EP0956326A1 - Process and catalysts for the production of motor fuels from shale oils - Google Patents

Process and catalysts for the production of motor fuels from shale oils

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Publication number
EP0956326A1
EP0956326A1 EP96938442A EP96938442A EP0956326A1 EP 0956326 A1 EP0956326 A1 EP 0956326A1 EP 96938442 A EP96938442 A EP 96938442A EP 96938442 A EP96938442 A EP 96938442A EP 0956326 A1 EP0956326 A1 EP 0956326A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
process according
stage
coo
nio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96938442A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0956326A4 (enrdf_load_stackoverflow
Inventor
Miron V. Landau
Mordechay Herskowitz
Dany Givony
Sarit Laichter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Pama (Energy Resources Development) Ltd
Ben Gurion University of the Negev Research and Development Authority Ltd
Ben Gurion University of the Negev BGU
Original Assignee
Pama (Energy Resources Development) Ltd
Ben Gurion University of the Negev Research and Development Authority Ltd
Ben Gurion University of the Negev BGU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Pama (Energy Resources Development) Ltd, Ben Gurion University of the Negev Research and Development Authority Ltd, Ben Gurion University of the Negev BGU filed Critical Pama (Energy Resources Development) Ltd
Publication of EP0956326A4 publication Critical patent/EP0956326A4/xx
Publication of EP0956326A1 publication Critical patent/EP0956326A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8871—Rare earth metals or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps

Definitions

  • This invention relates to a process and catalysts for the production of motor fuels from shale oils that are difficult to treat by known processes because of their chemical composition, in particular because of their high sulfur and nitrogen concentration, an example of such shale oils being those extracted from the bituminous marls deposits in the southern part of Israel.
  • HDN hydrodenitrogenation
  • IBP and FBP are hereinafter Initial Boiling Point and Final Boiling Point , respectively.
  • Table I the data relating to American Occidental shale oil were taken from European Patent No. 005091 1; those relating to American Colorado shale oil, from P.F. Lovell et al. Hydrocarbon Processing, 60(5), 125, (1981); those relating to Australian Rundle shale oil, from T.G. Harvey et al, Ind. Eng. Chem. Proc. des. Dev., 25, 521, (1986); and those relating to Brasilian Irati shale oil, from G.L.M. Souza et al, Ind. Eng. Chem. Res., 31 , 2127, (1992).
  • Table II shows the results of the hydrotreatment of various shale oils according to prior art techniques, and evidences the very difficult problem involved in achieving deep HDN.
  • the desired final nitrogen level below 0.2% wt. was not achieved even under very severe conditions, such as temperature above 400°C, in fixed bed or fiuidized bed reactors. Only lowering the distillation end point ofthe shale oil to 400°C and operating at 400°C yielded a product containing 0.005% wt. nitrogen, as reported by T.G. Harvey et al., Ind. Eng. Chem. Proc. des. Dev., 25, 521 (1986).
  • EP 005091 1 discloses the conversion of shale oil with experimental CO- Mo-Al-USY catalyst at 415-430°C to ⁇ 0.001% wt. nitrogen.
  • LHSV hereinafter, stands for Liquid Hourly Space Velocity
  • the process according to the invention is characterized in that the starting shale oil feedstock, in particular a feedstock having high sulfur, Ramsbottom carbon and nitrogen content, is treated in two stages, the first stage being a deep desulfurization with wide pore Co/Ni-Mo-RE-Al catalyst and the second stage being a deep hydrodenitrogenation (HDN) with a Co Ni-Mo-zeolite catalyst.
  • RE stands for Rare Earth elements.
  • the first deep desulfurization stage reduces the average molecular weight and therefore the distillation pattern of nitrogen-containing substances, making said substances easily hydrodenitrogenated in the second stage.
  • Temperature from 360 to 400 °C, and preferably from 370 to 380 °C.
  • LHSV not less than 0.5, and preferably from 0.5 to 3.0 h ⁇ l , and more preferably, from
  • Hydrogen pressure from 1000 to 3000, and preferably from 2000 to 2500 psi.
  • V H2 from 300 to 5000 and preferably from 2000 to 3500 Nl/1.
  • Temperature from 380 to 400 °C, and preferably from 380 to 390 °C.
  • LHSV not less than 0.5 h " , and preferably from 0.5 to 3.0 h"' , and more preferably, from 0.8 to 1.2 h" L
  • Hydrogen pressure from 1000 to 3000, and preferably from 2000 to 2500 psi.
  • VH 2 from 300 to 5000 and preferably from 2000 to 2500 Nl/1.
  • the shale oil is demetallized before submitting it to the aforesaid two treatment stages.
  • the two stages are carried out in fixed bed reactors with two different catalysts loaded in one reactor in series or in two reactors in series loaded with different catalysts .
  • an hydrocarbon organic solvent preferably chosen from among hydrocarbons or mixtures of hydrocarbons boiling out at less than 105°C, from 50 to 105°C
  • the catalysts used in the first stage comprise: NiO or/and CoO and M0O3, the content of each of the component oxides being: NiO from 0.0 to 3.0 %, CoO from 0.0 to 3.0 %, provided that the sum of NiO and CoO is at least 0.5%, and M0O3 from 8 to 15 %, all percentages being by weight calculated on the whole of the catalyst.
  • the oxides are supported on an AI2O3 substrate modified by RE-oxide, and the ratio of their combined weight to the support weight varies from 0.09 to 0.20, and preferably from 0.15 to 0.17.
  • the packed density of the catalyst g/cc varies from 0.30 to 0.90, and preferably from 0.35 to 0.40.
  • the surface area, in m ⁇ /g varies from 150 to 300 and preferably from 200 to 260.
  • the pore volume of the catalyst in cc/g varies from 0.70 to 1.20, and preferably from 0.80 to 1.00.
  • the average pore diameter, in Angstroms varies from 1 10 to 140, and preferably from 1 15 to 135
  • the alumina support, containing 1 -3 wt% of RE oxide must have large pores, e g , an average pore diameter of 140-180 Angstroms, preferably around 160 Angstroms, and can be prepared by known preparation methods, such as that described by R K Oberlander in "Applied Industrial Catalysis", B E Leach Ed Acad Press, v 3, 1984, p 64 It is impregnated, to prepare the catalyst, with nickel, cobalt and molybdenum salts in solution, by impregnating methods that are generally known - see W M eely, P Jerus, E K Dienes and A L Hausberger, "Preparation Techniques for
  • the catalyst used in the second stage comprises a zeolite stabilized on the same alumina-RE support
  • the zeolite-containing support is impregnated to prepare the catalyst with promoter solution, containing salts of Cr, P, Zr or Ti, and then with Co or/and Ni and Mo salts in solution by impregnation methods that are generally known
  • the zeolites are chosen from among Faujasite type, preferably zeolite Y with S ⁇ O 2 /Al 2 O 3 mole ratio from 4 to 6, preferably from 4 5 to 5 5 in hydrogen form with sodium content less than 0 5% wt , preferably less than 0 2 % wt
  • the zeolite content in the catalyst varies from 10 to 40% ww, and preferably from 25 to 35% ww
  • a promoter, e g Cr, P, Zr or Ti oxide can be added to the zeohte catalyst in amount from 2 to 6% ww, and preferably from 4 to 5% ww
  • the ratio between the volume of the catalysts and the volume of the feed in the two stages, in the case of fixed bed reactor, varies within the following limits:
  • First stage 0.5 to 3.0 and preferably 0.8 to 1.2 m /h per m of catalyst
  • Second stage 0.5 to 3.0 and preferably 0.8 to 1.2 m 3 /h per m 3 of catalyst.
  • the residence time of the feed in the two stages varies, for the first stage from 0.3 to 2.0. and preferably from 0.85. to 1.25 hours, and for the second stage, from 0.3 to 2.0, and preferably from 0.85 to 1.25 hours, and correspondingly, the LHSV for the first stage is not less than 0.5 h " , and preferably varies from 0.5 to 3.0 h"*, and more preferably, from 0.8 to 1.2 h ⁇ l , and for the second stage is not less than 0.5 h "1 , and preferably varies from 0.5 to 3.0 h' and more preferably, betwen 0.8 and 1.2 h-i .
  • FIG. 1 is a schematic illustration of a fixed bed reactor pilot plant used in carrying out an embodiment of the invention
  • the embodiment hereinafter described refers to a process carried out in a fixed bed reactor pilot plant, such as illustrated in Fig. 1.
  • Fig. 1 is a schematic illustration of a hydrodesulfiirization plant.
  • the hydrotreating of shale oil was studied in the pilot plant apparatus shown in Figure 1.
  • the shale oil (individual or mixed with a light hydrocarbon solvent) to be treated was charged to a reservoir (1).
  • the liquid from reservoir (1) passed by way of metering pump (2) to the mixing zone of the tubular reactor (3) to join a flow of hydrogen from cylinder (4) that passed a mass flow controller (5).
  • the shale oil passed the heating zone 1 1 of the reactor (3) and then to two hydrotreating zones 12 (the first-stage zone) and 13 (the second-stage zone) charged with the same volume of different catalysts (see above).
  • appropriate amount of silica particles 20-35 mesh, indicated at 14, were charged to improve the liquid distribution.
  • Reactor (3) consists of a 25 mm internal diameter vertical tube 1.15 meter long with axial thermocouple pocket (not shown). It was heated by two individually and automatically controlled electric heaters (6) and (7), each arranged to heat a hydrotreating zone of the reactor. From the bottom of the reactor (3) there emerged a two-phase fluid which passed high-pressure separator (8) and then low-pressure separator (9), where the liquid products were separated from the gases (H 2 , H 2 S, NH 3 ), that were subsequently passed to a discharge line containing flow measurement equipment (10) and analytical equipment (not shown) and vented to the atmosphere. To prevent blockings of the tube at the reactor outlet with ammonium sulfide crystals, water was pumped immediately to the reactor outlet point (not shown) to dissolve this salt and was collected subsequently in the high-pressure separator (8).
  • the crude shale oil feedstock was the Israeli Negev shale oil, the characteristics of which are listed hereinbefore in Table I.
  • the catalyst used for the first step of the process was a DMN catalyst prepared in the following manner.
  • An alumina support was prepared by the preparation method of Wakabayshi et al., described in "Applied Industrial Catalysis, v.3, 1984, p. 92, which consists of pH oscillating precipitation from an aqueous solution of aluminum nitrate by hydroxide.
  • the cake was impregnated with La(NO 3 ) 3 water solution, washed, extruded into 1.2 mm diameter pellets, dried at 120°C for two hours and calcined at 550°C for five hours.
  • the extruded pellets were impregnated with nickel nitrate, cobalt nitrate and ammonium molibdate in ammonious solutions (15% NH 4 OH, 2.5% NiO or CoO, and 10% MoO 3 ).
  • the impregnated pellets were dried at 120°C for two hours and calcined at 550°C for three hours.
  • Three catalysts - DNM- 1,2,3 - were prepared. Their characteristics are set forth in Table III. Table III Characteristics of the first-stage hydrotreating catalysts
  • Catalysts properties packed 0.35 0.51 0.39 density, g/cc surface area, 240 220 230 m 2 /g pore volume, 0.88 0.65 0.80 cc/g
  • catalysts designated as HTN were prepared. They contained HY zeolite, LZ-Y62 (manufactured by Linde AG) stabilized in an alumina support. The zeolite was mixed with the alumina cake, prepared by the pH oscillating precipitation method, hereinbefore mentioned, impregnated with La(NO 3 ) 3 water solution, extruded into 1.2 mm diameter pellets, dried at 120°C for two hours and calcined at 550°C for five hours.
  • HY zeolite LZ-Y62 (manufactured by Linde AG) stabilized in an alumina support.
  • the zeolite was mixed with the alumina cake, prepared by the pH oscillating precipitation method, hereinbefore mentioned, impregnated with La(NO 3 ) 3 water solution, extruded into 1.2 mm diameter pellets, dried at 120°C for two hours and calcined at 550°C for five hours.
  • the extruded pellets were twice impregnated with (NH 4 ) 2 CrO 4 water solution (4.1% Cr 2 O 3 in water) or H 3 PO 4 water solution (3.2% P 2 O 5 in water) and then with cobalt nitrate (or nickel nitrate) and ammonium molibdate in ammonious water solution (15% NH 4 OH, 8.5% CoO (or NiO) and 20% MoO 3 ).
  • the catalyst was dried at 120°C for two hours and calcined at 550°C for five hours.
  • Five second-stage catalysts HTN- 1,2,3,4,5 were prepared. Their characteristics are set forth in Table IV. Table IV Characteristics of the second-stage hydrotreating catalysts
  • Catalysts properties packed density, 0.46 0.40 0.51 0.45 0.39 g/cc surface area, 280 270 300 340 230 2 /g pore volume, 0.69 0.70 0.63 0.74 0.80 cc/g
  • the fixed bed reactor plant used in this embodiment of the invention is the one illustrated in Fig. 1
  • the process was carried out in the following way.
  • the DMN catalyst was loaded in the upper, first-stage hydrotreating zone of the reactor and the same volume of HDN catalyst was loaded in the lower, second-stage hydrotreating zone of the reactor located immediately after the first-stage zone.
  • Amount of cyclohexane solvent in the feedstock % vol. 80 80 0 0 0
  • the optimal SOR (Start Of Run) temperature for the hydrotreatment in the first stage is 380°C
  • This product could be used for production of motor fuels by further distillation: 10-25 volume % gasoline boiling out at ⁇ 180°C, 20-35% volume jet fuel boiling out in the range 160-270°C or 70-80 volume % diesel fuel boiling out in the range 160-380°C.
  • This product could be also used as a feedstock for hydrocracking process that will increase the yield of light motor fuels - gasoline and jet fuel.
  • the hydrotreated shale oil was distilled to separate gasoline fraction IBP- 160° jet fuel fraction 160-270°C and diesel fuel fraction 160-380°C. The yields of those three fuels were 12, 26 and 75% vol., conformably, calculated on the basis of hydrotreated shale oil.
  • IBP not limited 78
  • Aromatics content ASTM D-1319 ⁇ 25 22 % mas.
  • Olefins content ASTM D-1319 not limited 0.5 % mas.
  • WISM ASTM D-3948 not limited 88
  • Residue % not limited 365

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP96938442A 1995-11-23 1996-11-21 Process and catalysts for the production of motor fuels from shale oils Withdrawn EP0956326A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IL11612195A IL116121A0 (en) 1995-11-23 1995-11-23 Process and catalysts for the production of motor fuels from shale oils
IL11612195 1995-11-23
PCT/IL1996/000158 WO1997019150A1 (en) 1995-11-23 1996-11-21 Process and catalysts for the production of motor fuels from shale oils

Publications (2)

Publication Number Publication Date
EP0956326A4 EP0956326A4 (enrdf_load_stackoverflow) 1999-11-17
EP0956326A1 true EP0956326A1 (en) 1999-11-17

Family

ID=11068222

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96938442A Withdrawn EP0956326A1 (en) 1995-11-23 1996-11-21 Process and catalysts for the production of motor fuels from shale oils

Country Status (4)

Country Link
EP (1) EP0956326A1 (enrdf_load_stackoverflow)
AU (1) AU7585496A (enrdf_load_stackoverflow)
IL (1) IL116121A0 (enrdf_load_stackoverflow)
WO (1) WO1997019150A1 (enrdf_load_stackoverflow)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920539A (en) * 1974-04-19 1975-11-18 Exxon Research Engineering Co Hydrocarbon hydrodesulfurization utilizing a catalyst of germanium group VI-B and VIII components on alumina
US4003828A (en) * 1975-07-23 1977-01-18 Exxon Research And Engineering Company Catalyst and process for removing sulfur and metal contaminants from hydrocarbon feedstocks
US4022682A (en) * 1975-12-22 1977-05-10 Gulf Research & Development Company Hydrodenitrogenation of shale oil using two catalysts in series reactors
US4618594A (en) * 1979-03-19 1986-10-21 Standard Oil Company (Indiana) Catalyst and process for the hydrodenitrogenation and hydrocracking of high-nitrogen feeds
JPS594182B2 (ja) * 1979-11-27 1984-01-28 千代田化工建設株式会社 重質炭化水素油の水素化処理用触媒およびその製造法
JPS595011B2 (ja) * 1979-11-27 1984-02-02 千代田化工建設株式会社 重質炭化水素油の水素化処理用触媒ならびにその製法
US4431526A (en) * 1982-07-06 1984-02-14 Union Oil Company Of California Multiple-stage hydroprocessing of hydrocarbon oil
US4519900A (en) * 1982-12-28 1985-05-28 Mobil Oil Corporation Zeolite containing catalyst support for denitrogenation of oil feedstocks
US4657663A (en) * 1985-04-24 1987-04-14 Phillips Petroleum Company Hydrotreating process employing a three-stage catalyst system wherein a titanium compound is employed in the second stage
GB2267233B (en) * 1992-05-15 1996-09-04 Nikki Universal Co Ltd Hydrodesulfurization catalyst and preparation thereof
US5403806A (en) * 1993-10-22 1995-04-04 Union Oil Company Of California Phosphorous-containing hydroprocessing catalyst and method of preparation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *
See also references of WO9719150A1 *

Also Published As

Publication number Publication date
EP0956326A4 (enrdf_load_stackoverflow) 1999-11-17
WO1997019150A1 (en) 1997-05-29
AU7585496A (en) 1997-06-11
IL116121A0 (en) 1996-01-31

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