EP0701595B1 - Elimination de composes soufres d' hydrocarbures contenant en majorite des composes insatures reactifs - Google Patents

Elimination de composes soufres d' hydrocarbures contenant en majorite des composes insatures reactifs Download PDF

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Publication number
EP0701595B1
EP0701595B1 EP94919268A EP94919268A EP0701595B1 EP 0701595 B1 EP0701595 B1 EP 0701595B1 EP 94919268 A EP94919268 A EP 94919268A EP 94919268 A EP94919268 A EP 94919268A EP 0701595 B1 EP0701595 B1 EP 0701595B1
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EP
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Prior art keywords
sulfur
metal oxide
contacting
unsaturates
reactive
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Expired - Lifetime
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EP94919268A
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German (de)
English (en)
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EP0701595A1 (fr
Inventor
John Di-Yi Ou
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03

Definitions

  • This invention relates to processes for removal of sulfur from hydrocarbon streams, and more particularly to removal of elemental sulfur and mercaptans (thiols) from hydrocarbon streams containing reactive unsaturates, using metals or compounds of metals from Groups IB, IIB and IIIA of the Periodic Chart of Elements (as denoted in the Merck Index).
  • This invention provides a process in which sulfur and mercaptans in hydrocarbon streams comprising reactive unsaturates are removed by contacting the hydrocarbon stream at mild temperatures with a hydrogen reduced metal oxide, such as copper, zinc and/or aluminum oxide, without the undesirable byproduct reaction of oligomerization or polymerization of the reactive unsaturates.
  • a hydrogen reduced metal oxide such as copper, zinc and/or aluminum oxide
  • sulfur and mercaptan removal technique is especially useful in the petrochemical industry where the hydrocarbon streams often contain very high levels of reactive unsaturates and is desired to reduce sulfur levels to very low levels to meet product quality requirements.
  • Elemental sulfur contaminants are difficult to remove. Mercaptan contaminants are very reactive and are often dimerized into disulfides when one tries to remove them. See, e.g. US-A-5,169,516. The resulting disulfides remain in the hydrocarbon stream, failing to achieve the goal of sulfur removal. The problem is even more difficult to solve if the hydrocarbon stream contains reactive unsaturates such as acetylenes, diolefins, olefins or aromatics.
  • Metal oxides and metals including those of Groups IB, IIB and IIIA, have been used in processes seeking to remove sulfur and sulfur containing compounds from hydrocarbons.
  • Metal oxides of copper (Group IB) and zinc (Group IIB) have long been used to remove hydrogen sulfide (e.g. ZnO + H 2 S ⁇ ZnS + H 2 O). See, for example, US-A-2,959,538; US-A-3,660,276; US-A-4,314,902; US-A-4,978,439; US-A-5,106,484; US-A-5,130,109; and US-A-5,157,201.
  • Metallic copper or zinc has been used in certain circumstances, normally involving elevated temperatures, in sulfur and sulfur compound removal.
  • US-A-2,768,932 contacting a hydrofixed, sulfur-containing petroleum distillate with finely divided metallic copper, copper alloys and copper oxides at elevated temperatures up to about 350° C
  • US-A-2,897,142 contacting a hydrodesulfurized petroleum distillate boiling in the range 149° C - 204° C [300° F to 400° F] with free copper or silver in the absence of hydrogen
  • US-A-3,945,914 contacting an oxidized sulfur-containing hydrocarbon material with copper or zinc at a temperature from 260° C to 732° C [500°F to 1350°F]
  • US-A-4,113,606 contacting a refined hydrocarbon feed with particulate copper, iron or zinc or compounds thereof or composites of them and refractory oxides of Groups II to IV metals supported in a binder of a refractory material and having a surface area of 2 to 700
  • Conditions that include elevated temperatures are unsuitable for removal of sulfur and mercaptans from hydrocarbon streams containing reactive unsaturates because at elevated temperatures, the reactive unsaturates tend to oligomerize and polymerize, especially the very labile alkyne and diolefin components such as acetylene and butadiene.
  • US-A-4,204,947 teaches a method to remove only thiol (mercaptan) and hydrogen sulfide (column 2, lines 49-56) with the limitation that at least 0.4 ppm of the total sulfur impurity must be thiol. Removal of elemental sulfur is not addressed.
  • this patent utilizes high operating temperatures.
  • the operating temperature for contacting the oil feedstream with the copper is from 120° C to 400° C (column 1, line 66). At these temperatures, the reactive unsaturates in the hydrocarbon feedstream will polymerize. This patent does not address sulfur removal for a hydrocarbon stream containing a major portion of reactive unsaturates.
  • the feed contained less than 15% olefins which are unsaturates.
  • the olefins as unsaturates, are not reactive.
  • Less than 1% of the total olefins present in the gasoline contains olefins with a carbon number of 4 or less as most of the olefins in a typical gasoline feed have a carbon number greater than 5.
  • the olefins are sufficiently diluted and hence, non-reactive.
  • EP-A-0 527 000 discloses a process of removing elemental sulfur from gaseous or liquid organic material by contact with an absorbent material comprising metallic copper, produced by reduction of a reducible copper compound.
  • Suitable organic materials are disclosed as carbon tetrachloride and hydrocarbons such as benzene and petroleum.
  • a process for producing a hydrocarbon stream having reduced sulfur contamination levels from a hydrocarbon stream comprising reactive unsaturates and contaminant sulfur which comprises contacting the stream with a scavenger comprising a Group IB, IIB or IIIA metal obtained by hydrogen reduction of a metal oxide, characterised in that the contaminant sulfur is initially present as elemental sulfur or mercaptan and the stream comprises greater than 70 wt% of the reactive unsaturates, and in that the contacting is performed under temperature conditions which avoid substantial oligomerisation or polymerisation of the reactive unsaturates.
  • the temperature of contacting is not greater than 35° C. In a more preferred embodiment, the temperature is from 15° C to 30° C, and most preferably 20° C to 25° C.
  • the sulfur contaminant level in the hydrocarbon stream may be less than 500 wppm sulfur.
  • the contacting is performed under conditions to reduce the sulfur level by at least 95% , and preferably at least 99.5%.
  • the hydrocarbon stream comprises greater than 80 wt%, of the reactive unsaturates.
  • the metal oxide is carried as a porous support.
  • the hydrogen-reduced metal oxide is produced by contacting the supported metal oxide with hydrogen under reducing conditions effective to reduce the metal oxide to elemental metal reactive with elemental sulfur and mercaptans to form sulfides of the metal.
  • the metal oxide is contacted first with a gas consisting of a first predetermined minor amount of hydrogen gas and a major amount of an inert gas at a first temperature in the range from 100° C to 250° C at a pressure in the range from 0.35 to 6.9 MPag (50 to 1000 psig) for a first predetermined period of time effective to reduce a major proportion of the metal oxide to elemental metal, after which the metal oxide is contacted next with a gas consisting of a higher predetermined minor amount of hydrogen gas and a major amount of an inert gas at a higher temperature in the range from 175° C to 300° C at a pressure in the range from 0.35 to 6.9 MPag (50 to 1000 psig) for a second predetermined period of time effective to reduce a major remaining proportion of the metal oxide to elemental metal.
  • the metal oxide is an oxide of copper, zinc, aluminum or mixtures thereof.
  • free (elemental) sulfur and mercaptans are removed, preferably to a level less than 0.1 ppm, from a hydrocarbon stream containing reactive unsaturates such as aromatics, olefins, diolefins or acetylenes.
  • the method of this invention is especially suited to removal of sulfur and mercaptans from a hydrocarbon stream containing a major proportion of a reactive diolefin, for example, 1,4-butadiene, or from a fuel rich in aromatics, such as aviation gasoline.
  • mercaptan and “thiol” refer to compounds of the general formula R-SH wherein “R” means an alkyl group, normally one of from one to ten carbon atoms, and “SH” means a sulfhydryl group, sometimes called a mercapto group.
  • the sulfur contaminant level in the hydrocarbon stream is less than 500 wppm sulfur, preferably less than 400 wppm sulfur, and most preferably less than 100 wppm.
  • a hydrogen-reduced metal oxide selected from oxides of Group IB, IIB, and IIIA and mixtures thereof is employed. Especially suitable are reduced metal oxides of copper, zinc and aluminum.
  • the metal oxides are reduced by contacting them with a gas consisting of a major volume percentage of an inert gas and a minor volume percentage of hydrogen gas at a temperature in the range from 100° C to 300° C at a pressure in the range from 0.35 to 6.9 MPag (50 to 1000 psig).
  • the metal oxide reduction is accomplished in at least a two step reduction to control heats of reaction and reduce the oxides efficiently.
  • the metal oxide(s) is contacted first with a gas consisting of a first predetermined minor amount of hydrogen gas and a major amount of an inert gas at a first temperature in the range from 100° C to 250° C at a pressure in the range from 0.35 to 6.9 MPag (50 to 1000 psig) for a first predetermined period of time effective to reduce a major proportion of the metal oxide to elemental metal, after which the metal oxide in mixture with already reduced metal oxide is contacted next with a gas consisting of a higher predetermined minor amount of hydrogen gas and a major amount of an inert gas at a higher temperature in the range from 175° C to 300° C at a pressure in the range from 0.35 to 6.9 MPag (50 to 1000 psig) for a second predetermined period of time effective to reduce a major remaining proportion of the metal oxide to elemental metal.
  • mixed metal oxides of copper oxide, zinc oxide and alumina powder are exposed first to an atmosphere of about 99% nitrogen and 1% hydrogen at a temperature of about 160° C and a pressure of 1.400 MPag (200 psig) for about 24 hours, then to an atmosphere of about 98% nitrogen and 2% hydrogen at a temperature of about 200° C and a pressure of about 1.400 MPag (200 psig) for about 24 hours.
  • the hydrogen-reduced metal oxide is produced by contacting the metal oxide with hydrogen under reducing conditions effective to reduce the metal oxide to elemental metal reactive with elemental sulfur and mercaptans to form sulfides of the metal.
  • the removal mechanism is believed to involve the formation of metal sulfide.
  • the reduction of metal oxides provides fresh metal surface which is much more reactive toward sulfur than plain metal, which is usually protected by a thin layer of surface oxides.
  • Another advantage of the reduced metal oxides is their porosity. Metal oxide could be made porous via the addition of a porous binder such as alumina, silica, and clay. The porosity increases the scavengers' surface area which improves the removal efficiency.
  • the resulting scavenger has a specific surface area of from 50 to 750 m 2 /g, preferably 50 to 600 m 2 /g, and most preferably 50 to 500 m 2 /g.
  • the reduced metal oxide has a specific surface area sufficient for reducing the sulfur and mercaptans in the hydrocarbon stream to a level less than 0.1 ppm.
  • elemental sulfur and mercaptans in a hydrocarbon stream containing reactive unsaturates are removed by contacting the stream with a hydrogen-reduced metal oxide (suitably prepared as just described) under mild sulfur and mercaptan removing conditions, preferably at ambient temperature, and preferably for a time sufficient to reduce the sulfur or mercaptan content of the hydrocarbon stream to less than 0.1 ppm.
  • a hydrogen-reduced metal oxide suitable as just described
  • the temperature of contacting must be above the freezing point of the hydrocarbon stream and can be as low as 0° C, but not greater than 35° C, preferably from 15° C to 30° C, and most preferably 20° C to 25° C. It is important that the temperature of contacting for sulfur removal is done below the temperature at which oligomerization or polymerization of the reactive unsaturates occurs.
  • the contacting is performed under conditions which reduce the contaminant sulfur level to the desired level, while oligomerizing or polymerizing less than 0.01 wt% of the reactive unsaturates in the hydrocarbon stream.
  • the contacting is performed under conditions to reduce the sulfur level by at least 95%, preferably at least 99%, and most preferably at least 99.5%.
  • This example illustrates the preparation of the sulfur and mercaptan removing scavengers (reduced metal oxides) which may be used in the process of this invention.
  • a mixed metal oxides containing 33% copper oxide, 33% zinc oxide, and 34% alumina in the form of pellets (Katalco Corp, Houston, Texas) were ground to 0.1425 cm / 0.025 cm (40/60 mesh) particles and reduced first in an atmosphere of 99% nitrogen/1% hydrogen by volume, at 163° C (325° F) and 1.38 MPag (200 psig) for 24 hours, followed by an atmosphere of 98% nitrogen/2% hydrogen at 204° C (400° F) and 1.38 MPag (200 psig) for another 24 hours.
  • the reduced metal oxides so produced were used in the following Examples.
  • This example illustrates the effectiveness of the scavenger produced in Example 1 in removing elemental sulfur from aviation gasoline.
  • the aviation gasoline used in this test was of typical aviation grade and contained 3.3 ppm by weight of elemental sulfur.
  • Five grams of the reduced metal oxides produced in Example 1 were mixed with 50 cc of the aviation gasoline in a sealed bottle at ambient temperature (22° C) and atmospheric pressure for two hours. The liquid phase from the bottle was then sampled and analyzed by polarograph, which showed that the elemental sulfur concentration was reduced from 3.3 ppm to less than 0.1 ppm.
  • caustic-treated lime absorbs the acidic mercaptans through an acid-base reaction which removes them from hydrocarbons.
  • the problem is that basic materials catalyze the dimerization of mercaptans.
  • a caustic-treated lime (“Sofnolime” from Molecular Products Ltd., Houston, Texas) was used to treat a butadiene stream comprising greater than 99.9 wt.% butadiene and containing 45 ppm by weight methyl mercaptan.
  • This example illustrates the effectiveness of the reduced metal oxide scavengers from Example 1 in removing methyl mercaptan from butadiene as opposed to converting the mercaptan to a disulfide still resident in the butadiene.
  • the reduced metal oxide scavenger was loaded into a 0.635 x 7.62 cm (0.25 x 3 inch) stainless steel column.
  • a butadiene stream with a purity of greater than 99.9 wt.% butadiene and containing 45 ppm by weight of methyl mercaptan was pumped through the column at a liquid hourly space velocity of 1 hr -1 at ambient temperature and 0.41 MPag (60 psig).
  • Column effluent was sampled periodically and analyzed for sulfur.

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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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Claims (11)

  1. Procédé pour la production d'un courant d'hydrocarbures ayant des taux réduits de contamination par le soufre à partir d'un courant d'hydrocarbures contenant des composés insaturés réactifs et du soufre contaminant, qui comprend la mise en contact du courant avec un accepteur comprenant un métal du Groupe IB, IIB ou IIIA obtenu en réduisant par l'hydrogène un oxyde métallique, caractérisé en ce que le soufre contaminant est présent initialement sous forme de soufre élémentaire ou de mercaptan et le courant contient plus de 70 % en poids de composés insaturés, et en ce que la mise en contact est effectuée dans des conditions de température qui évitent une oligomérisation ou polymérisation notable des composés insaturés réactifs.
  2. Procédé suivant la revendication 1, caractérisé en ce que le courant contient plus de 80 % en poids de composés insaturés.
  3. Procédé suivant la revendication 1 ou 2, dans lequel la température de la mise en contact est non supérieure à 35°C.
  4. Procédé suivant la revendication 3, dans lequel la température est comprise dans l'intervalle de 15 à 30°C, de préférence de 20 à 25°C.
  5. Procédé suivant l'une quelconque des revendications précédentes, dans lequel la teneur en soufre contaminant dans le courant d'hydrocarbures est inférieure à 500 ppmp de soufre.
  6. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'oxyde métallique est porté par un liant poreux.
  7. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'oxyde métallique est un oxyde de cuivre, de zinc ou d'aluminium ou un mélange de deux ou plus de deux de ces oxydes.
  8. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'oxyde métallique est réduit par l'hydrogène
    (a) dans une première étape, en mettant en contact l'oxyde métallique avec un gaz comprenant un gaz inerte et une première petite proportion d'hydrogène gazeux ; et
    (b) dans une seconde étape, en mettant en contact l'oxyde métallique traité de l'étape (a) avec un gaz comprenant un gaz inerte et une seconde petite proportion d'hydrogène gazeux, qui est supérieure à la première petite proportion, pour réduire l'oxyde métallique restant en métal élémentaire.
  9. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'accepteur a une surface spécifique comprise dans l'intervalle de 50 à 750 m2/g.
  10. Procédé suivant l'une quelconque des revendications précédentes, dans lequel les composés insaturés réactifs comprennent une oléfine, un diène ou un acétylène.
  11. Procédé suivant la revendication 10, dans lequel le diène consiste en 1,3-butadiène.
EP94919268A 1993-05-28 1994-05-27 Elimination de composes soufres d' hydrocarbures contenant en majorite des composes insatures reactifs Expired - Lifetime EP0701595B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US6894293A 1993-05-28 1993-05-28
US68942 1993-05-28
PCT/US1994/005994 WO1994028089A1 (fr) 1993-05-28 1994-05-27 Elimination de soufre et de mercaptan de courants d'hydrocarbures contenant des insatures reactifs

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EP0701595A1 EP0701595A1 (fr) 1996-03-20
EP0701595B1 true EP0701595B1 (fr) 2000-12-27

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EP (1) EP0701595B1 (fr)
JP (1) JP3637569B2 (fr)
AU (1) AU679759B2 (fr)
CA (1) CA2163866C (fr)
DE (1) DE69426493T2 (fr)
ES (1) ES2154678T3 (fr)
SG (1) SG49007A1 (fr)
WO (1) WO1994028089A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6274533B1 (en) * 1999-12-14 2001-08-14 Phillips Petroleum Company Desulfurization process and novel bimetallic sorbent systems for same
JP4609961B2 (ja) * 2000-01-28 2011-01-12 Ｊｘ日鉱日石エネルギー株式会社 硫黄化合物の除去方法
DE102013225724A1 (de) * 2013-12-12 2015-06-18 Evonik Industries Ag Reinigung flüssiger Kohlenwasserstoffströme mittels kupferhaltiger Sorptionsmittel
SG10201604013RA (en) 2015-05-28 2016-12-29 Evonik Degussa Gmbh Hydrogen-assisted adsorption of sulphur compounds from olefin mixtures
FR3104459B1 (fr) * 2019-12-17 2022-07-01 Ifp Energies Now Masse de captation de mercaptans préparée par voie sels fondus

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB332910A (en) * 1929-02-26 1930-07-28 Stadtberger Huette Act Ges Improvements in or relating to the desulphurisation of liquid hydrocarbons
US1904381A (en) * 1929-11-11 1933-04-18 Universal Oil Prod Co Refining of hydrocarbon oils
GB9116907D0 (en) * 1991-08-06 1991-09-18 Ici Plc Sulphur removal process

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Publication number Publication date
EP0701595A1 (fr) 1996-03-20
CA2163866C (fr) 2005-03-01
CA2163866A1 (fr) 1994-12-08
JPH08511813A (ja) 1996-12-10
AU679759B2 (en) 1997-07-10
DE69426493T2 (de) 2001-08-09
ES2154678T3 (es) 2001-04-16
WO1994028089A1 (fr) 1994-12-08
JP3637569B2 (ja) 2005-04-13
DE69426493D1 (de) 2001-02-01
SG49007A1 (en) 1998-05-18
AU7046994A (en) 1994-12-20

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