Method for producing propylene

Abstract

To provide a method for producing propylene capable of producing propylene with a comparatively excellent yield.SOLUTION: A method for producing propylene pertaining to the present invention includes: a reaction process A of obtaining a crude product (A) from a raw material including ethanol in the presence of a catalyst (A); and a reaction process B of obtaining a crude product (B) from the crude product (A) in the presence of a catalyst (B), where compositions of the catalyst (A) and the catalyst (B) are mutually different, the catalyst (A) includes at least two metals M and N selected from the group consisting of zirconium or the like, the mole ratio of the metal M to the metal N is less than 100, and the amount of an acid sites of the catalyst (B) is 50 μ mol / g or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing propylene. [Background technology]

[0002] Propylene is one of the major products in the petrochemical industry, and is obtained by thermally cracking raw materials such as naphtha and fractionating the resulting cracked gas. Polypropylene, which is made from propylene, is a commonly used resin, and there is a demand for technology that can efficiently produce the raw material propylene.

[0003] Patent Document 1 discloses an invention of a zirconium catalyst for producing propylene using ethanol as a starting material. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2012 / 077723 Summary of the Invention [Problem to be solved by the invention]

[0005] In a conventional method for producing propylene from ethanol using a zirconium catalyst, increasing the activity of the zirconium catalyst increases the amount of by-products produced, resulting in a decrease in the yield of propylene. On the other hand, decreasing the activity of the zirconium catalyst also decreases the yield of propylene, which is the target product. In other words, the method for producing propylene has a problem in that it is difficult to improve the yield of propylene.

[0006] The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing propylene that can produce propylene in a relatively good yield. [Means for solving the problem]

[0007] The method for producing propylene according to the present invention comprises the steps of: a reaction step A in which a crude product (A) is obtained from a raw material containing ethanol in the presence of a catalyst (A); a reaction step B of obtaining a crude product (B) containing propylene, carbon dioxide, and hydrogen from the crude product (A) in the presence of a catalyst (B) containing zirconium, the catalyst (A) and the catalyst (B) have different compositions, The catalyst (A) comprises at least two metals M and N, the metal M is one metal selected from the group consisting of zirconium, indium, and cerium; the metal N is one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, cerium, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium; the molar ratio of the metal M to the metal N in the catalyst (A) is less than 100; The catalyst (B) has an acid site amount of 50 μmol / g or more as measured at 100 to 500° C. by an ammonia temperature programmed desorption method. [Effects of the Invention]

[0008] According to the present invention, there is provided a method for producing propylene, which is capable of producing propylene in a relatively good yield. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0010] The method for producing propylene according to this embodiment includes a reaction step A in which a crude product (A) is obtained from a raw material containing ethanol in the presence of a catalyst (A), and a reaction step B in which a crude product (B) containing propylene, carbon dioxide, and hydrogen is obtained from the crude product (A) in the presence of a catalyst (B) containing zirconium.

[0011] [Reaction Step A] In the reaction step A, a crude product (A) is obtained from a raw material containing ethanol in the presence of a catalyst (A).

[0012] The raw material in the propylene production method according to this embodiment includes ethanol. The raw material may further include, for example, acetone, 2-propanol, and water. In a first aspect, the raw material includes acetone. In a second aspect, the raw material includes 2-propanol. In a third aspect, the raw material includes acetone and 2-propanol. When the raw material includes at least one of acetone and 2-propanol, the propylene yield can be further improved. In a fourth aspect, the raw material includes water.

[0013] The ethanol can be produced by various methods, including, for example, ethanol produced by the hydration reaction of petrochemical-derived ethylene, ethanol produced by decomposing sugars such as glucose, fructose, and sucrose, ethanol obtained by distilling wood vinegar, ethanol synthesized from carbon monoxide and hydrogen obtained by decomposing waste plastics, and ethanol synthesized from carbon dioxide and hydrogen.

[0014] The 2-propanol can be produced by various production methods. For example, isopropyl alcohol derived from fossil resources or isopropyl alcohol derived from biomass (also referred to as bioisopropyl alcohol) can be used as the 2-propanol. Examples of bioisopropyl alcohol include isopropyl alcohol obtained from plant-derived raw materials using isopropyl alcohol-producing bacteria (see WO 2009 / 008377), isopropyl alcohol obtained by reducing acetone obtained using bioethanol, and isopropyl alcohol obtained by hydrating propylene obtained using bioethanol. The 2-propanol is preferably recycled and used by supplying 2-propanol produced as a by-product in the propylene production method according to this embodiment to the raw material.

[0015] The acetone that can be used is produced by various production methods. For example, acetone derived from fossil resources or acetone derived from fermentation may be used. The acetone is preferably recycled and used by supplying acetone produced as a by-product in the propylene production method according to this embodiment to the raw material.

[0016] When the raw material contains acetone, the molar ratio of ethanol to acetone in the raw material is preferably 2 or more and 1,000 or less, and more preferably 4 or more and 1,000 or less.

[0017] When the raw material contains 2-propanol, the molar ratio of ethanol to 2-propanol in the raw material is preferably 12 or more and 1,000 or less, and more preferably 30 or more and 1,000 or less.

[0018] When the raw material contains water, the molar ratio of ethanol to water in the raw material is preferably 0.25 or more and 100 or less, and more preferably 0.3 or more and 100 or less.

[0019] The content of the water contained in the raw material is preferably 10 mol % or more and 70 mol % or less, and more preferably 25 mol % or more and 65 mol % or less, relative to the total of 100 mol % of the components contained in the raw material.

[0020] The content of the ethanol contained in the raw material is preferably 10 mol % or more, and more preferably 12 mol % or more and 70 mol % or less, relative to the total of 100 mol % of the components contained in the raw material.

[0021] In one aspect of the method for producing propylene according to the present embodiment, the raw material contains water, and the content of the water contained in the raw material is 10 mol % or more and 70 mol % or less, relative to 100 mol % in total of the components contained in the raw material, and the content of the ethanol contained in the raw material is 10 mol % or more.

[0022] In one embodiment, reaction step A is carried out by bringing the raw material into contact with the catalyst (A). In reaction step A, the raw material is preferably in a vaporized state by preheating when it comes into contact with the catalyst (A). That is, the propylene production method according to this embodiment may have a preheating step of vaporizing the raw material before reaction step A is carried out.

[0023] A mixed gas obtained by mixing vaporized raw materials with nitrogen gas may be used in reaction step A. The molar ratio of raw materials to nitrogen gas in the mixed gas is preferably 4 or more and 1,000 or less, more preferably 9 or more and 1,000 or less.

[0024] The gas mixture may further include, for example, oxygen, carbon dioxide, saturated hydrocarbons such as methane, hydrogen, helium, and water vapor.

[0025] The preheating step is preferably carried out at a temperature of 150° C. or higher and 550° C. or lower in order to sufficiently vaporize the raw material.

[0026] Reaction step A can be carried out using a reactor. Examples of reactors include an external heat exchange type fixed bed reactor, an adiabatic fixed bed reactor, a fluidized bed reactor, a simulated moving bed reactor, a riser type fluidized bed reactor, and a radial flow type fixed bed reactor. One type of reactor may be used, or two or more types may be used in combination.

[0027] The reaction temperature in reaction step A is preferably 300°C or higher and 550°C or lower, more preferably 350°C or higher and 495°C or lower, and even more preferably 380°C or higher and 490°C or lower. When reaction step A is carried out using a reactor, the temperature of the mixed gas inside the reactor may be used as the reaction temperature. The reactor may be equipped with a thermometer inside the reactor for measuring the temperature of the mixed gas inside the reactor.

[0028] The space velocity A, which is expressed as the ratio of the volumetric feed rate of the raw material to the catalyst packed volume in the reaction step A, is preferably 500 / h or more and 15,000 / h or less. The space velocity A is the volumetric feed rate (Nm 3 / h) and the catalyst packing volume (m 3 ) can be calculated by dividing by

[0029] The reaction pressure in the reaction step A is preferably 0 MPa-G or more and 4 MPa-G or less.

[0030] In one embodiment, the crude product (A) contains acetone and 2-propanol. The crude product (A) may further contain ethylene.

[0031] [Reaction Step B] In the reaction step B, a crude product (B) containing propylene, carbon dioxide, and hydrogen is obtained from the crude product (A) in the presence of a catalyst (B) containing zirconium.

[0032] In one embodiment, reaction step B is carried out by bringing crude product (A) into contact with catalyst (B). In reaction step B, crude product (A) is preferably kept warm during the period from reaction step A until the crude product (A) is transferred to reaction step B from reaction step A, thereby maintaining the crude product (A) in a gasified state when the crude product (A) contacts catalyst (B). That is, the propylene production method according to this embodiment may include a warming step or a reheating step for maintaining the crude product (A) in a gasified state after reaction step A and before reaction step B is carried out.

[0033] The temperature-keeping step or the reheating step is preferably carried out at a temperature of 150° C. or higher and 550° C. or lower, from the viewpoint of sufficiently maintaining the crude product (A) in a vaporized state.

[0034] The reaction temperature in reaction step B is preferably 250°C or higher and 550°C or lower, more preferably 300°C or higher and 500°C or lower, and even more preferably 380°C or higher and 495°C or lower. When reaction step B is carried out using a reactor, the temperature of the crude product (A) in a vaporized state inside the reactor may be used as the reaction temperature. The reactor may be equipped with a thermometer therein for measuring the temperature of the crude product (A) in a vaporized state inside the reactor. In one aspect of the method for producing propylene according to this embodiment, the reaction temperature in reaction step A is 300°C or higher and 550°C or lower, and the reaction temperature in reaction step B is 250°C or higher and 550°C or lower.

[0035] The space velocity B, which is the ratio of the volumetric supply rate of the crude product (A) to the catalyst packed volume in the reaction step B, is preferably 500 / h or more and 45,000 / h or less. The space velocity B is the volumetric supply rate (Nm 3 / h) and the catalyst packing volume (m 3 ) can be calculated by dividing by

[0036] The reactor used in reaction step B and the reaction pressure in reaction step B are the same as those in reaction step A. In addition, reaction step A and reaction step B in this embodiment may be performed in one reactor, or may be performed in different reactors.

[0037] In one embodiment, the crude product (B) further comprises acetone. The crude product (B) may further comprise 2-propanol or ethylene.

[0038] The propylene production method according to this embodiment may include a separation step of separating acetone and / or 2-propanol from the crude product (B) after the reaction step B. The propylene production method according to this embodiment may include a recycling step of recycling the acetone and / or 2-propanol separated in the separation step by supplying them to the raw materials.

[0039] [Catalyst (A) and Catalyst (B)] The catalyst (A) contains at least two metals, M and N.

[0040] The metal M is one metal selected from the group consisting of zirconium, indium, and cerium, and is preferably zirconium.

[0041] The metal N is one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, cerium, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium. The metal N is preferably one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, cerium, neodymium, copper, silver, manganese, and zinc, more preferably one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, neodymium, copper, manganese, and zinc, and even more preferably one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, lanthanum, cerium, and neodymium.

[0042] However, since the metal M and the metal N are two different metals, this does not include the case where both the metal M and the metal N are cerium.

[0043] The catalyst (B) contains zirconium and preferably further contains one metal P selected from the group consisting of indium, cerium, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium.

[0044] The zirconium in the catalyst (A) and the catalyst (B) may be organic zirconium or inorganic zirconium. The catalyst (A) and the catalyst (B) preferably contain inorganic zirconium as the zirconium.

[0045] Examples of organic zirconium include zirconium alkoxides such as zirconium propoxide and zirconium butoxide; zirconium chelates such as zirconium tetraacetylacetonate and zirconium monoacetylacetonate; and zirconocene compounds such as zirconocene dichloride and zirconocene chloride hydride.

[0046] Examples of inorganic zirconium include zirconium oxide, zirconium chloride, potassium hexafluorozirconate, ammonium zirconium carbonate, potassium zirconium carbonate, zirconium carbonate n-hydrate, zirconium oxide dichloride n-hydrate, zirconium dinitrate oxide n-hydrate, zirconium acetate, zirconium nitrate, and zirconium hydroxide.

[0047] The zirconium is preferably zirconium oxide.

[0048] In one embodiment, the zirconium content in each of the catalysts (A) and (B) is 40.0% by mass or more, and preferably 50.0% by mass or more and 74.0% by mass or less, more preferably 55.0% by mass or more and 74.0% by mass or less.

[0049] The zirconium content of catalyst (A) and catalyst (B) can be determined by acid dissolution / inductively coupled plasma atomic emission spectrometry analysis, which can be performed using, for example, Agilent 5800 (Agilent Technologies) or Optima 8300 (PerkinElmer).

[0050] In the method for producing propylene according to this embodiment, the catalyst (A) and the catalyst (B) have different compositions.

[0051] In one aspect of the propylene production method according to the present embodiment, the molar ratio of the metal M to the metal N in the catalyst (A) is less than 100, and the amount of acid sites in the catalyst (B) measured by an ammonia temperature programmed desorption method at 100 to 500°C is 50 μmol / g or more.

[0052] The molar ratio of the metal M to the metal N in the catalyst (A) is preferably 0.1 or more and 70 or less, more preferably 0.5 or more and 50 or less, and even more preferably 1.0 or more and 30 or less. When the molar ratio of the metal M to the metal N in the catalyst (A) is within the above-mentioned range, the number of acid sites in the catalyst (A) measured at 100 to 500°C by an ammonia temperature programmed desorption method can be adjusted to a value suitable for the reaction step A. As a result, the propylene production method according to this embodiment can further improve the propylene yield.

[0053] The amount of the acid sites in the catalyst (B) is preferably 70 μmol / g or more and 500 μmol / g or less, and more preferably 80 μmol / g or more and 300 μmol / g or less.

[0054] The molar ratio of zirconium to the metal P in the catalyst (B) may be 20 or more and 10,000 or less.

[0055] In another aspect of the propylene production method according to the present embodiment, the catalyst (A) has an acid site amount of 100 μmol / g or less as measured by an ammonia temperature programmed desorption method at 100 to 500°C, and the catalyst (B) has an acid site amount of 50 μmol / g or more as measured by an ammonia temperature programmed desorption method at 100 to 500°C.

[0056] The amount of acid sites in the catalyst (A) is preferably 100 μmol / g or less, more preferably 1 μmol / g or more and 80 μmol / g or less, and the amount of acid sites in the catalyst (B) is preferably 70 μmol / g or more and 500 μmol / g or less, more preferably 80 μmol / g or more and 300 μmol / g or less.

[0057] The amount of acid sites in catalyst (A) and catalyst (B) can be measured by an ammonia adsorption-desorption method, for example, using a temperature-programmed desorption apparatus TPD-1-Atw (manufactured by Microtrack Bell) according to the following measurement method.

[0058] 50 mg of catalyst was weighed and placed under vacuum at 500°C for 60 minutes. The temperature was then lowered to 100°C, and 0.5% ammonia / helium was passed through at 100 mL / min for 30 minutes at 100°C to adsorb the ammonia onto the catalyst surface. Helium was then passed through the catalyst at 50 mL / min for 30 minutes at 100°C. The catalyst was then heated from 100°C to 500°C at a heating rate of 10°C / min while passing helium through at 50 mL / min. The amount of desorbed ammonia was measured using a quadrupole mass spectrometer. The amount of ammonia desorbed per unit mass was calculated from the area value of the TPD spectrum obtained by the absolute calibration curve method, and this was determined as the number of acid sites per unit mass of the catalyst.

[0059] Methods for adjusting the number of acid sites in catalyst (A) and catalyst (B) include, for example, adjusting the amount of metal other than zirconium added, treatment with an inorganic compound having acidity such as sulfuric acid, and adjusting the catalyst calcination temperature.

[0060] The method for adjusting the number of acid sites of catalyst (A) and catalyst (B) means adjusting the number of active sites on the catalyst. That is, diluting the catalyst with a substance that does not contribute to acid sites, such as silicon carbide, silica gel, or alumina, is not included in the method for adjusting the number of acid sites of the present invention. Therefore, the number of acid sites quantified in the method for measuring the number of acid sites is the value quantified when using only the catalyst without a diluent.

[0061] In one aspect of the propylene production method according to the present embodiment, the metal N in the catalyst (A) and the metal P in the catalyst (B) are each calcium, and the calcium content in the catalyst (A) is greater than the calcium content in the catalyst (B). By increasing the calcium content in the catalyst, the number of acid sites can be reduced.

[0062] The calcium content per catalyst mass of the catalyst (A) may be 0.70% by mass or more and 23.0% by mass or less, and the calcium content per catalyst mass of the catalyst (B) may be 0.001% by mass or more and 1.50% by mass or less. The calcium content per catalyst mass of the catalyst (A) is preferably 0.75% by mass or more and 15.0% by mass or less, and more preferably 1.50% by mass or more and 10.0% by mass or less. The calcium content per catalyst mass of the catalyst (B) is preferably 0.002% by mass or more and 1.00% by mass or less, and more preferably 0.002% by mass or more and 0.50% by mass or less.

[0063] In the propylene production method according to the present embodiment, since the calcium content per catalyst mass of the catalyst (A) satisfies the above-mentioned lower limit, it is possible to suppress the production of by-products in reaction step A, thereby further improving the propylene yield. In the propylene production method according to the present embodiment, since the calcium content per catalyst mass of the catalyst (B) satisfies the above-mentioned upper limit, it is possible to promote the dehydration reaction of 2-propanol in reaction step B, thereby further improving the propylene yield.

[0064] In another aspect of the propylene production method according to the present embodiment, the metal N in the catalyst (A) is neodymium, the metal P in the catalyst (B) is calcium, and the neodymium content in the catalyst (A) is greater than the calcium content in the catalyst (B). By making the neodymium content in the catalyst (A) greater than the calcium content in the catalyst (B), the number of acid sites in the catalyst (A) can be made smaller than the number of acid sites in the catalyst (B).

[0065] The neodymium content per catalyst mass of the catalyst (A) may be 0.80% by mass or more and 15.0% by mass or less, and the calcium content per catalyst mass of the catalyst (B) may be 0.001% by mass or more and 1.50% by mass or less. The neodymium content per catalyst mass of the catalyst (A) is preferably 1.50% by mass or more and 12.0% by mass or less, and more preferably 3.0% by mass or more and 12.0% by mass or less. The calcium content per catalyst mass of the catalyst (B) is preferably 0.002% by mass or more and 1.00% by mass or less, and more preferably 0.002% by mass or more and 0.50% by mass or less.

[0066] In the propylene production method according to this embodiment, since the neodymium content per catalyst mass of the catalyst (A) satisfies the above-mentioned lower limit, it is possible to suppress the production of by-products in reaction step A, thereby further improving the propylene yield. In the propylene production method according to this embodiment, since the calcium content per catalyst mass of the catalyst (B) satisfies the above-mentioned upper limit, it is possible to promote the dehydration reaction of 2-propanol in reaction step B, thereby further improving the propylene yield.

[0067] The calcium content in catalyst (A) and catalyst (B) and the neodymium content in catalyst (A) can be determined by the method for measuring the zirconium content described above. The same applies when catalyst (A) and catalyst (B) contain metals other than zirconium, calcium, and neodymium.

[0068] The shape of the catalyst (A) and the catalyst (B) is not particularly limited, and may be, for example, a powder form, a granular form, a pelletized form, a spherical form, or an extruded form.

[0069] When catalyst (A) and catalyst (B) are in the form of pellets, the pellet diameter of catalyst (A) and catalyst (B) is preferably 1.0 mm or more and 10.0 mm or less, more preferably 1.5 mm or more and 4.0 mm or less.

[0070] When catalyst (A) and catalyst (B) are in the form of granules, the particle size of catalyst (A) and catalyst (B) is preferably 0.15 mm or more and 1.00 mm or less, more preferably 0.30 mm or more and 0.60 mm or less.

[0071] By having the pellet diameter or particle size of catalyst (A) and catalyst (B) within the above numerical range, sufficient surface area can be ensured for catalyst (A) and catalyst (B), thereby suppressing the generation of unreacted by-products.

[0072] The structure of catalyst (A) and catalyst (B) may be a crystalline structure such as a monoclinic, tetragonal, or cubic structure, or may be a non-crystalline structure such as an amorphous structure. The structure of catalyst (A) and catalyst (B) is preferably a crystalline structure, more preferably a monoclinic structure.

[0073] When catalyst (A) and catalyst (B) have a crystalline structure, the crystalline structure can be identified by X-ray diffraction, which can be either single crystal X-ray diffraction or powder X-ray diffraction.

[0074] In the propylene production method according to this embodiment, the mass ratio of the amount of catalyst (A) filled to the amount of catalyst (B) filled is preferably 0.1 or more and 10 or less, and more preferably 0.3 or more and 5 or less.

[0075] Propylene produced by the propylene production method according to this embodiment can be suitably used as a raw material for synthesizing various compounds, such as polypropylene, propylene oxide, resorcinol, methionine, acrylonitrile, epichlorohydrin, acrylic acid, and phenol.

[0076] The propylene production method according to this embodiment can produce propylene in a relatively good yield by being carried out in the above-described manner.

[0077] The present invention includes the following aspects. [1] a reaction step A in which a crude product (A) is obtained from a raw material containing ethanol in the presence of a catalyst (A); a reaction step B of obtaining a crude product (B) containing propylene, carbon dioxide, and hydrogen from the crude product (A) in the presence of a catalyst (B) containing zirconium, the catalyst (A) and the catalyst (B) have different compositions, The catalyst (A) comprises at least two metals M and N, the metal M is one metal selected from the group consisting of zirconium, indium, and cerium; the metal N is one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, cerium, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium; the molar ratio of the metal M to the metal N in the catalyst (A) is less than 100; The catalyst (B) has an acid site amount of 50 μmol / g or more as measured by an ammonia temperature-programmed desorption method at 100 to 500°C. Propylene production method. [2] a reaction step A in which a crude product (A) is obtained from a raw material containing ethanol in the presence of a catalyst (A); a reaction step B of obtaining a crude product (B) containing propylene, carbon dioxide, and hydrogen from the crude product (A) in the presence of a catalyst (B) containing zirconium, the catalyst (A) and the catalyst (B) have different compositions, The catalyst (A) comprises at least two metals M and N, the metal M is one metal selected from the group consisting of zirconium, indium, and cerium; the metal N is one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, cerium, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium; the catalyst (A) has an acid site content of 100 μmol / g or less as measured by an ammonia temperature-programmed desorption method at 100 to 500°C; The catalyst (B) has an acid site amount of 50 μmol / g or more as measured by an ammonia temperature-programmed desorption method at 100 to 500°C. Propylene production method. [3] the reaction temperature in the reaction step A is 300°C or higher and 550°C or lower, The reaction temperature in the reaction step B is 250°C or higher and 550°C or lower. The method for producing propylene according to [1] or [2]. [4] The raw material includes acetone. The method for producing propylene according to any one of [1] to [3]. [5] The raw material contains 2-propanol. The method for producing propylene according to any one of [1] to [4]. [6] The raw material comprises acetone and 2-propanol. The method for producing propylene according to any one of [1] to [5]. [7] the metal M is zirconium; the content of zirconium in each of the catalyst (A) and the catalyst (B) is 40.0% by mass or more; The method for producing propylene according to any one of [1] to [6]. [8] The zirconium is zirconium oxide. [7] The method for producing propylene according to [7]. [9] The catalyst (B) further contains one metal P selected from the group consisting of indium, cerium, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium; The method for producing propylene according to any one of [1] to [8].

[10] the metal N in the catalyst (A) and the metal P in the catalyst (B) are each calcium; the calcium content of the catalyst (A) is greater than the calcium content of the catalyst (B); [9] The method for producing propylene according to [9].

[11] The content of calcium in the catalyst (A) per catalyst mass is 0.70 mass% or more and 23.0 mass% or less, and The content of calcium in the catalyst (B) per catalyst mass is 0.001 mass% or more and 1.50 mass% or less.

[10] The method for producing propylene according to

[10] .

[12] The metal N in the catalyst (A) is neodymium, The metal P in the catalyst (B) is calcium, The content of the neodymium in the catalyst (A) is greater than the content of the calcium in the catalyst (B). [9] The method for producing propylene according to [9].

[13] The content of the neodymium in the catalyst (A) per catalyst mass is 0.80 mass% or more and 15.0 mass% or less, and The content of calcium in the catalyst (B) per catalyst mass is 0.001 mass% or more and 1.50 mass% or less.

[12] The method for producing propylene according to

[12] .

[14] The raw material contains water, With respect to the total 100 mol% of the components contained in the raw materials, the content of the water contained in the raw material is 10 mol % or more and 70 mol % or less, The content of the ethanol contained in the raw material is 10 mol% or more. The method for producing propylene according to any one of [1] to

[13] .

[0078] The propylene production method according to the present invention is not limited to the above-described embodiment, and various modifications are possible without departing from the spirit of the present invention. In addition, the configurations, methods, etc. of embodiments other than those described above may be arbitrarily adopted and combined, and the configurations, methods, etc. of one embodiment described above may be applied to the configurations, methods, etc. of other embodiments described above. [Example]

[0079] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0080] The catalysts (A) and (B) prepared in each preparation example were measured by the following methods.

[0081] <Composition of catalyst (A) and catalyst (B)> The compositions of catalysts (A) and (B), described below, were measured using an Agilent 5800 (Agilent Technologies) and an Optima 8300 (PerkinElmer). The zirconium contents in catalysts (A) and (B), the metal nitrogen content in catalyst (A), and the metal phosphorus content in catalyst (B) were measured using acid dissolution / inductively coupled plasma atomic emission spectrometry. The molar ratio of zirconium to metal nitrogen or metal phosphorus was calculated from the zirconium content, metal nitrogen content, and metal phosphorus content obtained by the measurements.

[0082] <Amount of acid sites in catalyst (A) and catalyst (B)> The amount of acid sites in catalysts (A) and (B) was measured by the ammonia adsorption-desorption method using a temperature-programmed desorption apparatus TPD-1-Atw (Microtrack Bell) according to the following method.

[0083] 50 mg of catalyst was weighed and placed under vacuum at 500°C for 60 minutes. The temperature was then lowered to 100°C, and 0.5% ammonia / helium was passed through at 100 mL / min for 30 minutes at 100°C to adsorb ammonia onto the catalyst surface. Helium was then passed through at 50 mL / min for 30 minutes at 100°C. The catalyst was then heated from 100°C to 500°C at a heating rate of 10°C / min while passing helium through at 50 mL / min. The amount of ammonia desorbed was measured using a quadrupole mass spectrometer. The amount of ammonia desorbed per unit mass was calculated from the area value of the TPD spectrum obtained by the absolute calibration curve method, and this was determined as the number of acid sites per unit mass of the catalyst.

[0084] Catalyst (A) and catalyst (B) were prepared by the following method.

[0085] [Preparation Example 1] Zirconium oxide (RC-100, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) was sized to 0.3-0.6 mm. To 20 g of sized zirconium oxide, 10.7 g of a solution consisting of 2.60 g of calcium acetate monohydrate (manufactured by Nacalai Tesque, Inc.) and 8.1 g of Millipore water purified with Simplicity UV (manufactured by Merck) was added in small increments while allowing the mixture to penetrate, yielding a pore-filled material. This pore-filled material was held in air at 120°C for 3 hours and then in air at 500°C for 2 hours, yielding 21 g of catalyst (A-1). In catalyst (A-1), the content of zirconium as metal M was 64% by mass, the content of calcium as metal N was 2.7% by mass, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 73 μmol / g.

[0086] [Preparation Example 2] The same procedure as in Preparation Example 1 was carried out except that the mass of calcium acetate monohydrate was changed from 2.60 g to 0.26 g, to obtain 20 g of catalyst (B-1). In catalyst (B-1), the zirconium content was 67 mass%, the calcium content as metal P was 0.29 mass%, the molar ratio of zirconium to metal P was 110, and the number of acid sites was 120 μmol / g.

[0087] [Preparation Example 3] The same procedure as in Preparation Example 1 was performed, except that the mass of zirconium oxide after sieving was changed from 20 g to 8 g and the amount of calcium acetate monohydrate was changed from 2.60 g to 0.95 g, to obtain 9 g of catalyst (A-2). In catalyst (A-2), the content of zirconium as metal M was 56 mass%, the content of calcium as metal N was 4.2 mass%, the molar ratio of zirconium to metal N was 6, and the amount of acid sites was 64 μmol / g.

[0088] [Preparation Example 4] The same procedure as in Preparation Example 3 was performed except that the mass of calcium acetate monohydrate was changed from 0.95 g to 0.52 g, to obtain 8 g of catalyst (A-3). In catalyst (A-3), the content of zirconium as metal M was 64 mass%, the content of calcium as metal N was 1.3 mass%, the molar ratio of zirconium to metal N was 22, and the amount of acid sites was 58 μmol / g.

[0089] [Preparation Example 5] The same procedure as in Preparation Example 3 was carried out except that 0.60 g of lithium acetate dihydrate was used instead of calcium acetate monohydrate, to obtain 8 g of catalyst (A-4). In catalyst (A-4), the content of zirconium as metal M was 63 mass%, the content of lithium as metal N was 0.46 mass%, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 7 μmol / g.

[0090] [Preparation Example 6] The same procedure as in Preparation Example 3 was carried out except that 0.48 g of sodium acetate was used instead of calcium acetate monohydrate, to obtain 8 g of catalyst (A-5). In catalyst (A-5), the content of zirconium as metal M was 63 mass%, the content of sodium as metal N was 0.96 mass%, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 12 μmol / g.

[0091] [Preparation Example 7] The same procedure as in Preparation Example 3 was carried out except that 0.58 g of potassium acetate was used instead of calcium acetate monohydrate, to obtain 8 g of catalyst (A-6). In catalyst (A-6), the content of zirconium as metal M was 62 mass%, the content of potassium as metal N was 2 mass%, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 6.8 μmol / g.

[0092] [Preparation Example 8] The same procedure as in Preparation Example 3 was carried out except that 0.87 g of rubidium nitrate was used instead of calcium acetate monohydrate, to obtain 9 g of catalyst (A-7). In catalyst (A-7), the content of zirconium as metal M was 60 mass%, the content of rubidium as metal N was 4.8 mass%, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 8.5 μmol / g.

[0093] [Preparation Example 9] The same procedure as in Preparation Example 3 was carried out except that 0.58 g of cesium nitrate was used instead of calcium acetate monohydrate, to obtain 8 g of catalyst (A-8). In catalyst (A-8), the content of zirconium as metal M was 60 mass%, the content of cesium as metal N was 4.3 mass%, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 9.2 μmol / g.

[0094] [Preparation Example 10] The same procedure as in Preparation Example 3 was carried out except that 1.51 g of magnesium nitrate hexahydrate was used instead of calcium acetate monohydrate, to obtain 8 g of catalyst (A-9). In catalyst (A-9), the content of zirconium as metal M was 57 mass%, the content of magnesium as metal N was 1.5 mass%, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 65 μmol / g.

[0095] [Preparation Example 11] The same procedure as in Preparation Example 3 was carried out except that 1.25 g of strontium nitrate was used instead of calcium acetate monohydrate, to obtain 9 g of catalyst (A-10). In catalyst (A-10), the content of zirconium as metal M was 59 mass%, the content of strontium as metal N was 5.3 mass%, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 9.7 μmol / g.

[0096] [Preparation Example 12] The same procedure as in Preparation Example 3 was carried out except that 1.51 g of barium acetate was used instead of calcium acetate monohydrate, to obtain 9 g of catalyst (A-11). In catalyst (A-11), the content of zirconium as metal M was 57 mass%, the content of barium as metal N was 8.3 mass%, the molar ratio of zirconium to metal N was 11, and the amount of acid sites was 9.4 μmol / g.

[0097] [Preparation Example 13] The same procedure as in Preparation Example 3 was performed, except that 2.59 g of neodymium nitrate hexahydrate was used instead of calcium acetate monohydrate, to obtain 9 g of catalyst (A-12). In catalyst (A-12), the content of zirconium as metal M was 65 mass%, the content of neodymium as metal N was 9.3 mass%, the molar ratio of zirconium to metal N was 11, and the number of acid sites was 21 μmol / g. The contents of zirconium and neodymium in catalyst (A-12) were calculated by converting the amounts of zirconium oxide and neodymium nitrate hexahydrate to the masses of zirconium and neodymium alone and dividing each by the mass of catalyst (A-12) (9 g).

[0098] [Preparation Example 14] The same procedure as in Preparation Example 3 was carried out except that 0.59 g of manganese acetate tetrahydrate was used instead of calcium acetate monohydrate, to obtain 8 g of catalyst (A-13). In catalyst (A-13), the content of zirconium as metal M was 63 mass%, the content of manganese as metal N was 1.5 mass%, the molar ratio of zirconium to metal N was 27, and the amount of acid sites was 93 μmol / g.

[0099] [Preparation Example 15] The same procedure as in Preparation Example 3 was carried out except that 0.79 g of cobalt nitrate hexahydrate was used instead of calcium acetate monohydrate, to obtain 9 g of catalyst (A-14). In catalyst (A-14), the content of zirconium as metal M was 65 mass%, the content of cobalt as metal N was 1.9 mass%, the molar ratio of zirconium to metal N was 24, and the amount of acid sites was 76 μmol / g.

[0100] [Preparation Example 16] The same procedure as in Preparation Example 3 was carried out except that 0.34 g of silver nitrate was used instead of calcium acetate monohydrate, to obtain 9 g of catalyst (A-15). In catalyst (A-15), the content of zirconium as metal M was 67 mass%, the content of silver as metal N was 2.3 mass%, the molar ratio of zirconium to metal N was 32, and the amount of acid sites was 63 μmol / g.

[0101] [Preparation Example 17] The same procedure as in Preparation Example 1 was carried out, except that the mass of zirconium oxide after sieving was changed from 20 g to 10 g and 0.28 g of yttrium nitrate hexahydrate was used instead of calcium acetate monohydrate, to obtain 10 g of catalyst (B-2). In catalyst (B-2), the zirconium content was 68 mass%, the yttrium content as metal P was 0.57 mass%, the molar ratio of zirconium to metal P was 110, and the number of acid sites was 150 μmol / g.

[0102] [Preparation Example 18] The same procedure as in Preparation Example 3 was carried out except that 0.04 g of zinc nitrate hexahydrate was used instead of calcium acetate monohydrate, to obtain 9 g of catalyst (B-3). In catalyst (B-3), the zirconium content was 66 mass%, the zinc content as metal P was 0.1 mass%, the molar ratio of zirconium to metal P was 500, and the amount of acid sites was 170 μmol / g.

[0103] For catalyst (A) and catalyst (B) obtained in each preparation example, the zirconium content, metal N or metal P content, molar ratio of zirconium to metal N or metal P, and number of acid sites are shown in Table 1.

[0104] [Table 1]

[0105] Example 1 2 g of catalyst (A-1) was packed into a quartz reactor 1 with an inner diameter of 12 cm and a sheath tube with an inner diameter of 6 mm inserted therein, and 1 g of catalyst (B-1) was packed into a reactor 2 having the same shape as reactor 1. Reactor 1 and reactor 2 were connected in series. The raw materials, ethanol and water, were heated to 180°C in a preheater and vaporized, and then nitrogen was supplied to form a mixed gas. The ethanol / water / nitrogen molar ratio in the mixed gas was set to 38.0 / 45.0 / 17.0. The mixed gas was supplied to reactor 1 at a rate of 54 NmL / min. The reaction pressure was 0.5 MPa-G and the reaction temperature was 450°C. The mixed gas was brought into contact with catalyst (A-1) in reactor 1 to react, yielding crude product (A). The crude product (A) was continuously discharged from the outlet of reactor 1 so that the internal pressure of reactor 1 was 0.5 MPa-G. The gas flowing out from the outlet of reactor 1 was supplied directly to reactor 2 through a heat-insulated pipe. The reaction pressure was set to 0.5 MPa-G and the reaction temperature to 450°C, and the crude product (A) was brought into contact with the catalyst (B-1) in reactor 2 to carry out a reaction, thereby obtaining a crude product (B) consisting of a mixture of liquid and gas. The crude product (B) was continuously collected from the outlet of reactor 2 so that the internal pressure of reactor 2 was 0.5 MPa-G. The time from the start of the reaction until the crude product (B) was collected from the outlet of reactor 2 was 1.5 hours.

[0106] Example 2 The reaction was carried out in the same manner as in Example 1, except that the raw materials were ethanol, water, and acetone, and the molar ratio of ethanol / water / acetone / nitrogen in the mixed gas was 36.4 / 45.0 / 1.6 / 17.0.

[0107] Example 3 The reaction was carried out in the same manner as in Example 1, except that the raw materials were ethanol, water, and 2-propanol, the molar ratio of ethanol / water / 2-propanol / nitrogen in the mixed gas was 38.0 / 49.0 / 3.0 / 10.0, reactor 1 was filled with 4 g of catalyst (A-1), and reactor 2 was filled with 2 g of catalyst (B-1).

[0108] Example 4 The reaction was carried out in the same manner as in Example 1, except that the raw materials were ethanol, water, and acetone, the molar ratio of ethanol / water / acetone / nitrogen in the mixed gas was 13.8 / 60.0 / 6.2 / 20.0, reactor 1 was filled with 8 g of catalyst (A-1), and reactor 2 was filled with 2 g of catalyst (B-1).

[0109] Example 5 The reaction was carried out in the same manner as in Example 1, except that reactor 1 was filled with 1 g of catalyst (A-2) instead of catalyst (A-1), and reactor 2 was filled with 2 g of catalyst (B-1).

[0110] Example 6 The reaction was carried out in the same manner as in Example 1, except that the molar ratio of ethanol / water / nitrogen in the mixed gas was 41.3 / 48.6 / 10.1, 1 g of catalyst (A-3) was packed in reactor 1 instead of catalyst (A-1), and 2 g of catalyst (B-1) was packed in reactor 2.

[0111] Example 7 The reaction was carried out in the same manner as in Example 6, except that 1 g of catalyst (A-4) was packed into the reactor 1 instead of the catalyst (A-3).

[0112] Example 8 The reaction was carried out in the same manner as in Example 6, except that 1 g of catalyst (A-12) was packed into the reactor 1 instead of the catalyst (A-3).

[0113] Example 9 The reaction was carried out in the same manner as in Example 6, except that 1 g of catalyst (A-13) was packed into the reactor 1 instead of the catalyst (A-3).

[0114] Example 10 The reaction was carried out in the same manner as in Example 6, except that 1 g of catalyst (A-1) was loaded into reactor 1 instead of catalyst (A-3), and 2 g of catalyst (B-2) was loaded into reactor 2 instead of catalyst (B-1).

[0115] (Comparative Example 1) The reaction was carried out in the same manner as in Example 1, except that 1 g of catalyst (A-1) was packed into reactor 2 instead of catalyst (B-1).

[0116] (Comparative Example 2) The reaction was carried out in the same manner as in Example 1, except that 2 g of catalyst (B-1) was packed into the reactor 1 instead of the catalyst (A-1).

[0117] The crude product (B) collected in each example and comparative example was analyzed by gas chromatography, and the composition of the crude product (B) was calculated using the following formula (1). Composition of crude product (B) = (number of moles of carbon in crude product (B)) / (number of moles of carbon in raw materials used in the reaction) × 100 (%) (1)

[0118] The crude product (B) consisted mainly of propylene, acetone, 2-propanol, ethylene, and carbon dioxide.

[0119] In the composition of the crude product (B), the amount of hydrogen produced that was not contained in the above-mentioned main component was calculated by the following formula (2). Amount of hydrogen produced = (number of moles of hydrogen atoms produced) / (number of moles of hydrogen atoms in the organic compound used as the raw material in the reaction) × 100 (%) (2)

[0120] The composition of the crude product (B) was determined by gas chromatography under the following conditions.

[0121] Hydrogen was measured under the following conditions after pretreatment of the sample gas using a backflush column manufactured by Agilent. Quantitative determination was performed by converting the area value to mol% using the absolute calibration curve method. Measuring device: 990 Micro GC (manufactured by Agilent) Measurement column: MS5A (length: 10 m) Measurement detector:TCD Measurement temperature condition: 80℃ Carrier gas: Argon Carrier gas control method: Pressure control (190KPa)

[0122] Carbon dioxide, ethylene, and propylene were measured under the following conditions after pretreatment of the sample gas using a backflush column manufactured by Agilent. Quantitative analysis was performed by converting area values ​​to mol% using the absolute calibration curve method. Measuring device: 990 Micro GC (manufactured by Agilent) Measurement column: PoraPLOT Q (length: 10 m) Measurement detector:TCD Measurement temperature condition: 100℃ Carrier gas: Helium Carrier gas control method: Pressure control (190KPa)

[0123] Acetone and 2-propanol were measured under the following conditions. Quantitative analysis was performed by converting area values ​​into mol% using the absolute calibration curve method. Measuring device: GC-2014s (Shimadzu Corporation) Measurement column: DB-WAX (length 60m) Measurement detector: FID Measurement temperature conditions: 40℃ (held for 27 minutes) Heat up to 200°C (20°C / min) 200℃ (held for 5 minutes) Carrier gas: Helium Carrier gas control method: Linear speed control (20 cm / sec)

[0124] The results of each example and each comparative example are shown in Table 2.

[0125] [Table 2]

[0126] As can be seen from Table 2, the production methods of the examples that satisfy the constituent requirements of the present invention provide better results in terms of propylene yield than the production methods of the comparative examples.

[0127] From the above, it can be seen that the present invention can provide a method for producing propylene that can produce propylene in a relatively good yield.

Claims

1. a reaction step A of obtaining a crude product (A) from a raw material containing ethanol in the presence of a catalyst (A); a reaction step B of obtaining a crude product (B) containing propylene, carbon dioxide, and hydrogen from the crude product (A) in the presence of a catalyst (B) containing zirconium, the catalyst (A) and the catalyst (B) have different compositions, The catalyst (A) comprises at least two metals M and N, the metal M is one metal selected from the group consisting of zirconium, indium, and cerium; the metal N is one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, cerium, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium; the molar ratio of the metal M to the metal N in the catalyst (A) is less than 100; the catalyst (B) has an acid site amount of 50 μmol / g or more as measured by an ammonia temperature-programmed desorption method at 100 to 500°C; Propylene production method.

2. a reaction step A of obtaining a crude product (A) from a raw material containing ethanol in the presence of a catalyst (A); a reaction step B of obtaining a crude product (B) containing propylene, carbon dioxide, and hydrogen from the crude product (A) in the presence of a catalyst (B) containing zirconium, the catalyst (A) and the catalyst (B) have different compositions, The catalyst (A) comprises at least two metals M and N, the metal M is one metal selected from the group consisting of zirconium, indium, and cerium; the metal N is one metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, cerium, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium; the catalyst (A) has an acid site content of 100 μmol / g or less as measured by an ammonia temperature-programmed desorption method at 100 to 500°C; the catalyst (B) has an acid site amount of 50 μmol / g or more as measured by an ammonia temperature-programmed desorption method at 100 to 500°C; Propylene production method.

3. The reaction temperature in the reaction step A is 300° C. or higher and 550° C. or lower, The reaction temperature in the reaction step B is 250°C or higher and 550°C or lower. The method for producing propylene according to claim 1 or 2.

4. The raw material includes acetone. The method for producing propylene according to claim 1 or 2.

5. The raw material contains 2-propanol. The method for producing propylene according to claim 1 or 2.

6. The raw material comprises acetone and 2-propanol. The method for producing propylene according to claim 1 or 2.

7. the metal M is zirconium; The content of zirconium in each of the catalyst (A) and the catalyst (B) is 40.0 mass% or more. The method for producing propylene according to claim 1 or 2.

8. The zirconium is zirconium oxide. The method for producing propylene according to claim 7.

9. the catalyst (B) further contains one metal P selected from the group consisting of indium, cerium, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, yttrium, lanthanum, neodymium, copper, silver, titanium, vanadium, manganese, iron, cobalt, nickel, zinc, gallium, and germanium; The method for producing propylene according to claim 8.

10. The metal N in the catalyst (A) and the metal P in the catalyst (B) are each calcium, the calcium content in the catalyst (A) is greater than the calcium content in the catalyst (B); The method for producing propylene according to claim 9.

11. The content of calcium in the catalyst (A) per catalyst mass is 0.70 mass% or more and 23.0 mass% or less, and The content of calcium per catalyst mass of the catalyst (B) is 0.001 mass% or more and 1.50 mass% or less. The method for producing propylene according to claim 10.

12. The metal N in the catalyst (A) is neodymium, The metal P in the catalyst (B) is calcium, The content of the neodymium in the catalyst (A) is greater than the content of the calcium in the catalyst (B). The method for producing propylene according to claim 9.

13. The content of the neodymium per catalyst mass of the catalyst (A) is 0.80 mass% or more and 15.0 mass% or less, and The content of calcium per catalyst mass of the catalyst (B) is 0.001 mass% or more and 1.50 mass% or less. The method for producing propylene according to claim 12.

14. The raw material contains water, With respect to the total 100 mol% of the components contained in the raw materials, the content of the water contained in the raw material is 10 mol% or more and 70 mol% or less, The content of the ethanol contained in the raw material is 10 mol% or more. The method for producing propylene according to claim 1 or 2.

Images