JP2013095672A - Method for producing propylene - Google Patents
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- -1 ethylene, propylene, butene Chemical class 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、プロピレンの製造方法に関する。 The present invention relates to a method for producing propylene.
プロピレンは、工業的には主にナフサのクラッキング反応によって、エチレンが製造される際の副産物として生産されている。 Propylene is industrially produced as a by-product when ethylene is produced mainly by naphtha cracking reaction.
こうした工業的な手法とは異なり、ある種のゼオライト触媒を用いると、低級炭化水素や低級オキシジェネートからプロピレン等の低級オレフィンを合成することができる。その反応機序については、原料であるエチレンのオリゴマー化に続き、高級オレフィンの分解が起こることによってプロピレンが生成される一方、副反応としてアルカンが生成されることにより、プロピレンが消失することが知られている（非特許文献１）。このプロピレンの生成反応は一般に、反応圧力を増加させると反応が促進される（エチレン転化率が向上する）が、同時に、アルカン等の副生成物が生成してプロピレンの選択率（収率）が低下する。 Unlike such industrial methods, when a certain type of zeolite catalyst is used, a lower olefin such as propylene can be synthesized from a lower hydrocarbon or a lower oxygenate. Regarding the reaction mechanism, it is known that propylene is generated by the decomposition of higher olefins following the oligomerization of ethylene, which is a raw material, while propylene is lost by the formation of alkanes as a side reaction. (Non-Patent Document 1). In general, the propylene production reaction is promoted by increasing the reaction pressure (the ethylene conversion rate is improved). At the same time, by-products such as alkanes are produced and the propylene selectivity (yield) is increased. descend.
特許文献１には、ＣＨＡ型アルミノシリケートを用いたプロピレンの製造方法が開示されている。本文献では、加圧することによりパラフィン類等の副生成物が生成され、プロピレンの選択率が低下すること、また、反応圧力を減少させると、反応が遅くなることが記載されている。実施例で用いられている反応圧力は、常圧である０．１ＭＰａである。 Patent Document 1 discloses a method for producing propylene using CHA type aluminosilicate. In this document, it is described that by-products such as paraffins are generated by pressurization, the selectivity of propylene is lowered, and that the reaction is slowed down when the reaction pressure is decreased. The reaction pressure used in the examples is 0.1 MPa, which is a normal pressure.
特許文献２には、エタノールを原料としたプロピレンの製造方法が開示されている。本文献では、１０員環ゼオライト（ＭＦＩ型アルミノシリケート、Ｐ−ＺＳＭ−５）を用いて、低温反応器（３００〜４５０℃）でエタノールの脱水及びエチレンのオリゴマー化を行った後、高温反応器（４５０〜６００℃）でクラッキングによりプロピレンを製造している。また、このエタノールの脱水及びエチレンのオリゴマー化における反応圧力は、０．２ＭＰａ以上にすると有利であることが記載されている。この圧力範囲は、加圧することにより反応器中のエチレン濃度を増加させ、エチレンの消失反応を促進させるために採用されているが、エチレン転化率は向上する（反応が促進される）ものの、副反応も生じ、プロピレンやブテン等のオレフィン選択率は低下している。 Patent Document 2 discloses a method for producing propylene using ethanol as a raw material. In this document, a 10-membered ring zeolite (MFI-type aluminosilicate, P-ZSM-5) is used, and after dehydration of ethanol and oligomerization of ethylene in a low-temperature reactor (300 to 450 ° C.), a high-temperature reactor Propylene is produced by cracking at (450 to 600 ° C.). Further, it is described that the reaction pressure in the dehydration of ethanol and the oligomerization of ethylene is advantageously 0.2 MPa or more. This pressure range is adopted to increase the ethylene concentration in the reactor by pressurization and promote the disappearance reaction of ethylene. However, although the ethylene conversion is improved (the reaction is promoted), A reaction also occurs, and the selectivity for olefins such as propylene and butene is reduced.
このように、低級炭化水素（例えば、エチレン）や低級オキシジェネート（例えば、エタノール）から低級オレフィン（例えば、プロピレン）を製造する方法では一般に、反応圧力を増加させると反応が促進される（エチレン転化率が向上する）一方、副生成物が生成してプロピレン選択率が低下することが問題となる。 As described above, in a method for producing a lower olefin (for example, propylene) from a lower hydrocarbon (for example, ethylene) or a lower oxygenate (for example, ethanol), the reaction is generally promoted by increasing the reaction pressure (ethylene. On the other hand, a problem arises in that by-products are produced and propylene selectivity is lowered.
そこで、本発明は、反応圧力を増加させることにより、反応が促進されるだけでなく、プロピレンの選択率も向上する、プロピレンの製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing propylene which not only promotes the reaction but also improves the selectivity of propylene by increasing the reaction pressure.
本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、プロピレンの製造方法において、８員環ゼオライトを用いて、圧力を０．２ＭＰａ以上にすることによって、原料の転化率が向上するだけでなく、プロピレン選択率も向上することを見い出し、本発明を完成させるに至った。即ち、本発明は、以下の発明を包含する。 As a result of intensive studies to solve the above-mentioned problems, the present inventor improves the conversion rate of raw materials by using 8-membered ring zeolite and setting the pressure to 0.2 MPa or more in the method for producing propylene. In addition, the inventors have found that propylene selectivity is improved, and have completed the present invention. That is, the present invention includes the following inventions.
［１］８員環ゼオライトを含む触媒を用いて、０．２ＭＰａ以上の圧力下で、炭化水素及びオキシジェネートからなる群より選択される少なくとも１種の原料からプロピレンを製造する方法。
［２］圧力が０．５ＭＰａ以上である、［１］に記載の方法。
［３］８員環ゼオライトがＣＨＡ構造を有する、［１］又は［２］に記載の方法。
［４］８員環ゼオライトがシリコアルミノフォスフェートである、［３］に記載の方法。
［５］８員環ゼオライトの平均粒子径が１．０μｍ以下である、［１］〜［４］のいずれかに記載の方法。
［６］８員環ゼオライトの平均粒子径が０．７μｍ以下である、［１］〜［４］のいずれかに記載の方法。
［７］原料が、Ｃ１−６炭化水素及びＣ１−６オキシジェネートからなる群より選択される少なくとも１種である、［１］〜［６］のいずれかに記載の方法。
[1] A method for producing propylene from at least one raw material selected from the group consisting of hydrocarbons and oxygenates under a pressure of 0.2 MPa or more using a catalyst containing 8-membered ring zeolite.
[2] The method according to [1], wherein the pressure is 0.5 MPa or more.
[3] The method according to [1] or [2], wherein the 8-membered ring zeolite has a CHA structure.
[4] The method according to [3], wherein the 8-membered zeolite is silicoaluminophosphate.
[5] The method according to any one of [1] to [4], wherein the average particle size of the 8-membered ring zeolite is 1.0 μm or less.
[6] The method according to any one of [1] to [4], wherein the average particle diameter of the 8-membered ring zeolite is 0.7 μm or less.
[7] The method according to any one of [1] to [6], wherein the raw material is at least one selected from the group consisting of C 1-6 hydrocarbons and C 1-6 oxygenates.
本発明によると、反応圧力を増加させることにより、原料の転化率が向上するだけでなく、プロピレン選択率も向上させて、プロピレンを製造することができる。 According to the present invention, by increasing the reaction pressure, not only the conversion rate of the raw materials is improved, but also the propylene selectivity is improved, and propylene can be produced.
以下、本発明を詳細に説明する。
本発明で用いられる８員環ゼオライトは、細孔が酸素の８員環で構成されているゼオライトであり、その骨格構造としては、特に限定されず、例えば、ＡＦＸ、ＣＡＳ、ＣＨＡ、 ＤＤＲ、ＥＲＩ、ＥＳＶ、ＧＩＳ、ＧＯＯ、ＩＴＥ、ＪＢＷ、ＫＦＩ、ＬＥＶ、ＬＴＡ、ＭＥＲ、ＭＯＮ、ＭＴＦ、ＰＡＵ、ＰＨＩ、ＲＨＯ、ＲＴＥ、ＲＴＨが挙げられる。このうち、本発明のゼオライトの構造としては、ＡＦＸ、ＣＨＡ、ＤＤＲ、ＥＲＩ、ＬＥＶ、ＲＨＯ、ＲＴＨが好ましく、より好ましくはＣＨＡである。
Hereinafter, the present invention will be described in detail.
The 8-membered zeolite used in the present invention is a zeolite whose pores are composed of 8-membered rings of oxygen, and the skeleton structure is not particularly limited. For example, AFX, CAS, CHA, DDR, ERI ESV, GIS, GOO, ITE, JBW, KFI, LEV, LTA, MER, MON, MTF, PAU, PHI, RHO, RTE, and RTH. Among these, as the structure of the zeolite of the present invention, AFX, CHA, DDR, ERI, LEV, RHO, and RTH are preferable, and CHA is more preferable.
本発明におけるＣＨＡ構造を有する８員環ゼオライトとしては、具体的には、構成元素がケイ素及びアルミニウムからなるアルミノシリケートや、ケイ素、アルミニウム及びリンからなるシリコアルミノホスフェート等が挙げられるが、シリコアルミノホスフェートが好ましく、より好ましくはＳＡＰＯ−３４、ＳＡＰＯ−４４又はＳＡＰＯ−４７である。 Specific examples of the 8-membered ring zeolite having a CHA structure in the present invention include aluminosilicates whose constituent elements are silicon and aluminum, and silicoaluminophosphates which are composed of silicon, aluminum and phosphorus, and silicoaluminophosphates. Is more preferable, and SAPO-34, SAPO-44 or SAPO-47 is more preferable.
本発明で用いられる８員環ゼオライトは、プロピレンの選択率を向上させる点から、平均粒子径が１．０μｍ以下のものが好ましく、より好ましくは０．７μｍ以下、さらに好ましくは０．５μｍ以下、特に好ましくは０．２μｍ以下の平均粒子径を有する。 The 8-membered ring zeolite used in the present invention preferably has an average particle size of 1.0 μm or less, more preferably 0.7 μm or less, and still more preferably 0.5 μm or less, from the viewpoint of improving the selectivity of propylene. Particularly preferably, it has an average particle diameter of 0.2 μm or less.
このような８員環ゼオライトの製造方法としては、特に限定されず、例えば米国特許第４５４４５３８号明細書に記載の製造方法のような公知の方法を用いることができる。通常、水熱合成法により製造することができ、水熱合成後にイオン交換、脱アルミニウム処理、含浸等で組成を変化させたものも使用できる。また、担体や結合剤等を混合して触媒とすることもできる。 A method for producing such an 8-membered ring zeolite is not particularly limited, and for example, a known method such as a production method described in US Pat. No. 4,544,538 can be used. Usually, it can be produced by a hydrothermal synthesis method, and the one whose composition is changed by ion exchange, dealumination treatment, impregnation or the like after hydrothermal synthesis can also be used. In addition, a carrier, a binder and the like can be mixed to form a catalyst.
本発明のプロピレンの製造方法では、上記の８員環ゼオライトを含む触媒を用いて、０．２ＭＰａ以上の圧力下で、炭化水素及びオキシジェネートからなる群より選択される少なくとも１種を原料として製造する。 In the method for producing propylene of the present invention, using the catalyst containing the above 8-membered ring zeolite, at least one selected from the group consisting of hydrocarbon and oxygenate is used as a raw material under a pressure of 0.2 MPa or more. To manufacture.
炭化水素としては、例えば、アルカン及びアルケンが挙げられ、好ましくはＣ１−１２アルカン及びＣ２−１２アルケン等のＣ１−１２炭化水素、より好ましくはＣ１−８アルカン及びＣ２−８アルケン等のＣ１−８炭化水素、特に好ましくはＣ１−６アルカン及びＣ２−６アルケン等のＣ１−６炭化水素を使用する。前記炭化水素は、本発明の目的を損なわない範囲でプロピレンを含むことができる。 Examples of the hydrocarbon include, for example, alkanes and alkenes, preferably C 1-12 C 1-12 hydrocarbons such as alkanes and C 2-12 alkene, more preferably C 1-8 alkane and C 2-8 alkene C 1-8 hydrocarbons etc., particularly preferably using a C 1-6 hydrocarbon such as C 1-6 alkanes and C 2-6 alkene. The said hydrocarbon can contain a propylene in the range which does not impair the objective of this invention.
オキシジェネートとしては、例えば、アルコール、エーテル及びカルボニル化合物（アルデヒド、ケトン、カルボン酸、カーボネート等）が挙げられ、好ましくはＣ１−１２アルコール、Ｃ２−１２エーテル及びＣ１−１２カルボニル化合物等のＣ１−１２オキシジェネート、より好ましくはＣ１−８アルコール、Ｃ２−８エーテル及びＣ１−８カルボニル化合物等のＣ１−８オキシジェネート、特に好ましくはＣ１−６アルコール、Ｃ２−６エーテル及びＣ１−６カルボニル化合物等のＣ１−６オキシジェネートを使用する。 Examples of oxygenates include alcohols, ethers and carbonyl compounds (aldehydes, ketones, carboxylic acids, carbonates, etc.), preferably C 1-12 alcohols, C 2-12 ethers, C 1-12 carbonyl compounds, and the like. C 1-12 oxygenates, more preferably C 1-8 alcohols, C 1-8 oxygenates such as C 2-8 ether and C 1-8 carbonyl compounds, particularly preferably C 1-6 alcohol, C C 1-6 oxygenates such as 2-6 ether and C 1-6 carbonyl compounds are used.
炭化水素及びオキシジェネートのより具体的な例としては、例えば、ブタン、ヘキサン、エチレン、メタノール、エタノール、プロパノール、ジメチルエーテル、メチルエチルエーテル、ジエチルエーテル、ホルムアルデヒド、ジメチルケトン、酢酸、ジメチルカーボネート等を挙げることができる。このうち、エチレン又はエタノールを使用することが特に好ましい。 More specific examples of hydrocarbons and oxygenates include butane, hexane, ethylene, methanol, ethanol, propanol, dimethyl ether, methyl ethyl ether, diethyl ether, formaldehyde, dimethyl ketone, acetic acid, dimethyl carbonate, and the like. be able to. Among these, it is particularly preferable to use ethylene or ethanol.
原料はそのまま供給してもよいし、希釈ガスとの混合ガスとして供給してもよい。希釈ガスとしては原料が気体で存在する条件下において気体で存在し、原料からプロピレンへの変換に悪影響を与えないものであれば特に限定されない。例えば、不活性ガスの窒素やアルゴン等を使用することができる。工業的に利用するためには原料を高濃度で使用することが好ましい。例えば、原料濃度（モル比）が５０％以上であることが好ましく、７０％以上であることがより好ましく、９０％以上であることが特に好ましい。また、水（水蒸気）を共存させてもよい。 The raw material may be supplied as it is or may be supplied as a mixed gas with a dilution gas. The diluent gas is not particularly limited as long as it exists in a gaseous state under conditions where the raw material is present in a gaseous state and does not adversely affect the conversion of the raw material into propylene. For example, an inert gas such as nitrogen or argon can be used. In order to use industrially, it is preferable to use a raw material in high concentration. For example, the raw material concentration (molar ratio) is preferably 50% or more, more preferably 70% or more, and particularly preferably 90% or more. Further, water (water vapor) may coexist.
反応圧力は、プロピレンの選択率を向上させる点から、０．２ＭＰａ（絶対圧、以下同様）以上であることが必要であり、適宜０．５ＭＰａ以上、場合によっては０．６ＭＰａ以上の圧力を使用することができる。反応圧力の上限は、実用的な圧力範囲であればよく、特に限定されないが、通常１．０ＭＰａ以下、好ましくは０．８ＭＰａ以下である。 The reaction pressure needs to be 0.2 MPa (absolute pressure, the same shall apply hereinafter) or more from the viewpoint of improving the selectivity of propylene, and a pressure of 0.5 MPa or more, or 0.6 MPa or more is used as appropriate. can do. The upper limit of the reaction pressure is not particularly limited as long as it is within a practical pressure range, but is usually 1.0 MPa or less, preferably 0.8 MPa or less.
反応温度は、原料が効率的かつ選択的にプロピレンに変換されれば特に限定されないが、例えば、２００〜７００℃が好ましく、３００〜６００℃がより好ましい。 Although reaction temperature will not be specifically limited if a raw material is efficiently and selectively converted into propylene, For example, 200-700 degreeC is preferable and 300-600 degreeC is more preferable.
空間速度ＷＨＳＶ（ｈ−１）は、エタノール等の反応原料の流量（ｇ／ｈ）を触媒重量（ｇ）で除して求められる。ここで、触媒重量とは、触媒の造粒・成型に使用する不活性成分や結合剤を含まない触媒活性成分の重量である。本発明において、空間速度は特に限定されないが、通常０．０１〜５００ｈ−１であり、０．１〜１００ｈ−１がより好ましい。 The space velocity WHSV (h −1 ) is obtained by dividing the flow rate (g / h) of a reaction raw material such as ethanol by the catalyst weight (g). Here, the catalyst weight is the weight of a catalyst active component that does not contain an inactive component or a binder used for granulation / molding of the catalyst. In the present invention, the space velocity is not particularly limited, but is usually 0.01 to 500 h −1 , more preferably 0.1 to 100 h −1 .
以下、実施例により本発明をさらに具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the scope of the present invention is not limited thereto.
固体酸触媒の物性評価
結晶形態及び結晶径は、ＳＥＭ（走査型電子顕微鏡）（ＪＣＭ−５１００、日本電子）で得られた画像により評価した。平均粒子径は、異なる３視野の画像中から、５０〜１００個のゼオライトを任意に選択して、相加平均をとることにより算出した。
Evaluation of Physical Properties of Solid Acid Catalyst The crystal form and the crystal diameter were evaluated based on images obtained with SEM (scanning electron microscope) (JCM-5100, JEOL). The average particle size was calculated by arbitrarily selecting 50 to 100 zeolites from images of three different fields of view and taking the arithmetic average.
ＳＡＰＯ−３４の同定は、測定したＸ線回折（ＸＲＤ）の構造パターンを、米国特許４４４０８７１号明細書に示されている構造パターンと比較することにより行った。 SAPO-34 was identified by comparing the measured X-ray diffraction (XRD) structural pattern with the structural pattern shown in US Pat. No. 4,440,871.
（Ａ）平均粒子径０．２μｍのＳＡＰＯ−３４（８員環ゼオライト）の調製
６．８５ｇのＬｕｄｏｘ（登録商標）ＨＳ−３０（水中３０重量％、Ａｌｄｒｉｃｈ、以下同様）及び１９３．８６ｇの水酸化テトラエチルアンモニウム（ＴＥＡＯＨ）水溶液（水中３５重量％、Ａｌｄｒｉｃｈ、以下同様）を含む溶液をテフロン（登録商標）ビーカーにて調製した。この溶液に、２４．１１ｇのアルミニウムイソプロポキシド（純度９８％以上、Ａｌｄｒｉｃｈ、以下同様）を添加し、さらに、５３．２７ｇのリン酸（水中８５重量％、Ａｌｄｒｉｃｈ、以下同様）を添加した。モル比で以下の組成：
０．６ＳｉＯ２／Ａｌ２Ｏ３／４Ｐ２Ｏ５／８ＴＥＡＯＨ／１３３Ｈ２Ｏ
を有する均質な混合物を得た。この混合物を、９０℃の恒温槽に移し、水分を除去して乾燥ゲルを得た。乾燥ゲルと脱イオン水とを互いに接触させないようにして、テフロン内筒を有するＳＵＳ３１６製オートクレーブに移し、１８０℃で７２時間加熱処理した。オートクレーブから取り出した後、脱イオン水で洗浄し、１００℃で１２時間乾燥させて、粉末状の生成物を得た。ＸＲＤ、ＳＥＭにより、この生成物が平均粒子径０．２μｍのＳＡＰＯ−３４であることを確認した。
(A) Preparation of SAPO-34 (8-membered ring zeolite) with an average particle size of 0.2 μm 6.85 g Ludox® HS-30 (30 wt% in water, Aldrich, the same below) and 193.86 g water A solution containing an aqueous solution of tetraethylammonium oxide (TEAOH) (35% by weight in water, Aldrich, hereinafter the same) was prepared in a Teflon (registered trademark) beaker. To this solution, 24.11 g of aluminum isopropoxide (purity 98% or higher, Aldrich, the same applies below) was added, and 53.27 g of phosphoric acid (85 wt% in water, Aldrich, the same applies below) was added. The following composition in molar ratio:
0.6SiO 2 / Al 2 O 3 / 4P 2
A homogeneous mixture with This mixture was transferred to a constant temperature bath at 90 ° C. to remove moisture and obtain a dry gel. The dried gel and deionized water were not brought into contact with each other, transferred to an SUS316 autoclave having a Teflon inner cylinder, and heat-treated at 180 ° C. for 72 hours. After taking out from the autoclave, it was washed with deionized water and dried at 100 ° C. for 12 hours to obtain a powdered product. It was confirmed by XRD and SEM that this product was SAPO-34 having an average particle size of 0.2 μm.
得られたＳＡＰＯ−３４を金属塩で処理するため、まず、２ｇのＳＡＰＯ−３４を空気中６００℃で５時間焼成した後、０．１４ｗｔ％の酢酸バリウム水溶液１０ｍＬに添加し、５０℃、減圧下で水を留去した。その後、空気中５５０℃で１０時間焼成した。 In order to treat the obtained SAPO-34 with a metal salt, first, 2 g of SAPO-34 was calcined in air at 600 ° C. for 5 hours, and then added to 10 mL of a 0.14 wt% barium acetate aqueous solution. Water was distilled off underneath. Then, it baked at 550 degreeC in the air for 10 hours.
［実施例１］
得られた上記ＳＡＰＯ−３４の粉末を１６〜３２メッシュに成型して、ＳＡＰＯ−３４触媒を得た。触媒性能評価は、原料タンク、原料供給ポンプ、不活性ガス導入装置、反応管、試料採取タンク、及び背圧弁等を備えた流通反応装置を用いて行った。反応管には、内管が石英製で外管がステンレス製からなる二重管式反応容器（石英管の内径は１０ｍｍ）を使用した。１ｇのＳＡＰＯ−３４触媒を反応器に充填し、エタノール及び窒素を、エタノールの空間速度１．６ｈ−１でエタノール８０体積％と窒素２０体積％となるように、蒸発器を通じて反応器に供給した。温度４００℃、圧力０．２ＭＰａにて反応を行い、ガスクロマトグラフィーで生成物の分析を行った。反応開始１時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Example 1]
The obtained SAPO-34 powder was molded into 16-32 mesh to obtain a SAPO-34 catalyst. The catalyst performance evaluation was performed using a flow reactor equipped with a raw material tank, a raw material supply pump, an inert gas introduction device, a reaction tube, a sampling tank, a back pressure valve, and the like. As the reaction tube, a double-tube reaction vessel (inner diameter of the quartz tube is 10 mm) in which the inner tube is made of quartz and the outer tube is made of stainless steel was used. 1 g of SAPO-34 catalyst was charged into the reactor, and ethanol and nitrogen were fed into the reactor through the evaporator so that the ethanol space velocity was 1.6 h −1 , 80% ethanol and 20% nitrogen. . The reaction was performed at a temperature of 400 ° C. and a pressure of 0.2 MPa, and the product was analyzed by gas chromatography. Table 1 shows the yield (carbon mol%) of ethylene, propylene, butene, C 1 -C 4 alkane, and C 5 or higher hydrocarbons 1 hour after the start of the reaction.
なお、一般に、エチレン転化率が低いとき（反応が比較的進行していないとき）の方が、副反応の影響が少なくプロピレン選択率は高くなる。従って、プロピレン選択率の優劣を比較するためには、各試験でのエチレン転化率を揃える必要がある。本発明では、各試験のエチレン転化率が７０〜７５％となるように行った。 In general, when the ethylene conversion rate is low (when the reaction is relatively not progressing), the side reaction is less affected and the propylene selectivity is high. Therefore, in order to compare the superiority and inferiority of the propylene selectivity, it is necessary to align the ethylene conversion rate in each test. In this invention, it carried out so that the ethylene conversion rate of each test might be set to 70 to 75%.
［実施例２］
実施例１と同様の方法で触媒性能評価を行った。温度４００℃、圧力０．５ＭＰａにおける反応開始１．２５時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Example 2]
The catalyst performance was evaluated in the same manner as in Example 1. Table 1 shows the yield (carbon mol%) of ethylene, propylene, butene, C 1 to C 4 alkane, and C 5 or higher hydrocarbons after 1.25 hours from the start of the reaction at a temperature of 400 ° C. and a pressure of 0.5 MPa.
［比較例１］
実施例１と同様の方法で触媒性能評価を行った。温度４００℃、圧力０．１ＭＰａにおける反応開始０．７５時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Comparative Example 1]
The catalyst performance was evaluated in the same manner as in Example 1. Table 1 shows the yield (carbon mol%) of ethylene, propylene, butene, C 1 to C 4 alkane, and C 5 or higher hydrocarbons after 0.75 hours from the start of the reaction at a temperature of 400 ° C. and a pressure of 0.1 MPa.
（Ｂ）平均粒子径０．５μｍのＳＡＰＯ−３４（８員環ゼオライト）の調製
６．８５ｇのＬｕｄｏｘ（登録商標）ＨＳ−３０及び１９３．８６ｇの水酸化テトラエチルアンモニウム（ＴＥＡＯＨ）水溶液を含む溶液をテフロン（登録商標）ビーカーにて調製した。この溶液に、２４．１１ｇのアルミニウムイソプロポキシドを添加し、さらに、５３．２７ｇのリン酸を添加した。モル比で以下の組成：
０．６ＳｉＯ２／Ａｌ２Ｏ３／４Ｐ２Ｏ５／８ＴＥＡＯＨ／１３３Ｈ２Ｏ
を有する均質な混合物を得た。この混合物をテフロン内筒を有するＳＵＳ３１６製オートクレーブに移し、１８０℃で６４時間加熱処理した。オートクレーブから取り出した後、脱イオン水で洗浄を行い、１００℃で１２時間乾燥させて、粉末状の生成物を得た。ＸＲＤ、ＳＥＭにより、この生成物が平均粒子径０．５μｍのＳＡＰＯ−３４であることを確認した。
(B) Preparation of SAPO-34 (8-membered ring zeolite) having an average particle size of 0.5 μm A solution containing 6.85 g of Ludox® HS-30 and 193.86 g of tetraethylammonium hydroxide (TEAOH) aqueous solution It was prepared in a Teflon (registered trademark) beaker. To this solution, 24.11 g of aluminum isopropoxide was added, and 53.27 g of phosphoric acid was added. The following composition in molar ratio:
0.6SiO 2 / Al 2 O 3 / 4P 2
A homogeneous mixture with This mixture was transferred to a SUS316 autoclave having a Teflon inner cylinder and heat-treated at 180 ° C. for 64 hours. After removing from the autoclave, it was washed with deionized water and dried at 100 ° C. for 12 hours to obtain a powdered product. This product was confirmed to be SAPO-34 having an average particle size of 0.5 μm by XRD and SEM.
得られたＳＡＰＯ−３４をシラン化合物で処理するため、まず、２ｇのＳＡＰＯ−３４に２６．８ｍＬのトルエン、１７．６ｍＬのメトキシトリメチルシラン（ＭＴＭＳ）を添加し、温度８０℃で６時間反応させた。その後、トルエン、エタノール、水で洗浄し、空気中６００℃で５時間焼成した。上記の一連の作業を再度繰り返した。 In order to treat the obtained SAPO-34 with a silane compound, first, 26.8 mL of toluene and 17.6 mL of methoxytrimethylsilane (MTMS) were added to 2 g of SAPO-34 and reacted at a temperature of 80 ° C. for 6 hours. It was. Then, it wash | cleaned with toluene, ethanol, and water, and baked at 600 degreeC in the air for 5 hours. The above series of operations was repeated again.
［実施例３］
得られた上記ＳＡＰＯ−３４の粉末を１６〜３２メッシュに成型して、ＳＡＰＯ−３４触媒を得た。実施例１と同様の方法で触媒性能評価を行った。温度４００℃、圧力０．２ＭＰａにおける反応開始０．７５時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Example 3]
The obtained SAPO-34 powder was molded into 16-32 mesh to obtain a SAPO-34 catalyst. The catalyst performance was evaluated in the same manner as in Example 1. Table 1 shows the yield (carbon mol%) of ethylene, propylene, butene, C 1 to C 4 alkane, and C 5 or higher hydrocarbons after 0.75 hours from the start of the reaction at a temperature of 400 ° C. and a pressure of 0.2 MPa.
［比較例２］
実施例３と同様の方法で触媒性能評価を行った。温度４００℃、圧力０．１ＭＰａにおける反応開始０．７５時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Comparative Example 2]
The catalyst performance was evaluated in the same manner as in Example 3. Table 1 shows the yield (carbon mol%) of ethylene, propylene, butene, C 1 to C 4 alkane, and C 5 or higher hydrocarbons after 0.75 hours from the start of the reaction at a temperature of 400 ° C. and a pressure of 0.1 MPa.
（Ｃ）平均粒子径２．８μｍのＳＡＰＯ−３４（８員環ゼオライト）の調製
３．１８ｇのＬｕｄｏｘ（登録商標）ＡＳ−４０（Ａｌｄｒｉｃｈ）、３９．６１ｇの脱イオン水、及び３５．５８ｇの水酸化テトラエチルアンモニウム（ＴＥＡＯＨ）水溶液を含む溶液をテフロン（登録商標）ビーカーに調製した。この溶液に、２９．４４ｇのアルミニウムイソプロポキシドを添加し、さらに、３５．５７ｇのリン酸を添加した。モル比で以下の組成：
０．３ＳｉＯ２／Ａｌ２Ｏ３／Ｐ２Ｏ５／１．２ＴＥＡＯＨ／５５Ｈ２Ｏ
を有する均質な混合物を得た。この混合物を、テフロン内筒を有するＳＵＳ３１６製オートクレーブに移し、２２０℃で２４時間加熱処理した。オートクレーブから取り出した後、脱イオン水で洗浄を行い、１００℃で１２時間乾燥させて、粉末状の生成物を得た。ＸＲＤ、ＳＥＭにより、この生成物が平均粒子径２．８μｍのＳＡＰＯ−３４であることを確認した。
(C) Preparation of SAPO-34 (8-membered ring zeolite) with an average particle size of 2.8 μm 3.18 g Ludox® AS-40 (Aldrich), 39.61 g deionized water, and 35.58 g A solution containing an aqueous tetraethylammonium hydroxide (TEAOH) solution was prepared in a Teflon (registered trademark) beaker. To this solution, 29.44 g of aluminum isopropoxide was added, followed by 35.57 g of phosphoric acid. The following composition in molar ratio:
0.3SiO 2 / Al 2 O 3 / P 2
A homogeneous mixture with This mixture was transferred to an SUS316 autoclave having a Teflon inner cylinder and heat-treated at 220 ° C. for 24 hours. After removing from the autoclave, it was washed with deionized water and dried at 100 ° C. for 12 hours to obtain a powdered product. It was confirmed by XRD and SEM that this product was SAPO-34 having an average particle diameter of 2.8 μm.
［比較例３］
得られた上記ＳＡＰＯ−３４の粉末を１６〜３２メッシュに成型して、ＳＡＰＯ−３４触媒を得た。実施例１と同様の方法で触媒性能評価を行った。温度４００℃、圧力０．４ＭＰａにおける反応開始０．７５時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Comparative Example 3]
The obtained SAPO-34 powder was molded into 16-32 mesh to obtain a SAPO-34 catalyst. The catalyst performance was evaluated in the same manner as in Example 1. Table 1 shows the yield (carbon mol%) of ethylene, propylene, butene, C 1 to C 4 alkane, and C 5 or higher hydrocarbons after 0.75 hours from the start of the reaction at a temperature of 400 ° C. and a pressure of 0.4 MPa.
［比較例４］
比較例３と同様の方法で触媒性能評価を行った。温度４００℃、圧力０．１ＭＰａにおける反応開始０．７５時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Comparative Example 4]
The catalyst performance was evaluated in the same manner as in Comparative Example 3. Table 1 shows the yield (carbon mol%) of ethylene, propylene, butene, C 1 to C 4 alkane, and C 5 or higher hydrocarbons after 0.75 hours from the start of the reaction at a temperature of 400 ° C. and a pressure of 0.1 MPa.
（Ｄ）平均粒子径０．２μｍのＺＳＭ−５（１０員環ゼオライト）の調製
文献（Fujitani T, et al. Applied Catalysis A: General 384 (2010) 201-205）に従い、１０員環ゼオライトであるＺＳＭ−５触媒を調製した。その際に使用したＺＳＭ−５はＺｅｏｌｙｓｔ製のＣＢＶ８０１４（Ｓｉ／Ａｌ＝８０）であり、Ｐ含有量は０．６ｗｔ％となるように調製した。
(D) Preparation of ZSM-5 (10-membered ring zeolite) with an average particle size of 0.2 μm (Fujitani T, et al. Applied Catalysis A: General 384 (2010) 201-205). A ZSM-5 catalyst was prepared. ZSM-5 used at that time was CBV8014 (Si / Al = 80) manufactured by Zeolist, and the P content was adjusted to 0.6 wt%.
［比較例５］
得られたＺＳＭ−５の粉末を１６〜３２メッシュに成型して、ＺＳＭ−５触媒を得た。１ｇのＺＳＭ−５触媒を反応器に充填し、エタノール及び窒素を、エタノールの空間速度１２．３ｈ−１でエタノール８０体積％と窒素２０体積％となるように、蒸発器を通じて反応器に供給した。温度５５０℃、圧力０．２ＭＰａにおいて反応を行い、ガスクロマトグラフィーで生成物の分析を行った。反応開始２時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Comparative Example 5]
The obtained ZSM-5 powder was molded into 16-32 mesh to obtain a ZSM-5 catalyst. 1 g of ZSM-5 catalyst was charged into the reactor, and ethanol and nitrogen were fed to the reactor through the evaporator so that the ethanol space velocity was 12.3 h −1 , 80 vol% ethanol and 20 vol% nitrogen. . The reaction was performed at a temperature of 550 ° C. and a pressure of 0.2 MPa, and the product was analyzed by gas chromatography. Table 1 shows the yield (carbon mole%) of ethylene, propylene, butene, C 1 -C 4 alkane, and C 5 or higher hydrocarbons 2 hours after the start of the reaction.
［比較例６］
比較例５と同様の方法で、１ｇのＺＳＭ−５触媒を反応器に充填し、エタノール及び窒素を、エタノールの空間速度９．２ｈ−１でエタノール８０体積％と窒素２０体積％となるように、蒸発器を通じて反応器に供給した。温度５５０℃、圧力０．１ＭＰａにおいて反応を行い、ガスクロマトグラフィーで生成物の分析を行った。反応開始２時間後のエチレン、プロピレン、ブテン、Ｃ１〜Ｃ４アルカン、Ｃ５以上の炭化水素の収率（炭素モル％）を表１に示す。
[Comparative Example 6]
In the same manner as in Comparative Example 5, 1 g of ZSM-5 catalyst was charged into the reactor so that ethanol and nitrogen were 80% by volume ethanol and 20% by volume nitrogen at a space velocity of 9.2 h −1. And fed to the reactor through an evaporator. The reaction was conducted at a temperature of 550 ° C. and a pressure of 0.1 MPa, and the product was analyzed by gas chromatography. Table 1 shows the yield (carbon mole%) of ethylene, propylene, butene, C 1 -C 4 alkane, and C 5 or higher hydrocarbons 2 hours after the start of the reaction.
Ｃ２Ｈ４転化率及びＣ３Ｈ６選択率を以下のように定義する：
（Ｃ２Ｈ４転化率）＝１００−（Ｃ２Ｈ４収率）
（Ｃ３Ｈ６選択率）＝（Ｃ３Ｈ６収率）／（Ｃ２Ｈ４転化率）×１００
表１中、実施例１、実施例２及び比較例１では、平均粒子径０．２μｍの８員環ゼオライトであるＳＡＰＯ−３４を用いた、プロピレン選択率の圧力依存性を比較している（以下、試験例Ａと称す）。
C 2 H 4 conversion and C 3 H 6 selectivity are defined as follows:
(C 2 H 4 conversion) = 100− (C 2 H 4 yield)
(C 3 H 6 selectivity) = (C 3 H 6 yield) / (C 2 H 4 conversion) × 100
In Table 1, Example 1, Example 2 and Comparative Example 1 compare the pressure dependency of propylene selectivity using SAPO-34, which is an 8-membered ring zeolite having an average particle diameter of 0.2 μm ( Hereinafter, this is referred to as Test Example A).
また、実施例３及び比較例２では、平均粒子径０．５μｍの８員環ゼオライトであるＳＡＰＯ−３４を用いた、プロピレン選択率の圧力依存性を比較している（試験例Ｂ）。 In Example 3 and Comparative Example 2, the pressure dependency of propylene selectivity using SAPO-34, which is an 8-membered ring zeolite having an average particle size of 0.5 μm, is compared (Test Example B).
また、比較例３及び比較例４では、平均粒子径２．８μｍの８員環ゼオライトであるＳＡＰＯ−３４を用いた、プロピレン選択率の圧力依存性を比較している（試験例Ｃ）。 In Comparative Example 3 and Comparative Example 4, the pressure dependency of propylene selectivity using SAPO-34, which is an 8-membered ring zeolite having an average particle diameter of 2.8 μm, is compared (Test Example C).
さらに、比較例５及び比較例６では、１０員環ゼオライトであるＺＳＭ−５を用いた、プロピレン選択率の圧力依存性を比較している（試験例Ｄ）。 Furthermore, in Comparative Example 5 and Comparative Example 6, the pressure dependency of propylene selectivity using ZSM-5 which is a 10-membered ring zeolite is compared (Test Example D).
試験例Ａでは、反応圧力が０．１ＭＰａである場合、プロピレン選択率は４８％であったが、反応圧力を０．２ＭＰａにすると、プロピレン選択率は６９％と増加し、この値は反応圧力を０．５ＭＰａにしてもほとんど変化しなかった。 In Test Example A, when the reaction pressure was 0.1 MPa, the propylene selectivity was 48%. However, when the reaction pressure was 0.2 MPa, the propylene selectivity increased to 69%, which was the reaction pressure. Even when the pressure was 0.5 MPa, there was almost no change.
この傾向は、平均粒子径が０．５μｍであるＳＡＰＯ−３４を用いた試験例Ｂでも同様であった。
一方、試験例Ｃでは、プロピレン選択率は大きく変化しなかった。
This tendency was the same in Test Example B using SAPO-34 having an average particle size of 0.5 μm.
On the other hand, in Test Example C, the propylene selectivity did not change significantly.
これらに対して、１０員環ゼオライトであるＺＳＭ−５を用いた試験例Ｄでは、反応圧力を０．１ＭＰａから０．２ＭＰａに上げた場合でも、プロピレン選択率は３９％のままで、試験例Ａ及びＢのようにプロピレンの選択率は増加しなかった。 On the other hand, in Test Example D using ZSM-5, which is a 10-membered ring zeolite, even when the reaction pressure is increased from 0.1 MPa to 0.2 MPa, the propylene selectivity remains 39%. Like A and B, propylene selectivity did not increase.
Claims (7)
The method according to any one of claims 1 to 6, wherein the raw material is at least one selected from the group consisting of C 1-6 hydrocarbons and C 1-6 oxygenates.
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| JP2003511484A (en) * | 1999-09-29 | 2003-03-25 | エクソンモービル・ケミカル・パテンツ・インク | Formation of olefin products from oxygenates |
| JP2007503375A (en) * | 2003-06-13 | 2007-02-22 | エクソンモービル・ケミカル・パテンツ・インク | Method for protecting SAPO molecular sieves from loss of catalytic activity |
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| JP2007534582A (en) * | 2003-12-23 | 2007-11-29 | エクソンモービル・ケミカル・パテンツ・インク | Kabasite type molecular sieves, their synthesis, and their use in converting oxydinate to olefin |
| JP2009018247A (en) * | 2007-07-11 | 2009-01-29 | Toyota Motor Corp | Propylene producing catalyst |
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| JP2003511484A (en) * | 1999-09-29 | 2003-03-25 | エクソンモービル・ケミカル・パテンツ・インク | Formation of olefin products from oxygenates |
| JP2007503375A (en) * | 2003-06-13 | 2007-02-22 | エクソンモービル・ケミカル・パテンツ・インク | Method for protecting SAPO molecular sieves from loss of catalytic activity |
| JP2007516152A (en) * | 2003-12-23 | 2007-06-21 | エクソンモービル・ケミカル・パテンツ・インク | Kabasite-containing molecular sieve, its synthesis and its use in the conversion of eusigenate to olefins |
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