EP1463789B9 - Steam-cracking of fcc-gasoline - Google Patents
Steam-cracking of fcc-gasoline Download PDFInfo
- Publication number
- EP1463789B9 EP1463789B9 EP03712222A EP03712222A EP1463789B9 EP 1463789 B9 EP1463789 B9 EP 1463789B9 EP 03712222 A EP03712222 A EP 03712222A EP 03712222 A EP03712222 A EP 03712222A EP 1463789 B9 EP1463789 B9 EP 1463789B9
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- gasoline
- component
- naphtha
- feedstock
- 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 - Lifetime
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- 239000003502 gasoline Substances 0.000 title claims abstract description 98
- 238000004230 steam cracking Methods 0.000 title claims abstract description 55
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 51
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001294 propane Substances 0.000 claims abstract description 49
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 45
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 44
- 239000001273 butane Substances 0.000 claims abstract description 41
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 31
- 239000012188 paraffin wax Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 45
- 150000001336 alkenes Chemical class 0.000 claims description 44
- 235000013844 butane Nutrition 0.000 claims description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 34
- 239000005977 Ethylene Substances 0.000 claims description 33
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims 3
- 239000000047 product Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000945 filler Substances 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 230000008901 benefit Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- -1 butadiene Chemical class 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- VBUBYMVULIMEHR-UHFFFAOYSA-N propa-1,2-diene;prop-1-yne Chemical compound CC#C.C=C=C VBUBYMVULIMEHR-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Chemical class 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 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
- 238000004227 thermal cracking Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Images
Classifications
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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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
- C10G2300/805—Water
- C10G2300/807—Steam
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S208/00—Mineral oils: processes and products
- Y10S208/01—Automatic control
Definitions
- the present invention relates to a process for the steam cracking of naphtha, a hydrocarbon composition suitable for steam cracking, a method for controlling a steam cracker, apparatus for controlling a steam cracker and a process for treating a sulfur gasoline feedstock.
- olefins are mainly obtained by steam cracking charges obtained from refineries.
- the available feedstocks are mainly naphtha feeds including paraffins, isoparaffins and aromatics.
- a naphtha feedstock useful in steam cracking is known in the art as comprising a petroleum cutter whose lightest constituents have five carbon atoms and which has a final boiling point of about 200 ° C, the naphtha comprising high carbon components having a boiling point of at least 200 ° C.
- Steam cracking of naphtha gives light olefins such as ethylene and propylene, and diolefins such as butadiene, as well as aromatics-containing gasolines.
- the cracked product When a typical naphtha is subjected to steam cracking, the cracked product typically has the following composition (in% by weight) at the outlet of the oven: % in weight (approximate) Hydrogen 1 Methane 16 Acetylene 0.2 Ethylèue 22 Ethane 5 Methylacetylene, Propadiene 0.3 propylene 14 Propane 0.5 butadiene 4 C4 5 C5 4 Benzene 9 Toluene 5 Non-aromatic essence 2 Aromatic essence 6 oil 6 Total 100
- the most interesting cuts in the cracked product are light olefins, namely ethylene and propylene.
- Their yield is directly related to the presence of paraffins in the load. When straight chain paraffins are present, the formation of ethylene is favored. When isoparaffins are present, propylene formation is favored.
- the relative yield of propylene is expressed as the ratio by weight of propylene to ethylene and is typically between 0.5 and 0.75.
- DE-A-3708332 discloses a method of thermal cracking of ethylene in a steam cracker, wherein the ethylene is mixed with the naphtha so as to prepare a feedstock consisting essentially of naphtha and 10 to 80% by weight of ethylene, optionally containing , in addition to naphtha, fractions up to the fuel oil (boiling temperature up to 350 ° C) and / or by-products recycled from a petrochemical plant up to 50% of the naphtha.
- This process has the disadvantage that it requires relatively large amounts of ethylene (at least 10%) in the raw materials and that then the ethylene (relative to ethylene feedstock) and propylene yields do not increase. are not particularly high.
- US-A-3786110 describes a process for the production of unsaturated hydrocarbons obtained by pyrolysis, where the undesirable fractions are reduced by the addition to the products of the pyrolysis of a polymerization inhibitor containing asphaltic hydrocarbons.
- a process for steam cracking of naphtha capable of providing a commercially acceptable yield of olefins, especially light olefins such as ethylene and propylene, while reducing the amount of paraffinic naphtha starting material required, is therefore necessary in the art. technical.
- Ethane and propane are used as fillers for steam cracking, particularly in the United States, where natural gas, from which they are extracted, is abundant. These paraffins generate a large amount of ethylene (greater than 50%), when they are steam-cracked, which leads to treating these charges in specifically sized units for this type of charges.
- Some refinery hydrocarbon gases, such as FCC gases contain substantial amounts of paraffins (ethane and propane) and olefins (ethylene, propylene).
- FCC gases Some refinery hydrocarbon gases, such as FCC gases, contain substantial amounts of paraffins (ethane and propane) and olefins (ethylene, propylene).
- FCC gases include substantial amounts of paraffins (ethane and propane) and olefins (ethylene, propylene).
- Butane and propane are also used, either alone or mixed with naphtha, as steam cracker feedstocks. When attempting to use them exclusively, the problem of imbalance in the downstream section of a naphtha steam cracker is also apparent. Depending on the availability of the refinery or the market, these liquefied gases can be in excess and it is therefore interesting to use them as a steam cracker load.
- DE-A-3708332 does not address the technical problem of producing an effluent whose composition corresponds to that produced by the steam-cracking of a naphtha.
- the composition of the effluent particularly with respect to ethylene and propylene, is substantially altered compared to the cracking of naphtha. only under the same conditions, which can lead to significantly reduce the capacity of the steam-cracking unit.
- the invention aims to at least partially satisfy these needs.
- the invention provides a process for the steam-cracking of naphtha, which process comprises the passage in a steam-steam cracker of a hydrocarbon charge, which comprises a portion of a paraffinic naphtha modified with adding the combination of a first component, comprising a portion of gasoline, and a second component, comprising a portion of at least one hydrocarbon refinery gas, and a paraffin-rich feed comprising at least one paraffin selected from propane and butane or a mixture of both.
- the invention also provides a hydrocarbon composition suitable for steam cracking, comprising a part of a paraffinic naphtha, modified by the addition of the combination of a first component, comprising one part of gasoline, and a second component, comprising a portion of at least one hydrocarbon refinery gas, and a paraffin-rich filler comprising at least one paraffin selected from propane and butane or a mixture of both.
- the invention further provides a method for controlling a steam cracker, which process comprises supplying a steam cracker and a hydrocarbon feedstock comprising a part of a paraffinic naphtha, modified by the addition of the combination of a first component, comprising a portion of gasoline, and a second component, comprising a portion of at least one hydrocarbon refinery gas and a paraffin-rich feedstock comprising at least one paraffin selected from propane and butane or a mixture of both, and continuously controlling feed intakes. paraffinic naphtha, the second component and gasoline in the feed to give the effluent a desired target composition.
- the invention also provides a process for treating a sulfur-containing gasoline charge, which process comprises the steps of: combining a sulfur-containing gasoline charge with a naphtha charge to provide a composite charge; passing the composite feed through a steam cracker, in the presence of steam, to produce an effluent, the effluent containing at least light olefins, the light olefins comprising at least one of C2 to C4 olefins, and C5 + hydrocarbons; and separating from the effluent a first fraction that is substantially free of sulfur and includes light olefins, and a second fraction that contains sulfur and includes C5 + hydrocarbons.
- the invention is based on the surprising discovery by the Applicant that by selecting certain quantities and qualities of these gasolines and gaseous hydrocarbons and by using them as fillers in combination with naphtha, it is possible to steam crack the composite charge to thereby produce a composition for the cracked product (referred to in the "product palette" technique) that strongly resembles a pallet of products resulting from steam cracking, under similar conditions, of a paraffinic naphtha feedstock only.
- the composition of the effluent produced according to the invention is within a range of ⁇ 20% by weight and preferably, ⁇ 10% by weight, for each component, relative to that of the effluent, when it is an unmodified paraffinic naphtha.
- a part of the paraffinic naphtha feed is, according to the invention, replaced by a combination of a gasoline feedstock and a hydrocarbon refinery gas feedstock and / or feedstock. butane or propane or a mixture of both.
- a process for the steam cracking of naphtha uses a filler of a hydrocarbon composition, which comprises a portion of a paraffinic naphtha, modified by a portion of a gasoline in combination with a portion of a gas hydrocarbon refinery and / or a portion of butane or propane or a mixture of both
- the paraffinic naphtha for use in the process of the invention comprises from 10 to 60% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 35% by weight of naphthenes, from 0 to 1% by weight. % by weight of olefins and from 0 to 20% by weight of aromatics.
- a typical paraffinic naphtha for use in the process of the invention comprises about 31% by weight of n-paraffins, 35% by weight of isoparaffins (giving a total paraffinic content of 66% by weight), 26% by weight of naphthenes. 0% by weight of olefins (typically 0.05% by weight of olefins) and 8% by weight of aromatics.
- this starting paraffinic naphtha feed is modified by adding thereto a gasoline and a hydrocarbon refinery gas and / or butane or propane or a mixture of the two.
- the gasoline is preferably a fraction from a fluidized-bed catalytic cracking (FCC) unit of an oil refinery (herein referred to as FCC gasoline), which advantageously has not has not been subjected to a hydrogenation treatment (referred to in the art as "hydrorefining"), which increases the paraffin content of gasoline by hydrogenating the unsaturated functions (such as those present in olefins and diolefins) of gasoline
- FCC gasoline fluidized-bed catalytic cracking unit of an oil refinery
- hydroorefining referred to in the art as "hydrorefining”
- the advantage of using a non-hydrorefined FCC gasoline is that by avoiding a hydrogenation process, production costs are reduced by eliminating or reducing the use of hydrogen and avoiding the need for a hydrogenation process. additional hydrorefining capacity.
- FCC gasoline is a slice or slice of the FCC unit typically having a distillation range of from 30 to 160 ° C, preferably a slice of cup or mixture of slices within the range of between 30 and 65 ° C, 65 to 105 ° C and 105 to 145 ° C.
- the choice of the particular FCC gasoline or blend of it to be used may be determined based on the requirements at any time for the various cuts produced by the refinery. For example, some gasoline cuts have an octane deficit and could be better valued in a steam cracker than having to increase the octane number in the refinery.
- the FCC gasoline to be used may have a sulfur content that would be too high for gasolines to be used in the automotive sector and that would require a desulphurization treatment with hydrogen, which is expensive because it consumes more fuel. hydrogen and requires the corresponding capacity on a desulfurization unit.
- non-hydrorefined FCC gasoline it is preferred to use a non-hydrorefined FCC gasoline, because in the refinery, where there is a need for hydrorefined gasoline for other uses, this can cause bottlenecks in processing by the unit of hydroprocessing.
- this can freeze appliances and appliances. hydrorefining units, thereby improving the flow management in the refinery, and also by reducing the need for hydrogen.
- the non-hydrorefined FCC gasoline comprises from 0 to 30% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 80% by weight of naphthenes, from 5 to 80% by weight olefins and from 0 to 60% by weight of aromatics. More typically, the non-hydrorefined FCC gasoline comprises approximately 3.2% by weight of n-paraffins, 19.2% by weight of isoparaffins (giving a total paraffin content of 22.4% by weight), 18% by weight of naphthenes, 30% by weight of olefins and 29.7% by weight of aromatics.
- this gas hydrocarbon is rich in C 2 and C 3 hydrocarbons, in particular paraffins (ethane and propane) and olefins (ethylene and propylene).
- the refinery gas has the following compositional ranges: 0 to 5% by weight hydrogen, 0 to 40% by weight methane, 0 to 50% by weight ethylene, 0 to 80% by weight d ethane, 0 to 50% by weight of propylene, 0 to 80% by weight of propane and 0 to 30% by weight of butane.
- a typical composition of a refinery gas of this type is approximately 1% by weight of hydrogen, 2% by weight of nitrogen, 0.5% by weight of carbon monoxide, 0% by weight of carbon dioxide. carbon, 10% by weight of methane, 15% by weight of ethylene, 32% by weight of ethane, 13% by weight of propylene, 14% by weight of propane, 2% by weight of isobutane, 4% by weight of weight of n-butane, 3% by weight of butene, 2% by weight of n-pentane, and 1.5% by weight of n-hexane.
- this butane and / or propane or the mixture of both which is added to the paraffinic naphtha, in combination with the FCC gasoline and optionally the refinery gas, to produce a composite filler for steam cracking
- this butane and / or this propane or the mixture of two may contain compounds olefins such as butenes and / or propylene, or saturated compounds such as butanes (normal and / or iso) and / or propane.
- butane and / or propane or the mixture of both contain more than 50% by weight of saturated compounds to maximize the production of light olefins such as ethylene and propylene.
- Butane and propane are preferably n-butane and n-propane.
- the composite filler comprises from 5 to 95% by weight of naphtha, from 5 to 95% by weight of a mixture of refinery gas, butane or propane or a mixture of both, and gasoline.
- the mixture of refinery gas, butane or propane or a mixture of both, and gasoline which is added to the naphtha comprises up to 60% by weight of refinery gas and / or butane or propane gas or a mixture of both, and at least 40% by weight of gasoline, more typically up to 50% by weight of refinery gas and / or butane or propane gas or a mixture of both, and up to 50% by weight of gasoline.
- the composite naphtha comprises 80% by weight of naphtha, 7% by weight of refinery gas and / or butane or propane or a mixture of both, and 13% by weight of non-hydrorefined FCC gasoline. .
- the composite filler of naphtha, gasoline, refinery gas and / or butane or propane or a mixture of both. is typically subjected to steam cracking under conditions similar to those known in the art, namely a temperature of between 780 and 880 ° C, preferably between 800 and 850 ° C.
- the amount of steam may also fall within ranges known in the art, typically between 25 and 60% by weight based on the weight of the hydrocarbon feed.
- the steam cracking unit for use in the method of the invention is schematically represented.
- the steam cracking unit comprises a heating assembly consisting of ovens 4, which is provided with coils 6 having a first inlet 8 for the hydrocarbon feed to be cracked and a second inlet 10 for the steam.
- An outlet pipe 12 of the set of Heating is connected to a primary fractionation column 14.
- the primary fractionation column 14 comprises overhead gasoline reflux 15 and outlets for the various fractionated products, including an upper outlet 16 for light hydrocarbons and a lower outlet 18 for heavy hydrocarbons, which can be returned to 19 after cooling in line 12 to control the temperature or withdrawn at 17 in the form of heavy products called pyrolysis oil.
- the entire composite feedstock of naphtha, refinery gas, and / or butane or propane or a mixture of both and gasoline may be fed from the common hydrocarbon inlet or alternatively, the four components of naphtha, FCC gasoline, refinery gas and / or butane or propane or a mixture of the two can be cracked separately in specific tubular coils.
- the naphtha and the FCC gasoline, on the one hand, butane and / or propane or a mixture of both, and the refinery gas, on the other hand, are cracked separately.
- naphtha and FCC gasoline are typically cracked at temperatures that are close to each other, typically in the range of 750 to 850 ° C, while butane, propane, refineries that contain ethane and propane must be cracked at higher temperatures, typically in the range of 800 to 900 ° C.
- the two effluents can be combined at the outlet of the heating assembly before the primary fractionation column.
- the process of the invention can operate continuously and has the advantage of eliminating excess gasoline from the refinery, and also reducing the need in the refinery for a desulphurization process.
- Gasoline contains sulfur and, as a result of the steam cracking process, in which gasoline provides some of the composite filler, the most valuable light olefins in the effluent are sulfur free, while the sulfur remains concentrated in the game C5 + of the effluent stream. Therefore, the use of gasoline as part of a feed to be cracked to produce lighter olefins results in partial desulphurization of the gasoline portion of the feed because the sulfur is concentrated in the carbon number fraction. higher and commercially less attractive effluent, namely the C5 + current.
- the invention provides a process for treating a sulfurized gasoline feedstock, the process comprising the steps of: combining a sulfur gasoline feedstock with a naphtha feedstock to provide a composite feedstock; passing the composite feed through a steam cracker, in the presence of steam, to produce an effluent, the effluent containing at least light olefins, the light olefins comprising at least one of C2 to C4 olefins, and C5 + hydrocarbons; and separating from the effluent a first fraction that is substantially free of sulfur and includes light olefins, and a second fraction that contains sulfur and includes C5 + hydrocarbons.
- the sulfur is redistributed in the higher carbon number fraction, producing a lower sulfur-free olefinic fraction, which is an effective way of partially desulfurizing the gasoline charge.
- the process has the advantage that the steam cracking process at least partially dehydrogenates the ethane present in the refinery gases, the dehydrogenation being carried out at a sufficiently high temperature to efficiently produce ethylene.
- the invention also has the advantage that by adding to the naphtha feed, which contains no or only a small amount of olefins, a non-hydrorefined gasoline which contains a relatively high amount of olefins, typically from 5 to 80% by weight of olefins, the composite feedstock for steam cracking has a higher overall olefin content, compared with the single naphtha, and this translates into a lower energy expenditure for the production of light oliimes (that is, that is, ethylene and propylene) from this feed, as compared with the steam cracking of paraffins or paraffinic feedstocks to such light olefins.
- light oliimes that is, that is, ethylene and propylene
- software using linear or non-linear programming, is used continuously to control steam cracking conditions, in particular to control parts of paraffinic naphtha, refinery gas, butane and / or or propane or a mixture of both and the FCC gasoline in the feed, so that stirring presents the desired target composition.
- the target composition may have substantially the same effluent composition for the important constituents, i.e., ⁇ 20% by weight, preferably ⁇ 10% by weight, relative to that of the unmodified filler.
- the software can also control the shipment of refinery gas and / or control the quantities of FCC and / or butane or propane gasoline or the mixture of both, taken from the refinery, for example by shipping excess quantities to the refinery. storage tanks.
- a composite feed comprising 80% by weight of naphtha and 20% of a mixture of refinery gas and non-hydrorefined FCC gasoline, in a weight ratio of one-third gas and two-thirds gasoline. , was subjected to steam cracking.
- composition of the effluent of the composite filler of Example 1 is similar ( ⁇ 10% by weight for each constituent) to that of the only naphtha, but a part of the naphtha has been replaced by the addition of the gas of FCC refinery and gasoline for the reasons and with the benefits outlined above. It can be seen that high yields of ethylene and propylene are obtained according to the process of the invention, similar to those obtainable simply by steam-cracking of paraffinic naphtha.
- Table 2 also shows, in contrast, the effluent compositions obtained by steam cracking of the single refinery gas and, separately, of the single FCC gasoline. It can be seen that the steam cracking of the non-hydrorefined FCC gasoline produces a low yield of ethylene and propylene and that the steam cracking of the refinery gas produces a high ethylene yield, but a low propylene yield. However, when the three feeds of naphtha, refinery gas, and non-hydrorefined FCC gasoline are combined, the composition of the effluent is very similar to that of a normal naphtha.
- a composite filler comprising 60% by weight of naphtha and 40% by weight of a mixture of butane and non-hydrorefined FCC gasoline, in a ratio by weight of half gas and half gasoline, has was subjected to steam cracking.
- the naphtha has the same starting composition as in the previous example.
- butane is pure normal butane, such that it can be produced at the outlet of an alkylation unit in a refinery.
- the non-hydrorefined FCC gasoline has the same starting composition as in the previous example.
- composition of the effluent of the composite filler of Example 2 is similar ( ⁇ 10% by weight for each constituent) to that of the only naphtha, but part of the naphtha was replaced by the addition of butane and FCC gasoline for the reasons and with the benefits outlined above. It can be seen that high yields of ethylene and propylene are obtained according to the process of the invention, similar to those obtainable simply by steam-cracking of paraffinic naphtha.
- Table 4 also shows, in contrast, the compositions of the effluents obtained by steam cracking of butane alone and, separately, of the sole essence of FCC. It can be seen that the steam cracking of non-hydrorefined FCC gasoline produces a low yield of ethylene and propylene and that steam cracking of butane produces high yields of ethylene, propylene and C4 and low yields of heavy products. However, when the three feeds of naphtha, butane and non-hydrorefined FCC gasoline are combined, the composition of the effluent is very similar to that of a normal naphtha.
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Abstract
Description
La présente invention concerne un procédé pour le vapocraquage de naphta, une composition d'hydrocarbures appropriée pour le vapocraquage, un procédé pour contrôler un vapocraqueur, un appareillage pour contrôler un vapocraqueur et un procédé pour traiter une charge d'essence soufrée.The present invention relates to a process for the steam cracking of naphtha, a hydrocarbon composition suitable for steam cracking, a method for controlling a steam cracker, apparatus for controlling a steam cracker and a process for treating a sulfur gasoline feedstock.
L'industrie pétrochimique exige des monomères (en anglais, "Building Blocks") constitués, par exemple, par des oléfines, des dioléfines et des aromatiques. En Europe, les oléfines sont principalement obtenues par vapocraquage de charges obtenues des raffineries. Les charges disponibles sont principalement des charges de naphta incluant les paraffines, les isoparaffines et les aromatiques. Une charge de naphta utilisable dans le vapocraquage est connue dans la technique comme comprenant une coupe de pétrole dont les constituants les plus légers comportent cinq atomes de carbone et qui présente un point d'ébullition final d'environ 200 °C, le naphta comprenant des constituants à haut indice de carbone présentant un point d'ébullition d'au moins 200 °C. Le vapocraquage de naphta donne des oléfines légères telles que l'éthylène et le propylène, et des dioléfines telles que le butadiène, ainsi que des essences contenant des aromatiques.The petrochemical industry requires monomers ("Building Blocks") consisting of, for example, olefins, diolefins and aromatics. In Europe, olefins are mainly obtained by steam cracking charges obtained from refineries. The available feedstocks are mainly naphtha feeds including paraffins, isoparaffins and aromatics. A naphtha feedstock useful in steam cracking is known in the art as comprising a petroleum cutter whose lightest constituents have five carbon atoms and which has a final boiling point of about 200 ° C, the naphtha comprising high carbon components having a boiling point of at least 200 ° C. Steam cracking of naphtha gives light olefins such as ethylene and propylene, and diolefins such as butadiene, as well as aromatics-containing gasolines.
Lorsqu'un naphta typique est soumis à un vapocraquage, le produit craqué présente typiquement la composition suivante (en % en poids) à la sortie du four :
Les coupes les plus intéressantes, dans le produit craqué, sont les oléfines légères, à savoir l'éthylène et le propylène. Leur rendement est directement lié à la présence de paraffines dans la charge. Lorsque des paraffines en chaînes droites sont présentes, la formation d'éthylène est favorisée. Lorsque des isoparaffines sont présentes, la formation de propylène est favorisée. Le rendement relatif en propylène est exprimé comme le rapport en poids du propylène par rapport à l'éthylène et est typiquement compris entre 0,5 et 0,75.The most interesting cuts in the cracked product are light olefins, namely ethylene and propylene. Their yield is directly related to the presence of paraffins in the load. When straight chain paraffins are present, the formation of ethylene is favored. When isoparaffins are present, propylene formation is favored. The relative yield of propylene is expressed as the ratio by weight of propylene to ethylene and is typically between 0.5 and 0.75.
Récemment, en raison de la croissance des besoins en oléfines, la fourniture de la charge de départ de naphta paraffinique, dans une usine pétrochimique alimentée depuis une raffinerie, a eu tendance à être quelque peu limitée.Recently, due to the growth in olefin requirements, the supply of paraffinic naphtha feedstock to a petrochemical plant fed from a refinery has tended to be somewhat limited.
DE-A-3708332 décrit un procédé de craquage thermique d'éthylène dans un vapocraqueur, où l'éthylène est mélangé au naphta de manière à préparer une charge composée essentiellement de naphta et de 10 à 80 % en poids d'éthylène, contenant optionnellement, en plus du naphta, des fractions allant jusqu'au gasoil (température d'ébullition jusqu'à 350°C) et/ou des sous-produits recyclés d'une usine pétrochimique pouvant aller jusqu'à 50% du naphta. Ce procédé a comme inconvénient qu'il exige des quantités relativement importantes d'éthylène (au moins 10%) dans les matières premières et qu'ensuite les rendements en éthylène (par rapport à l'éthylène introduit dans la charge) et en propylène ne sont pas particulièrement élevés.DE-A-3708332 discloses a method of thermal cracking of ethylene in a steam cracker, wherein the ethylene is mixed with the naphtha so as to prepare a feedstock consisting essentially of naphtha and 10 to 80% by weight of ethylene, optionally containing , in addition to naphtha, fractions up to the fuel oil (boiling temperature up to 350 ° C) and / or by-products recycled from a petrochemical plant up to 50% of the naphtha. This process has the disadvantage that it requires relatively large amounts of ethylene (at least 10%) in the raw materials and that then the ethylene (relative to ethylene feedstock) and propylene yields do not increase. are not particularly high.
US-A-3786110 décrit un procédé de production d'hydrocarbures insaturés obtenus par pyrolyse, où les fractions indésirables sont réduites par l'addition aux produits de la pyrolyse d'un inhibiteur de polymérisation contenant des hydrocarbures asphaltiques.US-A-3786110 describes a process for the production of unsaturated hydrocarbons obtained by pyrolysis, where the undesirable fractions are reduced by the addition to the products of the pyrolysis of a polymerization inhibitor containing asphaltic hydrocarbons.
Un procédé pour le vapocraquage de naphta capable de fournir un rendement commercialement acceptable d'oléfines, en particulier des oléfines légères comme l'éthylène et le propylène, tout en réduisant la quantité de matière de départ de naphta paraffinique requise, est donc nécessaire dans la technique.A process for steam cracking of naphtha capable of providing a commercially acceptable yield of olefins, especially light olefins such as ethylene and propylene, while reducing the amount of paraffinic naphtha starting material required, is therefore necessary in the art. technical.
Les raffineries produisent un large éventail de produits. Certains d'entre eux peuvent, en fonction des exigences techniques des marchés locaux et d'autres considérations commerciales, présenter une faible valeur commerciale et sont par conséquent considérés comme étant "excédentaires". Actuellement, des produits comme les essences et certains hydrocarbures gazeux sont considérés comme obtenus en trop grande quantité. Si des produits de ce type peuvent être utilisés dans certains procédés pétrochimiques, ils ne sont pas utilisés couramment dans les opérations de vapocraquage, car, pour les produits liquides, ils n'ont pas la quantité requise de paraffines.Refineries produce a wide range of products. Some of them may, depending on the technical requirements of local markets and other commercial considerations, have low commercial value and are therefore considered "surplus". At present, products such as gasolines and certain gaseous hydrocarbons are considered to be obtained in too large a quantity. If products of this type can be used in certain petrochemical processes, they are not commonly used in steam cracking operations because, for liquid products, they do not have the required amount of paraffins.
L'éthane et le propane sont utilisés comme charges pour vapocraquage, en particulier aux Etats-Unis, où le gaz naturel, dont ils sont extraits, est abondant. Ces paraffines génèrent une grande quantité d'éthylène (supérieure à 50%), lorsqu'elles sont vapocraquées, ce qui conduit à traiter ces charges dans des unités spécifiquement dimensionnées pour ce type de charges. Certains gaz hydrocarbonés de raffinerie, comme les gaz de FCC, contiennent des quantités substantielles de paraffines (éthane et propane) et d'oléfines (éthylène, propylène). Toutefois, lorsqu'ils sont vapocraqués en tant que tels, ils ont tendance à générer des effluents gazeux craqués présentant une composition qui est différente de celle des effluents de vapocraquage de naphta normal. Cela pose un problème, car cela génère un déséquilibre dans la section, en aval (en particulier, les colonnes de distillation) d'un vapocraqueur craquant du naphta.Ethane and propane are used as fillers for steam cracking, particularly in the United States, where natural gas, from which they are extracted, is abundant. These paraffins generate a large amount of ethylene (greater than 50%), when they are steam-cracked, which leads to treating these charges in specifically sized units for this type of charges. Some refinery hydrocarbon gases, such as FCC gases, contain substantial amounts of paraffins (ethane and propane) and olefins (ethylene, propylene). However, when they are steam-cracked as such, they tend to generate cracked gaseous effluents having a composition which is different from that of normal steam-cracking effluents. This poses a problem because it generates an imbalance in the downstream section (in particular the distillation columns) of a cracking naphtha steam cracker.
Le butane et le propane sont également utilisés, soit seuls ou en mélange avec du naphta, comme charges des vapocraqueurs. Lorsqu'on tente de les utiliser exclusivement, le problème du déséquilibre dans la section aval d'un vapocraqueur au naphta se manifeste également. Selon les disponibilités de la raffinerie ou du marché, ces gaz liquéfiés peuvent être en excédent et il est par conséquent intéressant de les utiliser comme charge d'un vapocraqueur.Butane and propane are also used, either alone or mixed with naphtha, as steam cracker feedstocks. When attempting to use them exclusively, the problem of imbalance in the downstream section of a naphtha steam cracker is also apparent. Depending on the availability of the refinery or the market, these liquefied gases can be in excess and it is therefore interesting to use them as a steam cracker load.
DE-A-3708332 , déjà cité, n'aborde pas le problème technique qui consiste à produire un effluent dont la composition correspond à celle produite par le vapocraquage d'un naphta. Dans les exemples de DE-A-3708332, quand l'éthylène est ajouté (seul) au naphta, la composition de l'effluent, particulièrement en ce qui concerne l'éthylène et le propylène, est substantiellement altérée par rapport au craquage du naphta seul dans les mêmes conditions, ce qui peut conduire à réduire sensiblement la capacité de l'unité de vapocraquage.DE-A-3708332, already cited, does not address the technical problem of producing an effluent whose composition corresponds to that produced by the steam-cracking of a naphtha. In the examples of DE-A-3708332, when ethylene is added (alone) to naphtha, the composition of the effluent, particularly with respect to ethylene and propylene, is substantially altered compared to the cracking of naphtha. only under the same conditions, which can lead to significantly reduce the capacity of the steam-cracking unit.
Un procédé pétrochimique qui apporte une plus grande valeur économique aux produits de raffinage "excédentaires", tels que les essences et les hydrocarbures gazeux, est également nécessaire à la technique.A petrochemical process that brings greater economic value to "surplus" refining products, such as gasoline and gaseous hydrocarbons, is also necessary in the art.
L'invention vise à satisfaire au moins partiellement ces besoins.The invention aims to at least partially satisfy these needs.
A cet effet, l'invention propose un procédé pour le vapocraquage de naphta, ce procédé comprenant le passage dans un vapocraqueur, en présence de vapeur, d'une charge d'hydrocarbures, qui comprend une partie d'un naphta paraffinique modifié par l'addition de la combinaison d'un premier composant, comprenant une partie d'essence, et d'un second composant, comprenant une partie d'au moins un gaz de raffinerie hydrocarboné, et d'une charge riche en paraffines comprenant au moins une paraffine sélectionnée à partir du propane et du butane ou un mélange des deux.For this purpose, the invention provides a process for the steam-cracking of naphtha, which process comprises the passage in a steam-steam cracker of a hydrocarbon charge, which comprises a portion of a paraffinic naphtha modified with adding the combination of a first component, comprising a portion of gasoline, and a second component, comprising a portion of at least one hydrocarbon refinery gas, and a paraffin-rich feed comprising at least one paraffin selected from propane and butane or a mixture of both.
L'invention propose également une composition d'hydrocarbures appropriée pour le vapocraquage, comprenant une partie d'un naphta paraffinique, modifié par l'addition de la combinaison d'un premier composant, comprenant une partie d'essence, et d'un second composant, comprenant une partie d'au moins un gaz de raffinerie hydrocarboné, et d'une charge riche en paraffines comprenant au moins une paraffine sélectionnée à partir du propane et du butane ou un mélange des deux.The invention also provides a hydrocarbon composition suitable for steam cracking, comprising a part of a paraffinic naphtha, modified by the addition of the combination of a first component, comprising one part of gasoline, and a second component, comprising a portion of at least one hydrocarbon refinery gas, and a paraffin-rich filler comprising at least one paraffin selected from propane and butane or a mixture of both.
L'invention propose en outre un procédé pour contrôler un vapocraqueur, ce procédé comprenant la fourniture à un vapocraqueur de vapeur et d'une charge d'hydrocarbures comprenant une partie d'un naphta paraffinique, modifié par l'addition de la combinaison d'un premier composant, comprenant une partie d'essence, et d'un second composant, comprenant une partie d'au moins un gaz de raffinerie hydrocarboné et d'une charge riche en paraffines comprenant au moins une paraffine sélectionnée à partir du propane et du butane ou un mélange des deux, et le contrôle de manière continue des apports de naphta paraffinique, du second composant et de l'essence dans la charge, afin de donner à l'effluent une composition cible souhaitée.The invention further provides a method for controlling a steam cracker, which process comprises supplying a steam cracker and a hydrocarbon feedstock comprising a part of a paraffinic naphtha, modified by the addition of the combination of a first component, comprising a portion of gasoline, and a second component, comprising a portion of at least one hydrocarbon refinery gas and a paraffin-rich feedstock comprising at least one paraffin selected from propane and butane or a mixture of both, and continuously controlling feed intakes. paraffinic naphtha, the second component and gasoline in the feed to give the effluent a desired target composition.
L'invention propose également un procédé pour traiter une charge d'essence soufrée, ce procédé comprenant les phases suivantes: combiner une charge d'essence soufrée à une charge de naphta pour fournir une charge composite ; faire passer la charge composite dans un vapocraqueur, en présence de vapeur, pour produire un effluent, l'effluent contenant au moins des oléfines légères, les oléfines légères comprenant au moins une des oléfines en C2 à C4, et des hydrocarbures en C5+ ; et séparer de l'effluent une première fraction qui est pratiquement exempte de soufre et comprend les oléfines légères, et une deuxième fraction qui contient du soufre et comprend les hydrocarbures en C5+.The invention also provides a process for treating a sulfur-containing gasoline charge, which process comprises the steps of: combining a sulfur-containing gasoline charge with a naphtha charge to provide a composite charge; passing the composite feed through a steam cracker, in the presence of steam, to produce an effluent, the effluent containing at least light olefins, the light olefins comprising at least one of C2 to C4 olefins, and C5 + hydrocarbons; and separating from the effluent a first fraction that is substantially free of sulfur and includes light olefins, and a second fraction that contains sulfur and includes C5 + hydrocarbons.
L'invention repose sur la découverte surprenante par la Demanderesse qu'en sélectionnant certaines quantités et qualités de ces essences et de ces hydrocarbures gazeux et en les utilisant comme charges en combinaison avec du naphta, il est possible de vapocraquer la charge composite pour produire ainsi une composition pour le produit craqué (appelée dans la technique "palette de produits") qui ressemble fortement à une palette de produits résultant d'un vapocraquage, dans des conditions similaires, d'une charge de naphta paraffinique seulement. La composition de l'eflluent produit suivant l'invention est comprise dans un intervalle de ± 20 % en poids et, de préférence, ± 10% en poids, pour chaque composant, par rapport à celle de l'effluent, lorsque celui-ci est un naphta paraffinique non modifié.The invention is based on the surprising discovery by the Applicant that by selecting certain quantities and qualities of these gasolines and gaseous hydrocarbons and by using them as fillers in combination with naphtha, it is possible to steam crack the composite charge to thereby produce a composition for the cracked product (referred to in the "product palette" technique) that strongly resembles a pallet of products resulting from steam cracking, under similar conditions, of a paraffinic naphtha feedstock only. The composition of the effluent produced according to the invention is within a range of ± 20% by weight and preferably, ± 10% by weight, for each component, relative to that of the effluent, when it is an unmodified paraffinic naphtha.
En réalité, par conséquent, une partie de la charge de naphta paraffinique est, suivant l'invention, remplacée par une combinaison d'une charge d'essence et d'une charge de gaz de raffinerie hydrocarboné et/ou d'une charge de butane ou de propane ou un mélange des deux.In fact, therefore, a part of the paraffinic naphtha feed is, according to the invention, replaced by a combination of a gasoline feedstock and a hydrocarbon refinery gas feedstock and / or feedstock. butane or propane or a mixture of both.
Cela offre les avantages combinés (a) de réduire la quantité des charges de naphta paraffinique nécessaire pour le procédé de vapocraquage et (b) d'utiliser les produits hydrocarbonés gazeux et d'essence "excédentaires" dans le procédé de vapocraquage, pour produire des produits économiquement bénéfiques et utiles, à savoir des oléfines légères, en n'apportant que quelques modifications mineures à l'unité de vapocraquage, car le bilan de matières global n'est que légèrement modifié.This offers the combined advantages of (a) reducing the amount of paraffinic feedstock required for the steam cracking process and (b) utilizing the "excess" gaseous hydrocarbon and gasoline products in the steam cracking process to produce economically beneficial and useful products, namely light olefins, with only minor modifications to the steam cracking unit, since the overall material balance is only slightly modified.
Des formes de réalisation de l'invention vont à présent être décrites, à titre d'exemple uniquement, avec référence au dessin annexé, dans lequel :
- La Figure 1 montre de manière schématique une unité pour le vapocraquage de charges contenant du naphta suivant une forme de réalisation de l'invention.
- Figure 1 schematically shows a unit for steam cracking naphtha-containing feeds according to one embodiment of the invention.
Suivant l'invention, un procédé pour le vapocraquage de naphta utilise une charge d'une composition d'hydrocarbures, qui comprend une partie d'un naphta paraffinique, modifié par une partie d'une essence en combinaison avec une partie d'un gaz de raffinerie hydrocarboné et/ou une partie de butane ou de propane ou un mélange des deuxAccording to the invention, a process for the steam cracking of naphtha uses a filler of a hydrocarbon composition, which comprises a portion of a paraffinic naphtha, modified by a portion of a gasoline in combination with a portion of a gas hydrocarbon refinery and / or a portion of butane or propane or a mixture of both
Le naphta paraffinique à utiliser dans le procédé de l'invention comprend de 10 à 60 % en poids de n-paraffines, de 10 à 60 % en poids d'isoparaffines, de 0 à 35 % en poids de naphtènes, de 0 à 1 % en poids d'oléfines et de 0 à 20 % en poids d'aromatiques. Un naphta paraffinique typique à utiliser dans le procédé de l'invention comprend environ 31 % en poids de n-paraffines, 35 % en poids d'isoparaffines (donnant une teneur paraffinique totale de 66 % en poids), 26 % en poids de naphtènes, 0 % en poids d'oléfines (typiquement 0,05 % en poids d'oléfines) et 8 % en poids d'aromatiques.The paraffinic naphtha for use in the process of the invention comprises from 10 to 60% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 35% by weight of naphthenes, from 0 to 1% by weight. % by weight of olefins and from 0 to 20% by weight of aromatics. A typical paraffinic naphtha for use in the process of the invention comprises about 31% by weight of n-paraffins, 35% by weight of isoparaffins (giving a total paraffinic content of 66% by weight), 26% by weight of naphthenes. 0% by weight of olefins (typically 0.05% by weight of olefins) and 8% by weight of aromatics.
Suivant l'invention, cette charge de naphta paraffinique de départ est modifiée par l'addition à celle-ci d'une essence et d'un gaz de raffinerie hydrocarboné et/ou de butane ou de propane ou un mélange des deuxAccording to the invention, this starting paraffinic naphtha feed is modified by adding thereto a gasoline and a hydrocarbon refinery gas and / or butane or propane or a mixture of the two.
L'essence est de préférence une coupe provenant d'une unité de FCC ("fluidised-bed catalytic cracking ou craquage catalytique en lit fluidisé) d'une raffinerie de pétrole (appelée ici essence de FCC), qui, avantageusement, n'a pas été soumise à un traitement d'hydrogénation (désigné dans la technique par "hydroraffinage"), qui augmente la teneur en paraffines de l'essence en hydrogénant les fonctions insaturées (comme celles présentes dans les oléfines et les dioléfines) de l'essence. L'avantage d'utiliser une essence de FCC non hydroraffinée est qu'en évitant un processus d'hydrogénation, on réduit les coûts de production, en supprimant ou en réduisant l'utilisation d'hydrogène et en évitant la nécessité d'une capacité d'hydroraffinage supplémentaire.The gasoline is preferably a fraction from a fluidized-bed catalytic cracking (FCC) unit of an oil refinery (herein referred to as FCC gasoline), which advantageously has not has not been subjected to a hydrogenation treatment (referred to in the art as "hydrorefining"), which increases the paraffin content of gasoline by hydrogenating the unsaturated functions (such as those present in olefins and diolefins) of gasoline The advantage of using a non-hydrorefined FCC gasoline is that by avoiding a hydrogenation process, production costs are reduced by eliminating or reducing the use of hydrogen and avoiding the need for a hydrogenation process. additional hydrorefining capacity.
L'essence de FCC est une coupe ou un mélange de coupes de l'unité de FCC présentant typiquement un intervalle de distillation compris entre 30 et 160 °C, de préférence une coupe ou un mélange de coupes venant à ébullition dans l'intervalle compris entre 30 et 65 °C, 65 à 105 °C et 105 à 145 °C. Le choix de l'essence de FCC particulière ou du mélange de celle-ci à utiliser peut être déterminé en fonction des exigences à tout moment pour les diverses coupes produites par la raffinerie. Par exemple, certaines coupes d'essence ont un déficit d'octane et pourraient être mieux valorisées dans un vapocraqueur plutôt que d'avoir à augmenter l'indice d'octane dans la raffinerie. De plus, l'essence de FCC à utiliser peut présenter une teneur en soufre qui serait trop élevée pour des essences à utiliser dans le secteur automobile et qui exigerait un traitement de désulfuration par l'hydrogène, lequel est coûteux, car il consomme de l'hydrogène et nécessite la capacité correspondante sur une unité de désulfuration.FCC gasoline is a slice or slice of the FCC unit typically having a distillation range of from 30 to 160 ° C, preferably a slice of cup or mixture of slices within the range of between 30 and 65 ° C, 65 to 105 ° C and 105 to 145 ° C. The choice of the particular FCC gasoline or blend of it to be used may be determined based on the requirements at any time for the various cuts produced by the refinery. For example, some gasoline cuts have an octane deficit and could be better valued in a steam cracker than having to increase the octane number in the refinery. In addition, the FCC gasoline to be used may have a sulfur content that would be too high for gasolines to be used in the automotive sector and that would require a desulphurization treatment with hydrogen, which is expensive because it consumes more fuel. hydrogen and requires the corresponding capacity on a desulfurization unit.
On préfère utiliser une essence de FCC non hydroraffinée, car, dans la raffinerie, où il existe un besoin pour de l'essence hydroraffinée pour d'autres usages, cela peut provoquer des goulots d'étranglement dans le traitement par l'unité d'hydroraffinage. En réduisant la quantité d'essence non hydroraffinée présente dans la raffinerie, à savoir en consommant l'essence non hydroraffinée dans le procédé de vapocraquage de l'invention, cela peut dégoulotter les appareils et les unités d'hydroraffinage, en améliorant de ce fait la gestion des flux dans la raffinerie, et également en réduisant les besoins en hydrogène.It is preferred to use a non-hydrorefined FCC gasoline, because in the refinery, where there is a need for hydrorefined gasoline for other uses, this can cause bottlenecks in processing by the unit of hydroprocessing. By reducing the amount of non-hydrorefined gasoline present in the refinery, namely by consuming the non-hydrorefined gasoline in the steam cracking process of the invention, this can freeze appliances and appliances. hydrorefining units, thereby improving the flow management in the refinery, and also by reducing the need for hydrogen.
Typiquement, l'essence de FCC non hydroraffinée comprend de 0 à 30 % en poids de n-paraffines, de 10 à 60 % en poids d'isoparaffines, de 0 à 80 % en poids de naphtènes, de 5 à 80 % en poids d'oléfines et de 0 à 60 % en poids d'aromatiques. Plus typiquement, l'essence de FCC non hydroraffinée comprend approximativement 3,2 % en poids de n-paraffines, 19,2 % en poids d'isoparaffines (donnant une teneur en paraffines totale de 22,4 % en poids), 18 % en poids de naphtènes, 30 % en poids d'oléfines et 29,7 % en poids d'aromatiques.Typically, the non-hydrorefined FCC gasoline comprises from 0 to 30% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 80% by weight of naphthenes, from 5 to 80% by weight olefins and from 0 to 60% by weight of aromatics. More typically, the non-hydrorefined FCC gasoline comprises approximately 3.2% by weight of n-paraffins, 19.2% by weight of isoparaffins (giving a total paraffin content of 22.4% by weight), 18% by weight of naphthenes, 30% by weight of olefins and 29.7% by weight of aromatics.
Si, toutefois, une essence de FCC hydroraffinée était utilisée, une quantité substantielle d'hydrogène serait nécessaire pour l'hydrogéner et la composition hydroraffinée ressemblerait à un naphta typique utilisé pour le vapocraquage.If, however, a hydrorefined FCC gasoline were used, a substantial amount of hydrogen would be required to hydrogenate it and the hydrorefined composition would resemble a typical naphtha used for steam cracking.
En ce qui concerne le gaz de raffinerie hydrocarboné qui est ajouté, en combinaison avec l'essence de FCC et/ou le butane ou le propane ou un mélange des deux, au naphta paraffinique, pour produire une charge composite pour le vapocraquage, ce gaz hydrocarboné est riche en hydrocarbures en C2 et C3, en particulier en paraffines (éthane et propane) et en oléfines (éthylène et propylène). De préférence, le gaz de raffinerie présente les intervalles de composition suivants : 0 à 5 % en poids d'hydrogène, 0 à 40 % en poids de méthane, 0 à 50 % en poids d'éthylène, 0 à 80 % en poids d'éthane, 0 à 50 % en poids de propylène, 0 à 80 % en poids de propane et 0 à 30 % en poids de butane. Une composition typique d'un gaz de raffinerie de ce type est, approximativement, 1 % en poids d'hydrogène, 2 % en poids d'azote, 0,5 % en poids de monoxyde de carbone, 0 % en poids de dioxyde de carbone, 10 % en poids de méthane, 15 % en poids d'éthylène, 32 % en poids d'éthane, 13 % en poids de propylène, 14 % en poids de propane, 2 % en poids d'isobutane, 4 % en poids de n-butane, 3 % en poids de butène, 2 % en poids de n-pentane, et 1,5 % en poids de n-hexane.With respect to the hydrocarbon refinery gas that is added, in combination with the FCC gasoline and / or butane or propane or a mixture of both, to the paraffinic naphtha, to produce a composite filler for the steam cracking, this gas hydrocarbon is rich in C 2 and C 3 hydrocarbons, in particular paraffins (ethane and propane) and olefins (ethylene and propylene). Preferably, the refinery gas has the following compositional ranges: 0 to 5% by weight hydrogen, 0 to 40% by weight methane, 0 to 50% by weight ethylene, 0 to 80% by weight d ethane, 0 to 50% by weight of propylene, 0 to 80% by weight of propane and 0 to 30% by weight of butane. A typical composition of a refinery gas of this type is approximately 1% by weight of hydrogen, 2% by weight of nitrogen, 0.5% by weight of carbon monoxide, 0% by weight of carbon dioxide. carbon, 10% by weight of methane, 15% by weight of ethylene, 32% by weight of ethane, 13% by weight of propylene, 14% by weight of propane, 2% by weight of isobutane, 4% by weight of weight of n-butane, 3% by weight of butene, 2% by weight of n-pentane, and 1.5% by weight of n-hexane.
En ce qui concerne le butane et/ou le propane ou le mélange des deux qui est ajouté au naphta paraffinique, en combinaison avec l'essence de FCC et optionnellement le gaz de raffinerie, pour produire une charge composite pour le vapocraquage, ce butane et /ou ce propane ou le mélange de deux peuvent contenir des composés oléfiniques tels que butènes et/ou propylène, ou des composés saturés tels que butanes (normal et/ou iso) et/ou propane. De préférence, le butane et/ou le propane ou le mélange des deux contiennent plus de 50% en poids de composés saturés pour maximiser la production d'oléfines légères telles qu'éthylène et propylène. Le butane et le propane sont de préférence du n-butane et du n-propane.With respect to butane and / or propane or the mixture of both which is added to the paraffinic naphtha, in combination with the FCC gasoline and optionally the refinery gas, to produce a composite filler for steam cracking, this butane and / or this propane or the mixture of two may contain compounds olefins such as butenes and / or propylene, or saturated compounds such as butanes (normal and / or iso) and / or propane. Preferably, butane and / or propane or the mixture of both contain more than 50% by weight of saturated compounds to maximize the production of light olefins such as ethylene and propylene. Butane and propane are preferably n-butane and n-propane.
Suivant le procédé de l'invention, les parties de naphta, de gaz de raffinerie, de butane ou de propane ou un mélange des deux, et d'essence sont combinées pour former une charge composite, qui est ensuite soumise au vapocraquage. De préférence, la charge composite comprend de 5 à 95 % en poids de naphta, de 5 à 95 % en poids d'un mélange de gaz de raffinerie, de butane ou de propane ou un mélange des deux, et d'essence. Typiquement, le mélange de gaz de raffinerie, de butane ou de propane ou un mélange des deux, et d'essence qui est ajouté au naphta comprend jusqu'à 60 % en poids de gaz de raffinerie et/ou de butane ou de propane ou un mélange des deux., et au moins 40 % en poids d'essence, plus typiquement jusqu'à 50 % en poids de gaz de raffinerie et/ou de butane ou de propane ou un mélange des deux, et jusqu'à 50 % en poids d'essence. De façon plus préférée, le naphta composite comprend 80 % en poids de naphta, 7 % en poids de gaz de raffinerie et/ou de butane ou de propane ou un mélange des deux, et 13 % en poids d'essence de FCC non hydroraffinée.According to the process of the invention, parts of naphtha, refinery gas, butane or propane or a mixture of both, and gasoline are combined to form a composite filler, which is then subjected to steam cracking. Preferably, the composite filler comprises from 5 to 95% by weight of naphtha, from 5 to 95% by weight of a mixture of refinery gas, butane or propane or a mixture of both, and gasoline. Typically, the mixture of refinery gas, butane or propane or a mixture of both, and gasoline which is added to the naphtha comprises up to 60% by weight of refinery gas and / or butane or propane gas or a mixture of both, and at least 40% by weight of gasoline, more typically up to 50% by weight of refinery gas and / or butane or propane gas or a mixture of both, and up to 50% by weight of gasoline. More preferably, the composite naphtha comprises 80% by weight of naphtha, 7% by weight of refinery gas and / or butane or propane or a mixture of both, and 13% by weight of non-hydrorefined FCC gasoline. .
La charge composite de naphta, d'essence, de gaz de raffinerie et/ou de butane ou de propane ou un mélange des deux. est typiquement soumise à un vapocraquage dans des conditions similaires à celles connues dans la technique, à savoir une température comprise entre 780 et 880 °C, de préférence entre 800 et 850 °C. La quantité de vapeur peut également tomber dans des intervalles connus dans la technique, typiquement entre 25 et 60 % en poids sur la base du poids de la charge d'hydrocarbures.The composite filler of naphtha, gasoline, refinery gas and / or butane or propane or a mixture of both. is typically subjected to steam cracking under conditions similar to those known in the art, namely a temperature of between 780 and 880 ° C, preferably between 800 and 850 ° C. The amount of steam may also fall within ranges known in the art, typically between 25 and 60% by weight based on the weight of the hydrocarbon feed.
Avec référence à la Figure 1 du dessin annexé, la section chaude d'une unité de vapocraquage à utiliser dans le procédé de l'invention est représentée de manière schématique. L'unité de vapocraquage, indiquée généralement par 2, comprend un ensemble de chauffage constitué de fours 4, qui est pourvu de serpentins 6 comportant une première entrée 8 pour la charge d'hydrocarbures à craquer et une deuxième entrée 10 pour la vapeur. Une conduite de sortie 12 de l'ensemble de chauffage est reliée à une colonne de fractionnement primaire 14. La colonne de fractionnement primaire 14 comprend un reflux d'essence en tête 15 et des sorties pour les divers produits fractionnés, y compris une sortie supérieure 16 pour les hydrocarbures légers et une sortie inférieure 18 pour les hydrocarbures lourds, qui peuvent être renvoyés en 19 après refroidissement dans la conduite 12 pour en contrôler la température ou soutirés en 17 sous forme de produits lourds appelés huile de pyrolyse.With reference to Figure 1 of the accompanying drawing, the hot section of a steam cracking unit for use in the method of the invention is schematically represented. The steam cracking unit, generally indicated by 2, comprises a heating assembly consisting of ovens 4, which is provided with
Dans cette description simplifiée et dans la présentation des exemples qui suit, on ne considère que les charges venant de l'extérieur du vapocraqueur, communément appelées charges fraîches, et non les recycles éventuels de produits provenant du vapocraqueur lui-même, tels que l'éthane souvent recraqué jusqu'à extinction.In this simplified description and in the presentation of the examples which follow, only the feeds coming from outside the steam cracker, commonly called fresh feeds, and not the possible recycles of products from the steam cracker itself, such as the feedstock, are considered. ethane often re-traced until extinction.
Si on le souhaite, la charge composite tout entière du naphta, du gaz de raffinerie, et/ou du butane ou du propane ou du mélange des deux et de l'essence peut être alimentée par l'entrée commune 8 d'hydrocarbures ou, en variante, les quatre composants de naphta, d'essence de FCC, de gaz de raffinerie et/ou de butane ou de propane ou de mélange des deux peuvent être craqués séparément dans des serpentins tubulaires spécifiques. Dans une forme de réalisation particulière, le naphta et l'essence de FCC, d'une part, le butane et/ou le propane ou un mélange des deux, et le gaz de raffinerie, d'autre part, sont craqués séparément. La raison en est que le naphta et l'essence de FCC sont typiquement craqués à des températures qui sont proches les unes des autres, typiquement dans l'intervalle de 750 à 850 °C, alors que le butane, le propane et les gaz de raffinerie qui contiennent de l'éthane et du propane doivent être craqués à des températures supérieures, typiquement dans l'intervalle de 800 à 900 °C. Les deux effluents peuvent être combinés à la sortie de l'ensemble de chauffage avant la colonne de fractionnement primaire.If desired, the entire composite feedstock of naphtha, refinery gas, and / or butane or propane or a mixture of both and gasoline may be fed from the common hydrocarbon inlet or alternatively, the four components of naphtha, FCC gasoline, refinery gas and / or butane or propane or a mixture of the two can be cracked separately in specific tubular coils. In a particular embodiment, the naphtha and the FCC gasoline, on the one hand, butane and / or propane or a mixture of both, and the refinery gas, on the other hand, are cracked separately. This is because naphtha and FCC gasoline are typically cracked at temperatures that are close to each other, typically in the range of 750 to 850 ° C, while butane, propane, refineries that contain ethane and propane must be cracked at higher temperatures, typically in the range of 800 to 900 ° C. The two effluents can be combined at the outlet of the heating assembly before the primary fractionation column.
Le procédé de l'invention peut fonctionner de manière continue et offre l'avantage d'éliminer l'essence excédentaire de la raffinerie, et de réduire également le besoin dans la raffinerie pour un procédé de désulfuration. L'essence contient du soufre et, à la suite du procédé de vapocraquage, dans lequel l'essence fournit une partie de la charge composite, les oléfines légères les plus intéressantes dans l'effluent sont exemptes de soufre, alors que le soufre reste concentré dans la partie C5+ du courant d'effluent. Par conséquent, l'utilisation de l'essence comme partie d'une charge à vapocraquer pour produire des oléfines plus légères amène une désulfuration partielle de la partie d'essence de la charge, car le soufre est concentré dans la fraction à nombre de carbone plus élevé et commercialement moins intéressante de l'effluent, à savoir le courant de C5+.The process of the invention can operate continuously and has the advantage of eliminating excess gasoline from the refinery, and also reducing the need in the refinery for a desulphurization process. Gasoline contains sulfur and, as a result of the steam cracking process, in which gasoline provides some of the composite filler, the most valuable light olefins in the effluent are sulfur free, while the sulfur remains concentrated in the game C5 + of the effluent stream. Therefore, the use of gasoline as part of a feed to be cracked to produce lighter olefins results in partial desulphurization of the gasoline portion of the feed because the sulfur is concentrated in the carbon number fraction. higher and commercially less attractive effluent, namely the C5 + current.
De manière correspondante, selon un autre aspect, l'invention propose un procédé pour traiter une charge d'essence soufrée, le procédé comprenant les phases suivantes: combiner une charge d'essence soufrée à une charge de naphta pour fournir une charge composite ; faire passer la charge composite par un vapocraqueur, en présence de vapeur, pour produire un effluent, l'effluent contenant au moins des oléfines légères, les oléfines légères comprenant au moins une des oléfines en C2 à C4, et des hydrocarbures en C5+ ; et séparer de l'effluent une première fraction qui est pratiquement exempte de soufre et comprend les oléfines légères, et une deuxième fraction qui contient du soufre et comprend les hydrocarbures en C5+. De cette façon, le soufre est redistribué dans la fraction à nombre de carbone plus élevé, produisant une fraction oléfinique à nombre de carbone moindre exempte de soufre, ce qui est une manière efficace de désulfurer partiellement la charge d'essence.Correspondingly, in another aspect, the invention provides a process for treating a sulfurized gasoline feedstock, the process comprising the steps of: combining a sulfur gasoline feedstock with a naphtha feedstock to provide a composite feedstock; passing the composite feed through a steam cracker, in the presence of steam, to produce an effluent, the effluent containing at least light olefins, the light olefins comprising at least one of C2 to C4 olefins, and C5 + hydrocarbons; and separating from the effluent a first fraction that is substantially free of sulfur and includes light olefins, and a second fraction that contains sulfur and includes C5 + hydrocarbons. In this way, the sulfur is redistributed in the higher carbon number fraction, producing a lower sulfur-free olefinic fraction, which is an effective way of partially desulfurizing the gasoline charge.
En outre, le procédé offre l'avantage que le traitement de vapocraquage déshydrogène au moins partiellement l'éthane présent dans les gaz de raffinerie, la déshydrogénation étant effectuée à une température suffisamment élevée pour produire efficacement de l'éthylène.In addition, the process has the advantage that the steam cracking process at least partially dehydrogenates the ethane present in the refinery gases, the dehydrogenation being carried out at a sufficiently high temperature to efficiently produce ethylene.
L'invention offre également l'avantage qu'en ajoutant à la charge de naphta, qui ne contient pas ou seulement une faible quantité d'oléfines, une essence non hydroraffinée, qui contient une quantité relativement élevée d'oléfines, typiquement de 5 à 80 % en poids d'oléfines, la charge composite pour le vapocraquage présente une teneur globale supérieure en oléfines, par comparaison avec le seul naphta, et cela se traduit par une dépense énergétique moindre pour la production d'oléimes légères (c'est-à-dire en d'éthylène et de propylène) à partir de cette charge, par comparaison avec le vapocraquage de paraffines ou charges paraffiniques en oléfines légères de ce type.The invention also has the advantage that by adding to the naphtha feed, which contains no or only a small amount of olefins, a non-hydrorefined gasoline which contains a relatively high amount of olefins, typically from 5 to 80% by weight of olefins, the composite feedstock for steam cracking has a higher overall olefin content, compared with the single naphtha, and this translates into a lower energy expenditure for the production of light oléimes (that is, that is, ethylene and propylene) from this feed, as compared with the steam cracking of paraffins or paraffinic feedstocks to such light olefins.
Suivant un autre aspect de l'invention, un logiciel, utilisant une programmation linéaire ou non linéaire, est utilisé de manière continue pour contrôler les conditions de vapocraquage, en particulier contrôler les parties du naphta paraffinique, du gaz de raffinerie, du butane et/ou du propane ou du mélange des deux et de l'essence FCC dans la charge, afin que remuent présente la composition cible souhaitée. Par exemple, la composition cible peut avoir sensiblement la même composition d'effluent pour les constituants importants, c'est-à-dire ± 20 % en poids, de préférence ± 10 % en poids par rapport à celle de la charge non modifiée. Le logiciel peut également contrôler l'envoi du gaz de raffinerie et/ou contrôler les quantités d'essence de FCC et/ou de butane ou de propane ou de mélange des deux, reprises de la raffinerie, par expédition par exemple des quantités excédentaires vers les réservoirs de stockage.According to another aspect of the invention, software, using linear or non-linear programming, is used continuously to control steam cracking conditions, in particular to control parts of paraffinic naphtha, refinery gas, butane and / or or propane or a mixture of both and the FCC gasoline in the feed, so that stirring presents the desired target composition. For example, the target composition may have substantially the same effluent composition for the important constituents, i.e., ± 20% by weight, preferably ± 10% by weight, relative to that of the unmodified filler. The software can also control the shipment of refinery gas and / or control the quantities of FCC and / or butane or propane gasoline or the mixture of both, taken from the refinery, for example by shipping excess quantities to the refinery. storage tanks.
L'invention va à présent être décrite plus en détail avec référence aux deux exemples suivants.The invention will now be described in more detail with reference to the following two examples.
Dans cet exemple, une charge composite comprenant 80 % en poids de naphta et 20 % d'un mélange de gaz de raffinerie et d'essence de FCC non hydroraffinée, selon un rapport en poids de un tiers de gaz et deux tiers d'essence, a été soumise à un vapocraquage.In this example, a composite feed comprising 80% by weight of naphtha and 20% of a mixture of refinery gas and non-hydrorefined FCC gasoline, in a weight ratio of one-third gas and two-thirds gasoline. , was subjected to steam cracking.
Le naphta a la composition de départ approximative suivante :
- 31 % en poids de n-paraffines,
- 35 % en poids d'isoparaffines (donnant une teneur paraffinique totale de 66 % en poids),
- 26 % en poids de naphtènes,
- 0,05 % en poids d'oléfines,
- 0 % en poids de dioléfines,
- 8 % en poids d'aromatiques.
- 31% by weight of n-paraffins,
- 35% by weight of isoparaffins (giving a total paraffinic content of 66% by weight),
- 26% by weight of naphthenes,
- 0.05% by weight of olefins,
- 0% by weight of diolefins,
- 8% by weight of aromatics.
Le gaz de raffinerie a la composition de départ approximative suivante :
- 1 % en poids d'hydrogène,
- 2 % en poids d'azote,
- 0,5 % en poids de monoxyde de carbone,
- 0 % en poids de dioxyde de carbone,
- 10 % en poids de méthane,
- 15 % en poids d'éthylène,
- 32 % en poids d'éthane,
- 13 % en poids de propylène,
- 14 % en poids de propane,
- 2 % en poids d'isobutane,
- 4 % en poids de n-butane,
- 3 % en poids de butène,
- 2 % en poids de n-pentane,
- et 1,5 % en poids de n-hexane.
- 1% by weight of hydrogen,
- 2% by weight of nitrogen,
- 0.5% by weight of carbon monoxide,
- 0% by weight of carbon dioxide,
- 10% by weight of methane,
- 15% by weight of ethylene,
- 32% by weight of ethane,
- 13% by weight of propylene,
- 14% by weight of propane,
- 2% by weight of isobutane,
- 4% by weight of n-butane,
- 3% by weight of butene,
- 2% by weight of n-pentane,
- and 1.5% by weight of n-hexane.
L'essence de FCC non hydroraffinée a la composition de départ approximative suivante :
- 3 % en poids de n-paraffines,
- 19 % en poids d'isoparaffines (donnant une teneur paraffinique totale de 22 % en poids),
- 18 % en poids de naphtènes,
- 30 % en poids d'oléfines,
- 30 % en poids d'aromatiques.
- 3% by weight of n-paraffins,
- 19% by weight of isoparaffins (giving a total paraffinic content of 22% by weight),
- 18% by weight of naphthenes,
- 30% by weight of olefins,
- 30% by weight of aromatics.
Après vapocraquage, l'effluent global de l'ensemble des fours en sortie 12 sans recycle éventuel de l'éthane produit par le vapocraqueur a la composition indiquée au Tableau 1.
Par contraste, lorsque 100% du même naphta était soumis à un vapocraquage dans les mêmes conditions, l'effluent obtenu avait la composition indiquée au Tableau 2.
On peut voir que l'effluent résultant du vapocraquage de la combinaison des trois charges de naphta paraffinique, de gaz de raffinerie et d'essence de FCC non hydroraffinée, ressemble très fort à l'effluent issu du vapocraquage du seul naphta paraffinique correspondant.It can be seen that the effluent resulting from the steam cracking of the combination of the three loads of paraffinic naphtha, refinery gas and non-hydrorefined FCC gasoline, very closely resembles the effluent from the steam cracking of the only paraffinic naphtha corresponding.
Ainsi, la composition de l'effluent de la charge composite de l'Exemple 1 est semblable (± 10 % en poids pour chaque constituant) à celle du seul naphta, mais une partie du naphta a été remplacée par l'addition du gaz de raffinerie et de l'essence de FCC pour les raisons et avec les avantages indiqués ci-dessus. On peut voir que des rendements d'éthylène et de propylène élevés sont obtenus suivant le procédé de l'invention, semblables à ceux pouvant être obtenus simplement par vapocraquage du naphta paraffinique.Thus, the composition of the effluent of the composite filler of Example 1 is similar (± 10% by weight for each constituent) to that of the only naphtha, but a part of the naphtha has been replaced by the addition of the gas of FCC refinery and gasoline for the reasons and with the benefits outlined above. It can be seen that high yields of ethylene and propylene are obtained according to the process of the invention, similar to those obtainable simply by steam-cracking of paraffinic naphtha.
Le Tableau 2 montre également, par contraste, les compositions des effluents obtenus par vapocraquage du seul gaz de raffinerie et, séparément, de la seule essence de FCC. On peut voir que le vapocraquage de l'essence de FCC non hydroraffinée produit un faible rendement d'éthylène et de propylène et que le vapocraquage du gaz de raffinerie produit un haut rendement d'éthylène, mais un faible rendement de propylène. Toutefois, lorsque les trois charges de naphta, de gaz de raffinerie et d'essence de FCC non hydroraffinée, sont combinées, la composition de l'effluent ressemble très fort à celle d'un naphta normal.Table 2 also shows, in contrast, the effluent compositions obtained by steam cracking of the single refinery gas and, separately, of the single FCC gasoline. It can be seen that the steam cracking of the non-hydrorefined FCC gasoline produces a low yield of ethylene and propylene and that the steam cracking of the refinery gas produces a high ethylene yield, but a low propylene yield. However, when the three feeds of naphtha, refinery gas, and non-hydrorefined FCC gasoline are combined, the composition of the effluent is very similar to that of a normal naphtha.
Dans cet exemple, une charge composite comprenant 60 % en poids de naphta et 40 % en poids d'un mélange de butane et d'essence de FCC non hydroraffinée, selon un rapport en poids de moitié de gaz et moitié d'essence, a été soumise à un vapocraquage.In this example, a composite filler comprising 60% by weight of naphtha and 40% by weight of a mixture of butane and non-hydrorefined FCC gasoline, in a ratio by weight of half gas and half gasoline, has was subjected to steam cracking.
Le naphta a la même composition de départ que dans l'exemple précédent.The naphtha has the same starting composition as in the previous example.
Le butane est dans cet exemple du normal butane pur, tel qu'il peut être produit en sortie d'une unité d'alkylation en raffinerie.In this example, butane is pure normal butane, such that it can be produced at the outlet of an alkylation unit in a refinery.
L'essence de FCC non hydroraffinée a la même composition de départ que dans l'exemple précédent.The non-hydrorefined FCC gasoline has the same starting composition as in the previous example.
Après vapocraquage, l'effluent global de l'ensemble des fours en sortie 12 sans recycle éventuelle de l'éthane produit par le vapocraqueur a la composition indiquée au Tableau 3.
Par contraste, lorsque 100% du même naphta était soumis à un vapocraquage dans les mêmes conditions, l'effluent obtenu avait la composition indiquée au Tableau 2 et rappelée au Tableau 4.
On peut voir que l'effluent résultant du vapocraquage de la combinaison des trois charges de naphta paraffinique, de butane et d'essence de FCC non hydroraffinée ressemble très fort à l'effluent issu du vapocraquage du seul naphta paraffinique correspondant.It can be seen that the effluent resulting from the steam cracking of the combination of the three feeds of paraffinic naphtha, butane and non-hydrorefined FCC gasoline is very similar to the effluent from the steam cracking of the only corresponding paraffinic naphtha.
Ainsi, la composition de l'effluent de la charge composite de l'Exemple 2 est semblable (± 10 % en poids pour chaque constituant) à celle du seul naphta, mais une partie du naphta a été remplacée par l'addition du butane et de l'essence de FCC pour les raisons et avec les avantages indiqués ci-dessus. On peut voir que des rendements d'éthylène et de propylène élevés sont obtenus suivant le procédé de l'invention, semblables à ceux pouvant être obtenus simplement par vapocraquage du naphta paraffinique.Thus, the composition of the effluent of the composite filler of Example 2 is similar (± 10% by weight for each constituent) to that of the only naphtha, but part of the naphtha was replaced by the addition of butane and FCC gasoline for the reasons and with the benefits outlined above. It can be seen that high yields of ethylene and propylene are obtained according to the process of the invention, similar to those obtainable simply by steam-cracking of paraffinic naphtha.
Le Tableau 4 montre également, par contraste, les compositions des effluents obtenus par vapocraquage du seul butane et, séparément, de la seule essence de FCC. On peut voir que le vapocraquage de l'essence de FCC non hydroraffinée produit un faible rendement d'éthylène et de propylène et que le vapocraquage du butane produit de hauts rendements en éthylène, propylène et C4 et de faibles rendements en produits lourds. Toutefois, lorsque les trois charges de naphta, de butane et d'essence de FCC non hydroraffinée sont combinées, la composition de l'effluent ressemble très fort à celle d'un naphta normal.Table 4 also shows, in contrast, the compositions of the effluents obtained by steam cracking of butane alone and, separately, of the sole essence of FCC. It can be seen that the steam cracking of non-hydrorefined FCC gasoline produces a low yield of ethylene and propylene and that steam cracking of butane produces high yields of ethylene, propylene and C4 and low yields of heavy products. However, when the three feeds of naphtha, butane and non-hydrorefined FCC gasoline are combined, the composition of the effluent is very similar to that of a normal naphtha.
Claims (20)
- A naphtha steam cracking process, said process being characterised in that it comprises transfer into a steam cracker, in the presence of steam, of a hydrocarbon feedstock comprising 5 to 95% by weight of a paraffinic naphtha and 95 to 5% by weight of a mixture of a first component, namely a gasoline originating from a fluidised bed catalytic cracking unit (FCC) and a second component comprising at least one hydrocarbon refinery gas and at least one paraffin-rich feedstock, the paraffinic naphtha comprising from 10 to 60% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 35% by weight of naphthenes, from 0 to 1% by weight of olefins and from 0 to 20% by weight of aromatics, the FCC gasoline being a non-hydrogenated gasoline comprising from 0 to 30% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 80% by weight of naphthenes, from 5 to 80% by weight of olefins and from 0 to 60% by weight of aromatics, the refinery gas comprising from 0 to 5% by weight of hydrogen, from 0 to 40% by weight of methane, from 0 to 50% by weight of ethylene, from 0 to 80% by weight of ethane, from 0 to 50% by weight of propylene, from 0 to 80% by weight of propane and from 0 to 30% by weight of butanes, and the paraffin-rich feedstock containing at least 50% by weight of saturated hydrocarbons, said feedstock comprising at least propane or butane.
- A process according to claim 1, in which the mixture of the first and second components comprises up to 60% by weight of the second component and at least 40% by weight of gasoline.
- A process according to claim 2, in which the mixture of the first and second components comprises up to 50% by weight of the second component and at least 50% by weight of gasoline.
- A process according to claim 2 or claim 3, in which the mixture of the first and second components comprises approximately a third in % by weight of the second component and approximately two-thirds in % by weight of gasoline.
- A process according to any one of the preceding claims, in which the feedstock comprises approximately 80% by weight of naphtha, approximately 7% by weight of the second component and approximately 13% by weight of gasoline.
- A process according to one of the preceding claims, in which the FCC gasoline is a cut or a mixture of cuts from an FCC unit having a distillation range of between 30 and 160°C.
- A process according to any one of claims 1 to 6, in which the second component consists at least of propane and butane.
- A process according to any one of claims 1 to 7, in which the composite feedstock of naphtha, gasoline and the second component is subjected to steam cracking under conditions including a temperature of between 780 and 880°C.
- A process according to any one of claims 1 to 8, in which the quantity of steam is from 25 to 60% by weight relative to the weight of the hydrocarbon feedstock.
- A hydrocarbon composition suitable for a steam cracking process, said composition comprising from 5 to 95% by weight of a paraffinic naphtha and 95 to 5% by weight of a mixture of a first component, namely a gasoline originating from a fluidised bed catalytic cracking unit (FCC) and a second component comprising at least one hydrocarbon refinery gas and at least one paraffin-rich feedstock, the paraffinic naphtha comprising from 10 to 60% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 35% by weight of naphthenes, from 0 to 1% by weight of olefins and from 0 to 20% by weight of aromatics, the FCC gasoline being a non-hydrogenated gasoline comprising from 0 to 30% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 80% by weight of naphthenes, from 5 to 80% by weight of olefins and from 0 to 60% by weight of aromatics, the refinery gas comprising from 0 to 5% by weight of hydrogen, from 0 to 40% by weight of methane, from 0 to 50% by weight of ethylene, from 0 to 80% by weight of ethane, from 0 to 50% by weight of propylene, from 0 to 80% by weight of propane and from 0 to 30% by weight of butanes, and the paraffin-rich feedstock containing at least 50% by weight of saturated hydrocarbons, said feedstock comprising at least propane or butane.
- A hydrocarbon composition according to claim 10, in which the mixture of the first and second components with the naphtha comprises up to 60% by weight of the second component and at least 40% by weight of gasoline.
- A hydrocarbon composition according to claim 11, in which the mixture of the first and second components comprises up to 50% by weight of the second component and at least 50% by weight of gasoline.
- A hydrocarbon composition according to claim 11 or claim 12, in which the mixture of the first and second components comprises approximately a third in % by weight of the second component and approximately two-thirds in % by weight of gasoline.
- A hydrocarbon composition according to claim 13, in which the feedstock comprises approximately 80% by weight of naphtha, approximately 7% by weight of the second component and approximately 13% by weight of gasoline.
- A hydrocarbon composition according to any one of claims 10 to 14, in which the second component consists at least of propane and butane.
- A process for monitoring a steam cracker, said process comprising:- supplying to a steam cracker steam and a hydrocarbon feedstock comprising 5 to 95% by weight of a paraffinic naphtha and 95 to 5% by weight of a mixture of a first component, namely a gasoline originating from a fluidised bed catalytic cracking unit (FCC) and a second component comprising at least one hydrocarbon refinery gas and at least one paraffin-rich feedstock, the paraffinic naphtha comprising from 10 to 60% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 35% by weight of naphthenes, from 0 to 1% by weight of olefins and from 0 to 20% by weight of aromatics, the FCC gasoline being a non-hydrogenated gasoline comprising from 0 to 30% by weight of n-paraffins, from 10 to 60% by weight of isoparaffins, from 0 to 80% by weight of naphthenes, from 5 to 80% by weight of olefins and from 0 to 60% by weight of aromatics, the refinery gas comprising from 0 to 5% by weight of hydrogen, from 0 to 40% by weight of methane, from 0 to 50% by weight of ethylene, from 0 to 80% by weight of ethane, from 0 to 50% by weight of propylene, from 0 to 80% by weight of propane and from 0 to 30% by weight of butanes, and the paraffin-rich feedstock containing at least 50% by weight of saturated hydrocarbons, said feedstock comprising at least propane or butane,- and continuously monitoring the inputs of paraffinic naphtha, the second component and the gasoline in the feedstock, in order to ensure that the effluent has the desired target composition.
- A process according to claim 16, in which the target composition is substantially the same, namely ± 20% by weight for any given effluent component, as that of the effluent obtained with non-modified paraffinic naphtha.
- A process according to claim 16 or claim 17, in which the second component and the gasoline are both supplied directly by a refinery and further comprising monitoring sending of the second excess component to the flare and/or monitoring the quantity of gasoline in the refinery.
- A process according to any one of claims 16 to 18, in which supply of the components of the feedstock to the steam cracker is controlled by software.
- Use of the process according to one of claims 1 to 16 for the treatment of sulfurous gasoline, characterised in that- the sulfurous gasoline is gasoline originating from a fluidised bed catalytic cracking unit,- and the steam cracker effluent containing at least light olefins, which comprise at least one of the C2 to C4 olefins and C5+ hydrocarbons, is separated into a first fraction, which is virtually sulfur-free and comprises light olefins, and a second fraction which contains sulfur and comprises C5+ hydrocarbons.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0200244A FR2834515B1 (en) | 2002-01-10 | 2002-01-10 | VAPOCRAQUAGE OF MODIFIED NAPHTA |
| FR0200244 | 2002-01-10 | ||
| PCT/FR2003/000047 WO2003057802A2 (en) | 2002-01-10 | 2003-01-09 | Steam-cracking of modified naphtha |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1463789A2 EP1463789A2 (en) | 2004-10-06 |
| EP1463789B1 EP1463789B1 (en) | 2006-06-14 |
| EP1463789B9 true EP1463789B9 (en) | 2007-02-28 |
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ID=8871219
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03712222A Expired - Lifetime EP1463789B9 (en) | 2002-01-10 | 2003-01-09 | Steam-cracking of fcc-gasoline |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US7838712B2 (en) |
| EP (1) | EP1463789B9 (en) |
| KR (1) | KR101062768B1 (en) |
| CN (1) | CN1306011C (en) |
| AT (1) | ATE329984T1 (en) |
| AU (1) | AU2003216795A1 (en) |
| CA (1) | CA2471491C (en) |
| DE (1) | DE60306105T2 (en) |
| DK (1) | DK1463789T3 (en) |
| ES (1) | ES2266792T3 (en) |
| FR (1) | FR2834515B1 (en) |
| PT (1) | PT1463789E (en) |
| WO (1) | WO2003057802A2 (en) |
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| US8775138B2 (en) * | 2008-11-21 | 2014-07-08 | Exxonmobil Chemical Patents Inc. | Methods for handling withdrawal of streams from a linear programming model developed from a thermodynamically-based reference tool |
| CN101734990B (en) * | 2008-11-25 | 2013-09-04 | 中国石油天然气股份有限公司 | Method for preparing ethylene by steam cracking in pipe type cracking furnace |
| EP2290045A1 (en) * | 2009-07-27 | 2011-03-02 | Total Petrochemicals Research Feluy | A process for the production of bio-naphtha from complex mixtures of natural occurring fats and oils |
| NZ599954A (en) * | 2009-10-27 | 2013-02-22 | Methods for producing hydrocarbon products from bio-oils and/or coal -oils | |
| CN104540925B (en) * | 2012-08-09 | 2017-04-05 | 林德股份公司 | The method that alkene is prepared by vapours cracking |
| RU2640592C2 (en) * | 2012-10-29 | 2018-01-10 | Чайна Петролеум Энд Кемикал Корпорейшн | Steam cracking process |
| CN104769082B (en) * | 2012-11-08 | 2017-03-29 | 林德股份公司 | The method that olefin-containing product is prepared by vapours cracking |
| US20140275669A1 (en) * | 2013-03-15 | 2014-09-18 | Exxonmobil Research And Engineering Company | Production of lubricant base oils from dilute ethylene feeds |
| US10041673B2 (en) | 2013-07-25 | 2018-08-07 | Honeywell International Inc. | Flare stack monitoring |
| CN107056568A (en) * | 2017-05-10 | 2017-08-18 | 中石化上海工程有限公司 | The method that MTO techniques are coupled with naphtha and Deposition During Propane Pyrolysis predepropanization technique |
| FI128839B (en) * | 2018-04-10 | 2021-01-15 | Neste Oyj | A method for producing a mixture of hydrocarbons |
| FI128378B (en) | 2019-04-03 | 2020-04-15 | Neste Oyj | A method and feedstock for producing hydrocarbons |
| EP3976735A4 (en) * | 2019-05-24 | 2023-03-15 | Eastman Chemical Company | Co-cracking pyoil with ethane |
| WO2020242912A1 (en) | 2019-05-24 | 2020-12-03 | Eastman Chemical Company | Blend small amounts of pyoil into a liquid stream processed into a gas cracker |
| WO2020242916A1 (en) * | 2019-05-24 | 2020-12-03 | Eastman Chemical Company | Cracking a c4-c7 fraction of pyoil |
| EP4003948A4 (en) * | 2019-07-29 | 2023-09-06 | Eastman Chemical Company | Recycle content (c4)alkanal |
| US11319262B2 (en) | 2019-10-31 | 2022-05-03 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
| EP4051767A4 (en) * | 2019-10-31 | 2024-03-20 | Eastman Chemical Company | Processes and systems for formation of recycle-content hydrocarbon compositions |
| KR20220092563A (en) * | 2019-10-31 | 2022-07-01 | 이스트만 케미칼 컴파니 | Methods and systems for the production of recycled hydrocarbon compositions |
| US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
| EP4054997A4 (en) | 2019-11-07 | 2024-02-21 | Eastman Chemical Company | Recycle content alpha olefins and fatty alcohols |
| US11021422B1 (en) * | 2019-12-04 | 2021-06-01 | Saudi Arabian Oil Company | Integrated processes to produce gasoline blending components from light naphtha |
| WO2021133889A1 (en) * | 2019-12-23 | 2021-07-01 | Chevron U.S.A. Inc. | Circular economy for plastic waste to polypropylene via refinery fcc unit |
| US11566182B2 (en) | 2020-03-30 | 2023-01-31 | Chevron U.S.A. Inc. | Circular economy for plastic waste to polyethylene via refinery FCC feed pretreater and FCC units |
| JP2023519064A (en) * | 2020-03-30 | 2023-05-10 | シェブロン ユー．エス．エー． インコーポレイテッド | Circular Economy of Waste Plastics into Polyethylene via Refining FCC or FCC/Alkylation Units |
| US11306253B2 (en) | 2020-03-30 | 2022-04-19 | Chevron U.S.A. Inc. | Circular economy for plastic waste to polyethylene via refinery FCC or FCC/alkylation units |
| CN114106867B (en) * | 2021-10-27 | 2023-05-23 | 中国石油化工股份有限公司 | Method for reducing sulfur content in carbon five fraction |
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|---|---|---|---|---|
| US3511771A (en) * | 1967-07-24 | 1970-05-12 | Exxon Research Engineering Co | Integrated hydrofining,hydrodesulfurization and steam cracking process |
| US3786110A (en) * | 1972-05-19 | 1974-01-15 | Marathon Oil Co | Asphaltenes for inhibiting polymerization of pyrolysis products |
| US4257105A (en) * | 1979-05-02 | 1981-03-17 | Phillips Petroleum Company | Control of a cracking furnace |
| DE3765324D1 (en) * | 1986-06-25 | 1990-11-08 | Naphtachimie Sa | METHOD AND OVEN FOR STEAM CRACKING HYDROCARBONS FOR THE PREPARATION OF OLEFINS AND DIOLEFINS. |
| DE3708332A1 (en) * | 1987-03-14 | 1988-09-22 | Erdoelchemie Gmbh | Process for the thermal conversion of ethylene |
| US4956509A (en) * | 1989-10-16 | 1990-09-11 | Mobil Oil Corp. | Integrated paraffin upgrading and catalytic cracking processes |
| US5481052A (en) * | 1992-04-22 | 1996-01-02 | Bp Chemicals Limited | Polymer cracking |
| CN1026594C (en) * | 1993-01-28 | 1994-11-16 | 化学工业部北京化工研究院 | Improvement for petroleum hydrocarbon steam cracking method |
| US5582714A (en) | 1995-03-20 | 1996-12-10 | Uop | Process for the removal of sulfur from petroleum fractions |
| FR2753717B1 (en) * | 1996-09-24 | 1998-10-30 | PROCESS AND PLANT FOR THE PRODUCTION OF LOW SULFUR CATALYTIC CRACKING ESSENCES |
-
2002
- 2002-01-10 FR FR0200244A patent/FR2834515B1/en not_active Expired - Fee Related
-
2003
- 2003-01-09 CN CNB038020823A patent/CN1306011C/en not_active Expired - Fee Related
- 2003-01-09 EP EP03712222A patent/EP1463789B9/en not_active Expired - Lifetime
- 2003-01-09 CA CA2471491A patent/CA2471491C/en not_active Expired - Fee Related
- 2003-01-09 DE DE60306105T patent/DE60306105T2/en not_active Expired - Lifetime
- 2003-01-09 DK DK03712222T patent/DK1463789T3/en active
- 2003-01-09 US US10/501,266 patent/US7838712B2/en not_active Expired - Fee Related
- 2003-01-09 AT AT03712222T patent/ATE329984T1/en active
- 2003-01-09 AU AU2003216795A patent/AU2003216795A1/en not_active Abandoned
- 2003-01-09 KR KR1020047010782A patent/KR101062768B1/en not_active IP Right Cessation
- 2003-01-09 PT PT03712222T patent/PT1463789E/en unknown
- 2003-01-09 ES ES03712222T patent/ES2266792T3/en not_active Expired - Lifetime
- 2003-01-09 WO PCT/FR2003/000047 patent/WO2003057802A2/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| CN1615353A (en) | 2005-05-11 |
| US20060089518A1 (en) | 2006-04-27 |
| EP1463789B1 (en) | 2006-06-14 |
| ES2266792T3 (en) | 2007-03-01 |
| DK1463789T3 (en) | 2006-10-16 |
| CA2471491C (en) | 2011-03-15 |
| DE60306105T2 (en) | 2007-01-04 |
| DE60306105D1 (en) | 2006-07-27 |
| PT1463789E (en) | 2006-10-31 |
| WO2003057802A2 (en) | 2003-07-17 |
| KR101062768B1 (en) | 2011-09-06 |
| KR20040086264A (en) | 2004-10-08 |
| FR2834515A1 (en) | 2003-07-11 |
| CN1306011C (en) | 2007-03-21 |
| AU2003216795A1 (en) | 2003-07-24 |
| CA2471491A1 (en) | 2003-07-17 |
| US7838712B2 (en) | 2010-11-23 |
| FR2834515B1 (en) | 2006-03-10 |
| ATE329984T1 (en) | 2006-07-15 |
| EP1463789A2 (en) | 2004-10-06 |
| WO2003057802A3 (en) | 2004-04-15 |
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