JPH0147223B2 - - Google Patents
Info
- Publication number
- JPH0147223B2 JPH0147223B2 JP56167014A JP16701481A JPH0147223B2 JP H0147223 B2 JPH0147223 B2 JP H0147223B2 JP 56167014 A JP56167014 A JP 56167014A JP 16701481 A JP16701481 A JP 16701481A JP H0147223 B2 JPH0147223 B2 JP H0147223B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- platinum
- aqueous solution
- impregnated
- weight
- 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.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 claims description 93
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 72
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- 229910052697 platinum Inorganic materials 0.000 claims description 34
- 150000003058 platinum compounds Chemical class 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 10
- 238000002407 reforming Methods 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 description 47
- 239000007864 aqueous solution Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 27
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 22
- 238000005470 impregnation Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 15
- 239000012279 sodium borohydride Substances 0.000 description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000007654 immersion Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 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 4
- 239000001257 hydrogen Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005273 aeration Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 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 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910008337 ZrO(NO3)2.2H2O Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Description
本発明はメタノール改質用白金触媒の製造方法に
関するものである。
従来白金触媒はメタノール改質用等に広く使用
されており、通常少くとも表面が活性アルミナか
ら成る担体を、そのまままたは助触媒を含有させ
た後、白金化合物、例えば塩化白金酸の水溶液ま
たはこれにチオ硫酸アンモニウムを添加した溶液
に浸漬し、担体に白金化合物を含浸し、乾燥し、
空気、水素域いは水蒸気雰囲気中で450〜600℃の
温度で焼成することにより製造されている。
このような製造方法で得られた白金触媒は、白
金の触媒としての有効性および白金の担持効率を
考慮して白金の担持量は通常0.1〜1.0重量％であ
り、この触媒をメタノール改質用触媒として用い
る場合には、低温活性が不充分である。このため
担体に多量の白金を担持させ活性を向上させるこ
とが提案されている。然しこのように多量の白金
を担持した触媒を製造する場合には、白金の担持
効率が悪くなるだけでなく、白金の分散状態がよ
くなくなり、このためメタノールの改質反応に対
して、担持させた白金が有効に作用していないと
いう問題点があつた。
本発明者は、このような従来の問題点を解決す
べく種々研究を行つた結果、担体に白金化合物を
含浸、乾燥し、次いで焼成し、更に例えば水素化
ホウ素ナトリウム（SBH）水溶液、ヒドラジン
水溶液またはホルマリンに浸漬するようにして還
元剤と接触させ、あるいは逆に還元剤と接触して
還元した後焼成することにより二段階で白金化合
物を還元することにより、予期せぬことには白金
の分散状態および結晶の微細化が達成され、白金
の担持量を増すことなく活性を向上させることが
でき前記問題点が解決されることを確かめ本発明
を達成するに至つた。
従つて本発明は少くとも表面が活性アルミナか
ら成る担体に白金化合物を含浸し、これら白金化
合物を焼成および還元剤により二段階の還元を行
うことを特徴とするメタノール改質用白金触媒の
製造方法に関するものである。
本発明の方法においては、先ず担体に白金化合
物を含浸して白金化合物を担体に担持させるが、
この方法は白金触媒の製造方法において従来用い
られている方法なら如何なる方法でもよい。そし
て得られた白金化合物を担持した担持体を前述の
ように二段階に還元する。還元剤を用いて還元す
る場合には焼成後の担体又は白金化合物を担持し
た担体をSBH水溶液、ヒドラジン水溶液または
ホルマリンに浸漬し、乾燥する。このようにして
得られた白金触媒は同量の白金量を担持した触媒
より活性が著しく向上する。この理由は二段階の
還元処理を行うことにより担体上の白金の結晶が
処理前より細かくなり、メタノールの改質反応に
対して白金が一層有効につかわれるようになつた
ためと考えられる。
本発明を次の実施例、比較例および試験例につ
き説明する。
実施例 １
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、該粒子１当り白金３ｇを
含む塩化白金酸水溶液にチオ硫酸アンモニウムを
Pt：Ｓ＝１：２となるように添加した溶液を流
動含浸法により含浸させ、次いで空気中において
自然乾燥した後、これを電磁波振動通気乾燥機に
セツトし、触媒粒子１当り100℃の熱風を2N
m3／minで下方より通気しつつ、2450MHzの電磁
波で出力7KWにて加熱し、５分間で完全に乾燥
し、含水率を１％にした。しかる後この乾燥した
触媒粒子を水蒸気中500℃で２時間加熱処理し、
冷却後さらにヒドラジン１重量％水溶液に浸漬さ
せた後乾燥することにより触媒を製造し、触媒Ａ
とした。触媒の白金担持量は0.4重量％であつた。
比較例 １
実施例において含浸済アルミナ粒子を電磁波振
動通気乾燥機にセツトし、同様の条件下で完全に
乾燥した。しかる後実施例１と同様に加熱処理
し、ヒドラジン水溶液に浸漬せずに触媒を製造
し、触媒Ｂとした。
実施例 ２
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、該粒子１当り白金3.0ｇ
を含む塩化白金酸水溶液にチオ硫酸アンモニウム
をPt：Ｓ＝１：２となるように添加した溶液を
流動含浸法により含浸させ、実施例１と同様な方
法で乾燥、加熱処理を行ない、さらに水素化ホウ
素ナトリウム（SBH）0.1重量％水溶液に浸漬し
た後乾燥し、触媒を製造し、触媒Ｃとした。
又、同量の担体に同量の塩化白金酸とチオ硫酸
アンモニウムを含む溶液を含浸した後、SBH0.1
重量％水溶液で処理してから水蒸気中500℃で２
時間加熱処理して触媒を製造し、触媒C′とした。
触媒の白金担持量は触媒Ｃ、C′共に0.4重量％で
あつた。
比較例 ２
実施例２における含浸済アルミナ粒子を比較例
１と同様な方法で加熱処理し、SBH0.1重量％水
溶液による還元を行わずに触媒を製造し、触媒Ｄ
とした。
同様に塩化白金酸とチオ硫酸アンモニウムの水
溶液に浸漬した担体を焼成することなくSBH0.1
重量％水溶液に浸漬した後、乾燥し、触媒を製造
し、触媒D′とした。
実施例 ３
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、アルミナ粒子１当り塩化
バナジウム〔VCl4〕31.5ｇ溶した水溶液にを流動
含浸法により含浸させ500℃で６時間空気焼成を
行い担体にバナジウムの酸化物を金属バナジウム
量として１重量％になるように担持させた。しか
る後実施例２と同様な方法で含浸、乾燥、熱処
理、浸漬、乾燥を行い触媒を製造し、触媒Ｅとし
た。
比較例 ３
実施例３の含浸済アルミナ粒子を比較例１と同
様な方法で加熱処理し、SBH0.1重量％水溶液に
浸漬処理することなく触媒を製造し、触媒Ｆとし
た。
実施例 ４
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、アルミナ粒子１当り塩化
マンガン〔MnCl2・4H2O〕31.0ｇ溶した水溶液
を流動含浸法により含浸させ、500℃で６時間空
気焼成を行い担体にマンガンの酸化物を金属マン
ガン量として１重量％になるように担持させた。
しかる後乾燥させ、実施例２と同様な方法で白金
の含浸、乾燥、熱処理を行い、さらにホルマリン
１重量％水溶液に浸漬した後、乾燥を行い触媒を
製造し、触媒G′とした。
比較例 ４
実施例４における含浸済アルミナ粒子を比較例
１と同様な方法で加熱処理し、ホルマリン１重量
％水溶液に浸漬せずに触媒を製造し、触媒Ｈとし
た。
実施例 ５
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、アルミナ粒子１当り硝酸
イツトリウム〔Ｙ（NO3）2・6H2O〕28.1ｇ溶した
水溶液を流動含浸法で含浸させ、500℃で６時間
空気焼成を行つて担体にイツトリウムの酸化物を
金属イツトリウムとして１重量％付着させた。し
かる後実施例２と同様な方法で、白金の含長、乾
燥、熱処理およびSBE0.1重量％水溶液への浸漬、
乾燥を行い、触媒を製造し、触媒Ｉとした。
比較例 ５
実施例５における含浸済アルミナ粒子を比較例
を比較例１と同様な方法で加熱処理し、SBH0.1
重量％水溶液に浸漬せずに触媒を製造し、触媒Ｊ
とした。
実施例 ６
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、アルミナ粒子１当り硝酸
ジルコニル〔ZrO（NO3）2・2H2O〕128ｇ溶した
水溶液を流動含浸法で含浸させ、500℃で６時間
空気焼成を行つてジルコニウムの酸化物を金属ジ
ルコニウム換算で１重量％付着させた。しかる後
実施例２と同様な方法で白金の含浸、乾燥、熱処
理、SBH0.1重量％水溶液への浸漬、乾燥を行い
触媒を製造し、触媒Ｋとした。
比較例 ６
実施例６における含浸済アルミナ粒子を比較例
２と同様な方法で加熱処理し、SBH0.1重量％水
溶液に浸漬せずに触媒を製造し、触媒Ｌとした。
実施例 ７
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、アルミナ粒子１当り硝酸
プラセオジム〔Pr（NO3）3〕20.5ｇ溶した水溶液
を流動含浸法で含浸させ、500℃で６時間空気焼
成を行つてプラセオジムの酸化物を金属プラセオ
ジム量として１重量％付着するようにした。しか
る後実施例２と同様な方法で白金の含浸、乾燥、
熱処理を行い、さらにSBH0.1重量％水溶液に浸
漬した後、乾燥して触媒を製造し、触媒Ｍとし
た。
比較例 ７
実施例７において含浸済アルミナ粒子を比較例
２と同様な方法で加熱処理し、SBH0.1重量％水
溶液に浸漬せずに触媒を製造し、触媒Ｎとした。
実施例 ８
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）にアルミナ粒子１当り硝酸ネ
オジム〔Nd（NO3）〕15.1ｇ溶した水溶液を流動
含浸法で含浸させ、500℃で６時間空気焼成を行
つてネオジムの酸化物を金属ネオジム量として１
重量％付着させた。しかる後実施例２と同様な方
法で白金の含浸、乾燥、熱処理を行い、さらにヒ
ドラジン１重量％水溶液に浸漬した後、乾燥し、
触媒を製造し、触媒Ｏとした。
比較例 ８
実施例８において含浸済アルミナ粒子を比較例
２と同様の方法で加熱処理し、ヒドラジン１重量
％水溶液に浸漬せずに触媒を製造し、触媒Ｐとし
た。
実施例 ９
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、アルミナ粒子１当り硝酸
ランタン〔La（NO3）3・6H2O〕21.3ｇ溶した水溶
液を流動含浸法で含浸させ、500℃で６時間空気
焼成を行つてランタンの酸化物を金属ランタン量
として１重量％となるよう付着させた。しかる
後、実施例２と同様な方法で、白金の含浸、乾
燥、熱処理を行い、さらにSHB0.1重量％水溶液
に浸漬した後乾燥し、触媒を製造し、触媒Ｑとし
た。
比較例 ９
実施例９において含浸済アルミナ粒子を比較例
２と同様な方法で加熱処理し、SHB0.1重量％水
溶液に浸漬せずに触媒を製造し、触媒Ｒとした。
実施例 10
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に、アルミナ粒子１当り硝酸
セリウム〔Ce（NO3）3・6H2O〕21.0ｇ溶した水溶
液を流動含浸法で含浸させ、500℃で６時間空気
焼成を行つて担体にセリウムの酸化物を金属セリ
ウム量として１重量％となるよう付着させた。し
かる後、実施例２と同様な方法で、白金の含浸、
乾燥、熱処理を行い、さらにSHB0.1重量％水溶
液に浸漬した後、乾燥し、触媒を製造し、触媒Ｓ
とした。
比較例 10
実施例10において含浸済アルミナ粒子を比較例
２と同様な方法で加熱処理し、SHB0.1重量％水
溶液に浸漬せずに触媒を製造し、触媒Ｔとした。
実施例 11
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に実施例９と同様にして硝酸ラ
ンタンを流動含浸法により含浸し、500℃で６時
間空気焼成を行つてランタンの酸化物を金属ラン
タン量として１重量％となるよう付着させた。し
かる後実施例２と同様な方法で白金の含浸、乾
燥、熱処理を行い、さらにヒドラジン１重量％水
溶液に浸漬した後、乾燥し、触媒を製造し、触媒
Ｕとした。
比較例 11
実施例11において含浸済アルミナ粒子を比較例
２と同様な方法で加熱処理し、ヒドラジン１重量
％水溶液に浸漬せずに触媒を製造し、触媒Ｖとし
た。
実施例 12
フランス国ローヌプーラン社製の活性アルミナ
粒子（粒径３mm）に実施例10と同様に硝酸セリウ
ムを流動含浸法で含浸させ、500℃で６時間空気
焼成を行つて担体にセリウムの酸化物を金属セリ
ウム量として１重量％となるよう付着させた。し
かる後、実施例２と同様な方法で、白金の含浸、
乾燥、熱処理を行い、さらにヒドラジン１重量％
水溶液に浸漬した後、乾燥し、触媒を製造し、触
媒Ｗとした。
比較例 12
実施例12において含浸済アルミナ粒子を比較例
２と同様な方法で加熱処理し、ヒドラジン１重量
％水溶液に浸漬せずに触媒を製造し、触媒Ｘとし
た。
試験例
(1) 実施例１〜12、比較例１〜12でつくつた触媒
Ａ〜Ｘにつき、次の方法により貴金属表面積を
測定し、得た結果を第１表に示す。表面積は
COの吸着法により測定した。
The present invention relates to a method for producing a platinum catalyst for methanol reforming. Conventionally, platinum catalysts have been widely used for methanol reforming, etc., and usually a carrier consisting of at least activated alumina on the surface is used as it is or after containing a co-catalyst, and then treated with a platinum compound such as an aqueous solution of chloroplatinic acid or an aqueous solution of chloroplatinic acid. The carrier is immersed in a solution containing ammonium thiosulfate, impregnated with a platinum compound, and dried.
It is manufactured by firing at a temperature of 450 to 600°C in an air, hydrogen, or steam atmosphere. The platinum catalyst obtained by such a production method usually has a supported amount of platinum of 0.1 to 1.0% by weight, considering the effectiveness of platinum as a catalyst and the platinum supporting efficiency, and this catalyst is used for methanol reforming. When used as a catalyst, low-temperature activity is insufficient. For this reason, it has been proposed to improve the activity by supporting a large amount of platinum on the carrier. However, when producing a catalyst with such a large amount of platinum supported, not only the platinum supporting efficiency deteriorates, but also the platinum dispersion state becomes poor. There was a problem that the platinum used was not working effectively. As a result of conducting various studies to solve these conventional problems, the present inventor impregnated a carrier with a platinum compound, dried it, then baked it, and further developed a solution of, for example, a sodium borohydride (SBH) aqueous solution or a hydrazine aqueous solution. Alternatively, by reducing the platinum compound in two steps by contacting it with a reducing agent by immersing it in formalin, or conversely by contacting it with a reducing agent, reducing it, and then firing it, the platinum compound can be unexpectedly dispersed. The present invention was accomplished by confirming that the state and crystals were made finer, the activity was improved without increasing the amount of platinum supported, and the above-mentioned problems were solved. Therefore, the present invention provides a method for producing a platinum catalyst for methanol reforming, which comprises impregnating a carrier whose surface is made of activated alumina with a platinum compound, and performing two-step reduction of these platinum compounds by calcination and a reducing agent. It is related to. In the method of the present invention, first, a carrier is impregnated with a platinum compound to support the platinum compound on the carrier.
This method may be any method conventionally used in the production of platinum catalysts. The platinum compound-supported support thus obtained is reduced in two stages as described above. In the case of reduction using a reducing agent, the carrier after firing or the carrier supporting a platinum compound is immersed in an aqueous SBH solution, an aqueous hydrazine solution, or formalin, and then dried. The platinum catalyst thus obtained has significantly improved activity compared to a catalyst carrying the same amount of platinum. The reason for this is thought to be that by carrying out the two-step reduction treatment, the platinum crystals on the carrier became finer than before the treatment, and platinum became more effectively used in the methanol reforming reaction. The present invention will be illustrated with reference to the following Examples, Comparative Examples and Test Examples. Example 1 Ammonium thiosulfate was added to an aqueous chloroplatinic acid solution containing 3 g of platinum per particle to activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc, France.
A solution added so that Pt:S=1:2 was impregnated by a fluidized impregnation method, and then air-dried naturally in the air. This was then set in an electromagnetic vibration aeration dryer, and hot air of 100°C was blasted per catalyst particle. 2N
While ventilating from below at m 3 /min, it was heated with 2450 MHz electromagnetic waves at an output of 7 KW, completely drying in 5 minutes, and the moisture content was reduced to 1%. Thereafter, the dried catalyst particles were heat-treated in steam at 500°C for 2 hours.
After cooling, the catalyst was further immersed in a 1% by weight aqueous solution of hydrazine and then dried to produce catalyst A.
And so. The amount of platinum supported on the catalyst was 0.4% by weight. Comparative Example 1 The impregnated alumina particles in the example were set in an electromagnetic vibration aeration dryer and completely dried under the same conditions. Thereafter, the catalyst was heat-treated in the same manner as in Example 1 to produce a catalyst without immersing it in an aqueous hydrazine solution, which was designated as Catalyst B. Example 2 3.0 g of platinum was added to activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc, France.
A solution of ammonium thiosulfate added to a chloroplatinic acid aqueous solution containing Pt:S=1:2 was impregnated by a fluidized impregnation method, dried and heat treated in the same manner as in Example 1, and further hydrogenated. A catalyst was produced by immersing it in a 0.1% by weight aqueous solution of sodium boron (SBH) and then drying it, which was designated as Catalyst C. In addition, after impregnating the same amount of carrier with a solution containing the same amount of chloroplatinic acid and ammonium thiosulfate, SBH0.1
After treatment with a wt% aqueous solution, 2
A catalyst was produced by heat treatment for a period of time and designated as catalyst C'.
The amount of platinum supported on the catalysts was 0.4% by weight for both catalysts C and C'. Comparative Example 2 The impregnated alumina particles in Example 2 were heat-treated in the same manner as in Comparative Example 1, and a catalyst was produced without reduction with a 0.1% by weight aqueous solution of SBH.
And so. Similarly, the carrier immersed in an aqueous solution of chloroplatinic acid and ammonium thiosulfate was SBH0.1 without calcination.
After being immersed in a wt % aqueous solution, it was dried to produce a catalyst, designated as catalyst D'. Example 3 Activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc in France were impregnated with an aqueous solution containing 31.5 g of vanadium chloride [VCl 4 ] per alumina particle using a fluidized impregnation method, and air-calcined at 500°C for 6 hours. This was carried out to make the carrier support a vanadium oxide in an amount of 1% by weight as metal vanadium. Thereafter, impregnation, drying, heat treatment, immersion, and drying were carried out in the same manner as in Example 2 to produce a catalyst, which was designated as Catalyst E. Comparative Example 3 The impregnated alumina particles of Example 3 were heat-treated in the same manner as in Comparative Example 1 to produce a catalyst without immersion treatment in a 0.1% by weight SBH aqueous solution, which was designated as Catalyst F. Example 4 Activated alumina particles (particle size: 3 mm) manufactured by Rhône-Poulenc, France, were impregnated with an aqueous solution containing 31.0 g of manganese chloride [MnCl 2 4H 2 O] per alumina particle using a fluidized impregnation method, and the mixture was heated at 500°C. Air calcination was performed for 6 hours to allow the carrier to support manganese oxide in an amount of 1% by weight as metallic manganese.
Thereafter, it was dried, impregnated with platinum, dried and heat treated in the same manner as in Example 2, further immersed in a 1% by weight formalin aqueous solution and dried to produce a catalyst, which was designated as Catalyst G'. Comparative Example 4 The impregnated alumina particles in Example 4 were heat-treated in the same manner as in Comparative Example 1 to produce a catalyst without immersing it in a 1% by weight formalin aqueous solution, which was designated as Catalyst H. Example 5 Activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc in France were impregnated with an aqueous solution containing 28.1 g of yttrium nitrate [Y(NO 3 ) 2.6H 2 O] per alumina particle using a fluidized impregnation method. Air firing was performed at 500° C. for 6 hours to deposit 1% by weight of yttrium oxide on the carrier as metallic yttrium. Thereafter, in the same manner as in Example 2, the platinum content was determined, dried, heat treated, and immersed in a 0.1% by weight SBE aqueous solution.
Drying was performed to produce a catalyst, designated as Catalyst I. Comparative Example 5 The impregnated alumina particles in Example 5 were heat-treated in the same manner as in Comparative Example 1 to obtain a SBH of 0.1
Catalyst J was produced without immersion in a wt% aqueous solution.
And so. Example 6 Activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc, France, were impregnated with an aqueous solution containing 128 g of zirconyl nitrate [ ZrO (NO 3 ) 2.2H 2 O] per alumina particle using a fluidized impregnation method. Air firing was performed at 500° C. for 6 hours to deposit 1% by weight of zirconium oxide in terms of metallic zirconium. Thereafter, in the same manner as in Example 2, platinum impregnation, drying, heat treatment, immersion in a 0.1% by weight aqueous solution of SBH, and drying were performed to produce a catalyst, which was designated as Catalyst K. Comparative Example 6 The impregnated alumina particles in Example 6 were heat-treated in the same manner as in Comparative Example 2 to produce a catalyst without immersing it in a 0.1 wt % SBH aqueous solution, which was designated as Catalyst L. Example 7 Activated alumina particles (particle size: 3 mm) manufactured by Rhône-Poulenc, France, were impregnated with an aqueous solution containing 20.5 g of praseodymium nitrate [Pr(NO 3 ) 3 ] per alumina particle using a fluidized impregnation method, and the mixture was heated at 500°C. Air firing was performed for 6 hours to deposit praseodymium oxide in an amount of 1% by weight as metal praseodymium. After that, platinum impregnation, drying, and the same method as in Example 2 were carried out.
After heat treatment, the catalyst was further immersed in a 0.1% by weight aqueous solution of SBH, and then dried to produce a catalyst, which was designated as Catalyst M. Comparative Example 7 In Example 7, the impregnated alumina particles were heat-treated in the same manner as in Comparative Example 2 to produce a catalyst without immersing it in a 0.1% by weight aqueous solution of SBH, which was designated as Catalyst N. Example 8 Activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc, France, were impregnated with an aqueous solution containing 15.1 g of neodymium nitrate [Nd (NO 3 )] per alumina particle using a fluidized impregnation method, and the mixture was heated at 500°C for 6 hours. Perform air firing to reduce neodymium oxide to 1 as metallic neodymium amount.
% by weight was deposited. Thereafter, impregnation with platinum, drying, and heat treatment were performed in the same manner as in Example 2, and further immersion in a 1% by weight aqueous solution of hydrazine, followed by drying.
A catalyst was produced and designated as catalyst O. Comparative Example 8 In Example 8, the impregnated alumina particles were heat-treated in the same manner as in Comparative Example 2 to produce a catalyst without immersing it in a 1% by weight hydrazine aqueous solution, which was designated as Catalyst P. Example 9 Activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc in France were impregnated with an aqueous solution containing 21.3 g of lanthanum nitrate [La(NO 3 ) 3 6H 2 O] per alumina particle using a fluidized impregnation method. Air firing was performed at 500° C. for 6 hours to deposit lanthanum oxide in an amount of 1% by weight of lanthanum metal. Thereafter, platinum impregnation, drying, and heat treatment were performed in the same manner as in Example 2, followed by immersion in a 0.1% by weight SHB aqueous solution and drying to produce a catalyst, which was designated as Catalyst Q. Comparative Example 9 In Example 9, the impregnated alumina particles were heat-treated in the same manner as in Comparative Example 2 to produce a catalyst without immersing it in a 0.1% by weight SHB aqueous solution, which was designated as Catalyst R. Example 10 Activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc in France were impregnated with an aqueous solution containing 21.0 g of cerium nitrate [Ce(NO 3 ) 3.6H 2 O] per alumina particle using a fluidized impregnation method. , air firing was performed at 500° C. for 6 hours to deposit cerium oxide on the carrier so that the amount of metallic cerium was 1% by weight. After that, in the same manner as in Example 2, impregnation with platinum,
Drying, heat treatment, further immersion in SHB0.1% by weight aqueous solution, drying to produce catalyst, catalyst S
And so. Comparative Example 10 In Example 10, the impregnated alumina particles were heat-treated in the same manner as in Comparative Example 2 to produce a catalyst without immersing it in a 0.1% by weight SHB aqueous solution, which was designated as Catalyst T. Example 11 Activated alumina particles (particle size: 3 mm) manufactured by Rhone-Poulenc, France were impregnated with lanthanum nitrate by the fluidized impregnation method in the same manner as in Example 9, and air-calcined at 500°C for 6 hours to obtain lanthanum oxide. was deposited so that the amount of lanthanum metal was 1% by weight. Thereafter, it was impregnated with platinum, dried, and heat treated in the same manner as in Example 2, and then immersed in a 1% by weight aqueous solution of hydrazine and dried to produce a catalyst, which was designated as Catalyst U. Comparative Example 11 In Example 11, the impregnated alumina particles were heat-treated in the same manner as in Comparative Example 2 to produce a catalyst without immersing it in a 1% by weight aqueous hydrazine solution, which was designated as Catalyst V. Example 12 Activated alumina particles (particle size: 3 mm) manufactured by Rhone Poulenc, France were impregnated with cerium nitrate using the fluidized impregnation method in the same manner as in Example 10, and air-calcined at 500°C for 6 hours to oxidize cerium on the carrier. The material was deposited so that the amount of metallic cerium was 1% by weight. After that, in the same manner as in Example 2, impregnation with platinum,
After drying and heat treatment, add 1% by weight of hydrazine.
After immersing it in an aqueous solution, it was dried to produce a catalyst, which was designated as Catalyst W. Comparative Example 12 In Example 12, the impregnated alumina particles were heat-treated in the same manner as in Comparative Example 2 to produce a catalyst without immersing it in a 1% by weight aqueous hydrazine solution, which was designated as Catalyst X. Test Example (1) The noble metal surface areas of catalysts A to X prepared in Examples 1 to 12 and Comparative Examples 1 to 12 were measured by the following method, and the results are shown in Table 1. The surface area is
Measured by CO adsorption method.
【表】【table】
【表】
(2) 次に触媒Ａ〜Ｘにつき耐久前の活性および触
媒を電気炉中400℃で200時間空気雰囲気にて加
熱耐久後の活性を評価し、得た結果を第２表に
示す。改質ガスの組成分析はガスクロマトグラ
フによつて行なつた。
即ち工業用メタノール100％を蒸発器（エバ
ポレータ）を用い触媒床温度を310℃としその
時のメタノールの分解率（H2濃度）をガスク
ロマトグラフによつて測定した。評価触媒量10
ml、評価空間速度2100hr-1である。[Table] (2) Next, the activity of Catalysts A to X before durability was evaluated, and the activity after durability of heating the catalysts in an electric furnace at 400℃ for 200 hours in an air atmosphere was evaluated, and the obtained results are shown in Table 2. . Compositional analysis of the reformed gas was performed using a gas chromatograph. That is, 100% industrial methanol was used in an evaporator at a catalyst bed temperature of 310° C., and the decomposition rate (H 2 concentration) of methanol at that time was measured using a gas chromatograph. Evaluation catalyst amount 10
ml, and the estimated space velocity is 2100hr -1 .
【表】【table】
【表】
また第１図に触媒Ａ、Ｂのメタノール改質性
能を水素濃度で示し、第２図に触媒Ｑ、Ｒのメ
タノール改質性能を水素濃度で示す。第１図に
おいて線１は触媒Ａの耐久前の性能、線２は触
媒Ｂの耐久前の性能、線３は触媒Ａの耐久後の
性能、線４は触媒Ｂの耐久後の性能を示し、第
２図において線５は触媒Ｑの耐久前の性能、線
６は触媒Ｒの耐久前の性能、線７は触媒Ｑの耐
久後の性能、線８は触媒Ｒの耐久後の性能を示
す。
以上の(1)および(2)の試験結果より本発明の方法
で得られた触媒Ａ、Ｃ、C′、Ｅ、Ｇ、Ｉ、Ｋ、
Ｍ、Ｏ、Ｑ、Ｓ、Ｕ、ＷはSBH、ヒドラジンま
たはホルマリンによる還元処理を行つていない比
較例の触媒Ｂ、Ｄ、D′、Ｆ、Ｈ、Ｊ、Ｌ、Ｎ、
Ｐ、Ｒ、Ｔ、Ｖ、Ｘより白金の分散がよく、メタ
ノール改質性能が著しく向上していることがわか
る。また触媒Ｃ、C′、Ｄ、D′に関する第１表およ
び第２表の結果から加熱焼成後還元剤で還元処理
した本発明の方法でつくつた触媒Ｃは、還元剤で
還元処理後加熱処理した触媒C′よりも性能が良
く、これら触媒Ｃ、C′は加熱焼成を行わず還元剤
のみで還元処理した触媒D′および加熱焼成のみ
を行つた比較例の触媒Ｄより白金の分散およびメ
タノール改質性能が優れていることがわかる。[Table] Fig. 1 shows the methanol reforming performance of catalysts A and B in terms of hydrogen concentration, and Fig. 2 shows the methanol reforming performance of catalysts Q and R in terms of hydrogen concentration. In FIG. 1, line 1 shows the performance of catalyst A before durability, line 2 shows the performance of catalyst B before durability, line 3 shows the performance of catalyst A after durability, and line 4 shows the performance of catalyst B after durability. In FIG. 2, line 5 shows the performance of catalyst Q before durability, line 6 shows the performance of catalyst R before durability, line 7 shows the performance of catalyst Q after durability, and line 8 shows the performance of catalyst R after durability. From the test results of (1) and (2) above, catalysts A, C, C', E, G, I, K,
M, O, Q, S, U, W are SBH, comparative example catalysts B, D, D', F, H, J, L, N, which were not subjected to reduction treatment with hydrazine or formalin.
It can be seen that the dispersion of platinum is better than that of P, R, T, V, and X, and the methanol reforming performance is significantly improved. Furthermore, from the results of Tables 1 and 2 regarding catalysts C, C', D, and D', catalyst C produced by the method of the present invention, which was heat-calcined and then reduced with a reducing agent, was heat-treated after being reduced with a reducing agent. Catalysts C and C' had better performance than Catalyst C', which was treated with a reducing agent without heating and calcination, and Catalyst D, a comparative example, which was heated and calcinated only, with platinum dispersion and methanol. It can be seen that the reforming performance is excellent.
第１図は触媒ＡおよびＢの耐久前および耐久後
の性能を水素濃度により表わした線図、第２図は
触媒ＱおよびＲの同様の線図である。
FIG. 1 is a diagram showing the performance of catalysts A and B before and after durability in terms of hydrogen concentration, and FIG. 2 is a similar diagram of catalysts Q and R.
Claims (1)
白金化合物を含浸し、次いで焼成および還元剤と
接触させることによる二段階の還元を行うことを
特徴とするメタノール改質用白金触媒の製造方
法。 ２ 還元は先に焼成してから還元剤と接触させる
ようにすることを特徴とする特許請求の範囲第１
項記載のメタノール改質用白金触媒の製造方法。[Claims] 1. A platinum catalyst for methanol reforming, characterized in that a carrier whose surface is at least made of activated alumina is impregnated with a platinum compound, and then reduced in two stages by calcination and contact with a reducing agent. manufacturing method. 2. Claim 1, characterized in that the reduction is performed by first firing and then contacting with a reducing agent.
A method for producing a platinum catalyst for methanol reforming as described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56167014A JPS5870837A (en) | 1981-10-21 | 1981-10-21 | Preparation of platinum catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56167014A JPS5870837A (en) | 1981-10-21 | 1981-10-21 | Preparation of platinum catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5870837A JPS5870837A (en) | 1983-04-27 |
| JPH0147223B2 true JPH0147223B2 (en) | 1989-10-12 |
Family
ID=15841781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56167014A Granted JPS5870837A (en) | 1981-10-21 | 1981-10-21 | Preparation of platinum catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5870837A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2893262A1 (en) * | 2005-11-14 | 2007-05-18 | Inst Francais Du Petrole | PROCESS FOR SYNTHESIS IN THE PRESENCE OF CATALYST REDUCER BASED ON ANISOTROPIC METAL NANOPARTICLES. |
-
1981
- 1981-10-21 JP JP56167014A patent/JPS5870837A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5870837A (en) | 1983-04-27 |
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