GB2435883A - Autothermal cracking process for ethylene production - Google Patents
Autothermal cracking process for ethylene production Download PDFInfo
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- GB2435883A GB2435883A GB0604874A GB0604874A GB2435883A GB 2435883 A GB2435883 A GB 2435883A GB 0604874 A GB0604874 A GB 0604874A GB 0604874 A GB0604874 A GB 0604874A GB 2435883 A GB2435883 A GB 2435883A
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- Prior art keywords
- ethylene
- ethane
- lng
- stream
- product stream
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- 238000000034 method Methods 0.000 title claims abstract description 60
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000005977 Ethylene Substances 0.000 title claims abstract description 33
- 238000005336 cracking Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 238000002485 combustion reaction Methods 0.000 claims abstract description 9
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 238000005057 refrigeration Methods 0.000 claims abstract description 8
- 239000003949 liquefied natural gas Substances 0.000 description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 25
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 24
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 239000001294 propane Substances 0.000 description 12
- 239000001273 butane Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000004230 steam cracking Methods 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- -1 niascon Chemical compound 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C4/025—Oxidative cracking, autothermal cracking or cracking by partial combustion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- 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
- C10G11/22—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert heated gases or vapours produced by partial combustion of the material to be cracked
-
- 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
- C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
-
- 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
- C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
-
- 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
- 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
- C07C2523/44—Palladium
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- 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
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
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- 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
- C07C2523/48—Silver or gold
- C07C2523/50—Silver
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- 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
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- C07C2523/52—Gold
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- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- General Chemical & Material Sciences (AREA)
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- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a process for the production of ethylene by autothermal cracking of ethane, said process comprising: <SL> <LI>(i) separating an ethane-containing stream from LNG at an LNG regasification plant, <LI>(ii) autothermally cracking the ethane-containing stream from step (i) by contacting with a catalyst capable of supporting combustion beyond the fuel-rich limit of flammability in the presence of oxygen, to produce a product stream comprising ethylene, and <LI>(iii) passing the product stream comprising ethylene to a separations train, to separate ethylene from other components in the product stream, wherein the separations train comprises one or more steps in which refrigeration is provided from the LNG regasification plant. </SL>
Description
<p>----I</p>
<p>PROCESS</p>
<p>The present invention relates to a process for the production of ethylene by autothermal cracking of ethane separated from liquefied natural gas (LNG).</p>
<p>Natural gas comprises a mixture of paraffinic hydrocarbon gases, and may typically be found in either isolated gas fields ("stranded gas") or associated with crude oil. The principal component of natural gas is methane, with smaller amounts of ethane, propane and butane. The natural gas usually needs to be shipped to where it is desired. In order reduce the volume of natural gas so that it can be economically shipped the natural gas is liquefied, typically by cooling to approximately -16 1 C at atmospheric pressure in an LNG process, to form liquified natural gas (LNG).</p>
<p>Once shipped the LNG is regasified (regas LNG) for use. The natural gas is typically used directly as a fuel for a purpose built power station or passed to a suitable natural gas distribution grid. Because the regas LNG can have a varying composition, ethane (and higher hydrocarbons) in the LNG may need to be separated to meet lean gas specifications for use. The volumes of recovered ethane are too small to provide enough feed for a conventional steam cracking process for the production of ethylene, such processes generally requiring over lmtpa (million tonnes per annum) of ethane to be economically attractive.</p>
<p>However, it has now been found that ethane from an LNG regasification plant can be advantageously utilized to produce ethylene in a co-located autothermal cracking process for production of ethylene.</p>
<p>Hence, in a first aspect, the process of the present invention provides a process for the production of ethylene by autothermal cracking of ethane, said process comprising: (i) separating an ethane-containing stream from LNG at an LNG regasification plant, (ii) autothermally cracking the ethane-containing stream from step (i) by contacting with a catalyst capable of supporting combustion beyond the fuel-rich limit of flammability in the presence of oxygen, to produce a product stream comprising ethylene, and (iii) passing the product stream comprising ethylene to a separations train, to separate ethylene from other components in the product stream, wherein the separations train comprises one or more steps in which refrigeration is provided from the LNG regasification plant.</p>
<p>The present invention takes advantage of the fact that autothermal cracking processes can be economically operated at lower scale than other ethylene production processes, such as steam cracking processes.</p>
<p>In particular, the autothermal cracking process of step (ii) could operate at a scale below I 000ktpa (kilotonnes per annum) of ethane. Preferably the autothermal cracking process of step (ii) is at a scale of 500ktpa or above of ethane, for example in the range 500ktpa to 700ktpa.</p>
<p>Thus, the ethane for the autothermal cracking step (ii) can be provided solely from ethane separated from LNG during regasification. This enables the ATC process (including the separations train) to be located close to the LNG regasification plant such that refrigeration for the ATC separations train can be provided from the LNG regasification plant. The heat which must be removed from the downstream separation section of the ATC plant is thus used to provide energy for regasification of the LNG, thereby maximising the heat integration of the two processes.</p>
<p>The ethane-containing stream separated in step (i) generally comprises predominantly ethane, by which is meant at least 50 vol% ethane, with smaller quantities of higher hydrocarbons, especially propane and butane, and a further advantage of the process of the present invention is that autothermal cracking processes are more tolerant of variations in the feed composition than steam cracking processes. This can be important since the LNG supply may come from sources with different compositions. In particular, varying quantities of propane and butane may be fed with ethane to the autothermal cracker in the process of the present invention whilst still maintaining high ethylene selectivities.</p>
<p>Variations of propane and butane in the ethane-containing stream may be due to natural variations in the composition of the LNG from which the ethane-containing stream has been separated, but the process of the present invention also allows different amounts of propane and butane to be deliberately fed with the ethane.</p>
<p>For example, in one embodiment, propane and butane in the LNG may be separated with the ethane from the LNG as a single, mixed, stream, and the mixed stream is passed to the autothermal cracking step (ii). The autothermal cracking process is tolerant to changes in the relative amounts of ethane, propane and butane due to variations in the LNG source, and the overall process has the added advantage that no separation of ethane from propane and butane is required during the LNG regasification.</p>
<p>In a second, alternative, embodiment, it may generally be preferred to separate at least some of the propane and butane in the LNG as a separate stream for sale as LPG (liquified petroleum gas). However, if the LPG market becomes oversupplied, this propane and/or butane may instead be fed to the autothermal cracker with the ethane-containing stream.</p>
<p>Thus, the process of the present invention has significant versatility to cope with variations in the LNG composition and in local market conditions.</p>
<p>Step (I) of the process of the present invention typically comprises separation of the ethane-containing stream during regasification. Regasification is generally achieved through the transfer of heat into the LNG, usually through at least one heat exchanger. One common technique is to burn a small amount of the LNG to produce the heat needed to gasi the stream of LNG. Another common technique for regasification of LNG uses heat from ambient water, such as seawater or river water.</p>
<p>In the process of the present invention, at least part of the heat required for regasification is provided from the product stream comprising ethylene of the autothermal cracking reaction.</p>
<p>In step (ii) the ethane-containing stream separated in step (I) is autothermally cracked by contacting with a catalyst capable of supporting combustion beyond the fuel-rich limit of flammability in the presence of oxygen, to produce a product stream comprising ethylene. In the autothermal cracking (ATC) process combustion of the feed is initiated on the catalyst surface and the heat required to raise the reactants to process temperature and to carry out the endothermic cracking process is generated in situ.</p>
<p>Autothermal cracking (ATC) is described generally for example in EP 0332289B; EP 0529793B; EP 0709446A and WO 00/14035.</p>
<p>The oxygen may be provided as any suitable molecular oxygen containing gas, such as molecular oxygen itself or air. Generally, pure or essentially pure molecular oxygen is utilised after being separated from air on-site, and in this case, the cost and energy demand for molecular oxygen separation can be reduced by also using some of the "cold" from the LNG regasification to pre-chill the air.</p>
<p>The hydrocarbon to be cracked (ethane and any higher hydrocarbons) and molecular oxygen-containing gas may be contacted with the catalyst capable of supporting combustion in any suitable molar ratio, provided ethylene is produced. The preferred stoichiometric ratio of hydrocarbon to oxygen-containing gas is 5 to 16, preferably, 5 to 13.5 times, preferably, 6 to 10 times the stoichiometric ratio of hydrocarbon to oxygen-containing gas required for complete combustion of the hydrocarbon to carbon dioxide and water.</p>
<p>The hydrocarbon is passed over the catalyst at a gas hourly space velocity of greater than 10,000 h, preferably above 20,000 h' and most preferably, greater than 100,000 h'.</p>
<p>It will be understood, however, that the optimum gas hourly space velocity will depend upon the pressure and nature of the feed composition.</p>
<p>Preferably, hydrogen is co-fed with the ethane-containing stream, oxygen and, where fed, any additional propane and/or butane feeds. The molar ratio of hydrogen to oxygen can vary over any operable range provided that the product stream comprising ethylene is produced. Suitably, the molar ratio of hydrogen to oxygen is in the range 0.2 to 4, preferably, in the range 1 to 3.</p>
<p>Hydrogen co-feeds are advantageous because, in the presence of the catalyst, the hydrogen combusts preferentially relative to hydrocarbon, thereby increasing the olefin selectivity of the overall process.</p>
<p>The autothermal cracking step may suitably be carried out at a catalyst exit temperature in the range 600 C to 1200 C, preferably, in the range 85 0 C to 1050 C and, most preferably, in the range 900 C to 1000 C.</p>
<p>The autothermal cracking step is usually operated at a pressure of greater than 0.5barg. Preferably the autothermal cracking process is operated at a pressure of between 0.5-4obarg.</p>
<p>The catalyst capable of supporting combustion beyond the fuel rich limit of flammability usually comprises a Group VIII metal as its catalytic component. Suitable Group VIII metals include platinum, palladium, ruthenium, rhodium, osmium and iridium.</p>
<p>Rhodium, and more particularly, platinum and palladium are preferred. Typical Group VIII metal loadings range from 0.01 to lOOwt %, preferably, between 0.01 to 20 wt %, and more preferably, from 0.01 to 10 wt % based on the total dry weight of the catalyst.</p>
<p>Where a Group VIII catalyst is employed, it is preferably employed in combination with a catalyst promoter. The promoter may be a Group lIlA, IVA, and/or VA metal. Alternatively, the promoter may be a transition metal; the transition metal promoter being a different metal to that which may be employed as the Group VIII transition metal catalytic component. Preferred promoters are selected from the group consisting of Ga, In, Sn, Ge, Ag, Au or Cu. The atomic ratio of Group VIII B metal to the catalyst promoter may be 1: 0.1 -50.0, preferably, 1: 0.1 -12.0.</p>
<p>Preferred examples of promoted catalysts include Pt/Ga, Pt/In, Pt/Sn, Pt/Ge, Pt/Cu, Pd/Sn, Pd/Ge, Pd/Cu, Rh/Sn, Pt/Pd/Cu and Pt/Pd/Sn catalysts.</p>
<p>For the avoidance of doubt, the Group VIII metal and promoter in the catalyst may be present in any form, for example, as a metal, or in the form of a metal compound, such as an oxide.</p>
<p>The catalyst may be unsupported, such as in the form of a metal gauze, but is preferably supported. Any suitable support may be used such as ceramic or metal supports, but ceramic supports are generally preferred. Where ceramic supports are used, the composition of the ceramic support may be any oxide or combination of oxides that is stable at high temperatures of, for example, between 600 C and 1200 C. The support material preferably has a low thermal expansion co-efficient, and is resistant to phase separation at high temperatures.</p>
<p>Suitable ceramic supports include corderite, lithium aluminium silicate (LAS), alumina (a-A1203), yttria stabilised zirconia, alumina titanate, niascon, and calcium zirconyl phosphate. The ceramic supports may be wash-coated, for example, with y-Al203.</p>
<p>The catalyst capable of supporting combustion beyond the fuel rich limit of flammability may be prepared by any method known in the art. For example, gel methods and wet-impregnation techniques may be employed. Typically, the support is impregnated with one or more solutions comprising the metals, dried and then calcined in air. The support may be impregnated in one or more steps. Preferably, multiple impregnation steps are employed. The support is preferably dried and calcined between each impregnation, and then subjected to a final calcination, preferably, in air. The calcined support may then be reduced, for example, by heat treatment in a hydrogen atmosphere.</p>
<p>The product stream comprises ethylene, and may also comprise propylene and butylene. The product stream is quenched as it emerges from the reaction chamber to avoid further reactions taking place. Usually the product stream is cooled to between 750-600 C within less than 1 OOmilliseconds of formation, preferably within 5Omilliseconds of formation and most preferably within 20milliseconds of formation e.g. within lOmilliseconds of formation. The heat from the quenching is used to generate high-pressure steam, which is used to provide power for those parts of the overall process requiring it.</p>
<p>In addition to olefins, the autothermal cracking reaction produces hydrogen, carbon monoxide, methane, and small amounts of acetylenes, aromatics and carbon dioxide.</p>
<p>In step (iii) of the process of the present invention this product stream is passed to a separations train to separate ethylene from the other components in said stream. The carbon dioxide is usually removed first, typically using an amine-based absorption system such as MEA or TEA (or mixtures of both), or any other commercially available CO2 removal process. The reaction products are then treated in a refrigeration facility (cryogenic separation unit) to separate methane, hydrogen and carbon monoxide from ethylene and higher hydrocarbons.</p>
<p>In the process of the present invention, the refrigeration for this refrigeration facility is provided from the LNG regasification plant.</p>
<p>This has significant synergistic advantages since a separate refrigeration facility for the autothermal cracking process is not required, saving cost and energy requirements. In addition, the heat which must be removed from the downstream separation section of the ATC plant provides energy for regasification of the LNG.</p>
<p>The ethylene may be separated from ethane and higher hydrocarbons by any suitable technique, for example by passing to a de-ethaniser to separate ethane and ethylene from propane, propylene and any higher hydrocarbons, followed by subsequent separation of ethane from ethylene.</p>
<p>In a preferred embodiment of the process of the present invention, the LNG regasification and ATC processes also share one or more other process facilities (services) such as power, control room and flare facilities.</p>
<p>The autothermal cracking process also produces, as one or more by-products streams, methane, hydrogen and carbon monoxide. In a typical ATC process, a process stream comprising methane, hydrogen and carbon monoxide is used as fuel gas in a gas turbine to provide energy for the overall autothermal cracking process. Where the LNG is --7 to be utilised directly as a fuel in a power plant, this process stream may instead be supplied as a fuel gas stream to the power plant to generate energy this way. Thus, a separate turbine can be avoided.</p>
<p>The ethylene produced, along with any other olefins, may be used as feedstocks for olefin derivative processes, such as polymerization processes to produce polyethylene, polypropylene and other polymers. Such processes may be located with the ATC process and LNG regasification plant, or may be remote from said processes.</p>
<p>Production of ethylene according to the process of the present invention has the added advantage that the scale of the ethylene production can be matched to the feed requirements of a single downstream ethylene derivative plant. In contrast, for a "conventional" steam cracking process of I mtpa scale several derivative plants are required to utilise all the ethylene produced.</p>
Claims (1)
- <p>CLAIMS</p><p>1. A process for the production of ethylene by autothermal cracking of ethane, said process comprising: (i) separating an ethane-containing stream from LNG at an LNG regasification plant, (ii) autothermally cracking the ethane-containing stream from step (i) by contacting with a catalyst capable of supporting combustion beyond the fuel-rich limit of flammability in the presence of oxygen, to produce a product stream comprising ethylene, and (iii) passing the product stream comprising ethylene to a separations train, to separate ethylene from other components in the product stream, wherein the separations train comprises one or more steps in which refrigeration is provided from the LNG regasification plant.</p>
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GB0604874A GB2435883A (en) | 2006-03-10 | 2006-03-10 | Autothermal cracking process for ethylene production |
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Cited By (7)
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US20140374660A1 (en) * | 2013-06-25 | 2014-12-25 | Massachusetts Institute Of Technology | Engine Chemical Reactor With Catalyst |
US10815439B2 (en) | 2018-08-22 | 2020-10-27 | Exxonmobil Research And Engineering Company | Manufacturing hydrocarbons |
US10843980B2 (en) | 2018-08-22 | 2020-11-24 | Exxonmobil Research And Engineering Company | Manufacturing a base stock from ethanol |
US10858600B2 (en) | 2018-08-22 | 2020-12-08 | Exxonmobil Research And Engineering Company | Manufacturing a base stock |
US10858599B2 (en) | 2018-08-22 | 2020-12-08 | Exxonmobil Research And Engineering Company | Manufacturing hydrocarbons |
US10889769B2 (en) | 2018-08-22 | 2021-01-12 | Exxonmobil Research And Engineering Company | Manufacturing a base stock from ethanol |
US11015131B2 (en) | 2018-08-22 | 2021-05-25 | Exxonmobil Research And Engineering Company | Manufacturing hydrocarbons |
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US3548024A (en) * | 1963-10-14 | 1970-12-15 | Lummus Co | Regasification of liquefied natural gas at varying rates with ethylene recovery |
US6566573B1 (en) * | 1998-09-03 | 2003-05-20 | Dow Global Technologies Inc. | Autothermal process for the production of olefins |
WO2004097626A2 (en) * | 2003-04-28 | 2004-11-11 | Koninklijke Philips Electronics N.V. | Parallel processing system |
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- 2006-03-10 GB GB0604874A patent/GB2435883A/en not_active Withdrawn
Patent Citations (3)
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US3548024A (en) * | 1963-10-14 | 1970-12-15 | Lummus Co | Regasification of liquefied natural gas at varying rates with ethylene recovery |
US6566573B1 (en) * | 1998-09-03 | 2003-05-20 | Dow Global Technologies Inc. | Autothermal process for the production of olefins |
WO2004097626A2 (en) * | 2003-04-28 | 2004-11-11 | Koninklijke Philips Electronics N.V. | Parallel processing system |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US20140374660A1 (en) * | 2013-06-25 | 2014-12-25 | Massachusetts Institute Of Technology | Engine Chemical Reactor With Catalyst |
US10815439B2 (en) | 2018-08-22 | 2020-10-27 | Exxonmobil Research And Engineering Company | Manufacturing hydrocarbons |
US10843980B2 (en) | 2018-08-22 | 2020-11-24 | Exxonmobil Research And Engineering Company | Manufacturing a base stock from ethanol |
US10858600B2 (en) | 2018-08-22 | 2020-12-08 | Exxonmobil Research And Engineering Company | Manufacturing a base stock |
US10858599B2 (en) | 2018-08-22 | 2020-12-08 | Exxonmobil Research And Engineering Company | Manufacturing hydrocarbons |
US10889769B2 (en) | 2018-08-22 | 2021-01-12 | Exxonmobil Research And Engineering Company | Manufacturing a base stock from ethanol |
US11015131B2 (en) | 2018-08-22 | 2021-05-25 | Exxonmobil Research And Engineering Company | Manufacturing hydrocarbons |
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