CN101103094A - 通过自热裂化生产烯烃的方法 - Google Patents
通过自热裂化生产烯烃的方法 Download PDFInfo
- Publication number
- CN101103094A CN101103094A CNA2005800468881A CN200580046888A CN101103094A CN 101103094 A CN101103094 A CN 101103094A CN A2005800468881 A CNA2005800468881 A CN A2005800468881A CN 200580046888 A CN200580046888 A CN 200580046888A CN 101103094 A CN101103094 A CN 101103094A
- Authority
- CN
- China
- Prior art keywords
- hydrocarbon
- gas
- feedstream
- paraffinic hydrocarbon
- liquid paraffinic
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000005336 cracking Methods 0.000 title claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 71
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 71
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- 239000000446 fuel Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000010790 dilution Methods 0.000 claims description 23
- 239000012895 dilution Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 22
- 229930194542 Keto Natural products 0.000 claims description 21
- 125000000468 ketone group Chemical group 0.000 claims description 21
- 230000008016 vaporization Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 235000011089 carbon dioxide Nutrition 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 35
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 229910052697 platinum Inorganic materials 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052763 palladium Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052723 transition metal Inorganic materials 0.000 description 12
- 150000003624 transition metals Chemical group 0.000 description 12
- 239000010949 copper Substances 0.000 description 9
- 229910052703 rhodium Inorganic materials 0.000 description 9
- 239000010948 rhodium Substances 0.000 description 9
- 239000011135 tin Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 7
- 238000009834 vaporization Methods 0.000 description 7
- 238000010791 quenching Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- ZAPRYTOPZGSBKE-UHFFFAOYSA-K [O-]P([O-])([O-])=O.O.[Ca+2].[Zr+4] Chemical compound [O-]P([O-])([O-])=O.O.[Ca+2].[Zr+4] ZAPRYTOPZGSBKE-UHFFFAOYSA-K 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- -1 platinum metals Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000011364 vaporized material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- C10G11/20—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert heated gases or vapours
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- 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
- B01J23/74—Iron group metals
-
- 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
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供通过含液态链烷烃的原料在含分子氧的气体存在下自热裂化生产烯烃的方法，所述方法包括：(a)提供含液态链烷烃的原料，(b)将所述含液态链烷烃的原料与包含蒸汽的稀释剂(所述稀释剂被预热到至少300℃)混合以产生包含至少20％体积稀释剂的已汽化、稀释的含液态链烷烃的原料流，(c)随后将所述已汽化、稀释的含液态链烷烃的原料流与含分子氧的气体混合产生稀释的混合原料流。(d)随后使所述稀释的混合原料流与能在超过正常富油可燃极限支持燃烧的催化剂接触来提供包含烯烃的烃产物流。
Description
本发明涉及烯烃生产方法。具体地讲，本发明涉及通过自热裂化生产烯烃的方法。
自热裂化是生产烯烃的一种途径，其中使烃进料与氧混合并通过自热裂化催化剂。自热裂化催化剂能在超过富油可燃极限支持燃烧。在催化剂表面引发燃烧并原位产生将反应物提高到操作温度和进行吸热裂解过程所需的热量。一般使得烃进料和分子氧通过载体上的催化剂来产生烯烃产物。通常催化剂包括至少一种铂族金属，例如铂。自热裂化法已在EP 332289B、EP-529793B、EP-A-0709446和WO00/14035中描述。
已知也可使其它进料组分通过自热裂化装置。合适的其它进料组分包括例如氢气和蒸汽。例如通常喂入氢气，因为它优先与含分子氧的气体反应产生烃进料自热裂化所需的热量，降低了燃烧更有价值烃进料来产生所述热量的要求。
我们现在已经发现通过采用包含蒸汽的稀释剂可有利地进行液态烃的自热裂化，其中所述稀释剂与液态烃预先经过混合。
因此，本发明第一方面提供在含分子氧的气体存在下，通过含液态链烷烃的原料自热裂化产生烯烃的方法，所述方法包括：
(a)提供含液态链烷烃的原料，
(b)将所述含液态链烷烃的原料与包含蒸汽的稀释剂(所述稀释剂被预热到至少300℃)混合，以产生包含至少20％体积稀释剂的已汽化、稀释的含液态链烷烃的原料流，
(c)随后将所述已汽化、稀释的含液态链烷烃的原料流与含分子氧的气体混合产生稀释的混合原料流，
(d)随后使所述稀释的混合原料流与能在超过正常富油可燃极限支持燃烧的催化剂接触来提供包含烯烃的烃产物流。
本文中所用的“液态链烷烃”是指在标准温度和压力(s.t.p)下为液态的链烷烃。
适合于本发明方法的液态烃包括石脑油、瓦斯油、真空瓦斯油及其混合物。
本发明方法步骤(b)包括将所述含液态链烷烃的原料与包含蒸汽的稀释剂(所述稀释剂被预热到至少300℃)混合以产生包含至少20％体积稀释剂的已汽化、稀释的含液态链烷烃的原料流。
因此，步骤(b)包括含液态链烷烃的原料的汽化。这可通过使所述含液态链烷烃的原料在与稀释剂混合之前汽化来实现，但优选可将所述含液态链烷烃的原料与稀释剂混合并同时或随后汽化。优选使用(至少部分)预热稀释剂来使得含液态链烷烃的原料汽化。
在原料汽化之前或过程中使用稀释剂或将稀释剂加入已汽化的原料降低了已汽化的原料自燃的风险。具体地讲，已汽化的液态烃一般在低温到高温区域之间仅具有一个狭窄的自燃温度范围。该范围受压力影响并随着压力提高而降低。因此，希望已汽化原料具有良好(狭窄范围)温度控制且停留时间短。此外，当压力提高时液态烃汽化通常变得更难，从而尽管希望在提高压力的情况下缩短已汽化液态烃的停留时间，但这首先由于难以将液态烃汽化而变得困难。本发明方法使用稀释剂降低了已汽化烃的分压同时保持了总压明显更高。因此已汽化烃的稳定温度范围大于相同总压下的稳定温度范围，停留时间也变成次要问题。通过稀释剂稀释混合的原料流同样可得到更高流速，这使得含液态链烷烃的流与含分子氧的气体的混合更快和更容易。(总的来说，当含分子氧的气体和含烃的流的流速为2∶1-5∶1时含烃的流与含分子氧的气体的混合最有效。没有其它组分的情况下，为了得到本发明中合适的烃和氧摩尔比，液态烃的所需流速(即使在汽化后)比氧所需的流速低许多，但本发明将稀释剂加入液态烃减小了该差异)。此外，得到的较高流速使得可在较短停留时间内将稀释的混合原料流喂到催化剂，又减少了着火问题。
此外，可用稀释剂来帮助液态烃汽化。
总之，需要较高总压，因为它们能产生改进的选择性。含液态链烷烃的原料的较低分压也会导致产物流中较低产物分压，这将减少产物流中发生的进一步反应，并从而减少对产物流的骤冷要求。
可采用热交换器来在混合之前预热稀释剂。优选将所述稀释剂预热到300℃-400℃。
除了蒸汽外，或其它供选实施方案中，所述稀释剂包括一氧化碳、二氧化碳、惰性气体(如氦、氖、氩或氮气)，或其混合物。
一氧化碳和二氧化碳例如可作为步骤(d)的自热裂化过程的副产物获得。
优选稀释剂包含20-100％体积蒸汽，更优选50-100％体积蒸汽且最优选至少75％体积蒸汽。
已汽化、稀释的含液态链烷烃的原料优选包含20％体积蒸汽，如至少40％体积蒸汽。
通常稀释的混合原料流包含20-80％体积，例如40-60％体积稀释剂。
最优选稀释的混合原料流包含20-80％体积蒸汽，例如40-60％体积蒸汽。
采用任何合适混合设备将稀释剂与含液态链烷烃的原料混合。
引入稀释剂的优选方法是采用喷雾器。
可采用稀释剂来将一定量的其它烃(不同于含液态链烷烃的原料的烃)引入本发明方法中。因此，稀释剂可还包含至多20％体积不同于含液态链烷烃的原料的烃，例如丁二烯等二烯烃和/或在室温和压力下为气体的烃。
也可采用稀释剂来将一定量的高温氢气供给反应，从而所述稀释剂可包含至多20％体积氢气。
或者，在稀释剂中没有烃或氢气的情况下，所述稀释剂包含至多20％体积分子氧。
蒸汽的加入具有其它优点：蒸汽将阻止催化剂上形成热解碳和裂化反应中形成乙炔。蒸汽(水)也比在标准温度和压力下为气态的稀释剂(氮气、一氧化碳和二氧化碳等)更容易从产物流中除去。通常，在产物流处理(例如通常用来冷却反应的产物骤冷)过程中将蒸汽(水)作为含水相回收且因此可容易地从产物气体分离。
一个实施方案中，可通过如下制备包含蒸汽的预热稀释剂：提供含有氢和分子氧的蒸汽，所述氢和分子氧反应生成蒸汽(水)并产生将所述蒸汽加热到所需预热温度所需的热量。
在一个供选实施方案中，可通过如下制备包含蒸汽的预热稀释剂：提供包含甲烷(和任选氢)的蒸汽并使其与分子氧反应，产生包含蒸汽(水)、二氧化碳和任选任何未反应甲烷的热气流，其至少部分被用作预热稀释剂。包含从氢和分子氧产生的蒸汽或从甲烷和分子氧产生的蒸汽、二氧化碳和任何未反应甲烷的热气流的初始温度通常远高于400℃，因此远高于稀释剂流所需温度。所述蒸汽可通过热交换和/或经过稀释冷却，产生所需温度的稀释剂流。当所述蒸汽通过热交换冷却时移走的热量可用作进入该加工的其它进料(如下所述的含分子氧的气体等)的预热。
优选用作稀释剂的至少部分所述蒸汽可从下游加工步骤(如从用于冷却反应的骤冷步骤)获得。蒸汽的另一合适源为工艺水，本文中所述工艺水定义为本发明方法中的反应形成的水。
在循环和用作蒸汽之前，来自下游加工步骤的所有水可经过处理，以便可将其喂入锅炉并汽化而不会产生不当污垢。合适的处理步骤可包括除去有机液体组分、除去固体和调整水酸性的处理(避免腐蚀)。在汽化阶段不会产生不当污垢的组分可留在蒸汽中且至少部分会在反应段消耗掉。
本发明步骤(c)中，使得已汽化、稀释含链烷烃的原料流随后与含分子氧的气体混合产生稀释的混合原料流。
可使用任何合适含分子氧的气体。含分子氧的气体合适为分子氧、空气和/或其混合物。含氧分子分子氧的气体可与氮气或氩气等惰性气体混合。
含分子氧的气体可在混合之前经过预热。预热时，通常将含分子氧的气体预热到低于150℃，优选低于100℃的温度。
通常被混合的各气流的预热量应使稀释的混合原料流的温度低于混合物的自燃温度。通常明显低于混合原料流接触催化剂时得到的反应温度。通常，产生的稀释的混合原料流的温度为250℃-500℃，如350℃-450℃，尽管优选范围将依赖于压力。
优选稀释的混合原料流包括链烷烃(液态链烷烃和任选任何其它可引入的活性链烷烃)，其中链烷烃与含分子氧的气体之比为链烷烃完全燃烧成二氧化碳和水所需的所述烃与含分子氧的气体的化学计量比的5-16倍，优选5-13.5倍，更优选6-10倍。
氢(分子氢)可作为稀释的混合原料流的组分共喂入本发明方法中。在适当的情况下，氢与含分子氧的气体的摩尔比为0.2-4，优选1-3。
优选使氢在与含分子氧的气体混合之前和含液态链烷烃的原料预混合。
与加入冷稀释剂相比，使用热稀释剂减少了稀释的混合原料流的加热要求。使用热稀释剂同样还有利于自热裂化反应的启动和停车。启动过程中，可在引入反应物之前将热稀释剂引到催化剂，使得催化剂被预热到稀释剂的温度。当引入反应物时，催化剂快速加热到反应温度，催化剂出口处的温度通常为600℃-1200℃。因为由于在引入反应物之前使用热稀释剂，催化剂已经处于较高温度，反应开始时催化剂上的热应力减小。
同样地，停车时催化剂上的热应力可通过采用热稀释剂，任选和氮气等吹扫气体一起而不是仅吹扫气体来减小。
本发明步骤(d)中，使稀释的混合原料流与能在超过正常富油可燃极限支持燃烧的催化剂接触来提供包含烯烃的烃产物流。
能在超过富油可燃极限支持燃烧的催化剂通常包含VIII族金属作为催化组分。合适的VIII族金属包括铂、钯、钌、铑、锇和铱。优选铑且更特别优选铂和钯。通常的VIII族金属负载范围为0.01-100％重量，优选0.01-20％重量且更优选0.01-10％重量，以催化剂的总干重量计。
反应适合在催化剂出口温度为600℃-1200℃，优选850℃-1050℃且更优选900℃-1000℃下进行。
本发明方法优选在至少1barg(巴(表压)，稀释的混合原料流总压)，最优选1-5barg的较高压力下运行。本发明方法优选在稀释的混合原料流中含液态链烷烃的原料与含分子氧的气体的分压超过0.5barg，如0.5-4barg的情况下进行。
使稀释的混合原料流以一定气时空速通过催化剂，所述气时空速受到压力影响且通常超过10,000h-1barg-1，优选超过20,000h-1barg-1且最优选超过100,000h-1barg-1。例如在20barg压力下，气时空速最优选超过2,000,000h-1barg-1，然而应该理解最佳气时空速将依赖于进料组合物的性质。
优选当反应产物从自热裂化装置出来时用水使其骤冷，通常是在合适冷却塔中进行骤冷。
为了避免进一步发生反应，通常将产物流在形成100毫秒内，优选形成50毫秒内且最优选形成20毫秒内冷却到750-600℃。如上所述，与在没有稀释剂的情况下反应相比，本发明使用稀释剂减少了产物流中进一步发生反应的速率。因此本发明提供了消除直接骤冷的可能并替代为废热锅炉等更“常规的”热回收系统。
烃产物流除了烯烃外还包含未反应链烷烃、氢、一氧化碳、甲烷和少量乙炔、芳族化合物和二氧化碳，这些需要与所需烯烃分离开来。
当使用VIII族催化剂时，优选其与催化剂促进剂结合使用。所述促进剂可为III、IVA和/或VA族金属。或者所述促进剂可为过渡金属；过渡金属促进剂为不同于用作VIII族过渡金属催化组分的金属。
优选的IIIA族金属包括Al、Ga、In和Tl。其中优选Ga和In。优选的IVA族金属包括Ge、Sn和Pb。其中优选Ge和Sn。优选的VA金属为Sb。VIIIB族金属与IIIA、IVA或VA族金属的原子比可为1∶0.1-50.0，优选1∶0.1-12.0。
过渡金属系列中的合适金属包括周期表中IB-VIII族中的那些金属。具体地讲，优选选自周期表IB、IIB、VIB、VIIB和VIII族的过渡金属。这类金属的实例包括Cr、Mo、W、Fe、Ru、Os、Co、Rh、Ir、Ni、Pt、Cu、Ag、Au、Zn、Cd和Hg。优选的过渡金属促进剂为Mo、Rh、Ru、Ir、Pt、Cu和Zn。VIII族金属与过渡金属促进剂的原子比可为1∶0.1-50.0，优选1∶0.1-12.0。
优选催化剂仅包含一种促进剂；所述促进剂选自VIIIA族、IVA族、VB族和过渡金属系列。例如所述催化剂可包含选自铑、铂和钯的金属和选自Ga、In、Sn、Ge、Ag、Au或Cu的促进剂。这类催化剂的优选实例包括Pt/Ga、Pt/In、Pt/Sn、Pt/Ge、Pt/Cu、Pd/Sn、Pd/Ge、Pd/Cu和Rh/Sn。Rh、Pt或Pd占催化剂总重的0.01-5.0％重量，优选0.01-2.0％重量且更优选0.05-1.0％重量。Rh、Pt或Pd与IIIA、IVA族或过渡金属促进剂的原子比可为1∶0.1-50.0，优选1∶0.1-12.0。例如Rh、Pt或Pd与Sn的原子比可为1∶0.1-50.0，优选1∶0.1-12.0，更优选1∶0.2-3.0且最优选1∶0.5-1.5。另一方面Pt或Pd与Ge的原子比可为1∶0.1-50.0，优选1∶0.1-12.0且更优选1∶0.5-8.0。Pt或Pd与Cu的原子比可为1∶0.1-3.0，优选1∶0.2-2.0且更优选1∶0.5-1.5。
作为选择的促进剂可包含至少两种选自IIIA、IVA和过渡金属系列的金属。例如当催化剂包含铂时，所述铂可用选自过渡金属系列的两种金属(例如钯和铜)促进。这种Pt/Pd/Cu催化剂可包含0.01-5％重量，优选0.01-2％重量且更优选0.01-1％重量铂，以干催化剂总重计。Pt与Pd的原子比可为1∶0.1-10.0，优选1∶0.5-8.0且更优选1∶1.0-5.0。铂与铜的原子比优选为1∶0.1-3.0，更优选1∶0.2-2.0，且最优选1∶0.5-1.5。
当催化剂包含铂时，它可任选用一种过渡金属和另一种选自周期表IIIA族或IVA族的金属促进。这类催化剂中，钯的量为0.01-5％重量，优选0.01-2.0％重量且更优选0.05-1.0％重量，以催化剂的总重计。Pt与Pd的原子比可为1∶0.1-10.0，优选1∶0.5-8.0且更优选1∶1.0-5.0。Pt与IIIA或IVA族金属的原子比可为1∶0.1-60，优选1∶0.1-50.0。优选所述IIIA或IVA族金属为Sn或Ge，最优选Sn。
为避免疑义，催化剂中的VIII族金属和促进剂可以任何形式存在，例如金属或氧化物等金属化合物。
催化剂可为无载体支持的(例如金属网形式)，但优选有载体支持。可使用任何合适载体材料，例如陶瓷或金属载体，但一般优选陶瓷载体。当使用陶瓷载体时，陶瓷载体组分可为在例如600℃-1200℃高温下稳定的任何氧化物或氧化物组合物。载体材料优选具有低的热膨胀系数并在高温下能抵抗相分离。
合适的陶瓷载体包括堇青石、硅酸铝锂(LAS)、氧化铝(α-Al2O3)、钇稳定的二氧化锆、钛酸铝、niascon和磷酸氧锆钙。所述陶瓷载体可用例如γ-Al2O3洗涤涂布。
所述载体优选为泡沫或蜂窝体。
可通过本领域中已知的方法制备能在超过富油可燃极限支持燃烧的催化剂。例如可采用凝胶法和湿法浸入技术。通常采用一种或多种包含金属的溶液浸渍所述载体，干燥并然后在空气中煅烧。所述载体可在一个或多个步骤中浸渍。优选采用多步浸渍步骤。优选在每次浸渍之间将所述载体干燥和煅烧并然后使之经过最后煅烧，优选在空气中煅烧。煅烧的载体可随后例如通过在氢气气氛中热处理来还原。
Claims (7)
1.一种通过含液态链烷烃的原料在含分子氧的气体存在下自热裂化生产烯烃的方法，所述方法包括：
(a)提供含液态链烷烃的原料，
(b)将所述含液态链烷烃的原料与被预热到至少300℃的包含蒸汽的稀释剂混合以产生包含至少20％体积稀释剂的已汽化、稀释的含液态链烷烃的原料流，
(c)随后将所述已汽化、稀释的含液态链烷烃的原料流与含分子氧的气体混合产生稀释的混合原料流，
(d)随后使所述稀释的混合原料流与能在超过正常富油可燃极限支持燃烧的催化剂接触来提供包含烯烃的烃产物流。
2.权利要求1的方法，其中所述含液态链烷烃的原料包含石脑油、瓦斯油、真空瓦斯油或其混合物。
3.权利要求1或2的方法，其中所述稀释的混合原料流包含链烷烃，使链烷烃与含分子氧的气体之比为链烷烃完全燃烧成二氧化碳和水所需的所述烃与含分子氧的气体的化学计量比的5-16倍，优选5-13.5倍，更优选6-10倍。
4.上述权利要求中任一项的方法，其中所述稀释的混合原料流包含20-80％体积蒸汽，例如40-60％体积。
5.上述权利要求中任一项的方法，其中所述稀释剂包含50-100％体积蒸汽。
6.上述权利要求中任一项的方法，其中所述稀释剂还包含至多20％体积不同于甲烷或含液态链烷烃的原料的烃。
7.上述权利要求中任一项的方法，其中所述能在超过富油可燃极限支持燃烧的催化剂通常包含VIII族金属作为催化组分。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0501255.4 | 2005-01-21 | ||
| GBGB0501255.4A GB0501255D0 (en) | 2005-01-21 | 2005-01-21 | Process for the production of olefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101103094A true CN101103094A (zh) | 2008-01-09 |
Family
ID=34259454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800468881A Pending CN101103094A (zh) | 2005-01-21 | 2005-12-22 | 通过自热裂化生产烯烃的方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20080119681A1 (zh) |
| EP (1) | EP1836277A1 (zh) |
| JP (1) | JP2008528724A (zh) |
| CN (1) | CN101103094A (zh) |
| CA (1) | CA2593852A1 (zh) |
| EA (1) | EA200701392A1 (zh) |
| GB (1) | GB0501255D0 (zh) |
| WO (1) | WO2006077370A1 (zh) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4788371A (en) * | 1987-12-30 | 1988-11-29 | Uop Inc. | Catalytic oxidative steam dehydrogenation process |
| GB9217685D0 (en) * | 1992-08-20 | 1992-09-30 | British Petroleum Co Plc | Process for the production of mono-olefins |
| EP1114013B1 (en) * | 1998-09-03 | 2002-11-27 | The Dow Chemical Company | On-line synthesis and regeneration of a catalyst used in autothermal oxidation |
| KR100668999B1 (ko) * | 1998-09-03 | 2007-01-17 | 다우 글로벌 테크놀로지스 인크. | 산화 촉매의 온-라인 합성 또는 재생방법 |
| GB0017173D0 (en) * | 2000-07-12 | 2000-08-30 | Bp Chem Int Ltd | Process for the production of olefins |
| GB0312966D0 (en) * | 2003-06-05 | 2003-07-09 | Bp Chem Int Ltd | Process for the production of olefins |
-
2005
- 2005-01-21 GB GBGB0501255.4A patent/GB0501255D0/en not_active Ceased
- 2005-12-22 US US11/795,818 patent/US20080119681A1/en not_active Abandoned
- 2005-12-22 WO PCT/GB2005/005048 patent/WO2006077370A1/en active Application Filing
- 2005-12-22 EA EA200701392A patent/EA200701392A1/ru unknown
- 2005-12-22 JP JP2007551730A patent/JP2008528724A/ja active Pending
- 2005-12-22 CN CNA2005800468881A patent/CN101103094A/zh active Pending
- 2005-12-22 CA CA002593852A patent/CA2593852A1/en not_active Abandoned
- 2005-12-22 EP EP05843723A patent/EP1836277A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US20080119681A1 (en) | 2008-05-22 |
| CA2593852A1 (en) | 2006-07-27 |
| GB0501255D0 (en) | 2005-03-02 |
| EA200701392A1 (ru) | 2008-02-28 |
| WO2006077370A1 (en) | 2006-07-27 |
| JP2008528724A (ja) | 2008-07-31 |
| EP1836277A1 (en) | 2007-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2781762C (en) | Catalytic oxidative dehydrogenation, and microchannel reactors for catalytic oxidative dehydrogenation | |
| NO179140B (no) | Fremgangsmåte for fremstilling av mono-olefiner ved katalytisk oksydativ dehydrogenering av gassformige paraffiniske hydrokarboner som har minst to karbonatomer | |
| EP1628939A1 (en) | Process for the production of olefins | |
| JP2577830B2 (ja) | 脱水素および、または脱水素環化用触媒組成物およびその使用方法 | |
| CA2161498C (en) | Hydrocarbon conversion process | |
| UA56344C2 (uk) | Спосіб одержання олефінів | |
| NO176092B (no) | Fremgangsmåte for omdanning av alifatiske C2 - C6-hydrocarboner til cycloalkaner | |
| ZA200504359B (en) | Process for the production of olefins. | |
| CN1942559B (zh) | 生产烯烃和合成气的方法 | |
| CN101103095A (zh) | 通过自热裂化生产烯烃的方法 | |
| EP1819653A1 (en) | Process for the production of methanol | |
| US20080154075A1 (en) | Process for the Production of Olefins | |
| CN101103094A (zh) | 通过自热裂化生产烯烃的方法 | |
| WO2004076063A1 (ja) | 液化石油ガス製造用触媒、その製造方法、および、この触媒を用いた液化石油ガスの製造方法 | |
| CA2560129A1 (en) | Oxidation reaction in the gaseous phase in a porous medium | |
| TW537924B (en) | Process for the production of olefins | |
| US10221110B2 (en) | Dehydrogenation of olefin-rich hydrocarbon mixtures | |
| EP0636114A1 (en) | METHOD FOR THE PRODUCTION OF OLEFINS. | |
| WO1993021138A1 (en) | Olefin production | |
| AU2006201072A1 (en) | Process for the production of olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080109 |