AU634612B2 - Process for preparing one or more light hydrocarbon oil distillates - Google Patents
Process for preparing one or more light hydrocarbon oil distillates Download PDFInfo
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- AU634612B2 AU634612B2 AU68226/90A AU6822690A AU634612B2 AU 634612 B2 AU634612 B2 AU 634612B2 AU 68226/90 A AU68226/90 A AU 68226/90A AU 6822690 A AU6822690 A AU 6822690A AU 634612 B2 AU634612 B2 AU 634612B2
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- hydrocarbon oil
- distillates
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Description
I'
63461 S F Ref: 150087 S F Ref: 150087 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE: Class Int Class o 0 02 o 0 o 00 0 0 0 0 0 0 00 0 00 «I 0 C Complete Specification Lodged: A:.cepted: Published: Priority: Related Art: Name and Address of Applicant: Address for Service: o o 0 9a O 0005
S.
4*50 Ii Shell Internationale Research Maatschappij B.V.
Carel van Bylandtlaan 2596 HR The Hague THE NETHERLANDS Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: Process for Preparing One or More Light Hydrocarbon Oil Distillates The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/5 *arrp" 1 T 5019 PROCESS FOR PREPARING ONE OR MORE LIGHT HYDROCARBON OIL DISTILLATES The present invention relates to a process for preparing one or more light hydrocarbon oil distillates from a hydrocarbonaceous feedstock.
In the atmospheric distillation of crude mineral oil, as applied on a large scale in refineries in the preparation of light hydrocarbon oil distillates, for o 0 example gasoline fractions, a residual oil is obtained I oo a as a by-product. Gasolines, as referred to herein, are S° those fractions having a boiling range at atmospheric 0 o. 010 pressure between that of n-pentane and 220 To increase the yield of light hydrocarbon oil distillates from the crude oil concerned, a heavy hydrocarbon oil distillate can be separated from said residual oil by vacuum distillation, which hydrocarbon oil distillate can be converted in a relatively simple way by hydrocracking or catalytic cracking into one or more light hydrocarbon oil distillates.
A process is described in Oil and Gas Journal, Feb. 16, 1987, pp 55-66, which meets the increasing demands for middle distillates, i.e. those having an atmospheric boiling range from between 180 °C and 370 °C.
It has now been found that, among the light hydrocarbon oil distillates, gasoline fractions are obtained in a surprisingly high yield when integrating the steps of hydrocracking and catalytic cracking in a specific manner.
2 The present invention therefore relates to a process for preparing one or more light hydrocarbon oil distillates comprising: a) hydrocracking a first hydrocarbon oil fraction, b) catalytically cracking a second hydrocarbon oil fracticn substantially identical to the first i hydrocarbon oil fraction or differing therefrom, c) separating the product obtained in step b) by means i of distillation into one or more distillates and a residue, d) subjecting the residue obtained in step c) together with the first hydrocarbon oil fraction to the hydrocracking in step and 1 e) isolating one or more light hydrocarbon oil distillates from the product obtained in steps a) and b).
In Figures 1 and 2 suitable embodiments of the process according to the present invention are schematically shown, in which reference numerals relating to corresponding parts are the same.
Referring to Figure i, a heavy vacuum hydrocarbon oil distillate is introduced via a line 1 into a i hydrocracker 2 in which the oil is hydrocracked (step The product obtained in hydrocracker 2 is withdrawn therefrom via a line 3 and introduced via this line into a distillation column 4. From the distillation column 4 a gas fraction is withdrawn via a line 5, a gasoline fraction via a line 6, a kerosine i fraction via a line 7, a gas oil fraction via a line 8 and a residue via a line 9. Hydrogen is introduced into the hydrocracker 2 via a line 10. A substantially identical heavy vacuum hydrocarbon oil distillate is introduced via a line 11 into a catalytic cracker 12 in which the distillate is catalytically cracked (step The product obtained in catalytic cracker 12 3 is withdrawn therefrom via a line 13 and introduced via this line into a distillation column 14 from which a gasoline fraction is withdrawn via a line 15 and a middle distillate fraction via a line 16. Catalyst with coke deposited thereupon is withdrawn from the catalytic cracker via a line 17, subjected to a regeneration treatment and recycled thereafter via a line not shown to the catalytic cracker. From the distillation column 1< a residue is withdrawn via a line 18 and a gas fraction via a line 19. The residues from columns 4 ard 14 are introduced via the lines 18 and 1 into the hydrocracker 2 in which the residues are hydrocracked (step In this way the residues :obtained in steps a) and b) are hydrocracked in step d) advantageously together with the heavy vacuum hydrocarbon oil distillate.
Referring to Figure 2, a heavy vacuum hydrocarbon distillate is introduced into the hydrocracker 2 via a line la and line 1, and into the catalytic cracker 12 via line la and line 11. Moreover, the residue which i= withdrawn from column 4 is introduced via line 9 and line 11 into the catalytic cracker 12. In this way the 'residue obtained from the distillation column 14 is hydrocracked in step a) together with a 2urther quantity of heavy vacuum hydrocarbon oil distillate, whilst the residue obtained from the distillation column 4 is catalytically cracked in step b) together with a further quantity of heavy vacuum hydrocarbon oil a distillate. This use of of the hydrocracker and the catalytic cracker results in a surprisingly high yield of gasoline.
The hydrocarbon oil fractions to be converted in the process according to the present invention may be any vacuum hydrocarbon oil distillate obtained from crude mineral oil. Preferably, the vacuum hydrocarbon
T_
4 oil distillate is a vacuum oil having a boiling range at atmospheric pressure in the range of from 220 0C to 700 Such oils may be a mixture of gas oils obtained by vacuum distillation at sub-atmospheric pressure) and gas oils obtained by distillation at atmospheric pressure. Suitably the hydrocarbon oil fractions to be converted in the process according to the present invention comprise at least 10 %wt of material boiling above 540 In another suitable embodiment of the process according to the present invention the first hydrocarbon oil fraction is less heavy than the second hydrocarbon oil fraction.
Suitably, the first hydrocarbon oil fraction comprises at most 10 %wt of material boiling above 540 0C, for instance a light vacuum hydrocarbon oil distillate, whilst the second hydrocarbon oil fraction comprises at least 10 %wt of material boiling above 540 for instance a heavy vacuum hydrocarbon oil distillate.
Preferably, the product obtained in step a) is separated by means of distillation into one or more distillates and a residue which is subsequently subjected together with the second hydrocarbon oil fraction to the catalytic cracking in step In another preferred embodiment of the process according to the present invention, the product obtained in step a) is separated by means of distillation into one or more distillates and a residue which is subsequently subjected together with the residue obtained in step b) and the first hydrocarbon oil fraction to the hydrocracking in step a).
The hydrocracking in step a) is carried out using a catalyst system whic!L comprises at least a catalyst comprising at least one metal of the group consisting of Ni, Mo and Co on a carrier, preferably alumina, in the presence of hydrogen at a temperature of from 5 350-450 a pressure of from 10-300 bar, a space -1 -1 velocity of from 0.02-10 g.g .h and a H2/feed ratio -1 of from 100-5000 Nl.kg Very suitable catalysts comprise cobalt and molybdenum on alumina or nickel and molybdenum on alumina.
The hydrocracking in step a) can suitably be carried out in a stacked-bed catalyst system comprising as upper bed catalyst a catalyst as described hereinabove and as lower bed catalyst for instance a metal-containing zeolite Y. The lower bed catalyst preferably comprises Ni and/or W on a zeolite Y.
In the process according to the present invention a considerable portion of the feed to the catalytic cracker is converted into distillate fractions. In the catalytic cracking process, which is preferably carried out in the presence of a zeolitic catalyst, coke is deposited on the catalyst. This coke is removed from the catalyst by burning off during a catalyst regeneration step, whereafter the regenerated catalyst is recycled to the catalytic cracker. Catalytic cracking can suitably be carried out at a temperature of 400-900 *C and a pressure in the range of 1-10 bar.
In a suitable embodiment of the present invention the catalytic cracking in step b) is attractively carried out by contacting the second hydrocarbon oil Sfraction with a zeolitic catalyst comprising a zeolite ij with a pore diameter of 0.3 to 0.7 nm at a temperature S above 480 °C during less than 10 seconds. In this way i high yields of lower olefins (C 2
-C
4 can be co-produced. Ethylene and propylene are valuable starting materials for chemical processes, while C 4 olefins can find use as a starting material for alkylating and/or oligomerization procedures in order to produce high octane gasoline and/or middle 6 0 00 o o o cO oo 0 0 O 00 distillates. Isobutene can usefully be converted to methyl t-butyl ether.
Suitably, the minimum contact time is 0.1 second.
Very good results are obtainable with a process in which the second hydrocarbon oil fraction is contacted with the zeolitic catalyst during 0.2 to 6 seconds.
The temperature during the catalytic cracking reaction is relatively high. It is this combination of high temperature and short contact time which allows a high conversion to olefins. A preferred temperature range is 480 to 900 more preferably 550 to 800 "C.
The zeolitic catalyst to be used in step b) may comprise one or more zeolites with a pore diameter of from 0.3 to 0.7 nm, preferably from 0.5 to 0.7 nm. The catalyst suitably further comprises a refractory oxide that serves as binder material. Suitable refractory oxides include alumina, silica, silica-alumina, magnesia, titania. zirconia and mixtures thereof.
Alumina is especially preferred. The weight ratio of refractory oxide and zeolite suitably ranges from 10:90 to 90:10, preferably from 50:50 to 85:15. The zeolitic catalyst may comprise up to about 40% by weight of further zeolites with a pore diameter above 0.7 nm.
Suitable examples of such zeolites include the 25 faujasite-type zeolites, zeolite beta, zeolite omega and in particular zeolite X and Y. Suitably, the zeolitic catalyst consists substantially of a zeolite with a pore diameter of from 0.3 to 0.7 nm.
The term zeolite in this specification is not to be regarded as comprising only crystalline aluminium silicates. The term also includes crystalline silica (silicalite), silicoaluminophosphates (SAPO), chromosilicates, gallium silicates, iron silicates, aluminium phosphates (ALPO), titanium aluminosilicates (TAPO) and iron aluminosilicates.
1i 0 00
I,
*1 9; 1 L I -7- Examples of zeolites that may be used in step b) of the process of the present invention and that have a pore diameter of 0.3 to 0.7 nm, include SAPO-4 and SAPO-11, which are described in US-A-4,440,871, ALPO-11, described in US-A-4,310,440, TAPO-11, described in US-A-4,500;651, TASO-45, described in EP-A-229,295, boron silicates, described in e.g.
US-A-4,254,297, aluminium silicates like erionite, ferrierite, theta and the ZSM-type zeolites such as ZSM-5, ZSM-11, ZSM-12, ZoM-35, ZSM-23, and ZSM-38.
Preferably, the zeolite is selected from the group consisting of crystalline metal silicates having a ZSM-5 structure, ferrierite, erionite and mixtures Sthereof. Suitable examples of crystalline metal 1* 5 silicates with ZSM-5 structure are aluminium, gallium, iron, scandium, rhodium and/or scandium silicates as described in e.g. GB-B-2,110,559.
The weight ratio of the catalyst used in step b) relative to the fraction of the mixture of hydrocarbons to be converted (catalyst/oil ratio, g/g) may vary widely, for example up to 150 kg of catalyst per kg of the fraction of the mixture of hydrocarbons or even more.
The present invention will now be illustrated by means of the following Examples. In the Examples the I boiling points are given at atmospheric pressure.
V Example 1 A process was carried out in accordance with tne flow diagram as schematically shown in Figures 1 The feed, an Arabian heavy flashed distillate, I conducted through line 1 had the following properties:
L
8 initial boiling point 350 °C 11 %wt recovered at 400 °C %wt recovered at 500 °C 92 %wt recovered at 575 °C final boiling point 650 °C The hydrocracking in step a) was carried out at a temperature of 370 a pressure of 120 bar, a weight hourly space velocity of 1 kg.kg- .h and a hydrogen/feed ratio of 1000 Nl.kg The catalyst system used comprised a stacked-bed of which the upper bed catalyst comprised 2.8 %wt Ni and 12.8 %wt Mo (both on total catalyst) on alumina as carrier, and the lower bed catalyst comprised 8.2 %wt W and 2.6 %wt Ni (both o °o o on total catalyst) on a zeolite Y as carrier. The upper 0 m2 o 15 bed catalyst had a surface area of 171 m a pore volume of 0.46 ml/g and a compacted bulk density of 0 0o o 0.84 g/ml. The lower bed catalyst had a surface area of 492 m2/g, a pore volume of 0.43 ml/g and a compacted bulk density of 0.64 kg/l.
The same feed as described hereinabove was 0o.O conducted through the line 11.
The catalytic cracking in step b) is carried out at a temperature of 530 a pressure of 1 bar, and a Voorhies severity of 4.5. The zeolitic catalyst used comprised a zeolite Y. The catalyst had a surface area S* of 113 m a pore volume of 0.29 ml/g and a bulk o* density of 0.43 ml/g.
The catalytic cracker 12 is operated so as to obtain the maximum gasoline yield and to produce in total 7 %wt of coke.
pbw of the above feed in line 1 and 10 pbw of the above feed in line 11 yielded the various product fractions in the following quantities:
II
f~ 11~-1--7 I I~II) 1_ ~il i. i: 9 8.9 pbw gas fraction (line 57.9 pbw gasoline fraction (line 6), 15.0 pbw kerosine fraction (line 7), 12.5 pbw gas oil fraction (line 8), 31.6 pbw residue fraction (line 9), 2.4 pbw gas fraction (line 19), 4.1 pbw gasoline fraction (line 1.8 pbw middle distillate fraction (line 16), 1.1 pbw residue fraction (line 18).
Example 2 A process was carried out in accordance with the flow diagram as schematically shown in Figure 2.
.o"g The same feed was used as in Example 1. The °o hydrocracking in step a) was carried out in o 0o 15 substantially the same manner as described in Example 1. The catalytic cracking in step b) using the same catalyst as applied in Example 1 was carried out at a temperature of 490 a pressure of 2 bar, and a Voorhies severity of 2.5. The catalytic cracker 12 is operated so as to obtain the maximum gasoline yield and to produce in total 4 %wt of coke.
100 pbw of the feed in line la yielded the various '(product) fractions in the following quantities: pbw heavy flashed distillate fraction (line 1), 10 pbw heavy flashed distillate fraction (line 11), pbw gas fraction (line 18.1 pbw gasoline fraction (line 6), 11.5 pbw kerosine fraction (line 7), 15.3 pbw gas oil fraction (line 8), 43.7 pbw residue fraction (line 9), 11.1 pbw gas fraction (line 19), 30.3 pbw gasoline fraction (line 8.1 pbw middle distillate fraction (line 16), 1.9 pbw residue fraction (line 18).
Claims (7)
1. A process for preparing one or more light hydrocarbon oil distillates comprising: a) hydrocracking a first hydrocarbon oil fraction, b) catalytically cracking a second hydrocarbon oil fraction substantially identical to the first hydrocarbon oil fraction or differing therefrom, c) separating the product obtained in step b) by mears 'i of distillation into one or more distillates and a residue, I 0 subjecting the residue obtained in step c) together with the first hydrocarbon oil fraction to the hydrocracking in step and e) isolating one or more light hydrocarbon oil distillates from the product obtained in steps a) and b)
2. A process according to claim 1, wherein both the first and the second hydrocarbon oil fraction comprise at least 10 %wt of material boiling above 540 "C.
3. A process according to claim 1, wherein the first hydrocarbon oil fraction comprises at most 10 %wt of material boiling above 540 °C and the second hydrocarbon oil fraction comprises at least 10 %wt of material boiling above 540 °C.
4. A process according to any one of claims 1-3, wherein the product obtained in step a) is separated by means of distillation into one or more distillates and a residue which residue is subsequently subjected together with the second hydrocarbon oil fraction to the catalytic cracking in step b). U I 11 A process according to any one of claims 1-3, wherein the product obtained in step a) is separated by means of distillation into one or more distillates and a residue which residue is subsequently subjected together with the residue obtained in step C) and the first hydrocarbon oil fraction to the hydrocracking in step a).
6. A process according to any one of claims wherein step a) is carried out at a temperature of
350-450 "C and a pressure of 10-300 bar. 7. A process according to any one of claims 1-6, wherein in step a) a catalyst system is used which comprises at least a catalyst comprising one metal of 5 the group consisting of Ni, Mo and Co on alumina as carrier. 8. A process according to any one of claims 1-7, wherein step b) is carried out at a temperature of
400-900 °C and a pressure of 1-10 bar. 9. A process according to any one of claims 1-8, wherein in step b) a zeolitic catalyst is used. A process for preparing one or more light hydrocarbon oil distillates substantially as hereinbefore described with reference to o" any one of the Examples. 11. A process for preparing one or more light hydrocarbon oil distillates substantially as hereinbefore described 'ith reference to S the accompanying drawings. 12. Light hydrocarbon oil distillates whenever prepared by a process as described in any one of claims 1-11. DATED this FOURTEENTH day of DECEMBER 1990 Shell Internationale Research Maatschappij B.V. Patent Attorneys for the Applicant SPRUSON FERGUSON
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909000024A GB9000024D0 (en) | 1990-01-02 | 1990-01-02 | Process for preparing one or more light hydrocarbon oil distillates |
| GB9000024 | 1990-01-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6822690A AU6822690A (en) | 1991-07-04 |
| AU634612B2 true AU634612B2 (en) | 1993-02-25 |
Family
ID=10668749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU68226/90A Ceased AU634612B2 (en) | 1990-01-02 | 1990-12-18 | Process for preparing one or more light hydrocarbon oil distillates |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0436253A1 (en) |
| JP (1) | JPH04132794A (en) |
| AU (1) | AU634612B2 (en) |
| CA (1) | CA2031781A1 (en) |
| GB (1) | GB9000024D0 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2815041B1 (en) * | 2000-10-05 | 2018-07-06 | IFP Energies Nouvelles | PROCESS FOR THE PRODUCTION OF DIESEL BY MODERATE PRESSURE HYDROCRACKING |
| US9080114B2 (en) | 2012-02-14 | 2015-07-14 | Ypf S.A. | Method for producing diesel fuel with improved yield and quality by integration of fluidized catalytic cracking (FCC) and hydrocracking (HC) |
| US9387413B2 (en) | 2013-12-17 | 2016-07-12 | Uop Llc | Process and apparatus for recovering oligomerate |
| US9914884B2 (en) | 2013-12-17 | 2018-03-13 | Uop Llc | Process and apparatus for recovering oligomerate |
| WO2016016748A1 (en) * | 2014-07-28 | 2016-02-04 | Reliance Industries Limited | A process for separating valuable petroleum products from clarified slurry oil |
| WO2018060938A1 (en) * | 2016-09-30 | 2018-04-05 | Hindustan Petroleum Corporation Limited | A process for upgrading heavy hydrocarbons |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2360622A (en) * | 1943-04-30 | 1944-10-17 | Standard Oil Dev Co | Method of producing aviation gasoline |
| US3245900A (en) * | 1963-12-26 | 1966-04-12 | Chevron Res | Hydrocarbon conversion process |
| US3726789A (en) * | 1971-04-05 | 1973-04-10 | Ashland Oil Inc | Hydrocarbon conversion process for the production of olefins and aromatics |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1001449A (en) * | 1962-03-30 | 1965-08-18 | California Research Corp | Hydrocarbon conversion process |
| US3755141A (en) * | 1971-02-11 | 1973-08-28 | Texaco Inc | Catalytic cracking |
| GB8726838D0 (en) * | 1987-11-17 | 1987-12-23 | Shell Int Research | Preparation of light hydrocarbon distillates |
-
1990
- 1990-01-02 GB GB909000024A patent/GB9000024D0/en active Pending
- 1990-12-07 CA CA 2031781 patent/CA2031781A1/en not_active Abandoned
- 1990-12-18 AU AU68226/90A patent/AU634612B2/en not_active Ceased
- 1990-12-20 EP EP90203477A patent/EP0436253A1/en not_active Ceased
- 1990-12-28 JP JP2415513A patent/JPH04132794A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2360622A (en) * | 1943-04-30 | 1944-10-17 | Standard Oil Dev Co | Method of producing aviation gasoline |
| US3245900A (en) * | 1963-12-26 | 1966-04-12 | Chevron Res | Hydrocarbon conversion process |
| US3726789A (en) * | 1971-04-05 | 1973-04-10 | Ashland Oil Inc | Hydrocarbon conversion process for the production of olefins and aromatics |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2031781A1 (en) | 1991-07-03 |
| AU6822690A (en) | 1991-07-04 |
| GB9000024D0 (en) | 1990-03-07 |
| JPH04132794A (en) | 1992-05-07 |
| EP0436253A1 (en) | 1991-07-10 |
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