JP5502192B2 - 水素化変換多金属触媒及びその作製方法 - Google Patents
水素化変換多金属触媒及びその作製方法 Download PDFInfo
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- JP5502192B2 JP5502192B2 JP2012508735A JP2012508735A JP5502192B2 JP 5502192 B2 JP5502192 B2 JP 5502192B2 JP 2012508735 A JP2012508735 A JP 2012508735A JP 2012508735 A JP2012508735 A JP 2012508735A JP 5502192 B2 JP5502192 B2 JP 5502192B2
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 210000004317 gizzard Anatomy 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- B01J35/30—
-
- B01J35/31—
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- B01J35/60—
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- B01J35/613—
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- B01J35/615—
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- B01J35/633—
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- B01J35/647—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—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
- 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
- C10G45/08—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 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
IV型吸着脱着等温線を有する触媒前駆体は、硫化することで触媒に変換され(触媒活性になり)、続く水素化脱硫(HDS)、水素化脱芳香族(HDA)及び水素化脱窒素(HDN)プロセスの使用に供される。触媒前駆体は、少なくとも1つの助触媒金属前駆体及び少なくとも1つのVIB族金属前駆体から調製される、水酸化物又は酸化物の物質であってもよい。
参照は図1によってなされ、これはIV型吸着等温線を示す触媒前駆体から嵩高触媒を作製する一般的プロセスの実施態様を概略的に示すブロック図である。
プロセスの最初のステップ10は、沈殿又は共ゲル化ステップであり、金属前駆体11、例えば助触媒金属成分(単数又は複数)及びVIB族金属成分の混合物において反応させて、沈殿物又は共ゲル化物を得ることに関わる。用語「共ゲル化物」は、少なくとも2つの金属化合物の共沈殿物(又は沈殿物)を意味する。金属前駆体を、固体、溶液、懸濁液又はこれらの組み合わせとして反応混合物に加えることができる。可溶性塩がそのまま添加される場合、これらは反応混合物に溶解し、続いて沈殿するか若しくは共ゲル化するか又は懸濁液を形成する。溶液を、任意選択で真空下で加熱して、沈殿及び液体の蒸発を実施することができる。
次のステップ20において、少なくとも50重量%の液体(上澄み/水)が、当業界で既知の分離プロセス、例えば、濾過、デカント、遠心分離などを介して沈殿物(又は懸濁液)から除去される。一実施態様において、沈殿物における液体は、真空技術又は当業界で既知の装置による濾過によって除去されて、湿潤フィルターケーキを得る。湿潤フィルターケーキは、一般に、およそ10〜50重量%の液体を有するフィルターケーキとして定義され、したがって一般に水又は他の溶媒、例えばメタノールなどを含まない。
このステップ30において、フィルターケーキは、水、並びに造形助剤32、解膠剤、孔形成剤及び希釈物質13が含まれるが、これらに限定されない他の任意選択の物質と一緒に混合される。一実施態様において、前の操作からのフィルターケーキ物質、前駆体物質の押出軟塊及び/又は乾燥粒子/断片の形態の再処理物質を、物質群に任意選択で含めて、触媒前駆体ミックスの新たなバッチを形成することができる。一実施態様において、水の量及び/又は任意選択の物質の量/種類を変えて、形成される触媒前駆体のメソ多孔性を制御及び/又は調整する。一実施態様において、水の添加は、触媒前駆体の表面積を増大させることに役立つ。
このステップ40において、触媒前駆体ミックスは、ペレット化、押し出し、錠剤化、成形、混転、加圧、噴霧及び噴霧乾燥を含む当業界で既知の方法のいずれかを使用して、形成粒子、例えば長球、丸剤、錠剤、円柱、不規則押出物、単にゆるく結合した凝集体又は集合体などに造形される。
一実施態様において、造形触媒前駆体は、熱処理ステップ50を受ける。一実施態様において、触媒前駆体は、直接又は間接加熱オーブン、トレー乾燥機又はベルト乾燥機により、約50℃〜325℃で約15分間から24時間空気(又は窒素)乾燥され、ここで温度は、1分あたり1〜50℃の速度で室温から乾燥温度である。一実施態様において、温度は、1分あたり1〜2℃のゆっくりとした速度で昇温する。第2の実施態様において、空気乾燥は、1分あたり少なくとも25℃の大きな昇温速度で実施される。一実施態様において、乾燥は、100℃又はそれ未満の温度である。
元素硫黄それ自体;優勢な条件下で分解して硫化水素になる硫黄含有化合物;H2Sそれ自体又は任意の不活性若しくは還元条件下のH2S、例えばH2の群から選択される少なくとも1つの硫化剤62の使用により、硫化ステップ60において、造形触媒前駆体(任意選択の再処理物質と共に)を硫化して、活性触媒を形成することができる。硫化剤の例には、硫化アンモニウム、ポリ硫化アンモニウム((NH4)2Sx)、チオ硫酸アンモニウム((NH4)2S2O3)、チオ硫酸ナトリウム(Na2S2O3)、チオ尿素(CSN2H4)、二硫化炭素、ジメチルジスルフィド(DMDS)、硫化ジメチル(DMS)、ジブチルポリスルフィド(DBPS)、メルカプタン、第三級ブチルポリスルフィド(PSTB)、第三級ノニルポリスルフィド(PSTN)などが含まれる。一実施態様において、炭化水素原料が、触媒前駆体の硫化を実施するための硫黄供給源として使用される。
触媒前駆体は、時々、その場で(in−situで)、例えば水素化処理の際に同じ水素化処理反応器において硫化されうるので、触媒性能は、硫化前の触媒前駆体の特性により特徴付けることができる。
式:(NH4){[Ni2.6(OH)2.08(C4H2O4 2−)0.06](Mo0.35W0.65O4)2}の触媒前駆体を、以下のように調製した:954.8gのヘプタモリブデン酸アンモニウム(NH4)6Mo7O24・4H2Oを、4.8Lの脱イオン水に室温で溶解した。得られた溶液のpHは2〜3の範囲内であった。1334gのメタタングステン酸アンモニウム(NH4)6H2W12O40・4.7H2Oを、1.3Lの水に溶解した。モリブデン酸塩及びタングステン酸塩溶液を、34.9Lの脱イオン水に加えた。この混合モリブデン酸塩及びタングステン酸塩溶液に、2.03Lの7.0重量%のNH4OH(アンモニア)溶液を加え、常に撹拌しながら、温度を77℃に上げた。溶液は、8〜10の範囲のpHを有した。2.7Lの脱イオン水に溶解した3149gのNi(NO3)2・6H2Oを含有する第2溶液を調製した。このニッケル溶液に、1.2Lの28重量%のNH4OH溶液、続いて0.25Lの脱イオン水中の108gのマレイン酸の溶液を加えた。次にニッケル溶液を、モリブデン酸塩/タングステン酸塩溶液に、温度を77℃に維持しながら10分間かけて加えた。得られた混合物を77℃で保持し、撹拌を1時間続けた。懸濁液のpHは6〜7の範囲であった。0.72Lの7.0重量%のNH4OH溶液を添加し、60℃に冷却した後、青緑色の沈殿物を濾過により収集し、フィルタープレスにより150psiで加圧することにより乾燥した。収集し、加圧された沈殿物を、密閉容器において50℃で15時間熟成させた。熟成の後、沈殿物を4重量%のメトセルと混合し、45重量%の強熱減量(LOI)及び1500psiの空洞を示すまで50℃で乾燥し、NAQダイを持つWolfスクリュー押出機で押し出した。
式:(NH4){[Ni2.6(OH)2.08(C4H2O4 2−)0.06](Mo0.35W0.65O4)2}の触媒前駆体を、以下のように調製した:477.2gのヘプタモリブデン酸アンモニウム(NH4)6Mo7O24・4H2Oを、2.9Lの脱イオン水に室温で溶解した。666.6gのメタタングステン酸アンモニウム(NH4)6H2W12O40・4.7H2Oを、0.67Lの水に溶解した。モリブデン酸塩及びタングステン酸塩溶液を、15.4Lの脱イオン水に加えた。この混合モリブデン酸塩及びタングステン酸塩溶液に、1.9Lの7.0重量%のNH4OH(アンモニア)溶液を、pHが9〜10の範囲に達するように加えた。この後、温度を、常に撹拌しながら76℃に増加させた。1.5Lの脱イオン水に溶解した1575gのNi(NO3)2・6H2Oを含有する第2溶液を調製した。次にニッケル溶液を、モリブデン酸塩/タングステン酸塩溶液に、温度を76℃に維持しながら25分間かけて加えた。得られた混合物を76℃で保持し、30分間撹拌した。続いて、95gのマレイン酸を懸濁液に加え、撹拌を更に30分間続けた。懸濁液のpHは5〜6の範囲であった。60℃に冷却した後、青緑色の沈殿物を濾過により収集し、フィルタープレスにより150psiで30分間加圧することにより乾燥した。50重量%の強熱減量(LOI)及び800psiの空洞で、沈殿物を4重量%のMethocel(商標)と混合し、NAQダイを持つWolfスクリュー押出機で押し出した。
式:(NH4){[Ni2.6(OH)2.08(C4H2O4 2−)0.06](Mo0.35W0.65O4)2}の触媒前駆体を、以下のように調製した:954.4gのヘプタモリブデン酸アンモニウム(NH4)6Mo7O24・4H2Oを、5.8Lの脱イオン水に室温で溶解した。1333gのメタタングステン酸アンモニウム(NH4)6H2W12O40・4.7H2Oを、1.3Lの水に溶解した。モリブデン酸塩及びタングステン酸塩溶液を、15.0Lの脱イオン水に加えた。この混合モリブデン酸塩及びタングステン酸塩溶液に、5.0Lの7.0重量%のNH4OH(アンモニア)溶液を、pHが9.8に達するまで加えた。6.38Lの脱イオン水に溶解した2835gのNi(NO3)2・6H2Oを含有する第2溶液を調製した。第3の溶液は、284.9gのNi(SO4)・6H2Oを2.0Lの水に溶解することにより調製し、続いて濃硫酸によりpHを1.0に調整した。2つのニッケル溶液を合わせた後、0.60Lの水に溶解した110.0gのマレイン酸をニッケル溶液に加えた。混合モリブデン酸塩/タングステン酸塩溶液を、直列型高剪断混合機によりニッケル溶液と合わせ、合わせた溶液を9.78Lの脱イオン水に排出した。得られた懸濁液を連続的に撹拌し、77℃で維持した。この懸濁液のpHを、7.0重量%のNH4OH溶液の添加により6.5に上昇させ、77℃での連続的な撹拌により90分間老化させた。青緑色の沈殿物を濾過により収集し、5000psiの空洞になるまで115℃で乾燥した。続いて、ペーストを湿潤して、1500psiの空洞にし、4重量%のMethocel(商標)を加え、ペーストを、NAQダイを持つWolfスクリュー押出機で押し出した。
Claims (15)
- 水素化プロセシング条件下で炭化水素供給原料を水素化処理するための非担持多金属触媒を、硫化することで形成する触媒前駆体であって、
少なくとも1つのVIB族金属化合物;
VIII族、IIB族、IIA族、IVA族及びこれらの組み合わせから選択される、少なくとも1つの助触媒金属化合物;
を含み、
窒素のIV型吸着脱着等温線を持ち、0.35のヒステリシス起点値P/Poを有し、積層が不規則であり、不十分な結晶構造を有することによって特徴付けられる触媒前駆体。 - H3型ヒステリシスループを有する、請求項1に記載の触媒前駆体。
- ヒステリシスループが、0.55のP/Poを超えて十分に展開している平坦域を有する、請求項1に記載の触媒前駆体。
- 25〜400m2/gの範囲のBET表面積のメソ多孔性構造を有することによって特徴付けられる、請求項1に記載の触媒前駆体。
- BET表面積が40〜200m2/gの範囲である、請求項1から4までのいずれか一項に記載の触媒前駆体。
- 2nm〜200nmの範囲の平均孔径のメソ多孔性構造を有することによって特徴付けられる、請求項1から4までのいずれか一項に記載の触媒前駆体。
- 平均孔径が10〜125mnの範囲である、請求項1から4までのいずれか一項に記載の触媒前駆体。
- 孔容積が0.01〜0.50cm3/gの範囲である、請求項1から4までのいずれか一項に記載の触媒前駆体。
- 孔容積が0.02〜0.20cm3/gの範囲である、請求項1から4までのいずれか一項に記載の触媒前駆体。
- 少なくとも100℃の温度で少なくとも30分間硫化することで、10%未満の残留幾何学量体積収縮率(硫化の前後の触媒前駆体の幾何学量体積の変化を意味する)を有する、請求項1から4までのいずれか一項に記載の触媒前駆体。
- 最大1.6g/ccの圧縮嵩密度を有する、請求項1から4までのいずれか一項に記載の触媒前駆体。
- 少なくとも1つの配位剤L及び少なくとも1つの希釈剤を更に含む、請求項1から4までのいずれか一項に記載の触媒前駆体。
- 式:Av[(MP)(OH)x(L)n y]z(MVIBO4)[式中、
Aは、アルカリ金属カチオン、アンモニウム、有機アンモニウム及びホスホニウムカチオンのうちの少なくとも1つであり;
MPは、少なくとも1つの助触媒金属化合物であり、MPは、VIII族、IIB族、IIA族、IVA族及びこれらの組み合わせから選択され;
Lは、少なくとも1つの配位剤であり;
MVIBは、+6の酸化状態を有する少なくとも1つのVIB族金属であり;
MP:MVIBは、100:1〜1:100の原子比を有し;
v−2+P*z−x*z+n*y*z=0;0≦y≦−P/n;0≦x≦P;0≦v≦2;0≦zである。]で表される、請求項1から4までのいずれか一項に記載の触媒前駆体。 - MPが、少なくとも1つのVIII族金属であり、MVIBが、モリブデン、タングステン及びこれらの組み合わせから選択され、Lが、カルボキシレート、エノレート及びこれらの組み合わせのうちの少なくとも1つである、請求項13に記載の触媒前駆体。
- 式:(X)b(M)c(W)dOz[式中、Mは、少なくとも1つのVIB族金属化合物であり、Xは、Ni及びCoの群から選択される少なくとも1つの助触媒金属であり、b:(c+d)のモル比は0.5/1〜3/1であり、c:dのモル比は>0.01/1であり、かつz=[2b+6(c+d)]/2である。]で表される、請求項1から4までのいずれか一項に記載の触媒前駆体。
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