US2760906A - Desulfurization of hydrocarbon oils with vanadium oxide catalyst in the presence of naphthenes - Google Patents

Desulfurization of hydrocarbon oils with vanadium oxide catalyst in the presence of naphthenes Download PDF

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Publication number
US2760906A
US2760906A US245076A US24507651A US2760906A US 2760906 A US2760906 A US 2760906A US 245076 A US245076 A US 245076A US 24507651 A US24507651 A US 24507651A US 2760906 A US2760906 A US 2760906A
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United States
Prior art keywords
sulfur
catalyst
naphthenes
hydrogen
reaction
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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.)
Expired - Lifetime
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US245076A
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English (en)
Inventor
Jr William F Arey
Jr Charles N Kimberlin
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Publication date
Priority to NL80929D priority Critical patent/NL80929C/xx
Priority to NLAANVRAGE7510134,A priority patent/NL172020B/xx
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US245076A priority patent/US2760906A/en
Priority to GB20707/52A priority patent/GB717012A/en
Priority to FR1064811D priority patent/FR1064811A/fr
Application granted granted Critical
Publication of US2760906A publication Critical patent/US2760906A/en
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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
    • C10G45/24—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 hydrogen-generating compounds
    • C10G45/28—Organic compounds; Autofining
    • C10G45/30—Organic compounds; Autofining characterised by the catalyst used
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium

Definitions

  • the present invention relates to the treatment of sulfurcontaining organic materials, in particular, sulfur-bearing hydrocarbon material, to desulfurize the same. More particularly, the present invention relates to the desulfurization of sulfur-containing petroleum fractions, in particular fractions containing ring type sulfur compounds.
  • Sulfur occurs in petroleum stocks, generally i'n two main forms, as mercaptans and as part of a more or less substituted ring, of which thiophenef is the prototype.
  • the former type is generally found in the lower boiling fractions, in the naphtha, kerosene, and light gas oil material, whereas the ring-sulfur compounds form the bulk of the sulfur-bearing material of the higher boiling petroleum fraction.
  • the present invention relates to a novel process for removing catalytically sulfur of the ring type from sulfurcontaining crude and distillates without the necessity of adding extraneous hydrogen, by a process involving a transfer of hydrogen from a hydrogen donor compound to the sulfur compound. It has been discovered that sulfur-containing fractions may be freed of substantial amounts of such sulfur by contacting the sulfur-containing materials in the presence of a compound adapted for use as a hydrogen donor in a hydrogen transfer reaction. Among the hydrogen donors found to be most practicable are the naphthenes.
  • This invention further dilfers from conventional hydrogenation reactions in that molecular hydrogen is not supplied to the reaction as such, but is supplied in situ from a hydrogen donor such as a naphthene or an isoparafiin.
  • the invention is especially applicable to catalyzed reactions in which hydrogen is directly transferred from the hydrogen donor to the sulfur being removed from the organic molecule.
  • the sulfur removed from the'organic compounds is subsequently converted by the hydrogen transfer reaction to a sulfide, usually hydrogen sulfide.
  • the hydrogen transfer reaction is carried out in the vapor phase with the use of a catalyst.
  • the use of the selective catalyst results in much greater selectivities in the removal of sulfur to give the desired sulfur-free products and a substantial reduction in undesirable degradation reactions of the starting materials to gaseous products and carbonaceaus by-products.
  • Naphthenes can be defined as saturated compounds of the general formula C2H2n having closed links composed of methylene groups.
  • the naphthenic hydrocarbons which can be employed as hydrogen donors may be those having six cyclic carbon atoms or more, that is, cyclohexane and its derivatives. Naphthenic rings having four or less carbon atoms are too unstable to function satisfactorily. Alkylated derivatives of these naphthenes such as methylcyclohexane can also be employed. During the course of the reaction, the naphthenes are dehydrogenated to produce aromatic type products.
  • cyclohexane when cyclohexane is used, it is converted to benzene and when methylcyclohexane is used, it is converted to toluene.
  • the hydrogen atoms which are thus. removed from the naphthenes are catalytically utilized in the presence of the catalyst to combine with the sulfur'present as organically bound sulfur in the feed stock, thereby removing the sulfur from the feed stock and converting it into an easily separable form.
  • Cyclohexane and its higher homologues are particularly adapted for use in the role of hydrogen donors because the removal of six hydrogen atoms from cyclohexane converts it to the completely f aromatized benzene.
  • the reaction is carried out in vapor phase in the presence of the catalyst and under conditions of temperature, pressure, feed rates, and the like, so chosen as to produce the maximum possible removal of sulfur from the feed stock and at the same time to obtain high selectivity and relatively pure final sulfur-free products.
  • the equipment employed for this process may be of any type known to those skilled in the art for effecting a vapor phase catalytic reaction.
  • liquid feed is charged to a vaporizer fromwhich the resulting feed vapors pass through a preheatingi zone and thence into the catalytic reaction zone iniwhi'ch the vapors are contacted with the catalyst.
  • reaction product and non-condensible gases.
  • the catalyst which has been found to be particularly useful 'in carrying out the reaction to remove organically bound sulfur is a'specially prepared vanadiunroxide cat-' alyst supported on alumina.
  • vanadium catalysts for certain specific refinery operations has previously been suggested, for instance, hydroforming and isomerization and'the like. In these operationsit has been. the general equivalent of related compounds such as molyb denum, chromium and the like These processes are generally ones involving added'hydrogen, andthe catalystsgenerally have behavior and activities of a comparable nature.
  • the catalyst In order to. reactivate the. catalyst, carbonaceous deposits-are removed andthe catalyst regenerated by a strippingsprocessaas With steam, nitrogen, flue gas and thelike, at elevated .temperaturesof about 1300-1600 F. Also, the organic mattermay be burnedoif directly Withair. In its ease of regeneration, the catalyst has a decided. advantage over such materials. as activated carbon, vor catalysts supported on activated carbon.
  • the desulfurized reactionmixture is taken from the catalytic reaction; zone and preferably condensed to a liquid comprising-the reactionproducts and non-condensible'gases.
  • Theliquid reaction product so obtained can bezworkedup inany suitablemauner, for example, by.
  • any hydrogenrsulfide'presentin the liquid may be removed by-- extraction, caustic :washing, or by other'conventional methodsxfor. removal: of hydrogen sulfide.
  • Unchanged or-zincompletely, desulfurized reactants can be recycled, together. with freshsulfur-containing ,feed and fresh hydrogen donor material.
  • an inert diluent such as; :for example, a portion of. .the non-condensible gaseous products.
  • therange of'temperaturesfor car ying outthe desulfurization reaction is: of the order'of 6009-1 100 F.
  • Optimumvtemperatures: for the-reaction are; consid ered to beabout.750.”-95'0 F.
  • temperatures .higherthan this limit
  • This may be determined by ascertaining the naphthene content of the feedand, if'necessary, augmenting thiswith extraneous naphthenes, such as cyclohexane, etc.
  • sulfur-containing feed stocks which may be desulfurized by this novel hydrogen transfer reaction
  • these include various types of organic materials having organically bound.
  • sulfur suchfas thiophene, alkylated thiophenes, and other thiophene derivatives, diethyl sulfide, diethyl disulfide, dipropyl sulfide, dibutyl sulfide, diamyl sulfide,- mercaptans, various types of sulfur acids, etc.
  • The-process isespecially useful for desulfurizing petroleum fractions, as for instance, naphtha fractions containing organically bound sulfur which must be removed before the fractions can be used for many purposes.
  • compounds must be used whose desulfurized products are sufiiciently stable to withstand the relatively high temperatures and yet emerge from the reaction zone as intact molecules.
  • The. process may be executed in a batch or continuous manner. Generally, better conversions are obtained with multipassprocesses.
  • the catalyst may be employed in a fixed bed, movingbed, or in a fluidized manner, depending on the type of operation desired.
  • Aluminum amylate washydrolyzed by the addition of water to give an aqueous slurry containing about 5 weight percent alumina. Glacial acetic acid was added to this slurry to theextent of 6 weight percent based on alumina and the resulting slurry was dried for twenty-four hours inasteam oven (250" F.).
  • the recovered dry gel was, 1000 grams of dry alumina was ground to a powder, treated with 85.2 grams of ammonium meta vanadate dissolved. in 1400 grams of hot water. The resulting paste was well mixed and dried in a steam oven.
  • the po,wder was reimpregnated with another 85,2 grams ofammonium meta vanadate as above and again dried to give a final composition of 10% V205 on alumina.
  • the catalyst was activated by heating at 850 F. overnight prior to use.
  • catalysts can be prepared from alumina obtainedfrom other sources, such as by precipitation from aqueous solutions of alumina nitrate, chloride, etc., by the addition of ammonium hydroxide;
  • Example-I Thathighjsulfur removal by hydrogen transfer is apparently specific to the vanadia-alumina system and is not shown by vanadia supported on other carriers, oralumina alone, is demonstrated by the following data.
  • a mixture off'10' volume percent thiophene in methyl cycl heX-ane was. passed through a vaporizer and preheate" andthe vapors passed over the respective catalyst bed at a temperature of 800" F. and a pressure of 200 After analyzed for sulfur.
  • the catalyst compositions in these ruiis were all prepared by impregnation of the hydrous ge s.
  • Example ll That the method of preparation of the catalyst is a very important factor in its activity as a hydrogen transfer desulfurizing catalyst is shown by the following data.
  • the catalyst produced by the dry impregnation of the gel was considerably more active than that prepared by impregnation of the hydrous gel.
  • the reaction conditions of Example I were employed.
  • Impregnated Dry Gel-. 2. 7 1.0 96. 3 4. 2 0. 5 88 Impregnated Hydrous Gel 11.7 0.7 87. 6 4. 9 1.2 75
  • V205-A1203 catalyst over activated carbon, which is also a hydrogen transfer catalyst, and over a molybdena-alumina catalyst, which is a known efficient hydrogenationdehydrogenation catalyst.
  • the feeds and the reaction conditions are the same as those previously employed.
  • the vanadia-chromia and molybdena catalysts were prepared by impregnation of the dry gel.
  • Example IV T 0 determine the effectiveness of this method of desulfurizing upon refinery streams, a heavy naphtha containing 0.66 wt. percent thiophene sulfur and a naphthene 6 content of 40 vol. percent was passed over a catalyst consisting of 10% V205 on A1203 at 0.5 v./v./hr. under a pressure of 200 p. s. i. g. at 800 F. After caustic washing, the oil product had a sulfur content of 0.17, equivalent to a 74% reduction in sulfur.
  • the hydrogen donating naphthene may be present initially in the stream being treated. In these cases, it is not necessary to add extraneous naphthenes. Where there is only a relatively small amount of naphthenes present, it is desirable to add extraneous naphthenes, such as cyclohexane and cyclopentane, and their homologues and analogues.
  • a process for catalytic desulfurization of hydrocarbons containing ring sulfur which comprises reacting in the vapor phase, a gaseous mixture containing added naphthenes and hydrocarbons containing ring sulfur in the presence of a hydrogen transfer gel type catalyst consisting essentially of vanadium oxide supported on alumina, prepared by impregnating dry alumina gel with a water soluble vanadium compound followed by thermal conversion of said compound to vanadium oxide and thereafter activating the catalyst by heating at elevated temperatures, at temperatures of between about 750 to about 950 F.
  • a hydrogen transfer gel type catalyst consisting essentially of vanadium oxide supported on alumina, prepared by impregnating dry alumina gel with a water soluble vanadium compound followed by thermal conversion of said compound to vanadium oxide and thereafter activating the catalyst by heating at elevated temperatures, at temperatures of between about 750 to about 950 F.
  • a process for the catalytic removal of ring sulfur from sulfur-containing hydrocarbons which comprises vaporizing said hydrocarbons, forming a gaseous stream containing said vapors in the presence of a vaporized naphthenic hydrocarbon and in the substantial absence of added free hydrogen, passing said gaseous stream at a temperature of between 750 to about 950 F.
  • a hydrodesulfurization catalyst prepared by impregnating dry alumina gel with a vanadium-containing compound followed by the thermal conversion of said vanadium compound to vanadium oxide and thereafter activating the catalyst by a heat treatment, transferring hydrogen from said naphthenic compound to said hydrocarbons containing ring sulfur by the catalytic action of said vanadium catalyst whereby said ring sulfur is removed from said hydrocarbons and said naphthenic hydrocarbon is converted at least partly to aromatic hydrocarbons.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US245076A 1951-09-04 1951-09-04 Desulfurization of hydrocarbon oils with vanadium oxide catalyst in the presence of naphthenes Expired - Lifetime US2760906A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL80929D NL80929C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1951-09-04
NLAANVRAGE7510134,A NL172020B (nl) 1951-09-04 Werkwijze voor het bereiden van een dessertprodukt met lage calorische waarde.
US245076A US2760906A (en) 1951-09-04 1951-09-04 Desulfurization of hydrocarbon oils with vanadium oxide catalyst in the presence of naphthenes
GB20707/52A GB717012A (en) 1951-09-04 1952-08-18 Improvements in or relating to desulfurization of petroleum fractions
FR1064811D FR1064811A (fr) 1951-09-04 1952-08-29 Désulfuration d'hydrocarbures

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US245076A US2760906A (en) 1951-09-04 1951-09-04 Desulfurization of hydrocarbon oils with vanadium oxide catalyst in the presence of naphthenes

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US (1) US2760906A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR1064811A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB717012A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (2) NL80929C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2911359A (en) * 1956-04-30 1959-11-03 Union Oil Co Desulfurization process and catalyst
US2977324A (en) * 1957-06-26 1961-03-28 Ici Ltd Catalysts
CN110252367A (zh) * 2019-05-06 2019-09-20 江苏大学 溶剂热法制备少层氮化碳负载二氧化钒催化剂及其脱硫应用

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2075171A (en) * 1932-06-10 1937-03-30 Phillips Petroleum Co Process for desulphurizing hydrocarbons
US2253308A (en) * 1937-05-05 1941-08-19 Standard Catalytic Co Desulphurization of hydrocarbons
US2324066A (en) * 1940-08-03 1943-07-13 Standard Oil Dev Co Purification of hydrocarbon oils
US2324067A (en) * 1940-08-03 1943-07-13 Standard Oil Dev Co Purification of hydrocarbon oils
US2372084A (en) * 1942-10-24 1945-03-20 Standard Oil Dev Co Process of desulphurizing motor fuels and improving octane rating
US2498559A (en) * 1945-10-15 1950-02-21 Kellogg M W Co Desulfurization and conversion of a naphtha
US2500146A (en) * 1946-07-08 1950-03-14 Union Oil Co Catalysts for conversion of hydrocarbons
US2547380A (en) * 1945-10-01 1951-04-03 Union Oil Co Catalyst for hydrocarbon conversion
US2573726A (en) * 1947-06-30 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulphurisation of naphthas
US2591525A (en) * 1947-12-22 1952-04-01 Shell Dev Process for the catalytic desulfurization of hydrocarbon oils
US2640802A (en) * 1949-11-16 1953-06-02 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2075171A (en) * 1932-06-10 1937-03-30 Phillips Petroleum Co Process for desulphurizing hydrocarbons
US2253308A (en) * 1937-05-05 1941-08-19 Standard Catalytic Co Desulphurization of hydrocarbons
US2324066A (en) * 1940-08-03 1943-07-13 Standard Oil Dev Co Purification of hydrocarbon oils
US2324067A (en) * 1940-08-03 1943-07-13 Standard Oil Dev Co Purification of hydrocarbon oils
US2372084A (en) * 1942-10-24 1945-03-20 Standard Oil Dev Co Process of desulphurizing motor fuels and improving octane rating
US2547380A (en) * 1945-10-01 1951-04-03 Union Oil Co Catalyst for hydrocarbon conversion
US2498559A (en) * 1945-10-15 1950-02-21 Kellogg M W Co Desulfurization and conversion of a naphtha
US2500146A (en) * 1946-07-08 1950-03-14 Union Oil Co Catalysts for conversion of hydrocarbons
US2573726A (en) * 1947-06-30 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulphurisation of naphthas
US2591525A (en) * 1947-12-22 1952-04-01 Shell Dev Process for the catalytic desulfurization of hydrocarbon oils
US2640802A (en) * 1949-11-16 1953-06-02 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2911359A (en) * 1956-04-30 1959-11-03 Union Oil Co Desulfurization process and catalyst
US2977324A (en) * 1957-06-26 1961-03-28 Ici Ltd Catalysts
CN110252367A (zh) * 2019-05-06 2019-09-20 江苏大学 溶剂热法制备少层氮化碳负载二氧化钒催化剂及其脱硫应用
CN110252367B (zh) * 2019-05-06 2022-01-11 江苏大学 溶剂热法制备少层氮化碳负载二氧化钒催化剂及其脱硫应用

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NL80929C (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL172020B (nl)
FR1064811A (fr) 1954-05-18
GB717012A (en) 1954-10-20

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