WO1996009891A1 - Procedes destines a la demercaptanisation de produits de la distillation du petrole - Google Patents

Procedes destines a la demercaptanisation de produits de la distillation du petrole Download PDF

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Publication number
WO1996009891A1
WO1996009891A1 PCT/US1995/012339 US9512339W WO9609891A1 WO 1996009891 A1 WO1996009891 A1 WO 1996009891A1 US 9512339 W US9512339 W US 9512339W WO 9609891 A1 WO9609891 A1 WO 9609891A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
mass
iron
catalyst
water
Prior art date
Application number
PCT/US1995/012339
Other languages
English (en)
Inventor
Akhmet Mazgarovich Mazgarov
Azat Faridovich Vildanov
Nailya Gilmutdinovna Bazhirova
Original Assignee
Chevron U.S.A. Inc.
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 US08/313,635 external-priority patent/US5741415A/en
Priority claimed from RU94039238A external-priority patent/RU2076892C1/ru
Application filed by Chevron U.S.A. Inc. filed Critical Chevron U.S.A. Inc.
Priority to MX9702145A priority Critical patent/MX9702145A/es
Priority to AU36861/95A priority patent/AU3686195A/en
Priority to EP95934553A priority patent/EP0783369A4/fr
Publication of WO1996009891A1 publication Critical patent/WO1996009891A1/fr
Priority to NO971379A priority patent/NO971379D0/no

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
    • 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
    • B01J21/18—Carbon
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins

Definitions

  • the invention relates to the field of the removal of mercaptan sulfur from petroleum distillates by means of oxidation, and may be used in the oil refining industry for the demercaptanization of gasoline, kerosene, and diesel fractions.
  • the method which most closely resembles the method described herein is the method for the demercaptanization of high-boiling-point petroleum distillates by means of mercaptan oxidation using the oxygen of the air, in the presence of a 5% to 20% solution containing an alkali and a heterogeneous phthalocyanine catalyst, comprising cobalt phthalocyanine in an amount ranging from 0.005 to 0.9 mass %, deposited on a carbonaceous fibrous material in the form of a carbonaceous or graphite fiber.
  • the objective of the present invention consists in achieving an increase in the degree of demercaptanization of petroleum distillates, an increase in the stability of the catalytic activity of the catalyst, and the elimination of the necessity of using significant quantities of the base.
  • a method for the demercaptanization of mercaptan- containing petroleum distillates by means of the oxidation of said mercaptans with the oxygen of the air in the presence of a heterogeneous catalyst comprising contacting said mercaptans with oxygen in the presence of a catalyst comprising a water-soluble salt of copper, iron, nickel, or cobalt, in an amount ranging from about 0.01 to about 10.0 mass %, which is deposited onto a fibrous carbonaceous material, said material containing oxides of metals of variable valence; said method being carried out at a temperature falling within the range of about 80° to about 200 ⁇ C.
  • a catalyst comprising a fibrous carbonaceous material containing oxides of metals of variable valence, and having deposited on said material, in an amount from about 0.01 to about 10.0 mass %, a water-soluble salt of copper, iron, nickel or cobalt.
  • the stated objective is achieved by providing a method for the demercaptanization of petroleum distillates by means of the oxidation of mercaptans using the oxygen of the air, in the presence of a heterogeneous catalyst.
  • a water-soluble salt of copper, iron, nickel, or cobalt may be used, in an amount ranging from 0.01 to 10.0 mass %, deposited on a fibrous carbon material in the form of a fabric-type material, felt, or rope, containing oxides of metals of variable valence, the process being carried out at a temperature ranging from about 80° to about 220°C.
  • a carbonaceous fibrous material is used, containing oxides of calcium, magnesium, copper, manganese, iron, zinc and aluminum, in quantities which provide sufficient basicity for the oxidation of the mercaptans to occur. Typically, this amount will be up to about 0.03 mass %.
  • the distinguishing features of the proposed method consist in the use of a heterogeneous catalyst, containing from about 0.01 to about 10.0 mass % of a water-soluble salt of copper, iron, nickel, or cobalt, on a material which consists of carbonaceous fibers; the use of a carbonaceous fibrous material in the form of a woven fabric (cloth) , felt, or rope (twisted strand) , containing the oxides of the above mentioned metals of variable valence in an amount of up to about 0.03 mass %; and the performance of the process at a temperature ranging from about 80° to about 220°C.
  • water-soluble salts of copper, iron, nickel, and cobalt include, but are not limited to, salts of inorganic acids such as the sulfates, chlorides and nitroxides (nitrates) of these metals.
  • Phenylates i.e., Ph-O-Me-O-Ph where Me is the metal and Ph is phenyl
  • copper sulfate, copper chloride, copper phenylate, iron sulfate, nickel nitroxide and cobalt nitroxide are useful in the practice of this invention, with copper phenylate being particularly preferred because it does not carry over into the demercaptanized product.
  • the proposed content of the water-soluble salt of Cu, Fe, Ni, or Co on the carbonaceous fibrous material in an amount ranging from 0.01 to 10.0 mass % is both necessary and sufficient, since with a content of the water-soluble salt of copper, iron, nickel, or cobalt which is less than 0.01 mass %, the required degree of mercaptan oxidation is not achieved.
  • the higher limit for the content of a water-soluble salt of copper, iron, nickel, or cobalt (10.0 mass %) is determined by the adsorptive properties of the carbonaceous fibrous material with respect to the water-soluble salt of copper, iron, nickel, or cobalt.
  • Typical oxides of metals of variable valence which are useful in this invention include, but are not limited to, oxides of calcium, magnesium, iron, manganese, copper, zinc and aluminum. Generally, these oxides are considered to but water-insoluble or only slightly soluble in water.
  • Carbonaceous fibrous materials in the form of a woven fabric, felt, or rope (twisted strand) , containing the oxides of metals of variable valence in an amount of up to about 0.03 mass % are industrially produced by a process involving the soaking of the material in solutions of salts of the aforesaid metals, with their subsequent thermal treatment.
  • the preparation of the proposed catalyst is carried out in accordance with the known method of soaking a carbonaceous fibrous material containing oxides of calcium, magnesium, copper, manganese, iron, zinc, and aluminum in aqueous solutions of the salts of copper, iron, nickel, or cobalt, at the required concentration, with subsequent drying.
  • the proposed method has found approbation under laboratory conditions in examples involving the demercaptanization of a model mixture of dodecylmercaptan in dodecane, a gasoline fraction (boiling-off range 60° to 180°C) , a kerosene fraction 120° to 240°C) , and a diesel fraction (180° to 350°C) .
  • a heterogeneous catalyst containing 10 mass % copper sulfate on a carbonaceous fabric which further contains oxides of calcium, magnesium, copper, manganese, iron, zinc, and aluminum in a quantity of 0.03 mass % are loaded into a batch reactor.
  • the copper sulfate is deposited onto the carbonaceous fabric by the method of soaking to saturation using an aqueous solution.
  • 35 ml of a model solution of n-dodecylmercaptan in dodecane are loaded into the reactor.
  • the reactor constitutes a cylindrical vessel made of glass, having a capacity of 100 ml, heated from the outside by a metallic spiral. Air is supplied to the reactor from the bottom; this air is evenly distributed within the reactor space due to the Schott filter which has been installed in the lower part of the reactor.
  • the oxidation of the mercaptans is carried out with the oxygen of the air, at a temperature of 100°C and atmospheric pressure, with air being supplied at a rate of 0.5 1/min. The time of oxidation is 4 minutes.
  • the mercaptan sulfur content in the starting and refined raw material is determined by method of potentiometric titration.
  • the demercaptanization of a model mixture of dodecylmercaptan in dodecane is carried out by a method similar to the one described for Example 1.
  • the composition of the catalyst and the results of the experiment are given in Table 1.
  • Example 2 Under the same conditions as those described in Example 1, in the presence of a heterogeneous catalyst which contained l mass % copper sulfate on a carbonaceous fabric containing 0.03 mass % of the oxides of metals indicated in Example 1, at a temperature of 220°C, over a period of 5 minutes, the demercaptanization of a diesel fraction having a mercaptan sulfur content equal to 0.02 mass % is carried out. Analysis of the de ercaptanized diesel fraction showed the residual content of mercaptan sulfur to be 0.0005 mass %. At the same time, the degree of oxidation of mercaptans in the diesel fraction constitutes 97.5%.
  • Example 2 Under the same conditions as those described in Example 1, in the presence of a known heterogeneous catalyst which contains 0.5 mass % of cobalt disulophthalocyanine on a carbonaceous fabric (without oxides of metals) and a 20% alkali solution, at a temperature of 220°C, over a period of 5 minutes, the demercaptanization of a diesel fraction with a mercaptan sulfur content equal to 0.02 mass % is carried out. Analysis of the demercaptanized diesel fraction showed the residual content of mercaptan sulfur to be 0.0075 mass %. At the same time, the degree of oxidation of mercaptans in the diesel fraction constitutes 62.5%.
  • the demercaptanization of a gasoline fraction having a mercaptan sulfur content of 0.077 mass % is carried out.
  • Analysis of the demercaptanized fraction indicated the residual content of mercaptan sulfur to be 0.0001 mass %.
  • the degree of oxidation of the mercaptans in the gasoline fraction constitutes 99.87%.
  • Example 2 Under the same conditions as those described in Example 1, in the presence of a known heterogeneous catalyst which contains 0.5 mass % of cobalt disulophthalocyanine on a carbonaceous fabric (without oxides of metals) and a 20% alkali solution, at a temperature of 80°C, over a period of time lasting 3 minutes, the demercaptanization of a gasoline fraction with a mercaptan sulfur content of 0.077 mass % is carried out.
  • a known heterogeneous catalyst which contains 0.5 mass % of cobalt disulophthalocyanine on a carbonaceous fabric (without oxides of metals) and a 20% alkali solution, at a temperature of 80°C, over a period of time lasting 3 minutes.
  • the degree of mercaptan oxidation in the gasoline fraction constitutes 63.6%.
  • the following example illustrates the preservation of high catalytic activity after prolonged use of the catalyst.
  • a kerosene fraction 120 + 240 originating from the petroleum refinery of Ryazan, having a content of mercaptan sulfur of 0.0082% mass %, is subjected to demercaptanization over a period of 10 minutes.
  • the purified kerosene is drained off, and a fresh portion of kerosene is poured into the reactor and subjected to oxidation. The process is repeated for several tens of cycles.
  • the demercaptanization of a kerosene fraction is carried out in the presence of a known catalyst. The results of the experiment are given in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La démercaptanisation de produits de la distillation du pétrole peut être réalisée par oxydation des mercaptans contenus dans ces produits à l'aide de l'oxygène de l'air, à une température comprise entre environ 80° et environ 220 °C, en présence d'environ 0,01 à environ 10 % du volume d'un sel de cuivre, fer, nickel ou cobalt soluble dans l'eau, sur un matériau carboné fibreux se présentant sous la forme d'un tissu non tissé, feutre, corde ou cordon toronné, utilisé comme catalyseur hétérogène. Le matériau carboné fibreux utilisé dans le procédé contient des oxydes de calcium, magnésium, cuivre, manganèse, fer, zinc et aluminium dans une quantité représentant jusqu'à environ 0,03 % du volume.
PCT/US1995/012339 1994-09-27 1995-09-26 Procedes destines a la demercaptanisation de produits de la distillation du petrole WO1996009891A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
MX9702145A MX9702145A (es) 1994-09-27 1995-09-26 Un metodo para la desmercaptanizacion de destilados del petroleo.
AU36861/95A AU3686195A (en) 1994-09-27 1995-09-26 A method for the demercaptanization of petroleum distillates
EP95934553A EP0783369A4 (fr) 1994-09-27 1995-09-26 Procedes destines a la demercaptanisation de produits de la distillation du petrole
NO971379A NO971379D0 (no) 1994-09-27 1997-03-24 Fremgangsmåte for demerkaptanisering av petroleumsdestillater

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/313,635 US5741415A (en) 1994-09-27 1994-09-27 Method for the demercaptanization of petroleum distillates
US08/313,635 1994-09-27
RU940392/38 1994-10-18
RU94039238A RU2076892C1 (ru) 1994-10-18 1994-10-18 Способ демеркаптанизации нефтяных дистиллятов

Publications (1)

Publication Number Publication Date
WO1996009891A1 true WO1996009891A1 (fr) 1996-04-04

Family

ID=26653803

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/012339 WO1996009891A1 (fr) 1994-09-27 1995-09-26 Procedes destines a la demercaptanisation de produits de la distillation du petrole

Country Status (7)

Country Link
EP (1) EP0783369A4 (fr)
CN (1) CN1071136C (fr)
AU (1) AU3686195A (fr)
CA (1) CA2199373A1 (fr)
MX (1) MX9702145A (fr)
NO (1) NO971379D0 (fr)
WO (1) WO1996009891A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005116169A1 (fr) * 2004-05-31 2005-12-08 Agency For Science, Technology And Research Nouveau procede permettant d'oter du soufre de carburants
US8016999B2 (en) 2004-05-31 2011-09-13 Agency For Science, Technology And Research Process for removing sulfur from fuels

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1067709C (zh) * 1998-10-23 2001-06-27 中国石化广州石油化工总厂 催化裂化汽油脱硫醇的方法
CN1320958C (zh) * 2005-05-30 2007-06-13 北京三聚环保新材料有限公司 双效催化剂及其制造方法
US9068128B2 (en) * 2011-10-18 2015-06-30 Baker Hughes Incorporated Method for reducing hydrogen sulfide evolution from asphalt and heavy fuel oils

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029201A (en) * 1959-12-28 1962-04-10 Universal Oil Prod Co Water treatment
US4028269A (en) * 1975-08-21 1977-06-07 Uop Inc. Process for the preparation of a solid bed catalyst system
US4364843A (en) * 1979-11-28 1982-12-21 Uop Inc. Catalytic composite, method of manufacture, and process for use

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4672047A (en) * 1984-03-08 1987-06-09 Travis Chandler Mercaptan oxidation catalyst
FR2601263B1 (fr) * 1986-07-11 1988-11-25 Total France Nouveau produit composite catalytique pour l'oxydation des mercaptans et son utilisation pour l'adoucissement des coupes petrolieres.
JPS63283750A (ja) * 1987-05-14 1988-11-21 Asahi Chem Ind Co Ltd 炭素繊維を担体とする触媒
JPH05184940A (ja) * 1992-01-14 1993-07-27 Nippon Steel Corp 窒素酸化物除去用触媒、除去方法及び装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029201A (en) * 1959-12-28 1962-04-10 Universal Oil Prod Co Water treatment
US4028269A (en) * 1975-08-21 1977-06-07 Uop Inc. Process for the preparation of a solid bed catalyst system
US4364843A (en) * 1979-11-28 1982-12-21 Uop Inc. Catalytic composite, method of manufacture, and process for use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0783369A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005116169A1 (fr) * 2004-05-31 2005-12-08 Agency For Science, Technology And Research Nouveau procede permettant d'oter du soufre de carburants
US8016999B2 (en) 2004-05-31 2011-09-13 Agency For Science, Technology And Research Process for removing sulfur from fuels

Also Published As

Publication number Publication date
AU3686195A (en) 1996-04-19
CA2199373A1 (fr) 1996-04-04
EP0783369A4 (fr) 1998-12-09
CN1155853A (zh) 1997-07-30
NO971379L (no) 1997-03-24
EP0783369A1 (fr) 1997-07-16
MX9702145A (es) 1997-06-28
NO971379D0 (no) 1997-03-24
CN1071136C (zh) 2001-09-19

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