TWI637001B - 樹脂氫化之製程與觸媒 - Google Patents
樹脂氫化之製程與觸媒 Download PDFInfo
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- TWI637001B TWI637001B TW103124495A TW103124495A TWI637001B TW I637001 B TWI637001 B TW I637001B TW 103124495 A TW103124495 A TW 103124495A TW 103124495 A TW103124495 A TW 103124495A TW I637001 B TWI637001 B TW I637001B
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- nickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229920005989 resin Polymers 0.000 title abstract description 6
- 239000011347 resin Substances 0.000 title abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 41
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 28
- 239000010941 cobalt Substances 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 150000003464 sulfur compounds Chemical class 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 150000001868 cobalt Chemical class 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 150000004760 silicates Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910000029 sodium carbonate Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 3
- -1 nickel-cobalt-copper-silicon oxide Chemical compound 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
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Abstract
本發明係為觸媒領域。詳而言之，本發明有關於觸媒氫化製程和其中所使用的觸媒。
依據本發明，係提供一種用於碳氫樹脂之氫化的製程、觸媒本身、以及製備該觸媒的製程，特別是使用一鈷促進之在氧化矽/氧化鋁上的鎳觸媒，碳氫樹脂進料有相當高的硫含量。
Description
本發明係有關於觸媒領域。更詳細地，本發明有關於觸媒氫化製程和製程中所使用之觸媒。
WO-A-01/36093敘述用於碳氫樹脂之氫化的鎳-鐵-氧化矽-氧化鋁觸媒。這些和其他習知的鎳氫化觸媒，在碳氫樹脂進料中具有低活性，特別是當在進料中的硫量超過100ppm時。因此，有需要提供一種觸媒和製程，對於有較高量硫之碳氫樹脂的氫化，可得到良好的觸媒活性。
因此，本發明之目的為提供用於碳氫樹脂之氫化的一觸媒和製程，而得到此優點。另一目的為提供製備此觸媒的一製程。本發明之再一目的為，提供適用於碳氫樹脂之氫化的一觸媒，而有成本效益。
US-A-4 263 225敘述鎳-鈷-氧化矽和鎳-鈷-銅-氧化矽之氫化觸媒，以及使用這些觸媒的氫化單體芳香族化合物之製程。在此文件中沒有提到碳氫樹脂的氫化。
US-A-3 945 944敘述一種鈷促進之鎳觸媒，承載於一耐火物質上，以及使用此觸媒以製造含氫或富含甲烷之氣體。如US-A-4 263 225一樣，此文件中沒有提到碳氫樹脂的氫
化。
US-A-4 532 351敘述一種氫化製程，係使用包括鎳、鈷、銅、氧化鋁和氧化矽之觸媒以氫化有機化合物例如烯烴。US-A-4 532 351亦敘述此觸媒可適用於加氫脫硫製程。然而，此文件並未提及碳氫樹脂的氫化。
WO-A-2004/035204敘述一種鎂促進之鎳觸媒，適用於不飽和有機化合物的氫化，特別是具有高硫量的脂肪油。WO-A-2004/035204亦敘述一種包括鎳、氧化矽、氧化鋁和鈷的觸媒，其不適用於該氫化反應。此文件中沒有提到碳氫樹脂的氫化。
AU-B-66865/81敘述一種經承載的共沈澱觸媒，係由鋁、一種或多種第VIII族非鐵金屬之鹽類、和固體多孔粒子而得，以及製造此觸媒的方法。AU-B-66865/81沒有提到碳氫樹脂的氫化，也沒有提到具有含硫化合物的碳氫樹脂。
本發明之發明人發現，鈷促進之承載於氧化矽/氧化鋁上之鎳觸媒，非常適合於碳氫樹脂之氫化，特別是有相當高硫含量的碳氫樹脂進料。
因此，本發明之一特徵為，用於一碳氫樹脂進料之氫化的製程，該碳氫樹脂進料包括一種或多種硫化合物，該製程包括在一觸媒的存在下將該碳氫樹脂進料與氫接觸的步驟，其中該觸媒為一以鈷促進之承載於氧化矽和氧化鋁上之鎳觸媒，該觸媒具有45至85wt%之鎳含量(以Ni作計算)，13.75至45wt%之矽含量(以SiO2作計算)，1至15wt%之鋁含量(以
Al2O3作計算)，以及0.25至12wt%之鈷含量(較佳以Co計算)，且該觸媒具孔洞直徑介於2和60nm之間的孔洞體積為至少0.35ml/g觸媒，較佳為介於10和60nm之間的孔洞體積為至少0.20ml/g觸媒。
在此使用之有關於觸媒的所有重量百分比，都是以還原之觸媒的基礎作計算的。在此使用之所有ppm值，都是以重量為基準，除非另有說明。
本發明更有關於上述觸媒本身，以及使用此觸媒的製程。
第1圖顯示，相較於實施例2中非促進之觸媒，實施例3-8中本發明之觸媒具有改良的氫化反應速率。
令人驚訝地發現到，相較於不含有鈷促進劑的那些配方，本發明之觸媒在含有硫化合物的碳氫樹脂進料中提供增進的活性。更令人驚訝的是，發現到鈷促進劑的量可為非常低。相較於已知的氫化樹脂觸媒，這提供了顯著的經濟費用的節省。
依據本發明，鈷含量較佳為0.25至12wt%(以Co作計算)，更佳為0.25至4.5wt%(以Co作計算)，且甚至更佳為0.3至4wt%(以Co作計算)。令人驚訝地，發現到相較於非促進之鎳觸媒，只有約0.3wt%之鈷即可導致觸媒活性有>40%之增加。甚至更令人驚訝地，發現到相較於WO-A-01/36093
非鈷促進之類似物，如此低量的鈷，導致觸媒活性有大約300%的增加。
希望不受任何理論拘束，假設經承載之鎳觸媒中的鈷的促進效果，是源於在Ni結晶晶格中無序(disorder)程度的增加，因此可提供觸媒之硫容忍度的增進。
因此，本發明亦有關於一種鈷促進之承載於氧化矽和氧化鋁上之鎳觸媒，其中該觸媒之鎳含量(以Ni作計算)為45至85wt.%，矽含量(以SiO2作計算)為13.75至45wt.%，鋁含量(以Al2O3作計算)為1至15wt.%，以及鈷含量(以Co作計算)為0.25至1.5wt.%，且此觸媒具孔洞直徑較佳介於2和60nm之間的孔洞體積為至少0.35ml/g觸媒，更佳為介於10和60nm之間的孔洞體積為至少0.20ml/g觸媒。
觸媒的鎳含量，一般為45至85wt%之間，且較佳為55和75wt%之間。在這些範圍內，可得到最佳的活性和選擇性。
承載物質是氧化矽和氧化鋁的組合。此可為這兩種成份的混合物，但是矽和鋁離子至少部分在相同結晶晶格中也是可能的。
本發明觸媒之BET表面積，較佳為介於200至350m2/g之間。在此所用的BET表面積，係以微晶粒孔徑分析儀ASAP 2420測量，觸媒樣品在180℃脫氣之後，測量在77K之下，P/Po大約0.3之下的氮吸附量，假設氮的截面積為16.2Å2。
一般而言，本發明之觸媒具孔洞直徑介於2和60nm之間的孔洞體積為至少0.35ml/g觸媒，更佳為介於10和60nm之間
的孔洞體積為至少0.20ml/g觸媒。在此所用之孔洞體積，係使用排氣溫度300℃、壓力<15μm Hg，在微晶粒孔徑分析儀ASAP 2420上測量在孔洞直徑為2和200nm內的N2脫附，且假設孔洞是圓柱形的，樣品係在375℃之下煅燒1.5小時。
S-毒化程度，係以所使用反應介質中的鎳毒化的百分比表示。這是測定氫化碳氫樹脂之觸媒的反應速率而得，以觸媒之鎳含量wt.%為函數。與x軸之交錯處為門檻，在觸媒最低量的鎳wt.%係沒有氫化活性。一般而言，在此函數中，S-毒化的程度越低，觸媒的S-容忍度越高。
觸媒氫化碳氫樹脂的反應速率係以反應速率常數表示，係在30%至70%轉換(conversion)之間進行一線性迴歸(linear regression)而得，以1/h表示。
氫化吸附力(HAC；hydrogen adsorption capacity)，是測定可用於觸媒作用之鎳表面積程度的一般量測。本發明之觸媒一般而言HAC的範圍為15至25ml H2/g觸媒。於在線上之與氫的還原反應，10℃/min至375℃之溫度坡度之下，在375℃之下停留2小時，接著在-75℃之下氬氣下進行脫氣45分鐘之後，在氬氣氣氛下以10℃/min的速率由-75℃至700℃的溫度坡度，藉由氫的脫附量而測定HAC。
本發明之觸媒可為粉末、粒子、顆粒、和成形體(如球體、擠出物、或錠狀)的形式。較佳者，本發明之觸媒為一粉末觸媒。
本發明之觸媒可以各種方式製備，例如將活性成份在一預成形的含有氧化矽和氧化鋁的載體上浸漬
(impregnation)或沈澱，或在該載體上沈澱。
然而，較佳為以共沈澱法製備經承載之觸媒。這包括由溶液中沈澱出觸媒成份(觸媒前驅物)，特別是由一種或多種之鎳鹽、鈷鹽、鋁鹽，以及一種或多種矽化合物等各種溶液中，且選擇性地為其他成份，例如鐵鹽、鋅鹽、和鎂鹽及其組合，通常藉由加入一鹼或藉由電化學方式而增加或維持pH到7.0以上。可使用通常的技術，例如將所有溶液同時加到沈澱容器中，或提供一種或多種成份以及加入其他成份至容器中。
本發明亦有關於製備上述類型之承載於氧化矽和氧化鋁上之鎳觸媒的一種製程，該方法包括在pH值7.0至9.0之下共沈澱觸媒成份，由沈澱液體中回收該共沈澱之物質，清洗它，且更處理它以製造出該觸媒。
在沈澱之後，接著可將沈澱物過濾出，清洗，且更依需要作處理。這可包括煅燒(calcination)、還原、鈍化、或其組合。
在本發明中，可使用碳氫樹脂進料。可使用的碳氫樹脂進料，一般係經由蒸餾、預處理、和聚合，而由C5或C9石油分餾物(petroleum fractions)和副產物，以及其組合物而製得。一般而言，此類碳氫樹脂是低分子量聚合物(介於300至3000道耳頓(Daltons)之間)，其包括一脂肪族主幹和選擇的一種或多種芳香族和/或脂肪族側基團。
一般而言，適用於本發明製程中的碳氫樹脂進料包括一種或多種硫化合物。碳氫樹脂進料的硫化合物含量(以
硫作計算)通常為大於40ppm，較佳為大於100ppm，依據碳氫樹脂進料之重量為基礎。
不希望被理論所拘束，相信在碳氫樹脂進料中存在的硫化合物是在碳氫樹脂分子中。
本發明之製程，亦包括使用前述之觸媒以氫化一碳氫樹脂進料，特別是含有一種或多種硫化物之一碳氫樹脂進料。適合的溫度和壓力是基於樹脂的性質、最終產物所需之性質、和觸媒的真實組成和構造。
通常，適合的溫度為介於100和350℃之間，較佳為介於250和325℃之間。適合的部分氫壓力可介於1和150bar(abs)之間。氫化時間主要是依據時間、觸媒量、和樹脂所需氫化程度而定。
製程較佳為批次進行，其中觸媒是以粉末而分散在碳氫樹脂中。本發明粉末觸媒的適合粒子尺寸為介於1和1000μm之間。在氫化製程中新鮮觸媒的裝載為，通常相對於樹脂介於0.25和4wt.%之間。
製程可在適用於漿液氫化的不同反應器中進行，例如攪拌槽反應器(選擇性梯級(cascaded))或循環反應器。
使用前述之觸媒，造成碳氫樹脂之氫化，而產生具有仔細平衡性質(化學和物理)的一產物。同時，氫化造成最終產物雜質含量的減少。
本發明依照以下實施例而加以說明。
實施例1(比較)
依據WO-A-01/36093而製備一鎳觸媒，係在溫度
95℃下，將含有鎳、鐵、和氧化鋁等之鹽類、矽酸鹽、和碳酸鈉的各種溶液，在一充分攪拌的沈澱容器中混合。所形成之漿液的pH為大約7.5，1小時後沈澱完成。在清洗沈澱物後，將觸媒前驅物過濾，在110℃的爐中乾燥。將觸媒以氫活化，在空氣存在下鈍化。所得觸媒之組成和物理性質，詳列於表1。
實施例2(比較)
在溫度95℃下，將含有鎳和氧化鋁之鹽類、矽酸鹽、和碳酸鈉的各種溶液，在一充分攪拌的沈澱容器中混合。所形成之漿液的pH為大約7.5，1小時後沈澱完成。在清洗沈澱物後，將觸媒前驅物過濾，在110℃的爐中乾燥。將觸媒以氫活化，在空氣存在下鈍化。所得觸媒之組成和物理性質，詳列於表1。
實施例3
在溫度95℃下，將含有鎳、鈷、和氧化鋁等之鹽類、矽酸鹽、和碳酸鈉的各種溶液，在一充分攪拌的沈澱容器中混合。所形成之漿液的pH為大約7.5，1小時後沈澱完成。在清洗沈澱物後，將觸媒前驅物過濾，在110℃的爐中乾燥。將觸媒以氫活化，在空氣存在下鈍化。所得物質含有64wt.% Ni，25wt.% SiO2，2wt.% Al2O3和0.3wt.% Co。所得觸媒之其他物理性質，詳列於表1。
實施例4
依據實施例3而製備一觸媒，但使用不同濃度的含有鎳、鈷、和氧化鋁等之鹽類、矽酸鹽、和鈉的各種溶液。所得物質含有61wt.% Ni，25wt.% SiO2，2wt.% Al2O3，和
0.6wt.% Co。所得觸媒的其他物理性質，詳列於表1。
實施例5
依據實施例3而製備一觸媒，但使用不同濃度的含有鎳、鈷、和氧化鋁等之鹽類、矽酸鹽、和碳酸鈉的各種溶液。所得物質含有59wt.% Ni，25wt.% SiO2，2wt.% Al2O3，和1.5wt.% Co。所得觸媒的其他物理性質，詳列於表1。
實施例6
依據實施例3而製備一觸媒，但使用不同濃度的含有鎳、鈷、和氧化鋁等之鹽類、矽酸鹽、和碳酸鈉的各種溶液。所得物質含有61wt.% Ni，25wt.% SiO2，2wt.% Al2O3，和2.4wt.% Co。所得觸媒的其他物理性質，詳列於表1。
實施例7
依據實施例3而製備一觸媒，但使用不同濃度的含有鎳、鈷、和氧化鋁等之鹽類、矽酸鹽、和碳酸鈉的各種溶液。所得物質含有59wt.% Ni，25wt.% SiO2，2wt.% Al2O3，和3.7wt.% Co。所得觸媒的其他物理性質，詳列於表1。
實施例8
依據實施例3而製備一觸媒，但使用不同濃度的含有鎳、鈷、和氧化鋁等之鹽類、矽酸鹽、和碳酸鈉的各種溶液。所得物質含有56wt.% Ni，25wt.% SiO2，2wt.% Al2O3，和9.2wt.% Co。所得觸媒的其他物理性質，詳列於表1。
實施例9-觸媒之測試
75克之50wt.%碳氫樹脂(含有140ppm的硫化合物，依據碳氫樹脂的重量以硫作計算)在Shellsol D40中的溶
液，與0.75克之一鎳觸媒混合，在20bars氫氣下，在高壓反應器中加熱，以1400rpm攪拌。當溫度一達到270℃時，將氫壓力增加到80bar。接下來的氫化製程係由記錄氫消耗來監控。氫化碳氫樹脂的觸媒之反應速率，係以反應速率常數來表示，係在30%和70%的轉化進行線性迴歸而得，且以1/h表示。2小時後，完成氫化製程。將實施例1-8中所述的觸媒進行上述的活性測試。這些測試結果，列於表1。實施例表1中的總重量百分比並沒有加到100wt.%，因為觸媒中的金屬被部分氧化，因此含有另外的氧原子。此氧含量並沒有列於以下的表1中。
表1顯示，相較於實施例2中非促進之觸媒和實施例1中鐵促進之觸媒，實施例3-8中本發明之觸媒具有改良的氫化反應速率和改良的對於S-毒化的容忍度。表1亦顯示，使用非常低的鈷含量(只有0.3wt%)(見表1，實施例3)，可得
到改良的S-容忍度。
圖1亦顯示，相較於實施例2中非促進之觸媒，實施例3-8中本發明之觸媒具有改良的氫化反應速率。
Claims (9)
- 一種用於碳氫樹脂進料之氫化的製程，該碳氫樹脂進料包括一種或多種硫化合物，該製程包括在觸媒的存在下將該碳氫樹脂進料與氫接觸的步驟，其中該觸媒為以鈷促進之承載於氧化矽和氧化鋁上之鎳觸媒，該以鈷促進之觸媒具有0.25至4wt%之鈷含量(以Co作計算)、45至85wt%之鎳含量(以Ni作計算)、13.75至45wt%之矽含量(以SiO2作計算)，以及1至15wt%之鋁含量(以Al2O3作計算)，依據還原之觸媒的重量為基礎，且其中該觸媒具孔洞直徑介於2和60nm之間的孔洞體積為至少0.35ml/g觸媒。
- 如申請專利範圍第1項之製程，其中該觸媒具孔洞直徑介於10和60nm之間的孔洞體積為至少0.20ml/g觸媒。
- 如申請專利範圍第1或2項之製程，其中該碳氫樹脂之硫化合物含量(以硫作計算)為大於40ppm，依據碳氫樹脂進料之重量為基礎。
- 一種以鈷促進之承載於氧化矽和氧化鋁上之鎳觸媒，其中該觸媒具有45至85wt%之鎳含量(以Ni作計算)、13.75至45wt%之矽含量(以SiO2作計算)、1至15wt%之鋁含量(以Al2O3作計算)，以及0.25至1.5wt%之鈷含量(以Co作計算)，依據還原之觸媒的重量為基礎，且其中該觸媒具孔洞直徑介於2和60nm之間的孔洞體積為至少0.35ml/g觸媒。
- 如申請專利範圍第4項之觸媒，其中該觸媒具孔洞直徑介於10和60nm之間的孔洞體積為至少0.20ml/g觸媒。
- 一種製備以鈷促進之承載於氧化矽和氧化鋁上之鎳觸媒的製程，其中該觸媒具有45至85wt%之鎳含量(以Ni作計算)、13.75至45wt%之矽含量(以SiO2作計算)、1至15wt%之鋁含量(以Al2O3作計算)，以及0.25至4wt%之鈷含量(以Co作計算)，依據還原之觸媒的重量為基礎，且其中該觸媒具孔洞直徑介於2和60nm之間的孔洞體積為至少0.35ml/g觸媒，該製程包括在pH值為7.0至9.0之下共沈澱一種或多種鎳鹽、鈷鹽、鋁鹽、和一種或多種矽化合物，接著由沈澱液體中回收該共沈澱物質，清洗它、以及處理它而製造該觸媒。
- 如申請專範圍第6項之製程，其中該觸媒之鈷含量(以Co作計算)為0.25至1.5wt%，依據還原之觸媒的重量為基礎。
- 如申請專利範圍第6或7項之製程，其中該觸媒具孔洞直徑介於10和60nm之間的孔洞體積為至少0.20ml/g觸媒。
- 一種如申請專利範圍第4或5項之觸媒之用途，其係用於碳氫樹脂之氫化作用。
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| KR102528310B1 (ko) * | 2019-06-28 | 2023-05-02 | 한화솔루션 주식회사 | 수소화반응용 촉매 및 이의 제조방법 |
| KR20210001784A (ko) | 2019-06-28 | 2021-01-06 | 한화솔루션 주식회사 | 수소화반응용 촉매 및 그 제조방법 |
| KR20210001783A (ko) * | 2019-06-28 | 2021-01-06 | 한화솔루션 주식회사 | 수소화반응용 니켈 촉매 및 그 제조방법 |
| EP3865558A1 (en) | 2020-02-14 | 2021-08-18 | BASF Corporation | Process for the hydrogenation of hydrocarbon resins using catalysts with protective coatings |
| EP3865210A1 (en) * | 2020-02-14 | 2021-08-18 | BASF Corporation | Aluminium-silicon-supported nickel-based catalyst, its precursor with high total intrusion volume, their preparation processes, and process for hydrogenation of petrochemical resins using said catalyst |
| EP4091711A1 (en) | 2021-05-21 | 2022-11-23 | BASF Corporation | A hydrogenation catalyst and its precursor comprising ni, al, and a support material comprising sio2 |
| CN114225940A (zh) * | 2021-12-27 | 2022-03-25 | 中国科学院兰州化学物理研究所 | 一种用于苯乙烯系热塑性弹性体加氢的非均相催化剂 |
| EP4215269A1 (en) | 2022-01-19 | 2023-07-26 | BASF Corporation | Packaged hydrogenation catalyst |
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| US4532351A (en) * | 1982-06-16 | 1985-07-30 | Exxon Research And Engineering Co. | Process for hydrogenating organic compounds by use of Group VIII aluminum-silicate catalysts |
| WO2001036093A1 (en) * | 1999-11-19 | 2001-05-25 | Engelhard Corporation | Nickel-iron-silica-alumina |
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| AU540819B2 (en) * | 1981-02-04 | 1984-12-06 | Exxon Research And Engineering Company | Catalyst containing group 8 noble metal,aluminium its use for hydrogenation |
| US4593014A (en) * | 1982-06-16 | 1986-06-03 | Exxon Research And Engineering Co. | Catalyst support compositions |
| US5820749A (en) * | 1996-11-22 | 1998-10-13 | Exxon Chemical Patents, Inc. | Hydrogenation process for unsaturated hydrocarbons |
| US6162350A (en) * | 1997-07-15 | 2000-12-19 | Exxon Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901) |
| DE60030590T2 (de) | 1999-11-02 | 2007-09-13 | Engelhard Corp. | Hydrierung von kohlenwasserstoffharzen |
| KR20050072109A (ko) | 2002-10-18 | 2005-07-08 | 엥겔하드 코포레이션 | 수소첨가 반응을 위한 니켈 촉매 |
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2014
- 2014-07-17 CA CA2918454A patent/CA2918454C/en active Active
- 2014-07-17 EP EP14766808.1A patent/EP3021967B1/en active Active
- 2014-07-17 CN CN201480045236.5A patent/CN105682797B/zh active Active
- 2014-07-17 WO PCT/IB2014/063181 patent/WO2015008247A2/en active Application Filing
- 2014-07-17 JP JP2016526746A patent/JP6250156B2/ja active Active
- 2014-07-17 DK DK14766808.1T patent/DK3021967T3/da active
- 2014-07-17 KR KR1020167002156A patent/KR101797406B1/ko active IP Right Grant
- 2014-07-17 AR ARP140102643A patent/AR096953A1/es unknown
- 2014-07-17 US US14/904,793 patent/US9644044B2/en active Active
- 2014-07-17 TW TW103124495A patent/TWI637001B/zh active
- 2014-07-17 BR BR112016000768-9A patent/BR112016000768B1/pt active IP Right Grant
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- 2016-01-25 ZA ZA2016/00529A patent/ZA201600529B/en unknown
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| US4532351A (en) * | 1982-06-16 | 1985-07-30 | Exxon Research And Engineering Co. | Process for hydrogenating organic compounds by use of Group VIII aluminum-silicate catalysts |
| WO2001036093A1 (en) * | 1999-11-19 | 2001-05-25 | Engelhard Corporation | Nickel-iron-silica-alumina |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015008247A3 (en) | 2015-04-16 |
| CA2918454C (en) | 2019-02-12 |
| KR101797406B1 (ko) | 2017-11-13 |
| KR20160040177A (ko) | 2016-04-12 |
| JP2016531977A (ja) | 2016-10-13 |
| EP3021967B1 (en) | 2018-11-21 |
| US20160159941A1 (en) | 2016-06-09 |
| WO2015008247A2 (en) | 2015-01-22 |
| DK3021967T3 (da) | 2019-08-26 |
| AR096953A1 (es) | 2016-02-10 |
| ZA201600529B (en) | 2017-05-31 |
| CN105682797B (zh) | 2018-05-18 |
| EP3021967A2 (en) | 2016-05-25 |
| CA2918454A1 (en) | 2015-01-22 |
| US9644044B2 (en) | 2017-05-09 |
| CN105682797A (zh) | 2016-06-15 |
| BR112016000768B1 (pt) | 2021-03-23 |
| TW201509971A (zh) | 2015-03-16 |
| JP6250156B2 (ja) | 2017-12-20 |
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