WO2006137616A1 - Process for increasing production of benzene from hydrocarbon mixture - Google Patents
Process for increasing production of benzene from hydrocarbon mixture Download PDFInfo
- Publication number
- WO2006137616A1 WO2006137616A1 PCT/KR2005/002708 KR2005002708W WO2006137616A1 WO 2006137616 A1 WO2006137616 A1 WO 2006137616A1 KR 2005002708 W KR2005002708 W KR 2005002708W WO 2006137616 A1 WO2006137616 A1 WO 2006137616A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aromatic
- hydrocarbons
- benzene
- stream
- hydrocarbon
- Prior art date
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 90
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 61
- 238000000638 solvent extraction Methods 0.000 claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 25
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000008096 xylene Substances 0.000 claims description 22
- 150000001491 aromatic compounds Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 230000020335 dealkylation Effects 0.000 claims description 10
- 238000006900 dealkylation reaction Methods 0.000 claims description 10
- 238000010555 transalkylation reaction Methods 0.000 claims description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 6
- 239000003502 gasoline Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- -1 naphtha Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 239000000047 product Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 238000005194 fractionation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/08—Azeotropic or extractive distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/27—Organic compounds not provided for in a single one of groups C10G21/14 - C10G21/26
-
- 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
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/68—Aromatisation of hydrocarbon oil fractions
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
-
- 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
- C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
- C10G61/08—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural parallel stages only
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/16—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural parallel stages only
-
- 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
- C10G2400/28—Propane and butane
-
- 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
- C10G2400/30—Aromatics
Definitions
- the present invention relates to a process for increasing the production of benzene from a hydrocarbon mixture. More particularly, the present invention pertains to a process for increasing the production of benzene by integrating a process for producing an aromatic hydrocarbon mixture and liquefied petroleum gas (LPG) from a hydrocarbon mixture with a solvent extraction process for separating and recovering polar hydrocarbons from the hydrocarbon mixture.
- LPG liquefied petroleum gas
- aromatic hydrocarbons are obtained by separating a feedstock fraction, which is rich in aromatic compounds, such as reformates produced through a catalytic reforming process and pyrolysis gasolines produced through a naphtha cracking process, from non-aromatic hydrocarbons using a solvent extraction process.
- the aromatic hydrocarbon mixture thus obtained is separated into benzene, toluene, xylene, and C9+ aromatic compounds using a difference in boiling point to use them as basic petrochemical materials, and the non-aromatic hydrocarbons are used as a feedstock or a fuel for the naphtha cracking process.
- U.S. Patent No. 4,058,454 discloses a solvent extraction process for separating and recovering polar hydrocarbons from a hydrocarbon mixture containing the polar hydrocarbons and nonpolar hydrocarbons.
- Most solvent extraction processes, as well as the above patent, take advantage of the fact that all aromatic hydrocarbons are polar. That is to say, if a solvent capable of dissolving polar material, such as sulfolane, therein is added to a hydrocarbon mixture, polar aromatic hydrocarbons are selectively dissolved and thus separated from nonpolar non-aromatic hydrocarbons.
- This process has an advantage in that it is possible to produce a highly pure aromatic hydrocarbon mixture, but is disadvantageous in that an additional solvent extraction device is necessary and a solvent must be continuously supplied during operation. Accordingly, there remains a need for a process for separating aromatic hydrocarbons and non-aromatic hydrocarbons from feedstock oil without an additional solvent extraction step.
- step (f) separating reaction products of step (e) into an overhead stream, which contains hydrogen, methane, ethane, and the liquefied petroleum gas, and a bottom stream, which contains the aromatic hydrocarbons, and a small amount of hydrogen and non- aromatic hydrocarbons, using a gas-liquid separation process; and
- steps (c) and (g) be simultaneously conducted using a same device or be independently conducted using separately provided devices.
- the process may further comprise recovering the liquefied petroleum gas from the overhead stream.
- zeolite which is at least one selected from a group consisting of mordenite, a beta type of zeolite, and a ZSM-5 type of zeolite, and which has a silica/alumina molar ratio of 200 or less, is mixed with 5-90 wt% inorganic binder to produce a support, and platinum/tin or platinum/lead is supported on the mixture support to produce the catalyst of step (e).
- the hydrocarbon feedstock be selected from a group consisting of reformate, pyrolysis gasoline, desulfurized/denitrified fluidized catalytic cracking gasoline, C9+ aromatic-containing mixture, naphtha, and a mixture thereof.
- step (e) separating reaction products of step (d) into an overhead stream, which contains hydrogen, methane, ethane, and the liquefied petroleum gas, and a bottom stream, which contains the aromatic hydrocarbons, and a small amount of hydrogen and non- aromatic hydrocarbons, using a gas-liquid separation process; and
- hydrocarbons in which the number of carbon atoms is 7 or higher are used as a feedstock of a process for producing an aromatic hydrocarbon mixture and LPG, and hydrocarbons in which the number of carbon atoms is 6 or lower are fed as a feedstock of a solvent extraction process.
- the mixture converted through the catalytic reaction, and the fraction which is separated through the extraction and is rich in benzene, toluene, and xylene, are separated into benzene, toluene, xylene, and C9+ aromatic compounds using a difference in boiling point and a separation device which includes a distillation column, resulting in the improved production of benzene.
- FlG. 1 illustrates one embodiment of a procedure of increasing the production of benzene from a hydrocarbon mixture, according to the present invention.
- FlG. 2 illustrates another embodiment of a procedure of increasing the production of benzene from a hydrocarbon mixture, according to the present invention. Best Mode for Carrying Out the Invention
- FIGS. 1 and 2 illustrate procedures of increasing the production of benzene from a hydrocarbon mixture, according to preferred embodiments of the present invention.
- a hydrocarbon feedstock 11 as feedstock oil of a process according to the present invention is separated into a fraction 12 in which the number of carbon atoms is 6 or lower and a fraction 13 in which the number of carbon atoms is 7 or higher in a fractionation unit 8.
- the fraction 12 in which the number of carbon atoms is 6 or lower is fed as a feedstock for a solvent extraction process 9, and the fraction 13 in which the number of carbon atoms is 7 or higher is fed as a feedstock for a process of producing aromatic hydrocarbons and LPG from a hydrocarbon mixture.
- the hydrocarbon feedstock used in the present invention preferably includes hydrocarbons having a boiling point of 30-250°C, and may be selected from the group consisting of reformate, pyrolysis gasoline, desulfurized/denitrified fluidized catalytic cracking gasoline, C9+ aromatic-containing mixture, naphtha, and a mixture thereof.
- a separate heater 2 is provided in order to increase the temperature of the hydrogen/feedstock mixture to a reaction temperature.
- the hydrogen/feedstock mixture is heated to some extent 15 through heat exchange with reaction products 17 which are discharged from the reactor 3 and then fed into a heat exchanger 1, and is then fed into the heater 2.
- the hydrogen/feedstock mixture 16 which is fed into the reactor 3 is subjected to dealkylation, transalkylation, and hydrogenation reactions in the presence of a catalyst.
- a catalyst which is packed in the reactor 3 to cause the dealkylation, transalkylation, and hydrogenation reactions, is not limited as long as it is known to those skilled in the art, and, preferably, may be a catalyst disclosed in U.S. Patent No. 6,635,792.
- 10-95 wt% zeolite which is at least one selected from the group consisting of mordenite, a beta type of zeolite, and a ZSM-5 type of zeolite and which has a silica/alumina molar ratio of 200 or less, is mixed with 5-90 wt% inorganic binder to produce a support, and platinum/tin or platinum/lead is supported on the mixture support, thereby the catalyst is created.
- the products 17 are present in a gaseous form at a relatively high temperature after the reactions are finished, are circulated into the heat exchanger 1 before they are fed into a gas-liquid separator 4, emit heat to the hydrogen/feedstock mixture therein, and are fed into a cooler 5.
- a product stream 19 passing through the cooler 5 is fed into the gas-liquid separator
- the gaseous component is discharged in an overhead stream 21 from the gas-liquid separator 4, and the liquid component is discharged in a bottom stream 20 therefrom.
- the gaseous component 21 includes about 60-75 mol% hydrogen and 25-40 mol% hydrocarbon components, and the hydrocarbon components include methane, ethane, and LPG which have relatively small numbers of carbon atoms.
- the hydrogen component is compressed by a compressor 6, mixed with highly pure hydrogen 14 which is fed to control the purity of hydrogen, and is fed in conjunction with the feedstock 13 into a reaction area. Methane, ethane, and the LPG which are contained in the overhead stream 21 may selectively be recovered using an additional distillation process.
- the bottom stream 20 consists mostly of aromatic components, and also includes residual hydrogen and light non-aromatic components in a small amount. Accordingly, the liquid component is additionally subjected to a separation and purification process, and is separated into residual hydrogen 22, a non-aromatic component 23, and benzene 24, toluene 25, xylene 26, and C9+ aromatic compounds 27, which have purity of 99 % or more, using a difference in boiling point in a fractionation unit 7.
- the hydrocarbon mixture in which the number of carbon atoms is 7 or higher, is subjected to dealkylation, transalkylation, and hydrogenation reactions in the presence of the catalyst, thereby C9, ClO, and CIl aromatic compounds are converted into benzene, toluene, and xylene.
- the fraction 12 which is separated by the fractionation unit 8 and is then fed as a feedstock of a solvent extraction process 9 and in which the number of carbon atoms is 6 or lower, is separated into non-aromatic hydrocarbons 28 which are nonpolar hydrocarbons and aromatic hydrocarbons 29 which are polar hydrocarbons.
- the aromatic hydrocarbons 29, which are the polar hydrocarbons are fed into a fractionation unit 10 at a rear stage to produce benzene 30, or, as shown in FlG. 2, they are fed into the fractionation unit 7 of the process using the C7 or higher hydrocarbon mixture as a feedstock to produce benzene 24, toluene 25, and xylene 26 using a difference in boiling point.
- the two separate processes are integrated, the hydrocarbon mixture is separated into the fraction in which the number of carbon atoms is 6 or lower and the fraction in which the number of carbon atoms is 7 or higher, and they are, respectively, used as a feedstock in the two processes. That is to say, the hydrocarbons in which the number of carbon atoms is 7 or higher are used as the feedstock of the process for producing the aromatic hydrocarbon mixture and the LPG, and the hydrocarbons in which the number of carbon atoms is 6 or lower are used as the feedstock of the solvent extraction process for separating and recovering the polar hydrocarbons from the hydrocarbons containing the polar hydrocarbons and the nonpolar hydrocarbons.
- the mixture converted through the catalytic reaction, and the fraction which is separated through extraction and is rich in benzene, toluene, and xylene are separated into benzene, toluene, xylene, and C9+ aromatic compounds, respectively using a difference in boiling point through a separation device which includes a distillation column, resulting in the improved production of benzene.
Abstract
Disclosed herein is a process for increasing the production of benzene from a hydrocarbon mixture. A process for producing an aromatic hydrocarbon mixture and LPG from a hydrocarbon mixture, and a solvent extraction process for separating and recovering polar hydrocarbons from a hydrocarbon mixture containing polar hydrocarbons (that is, aromatic hydrocarbons) and nonpolar hydrocarbons (that is, non-aromatic hydrocarbons) are integrated, thereby it is possible to increase the production of benzene.
Description
Description
PROCESS FOR INCREASING PRODUCTION OF BENZENE FROM HYDROCARBON MIXTURE
Technical Field
[1] The present invention relates to a process for increasing the production of benzene from a hydrocarbon mixture. More particularly, the present invention pertains to a process for increasing the production of benzene by integrating a process for producing an aromatic hydrocarbon mixture and liquefied petroleum gas (LPG) from a hydrocarbon mixture with a solvent extraction process for separating and recovering polar hydrocarbons from the hydrocarbon mixture. Background Art
[2] Generally, aromatic hydrocarbons are obtained by separating a feedstock fraction, which is rich in aromatic compounds, such as reformates produced through a catalytic reforming process and pyrolysis gasolines produced through a naphtha cracking process, from non-aromatic hydrocarbons using a solvent extraction process. The aromatic hydrocarbon mixture thus obtained is separated into benzene, toluene, xylene, and C9+ aromatic compounds using a difference in boiling point to use them as basic petrochemical materials, and the non-aromatic hydrocarbons are used as a feedstock or a fuel for the naphtha cracking process.
[3] With respect to this, U.S. Patent No. 4,058,454 discloses a solvent extraction process for separating and recovering polar hydrocarbons from a hydrocarbon mixture containing the polar hydrocarbons and nonpolar hydrocarbons. Most solvent extraction processes, as well as the above patent, take advantage of the fact that all aromatic hydrocarbons are polar. That is to say, if a solvent capable of dissolving polar material, such as sulfolane, therein is added to a hydrocarbon mixture, polar aromatic hydrocarbons are selectively dissolved and thus separated from nonpolar non-aromatic hydrocarbons. This process has an advantage in that it is possible to produce a highly pure aromatic hydrocarbon mixture, but is disadvantageous in that an additional solvent extraction device is necessary and a solvent must be continuously supplied during operation. Accordingly, there remains a need for a process for separating aromatic hydrocarbons and non-aromatic hydrocarbons from feedstock oil without an additional solvent extraction step.
[4] In connection with this, effort has been made to employ another reaction system instead of a solvent extraction process in order to separate aromatic compounds from non-aromatic compounds. The non-aromatic compounds which are mixed with the aromatic compounds are converted into gaseous hydrocarbons through a hy-
drocracking reaction using a catalyst, and the aromatic compounds and the non- aromatic compounds are separated from each other using a gas-liquid separator at a rear part of a reactor. This technology has been developed from U.S. Patent No. 3,729,409.
[5] Furthermore, a process for producing aromatic hydrocarbons and LPG from a hydrocarbon mixture, in which aromatic compounds of the hydrocarbon mixture are converted into a fraction including benzene, toluene, xylene and the like through dealkylation and/or transalkylation reactions, and non-aromatic compounds are converted into gaseous material that is rich in LPG through a hydrocracking reaction, has been studied.
[6] The above-mentioned processes, respectively, which have the common object of producing aromatic hydrocarbon products, such as benzene, toluene, or xylene, have been independently developed as competitive, or complementary/substitution technologies. However, a process for improving productivity of aromatic hydrocarbons, particularly, benzene, by integrating competing processes has not yet been suggested.
Disclosure of Invention Technical Problem
[7] Leading to the present invention, the intensive and thorough research on production of benzene, carried out by the present inventors aiming to avoid the problems encountered in the prior arts, resulting in the finding that, when a process for producing an aromatic hydrocarbon mixture and LPG from a hydrocarbon mixture and a solvent extraction process for separating and recovering polar hydrocarbons from a hydrocarbon mixture are integrated, it is possible to improve the productivity and efficiency of each process or of the integrated process, thereby accomplishing the present invention.
[8] Therefore, it is an object of the present invention to provide a process for increasing the productivity of products by integrating two processes which have different functions and compete with or complement each other.
[9] It is another object of the present invention to provide a process for increasing the production of benzene from a hydrocarbon mixture so as to improve productivity.
Technical Solution
[10] In order to accomplish the above objects, according to a preferred embodiment of the present invention, there is provided a process for increasing the production of benzene from a hydrocarbon mixture, comprising the following steps of:
[11] (a) separating a hydrocarbon feedstock into a C6 or lower hydrocarbon stream and a
C7 or higher hydrocarbon stream;
[12] (b) separating the C6 or lower hydrocarbons into a non-aromatic hydrocarbon stream and an aromatic hydrocarbon stream through a solvent extraction process;
[13] (c) recovering benzene from the aromatic hydrocarbon stream;
[14] (d) feeding the C7 or higher hydrocarbons and hydrogen into at least one reaction area;
[15] (e) converting the C7 or higher hydrocarbons in presence of a catalyst in the reaction area into (i) aromatic hydrocarbons which are rich in benzene, toluene, and xylene through dealkylation/transalkylation reactions, and (ii) non-aromatic hydrocarbons which are rich in liquefied petroleum gas through a hydrocracking reaction;
[16] (f) separating reaction products of step (e) into an overhead stream, which contains hydrogen, methane, ethane, and the liquefied petroleum gas, and a bottom stream, which contains the aromatic hydrocarbons, and a small amount of hydrogen and non- aromatic hydrocarbons, using a gas-liquid separation process; and
[17] (g) recovering benzene, toluene, xylene, and C9 or higher aromatic compounds, respectively from the bottom stream.
[18] It is preferable that steps (c) and (g) be simultaneously conducted using a same device or be independently conducted using separately provided devices.
[19] The process may further comprise recovering the liquefied petroleum gas from the overhead stream.
[20] Preferably, 10-95 wt% zeolite, which is at least one selected from a group consisting of mordenite, a beta type of zeolite, and a ZSM-5 type of zeolite, and which has a silica/alumina molar ratio of 200 or less, is mixed with 5-90 wt% inorganic binder to produce a support, and platinum/tin or platinum/lead is supported on the mixture support to produce the catalyst of step (e).
[21] Meanwhile, it is preferable that the hydrocarbon feedstock be selected from a group consisting of reformate, pyrolysis gasoline, desulfurized/denitrified fluidized catalytic cracking gasoline, C9+ aromatic-containing mixture, naphtha, and a mixture thereof.
[22] According to another preferred embodiment of the present invention, there is provided a process for increasing the production of benzene from a hydrocarbon mixture, comprising the following steps of:
[23] (a) separating a hydrocarbon feedstock into a C6 or lower hydrocarbon stream and a
C7 or higher hydrocarbon stream;
[24] (b) separating the C6 or lower hydrocarbons into a non-aromatic hydrocarbon stream and an aromatic hydrocarbon stream through a solvent extraction process;
[25] (c) feeding the C7 or higher hydrocarbons and hydrogen into at least one reaction area;
[26] (d) converting the C7 or higher hydrocarbons in presence of a catalyst in the reaction area into (i) aromatic hydrocarbons which are rich in benzene, toluene, and
xylene through dealkylation/transalkylation reactions, and (ii) non-aromatic hydrocarbons which are rich in liquefied petroleum gas through a hydrocracking reaction;
[27] (e) separating reaction products of step (d) into an overhead stream, which contains hydrogen, methane, ethane, and the liquefied petroleum gas, and a bottom stream, which contains the aromatic hydrocarbons, and a small amount of hydrogen and non- aromatic hydrocarbons, using a gas-liquid separation process; and
[28] (f) combining the aromatic hydrocarbon stream separated in step (b) and the bottom stream separated in step (e) to recover benzene, toluene, xylene, and C9 or higher aromatic compounds, respectively. Advantageous Effects
[29] In the present invention, after a hydrocarbon mixture is separated into a fraction in which the number of carbon atoms is 6 or lower and a residual fraction, hydrocarbons in which the number of carbon atoms is 7 or higher are used as a feedstock of a process for producing an aromatic hydrocarbon mixture and LPG, and hydrocarbons in which the number of carbon atoms is 6 or lower are fed as a feedstock of a solvent extraction process. Thereby, the mixture converted through the catalytic reaction, and the fraction which is separated through the extraction and is rich in benzene, toluene, and xylene, are separated into benzene, toluene, xylene, and C9+ aromatic compounds using a difference in boiling point and a separation device which includes a distillation column, resulting in the improved production of benzene.
[30] Therefore, when the process for producing the highly pure aromatic hydrocarbon mixture, the LPG, and the non-aromatic hydrocarbons from the hydrocarbon feedstock, and the solvent extraction process for separating and recovering polar hydrocarbons from the hydrocarbon feedstock containing the polar hydrocarbons and nonpolar hydrocarbons are integrated according to the process of the present invention, it is possible to significantly improve the productivity of products in comparison with the separate use of each process. Brief Description of the Drawings
[31] The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
[32] FlG. 1 illustrates one embodiment of a procedure of increasing the production of benzene from a hydrocarbon mixture, according to the present invention; and
[33] FlG. 2 illustrates another embodiment of a procedure of increasing the production of benzene from a hydrocarbon mixture, according to the present invention. Best Mode for Carrying Out the Invention
[34] Hereinafter, a detailed description will be given of the present invention, referring
to the drawings.
[35] FIGS. 1 and 2 illustrate procedures of increasing the production of benzene from a hydrocarbon mixture, according to preferred embodiments of the present invention.
[36] With reference to FIGS. 1 and 2, a hydrocarbon feedstock 11 as feedstock oil of a process according to the present invention is separated into a fraction 12 in which the number of carbon atoms is 6 or lower and a fraction 13 in which the number of carbon atoms is 7 or higher in a fractionation unit 8. The fraction 12 in which the number of carbon atoms is 6 or lower is fed as a feedstock for a solvent extraction process 9, and the fraction 13 in which the number of carbon atoms is 7 or higher is fed as a feedstock for a process of producing aromatic hydrocarbons and LPG from a hydrocarbon mixture.
[37] The hydrocarbon feedstock used in the present invention preferably includes hydrocarbons having a boiling point of 30-250°C, and may be selected from the group consisting of reformate, pyrolysis gasoline, desulfurized/denitrified fluidized catalytic cracking gasoline, C9+ aromatic-containing mixture, naphtha, and a mixture thereof.
[38] The fraction 13, in which the number of carbon atoms is 7 or higher and which is fed as the feedstock for the process of producing the aromatic hydrocarbons and the LPG from the hydrocarbon mixture, is mixed with circulating hydrogen 22 and highly pure hydrogen 14, and is then fed in a hydrogen/feedstock mixture form 15 into a reactor 3.
[39] In connection with this, a separate heater 2 is provided in order to increase the temperature of the hydrogen/feedstock mixture to a reaction temperature. The hydrogen/feedstock mixture is heated to some extent 15 through heat exchange with reaction products 17 which are discharged from the reactor 3 and then fed into a heat exchanger 1, and is then fed into the heater 2.
[40] The hydrogen/feedstock mixture 16 which is fed into the reactor 3 is subjected to dealkylation, transalkylation, and hydrogenation reactions in the presence of a catalyst.
[41] That is to say, a hydrocracking reaction of non-aromatic hydrocarbon compounds, and the dealkylation and transalkylation reactions of aromatic hydrocarbon compounds are simultaneously carried out in the reactor 3 to produce main basic petrochemical materials, such as benzene, toluene, and xylene, and byproducts, such as LPG and non- aromatic compounds.
[42] In connection with this, a catalyst, which is packed in the reactor 3 to cause the dealkylation, transalkylation, and hydrogenation reactions, is not limited as long as it is known to those skilled in the art, and, preferably, may be a catalyst disclosed in U.S. Patent No. 6,635,792.
[43] That is to say, 10-95 wt% zeolite, which is at least one selected from the group consisting of mordenite, a beta type of zeolite, and a ZSM-5 type of zeolite and which
has a silica/alumina molar ratio of 200 or less, is mixed with 5-90 wt% inorganic binder to produce a support, and platinum/tin or platinum/lead is supported on the mixture support, thereby the catalyst is created.
[44] Meanwhile, the products 17 are present in a gaseous form at a relatively high temperature after the reactions are finished, are circulated into the heat exchanger 1 before they are fed into a gas-liquid separator 4, emit heat to the hydrogen/feedstock mixture therein, and are fed into a cooler 5.
[45] A product stream 19 passing through the cooler 5 is fed into the gas-liquid separator
4 at about 30-50°C, and is then separated into a gaseous component and a liquid component.
[46] The gaseous component is discharged in an overhead stream 21 from the gas-liquid separator 4, and the liquid component is discharged in a bottom stream 20 therefrom. In connection with this, the gaseous component 21 includes about 60-75 mol% hydrogen and 25-40 mol% hydrocarbon components, and the hydrocarbon components include methane, ethane, and LPG which have relatively small numbers of carbon atoms. The hydrogen component is compressed by a compressor 6, mixed with highly pure hydrogen 14 which is fed to control the purity of hydrogen, and is fed in conjunction with the feedstock 13 into a reaction area. Methane, ethane, and the LPG which are contained in the overhead stream 21 may selectively be recovered using an additional distillation process.
[47] Meanwhile, the bottom stream 20 consists mostly of aromatic components, and also includes residual hydrogen and light non-aromatic components in a small amount. Accordingly, the liquid component is additionally subjected to a separation and purification process, and is separated into residual hydrogen 22, a non-aromatic component 23, and benzene 24, toluene 25, xylene 26, and C9+ aromatic compounds 27, which have purity of 99 % or more, using a difference in boiling point in a fractionation unit 7.
[48] In summary, the hydrocarbon mixture, in which the number of carbon atoms is 7 or higher, is subjected to dealkylation, transalkylation, and hydrogenation reactions in the presence of the catalyst, thereby C9, ClO, and CIl aromatic compounds are converted into benzene, toluene, and xylene.
[49] Meanwhile, the fraction 12, which is separated by the fractionation unit 8 and is then fed as a feedstock of a solvent extraction process 9 and in which the number of carbon atoms is 6 or lower, is separated into non-aromatic hydrocarbons 28 which are nonpolar hydrocarbons and aromatic hydrocarbons 29 which are polar hydrocarbons.
[50] As shown in FlG. 1, the aromatic hydrocarbons 29, which are the polar hydrocarbons, are fed into a fractionation unit 10 at a rear stage to produce benzene 30, or, as shown in FlG. 2, they are fed into the fractionation unit 7 of the process using
the C7 or higher hydrocarbon mixture as a feedstock to produce benzene 24, toluene 25, and xylene 26 using a difference in boiling point.
[51] As described above, separate processes which are integrated in the present invention have the common object of producing aromatic hydrocarbon products, such as benzene, toluene, and xylene. However, they are different from each other in that, in one process, the contents of benzene, toluene, and xylene in feedstock oil are changed through dealkylation and transalkylation reactions using the catalyst, while, in the other process, the contents of benzene, toluene, and xylene in feedstock oil are not changed.
[52] In the present invention, the two separate processes are integrated, the hydrocarbon mixture is separated into the fraction in which the number of carbon atoms is 6 or lower and the fraction in which the number of carbon atoms is 7 or higher, and they are, respectively, used as a feedstock in the two processes. That is to say, the hydrocarbons in which the number of carbon atoms is 7 or higher are used as the feedstock of the process for producing the aromatic hydrocarbon mixture and the LPG, and the hydrocarbons in which the number of carbon atoms is 6 or lower are used as the feedstock of the solvent extraction process for separating and recovering the polar hydrocarbons from the hydrocarbons containing the polar hydrocarbons and the nonpolar hydrocarbons. Thereby, the mixture converted through the catalytic reaction, and the fraction which is separated through extraction and is rich in benzene, toluene, and xylene are separated into benzene, toluene, xylene, and C9+ aromatic compounds, respectively using a difference in boiling point through a separation device which includes a distillation column, resulting in the improved production of benzene.
[53] Therefore, when the process for producing the highly pure aromatic hydrocarbon mixture, the LPG, and the non-aromatic hydrocarbons from the hydrocarbon feedstock, and the solvent extraction process for separating and recovering the polar hydrocarbons from the hydrocarbon feedstock containing the polar hydrocarbons and the nonpolar hydrocarbons are integrated according to the method of the present invention, it is possible to significantly improve the productivity of products in comparison with the separate use of each process. Mode for the Invention
[54] A better understanding of the present invention may be obtained through the following examples and comparative examples which are set forth to illustrate, but are not to be construed as the limit of the present invention.
[55]
[56] EXAMPLE 1 AND COMPARATIVE EXAMPLES 1 AND 2
[58] It is necessary to confirm the productivities of separate processes and the integrated process according to the process of the present invention, therefore tests were conducted to achieve the confirmation in the following examples.
[59] [60] COMPARATIVE EXAMPLE 1 [61] [62] The productivity of products in a solvent extraction process using pyrolysis gasolines as a feedstock was confirmed, and the results are described in the following Table 1.
[63] Table 1
[64] Temp.: Extraction temperature [65] Press.: Extraction pressure [66] Ratio: Solvent/H.C. volume Ratio [67] [68] COMPARATIVE EXAMPLE 2 [69] [70] The productivity of a process for producing aromatic hydrocarbons and LPG from a hydrocarbon mixture using pyrolysis gasolines as a feedstock was confirmed, and the results are described in the following Table 2.
[71] Table 2
[72] EXAMPLE l [73] [74] The productivity of the integrated process shown in FIG. 1 using pyrolysis gasolines as a feedstock was confirmed, and the results are described in the following Table 3.
[75] Table 3
[76] The present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description
rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.
Claims
[ 1 ] A process for increasing production of benzene from a hydrocarbon mixture, comprising the following steps of:
(a) separating a hydrocarbon feedstock into a C6 or lower hydrocarbon stream and a C7 or higher hydrocarbon stream;
(b) separating the C6 or lower hydrocarbons into a non-aromatic hydrocarbon stream and an aromatic hydrocarbon stream through a solvent extraction process;
(c) recovering benzene from the aromatic hydrocarbon stream;
(d) feeding the C7 or higher hydrocarbons and hydrogen into at least one reaction area;
(e) converting the C7 or higher hydrocarbons in presence of a catalyst in the reaction area into (i) aromatic hydrocarbons which are rich in benzene, toluene, and xylene through dealkylation/transalkylation reactions, and (ii) non-aromatic hydrocarbons which are rich in liquefied petroleum gas through a hydrocracking reaction;
(f) separating reaction products of step (e) into an overhead stream, which contains hydrogen, methane, ethane, and the liquefied petroleum gas, and a bottom stream, which contains the aromatic hydrocarbons, and a small amount of hydrogen and non-aromatic hydrocarbons, using a gas-liquid separation process; and
(g) recovering benzene, toluene, xylene, and C9 or higher aromatic compounds, respectively from the bottom stream.
[2] The process as set forth in claim 1, wherein steps (c) and (g) are simultaneously conducted using a same device or are independently conducted using separately provided devices.
[3] The process as set forth in claim 1, further comprising recovering the liquefied petroleum gas from the overhead stream.
[4] The process as set forth in claim 1, wherein 10-95 wt% zeolite, which is at least one selected from a group consisting of mordenite, a beta type of zeolite, and a ZSM-5 type of zeolite, and which has a silica/alumina molar ratio of 200 or less, is mixed with 5-90 wt% inorganic binder to produce a support, and platinum/tin or platinum/lead is supported on the mixture support to produce the catalyst of step (e).
[5] The process as set forth in claim 1, wherein the hydrocarbon feedstock is selected from a group consisting of reformate, pyrolysis gasoline, desulfurized/ denitrified fluidized catalytic cracking gasoline, C9+ aromatic-containing mixture, naphtha, and a mixture thereof.
[6] A process for increasing production of benzene from a hydrocarbon mixture, comprising the following steps of:
(a) separating a hydrocarbon feedstock into a C6 or lower hydrocarbon stream and a C7 or higher hydrocarbon stream;
(b) separating the C6 or lower hydrocarbons into a non-aromatic hydrocarbon stream and an aromatic hydrocarbon stream through a solvent extraction process;
(c) feeding the C7 or higher hydrocarbons and hydrogen into at least one reaction area;
(d) converting the C7 or higher hydrocarbons in presence of a catalyst in the reaction area into (i) aromatic hydrocarbons which are rich in benzene, toluene, and xylene through dealkylation/transalkylation reactions, and (ii) non-aromatic hydrocarbons which are rich in liquefied petroleum gas through a hydrocracking reaction;
(e) separating reaction products of step (d) into an overhead stream, which contains hydrogen, methane, ethane, and the liquefied petroleum gas, and a bottom stream, which contains the aromatic hydrocarbons, and a small amount of hydrogen and non-aromatic hydrocarbons, using a gas-liquid separation process; and
(f) combining the aromatic hydrocarbon stream separated in step (b) and the bottom stream separated in step (e) to recover benzene, toluene, xylene, and C9 or higher aromatic compounds, respectively.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008518007A JP2008543930A (en) | 2005-06-21 | 2005-08-17 | Methods for increasing benzene production from hydrocarbon mixtures |
| EP05780594.7A EP1893722B1 (en) | 2005-06-21 | 2005-08-17 | Process for increasing production of benzene from hydrocarbon mixture |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2005-0053619 | 2005-06-21 | ||
| KR1020050053619A KR100645659B1 (en) | 2005-06-21 | 2005-06-21 | The method of production increase of benzene from hydrocarbon feedstock |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006137616A1 true WO2006137616A1 (en) | 2006-12-28 |
Family
ID=37570611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2005/002708 WO2006137616A1 (en) | 2005-06-21 | 2005-08-17 | Process for increasing production of benzene from hydrocarbon mixture |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7304195B2 (en) |
| EP (1) | EP1893722B1 (en) |
| JP (1) | JP2008543930A (en) |
| KR (1) | KR100645659B1 (en) |
| CN (1) | CN101208409A (en) |
| WO (1) | WO2006137616A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110288354A1 (en) * | 2008-11-26 | 2011-11-24 | Sk Innovation Co., Ltd. | Process for the preparation of clean fuel and aromatics from hydrocarbon mixtures catalytic cracked on fluid bed |
| WO2015013223A1 (en) * | 2013-07-23 | 2015-01-29 | Uop Llc | Processes and apparatuses for preparing aromatic compounds |
| KR101801975B1 (en) | 2009-05-26 | 2017-11-27 | 아이에프피 에너지스 누벨 | Process for the production of a hydrocarbon fraction with a high octane number and a low sulfur content |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009076393A2 (en) * | 2007-12-12 | 2009-06-18 | Shell Oil Company | Process for the conversion of ethane or mixed lower alkanes to aromatic hydrocarbons |
| US8809608B2 (en) * | 2008-02-18 | 2014-08-19 | Shell Oil Company | Process for the conversion of lower alkanes to aromatic hydrocarbons |
| EA024491B1 (en) | 2008-02-18 | 2016-09-30 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Process for the conversion of ethane to aromatic hydrocarbons |
| AU2009215686B2 (en) * | 2008-02-18 | 2012-03-15 | Shell Internationale Research Maatschappij B.V. | Process for the conversion of ethane to aromatic hydrocarbons |
| CN101945702B (en) | 2008-02-20 | 2014-05-28 | 国际壳牌研究有限公司 | Process for the conversion of ethane to aromatic hydrocarbons |
| CN102648169B (en) | 2009-11-02 | 2015-09-16 | 国际壳牌研究有限公司 | Mixing lower alkanes becomes the method for aromatic hydrocarbon |
| WO2011143306A2 (en) | 2010-05-12 | 2011-11-17 | Shell Oil Company | Process for the conversion of lower alkanes to aromatic hydrocarbons |
| CN102372583B (en) * | 2010-08-23 | 2014-03-26 | 中国石油化工股份有限公司 | Fluidized catalytic method for preparing p-xylene by alkylating toluene |
| CN102372586B (en) * | 2010-08-23 | 2014-03-26 | 中国石油化工股份有限公司 | Fluidized catalytic method of p-xylene by methylation of aromatic hydrocarbon |
| SG189484A1 (en) * | 2010-10-22 | 2013-05-31 | Sk Innovation Co Ltd | The method for producing valuable aromatics and light paraffins from hydrocarbonaceous oils derived from oil, coal or wood |
| US8766028B2 (en) * | 2011-11-04 | 2014-07-01 | Amt International Inc. | Separating styrene from C6-C8 aromatic hydrocarbons |
| US9284237B2 (en) | 2013-12-13 | 2016-03-15 | Uop Llc | Methods and apparatuses for processing hydrocarbons |
| US20150166435A1 (en) * | 2013-12-13 | 2015-06-18 | Uop Llc | Methods and apparatuses for processing hydrocarbons |
| RU2544017C1 (en) * | 2014-01-28 | 2015-03-10 | Ольга Васильевна Малова | Catalyst and method for aromatisation of c3-c4 gases, light hydrocarbon fractions of aliphatic alcohols, as well as mixtures thereof |
| JP2017527527A (en) | 2014-06-13 | 2017-09-21 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Process for producing benzene from C5 to C12 hydrocarbon mixtures |
| EA201790013A1 (en) * | 2014-06-13 | 2017-04-28 | Сабик Глоубл Текнолоджиз Б.В. | Method of producing benzene from a mixture of C-C-hydrocarbons |
| US10053403B2 (en) | 2015-02-04 | 2018-08-21 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and their use in transalkylation of heavy aromatics to xylenes |
| US10118165B2 (en) | 2015-02-04 | 2018-11-06 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and use in heavy aromatics conversion processes |
| WO2017032672A1 (en) | 2015-08-21 | 2017-03-02 | Sabic Global Technologies B.V. | Process for producing btx from a c5-c12 hydrocarbon mixture |
| KR101674655B1 (en) * | 2015-12-01 | 2016-11-09 | 동아대학교 산학협력단 | Benzene Removal Equipment and Removal Method in Gasoline Blend from Fluidized Catalytic Cracker Reformate |
| KR101674660B1 (en) * | 2015-12-07 | 2016-11-09 | 동아대학교 산학협력단 | Aromatic compounds separation equipment and separation method with reduced extraction load |
| US10865167B2 (en) | 2016-09-12 | 2020-12-15 | Sabic Global Technologies B.V. | Hydrocracking process |
| WO2018073743A1 (en) | 2016-10-17 | 2018-04-26 | Sabic Global Technologies B.V. | Process for producing btx from a c5-c12 hydrocarbon mixture |
| KR102464478B1 (en) * | 2020-06-16 | 2022-11-07 | 주식회사 엘지화학 | Apparatus for preparing aromatic hydrocarbon |
| KR102583535B1 (en) * | 2020-06-16 | 2023-09-27 | 주식회사 엘지화학 | Method for preparing aromatic hydrocarbon |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702293A (en) * | 1971-12-30 | 1972-11-07 | Universal Oil Prod Co | Hydrocarbon conversion process with a bimetallic catalyst |
| US3729409A (en) * | 1970-12-24 | 1973-04-24 | Mobil Oil Corp | Hydrocarbon conversion |
| US4058454A (en) * | 1976-04-22 | 1977-11-15 | Uop Inc. | Aromatic hydrocarbon separation via solvent extraction |
| US5278344A (en) * | 1992-12-14 | 1994-01-11 | Uop | Integrated catalytic reforming and hydrodealkylation process for maximum recovery of benzene |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO129751B (en) * | 1970-04-13 | 1974-05-20 | Mobil Oil Corp | |
| US3928174A (en) * | 1975-01-02 | 1975-12-23 | Mobil Oil Corp | Combination process for producing LPG and aromatic rich material from naphtha |
| US4053388A (en) * | 1976-12-06 | 1977-10-11 | Moore-Mccormack Energy, Inc. | Process for preparing aromatics from naphtha |
| US4167533A (en) * | 1978-04-07 | 1979-09-11 | Uop Inc. | Co-production of ethylene and benzene |
| US4594145A (en) * | 1984-12-07 | 1986-06-10 | Exxon Research & Engineering Co. | Reforming process for enhanced benzene yield |
| JP3457670B2 (en) * | 1992-10-28 | 2003-10-20 | シェブロン ケミカル カンパニー | Production of high purity benzene using extractive distillation |
| JPH08119882A (en) * | 1994-10-07 | 1996-05-14 | Chevron Usa Inc | Production of highly pure benzene and predominantly para xylenol by combination of aromatization and selective disproportionation of impure toluene |
| US6258989B1 (en) | 1999-09-30 | 2001-07-10 | Phillips Petroleum Company | Hydrocarbon upgrading process |
| KR100557558B1 (en) * | 2000-11-30 | 2006-03-03 | 에스케이 주식회사 | Process for Producing Aromatic Hydrocarbons and Liquefied Petroleum Gas from Hydrocarbon Mixture |
| US6677496B2 (en) | 2001-08-29 | 2004-01-13 | David Netzer | Process for the coproduction of benzene from refinery sources and ethylene by steam cracking |
| CN1164541C (en) * | 2001-10-22 | 2004-09-01 | 中国石油化工股份有限公司 | Toluene selective disproportion and toluene and C9 and its above aromatic disproportion and alkyl transfusion method |
| US6740788B1 (en) * | 2002-12-19 | 2004-05-25 | Uop Llc | Integrated process for aromatics production |
-
2005
- 2005-06-21 KR KR1020050053619A patent/KR100645659B1/en active IP Right Grant
- 2005-08-17 EP EP05780594.7A patent/EP1893722B1/en active Active
- 2005-08-17 JP JP2008518007A patent/JP2008543930A/en active Pending
- 2005-08-17 WO PCT/KR2005/002708 patent/WO2006137616A1/en active Application Filing
- 2005-08-17 CN CNA2005800502187A patent/CN101208409A/en active Pending
- 2005-09-13 US US11/226,674 patent/US7304195B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3729409A (en) * | 1970-12-24 | 1973-04-24 | Mobil Oil Corp | Hydrocarbon conversion |
| US3702293A (en) * | 1971-12-30 | 1972-11-07 | Universal Oil Prod Co | Hydrocarbon conversion process with a bimetallic catalyst |
| US4058454A (en) * | 1976-04-22 | 1977-11-15 | Uop Inc. | Aromatic hydrocarbon separation via solvent extraction |
| US5278344A (en) * | 1992-12-14 | 1994-01-11 | Uop | Integrated catalytic reforming and hydrodealkylation process for maximum recovery of benzene |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP1893722A4 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110288354A1 (en) * | 2008-11-26 | 2011-11-24 | Sk Innovation Co., Ltd. | Process for the preparation of clean fuel and aromatics from hydrocarbon mixtures catalytic cracked on fluid bed |
| US8933283B2 (en) | 2008-11-26 | 2015-01-13 | Sk Innovation Co., Ltd. | Process for the preparation of clean fuel and aromatics from hydrocarbon mixtures catalytic cracked on fluid bed |
| KR101801975B1 (en) | 2009-05-26 | 2017-11-27 | 아이에프피 에너지스 누벨 | Process for the production of a hydrocarbon fraction with a high octane number and a low sulfur content |
| WO2015013223A1 (en) * | 2013-07-23 | 2015-01-29 | Uop Llc | Processes and apparatuses for preparing aromatic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1893722A1 (en) | 2008-03-05 |
| US20060287564A1 (en) | 2006-12-21 |
| JP2008543930A (en) | 2008-12-04 |
| KR100645659B1 (en) | 2006-11-14 |
| EP1893722B1 (en) | 2017-05-10 |
| CN101208409A (en) | 2008-06-25 |
| US7304195B2 (en) | 2007-12-04 |
| EP1893722A4 (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7304195B2 (en) | Process for increasing production of benzene from hydrocarbon mixture | |
| US7301063B2 (en) | Process for increasing production of light olefin hydrocarbon from hydrocarbon feedstock | |
| CN101376823B (en) | Benzin naphtha catalytic reforming method | |
| JP2019048870A (en) | Method for decomposition of hydrocarbon raw material in steam decomposition unit | |
| KR101572702B1 (en) | Novel system for optimising the production of high octane gasoline and the coproduction of aromatic bases | |
| CN110139845A (en) | Conversion of the waste plastics to propylene and cumene | |
| CN1263831C (en) | Method for producing C2 and C3 olefins of hydrocarbons | |
| US4229602A (en) | Dehydrocyclization process | |
| KR20130045369A (en) | Process for the production of para-xylene | |
| EP0083762A1 (en) | Recovery of C3+hydrocarbon conversion products and net excess hydrogen in a catalytic reforming process | |
| WO2015147700A1 (en) | Method for producing a concentrate of aromatic hydrocarbons from light aliphatic hydrocarbons, and installation for implementing same | |
| CN111808633A (en) | Production method of BTX and LPG | |
| CN105358509B (en) | C8-C10 aromatic compound feed steam is handled to prepare and recycle tri-methylated benzene | |
| WO2006118780A2 (en) | Ethyl benzene from refinery grade feedstocks | |
| CN112313193B (en) | Method and system for producing para-xylene | |
| CN106661465A (en) | Process for producing benzene from C5-C12 hydrocarbon mixture | |
| CN110382450B (en) | Treatment of a C8-C10 aromatic feed stream to produce and recover trimethylated benzenes | |
| RU2144056C1 (en) | Method for production of motor fuel components | |
| JPS622566B2 (en) | ||
| JP2017061651A (en) | Method for producing reformed gasoline | |
| JP2019206714A (en) | Method for producing reformed gasoline | |
| CN117660056A (en) | Combined method for producing industrial white oil | |
| HU194525B (en) | Process for the production of extra-clean normal hexan and aroma-free special petrol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 200580050218.7 Country of ref document: CN |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| DPE2 | Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101) | ||
| REEP | Request for entry into the european phase |
Ref document number: 2005780594 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2005780594 Country of ref document: EP |
|
| ENP | Entry into the national phase |
Ref document number: 2008518007 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |