JP2022127708A - Method of producing benzene - Google Patents
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- JP2022127708A JP2022127708A JP2021025847A JP2021025847A JP2022127708A JP 2022127708 A JP2022127708 A JP 2022127708A JP 2021025847 A JP2021025847 A JP 2021025847A JP 2021025847 A JP2021025847 A JP 2021025847A JP 2022127708 A JP2022127708 A JP 2022127708A
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- benzene
- catalyst
- aliphatic hydrocarbon
- producing
- producing benzene
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 32
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 29
- 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 29
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 28
- 239000010457 zeolite Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 18
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- -1 Alicyclic hydrocarbon compounds Chemical class 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 2
- IFTRQJLVEBNKJK-UHFFFAOYSA-N Ethylcyclopentane Chemical compound CCC1CCCC1 IFTRQJLVEBNKJK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000020335 dealkylation Effects 0.000 description 2
- 238000006900 dealkylation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RBAKORNXYLGSJB-UHFFFAOYSA-N azane;platinum(2+);dinitrate Chemical compound N.N.N.N.[Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RBAKORNXYLGSJB-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 1
- YVFORYDECCQDAW-UHFFFAOYSA-N gallium;trinitrate;hydrate Chemical compound O.[Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YVFORYDECCQDAW-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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、ベンゼンの製造方法に関するものであり、さらに詳細には、触媒に脂肪族炭化水素化合物を接触し芳香族化合物を含む生成物を製造する工程と該生成物を水素化脱アルキル化触媒とを接触する工程とを経ることにより、生産性に優れ、エネルギー消費の抑制されたベンゼンの製造方法に関するものである。 TECHNICAL FIELD The present invention relates to a method for producing benzene, and more particularly, a step of contacting an aliphatic hydrocarbon compound with a catalyst to produce a product containing an aromatic compound, and a hydrodealkylation catalyst for the product. The present invention relates to a method for producing benzene with excellent productivity and reduced energy consumption by going through the step of contacting with.
ベンゼンやトルエン、キシレン等の芳香族化合物は、多くの場合、石油精製により得られた原料油（例えばナフサなど）を、熱分解反応装置にて分解し、得られた熱分解生成物から蒸留又は抽出によって分離精製することで得られる。これらの芳香族化合物の製造方法では、芳香族化合物以外の熱分解生成物として、脂肪族炭化水素化合物（パラフィン系、オレフィン系、アセチレン系、脂環系）が副生する。そのため、芳香族化合物の製造に伴って、脂肪族炭化水素化合物が同時に製造されるため、芳香族化合物の生産量は脂肪族炭化水素化合物の生産量に見合って調整がなされ、おのずと生産量が制限されるものであった。一方、脂肪族炭化水素化合物は、細孔径約５～６オングストロームの細孔を有する中細孔径ゼオライトを主に含んだ触媒と４００℃～８００℃程度の温度で接触させることにより、芳香族化合物に転化製造することができることが報告されている（例えば非特許文献１～４参照。）。該製造方法は、原料油の熱分解による芳香族化合物の製造方法と比較して、脂肪族炭化水素化合物から有用な芳香族化合物が製造できる利点がある。そのため、このような脂肪族炭化水素化合物からの芳香族化合物を製造可能な触媒の開発が行われている。例えば、脂肪族炭化水素化合物を原料とした芳香族化合物製造触媒として亜鉛及び／又はガリウムを含有したＭＦＩ型ゼオライト触媒（例えば特許文献１参照。）、等が提案されている。 Aromatic compounds such as benzene, toluene, and xylene are often produced by decomposing feedstock oil (such as naphtha) obtained by petroleum refining in a thermal cracking reactor, and distilling or Obtained by separation and purification by extraction. In these processes for producing aromatic compounds, aliphatic hydrocarbon compounds (paraffinic, olefinic, acetylenic, alicyclic) are by-produced as thermal decomposition products other than aromatic compounds. Therefore, since aliphatic hydrocarbon compounds are produced at the same time as aromatic compounds are produced, the production of aromatic compounds is adjusted according to the production of aliphatic hydrocarbon compounds, naturally limiting production. It was something to be done. On the other hand, the aliphatic hydrocarbon compound is brought into contact with a catalyst mainly containing medium pore size zeolite having pores with a pore size of about 5 to 6 angstroms at a temperature of about 400 ° C. to 800 ° C., and is converted into an aromatic compound. It has been reported that conversion production is possible (see, for example, Non-Patent Documents 1 to 4). This production method has the advantage of being able to produce useful aromatic compounds from aliphatic hydrocarbon compounds, as compared with a method of producing aromatic compounds by thermal cracking of feedstock oil. Therefore, catalysts capable of producing aromatic compounds from such aliphatic hydrocarbon compounds have been developed. For example, an MFI-type zeolite catalyst containing zinc and/or gallium (see, for example, Patent Document 1) has been proposed as an aromatic compound production catalyst using an aliphatic hydrocarbon compound as a raw material.
しかし、特許文献１で提案された亜鉛及び／又はガリウムを含有したＭＦＩ型ゼオライト触媒においては、トルエンやキシレン等のアルキル化芳香族化合物を同時に生成し易い傾向にあり、その結果ベンゼン選択率が抑制されるという課題を有するものであった。 However, in the MFI-type zeolite catalyst containing zinc and / or gallium proposed in Patent Document 1, alkylated aromatic compounds such as toluene and xylene tend to be generated at the same time, and as a result, benzene selectivity is suppressed. It had the problem of being
また、非特許文献５においては、芳香族化反応で得られた生成物を熱分解反応することでベンゼンの収率が増加することが報告されている。しかし、その際の熱分解反応温度は、７５０℃と極めて高いものであり、該方法はエネルギー多消費型のプロセスであるため多大の制約を受ける可能性の高いものであった。 In addition, Non-Patent Document 5 reports that the yield of benzene is increased by thermally decomposing the product obtained by the aromatization reaction. However, the thermal decomposition reaction temperature at that time was as high as 750° C., and since this method consumes a lot of energy, there is a high possibility that it will be greatly restricted.
そこで、本発明は、脂肪族炭化水素化合物、特に低級脂肪族炭化水素化合物を原料として、ベンゼンを選択的かつ効率よく製造することが可能となるベンゼンの製造方法を提供するものである。 Accordingly, the present invention provides a method for producing benzene, which enables the selective and efficient production of benzene using aliphatic hydrocarbon compounds, particularly lower aliphatic hydrocarbon compounds, as raw materials.
本発明者らは、上記の課題を解決するため鋭意検討を行った結果、脂肪族炭化水素化合物からベンゼンを製造する際に、特定の触媒を用いた一連の工程を組み合わせて経ることにより選択的かつ効率よくベンゼンを製造することが可能となることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that when producing benzene from an aliphatic hydrocarbon compound, a series of steps using a specific catalyst can be combined to selectively In addition, they have found that it is possible to produce benzene efficiently, and have completed the present invention.
即ち、本発明は、触媒との接触反応により脂肪族炭化水素化合物からベンゼンを製造する際に、少なくとも下記（ａ）工程および（ｂ）工程を同一の反応器又は一連の複数の反応器にて行うことを特徴とするベンゼンの製造方法に関するものである。
（ａ）工程；炭素数１０以下の脂肪族炭化水素化合物をＭＦＩ型ゼオライト及び／又は金属含有ＭＦＩ型ゼオライトを含む触媒に接触し、芳香族化合物を含む生成物を製造する工程。
（ｂ）工程；（ａ）工程の生成物を水素化脱アルキル化触媒に接触し、ベンゼンを製造する工程。
That is, the present invention provides at least the following steps (a) and (b) in the same reactor or a series of multiple reactors when producing benzene from an aliphatic hydrocarbon compound by a catalytic reaction with a catalyst. The present invention relates to a method for producing benzene characterized by performing
(a) step; a step of contacting an aliphatic hydrocarbon compound having 10 or less carbon atoms with a catalyst containing an MFI zeolite and/or a metal-containing MFI zeolite to produce a product containing an aromatic compound.
(b) step; contacting the product of step (a) with a hydrodealkylation catalyst to produce benzene.
以下に、本発明について詳細に説明する。 The present invention will be described in detail below.
本発明は、触媒との接触反応により脂肪族炭化水素化合物からベンゼンを製造する方法に関するものであり、その際に下記（ａ）工程および（ｂ）工程を経ることで選択的かつ効率よくベンゼンを製造するベンゼンの製造方法に関するものである。また、その際には同一の反応器又は一連の複数の反応器にて下記（ａ）工程、（ｂ）工程を経るものである。
（ａ）工程；炭素数１０以下の脂肪族炭化水素化合物をＭＦＩ型ゼオライト及び／又は金属含有ＭＦＩ型ゼオライトを含む触媒に接触し、芳香族化合物を含む生成物を製造する工程。
（ｂ）工程；（ａ）工程の生成物を水素化脱アルキル化触媒に接触し、ベンゼンを製造する工程。
The present invention relates to a method for producing benzene from an aliphatic hydrocarbon compound by contact reaction with a catalyst, in which case the following steps (a) and (b) are performed to selectively and efficiently produce benzene. It relates to a method for producing benzene to be produced. In this case, the following steps (a) and (b) are performed in the same reactor or a series of multiple reactors.
(a) step; a step of contacting an aliphatic hydrocarbon compound having 10 or less carbon atoms with a catalyst containing an MFI zeolite and/or a metal-containing MFI zeolite to produce a product containing an aromatic compound.
(b) step; contacting the product of step (a) with a hydrodealkylation catalyst to produce benzene.
本発明における（ａ）工程は、炭素数１０以下の脂肪族炭化水素化合物をＭＦＩ型ゼオライト及び／又は金属含有ＭＦＩ型ゼオライトを含む触媒に接触し、芳香族化合物を含む生成物を製造する工程である。その際の炭素数１０以下の脂肪族炭化水素化合物としては、その範疇に属するものであればよく、例えばメタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン等のパラフィン系；エチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン等のオレフィン系；アセチレン等のアセチレン系；シクロプロパン、シクロブタン、シクロペンタン、メチルシクロペンタン、シクロヘキサン等の脂環系等の脂肪族炭化水素化合物を挙げることができ、中でも選択的に効率よくベンゼンを製造できることから炭素数４～９の脂肪族炭化水素化合物が好ましく、具体的にはブタン、ヘキサン、ヘプタン、オクタン、ノナン等のパラフィン系；ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン等のオレフィン系；シクロブタン、シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環系及びそれらの混合物等を挙げることができる。ここで、炭素数１０を越える炭化水素化合物である場合、ベンゼンの選択率に劣るものとなる。 The step (a) in the present invention is a step of contacting an aliphatic hydrocarbon compound having 10 or less carbon atoms with a catalyst containing an MFI zeolite and/or a metal-containing MFI zeolite to produce a product containing an aromatic compound. be. At that time, the aliphatic hydrocarbon compound having 10 or less carbon atoms may be one that belongs to that category, such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, paraffinic compounds such as nonane; ethylene; , Olefins such as propylene, butene, pentene, hexene, heptene, octene, and nonene; Acetylenes such as acetylene; Alicyclic hydrocarbon compounds such as cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, and cyclohexane Among them, aliphatic hydrocarbon compounds having 4 to 9 carbon atoms are preferable because benzene can be produced selectively and efficiently. Specifically, paraffinic compounds such as butane, hexane, heptane, octane, and nonane; , pentene, hexene, heptene, octene, nonene, etc.; cyclobutane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc., and mixtures thereof. Here, in the case of a hydrocarbon compound having more than 10 carbon atoms, the benzene selectivity is inferior.
該（ａ）工程における触媒とは、脂肪族炭化水素化合物を芳香族化合物に転化する作用を有する芳香族化合物製造触媒とも称されるものであり、その際の生成物である芳香族化合物はベンゼンを含有するものである。該触媒は、ＭＦＩ型ゼオライト及び／又は金属含有ＭＦＩ型ゼオライトを含む触媒であり、特に芳香族選択率を向上させることが可能となることから金属含有ＭＦＩ型ゼオライトを含む触媒であることが好ましく、その際の金属としては、例えば銀、カルシウム、マグネシウム、ストロンチウム、バリウム、ガリウム及び亜鉛から選択される少なくとも１種の金属を挙げることができ、特に亜鉛及び／又はガリウムであることが好ましい。ここで、ＭＦＩ型ゼオライト以外のゼオライトである場合、芳香族化合物の選択率に劣るものとなる。 The catalyst in the step (a) is also referred to as an aromatic compound production catalyst that has the action of converting an aliphatic hydrocarbon compound into an aromatic compound, and the aromatic compound that is the product at that time is benzene contains The catalyst is a catalyst containing MFI-type zeolite and/or metal-containing MFI-type zeolite, and it is particularly preferable that it is a catalyst containing metal-containing MFI-type zeolite because it is possible to improve the aromatic selectivity. Examples of the metal in this case include at least one metal selected from silver, calcium, magnesium, strontium, barium, gallium and zinc, with zinc and/or gallium being particularly preferred. Here, when the zeolite other than the MFI-type zeolite is used, the selectivity for aromatic compounds is inferior.
また、該触媒の形状としては、粉粒状、円柱状、三角柱、四角柱、多角柱、さらにこれらの中空形状であってもよく、さらにはハニカム、シリンダー、独立孔、連通孔を有する（不）定形状であってもよく、そのような形状とする際には、バインター等を含むものであってもよい。 Further, the shape of the catalyst may be powdery, cylindrical, triangular, quadrangular, polygonal, or hollow shapes thereof, and may have honeycombs, cylinders, independent pores, or communicating pores (not). It may have a fixed shape, and when it is formed into such a shape, it may contain a binder or the like.
該（ａ）工程の接触反応条件としては、ベンゼンを含む芳香族化合物の製造が可能であれば制限はなく、中でも副生するパラフィン、オレフィン又はアルカンの生成を抑制し、必要以上の耐熱反応装置を要せず、芳香族化合物の効率的な製造が可能となることから４００～８００℃の範囲が望ましい。また、反応圧力にも制限はなく、例えば０．０５～５ＭＰａの圧力範囲での運転が望ましい。そして、その際の芳香族化合物製造触媒に対する反応原料である脂肪族炭化水素化合物の供給は、触媒体積に対し原料ガスの体積の比として特に制限されるものではなく、例えば０．１ｈ－１～５００００ｈ－１程度の空間速度を挙げることができる。脂肪族炭化水素化合物を原料ガスとして供給する際には、単一ガス、混合ガス、およびこれらを窒素等の不活性ガス、水素、一酸化炭素、二酸化炭素から選ばれる単一または混合ガスにより希釈したものとして用いることもできる。 The contact reaction conditions in the step (a) are not limited as long as aromatic compounds containing benzene can be produced. A temperature range of 400 to 800° C. is desirable because it enables efficient production of aromatic compounds. Moreover, there is no restriction on the reaction pressure, and it is desirable to operate within a pressure range of, for example, 0.05 to 5 MPa. In addition, the supply of the aliphatic hydrocarbon compound as a reaction raw material to the aromatic compound production catalyst at that time is not particularly limited as a ratio of the volume of the raw material gas to the volume of the catalyst. Spatial velocities of the order of 50000 h −1 can be mentioned. When supplying an aliphatic hydrocarbon compound as a raw material gas, a single gas, a mixed gas, and a single or mixed gas selected from inert gases such as nitrogen, hydrogen, carbon monoxide, and carbon dioxide are diluted. It can also be used as a
本発明における（ｂ）工程は、（ａ）工程の生成物を水素化脱アルキル化触媒に接触し、ベンゼンを製造する工程である。その際の水素化脱アルキル化触媒は、水素化脱アルキル化触媒として知られているものを用いることができ、中でも脱アルキル化反応性に優れ、ベンゼンの選択性及び生産効率に優れるベンゼンの製造方法となることから、白金族を担持した担持触媒であることが好ましく、特にシリカやアルミナ等の担体に、白金族の金属及び／又はそれらを含む金属化合物を担持した水素化脱アルキル化用触媒が好ましい。その際の白金族の担持量は０．１～５重量％が好ましい。 The step (b) in the present invention is a step of contacting the product of the step (a) with a hydrodealkylation catalyst to produce benzene. The hydrodealkylation catalyst at that time can be one known as a hydrodealkylation catalyst, which has excellent dealkylation reactivity, benzene selectivity, and production efficiency. Since it becomes a method, it is preferably a supported catalyst supporting a platinum group, especially a catalyst for hydrodealkylation in which a platinum group metal and / or a metal compound containing them is supported on a support such as silica or alumina. is preferred. At that time, the supported amount of the platinum group metal is preferably 0.1 to 5% by weight.
該（ｂ）工程の接触反応条件としては、水素化脱アルキル化反応が可能でベンゼンの製造が可能であれば制限は無く、中でも４００～６００℃の範囲が望ましい。また、反応圧力にも制限はなく、例えば０．０５～５ＭＰａの圧力範囲での製造が好ましい。（ａ）工程からの生成物の供給は、触媒体積に対し原料ガスの体積の比として特に制限されるものではなく、例えば０．１ｈ－１～５００００ｈ－１程度の空間速度を挙げることができる。該（ａ）工程からの生成物を原料として供給する際には、単一ガス、混合ガス、およびこれらを窒素等の不活性ガス、水素、一酸化炭素、二酸化炭素から選ばれる単一または混合ガスにより希釈したものとして用いることもできる。そして、水素化脱アルキル化反応を進行させる際の水素は、別途反応系に適宜供給することができる。また、上記（ａ）工程にて副生する水素をそのまま水素源としてもよい。 The contact reaction conditions in the step (b) are not limited as long as the hydrodealkylation reaction is possible and the production of benzene is possible. Moreover, there is no restriction on the reaction pressure, and production within a pressure range of, for example, 0.05 to 5 MPa is preferred. The supply of the product from the step (a) is not particularly limited as a ratio of the volume of the raw material gas to the volume of the catalyst. . When supplying the product from the step (a) as a raw material, a single gas, a mixed gas, and a single or mixed gas selected from inert gases such as nitrogen, hydrogen, carbon monoxide, and carbon dioxide It can also be used as diluted with gas. Hydrogen for advancing the hydrodealkylation reaction can be separately supplied to the reaction system as appropriate. Alternatively, the hydrogen produced as a by-product in the above step (a) may be directly used as the hydrogen source.
そして、ベンゼンを製造する際の該（ａ）工程、（ｂ）工程における接触反応形式、反応器にともに制限はなく、例えば固定床、流動床、さらにはその組み合わせであってもよい。また、反応器は単管式反応器でも多管式反応器でもよい。 There are no restrictions on the contact reaction type and reactor in the steps (a) and (b) in the production of benzene. Also, the reactor may be a single-tube reactor or a multi-tube reactor.
本発明のベンゼンの製造方法は、ベンゼンの製造が可能であれば如何なる方法を用いてもよく、例えば該（ａ）工程と該（ｂ）工程は同一の反応器で分離した触媒層として連続して製造できる他、それぞれの工程を連続する複数の反応器により個別に行うことによっても実施することができる。その際に各工程の反応条件はそれぞれの工程に適した個別の条件にて実施することができる。このような製造方法とすることにより、芳香族化合物製造触媒との接触により芳香族化合物を生成した後、連続して生成物を水素化脱アルキル化触媒に接触することにより該芳香族化合物中に含まれるアルキル化ベンゼン等を効率よくベンゼンに転化することが可能となり、効率に優れるものとなる。 Any method may be used as the method for producing benzene of the present invention as long as it is possible to produce benzene. Alternatively, each step can be performed individually in a plurality of continuous reactors. In that case, the reaction conditions of each step can be implemented under individual conditions suitable for each step. By adopting such a production method, after the aromatic compound is produced by contact with the aromatic compound production catalyst, the product is continuously brought into contact with the hydrodealkylation catalyst to produce the aromatic compound. It becomes possible to efficiently convert the contained alkylated benzene and the like into benzene, resulting in excellent efficiency.
また、本発明のベンゼンの製造方法においては、適宜芳香族化合物を含む生成物の分離・精製工程、ベンゼンの分離・精製工程等の付随工程を付加することもできる。 In addition, in the method for producing benzene of the present invention, an accompanying step such as a step of separating/purifying a product containing an aromatic compound, a step of separating/purifying benzene, and the like can be added as appropriate.
本発明は、ベンゼンを高い選択率、収率、効率で得ることができる新規なベンゼンの製造方法を提供するものであり、工業的にも非常に有用なものである。 INDUSTRIAL APPLICABILITY The present invention provides a novel method for producing benzene by which benzene can be obtained with high selectivity, yield and efficiency, and is industrially very useful.
以下に、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these.
なお、実施例における評価方法を以下に示す。 In addition, the evaluation method in an Example is shown below.
～反応生成物の分析～
反応後のガス成分は、ＴＣＤ検出器を備えたガスクロマトグラフ（島津製作所製、（商品名）ＧＣ－１４Ｂ）及びＦＩＤ検出器を備えたガスクロマトグラフ（島津製作所製、（商品名）ＧＣ－１４Ａ）を用いて分析した。ＴＣＤ検出器を備えたガスクロマトグラフ（島津製作所製、（商品名）ＧＣ－１４Ｂ）の充填剤は、ＧＬサイエンス社製ＭＳ－５Ａ（商品名）を用いた。ＦＩＤ検出器を備えたガスクロマトグラフ（島津製作所製、（商品名）ＧＣ－１４Ａ）の分離カラムは、アジレント・テクノロジー社製ＣＰ－Ａｌ２Ｏ３／ＫＣｌ（商品名）を用いた。液成分はＦＩＤ検出器を備えたガスクロマトグラフ（島津製作所製、（商品名）ＧＣ－２０２５）を用いて分析した。分離カラムは、ＧＬサイエンス社製、ＴＣ－１（商品名）を用いた。
～Analysis of reaction products～
The gas components after the reaction were analyzed by a gas chromatograph equipped with a TCD detector (manufactured by Shimadzu Corporation, (trade name) GC-14B) and a gas chromatograph equipped with an FID detector (manufactured by Shimadzu Corporation, (trade name) GC-14A). was analyzed using MS-5A (trade name) manufactured by GL Sciences was used as a packing material for a gas chromatograph (trade name) GC-14B manufactured by Shimadzu Corporation equipped with a TCD detector. A gas chromatograph equipped with an FID detector (manufactured by Shimadzu Corporation, (trade name) GC-14A) used a separation column of CP-Al 2 O 3 /KCl (trade name) manufactured by Agilent Technologies. The liquid components were analyzed using a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-2025) equipped with an FID detector. As a separation column, TC-1 (trade name) manufactured by GL Sciences was used.
～ベンゼン収率～
ベンゼン収率を ベンゼン収率＝ベンゼン生成重量／供給原料重量×１００ として求めた。
~ Benzene Yield ~
Benzene yield was determined as: Benzene yield=weight of benzene produced/weight of feedstock×100.
調製例１（ＭＦＩ型ゼオライトの調製）
特開２０１３－２２７２０３号公報に記載の方法により、ＭＦＩ型ゼオライトの製造を行った。
Preparation Example 1 (Preparation of MFI-type zeolite)
MFI-type zeolite was produced by the method described in JP-A-2013-227203.
テトラプロピルアンモニウム（以降、ＴＰＡと略記する場合がある。）水酸化物と水酸化ナトリウムの水溶液に不定形アルミノシリケートゲルを添加して懸濁させた。得られた懸濁液にＭＦＩ型ゼオライトを種晶として加え原料組成物とした。その際の種晶の添加量は、原料組成物中のＡｌ２Ｏ３とＳｉＯ２の重量に対して、０．７重量％とした。 An amorphous aluminosilicate gel was added to and suspended in an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide. MFI-type zeolite was added as seed crystals to the resulting suspension to prepare a raw material composition. The amount of seed crystals added at that time was 0.7% by weight with respect to the weight of Al 2 O 3 and SiO 2 in the raw material composition.
該原料組成物の組成は以下のとおりである。
ＳｉＯ２／Ａｌ２Ｏ３モル比＝４８、ＴＰＡ／Ｓｉモル比＝０．０５、Ｎａ／Ｓｉモル比＝０．１６、ＯＨ／Ｓｉモル比＝０．２１、Ｈ２Ｏ／Ｓｉモル比＝１０。
The composition of the raw material composition is as follows.
SiO2 / Al2O3 molar ratio = 48 , TPA/Si molar ratio = 0.05, Na/Si molar ratio = 0.16, OH/Si molar ratio = 0.21, H2O /Si molar ratio = 10.
得られた原料組成物をステンレス製オートクレーブに密閉し、１１５℃で攪拌しながら４日間結晶化させ、スラリー状混合液を得た。結晶化後のスラリー状混合液を遠心沈降機で固液分離した後、十分量の純水で固体粒子を洗浄し、１１０℃で乾燥して乾燥粉末を得た。得られた乾燥粉末を１ｍｏｌ／Ｌの塩酸中に分散し、ろ過、乾燥させた。空気下、５５０℃で１時間焼成後、６００℃、５０％の水蒸気で２時間のスチーム処理を含む焼成処理を行った。得られた粉末を１ｍｏｌ／Ｌの塩酸中に分散し、ろ過、洗浄し、ＭＦＩ型ゼオライトを得た。 The resulting raw material composition was sealed in a stainless steel autoclave and crystallized at 115° C. for 4 days with stirring to obtain a slurry mixture. After solid-liquid separation of the slurry mixed liquid after crystallization by a centrifugal sedimentation machine, the solid particles were washed with a sufficient amount of pure water and dried at 110° C. to obtain a dry powder. The resulting dry powder was dispersed in 1 mol/L hydrochloric acid, filtered and dried. After calcining in air at 550° C. for 1 hour, a calcining treatment was performed which included steaming at 600° C. and 50% water vapor for 2 hours. The resulting powder was dispersed in 1 mol/L hydrochloric acid, filtered and washed to obtain MFI zeolite.
調製例２（ＭＦＩ型ゼオライト成形体の調製）
調製例１で得られたＭＦＩ型ゼオライト１００重量部に対して、シリカ（日産化学工業社製、（商品名）スノーテックスＮ－３０Ｇ）４３重量部、セルロース４重量部、純水３０重量部を加え混練した。そして、混練物を直径１．５ｍｍ、長さ１．０～７．０ｍｍ（平均長さ３．５ｍｍ）の円柱状の成形体とした。これを１００℃で１晩乾燥した。
Preparation Example 2 (Preparation of MFI type zeolite compact)
To 100 parts by weight of the MFI type zeolite obtained in Preparation Example 1, 43 parts by weight of silica (manufactured by Nissan Chemical Industries, Ltd., (trade name) Snowtex N-30G), 4 parts by weight of cellulose, and 30 parts by weight of pure water are added. added and kneaded. Then, the kneaded material was formed into a columnar compact having a diameter of 1.5 mm and a length of 1.0 to 7.0 mm (average length of 3.5 mm). It was dried overnight at 100°C.
調製例３（芳香族化合物製造触媒の調製）
硝酸ガリウム（ＩＩＩ）ｎ水和物６．４２ｇと水３２７ｇからなる水溶液に調製例２で得たＭＦＩ型ゼオライト成形体１００ｇを入れて３時間撹拌することでイオン交換を行った。その後、ろ過、水洗浄を行い、１２０℃で１時間乾燥した後、５００℃で２時間焼成することでＭＦＩ型ゼオライトに対してガリウム重量として０．２％相当を含有したガリウム含有ＭＦＩ型ゼオライトを含む芳香族化合物製造触媒を調製した。
Preparation Example 3 (Preparation of aromatic compound production catalyst)
100 g of the MFI-type zeolite compact obtained in Preparation Example 2 was added to an aqueous solution of 6.42 g of gallium (III) nitrate n-hydrate and 327 g of water, and the mixture was stirred for 3 hours to perform ion exchange. After that, it is filtered and washed with water, dried at 120° C. for 1 hour, and then calcined at 500° C. for 2 hours to obtain a gallium-containing MFI zeolite containing 0.2% by weight of gallium relative to the MFI zeolite. Aromatic compound production catalysts containing
調製例４（水素化脱アルキル化触媒の調製）
硝酸テトラアンミンン白金（ＩＩ）０．８９ｇと水１５．２ｇからなる水溶液をγ－アルミナ１５．０ｇに撹拌しながら徐々に滴下し、１１０℃で３時間乾燥した後、５５０℃で６時間焼成することで担体であるγ－アルミナに対して白金重量として２．６％相当を担持した水素化脱アルキル化用触媒を調製した。ベンゼンの製造には、調製した触媒粉末を油圧プレスで４００ｋｇｆ／ｃｍ２で１分間圧縮成型した後に粉砕し、目開き１．７ｍｍの篩を通過し、目開き８５０μｍの篩上に堆積したペレットを用いた
実施例１
固定床気相流通式反応装置のステンレス製反応管（内径１６ｍｍ、長さ６００ｍｍ）の中段に、調製例３で得られた芳香族化合物製造触媒３．７５ｇと調製例４で得られた水素化脱アルキル化触媒３．７５ｇを芳香族化合物製造触媒が脂肪族炭化水素化合物の供給の際の上流側となるようにそれぞれを独立して充填し、空気５０ｍＬ／分で流通させながら５５０℃まで昇温し、流通ガスを窒素５０ｍＬ／分に切り替えた。この際の加熱はセラミック製管状炉を用い、触媒層の温度を制御した。
Preparation Example 4 (Preparation of hydrodealkylation catalyst)
An aqueous solution consisting of 0.89 g of tetraammineplatinum(II) nitrate and 15.2 g of water is gradually added dropwise to 15.0 g of γ-alumina with stirring, dried at 110° C. for 3 hours, and then calcined at 550° C. for 6 hours. Thus, a hydrodealkylation catalyst was prepared in which 2.6% by weight of platinum was supported on the γ-alumina carrier. For the production of benzene, the prepared catalyst powder was compressed and molded with a hydraulic press at 400 kgf/cm 2 for 1 minute, pulverized, passed through a sieve with an opening of 1.7 mm, and pellets deposited on a sieve with an opening of 850 μm were obtained. Used Example 1
3.75 g of the aromatic compound production catalyst obtained in Preparation Example 3 and the hydrogenation catalyst obtained in Preparation Example 4 were placed in the middle stage of a stainless steel reaction tube (inner diameter 16 mm, length 600 mm) of a fixed-bed gas-phase flow reactor. 3.75 g of the dealkylation catalyst was filled independently so that the aromatic compound production catalyst was on the upstream side when the aliphatic hydrocarbon compound was supplied, and the temperature was raised to 550 ° C. while air was circulated at 50 mL / min. It was warmed up and the flow gas was switched to nitrogen at 50 mL/min. A ceramic tubular furnace was used for heating at this time, and the temperature of the catalyst layer was controlled.
原料として脂肪族炭化水素化合物（メチルシクロペンタン２６重量％、ヘキサン１６重量％、メチルペンタン１５重量％、シクロペンタン８重量％、シクロヘキサン７重量％、ペンタン４重量％、メチルシクロヘキサン４重量％、ジメチルシクロペンタン４重量％、ヘプタン３重量％、メチルヘキサン３重量％、エチルシクロペンタン２重量％、ブタン１重量％、ジメチルブタン１重量％、エチルシクロヘキサン１重量％、オクタン１重量％、ノナン１重量％、その他３重量％の混合溶液）を０．１３６ｍＬ／分でフィードするとともに窒素を５０ｍＬ／分の流量で供給することで反応を開始させた。生成物の定量は、ガスクロマトグラフにより分析した。 Aliphatic hydrocarbon compounds as raw materials (methylcyclopentane 26% by weight, hexane 16% by weight, methylpentane 15% by weight, cyclopentane 8% by weight, cyclohexane 7% by weight, pentane 4% by weight, methylcyclohexane 4% by weight, dimethylcyclohexane Pentane 4% by weight, heptane 3% by weight, methylhexane 3% by weight, ethylcyclopentane 2% by weight, butane 1% by weight, dimethylbutane 1% by weight, ethylcyclohexane 1% by weight, octane 1% by weight, nonane 1% by weight, The reaction was started by feeding nitrogen at a flow rate of 50 mL/min while feeding other 3% by weight mixed solutions) at a rate of 0.136 mL/min. Quantification of products was analyzed by gas chromatography.
原料供給開始１５分後のベンゼン収率は２７．４重量％であった。 The benzene yield was 27.4% by weight 15 minutes after starting the raw material supply.
比較例１
調製例４で得られた水素化脱アルキル化反応触媒を用いなかった以外は、実施例１と同様の方法によりベンゼンの製造を行った。
Comparative example 1
Benzene was produced in the same manner as in Example 1, except that the hydrodealkylation reaction catalyst obtained in Preparation Example 4 was not used.
原料供給開始１５分後のベンゼン収率は２１．０重量％であった。 The benzene yield was 21.0% by weight 15 minutes after starting the raw material supply.
本発明のベンゼンの製造方法は、脂肪族炭化水素化合物からベンゼンを製造する際に、生産性に優れ、エネルギー消費の抑制されたベンゼンの製造方法となり、工業的に非常に有用なものとなる。 The method for producing benzene of the present invention is a method for producing benzene with excellent productivity and suppressed energy consumption when producing benzene from an aliphatic hydrocarbon compound, and is industrially very useful.
Claims (4)
（ａ）工程；炭素数１０以下の脂肪族炭化水素化合物をＭＦＩ型ゼオライト及び／又は金属含有ＭＦＩ型ゼオライトを含む触媒に接触し、芳香族化合物を含む生成物を製造する工程。
（ｂ）工程；（ａ）工程の生成物を水素化脱アルキル化触媒に接触し、ベンゼンを製造する工程。 At least the following steps (a) and (b) are performed in the same reactor or a series of multiple reactors when producing benzene from an aliphatic hydrocarbon compound by a contact reaction with a catalyst. A method for producing benzene.
(a) step; a step of contacting an aliphatic hydrocarbon compound having 10 or less carbon atoms with a catalyst containing an MFI zeolite and/or a metal-containing MFI zeolite to produce a product containing an aromatic compound.
(b) step; contacting the product of step (a) with a hydrodealkylation catalyst to produce benzene.
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