US3485884A - Purification of aromatic hydrocarbons - Google Patents

Purification of aromatic hydrocarbons Download PDF

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Publication number
US3485884A
US3485884A US630305A US3485884DA US3485884A US 3485884 A US3485884 A US 3485884A US 630305 A US630305 A US 630305A US 3485884D A US3485884D A US 3485884DA US 3485884 A US3485884 A US 3485884A
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catalyst
nickel
fraction
range
clay
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US630305A
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English (en)
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John H Davis
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • 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
    • C10G29/04—Metals, or metals deposited on a carrier
    • 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
    • C10G29/28—Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • Aromatic hydrocarbons such as benzene and the like, contaminated with olefins and sulfur compounds, are purified by treating the aromatic hydrocarbons in sequence with a clay such as aluminum silicate at an elevated temperature within the range of about 400 to about 500 F., followed by distillation to recover an overhead fraction which is subjected to contact with a supported nickel or nickel sulfide catalyst at a temperature within the range from about 300 to about 450 F.
  • a clay such as aluminum silicate
  • the present invention is directed to the purification of aromatic hydrocarbons. More particularly, the invention is concerned with purification of aromatic hydrocarbons in a particular sequence of operations. In its more specific aspects, the invention is concerned with treatment of an olefin and sulfur contaminated aromatic hydrocarbon in a sequence of treating steps involving contact with clay, distillation, and contact of an overhead fraction from the distillation with a nickel or nickel sulfide catalyst.
  • the present invention may be briefly described as involving a processing sequence for aromatic hydrocarbons such as benzene and the like.
  • an aromatic hydrocarbon fraction contaminated with olefins and at least one sulfur compound is contacted with a clay such as aluminum silicate at a temperature within the range of 400 to 500 F.
  • This contacting operation is believed to cause alkylation of olefins with a portion of the aromatic hydrocarbons to form heavier products.
  • the aluminum silicate contacted aromatic hydrocarbons is then distilled overhead to recover a distilled fraction amounting to about 85 to about 97 per volume of the contacted fraction.
  • the distilled fraction is contacted with a supported nickel or nickel sulfide catalyst in the absence of hydrogen.
  • the nickel sufide catalyst contains from about 1 to about 3% ond contacting a substantially purified hydrocarbon which does not have to be distilled.
  • the feedstock of the present invention is an aromatic hydrocarbon fraction which is contaminated with a small amount of olefins and at least one sulfur compound.
  • the aromatic hydrocarbon fraction is preferably substantially benzene, but may also be toluene, Xylenes, any one of the xylenes, durene, and other tetra-methyl benzenes. Other aromatic hydrocarbons may also be suitably purified.
  • the olefinic hydrocarbons making up part of the impurities may boil in the range of the aromatic hydrocarbons.
  • the sulfur compounds may suitably include by way of illustration and not by way of limitation thiophene, hydrogen sulfide, disulfides and other organic sulfur compounds found in aromatic hydrocarbon fractions which may be of petroleum origin but not limited thereto.
  • the catalyst employed in the present invention is suitably a nickel supported catalyst or a nickel supported catalyst which contains from about 1% to about 3% by Weight of sulfur. Ordinarily the catalyst will contain from about 1% to about 2% by weight of sulfur.
  • the nickel sulfide may be Ni S
  • the catalyst may contain from about 20% to about nickel on a suitable support such as but not limited to kieselguhr and the like.
  • the nickel sulfide catalyst contains from about 1% to about 3% by weight of sulfur.
  • a preferred catalyst contains 58% by weight of nickel on kieselguhr and the fresh catalyst may be free of sulfide.
  • the clay employed in the first contacting operation may suitably be commercially available clays known to the trade as Filtrol clay and the like. These clays are predominantly aluminum silicate. Other catalysts such as Attapulgus clay and the like may be used.
  • the contacting operation with aluminum silicate may be conducted at temperatures within the range from about 400 to about 500 F., pressures within the range from about 400 to about 500 p.s.i.g., and space velocities within the range from about 0.5 to about 5.0 v./v./hour.
  • the second contacting operation of the distilled fraction may be conducted at a temperature within the range from about 300 to about 450 F., a pressure within the range from about 0 to about 750 p.s.i.g., and at a superficial mass velocity (SMV) in pounds per square foot per hour Within the range from about to about 4,000, and in the absence of hydrogen. Hydrogen must be excluded in the second contacting operation even when using a nickel sulfide catalyst to produce pure aromatic hydrocarbons.
  • SMV superficial mass velocity
  • FIGURE 1 is a flow diagram of a preferred mode
  • FIGURE 2 is a graph of data to illustrate the clay treatment of benzene to remove olefins
  • FIGURE 3 is a graph of data illustrating the removal of thiophene from benzene with a nickel catalyst.
  • numeral 11 designates a charge line by way of which a benzene-rich feed boiling within the range from about to about 500 F. and containing about 85 to 97% per volume of benzene is introduced into a clay treating zone 12 from a source not shown.
  • Clay treating zone 12 contains a body or bed of aluminum silicate clay. Conditions prevail in clay treating zone 12 to remove substantially olefins contaminating the aromatic hydrocarbon fraction by reaction with a portion of the aromatic hydrocarbon.
  • the contacted or treated product from zone 12 is discharged therefrom by line 13 which introduces the contacted product directly into a distillation zone 14 which is illustrated as a single distillation tower but which may comprise a plurality of distillation towers as may be desired.
  • Distillation zone 14 is provided with a heating means illustrated by steam coil 15 for adjusting of temperatures as may be required, and is provided with an overhead line 16 and a bottom line 17.
  • Heavy fractions, including alkylated reacted olefinic material, are discharged by line 17 for further treatment or recovery as may be desired.
  • Taken overhead by line 16 is a fraction comprising from about 85 to 97% by volume of the contacted fraction charged by line 13. This fraction contains sulfur compounds of a nature described before which must be removed to make an acceptable product.
  • sulfur compounds are removed by introducing the distilled overhead fraction by line 16 into a contacting zone 18 which contains a body or bed of nickel or nickel sulfide catalyst of the nature described before. Contacting is provided in zone 18 to remove the sulfur and to allow recovery by line 19 of a treated aromatic hydrocarbon fraction.
  • the aromatic hydrocarbon fraction such as benzene has a total sulfur content of approximately 0.5 part of a million, a thiophene content of 0.5 part of a million, and contains only a small quantity of olefins as indicated by Bromine Index of approximately 5.0.
  • This product, a finished benzene meeting the specifications and comprising 998+ percent by volume benzene, is obtainable in accordance with the present invention.
  • a benzenerich feedstock containing olefins as indicated by a Bromine Index of 133 is subjected to clay treating at a space velocity f 2 v./v./hour, a temperature of 450 F., and a pressure of 450 p.s.i.g.
  • the Bromine Index of the treated product is 22 and this product is distilled to obtain a 95% overhead fraction.
  • This 95% overhead product has a Bromine Index of less than 5.0.
  • the 95% overhead fraction is submitted to treatment with a nickel catalyst at a temperature of 350 F., 300 p.s.i.g., and a superficial mass velocity of 2,830 pounds per hour per square foot.
  • the sulfur content of the finished benzene is .24 part per million and the thiophene content is 0.33 part per million.
  • the same fraction and the same feedstock are supplied to clay treating under the same conditions, nickel treating under the same conditions with the same catalyst, and distilled to recover a 95 overhead product.
  • This product contains 35 parts per million of thiophene and 12 parts per million of sulfur.
  • FIGURE 2 wherein conditions are given for treatment of a benzene fraction containing olefins, it will be seen that the Bromine Index of the product rises sharply after about 7,000 barrels of feed per ton of clay. Also FIGURE 2 shows for the 0.95 overhead fraction a sharp break at 6,700 barrels per ton of clay, which indicates that the clay is then no longer suitable for removal of olefins and must be regenerated under the following conditions: 8501,000 R, free 0 containing gas, until removal of C by burning i esSentially complete as measured by absence of CO in exit gas at end of regeneration. For example, regeneration is essentially complete when the carbon content on the clay is about 0.1 to about 0.8% by weight.
  • This may be accomplished in accordance with the present invention by contacting the catalyst with hydrogen at a temperature within the range from about 700 to about 950 F., at a pressure within the range from about to about 750 p.s.i.g., and at a hydrogen feed rate within the range from about 3 to about 10 standard cubic feet per pound of spent catalyst per hour until a sufficient amount of hydrogen sulfide has been removed from c spent catalyst to reduce the sulfide content to an amount within the range from about 1% to about 3% of sulfur on the catalyst. Thereafter the regenerated catalyst may be used in contacting additional amounts of the overhead fraction.
  • Fresh nickel catalysts may be used for long periods of time. Sulfided catalysts ordinarily may be used for substantial lengths of time also without regenera'ion.
  • the present invention is quite important and useful in that heretofore it was not known that a sequence of operations such as described and claimed here was necessary to provide a substantially purified aromatic hydrocarbon fraction. It was also not realized that by interposing a distillation operation between a clay treating and a particular nickel or nickel sulfide treating operation, a purified aromatic hydrocarbon could be obtained which would not require subsequent distillation.
  • the supported nickel catalyst is a nickel sulfide catalyst containing from about 1% to about 3% by weight of sulfur a5 Nl3S2,
  • a method in accordance with claim 6 in which said aroma-tic hydrocarbon fraction is contacted with said aluminum silicate until said aluminum silicate becomes sufiiciently spent that olefins appear in the aluminum silicate contacted product and then said spent aluminum silicate is regenerated by burning at a temperature within the range of 850 to 1,000 F. in the presence of a free oxygen containing gas to reduce the carbon content on the catalyst to about 0.10.8% by weight.
  • a method for treating an aromatic hydrocarbon fraction which comprises the steps in the order named of:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US630305A 1967-04-12 1967-04-12 Purification of aromatic hydrocarbons Expired - Lifetime US3485884A (en)

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US63030567A 1967-04-12 1967-04-12

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US (1) US3485884A (en:Method)
JP (1) JPS5016345B1 (en:Method)
BE (1) BE713540A (en:Method)
FR (1) FR1560127A (en:Method)
GB (1) GB1162945A (en:Method)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4336130A (en) * 1980-11-28 1982-06-22 Union Oil Company Of California Desulfurization of hydrocarbons
US4419224A (en) * 1980-11-28 1983-12-06 Union Oil Company Of California Desulfurization of hydrocarbons
US20030106841A1 (en) * 2001-08-16 2003-06-12 China Petroleum & Chemical Corporation Process for adsorptive desulfurization of light oil distillates
US20070004956A1 (en) * 2002-12-19 2007-01-04 Abdelghani Mohammed S Purification process of aromatics
CN106242937A (zh) * 2016-08-06 2016-12-21 江苏华伦化工有限公司 一种均四甲苯的提纯方法
EP3335787A1 (en) 2016-12-13 2018-06-20 Scg Chemicals Co. Ltd. Process for removing alkene and/or alkyne from a hydrocarbon feedstock

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19512137A1 (de) * 1995-03-31 1996-10-02 Sued Chemie Ag Verwendung von natursauren Smektiten zur Entfernung von Olefinen aus Aromaten oder Aromatengemischen
DE19512134A1 (de) * 1995-03-31 1996-10-02 Sued Chemie Ag Katalysator zur Entfernung von Olefinen aus Aromaten oder Aromatengemischen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2951034A (en) * 1957-04-09 1960-08-30 Sun Oil Co Desulfurization of hydrocarbons with a mixture of a group viii metal and group viii metal oxide or sulfide
US3251897A (en) * 1962-12-20 1966-05-17 Socony Mobil Oil Co Inc Alkylation of aromatic compounds in the presence of an alumino-silicate catalyst
US3367862A (en) * 1965-10-18 1968-02-06 Exxon Research Engineering Co Process for desulfurization by hydrolysis with metals on charcoal base catalysts

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2951034A (en) * 1957-04-09 1960-08-30 Sun Oil Co Desulfurization of hydrocarbons with a mixture of a group viii metal and group viii metal oxide or sulfide
US3251897A (en) * 1962-12-20 1966-05-17 Socony Mobil Oil Co Inc Alkylation of aromatic compounds in the presence of an alumino-silicate catalyst
US3367862A (en) * 1965-10-18 1968-02-06 Exxon Research Engineering Co Process for desulfurization by hydrolysis with metals on charcoal base catalysts

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4336130A (en) * 1980-11-28 1982-06-22 Union Oil Company Of California Desulfurization of hydrocarbons
US4419224A (en) * 1980-11-28 1983-12-06 Union Oil Company Of California Desulfurization of hydrocarbons
US20030106841A1 (en) * 2001-08-16 2003-06-12 China Petroleum & Chemical Corporation Process for adsorptive desulfurization of light oil distillates
US6875340B2 (en) 2001-08-16 2005-04-05 China Petroleum & Chemical Corporation Process for adsorptive desulfurization of light oil distillates
US20070004956A1 (en) * 2002-12-19 2007-01-04 Abdelghani Mohammed S Purification process of aromatics
US7420095B2 (en) 2002-12-19 2008-09-02 Saudi Basic Industries Corporation Purification process of aromatics
CN106242937A (zh) * 2016-08-06 2016-12-21 江苏华伦化工有限公司 一种均四甲苯的提纯方法
CN106242937B (zh) * 2016-08-06 2019-02-26 江苏华伦化工有限公司 一种均四甲苯的提纯方法
EP3335787A1 (en) 2016-12-13 2018-06-20 Scg Chemicals Co. Ltd. Process for removing alkene and/or alkyne from a hydrocarbon feedstock
WO2018108461A1 (en) 2016-12-13 2018-06-21 Scg Chemicals Co., Ltd. Process for removing alkene and/or alkyne from a hydrocarbon feedstock comprising an aromatic compound

Also Published As

Publication number Publication date
BE713540A (en:Method) 1968-10-11
JPS5016345B1 (en:Method) 1975-06-12
DE1770085B2 (de) 1976-05-06
DE1770085A1 (de) 1971-09-16
FR1560127A (en:Method) 1969-03-14
GB1162945A (en) 1969-09-04

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