EP0728832A1 - Process for the demetallation of residual oils - Google Patents

Process for the demetallation of residual oils Download PDF

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Publication number
EP0728832A1
EP0728832A1 EP96101974A EP96101974A EP0728832A1 EP 0728832 A1 EP0728832 A1 EP 0728832A1 EP 96101974 A EP96101974 A EP 96101974A EP 96101974 A EP96101974 A EP 96101974A EP 0728832 A1 EP0728832 A1 EP 0728832A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
demetallation
carrier
oil
group
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Withdrawn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
EP96101974A
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German (de)
English (en)
French (fr)
Inventor
Jesper Bartholdy
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.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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 Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of EP0728832A1 publication Critical patent/EP0728832A1/en
Withdrawn legal-status Critical Current

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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • the present invention relates to demetallation of petroleum crude oil, and, more particular, to the removal of metals in the oil by contact with a catalyst having Ni, Mo and/or CoMo supported on a zeolitic carrier.
  • Petroleum crudes are known to contain metals such as Ni, V, Fe, Co, etc. in ppm levels. To a large extent, these components are associated with the heaviest parts of the resid, i.e. the part of the resid with the highest boiling points. This means that these components are concentrated in the bottom fractions often designated atm. or vacuum residuum.
  • Heavy oil fractions containing metal compounds are predominantly those with an atmospheric boiling point above 350°C.
  • the heavy oil fractions will typically contain 50-500 ppm of mainly Ni and V.
  • Those trace metals are normally removed in a fixed bed catalytic process, where the residual oil comes into contact with a demetallation catalyst at high temperature, typically at 300-450°C at a high H 2 pressure, such as 20-200 bars and at a space velocity in the range of 0.25-4 h -1 .
  • the metals presented in the feedstock will react and accumulate on the catalyst surface.
  • demetallation catalysts consist of Ni and Mo or CoMo supported on alumina. It has now been found that metals are removed from petroleum crude oil with a high efficiency in a demetallation process, when employing a demetallation catalyst supported on a carrier comprising zeolitic material.
  • this invention provides a process for the demetallation of petroleum crude oil by contacting the oil together with hydrogen with a catalyst having at least one metal or compound thereof of Group VIII and/or Group VI of the Periodic Table as active material supported on a carrier, wherein the carrier comprises a zeolite with a SiO 2 /Al 2 O 3 ratio of at least 5 and a unit cell size of between 24.30 and 24.60.
  • Preferred metals for use in the process are Ni, Mo, CoMo or mixtures thereof.
  • the catalyst may be prepared by any method being conventional in the art and including impregnation of the calcined carrier with an aqueous solution of salts of the active metal or metals, drying the impregnated carrier and finally calcinating the carrier to obtain the active catalyst.
  • the catalyst is arranged as fixed bed in a demetallation reactor and crude oil feedstock passed together with hydrogen in a ratio of typically 200-2000 Nl/l through the catalyst bed.
  • the bed temperature is maintained at elevated temperature and pressure of usually 350-450 o C and 120-170 atm.
  • the metal content in the feedstock is reduced to few ppm.
  • the calcined carrier was impregnated by pore volume filling with an impregnation solution containing 18.3 g of Co(NO 3 ) 2 ⁇ 6H 2 O, 15 g of ammonium dimolybdate and distilled water up to 82 ml. After impregnation, the catalyst was dried at room temperature for 16 hrs. The dried and impregnated catalyst was finally calcined at 500°C for 2 hours.
  • the catalyst thus prepared is designated A.
  • a catalyst carrier was prepared by mixing 30 g of dried HY Zeolite CBV 500 with 62 g of Versal 300 alumina and 126 g of alumina gel.
  • the catalyst carrier was dried, calcined, impregnated and decomposed at the same conditions as described under Example 1.
  • the catalyst thus prepared is designated B.
  • the catalysts of Examples 1-3 were tested in a fixed bed with a small protective layer of commercial demetallation catalysts, in order to control the amounts of metals that will deposit on the catalyst of the invention.
  • the catalyst bed lay-out used in the test is summarized in Table 3.
  • Table 3 Catalyst Bed Lay-Out Vol.-% 1) Loading 1 Loading 2 Loading 3 Loading 4 10 TK-711 1/32"C 25 TK-751 1/32"C 60
  • Fig. 1-3 show the catalyst activity of catalyst loadings 1-3 in comparison with the conventional Al 2 O 3 based system.
  • Fig. 1-3 are Arrhenius plots giving the first order rate constants for demetallation.
  • Fig. 1-3 the activity obtained on a conventional catalyst system is given as solid lines.
  • Each of the catalysts of this invention shows an improved activity for demetallation as apparent from the data in Fig. 1-3.
  • the level of improvement in relation to known catalysts are in the order of 20-40%, which for the test conditions and feeds tested results in a substantially completely demetallized hydrocarbon product.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (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)
EP96101974A 1995-02-24 1996-02-12 Process for the demetallation of residual oils Withdrawn EP0728832A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DK020095A DK20095A (da) 1995-02-24 1995-02-24 Fremgangsmåde til afmetallisering af residualolie
DK200/95 1995-05-19

Publications (1)

Publication Number Publication Date
EP0728832A1 true EP0728832A1 (en) 1996-08-28

Family

ID=8090881

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96101974A Withdrawn EP0728832A1 (en) 1995-02-24 1996-02-12 Process for the demetallation of residual oils

Country Status (10)

Country Link
EP (1) EP0728832A1 (da)
JP (1) JPH08245967A (da)
AU (1) AU4567896A (da)
BR (1) BR9600797A (da)
CA (1) CA2170219A1 (da)
DK (1) DK20095A (da)
NO (1) NO960739L (da)
NZ (1) NZ286000A (da)
TW (1) TW394789B (da)
ZA (1) ZA961475B (da)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6332510B1 (en) 1996-09-30 2001-12-25 Silentor Holding A/S Gas flow silencer
US6520286B1 (en) 1996-09-30 2003-02-18 Silentor Holding A/S Silencer and a method of operating a vehicle
CN103801380A (zh) * 2012-11-13 2014-05-21 中国石油化工股份有限公司 含分子筛的加氢催化剂组合物的制备方法
CN103801378A (zh) * 2012-11-13 2014-05-21 中国石油化工股份有限公司 含分子筛和氧化铝的加氢催化剂

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0109064A2 (en) * 1982-11-16 1984-05-23 W.R. Grace & Co. Hydrocarbon conversion catalysts
US4554263A (en) * 1983-05-10 1985-11-19 Catalysts & Chemicals Industries Co., Ltd. Catalysts for hydrotreating heavy oils
EP0216938A1 (en) * 1985-03-29 1987-04-08 Catalysts & Chemicals Industries Co., Ltd. Hydrotreatment catalyst
EP0449144A2 (en) * 1990-03-30 1991-10-02 Cosmo Oil Company, Ltd Catalyst composition for hydrotreating of hydrocarbons and hydrotreating process using the same
WO1993002158A1 (en) * 1991-07-24 1993-02-04 Mobil Oil Corporation Demetallation of hydrocarbon feedstocks with a synthetic mesoporous crystalline material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0109064A2 (en) * 1982-11-16 1984-05-23 W.R. Grace & Co. Hydrocarbon conversion catalysts
US4554263A (en) * 1983-05-10 1985-11-19 Catalysts & Chemicals Industries Co., Ltd. Catalysts for hydrotreating heavy oils
EP0216938A1 (en) * 1985-03-29 1987-04-08 Catalysts & Chemicals Industries Co., Ltd. Hydrotreatment catalyst
EP0449144A2 (en) * 1990-03-30 1991-10-02 Cosmo Oil Company, Ltd Catalyst composition for hydrotreating of hydrocarbons and hydrotreating process using the same
WO1993002158A1 (en) * 1991-07-24 1993-02-04 Mobil Oil Corporation Demetallation of hydrocarbon feedstocks with a synthetic mesoporous crystalline material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6332510B1 (en) 1996-09-30 2001-12-25 Silentor Holding A/S Gas flow silencer
US6520286B1 (en) 1996-09-30 2003-02-18 Silentor Holding A/S Silencer and a method of operating a vehicle
CN103801380A (zh) * 2012-11-13 2014-05-21 中国石油化工股份有限公司 含分子筛的加氢催化剂组合物的制备方法
CN103801378A (zh) * 2012-11-13 2014-05-21 中国石油化工股份有限公司 含分子筛和氧化铝的加氢催化剂
CN103801380B (zh) * 2012-11-13 2015-12-16 中国石油化工股份有限公司 含分子筛的加氢催化剂组合物的制备方法
CN103801378B (zh) * 2012-11-13 2016-01-20 中国石油化工股份有限公司 含分子筛和氧化铝的加氢催化剂

Also Published As

Publication number Publication date
NO960739D0 (no) 1996-02-23
NZ286000A (en) 1997-02-24
NO960739L (no) 1996-08-26
AU4567896A (en) 1996-09-05
CA2170219A1 (en) 1996-08-25
TW394789B (en) 2000-06-21
DK20095A (da) 1996-10-04
ZA961475B (en) 1996-11-27
BR9600797A (pt) 1997-12-23
JPH08245967A (ja) 1996-09-24

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