JP4163292B2 - Hydrocarbon reforming catalyst and reforming method - Google Patents
Hydrocarbon reforming catalyst and reforming method Download PDFInfo
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- JP4163292B2 JP4163292B2 JP21313598A JP21313598A JP4163292B2 JP 4163292 B2 JP4163292 B2 JP 4163292B2 JP 21313598 A JP21313598 A JP 21313598A JP 21313598 A JP21313598 A JP 21313598A JP 4163292 B2 JP4163292 B2 JP 4163292B2
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- 239000003054 catalyst Substances 0.000 title claims description 137
- 229930195733 hydrocarbon Natural products 0.000 title claims description 31
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 31
- 238000002407 reforming Methods 0.000 title claims description 29
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 17
- 239000000395 magnesium oxide Substances 0.000 claims description 102
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 102
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 102
- 229910052751 metal Inorganic materials 0.000 claims description 51
- 239000002184 metal Substances 0.000 claims description 51
- 239000002253 acid Substances 0.000 claims description 47
- 239000010948 rhodium Substances 0.000 claims description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 26
- 239000007789 gas Substances 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- 230000008021 deposition Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 8
- 239000000347 magnesium hydroxide Substances 0.000 description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- -1 for example Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000000629 steam reforming Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【０００１】
【発明の属する技術分野】
本発明は、炭化水素改質用触媒及びそれを用いる炭化水素の改質方法に関するものである。
【０００２】
【従来の技術】
炭化水素を改質することによって得られる合成ガスは、水素と一酸化炭素からなる混合ガスで、アンモニア、メタノール、酢酸等の工業製品の合成原料として広く利用されている。一般に、合成ガスは、炭化水素に触媒の存在下でスチーム及び／又は炭酸ガスを反応させることによって製造することができる（特開平5-208801号、特開平6-279003号、特開平9-168740号等）。しかしながら、この反応に於いては、その副反応として、炭素析出反応が起こって炭素が析出し、この析出炭素によって触媒被毒が生じるという問題がある。この改質反応において、貴金属を触媒金属として使用すると、Ｎｉ等の遷移金属に比べ、炭素析出が抑制され易いことは良く知られているが、この場合、貴金属が非常に高価であるため、なるべく少量の金属の担持量で十分なる反応活性を有するとともに、炭素析出活性の抑制された安価な触媒の開発が望まれていた。また、USP.5,336,655号明細書には、ＲｈあるいはＲｕを担持した酸化マグネシウム、又は、ＲｈあるいはＲｕを担持した酸化アルミニウムに、シリカを添加する方法が示されている。しかし、シリカ添加すると、炭化水素の炭酸ガスリフォーミングにおいて、炭素抑制の効果があるとの記載があるが、還元ガス（水素、一酸化炭素）やスチームの存在する、高温、高圧のリフォーミング条件で、シリカのような揮散し易い元素が触媒中に存在すると、反応中に揮散に伴う触媒の粉化が起こり、リアクターの閉塞等の問題が生じる。従って、本発明では、担体ＭｇＯ中にシリカを添加することなく、また、ＭｇＯの酸量を規定することにより炭素析出を抑制することが可能となる。さらに、担体ＭｇＯの比表面積及び担持金属量を正確にコントロールすることにより、工業的に有用な高圧下（１０kg/cm2G以上）で、リホーミング活性を十分に有し、かつ炭素析出を起こさない、実用的な触媒を得ることが可能となる。
【０００３】
【発明が解決しようとする課題】
本発明は、貴金属の担持量が少なく、しかも使用に際しての炭素析出量が少なく、かつ粉化を生じることのない炭化水素改質用触媒及びそれを用いる炭化水素の改質方法を提供することをその課題とする。
【０００４】
【課題を解決するための手段】
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、本発明を完成するに至った。即ち、本発明によれば、担体酸化マグネシウムにロジウム及び／又はルテニウムからなる触媒金属を担持させた触媒であって、(i) 酸化マグネシウムが１０００℃以上の高温で焼成されたものであってその純度が９９．９%wt以上であること、 (ii) 比表面積が０．０１〜５m2/gであること、(iii) 酸強度（Ｈ0）が２以上の酸点のみであってその含量が０．０３mmol/g以下であること、(iv) 触媒金属の担持量が、担体酸化マグネシウムに対し、１０〜５０００wtppmの割合であること、を特徴とする炭化水素改質用触媒が提供される。また、本発明によれば、炭化水素を触媒の存在下において５００〜１２００℃の温度及び１０kg/cm2G以上の加圧条件下で炭酸ガス及び／又はスチームと反応させる方法において、該触媒として前記炭化水素改質用触媒を用いることを特徴とする炭化水素の改質方法が提供される。
【０００５】
【発明の実施の形態】
本発明においては、触媒担体として酸化マグネシウム（以下、単にＭｇＯとも言う）を用いる。炭素析出反応の抑制及び触媒粉化防止のためには、純度が９９．９wt%以上である酸化マグネシウムを担体として使用することが必要である。鉄、ニッケルは炭素析出反応の活性金属として作用する。一方、塩素は担体不純物の鉄、アルミニウムと反応してＦｅＣｌ3、ＡｌＣ１3等の酸触媒として作用する塩化物を形成する。従って、それらの不純物は、炭素析出反応を促進するだけでなく、活性金属の分散度を低下させるためその混入が好ましくない。また、シリカは還元ガス（水素、一酸化炭素）や水蒸気が存在する高温、高圧のリフォーミング条件で、揮散が起こり、これが原因となって、反応中に触媒の粉化が起こるため、その混入は好ましくない。このような担体ＭｇＯとしては、市販品を用いることができ、その形状は特に制約されず、触媒として用いられている各種の形状、例えば、粉末状、粒状、球状、柱状、筒状等の形状であることができるが、１０００℃以上の高温で焼成されていることが必要である。また、ＭｇＯとしては、水酸化マグネシウムを１０００〜１５００℃、好ましくは１１００〜１３００℃で焼成して得られたものや、炭酸マグネシウム又は塩基性炭酸マグネシウムを１０００〜１５００℃、好ましくは１１００〜１３００℃で焼成して得られたものが用いられる。
【０００６】
本発明の炭化水素改質用触媒（以下、単に触媒とも言う）を調製するには、先ず、第１工程（１次焼成工程）において、ＭｇＯを１０００℃以上の高温で比表面積が０．０１〜５m2/gのＭｇＯになるように焼成（１次焼成）する。市販のＭｇＯは、通常、水酸化マグネシウムや炭酸マグネシウムを１０００℃より低い温度で焼成することにより製造されているが、このようなＭｇＯは、結晶化度が低く、高比表面積のものであり、その表面に強い酸点が多量に残存するため、その酸点上で副反応である炭素析出反応が促進され、炭素が析出し、この析出炭素によって触媒被毒が生じるという問題が起こる。これに対し、ＭｇＯを１０００℃以上の高温で焼成し、結晶化度を高めると、そのＭｇＯの表面は安定化され、強酸点を極力抑えたＭｇＯとなる。そして、このような安定化されたＭｇＯでは、酸強度（Ｈ0）が２以上の酸点のみを有し、その量が０．０３mmol/g以下のＭｇＯが得られる。従って、１０００℃以上の高温で焼成された高結晶化度のＭｇＯを触媒金属担持用担体として用いることにより、強酸点の発現を極力抑え、炭素析出反応が抑制され安定した活性を有する触媒を得ることが可能となる。ＭｇＯを１０００℃以上の温度で１次焼成する場合、この１次焼成は、得られるＭｇＯの比表面積が０．０１〜５m2/g、好ましくは０．０５〜３m2/gとなるように行う。担体ＭｇＯの比表面積が前記範囲より高くなると、触媒金属の担持量が多くなり、また、触媒の酸強度が強くなりすぎて、触媒表面の酸的特性が不満足のものとなる。一方、担体ＭｇＯの比表面積が前記範囲より小さくなると、触媒金属の担持量が少なくなりすぎて、十分な活性を有する触媒が得られなくなる。酸化マグネシウムを焼成する際の雰囲気としては、通常の空気雰囲気が使用されるが、他のガス、例えば、窒素ガス等の不活性ガスであってもよい。焼成温度は１０００〜１５００℃、好ましくは１１００〜１３００℃である。焼成時間は１時間以上、好ましくは３時間以上であり、その上限値は、特に制約されないが、通常、７２時間程度である。
【０００７】
前記のようにして得た担体酸化マグネシウムに対しては、第２工程（触媒金属担持工程）において、触媒金属を含む溶液を用い、平衡吸着法にて触媒金属を担持させる。前記触媒金属を含む溶液は、水溶液や有機溶媒（メタノール、アセトン等）溶液であることができる。担持温度は５〜５０℃、好ましくは１５〜３０℃である。本発明では、触媒金属としては、ロジウム及び／又はルテニウムが用いられる。
前記担持工程では、触媒金属は溶液状で担体酸化マグネシウムに担持されるが、この場合の触媒金属は可溶性化合物の形態で用いられる。このようなものとしては、ハロゲン化物、硝酸塩、硫酸塩、有機酸塩（酢酸塩等）、錯塩（キレート）等が挙げられる。
担体ＭｇＯに対する触媒金属溶液の担持には、平衡吸着法が採用される。この方法は、担体を触媒溶液中に浸漬し、平衡条件下で溶液中の触媒金属を担体に吸着担持させる方法である。この場合、触媒金属を担体に担持させる時間（浸漬時間）は１時間以上、好ましくは３時間以上であり、その上限は、特に制約されないが、通常、４８時間程度である。この平衡吸着法の詳細は、文献「触媒調製化学」（１９８０年出版、講談社サイエンティフィク、Ｐ４９）に記載されている。
【０００８】
前記のようにして触媒水溶液を用いて触媒金属を担体ＭｇＯに担持させる場合、その触媒水溶液のｐＨは８以上、好ましくは８．５以上のアルカリ領域とするのがよい。その上限値は、特に制約されないが、通常、ｐＨ１３程度である。その水溶液のｐＨ調節には、水酸化ナトリウムや水酸化カリウム、水酸化カルシウム、水酸化マグネシウム等のアルカリ性物質が用いられる。本発明においては、担体ＭｇＯに対する触媒金属の担持量は、触媒金属換算量で、担体ＭｇＯに対して１０〜５０００wtppm、好ましくは１００〜２０００wtppmの割合に規定する。触媒金属担持量が前記範囲より多くなると、触媒コストが高くなるとともに、触媒の炭素析出活性が高くなり、触媒の使用に際し、炭素析出量が多くなる。一方、前記範囲より少ないと、十分な触媒活性が得られなくなる。触媒金属担持量の調節は、担体ＭｇＯに対して触媒金属溶液を担持する際の条件、例えば、溶液中の触媒金属濃度や、担体ＭｇＯの比表面積等によって行うことができる。
【０００９】
前記のようにして、担体ＭｇＯに触媒金属を溶液状で担持させることによって得られた触媒金属担持ＭｇＯは、第３工程（乾燥工程）において、３５℃以下の温度で６時間以上保持して乾燥させる。好ましい乾燥温度は１０〜２５℃である。乾燥時間は６時間以上であればよく、好ましくは１２時間以上であり、その上限値は、特に制約されないが、通常、約７２時間程度である。このような乾燥処理により、ＭｇＯからの急激な溶媒の蒸発が回避され、その結果、触媒金属は凝集することなく担体ＭｇＯに高分散状態で担持される。乾燥温度や乾燥時間が前記範囲を逸脱すると、高分散性の触媒金属を含む触媒を得ることができなくなる。
【００１０】
前記のようにして得られた乾燥物は、これを第４工程（２次焼成工程）において、８００℃以上の高温で１時間以上焼成（２次焼成）する。この場合、焼成雰囲気としては、通常、空気が用いられるが、他のガス（不活性ガス等）であってもよい。焼成温度は８００℃以上であり、好ましくは８５０℃以上であり、その上限値は、特に制約されないが、通常、１１００℃程度である。好ましい焼成時間は２時間以上であり、その上限値は、特に制約されないが、通常、２４時間程度である。この２次焼成により、触媒金属の熱安定性が高められ、熱安定性の良い触媒を得ることができる。
【００１１】
触媒コストの低減化を図るには、担体に担持させる触媒金属の担持量をできるだけ低減化させると同時に、十分な反応活性を発現するように、担体に担持された触媒金属粒子の凝集化をできるだけ抑制して微粒子することが必要となる。本発明者らの研究によれば、担体ＭｇＯの結晶化を高めてその比表面積を５m2/g以下に保持するとともに、その担体ＭｇＯに対する触媒金属の担持量を１０〜５０００wtppmと極く少量に保持し、かつその触媒金属を担体ＭｇＯに担持させるに際し、平衡吸着法により触媒金属を平衡条件下で長時間をかけてゆっくりと溶液状で担持させ、その担持後においては、３５℃以下の温度でゆっくりと乾燥するときには、均一に担持され、炭化水素改質用触媒として十分な活性を有する安価な触媒が得られることが見出された。
【００１２】
前記のようにして得られる本発明触媒において、その触媒金属担持量は、担体ＭｇＯに対して、１０〜５０００wtppm、好ましくは１００〜２０００wtppmであり、その比表面積は０．０１〜５m2/g、好ましくは０．０５〜３m2/gである。なお、本明細書中で触媒又は担体ＭｇＯに関して言う比表面積は「ＢＥＴ」法により、温度１５℃で測定されたものであり、その測定装置としては、柴田科学社製の「ＳＡ−１００」が用いられた。
【００１３】
前記のようにして得られる本発明の触媒は、炭化水素改質用触媒として好ましい酸的性質を有する。触媒表面に強い酸点が多量に存在すると、その酸点上で副反応である炭素析出反応が促進され、炭素が析出し、この析出炭素によって触媒被毒が生じるようになる。
【００１４】
本発明の触媒は、一般的には、その酸強度（Ｈ0）は２より大きい、好ましくは３．３以上の酸点のみからなり、その含量は０．０３ｍｍｏｌ／ｇより少なく、好ましくは０．０２ｍｍｏｌ／ｇ以下である。酸強度（Ｈ0）の調節は、担体ＭｇＯを１次焼成する際の温度及び時間により行うことができる。本発明の触媒は、強酸点の発現が抑制され、炭素析出活性が大きく抑制されたものである。
【００１５】
なお、本明細書で言う酸強度（Ｈ0）は、触媒が塩基性指示薬（Ｂ-）にプロトンを与える能力として表示され、次式で表される。
Ｈ0＝ｐＫａ（＝ｐＫB - H +）＋ｌｏｇ［Ｂ-］／［Ｂ-Ｈ+］ （１）
前記式中、ＫB - H +は、塩基性指示薬Ｂ-と酸性点Ｈ+Ｂとを反応させて、塩基性指示薬の酸性体（Ｂ-Ｈ+）を生成させる反応におけるその酸性体Ｂ-Ｈ+の解離定数を示す。［Ｂ-］／［Ｂ-Ｈ+］は、Ｂ-とＢ-Ｈ+の濃度比を示す。
強酸点ほど、ｐＫB - H +の小さな指示薬をより多くプロトン化するのでそのＨ0値は小さくなる。
【００１６】
本明細書における酸強度は以下のようにして測定されたものである。
（酸強度の測定方法）
酸強度Ｈ0（ハメット指数）関数は、酸強度関数で、触媒学会編「触媒実験ハンドブック」（１９８６年出版、講談社サイエンティフィク）、ｐ．１７２に記載の「Ｂｅｎｅｓｉ法」により測定されたものである。触媒にｐＫａが分かっている指示薬を添加し、変色すると、Ｈ0がそのｐＫａより小さい酸点があることを示す。塩基性分子であるブチルアミンを酸点に所定量吸着させ、ｐＫａの異なる指示薬で滴定すると、ブチルアミンの量から酸点の数が、ｐＫａの値から酸強度が測定できる。測定温度は室温である。
【００１７】
本発明の触媒を用いて炭化水素を改質するには、触媒の存在下において、炭化水素とスチーム及び／又は二酸化炭素（ＣＯ2）とを反応させればよい。炭化水素としては、メタン、エタン、プロパン、ブタン、ナフサ等の低級炭化水素が用いられるが、好ましくはメタンが用いられる。本発明においては、炭酸ガスを含む天然ガス（メタンガス）を反応原料として有利に用いることができる。
メタンと二酸化炭素（ＣＯ2）とを反応させる方法（ＣＯ2リフォーミング）の場合、その反応は次式で示される。
【化１】
【化２】
スチームリフォーミングにおいて、その反応温度は６００〜１２００℃、好ましくは６００〜１０００℃であり、その反応圧力は加圧であり、１〜４０ｋｇ/ｃｍ2Ｇ、好ましくは５〜３０ｋｇ/ｃｍ2Ｇである。また、この反応を固定床方式で行う場合、そのガス空間速度（ＧＨＳＶ）は１，０００〜１０，０００ｈｒ-1、好ましくは２，０００〜８，０００ｈｒ-1以下である。原料炭化水素に対するスチーム使用割合を示すと、原料炭化水素中の炭素１モル当り、スチーム（Ｈ2Ｏ）０．５〜５モル、好ましくは１〜２モル、より好ましくは１〜１．５モルの割合である。
本発明によりスチームリフォーミングを行う場合、前記のように、原料炭化水素の炭素１モル当りのスチーム（Ｈ2Ｏ）を２モル以下に保持しても、炭素析出を抑制して、工業的に有利に合成ガス（ＣＯとＨ2の混合ガス）を製造することができる。従来の場合には、原料炭化水素の炭素１モル当り２〜５モルのスチームを必要としていたことを考えると、２モル以下のスチームの使用によってリフォーミング反応を円滑に進行させ得ることは、本発明触媒の工業上の大きな利点である。
本発明の触媒は、炭化水素に、スチームとＣＯ2の混合物を反応させる際の触媒として有利に用いられる。この場合、スチームとＣＯ2との混合割合は特に制約されないが、一般的には、Ｈ2Ｏ／ＣＯ2モル比で、０．１〜１０である。
【００１８】
【実施例】
次に本発明を実施例によりさらに詳細に説明する。
［実施例１］
市販の純度９９．９wt%の酸化マグネシウム（ＭｇＯ）を用いて形成したＭｇＯの１／８ペレットを空気中で１０６０℃で３ｈ（時間）焼成し、これを触媒担体ＭｇＯ（Ａ）として用いた。次に、３．９wt%のＲｈを含むロジウム(III）アセテート水溶液に２６ｈ（時間）浸漬した。その水溶液は水酸化マグネシウム水溶液を用い、ｐＨ９．７に調整した。このようにしてＲｈを触媒担体ＭｇＯ（Ａ）に平衡吸着させた後、濾過して、Ｒｈを水溶液状で吸着した触媒担体ＭｇＯ（Ａ）を得た。この場合のＲｈ担持量は、Ｒｈ金属換算量で、担体ＭｇＯ（Ａ）に対して、３７５０wtppmである。次に、Ｒｈを吸着した担体ＭｇＯ（Ａ）を空気中において３５℃の温度で５２ｈ乾燥した後、空気中において８５０℃で２ｈ焼成し、本発明触媒（Ａ）を得た。この触媒（Ａ）は、ＲｈをＲｈ金属として担体ＭｇＯに対し３７５０wtppm含有するもので、その比表面積は１．２m2/gであった。また、その酸点は、酸強度（Ｈ0）が３．３以上の酸点のみからなり、その含量は０．０１mmol/gであった。
【００１９】
［実施例２］
市販の純度９９．９wt%の酸化マグネシウム（ＭｇＯ）を用いて形成したＭｇＯの１／８ペレットを空気中で１０００℃で２ｈ（時間）焼成し、これを触媒担体ＭｇＯ（Ｂ）として用いた。次に、０．１wt%のＲｕを含むルテニウム(III）クロライド水溶液に１９ｈ（時間）浸漬した。その水溶液は水酸化マグネシウム水溶液を用い、ｐＨは９．７に調整した。Ｒｕを触媒担体ＭｇＯ（Ｂ）に平衡吸着させた後、濾過して、水溶液状で吸着した触媒担体ＭｇＯ（Ｂ）を得た。この場合のＲｕ担持量は、Ｒｕ金属換算量で、担体ＭｇＯ（Ｂ）に対して、１２５wtppmである。次に、Ｒｕを吸着した担体ＭｇＯ（Ｂ）を空気中において３０℃の温度で７２ｈ乾燥した後、空気中において８６０℃で２．５ｈ焼成し、本発明触媒（Ｂ）を得た。この触媒（Ｂ）は、ＲｕをＲｕ金属として担体ＭｇＯ（Ｂ）に対し１２５wtppmの割合で含有するもので、その比表面積は４．８m2/gであった。また、その酸点は、酸強度（Ｈ0）が３．３以上の酸点のみからなり、その含量は０．０３mmol/gであった。
【００２０】
［実施例３］
市販の純度９９．９wt%の酸化マグネシウム（ＭｇＯ）を用いて形成したＭｇＯの１／８ペレットを空気中で１２００℃で２．５ｈ（時間）焼成し、これを触媒担体ＭｇＯ（Ｃ）として用いた。次に、２．６wt%のＲｈを含むロジウム(III）アセテート水溶液に２６ｈ（時間）浸漬した。その水溶液には水酸化マグネシウム水溶液を用い、ｐＨは９．７に調整した。このようにして、Ｒｈを触媒担体ＭｇＯ（Ｃ）に平衡吸着させた後、濾過して、Ｒｈを水溶液状で吸着した触媒担体ＭｇＯ（Ｃ）を得た。この場合のＲｈ担持量は、Ｒｈ金属換算量で、担体ＭｇＯ（Ｃ）に対して、１７５０wtppmである。次に、Ｒｈを吸着した担体ＭｇＯ（Ｃ）を空気中において２０℃の温度で３４ｈ乾燥した後、空気中において９５０℃で３．５ｈ焼成し、本発明触媒（Ｃ）を得た。この触媒（Ｃ）は、ＲｈをＲｈ金属として担体ＭｇＯに対し１７５０wtppm含有するもので、その比表面積は０．２m2/gであった。また、その酸点は、酸強度（Ｈ0）が３．３以上の酸点のみからなり、その含量は０．００２mmol/gであった。
【００２１】
［実施例４］
市販の純度９９．９wt%の酸化マグネシウム（ＭｇＯ）を用いて形成したＭｇＯの１／８ペレットを空気中で１０５０℃で３ｈ（時間）焼成し、これを触媒担体ＭｇＯ（Ｄ）として用いた。次に、０．５４wt%のＲｈを含むロジウム(III）アセテート水溶液に２４ｈ（時間）浸漬した。その水溶液は水酸化マグネシウム水溶液を用い、ｐＨは９．７に調整した。このようにして、Ｒｈを触媒担体ＭｇＯ（Ｄ）に平衡吸着させた後、濾過して、Ｒｈを水溶液状で吸着した触媒担体ＭｇＯ（Ｄ）を得た。この場合のＲｈ担持量は、Ｒｈ金属換算量で、担体ＭｇＯ（Ｄ）に対して、５００wtppmである。次に、Ｒｈを吸着した担体ＭｇＯ（Ｄ）を空気中において３０℃の温度で１８ｈ乾燥した後、空気中において９００℃で２ｈ焼成し、本発明触媒（Ｄ）を得た。この触媒（Ｄ）は、ＲｈをＲｈ金属として担体ＭｇＯに対し５００wtppm含有するもので、その比表面積は２．３m2/gであった。また、その酸点は、酸強度（Ｈ0）が３．３以上の酸点のみからなり、その含量は０．０２mmol/gであった。
【００２２】
［実施例５］
市販の純度９９．９wt%の酸化マグネシウム（ＭｇＯ）を用いて形成したＭｇＯの１／８ペレットを空気中で１２００℃で２ｈ（時間）焼成し、これを触媒担体ＭｇＯ（Ｅ）として用いた。次に、７．１wt%のＲｕを含むルテニウム(III）クロライド水溶液に１９ｈ（時間）浸漬した。その水溶液は水酸化マグネシウム水溶液を用い、ｐＨは９．７に調整した。このようにして、Ｒｕを触媒担体ＭｇＯ（Ｅ）に平衡吸着させた後、濾過して、Ｒｕを水溶液状で吸着した触媒担体ＭｇＯ（Ｅ）を得た。この場合のＲｕ担持量は、Ｒｕ金属換算量で、担体ＭｇＯ（Ｅ）に対して、５０００wtppmである。次に、Ｒｕを吸着した担体ＭｇＯ（Ｅ）を空気中において２５℃の温度で２０ｈ乾燥した後、空気中において８５０℃で２ｈ焼成し、本発明触媒（Ｅ）を得た。この触媒（Ｅ）は、ＲｕをＲｕ金属として担体ＭｇＯに対し５０００wtppm含有するもので、その比表面積は０．２m2/gであった。また、その酸点は、酸強度（Ｈ0）が３．３以上の酸点のみからなり、その含量は０．００２mmol/gであった。
【００２３】
［実施例６］
市販の純度９９．９wt%の酸化マグネシウム（ＭｇＯ）を用いて形成したＭｇＯの１／８ペレットを空気中で１１００℃で２ｈ（時間）焼成し、これを触媒担体ＭｇＯ（Ｆ）として用いた。この触媒担体ＭｇＯ（Ｆ）を０．６６wt%のＲｕを含むルテニウム(III）クロライドのメタノール溶液に２４ｈ（時間）浸漬した。このようにして、Ｒｕを触媒担体ＭｇＯ（Ｆ）に平衡吸着させた後、濾過して、Ｒｕを溶液状で吸着した触媒担体ＭｇＯ（Ｆ）を得た。この場合のＲｕ担持量は、Ｒｕ金属換算量で、担体ＭｇＯ（Ｆ）に対して、５００wtppmである。次に、Ｒｕを吸着した担体ＭｇＯ（Ｆ）を空気中において３５℃の温度で５２ｈ乾燥した後、空気中において８００℃で２．５ｈ焼成し、本発明触媒（Ｆ）を得た。この触媒（Ｆ）は、ＲｕをＲｕ金属として担体ＭｇＯに対し５００wtppm含有するもので、その比表面積は１．１m2/gであった。また、その酸点は、酸強度（Ｈ0）が３．３以上の酸点のみからなり、その含量は０．０１mmol/gであった。
【００２４】
反応例１
実施例１で調製した触媒（Ａ）３０ｃｃを反応器に充填し、メタンのＣＯ2リフォーミング試験を実施した。
触媒は、予めＨ2気流中９００℃で１ｈ還元処理を行った後、ＣＨ4：ＣＯ2モル比＝１：０．４、ＣＨ4：Ｈ2Ｏモル比＝１：０．８５の原料ガスを、圧力２０ｋｇ／ｃｍ2Ｇ，温度８２０℃，メタン基準のＧＨＳＶ＝４０００ｈｒ-1の条件で処理した。反応開始から５ｈ経過後のＣＨ4転化率は、５０％（実験条件下でのＣＨ4の平衡転化率＝５０％）であり、また反応開始から１２００ｈ経過後のＣＨ4の転化率は、５０％であった。
ここで、ＣＨ4の転化率は、次式で定義される。
ＣＨ4の転化率（％）＝（Ａ−Ｂ）／Ａ×１００
Ａ：原料中のＣＨ4モル数
Ｂ：生成物中のＣＨ4モル数
また、前記触媒は、シリカ含有量が極く微量であるため、反応中に粉化することもなかった。
【００２５】
反応例２
実施例２で調製した触媒（Ｂ）３０ｃｃを反応器に充填し、メタンのＣＯ2リフォーミング試験を実施した。
触媒は、予めＨ2気流中９００℃で１ｈ還元処理を行った後、ＣＨ4：ＣＯ2モル比＝１：１の原料ガスを、圧力１０ｋｇ／ｃｍ2Ｇ，温度８４０℃，メタン基準のＧＨＳＶ＝５０００ｈｒ-1の条件で処理した。反応開始から５ｈ経過後のＣＨ4転化率は、６５％（実験条件下でのＣＨ4の平衡転化率＝６５％）であり、また反応開始から４６０ｈ経過後のＣＨ4の転化率は、６５％であった。
【００２６】
反応例３
実施例３で調製した触媒（Ｃ）３０ｃｃを反応器に充填し、メタンのＣＯ2リフォーミング試験を実施した。
触媒は、予めＨ2気流中９００℃で１ｈ還元処理を行った後、ＣＨ4：ＣＯ2モル比＝１：１の原料ガスを、圧力２０ｋｇ／ｃｍ2Ｇ，温度８４０℃，メタン基準のＧＨＳＶ＝３５００ｈｒ-1の条件で処理した。反応開始から５ｈ経過後のＣＨ4転化率は、５３％（実験条件下でのＣＨ4の平衡転化率＝５３％）であり、また反応開始から２５０ｈ経過後のＣＨ4の転化率は、５３％であった。
【００２７】
反応例４
実施例４で調製した触媒（Ｄ）３０ｃｃを反応器に充填し、メタンのＣＯ2リフォーミング試験を実施した。
触媒は、予めＨ2気流中９００℃で１ｈ還元処理を行った後、ＣＨ4：ＣＯ2モル比＝１：０．４、ＣＨ4：Ｈ2Ｏモル比＝１：０．８５の原料ガスを、圧力２０ｋｇ／ｃｍ2Ｇ，温度８５０℃，メタン基準のＧＨＳＶ＝４０００ｈｒ-1の条件で処理した。反応開始から５ｈ経過後のＣＨ4転化率は、５７％（実験条件下でのＣＨ4の平衡転化率＝５７％）であり、また反応開始から１０００ｈ経過後のＣＨ4の転化率は、５７％であった。
【００２８】
反応例５
実施例５で調製した触媒（Ｅ）３０ｃｃを反応器に充填し、メタンのＣＯ2リフォーミング試験を実施した。
触媒は、予めＨ2気流中９００℃で１ｈ還元処理を行った後、ＣＨ4：ＣＯ2モル比＝１：１の原料ガスを、圧力１０ｋｇ／ｃｍ2Ｇ，温度８７０℃，メタン基準のＧＨＳＶ＝５０００ｈｒ-1の条件で処理した。反応開始から５ｈ経過後のＣＨ4転化率は、７１％（実験条件下でのＣＨ4の平衡転化率＝７１％）であり、また反応開始から６９０ｈ経過後のＣＨ4の転化率は、７１％であった。
【００２９】
反応例６
実施例６で調製した触媒（Ｆ）３０ｃｃを反応器に充填し、メタンのＣＯ2リフォーミング試験を実施した。
触媒は、予めＨ2気流中９００℃で１ｈ還元処理を行った後、ＣＨ4：ＣＯ2モル比＝１：１の原料ガスを、圧力２０ｋｇ／ｃｍ2Ｇ，温度８５０℃，メタン基準のＧＨＳＶ＝６０００ｈｒ-1の条件で処理した。反応開始から５ｈ経過後のＣＨ4転化率は、５５％（実験条件下でのＣＨ4の平衡転化率＝５５％）であり、また反応開始から１０００ｈ経過後のＣＨ4の転化率は、５５％であった。
【００３０】
【発明の効果】
本発明によれば、触媒金属の担持量が極く少量でありながら、炭素析出活性が著しく抑制されるとともに、反応中の触媒粉化が防止された安価な炭化水素改質用触媒を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrocarbon reforming catalyst and a hydrocarbon reforming method using the catalyst.
[0002]
[Prior art]
Syngas obtained by reforming hydrocarbons is a mixed gas composed of hydrogen and carbon monoxide, and is widely used as a raw material for synthesizing industrial products such as ammonia, methanol, and acetic acid. In general, synthesis gas can be produced by reacting hydrocarbons with steam and / or carbon dioxide gas in the presence of a catalyst (JP-A-5-208801, JP-A-6-279003, JP-A-9-18740). Issue). However, in this reaction, as a side reaction, there is a problem that a carbon deposition reaction occurs to deposit carbon, which causes catalyst poisoning. In this reforming reaction, it is well known that when a noble metal is used as a catalyst metal, carbon deposition is more easily suppressed than a transition metal such as Ni, but in this case, the noble metal is very expensive, so Development of an inexpensive catalyst having sufficient reaction activity with a small amount of supported metal and suppressing carbon deposition activity has been desired. US Pat. No. 5,336,655 discloses a method of adding silica to magnesium oxide supporting Rh or Ru or aluminum oxide supporting Rh or Ru. However, when silica is added, carbon dioxide gas reforming of hydrocarbons has been described as having an effect of carbon suppression, but under high temperature and high pressure reforming conditions where reducing gas (hydrogen, carbon monoxide) and steam are present. When an easily volatile element such as silica is present in the catalyst, the catalyst is pulverized during the reaction, causing problems such as reactor clogging. Therefore, in the present invention, it is possible to suppress carbon deposition without adding silica to the support MgO and by regulating the acid amount of MgO. Furthermore, by precisely controlling the specific surface area of the support MgO and the amount of supported metal, it has sufficient reforming activity and carbon deposition under industrially useful high pressure (10 kg / cm 2 G or more). No practical catalyst can be obtained.
[0003]
[Problems to be solved by the invention]
The present invention provides a hydrocarbon reforming catalyst with a small amount of noble metal supported, a small amount of carbon deposition during use, and no pulverization, and a hydrocarbon reforming method using the same. Let that be the issue.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, according to the present invention, there is provided a catalyst in which a catalyst metal made of rhodium and / or ruthenium is supported on a support magnesium oxide, and (i) magnesium oxide is calcined at a high temperature of 1000 ° C. or higher. purity of at 99.9% wt or more, (ii) a specific surface area to be 0.01~5m 2 / g, be only (iii) acid strength (H 0) 2 or more acid points Provided is a hydrocarbon reforming catalyst characterized in that its content is 0.03 mmol / g or less, and (iv) the supported amount of catalyst metal is 10 to 5000 wtppm with respect to the supported magnesium oxide. Is done. Further, according to the present invention, in the method of reacting a hydrocarbon with carbon dioxide and / or steam under a pressure condition of 500 to 1200 ° C. and a pressure of 10 kg / cm 2 G or more in the presence of a catalyst, There is provided a hydrocarbon reforming method using the hydrocarbon reforming catalyst.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, magnesium oxide (hereinafter also simply referred to as MgO) is used as the catalyst carrier. In order to suppress the carbon deposition reaction and prevent catalyst dusting, it is necessary to use magnesium oxide having a purity of 99.9 wt% or more as a support. Iron and nickel act as active metals for the carbon deposition reaction. Meanwhile, chlorine forms a chloride which acts as an acid catalyst such as FeCl 3, AlCl 3 reacts iron carriers impurities, and aluminum. Accordingly, these impurities not only promote the carbon deposition reaction but also reduce the dispersity of the active metal, so that their incorporation is not preferred. In addition, silica volatilizes under high temperature and high pressure reforming conditions where reducing gas (hydrogen, carbon monoxide) or water vapor is present, which causes catalyst pulverization during the reaction. Is not preferred. As such support MgO , a commercial product can be used, and the shape is not particularly limited, and various shapes used as a catalyst, for example, powder, granular, spherical, columnar, cylindrical, etc. However, it must be fired at a high temperature of 1000 ° C. or higher . Moreover, as MgO, what was obtained by baking magnesium hydroxide at 1000-1500 degreeC, Preferably it is 1100-1300 degreeC, or magnesium carbonate or basic magnesium carbonate is 1000-1500 degreeC, Preferably it is 1100-1300 degreeC. What was obtained by baking with is used.
[0006]
To prepare the hydrocarbon reforming catalyst of the present invention (hereinafter also simply referred to as catalyst), first, in the first step (primary calcination step), MgO is used at a high temperature of 1000 ° C. or higher and the specific surface area is 0.01. Calcination (primary calcination) so as to be ˜5 m 2 / g MgO. Commercially available MgO is usually produced by firing magnesium hydroxide or magnesium carbonate at a temperature lower than 1000 ° C., but such MgO has a low crystallinity and a high specific surface area . Since a large amount of strong acid sites remain on the surface, a carbon deposition reaction, which is a side reaction, is promoted on the acid sites, so that carbon is deposited and catalyst deposition is caused by the deposited carbon. On the other hand, when MgO is baked at a high temperature of 1000 ° C. or higher to increase the degree of crystallinity, the surface of MgO is stabilized and becomes MgO with a strong acid point suppressed as much as possible. In such stabilized MgO, MgO having only acid sites having an acid strength (H 0 ) of 2 or more and an amount of 0.03 mmol / g or less is obtained. Therefore, by using MgO having a high degree of crystallinity calcined at a high temperature of 1000 ° C. or higher as a support for supporting a catalytic metal, a catalyst having a stable activity is obtained by suppressing the expression of strong acid points as much as possible and suppressing the carbon deposition reaction. It becomes possible. When the primary firing of MgO is performed at a temperature of 1000 ° C. or higher, the primary firing is performed so that the specific surface area of MgO obtained is 0.01 to 5 m 2 / g, preferably 0.05 to 3 m 2 / g. Do. When the specific surface area of the support MgO is higher than the above range, the amount of the catalyst metal supported increases, and the acid strength of the catalyst becomes too strong, so that the acid characteristics of the catalyst surface become unsatisfactory. On the other hand, when the specific surface area of the support MgO is smaller than the above range, the amount of the catalyst metal supported becomes too small to obtain a catalyst having sufficient activity. A normal air atmosphere is used as an atmosphere for firing magnesium oxide, but other gases such as an inert gas such as nitrogen gas may be used. The firing temperature is 1000 to 1500 ° C, preferably 1100 to 1300 ° C. The firing time is 1 hour or longer, preferably 3 hours or longer, and the upper limit is not particularly limited, but is usually about 72 hours.
[0007]
For the carrier magnesium oxide obtained as described above, in the second step (catalyst metal supporting step), a catalyst metal is supported by an equilibrium adsorption method using a solution containing the catalyst metal. The solution containing the catalytic metal may be an aqueous solution or an organic solvent (methanol, acetone, etc.) solution. The supporting temperature is 5 to 50 ° C, preferably 15 to 30 ° C. In the present invention, rhodium and / or ruthenium is used as the catalyst metal.
In the supporting step, the catalyst metal is supported on the support magnesium oxide in the form of a solution. In this case, the catalyst metal is used in the form of a soluble compound. Examples of such compounds include halides, nitrates, sulfates, organic acid salts (such as acetates), complex salts (chelates), and the like.
An equilibrium adsorption method is adopted for supporting the catalyst metal solution on the support MgO. In this method, the support is immersed in the catalyst solution, and the catalyst metal in the solution is adsorbed and supported on the support under equilibrium conditions. In this case, the time for which the catalyst metal is supported on the carrier (immersion time) is 1 hour or more, preferably 3 hours or more, and the upper limit is not particularly limited, but is usually about 48 hours. Details of this equilibrium adsorption method are described in the document “Catalyst Preparation Chemistry” (published in 1980, Kodansha Scientific, P49).
[0008]
When the catalyst metal is supported on the carrier MgO using the catalyst aqueous solution as described above, the pH of the catalyst aqueous solution is 8 or more, preferably 8.5 or more. The upper limit is not particularly limited, but is usually about pH 13. For adjusting the pH of the aqueous solution, an alkaline substance such as sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide is used. In the present invention, the amount of the catalyst metal supported on the support MgO is defined as a catalyst metal equivalent amount of 10 to 5000 wtppm, preferably 100 to 2000 wtppm with respect to the support MgO. When the amount of the catalyst metal supported exceeds the above range, the catalyst cost increases and the carbon deposition activity of the catalyst increases, and the amount of carbon deposition increases when the catalyst is used. On the other hand, if the amount is less than the above range, sufficient catalytic activity cannot be obtained. The amount of the catalyst metal supported can be adjusted by the conditions for supporting the catalyst metal solution on the support MgO, for example, the concentration of the catalyst metal in the solution, the specific surface area of the support MgO, and the like.
[0009]
In the third step (drying step), the catalyst metal-supported MgO obtained by supporting the catalyst metal in the form of a solution on the carrier MgO as described above is held at a temperature of 35 ° C. or lower for 6 hours or more and dried. Let A preferable drying temperature is 10 to 25 ° C. The drying time may be 6 hours or more, preferably 12 hours or more, and the upper limit is not particularly limited, but is usually about 72 hours. By such a drying treatment, rapid evaporation of the solvent from MgO is avoided, and as a result, the catalyst metal is supported on the support MgO in a highly dispersed state without agglomeration. When the drying temperature or drying time is out of the above range, a catalyst containing a highly dispersible catalyst metal cannot be obtained.
[0010]
The dried product obtained as described above is baked (secondary baking) at a high temperature of 800 ° C. or higher for 1 hour or longer in the fourth step (secondary baking step). In this case, air is usually used as the firing atmosphere, but other gases (inert gas or the like) may be used. The firing temperature is 800 ° C. or higher, preferably 850 ° C. or higher, and the upper limit is not particularly limited, but is usually about 1100 ° C. The preferred firing time is 2 hours or longer, and the upper limit is not particularly limited, but is usually about 24 hours. By this secondary calcination, the thermal stability of the catalyst metal is enhanced, and a catalyst with good thermal stability can be obtained.
[0011]
In order to reduce the catalyst cost, the amount of catalyst metal supported on the support should be reduced as much as possible, and at the same time, the catalyst metal particles supported on the support should be agglomerated as much as possible so as to develop sufficient reaction activity. It is necessary to suppress and form fine particles. According to the study by the present inventors, the crystallization of the support MgO is increased to maintain the specific surface area at 5 m 2 / g or less, and the supported amount of the catalyst metal on the support MgO is reduced to a very small amount of 10 to 5000 wtppm. When the catalyst metal is supported and supported on the support MgO, the catalyst metal is slowly supported in the form of a solution under equilibrium conditions over a long period of time by the equilibrium adsorption method. It has been found that when it is slowly dried, an inexpensive catalyst is obtained which is uniformly supported and has sufficient activity as a hydrocarbon reforming catalyst.
[0012]
In the catalyst of the present invention obtained as described above, the amount of the catalyst metal supported is 10 to 5000 wtppm, preferably 100 to 2000 wtppm with respect to the support MgO, and the specific surface area is 0.01 to 5 m 2 / g, Preferably it is 0.05-3 m < 2 > / g. In this specification, the specific surface area for the catalyst or support MgO is measured at a temperature of 15 ° C. by the “BET” method. As a measuring device, “SA-100” manufactured by Shibata Kagakusha is used. Used.
[0013]
The catalyst of the present invention obtained as described above has an acidic property that is preferable as a catalyst for hydrocarbon reforming. When a large amount of strong acid sites are present on the catalyst surface, a carbon deposition reaction as a side reaction is promoted on the acid sites, carbon is deposited, and catalyst poisoning occurs due to the deposited carbon.
[0014]
In general, the catalyst of the present invention has an acid strength (H 0 ) of more than 2, preferably only 3.3 or more, and its content is less than 0.03 mmol / g, preferably 0. 0.02 mmol / g or less. The acid strength (H 0 ) can be adjusted depending on the temperature and time when the support MgO is first calcined. In the catalyst of the present invention, the expression of a strong acid point is suppressed and the carbon deposition activity is greatly suppressed.
[0015]
The acid strength (H 0 ) referred to in this specification is expressed as the ability of the catalyst to give protons to the basic indicator (B − ), and is represented by the following formula.
H 0 = pKa (= pK B - H +) + log [B -] / [B - H +] (1)
In the formula, K B - H + is a basic indicator B - and the acidic sites H + B is reacted, the acid of basic indicator (B - H +) its acidic substance in the reaction to produce the B - The dissociation constant of H + is shown. [B − ] / [B − H + ] represents the concentration ratio of B − and B − H + .
The stronger the acid point, the more protonated indicator with a small pK B − H + , so the H 0 value becomes smaller.
[0016]
The acid strength in this specification is measured as follows.
(Measurement method of acid strength)
The acid strength H 0 (Hammett index) function is an acid strength function, edited by the Catalysis Society of Japan, “Catalyst Experiment Handbook” (published in 1986, Kodansha Scientific), p. 172, measured by “Benesi method”. Addition of an indicator with known pKa to the catalyst and discoloration indicates that H 0 has an acid point less than its pKa. When a predetermined amount of butylamine, which is a basic molecule, is adsorbed to an acid point and titrated with an indicator having a different pKa, the number of acid points can be measured from the amount of butylamine and the acid strength can be measured from the value of pKa. The measurement temperature is room temperature.
[0017]
In order to reform the hydrocarbon using the catalyst of the present invention, the hydrocarbon may be reacted with steam and / or carbon dioxide (CO 2 ) in the presence of the catalyst. As the hydrocarbon, lower hydrocarbons such as methane, ethane, propane, butane, and naphtha are used, and methane is preferably used. In the present invention, natural gas (methane gas) containing carbon dioxide gas can be advantageously used as a reaction raw material.
In the case of a method of reacting methane and carbon dioxide (CO 2 ) (CO 2 reforming), the reaction is represented by the following formula.
[Chemical 1]
[Chemical 2]
In steam reforming, the reaction temperature is 600 to 1200 ° C., preferably 600 to 1000 ° C., the reaction pressure is pressurized, 1 to 40 kg / cm 2 G, preferably 5 to 30 kg / cm 2 G. is there. When this reaction is carried out in a fixed bed system, the gas space velocity (GHSV) is 1,000 to 10,000 hr −1 , preferably 2,000 to 8,000 hr −1 or less. In terms of the steam usage ratio relative to the raw material hydrocarbon, 0.5 to 5 mol, preferably 1 to 2 mol, more preferably 1 to 1.5 mol of steam (H 2 O) per mol of carbon in the raw material hydrocarbon. Is the ratio.
When performing steam reforming according to the present invention, as described above, even if the steam (H 2 O) per mole of the raw material hydrocarbon is kept at 2 moles or less, carbon deposition is suppressed and industrially produced. Advantageously, synthesis gas (a mixed gas of CO and H 2 ) can be produced. In the conventional case, considering that 2 to 5 mol of steam is required per 1 mol of carbon of the raw material hydrocarbon, the reforming reaction can proceed smoothly by using 2 mol or less of steam. This is a great industrial advantage of the inventive catalyst.
The catalyst of the present invention is advantageously used as a catalyst for reacting a mixture of steam and CO 2 with a hydrocarbon. In this case, the mixing ratio of steam and CO 2 is not particularly limited, but is generally 0.1 to 10 in terms of H 2 O / CO 2 molar ratio.
[0018]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[Example 1]
1/8 pellets of MgO formed using commercially available 99.9 wt% magnesium oxide (MgO) were calcined in air at 1060 ° C. for 3 h (hours) and used as catalyst support MgO (A). Next, it was immersed in a rhodium (III) acetate aqueous solution containing 3.9 wt% Rh for 26 h (hours). The aqueous solution was adjusted to pH 9.7 using an aqueous magnesium hydroxide solution. In this way, Rh was adsorbed on the catalyst carrier MgO (A) by equilibrium, and then filtered to obtain a catalyst carrier MgO (A) on which Rh was adsorbed in the form of an aqueous solution. The amount of Rh supported in this case is 3750 wtppm with respect to the carrier MgO (A) in terms of Rh metal. Next, the carrier MgO (A) adsorbing Rh was dried in air at a temperature of 35 ° C. for 52 h, and then calcined in air at 850 ° C. for 2 h to obtain the catalyst (A) of the present invention. This catalyst (A) contains 3750 wtppm of Rh as Rh metal with respect to the carrier MgO, and its specific surface area was 1.2 m 2 / g. Moreover, the acid point consisted only of an acid point having an acid strength (H 0 ) of 3.3 or more, and its content was 0.01 mmol / g.
[0019]
[Example 2]
A 1/8 pellet of MgO formed using commercially available 99.9 wt% magnesium oxide (MgO) was calcined in air at 1000 ° C. for 2 h (hours), and this was used as the catalyst support MgO (B). Next, it was immersed in a ruthenium (III) chloride aqueous solution containing 0.1 wt% Ru for 19 hours (hours). The aqueous solution was an aqueous magnesium hydroxide solution, and the pH was adjusted to 9.7. Ru was allowed to equilibrate to the catalyst support MgO (B) and then filtered to obtain catalyst support MgO (B) adsorbed in the form of an aqueous solution. The amount of Ru supported in this case is 125 wtppm with respect to the carrier MgO (B) in terms of Ru metal. Next, the carrier MgO (B) on which Ru was adsorbed was dried in air at a temperature of 30 ° C. for 72 h and then calcined in air at 860 ° C. for 2.5 h to obtain the catalyst (B) of the present invention. This catalyst (B) contains Ru as a Ru metal in a proportion of 125 wtppm with respect to the carrier MgO (B), and its specific surface area was 4.8 m 2 / g. Moreover, the acid point consisted only of an acid point having an acid strength (H 0 ) of 3.3 or more, and its content was 0.03 mmol / g.
[0020]
[Example 3]
1/8 pellets of MgO formed using commercially available 99.9 wt% magnesium oxide (MgO) were calcined in air at 1200 ° C. for 2.5 h (hours) and used as catalyst support MgO (C) It was. Next, it was immersed in a rhodium (III) acetate aqueous solution containing 2.6 wt% Rh for 26 h (hour). A magnesium hydroxide aqueous solution was used as the aqueous solution, and the pH was adjusted to 9.7. In this way, Rh was adsorbed on the catalyst support MgO (C) by equilibrium, and then filtered to obtain a catalyst support MgO (C) in which Rh was adsorbed in the form of an aqueous solution. The amount of Rh supported in this case is 1750 wtppm with respect to the carrier MgO (C) in terms of Rh metal. Next, the carrier MgO (C) adsorbing Rh was dried in air at a temperature of 20 ° C. for 34 h, and then calcined in air at 950 ° C. for 3.5 h to obtain the catalyst (C) of the present invention. This catalyst (C) contains 1750 wtppm of Rh as Rh metal with respect to the carrier MgO, and its specific surface area was 0.2 m 2 / g. Moreover, the acid point consisted only of an acid point having an acid strength (H 0 ) of 3.3 or more, and its content was 0.002 mmol / g.
[0021]
[Example 4]
A 1/8 pellet of MgO formed using commercially available 99.9 wt% magnesium oxide (MgO) was calcined in air at 1050 ° C. for 3 h (hours), and this was used as the catalyst support MgO (D). Next, it was immersed in an aqueous rhodium (III) acetate solution containing 0.54 wt% Rh for 24 hours (hours). The aqueous solution was an aqueous magnesium hydroxide solution, and the pH was adjusted to 9.7. In this way, Rh was adsorbed on the catalyst carrier MgO (D) by equilibrium, and then filtered to obtain a catalyst carrier MgO (D) on which Rh was adsorbed in the form of an aqueous solution. In this case, the amount of Rh supported is 500 wtppm with respect to the support MgO (D) in terms of Rh metal. Next, the carrier MgO (D) adsorbing Rh was dried in air at a temperature of 30 ° C. for 18 hours and then calcined in air at 900 ° C. for 2 hours to obtain the catalyst (D) of the present invention. This catalyst (D) contains Rh as Rh metal and 500 wtppm with respect to the carrier MgO, and its specific surface area was 2.3 m 2 / g. Moreover, the acid point consisted only of an acid point having an acid strength (H 0 ) of 3.3 or more, and its content was 0.02 mmol / g.
[0022]
[Example 5]
1/8 pellets of MgO formed using commercially available 99.9 wt% magnesium oxide (MgO) were calcined in air at 1200 ° C. for 2 hours (hours) and used as catalyst support MgO (E). Next, it was immersed in a ruthenium (III) chloride aqueous solution containing 7.1 wt% Ru for 19 hours (hours). The aqueous solution was an aqueous magnesium hydroxide solution, and the pH was adjusted to 9.7. In this way, Ru was adsorbed on the catalyst support MgO (E) in equilibrium, and then filtered to obtain a catalyst support MgO (E) on which Ru was adsorbed in the form of an aqueous solution. In this case, the amount of Ru supported is 5000 wtppm with respect to the support MgO (E) in terms of Ru metal. Next, the carrier MgO (E) having adsorbed Ru was dried in air at a temperature of 25 ° C. for 20 hours, and then calcined in air at 850 ° C. for 2 hours to obtain the catalyst (E) of the present invention. This catalyst (E) contains Ru as Ru metal and 5000 wtppm with respect to the carrier MgO, and its specific surface area was 0.2 m 2 / g. Moreover, the acid point consisted only of an acid point having an acid strength (H 0 ) of 3.3 or more, and its content was 0.002 mmol / g.
[0023]
[Example 6]
1/8 pellets of MgO formed using commercially available 99.9 wt% magnesium oxide (MgO) were calcined in air at 1100 ° C. for 2 h (hours) and used as catalyst support MgO (F). This catalyst support MgO (F) was immersed in a methanol solution of ruthenium (III) chloride containing 0.66 wt% Ru for 24 hours (hours). In this way, Ru was adsorbed on the catalyst carrier MgO (F) in equilibrium, and then filtered to obtain a catalyst carrier MgO (F) on which Ru was adsorbed in the form of a solution. In this case, the amount of Ru supported is 500 wtppm with respect to the support MgO (F) in terms of Ru metal equivalent. Next, the carrier MgO (F) on which Ru was adsorbed was dried in air at a temperature of 35 ° C. for 52 hours and then calcined in air at 800 ° C. for 2.5 hours to obtain the catalyst (F) of the present invention. This catalyst (F) contains Ru as a Ru metal in an amount of 500 wtppm with respect to the carrier MgO, and its specific surface area was 1.1 m 2 / g. The acid point was composed only of acid points having an acid strength (H0) of 3.3 or more, and the content was 0.01 mmol / g.
[0024]
Reaction example 1
30 cc of the catalyst (A) prepared in Example 1 was charged into a reactor, and a CO 2 reforming test of methane was performed.
The catalyst, after 1h reduction treatment beforehand with H 2 900 ° C. in a stream, CH 4: CO 2 molar ratio = 1: 0.4, CH 4: H 2 O molar ratio = 1: 0.85 of the raw material gas Was treated under the conditions of a pressure of 20 kg / cm 2 G, a temperature of 820 ° C., and a methane standard GHSV = 4000 hr −1 . The CH 4 conversion after 5 hours from the start of the reaction is 50% (equilibrium conversion of CH 4 under experimental conditions = 50%), and the CH 4 conversion after 1200 hours from the start of the reaction is 50%. %Met.
Here, the conversion rate of CH 4 is defined by the following equation.
CH 4 conversion (%) = (A−B) / A × 100
A: CH 4 molar number in the raw material B: CH 4 moles in the product also, the catalyst, since the silica content is very small amount, did be powdered during the reaction.
[0025]
Reaction example 2
30 cc of the catalyst (B) prepared in Example 2 was charged into a reactor, and a CO 2 reforming test of methane was performed.
The catalyst was previously reduced in an H 2 stream at 900 ° C. for 1 h, and then a raw material gas of CH 4 : CO 2 molar ratio = 1: 1 was used, a pressure of 10 kg / cm 2 G, a temperature of 840 ° C., and a methane standard GHSV. = Treated under the condition of 5000 hr -1 . The CH 4 conversion after 5 h from the start of the reaction is 65% (equilibrium conversion of CH 4 under the experimental conditions = 65%), and the CH 4 conversion after 460 h from the start of the reaction is 65%. %Met.
[0026]
Reaction example 3
30 cc of the catalyst (C) prepared in Example 3 was charged into the reactor, and a CO 2 reforming test of methane was performed.
The catalyst was previously reduced in an H 2 stream at 900 ° C. for 1 h, and then a raw material gas having a CH 4 : CO 2 molar ratio = 1: 1 was used, a pressure of 20 kg / cm 2 G, a temperature of 840 ° C., and a methane standard GHSV. = 3500 hr -1 . The CH 4 conversion after 5 hours from the start of the reaction is 53% (CH 4 equilibrium conversion under experimental conditions = 53%), and the CH 4 conversion after 250 hours from the start of the reaction is 53%. %Met.
[0027]
Reaction example 4
30 cc of the catalyst (D) prepared in Example 4 was charged into the reactor, and a CO 2 reforming test of methane was performed.
The catalyst, after 1h reduction treatment beforehand with H 2 900 ° C. in a stream, CH 4: CO 2 molar ratio = 1: 0.4, CH 4: H 2 O molar ratio = 1: 0.85 of the raw material gas Was treated under the conditions of a pressure of 20 kg / cm 2 G, a temperature of 850 ° C., and a methane standard GHSV = 4000 hr −1 . The CH 4 conversion after 5 hours from the start of the reaction was 57% (equilibrium conversion of CH 4 under the experimental conditions = 57%), and the CH 4 conversion after 1000 hours from the start of the reaction was 57%. %Met.
[0028]
Reaction example 5
30 cc of the catalyst (E) prepared in Example 5 was charged into the reactor, and a CO 2 reforming test of methane was performed.
The catalyst was previously reduced in an H 2 stream at 900 ° C. for 1 h, and then a raw material gas having a CH 4 : CO 2 molar ratio = 1: 1 was used, a pressure of 10 kg / cm 2 G, a temperature of 870 ° C., and a methane standard GHSV. = Treated under the condition of 5000 hr -1 . The CH 4 conversion after 5 hours from the start of the reaction was 71% (equilibrium conversion of CH 4 under the experimental conditions = 71%), and the CH 4 conversion after 690 h from the start of the reaction was 71 %Met.
[0029]
Reaction Example 6
30 cc of the catalyst (F) prepared in Example 6 was charged into a reactor, and a CO 2 reforming test of methane was performed.
The catalyst was previously reduced in an H 2 stream at 900 ° C. for 1 h, and then a raw material gas having a CH 4 : CO 2 molar ratio = 1: 1 was used, a pressure of 20 kg / cm 2 G, a temperature of 850 ° C., and a methane standard GHSV. = Treated under the condition of 6000 hr -1 . The CH 4 conversion after 5 hours from the start of the reaction is 55% (equilibrium conversion of CH 4 under the experimental conditions = 55%), and the CH 4 conversion after 1000 hours from the start of the reaction is 55%. %Met.
[0030]
【The invention's effect】
According to the present invention, it is possible to obtain an inexpensive hydrocarbon reforming catalyst in which carbon deposition activity is remarkably suppressed and catalyst dusting during the reaction is prevented while the amount of catalyst metal supported is extremely small. Can do.
Claims (2)
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| JP21313598A JP4163292B2 (en) | 1998-07-28 | 1998-07-28 | Hydrocarbon reforming catalyst and reforming method |
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| JP21313598A JP4163292B2 (en) | 1998-07-28 | 1998-07-28 | Hydrocarbon reforming catalyst and reforming method |
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| US7026268B2 (en) | 2001-03-02 | 2006-04-11 | Japan Energy Corporation | Solid acid catalyst containing platinum group metal component and method for preparation thereof |
| JP3995241B2 (en) * | 2001-03-02 | 2007-10-24 | 株式会社ジャパンエナジー | Solid acid catalyst containing platinum group metal component and method for producing the same |
| JP2007325991A (en) * | 2006-06-06 | 2007-12-20 | Chiyoda Corp | Pretreatment method of catalyst |
| CN104080530B (en) * | 2012-02-10 | 2018-08-07 | 巴斯夫欧洲公司 | The catalyst and reforming method containing hexa-aluminate for reforming hydrocarbon |
| JP6131370B1 (en) * | 2016-06-10 | 2017-05-17 | 千代田化工建設株式会社 | Syngas production catalyst carrier and production method thereof, synthesis gas production catalyst and production method thereof, and synthesis gas production method |
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| JP7224220B2 (en) | 2019-03-25 | 2023-02-17 | 日立Astemo株式会社 | Outboard motor lifting device |
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