CN1189542C - 采用流化催化裂化工艺选择性生产c3烯烃的方法 - Google Patents
采用流化催化裂化工艺选择性生产c3烯烃的方法 Download PDFInfo
- Publication number
- CN1189542C CN1189542C CNB99805805XA CN99805805A CN1189542C CN 1189542 C CN1189542 C CN 1189542C CN B99805805X A CNB99805805X A CN B99805805XA CN 99805805 A CN99805805 A CN 99805805A CN 1189542 C CN1189542 C CN 1189542C
- Authority
- CN
- China
- Prior art keywords
- alkene
- catalyzer
- conversion zone
- weight
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 16
- 238000004231 fluid catalytic cracking Methods 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010457 zeolite Substances 0.000 claims abstract description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 11
- 239000012188 paraffin wax Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000005194 fractionation Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- 238000005336 cracking Methods 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 description 6
- 238000004523 catalytic cracking Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical compound C1CN1P(N1CC1)(=O)N1CC1 FYAMXEPQQLNQDM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005235 decoking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils 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
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
- C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
从催化裂化的或热裂化的石脑油流中选择性生产C3烯烃的方法。该方法包括在含约10～50%重量平均孔直径小于约0.7纳米的结晶状沸石的催化剂存在下反应条件包括：温度从约500℃到650℃，烃分压从约10到40英磅/英寸2。
Description
本发明涉及从催化裂化或热裂化的石脑油物流中选择性生产C3烯烃的方法。石脑油流被引入包括反应段、汽提段、催化剂再生区和分馏段的工艺装置。石脑油原料在反应段与包括10～50％重量平均孔径小于约0.7纳米的结晶状沸石的催化剂在温度约500到650℃，烃分压约10到40英磅/英寸2(68.95-275.79kPa)的反应条件下接触。气态产物于塔顶收集，催化剂颗粒在被送往催化剂再生区的途中经过汽提段。挥发分在汽提段被蒸汽汽提，催化剂颗粒被送往催化剂再生区，在那里催化剂上的焦炭被燃烧，催化剂随后再次被循环到反应段。从反应段得到的塔顶产物被送往一分馏段，在那里回收C3物流，富含C4和/或C5烯烃的物流再循环到汽提段。
对低排放燃料的需要造成对用于烷基化、低聚、MTBE和ETBE合成工艺的轻质烯烃的需求增加。另外，轻质烯烃，特别是丙烯的低成本供应使其成为聚烃烯，特别是聚丙稀产物的原料。
轻质烷烃脱氢的各种固定床法最近吸引了重新燃起的对增加烯烃生产的兴趣。然而，这些类型的方法一般都需要相对大的投资和高运行成本。因此，使用较少投资的方法增加烯烃产量就有优势。采用催化裂化方法提高烯烃产量特别有优势。
美国专利第4830728号介绍了可使烯烃产量达到最大的流化催化裂化装置。该流化催化裂化装置有两个分开的其中导入不同进料流的提升管。提升管的操作方式被设计成使得一种合适的催化剂在一个提升管内转化重质粗柴油，另一种合适的催化剂在另一提升管内裂化较轻质烯烃/石脑油进料。可调整重质粗柴油提升管内的条件以便最大限度地生产汽油或烯烃。最大限度地生产所需产物的主要方法是采用特殊催化剂。
ARCO公司拥有的美国专利第5026936号也介绍了一种联合使用裂化和复分解作用从C4或更高级烃进料制备丙烯的方法，在此，高级烃裂化形成乙烯和丙烯，同时至少一部分乙烯复分解为丙烯。同样可参见美国专利第5026935、5171921和5043522号。
第5069776号美国专利介绍了一种通过使原料流与包括孔径从0.3纳米到0.7纳米的沸石的沸石催化剂移动床在高于约500℃温度，停留时间少于约10秒的情况下接触，从而实现烃原料转化的方法。在制备烯烃的同时只有很少饱和气态烃制成。
美孚公司拥有的第3928172号美国专利也介绍了一种转化烃原料流的方法，在此，烯烃在ZSM-5催化剂存在下由上述原料反应制成。
用流化催化裂化装置生产烯烃产物的固有问题是该方法依靠特殊的催化剂平衡在获得沸点高于650°F(343.33℃)的原料成分的高转化率的同时使轻烯烃的产量最大。另外，即使能保持特殊的催化剂平衡使烯烃的综合产量最大，但是烯烃选择性也会由于不希望有的副反应如深度裂化、异构化、芳构化和氢转移反应而一般很低。由不希望有的副反应产生的轻质饱和气体导致回收目的轻质烯烃成本增加。因此，希望采用允许对C3和C4烯烃的选择性有较高程度控制的方法最大限度地生产烯烃。
根据本发明，现提供一种在包括反应段、汽提段、催化剂再生区和分馏段的工艺装置中从石脑油原料选择性生产C3烯烃的方法。石脑油流在包括优选呈流化态的催化剂床的反应段内接触。该催化剂由一平均孔径小于的0.7纳米的沸石制成，反应段在这样的条件下运行并生产反应产物：温度从约500到650℃、烃分压从10到40英磅/英寸2(68.95-275.79kPa)，烃停留时间从1到10秒，催化剂与原料比率从约2到10，不超过约20％重量石蜡转化为烯烃。催化剂从反应段送到汽提段，在此挥发组分在蒸汽作用下被汽提，随后催化剂被送到催化剂再生区，在含氧气体存在下，沉积的焦炭被燃烧。再生过的催化剂被循环到反应段与新原料接触。反应产物被送往分馏段，生产出C3馏分和C4馏分。C3馏分被回收，富含烯烃的C4和/或C5馏分被循环到汽提段或反应段。
在本发明的另一优选实施方案中，催化剂是ZSM-5型催化剂。
在本发明的优选实施方案中，一种富含烯烃的C5馏分也被循环。
在本发明的另一优选实施方案中，原料包括大约10～30％重量石蜡，约20～70％重量烯烃。
在本发明的另一优选实施方案中，反应段在约525℃到600℃的温度下运行。
适于制备较高C2、C3和C4烯烃产量的原料流是在石脑油沸程沸腾的包括约5～35％重量，优选约10～30％重量，更优选约10～25％重量石蜡和约15％，优选约20～70％重量烯烃。原料中还含有环烷烃和芳烃。石脑油沸程流一般是沸程为约65°F(18.33℃)到约430°F(221.11℃)，优选约65°F(18.33℃)到约300°F(148.89℃)的物流。石脑油可以是热裂化的或催化裂化的。这样的物流可以从任何适当的来源得到，例如，可以从粗柴油和残油的流化催化裂化中得到，或从残油的延迟焦化或流化焦化中得到。本发明的实践中用到的石脑油流以从粗柴油和残油的流化催化裂化中得到的为佳。这样的石脑油一般富含烯烃和/或双烯烃而石蜡相对少。作为未经催化裂化或热裂化的石脑油流如甲基叔丁基醚萃余液的其它烯属物流与初始原料一同导入上述反应段也属于本发明范围。可以相信这将增加丙烯产量。
本发明方法在包括反应段、汽提段、催化剂再生区和分馏段的工艺装置中完成。石脑油原料流注入反应段，在这里，它接触一热源，即再生过的催化剂。热的催化剂在约500℃到650℃，最好约525℃到600℃的温度下使原料蒸发并裂化。裂化反应使含碳烃或焦炭沉积在催化剂上，因此钝化了催化剂。裂化产物从焦化的催化剂上分离出来并送往分馏器。焦化的催化剂通过汽提段，在此挥发成分被蒸汽从催化剂颗粒中汽提出来。汽提可在不太苟刻的条件下进行以保持吸附烃用于实现热平衡。
汽提过的催化剂被送到再生区，在含氧气体、优选空气存在下通过燃烧催化剂上的焦炭得以再生。除焦恢复了催化剂的活性，同时将催化剂加热到约650℃到约750℃。热的催化剂循环到反应段与新的石脑油原料接触。在再生器中通过燃烧焦炭而形成的烟道气可经过处理以便脱除颗粒和转化一氧化碳，处理后烟道气一般排入大气。从反应段出来的裂化产物被送入分馏段，在此，不同的产物，特别是C3馏分、C4馏分，和任选的C5馏分被回收。C4馏分和C5馏分一般富含烯烃。这些馏分中的一种或两种可循环到反应器中。它们可循环至反应器的主段，或提升管段，或汽提段。它们最好循环到汽提段的上部，或汽提段。这些馏分的一种或两种的循环过程将至少一部分的这些烯烃转化为丙烯。
试图在流化催化裂化工艺装置自身内提高轻烯烃产量的同时，本发明的实践使用了上述独特的接收来自炼油厂中适当来源的石脑油的工艺装置。反应段在最大限度生产C2到C4烯烃，特别是丙烯并且最大限度地提高选择性和高C5+烯烃转化率的工艺条件下工作。本发明实践中适用的催化剂是那种由一结晶状沸石组成的催化剂，该结晶状沸石的平均孔径小于约0.7纳米，上述结晶状沸石占整个流化催化剂组合物的约10～50％重量。结晶状沸石最好从中等孔尺寸(＜约0.7纳米)、其它特征与沸石相同的结晶状硅铝酸盐中选取。特别令人感兴趣的是其二氧化硅与氧化铝的摩尔比例小于约75∶1，优选小于约50∶1，更优选小于约40∶1的中等孔的沸石。孔径有时也被称做有效孔径，它能用标准吸附技术和已知最小动力学直径的烃组分进行测量。参见布瑞克的《沸石分子筛》1974，和安得森等的《催化作用杂志》1979，第58期、114页，两者并入本文作为参考。
1992年由W.H.Meier和D.H.Olson，Butterworth-Heineman出版的“沸石结构类型汇编”第三版中对可用于本发明实践的中等孔尺寸沸石做了描述，该书并入本文作为参考。中等孔尺寸沸石的孔尺寸一般从约5埃到7埃，并包括如MFI、MFS、MEL、MTW、EUO、MTT、HEU、FER，和TON构型沸石(国际理论化学和应用化学联合会沸石术语委员会)。这样的中等孔尺寸沸石的非限制实例包括ZSM-5，ZSM-12，ZSM-22，ZSM-23，ZSM-34，ZSM-35，ZSM-38，ZSM-48，ZSM-50，硅质岩，和硅质岩2。最优选ZSM-5，在美国专利3702886和3770614中有描述，ZSM-11在美国专利3709979中有描述；ZSM-12被描述于在美国专利3832449中；ZSM-21和ZSM-38被描述于在美国专利3948758中；ZSM-23被描述于在美国专利4076842中；ZSM-35被描述于在美国专利4016245中。上面所有专利都并入本文作为参考。其它适合的中等孔尺寸沸石包括硅铝磷酸盐(SAPO)，如在美国专利4440871号中描述的SAPO-4和SAPO-11；硅铬酸盐；硅酸镓；硅酸铁；磷酸铝(ALPO)，如美国专利4310440中描述的ALPO-11；硅铝酸钛(TASO)，如在EP-A专利229295号中描述的TASO-45；在美国专利4254297中描述的硅酸硼；磷铝酸钛(TAPO)，如在美国专利4500651中描述的TAPO-11；和硅铝酸铁。在本发明的实施方案中，上述沸石中的硅/铝比例大于约40。
中等孔尺寸沸石可包括“结晶状混合物”，“结晶状混合物”被认为是在沸石合成过程中在晶体或结晶区内产生缺陷的结果。ZSM-5和ZSM-11的结晶状混合物的例子在美国专利4229424中做了介绍，该专利并入本文作为参考。结晶状混合物自身属于中等孔尺寸沸石，不能将其与沸石的物理混合物相混淆，在沸石的物理混合物中，不同沸石的独特微晶以物理方式存在于同种催化剂复合物或水热反应混合物中。
本发明的催化剂与无机氧化物基体成分结合在一起。该无机氧化物基体成分与催化剂成分粘合在一起，使得催化剂产物有足够的硬度抵御颗粒间和反应器壁的碰撞。该无机氧化物基体可做成一无机氧化物溶胶或凝胶，一旦干燥便可将催化剂成分粘合在一起。优选地，无机氧化物基体没有催化活性，由硅和铝的氧化物组成。同样优选地，分离的氧化铝相被加入无机氧化物基体中。可以使用碱式氢氧化铝-g-氧化铝，勃姆石，水铝石和迁移氧化铝如a-氧化铝、b-氧化铝、g-氧化铝、d-氧化铝、e-氧化铝、k-氧化铝，和r-氧化铝都可用。优选地，氧化铝是氢氧化铝如三水铝石、三羟铝石、诺三水铝石，或doyelite。基体材料也可含磷化合物或磷酸铝。
优选的工艺条件包括：温度从约500℃到650℃，优选约500℃到600℃；烃分压从约10到40英磅/英寸2(68.95-275.79kPa)，优选约20到35英磅/英寸2(137.90-241.32kPa)；和催化剂对石脑油重量比为约3到12，优选约4到10，这里，催化剂的重量是催化剂复合物的总重量。蒸汽和石脑油原料优选同时被加入反应段，蒸汽占烃原料的至多约50％重量。石脑油在反应段的停留时间优选少于10秒，如约1到10秒。上述条件使得石脑油原料流中至少约60％重量C5+烯烃转化为C4-产物；少于约25％重量，优选少于20％重量石蜡转化为C4-产物，而且丙烯占总的C3反应产物至少约90摩尔％，优选大于约95摩尔％，同时丙烯与总的C2-产物的重量比大于约3.5。优选乙烯占C2产物至少约90摩尔％，同时丙烯与乙烯的重量比大于约4，并且“全馏程”C5+石脑油产物与石脑油原料相比在马达法辛烷值和研究法辛烷值两方面都得以提高。为更大地提高丙烯的选择性，在进料前对催化剂进行预焦化属于本发明范围内。同样为提高丙烯相对于乙烯的选择性而向反应段导入有效量单环芳烃也属于本发明范围内。芳烃可从外部来源如重整工装置得到或者可由即时工艺的重石脑油循环产物组成。
下列实施例仅用于说明目的，不用来以任何方式限制本发明。
实施例1-12
下列实施例说明用于借助ZCAT-40(含ZSM-5的催化剂)裂化的催化石脑油馏分样品来保持化学等级丙烯纯度的工艺操作条件的临界状态，为模拟商业平衡，ZCAT-40已用蒸汽在1500°F(815.56℃)处理16小时。实施例1和2的比较结果显示：增加催化剂与油的比率会提高丙烯产量，但会降低丙烯纯度。实施例3与4、5与6的比较结果显示：降低油的分压可极大提高丙烯纯度又不影响丙烯产量。实施例7与8、9与10的比较结果显示：提高温度可提高丙烯的产量和纯度。实施例11与12的比较结果显示：减少催化剂的停留时间可提高丙烯的产量和纯度。实施例13展示在设计用于第二级的常规流化催化裂化反应器/再生器中可得到的反应器温度和催化剂/油比率下可获得高的丙烯产量和纯度。
表1(其中：1英磅/英寸2＝6.89kPa)
| 实施 例 | 原料 烯烃 wt.％ | 温度， ℃ | 催化剂/ 油 | 油英磅/英寸 2 | 油停留时 间，秒 | 催化剂停留时 间，秒 | wt.％C 3 ＝ | wt.％C 3 - | 丙烯纯度，％ |
| 1 | 38.6 | 566 | 4.2 | 36 | 0.5 | 4.3 | 11.4 | 0.5 | 95.8％ |
| 2 | 38.6 | 569 | 8.4 | 32 | 0.6 | 4.7 | 12.8 | 0.8 | 94.1％ |
| 3 | 22.2 | 510 | 8.8 | 18 | 1.2 | 8.6 | 8.2 | 1.1 | 88.2％ |
| 4 | 22.2 | 511 | 9.3 | 38 | 1.2 | 5.6 | 6.3 | 1.9 | 76.8％ |
| 5 | 38.6 | 632 | 16.6 | 20 | 1.7 | 9.8 | 16.7 | 1.0 | 94.4％ |
| 6 | 38.6 | 630 | 16.6 | 13 | 1.3 | 7.5 | 16.8 | 0.6 | 96.6％ |
| 7 | 22.2 | 571 | 5.3 | 27 | 0.4 | 0.3 | 6.0 | 0.2 | 96.8％ |
| 8 | 22.2 | 586 | 5.1 | 27 | 0.3 | 0.3 | 7.3 | 0.2 | 97.3％ |
| 9 | 22.2 | 511 | 9.3 | 38 | 1.2 | 5.6 | 6.3 | 1.9 | 76.8％ |
| 10 | 22.2 | 607 | 9.2 | 37 | 1.2 | 6.0 | 10.4 | 2.2 | 82.5％ |
| 11 | 22.2 | 576 | 18.0 | 32 | 1.0 | 9.0 | 9.6 | 4.0 | 70.6％ |
| 12 | 22.2 | 574 | 18.3 | 32 | 1.0 | 2.4 | 10.1 | 1.9 | 84.2％ |
| 13 | 38.6 | 606 | 8.5 | 22 | 1.0 | 7.4 | 15.0 | 0.7 | 95.5％ |
续表1
| 实施例 | wt.％C 2 ＝ | wt.％C 2 - | C ＝ 与C ＝ 之比 | C ＝ 与C - 之比 | wt.％C 3 ＝ |
| 1 | 2.35 | 2.73 | 4.9 | 4.2 | 11.4 |
| 2 | 3.02 | 3.58 | 4.2 | 3.6 | 12.8 |
| 3 | 2.32 | 2.53 | 3.5 | 3.2 | 8.2 |
| 4 | 2.16 | 2.46 | 2.9 | 2.6 | 6.3 |
| 5 | 6.97 | 9.95 | 2.4 | 1.7 | 16.7 |
| 6 | 6.21 | 8.71 | 2.7 | 1.9 | 16.8 |
| 7 | 1.03 | 1.64 | 5.8 | 3.7 | 6.0 |
| 8 | 1.48 | 2.02 | 4.9 | 3.6 | 7.3 |
| 9 | 2.16 | 2.46 | 2.9 | 2.6 | 6.3 |
| 10 | 5.21 | 6.74 | 2.0 | 1.5 | 10.4 |
| 11 | 4.99 | 6.67 | 1.9 | 1.4 | 9.6 |
| 12 | 4.43 | 6.27 | 2.3 | 1.6 | 10.1 |
| 13 | 4.45 | 5.76 | 3.3 | 2.6 | 15.0 |
C2 -＝CH4+C2H4+C2H6
上述实施例(1，2，7和8)表明，通过选择合适的反应器条件，可达到C3 ＝/C2 ＝＞4和C3 ＝/C2 -＞3.5。
实施例14-17
被包含在石脑油流(如流化催化石脑油，焦化石脑油)中的烯烃和石蜡，经过诸如ZSM-5之类小或中等孔沸石的裂化，可产出相当数量乙烯和丙烯。乙烯或丙烯的选择性以及丙烯相对于丙烷的选择性随着催化剂和工艺操作条件而变化。业已发现，当蒸汽和催化石脑油一同导入反应器时，丙烯产量可以提高。催化剂可以是ZSM-5或其它小或中等孔沸石。下面的表2表明当5％重量蒸汽与含有38.8％重量烯烃的催化裂化石脑油一同导入时丙烯产量增加。虽然丙烯产量增加，但丙烯纯度降低。因此，有必要调整其它操作条件以保持目的丙烯选择性。
表2(其中：1英磅/英寸2＝6.89kPa)
| 实施 例 | 同步导入 蒸汽 | 温度， ℃ | 摧化剂/ 油 | 油英磅/英寸 2 | 油停留时 间，秒 | 催化剂停留时 间，秒 | Wt.％丙烯 | wt.％丙烷 | 丙烯纯度，％ |
| 14 | 否 | 630 | 8.7 | 18 | 0.8 | 8.0 | 11.7 | 0.3 | 97.5％ |
| 15 | 是 | 631 | 8.8 | 22 | 1.2 | 6.0 | 13.9 | 0.6 | 95.9％ |
| 16 | 否 | 631 | 8.7 | 18 | 0.8 | 7.8 | 13.6 | 0.4 | 97.1％ |
| 17 | 是 | 632 | 8.4 | 22 | 1.1 | 6.1 | 14.6 | 0.8 | 94.8％ |
实施例18-21
ZCAT-40如上述实施例所述被用于裂化催化裂化石脑油。在如下表所示的温度和空速下，在一反应器内，焦化催化剂随后被用于裂化包括6％重量正丁烷，9％重量异丁烷，47％重量比例的1-丁烷和38％重量异丁烷的C4物流。由下表的结果可见，原料流的相当部分转化为丙烯。
表3
| WHSV，Hr-1 | 35 | 18 | 12 | 6 |
| 温度℃ | 575 | 575 | 575 | 575 |
| 丁烯转化率wt％ | ||||
| 产物产量，wt％ | ||||
| 乙烯 | 2.4 | 4.7 | 5.9 | 8.8 |
| 丙烯 | 20.5 | 27.1 | 28.8 | 27.4 |
| 丁烯 | 39.7 | 29.0 | 25.5 | 19.2 |
| C1-C4轻质饱和烃 | 18.2 | 19.2 | 19.8 | 22.0 |
| C5+产物 | 19.3 | 20.0 | 20.0 | 22.6 |
Claims (7)
1、在包括反应段、汽提段、催化剂再生区和分馏段的工艺装置中从石脑油原料流选择性生产C3烯烃的方法，该方法包括：
a)包含10-30％重量石蜡和15-70％重量烯烃的石脑油流在包括催化剂流化床的反应段内反应，催化剂由平均孔径小于0.7纳米的结晶状沸石组成，反应段在温度500℃到650℃，烃分压从68.95到275.79kPa，烃停留时间从1到10秒，催化剂与原料的重量比从4到10的条件下操作，由此生产一反应产物，其中不多于20％重量石蜡转化为烯烃，且其中丙烯占全部C3产物的至少90％摩尔；
b)催化剂经过汽提段，在此挥发物通过采用汽提介质被汽提；
c)汽提过的催化剂从汽提段到达催化剂再生区，在此，任何焦炭沉积物在含氧气体存在下燃烧；
d)再生过的催化剂循环到反应段，在此接触新的原料；
e)分馏汽态产物流以生产C3馏分、富含烯烃的C4馏分和任选的富含烯烃的C5馏分；以及
f)C4馏分被送往反应段或汽提段，或被送往这两段。
2、根据权利要求1的方法，其特征在于结晶状沸石从ZSM系列中选取。
3、根据权利要求2的方法，其特征在于结晶状沸石是ZSM-5。
4、根据权利要求1的方法，其特征在于反应温度从500℃到600℃。
5、根据权利要求1的方法，其特征在于原料流中至少60％重量C5+烯烃转化为C4-产物，和小于25％重量石蜡转化为C4-产物。
6、根据权利要求1的方法，其特征在于在步骤a)中丙烯与全部C2-产物的重量比大于3.5。
7、根据权利要求1的方法，其特征在于也制出富含烯烃的C5馏分，并将其循环到反应段、汽提段或循环至这两段。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/073,083 | 1998-05-05 | ||
| US09/073,083 US6093867A (en) | 1998-05-05 | 1998-05-05 | Process for selectively producing C3 olefins in a fluid catalytic cracking process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1299402A CN1299402A (zh) | 2001-06-13 |
| CN1189542C true CN1189542C (zh) | 2005-02-16 |
Family
ID=22111621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB99805805XA Expired - Fee Related CN1189542C (zh) | 1998-05-05 | 1999-04-27 | 采用流化催化裂化工艺选择性生产c3烯烃的方法 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6093867A (zh) |
| EP (1) | EP1112336B1 (zh) |
| JP (1) | JP2002513845A (zh) |
| KR (1) | KR100588891B1 (zh) |
| CN (1) | CN1189542C (zh) |
| AU (1) | AU762178B2 (zh) |
| BR (1) | BR9910216A (zh) |
| CA (1) | CA2329244A1 (zh) |
| DE (1) | DE69918139T2 (zh) |
| TW (1) | TW510894B (zh) |
| WO (1) | WO1999057225A1 (zh) |
Families Citing this family (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6106697A (en) * | 1998-05-05 | 2000-08-22 | Exxon Research And Engineering Company | Two stage fluid catalytic cracking process for selectively producing b. C.su2 to C4 olefins |
| US6388152B1 (en) * | 1998-05-05 | 2002-05-14 | Exxonmobil Chemical Patents Inc. | Process for producing polypropylene from C3 olefins selectively produced in a fluid catalytic cracking process |
| US6118035A (en) * | 1998-05-05 | 2000-09-12 | Exxon Research And Engineering Co. | Process for selectively producing light olefins in a fluid catalytic cracking process from a naphtha/steam feed |
| US6339180B1 (en) * | 1998-05-05 | 2002-01-15 | Exxonmobil Chemical Patents, Inc. | Process for producing polypropylene from C3 olefins selectively produced in a fluid catalytic cracking process |
| US6455750B1 (en) * | 1998-05-05 | 2002-09-24 | Exxonmobil Chemical Patents Inc. | Process for selectively producing light olefins |
| US6803494B1 (en) * | 1998-05-05 | 2004-10-12 | Exxonmobil Chemical Patents Inc. | Process for selectively producing propylene in a fluid catalytic cracking process |
| US6315890B1 (en) * | 1998-05-05 | 2001-11-13 | Exxonmobil Chemical Patents Inc. | Naphtha cracking and hydroprocessing process for low emissions, high octane fuels |
| US6339181B1 (en) * | 1999-11-09 | 2002-01-15 | Exxonmobil Chemical Patents, Inc. | Multiple feed process for the production of propylene |
| WO2001064761A2 (en) * | 2000-03-02 | 2001-09-07 | Exxonmobil Chemical Patents, Inc. | Process for producing polypropylene from c3 olefins selectively produced in a fluid catalytic cracking process from a naphtha/steam feed |
| EP1289887A1 (en) * | 2000-05-19 | 2003-03-12 | ExxonMobil Chemical Patents Inc. | Process for selectively producing c3 olefins in a fluid catalytic cracking process |
| US6709572B2 (en) * | 2002-03-05 | 2004-03-23 | Exxonmobil Research And Engineering Company | Catalytic cracking process |
| US6867341B1 (en) * | 2002-09-17 | 2005-03-15 | Uop Llc | Catalytic naphtha cracking catalyst and process |
| US7267759B2 (en) * | 2003-02-28 | 2007-09-11 | Exxonmobil Research And Engineering Company | Fractionating and further cracking a C6 fraction from a naphtha feed for propylene generation |
| US7425258B2 (en) * | 2003-02-28 | 2008-09-16 | Exxonmobil Research And Engineering Company | C6 recycle for propylene generation in a fluid catalytic cracking unit |
| FR2859994B1 (fr) * | 2003-09-19 | 2005-10-28 | Inst Francais Du Petrole | Procede de conversion directe d'une charge comprenant des olefines a quatre, et/ou cinq atomes de carbone ou plus, pour la production de propylene |
| US7326332B2 (en) * | 2003-09-25 | 2008-02-05 | Exxonmobil Chemical Patents Inc. | Multi component catalyst and its use in catalytic cracking |
| TWI294415B (en) * | 2004-02-10 | 2008-03-11 | Maruzen Petrochemical Company Ltd | Process for producing alcohols and/or ketones from alkenes using oxide catalysts |
| US7374660B2 (en) * | 2004-11-19 | 2008-05-20 | Exxonmobil Chemical Patents Inc. | Process for selectively producing C3 olefins in a fluid catalytic cracking process with recycle of a C4 fraction to a secondary reaction zone separate from a dense bed stripping zone |
| CN100338184C (zh) * | 2004-12-23 | 2007-09-19 | 中国石油化工股份有限公司 | 一种催化裂解的方法 |
| BRPI0502015A (pt) * | 2005-06-01 | 2007-01-23 | Petroleo Brasileiro Sa | processo de craqueamento catalìtico seletivo da fração lìquida do gás natural a olefinas leves e outros produtos |
| CN1986505B (zh) * | 2005-12-23 | 2010-04-14 | 中国石油化工股份有限公司 | 一种增产低碳烯烃的催化转化方法 |
| KR101586093B1 (ko) * | 2006-11-07 | 2016-01-15 | 사우디 아라비안 오일 컴퍼니 | 석유 공급원료의 유동 접촉 분해 방법 |
| US20090095657A1 (en) * | 2006-11-07 | 2009-04-16 | Saudi Arabian Oil Company | Automation and Control of Energy Efficient Fluid Catalytic Cracking Processes for Maximizing Value Added Products |
| US9764314B2 (en) * | 2006-11-07 | 2017-09-19 | Saudi Arabian Oil Company | Control of fluid catalytic cracking process for minimizing additive usage in the desulfurization of petroleum feedstocks |
| US8137631B2 (en) * | 2008-12-11 | 2012-03-20 | Uop Llc | Unit, system and process for catalytic cracking |
| US8246914B2 (en) * | 2008-12-22 | 2012-08-21 | Uop Llc | Fluid catalytic cracking system |
| US8889076B2 (en) * | 2008-12-29 | 2014-11-18 | Uop Llc | Fluid catalytic cracking system and process |
| EP2591073B1 (en) * | 2010-07-08 | 2019-07-03 | Indian Oil Corporation Ltd. | Two stage fluid catalytic cracking process |
| CN102533322B (zh) * | 2010-12-30 | 2014-04-30 | 中国石油化工股份有限公司 | 一种费托合成油催化裂化生产丙烯的方法 |
| US9745519B2 (en) | 2012-08-22 | 2017-08-29 | Kellogg Brown & Root Llc | FCC process using a modified catalyst |
| CN103664454B (zh) * | 2012-08-31 | 2015-08-26 | 中国石油化工股份有限公司 | 一种低能耗的费托合成油催化改质生产丙烯的方法 |
| CN103666551B (zh) * | 2012-08-31 | 2015-05-20 | 中国石油化工股份有限公司 | 一种高温费托合成油的催化加工方法和装置 |
| WO2016157014A1 (en) * | 2015-03-31 | 2016-10-06 | Hindustan Petroleum Corporation Limited | A fluid catalytic cracking process for production of cracked run naphtha with low olefin content |
| WO2016199164A1 (en) | 2015-06-09 | 2016-12-15 | Hindustan Petroleum Corporation Ltd. | Catalyst composition for fluid catalytic cracking, and use thereof |
| US10435339B2 (en) | 2017-05-12 | 2019-10-08 | Marathon Petroleum Company Lp | FCC feed additive for propylene/butylene maximization |
| US10696906B2 (en) | 2017-09-29 | 2020-06-30 | Marathon Petroleum Company Lp | Tower bottoms coke catching device |
| US11975316B2 (en) | 2019-05-09 | 2024-05-07 | Marathon Petroleum Company Lp | Methods and reforming systems for re-dispersing platinum on reforming catalyst |
| US11384301B2 (en) | 2020-02-19 | 2022-07-12 | Marathon Petroleum Company Lp | Low sulfur fuel oil blends for stability enhancement and associated methods |
| US11898109B2 (en) | 2021-02-25 | 2024-02-13 | Marathon Petroleum Company Lp | Assemblies and methods for enhancing control of hydrotreating and fluid catalytic cracking (FCC) processes using spectroscopic analyzers |
| US11905468B2 (en) | 2021-02-25 | 2024-02-20 | Marathon Petroleum Company Lp | Assemblies and methods for enhancing control of fluid catalytic cracking (FCC) processes using spectroscopic analyzers |
| US20220268694A1 (en) | 2021-02-25 | 2022-08-25 | Marathon Petroleum Company Lp | Methods and assemblies for determining and using standardized spectral responses for calibration of spectroscopic analyzers |
| US11692141B2 (en) | 2021-10-10 | 2023-07-04 | Marathon Petroleum Company Lp | Methods and systems for enhancing processing of hydrocarbons in a fluid catalytic cracking unit using a renewable additive |
| US11802257B2 (en) | 2022-01-31 | 2023-10-31 | Marathon Petroleum Company Lp | Systems and methods for reducing rendered fats pour point |
Family Cites Families (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324688A (en) * | 1972-07-17 | 1982-04-13 | Texaco Inc. | Regeneration of cracking catalyst |
| US3812029A (en) * | 1972-10-13 | 1974-05-21 | Mobil Oil Corp | Device for injecting easily coked fluids into a high temperature vessel |
| US3928172A (en) * | 1973-07-02 | 1975-12-23 | Mobil Oil Corp | Catalytic cracking of FCC gasoline and virgin naphtha |
| US3974062A (en) * | 1974-10-17 | 1976-08-10 | Mobil Oil Corporation | Conversion of full range crude oils with low molecular weight carbon-hydrogen fragment contributors over zeolite catalysts |
| US4282085A (en) * | 1978-10-23 | 1981-08-04 | Chevron Research Company | Petroleum distillate upgrading process |
| US4251348A (en) * | 1979-12-26 | 1981-02-17 | Chevron Research Company | Petroleum distillate upgrading process |
| US4370222A (en) * | 1981-03-02 | 1983-01-25 | Mobil Oil Corporation | FCC Regeneration |
| US4385985A (en) * | 1981-04-14 | 1983-05-31 | Mobil Oil Corporation | FCC Reactor with a downflow reactor riser |
| US4830728A (en) * | 1986-09-03 | 1989-05-16 | Mobil Oil Corporation | Upgrading naphtha in a multiple riser fluid catalytic cracking operation employing a catalyst mixture |
| US4863585A (en) * | 1986-09-03 | 1989-09-05 | Mobil Oil Corporation | Fluidized catalytic cracking process utilizing a C3-C4 paraffin-rich Co-feed and mixed catalyst system with selective reactivation of the medium pore silicate zeolite component thereofo |
| US4892643A (en) * | 1986-09-03 | 1990-01-09 | Mobil Oil Corporation | Upgrading naphtha in a single riser fluidized catalytic cracking operation employing a catalyst mixture |
| CN1004878B (zh) * | 1987-08-08 | 1989-07-26 | 中国石油化工总公司 | 制取低碳烯烃的烃类催化转化方法 |
| US5286370A (en) * | 1987-12-28 | 1994-02-15 | Mobil Oil Corporation | Catalytic cracking using a layered cracking catalyst |
| US4918256A (en) * | 1988-01-04 | 1990-04-17 | Mobil Oil Corporation | Co-production of aromatics and olefins from paraffinic feedstocks |
| BR8902859A (pt) * | 1988-06-16 | 1990-02-01 | Shell Int Research | Processo para conversao de uma carga de alimentacao hidrocarbonada e produto hidrocarbonado |
| US5055176A (en) * | 1988-12-30 | 1991-10-08 | Mobil Oil Corporation | Multi component catalyst and a process for catalytic cracking of heavy hydrocarbon feed to lighter products |
| US5043522A (en) * | 1989-04-25 | 1991-08-27 | Arco Chemical Technology, Inc. | Production of olefins from a mixture of Cu+ olefins and paraffins |
| US5059735A (en) * | 1989-05-04 | 1991-10-22 | Mobil Oil Corp. | Process for the production of light olefins from C5 + hydrocarbons |
| US5026936A (en) * | 1989-10-02 | 1991-06-25 | Arco Chemical Technology, Inc. | Enhanced production of propylene from higher hydrocarbons |
| US5026935A (en) * | 1989-10-02 | 1991-06-25 | Arco Chemical Technology, Inc. | Enhanced production of ethylene from higher hydrocarbons |
| US5171921A (en) * | 1991-04-26 | 1992-12-15 | Arco Chemical Technology, L.P. | Production of olefins |
| CA2102203A1 (en) * | 1991-05-02 | 1992-11-03 | Willibald Serrand | Catalytic cracking process and apparatus |
| US5389232A (en) * | 1992-05-04 | 1995-02-14 | Mobil Oil Corporation | Riser cracking for maximum C3 and C4 olefin yields |
| CN1034586C (zh) * | 1993-11-05 | 1997-04-16 | 中国石油化工总公司 | 多产低碳烯烃的催化转化方法 |
| US5549813A (en) * | 1994-03-07 | 1996-08-27 | Dai; Pei-Shing E. | FCC process employing low unit cell size y-zeolites |
| US5472594A (en) * | 1994-07-18 | 1995-12-05 | Texaco Inc. | FCC process for producing enhanced yields of C4 /C5 olefins |
| US5723040A (en) * | 1994-09-22 | 1998-03-03 | Stone & Webster Engineering Corporation | Fluid catalytic cracking process and apparatus |
| US5846403A (en) * | 1996-12-17 | 1998-12-08 | Exxon Research And Engineering Company | Recracking of cat naphtha for maximizing light olefins yields |
| US5846402A (en) * | 1997-05-14 | 1998-12-08 | Indian Oil Corporation, Ltd. | Process for catalytic cracking of petroleum based feed stocks |
-
1998
- 1998-05-05 US US09/073,083 patent/US6093867A/en not_active Expired - Fee Related
-
1999
- 1999-04-27 CN CNB99805805XA patent/CN1189542C/zh not_active Expired - Fee Related
- 1999-04-27 WO PCT/US1999/009111 patent/WO1999057225A1/en active IP Right Grant
- 1999-04-27 EP EP99918854A patent/EP1112336B1/en not_active Expired - Lifetime
- 1999-04-27 KR KR1020007012214A patent/KR100588891B1/ko not_active IP Right Cessation
- 1999-04-27 BR BR9910216-1A patent/BR9910216A/pt not_active IP Right Cessation
- 1999-04-27 CA CA002329244A patent/CA2329244A1/en not_active Abandoned
- 1999-04-27 JP JP2000547182A patent/JP2002513845A/ja not_active Withdrawn
- 1999-04-27 AU AU36670/99A patent/AU762178B2/en not_active Ceased
- 1999-04-27 DE DE69918139T patent/DE69918139T2/de not_active Expired - Fee Related
- 1999-08-07 TW TW088107314A patent/TW510894B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| CN1299402A (zh) | 2001-06-13 |
| EP1112336B1 (en) | 2004-06-16 |
| EP1112336A4 (en) | 2001-10-10 |
| WO1999057225A1 (en) | 1999-11-11 |
| JP2002513845A (ja) | 2002-05-14 |
| AU3667099A (en) | 1999-11-23 |
| EP1112336A1 (en) | 2001-07-04 |
| BR9910216A (pt) | 2001-01-09 |
| DE69918139D1 (de) | 2004-07-22 |
| AU762178B2 (en) | 2003-06-19 |
| DE69918139T2 (de) | 2005-07-07 |
| TW510894B (en) | 2002-11-21 |
| KR20010043263A (ko) | 2001-05-25 |
| CA2329244A1 (en) | 1999-11-11 |
| US6093867A (en) | 2000-07-25 |
| KR100588891B1 (ko) | 2006-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1189542C (zh) | 采用流化催化裂化工艺选择性生产c3烯烃的方法 | |
| CN1165502C (zh) | 采用流化催化裂化工艺从石脑油/蒸汽进料选择性生产轻质烯烃的方法 | |
| CN1171835C (zh) | 流化床催化裂化过程中选择性生产轻质烯烃的方法 | |
| CN1205319C (zh) | 用于选择性生产c2－c4烯烃的两段流化催化裂化方法 | |
| US7267759B2 (en) | Fractionating and further cracking a C6 fraction from a naphtha feed for propylene generation | |
| CN1380899A (zh) | 在流化床催化裂化工艺中选择性生产c3烯烃的方法 | |
| CN1406253A (zh) | 由流化床催化裂化过程中选择性生产的c3烯烃制备聚丙烯的方法 | |
| CN1380898A (zh) | 在流化床催化裂化工艺中选择性生产丙烯的方法 | |
| JP2004509928A (ja) | 流動接触分解法においてｃ３オレフィンを選択的に製造する方法。 | |
| MXPA00010668A (en) | Process for selectively producing light olefins in a fluid catalytic cracking process from a naphtha/steam feed | |
| MXPA00010670A (en) | Process for selectively producing c3 | |
| MXPA00010669A (en) | Process for selectively producing light olefins in a fluid catalytic cracking process | |
| ZA200206890B (en) | Process for producing polypropylene from C3 olefins selectively produced in a fluid catalytic cracking process from a naphtha/steam feed. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050216 Termination date: 20100427 |