TWI558806B - 在沸騰床反應器系統中處理減壓渣油以及減壓瓦斯油的製程 - Google Patents
在沸騰床反應器系統中處理減壓渣油以及減壓瓦斯油的製程 Download PDFInfo
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- TWI558806B TWI558806B TW104104821A TW104104821A TWI558806B TW I558806 B TWI558806 B TW I558806B TW 104104821 A TW104104821 A TW 104104821A TW 104104821 A TW104104821 A TW 104104821A TW I558806 B TWI558806 B TW I558806B
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- Prior art keywords
- oil
- hydrocarbon
- hydrocarbons
- catalyst
- heavy
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- 229930195733 hydrocarbon Natural products 0.000 claims description 114
- 150000002430 hydrocarbons Chemical class 0.000 claims description 104
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 92
- 239000004215 Carbon black (E152) Substances 0.000 claims description 81
- 239000003054 catalyst Substances 0.000 claims description 81
- 239000003921 oil Substances 0.000 claims description 77
- 239000007789 gas Substances 0.000 claims description 62
- 239000001257 hydrogen Substances 0.000 claims description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 52
- 239000010457 zeolite Substances 0.000 claims description 49
- 229910021536 Zeolite Inorganic materials 0.000 claims description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 32
- 238000009835 boiling Methods 0.000 claims description 21
- 230000005587 bubbling Effects 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 238000005194 fractionation Methods 0.000 claims description 16
- 239000012263 liquid product Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- -1 hydrocarbon hydrocarbons Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 239000010953 base metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010779 crude oil Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010426 asphalt Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000003784 tall oil Substances 0.000 claims description 3
- 239000011275 tar sand Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000012013 faujasite Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- 239000010815 organic waste Substances 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 239000010724 circulating oil Substances 0.000 claims 1
- 238000004939 coking Methods 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000003079 shale oil Substances 0.000 claims 1
- 210000002268 wool Anatomy 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
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- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- C—CHEMISTRY; METALLURGY
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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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- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
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- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
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- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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- C10G47/12—Inorganic carriers
- C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
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- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/30—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles according to the "fluidised-bed" technique
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- 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
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- 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
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- C10G49/10—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 with moving solid particles
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- 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
- 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
- C10G49/10—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 with moving solid particles
- C10G49/16—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 with moving solid particles according to the "fluidised-bed" technique
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- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
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Description
本發明關於一種加氫轉化過程，包括用以提高減壓渣油、減壓瓦斯油以及其他重碳氫化合物餾分的製程。本發明特別是關於在沸騰床殘留物加氫轉化單元以及沸騰床加氫裂解單元中分別處理該減壓渣油以及減壓瓦斯油。
由於汽油和其它餾分煉油廠產品如煤油、航空用油和柴油的全球需求正穩步增加，出現了朝著轉換的高沸點化合物為較低沸點化合物的一個顯著的趨勢。為了滿足對餾出燃料的需求不斷增加，精煉者已經研究了許多反應，如加氫裂解渣油、轉化減壓瓦斯油(VGO)和其它重石油原料為航空和柴油燃料。
滴流床(Trickle-bed)，在其中一個反應器中裝有非均相催化劑顆粒且與液體碳氫化合物和氫氣共同進料的三相反應器代表在石油精煉和石化工業中所使用的關鍵的反應器類型中的一種。滴流床反應器具有對氫氣的富相的擴散速率進入液體碳氫化合物相，以及含有溶解的氫的液體碳氫化合物相進入固體催化相的擴散限制。也有控制溫度上升、裝載催化劑以及不同的產品質量使連續的催化劑在一個週期內失活(deactivation)
的結果的困難。也有結垢/堵塞在入口區域中的催化劑，由於進入的液體和氣體流的動能伴隨活性位置的細孔口被堵塞的催化劑所造成的催化劑顆粒的磨損。
沸騰床反應器是漿質加氫裂解技術渣油原料之下的所因應而生的器具。催化劑已開發出對於重質原料具有優越的餾分選擇性，合理轉化活性和穩定性。然而各種製程中可達到的轉化率是有限的，儘管如此，還是需要經濟的製程以實現高碳氫化合物轉換。
在一方面，此處公開的實施例關於一種提高渣油碳氫化合物以及重餾出原料的製程。該製程包括使渣油碳氫化合物和氫在一第一沸騰床加氫轉化反應器系統內與一非沸石卑金屬加氫轉化催化劑(non-zeolitic base metal hydroconversion catalyst)接觸，以製造一第一流出物。從該第一沸騰床加氫轉化反應器流出的該第一流出物係被分餾，以回收一液態產物以及一蒸汽產物。該蒸汽產物和一重餾出原料在一第二沸騰床加氫裂解反應器系統中與一沸石選擇性加氫裂解催化劑(zeolitic selective hydrocracking catalyst)接觸，以製造一第二流出物。從該第二沸騰床加氫裂解反應器系統流出的該第二流出物係被回收且分餾，以回收一或多個碳氫化合物餾分(hydrocarbon fractions)。
在另一方面，此處公開的實施例關於一種提高重餾出原料的製程，藉由氫和該重餾出原料在一沸騰床加氫裂解反應系統中與一沸石選擇性加氫裂解催化劑接觸，以製造一流出物。自該沸騰床加氫裂解反應器系統流出的該流出物被回收並分餾，以回收一或多個碳氫化合物餾分。
在另一方面，此處公開的實施例關於一種提高渣油碳氫化合物以及重餾出原料的系統。該系統包含一第一沸騰床加氫裂解反應器系統，其容納一沸石選擇性加氫裂解催化劑用以反應該重餾出原料和氫，以製造一第一流出物；以及一第一分餾單元用以分餾該第一流出物，以回收一或多個碳氫化合物餾分。
其他方面及優勢將從以下說明和所附申請專利範圍可清楚了解。
4‧‧‧該含瓦斯油流
10‧‧‧渣油碳氫化合物
12‧‧‧加熱器
14‧‧‧熱渣油碳氫化合物餾分
15‧‧‧熱氫流
16‧‧‧氫流
18‧‧‧加熱器
20‧‧‧第一沸騰床加氫轉化反應器系統
22‧‧‧流程線
40‧‧‧第二沸騰床加氫裂解反應器系統
46‧‧‧分餾系統
47‧‧‧吸收塔
48‧‧‧蒸汽餾分
49‧‧‧蒸汽餾分
50‧‧‧液態產物
52‧‧‧重餾出原料
54‧‧‧中間餾出物富含瓦斯油流
60‧‧‧氫氣
66‧‧‧流出物
146‧‧‧分餾系統
148‧‧‧排出氣體
150‧‧‧輕石腦油餾分
152‧‧‧重石腦油餾分
154‧‧‧煤油餾分
156‧‧‧柴油餾分
158‧‧‧輕減壓瓦斯油餾分
160‧‧‧重瓦斯油餾分
第1圖：本發明一實施例之用於提高渣油以及重餾出碳氫原料的製程之簡化流程圖。
在一方面，在此的實施例一般關於加氫轉化製程，包含加氫裂解殘留物、減壓瓦斯油以及其他重碳氫化合物餾分的製程。更特別的是，在此公開的實施例係關於在一第一沸騰床加氫轉化單元中處理一渣油碳氫化合物原料，該第一沸騰床加氫轉化單元容納一卑金屬加氫轉化催化劑；分離該流出物以回收一蒸汽產物；以及在一第二沸騰床加氫裂解單元中處理該蒸汽產物和減壓瓦斯油，該第二沸騰床加氫裂解單元容納有選擇性加氫裂解催化劑。
在此公開的加氫轉化(Hydroconversion)製程可在高溫度及壓力的環境中，當氫以及一或多個加氫轉化催化劑存在時，用來反應渣油碳氫化合物原料以及減壓瓦斯油，以轉化該原料成為較低分子重量的產
物，伴隨降低的污染物(例如硫及/或氮)等級。加氫轉化製程可包含，例如，氫化(hydrogenation)、加氫脫硫(hydrodesulfurization)、加氫脫氮(hydrodenitrogenation)、加氫裂解(hydrocracking)、加氫脫氧(hydrodeoxygenation)、加氫脫金屬(hydrodemetallization)、加氫脫康拉遜殘碳(hydroDe Conradson Carbon Residue)或加氫脫瀝青(hydrodeasphaltenization)等等。
在此所使用的渣油碳氫化合物餾分或是其他意指渣油碳氫化合物的相似用語，係定義為一碳氫化合物餾分具有沸點或一沸騰範圍在大約340℃以上，但也可以包含全部重原油加工。可被使用在此處公開的製程中的渣油碳氫化合物原料可包含不同精煉廠及其他碳氫化合物流，如石油常壓或減壓渣油、脫瀝青油(deasphalted oils)、脫瀝青器瀝青(deasphalter pitch)、加氫裂解常壓塔或減壓塔底層(hydrocracked atmospheric tower or vacuum tower bottom)、流體裂解觸媒漿質油(fluid catalytically cracked slurry oils)、頁岩衍生油所衍生的渣油(residua derived from one or more of shale-derived oils)、煤衍生油(coal-derived oils)、焦油砂瀝青(tar sands bitumen)、妥爾油(tall oils)、生物衍生原油(bio-derived crude oils)、黑油(black oils)以及其他相似的碳氫化合物流，或這些的結合，其中的每一個可為直餾、製程衍生、加氫裂解、部分脫硫及/或部分脫金屬的碳氫化合物流。在一些實施例中，渣油碳氫化合物餾分可包括碳氫化合物具有一正常沸點至少480℃、至少524℃或至少565℃。如在此所使用的重餾出原料或是其他意指蒸餾碳氫化合物的相似用語，係定義為一碳氫化合物餾分具有沸點或一沸騰範圍在大約565℃以下。可被使用在此處公開的製程中的重餾
出原料可包含不同精煉廠及其他碳氫化合物流，如石油瓦斯油、直餾減壓瓦斯油、加氫裂解減壓瓦斯油、自一沸騰床加氫轉化製程而來之減壓瓦斯油、自一或多個頁岩衍生油衍生之瓦斯油、煤衍生油、焦油砂瀝青、妥爾油、生物衍生原油、黑油以及其他相似的碳氫化合物流，或這些的結合，其中的每一個可為直餾、製程衍生、加氫裂解、部分脫硫及/或部分脫金屬的碳氫化合物流。
在此公開的實施例可利用選擇性加氫裂解催化劑於餾出物進料之沸騰床反應器系統，以加氫裂解減壓瓦斯油流。這些沸騰床反應器系統可包含選擇性沸石帶有與金屬氫化成分一起載入之加氫裂解催化劑。該催化劑可被設計為具有好的流態化性質以及磨損抗性和選擇性加氫裂解效能的特性。沸騰床系統吸收反應熱能作為該進入系統的瓦斯油流的焓(enthalpy)，且該沸騰床實質上在等溫環境下操作，因為藉由該沸騰幫浦的能量可供應較佳的熱(和質量)的轉移。瓦斯油流進料和該等溫沸騰床溫度之間可允許的溫度分布範圍可從大約50到150℃、大約75到125℃或從大約90到100℃。再者，該沸騰床反應器可以在大致上均勻的催化劑溫度下運行整個循環週期，不像那些典型的固定床加氫反應器。
在一些實施例中，一上游渣油進料(resid-fed)沸騰床加氫轉化反應器系統可製造一高溫/高壓蒸汽流，其可以被注入到該餾出物進料沸騰床加氫裂解系統。在另外可選的實施例中，多個沸騰床系統可用於一普通產物回收系統的進料。
在一些實施例中，該沸騰床選擇性加氫裂解系統提供氫化放熱反應的熱的移除而不需要像在滴流床(trickle-bed)加氫裂解反應器中
再壓縮和再循環富含氫的氣體作為冷淬(cold quench)。該沸騰床選擇性加氫裂解系統也可以使用可流態化且抗磨損的選擇性加氫裂解催化劑。
此處實施例一般關於一種提高渣油碳氫化合物以及重餾出原料的製程。該製程可包括使渣油碳氫化合物和氫在一第一沸騰床加氫轉化反應器系統內與一非沸石卑金屬加氫轉化催化劑接觸，以製造一第一流出物。自該第一沸騰床加氫轉化反應器中流出的該第一流出物可被分餾，以回收一液態產物和一蒸汽產物。使該蒸汽產物和該重餾出原料可在一第二沸騰床加氫裂解反應器系統中與一沸石選擇性加氫裂解催化劑接觸，以製造一第二流出物。該第二流出物可自該第二沸騰床加氫裂解反應器系統被回收及分餾，以回收一或多個碳氫化合物餾分。在另外的實施例中，該被回收的蒸汽產物可在進一步於該第二沸騰床加氫裂解反應器系統加工之前，先在一吸收管柱中處理以去除中間餾出產物。
在一些實施例中，描述了一種提高重餾出原料的製程，該製程可包含使氫和該重餾出原料在一沸騰床加氫裂解反應器系統中與一沸石選擇性加氫裂解催化劑接觸，以製造一流出物。從該沸騰床加氫反應器系統流出的該流出物可被回收及分餾，以回收一或多個碳氫化合物餾分。在其他實施例中，一渣油碳氫化合物原料和氫可在一第二沸騰床加氫轉化反應器系統中與一非沸石卑金屬加氫轉化催化劑接觸，以製造一第二流出物，該第二流出物可被分餾以回收一液態產物和一蒸汽產物。該蒸汽產物可隨著該氫和重餾出物被注入到該沸騰床加氫裂解反應器系統。
現在參考第1圖，一渣油碳氫化合物10，如渣油，係被注入到一加熱器12。在加熱器12中，該渣油碳氫化合物被加熱以製造一熱渣
油碳氫化合物餾分14，其具有一溫度範圍從250到大約360℃。一氫流16可被注入到一加熱器18，以製造一熱氫流15，其具有一溫度範圍從250到大約520℃。在一些實施例中，一單一加熱器可被使用但分開管線是必須的。該熱渣油碳氫化合物餾分14和該熱氫流15可結合且被注入到一第一沸騰床加氫轉化反應器系統20，該第一沸騰床加氫轉化反應器系統20可包含一或多個沸騰床加氫轉化反應器，該碳氫化合物和氫可在其中與一加氫轉化催化劑接觸而使至少一部份的該渣油碳氫化合物和氫反應，以形成較輕的碳氫化合物、使該瀝青碳氫化合物脫金屬化、除去康拉遜殘碳或轉化該渣油為有用的產物。
在該第一沸騰床加氫轉化反應器系統20的反應器可在溫度從200到大約600℃、300到大約500℃、350到大約475℃或380到大約450℃的範圍中操作，氫分壓的範圍從大約5到大約250 bara、大約25到大約200 bara、大約50到大約175 bara或大約70到大約150 bara，且每小時液體空間速度(liquid hourly space velocities，LHSV)範圍在每小時大約0.1到大約5、大約0.15到大約3或從大約0.2到大約2.0。在該沸騰加氫轉化床反應器內，該催化劑可藉由該液態產物的再循環被回混且維持於一隨機運動狀態。這可以藉由自該氣態產物中先分離出該再循環的油而被實現。該油可接著以一外部幫浦的方式被再循環，或者，如圖所示，藉由具有一推動器架設在該反應器底端的一幫浦來達成。
在該沸騰床加氫轉化反應器系統中，該催化劑係被埋沒於液體中且不斷移動和彼此碰撞。該催化劑的運動提供該催化劑的外表面變成可用於和他們懸浮於其中的液體進行反應。該沸騰床加氫轉化反應器系
統可在接近恆溫反應溫度下操作。恆溫反應溫度可導致對中間餾出產物具有較高的選擇性。
在該第一沸騰床加氫轉化反應系統20中的目標轉化率可為至少大約50%、至少60%或至少約70%，視該被加工的原料而定。在任何程序中，目標轉化率應該被維持在沉積物形成過量的程度以下，藉此預防操作的連續性。轉化率可被定義為在高於至少480℃、至少524℃或至少565℃以上沸騰的材料的消失，在一ASTM D1160蒸餾重碳氫化合物的混合物中。除了轉化該渣油碳氫化合物為較輕的碳氫化合物，硫的脫除可在大約40重量%到大約80重量%的範圍，金屬的脫除可在大約60重量%到大約85重量%的範圍，且康拉遜殘碳(CCR)的脫除可在大約30重量%到大約65重量%的範圍。
根據在此公開的實施例可被使用於該第一沸騰床加氫轉化系統20的非沸石的加氫轉化催化劑組合物是所屬領域已知的，且多數是可以商業上從W.R.Grace & Co.、Criterion Catalyst & Technologies以及Albemarle或其他處獲得。適當的非沸石加氫轉化催化劑可包含一或多個元素選自於元素週期表中的4-12族。在一些實施例中，根據在此公開的實施例之非沸石加氫轉化催化劑可包含一或多個鎳、鈷、鎢、鉬以及其組合，可以未支撐或有支撐的形成於一多孔基材如二氧化矽、氧化鋁、二氧化鈦或其組合。當從一製造商供應或從一再生處理後獲得，該非沸石加氫轉化催化劑可以是金屬氧化物的型態，舉例來說。在一些實施例中，該非沸石加氫轉化催化劑可在導入該沸騰床加氫轉化反應器之前被預先硫化及/或預先調整。
接著在該第一沸騰床加氫轉化反應器系統20中轉化，該部分轉化的碳氫化合物可經由流程線22被回收為一混合蒸汽/液態流出物，且注入到一分餾系統46，以回收一或多個碳氫化合物餾分。在流程線22中的該部分轉化的碳氫化合物可為一種氫的混合物、硫化氫及其他酸性氣體以及一廣範圍的加氫裂解碳氫化合物包括石腦油(naphtha)、煤油(kerosene)、航空用油(jet)、柴油(diesel)以及輕柴油(gasoil)系列材料。如圖所示，分餾系統46可被使用於回收含有未轉化的氫、酸性氣體和揮發的碳氫化合物的一蒸汽餾分48以及一液態產物50。在一些實施例中，該液態產物50可被循環進一步處理，例如到該第一沸騰床加氫轉化反應器系統20，或其他反應單元。在其他實施例中，液態產物50可與一餾出的餾分混合以製造一燃料油。
分餾系統46可包含例如一高壓高溫(HP/HT)分離器，以分離該流出蒸汽和該流出液體。被分離的蒸汽可按規劃流程路線經過氣體冷卻、純化以及循環氣體壓縮，或者，如圖所示，可以在被注入到包含選擇性沸石加氫裂解催化劑的該第二沸騰床加氫裂解反應器之前，先經過一吸收塔47處理，以除去中間餾出產物。
自該HP/HT分離器被分離的該液態產物50可被迅速且按照規劃流程路線導入一常壓蒸餾系統(未繪示)伴隨從該氣體冷卻和純化區中回收的其他餾出產物。該常壓塔底層，如具有一初始沸點至少大約340℃，例如初始沸點在大約340℃到大約427℃的碳氫化合物的範圍，可接著經過一減壓蒸餾系統被進一步處理，以回收減壓餾出物。
如第1圖所示，該蒸汽餾分48被送至一吸收塔47，在其中
可以逆流方式與一含瓦斯油流4接觸以吸收在第一沸騰床反應器加氫轉化系統20製造出來而包含於蒸汽餾分48的中間餾出產物。一第二蒸汽流49被產出可少量存在於中間餾出物含量中。一中間餾出物富含瓦斯油流54可被送到下游分餾，其中該中間餾出物可被回收作為產物，且該含瓦斯油流的部份則可被循環並與該含瓦斯油流4混合。該吸收塔47可為任意形式的質量轉移裝置，其包含但不限於填充床、噴霧塔、板式塔(tray towers)、賽貝爾管柱(Scheibel columns)或微流道接觸器(microchannel contactors)。
混合第二蒸汽流49與一重餾出原料52，如減壓瓦斯油(VGO)，且注入一第二沸騰床加氫裂解反應器系統40，包括一或多個沸騰床加氫裂解反應器，該重餾出原料52和氫可在其中與一選擇性加氫裂解催化劑接觸，使至少一部分的該重餾出原料52和氫進行加氫裂解，以形成中間餾出物及較輕的碳氫化合物，或者轉化該重餾出原料成為可使用的產物。藉著使用該氫在該蒸汽餾分49中，一分離氫的壓縮迴圈可被避免。在一些實施例中，額外的氫可被注入系統，當有需要的時候，經由流體60，其可與該蒸汽餾分49和重餾出原料52結合。在一些實施例中，該蒸汽餾分49可維持該第二沸騰加氫裂解床反應器系統40入口處的分壓在大約134到141 bara氫氣的壓力範圍。在一些實施例中，可提供額外的氫到該第二沸騰床加氫裂解反應器系統40中，該第二沸騰床加氫裂解反應器系統40可支持較高的重餾出原料52的生產率。在一些實施例中，過量的氫可被注入該第一沸騰床加氫轉化反應器系統20且被攜帶經過該製程到該第二沸騰床加氫裂解反應器系統40。在該第二沸騰床反應器系統40中，藉著利用該蒸汽餾分48來供應氫的需求，提供了一種連合作用(synergism)可以選擇
性沸石卑金屬加氫裂解催化劑共同加氫裂解該重餾出原料52以及加氫裂解後的該碳氫化合物，該碳氫化合物包括從該第一沸騰床系統20而來存在該蒸汽餾分49的輕柴油系列材料。
在該第二沸騰床加氫轉化反應器系統40的反應器可在溫度從200到大約550℃、300到大約500℃、350到大約475℃，或者380到大約430℃的範圍中操作，氫氣分壓的範圍從大約5到大約300 bara、大約25到大約250 bara、大約50到大約200 bara，或大約70到大約175 bara，且每小時液體空間速度(liquid hourly space velocities，LHSV)範圍在每小時大約0.1到大約4、大約0.15到大約3，或從大約0.2到大約2.0。在一些實施例中，該氫氣分壓在該第二沸騰床加氫裂解反應氣系統40中將大致相等或大於在流體49中的氫氣分壓，視該第二沸騰床加氫裂解反應器系統40在自生壓力(autogeneous pressure)的環境下運作所補充的氫氣60的量而定，意即，該壓力在沸騰床加氫轉化反應器系統20和沸騰床加氫裂解反應器系統40之間沒有任何壓力降低的狀況，除了在該兩個反應器系統之間以正常引流壓力滴入該管道線路時才有可能發生。在該沸騰床反應器20或40中，該催化劑可藉由該液態產物的再循環被回混且維持於一隨機運動狀態。這可以藉由自該氣態產物中先分離出該再循環的油而被實現。該油可接著以一外部幫浦的方式被再循環，或者，如圖所示，藉由具有一推動器架設在該反應器底端的一幫浦來達成。在一些實施例中，該反應熱被吸收作為該進入系統的重餾出原料52的焓(enthalpy)，且該第二沸騰床加氫裂解反應器系統40在等溫環境下運作，因為藉由該沸騰幫浦的能量可供應較佳的熱(和質量)的轉移。
在該第二沸騰床加氫裂解反應系統40中的目標轉化率可為至少大約60%、至少70%或至少約80%，視該被加工的原料而定。轉化率可被定義為在一ASTM D1160蒸餾重碳氫化合物的混合物中，沸點溫度低於大約370℃的材料的生成。除了轉化該重碳氫化合物為較輕的碳氫化合物，該餾出選擇性可被定義為五個已定義的餾出燃料系列中的每一個的體積百分比(lv%)除以該較輕的碳氫化合物的全部液體體積百分，該較輕的碳氫化合物在低於大約370℃沸騰且油一航空用油系列選擇性大約40到80液體體積%；一柴油系列選擇性大約10到35 lv%；一石腦油系列選擇性大約5到18 lv%；以及一液化石油氣(LPG)系列選擇性大約從0.5到4 lv%。
可使用在該第二沸騰床加氫裂解反應器系統40的沸石催化劑可包含任何具有可用在氫處理及加氫裂解一碳氫化合物原料的觸媒的任何沸石。一種具有氫處理觸媒的沸石，舉例來說，可包括任何用來催化碳氫化合物原料氫化的沸石催化劑組合物，以增加其氫含量及/或去除異質原子的污染物。一種沸石加氫裂解催化劑，舉例來說，可包括任何用來催化大型或複雜的碳氫化合物分子進行氫加成及裂解的沸石催化劑組合物，以獲得較小、較低分子量的分子。
根據在此公開的實施例，用於該瓦斯油加氫裂解製程中具有氫處理和加氫裂解催化劑組合物的沸石是所屬領域中已知的，且多數是可以商業上從W.R.Grace & Co.、Criterion Catalyst & Technologies以及Albemarle或其他處獲得。可用性與選擇耐用、具有活性以及選擇性的催化劑用於減壓渣油的加氫裂解vs.常壓及減壓餾出物的加氫裂解對於石油精煉
者從兩個觀點上表現一挑戰區域。首先，當大多數具有氫處理和加氫裂解催化劑的沸石具有高活性極高選擇性時，他們就不夠耐用且對於許多含碳氫進料污染物很敏感，導致催化劑的活性位置被毒化。如此，這類具有加氫轉化催化劑的沸石不能被商業上使用以加氫轉化減壓渣油原料，而後者具有相對高濃度的催化劑毒物如有機金屬物質和焦碳前驅物(coke precursors)。而減壓渣油代表具有相對低的經濟價值的機率原料，他們的加氫轉化，特別是以具有催化劑的沸石進行他們的加氫裂解，將導致一個不經濟的情況在每桶減壓渣油處理時需補充加氫轉化催化劑的成本。為了可以成本有效的處理在減壓渣油原料中的該污染物，精煉者必須採取使用非晶形、非沸石加氫轉化催化劑，其成本相對較低且可以困住許多有機金屬物質所衍生的金屬以及焦碳前驅物，例如康拉遜殘碳，藉以製造減壓瓦斯油、常壓瓦斯油以及中間餾出物。即使有此一初始減壓渣油加氫轉化步驟，有些減壓瓦斯油，特別是重減壓瓦斯油以及那些自熱處理單元衍生的例如焦化瓦斯油，仍含有小量的金屬污染物以及焦碳前驅物，後者是以重多核芳香族化合物中之含量而定義的。
其次，這些重餾出原料的氫處理在傳統固定床加氫裂解反應器中，仍然在反應器的入口區域存在催化劑粒子的結垢/堵塞的問題。在此描述的該系統利用低成本非晶形、非沸石加氫轉化催化劑，在一第一沸騰床加氫轉化反應系統中進行氫加工含污染物的減壓渣油，以製造瓦斯油餾出物，後者接著以活性、選擇性且可流態化的含沸石加氫裂解催化劑在一第二沸騰床加氫裂解反應系統中進行裂解，其中反應狀態以一較為經濟的方式有效地提昇所想要的加氫裂解反應，然後可以在沸騰床反應系統中
利用非沸石加氫轉化催化劑達成。
適當的沸石加氫裂解催化劑可包含一或多個元素選自於元素週期表中的4-12族。在一些實施例中，根據在此公開的實施例之沸石加氫裂解催化劑可包含一或多個鎳、鈷、鎢、鉬以及其組合，可以未支撐或有支撐的形成於一多孔基材如H Y-沸石、H ZSM-5、絲光沸石、毛沸石或超穩八面沸石、USY沸石、β沸石、ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、ZSM-34、REY分子篩、REHY分子篩或其組合。當從一製造商供應或從一再生處理後獲得，該沸石加氫裂解催化劑可以是金屬氧化物的型態，舉例來說。合適的減壓瓦斯油加氫裂解催化劑的範例可在以下美國公告專利US5,073,530、US 5,141,909、US5,277,793、US5,366,615、US5,340,563、US6,860,986以及US5,069,890被發現到，他們全部係在此一併作為參考。在一些實施例中，具有加氫裂解催化劑的沸石可在導入加氫裂解反應器之前被預先硫化及/或預先調整。在一些實施例中，具有加氫裂解催化劑的沸石在沸騰床選擇性加氫裂解環境中可具有一經濟上可行的磨損抗性。
該第二沸騰床加氫裂解反應器系統40可包含沸石催化劑搭載對於中間餾出物系列具有較高選擇性的卑金屬加氫裂解催化劑。出自該第二沸騰床加氫裂解反應器系統40的該產物石板可包含大約57體積%的航空燃料、大約20體積%的柴油、大約20體積%的石腦油和大約3體積%的液化石油氣(LPG)，舉例來說。
接下來在該第二沸騰床加氫裂解反應器系統40進行轉化，該至少部份轉化的碳氫化合物可以經由流程線68被回收作為一混合蒸汽/
液體流出物，且被送出進行進一步的產物回收。
在一些實施例中，該流出物66可被注入到一分餾系統146以回收一或多個碳氫化合物餾分。在一些實施例中，被分開的液體產物50也可以被迅速通過且注入到該分餾系統146中。如圖所示，分餾系統146可被使用來回收一排出氣體148包含氫碳氫化合物氣體以及硫化氫、一輕石腦油餾分150、一重石腦油餾分152、一煤油餾分154、一柴油餾分156、一輕減壓瓦斯油餾分158以及重瓦斯油餾分160。該輕減壓瓦斯油餾分158或重瓦斯油餾分160，如具有一齣使沸點範圍大約340℃到大約427℃的碳氫化合物，可接著通過一減壓蒸餾系統被進一步處理，以回收減壓餾出物。
如上所述，在此公開的實施例有效地整合減壓渣油加氫轉化以及減壓瓦斯油加氫裂解，擴大被氫處理的中間餾出產物的產率高於那些藉由單獨加氫轉化渣油實現的方法之上。再者，較高的產率可使用相較於其他被提出達成相似轉換的方案較少的催化反應氣體積來實現。因此，在此公開的實施例可提供對於被選擇的產物具有競爭力或較高的轉化率而需求一較低的資本投資。此外，在此公開的實施例可以用於從一高含硫殘留物進料中製造具有低於1重量%的硫的一燃料油，且同時最大化所有的轉化率。實施例可以減少氫消耗以及允許額外補充催化劑而不需關閉廠房，故有較長的週期時間。
雖然本發明已以較佳實施例揭露，然其並非用以限制本發明，任何熟習此項技藝之人士，在不脫離本發明之精神和範圍內，當可作各種更動與修飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
4‧‧‧該含瓦斯油流
10‧‧‧渣油碳氫化合物
12‧‧‧加熱器
14‧‧‧熱渣油碳氫化合物餾分
15‧‧‧熱氫流
16‧‧‧氫流
18‧‧‧加熱器
20‧‧‧第一沸騰床加氫轉化反應器系統
22‧‧‧流程線
40‧‧‧第二沸騰床加氫裂解反應器系統
46‧‧‧分餾系統
47‧‧‧吸收塔
48‧‧‧蒸汽餾分
49‧‧‧蒸汽餾分
50‧‧‧液態產物
52‧‧‧重餾出原料
54‧‧‧中間餾出物富含瓦斯油流
60‧‧‧氫氣
66‧‧‧流出物
146‧‧‧分餾系統
148‧‧‧排出氣體
150‧‧‧輕石腦油餾分
152‧‧‧重石腦油餾分
154‧‧‧煤油餾分
156‧‧‧柴油餾分
158‧‧‧輕減壓瓦斯油餾分
160‧‧‧重瓦斯油餾分
Claims (18)
- 一種提高渣油碳氫化合物以及重餾出原料的製程，該製程包含步驟：使渣油碳氫化合物和氫在一第一沸騰床加氫轉化反應器系統中與一非沸石卑金屬加氫轉化催化劑接觸，以製造一第一流出物；從該第一沸騰床加氫轉化反應器中分餾該第一流出物，以回收一液態產物以及一蒸汽產物；接觸該蒸汽產物與一碳氫化合物流，以形成一第二蒸汽產物以及一第二液態產物；使該第二蒸汽產物和一重餾出原料在一第二沸騰床加氫裂解反應器系統中與一沸石選擇性加氫裂解催化劑接觸，以製造一第二流出物；從該第二沸騰床加氫裂解反應器系統回收該第二流出物；以及從該第二沸騰床加氫裂解反應器系統分餾該第二流出物，以回收一或多個碳氫化合物餾分。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重餾出原料的製程，另包含：在接觸該催化劑之前，加熱該渣油碳氫化合物和氫。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中該渣油碳氫化合物係選自石油原油、頁岩油、焦油砂瀝青、煤衍生油、妥爾油、黑油、有機廢物、生物質衍生的液體及任何重油渣油流的其中之一 或多個。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中該重餾出原料係選自常壓瓦斯油、輕減壓瓦斯油、重減壓瓦斯油、重焦化瓦斯油、流體裂解觸媒循環油以及自石油、瀝青、油母岩質、生物質或有機廢物來源所衍生的脫瀝青油的其中之一或多個。
- 如申請專利範圍第4項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中該重餾出原料係該原油頂端覆蓋的該初次減壓瓦斯油，該渣油碳氫化合物係衍生自該原油。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中該渣油碳氫化合物餾分包含石油常壓或減壓殘留物、脫瀝青油、脫瀝青器瀝青、加氫裂解常壓塔或減壓塔底層、流體裂解觸媒漿質油、頁岩衍生油所衍生的渣油、煤衍生油、生物衍生原油、焦油砂瀝青、妥爾油及黑油中的至少一種。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中使渣油碳氫化合物和氫在該第一沸騰床加氫轉化反應器系統中與該非沸石卑金屬加氫轉化催化劑接觸的步驟包含：操作該第一沸騰床加氫轉化反應器系統於一反應器程度，以達成一碳氫轉化至少大約50重量%以及一脫金屬率至少50%，其中該轉化係定義為在一ASTM蒸餾重碳氫化合物的混合物時，在高於480℃沸騰的材料中所減少的重量%。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重 餾出原料的製程，其中使該蒸汽產物和該重餾出原料在該第二沸騰床加氫裂解反應器系統中與該沸石選擇性加氫裂解催化劑接觸的步驟包含：操作該第二沸騰床加氫裂解反應器系統於一反應器程度，以達成一碳氫轉化至少大約60重量%，其中該轉化係定義為在一ASTMD1160蒸餾重碳氫化合物的混合物時，低於370℃沸騰的材料中所形成的部份。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中該沸石選擇性加氫轉化催化劑包含至少一H Y-沸石、H ZSM-5、絲光沸石、毛沸石或超穩八面沸石、USY沸石、β沸石、ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、ZSM-34、REY分子篩或REHY分子篩。
- 如申請專利範圍第9項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中該沸石選擇性加氫裂解催化劑另包含煤、鉬、鎢、鎳、鉑或鈀的其中之一或多個。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中該碳氫化合物流係一碳氫化合物流衍生自該第二分餾系統內回收的一或多個該碳氫化合物餾分。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重餾出原料的製程，其中該碳氫化合物流在常壓或減壓瓦斯油的範圍中沸騰。
- 如申請專利範圍第1項所述之提高渣油碳氫化合物以及重 餾出原料的製程，其中接觸該蒸汽產物與一碳氫化合物流的步驟是在一逆流吸收管柱中進行。
- 如申請專利範圍第1項所述之提高重餾出原料的製程，另包含：在該沸騰加氫轉化床中使一渣油碳氫化合物原料和氫接觸。
- 如申請專利範圍第1項所述之提高重餾出原料的製程，其中該沸石選擇性加氫裂解催化劑係被製成可流態化的，且在該沸騰床加氫裂解反應器的反應環境中具有磨損抗性。
- 如申請專利範圍第15項所述之提高重餾出原料的製程，其中該沸石選擇性加氫裂解催化劑係由一貴金屬結合於一沸石支撐體上所組成。
- 一種提高渣油碳氫化合物以及重餾出原料的系統，該系統包含：一第一沸騰床加氫裂解反應器系統，其容納一沸石選擇性加氫裂解催化劑用以反應該重餾出原料和氫，以製造一第一流出物；一第一分餾單元用以分餾該第一流出物，以回收一或多個碳氫化合物餾分；一第二沸騰床加氫轉化反應器系統，其容納一非沸石卑金屬加氫轉化催化劑用以反應該渣油碳氫化合物和氫，以製造一第二流出物；一第一分離器用以分離該第二流出物，並回收一液態餾分和一蒸汽餾分；以及一吸收塔使用一瓦斯油範圍碳氫化合物流，以從該蒸汽餾 分回收一第二蒸汽餾分以及一第二液態餾分；其中該第二蒸汽餾分被送至該第一沸騰床加氫裂解反應器系統；該碳氫化合物流係一碳氫化合物流衍生自該第二分餾系統內回收的一或多個該碳氫化合物餾分。
- 一種提高渣油碳氫化合物以及重餾出原料的系統，該系統包含：一第一沸騰床加氫轉化反應器系統，其容納一非沸石卑金屬加氫轉化催化劑用以反應該渣油原料和氫，以製造一第一流出物；一第一分離器用以分離該第一流出物，並回收一液態餾分和一蒸汽餾分；一吸收塔使用一瓦斯油範圍碳氫化合物流，以從該蒸汽餾分回收一第二蒸汽餾分以及一第二液態餾分；一第二沸騰床加氫裂解反應器系統，其容納一沸石選擇性加氫裂解催化劑用以反應該重餾出原料、該第二蒸汽餾分和氫，以製造一第二流出物；以及一第一分餾單元用以分餾該第二流出物，以回收一或多個碳氫化合物餾分。
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- 2015-02-03 BR BR112016016710-4A patent/BR112016016710B1/pt active IP Right Grant
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- 2015-02-03 KR KR1020167016810A patent/KR101899699B1/ko active IP Right Grant
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- 2015-02-03 CN CN201580007004.5A patent/CN105980532B/zh active Active
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|---|---|
| RU2016136357A (ru) | 2018-03-15 |
| RU2654478C2 (ru) | 2018-05-21 |
| KR20160090353A (ko) | 2016-07-29 |
| CN105980532A (zh) | 2016-09-28 |
| BR112016016710A2 (pt) | 2018-05-08 |
| BR112016016710B1 (pt) | 2021-01-05 |
| ES2748682T3 (es) | 2020-03-17 |
| EP3105305A4 (en) | 2017-10-25 |
| MY174114A (en) | 2020-03-10 |
| PT3105305T (pt) | 2019-10-18 |
| US10894922B2 (en) | 2021-01-19 |
| EP3105305B1 (en) | 2019-07-10 |
| CA2931241A1 (en) | 2015-08-20 |
| RS59510B1 (sr) | 2019-12-31 |
| HUE045621T2 (hu) | 2020-01-28 |
| US20150225657A1 (en) | 2015-08-13 |
| EP3105305A1 (en) | 2016-12-21 |
| RU2016136357A3 (zh) | 2018-03-15 |
| HRP20191810T1 (hr) | 2019-12-27 |
| MX2016010102A (es) | 2016-10-07 |
| SG11201606703XA (en) | 2016-09-29 |
| CA2931241C (en) | 2019-01-15 |
| US20190249095A1 (en) | 2019-08-15 |
| TW201536911A (zh) | 2015-10-01 |
| KR101899699B1 (ko) | 2018-10-04 |
| CN105980532B (zh) | 2018-01-19 |
| US10208261B2 (en) | 2019-02-19 |
| PL3105305T3 (pl) | 2020-01-31 |
| WO2015123052A1 (en) | 2015-08-20 |
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