Method for producing valuable aromatics and light paraffins from hydrocarbonaceous oils derived from oil, coal or wood

• US 8,962,900 B2
• Filed: 10/20/2011
• Issued: 02/24/2015
• Est. Priority Date: 10/22/2010
• Status: Active Grant

• Current Assignee: SK Innovation Company Limited
• Original Assignee: SK Innovation Company Limited
• Inventors: Kim, Hong Chan, Kim, Yong Seung, Lee, Hyuck Jae, Koh, Jae Suk, Kim, Gyung Rok, Noh, Myoung Han, Lee, Sang Il, Lee, Seung Woo, Kim, Do Woan, Koh, Jae Hyun, Choi, Sun, Oh, Seung Hoon, Oh, Kyung Jong, Oh, Sang Hun, Lee, Jong Hyung
• Primary Examiner(s): Bullock, In Suk
• Assistant Examiner(s): LOUIE, PHILIP Y
• Application Number:
  US13/880,838
• Publication Number:
  US 20130267744A1
• Time in Patent Office: 1,223 Days
• Field of Search: 585/253, 585/240, 585/242, 585/251
• US Class Current: 585/251
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 23/24 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 23/74 Iron group metals
• CPC Class Codes: B01J 23/85 Chromium, molybdenum or tungsten
• CPC Class Codes: B01J 29/072 Iron group metals or copper
• CPC Class Codes: B01J 29/076 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: B01J 29/7057 Zeolite Beta
• CPC Class Codes: B01J 29/7615 Zeolite Beta
• CPC Class Codes: C07C 15/08 Xylenes
• CPC Class Codes: C07C 2521/04 Alumina
• CPC Class Codes: C07C 2521/08 Silica
• CPC Class Codes: C07C 2521/12 Silica and alumina
• CPC Class Codes: C07C 2521/16 Clays or other mineral silicates
• CPC Class Codes: C07C 2523/08 of gallium, indium or thallium
• CPC Class Codes: C07C 2523/14 of germanium, tin or lead
• CPC Class Codes: C07C 2523/42 Platinum
• CPC Class Codes: C07C 2529/18 of the mordenite type
• CPC Class Codes: C07C 2529/70 of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
• CPC Class Codes: C07C 5/02 by hydrogenation simultaneous hydrogenation and dehydrogenation C07C5/52
• CPC Class Codes: C07C 5/2737 with crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C07C 6/126 : of more than one hydrocarbon
• CPC Class Codes: C10G 1/002 : in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 1/06 : by destructive hydrogenation
• CPC Class Codes: C10G 2400/30 : Aromatics
• CPC Class Codes: C10G 45/34 : characterised by the catalyst used
• CPC Class Codes: C10G 47/20 : the catalyst containing other metals or compounds thereof
• CPC Class Codes: C10G 65/12 : including cracking steps and other hydrotreatment steps
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

This invention relates to a method of producing aromatics and light paraffins from hydrocarbonaceous oils derived from oil, coal or wood, including partially saturating and hydrocracking the oils derived from oil in a hydrogenation and reaction area, separating them depending on the number of carbons, recirculating heavy oils having 11 or more carbons to the hydrogenation and reaction area, feeding oils suitable for producing BTX to an aromatic separation process and a transalkylation process to recover aromatics, and feeding hydrocarbonaceous components having 5 or fewer carbons to a light separation process, thus obtaining light paraffins.

Claims

1. A method of producing aromatics and light paraffins, comprising:

a) introducing oils derived from oil, coal or wood into a hydrogenation and reaction area comprising a hydroprocessing process and a hydrocracking process;

b) hydroprocessing the oils in the presence of a hydroprocessing catalyst to partially saturate aromatic components having two or more aromatic rings into aromatic components having one aromatic ring, such that an amount of aromatic components having one aromatic ring in the oils is increased;

c) hydrocracking the hydroprocessed oils in the presence of a hydrocracking catalyst to form hydrocracked oils;

d) separating the hydrocracked oils into

i. hydrocarbonaceous components having 11 or more carbons,

ii. hydrocarbonaceous components having 6-10 carbons, and

iii. hydrocarbonaceous components having 5 or fewer carbons; and

e) recirculating the hydrocarbonaceous components having 11 or more carbons to the hydrogenation and reaction area;

f) feeding the hydrocarbonaceous components having 6-10 carbons to an aromatic separation process or a transalkylation process,

wherein;

hydrocarbonaceous components having 6-10 carbons fed to the aromatic separation are separated into a first portion and a second portion,

the first portion is fed to a transalkylation process and contacted with a transalkylation catalyst to form a transalkylated product comprising benzene, toluene, xylenes and hydrocarbonaceous components having 9 or more carbons,

the transalkylated product is mixed with the second portion in the aromatic separation process, and

hydrocarbonaceous components having 11 or more carbons, hydrocarbonaceous components having 6-10 carbons, a xylene mixture comprising ortho-xylene, meta-xylene, and para-xylene, and/or an aromatics stream comprising benzene, toluene, xylenes or mixtures thereof, are separated in the aromatic separation process;

or

hydrocarbonaceous components having 6-10 carbons fed to the transalkylation process are contacted with a transalkylation catalyst to form a transalkylated product comprising benzene, toluene, xylenes and hydrocarbonaceous components having 9 or more carbons

the transalkylated product is fed to an aromatic separation process, and

hydrocarbonaceous components having 11 or more carbons, hydrocarbonaceous components having 6-10 carbons, a xylene mixture comprising ortho-xylene, meta-xylene, and para-xylene, and/or an aromatics stream comprising benzene, toluene, xylenes or mixtures thereof, are separated in the aromatic separation process; and

g) feeding the hydrocarbonaceous components having 5 or fewer carbons to a light separation process to recover paraffins;

wherein the oils derived from oil contain 15-99 wt % aromatic components based on total hydrocarbonaceous components and have a boiling point of 70-700°

C.; and

wherein the oils derived from coal or wood contain 40-99 wt % aromatic components based on total hydrocarbonaceous components and have a boiling point of 70-700°

C.

2. The method of claim 1, further comprising (h) feeding the xylene mixture separated in the aromatic separation process to a xylene process, separating para-xylene from the xylene mixture, isomerizing meta- and ortho-xylenes into para-xylene, and recirculating isomerized product other than para-xylene to the aromatic separation process.

3. The method of claim 1, wherein the hydroprocessing catalyst comprises an alumina carrier and one or more metals selected from the group consisting of of Groups 6, 9 and 10 metals supported thereon.

4. The method of claim 1, wherein the hydrocracking catalyst is a modified zeolite catalyst having one or more metals selected from the group consisting of Mo, W, Co and Ni supported thereon.

5. The method of claim 4, wherein the modified zeolite catalyst comprises one or more zeolites having a pore size of 4 Å

or more, and is modified with a binder.

6. The method of claim 5, wherein the modified zeolite catalyst comprises one or more zeolites selected form the group consisting of MOR, MEL, FAU, and BEA.

7. The method of claim 1, wherein the oils derived from oil, coal or wood are selected from raw pyrolysis gasoline (RPG), heavy raw pyrolysis gasoline (heavy RPG), treated pyrolysis gasoline (TPG), reformate, heavy aromatics, kerosene, jet oil, atmospheric gas oil, FCC (fluid catalytic cracking) gasoline, light cracked naphtha, heavy cracked naphtha, FCC decanted oil, vacuum gas oil, coker gas oil, coker diesel, coker naphtha, heavy and reduced petroleum crude oil, petroleum atmospheric distillation bottom, petroleum vacuum distillation bottoms, asphalt, bitumen, tar sand oil, shale oil, coal tar, tar oil, light oil, phenolic oil or carbolic oil, naphthalene oil, wash oil, anthracene oil, light anthracene oil, heavy anthracene oil, pitch, wood tar, hardwood tar, resinous tar, and mixtures thereof.

8. The method of claim 2, further comprising recirculating the hydrocarbonaceous components having 11 or more carbons obtained from the aromatic separation process to the hydrogenation and reaction area and feeding the hydrocarbonaceous components having 6-10 carbons obtained from the aromatic separation process to the transalkylation process.

9. The method of claim 1, further comprising (d′

) separating saturated hydrocarbons including cyclohexane from the (ii) hydrocarbonaceous components having 6-10 carbons prior to step (f), feeding the saturated hydrocarbonaceous components to a reformer to form unsaturated hydrocarbon components, and feeding the unsaturated hydrocarbon components to step (f).

10. The method of claim 9, wherein the reformer is operated at a temperature of 400-600°

C. in a hydrogen atmosphere using a Pt/Al₂O₃, Pt—

Re/Al₂O₃ or Pt—

Sn/Al₂O₃ catalyst.

11. The method of claim 1, wherein the transalkylation catalyst comprises:

a carrier composed of 10-95 wt % of beta-zeolite or mordenite having a molar ratio of silica/alumina adjusted to 20-200 based on alumina and 5-90 wt % of one or more inorganic binders selected from the group consisting of gamma-alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite and montmorillonite; and

a hydrogenation metal composed of, based on 100 parts by weight of the carrier, 0.001-0.5 parts by weight of one or more metals selected form the group consisting of platinum, tin, indium and lead.

12. A method of producing aromatics and light paraffins, comprising:

a) introducing oils derived from oil, coal or wood into a hydrogenation and reaction area comprising a hydrocracking process and a hydroprocessing process;

b) hydrocracking the oils in the presence of a hydrocracking catalyst to form hydrocracked oils;

c) hydroprocessing the hydrocracked oils in the presence of a hydroprocessing catalyst to partially saturate aromatic components having two or more aromatic rings into aromatic components having one aromatic ring, such that an amount of aromatic components having one aromatic ring in the hydrocracked oils is increased, and to form hydroprocessed oils;

d) separating the hydroprocessed oils into

i. hydrocarbonaceous components having 11 or more carbons,

ii. hydrocarbonaceous components having 6-10 carbons, and

iii. hydrocarbonaceous components having 5 or fewer carbons; and

e) recirculating the hydrocarbonaceous components having 11 or more carbons to the hydrogenation and reaction area;

f) feeding the hydrocarbonaceous components having 6-10 carbons to an aromatic separation process or a transalkylation process,

wherein;

hydrocarbonaceous components having 6-10 carbons fed to the aromatic separation are separated into a first portion and a second portion,

the first portion is fed to a transalkylation process and contacted with a transalkylation catalyst to form a transalkylated product comprising benzene, toluene, xylenes and hydrocarbonaceous components having 9 or more carbons,

the transalkylated product is mixed with the second portion in the aromatic separation process, and

hydrocarbonaceous components having 11 or more carbons, hydrocarbonaceous components having 6-10 carbons, a xylene mixture comprising ortho-xylene, meta-xylene, and para-xylene, and/or an aromatics stream comprising benzene, toluene, xylenes or mixtures thereof, are separated in the aromatic separation process;

or

hydrocarbonaceous components having 6-10 carbons fed to the transalkylation process are contacted with a transalkylation catalyst to form a transalkylated product comprising benzene, toluene, xylenes and hydrocarbonaceous components having 9 or more carbons

the transalkylated product is fed to an aromatic separation process, and

hydrocarbonaceous components having 11 or more carbons, hydrocarbonaceous components having 6-10 carbons, a xylene mixture comprising ortho-xylene, meta-xylene, and para-xylene, and/or an aromatics stream comprising benzene, toluene, xylenes or mixtures thereof, are separated in the aromatic separation process; and

g) feeding the hydrocarbonaceous components having 5 or fewer carbons to a light separation process to recover paraffins;

wherein the oils derived from oil contain 15-99 wt % aromatic components based on total hydrocarbonaceous components and have a boiling point of 70-700°

C.; and

wherein the oils derived from coal or wood contain 40-99 wt % aromatic components based on total hydrocarbonaceous components and have a boiling point of 70-700°

C.

13. The method of claim 12, further comprising (h) feeding the xylene mixture separated in the aromatic separation process to a xylene process, separating para-xylene from the xylene mixture, isomerizing meta- and ortho-xylenes into para-xylene, and recirculating isomerized product other than para-xylene to the aromatic separation process.

14. The method of claim 12, wherein the hydroprocessing catalyst comprises an alumina carrier and one or more metals selected from the group consisting of Groups 6, 9 and 10 metals supported thereon.

15. The method of claim 12, wherein the hydrocracking catalyst is a modified zeolite catalyst having one or more metals selected from the group consisting of Mo, W, Co and Ni supported thereon.

16. The method of claim 15, wherein the modified zeolite catalyst comprises one or more zeolites having a pore size of 4 Å

or more, and is modified with a binder.

17. The method of claim 16, wherein the modified zeolite catalyst comprises one or more zeolites selected form the group consisting of MOR, MEL, FAU, and BEA.

18. The method of claim 12, wherein the oils derived from oil, coal or wood are selected from raw pyrolysis gasoline (RPG), heavy raw pyrolysis gasoline (heavy RPG), treated pyrolysis gasoline (TPG), reformate, heavy aromatics, kerosene, jet oil, atmospheric gas oil, FCC (fluid catalytic cracking) gasoline, light cracked naphtha, heavy cracked naphtha, FCC decanted oil, vacuum gas oil, coker gas oil, coker diesel, coker naphtha, heavy and reduced petroleum crude oil, petroleum atmospheric distillation bottom, petroleum vacuum distillation bottoms, asphalt, bitumen, tar sand oil, shale oil, coal tar, tar oil, light oil, phenolic oil or carbolic oil, naphthalene oil, wash oil, anthracene oil, light anthracene oil, heavy anthracene oil, pitch, wood tar, hardwood tar, resinous tar, and mixtures thereof.

19. The method of claim 13, further comprising recirculating the hydrocarbonaceous components having 11 or more carbons obtained from the aromatic separation process to the hydrogenation and reaction area and feeding the hydrocarbonaceous components having 6-10 carbons obtained from the aromatic separation process to the transalkylation process.

20. The method of claim 12, further comprising (d′

) separating saturated hydrocarbons including cyclohexane from the (ii) hydrocarbonaceous components having 6-10 carbons prior to step (f), feeding the saturated hydrocarbonaceous components to a reformer to form unsaturated hydrocarbon components, and feeding the unsaturated hydrocarbon components to step (f).

21. The method of claim 20, wherein the reformer is operated at a temperature of 400-600°

C. in a hydrogen atmosphere using a Pt/Al₂O₃, Pt—

Re/Al₂O₃ or Pt—

Sn/Al₂O₃ catalyst.

22. The method of claim 12, wherein the transalkylation catalyst comprises:

a carrier composed of 10-95 wt % of beta-zeolite or mordenite having a molar ratio of silica/alumina adjusted to 20-200 based on alumina and 5-90 wt % of one or more inorganic binders selected from the group consisting of gamma-alumina, silica, silica alumina, bentonite, kaolin, clinoptilolite and montmorillonite; and

a hydrogenation metal composed of, based on 100 parts by weight of the carrier, 0.001-0.5 parts by weight of one or more metals selected form the group consisting of platinum, tin, indium and lead.