Catalyst for producing linear butene and use thereof

Abstract

To provide a novel catalyst for producing linear butene from a monoalcohol having 4 or more carbon atoms, particularly for producing 1-butene with high selectivity by dehydration of an n-butanol raw material.SOLUTION: The present invention provides a dehydration catalyst containing aluminum as an essential component, having diffraction peaks at diffraction angles 2θ of 36-39° and 66-68° in an X-ray diffraction pattern measured using Cu-Kα radiation, and exhibiting a peak intensity ratio R1 / R2 of 0.4 or more, where R1 is the maximum peak intensity within the range of 2θ=36-39° and R2 is the maximum peak intensity within the range of 2θ=66-68°. Use of this catalyst enables 1-butene to be produced stably and with high selectivity.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a catalyst for producing linear butene, a method for producing linear butene, and a method for producing butadiene using the obtained linear butene. [Background technology]

[0002] Butadienes such as 1,3-butadiene are used as raw materials for styrene-butadiene rubber (SBR) and other products. Traditionally, butadiene has been produced by refining C4 fractions, which are by-products of naphtha cracking, a process used to synthesize ethylene from petroleum. However, in recent years, efforts to derive chemical industrial raw materials from biomass-derived raw materials instead of petroleum-derived chemical industrial raw materials have been attracting attention. For example, there is a strong demand for technology to convert bioethanol and biobutanol derived from biomass, such as sugarcane and corn, into 1,3-butadiene.

[0003] As a method for producing conjugated dienes from biomass-derived raw materials, for example, a method has been developed in which ethanol is converted into acetaldehyde under heating in the presence of a catalyst, and then the ethanol and acetaldehyde are converted into 1,3-butadiene (Patent Documents 1 and 2). However, this method has the drawback that the butadiene yield is low at around 50%, and the catalyst is easily deteriorated by heat, making it difficult to recycle.

[0004] In addition, a method for producing 1,3-butadiene from a mixed gas containing n-butene and molecular oxygen by oxidative dehydrogenation of n-butene in the presence of a catalyst has been developed (Patent Documents 3 to 9). n-Butene can be produced by dehydration of n-butanol, a biomass-derived raw material, but the product is known to be a mixture of 1-butene and 2-butene, which has poor reactivity with 1-butene. Therefore, when producing n-butene from n-butanol, a technology is needed that can convert it to 1-butene in a higher yield.

[0005] Known solid acid catalysts used in the dehydration of monoalcohols include alumina, zeolite, zirconia, and titania. When n-butanol dehydration occurs in the presence of a solid acid catalyst, 1-butene is preferentially produced. However, the subsequent isomerization reaction produces cis-2-butene and trans-2-butene, resulting in a decrease in the yield of 1-butene. Prior art (Non-Patent Document 1) has revealed that the isomerization of 1-butene to 2-butene proceeds preferentially in the presence of a Brønsted acid and a base. However, no catalysts that suppress the isomerization of 1-butene are known. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2014 / 129248 [Patent Document 2] Special Publication No. 2017-532318 [Patent Document 3] International Publication No. 2014 / 086641 [Patent Document 4] Patent No. 6229201 [Patent Document 5] International Publication No. 2013 / 161702 [Patent Document 6] Patent No. 5908595 [Patent Document 7] Patent No. 6049156 [Patent Document 8] Patent No. 5825981 [Patent Document 9] International Publication No. 2009 / 119975 [Non-Patent Document 1] Journal of Catalysis, 330, 38-45, 2015 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention relates to a novel catalyst for synthesizing linear butene from monoalcohols having 4 or more carbon atoms, and more specifically, to a catalyst that enables highly selective production of 1-butene from n-butanol as a raw material by a dehydration reaction. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the isomerization reaction of 1-butene to 2-butene can be suppressed and 1-butene can be produced with high selectivity by using alumina, which is a pure Lewis acid having no Bronsted acid sites or basic sites, as a catalyst.

[0009] Furthermore, as a result of intensive research by the present inventors to further increase 1-butene selectivity, they discovered that it is possible to produce 1-butene highly selectively by dehydration reaction from n-butanol as a raw material by using a catalyst that contains aluminum as an essential component, has diffraction peaks at diffraction angles 2θ of 36 to 39° and 66 to 68° in an X-ray diffraction pattern using Cu-Kα radiation, and exhibits a peak intensity ratio R1 / R2 of 0.4 or more between the maximum peak intensity R1 in the range of 2θ = 36 to 39° and the maximum peak intensity R2 in the range of 2θ = 66 to 68°, thereby completing the present invention. Note that in this specification, the symbol "to" is intended to include the numerical values ​​before and after it as upper and lower limits.

[0010] That is, the present invention relates to the following 1) to 11). 1) Aluminum is an essential component, The X-ray diffraction pattern has diffraction peaks at diffraction angles 2θ of 36 to 39° and 66 to 68°, The peak intensity ratio R1 / R2 between the maximum peak intensity R1 in the range of 2θ=36 to 39° and the maximum peak intensity R2 in the range of 2θ=66 to 68° is 0.40 or more. Catalyst for the production of linear butene. 2) 1) The catalyst for producing linear butene according to 1), wherein R1 / R2 is 0.50 or more. 3) 1) The catalyst for producing linear butene according to 1), wherein R1 / R2 is 0.90 or more. 4) The catalyst for producing linear butene according to any one of 1) to 3), wherein the active component is alumina. 5) 4) The catalyst for producing linear butenes according to 4), wherein the alumina is γ-alumina or alumina hydrate. 6) 4) The catalyst for producing linear butene according to 4), wherein the alumina is boehmite. 7) The catalyst for producing linear butene according to any one of 1) to 6) above, further containing one or more fourth period elements. 8) A method for producing linear butene by dehydrating an alcohol having 4 carbon atoms using the catalyst according to any one of 1) to 7). 9) A method for producing 1-butene by dehydrating an alcohol having 4 carbon atoms using the catalyst according to any one of 1) to 7). 10) Using the catalyst according to any one of 1) to 7) Producing butadiene from n-butene obtained by dehydrating n-butanol. Method for producing butadiene. 11) Producing butadiene from 1-butene obtained by using the catalyst according to any one of 1) to 7). Method for producing butadiene. [Effects of the Invention]

[0011] The catalyst for producing linear butene (hereinafter sometimes simply referred to as catalyst) of the present invention makes it possible to highly selectively produce 1-butene from n-butanol through a dehydration reaction. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention relates to a catalyst that can be used in a reaction for producing linear butenes by dehydration from a mixed gas containing a monoalcohol having 4 or more carbon atoms and nitrogen as an inert gas, and preferably a catalyst that can be used in a reaction for selectively producing 1-butene by dehydration from a mixed gas containing n-butanol and nitrogen as an inert gas, and a method for producing the catalyst, which will be described in detail below.

[0013] [Maximum Peak Intensity Ratio R1 / R2 at Diffraction Angle 2θ Values ​​in the Ranges of 36-39° and 66-68° in the X-ray Diffraction Pattern] The catalyst of the present invention is characterized by the maximum peak intensity ratio R1 / R2 in the ranges of 2θ = 36-39° and 2θ = 66-68° in the X-ray diffraction pattern. This X-ray diffraction pattern was obtained using Cu-Kα, and specifically refers to the value obtained by dividing the peak intensity (R1) at 2θ = 36-39° by the maximum peak intensity (R2) in the range of 2θ = 66-68°. The X-ray diffraction angle (2θ) can be measured, for example, using an Ultima IV (manufactured by Rigaku Corporation) with CuKα X-rays (λ = 0.154 nm), an output of 40 kV, 30 mA, a measurement range of 10-60°, and a measurement rate of 10° per minute. However, the measurement method is not limited thereto as long as it does not deviate from the measurement principle.

[0014] The value of R1 of the catalyst for producing linear butene of the present invention, obtained by the above measurement method, is preferably 500 or more. The lower limit of R1 is more preferably 550, 600, 650, 700, 750, 800, or 850, in that order, and particularly preferably 880. The upper limit may be about 1,000, more preferably 950, and even more preferably 930. Therefore, the most preferable range for the value of R1 is 880 or more and 930 or less.

[0015] The R2 value of the catalyst for producing linear butene of the present invention, obtained by the above measurement method, is preferably 1000 or less. More preferred upper limits of R2 are, in order from top to bottom, 1000, 950, 900, 850, 800, and 750, and particularly preferably 730. The lower limit may be about 500, more preferably 600, and even more preferably 700. Therefore, the most preferred range for the R2 value is 700 or more and 730 or less.

[0016] The R1 / R2 ratio of the catalyst for producing linear butene of the present invention is 0.4 or more, which has a significant effect on the selectivity of 1-butene. The lower limit of R1 / R2 is preferably 0.45, 0.50, 0.55, 0.60, 0.70, 0.80, 0.90, 1.00, 1.05, 1.10, or 1.15, and particularly preferably 1.20. The upper limit may be about 2.00, more preferably 1.50, and even more preferably 1.30. Therefore, the most preferred range for R1 / R2 is 1.20 or more and 1.30 or less.

[0017] [Dehydration Catalyst Containing Aluminum as an Essential Component] The aluminum-based catalyst of the present invention is not particularly limited as long as it contains aluminum as an active component. Examples include zeolites, alumina, aluminum phosphate, silica-alumina phosphate, amorphous silica-alumina, aluminosilicates, phosphoric alumina, and any combination thereof. Alumina is particularly preferred from the viewpoint of 1-butene selectivity. The alumina crystal system is not particularly limited as long as it contains alumina consisting of one or more of monoclinic, tetragonal, and cubic alumina crystal phases. Various aluminas, such as α-alumina, β-alumina, γ-alumina, σ-alumina, θ-alumina, δ-alumina, η-alumina, and alumina hydrate, can be used as the crystal phase. From the viewpoints of activity and selectivity, γ-alumina, δ-alumina, θ-alumina, η-alumina, and alumina hydrate are particularly preferred, with γ-alumina and alumina hydrate being more preferred. Furthermore, boehmite, which is one of the alumina hydrates, is even more preferred. Alumina having these crystal forms may be used singly or in combination of two or more. When two or more types are used in combination, those with different crystal forms may be used, or they may be in a mixed phase crystal state. When two or more types are used in combination, the above R1 / R2 is measured by mixing two or more types as the catalyst of the present invention.

[0018] The alumina used in the catalyst of the present invention can be easily produced by known methods, including, for example, thermal decomposition, precipitation, deposition, kneading, or a combination of these methods. Examples of raw materials for alumina include nitrates, acetates, alkoxides, sulfates, chlorides, alkali aluminates, alum, and other materials that produce alumina or alumina hydrate upon heating or hydrolysis. Examples of alkalis used for hydrolysis include caustic alkalis, alkali carbonates, aqueous ammonia, and ammonium carbonate.

[0019] The shape of the alumina used in the catalyst of the present invention is not particularly limited and may be any shape such as spherical, granular, or cylindrical, but spherical is preferred.

[0020] Commercially available alumina may also be used for the catalyst of the present invention, such as NKHD-24 (trade name) manufactured by Sumitomo Chemical Co., Ltd., KHD-24 (trade name) manufactured by Sumitomo Chemical Co., Ltd., Neobead (registered trademark) GB-45 (trade name) manufactured by Mizusawa Industrial Chemicals, Inc., JRC-ALO-6 (trade name) manufactured by Nikki-Universal Co., Ltd., AA-101 (trade name) manufactured by Nippon Light Metal Co., Ltd., P112-01 255 FR (trade name) manufactured by Exacer Srl, and P112-01 155 FR (trade name) manufactured by Exacer Srl.

[0021] [Catalyst Surface Modification] The aluminum-based catalyst used in the present invention may be modified with various metal elements. The surface modification method is not particularly limited, but examples include dissolving a metal-containing compound in water to prepare an aqueous solution, and then impregnating the aluminum-based catalyst into the aqueous solution. Period 4 elements are preferred as the metal element. Supporting and modifying a basic element such as Zn weakens the Bronsted acid sites on the catalyst surface, thereby suppressing the isomerization reaction between 1-butene and 2-butene. Furthermore, the diffraction angle 2θ can be adjusted by surface modification. When modifying the surface with various metals, the modification can be performed appropriately while checking the R1 / R2 ratio. The amount of metal to be used is approximately 1 mmol to 0.1 mmol, and more preferably 0.5 mmol to 0.1 mmol, per gram of aluminum-based catalyst.

[0022] [Particle diameter of catalyst] The average particle diameter of the catalyst of the present invention can be determined by measuring the outer diameter of 10 catalyst particles using, for example, a vernier caliper (manufactured by Mitutoyo Corporation, product name "ABS Digimatic Caliper CD-AX") and taking the average value. The average particle diameter is preferably 1.0 mm to 15.0 mm, more preferably 1.5 mm to 10.0 mm, even more preferably 2.0 mm to 8.0 mm, and particularly preferably 2.0 mm to 4.0 mm.

[0023] [Specific Surface Area of ​​Catalyst] The specific surface area means the surface area per gram of precursor, and can be measured by methods known to those skilled in the art, without any particular restrictions. For example, it can be measured by the following method. That is, a sample volume of 0.05 mL to 3.0 mL is placed in a sample tube with an inner diameter of 7 mm, and pretreated at 300°C for 2 hours or more. Then, using a gas adsorption measurement device (Belsorp-mini (manufactured by MicrotrackBell)), measurements are made under the conditions of a nitrogen molecular diameter of 0.364 nm, a relative pressure ratio of 0.4, an adsorption temperature of -196°C, a measurement pore diameter range of 0.7 nm to 400 nm, and nitrogen as the adsorbed gas species. The measurement results are analyzed by the BET method to obtain the specific surface area value. The specific surface area of ​​the catalyst of the present invention is 200 m 2 / g~350m 2 / g, and more preferably 250m 2 / g~330m 2 / g, and more preferably 270m 2 / g~300m 2 / g, and particularly 280m 2 / g~300m 2 / g is preferred.

[0024] [Pore Volume of Catalyst] The pore volume of the catalyst of the present invention can be determined by mercury intrusion porosimetry, which involves applying pressure to mercury, which has a high surface tension, to force it into pores or gaps on the surface of a solid, and determining the pore distribution and pore volume from the relationship between the applied pressure and the volume of the mercury forced in. In this specification, the term "mercury intrusion porosimetry" is not particularly limited in detail as long as it is a common method, but examples include a method in which, without pretreatment, a fully automatic pore size distribution analyzer (Pore Master 60-GT (Quanta Chrome Co.)) is used to place a sample weight of about 5 g into a large cell (10 mmΦ×6 cm) with a cell volume of 2 cc, and measurements are performed under conditions of a mercury surface tension of 480 dyn / cm, a mercury contact angle of 140°, a measurement temperature of 20°C, and a measurement pore diameter range of 0.0036 μm to 400 μm, with the measurement results assuming that all pores are cylindrical, and analysis is performed using the pressure applied during measurement and the Washburn equation to obtain the pore size distribution of each pore diameter of the catalyst. The pore volume of the catalyst of the present invention is preferably 0.01 mL / g to 1.0 mL / g, more preferably 0.1 mL / g to 0.80 mL / g, even more preferably 0.30 mL / g to 0.75 mL / g, and particularly preferably 0.40 mL / g to 0.70 mL / g.

[0025] [Use of the Catalyst of the Present Invention] The catalyst of the present invention is used in a dehydration reaction to obtain 1-butene from n-butanol. Specifically, this method obtains 1-butene by continuously contacting a mixed gas containing n-butanol with the catalyst of the present invention. The mixed gas may contain other gas components as long as they do not interfere with the dehydration reaction of n-butanol. Examples of other gas components include oxygen, air, and nitrogen. 1-butene is produced by filling a reaction tube having a diameter of several tens of centimeters with the catalyst of the present invention, and contacting and flowing the mixed gas at a constant flow rate under an atmosphere of 200°C to 400°C.

[0026] The catalyst for producing linear butene of the present invention is extremely useful in the reaction for obtaining 1-butene by the dehydration reaction of n-butanol. That is, 1-butene can be obtained with high selectivity and high yield using n-butanol as a starting material. The effect obtained here is also very useful in terms of yield in the subsequent process of converting 1-butene to butadiene by oxidative dehydration. Therefore, the present invention is a catalyst that can obtain 1-butene from n-butanol with high selectivity and high yield, and also contributes to high yield, high selectivity, and stable operation in the industrial production of butadiene. [Example]

[0027] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Hereinafter, for convenience, "parts by mass" may be written as "parts." The 1-butene selectivity in the examples and comparative examples was calculated using the following formula: 1-butene selectivity (mol %) = (number of moles of 1-butene produced) / (number of moles of n-butanol reacted) × 100

[0028] Measurement of X-ray diffraction of catalysts X-ray powder diffraction spectra were obtained in all examples using a Rigaku Ultima IV with Cu-Kα radiation (X-ray power: 40 kV / 30 mA, Kα1 wavelength: 1.5406 Å).

[0029] [Example 1] NKHD-24 (trade name) manufactured by Sumitomo Chemical Co., Ltd. was used as a catalyst. The ratio R1 (3 The catalyst was spherical, with a particle diameter of 3.1 mm and a specific surface area of ​​290 m 2 / g, and the pore volume was 0.6 mL / g.

[0030] [Example 2] KHD-24 (trade name) manufactured by Sumitomo Chemical Co., Ltd. was used as a catalyst. The ratio R1 (38.4°) / R2 (67.4°) of the peak intensity R1 at a diffraction angle 2θ = 38.4° to the peak intensity R2 at a diffraction angle 2θ = 67.4° was 0.90. The catalyst was spherical in shape, had a particle diameter of 3.3 mm, and a specific surface area of ​​280 m 2 / g, and the pore volume was 0.38 mL / g.

[0031] Example 3: AA-101 (trade name) manufactured by Nippon Light Metal Co., Ltd. was used as the catalyst. Since the catalyst was a powder, it was tableted, solidified, pulverized, and classified through a 6.5 to 10 mesh to obtain a molded product. The ratio R1 (37.7°) / R2 (66.9°) of the peak intensity R1 at a diffraction angle 2θ = 37.7° to the peak intensity R2 at a diffraction angle 2θ = 66.9° was 0.90.

[0032] Example 4: Alumina surface-modified with Zn (NKHD-24, product name, manufactured by Sumitomo Chemical Co., Ltd.) was used as the catalyst. (Catalyst Surface Modification) 2.68 g (0.014 mol) of zinc nitrate was dissolved in 100 g of pure water. 30 g of NHKD-24 was added to 100 g of this solution and stirred at room temperature for 3 hours. The stirred solution was then heated to a temperature between 80°C and 100°C to evaporate and solidify. The resulting solid was dried at 100°C for 5 hours. It was then calcined at 600°C for 5 hours to obtain a Zn-modified catalyst. In X-ray diffraction analysis of the modified catalyst, the ratio R1 (37.5°) / R2 (67.1°) of the peak intensity R1 at a diffraction angle 2θ = 37.5° to the peak intensity R2 at a diffraction angle 2θ = 67.1° was 0.59. The average particle size of the catalyst was 3.1 mm.

[0033] Comparative Example 1: P112-01 255 FR (trade name) manufactured by Exacer Srl was used as a catalyst. The ratio R1 (37.3°) / R2 (66.8°) of the peak intensity R1 at a diffraction angle 2θ = 37.3° to the peak intensity R2 at a diffraction angle 2θ = 66.8° was 0.37. The catalyst was cylindrical, with an average particle diameter of 3.5 mm and a specific surface area of ​​253 m. 2 / g.

[0034] Comparative Example 2 Neobead (registered trademark) GB-45 (product name) manufactured by Mizusawa Chemical Industries, Ltd. was used as a catalyst. The ratio R1 (37.0°) / R2 (66.6°) of the peak intensity R1 at a diffraction angle 2θ = 37.0° to the peak intensity R2 at a diffraction angle 2θ = 66.6° was 0.32. The catalyst was spherical in shape, had an average particle diameter of 3.8 mm, and a specific surface area of ​​180 m 2 / g, and the pore volume was 0.5 mL / g.

[0035] Comparative Example 3: JRC-ALO-6 (trade name) manufactured by Nikki-Universal Co., Ltd. was used as a catalyst. The ratio R1 (37.0°) / R2 (66.8°) of the peak intensity R1 at a diffraction angle 2θ = 37.0° to the peak intensity R2 at a diffraction angle 2θ = 66.8° was 0.24. The catalyst was spherical, with an average particle size of 3.4 mm and a specific surface area of ​​180 m 2 / g.

[0036] Comparative Example 4: P112-01 155 FR (trade name) manufactured by Exacer Srl was used as a catalyst. The ratio R1 (37.0°) / R2 (67.2°) of the peak intensity at a diffraction angle 2θ = 37.0° to the peak intensity at a diffraction angle 2θ = 67.2° was 0.35. The catalyst was spherical, with an average particle size of 3.6 mm and a specific surface area of ​​149 m. 2 / g.

[0037] [Dehydration Reaction] The catalysts of the above Examples and Comparative Examples were evaluated for reaction by the following method. 7.5 g of the catalyst was packed into a stainless steel reaction tube, and a feed gas (composition (molar ratio) of n-butanol:nitrogen=1:9) was added at a space velocity (WHSV) of 5 h -1 The dehydration reaction of n-butanol was carried out under the conditions shown below. The reaction bath temperature was adjusted between 250°C and 450°C, and the 1-butene selectivity was calculated when the n-butanol conversion rate was 95 mol%.

[0038] Table 1 shows the results of the ratios R1 / R2 of peak intensities at diffraction angles 2θ=36 to 39° and 66 to 68° and the 1-butene selectivity for Examples 1 to 4 and Comparative Examples 1 to 4.

[0039] [Table 1]

[0040] As is clear from Table 1, the catalyst according to the present invention makes it possible to produce 1-butene with high selectivity. [Industrial Applicability]

[0041] The present invention provides a catalyst capable of highly selectively producing 1-butene from 1-butanol as a raw material through a dehydration reaction. Therefore, in a gas-phase catalytic oxidation reaction using the catalyst, 1-butene can be obtained with higher selectivity and yield.

Claims

1. Aluminum is an essential component, The X-ray diffraction pattern has diffraction peaks at diffraction angles 2θ of 36 to 39° and 66 to 68°, Maximum peak intensity R within the range of 2θ = 36 to 39° １ and the maximum peak intensity R within the range of 2θ = 66 to 68° ２ The peak intensity ratio R １ / R ２ A catalyst for producing linear butene, characterized in that

2. The R １ / R ２ 2. The catalyst for producing linear butene according to claim 1, wherein the β-

3. The R １ / R ２ 2. The catalyst for producing linear butene according to claim 1, wherein the β-dispersion constant is 0.90 or more.

4. 4. The catalyst for producing linear butenes according to claim 1, wherein the active component is alumina.

5. 5. The catalyst for producing linear butenes according to claim 4, wherein the alumina is γ-alumina or alumina hydrate.

6. 5. The catalyst for producing linear butenes according to claim 4, wherein the alumina is boehmite.

7. The catalyst for producing linear butene according to any one of claims 1 to 3, further comprising one or more fourth period elements.

8. A method for producing linear butene by dehydrating a C4 alcohol using the catalyst according to any one of claims 1 to 3.

9. A method for producing 1-butene by dehydrating a C4 alcohol using the catalyst according to any one of claims 1 to 3.

10. 4. The method of producing butadiene from n-butene obtained by dehydrating n-butanol using the catalyst according to claim 1. Method for producing butadiene.

11. Producing butadiene from 1-butene obtained using the catalyst according to any one of claims 1 to 3. Method for producing butadiene.

Images