth, phosphorus and silver was prepared in the same manner as in Example 1 except that the amount of silver nitrate used was 7.875 parts by mass. The obtained catalyst (Catalyst B) contained lanthanum: 6.4% by mass, phosphorus: 3.0% by mass, and silver: 3.0% by mass. When the particle diameter of silver was examined by a transmission electron microscope and X-ray powder diffraction analysis in the same manner as in Example 1, the average particle diameter of the observed silver was 1.2 nm, which was larger than 1 nm. It was. The particle size was measured with a transmission electron microscope by observing three or more 200 nm × 200 nm regions at a magnification of 100,000, and clearly identifying five randomly selected 20 nm × 20 nm regions. The number of particles that can be observed and the length in the long axis direction were visually measured and averaged. In the X-ray powder diffraction analysis, the Scherrer equation was used.
As in Example 1, the catalyst of Comparative Example 1 showed absorption based on acidic protons by infrared spectroscopic analysis, and the amount of acid measured by the ammonia TPD method was 0.13 mmol / g.

[Light olefin production experiment]
1 g of catalyst B was used and 1-butene was reacted under the same conditions as in Example 1. The propylene yield was as low as 13.8% by mass, and the raw material conversion was also as low as 31.2%.
The analysis results of the reaction product are shown in Table 1.

Example 2
[Preparation of zeolite catalyst]
A zeolite catalyst (catalyst C) containing rare earth, phosphorus and zinc was prepared in the same manner as in Example 1 except that instead of 1.575 parts by mass of silver nitrate, 13.65 parts by mass of zinc nitrate hexahydrate was used. Prepared.
The obtained catalyst (catalyst C) contained lanthanum: 6.4% by mass, phosphorus: 3.0% by mass, and zinc: 1.6% by mass. In transmission electron microscope and X-ray powder diffraction analysis, no clear particles based on zinc were observed, and it was confirmed that the particle diameter of supported zinc was 1 nm or less. As in Example 1, absorption based on acidic protons was observed in infrared spectroscopic analysis, and the amount of acid measured by the ammonia TPD method was 0.13 mmol / g.
[Light olefin production experiment]
1g of catalyst C was used and 1-butene was reacted under the same conditions as in Example 1. The propylene yield was 30.3% by mass, and the raw material conversion was 66.7%.
The analysis results of the reaction product are shown in Table 1.

Example 3
[Preparation of zeolite catalyst]
A zeolite catalyst (catalyst D) containing rare earth, phosphorus and palladium was prepared in the same manner as in Example 1 except that 2.165 parts by mass of palladium nitrate was used instead of 1.575 parts by mass of silver nitrate.
The obtained catalyst (catalyst D) contained lanthanum: 6.2% by mass, phosphorus: 3.1% by mass, and palladium: 0.6% by mass. In a transmission electron microscope and X-ray powder diffraction analysis, no clear particles based on palladium were observed, and it was confirmed that the particle diameter of supported palladium was 1 nm or less. Similarly to Example 1, absorption based on acidic protons was observed in infrared spectroscopic analysis, and the amount of acid measured by the ammonia TPD method was 0.29 mmol / g.
[Light olefin production experiment]
1g of catalyst D was used and 1-butene was reacted under the same conditions as in Example 1. The propylene yield was 31.8% by mass, and the raw material conversion was 83.1%.
The analysis results of the reaction product are shown in Table 1.

Comparative Example 2
[Preparation of zeolite catalyst]
In the same manner as in Example 1, a zeolite catalyst (catalyst E) modified only with silver and phosphorus was prepared without using lanthanum chloride.
In the transmission electron microscope and X-ray powder diffraction analysis, clear particles based on silver were not observed, and it was confirmed that the particle diameter of the supported silver was 1 nm or less. As in Example 1, absorption based on acidic protons was observed in infrared spectroscopic analysis, and the amount of acid measured by the ammonia TPD method was 0.13 mmol / g.
[Light olefin production experiment]
1 g of catalyst E was used and 1-butene was reacted under the same conditions as in Example 1. The raw material conversion was as high as 91.5%, but the propylene yield was as low as 20.4% by mass.
The analysis results of the reaction product are shown in Table 1.

〔note〕
“C5”: pentane, pentenes, “C6 +” is a product having 6 or more carbon atoms,
“Other light gases”: hydrogen and saturated hydrocarbons having 1 to 4 carbon atoms

  From Table 1, it can be seen that in the production methods of Examples 1 to 3, the raw material conversion rate is high, the yield of propylene is high, and a product containing propylene as a main component can be obtained. On the other hand, in the method of Comparative Example 1 using a zeolite having a supported silver particle diameter of 1 nm or more and the method of Comparative Example 2 using a zeolite that does not support a rare earth, the conversion rate of the raw material is low and the yield of propylene is also low. Low.

  According to the light olefin production method of the present invention, it is possible to provide a light olefin production method capable of industrially obtaining propylene in a high yield using hydrocarbon as a raw material. Therefore, it can be utilized as a very useful technique in various fields using propylene.

Claims (7)

  In a method for producing a light olefin by catalytic conversion of a hydrocarbon raw material, a zeolite containing phosphorus and a rare earth element and containing at least one element of Groups 10 to 12 of the periodic table is used as a catalyst, and the zeolite A method for producing a light olefin, wherein the particle size of the supported group 10-12 element is 1 nm or less.   The method for producing a light olefin according to claim 1, wherein the elements of Groups 10 to 12 of the periodic table are at least one element selected from silver, zinc, and palladium.   The method for producing a light olefin according to claim 1 or 2, wherein the zeolite is a pentasil-type zeolite.   The method for producing a light olefin according to any one of claims 1 to 3, wherein the zeolite is a zeolite having an MFI type structure.   The method for producing a light olefin according to any one of claims 1 to 4, wherein the hydrocarbon raw material contains 10 mass% or more of hydrocarbons having 4 or more carbon atoms.   The method for producing a light olefin according to any one of claims 1 to 5, wherein the hydrocarbon raw material is butenes.   The method for producing a light olefin according to any one of claims 1 to 6, wherein the light olefin is mainly composed of propylene.