TWI268806B - A catalyst useful for oxidation of alkanes - Google Patents
A catalyst useful for oxidation of alkanes Download PDFInfo
- Publication number
- TWI268806B TWI268806B TW089117981A TW89117981A TWI268806B TW I268806 B TWI268806 B TW I268806B TW 089117981 A TW089117981 A TW 089117981A TW 89117981 A TW89117981 A TW 89117981A TW I268806 B TWI268806 B TW I268806B
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- Prior art keywords
- catalyst
- acid
- mixtures
- group
- lanthanide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 230000003647 oxidation Effects 0.000 title claims abstract description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 18
- 150000002602 lanthanoids Chemical class 0.000 claims description 18
- 239000011964 heteropoly acid Substances 0.000 claims description 16
- 229910052758 niobium Inorganic materials 0.000 claims description 15
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 229910052715 tantalum Inorganic materials 0.000 claims description 14
- 229910052787 antimony Inorganic materials 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
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- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 8
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 14
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- 125000004429 atom Chemical group 0.000 description 11
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- 239000000243 solution Substances 0.000 description 11
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
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- -1 B i Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000007605 air drying Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- WRIQZMMFAMFZSM-UHFFFAOYSA-N prop-2-enethioic s-acid Chemical compound SC(=O)C=C WRIQZMMFAMFZSM-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- BGKZULDOBMANRY-UHFFFAOYSA-N sulfanyl prop-2-enoate Chemical class SOC(=O)C=C BGKZULDOBMANRY-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- QWSCWPXFBFCNQP-UHFFFAOYSA-N vanadium yttrium Chemical compound [V].[Y] QWSCWPXFBFCNQP-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Description
1268806
五、發明說明（2) 中，催化劑係由於偏飢酸銨，蹄酸及仲飢酸铵混合得—均 勻水溶液而製備。在此溶液中，再加入草酸銨鈮而得漿 體，自此漿體除去水，即得固體催化劑前驅物。將固體催 化劑前驅物模塑成錠，篩析至所要粒度，然後在6 0 0 °c及 氮氣流下煅燒即得所要催化劑。所得催化劑據宣稱可有致 使丙烷轉化成丙烯酸。
同在申請中之美國專利申請案編號09/3 1 6, 0 0 7揭示一種 製備用於丙烷轉化成丙烯酸之催化劑之改良方法。此方法 之特徵在於利用混合一金屬氧化物溶液，其經各種方法脫 水並在惰性氛圍中煅燒。_ 本發明人等現已發現一種甩於催化烧類氧化成不飽和醛 或魏酸之新穎催化劑。 本發明之一方面中’其提供者為一種催化劑，包括； 化學式AaMmNJxO。之混合金屬氧化物；及選自（丨）雜多元 酸，（i i)氧化鉻酸，（i i i )氧化鍅酸，（i V )氧化鈦酸，（v) 沸石及（vi)其酸組合中至少一種之酸；其中〇. 25<a<〇 ，〇·0 0 3<ιη<0·5，0·0 03<η<0·5，0·0 03<χ<0·5 ;酸之存在
量為〇· 05至5重量％，以催化劑總重量為準；〇係視其他元 素之氧化態而定；及Α係選自Mo，W，Fe，Nb，Ta，1，Ru 及其混合物；M係選自V，Ce，Cr，及其混合物；N係選自 Te，Bi，Sb’Se及其混合物，及χ係選自Nb，Ta，w'，Ti， A1 ， Zr ， Cr ， Μη ， Fe ， Ru ， Co ， Rh ， Ni ， Pd ， Pt ， Sb ， B i，B，I n，C e及其混合物。 在本發明之第二方面中，其提供者為一種製備催化劑之
第5頁 1268806 五、發明說明（4) 物；Μ係選自V，C e ’ c r，及其混合物；N係選自T e，B i， Sb，及其混合物；及X係選自Nb，Ta，Zr及其混合物。 本發明也提供一種製備由不飽和醛及羧酸所組成之族群 中所選出之化合物之方法，包括：使烷烴在上述催化劑之 存在下進行催化氧化作用。
如此處所用，”（曱基）丙烯酸”一詞意欲包括在其範圍内 之甲基丙烯酸及丙烯酸兩者，同樣地，π (甲基）丙烯酸g旨,, 一詞意欲包括在其範圍内之曱基丙烯酸酯及丙烯酸酯，而 π (曱基）丙烯醛”意欲包括在其範圍内之曱基丙烯醛及丙稀 酸。 .一 如此處所用，n (C3 - cs)燒烴一語係意指每一烧烴分子具 有3至8千碳原子之直鏈或支鏈烷烴。 如此處所用，”混合物π —詞意欲包括在其範圍内之各種 形式之混合物，包括’但不限於，簡單混合物及彳參合物， 合金等等。 為本申請案之用，π轉化率％π係等於（消耗之烷烴莫耳數 /供應之烷烴之莫耳數）X 100% ; ”選擇率％”係等於（形成
之所要不飽和羧酸或醛之莫耳數/消耗之烷烴之莫耳數） X 1 0 0 % ;及π產率％ "係等於（形成之所要不飽和羧酸或醛之 莫耳數/供應之烧炫之莫耳數）X (形成之所要不飽和叛酸 或醛之碳數/供應之烷烴之碳數）XI 0 0。 為本申5月案之用’ ’谷’夜係意指添加至溶劑之金屬固體 9 5%以上含溶解。應了解的是，初始即不存在於溶液中之 金屬固體之量愈大，則自其衍生之催化劑之性能將愈差。
1268806 五、發明說明（5) 為本申請案之用，"催化劑物質"係意欲包括任何形式之 催化劑，包括，但不限於，粉末，丸錠，結晶，有載體催 化劑及類似物。
如上所述，所揭示的是一種催化劑及製備該催化劑之方 法。在此方法，第一步驟中，溶液係由金屬化合物一其中 至少一種含有氧，及至少一種溶劑以適當量混合而成溶液 所形成。一般而言，金屬化合物含有元素A，M，N，X及 〇，在一具體例中，A係選自M0，w，Fe，Nb，Ta，Zr，RU
及其混合物，· M係選自v，ce，Cr，及其混合物；n係選自 Te，Βι，Sb，Se及其混合赉；及χ係選自Nb，Ta，w，τ i， A1 ， Zr ， Cr ， Mn ， Fe ， Ru ， Cq ， Rh ， Ni ， Pd ， Pt ， Sb ， B i，B，I n，C e及其混合物。在較佳具體例中，A係選自 Mo ’ W ’及其此合物，Μ係選自v，ce，，及其混合物；N 係選自Te，Bi，Sb，及其混合物；及乂係選自Nb，Ta，Zr 及其混合物。在更佳具體例中，A係，Μ係V，N係選自丁e 及X係Nb。 適當溶劑包括水’醇類（包括，但不限於曱醇，乙醇， 丙醇，二元醇等等），以及本技藝所知之其他極性溶劑， 一般而言，以水為較佳。水係適用於化學合成之任何水， 包括，但不限於，蒸餾水及去離子水。水之存在量係足以_ 將元素貫免保持於溶液中長時間至足以在製備步驟中避免 或減少組成及/或相分離之量。因此，水用量將隨混合之 物質之量及溶解度而異。然而，如上所述，水用量必須充 足以確保在混合時所形成的是含水溶液而非漿體。
第8頁 1268806 五、發明說明（6) 含水溶液一旦形成， 7k ^ ^ μ ^ - 本技☆所知任何適當方法移除 水以形成催化劑珂驅物。此箄方 乾燥，冷繼，嗔霧乾！寻，但不限於，真空 乾燥-般係在壓力二二二動4發及空氣乾燥。真空 :利用例如賴，再在真空中將經冷束 '合=二本。贺。務軋燥一般係在惰性氛圍如氮或氬下，以 ^ 口溫度自125°C至20 0 t及出口溫度自75。〇至15(rc進 仃，轉動蒸發一般係在浴溫度自25<t至 米/汞柱謂0毫米/汞柱下，較佳在浴溫度自^至9广 。〇及壓力自10¾米/汞柱至35〇毫米/汞柱下，更佳自4〇 S至60C及壓力自10宅米至4(}毫米/汞柱下進行。空氣乾 秌則可在溫度2 5 C至9 0 °C下進行。轉動蒸發或空氣乾燥一 般為較佳。 &一旦製成，即在惰性氛圍下將催化劑前驅物煅燒，惰性 氛圍可為貫負上惰性，亦即不含與催化劑前驅物反應或相 f作用之任何物質。適當實例包括，但不限於，氮，氬， 氙，氦或其混合物。惰性氛圍較佳為氬或氮，更佳為氬。 惰性氛圍可流過催化劑前驅物之表面，或可不流動（靜止 環）兄）。重要的疋要了解，所謂非流動氛圍係意指不讓惰 性氣體流過催化劑前驅物之表面。惰性氛圍較佳為不流過 催化劑前驅物之表面。然而，當惰性氛圍流過催化劑前.驅 物之表面時’則流速可在廣大範圍内變化，例如空間速度 自1至50 0 /小時。 、又 也燒一般係在溫度3 5 0 C至8 5 0 °C下，較佳4 0 0 °c至7 0 〇 °c
第9頁 1268806 五、發明說明（8) 可用於本發明之雜 之主原子由籠框架所 之金屬原子，相同或 之金屬原子不同，且 元素則稱為π框架π元 數雜多元酸都有位於 氧以四方體形式鍵結 (i)通常經由氧（Π0Π ) (i i )經由氧鍵結至其 端氧π原子之第6個非 示0 多元酸為 圍住，該 不相同。 有時稱為 素或金屬 中心之雜 於”框架π 以四方體 他四個框 架橋盖原 籠狀結構，其一般位於中心 框架含有眾多鍵結於氧原子 雜多元酸之中央元素與框架 ’雜π元素或原子；縮合配位 ，且通常為過渡金屬。大多 原子（π Χπ )，通常經由四個 金屬（ΠΜΠ)，框架金屬依次 形式鍵結至中央原子，及 架金屬及（i i i)具有稱為π終 子。此以化學式（I I I)顯 Μ-0、 Ο •Μ
Ml/ Μ-〇-Μ-〇-Μ Ο (III)
I
X 主框架金屬，Μ，係任何具有適當陽離子半徑且為良好 氧Ρ7Γ -電子受體者。一般而言，框架金屬係選自鉬、鶴、 釩、銳或钽。框架金屬較佳為鉬，鎢或钽。 習知雜多元酸（及其多氧陰離子）可藉一般化學式 He(XkMnOy)_e說明。在此化學式中，X，即中央原子一般係族
1111 I麗ρ·懸 第11頁 1268806 五、發明說明（9) 3 - 1 6元素’較佳係族1 3 - 1 6元素。、& a ^ 但不限於··磷、銻、矽及硼。中田知1 3 1 6元素包括， 下標文字"K" 一般係自1至5，較佳、=，X，、較佳為磷， 1或2 Μ —般為4目，破七 釩。下標文字” η” 一般係自5至2〇。 ^"為錮鎮或 18至62、較佳約40至62。符號"e"為一般係自 負電荷，且將視情況而異，但""二? n ‘义乳陰離子之 所需之質子數。 必疋為用以平衡化學式 雜多元酸已知可以各種結構存在，包括財（忌、 道生（D二son)及安德森（Anders〇n)結構。這些不同結構對 應於特定雜多7L酸組合物主特殊形狀且隨所存在金屬之配 位化學及原子半徑而異。任何這此έ士盖二 一 於本^。 構或其混合物都適用 終框架取代之雜多元酸也可用於本發明。這些化合物4 其中某些框架原子Μ(及雙鍵鍵結至彼等之氧原子）以過渡 金屬取代之雜多元酸。此種取代可例如為單取代，無規一 或區域-二取代，無規_或區域—三取代，或較高取代，全 部皆可產生用作為具有多氧金屬酸鹽載體之有載體雜多5 酸之有效組合物。此等多氧金屬酸鹽已為本技藝所知且〔 說明於例如美國專利5，7 〇 5，6 8 5號及美國專利申請案編號 0 9/0 02, 8 1 6。此等專利均併於以供參其有關多氧金屬酸鹽 之教示。催化劑可進一步藉以下所述各種方法促進。本發 明涵蓋以未取代及取代多氧金屬酸鹽支撐之未取代及取代 雜多元酸二者。
可用於製造經框架取代之組合物之典型雜多元酸具化學
第12頁 1268806 五、發明說明（10) 式為Η3ΡΜ〇12〇4。。當三個M〇 = 0單位由例如鐵（Fe)取代時，所 T經框架取代之雜多元酸即具化學式Η6ΡΜ〇々3〇37。因此， t述之經區域選擇性框架取代之雜多元酸之一般化學 變為：
HeUlA^Oy” 其中k為1至5 ’π為5至19，m么1尽。 ^ . , —人 m為1至6及y為18至62。在此化 干式中’ Μ 包含一或多個你十、乂工7 ,,Q ! η . M ^夕個鋅或任何過渡金屬，亦即週期表 過渡金屬較佳為自族8-10或族4-7之第-行 所選出之元素，如，但不限於 . t Γ ^ 鐵，鈷，鎳，釕，鍺， 〜娥’二’把（族81(^欽’ M，絡 仃）。更佳M1金屬當中有鐵，轻，力 ^ 全屬之组入。-咖Ml后工氧 銳及錄與鐵或其他過渡 贪屬之、，且〇 。二個M1原子不一定 子必須與被取代之三細原子不〜要相同。然而’三卿原 可用於本發明之雜多元一〜 如乙腈及醇類如甲醇中。此等谷於水及極性有機溶劑 t*寻亦隹多元酸具以下化 (e’、bz，）Gb(Xk，Mm、x· Μ\, Μ2 〇 , )-e 其中g係選自族卜16之元素或其y 之元素；My目，鶴或其組 3乳離子，X係選自族3-16 過渡元素；Z，=G之電荷；b=(^M'飢，,M2係與㈣1不同之 Y J - π 5 R ； η 1 Λ 丄乙 ’Κ 一1 至5;Π1’=55?Π; Χ -ο 至b ’η =〇 至3 ;y’ =18至62 m b 至Μ 離子之電荷。G之適當元争勺并， 為夕乳金屬酸鹽陰 釩，鈮，钽，铃，鉬，钱但不限於鈦，锆，铪， 鉻，錦，鎢，錳，鋏 铑，鈀，锇，銀，鉑’鋼，辞戈1八’ Γ ’鎳’釕， 含氧陰離子包括，但不限於；之元素之適當 虱鈦根，虱釩根，氧鈮根或
第13頁 1268806 五、發明說明（11) 其組合。X之適當過渡元素包括，但不限於妒 錯，砷’鍺’硼’鈷，鈽，镨，鈾，鉦，' 矽’銥， 適田過展兀f包括，但不限於鈦，錯，給 鎢，錳，銖，鐵，鈷，錄 釩，钽，鉬， 螺，釕，铑，鈀，錙，处 ,A 銅，鋅或其組合，較佳A 銀，鉑， 1土為當Μ為銦與鎢之组人芬 人4炎 凱津（Keggin)離子時，χ， 片:及化δ物為 Λ凱津離子睥，Y, n m 也#乂仏為* M為鉬及化合物 局⑼年雕于日守，X = 〇至3。 一 為凱津離子時，X，=〇至6。 .、、、田Μ為鎢及化合物 在上述化學式中，（e，—bz，）係說明存 酸組份中之質子（丨丨H+")之齡旦。爭I祌 m化」雜夕兀 士於式望wn ! ^ %里取時，（e bz,)較佳為 大於或寻於〇· 1。在本發明之广具體例中，（e, )為大 於或等於0. 5，在另一具體例中，則大於或等於i。在有些 具體例中，b z等於〇，而雜多元酸中之質子數量為e，。在 另一具體例中，（e，—bz，）正常為〇，而質子係以一種酸（如 硫酸）處理該系統而加入。 可用於本發明之雜多元酸之特定具體例包括，但不限於 h3pm〇12o40 ^ H3PW12O40 ^ (VO)1.5PM〇12040 ^ (VO), 5pw12o40 ^ (Ti0)L5PMo12040 ^ H(VO)PM〇12 040 j H(VO)PW12O40 ^ H6PV3Mo904〇 ^ h5pv2m〇10o40，H5PV2W10〇40，H4PVM〇1104。，H4PVWu04。，
RhPMo12040，BiPMo1204。ICrPVMonO^ ,ΗΒίΡνΜοηΟ^，或其組 合。雜多元酸較佳為H3PM〇12040，H3PW1204。，（VOL.sPMc^Ow， H(VO)PMo12〇4Q，H5PV2M〇1G04G，H4PVM〇1104Q，RhPMo12〇40， HCrPVMon04Q 或HBiPVMouOw。雜多元酸更佳為H3PMo1204〇 或 H3PW12〇4()。當雜多元酸為，例如’
第14頁 1268806 五、發明說明（12) (VCOuPMoni^，（TiOh.sPMc^C^ ’RhPMouO^ 或BiPMo1204◦，必 須之酸一般係來自另外酸源，如用以製造（VCOuPMc^Ow之 V0S04中之硫酸，此等酸量在本發明已充分。 可用於本發明之雜多元酸可自市面上購得或可藉本技藝 所知各種方法製備。可用於本發明之多氧金屬酸鹽及雜多 元酸之一般合成已說明於波普（P〇pe)等人之Heteropoly and Isopoly Oxometallates〆書中（Springer-Verlag ， New York ( 1 983 ))。一般而言，雜多元酸係藉由將所要金 屬氧化物溶解於水，除p Η調整炱約1至2 (用酸，如鹽酸）以
提供所需質子及然後將水鼻發直至所要雜多元酸沉澱為 止。以實例言之，雜多元酸H3PM〇12〇4g可藉由將Na3HP04與 Na2Mo04混合，用硫酸調整pH，用***淬取，並在水中將所 得雜多元酸結晶而製備。同時，經釩取代之雜多元酸也可 根據 V· F· Odyakov 等人之 Kinetics and Catalysis ( 1 9 9 5，ν〇1· 36· Ρ·733 )所述方法製備。Cs3PMo12 04。載 體’如以下將進一步說明，可藉以碳酸铯處理上述雜多元 酸’再收集所得沉澱之產物而製備。 可用本發明之氧化鋁類可為適用於混合金屬氧化物混合
以^形成催化劑物質之任何氧化鋁，且包括，但不限於，7 -氧化鋁及無晶形氧化矽氧化鋁類以及其酸混合物。 、、β I用於本發明之氧化錯類可為適用於與混合金屬氧化物 >匕a以形成催化劑物皙 认 ^ ^ /r d物貝之任何氧化锆，且包括，但不限 扯相” n甘〃 乳化锆鎢，氧化錯鉬及氧化矽氧化 錯類以及其酸混合物。
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1268806 五、發明說明（14) 氣體如惰性氣體 汽或二氧化碳也 料及/或調整起 壓。 烷烴/氧/稀 當莫耳比，以及 所知，例如，適 號。 起始原料烷烴 之任何烧烴。一 異丁烷或正丁烷 者’在另一具體 燒烴如甲烷及乙 該含至少一個 氣’富氧氣體或 在較佳具體例 混合物。起始原 進行催化氧化， 應一般係在大氣 進行。反應溫度 480 °c，更佳350 1 〇，ο ο 〇 / 時，較 /時。 同時，在本發 ，包括m於，氮，氬，t，氙，蒸 可包括在内。稀釋氣體可用以稀釋起始原 始原料之’空間速度，氧氣分壓及蒸汽分 釋氣體/水在起始原料氣體混合物中之適 烷烴/空氣/蒸汽之進料比，已為本技藝 當的範圍已揭不於美國專利5，3 8 〇，9 3 3 一般係適合於氣相氧化成不飽和醛或羧酸 般.而言、，荩烴為C3-C8烷烴，較佳為丙烷， ，更佳為丙烷或異丁烷，最佳為丙烷。再 例中，烷烴可為包括!^ — ^烷烴以及較低碳 烧之院類之混合物。 氧之氣體可為純氧氣體，含氧氣體如空 其混合物。 中，起始原料係丙垸，空氣盘装汽氣體 料氣體混合物係在本發明催化劑之存在下 ，化劑可在流化床或固定床反應器中，反 壓力下進行，但可在升高或降低之壓力下 一般係自200 °C至5 50 °C，較佳3〇〇t：至 C至440 C。氣體空間速度一般為1〇〇至 佳為300至6, 000 /時，更佳為3〇〇至3, 〇〇〇 明之方法中，應了解的是，也會形成不飽
1268806 五、發明說明（16) H2S04 (0.9 g)或（NH4)2S04 (0·9 g)將實例 1 之烘乾 Zr(0H)4 (1 0 g)浸潰至剛潮濕。將經浸潰之氧化锆於空氣中乾燥過 夜，並於空氣中於7 0 0 °c下煅燒3小時而得SZ固體酸。 實例3 本實例將說明鎢錯（” W/Zrn )固體酸之製備。使用溶於1〇 ml水中之偏鎢酸銨[(NH4)6H2W12O40 ·ηΗ20] (2.4 g)，將實例 1之烘乾Z r (Ο Η )4 (1 〇 g )浸潰至剛潮濕。將經浸潰之氧化 锆於空氣中乾燥過夜，並於空氣中於825 °C下煅燒3小時而 得W/Zr固體酸。 實例4 · 一 本實例將說明鉬鍅（n Mo/Zr"d固體酸之製備。利用鉬酸 銨溶液（3.6 g溶於5 ml水中）實例1之烘乾Zr(0H)4 (10 g) 浸潰至剛潮濕。將經浸潰之氧化锆於空氣中乾燥過夜，並 於空氣中於825 °C下煅燒3小時而得Mo/Zr固體酸。 實例5 本實例將說明混合金屬氧化物之製備，將裝有4 2 〇 g 水、2 5 · 7 g七鉬酸銨四水合物（A1 d r i ch化學公司），5 · 1 g 偏飢酸銨（Aldrich化學公司）及7· 7 g碲酸（Aldrich化學 公司）之燒瓶加熱至8 0 °C使之溶解。冷卻至3 9 °C後，將 114.6 g含有17.34 mmole鈮之草酸鈮（Reference金屬公 司）水溶液加入混合得一溶液。將此溶液中之水藉轉動蒸 發裔以溫水浴5〇 °c及28 mm/Hg除去。將44 g催化劑前驅物 固體置於預先經氬氣清洗之加蓋坩堝中，再置入非流動環 境中於6 0 0 °C下煅燒2小時，即得混合物金屬氧化物
第19頁 1268806 發明說明（19) 果顯不於表3 催化劍 工 丙烯酸產率f 〇/n、 100% ΜΜ0 ^ 14. 1 MM0+1% Mo/Zr ,π Λ , 19· 0 數據顯示，錯係一種良好酿他/μ如丨 _ * . 丙稀酸。 縣Ά催化劑，可幫助丙院氧化成 實麵 $備含有混合金屬氧化物催化劑及多 雜多元酸("ΗΡΑ")之混合物一之樣本。樣本含有。14 §载-上 OuaVo^Te^Nb^Ox作為混合金屬氧化物催化劑及1 C”乍為多氧金屬酸鹽載體。CS3PM〇12〇4。係藉將” ,31 g S2C〇3洛於1 225 g去離子水中之溶液於50 t下加至 159· 47克ΙΡΜο^4。溶於80 0 g去離子水中之溶液中。添加 係在2小時内進行，並將混合物保持於5〇 ^3〇分鐘。U 至室溫後，將混合物緩慢攪拌約7〇小時，然後藉蒸發V除去 水，所得固體產物置於真空烘箱或於高溫（例如3〇〇。〇下 烘乾’得約1 5 0 g之所要多氧金屬酸鹽載體。 樣本A係由多氧金屬酸鹽與煅燒混合金屬氧化物乾研 磨，繼之與20 mol%磷鉬酸作為ΗΡΑ乾研磨而製備。第二樣 本如上所述製備’但ΗΡΑ不包括在内。樣本β則係由多氧金 屬酸鹽與煅燒混合金屬氧化物乾研磨而製備。 ” 評估樣本Α-Β在實例5所述條件下，在微反應器中使丙燒 轉化成丙烯酸之效力，結果列示於表4中。
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第23頁
Claims (1)
- 六 1 · 一種催化劑，包含 化予式A^M mN nX x〇各混合金屬氧化物；及 自·（ ^雜多7L酸，（i i )氧化鋁類，（i i i )氧化鍅 類，（1 v )氧化鈦類，（v )沸石及（v i )其酸組合中至少一 種所選出之酸； 其中 〇.25<a<〇.98， 0.003<m<0.5， 0·003<η<0·5, 0· 003<χ<0· 5 ;酸之存在量為〇· 05至5重量％，以催化劑 總重量為準；〇係視其他元素之氧化態而定；及Α係選 自Mo’ W’ Fe’ Nb，Ta，Zr，Ru及其混合物；Μ係選自 V，Ce，Cr，及其混合物；Ν係選自Te，Bi，Sb，Se及 其混合物；及X係選自Nb，Ta，W，Ti，A卜Zr，Cr， Mn，Fe，Ru， Co，Rh，Ni，Pd，Pt，Sb，Bi，B， In， Ce及其混合物。 2.如申請專利範圍第1項之催化劑，其中催化劑包含 0.35<a<0.87， 0.045<m<0.37， 0·020<η<0·27， 0. 0 0 5<χ<0. 3 5及酸之存在量為〇. 1至5重量％，以催化劑 總重量為準。 3 ·如申請專利範圍第1項之催化劑’其中Α係選自Mo，W， 及其混合物；Μ係選自V ’ Ce，Cr，及其混合物；N係選 自T e，B i，S b，及其混合物；X係選自N b ’ T a ’ Z r及其 混合物，及酸之存在量為〇 · 5至5重量％ ’以催化劑之總 重量為準。 4.如申請專利範圍中第1項之催化劑，其中A係Mo，Μ係 V，Ν係Te及X係選自Nb。92919L修正版.ptc 第25頁 1268806 ^ α ^ _案號89117981 %年/月5日 修正_ 六、申請專利範圍 5. —種製備催化劑之方法，包含： (A )將金屬化合物，其中至少一種為含氧化合物， 與水混合以形成水溶液； (B)將水自水溶液中移除以獲得混合金屬氧化物催 化劑前驅物； (C )將催化劑前驅物於溫度4 0 0°C至8 0 0°C下，於惰 性氛團中椴燒；及 (D)將自（i)雜多元酸類，（i i)氧化鋁類，（i i i)氧 化錯類，（i v )氧化鈦類，（v )沸石及（v i )其酸組合中至 少一種所選出之酸摻入，以形成包含具以下化學式： A aM mN nX x0 0 之混合金屬氧化物及酸之催化劑，其中0 . 3 5 < a < 0 . 8 7， 0·045<ιη<0·37，0·0 2 0 <η<0·27，0·0 0 5 <χ<0·35;酸之 存在量為0 . 0 5至5重量％，以催化劑之總重量為準；ο 係視其他元素之氧化態而定；及Α係選自Mo，W，及其 混合物；Μ係選自V，Ce，Cr，及其混合物；N係選自 Te，Bi，Sb，及其混合物；及X係選自Nb，Ta，Zr及其 混合物。 6. 如申請專利範圍第1項之催化劑，其中催化劑係根據申 請專利範圍第5項之方法製備。 7. 如申請專利範圍第6項之催化劑，其中催化劑包含 0.35<a<0.87， 0.045<m<0.37， 0.020<η<0·27， 0. 0 0 5 <χ<0. 35及酸之存在量為0. 1至5重量％，以催化劑 之總重量為準。92919L修正版.ptc 第26頁 1268806 , , _案號89117981 f年 /月夕日 修正_ 六、申請專利範圍 8. 如申請專利範圍第6項之催化劑，其中A係Mo，Μ係V，N 係Te及X係Nb。 9. 一種製備催化劑之方法，包含： (A )將金屬化合物，其中至少一種為含氧化合物； 自（i )雜多元酸，（i i )氧化铭類，（i i i )氧化錯類， (i v )氧化鈦類，（v )沸石及（v i )其酸組合中至少一種所 選之酸；與水混合以形成水溶液； (B )將水自水溶液中移除以獲得混合金屬氧化物催 化劑前驅物；及 (C )將催化劑前驅物在溫度4 0 0°C至8 0 0°C下，於惰 性氛團中煅燒以形成包括具有以下化學式： A aM mN nX x0 0 之混合金屬氧化物及酸之催物質，其中0. 35<a<0. 87， 0.0 45<m<0.37，0·0 2 0 <η<0·27，0·0 0 5 <χ<0·35;酸之 存在量為0 . 0 5至5重量％，以催化劑總重量為準；ο係視 其他元素之氧化態而定；及Α係選自Μ 〇，W，及其混合 物；Μ係選自V，Ce，Cr，及其混合物；Ν係選自Te， Bi，Sb，及其混合物；及X係選自Nb，Ta，Zr及其混合 物。 10. —種製備自不飽和醛及羧酸所組成之族群中所選出之 化合物之方法，包括： 使烧烴在如申請專利範圍第1項之催化劑之存在下 進行催化氧化作用。92919L修正版.ptc 第27頁
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| MXPA00008754A (es) | 2002-06-04 |
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| BR0004144A (pt) | 2001-04-17 |
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| CN1129472C (zh) | 2003-12-03 |
| BR0004144B1 (pt) | 2011-02-22 |
| EP1080784A1 (en) | 2001-03-07 |
| EP1080784B1 (en) | 2005-04-13 |
| US20030109748A1 (en) | 2003-06-12 |
| DE60019381D1 (de) | 2005-05-19 |
| DE60019381T2 (de) | 2006-03-09 |
| US6518216B1 (en) | 2003-02-11 |
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| JP2001079412A (ja) | 2001-03-27 |
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