JPS5883635A - Preparation of hydrocarbon from methanol and/or dimethyl ether - Google Patents
Preparation of hydrocarbon from methanol and/or dimethyl etherInfo
- Publication number
- JPS5883635A JPS5883635A JP56179074A JP17907481A JPS5883635A JP S5883635 A JPS5883635 A JP S5883635A JP 56179074 A JP56179074 A JP 56179074A JP 17907481 A JP17907481 A JP 17907481A JP S5883635 A JPS5883635 A JP S5883635A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- catalyst
- methanol
- clay
- montmorillonite
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 25
- 239000002734 clay mineral Substances 0.000 claims abstract description 20
- 239000004927 clay Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000000440 bentonite Substances 0.000 claims abstract description 7
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- 230000002687 intercalation Effects 0.000 claims description 20
- 238000009830 intercalation Methods 0.000 claims description 20
- 239000011229 interlayer Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000001767 cationic compounds Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021647 smectite Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- -1 C140 olefins Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052902 vermiculite Inorganic materials 0.000 description 4
- 239000010455 vermiculite Substances 0.000 description 4
- 235000019354 vermiculite Nutrition 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005342 ion exchange 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000006200 vaporizer Substances 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
テル（以下「メタノール等」とｉう）を気相にて接触的
に反応させ，炭化水素類を製造する方法に関する．更に
詳しくは、粘土層間化合物を触媒として使用し、炭化水
嵩類特に炭素数２から４の不飽和炭ｆＭー水素＃（以下
ｒＯｔ ４のオレフィン」という）を製造するという新
しい方法に関する。DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for producing hydrocarbons by catalytically reacting esters (hereinafter referred to as "methanol, etc.") in a gas phase. More specifically, the present invention relates to a new method for producing hydrocarbons, particularly unsaturated carbons having 2 to 4 carbon atoms fM-Hydrogen (hereinafter referred to as rOt 4 olefins), using clay intercalation compounds as catalysts.
メタノール等の炭化水３Ｂ類への転化反応は、石油化学
の基礎ａ料及びエネルギー、特にガソリンに対する炭素
資源の多様化の有力な手段として広く研究され、酸性触
媒の使用が有効であることが良く知られている（ベトロ
チツク ３巻 １０５９頁 １９８０年）。The conversion reaction of methanol and other hydrocarbons to Class 3B hydrocarbons has been widely studied as a powerful means of diversifying carbon resources for petrochemical basic materials and energy, especially gasoline, and the use of acidic catalysts is often effective. It is known (Belotchik, vol. 3, p. 1059, 1980).
従って、多くの固体触媒が検討されてきてｉるが、工業
的価値ｔＭ、出しうるものとしては、ゼオライトを触媒
とする方法があるにすぎない、しかし、有効な触媒とな
りうるゼオライトは、従来のものと異なり、代表的には
２８Ｍ−５及び２８Ｍ−５４＠で衆知のアルミナ合歓の
少な％／＆特殊タイプである（０８Ｆ５８９４１０４号
明細書、特開昭Ｓ！ｌ−５８４９９号公報轡）これらの
ゼオライト、％ＫＺＢＭ−５４はＣｑ、ｓオレフィン生
成活性が＾〈注目されているが、訳素質の析出によって
劣化が極めて速やかに起仁ること、その製造には２０数
日以上の極めて長時間を費し、再稠性がよくないなど多
くの欠点を有すると指摘されてｉる（触媒 ２３巻 １
号 １０５頁 １９８１矩）。Therefore, many solid catalysts have been studied, but the only method that can provide industrial value is a method using zeolite as a catalyst. However, zeolite, which can be an effective catalyst, is These are typically 28M-5 and 28M-54@, which are low percentage/& special types of well-known alumina coalescence (08F5894104 specification, Japanese Patent Application Laid-Open No. Sho S!l-58499). Zeolite, %KZBM-54, is attracting attention for its Cq, s olefin-forming activity, but it deteriorates extremely quickly due to the precipitation of the olefins, and its production takes an extremely long time of more than 20 days. It has been pointed out that it has many drawbacks, such as poor re-consistency and poor re-consistency (Catalyst Vol. 23, 1).
No. 105, 1981).
更にこれらのゼオライトの製造には、＾−なアミン化合
物を必要とする等、工業触媒としてＦｉ満足すべきもの
でａｖｋ。Furthermore, the production of these zeolites requires ^- amine compounds, which should be satisfactory as industrial catalysts.
本発明者は、このような事情に鑑み、新たな工業触ｍを
開発すべく鋭意検討し良結果、階状構造を４つ結晶質フ
ィロケイ［ｉの粘土鉱物の層間イオンを陽イオン性化合
物でイオン交換して誘導される層間化合物（以下「、粘
土層間化合物」と−う）がメタノール郷から炭化水素類
特にＣ１４０オレフインを有利Ｋｌｌ造する触ＩｓＫな
るという新たな事実を見出し喪。In view of these circumstances, the inventor of the present invention has conducted intensive studies to develop a new industrial catalyst, and with good results has found that the interlayer ions of the clay mineral of crystalline phyllo-key [i] are replaced by a cationic compound. We discovered a new fact that intercalation compounds derived by ion exchange (hereinafter referred to as "clay intercalation compounds") can be used to advantageously produce hydrocarbons, particularly C140 olefins, from methanol.
本発明の方法における粘土鉱物に由来する層間化合物が
メタノール等の炭化水素類への転化に有効ケ触媒となる
理由は充分には明確でない。The reason why intercalation compounds derived from clay minerals in the process of the present invention are effective catalysts for conversion to hydrocarbons such as methanol is not fully clear.
一般に層状結晶質の粘土鉱物−は、その層間にイオン交
換しえる陽イオン、例えばＫ”＆びＮＩ！Ｌ＋等を有し
ている。この層間イオンを嵩高い陽イオン性化合物、例
えば多核錯イオン等でイオン交換、即ち通常、インタカ
レージ叢ンと称されるイオン化合物の挿入により層間隙
が増加した一種の複合体である層間化合物が生成する。In general, layered crystalline clay minerals have cations that can be ion-exchanged between the layers, such as K''&NI!L+. An intercalation compound, which is a type of complex with an increased interlayer gap, is produced by ion exchange, that is, the insertion of an ionic compound usually called an intercalation compound.
これらの化合物は、加熱条件では、通常、脱水郷によ）
生成する無機酸化物粒子等が層間を架橋して形成される
安定な細孔構造を保有することが餡められている（表面
１９巻 ２号 ５４頁 １９８１年）。These compounds are usually dehydrated under heated conditions)
It is believed that the produced inorganic oxide particles, etc. have a stable pore structure formed by cross-linking between layers (Kozen, Vol. 19, No. 2, p. 54, 1981).
このことより本発明の層間隙が増加した該粘土鉱物類は
、メタノール尋の転化反応の場に充分な細孔を持ち、同
時に層間の金属元素化合物ある％Ａはこれらと粘土鉱物
との総合的な作＃ｆＩＫより炭化水素類への転換の触媒
活性を発机すると推測される。From this, the clay minerals of the present invention with increased interlayer gaps have sufficient pores for the conversion reaction of methanol, and at the same time, the interlayer metal element compounds (%A) are the total amount of these and the clay minerals. It is presumed that the catalytic activity of conversion to hydrocarbons is triggered by #fIK.
本発明でいうところの粘土層間化合物の触媒としての利
用については、多様な触媒として、その可能性が期待さ
れているが、石油成分の接触分解。Regarding the use of clay intercalation compounds as catalysts as referred to in the present invention, various possibilities are expected as catalysts, including catalytic cracking of petroleum components.
水素化分解、異性化及び改質の触媒としてのｇｋ相が知
られているにすぎず（表ＥｉｌＯ：前出、化学経済１０
月号 ２真 １９８０年、％開昭５４−５８８４等）、
本発明Ｏ如きメタノール等の炭化水ｌｃａへの転化触媒
としての使用はい遣だその例を児な−。Only the gk phase is known as a catalyst for hydrocracking, isomerization and reforming (Table EilO: supra, Chemical Economics 10).
Monthly issue 2 true 1980, % Kaisho 54-5884, etc.),
An example of this is the use of the present invention as a catalyst for converting methanol and other hydrocarbons to lca.
本発明の方法における粘土層間化合物は、通常極めて安
蜘な粘土鉱物に所望の金鵬元素ｔ４ＩＩ＆元累とする罎
イオン性化合物を簡単な操作で挿入することにより、容
易Ｋまた再現性よ＜Ｘ裂される。The clay intercalation compound used in the method of the present invention can be produced easily and reproducibly by inserting an ionic compound containing the desired metal element t4II & element into clay minerals, which are usually extremely safe. be done.
ｊ！にハ０鵞〜４のオレフィン等の炭化水Ｊｃ類類比比
較的選択性く製造するととを可能にする等、従来技術の
欠点の多くを解消するものである。j! It overcomes many of the drawbacks of the prior art, such as allowing the production of hydrocarbons such as olefins of 0 to 4 with relative selectivity.
以上、本発明の要旨は、メタノール等を気相で接触的に
炭化水素類に転化するに当り、触媒として粘土層間化合
物を使用することによる畿化水累拳の製造方法にある。As described above, the gist of the present invention resides in a method for producing Kikasuiken by using a clay intercalation compound as a catalyst in catalytically converting methanol etc. into hydrocarbons in a gas phase.
なお、本明細書において「層関腺」とは、粘土鉱物又は
その層間化合物のＸＭｍ回収によつて＃ｊ定される（０
０１）ｒｊｊＪの面間隔からケイ酸塩−の厚みｔ差し引
−たものである０例えは、本発明の代表的粘土鉱物であ
るモンモリロナイトの鳩舎、その脱水状態のＸＨ回折に
より約１４の繰返し間隔の構造巣位を有していることが
値められる。従って、モンモリロナイトの層間化合物の
層間−は、その面間隔からｔ５ムを差し引けば良い。In addition, in this specification, "interlayer gland" is determined by XMm recovery of clay minerals or their interlayer compounds (#j
01) Subtracting the silicate thickness t from the interplanar spacing of rjjJ.0 An example is a pigeonhole of montmorillonite, which is a typical clay mineral of the present invention. It is valued for having a structural nest position. Therefore, the interlayer distance of the interlayer compound of montmorillonite can be determined by subtracting t5m from the interplanar spacing.
以下、本発明を更に詳しく説明する。The present invention will be explained in more detail below.
本発明において、触媒として粘土層間化合物が使用され
るが、その調製に際して、用意される粘土鉱物は結晶質
フィロケイ酸塩に属するものである。望ましくは、工業
触媒としての性能１Ｍ隣性勢の実用上の観点より、スメ
クタイト型、バーミキーライト型又はクロライド型に属
するものである。更に、これらには天然及び合成品があ
るが、いずれでも良ｖ”ｏシかし、一般に安価で容易に
入手しえるとｉう点で、天然品がより有利に使用される
。具体的には、スメクタイト型としては、モンモリロナ
イト、バイデライト、ヘクト２イト。In the present invention, a clay intercalation compound is used as a catalyst, and the clay mineral prepared in its preparation belongs to crystalline phyllosilicates. Desirably, it belongs to the smectite type, vermikeylite type, or chloride type from the practical point of view of its performance as an industrial catalyst of 1M neighborhood. Furthermore, although there are natural and synthetic products, both are good, but natural products are more advantageously used because they are generally inexpensive and easily available.Specifically. The smectite types include montmorillonite, beidellite, and hectite.
ノントロン石、ベントナイト等、バーミキエライト麺と
しては、バーミキュライト又はヒル石の名称で呼ばれる
もの、クロライド型としては、緑泥石として知られてい
るクックアイト、ベンニン等を挙げることができる。特
に望ましくはモンモリロナイト及びベントナイトである
。Examples of vermicierite noodles such as nontronite and bentonite include those called vermiculite or vermiculite, and examples of chloride types include cookite, bennine, etc. known as chlorite. Particularly preferred are montmorillonite and bentonite.
これらの粘土鉱物より、本発明の方法における触媒であ
る層間化合物を得るためＫＦｉ、 ＰｊＴ望の金属元素
を含有する金属イオン、錯イオン等の陽イオン性化合物
が該粘土鉱物の層間イオンとのイオン交換の形で挿入さ
れる。この陽イオン性の金属元素化合物は、生成鳩関化
合物を触媒として使用する際、その層間隙をほぼメタノ
ールの有効分子径に近％ｆｈｔｓ１以上に保持しうるも
のが望ましい。In order to obtain an intercalation compound which is a catalyst in the method of the present invention from these clay minerals, a cationic compound such as a metal ion or a complex ion containing the desired metal element of KFi or PjT is ionized with the intercalation ion of the clay mineral. inserted in the form of an exchange. This cationic metal element compound is desirably one that can maintain the interlayer gap at %fhts1 or more, which is close to the effective molecular diameter of methanol when the produced Hoseki compound is used as a catalyst.
層間隙が４５ム未渦のものは、本発明のメタノール等の
炭化水素類への転化反応活性が低く、ジメチルエーテル
の生成の段階でとどまる傾向が高くなる。一方、この炭
化水素類、特にＣ３〜４ のオレフィンへの選択性は挿
入される陽イオン化合物の構成金属元素の種によって左
右される。従うて、望ましくは周期律表第１−第１族か
ら選択される少なくとも一種を構成元素として會む化合
物である。特に望ましい元素と、しては、アルミニウム
。When the layer gap is less than 45 mm, the conversion reaction activity to hydrocarbons such as methanol of the present invention is low, and there is a high tendency to remain at the stage of producing dimethyl ether. On the other hand, the selectivity to hydrocarbons, particularly C3-4 olefins, depends on the species of the constituent metal elements of the cationic compound to be inserted. Therefore, it is preferably a compound containing at least one member selected from Group 1-1 of the periodic table as a constituent element. A particularly desirable element is aluminum.
ジルコニクム、ＵＳ、ビスマス、クロム、タングステン
、マンガン、ランタン及びマグネシウムを挙けることが
できる。これらはまた、ｌ−間Ｓｔ一本発明にとって好
ましい範囲である４、５ｘ以上に保持するのにも有効で
ある。Mention may be made of zirconium, US, bismuth, chromium, tungsten, manganese, lanthanum and magnesium. These are also effective in maintaining the l-St to 4.5x or more, which is the preferred range for the present invention.
所望する金属元素化合物が粘土鉱物へ挿入された粘土層
間化合物は、公知の方法によって容易にＩＩ製すること
ができる（表ｍ：前出、特開昭５４−５８６４号明細書
等）。A clay intercalation compound in which a desired metal element compound is inserted into a clay mineral can be easily produced by a known method (Table m, supra, JP-A-54-5864, etc.).
本発明に使用する粘土層間化合物はｔｓＸ以上の層間ｍ
ｔ有するものが好ましい。このように層間隙の大清いも
のを得るために、陽イオン性の金属元素化合物きして、
中心の核となる金属元素が一個のイオン中に２個以上、
好ましくは４個以上存在する多核錯体で、解離により陽
イオン性となる多核金属水酸化イオン轡の比較的高分子
１の多核錯イオン會該粘土鉱拗の層間陽イオンとイオン
交換させることが望ましい０例えば、挿入する金属の塩
を水に溶解して、父は通常、滴定法と称される方法によ
って金属塩の水溶液をアルカリで滴定等によ砂オール化
（上野景千著１入門キレート化学”１０真 昭和４４年
南江堂発行）し、陽イオン性の多核錯イオン、具体的
には、［Ｚｒ４ （０１１）ｓ ］龜＋ 、゛〔ム４
（０１１）ｎ）・＋、 、［Ｃｒ＠ （０Ｈ）ｔｔ
］“ 峠 。The clay interlayer compound used in the present invention has an interlayer m of tsX or more.
Those having t are preferable. In order to obtain a material with very clear interlayer gaps, we use a cationic metal element compound.
Two or more metal elements that serve as the central core are present in one ion,
Preferably, the polynuclear complex is a polynuclear complex in which 4 or more are present, and it is desirable to ion-exchange the polynuclear complex ion with a relatively high molecular weight 1 of the polynuclear metal hydroxide ion, which becomes cationic upon dissociation, with the interlayer cation of the clay mineral. 0 For example, the salt of the metal to be inserted is dissolved in water, and the aqueous solution of the metal salt is usually titrated with an alkali by a method called titration method (Introductory Chelate Chemistry 1 by Keichi Ueno). "10 Shin Published by Nankodo in 1962), and cationic polynuclear complex ions, specifically [Zr4 (011)s] 龜+, ゛[M4
(011)n)・+, ,[Cr@(0H)tt
] “Toge.
［Ｂ１５（ＯＨ）ｔｔ）−十勢で示される多核金員水酸
化イオンを＠製して、これらｔ含む溶液に該粘土層−を
分散させれば良φ、史Ｋｄアルミニウムの場合の如く、
金属アルミニウムと塩化アルミニウムより、一般Ｋ Ａ
ｌｔ４ｈ （ＤＨ）ＢｎＣＩ＠ （＊≧４を示す。）で
示されるアルミニウムクロ四ヒドロキシ錯体を調製して
使用しても良ｉ。[B15(OH)tt) - If a polynuclear metal hydroxide ion represented by 10 is prepared and the clay layer is dispersed in a solution containing these t, it is possible to obtain φ, as in the case of history Kd aluminum,
From metallic aluminum and aluminum chloride, general K A
It is also possible to prepare and use an aluminum tetrahydroxy complex represented by lt4h (DH)BnCI@ (*indicates ≧4).
このようＫして得られた粘土層間化合物は、そのまま本
発明の触媒として使用することができるが、例えば、層
間に存在する水酸化イオンの加熱による脱水等の良め、
若干の収縮が発生する場合がある。従って１本発明の方
法において安定性の・高−触媒とするためには、使用前
に加熱処理するのが望ましい、処理は通常の空気燐酸で
良い。その温度は挿入金属元素化合物の柚＃Ａ郷により
若干異なシ、ｉた、あ蓋り高すぎると挿入金属元素の酸
化物粒子等による層間の架橋が崩壊し、階間距離が保持
しえなくなる丸め、通Ｎ２００〜８００℃、好ましくは
５００〜６００℃である。処理時間は４１１には制限な
いが、１〜６時間であれば充分である。もちろん、本発
明における粘土層間化合物は適当な形状に成形して使用
しても何らさしつかえない。The clay intercalation compound obtained by K in this manner can be used as it is as the catalyst of the present invention, but for example, if the hydroxide ions present between the interlayers are dehydrated by heating,
Some shrinkage may occur. Therefore, in order to obtain a highly stable and highly stable catalyst in the method of the present invention, it is desirable to heat-treat the catalyst before use, and the treatment may be carried out using ordinary air phosphoric acid. The temperature differs slightly depending on the compound of the intercalated metal element.However, if it is too high, the interlayer bridges formed by the oxide particles of the intercalated metal element will collapse, making it impossible to maintain the interlayer distance. Rounding and rolling N is 200 to 800°C, preferably 500 to 600°C. The processing time is not limited to 411 hours, but 1 to 6 hours is sufficient. Of course, the clay intercalation compound in the present invention may be used after being molded into a suitable shape.
本発明の方法を実施するにあたりては、上記の方法で得
られた触媒上にメタノール等、即ちメタノールｉび／又
はジメチルエーテルをガス状で流通させる。この原料メ
タノール等は、各々個別にあるいは混合物として、その
まま反応器に供給しても良いが、本反応は大きな発熱を
伴うため、通常、 窒素、アルゴン、ヘリウム、二酸化
炭素、水蒸気等の反応に不活性なガスで希釈される。そ
の際、供給ガス中の原料メタノール等のガス濃度は特に
は制限ないが、経済的観点から５容蓋％以上であること
が望ましい。In carrying out the method of the present invention, methanol or the like, that is, methanol and/or dimethyl ether, is passed in a gaseous state over the catalyst obtained by the above method. These raw materials, such as methanol, may be supplied to the reactor as they are, either individually or as a mixture, but since this reaction is accompanied by a large amount of heat, usually nitrogen, argon, helium, carbon dioxide, water vapor, etc. Diluted with active gas. At this time, the concentration of gas such as raw material methanol in the supplied gas is not particularly limited, but from an economical point of view it is desirably 5% or more.
反応温度は通常２５０〜５００℃の範囲から選ばれるが
、低温度では触媒の活性が低くなり、一方、高すぎると
コーク等の生成を招き、触媒の活性低下の原因となるた
め、好ましくＦｉ３００〜４５０℃の範囲である。反応
圧力は常圧で艮−が、反応原料及び生成物が反応条件下
でガス状を保持しうる範囲であれば、加圧で行っても何
らさしつかえない。The reaction temperature is usually selected from the range of 250 to 500°C, but if the temperature is too low, the activity of the catalyst will be low, while if it is too high, it will lead to the formation of coke and the like, which will cause a decrease in the activity of the catalyst. The temperature range is 450°C. The reaction pressure may be normal pressure, but it may be carried out under increased pressure as long as the reaction raw materials and products can maintain their gaseous state under the reaction conditions.
供給されるメタノール等の原料ガスと触媒との接触時間
は、反応温度及び原料ガス＃１度によっても変るが、
ｗＡＩ（Ｗは触媒重量（ｆ）、 Ｆはメタノール等の原
料の供給速［（ｍｏｘ／ｍｔｎ） ｔ−示す）の表示で
１０〜２ ａＯＯＯ（ｆ−ｍｉ＄ｍｏｌ）の範囲、好ま
しくは４０〜Ｉ Ｑ、 ０００ （Ｆ＠ｍｉｎ／ｍｏｌ
）の範囲から選ばれる。The contact time between the supplied raw material gas such as methanol and the catalyst varies depending on the reaction temperature and the raw material gas #1 degree, but
wAI (W is the weight of the catalyst (f), F is the supply rate of raw materials such as methanol [(mox/mtn) t)] is in the range of 10 to 2 aOOO (f-mi$mol), preferably 40 to 2 I Q, 000 (F@min/mol
) is selected from the range.
反応は固定床、Ｒ動床あるいは移動床のいずれの型式に
よ−ても実施可能であｄ１白ヒ水１［＋は公知の方法に
より生成混合物ガス流から分離すれば良ｉ、もちろん、
本発明の方法において、メタノールを原料とする場合、
生成物中にはジメチルエーテルが１められる場合がある
が、これは原料として回収し、再循環される。なお、従
来技術において１められるコーク等の生成による触媒の
活性低下は、本発明の方法では小さい。しかし、反応が
長時間に及ぶと本発明においてもコーク等の生成はまぬ
がれ先な％Ａため、その場合は、本発明の触媒を公知の
再生処理、即ち、酸素含有ガス、例えば空気等により該
コーク郷を燃焼する轡の方法全実施すれば良い、
以下、実施例によって本発明の詳細な説明するが、本発
明の方法はこれら実施例に＠鉋されるものではな−。な
お、実施例において示された結果は、下記の通り定義さ
れる。The reaction can be carried out in fixed bed, R moving bed or moving bed format, and d1 white arsenic water 1[+ can of course be separated from the product mixture gas stream by known methods.
In the method of the present invention, when methanol is used as a raw material,
Dimethyl ether may be present in the product, but this is recovered as a raw material and recycled. Note that the method of the present invention reduces the reduction in catalyst activity due to the production of coke, etc., which is a problem in the prior art. However, if the reaction lasts for a long time, the production of coke and the like is inevitable even in the present invention. The present invention will be explained in detail by way of examples below, but the method of the present invention is not limited to these examples. Note that the results shown in the examples are defined as follows.
メタノールの全転化率〜：Ｘ
−（［ｃＨ８ｏｎ導入量］ −ＥＯＨ，ＯＨ未反応會月
×１００／［（！Ｈ，０１１１導入量］
メタノールの炭化水素への転化率１！！１１１９：Ｘ）
１Ｇ■（（（！Ｈ，ＯＨ導入鎗） −（（ａＨ，ＯＨ未
反応ｌｔｌ＋２ｘ［（ａＨ，）ｍＯ量］＋［ＯＯ量］＋
〔Ｃへ量）））ｘ１００／ＣＣＨ，ＯＨ４入量〕
Ｃ３〜、のオレフィンの選択率弼：８
−〔４〜、のオレフィン生成１ｔ（ＣＩベース）’］Ｘ
１００／〔嶽化水素生ＦＩＬｔ（ＣＩベース）〕巖 〔
〕：埜位１００１
電電 ジメチルエーテル（（ＯＨｓ）＊Ｏ） を原料
とする場合。Total conversion rate of methanol ~:
1G
[Amount to C))) x 100/CCH, OH4 input] Selectivity of olefin of C3~: 8 - [Olefin production 1t (CI base) of 4~)']
100/[Dake Hydrogen FILt (CI base)] Iwao [
]: Noi 1001 Denden When dimethyl ether ((OHs)*O) is used as a raw material.
メタノールとのモル関係を考慮し、！及びＸＨＯ１ｌＩ
出。Considering the molar relationship with methanol,! and XHO1lI
Out.
ま九、各実施例における粘土層間化合物は、元素記号と
粘土鉱物名で表示した。例えは、アルミニウム化合物と
モンモリロナイトより調製した層間化合物は１Ｍ−モン
モリロナイト”と表示した。(9) The clay intercalation compounds in each example were indicated by element symbols and clay mineral names. For example, an intercalation compound prepared from an aluminum compound and montmorillonite is expressed as 1M-montmorillonite.
実施例１〜２
〔ムｌ−モンモリロナイトの調製（ｌ）〕スメクタイト
型粘土として市販のモンモリロナイト（国峰工業製、ク
ニビア？）を用い友。このモンモリロナイト１５Ｆをア
ルミニウムクロロヒドロキシ錯体水浴液１０〇−中に加
えてスラリー状とし、６０℃で２時間加熱攪拌した後、
生成物をろ過分離し友、これを熱脱イオン水で十分に洗
浄し友後、湯浴上で攪拌しながら乾燥させた。Examples 1 to 2 [Preparation of mul-montmorillonite (l)] Commercially available montmorillonite (manufactured by Kunimine Kogyo, Kunivia) was used as a smectite-type clay. This montmorillonite 15F was added to aluminum chlorohydroxy complex water bath liquid 100- to form a slurry, and after heating and stirring at 60°C for 2 hours,
The product was separated by filtration, thoroughly washed with hot deionized water, and then dried on a hot water bath with stirring.
なお、アルミニウムクロロヒドロキシ錯体は次のようＫ
して調製した。まず、ＩＭの塩化アルミニウム（６水塩
を使用）水溶液中に８倍モル量の金属アルミニウム１加
え、湯浴上で加熱する。水素が発生し始めたら加熱を止
め、穏やかに水ｌＡを発生させる。水素の発生が終了し
たら未反応の金輌アルミニウムｔろ別する。ろ液を湯浴
上で加熱濃縮してアルミニウムクロロヒドロキシ錯体と
した。In addition, the aluminum chlorohydroxy complex is K as follows.
It was prepared by First, 8 times the molar amount of metal aluminum 1 is added to an aqueous solution of IM aluminum chloride (hexahydrate is used) and heated on a hot water bath. When hydrogen begins to be generated, stop heating and gently generate 1A of water. When hydrogen generation is completed, unreacted gold aluminum is filtered off. The filtrate was heated and concentrated on a hot water bath to obtain an aluminum chlorohydroxy complex.
以上のようにして調製したＡｔ−モンモリロナイトは、
１２０℃で乾燥後、４００℃で５時間空気焼成し触媒と
した。なお、層間隙はＸ線回折によって求めた。At-montmorillonite prepared as above is
After drying at 120°C, it was air-calcined at 400°C for 5 hours to obtain a catalyst. Note that the interlayer gap was determined by X-ray diffraction.
内径１０■、長さｓｏｏｗｒのステンレス製の固定床流
通反応装置に該触媒２ｆｇｔ充填した。次いで該触媒を
流動浴で所定偏置にした後、原料メタノールｔマイクロ
フィーダーによシ足量的に供給し、気化器中で窒素ガス
と混合して反応管に送入した０反応生成物はガス状で採
取し、すべてブスクロマトグラフで分析した。A fixed bed flow reactor made of stainless steel and having an inner diameter of 10 cm and a length of sowr was filled with 2 fgt of the catalyst. Next, the catalyst was made to have a predetermined eccentric position in a fluidized bath, and then a sufficient amount of raw methanol was supplied to a microfeeder, and the reaction product was mixed with nitrogen gas in a vaporizer and sent to a reaction tube. All samples were collected in gaseous form and analyzed by bus chromatography.
第１表に反応条件及び結果を示した。Table 1 shows the reaction conditions and results.
実施例５
〔ｈｔ−モンモリロナイトの調製（２）〕実施例１と同
じモンリロナイ）１用−滴定法により層間化合物を調製
した。まず、［１２Ｍの塩化アルミニウム（６水塩を使
用）水溶液５００−に１Ｍ−ＭａＯＨ水溶液２００−を
攪拌しながら、２００鴫＾ｒの速度で滴下した。次いで
、モンモリロナイト１五〇２４ｆを加え、１週間、攪拌
放置し良。Example 5 [Preparation of ht-montmorillonite (2)] An intercalation compound was prepared by the same titration method as in Example 1. First, 200 mm of a 1M aqueous solution of MaOH was added dropwise to 500 mm of a 12 M aqueous solution of aluminum chloride (hexahydrate was used) at a rate of 200 mm while stirring. Next, 15,024 f of montmorillonite was added, and the mixture was left stirring for one week.
その後、生成物をろ過し、純水でよく洗浄した。Thereafter, the product was filtered and thoroughly washed with pure water.
これを１１０℃で２４時間乾燥した後、４００℃で４時
間空気焼成し、触媒とした。This was dried at 110°C for 24 hours and then air-calcined at 400°C for 4 hours to obtain a catalyst.
実施例１と同方法で反応を行なった。０反応条件及び結
果を第１＠ＩＫ示した０表中の炭化水嵩以外の生成物は
ジメチルエーテルであ６、ｃｏ及びＣＯｔはほとんど認
められなかった。The reaction was carried out in the same manner as in Example 1. The products other than the hydrocarbon volume in Table 1 showing the reaction conditions and results were dimethyl ether6, and almost no co and COt were observed.
第 １ 表
Ｗ／Ｆ −２５４０（ｆ−Ｏａｔ、 ｍ１ｒＶ′ｍｏ
ｌ）％ ／ ＣＨＩＯＨ” ４ （ｍｏｌ／ｍｏｌ）
実施例４〜５
（Ｚｒ−モンモリロナイトの調製〕
実施例１と同じモンモリロナイ）４ｆを１ｔの（Ｌ２Ｍ
オキシ塩化ジルコニウム水溶液に加えスラリー状にした
ン６６℃にて１時間加熱攪拌後、実施例１と同様に処理
してＺｒ−モンモリロナイトを墳得した。これ１１２０
℃で乾燥後、各温度て４時間焼成した。Table 1 W/F-2540 (f-Oat, m1rV'mo
l)% / CHIOH” 4 (mol/mol)
Examples 4 to 5 (Preparation of Zr-montmorillonite) 4f of the same montmorillonite as in Example 1 was converted into 1t of (L2M
The mixture was added to an aqueous zirconium oxychloride solution to form a slurry, heated and stirred at 66° C. for 1 hour, and then treated in the same manner as in Example 1 to obtain Zr-montmorillonite. This is 1120
After drying at ℃, it was fired at each temperature for 4 hours.
実施例１と同方法で反応を行なった。反応条件及び結果
を第２表に示した。The reaction was carried out in the same manner as in Example 1. The reaction conditions and results are shown in Table 2.
なお、実施例１〜５と同様に炭化水ｇａ以外の生成物は
ほとんどがジメチルエーテルであった。Note that, as in Examples 1 to 5, most of the products other than the hydrocarbon ga were dimethyl ether.
９２表
触媒：ｚｒ−モンモリロナイト
Ｗ／Ｆ−２５４０（ｆ−Ｏａ ｔ、Ｉｎｉ Ｖ′１１１
０１ ）％ １０ＨＩＯＨ−４（ｍｏＶ！１１０１）比
較例１
実施例１と同じモンモリロナイトをそのまま４０ｔｌ’
Ｃで４時間空気焼成して触媒とした。その焼成モンモリ
ロナイトの層間隙は五〇Ｘであった。Table 92 Catalyst: zr-montmorillonite W/F-2540 (f-Oat, Ini V'111
01)% 10HIOH-4 (moV! 1101) Comparative Example 1 The same montmorillonite as in Example 1 was used as it was at 40 tl'
The catalyst was air-calcined at C for 4 hours. The interlayer gap of the calcined montmorillonite was 50×.
実施例１と同一条件で反応全行なった結果、Ｘｍ２１４
Ｘであり、生成−はジメチルエーテルのみで、炭化水素
類の生成ＦｉＭめられなかった。As a result of carrying out the entire reaction under the same conditions as in Example 1, Xm214
X, and only dimethyl ether was produced, and no hydrocarbons were observed.
比較例２
層構造を取らなｉ活性白土を触媒とし、実施例１と同様
にして反応を行なっ九結果、Ｘ＝７５．８％であり、ジ
メチルエーテルが生成されただけであった。Comparative Example 2 A reaction was carried out in the same manner as in Example 1 using active clay without a layered structure as a catalyst.The result was that X=75.8% and only dimethyl ether was produced.
実施例６〜９
実施例１のモンモリロナイトにかえて、第５表に示した
各種粘土鉱物のアルミニウム及びジルコニウム層間化合
−をｌｌ１ｌ製し、触媒とした。Examples 6 to 9 Instead of the montmorillonite of Example 1, 111L of aluminum and zirconium intercalation of various clay minerals shown in Table 5 were prepared and used as catalysts.
結果を第３表に示した。The results are shown in Table 3.
第５表
反応誕ｆ ３５０℃
Ｗ／Ｆ −２５４０（ｔ−（ｌｈｔ、ｍｉｌｍｏｘ）Ｎ
１／ＣＨｊＯＨ−４（ｍｏＶｍｏｌ）各粘土鉱物は次の
ものを使用し良。Table 5 Reaction birth f 350℃ W/F -2540(t-(lht, milmox)N
1/CHjOH-4 (moVmol) The following clay minerals may be used.
ベントナイト：豊鵬ベントナイト
バーミキュライト：アフリカ韮バーミキうライト縁泥石
：島根県鰐棚鉱山歴
実施例１０〜１８
実施１１１と同じモンモリロナイトｔＩ２用し、第４表
に示した各徨金属元累の化合物との鳩閣化合物を実施例
１〜４の方法に従って＃ｌｌｌ製した。ただし、８１に
ついては、〔８１（ア轡トたト）、〕 を合成し、こ
れをアセトン中でモンモリロナイトと混合した後、ろ別
乾燥してＷＡ製した。いずれも温度４００℃で４時間空
気焼成し、触媒として実施例１と同一条件で反応を行な
っ九。Bentonite: Toyoho Bentonite Vermiculite: African dwarf vermiculite Edge mud stone: Shimane Prefecture Wanidana Mine History Examples 10 to 18 Using the same montmorillonite tI2 as in Example 111, and the compounds of each of the metals listed in Table 4. #llll was prepared according to the method of Examples 1 to 4. However, regarding 81, [81 (Atato Tato)] was synthesized, mixed with montmorillonite in acetone, filtered and dried to produce WA. All were air-calcined at a temperature of 400° C. for 4 hours, and the reaction was carried out as a catalyst under the same conditions as in Example 1.
第４表
実施例１９
実施例１と同じＡ！−モンモリロナイトを触媒とし原料
をジメデルエーテル、その供給速ｊｆＷ／Ｆ＝５０７０
（ｆ−Ｏａｔ、 ｍ１ｒ１／／ｍｏｌ）とした以外は
実施例１と同じ条件で反応を行なった。Table 4 Example 19 Same as Example 1 A! - Montmorillonite is used as a catalyst and the raw material is dimedel ether, its supply rate jfW/F=5070
The reaction was carried out under the same conditions as in Example 1 except that (f-Oat, m1r1//mol).
その結果、Ｘ＝９ ＦＬ５Ｘ、 Ｘｇａ−６４，１％及
びＢ−４ｔｊＸであった。The results were: X=9 FL5X, Xga-64, 1%, and B-4tjX.
特許出願人 東洋曹達工業株式会社Patent applicant: Toyo Soda Kogyo Co., Ltd.
Claims (1)
て接触的に反応させて炭化水ｇｅｔ製造する方法におい
て、触媒として、結晶質フィロケイ酸塩に属する粘土鉱
物に陽イオン性の金属元素化合物を挿入することにより
形成される粘土層間化合物を使用すること１ｅ像とする
炭化水素類の製造方法。 （劾 粘土層間化合物の層間隙が４．５Ｘ以上である特
許請求の範囲第１項記載の方法。 （２）〉 粘土鉱物がスメクタイト型、パーミキエライ
ト型及びクロライド型のものより選択される特許請求の
範囲第１項又は第２項記載の方法。 （２）粘土鉱物がモンモリロナイト又はベントナイトで
ある特許請求の範囲第５項記載の方法。 （２）陽イオン性の金属元素化合物が埼期律表第璽〜第
１族から選択される少なくとも−ｒａｔ構成元素として
含□む特許請求の範囲第１〜４項のいずれかの記載の方
法。 （６）陽イオン性の金属元素化合物がアルばニウム、シ
ル４ニウム、ＵＳ、 ビスマス、クロム。 タングステン、マンガン、ランタン及ヒマグネシウムの
少なくとも一種着構成元素として含む特許請求の範囲第
５項記載の方法。[Claims] (1) In a method for producing hydrocarbons by catalytically reacting methanol and/or dimethyl ether in a gas phase, a cationic compound is added to a clay mineral belonging to crystalline phyllosilicates as a catalyst. A method for producing hydrocarbons using a clay intercalation compound formed by inserting a metal element compound. (The method according to claim 1, wherein the interlayer gap of the clay interlayer compound is 4.5X or more. (2)> A patent in which the clay mineral is selected from smectite, permicierite, and chloride types. The method according to claim 1 or 2. (2) The method according to claim 5, wherein the clay mineral is montmorillonite or bentonite. (2) The cationic metal element compound is montmorillonite or bentonite. The method according to any one of claims 1 to 4, wherein the cationic metal element compound contains at least -rat as a constituent element selected from Groups 1 to 1. 6. The method according to claim 5, comprising at least one of tungsten, manganese, lanthanum, and magnesium as a cohesive constituent element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56179074A JPS5883635A (en) | 1981-11-10 | 1981-11-10 | Preparation of hydrocarbon from methanol and/or dimethyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56179074A JPS5883635A (en) | 1981-11-10 | 1981-11-10 | Preparation of hydrocarbon from methanol and/or dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5883635A true JPS5883635A (en) | 1983-05-19 |
| JPH0216290B2 JPH0216290B2 (en) | 1990-04-16 |
Family
ID=16059630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56179074A Granted JPS5883635A (en) | 1981-11-10 | 1981-11-10 | Preparation of hydrocarbon from methanol and/or dimethyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5883635A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009034719A1 (en) * | 2007-09-13 | 2009-03-19 | Sangi Co., Ltd. | Process for production of composition by using alcohol as starting material |
-
1981
- 1981-11-10 JP JP56179074A patent/JPS5883635A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009034719A1 (en) * | 2007-09-13 | 2009-03-19 | Sangi Co., Ltd. | Process for production of composition by using alcohol as starting material |
| US8187347B2 (en) | 2007-09-13 | 2012-05-29 | Kabushiki Kaisha Sangi | Method for producing composition using alcohol as starting material |
| JP5354292B2 (en) * | 2007-09-13 | 2013-11-27 | 株式会社サンギ | Method for producing composition using alcohol as raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0216290B2 (en) | 1990-04-16 |
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