EP0359874A1 - Méthode catalytique non oxydant pour l'adoucissement de fractions hydrocarbonées - Google Patents

Méthode catalytique non oxydant pour l'adoucissement de fractions hydrocarbonées Download PDF

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Publication number
EP0359874A1
EP0359874A1 EP88308682A EP88308682A EP0359874A1 EP 0359874 A1 EP0359874 A1 EP 0359874A1 EP 88308682 A EP88308682 A EP 88308682A EP 88308682 A EP88308682 A EP 88308682A EP 0359874 A1 EP0359874 A1 EP 0359874A1
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EP
European Patent Office
Prior art keywords
hydrocarbon fraction
acid
catalyst
sour hydrocarbon
mercaptans
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Granted
Application number
EP88308682A
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German (de)
English (en)
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EP0359874B1 (fr
Inventor
Tamotsu Imai
Jeffrey C. Bricker
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Honeywell UOP LLC
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UOP LLC
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Priority to US07/065,243 priority Critical patent/US4775462A/en
Application filed by UOP LLC filed Critical UOP LLC
Priority to EP88308682A priority patent/EP0359874B1/fr
Priority to AT88308682T priority patent/ATE77639T1/de
Priority to DE8888308682T priority patent/DE3872392T2/de
Publication of EP0359874A1 publication Critical patent/EP0359874A1/fr
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Publication of EP0359874B1 publication Critical patent/EP0359874B1/fr
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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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier

Definitions

  • the present invention relates to a unique non-­oxidative method of sweetening sour hydrocarbon streams using an unsaturated hydrocarbon and an acid catalyst together with appropriate thioether producing conditions.
  • Processes for the treatment of a sour hydrocarbon fraction wherein the fraction is treated by contacting said fraction with an oxidation catalyst in the presence of an oxidizing agent and an alkaline component have become well-known and widely practiced in the petroleum refining industry. Said processes are typically designed to effect the oxidation of offensive mercaptans contained in a sour hydrocarbon fraction with the formation of innocuous disulfides--a process commonly referred to as sweetening.
  • the oxidizing agent is most often air.
  • Gasoline including natural, straight run and cracked gasolines, is the most frequently treated sour hydrocarbon fraction.
  • Other sour hydrocarbon fractions include the normally gaseous petroleum fractions as well as naphtha, kerosene, jet fuel, fuel oil, lube oil, and the like.
  • a commonly used continuous process for treating a sour hydrocarbon fraction entails treating the distillate in contact with a metal phthalocyanine catalyst dispersed in an aqueous caustic solution to yield a doctor sweet product.
  • the sour hydrocarbon fraction and the catalyst containing aqueous caustic solution provide a liquid-liquid system wherein mercaptans are converted to disulfides at the interface of the immiscible solutions in the presence of an oxidizing agent--usually air.
  • Sour hydrocarbon fractions containing more difficult to oxidize mercaptans are more effectively treated by contacting with a metal chelate catalyst disposed on a high surface area adsorptive support--usually a metal phthalocyanine on an activated charcoal.
  • the sour fraction is treated by contacting with the supported metal chelate catalyst at oxidation conditions in the presence of an alkaline agent.
  • an alkaline agent is most often air admixed with the hydrocarbon fraction to be treated, and the alkaline agent is most often an aqueous caustic solution charged continuously to the process or intermittently as required to maintain the catalyst in the caustic-wetted state.
  • U.S. Patent 3,894,107 teaches the conversion of heteroatom compounds to higher hydrocarbons over a particular type of aluminosilicate molecular sieve at temperatures of 300°C - 500°C, in the gas phase.
  • aluminosilicate molecular sieve at temperatures of 300°C - 500°C, in the gas phase.
  • the resultant products would be higher hydrocarbons and H2S.
  • the formation of H2S would present a disposal problem. Therefore, because of the H2S disposal problem and the high temperatures involved, this process is not useful as a hydrocarbon sweetening process.
  • the present invention discloses a non-oxidative method of sweetening a sour hydrocarbon fraction comprising contacting a mercaptan containing sour hydrocarbon fractions with an acid type catalyst in the presence of an unsaturated hydrocarbon, thereby converting said mercaptans to thioethers.
  • the instant invention has the advantage over the oxidative method of the prior art in that no alkaline agent is involved in the present invention and therefore the problem of disposing of the spent alkaline agent is eliminated.
  • one embodiment of the invention is a process for sweetening a sour hydrocarbon fraction containing mercaptans which comprises contacting said sour hydrocarbon fraction containing at least a concentration of an unsaturated hydrocarbon equal to the molar amount of mercaptans present in said sour hydrocarbon fraction with an acid-type catalyst at non-­oxidative reaction conditions selected to convert said mercaptans to thioethers and recovering said sweetened hydrocarbon fraction.
  • a sour hydrocarbon fraction which contains mercaptans and unsaturated hydrocarbons in appropriate amounts is continuously contacted with an acidic resin at conditions selected to convert the mercaptans to thioethers and recovering the sweetened hydrocarbon fraction.
  • This invention describes a catalytic method for converting mercaptans through reaction with unsaturated hydrocarbons in the presence of an acid catalyst and thereby provides a non-oxidative method of sweetening a sour hydrocarbon fraction.
  • the generalized reaction can be written as follows: where each R is individually selected from the group consisting of hydrogen, an alkyl hydrocarbon, a cycloalkyl hydrocarbon, an aryl hydrocarbon, an alkaryl hydrocarbon and an aralkyl hydrocarbon. If R is any of the hydrocarbons listed above, the hydrocarbon may contain up to about 25 carbon atoms.
  • R′SH represents any mercaptan compound where R′ is a hydrocarbon radical containing up to about 25 carbon atoms and is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl.
  • an acid type catalyst can catalyze the reaction of mercaptans with an unsaturated hydrocarbon to give thioethers which are acceptable products.
  • Typical catalysts which were found to be effective in promoting the thioetherification reaction include but are not limited to acidic reticular polymeric resins, intercalate compounds, solid acid catalysts, acidic inorganic oxides and metal sulfates. More specifically, examples of acidic polymeric resins are resins which contain a sulfonic acid group. Although both macro- and microreticular polymeric sulfonic acid resins may be used, it is preferred to use macroreticular polymeric sulfonic acid resins. These types of resins are well known in the art and are available commercially.
  • An intercalate compound is defined as a material which has a layer of cations between the planes of a crystal lattice. Only intercalate compounds which are acidic are contemplated as within the scope of this invention. Examples of acidic intercalate compounds are antimony halides in graphite, aluminum halides in graphite, and zirconium halides in graphite. A preferred intercalate compound is antimony pentafluoride in graphite. Again these compounds are commercially available.
  • Solid acid catalysts have also been found to catalyze the conversion of mercaptans to thioethers.
  • Examples of one type of solid acid catalysts are phosphoric acid, sulfuric acid or boric acid supported on an inorganic oxide support such as silica, alumina, silica-aluminas, kieselguhr or clays. These acid catalysts are usually prepared by reacting the desired liquid acid with the desired support and drying.
  • Examples of another type of solid acid catalysts are acidic inorganic oxides.
  • Acidic inorganic oxide catalysts which may be used in this invention may be selected from the group consisting of aluminas, silica-aluminas, natural and synthetic pillared clays, and natural and synthetic zeolites such as faujasites, mordenites, L, omega, X and Y zeolites. Many of these oxides can either be synthesized or preferably can be obtained from commercial sources.
  • a subgroup of acidic inorganic oxides which are within the scope of the invention are aluminas or silica-­aluminas which have been impregnated with aluminum halides or boron halides.
  • a preferred catalyst of this type is boron trifluoride deposited on alumina.
  • metal sulfates such as zirconium sulfate, nickel sulfate, chromium sulfate, cobalt sulfate, etc. can also be used in this invention.
  • the catalyst be in particulate form, which particles have an average diameter of less than 4.0 mm. Additionally, it is preferred that the average particle size (average diameter) be in the range of about 105 microns to about 4.0 mm. If the catalyst particle size is smaller than 105 microns, excessive backpressure is created in the treating zone.
  • hydrocarbons which have an unsaturated carbon-carbon bond with one of said unsaturated carbons also being a tertiary carbon atom are isobutylene, 3-methyl-1-butene, 2-methyl-2-butene, 2-methyl-1-butene, 2-methyl-1-pentene, etc. bond and a tertiary carbon atom are particularly preferred.
  • the concentration of the unsaturated hydrocarbon necessary to carry out the process of the instant invention can vary considerably. However, a concentration of unsaturated hydrocarbon of at least equal to the molar amount of the mercaptans present in said sour hydrocarbon fraction is necessary to effectively carry out the process.
  • the sour hydrocarbon fraction does not contain an unsaturated hydrocarbon, one can be added to the sour hydrocarbon fraction prior to contact with the fixed bed catalyst.
  • the unsaturated hydrocarbon is added to the sour hydrocarbon fraction, it is desirable that it be added in a concentration of at least the molar concentration of the mercaptans in said sour hydrocarbon fraction to about 20 weight percent of the sour hydrocarbon fraction.
  • the upper limit is imposed more by economic considerations rather than any practical limitations of the process.
  • a recommended concentration range of unsaturated hydrocarbon is about 0.01 weight percent to about 20 weight percent.
  • the process of the instant invention is carried out by passing the sour hydrocarbon fraction over a fixed bed acid-catalyst which is installed in a reaction zone.
  • the fixed bed catalyst can be placed in either a vertical or a horizontal reaction zone. If a vertical reaction zone is chosen, the sour hydrocarbon fraction can be passed upwardly or downwardly through the fixed bed.
  • the methods of supporting beds of solid material in reaction zones are well known and need not be described in detail herein.
  • the sour hydrocarbon fraction is introduced into the reaction zone by a feed line and the flow is controlled by means well known in the art.
  • the flow of the hydrocarbon fraction is controlled to give a contact time in the reaction zone so that the desired conversion of mercaptans to thioethers is achieved.
  • contact times equivalent to a liquid hourly space velocity (LHSV) of about 0.5 to about 10 are effective to achieve a desired conversion of mercaptans to thioethers.
  • treatment of the sour hydrocarbon fraction in the reaction zone is generally effected in a temperature range of about 25° to about 350°C with a preferred temperature range of about 25°C to about 200°C.
  • the reaction is carried out at a pressure of about 0.01 to about 25 atmospheres with a pressure in the range of about 1 to about 10 atmospheres being preferred.
  • the unsaturated hydrocarbon can be added to the sour hydrocarbon fraction at the start of the reaction zone but well before the fixed bed acid catalyst. This will ensure that the unsaturated hydrocarbon is well dispersed in the sour hydrocarbon fraction. It is contemplated that any unreacted unsaturated hydrocarbon could be separated at the reactor outlet and recycled to the inlet of the catalyst bed.
  • the sweetening of high molecular weight petroleum fractions might be accomplished by addition of excess isobutylene to the hydrocarbon feed over an acid catalyst.
  • the separation and recycle of unreacted isobutylene could be employed to increase sweetening rate and minimize the use of isobutylene.
  • the entire process can be carried out in a batch process.
  • the pressure conditions, temperature conditions and unsaturated hydrocarbon concentration employed for the flow type process can be used for a batch process.
  • the contact time in the reaction zone will depend on the amount of catalyst, the size of the reaction zone, and the amount of sour hydrocarbon in the reaction zone. Based on these considerations, an appropriate conversion of mercaptan to thioether is accomplished with a contact time in the range of from about 0.05 to about 2 hours.
  • the acid catalyst can be deactivated by basic nitrogen compounds present in the sour hydrocarbon fraction.
  • Removal of the basic nitrogen compounds can be accomplished by several methods known in the art, including an acid wash or the use of a guard bed positioned prior to the acid catalyst.
  • effective guard beds include A-zeolite, Y-zeolite, L-zeolite, mordenite and acidic reticular polymeric resins. If a guard bed technique is employed, it is contemplated that dual guard beds be placed prior to the reactor such that regeneration of one guard bed may be conducted while the alternate guard bed is functioning. In this manner continuous operation of the unit may be achieved.
  • the sour hydrocarbon fraction can be treated with an aqueous solution of the acid.
  • the concentration of said acid in said aqueous solution is not critical, but is conveniently chosen to be in the range of about 0.5 to about 30 weight percent.
  • the acid which can be used to treat the sour hydrocarbon fraction may be chosen from the group consisting of hydrochloric, sulfuric, acetic, etc., with hydrochloric acid being preferred.
  • One method of effecting the acid wash involves introducing a sour hydrocarbon stream into the lower portion of an extraction column.
  • the sour hydrocarbon stream rises upward through contacting plates or trays toward the top of the extractor counter-current to a descending stream of an aqueous acid solution.
  • the basic nitrogen compounds contained in said sour hydrocarbon fraction are extracted into the aqueous acid solution.
  • the sour hydrocarbon fraction continues upward past the point in the upper portion of the column at which the aqueous acid solution is introduced and then is removed.
  • the resultant basic nitrogen compound containing aqueous acid solution is removed from the bottom of the reactor and disposed.
  • This acid wash treatment is usually done at ambient temperature and atmospheric pressure, although temperatures in the range of about 20 to about 70°C and pressure in the range of about 1.0 to about 17.2 atmospheres can be used.
  • the rate of flow of the acid solution will be about 0.1 times to about 3.0 times of the rate of flow of the sour hydrocarbon feed. Carrying out the acid wash under the above conditions will generally result in the removal of about 60-95+ weight percent of the basic nitrogen compounds.
  • a macroreticular polymeric sulfonic acid resin was obtained from the Rohm and Haas Co. This resin is sold under the name Amberlite XE-372 and comes in the shape of spheres about 16-50 U.S. mesh size (1.19 mm to 297 micron diameter). The resin was used as received and was designated catalyst A.
  • a macroreticular polymeric sulfonic acid resin was obtained from the Rohm and Haas Co. This resin is sold under the name Amberlyst 15 and comes in the shape of spheres about 16-50 U.S. mesh size (1.19 mm to 297 micron diameter). The resin was used as received and was designated catalyst B.
  • a macroreticular polymeric sulfonic acid resin was obtained from the Rohm and Haas Co. This resin is sold under the name Amberlite 252 and comes in the shape of spheres about 16-50 U.S. mesh size (1.19 mm to 297 micron diameter). The resin was used as received and was designated catalyst C.
  • An intercalate compound consisting of antimony pentafluoride on graphite was obtained from Alfa Chemical Co. This catalyst was used as received and was designated catalyst D.
  • a solid phosphoric acid catalyst was prepared by adding kieselguhr powder to an 85% polyphosphoric acid solution and mixing for 3-7 minutes. After formation of a consistent mixture the material was extruded, sized and dried at 380°C. This catalyst was designated catalyst E.
  • Catalyst F was prepared by passing BF3 gas at an hourly space velocity of 700 hr ⁇ 1 over an anhydrous gamma alumina support for two hours. The catalyst was loaded into the reactor under a nitrogen atmosphere.
  • Example I to VI The catalysts of Example I to VI were studied in a test designed to evaluate the activity and durability of these catalysts.
  • the test involved loading a sample of the catalyst (50 cc) to be evaluated into a 0.5 ⁇ by 6.5 ⁇ (12.7 by 165.1 mm) catalyst reaction zone where it was supported by screens.
  • the reactor zone containing catalyst was purged with nitrogen for a sufficient time to remove all gaseous oxygen from the system.
  • the reactor zone inlet temperature was controlled at 30°C and the reactor pressure was one atmosphere.
  • a silica-alumina catalyst was prepared by binding mordenite zeolite in a gamma alumina binder. The mordenite content was 90%.
  • a new portion of catalyst A was evaluated according to the procedure specified hereinbefore, except for the following: 1) the sour hydrocarbon fraction was an FCC gasoline containing 355 ppm of mercaptans; 2) the liquid hourly space velocity (LHSV) was 5; 3) the reactor temperature was 50°C; 4) the pressure was 9.2 atm.; and 5) 13.6% weight percent of isobutylene added.
  • the evaluation was carried out for forty hours to determine the durability of the catalyst. The result of this evaluation are presented in Figure 1.
  • Figure 1 presents a graph of the amount of mercaptan left in the treated hydrocarbon fraction as a function of time. The results indicate that the catalyst is converting at least 235 ppm (66%) of the mercaptans to thioethers for the duration of the test.
  • a portion of an FCC gasoline was given an acid wash as follows.
  • the acid wash of the FCC gasoline was performed batchwise with a 10 weight percent solution of aqueous HCl and an FCC gasoline/H2O volumetric ratio of 4/1.
  • the acid wash removed 67% of the nitrogen compounds (single-stage extraction) while reducing the thiol content only slightly from 193 wppm to 171 wppm mercaptan sulfur.
  • FIG. 2 presents plots of mercaptan conversion to thioethers versus time on stream. The plots show that acid washing the sour hydrocarbon fraction prior to contacting it with the acid catalyst improves the durability of the catalyst. Thus, an acid wash is a means to improve the durability of the acid catalyst.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP88308682A 1987-06-22 1988-09-20 Méthode catalytique non oxydant pour l'adoucissement de fractions hydrocarbonées Expired EP0359874B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US07/065,243 US4775462A (en) 1987-06-22 1987-06-22 Non-oxidative method of sweetening a sour hydrocarbon fraction
EP88308682A EP0359874B1 (fr) 1988-09-20 1988-09-20 Méthode catalytique non oxydant pour l'adoucissement de fractions hydrocarbonées
AT88308682T ATE77639T1 (de) 1988-09-20 1988-09-20 Katalytische nichtoxidatives verfahren fuer das suessen von kohlenwasserstofffraktionen.
DE8888308682T DE3872392T2 (de) 1988-09-20 1988-09-20 Katalytische nichtoxidatives verfahren fuer das suessen von kohlenwasserstofffraktionen.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP88308682A EP0359874B1 (fr) 1988-09-20 1988-09-20 Méthode catalytique non oxydant pour l'adoucissement de fractions hydrocarbonées

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EP0359874A1 true EP0359874A1 (fr) 1990-03-28
EP0359874B1 EP0359874B1 (fr) 1992-06-24

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AT (1) ATE77639T1 (fr)
DE (1) DE3872392T2 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030655A1 (fr) * 1997-01-14 1998-07-16 Amoco Corporation Procede d'extraction du soufre
US5863419A (en) * 1997-01-14 1999-01-26 Amoco Corporation Sulfur removal by catalytic distillation
US6024865A (en) * 1998-09-09 2000-02-15 Bp Amoco Corporation Sulfur removal process
WO2000014181A1 (fr) * 1998-09-09 2000-03-16 Bp Amoco Corporation Procede d'elimination du soufre en plusieurs etapes
US6599417B2 (en) 2000-01-21 2003-07-29 Bp Corporation North America Inc. Sulfur removal process
US6602405B2 (en) 2000-01-21 2003-08-05 Bp Corporation North America Inc. Sulfur removal process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2726991A (en) * 1952-12-01 1955-12-13 Standard Oil Co Hydrocarbon desulfurization process with calcined reaction product of titanium halide and phosphoric acid
US3340184A (en) * 1964-10-30 1967-09-05 Exxon Research Engineering Co Process for removing sulfur from petroleum oils and synthesizing mercaptans
US3894941A (en) * 1973-12-14 1975-07-15 Gulf Research Development Co Process for converting mercaptans to alkyl sulfides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2726991A (en) * 1952-12-01 1955-12-13 Standard Oil Co Hydrocarbon desulfurization process with calcined reaction product of titanium halide and phosphoric acid
US3340184A (en) * 1964-10-30 1967-09-05 Exxon Research Engineering Co Process for removing sulfur from petroleum oils and synthesizing mercaptans
US3894941A (en) * 1973-12-14 1975-07-15 Gulf Research Development Co Process for converting mercaptans to alkyl sulfides

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030655A1 (fr) * 1997-01-14 1998-07-16 Amoco Corporation Procede d'extraction du soufre
US5863419A (en) * 1997-01-14 1999-01-26 Amoco Corporation Sulfur removal by catalytic distillation
US6048451A (en) * 1997-01-14 2000-04-11 Bp Amoco Corporation Sulfur removal process
US6024865A (en) * 1998-09-09 2000-02-15 Bp Amoco Corporation Sulfur removal process
WO2000014181A1 (fr) * 1998-09-09 2000-03-16 Bp Amoco Corporation Procede d'elimination du soufre en plusieurs etapes
US6059962A (en) * 1998-09-09 2000-05-09 Bp Amoco Corporation Multiple stage sulfur removal process
US6599417B2 (en) 2000-01-21 2003-07-29 Bp Corporation North America Inc. Sulfur removal process
US6602405B2 (en) 2000-01-21 2003-08-05 Bp Corporation North America Inc. Sulfur removal process

Also Published As

Publication number Publication date
DE3872392T2 (de) 1993-02-04
DE3872392D1 (de) 1992-07-30
EP0359874B1 (fr) 1992-06-24
ATE77639T1 (de) 1992-07-15

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