JPH02227141A - Methanol reforming catalyst - Google Patents
Methanol reforming catalystInfo
- Publication number
- JPH02227141A JPH02227141A JP1049387A JP4938789A JPH02227141A JP H02227141 A JPH02227141 A JP H02227141A JP 1049387 A JP1049387 A JP 1049387A JP 4938789 A JP4938789 A JP 4938789A JP H02227141 A JPH02227141 A JP H02227141A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carrier
- oxide
- methanol
- group metal
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 180
- 238000002407 reforming Methods 0.000 title claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 23
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 7
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 15
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 abstract description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- -1 iron group metals Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004115 Sodium Silicate Substances 0.000 abstract description 2
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052911 sodium silicate Inorganic materials 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 229910001960 metal nitrate Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 52
- 239000000203 mixture Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 240000001980 Cucurbita pepo Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 229910002645 Ni-Rh Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、メタノール改質用の３元組成系の触媒に関す
るものである。さらに詳しくは、メタノールをＨ２およ
びＣＯを含有するガスに改質する方法において、Ｈ２と
ＣＯとを選択的に生成させると共に、副反応をできるだ
け抑え、低温でも高活性を有し、かつ長寿命を有する触
媒に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a ternary composition catalyst for methanol reforming. More specifically, in the method of reforming methanol into a gas containing H2 and CO, H2 and CO are selectively generated, side reactions are suppressed as much as possible, and the method has high activity even at low temperatures and has a long life. The present invention relates to a catalyst having the following properties.
従来の技術
従来、メタノールを改質する触媒として、アルミナ、シ
リカ、その他の担体に、種々の触媒基質を担持させた触
媒が提案されている。2. Description of the Related Art Catalysts in which various catalyst substrates are supported on alumina, silica, or other carriers have been proposed as catalysts for reforming methanol.
たとえば、特開昭５７−６８１４０号公報には、アルミ
ナを予め塩基性物質の酸化物で被覆した担体上に白金、
パラジウムからなる群の１種以上の金属を担持させたメ
タノール改質用触媒が示されている。For example, in Japanese Patent Application Laid-Open No. 57-68140, platinum is coated on a carrier coated with alumina and an oxide of a basic substance.
A methanol reforming catalyst is shown that supports one or more metals from the group consisting of palladium.
特開昭５７−１４４０３１号公報には、アルミナＩｇ当
り、ニッケル２〜８ｍｇ原子およびカリウム２〜８ｍｇ
原子を含有させたアルミナ系メタノール分解用触媒が示
されている。JP-A-57-144031 discloses that 2 to 8 mg of nickel atoms and 2 to 8 mg of potassium per Ig of alumina.
An alumina-based catalyst for methanol decomposition containing atoms is shown.
特開昭５７−１７４１３８号公報には、銅、亜鉛、クロ
ムからなる群の一種以上の酸化物またはその水酸化物に
ニッケルを担持させたメタノール改質用触媒が示されて
いる。JP-A-57-174138 discloses a methanol reforming catalyst in which nickel is supported on one or more oxides of the group consisting of copper, zinc, and chromium, or hydroxides thereof.
特開昭５７−１７４１３９号公報には、銅、亜鉛、クロ
ムからなる群の一種以上の酸化物またはその水酸化物と
、ニッケルの酸化物またはその水酸化物とからなるメタ
ノール改質用触媒が示されている。JP-A-57-174139 discloses a methanol reforming catalyst comprising one or more oxides or hydroxides of the group consisting of copper, zinc, and chromium, and nickel oxides or hydroxides. It is shown.
特開昭５９−１９９０４３号公報には、アルミナを予め
アルカリ金属酸化物で被覆した担体上に白金、パラジウ
ムからなる群の一種以上の金属を担持させたメタノール
改質用触媒が示されている。JP-A-59-199043 discloses a methanol reforming catalyst in which one or more metals from the group consisting of platinum and palladium are supported on a carrier prepared by coating alumina with an alkali metal oxide.
特開昭６１−２３２２０１号公報には、銅、亜鉛、履族
金属からなる群の一種以上の金属またはその酸化物を含
有する触媒を用いてメタノールを分解して水素含有ガス
を製造する方法において、メタノール１００モルに対し
て水を１〜９９モルの割合で共存させる方法が示されて
いる。JP-A No. 61-232201 discloses a method for producing a hydrogen-containing gas by decomposing methanol using a catalyst containing one or more metals from the group consisting of copper, zinc, and metals of the group consisting of metals or their oxides. , a method is shown in which water is allowed to coexist at a ratio of 1 to 99 moles per 100 moles of methanol.
第４６回触媒討論会（Ａ）１９８０年、講演番号３Ｒ１
６には、シリカ担体にＮｉ単元、Ｒｕ単元、Ｒｈ単元、
Ｎｉ−Ｒｕ二元、Ｎｉ−Ｒｈ二元、Ｎｉ−Ｌａ２Ｏ３二
元、Ｎｉ−Ｌａ２０３−Ｒｕ三元系の触媒基質を担持さ
せた触媒をメタノールの接触分解による選元性高熱量ガ
スの選択的合成に用いることが示されている。比較のた
め、シリカ担体に代えてアルミナ担体を用いる場合につ
いても示されている。46th Catalyst Symposium (A) 1980, Lecture number 3R1
In 6, Ni units, Ru units, Rh units,
Selective synthesis of selective high-calorific gas by catalytic cracking of methanol using catalysts supported with Ni-Ru binary, Ni-Rh binary, Ni-La2O3 binary, and Ni-La203-Ru ternary catalyst substrates. It has been shown that it can be used for For comparison, a case where an alumina carrier is used instead of a silica carrier is also shown.
石油学会誌、５ｅｋｉｙｕ Ｇａｋｋａｉｓｈｉ、 ３
０． （３）。Journal of the Japan Petroleum Institute, 5ekiyu Gakkaishi, 3
0. (3).
１５９−ＩＥＩＯ（１９８？）、および石油学会誌、５
ｅｋｉｙｕＧａｋｋａｉｓｈｉ、 ３１． （２）、
１１３３−１７１ （１９８８）には、メタノールの
ＣＯとＨ２への分解触媒として、５１０２−Ｍｇ０担体
にＮｉを担持させた触媒が示されている。159-IEIO (198?) and Journal of Japan Petroleum Institute, 5
ekiyugakkaishi, 31. (2),
1133-171 (1988) discloses a catalyst in which Ni is supported on a 5102-Mg0 support as a catalyst for decomposing methanol into CO and H2.
発明が解決しようとする課題
しかしながら、特開昭５７−６８１４０号公報、特開昭
５７−１７４１３８号公報、特開昭５７−１７４１３９
号公報に記載の触媒は、低温活性が充分ではないこと、
カーボンの析出が起こりやすいため寿命が短いことなど
の問題点がある。（特開昭６１−２３２２０１号公報の
２頁上段右欄参照）
上記のうち特開昭５７−６８１４０号公報に記載の触媒
、あるいは特開昭５９−１９９０４３号公報に記載の触
媒は、塩基性物質の酸化物（アルカリ金属酸化物）で担
体を予め被覆処理しなければならないという工業的な不
利がある。Problems to be Solved by the Invention However, JP-A-57-68140, JP-A-57-174138, JP-A-57-174139
The catalyst described in the publication does not have sufficient low-temperature activity;
There are problems such as a short lifespan due to the tendency for carbon precipitation to occur. (Refer to the upper right column of page 2 of JP-A-61-232201) Of the above, the catalyst described in JP-A-57-68140 or the catalyst described in JP-A-59-199043 is a basic There is an industrial disadvantage in that the support has to be precoated with the oxide of the substance (alkali metal oxide).
特開昭６１−２３２２０１号公報に記載の触媒は、カー
ボン析出防止のためにスチームを原料メタノールと共に
反応器へ装入しなければならず、工業的見地からは問題
がある。The catalyst described in JP-A-61-232201 has a problem from an industrial standpoint because steam must be charged into the reactor together with raw methanol to prevent carbon precipitation.
特開昭５７−１４４０３１号公報に記載の触媒は、反応
温度３５０”Ｏにおける転化率がたとえば５２％と低い
こと、転化率を７５〜９１％にまで上げるためには触媒
をアルゴン気流中５００”Ｃで前処理しなければならな
いことなどの問題点がある。The catalyst described in JP-A-57-144031 has a low conversion rate of, for example, 52% at a reaction temperature of 350''O, and in order to increase the conversion rate to 75-91%, the catalyst must be heated at a temperature of 500'' in an argon stream. There are problems such as the need for preprocessing with C.
第４６回触媒討論会（Ａ）１９８０年に記載の触媒は、
初期の活性は高いものの１．触媒寿命が短いという問題
点がある。（特開昭５７−１４４０３１号公報の２頁下
段左欄参照）２件の石油学会誌に記載の触媒は、メタノ
ール転化率がたとえば４２〜７５％と低いという問題点
がある。The catalyst described in the 46th Catalyst Symposium (A) in 1980 is:
Although initial activity is high, 1. There is a problem that the catalyst life is short. (Refer to the lower left column of page 2 of JP-A-57-144031) The catalysts described in the two journals of the Japan Petroleum Institute have a problem in that the methanol conversion rate is as low as, for example, 42 to 75%.
このように従来提案されているメタノール改質用触媒は
、高触媒活性、副生物の抑制、長寿命、Ｔ業性などの要
求を兼ね備えたものがなく、・工業化の支障となってい
た。As described above, none of the methanol reforming catalysts proposed so far have met the requirements of high catalytic activity, suppression of by-products, long life, T-performance, etc., and this has been an obstacle to industrialization.
本発明は、このような状況に鑑み、工業化に酎えうる高
性能のメタノール改質用触媒を提供することを目的にな
されたものである。In view of these circumstances, the present invention was made with the object of providing a high-performance methanol reforming catalyst that can be applied to industrialization.
課題を解決するための手段
本発明のメタノール改質用触媒は、二酸化ケイ素（ａ１
）およびアルカリ土類金属酸化物または酸化ランタン（
ａ２）よりなる担体（Ａ）に、鉄族金属（ｂり、希土類
元素の酸化物（ｂ２）および白金族金属（ｂＢ）よりな
る触媒基質（Ｂ）を担持させてなるものである０図式化
すると、
担体（Ａ） ＝ （ａ１）＋ （ａ２）（ａ１）：二酸
化ケイ素
（ａ２） ：アルカリ土類金属酸化物または酸化ランタ
ン
触媒基質（Ｂ） ＝ （ｂ１）＋ （ｂ２）＋ （ｂＢ
）（ｂＢ ：鉄族金属
（ｂ２） ：希土類元素の酸化物
（ｂＢ） ：白金族金属
となる。Means for Solving the Problems The methanol reforming catalyst of the present invention comprises silicon dioxide (a1
) and alkaline earth metal oxides or lanthanum oxides (
A catalytic substrate (B) consisting of an oxide of an iron group metal (b2), an oxide of a rare earth element (b2), and a platinum group metal (bB) is supported on a carrier (A) consisting of a2). Then, support (A) = (a1) + (a2) (a1): silicon dioxide (a2): alkaline earth metal oxide or lanthanum oxide catalyst substrate (B) = (b1) + (b2) + (bB
) (bB: iron group metal (b2): rare earth element oxide (bB): platinum group metal.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
１札ｙ
本発明の触媒における担体としては、二酸化ケイ素（ａ
１）およびアルカリ土類金属酸化物または酸化ランタン
（ａ２）よりなる担体（Ａ）が用いられる。1 note y As a carrier in the catalyst of the present invention, silicon dioxide (a
1) and a carrier (A) consisting of an alkaline earth metal oxide or lanthanum oxide (a2).
（ａ２）成分であるアルカリ土類金属酸化物と酸化ラン
タンとは併用することもできる。アルカリ土類金属酸化
物としては、酸化マグネシウム、醇化カルシウム、酸化
バリウムまたは酸化ベリリウムが用いられる。The alkaline earth metal oxide and lanthanum oxide, which are components (a2), can also be used together. As the alkaline earth metal oxide, magnesium oxide, calcium oxide, barium oxide or beryllium oxide is used.
この神体（Ａ）は、共沈法や混線法で調製される。This sacred object (A) is prepared by coprecipitation method or cross-fermentation method.
共沈法の例としては、たとえば、アルカリ土類金属の硝
酸塩または硝酸ランタンの水溶液を攪拌下にケイ酸ナト
リウム水溶液に加え、所定時間静Ｗ後析出した沈澱を水
洗し、乾燥し、ついで空気中で焼成する方法があげられ
る。As an example of the coprecipitation method, for example, an aqueous solution of an alkaline earth metal nitrate or lanthanum nitrate is added to an aqueous sodium silicate solution while stirring, and after standing still for a predetermined period of time, the precipitate precipitated is washed with water, dried, and then placed in the air. One method is to bake it in
混練法の例としては、たとえば、シリカヒドロゲルとア
ルカリ土類金属の水酸化物または水酸化ランタンとを混
線後、乾燥し、ついで空気中で焼成する方法があげられ
る。An example of the kneading method is a method in which silica hydrogel and alkaline earth metal hydroxide or lanthanum hydroxide are mixed together, dried, and then fired in air.
担体（Ａ）における二酸化ケイ素（ａｔ）とアルカリ土
類金属酸化物または酸化ランタン（ａ２）との割合は、
重量比で４０ ： ６０〜９５：５、殊に５０＝５０〜
６５ ： ３５とすることが望ましく、この範囲におい
て最も良好な結果が得られる。The ratio of silicon dioxide (at) and alkaline earth metal oxide or lanthanum oxide (a2) in the carrier (A) is:
Weight ratio of 40:60 to 95:5, especially 50=50 to
A ratio of 65:35 is desirable, and the best results can be obtained within this range.
担体（Ａ）は通常粒子の形態で用いるが、場合によって
は無機質バインダーを加え、直径０．０５〜４１程度の
顆粒状またはペレット状にして用いることもできる。The carrier (A) is usually used in the form of particles, but it can also be used in the form of granules or pellets with a diameter of about 0.05 to 41 mm by adding an inorganic binder as the case may be.
鰍１］［鼠工旧 上記神体（Ａ）に担持させる触媒基質としては。1] [Nezuko old As the catalyst substrate supported on the above-mentioned divine body (A).
鉄族金属（ｂＢ、希土類元素の酸化物（ｂ２）および白
金族金属（ｂＢ）よりなる三元組成系の触媒基質が用い
られる。A ternary composition catalyst substrate consisting of an iron group metal (bB), an oxide of a rare earth element (b2), and a platinum group metal (bB) is used.
鉄族金属（ｂ１）としては、ニッケルまたはコバルトが
用いられる。Nickel or cobalt is used as the iron group metal (b1).
希土類元素の酸化物（ｂ２）としては、セリウム、ラン
タン、プラセオジウム、トリウム、サマリウムなどの酸
化物があげられる。Examples of the rare earth element oxide (b2) include oxides of cerium, lanthanum, praseodymium, thorium, samarium, and the like.
白金族金属（ｂＢ）としては、白金、ルテニウム、ロジ
ウム、パラジウム、イリジウムなどがあげられる。Examples of the platinum group metal (bB) include platinum, ruthenium, rhodium, palladium, and iridium.
上記触媒基質（Ｂ）の中では、触媒効果および経済性等
を総合考慮して、鉄族金属（ｂ１）としてはニッケルま
たはコバルト、希土類元素の酸化物（ｂ２）としては酸
化セリウムまたは酸化ランタン、白金族金属（ｂＢ）と
しては白金、ルテニウムまたはロジウムが重要である。Among the above catalyst substrates (B), taking into consideration the catalytic effect and economic efficiency, the iron group metal (b1) is nickel or cobalt, and the rare earth element oxide (b2) is cerium oxide or lanthanum oxide. Platinum, ruthenium or rhodium are important as platinum group metals (bB).
各グループに属する成分は、２種以上を併用することも
できる。Two or more types of components belonging to each group can also be used in combination.
触媒基質（Ｂ）としての鉄族金属（ｂｔ）、希土類元素
の酸化物（ｂ２）および白金族金属（ｂＢ）の担持量は
、全触媒（ｓＡ体（Ａ）と触媒基質（Ｂ）との合計量）
に対し、それぞれ２〜２５重量％（好ましくは６〜１０
重量％）、Ｏ，Ｓ〜１５重量％（好ましくは１〜６重量
％） 、 ０．０１〜２重量％（好ましくは０．１〜０
．８重量％）とすることが適当−であり、この範囲にお
いて最も好ましい結果が得られる。The amount of supported iron group metal (bt), rare earth element oxide (b2), and platinum group metal (bB) as catalyst substrate (B) is determined by the amount of the total catalyst (sA form (A) and catalyst substrate (B)). total amount)
2 to 25% by weight (preferably 6 to 10% by weight)
% by weight), O,S ~ 15% by weight (preferably 1-6% by weight), 0.01-2% by weight (preferably 0.1-0
．． 8% by weight) is suitable, and the most preferable results can be obtained within this range.
各成分の過少は触媒効果の不足を招き、一方各成分を必
要以上に担持させても、触媒効果は一定限度以上には向
上しないばかりか、担体細孔の閉塞を招いてかえって触
媒性能が低下することがある。Too little of each component will lead to a lack of catalytic effect; on the other hand, even if each component is supported in excess of what is necessary, the catalytic effect will not improve beyond a certain limit, and the pores of the carrier will become clogged, resulting in a decrease in catalytic performance. There are things to do.
蚊崖！ｌＥＬ誌
本発明のメタノール改質用触媒は、二酸化ケイ素（ａ１
）およびアルカリ土類金属酸化物または酸化ランタン（
ａ２）よりなる担体（Ａ）に、鉄族金属（ｂ１）、希土
類元素の酸化物（ｂ２）および白金族金属（ｂ３）より
なる触媒基質（Ｂ）を担持させることにより得られる。Mosquito cliff! IEL Magazine The methanol reforming catalyst of the present invention contains silicon dioxide (a1
) and alkaline earth metal oxides or lanthanum oxides (
It is obtained by supporting a catalyst substrate (B) consisting of an iron group metal (b1), an oxide of a rare earth element (b2) and a platinum group metal (b3) on a carrier (A) consisting of a2).
鉄族金属（ｂ１）、希土類元素の酸化物（ｂ２）および
白金族金属（ｂ３）は、それぞれ別個に任意の順序で、
あるいはその２種以上を予め混合してから担体（Ａ）に
担持させることができる。担体（Ａ）は、触媒基質ＣＢ
）を担持させる前に４５０〜７５０℃程度の温度で焼成
させておいてもよい。The iron group metal (b1), the rare earth element oxide (b2) and the platinum group metal (b3) are each separately in any order,
Alternatively, two or more of them can be mixed in advance and then supported on the carrier (A). The carrier (A) is a catalyst substrate CB
) may be baked at a temperature of about 450 to 750°C before being supported.
担体（Ａ）に触媒基質（Ｂ）を担持させるに際し。When supporting the catalyst substrate (B) on the carrier (A).
まず担体（Ａ）に白金族金属（ｂ３）を相持させ、つい
で鉄族金属（ｂ１）と希土類元素の酸化物（ｂ２）とを
同時に担持させるようにすると、メタノール分解性の特
にすぐれた触媒が得られる。さらに具体的に述べると、
次の手順が好適に採用される。First, a platinum group metal (b3) is supported on the carrier (A), and then an iron group metal (b1) and an oxide of a rare earth element (b2) are supported at the same time, and a catalyst with particularly excellent methanol decomposition properties is obtained. can get. To be more specific,
The following procedure is preferably adopted.
１、白金族金属（ｂ３）のたとえば塩化物、硝酸塩また
は塩化水素酸の水溶液を担体（Ａ）の空隙を充填する量
だけ含浸させ、６０〜１００℃程度の温度で乾燥する。1. The carrier (A) is impregnated with an aqueous solution of platinum group metal (b3) such as chloride, nitrate or hydrochloric acid in an amount sufficient to fill the voids, and dried at a temperature of about 60 to 100°C.
このときの白金族金属（ｂ３）の塩化物等の濃度は、含
浸液中に所定の相持量が含有されるようにする。At this time, the concentration of the chloride, etc. of the platinum group metal (b3) is set such that a predetermined amount is contained in the impregnating liquid.
２、次に、大気中で前記乾燥物を４００℃程度に加熱し
、含浸させた塩化物等を分解する。2. Next, the dried material is heated to about 400° C. in the atmosphere to decompose impregnated chlorides and the like.
３、引き続き、水素気流中３００〜４００℃程度の温度
で１〜６時間（好ましくは２〜５時間）保持して還元し
、ついで冷却する。3. Subsequently, the mixture is maintained at a temperature of about 300 to 400°C in a hydrogen stream for 1 to 6 hours (preferably 2 to 5 hours) for reduction, and then cooled.
４、このようにして得られた白金族金属（ｂ３）相持体
を、たとえば鉄族金属（ｂ１）の硝酸塩の水溶液と希土
類元素の硝酸塩の水溶液との混合溶液中に含浸させ、前
記白金族金属（ｂ３）を担持させる場合と同様に乾燥、
熱処理、還元を行う。4. The platinum group metal (b3) support obtained in this way is impregnated in a mixed solution of, for example, an aqueous solution of a nitrate of an iron group metal (b1) and an aqueous solution of a nitrate of a rare earth element, and Dry as in the case of supporting (b3),
Perform heat treatment and reduction.
なお、これらの処理において、希土類元素の酸化物（ｂ
２）は安定なため、還元されることなく酸化物の状態の
ままである。In addition, in these treatments, rare earth element oxides (b
Since 2) is stable, it remains in an oxide state without being reduced.
よ乙色ヱ二ソＬ立邂
メタノール分解は、典型的には、上述のようにして調製
した触媒を反応管に充填し、触媒層の温度を２５０〜４
５０℃程度に制御しながら、予熱ガス化したメタノール
をＬＨ３Ｖ （液空間速度）０．５〜１０ ｈ ｒ−′
で触媒層に導入すればよい、これによりメタノールはＨ
ｚとＣＯとに分解される。Typically, the catalyst prepared as described above is packed in a reaction tube, and the temperature of the catalyst bed is set at 250-400 ℃.
Preheated gasified methanol was heated to LH3V (liquid hourly space velocity) 0.5 to 10 h r-' while controlling the temperature to about 50°C.
Methanol can be introduced into the catalyst layer using
It is decomposed into z and CO.
肚垂
本発明の触媒は、内燃機関用の無公害高発熱量燃料ガス
の合成、燃料電池用の燃料ガスの合成、高純度有機合成
用原料ガスの合成などの用途に有用である。The catalyst of the present invention is useful for the synthesis of pollution-free high calorific value fuel gas for internal combustion engines, the synthesis of fuel gas for fuel cells, and the synthesis of raw material gas for high-purity organic synthesis.
作 用
メタノール改質触媒を用いてメタノールをＨｚとＣＯと
を含有するガスに改質する反応においては、主反応とし
ての
ＣＨ，ＯＨ→２Ｈ，Ｌ＋ ＧＯ
の反応のほかに、
ＣＩや、 ＣＯＺ、Ｈｚ、０生成反応
ＣＨ３０Ｈ＋ Ｈｚ ４ ＣＩ４＋ ＨｚＯＣＨ３０Ｈ
＋ Ｃｏ→ＣＨ峰＋ＣＯｚ
カーボン生成反応
ＣＨ３０Ｈ＝ Ｃ＋ Ｈｚ ＋Ｈ２Ｏ
２Ｃｌ３０Ｈ＋ Ｃ＋ＣＯル＋４Ｈ２０ジメチルエーテ
ル生成反応
２ ＣＨ，ＯＨ→ＣＨ３０ＣＨ３＋ ）＋２０の如き副
反応が進行する。 Ｈ２Ｏが副生ずると、ＧＯ＋ Ｉ２
０ →ＣＯ，＋ ）Ｉ２の反応も誘発される。Function: In the reaction of reforming methanol into a gas containing Hz and CO using a methanol reforming catalyst, in addition to the main reactions of CH, OH→2H, L+ GO, CI, COZ, Hz, 0 generation reaction CH30H+ Hz 4 CI4+ HzOCH30H
+Co→CH peak+COz Carbon production reaction CH30H= C+ Hz +H2O 2Cl30H+ C+CO+4H20 Dimethyl ether production reaction 2 CH, OH→CH30CH3+ )+20 Side reactions proceed. When H2O is produced as a by-product, GO + I2
0 → CO, + ) I2 reaction is also induced.
本発明の触媒を用いると、メタノール反応率が高いだけ
でなく、上記主反応のみが選択的に進行し、ＣＨ４−９
ＣＯＺ、 Ｈ，０生成反応、カーボン生成反応、ジメチ
ルエーテル生成反応などの副反応はほとんど生じない、
また本発明の触媒は寿命が長い。When the catalyst of the present invention is used, not only the methanol reaction rate is high, but only the above main reaction proceeds selectively, and CH4-9
Side reactions such as COZ, H,0 production reactions, carbon production reactions, and dimethyl ether production reactions hardly occur.
The catalyst of the present invention also has a long life.
このような作用効果は、１記特定の担体（Ａ）と上記特
定の触媒基質（Ｂ）との組み合せによりはじめて奏され
、上述の担体（Ａ）と他の触媒基質との組み合せ、ある
いは上述の触媒基質（Ｂ）と他の担体との組み合せによ
っては、このようなすぐれた作用効果は得られない。Such effects can only be achieved by a combination of the specific carrier (A) described in 1. and the specific catalyst substrate (B) described above. Such excellent effects cannot be obtained depending on the combination of the catalyst substrate (B) and other carriers.
実 施 例 次に実施例をあげて本発明をさらに説明する。Example Next, the present invention will be further explained with reference to Examples.
実施例１
１１辺１１
予め空気中で約５００℃に加熱して水分を除去した粒子
状のシリカマグネシア担体（主要成分は５ｉ０２：６０
重量％、ＭｇＯ：３０重量％、粒径１＋ａｍ） ３．
２ｇに、１．０３重量％濃度の塩化白金酸水溶液３．３
ｇを含浸させ、１１０℃で２時間乾燥後、さらにＮ２中
で約４００℃に加熱し、引き続きＨ２中で還元した。Example 1 11 sides 11 Particulate silica magnesia carrier (main component is 5i02:60
% by weight, MgO: 30% by weight, particle size 1+am) 3.
2 g of chloroplatinic acid aqueous solution with a concentration of 1.03% by weight 3.3
After drying at 110° C. for 2 hours, the sample was further heated to about 400° C. in N 2 and subsequently reduced in H 2 .
得られた白金担持体に、８．０８重量％濠度の硝酸セリ
ウム水溶液および２５．７重量％褒度の硝酸ニッケル水
溶液を含む混合液４．８ｇを含浸させ、前記と同様の方
法により乾燥、加熱、還元を行った。これにより、触媒
基質（Ｂ）の担持量が全触媒量に対して
ＰＬ Ｏ，４重量％
ＣｅＯ２４、０重量％
Ｎｉ ８．０重量％
である３元組成系触媒が得られた。The obtained platinum support was impregnated with 4.8 g of a mixed solution containing an 8.08% by weight aqueous cerium nitrate solution and a 25.7% by weight aqueous nickel nitrate solution, and dried by the same method as above. Heating and reduction were performed. As a result, a ternary composition catalyst was obtained in which the supported amount of the catalyst substrate (B) was 4% by weight of PLO, 0% by weight of CeO24, and 8.0% by weight of Ni, based on the total amount of catalyst.
メタノール −
上記で得た触媒を固定床流通式反応器に充填し、メタノ
ールの改質を行った０条件および結果を下記に示す、な
お、生成ガス組成中ｒＤＭＥＪとあるのはジメチルエー
テルのことである（以下も同様）。Methanol - The catalyst obtained above was packed into a fixed bed flow reactor and the conditions and results for methanol reforming are shown below. In the product gas composition, rDMEJ refers to dimethyl ether. (Same below).
反応条件
触」［量 ＬＨ９Ｖ 反玉Ｊ」度 圧−一カ２ｃｃ
Ｅｉｈｒ ３５０℃ 大気圧結果
メタノール反応率 ９７．５ ％
生成ガス組成（マｏｌ ％）
む 四 ら 山 懺 ■
８１．３ ３１．０ ３．２ ０．８ ２．５ ０．３
実施例２
反応条件を下記のように変更したほかは実施例１を繰り
返し、下記の結果を得た。Reaction conditions: [amount: LH9V, anti-ball J] degree, pressure: 2cc
Eihr 350℃ Atmospheric pressure result Methanol reaction rate 97.5% Produced gas composition (mol %) 81.3 31.0 3.2 0.8 2.5 0.3
Example 2 Example 1 was repeated except that the reaction conditions were changed as follows, and the following results were obtained.
反応条件
ＬＬｊｉ Ｌ）ＩＳＶ 反ｍ 医−Ｗ２ｃｃ
３ｈｒ ３００℃ 大気圧結果
メタノール反応率 ９５．５ ％
生成ガス組成（マｏｌ り
し ＣＯら 詭
５９．７ ３１．５ ４．４ ０．９
Ｈ２ＯＤＭＥ
２．１ ０．２
実施例３
シリカマグネシア担体として。Reaction conditions LLji L) ISV anti-m medicine-W2cc
3hr 300℃ Atmospheric pressure Result Methanol reaction rate 95.5% Produced gas composition (Maolishi CO et al. 59.7 31.5 4.4 0.9 H2ODME 2.1 0.2 Example 3 Silica as magnesia carrier .
主要成分 Ｓｉｎ、： ７０ ｗｔＬ ＭｇＯ： ２０
ｗｔ＄粒径 １■■
のものを用いたほかは実施例１と同条件でメタノールの
改質を行った。結果を下記に示す。Main components Sin: 70 wtL MgO: 20
Methanol was modified under the same conditions as in Example 1 except that particles having a wt$ particle size of 1■■ were used. The results are shown below.
結果
メタノール反応率 ９２．９ ＄
生成ガス組成（マｏｆ ％）
し 四 １ 山 Ｈｚｏ ０ＮＥ８０、＄ ３
０．８ ２．８ ０．７ ２．３ ０．２実施例４
実施例１で得た触媒を用い、下記の条件でメタノールの
改質を行って、触媒寿命を評価した。Result Methanol reaction rate 92.9 $ Produced gas composition (Ma of %) 4 1 Hzo 0NE80, $ 3
0.8 2.8 0.7 2.3 0.2 Example 4 Using the catalyst obtained in Example 1, methanol was reformed under the following conditions to evaluate the catalyst life.
ｔｏｏｏ時間反応棟および４０００時間反応後の結果は
次の通りであった。The results after too many hours of reaction and 4000 hours of reaction were as follows.
反応条件
紋蓋ＪＬＨ９Ｖ 父底星１ 瓜−」
２ ｃｃ １．２ ｈｒ ３９０℃ 大気圧結果
封刈幻Ｅ壷 籾皇倶匡径
メタノール反応率ｍ ９８．２ ９８．５選枳
率（Ｘ） ９３．９ ９２．４生成
ガス組成（マｏ１％）
Ｈ，８１，２８０，２
ＧＯ３１，５３１，２
ＣＩや ４，３ ５．８Ｇｏｚ１ 、
？ １ 、９
Ｈシｏ ｏ、ｅ ｏ、ｅＤＭＥ
Ｏ，０Ｇ、０
比較例１
シリカマグネシア担体に代えて市販のシリカ担体を用い
たほかは実施例１と同様にして触媒を製造し、下記の反
応条件でメタノールの改質を行った。Reaction conditions JLH9V Father bottom star 1 Gourd 2 cc 1.2 hr 390℃ Atmospheric pressure Result Seal-harvest phantom E pot Methanol reaction rate m 98.2 98.5 Selection rate (X) 93 .9 92.4 Produced gas composition (MaO1%) H,81,280,2 GO31,531,2 CI and 4,3 5.8Goz1,
? 1, 9 Hsi o, e o, eDME
O, 0G, 0 Comparative Example 1 A catalyst was produced in the same manner as in Example 1 except that a commercially available silica carrier was used in place of the silica-magnesia carrier, and methanol was reformed under the following reaction conditions.
結果は下記に示した通りであり、メタノール反応率が低
く、また生成ガス中には多量の未反応メタノールが存在
することが判明した。The results are shown below, and it was found that the methanol reaction rate was low and that a large amount of unreacted methanol was present in the generated gas.
反応条件
１姐ｊｉ ＬＨＳＶ Ｌ図１１ 医−Ｊ２ ｃｃ
３ ｈｒ” ３５０℃ 大気圧結果
メタノール反応率 ５３．０ ％
出口ガス組成（マｏｆ り
Ｈｚ ＣＯら 逸 匡 山」
５Ｇ、８ ２５．２ ０．８ ０．０ ０．１ ２３．
１比較例２
実施例１と同じシリカマグネシア担体３．２ｇに、１．
０３重量％濃度の塩化白金酸水溶液３．３ｇを含浸させ
、実施例１と同様の方法で乾燥、熱分解、還元を行った
。ついで得られた白金相持体に、２８．０重量％濃度の
硝酸ニッケル水溶液４．５ｇを含浸させ、前記と同様の
方法により乾燥、加熱、還元を行った。これにより、触
媒基質（Ｂ）の担持量が全触媒量に対して
Ｐｔ Ｏ，４重量％
Ｎｉ ８．０重量％
である２元組成系触媒が得られた。Reaction condition 1 ji LHSV L Figure 11 Medicine-J2 cc
3 hr" 350℃ Atmospheric pressure Result Methanol reaction rate 53.0% Outlet gas composition (MaofriHz CO et al. 5G, 8 25.2 0.8 0.0 0.1 23.
1 Comparative Example 2 To 3.2 g of the same silica magnesia carrier as in Example 1, 1.
The sample was impregnated with 3.3 g of an aqueous chloroplatinic acid solution having a concentration of 0.3% by weight, and dried, thermally decomposed, and reduced in the same manner as in Example 1. The obtained platinum phase support was then impregnated with 4.5 g of a 28.0% by weight aqueous nickel nitrate solution, and dried, heated, and reduced in the same manner as described above. As a result, a binary composition catalyst was obtained in which the supported amount of the catalyst substrate (B) was 4% by weight of Pt 2 O and 8.0% by weight of Ni based on the total amount of catalyst.
この触媒を用いてメタノールの改質を行った。Methanol was reformed using this catalyst.
条件および結果を下記に示す。The conditions and results are shown below.
反応条件
＃ＪＥＪ ＬＨＳＶ １区１１１Ｌｌｙ−！
２ｃｃ ３ｈｒ ３２０℃ 大気圧結果
メタノール反応率 ８８．２駕
出口ガス組成（マｏｆ駕）
Ｌ 東 ら ら 鍼 ｌ」
５９．１ ３１．５ ３．８ ０．０ １．０ ４．７
比較例３
実施例１と同じシリカマグネシア担体３．２ｇに、１．
０３重量％濃度の塩化白金酸水溶液３．３ｇを含浸させ
、実施例１と同様の方法で乾燥、熱分解、還元を行った
。これにより、触媒基質（Ｂ）の担持量が
ＰＬ Ｏ，４重量％
である単元組成系触媒が得られた。Reaction conditions #JEJ LHSV 1st section 111Lly-! 2cc 3hr 320℃ Atmospheric pressure result Methanol reaction rate 88.2 Exit gas composition (ma of palanquin) L 59.1 31.5 3.8 0.0 1.0 4.7
Comparative Example 3 To 3.2 g of the same silica magnesia carrier as in Example 1, 1.
The sample was impregnated with 3.3 g of an aqueous chloroplatinic acid solution having a concentration of 0.3% by weight, and dried, thermally decomposed, and reduced in the same manner as in Example 1. As a result, a monocomponent catalyst in which the supported amount of the catalyst substrate (B) was 4% by weight of PLO was obtained.
この触媒を用いてメタノールの改質を行った。Methanol was reformed using this catalyst.
条件および結果を下記に示す。The conditions and results are shown below.
反応条件
ｌｕＪ ＬＨＳＶ ｕ皇Ｊ１ 瓜−Ｊ２ ｃｃ
２ ｈｒ−１３５０℃ 大気圧結果
出口ガス組成（マｏｆ ％＞
し ｃｏ 門 ら Ｗ ジ」
５２．２ ２５．８ ０．５ ０．０ ０．１ ２１．
４実施例５〜７
実施例１と同じシリカマグネシア担体に、実施例１に準
じて下記の触媒基質を担持させ、触媒を調製した。Reaction conditions luJ LHSV uhuang J1 Melon-J2 cc
2 hr-1350°C Atmospheric pressure result Outlet gas composition (%) 52.2 25.8 0.5 0.0 0.1 21.
4 Examples 5 to 7 The following catalyst substrates were supported on the same silica magnesia carrier as in Example 1 according to Example 1 to prepare catalysts.
実施例５ 下記組成の３元組成系触媒
実施例６ 下記組成の３元組成系触媒
実施例７ 下記組成の３元組成系触媒
メタノール反応率 ５５．１ ！
これらの触媒を用いて、実施例１と同条件でメタノール
の改質を行った０反応開始後２時間経過後の結果を下記
に示す。Example 5 Three-component catalyst with the following composition Example 6 Three-component catalyst with the following composition Example 7 Methanol reaction rate of three-component catalyst with the following composition 55.1! Using these catalysts, methanol was reformed under the same conditions as in Example 1. The results obtained 2 hours after the start of the reaction are shown below.
実施例５
メタノール反応率 ９１．８ ％
生成ガス組成（マ０１ｚ）
し 四 山 鳴 リ 川
１１ｔ３．８ ３２．２ １．５ ０．３ １．３ ０
．２実施例６
メタノール反応率 ９３．２駕
生成ガス組成（マｏｆ ＄）
し 四 ら ら リ ■
Ｅｉ４．２ ３２．８ ０．４ ０．２ １．４ ０．
２実施例７
メタノール反応率 ８９．３ ％
生成ガス組成（マ０１ｚ）
し リ 山 山 賑 ■
８３．７ ３２．５ ０．８ ０．２ １．１３ ０．
２実施例８
予め空気中で約５００℃に加熱して水分を除去した粒子
状のシリカベリリア担体（主要成分は５ｔ０２ニア０重
量％、ＢｅＯ：２０重量％、粒径Ｉｓ■）３．２ｇに、
１．０３重量％濃度の塩化白金酸水溶液３．３ｇを含
浸させ、１１０℃で２時間乾燥後、ざらにＮ２中で約４
００℃に加熱し、引き統！！Ｈ２中で還元した。Example 5 Methanol reaction rate 91.8% Produced gas composition (Ma01z) Shiyama Narikawa 11t3.8 32.2 1.5 0.3 1.3 0
．． 2 Example 6 Methanol reaction rate 93.2 Colonial gas composition (ma of $) Ei4.2 32.8 0.4 0.2 1.4 0.
2 Example 7 Methanol reaction rate 89.3% Produced gas composition (Ma01z) 83.7 32.5 0.8 0.2 1.13 0.
2 Example 8 To 3.2 g of particulate silica beryllia carrier (main components: 5t02nia 0% by weight, BeO: 20% by weight, particle size Is■) which had been heated in advance to about 500°C in air to remove moisture,
After impregnating with 3.3 g of chloroplatinic acid aqueous solution having a concentration of 1.03% by weight and drying at 110°C for 2 hours,
Heat it to 00℃ and bring it on! ! Reduced in H2.
得られた白金担持体に、 ８．０８重量％濃度の硝酸セ
リウム水溶液および２５．７重量％濃度の硝酸ニッケル
水溶液を含む混合液４．８ｇを含浸させ、前記と同様の
方法により乾燥、加熱、還元を行った。これにより、触
媒基質（Ｂ）の担持量が全触媒量に対して
ＰＬ Ｏ，４重量％
ＣｅＯ□ ４．０重量％
旧 ８．０重量％
である３元組成系触媒が得られた。The obtained platinum support was impregnated with 4.8 g of a mixed solution containing an 8.08% by weight aqueous cerium nitrate solution and a 25.7% by weight aqueous nickel nitrate solution, and dried, heated, and dried in the same manner as above. I made a reduction. As a result, a ternary composition catalyst was obtained in which the supported amount of the catalyst substrate (B) was PLO, 4% by weight, CeO□, 4.0% by weight, and 8.0% by weight, based on the total amount of the catalyst.
この触媒を用い、反応条件を下記のように変更したほか
は実施例１を繰り返し、下記の結果を得た。Using this catalyst, Example 1 was repeated except that the reaction conditions were changed as shown below, and the following results were obtained.
反応条件 艦腹ＪＬＨ９Ｖ 反玉Ｊ１度 ２ ｃｃ Ｅｌ ｈｒ−’ ３７０℃結果 圧−一力 大気圧 メタノール反応率 ８５．５駕 生成ガス組成（マｏｆ ％） し 四 ら ５９．３ ３１．０ ３．７ ＣＯＺ Ｈｚｏ ０ＮＥ １．８ ３．０ ０．３ 実施例９ 担体として。Reaction conditions Belly JLH9V Antiball J1 degree 2 cc El hr-' 370℃ result pressure - force Atmospheric pressure Methanol reaction rate 85.5 units Generated gas composition (ma of %) Shi four et al. 59.3 31.0 3.7 COZ Hzo 0NE 1.8 3.0 0.3 Example 9 as a carrier.
主要成分 Ｓｉｎ、： ７０ ｗｔＬ ＭｇＯ： 、１
５ ｗｔ駕、ＣａＯ： ５ ｗｔ＄
粒径 １ｍ層
のちのを用いたほかは実施例１と同条件でメタノールの
改質を行った。結果を下記に示す。Main components Sin: 70 wtL MgO: , 1
Methanol was modified under the same conditions as in Example 1, except that a layer of 5 wt. CaO: 5 wt.$ and particle size of 1 m was used. The results are shown below.
結果
メタノール反応率 ９３．２ ％
生成ガス組成（マａｔ ＄）
し ＣＯら ル 園 ＤＭＥ
８０．２ ３０．０ ２．８ １．０ ３．２ ０．２
実施例１Ｏ
予め空気中で約５００℃に加熱して水分を除去した粒子
状のシリカ−ＣａＯ担体（主要成分は５ｉ０２：８０重
量％、Ｃａｂ：１０重量％、粒径ｌ■Ｗ） ３．２ｇ
に、１．０３重量％濃度の塩化白金酸水溶液３．３ｇを
含浸させ、１１０℃で２時間乾燥後、さらにＮ２中で約
４００℃に加熱し、引き続きＮ２中で還元した。Results Methanol reaction rate 93.2 % Produced gas composition ($) DME 80.2 30.0 2.8 1.0 3.2 0.2
Example 1O 3.2 g of particulate silica-CaO carrier (main components: 5i02: 80% by weight, Cab: 10% by weight, particle size 1■W), which was heated in advance to about 500°C in air to remove moisture.
was impregnated with 3.3 g of a 1.03% strength by weight aqueous chloroplatinic acid solution, dried at 110° C. for 2 hours, further heated to about 400° C. in N 2 and subsequently reduced in N 2 .
得られた白金担持体に、８．０６重量％濃度の硝酸セリ
ウム水溶液および２５．７重量％濃度の硝酸ニッケル水
溶液を含む混合液４．８ｇを含浸させ、前記と同様の方
法により乾燥、加熱、還元を行った。これにより、触媒
基質（Ｂ）の相持量が全触媒量に対して
Ｐｔ Ｏ，４重量％
Ｃｅ０ｚ ４．０重量％
旧 ８．０重量％
である３元組成系触媒が得られた。The obtained platinum support was impregnated with 4.8 g of a mixed solution containing an 8.06% by weight aqueous cerium nitrate solution and a 25.7% by weight aqueous nickel nitrate solution, and dried, heated, and dried in the same manner as described above. I made a reduction. As a result, a ternary composition catalyst was obtained in which the amount of catalyst substrate (B) supported was 4% by weight of Pt 2 O, 4.0% by weight of Ce0z, and 8.0% by weight of former, based on the total amount of catalyst.
この触媒を用い１反応条件を下記のように変更したほか
は実施例１を繰り返し、下記の結果を得た。Example 1 was repeated using this catalyst, except that the reaction conditions were changed as shown below, and the following results were obtained.
反応条件
隨望ＪＬＨＳＶ 瓦区皇渡 瓜−」
２ ｃｃ ｉｌｌ ｈｒ−’ ３９０”Ｏ大気圧
結果
メタノール反応率 ９Ｇ、０駕
生成ガス組成（マｏｆ ＄）
し 四 山 鳴 が 井
８１．３ ３０．０ ３．３ １．８ ２．５ ０．２
実施例１１
担体として。Reaction conditions: 2 cc ill hr-'390''O Atmospheric pressure Results: Methanol reaction rate: 9G, 0 Collapse gas composition (ma of $): 81.3 30. 0 3.3 1.8 2.5 0.2
Example 11 As a carrier.
主要成分 ＳｉＯ２： ７０ ｗｔＬ ＢａＯ： ２０
ｗｔＸ、粒径 ｌ １１層
のシリカバライタ担体を用いたほかは実施例１と同条件
でメタノールの改質を行った。結果を下記に示す。Main components SiO2: 70 wtL BaO: 20
Methanol was modified under the same conditions as in Example 1 except that a silica baryta carrier having 11 layers of wtX and particle size l was used. The results are shown below.
結果
メタノール反応率 ８５．１ ％
生成ガス組成（マｏｆ ％）
し 四 ａ ら 鍼 川
８０．９ ３０．６２．７ ０．７ ２．４ ０．１実
施例１２
予め空気中で約５００℃に加熱して水分を除去した粒状
のシリカ−マグネシアバライタ担体（主要成分は５ｉ０
２：６０重量％、ＭｇＯ：２０重量％、Ｂａｄ：１０重
量％、粒径１ｍｍ） ３．２ｇに、実施例１と同様に
して触媒基質（Ｂ）を担持させた。これにより、触媒基
質（Ｂ）の担持量が全触媒量に対して
ＰＬ Ｏ，４重量％
ＣｅＯ２４，０重量％
旧 ８．０重量％
である３元組成系触媒が得られた。Results Methanol reaction rate 85.1 % Produced gas composition (Ma of %) 80.9 30.62.7 0.7 2.4 0.1 Example 12 Preheated to approximately 500°C in air Granular silica-magnesia baryta carrier (main component is 5i0
2:60% by weight, MgO: 20% by weight, Bad: 10% by weight, particle size: 1 mm) 3.2g was loaded with the catalyst substrate (B) in the same manner as in Example 1. As a result, a ternary composition catalyst was obtained in which the supported amount of the catalyst substrate (B) was 4% by weight of PLO, 4.0% by weight of CeO, and 8.0% by weight of CeO2, based on the total amount of catalyst.
この触媒を用い、反応条件を下記のように変更したほか
は実施例１を繰り返し、下記の結果を得た。Using this catalyst, Example 1 was repeated except that the reaction conditions were changed as shown below, and the following results were obtained.
反応条件
成層ＪＬＨ９Ｖ 父庭皇遣 医−」
ｌ
２ｃｃ ８ｈｒ ３７０℃ 大気圧結果
メタノール反応率 ９０．５ ％
生成ガス組成（マｏｌ り
ヒ 四 山 ら 巨 川
８０．０ ３０．５ ４．０ １．２ ３．２ ０．４
であり、本発明は工業的意義が大きい。Reaction Conditions Stratified JLH9V Father's Garden Imperial Hospital 1 2cc 8hr 370°C Atmospheric pressure Results Methanol reaction rate 90.5% Produced gas composition (Maol Rihi Yoyama et al. Kyokawa 80.0 30.5 4.0 1. 2 3.2 0.4
Therefore, the present invention has great industrial significance.
特許出願人 乾 智 行
特許出願人 関西熱化学株式会社
発明の効果
本発明のメタノール改質用触媒は、低温でも触媒活性が
高いこと、Ｈ２およびＣＯへの分解反応が選択的に起こ
り、ＣＨ４，ｃｏｚ、 Ｈ，０生成反応、カーボン生成
反応、ジメチルエーテル生成反応などの副反応は有効に
抑制されること、触媒寿命が長いこと、担体に特殊な前
処理を要しないこと、触媒が比較的容易に調製される上
、特殊な前処理を要しないことなどの利点がある。Patent Applicant: Satoshi Inui Patent Applicant: Kansai Thermal Chemical Co., Ltd. Effects of the Invention The methanol reforming catalyst of the present invention has high catalytic activity even at low temperatures, and the decomposition reaction to H2 and CO occurs selectively. Side reactions such as coz, H,0 production reaction, carbon production reaction, and dimethyl ether production reaction are effectively suppressed, the catalyst life is long, no special pretreatment is required for the carrier, and the catalyst is relatively easy to prepare. It has the advantage of being easily prepared and requiring no special pretreatment.
Claims (1)
物または酸化ランタン（ａ２）よりなる担体（Ａ）に、
鉄族金属（ｂ１）、希土類元素の酸化物（ｂ２）および
白金族金属（ｂ３）よりなる触媒基質（Ｂ）を担持させ
てなるメタノール改質用触媒。 ２、メタノールを分解してＨ２およびＣＯを選択的に生
成させるための触媒である請求項１記載のメタノール改
質用触媒。 ３、担体（Ａ）に担持させる触媒基質（Ｂ）としての鉄
族金属（ｂ１）、希土類元素の酸化物（ｂ２）および白
金族金属（ｂ３）の担持量が、全触媒に対し、それぞれ
２〜２５重量％、０．５〜１５重量％、０．０１〜２重
量％である請求項１記載のメタノール改質用触媒。 ４、触媒基質（Ｂ）としての鉄族金属（ｂ１）がニッケ
ルまたはコバルト、希土類元素の酸化物（ｂ２）が酸化
セリウムまたは酸化ランタン、白金族金属（ｂ３）が白
金、ルテニウムまたはロジウムである請求項１または３
記載のメタノール改質用触媒。 ５、担体（Ａ）として、二酸化ケイ素（ａ１）およびア
ルカリ土類金属酸化物または酸化ランタン（ａ２）の割
合が重量比で４０：６０〜９５：５である担体を用いる
ことを特徴とする請求項１または３記載のメタノール改
質用触媒。 ６、アルカリ土類金属酸化物が、酸化マグネシウム、酸
化カルシウム、酸化バリウムおよび酸化ベリリウムより
なる群から選ばれた少なくとも１種の酸化物である請求
項１または５記載のメタノール改質用触媒。[Claims] 1. A carrier (A) consisting of silicon dioxide (a1) and an alkaline earth metal oxide or lanthanum oxide (a2),
A methanol reforming catalyst comprising a catalyst substrate (B) comprising an iron group metal (b1), a rare earth element oxide (b2) and a platinum group metal (b3). 2. The methanol reforming catalyst according to claim 1, which is a catalyst for selectively producing H2 and CO by decomposing methanol. 3. The amount of iron group metal (b1), rare earth element oxide (b2) and platinum group metal (b3) as catalyst substrate (B) supported on carrier (A) is 2% each with respect to the total catalyst. The catalyst for methanol reforming according to claim 1, wherein the content is 25% by weight, 0.5-15% by weight, 0.01-2% by weight. 4. A claim in which the iron group metal (b1) as the catalyst substrate (B) is nickel or cobalt, the rare earth element oxide (b2) is cerium oxide or lanthanum oxide, and the platinum group metal (b3) is platinum, ruthenium or rhodium. Item 1 or 3
The methanol reforming catalyst described above. 5. A claim characterized in that the carrier (A) is a carrier in which the weight ratio of silicon dioxide (a1) and alkaline earth metal oxide or lanthanum oxide (a2) is 40:60 to 95:5. Item 3. The methanol reforming catalyst according to item 1 or 3. 6. The methanol reforming catalyst according to claim 1 or 5, wherein the alkaline earth metal oxide is at least one oxide selected from the group consisting of magnesium oxide, calcium oxide, barium oxide, and beryllium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1049387A JPH0611401B2 (en) | 1989-02-28 | 1989-02-28 | Methanol reforming catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1049387A JPH0611401B2 (en) | 1989-02-28 | 1989-02-28 | Methanol reforming catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02227141A true JPH02227141A (en) | 1990-09-10 |
| JPH0611401B2 JPH0611401B2 (en) | 1994-02-16 |
Family
ID=12829613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1049387A Expired - Fee Related JPH0611401B2 (en) | 1989-02-28 | 1989-02-28 | Methanol reforming catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611401B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998046523A1 (en) * | 1997-04-11 | 1998-10-22 | Chiyoda Corporation | Catalyst for preparation of synthesis gas and process for preparing carbon monoxide |
| WO1998046525A1 (en) * | 1997-04-11 | 1998-10-22 | Chiyoda Corporation | Process for preparing synthesis gas by autothermal reforming |
| WO1998046524A1 (en) * | 1997-04-11 | 1998-10-22 | Chiyoda Corporation | Process for preparing synthesis gas |
| US6387843B1 (en) | 2001-04-05 | 2002-05-14 | Chiyoda Corporation | Method of preparing Rh- and/or Ru-catalyst supported on MgO carrier and reforming process using the catalyst |
| US6656978B2 (en) | 2001-04-05 | 2003-12-02 | Chiyoda Corporation | Process of producing liquid hydrocarbon oil or dimethyl ether from lower hydrocarbon gas containing carbon dioxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5233202B2 (en) * | 2007-01-12 | 2013-07-10 | Ｔｄｋ株式会社 | Reforming catalyst |
-
1989
- 1989-02-28 JP JP1049387A patent/JPH0611401B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998046523A1 (en) * | 1997-04-11 | 1998-10-22 | Chiyoda Corporation | Catalyst for preparation of synthesis gas and process for preparing carbon monoxide |
| WO1998046525A1 (en) * | 1997-04-11 | 1998-10-22 | Chiyoda Corporation | Process for preparing synthesis gas by autothermal reforming |
| WO1998046524A1 (en) * | 1997-04-11 | 1998-10-22 | Chiyoda Corporation | Process for preparing synthesis gas |
| US6312660B1 (en) | 1997-04-11 | 2001-11-06 | Chiyoda Corporation | Process for preparing synthesis gas |
| US6340437B1 (en) | 1997-04-11 | 2002-01-22 | Chiyoda Corporation | Process for preparing synthesis gas by autothermal reforming |
| US6376423B2 (en) | 1997-04-11 | 2002-04-23 | Chiyoda Corporation | Catalyst for preparation of synthesis gas and process for preparing carbon monoxide |
| US6387843B1 (en) | 2001-04-05 | 2002-05-14 | Chiyoda Corporation | Method of preparing Rh- and/or Ru-catalyst supported on MgO carrier and reforming process using the catalyst |
| US6656978B2 (en) | 2001-04-05 | 2003-12-02 | Chiyoda Corporation | Process of producing liquid hydrocarbon oil or dimethyl ether from lower hydrocarbon gas containing carbon dioxide |
| US6806296B2 (en) | 2001-04-05 | 2004-10-19 | Chiyoda Corporation | Process of producing liquid hydrocarbon oil or dimethyl ether from lower hydrocarbon gas containing carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0611401B2 (en) | 1994-02-16 |
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