JPH02115134A - Production of aromatic hydrocarbon - Google Patents
Production of aromatic hydrocarbonInfo
- Publication number
- JPH02115134A JPH02115134A JP63268148A JP26814888A JPH02115134A JP H02115134 A JPH02115134 A JP H02115134A JP 63268148 A JP63268148 A JP 63268148A JP 26814888 A JP26814888 A JP 26814888A JP H02115134 A JPH02115134 A JP H02115134A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- catalyst
- alumina
- mixture
- crystalline aluminosilicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011701 zinc Substances 0.000 claims abstract description 60
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 57
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 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 21
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000001704 evaporation Methods 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 208000028462 aluminosis Diseases 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 108010023700 galanin-(1-13)-bradykinin-(2-9)-amide Proteins 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、パラフィン、オレフィンおよび／またはナフ
テンを含有する炭化水素原料より芳香族炭化水素を製造
する方法に関する。さらに詳しくは、結晶性アルミノシ
リケート、亜鉛およびアルミナの混合物を水蒸気中で熱
処理して得られた触媒、または亜鉛およびアルミナの混
合物を水蒸気中で熱処理した後、結晶性アルミノシリケ
ートと１昆合して得られた触媒を用いることにより、単
環芳香族炭化水素を効率よく製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic hydrocarbons from hydrocarbon feedstocks containing paraffins, olefins and/or naphthenes. More specifically, a catalyst obtained by heat-treating a mixture of crystalline aluminosilicate, zinc and alumina in steam, or a catalyst obtained by heat-treating a mixture of zinc and alumina in steam and then combining it with crystalline aluminosilicate. The present invention relates to a method for efficiently producing monocyclic aromatic hydrocarbons by using the obtained catalyst.
（従来の技術）
結晶性アルミノシリケートを触媒として芳香族炭化水素
を製造する方法は公知である。特開昭５４−２４８３５
号はオレフィンを含有する熱分解ガソリンなどを、亜鉛
ならびにｒｂ、■族の少なくとも１種の元素を含む制御
指数１〜１２シリ力／アルミナ比１２以上の多孔質結晶
性アルミノシリケートを用いて改質する方法を開示して
いる。(Prior Art) A method for producing aromatic hydrocarbons using crystalline aluminosilicate as a catalyst is known. Japanese Patent Publication No. 54-24835
No. 1 is a method for modifying pyrolyzed gasoline containing olefins using a porous crystalline aluminosilicate containing zinc and at least one element of the RB group and a control index of 1 to 12 and a silica/alumina ratio of 12 or more. discloses a method to do so.
特開昭６０−２５９４０号はプロパンを高含量で含む０
２〜Ｃ１□炭化水素を、亜鉛とガリウムを含有する制御
指数１〜１２シリ力／アルミナ比１２以上の結晶性ゼオ
ライトを用いて芳香族に転化する方法を開示している。JP-A No. 60-25940 contains a high content of propane.
A method is disclosed for converting 2 to C1□ hydrocarbons to aromatics using a crystalline zeolite containing zinc and gallium and having a control index of 1 to 12 and a silica/alumina ratio of 12 or more.
（発明が解決しようとする課題）
上記従来技術による芳香族化合物の製造において、触媒
の結晶性アルミノシリケートに亜鉛を添加すると、芳香
族化合物の収率が向上することが知られているが、亜鉛
は反応条件下で還元され蒸発する性質があり、亜鉛の効
果は、次第に不可逆的に失われていく。さらに、亜鉛は
溶融状態でステンレス鋼や炭素鋼等を腐食し、いわゆる
液体金属脆化を発生させることが知られており、亜鉛の
７発の防止は、工業化の問題点となっている。この亜鉛
の蒸発損失を制御するために、パラジウムなどの■族貴
金属やガリウムを添加する方法が知られているが、■族
貴金属やガリウムは、資源的に稀少かつ高価である他に
、亜鉛の蒸発損失の制御効果が十分でないなどの問題点
がある。(Problem to be Solved by the Invention) In the production of aromatic compounds using the above-mentioned conventional technology, it is known that adding zinc to crystalline aluminosilicate as a catalyst improves the yield of aromatic compounds. has the property of being reduced and evaporated under the reaction conditions, and the effect of zinc is gradually irreversibly lost. Furthermore, it is known that zinc corrodes stainless steel, carbon steel, etc. in a molten state, causing so-called liquid metal embrittlement, and prevention of zinc explosions has become a problem in industrialization. In order to control the evaporation loss of zinc, a method of adding group III noble metals such as palladium or gallium is known, but group III noble metals and gallium are rare and expensive resources, and they are There are problems such as insufficient control effect on evaporation loss.
（課題を解決するための手段）
本発明者らは、上記従来技術の問題点を克服して、触媒
からの亜鉛の蒸発損失が少ない安定な芳香族炭化水素の
製造法を開発するため研究を重ね、本発明を完成するに
至った。(Means for Solving the Problem) The present inventors have conducted research in order to overcome the problems of the above-mentioned conventional technology and to develop a stable method for producing aromatic hydrocarbons with less evaporation loss of zinc from the catalyst. After repeated efforts, the present invention was completed.
すなわち、本発明は、パラフィン、オレフィンおよび／
またはナフテンを含有する炭化水素を、結晶性アルミノ
シリケートおよび亜鉛を含有する触媒の存在下に芳香族
炭化水素に添加する方法において、結晶性アルミノシリ
ケート、亜鉛成分およびアルミナの混合物を水蒸気中で
熱処理して得られた触媒、または亜鉛成分およびアルミ
ナの混合物を水蒸気中で熱処理した後、結晶性アルミノ
シリケートと混合して得られた触媒を用いることを特徴
とする芳香族炭化水素の製造方法に関する。That is, the present invention provides paraffins, olefins and/or
or a method in which a naphthene-containing hydrocarbon is added to an aromatic hydrocarbon in the presence of a crystalline aluminosilicate and a zinc-containing catalyst, in which a mixture of the crystalline aluminosilicate, zinc component and alumina is heat treated in steam; or a catalyst obtained by heat-treating a mixture of a zinc component and alumina in steam, and then mixing the mixture with crystalline aluminosilicate.
本発明の方法における結晶性アルミノシリケートは、中
間細孔径を有するもの、すなわち、約５〜６．５人の有
効細孔径を存するものが挙げられる。たとえば、ＺＳＭ
−５、ＺＳＭ−８、ＺＳＭ−１１、ＺＳＭ−１２、ＺＳ
Ｍ−３５、ＺＳＭ−３８などが挙げられるが、ＺＳＭ−
５、ＺＳＭ−８、ＺＳＭ−１１などのＺＳＭ−５型結晶
性アルミノシリケートが好ましい。The crystalline aluminosilicates used in the method of the present invention include those having intermediate pore sizes, ie, those having an effective pore size of about 5 to 6.5 people. For example, ZSM
-5, ZSM-8, ZSM-11, ZSM-12, ZS
Examples include M-35, ZSM-38, etc., but ZSM-
ZSM-5 type crystalline aluminosilicates such as 5, ZSM-8 and ZSM-11 are preferred.
本発明の方法における亜鉛含有率は、亜鉛金属として全
触媒に対し１〜１０重量％、好ましくは１〜６重量％で
ある。亜鉛の含量が１重量％未満では、芳香族の収率が
低く、１０重量％を越えて亜鉛を加えても、芳香族の収
率はそれ以上向上しない。The zinc content in the process of the invention is from 1 to 10% by weight, preferably from 1 to 6% by weight, based on the total catalyst as zinc metal. When the zinc content is less than 1% by weight, the aromatic yield is low, and even if zinc is added in excess of 10% by weight, the aromatic yield does not improve any further.
本発明の方法において触媒に亜鉛を含有させる方法とし
ては、結晶性アルミノシリケート、亜鉛成分およびアル
ミナの混合物を水蒸気処理する場合には、イオン交換法
、含浸法、混練性等公知の方法が用いられる。また、調
製の順序に特に制約はなく、結晶性アルミノシリケート
、亜鉛成分およびアルミナを同時に混合しても、先に任
意の２成分を混合した後、残る１成分を混合してもよい
が、いずれの場合にも、混合は十分に実施することが望
ましい。一方、亜鉛成分およびアルミナの混合物を水蒸
気処理する場合には、通常、含浸法、混練法等の公知の
方法により、亜鉛成分とアルミナを十分に混合させるこ
とが望ましい。In the method of the present invention, when a mixture of crystalline aluminosilicate, zinc component, and alumina is treated with steam, known methods such as ion exchange method, impregnation method, and kneading method can be used to incorporate zinc into the catalyst. . Furthermore, there are no particular restrictions on the order of preparation, and the crystalline aluminosilicate, zinc component, and alumina may be mixed at the same time, or any two components may be mixed first, and then the remaining one component may be mixed. Even in this case, it is desirable to mix thoroughly. On the other hand, when a mixture of a zinc component and alumina is treated with steam, it is generally desirable to thoroughly mix the zinc component and alumina by a known method such as an impregnation method or a kneading method.
本発明の方法における亜鉛成分は、たとえば、亜鉛金属
、酸化亜鉛、水酸化亜鉛、あるいは硝酸亜鉛、炭酸亜鉛
、硫酸亜鉛、塩化亜鉛、酢酸亜鉛、シュウ酸亜鉛などの
塩、あるいはアルキル亜鉛などの有機亜鉛化合物等が挙
げられる。The zinc component in the method of the present invention is, for example, zinc metal, zinc oxide, zinc hydroxide, or salts such as zinc nitrate, zinc carbonate, zinc sulfate, zinc chloride, zinc acetate, zinc oxalate, or organic compounds such as alkyl zinc. Examples include zinc compounds.
本発明の方法におけるアルミナとしては、無水アルミナ
またはアルミナの水和物があるが、その他に、たとえば
、アルミニウム塩のように加水分解または加熱分解、酸
化などにより、無水アルミナまたはアルミナ水和物を生
成する原料を使用することもできる。The alumina used in the method of the present invention includes anhydrous alumina or alumina hydrate, but in addition, for example, anhydrous alumina or alumina hydrate can be produced by hydrolysis, thermal decomposition, oxidation, etc., such as aluminum salts. It is also possible to use raw materials.
本発明の方法におけるアルミナ含有率は、１２０３とし
て全触媒に対し２〜５０重量％、好ましくは５〜４０重
量％であり、かつ、アルミナと亜鉛のモル比（Ａｆｚ（
ｈ ／ Ｚｎ ）が１以上である。The alumina content in the method of the present invention is 2 to 50% by weight, preferably 5 to 40% by weight based on the total catalyst as 1203, and the molar ratio of alumina to zinc (Afz (
h/Zn) is 1 or more.
アルミナ含有率が２重量％未満では、亜鉛蒸発防止の効
果が不充分であり、５０重量％を越えてアルミナを加え
ても、亜鉛蒸発防止効果はそれ以上向上せず、触媒活性
が低下するため好ましくない。If the alumina content is less than 2% by weight, the effect of preventing zinc evaporation is insufficient, and even if alumina is added in excess of 50% by weight, the effect of preventing zinc evaporation will not improve any further and the catalyst activity will decrease. Undesirable.
本発明においては、上記組成物を水蒸気中で熱処理した
後、触媒として使用しなければならない。In the present invention, the above composition must be heat treated in steam before being used as a catalyst.
水蒸気中で熱処理することにより、亜鉛が安定化され、
反応条件下での亜鉛の蒸発損失を大幅に低下させること
ができる。亜鉛成分とアルミナの混合物を空気中で焼成
し、酸化亜鉛とアルミナの混合物にした後、水蒸気中で
熱処理したものの粉末Ｘ線回折を測定したところ、酸化
亜鉛とアルミナの反応物であるアルミン酸亜鉛の生成が
観察された。したがって、この亜鉛の安定化は、酸化亜
鉛がアルミン酸亜鉛に変化したことが原因と推定される
。ここで、水蒸気中での処理条件は、酸化亜鉛とアルミ
ナからアルミン酸亜鉛を生成し得る条件から選択される
が、通常は水蒸気分圧０．１〜１０ｋｇ／ｃれ処理温度
５００〜８００°Ｃ１好ましくは５５０〜７００°Ｃ１
処理時間０．１〜５０時間である。水蒸気処理は通常、
水蒸気単独か、または窒素、空気等の希釈剤の存在下に
実施する。Zinc is stabilized by heat treatment in steam,
The evaporation loss of zinc under reaction conditions can be significantly reduced. Powder X-ray diffraction measurements of the mixture of zinc component and alumina were calcined in air to form a mixture of zinc oxide and alumina, which was then heat treated in steam.Zinc aluminate, which is a reaction product of zinc oxide and alumina, was measured. was observed. Therefore, it is presumed that this stabilization of zinc is caused by the change of zinc oxide into zinc aluminate. Here, the treatment conditions in steam are selected from those that can produce zinc aluminate from zinc oxide and alumina, but usually the steam partial pressure is 0.1 to 10 kg/c and the treatment temperature is 500 to 800°C. Preferably 550-700°C1
Processing time is 0.1 to 50 hours. Steam treatment is usually
It is carried out with water vapor alone or in the presence of a diluent such as nitrogen or air.
本発明の方法におけるパラフィン、オレフィンおよび／
またはナフテンを含有する炭化水素とは、パラフィンま
たはオレフィンまたはナフテンまたはこれらの混合物を
実質的に含有する炭化水素であり、炭素数２以上、９０
％留出温度１９０°Ｃ以下の炭化水素である。たとえば
、パラフィンとしては、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、ノナンであり
、オレフィンとしては、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、ノネンで
あり、ナフテンとしては、シクロペンタン、シクロペン
テン、メチルシクロペンクン、シクロヘキサン、メチル
シクロペンテン、シクロヘキセン、シクロへキサジエン
が挙げられる。混合物としては、上記のそれぞれの混合
物、あるいはナフサなどの熱分解生成物のＣ４留分、前
記Ｃ４留分よりブタジェンまたはブタジェンとｉ−ブテ
ンを除いた留分、ナフサなどの熱分解生成物のＣ３留分
、前記Ｃ５留分からジエン類を除いた留分、熱分解ガソ
リン、熱分解ガソリンよりＢＴＸ抽出を行ったラフィネ
ート、ＦＣＣ分解ガス、ＦＣＣ分解ガソリン、リフォメ
ートよりＢＴＸを抽出したラフィネートが挙げられる。Paraffins, olefins and/or
Alternatively, the naphthene-containing hydrocarbon is a hydrocarbon that substantially contains paraffin, olefin, naphthene, or a mixture thereof, and has a carbon number of 2 or more and 90
It is a hydrocarbon with a % distillation temperature of 190°C or less. For example, paraffins include ethane, propane, butane, pentane, hexane, heptane, octane, and nonane; olefins include ethylene, propylene, butene, pentene, hexene, heptene, octene, and nonene; and naphthenes include: Examples include cyclopentane, cyclopentene, methylcyclopenkune, cyclohexane, methylcyclopentene, cyclohexene, and cyclohexadiene. The mixture may be a mixture of each of the above, a C4 fraction of a thermal decomposition product such as naphtha, a fraction obtained by removing butadiene or butadiene and i-butene from the C4 fraction, or a C3 fraction of a thermal decomposition product such as naphtha. Examples include fractions, fractions obtained by removing dienes from the C5 fraction, pyrolyzed gasoline, raffinate obtained by extracting BTX from pyrolyzed gasoline, FCC cracked gas, FCC cracked gasoline, and raffinate obtained by extracting BTX from reformate.
本発明の方法における添加条件は、温度３５０〜６００
°Ｃ１圧力大気圧〜３０ ｋｇ／ｃｒＭ Ｇ、重量空間
速度（ＷＨＳＶ）０．１〜５０ｈｒ−’が好まし・：、
さらに好ましくは、温度４００〜５６０″Ｃ１圧力大気
圧〜’ｌ Ｏｋｇ／ａｌＧＳＷＨＳ Ｖ ０． ２〜２
０ｈｒ−１である。The addition conditions in the method of the present invention are a temperature of 350 to 600
°C1 pressure atmospheric pressure to 30 kg/crM G, weight hourly space velocity (WHSV) 0.1 to 50 hr-' is preferable.
More preferably, temperature 400~560'' C1 pressure atmospheric pressure ~'l Okg/alGSWHS V 0.2~2
It is 0hr-1.
（発明の効果）
本発明によれば、実施例および比較例から分かるように
、触媒からの亜鉛の蒸発損失を防止し、芳香族炭化水素
の収率を高く維持することができる。(Effects of the Invention) According to the present invention, as can be seen from the Examples and Comparative Examples, it is possible to prevent evaporation loss of zinc from the catalyst and maintain a high yield of aromatic hydrocarbons.
（実施例）
以下、実施例により本発明の方法をさらに詳しく説明す
る。(Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
実施例１
アンモニウムイオン型２３Ｍ−５結晶アルミノシ’Ｊ
’ｆ ） （Ｓｉｎｇ／ Ａ ｌ ｚｏｚ モル比７
０）２００ｇに対し、硝酸亜鉛（亜鉛金属として４．６
ｇ）およびアルミナソ゛ル（八！２０．として５０ｇ）
を加え、混練後、押出成型を実施し、直径１． ６ｍｍ
、長さ４〜６胴に成型した。次いで、１２０’Ｃ，４時
間乾燥後、５００°Ｃ１３時間焼成した。Example 1 Ammonium ion type 23M-5 crystal aluminosi'J
'f) (Sing/A l zoz molar ratio 7
0) Zinc nitrate (4.6 as zinc metal) per 200g
g) and alumina sole (50g as 8!20.)
was added and after kneading, extrusion molding was performed to obtain a diameter of 1. 6mm
, and was molded into a length of 4 to 6 barrels. Then, after drying at 120°C for 4 hours, it was fired at 500°C for 13 hours.
次に、この押出成型品２０ｇを内径１２ｍｍの石英ガラ
ス製反応器に充填し、水蒸気を８０容量％含む水蒸気−
窒素混合ガス中で、大気圧下６５０°Ｃ１１時間熱処理
して触媒を得た。この触媒の亜鉛濃度を蛍光Ｘ線分析に
より求めたところ、全触媒に対し１．８重量％であった
。Next, 20 g of this extruded product was filled into a quartz glass reactor with an inner diameter of 12 mm, and a water vapor containing 80% by volume of water vapor was heated.
A catalyst was obtained by heat treatment at 650° C. for 11 hours under atmospheric pressure in a nitrogen mixed gas. The zinc concentration of this catalyst was determined by fluorescent X-ray analysis and was found to be 1.8% by weight based on the total catalyst.
次に、この触媒の反応条件下における安定性を短時間で
評価するため、５５０ ’Ｃｌ２Ｏ時間の水素還元処理
を実施し、その前後のｎ−へキサン転化反応結果および
触媒中の亜鉛濃度を測定した。Next, in order to evaluate the stability of this catalyst under reaction conditions in a short time, hydrogen reduction treatment was performed for 550' Cl2O hours, and the n-hexane conversion reaction results and zinc concentration in the catalyst were measured before and after. did.
すなわち、この触媒１０ｇを内径１２ｍｍの石英ガラス
製反応器に充填し、大気圧下５３０″Ｃ，ＷＨＳＶ（重
量空間速度） １． ４４ｈｒ”の条件で、ｎ−ヘキサ
ンの反応を１．５時間実施した。次いで、ｎ−ヘキサン
の供給を停止し、水素２０ Ｎｊ２ ／ｈｒを大気圧下
５５０°Ｃｌ２Ｏ時間流した。次に、水素供給を停止し
、水素還元前と同条件で再びｎヘキサンの転化反応を１
．５時間実施した。さらに、反応後の触媒を取り出し、
５５０″Ｃ１２時間空気中で焼成して、触媒上の炭素質
を除去した後、蛍光Ｘ線分析により触媒中の亜鉛濃度を
測定した。That is, 10 g of this catalyst was packed into a quartz glass reactor with an inner diameter of 12 mm, and the n-hexane reaction was carried out for 1.5 hours under atmospheric pressure at 530"C and WHSV (weight hourly space velocity) of 1.44 hours". did. Then, the supply of n-hexane was stopped, and 20 Nj2/hr of hydrogen was flowed under atmospheric pressure at 550 DEG C.Cl2O for an hour. Next, the hydrogen supply was stopped, and the conversion reaction of n-hexane was carried out again under the same conditions as before hydrogen reduction.
．． It was conducted for 5 hours. Furthermore, take out the catalyst after the reaction,
After firing in air at 550''C for 12 hours to remove carbon on the catalyst, the zinc concentration in the catalyst was measured by fluorescent X-ray analysis.
反応結果および触媒中の亜鉛濃度測定結果を表１に示す
。ただし、表１． ２中のｎ−ヘキサン転化率、Ｃ５〜
Ｃ，芳香族選択率、亜鉛飛散率は以下の式で計算した。Table 1 shows the reaction results and the measurement results of zinc concentration in the catalyst. However, Table 1. n-hexane conversion rate in 2, C5~
C, aromatic selectivity, and zinc scattering rate were calculated using the following formulas.
ｎ−ヘキサン転化率（χ） ＝ １００− （生成物中
のＣ４非芳香族成分の濃度（重量％））
Ｃ１〜Ｃ７芳香族選択率（χ）＝〔生成物中のＣ５〜Ｃ
７芳香族濃度の和（重量％）÷ｎ−ヘキサン転化率）Ｘ
１００
亜鉛飛散率（χ）−〔水素還元前後の亜鉛濃度の差（重
量％）÷水素還元前の亜鉛濃度〕×実施例２
硝酸亜鉛（亜鉛金属として９．９ｇ）を使用した以外は
、実施例１と同一の方法により触媒を調製した。この触
媒の亜鉛濃度を蛍光Ｘ線分析により測定したところ、全
触媒に対し３．８重量％であった。n-hexane conversion rate (χ) = 100- (concentration of C4 non-aromatic components in the product (wt%)) C1-C7 aromatic selectivity (χ) = [C5-C in the product
7 Sum of aromatic concentrations (wt%) ÷ n-hexane conversion rate)
100 Zinc scattering rate (χ) - [difference in zinc concentration before and after hydrogen reduction (wt%) ÷ zinc concentration before hydrogen reduction] x Example 2 Except for using zinc nitrate (9.9 g as zinc metal) A catalyst was prepared by the same method as in Example 1. The zinc concentration of this catalyst was measured by fluorescent X-ray analysis and was found to be 3.8% by weight based on the total catalyst.
実施例１と同一の方法により、この触媒の反応条件下に
おける安定性の評価を実施した。結果を表１に示す。The stability of this catalyst under reaction conditions was evaluated by the same method as in Example 1. The results are shown in Table 1.
比較例１
実施例１と同一のアンモニウムイオン型２３Ｍ−５結晶
性アルミノシリケー＋−ｉ ｏ ｏ ｇを７重量％硝酸
亜鉛水溶液中に浸し、蒸発乾固後、１２０”Ｃ４時間乾
燥、５００°Ｃ３時間焼成し、亜鉛２゜０重量％を含有
する触媒を調製した。次いで、この触媒を圧縮成型後、
粉砕し、９〜２０メツシユにそろえたちの２０ｇを、内
径１２ｍｍの石英ガラス製反応器に充填し、水蒸気を８
０重量％含む水蒸気−窒素混合ガス中で、大気圧下６５
０ ’Ｃ１時間熱処理した。引き続き、ＷＨ５Ｖを１，
８に変えた以外は、実施例１，２と同一の条件で触媒の
安定性評価を実施した。結果を表１に示す。Comparative Example 1 The same ammonium ion type 23M-5 crystalline aluminosilicate +-i o o g as in Example 1 was immersed in a 7% by weight zinc nitrate aqueous solution, evaporated to dryness, and dried at 120"C for 4 hours at 500° C was calcined for 3 hours to prepare a catalyst containing 2.0% by weight of zinc.Next, after compression molding this catalyst,
20g of crushed and arranged into 9 to 20 meshes was packed into a quartz glass reactor with an inner diameter of 12mm, and water vapor was
65% under atmospheric pressure in a water vapor-nitrogen mixed gas containing 0% by weight.
Heat treatment was performed for 1 hour at 0'C. Continue to 1 WH5V,
The stability evaluation of the catalyst was carried out under the same conditions as in Examples 1 and 2, except that the temperature was changed to 8. The results are shown in Table 1.
実施例３
Ｔ−アルミナ５０ｇに１６゜４重量％硝酸亜鉛水溶液２
４０ｇを加え、藩発乾固後、ｌ ２０ ’Ｃ４時間乾燥
し、５００°Ｃ３時間焼成した。次いで、圧縮成型後、
粉砕し、９〜２０メツシユにそろえたちの２０ｇを、内
径１２Ｍの石英ガラス製反応器に充填し、水蒸気を８０
容量％含む水蒸気−窒素混合ガス中で、大気圧下６５０
°Ｃ５時間熱処理した。次に、この水蒸気処理を実施し
た亜鉛含有α−アルミナ５ｇに、プロトン型２３Ｍ−５
結晶性アルミノシリケート（ＳｉＯ□／Ａｆ２０３モル
比４０）３５ｇを加え、乳鉢により攪拌混合した後、圧
縮成型、粉砕し、９〜２０メツシユの触媒を得た。続い
て、Ｗ）ＩＳＶを８．０に変え反応を２゜５時間実施し
た以外は、実施例１と同一の方法により、この触媒の反
応条件下における安定性を評価した。結果を表２に示す
。Example 3 16° 4% by weight zinc nitrate aqueous solution 2 in 50g of T-alumina
40 g was added, dried to dryness at 120° C. for 4 hours, and calcined at 500° C. for 3 hours. Then, after compression molding,
20g of crushed and arranged into 9 to 20 meshes was packed into a quartz glass reactor with an inner diameter of 12M, and steam was added to 80g.
In water vapor-nitrogen mixed gas containing % by volume under atmospheric pressure 650
Heat treatment was performed at °C for 5 hours. Next, 5 g of zinc-containing α-alumina subjected to this steam treatment was added with proton type 23M-5
35 g of crystalline aluminosilicate (SiO□/Af203 molar ratio 40) was added, stirred and mixed in a mortar, then compression molded and pulverized to obtain a catalyst of 9 to 20 meshes. Subsequently, the stability of this catalyst under the reaction conditions was evaluated in the same manner as in Example 1, except that W) ISV was changed to 8.0 and the reaction was carried out for 2.5 hours. The results are shown in Table 2.
比較例２
Ｔ−アルミナ１６５．６ｇと酸化亜鉛３４．４ｇにイオ
ン交換水１００ｇを加え、室温で２時間混練後、１２０
’Ｃ６，５時間乾燥し、さらに、５００°Ｃ２時間焼成
した。次いで、この粉末５ｇに実施例３と同一のプロト
ン型２３Ｍ−５結晶性アルミノシリケート３５ｇを加え
、乳鉢により攪拌混合した後、圧縮成型、粉砕し、９〜
２０メツシユの触媒を得た。続いて、実施例３と同一の
条件で触媒の安定性評価を行った。結果を表２に示す。Comparative Example 2 100 g of ion-exchanged water was added to 165.6 g of T-alumina and 34.4 g of zinc oxide, and after kneading at room temperature for 2 hours,
It was dried at 500°C for 5 hours and then fired at 500°C for 2 hours. Next, 35 g of the same proton type 23M-5 crystalline aluminosilicate as in Example 3 was added to 5 g of this powder, and after stirring and mixing in a mortar, compression molding and pulverization were carried out.
20 meshes of catalyst were obtained. Subsequently, the stability of the catalyst was evaluated under the same conditions as in Example 3. The results are shown in Table 2.
表１．２から、本発明の方法は、亜鉛の蒸発損失を防止
し、芳香族炭化水素の収率を高く維持するためにきわめ
て有効な方法であることが明らかである。From Table 1.2, it is clear that the method of the present invention is a very effective method for preventing evaporation loss of zinc and maintaining a high yield of aromatic hydrocarbons.
表 ほか１名table 1 other person
Claims (1)
する炭化水素を、結晶性アルミノシリケートおよび亜鉛
を含有する触媒の存在下に芳香族炭化水素に転化する方
法において、結晶性アルミノシリケート、亜鉛成分およ
びアルミナの混合物を水蒸気中で熱処理して得られた触
媒、または亜鉛成分およびアルミナの混合物を水蒸気中
で熱処理した後、結晶性アルミノシリケートと混合して
得られた触媒を用いることを特徴とする芳香族炭化水素
の製造方法。A process for converting hydrocarbons containing paraffins, olefins and/or naphthenes to aromatic hydrocarbons in the presence of a catalyst containing crystalline aluminosilicate and zinc, comprising: a mixture of crystalline aluminosilicate, zinc component and alumina; An aromatic hydrocarbon characterized by using a catalyst obtained by heat-treating a mixture of a zinc component and alumina in steam, or a catalyst obtained by heat-treating a mixture of a zinc component and alumina in steam, and then mixing the mixture with crystalline aluminosilicate. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63268148A JPH0729948B2 (en) | 1988-10-26 | 1988-10-26 | Aromatic hydrocarbon manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63268148A JPH0729948B2 (en) | 1988-10-26 | 1988-10-26 | Aromatic hydrocarbon manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02115134A true JPH02115134A (en) | 1990-04-27 |
| JPH0729948B2 JPH0729948B2 (en) | 1995-04-05 |
Family
ID=17454562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63268148A Expired - Lifetime JPH0729948B2 (en) | 1988-10-26 | 1988-10-26 | Aromatic hydrocarbon manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0729948B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995009050A1 (en) * | 1993-09-30 | 1995-04-06 | Sanyo Petrochemical Co., Ltd. | Method of partial dealuminization of zeolitic catalyst |
| JP2011005488A (en) * | 2009-06-25 | 2011-01-13 | China Petroleum & Chemical Corp | Catalytic cracking catalyst having higher selectivity, processing method and use thereof |
| JP5221149B2 (en) * | 2006-01-16 | 2013-06-26 | 旭化成ケミカルズ株式会社 | Propylene and aromatic hydrocarbon production method and production apparatus thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999003949A1 (en) * | 1997-07-15 | 1999-01-28 | Phillips Petroleum Company | High stability zeolite catalyst composition and hydrocarbon conversion process |
-
1988
- 1988-10-26 JP JP63268148A patent/JPH0729948B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995009050A1 (en) * | 1993-09-30 | 1995-04-06 | Sanyo Petrochemical Co., Ltd. | Method of partial dealuminization of zeolitic catalyst |
| JP5221149B2 (en) * | 2006-01-16 | 2013-06-26 | 旭化成ケミカルズ株式会社 | Propylene and aromatic hydrocarbon production method and production apparatus thereof |
| JP2011005488A (en) * | 2009-06-25 | 2011-01-13 | China Petroleum & Chemical Corp | Catalytic cracking catalyst having higher selectivity, processing method and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0729948B2 (en) | 1995-04-05 |
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