TW201703856A - 催化劑與使用該催化劑的烴轉化製程 - Google Patents
催化劑與使用該催化劑的烴轉化製程 Download PDFInfo
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- TW201703856A TW201703856A TW105120547A TW105120547A TW201703856A TW 201703856 A TW201703856 A TW 201703856A TW 105120547 A TW105120547 A TW 105120547A TW 105120547 A TW105120547 A TW 105120547A TW 201703856 A TW201703856 A TW 201703856A
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- hydrocarbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 57
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 54
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000002516 radical scavenger Substances 0.000 claims abstract description 28
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
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- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 150000004678 hydrides Chemical class 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 21
- 150000001336 alkenes Chemical class 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 11
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
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- 238000005984 hydrogenation reaction Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 5
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910003203 NH3BH3 Inorganic materials 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 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
Classifications
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Abstract
本發明係關於一種烴轉化催化劑，包含：i)氧化物形式的催化劑，包含金屬M1、M2、M3、及M4，其中：M1係選自Si、Al、Zr、及其混合物；M2係選自Pt、Cr、及其混合物；M3係選自W、Mo、Re、及其混合物；且M4係選自Sn、K、Y、Yb、及其混合物；以及ii)氫清除劑，其係選自至少一種鹼金屬及/或鹼土金屬衍生物，較佳為金屬、氫化物、鹽、錯合物、或合金形式；以及關於一種使用該催化劑的烴轉化製程。
Description
本發明係關於一種烴轉化催化劑與一種用於將含有飽和烴化合物的烴進料轉化為烯烴產物的製程。
烯烴，尤其是包括乙烯與丙烯的輕烯烴，是重要的烴類產物。它們可用於製備廣泛種類的終端產物，包括環氧乙烷、環氧丙烷、乙苯、丙酮、酚、聚乙烯、聚丙烯、其他聚合物、以及其他石化產物。即使價格隨時間波動，其於產業中的需求仍持續增長。
因應產業需求，已使用多種方法生產烯烴。然而，通常由較低價值的進料(例如石蠟烴)製造烯烴較有經濟吸引力。將石蠟烴轉化為烯烴的傳統方法為熱裂解；其為一種具高度能量消耗的方法，且難以調整及控制產物選擇性。
催化裂解是較晚研發的方法；使用適當的催化材料，一般而言為沸石基礎的材料，烴類裂解可以在較不劇烈的操作環境下發生。
現有技術中，亦已知藉由使用適當催化劑進行脫氫反應，以將飽和石蠟烴轉化為具對應數量碳原子的烯烴的製程。脫氫反應後可接續適當的反應步驟，以將所獲得的烯烴完整轉化
為理想的產物。舉例而言，脫氫反應後可接續複分解反應步驟以將脫氫反應步驟獲得的烯烴轉化為不同的烯烴。
不同的副反應可能在脫氫反應與下一個反應步驟(例如複分解)時發生，例如乙烷、丙烷、或丁烷脫氫反應理想的終產物，乙烯、丙烯、或丁烯的(再)氫化反應。換句話說，氫氣的生成對於進一步反應所獲得烯烴而言成為缺點。
因此，本發明的一目的在於提供一種烴轉化催化劑與一種使用彼之製程，其中氫的副反應可被減少或實質避免。
該目的藉由一種烴轉化催化劑而達成，該催化劑包含：i)具氧化物形式的催化劑，其包含金屬M1、M2、M3、及M4，其中：M1係選自Si、Al、Zr、及其混合物；M2係選自Pt、Cr、及其混合物；M3係選自W、Mo、Re、及其混合物；且M4係選自Sn、K、Y、Yb、及其混合物；其中M1的質量分率係0.1至0.8；M2的質量分率係0.001至0.2；M3的質量分率係0.001至0.2；M4的質量分率係0.0001至0.2；且氧的質量分率係0.1至0.8；以及ii)氫清除劑，其係選自至少一種鹼金屬及/或鹼土金屬衍生物，較佳為金屬、氫化物、鹽、錯合物、或合金形式。
根據本發明，亦提供一種用於將含有飽和烴化合物的烴進料轉化為烯烴產物的製程，包含將烴進料流與如本發明烴轉化催化劑接觸。
較佳具體實施態樣如後附申請專利範圍所揭露。
在本發明另一實施態樣中，M1的質量分率係0.2至0.6；M2的質量分率係0.0015至0.15，較佳0.0015至0.05；M3的質量分率係0.005至0.15，較佳0.01至0.1；及/或M4的質量分率係0.00015至0.03，較佳0.0003至0.01。在另一實施態樣中，氧的質量分率係0.2至0.6。
在另一實施態樣中，M2係Pt且/或M3係W。
在一實施態樣中，本發明之用於轉化烴進料的製程於200℃至700℃溫度下進行，較佳300℃至650℃，更佳400℃至600℃。
在另一實施態樣中，具氧化物形式的催化劑進一步包含金屬M5(即，催化劑化學式為M1M2M3M4M5O)。
較佳地，M5選自Mg、Ca、Mn、Fe、Co、Ni、Cu、及其混合物；且M5的質量分率較佳係0.005至0.1，更佳0.005至0.05。
在本發明催化劑中，M1至M4與O的質量分率，以及M1至M5與O的質量分率，分別累加為1。
在一實施態樣中，該至少一種鹼金屬及/或鹼土金屬係選自Li、Na、K、Mg、Ca、及其混合物，較佳Na及Mg。
令人驚訝地發現用於本發明烴轉化催化劑的氫清除劑可以在不需要氫時將其清除。本發明所選擇的氫清除劑包含一些儲氫容量。氫清除劑的儲氫容量可為可逆的或不可逆的。
具氧化物形式的催化劑可藉由將所有的元素M1至M4或M1至M5之前驅物一起混合，接著進行適當的熱處理，以獲得所欲的多金屬組合物。元素前驅物為含有所欲元素的起始化
合物，其可藉由適當的熱處理被轉化為最終的催化劑中元素的所欲形式，較佳為氧化物。舉例而言，M1至M5的前驅物可包括元素的氧化物、鹵化物、烷氧化物、硝酸鹽、碳酸鹽、甲酸鹽、草酸鹽、胺類、或氫氧化物。
元素前驅物的混合可在乾式或濕式下進行。當彼等以乾式混合時，元素前驅物可方便地以粉末形式提供。元素前驅物的粉末可以簡單地藉由於攪拌機中物理混合而混合。之後元素前驅物的混合物經由適當的熱處理，較佳鍛燒，以獲得最終之具氧化物形式的烴轉化催化劑。當彼等以濕式混合時，元素前驅物可以溶液及/或懸浮液形式提供。然後，元素前驅物的溶液及/或懸浮液混合物被乾燥以去除溶劑。之後，乾燥的混合物經由適當的熱處理，較佳鍛燒，以獲得最終的催化劑。或是，部分元素前驅物以乾式提供且部分元素前驅物以濕式提供。乾與濕的元素前驅物可藉由傳統方法合併，包括浸滲、初始濕潤、離子交換、或其他本領域已知的方法。所獲得的混合物經由適當的熱處理，較佳鍛燒，以獲得最終的催化劑。適當的熱處理涉及所選擇的氣氛與所選擇的溫度，其足以移除及/或轉化至少一部份的元素前驅物為於最終催化劑中對應元素的所欲形式。尤其較佳的為元素在最終催化劑中為氧化物形式。所選擇的氣氛可包括氧化氣氛、還原氣氛、及惰性氣氛。在一較佳實施態樣中，所製備的催化劑粉末在空氣中於300℃至800℃溫度下經過1至24小時的鍛燒，甚至更佳於400℃至600℃溫度下經過2至10小時的鍛燒。
具氧化物形式的催化劑亦可藉由分別鍛燒一或多種的元素前驅物，然後將個別的氧化元素前驅物合併，並最終鍛燒
而製備。舉例而言，使用承載氧化鋯、氧化鋁、氧化矽、及/或沸石(M1)的載體以於其上分別或同時浸滲M2、M3、與M4及/或M5。對應製備的各個組合物接著以物理混合並最終鍛燒。氫清除劑可添加於該等混合物中，或可在製備所有金屬M1至M5與氫清除劑的最終混合物時添加。
在一較佳實施態樣中，烴轉化催化劑藉由物理混合鍛燒過且為固體形式的具氧化物形式的催化劑與氫清除劑而製備，該氫清除劑較佳也以固體形式提供。
適用於本發明的氫清除劑為鹼金屬及/或鹼土金屬的衍生物形式，較佳為金屬、氫化物、鹽、錯合物、合金，或其混合物。
該氫清除劑較佳藉由將氫清除劑前驅物適當的熱處理製備，較佳在於300℃至700℃溫度下，更佳於400℃至600℃溫度下，經過2至24小時的鍛燒。
氫清除劑前驅物可為鹼金屬及/或鹼土金屬的化合物，較佳為鹼金屬及/或鹼土金屬的鹽類。
在一實施態樣中，氫清除劑前驅物係選自Ca(BH4)2、Mg(BH4)2、Ca(NO3)2、K(NO3)2、Na(NO3)2、及其混合物。
發現在適當的熱處理溫度及/或烴轉化溫度下，氫清除劑前驅物將分解為鹼金屬及/或鹼土金屬的衍生物形式。在此狀況下，在本發明一實施態樣中，氫清除劑並不以氧化物形式存在於烴轉化催化劑中，而是以鹼金屬及/或鹼土金屬的衍生物形式存在，較佳為金屬、氫化物、鹽、錯合物、合金形式、或其混合物。
在另一實施態樣中，根據本發明之烴轉化催化劑的製備可進一步涉及將催化劑粉末形成為適用於商用反應器的形狀。適用於商用反應器的形狀可包括錠狀、擠出物、球狀、及類似者。可進一步於催化劑組合物中添加足夠的黏結材料以順利形成催化劑。
將烴進料流與i)催化劑和ii)氫清除劑接觸可分別發生或同時發生。在一較佳實施態樣中，i)催化劑和ii)氫清除劑被混合，且烴進料流與i)催化劑和ii)氫清除劑的接觸同時發生。混合i)催化劑和ii)氫清除劑可於微觀層級或巨觀層級進行。在一實施態樣中，氫清除劑或其前驅物在i)催化劑的製備步驟中加入。較佳地，i)催化劑和ii)氫清除劑的粉末在與烴進料流接觸前先物理混合。粉末混合物可在與烴進料流接觸前形成為適當的形狀，且可視需要可添加適當的黏結劑。亦較佳地，i)催化劑和ii)氫清除劑在與烴進料流接觸前以適當的重量比物理混合。於此情況下，i)催化劑和ii)氫清除劑的適當重量比可為1：99至99：1。i)催化劑和ii)氫清除劑的較佳重量比為1：30至1：1，更佳2：25至1：1，甚至更佳為4：20至1：1，甚至又更佳為5：15至1：1。
為了獲得烯烴產物，烴進料流有利地包含石蠟烴。在一較佳實施態樣中，烴進料流包含具有2至5個碳原子的石蠟烴。在一更具體的實施態樣中，烴進料流包含石蠟烴，其係選自乙烷、丙烷、丁烷、戊烷、及其混合物，較佳丙烷、丁烷、及其混合物。
烴轉化製程可於廣泛的操作條件下進行。然而，某些特定的操作條件範圍可獲致高的烯烴產物選擇性。在一實施態
樣中，製程於200℃至700℃溫度下進行，較佳300℃至650℃，甚至更佳400℃至600℃。在另一實施態樣中，製程於0.01至10巴表壓的壓力下進行，較佳0.05至5巴表壓。獲得所欲烯烴產物產率的所需接觸時間與數種因素相關，例如操作溫度、操作壓力、以及催化劑活性。在一實施態樣中，製程於0.01至20小時-1的每時重量空間速度(WHSV)下進行，較佳0.05至5小時-1。製程可以批次方式或連續方式進行。對於商業規模，使製程以連續操作較佳。連續操作可以固定床、流化床、或其他本領域已知技術進行，其中通常較佳為固定床。
在與烴進料流接觸前，i)催化劑和ii)氫清除劑可選擇性地預處理。預處理條件可包括將i)催化劑和ii)氫清除劑與惰性氣體、氧化氣體、還原氣體、烴(較佳C2-C6脂肪烴)、及其任意混合物接觸。該預處理可分為數個步驟，其中各步驟可採用不同的條件與氣氛。通常較佳在加熱的溫度下進行預處理，較佳200℃至700℃下，更佳300℃至600℃，甚至更佳350℃至550℃
在操作環境下與烴進料流接觸後，某些毒性物質、重烴、和煤焦可能沉積在催化劑與氫清除劑表面上。這通常影響催化劑混合物的活性，使其隨時間逐漸下降。可以對使用過的催化劑與氫清除劑混合物進行適當的再生以恢復至少一部份的活性。在一實施態樣中，烴轉化製程包含一再生步驟，其中再生步驟包括將烴轉化催化劑在高溫下與氧化劑接觸。再生步驟應小心地控制，以避免過熱並破壞催化劑的結構。在一實施態樣中，再生步驟於200℃至700℃溫度下進行，較佳300℃至600℃。可不受限制地使用其他已知的再生技術。
依據前述揭露內容，已製備並測試多種根據本發明的烴轉化催化劑。發明人驚訝地發現，在後附申請專利範圍中的本發明催化劑與本發明氫清除劑組成的催化劑系統相較於非本發明的催化劑系統展現更佳的催化活性與選擇性。
此外，令人驚訝地發現根據本發明的催化劑系統可在較溫和的條件下操作，即，溫度相較於本領域所知的更低。
實驗結果
在以下的實施例段落中，探討使用根據本發明的烴轉化催化劑與使用比較催化劑將丙烷轉化為烯烴(較佳乙烯與丁烯)。
實施例A
在於約500℃、0.1巴表壓、及0.2小時-1的WHSV下與C3H8接觸前，各實施例催化劑藉由於約500℃下與空氣接觸30分鐘，並於約500℃下與氫氣接觸90分鐘進行預處理。測量約60至65小時的反應產物流結果。反應的流出物被導引到氣相層析儀以測量其化學組成。所測量的流出物組成用以計算轉化率與選擇性。C3H8轉化百分率藉由C3H8在反應中被轉化的重量除以C3H8在進料流中的重量再乘以100計算。個別產物的選擇性百分率也藉由特定產物在反應中產生的重量除以所有產物在反應中產生的重量再乘以100計算。催化劑的組成藉由用於製備催化劑的前驅物用量計算。質量分率可由重量百分率除以100計算。
實施例1(比較例)
包含0.811重量% Al、1.792重量% Mg、50.495重量% O、0.501重量% Pt、42.526重量% Si、3.396重量% W、0.076重量% Yb、及0.403重量% Zr的催化劑樣本在進行反應試驗前，於空氣中550℃下鍛燒3小時。
此催化劑為不添加氫清除劑的用於將石蠟烴轉化為
烯烴的標準催化劑。
實施例2(比較例)
如下製備催化劑樣本：
1)提供包含0.810重量% Al、1.789重量% Mg、50.497重量% O、0.5重量% Pt、42.53重量% Si、3.391重量% W、0.076重量% Yb、及0.403重量% Zr的催化劑粉末。
2)將步驟1)的催化劑粉末於空氣中550℃下鍛燒3小時。
3)將NH3BH3於空氣中550℃下鍛燒3小時。
4)將80重量%步驟2)的鍛燒催化劑粉末與20重量%步驟3)的鍛燒NH3BH3物理混合。
使用此催化劑顯示較高的烯烴選擇性，然而NH3BH3似乎抑制了W的複分解活性，且因此明顯降低乙烯與丁烯的選擇性。
實施例3
如下製備催化劑樣本：
1)提供包含0.811重量% Al、1.791重量% Mg、50.448重量% O、0.501重量% Pt、42.573重量% Si、3.395重量% W、0.076重量% Yb、及0.403重量% Zr的催化劑粉末。
2)將步驟1)的催化劑粉末於空氣中550℃下鍛燒3小時。
3)將Na(NO3)於空氣中550℃下鍛燒3小時。
4)將80重量%步驟2)的鍛燒催化劑粉末與20重量%步驟3)的鍛燒Na(NO3)物理混合。
使用此催化劑可抑制氫化副反應。其可由相較於實施例1中的標準催化劑更高的C2H4與C4H8選擇性及較低的
C2H6與C4H10選擇性證實。
實施例4
此催化劑樣本由與實施例3相同的步驟製備，但使用10重量%的Na(NO3)。
使用此催化劑可抑制氫化副反應。其可由相較於實施例1中的標準催化劑更高的C2H4與C4H8選擇性及較低的C2H6與C4H10選擇性證實。
實施例5
此催化劑樣本由與實施例3相同的步驟製備，但使用10重量%的K(NO)3而非Na(NO3)。
使用此催化劑可抑制氫化副反應。其可由相較於實施例1中的標準P2Os催化劑更高的C2H4與C4H8選擇性及較低的C2H6與C4H10選擇性證實。
實施例B
在於約500℃、0.05至0.1巴表壓、及約0.4至0.7小時-1的WHSV下與C3H8接觸前，各實施例催化劑藉由於約500℃下與空氣接觸30分鐘，並於約500℃下與氫氣接觸90分鐘進行預處理。測量約155至160小時的反應產物流結果。
實施例6(比較例)
包含0.324重量% Al、0.715重量% Mg、49.624重量% O、4.277重量% Pt、42.700重量% Si、1.355重量% W、0.390重量% Yb、及0.641重量% Zr的催化劑樣本在進行反應試驗前，於空氣中550℃下鍛燒3小時。
實施例7
如下製備催化劑樣本：
1)提供包含0.801重量% Al、1.782重量% Mg、49.009重量% O、2.687重量% Pt、41.237重量% Si、3.379重量% W、0.714重量% Yb、及0.382重量% Zr的催化劑粉末。
2)將步驟1)的催化劑粉末於空氣中550℃下鍛燒3小時。
3)將Ca(BH4)2於空氣中550℃下鍛燒3小時。
4)將80重量%步驟2)的鍛燒催化劑粉末與20重量%步驟3)的鍛燒Ca(BH4)2物理混合。
使用此催化劑可抑制氫化副反應。其可由相較於實施例6中的標準催化劑更低的C2H6與C4H10選擇性證實。
實施例8
此催化劑樣本由與實施例7相同的步驟製備，但使用6.5重量%的Mg(BH4)2而非Ca(BH4)2。
使用此催化劑可抑制氫化副反應。其可由相較於實施例6中的標準P2Os催化劑更低的C2H6與C4H10選擇性證實。
前文敘述與申請專利範圍所揭露的特徵，不論是各自或是以任何組合，可作為以不同形式實現本發明的材料。
Claims (8)
- 一種烴轉化催化劑，包含：i)一具氧化物形式的催化劑，其包含金屬M1、M2、M3、及M4，其中：M1係選自Si、Al、Zr、及其混合物；M2係選自Pt、Cr、及其混合物；M3係選自W、Mo、Re、及其混合物；且M4係選自Sn、K、Y、Yb、及其混合物；其中M1的質量分率係0.1至0.8；M2的質量分率係0.001至0.2；M3的質量分率係0.001至0.2；M4的質量分率係0.0001至0.2；且氧的質量分率係0.1至0.8；以及ii)一氫清除劑，其係選自至少一種鹼金屬及/或鹼土金屬衍生物。
- 如請求項1所述之烴轉化催化劑，其中該至少一種鹼金屬及/或鹼土金屬係選自Li、Na、K、Mg、Ca、及其混合物。
- 如請求項1或2所述之烴轉化催化劑，其中催化劑i)與氫清除劑ii)的重量比係1：99至99：1。
- 如請求項1或2所述之烴轉化催化劑，其中M2為Pt且M3為W。
- 一種用於轉化一包含飽和烴化合物之烴進料的製程，包含將 一烴進料流與如請求項1至4任一項所述之烴轉化催化劑接觸。
- 如請求項5所述之製程，其中該烴進料流係包含至少一具有2至5個碳原子的石蠟烴。
- 如請求項5或6所述之製程，進一步包含一烴轉化催化劑再生步驟，包含將該烴轉化催化劑與一氧化劑於約200℃至700℃溫度下加熱。
- 如請求項7所述之製程，其中該氧化劑係包含空氣或氧。
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