WO1999010453A1 - Procede de reduction de l'indice d'acidite total du petrole brut - Google Patents

Procede de reduction de l'indice d'acidite total du petrole brut Download PDF

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Publication number
WO1999010453A1
WO1999010453A1 PCT/US1998/018041 US9818041W WO9910453A1 WO 1999010453 A1 WO1999010453 A1 WO 1999010453A1 US 9818041 W US9818041 W US 9818041W WO 9910453 A1 WO9910453 A1 WO 9910453A1
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WO
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Prior art keywords
oil
petroleum feed
kpa
metal
petroleum
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Application number
PCT/US1998/018041
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English (en)
Inventor
Roby Bearden, Jr.
Saul Charles Blum
William Neergaard Olmstead
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Exxon Research And Engineering Company
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
Priority claimed from US09/072,764 external-priority patent/US5914030A/en
Application filed by Exxon Research And Engineering Company filed Critical Exxon Research And Engineering Company
Priority to DK98942321T priority Critical patent/DK1062302T3/da
Priority to BR9811387-9A priority patent/BR9811387A/pt
Priority to DE69804026T priority patent/DE69804026T2/de
Priority to CA002295917A priority patent/CA2295917C/fr
Priority to KR1020007000641A priority patent/KR20010022072A/ko
Priority to EP98942321A priority patent/EP1062302B1/fr
Priority to AU90404/98A priority patent/AU733884B2/en
Priority to JP2000507762A priority patent/JP4283988B2/ja
Publication of WO1999010453A1 publication Critical patent/WO1999010453A1/fr
Priority to NO20000948A priority patent/NO20000948D0/no

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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
    • 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
    • C10G45/14—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 with moving solid particles
    • C10G45/16—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 with moving solid particles suspended in the oil, e.g. slurries

Definitions

  • the present invention is directed to a method for reducing the Total Acid Number (TAN) of crude oils, a number that is based on the amount of carboxylic acids, especially naphthenic acids, that are present in the oil.
  • TAN Total Acid Number
  • naphthenic acid removal by conversion or absorption.
  • many aqueous materials can be added to crudes or crude fractions to convert the naphthenic acids to some other material, e.g., salts, that can either be removed or are less corrosive.
  • Other methods for naphthenic acid removal are also well known including absorption, on zeolites, for example.
  • one common practice for overcoming naphthenic acid problems is the use of expensive corrosion resistant alloys in refinery or producer equipment that will encounter relatively high naphthenic acid concentrations.
  • Another common practice involves blending of crudes with high TAN with crudes of lower TAN, the latter, however being significantly more costly than the former.
  • Lazar, et al. (US 1,953,353) teaches naphthenic acid decomposition of topped crudes or distillates, effected at atmospheric pressure between 600 and 750°F (315.6 to 398.9°C). However, it only recognizes C0 2 as the sole gaseous non-hydrocarbon, naphthenic acid decomposition product and makes no provision for avoiding buildup of reaction inhibitors.
  • U.S. Patent No. 2,921,023 describes removal of naphthenic acids from heavy petroleum fractions by hydrogenation with a molybdenum oxide-on-silica/alumina catalyst. More specifically, the process preferentially hydrogenates oxo-compounds and/or olefinic compounds, for example, naphthenic acids, in the presence of sulfur compounds contained in organic mixtures without affecting the sulfur compounds. This is accomplished by subjecting the organic mixture to the action of hydrogen at temperatures between about 450 and 600°F (232.2 to 315.6°C), in the presence of a molybdenum oxide containing catalyst having a reversible water content of less than about 1.0 wt%. Catalyst life is prolonged by regeneration.
  • WO 96/06899 describes a process for removing essentially naphthenic acids from a hydrocarbon oil.
  • the process includes hydrogenation at 1 to 50 bar (100 to 5000 kPa) and at 100 to 300°C (212 to 572°F) of a crude that has not been previously distilled or from which a naphtha fraction has been distilled using a catalyst consisting of Ni-Mo or Co-Mo on an alumina carrier.
  • the specification describes the pumping of hydrogen into the reaction zone. No mention is made of controlling water and carbon dioxide partial pressure.
  • U.S. Patent No. 3,617,501 describes an integrated process for refining whole crude but does not discuss TAN reduction.
  • the first step of the process includes hydrotreating a feed, which can be a whole crude oil fraction, using a catalyst comprising one or more metals supported on a carrier material.
  • the metals are metal oxides or sulfides, such as molybdenum, tungsten, cobalt, nickel and iron supported on a suitable carrier material such as alumina or alumina that contains a small amount of silica.
  • the catalyst can be employed in the form of fixed bed, a slurry or fluidized bed reactor. With regard to slurry operation, no mention is made of catalyst particle size, catalyst concentration in feed or the use of unsupported catalysts (i.e., no carrier).
  • British Patent 1,236,230 describes a process for the removal of naphthenic acids from petroleum distillate fractions by processing over supported hydrotreating catalysts without the addition of gaseous hydrogen. No mention is made of controlling water and carbon dioxide partial pressure.
  • Another method for removal of such acids includes treatment at temperatures of at least about 400°F (204.44°C), preferably at least about 600°F (315.56°C) while sweeping the reaction zone with an inert gas to remove inhibitors indigenous to or formed during the treatment.
  • this approach is debited by the volatilization of some of the naphthenic acids, which are found in distillate and light oil fractions that flash during the thermal treatment.
  • treatment temperatures may be too high for this method to be used in downstream applications where it is desirable to destroy the acids prior to pipestill furnaces, i.e., at temperatures of about 550°F (287.78°C) or below.
  • the instant invention is directed to a method for destroying carboxylic acids in whole crudes and crude fractions.
  • the invention comprises a method for reducing the amount of carboxylic acids in petroleum feeds comprising the steps of (a) adding to said petroleum feed a catalytic agent comprising an oil soluble or oil dispersible compound of a metal selected from the group consisting of Group VB, VIB, VIIB and VIII metals, wherein the amount of metal in said petroleum feed is at least about 5 wppm, (b) heating said petroleum feed with said catalytic agent in a reactor at a temperature of about 400 to about 800°F (about 204.44 to about 426.67°C), under a hydrogen pressure of 15 psig to 1000 psig (204.75 to 6996.33 kPa) and (c) sweeping the reactor containing said petroleum feed and said catalytic agent with hydrogen- containing gas at a rate sufficient to maintain the combined water and carbon dioxide partial pressure below about 50 psia (about 344.75 kP
  • TAN is defined as the weight in milligrams of potassium hydroxide required to neutralize all acidic constituents in one gram of oil. (See ASTM method D-664.)
  • Vacuum bottoms conversion is defined as the conversion of material boiling above 1025°F (551.67°C) to material boiling below 1025°F (551.67°C).
  • Figure 1 is the calculated partial pressure for water as a function of reactor pressure and rate of hydrogen-containing gas sweep for the process of the instant invention.
  • the instant invention removes or destroys carboxylic acids (e.g., naphthenic acids) contained in petroleum feeds such as whole crude oils (including heavy crudes) and fractions thereof such as vacuum gas oil fractions, topped crudes, vacuum resids, atmospheric resids, topped crudes and vacuum gas oil.
  • carboxylic acids e.g., naphthenic acids
  • the instant method reduces TAN by at least about 40% in the petroleum feed.
  • the process is run at temperatures from about 400 to about 800°F (about 204.44 to about 426.67°C), more preferably about 450 to about 750°F (about 232.22 to about 398.89°C), and most preferably about 500 to about 650°F (about 260.00 to about 343.33°C).
  • Hydrogen pressures range from about atmospheric to about 2000 psig (atmospheric to about 13891.33 kPa), preferably about 15 psig to about 1000 psig (about 204.75 to about 6996.33 kPa), and most preferably about 50 psig to about 500 psig (about 446.08 to about 3548.83 kPa).
  • the amount of catalyst, calculated as catalyst metal or metals, used in the process ranges from at least about 5, preferably about 10 to about 1000 parts per million weight (wppm) and most preferably about 20 to 500 wppm of the petroleum feed being treated.
  • less than about 40% of the vacuum bottoms component of the feed i.e., the fraction boiling above about 1025°F (551.67°C) is converted to material boiling below about 1025°F (551.67°C) and, more preferably, less than about 30% vacuum bottoms conversion occurs.
  • Catalyst particle size ranges from about 0.5 to about 10 microns, preferably about 0.5 to 5 microns, and most preferably about 0.5 to 2.0 microns.
  • Catalysts are prepared from precursors, also referred to herein as catalytic agents, such as oil soluble or oil dispersible compounds of Group VB, VIB, VIIB, or VIII metals and mixtures thereof. Suitable catalyst metals and metal compounds are disclosed in U.S. Patent No. 4, 134,825 herein incorporated by reference.
  • An example of an oil soluble compound is the metal salt of a naphthenic acid such as molybdenum naphthenate.
  • oil dispersible compounds are phosphomolybdic acid and ammonium heptamolybdate, materials that are first dissolved in water and then dispersed in the oil as a water- in-oil mixture, wherein droplet size of the water phase is below about 10 microns.
  • a catalyst precursor concentrate is first prepared wherein the oil-soluble or oil- dispersible metal compound(s) is blended with a portion of the process feed to form a concentrate that contains at least about 0.2 wt% of catalyst metal, preferably about 0.2 to 2.0 wt% catalyst metal. See for example U.S. Patent No. 5,039,392 or 4,740,295 herein incorporated by reference.
  • the resultant precursor concentrate can be used directly in the process or first converted to a metal sulfide concentrate or an activated catalyst concentrate prior to use.
  • Catalyst precursor concentrate can be converted to a metal sulfide concentrate by treating with elemental sulfur (added to the portion of feed used to prepare the concentrate) or with hydrogen sulfide at 300 to 400°F (148.89 to 204.44°C) for 10-15 minutes (e.g., see U.S. Patent Nos. 5,039,392; 4,479,295; and 5,620,591 herein incorporated by reference).
  • the metal sulfide concentrate can be converted into catalyst concentrate by heating at 600 to 750°F (315.56 to 398.89°C for a time sufficient to form the catalyst, (e.g., see U.S. Patent Nos. 5,039,392; 4,740,295; and 5,620,591).
  • the catalyst of the concentrate consists of nano-scale metal sulfide sites distributed on a hydrocarbonaceous matrix that is derived from the oil component of the concentrate. Overall particle size can be varied, but falls within the range of 0.5 to 10 microns, preferably in the range of about 0.5 to 5.0 microns and, more preferably, 0.5 to 2.0 microns.
  • the precursor concentrate the metal sulfide concentrate, or the catalyst concentrate.
  • the petroleum feed is mixed with the concentrate to obtain the desired concentration of metal in the feed i.e., at least about 5 wppm, preferably about 10 to 1000 wppm.
  • catalyst having a particle size of about 0.5 to 10 microns, preferably 0.5 to 5 microns and most preferably 0.5 to 2.0 microns are formed in the heating step of the process in the TAN conversion reactor.
  • Preferred metals include molybdenum, tungsten, vanadium, iron, nickel, cobalt, and chromium.
  • heteropolyacids of the metals can be used.
  • Molybdenum is particularly well suited to the process of the instant invention.
  • Preferred molybdenum compounds are molybdenum naphthenates, dithiocarbamate complexes of molybdenum (e.g., see U.S. Patent No. 4,561,964 incorporated herein by reference), phosphomolybdic acid and phosphoro- dithioate complexes of molybdenum (e.g. MOLYVAN ® -L, molybdenum di(2- ethylhexyl) phosphorodithioate, supplied by R.T. Vanderbilt Company.
  • MOLYVAN ® -L molybdenum di(2- ethylhexyl) phosphorodithioate
  • small particle catalysts that are useful for the practice of the instant process include metals-rich ash from the controlled combustion of petroleum coke (e.g., see U.S. Patent Nos. 4, 169,038; 4, 178,227; and 4,204,943 herein incorporated by reference). Finely divided iron based materials, satisfying the particle size constraints noted herein, such as red mud from the processing of alumina can also be used.
  • Water vapor and carbon dioxide resulting from the decomposition of carboxylic acids act as inhibitors for the decomposition of remaining carboxylic acids.
  • Water is a particularly strong inhibitor.
  • a preflash step may be used to remove substantially all of the water.
  • water can have a strong inhibiting effect on the rate of carboxylic acid destruction.
  • Carbon dioxide is also an inhibitor but to a much lower degree.
  • the catalyst can be left in the treated crude (depending on the metal type and concentration) or removed by conventional means such as filtration.
  • Conradson Carbon content of the product i.e., the components of the product that yield coke under pyrolysis conditions.
  • Conradson Carbon in the product is increased relative to that contained in the feed. This effect is illustrated in comparative Examples 5 of Table 2.
  • the growth or increase of Conradson Carbon can be totally inhibited and Conradson Carbon components can be converted to non-Conradson Carbon components.
  • Conradson Carbon conversion will range from about 0 to 5%, more preferably, from about from 5 to 20% and, most preferably, from 10 to 40%.
  • This example was carried out in a 300 cc stirred autoclave reactor.
  • the reactor was operated in a batch mode with respect to the crude that was charged. Hydrogen was flowed through the autoclave to maintain constant hydrogen partial pressure and to control the pressure of water and carbon dioxide in the reaction zone.
  • the reactor was charged with 100 g of the Kome/Bolobo blend and 0.61 g. of MOLYVAN ⁇ -L * (8.1 wt% Mo), flushed with hydrogen and then pressured to 350 psig (2514.58 kPa) with hydrogen at room temperature. Hydrogen flow was then started through the autoclave at a rate of 0.1 liter/min while maintaining a pressure of 350 psig (2514.58 kPa) by use of a backpressure regulator at the reactor outlet. The reactor was then heated to 625°F (329.44°C) with stirring and was held at 625°F (329.44°C) for 60 minutes at 350 psig (2514.58 kPa).
  • the calculated partial pressures of hydrogen and water** were, respectively, 329 psia (2268.46 kPa) and 13 psia (89.64 kPa).
  • the reactor Upon cooling to 250°F (121.11°C), the reactor was vented and flushed with hydrogen to recover light hydrocarbon products including hydrocarbons that are normally gaseous at room temperature.
  • MOLYVAN ® -L supplied by the R.T. Vanderbilt Company, is molybdenum di(2-ethylhexyl) phosphorodithioate.
  • Example #1 illustrates the degree of TAN conversion obtained when Kome/Bolobo crude blend was heated at 625°F (329.44°C) for one hour in the absence of catalyst and hydrogen.
  • the procedure of Example #1 was repeated except that MOLYVAN ⁇ -L was omitted and that the run was carried out with an inert gas sweep at a reactor pressure of 30 psig (308.18 kPa).
  • TAN for the reactor product was 3.40.
  • Example #1 illustrates destruction of TAN in Kome/Bolobo crude (Table 2) using a small amount of a highly dispersed catalyst at relatively mild conditions and with a water partial pressure in the reactor below 20 psia (137.9 kPa). Such treatment provides substantially greater TAN reduction than can be attained by thermal treatment alone at comparable time and temperature (Example #2). TABLE 2
  • the feedstock used in this example was dry Campo-1-Bare crude.
  • Mo was supplied as a catalyst precursor concentrate which was prepared in the following way. A solution of 8 g. of Fisher reagent grade phosphomolybdic acid was dissolved in 92 g. of deionized water. Next, 10 g. of solution was injected into 90 g. of Campo-1-Bare crude while stirring at 176°F (80°C) in a 300 cc Autoclave Engineer's Magnedrive Autoclave. After stirring for 10 minutes at 176°F (80°C), the autoclave was swept with nitrogen and the temperature increased to 300°F (148.89°C) to remove water. The resultant precursor concentrate contained 0.45 wt% Mo.
  • the autoclave was charged with 99.43 g. of dry Campo-1-Bare crude and 0.57 g of precursor concentrate to provide a reactor charge that contained 25 wppm Mo.
  • the reactor was flushed with hydrogen and then pressured to 50 psig (446.08 kPa) with hydrogen sulfide.
  • the reactor pressure was increased to 300 psig (2169.83 kPa) with hydrogen and a flow of hydrogen of 0.12 liters/min. (380 SCF/B) was started through the autoclave. Pressure was maintained by use of a backpressure regulator at the reactor gas- outlet line.
  • Example #3 The procedures of Example #3 were repeated except that the run was carried out at a pressure of 400 psig (2859.33 kPa) and that water was fed to the reactor at the rate of 0.033 g/min. The partial pressure of water in the reactor during the run was about 92 psia (634.34 kPa). There were recovered 0.05 g. of catalyst containing residue, and 96.4 g. of product liquid blend that had a TAN of 0.43 and contained 15.4 wt% Conradson Carbon.
  • Example #4 The procedures of Example #4 were repeated except that catalyst was not added and that the experiment was carried out at 300 psig (2169.83 kPa) with argon as the sweep gas. There was recovered 97.4 g. of product liquid blend that had a TAN of 0.63 and contained 17.9 wt.% Conradson Carbon. Water partial pressure in the reactor was about 92 psia (634.34 kPa).
  • Example #6
  • Example #3 The procedures of Example #3 were repeated with the following changes.
  • the reactor was charged with 98.86 g. of crude and 1.14 g. of precursor concentrate which provided a reactor charge that contained 50 wppm Mo.
  • the run was carried out at 750°F (398.89°C) for 62 minutes at 300 psig (2169.83 kPa) with a hydrogen sweep of 0.12 liters/min. (380 SCF/B). Water was fed to the reactor at the rate of 0.017 g./min. to provide a water partial pressure in the reactor of 55 psia (379.22 kPa).
  • Example #6 The procedures of Example #6 were repeated except that the sweep rate of hydrogen was 0.24 liters/min (780 SCF/B), which resulted in a water partial pressure in the reactor of 26 psia (179.27 kPa). There were recovered 0.04 g. of catalyst residue and 96.8 g. of product liquid blend which had a TAN of 0.12, contained 15.4 wt% Conradson Carbon and a kinematic viscosity of 918 centistokes at 104°F (40°C).
  • Comparison of Example #3 with Example #4 illustrates the inhibiting effect of water on TAN conversion as does the comparison of Example #6 with Example #7, where a decrease in water partial pressure from 55 to 26 psia (379.22 to 179.27 kPa) reduced TAN from 0.31 to 0.12.
  • Comparison of Example #4 with Example #5 illustrates that use of catalyst plus hydrogen, in accordance with the process of this invention, gives higher TAN conversion at a given water partial pressure than can be obtained by thermal treatment in the absence of hydrogen and catalyst.
  • Conradson Carbon values were determined using the Micro Method, which is ASTM D 4530. This test determines the amount of carbon residue formed after evaporation and pyrolysis of petroleum materials under specified conditions. The test results are equivalent to those obtained using the Conradson Carbon Residue Test (Test Method D 189).

Abstract

La présente invention concerne un procédé de réduction de la quantité d'acides carboxyliques dans les alimentations en pétrole consistant à (a) ajouter d'abord à cette alimentation un agent catalytique renfermant un composé d'un métal pouvant se dissoudre ou se disperser dans le pétrole, ce composé étant sélectionné dans le groupe constitué par les métaux des groupes VB, VIB, VIIB et VIII, et la quantité de métal dans l'alimentation précitée étant d'au moins 5 wppm; puis,(b) chauffer l'alimentation avec ledit agent catalytique dans un réacteur à une température d'environ 400 à environ 800 °F (environ 204,44 à environ 426,67 °C), sous une pression d'hydrogène de 15 psig à 1000 psig (204,75 à 6996,33 kPa); et enfin, (c) balayer le réacteur contenant l'alimentation et l'agent catalytique avec un gaz renfermant de l'hydrogène à une vitesse suffisante pour maintenir la pression partielle de l'eau de constitution et du dioxyde de carbone en dessous de 50 psia (environ 344,75 kPa)
PCT/US1998/018041 1997-08-29 1998-08-28 Procede de reduction de l'indice d'acidite total du petrole brut WO1999010453A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DK98942321T DK1062302T3 (da) 1997-08-29 1998-08-28 Fremgangsmåde til reduktion af totalsyretal i råolie
BR9811387-9A BR9811387A (pt) 1997-08-29 1998-08-28 Processo para reduzir a quantidade de ácidos carboxìlicos em alimentações de petróleo
DE69804026T DE69804026T2 (de) 1997-08-29 1998-08-28 Verfahren zur reduzierung der gesamtanzahl von säuren in rohöl
CA002295917A CA2295917C (fr) 1997-08-29 1998-08-28 Procede de reduction de l'indice d'acidite total du petrole brut
KR1020007000641A KR20010022072A (ko) 1997-08-29 1998-08-28 원유의 총 산가 감소 방법
EP98942321A EP1062302B1 (fr) 1997-08-29 1998-08-28 Procede de reduction de l'indice d'acidite total du petrole brut
AU90404/98A AU733884B2 (en) 1997-08-29 1998-08-28 Process for reducing total acid number of crude oil
JP2000507762A JP4283988B2 (ja) 1997-08-29 1998-08-28 原油の全酸価を低減させるためのプロセス
NO20000948A NO20000948D0 (no) 1997-08-29 2000-02-25 Fremgangsmåte for å redusere totalsyretallet (TAN) i råolje

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US92044797A 1997-08-29 1997-08-29
US08/920,447 1997-08-29
US09/072,764 US5914030A (en) 1997-08-29 1998-05-05 Process for reducing total acid number of crude oil
US09/072,764 1998-05-05

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AU (1) AU733884B2 (fr)
BR (1) BR9811387A (fr)
CA (1) CA2295917C (fr)
DE (1) DE69804026T2 (fr)
DK (1) DK1062302T3 (fr)
ID (1) ID24702A (fr)
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WO (1) WO1999010453A1 (fr)

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CN100549132C (zh) * 2003-12-19 2009-10-14 国际壳牌研究有限公司 生产原油产品的系统,方法和催化剂
NL1027768C2 (nl) * 2003-12-19 2006-07-13 Shell Int Research Systemen, methoden en katalysatoren voor het produceren van een ruwe-oliehoudend product.
KR101898289B1 (ko) * 2011-01-10 2018-09-13 에스케이이노베이션 주식회사 탄화수소류 유분 내의 유기산을 저감하는 방법
US10195588B1 (en) * 2017-11-28 2019-02-05 Uop Llc Process for making and using iron and molybdenum catalyst for slurry hydrocracking

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2921023A (en) * 1957-05-14 1960-01-12 Pure Oil Co Removal of naphthenic acids by hydrogenation with a molybdenum oxidesilica alumina catalyst
WO1996006899A1 (fr) * 1994-08-29 1996-03-07 Den Norske Stats Oljeselskap A.S Procede pour eliminer essentiellement des acides naphteniques des huiles minerales
WO1996025471A1 (fr) * 1995-02-17 1996-08-22 Exxon Research And Engineering Company Decomposition thermique des acides naphteniques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2921023A (en) * 1957-05-14 1960-01-12 Pure Oil Co Removal of naphthenic acids by hydrogenation with a molybdenum oxidesilica alumina catalyst
WO1996006899A1 (fr) * 1994-08-29 1996-03-07 Den Norske Stats Oljeselskap A.S Procede pour eliminer essentiellement des acides naphteniques des huiles minerales
WO1996025471A1 (fr) * 1995-02-17 1996-08-22 Exxon Research And Engineering Company Decomposition thermique des acides naphteniques

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EP1062302B1 (fr) 2002-02-27
ID24702A (id) 2000-08-03
CN1268968A (zh) 2000-10-04
AU733884B2 (en) 2001-05-31
DE69804026D1 (de) 2002-04-04
CN1105769C (zh) 2003-04-16
NO20000948L (no) 2000-02-25
AU9040498A (en) 1999-03-16
JP2001514300A (ja) 2001-09-11
BR9811387A (pt) 2000-08-29
DK1062302T3 (da) 2002-04-02
EP1062302A1 (fr) 2000-12-27
CA2295917A1 (fr) 1999-03-04
DE69804026T2 (de) 2002-10-31
JP4283988B2 (ja) 2009-06-24
CA2295917C (fr) 2005-06-07
NO20000948D0 (no) 2000-02-25

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