US3177262A - Production of naphthalene - Google Patents

Production of naphthalene Download PDF

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Publication number
US3177262A
US3177262A US25531A US2553160A US3177262A US 3177262 A US3177262 A US 3177262A US 25531 A US25531 A US 25531A US 2553160 A US2553160 A US 2553160A US 3177262 A US3177262 A US 3177262A
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United States
Prior art keywords
hydrogen
naphthalene
mainly
aromatic hydrocarbons
temperature
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Expired - Lifetime
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US25531A
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English (en)
Inventor
James R Calkins
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Sunoco Inc
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Sun Oil Co
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Publication date
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Priority to US25531A priority Critical patent/US3177262A/en
Priority to DE1443096A priority patent/DE1443096C3/de
Priority to LU40049D priority patent/LU40049A1/xx
Application granted granted Critical
Publication of US3177262A publication Critical patent/US3177262A/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30Aromatics

Definitions

  • This invention relates to the preparation of naphthalene from hydrocarbon stocks. It particularly relates to the method of producing naphthalene from petroleum fractions containing alkylnaphthalenes in admixture with other aromatic and/or non-aromatic hydrocarbons.
  • Petroleum fractions which boil within the range of 400-550 F. generally contain substantial amounts of alkylnaphthalenes, such as mono-, di-, and .tri-methylnaphthalenes and in smaller quantity, the ethylnaphthw ,lenes.
  • Recycle fractions which are formed in the cracking of petroleum stocks and which include this boiling range, often contain major proportions of aromatic hydrocarbons that are mainly alkylnaphthalenes. Such fractions typically may have aromatic contents varying within the range of 25-97% but usually contain between 50% and 95% aromatics depending upon the particular operation in which the petroleum fractions are produced.
  • hydrocarbon charge stocks are obtained in both catalytic and thermal cracking processes and in operations in which combinations of catalytic and thermal cracking steps are utilized.
  • Stock-s having high alkylnaphthalene contents can also be obtained by extracting straight run petroleum fractions of appropriate boiling ranges, such as kerosene, or catalytic fractions such as catalytic gas oil, with solvents, such as furfural or sulfur dioxide, or by selective adsorption with silica gel.
  • These aromatic concentrates may contain 100% aromatic hydrocarbons.
  • the present invention is directed to the use of hydrothe preparation of naphthalene in high concentration.
  • the charge stock used in practicing the invention is a hydrocarbon fraction boiling substantially Within the range of 400-550" F. but more preferably between 450-- 550 F. and composed by weight of-35l00% aromatic hydrocarbons including substituted condensed ring aro matics such as alkylnaphth-alenes and from 65-0% nonaromatic hydrocarbons.
  • This charge material also commonly contains substantial amounts of sulfur compounds that normally occur Within this boiling range.
  • Charge stocks most typically employed have an aromatic content within the range of 50-95% by weight. In general, the substituted condensed ring aromatics constitute about 20% to 80% of the total aromatic hydrocarbons present in the charge stock.
  • the present invention provides a method of making naphthalene from change stocks as specified above wherein the temperature rise due to the hydrocracking of the non-aromatics and the dealkylation of the aromatics is minimized and controlled.
  • the charge material is first subjected to a conditioning treatment in the presence of a desulfurization catalyst and added hydrogen under conditions including a temperature within the range of 800- 980 F., at which the non-aromatic components are converted to lower boiling compounds at a slow enough rate to prevent excessive temperature rise. Under these conditions, substantial conversion of the alkylnaphthalenes into naphthalene does not occur.
  • a minor proportion of the aromatic hydrocarbons are at least partially hydrogenated.
  • the conditioned reaction product from this first step is then subjected in a second step to a temperature above 1000 .F., whereby deallrylation of the alkylnaphthalenes and dehydrogenation of the minor proportion of the aromatic hydrocarbons occurs.
  • the temperature in this second stage reaction does not rise excessively. Furthermore, those aromatic hydrocarbons which were hydrogenated in the first step are dehydrogenated in the second step thereby additionally aiding in the temperature control of the second step due to the endothermic nature of the dehydrogenation reaction.
  • the final reaction product is fractionated to obtain naphthalene in high concentration.
  • the present invention is a two-stage process for making naphthalene from a hydrocarbon charge stock wherewith by removing the non-aromatics in the first stage and'by regulating the temperature in the first stage to vary the degree of aromatic saturation, it is possible to control the temperature rise during the second stage. Further, better temperature control is realized in the first stage with charge stocks containing non-aromatics since the exothermic addition of hydrogen to the aromatic hydrocarbons and to the cleaved carbon-carbon bonds tends to counterbalance the endothermic cracking of the nonaromatic hydrocarbons.
  • the exothermic addition of hydrogen to the aromatic hydrocarbons provides additional heat so that the desired first stage temperature can be obtain-ed Without excessive external heat requirements.
  • the endothermic dehydrogenation of the hydrogenated aromatics from the first stage reaction at least partially counterbalances the exothermic dealkylation reaction of the alkylnaphthalenes thereby providing better temperature control.
  • hydrocracking primarily defined as the cumulative result of cleaving, i.e. cracking, carbon carbon bonds and of adding hydrogen to the cleaved bonds.
  • the overall hydrocracking reaction is generally exother- 1111C.
  • dealkylation is primarily defined: as the cumulative result of removing the alkyl side chains from the substituted condensed ring aromatic hydrocarbons and of adding hydrogen to form the 'dealkylated condensed
  • the overall dealkylation reaction is generally exothermic.
  • hydrocracking will also include the hydrogenation of a minor proportion of the aromatic hydrocarbonsand the term dealkylation will include the dehydrogenating of those aromatics hydrogenated during hydrocracking.
  • the critical feature of the first stage reaction is to condition the first stage product by balancing hydrogenation, cracking, and desulfurization in such a manner that example, if the dicyclic aromatic is considered to be naphthalene, then the equilibrium relationship for-the reaction:
  • naphthalene-i-Z hydrogenetetrahydronapthalene at 300 p.s.i.g. was found to be as follows.
  • the hydrogen consumption under these conditions should be between 65-500 s.c.f. per barrel of liquid feed per percent sulfur in the feed and preferably between 200 and 400 -s.c.f./barrel. The.
  • a still further manner practicing the invention involves catalyticallyconditioning the charge under the conditions set forth for the embodiment first mentioned above and then catalytically dealkylating the alkylnaphthalenes in the presence of a desulfurizationcatalyst.
  • the presence of the catalyst in the latter. step facilitates the dealkylation reaction and in some-cases permits'it to be carried out at a lower temperature than that required for thermal dealkylation.
  • the oatalyst also effects the conversion of any remaining sulfur into hydrogen sulfide and hence permits the preparation of naphthalene having negligible sulfur content.
  • the conditions for the catalytic dealkylation step'in include a pressure of 150-1000 p.s.i.g.
  • the first conditioning step is carried out in the-presence of a catalyst and added hydrogen while the second step involves a thermal treatment to effect dealkylation of the alky- V of the aromatic hydrocarbons is to be obtained.
  • the total reaction product from the first conditioning step can be charged to the second step. However, it is-preferable to subject the first reaction product.
  • distillation to distillation to obtain a fraction boiling mainly in the range of 400-550 -F. for use as charge to the second step.
  • This distillation removes material formed in the first hydrocracking reaction which boilsbelow .400 F. and which will not contributeto the formation of naph thalene inthe second reaction stage... It also removes a minor amount of polymeric material that boils above 550 P. which would tend to contribute to coke formation if allowed to remain in the charge to thesecondstep.
  • coking occurs after a time to such extent that coke removal from the reaction zone is required. This can 'be done in conventional manner by passing an oxygen-containing gas through the reaction zone to burn out the coke. In the steps inwhich a desulfurizing catalyst is used,.burning of coke from the catalyst restores its catalytic activity.
  • a chargestock was prepared by distilling a gas oil fraction obtained by a combination or, catalytic and thermal cracking operations.
  • the charge stock had a boiling range of 460-500 :F., an aromatic hydrocarbon content of 78% by weight, including about 1% naphthalene, and a sulfur content of.0.25 Hydrogen was mixed with the charge in a mole ratio of :1 and the mixture was heated to 900 F. and fed in vapor phase into a catalytic hydrocracking zone at a pressure of 500 p.s.i.g.
  • Thecatalyst was a cobalt molybdate on alumina'desulfurizing catalyst containing 3% cobalt and molybdenum.
  • the liquid space velocity of the charge in the reaction zone was 1 vol./vol. of catalyst/hr.
  • the reaction product contained 8.3% of C -400 F. fraction having an F-l clear octane rating of 82.7 and 86.1% of material boiling above 400 F.
  • the 400-450 F. fraction was composed predominantly of naphthalene and had a freezing point of 786 C. and a sulfur content of 0.06%.
  • the higher boiling fraction contained a small amount of naphthalene due to imperfect fractionation.
  • Overall yield of naphthalene, based on the original charge stock was 23.7%.
  • Example III The charge stock prepared as in Example II was subjected to a conventional thermal hydrodealkylation treatment, omitting the first conditioning step of the invention.
  • the charge stock' was admixed with hydrogen in a mole ratio of hydrogen to hydrocarbon of 10:1 under a pressure of 200 p.s.i.g. Heat was applied at a sufiicient rate to raise the temperature of the mixture to 1300 F. But beginning at a temperature of about 1125 F., the temperature rose rapidly to above 1600 F. before the reaction could be stopped. This was a characteristic runaway reaction.
  • Example IV A catalytic gas oil was solvent extracted with furfural to prepare aromatic concentrates of varying aromatic contents. These aromatic concentrates were first subj'ected to catalytic conditioning and then thermal dealkylation. The results, indicating temperature control characteristics, are as follows:
  • Samples C and D had 84% and 75% aromatic parting from the spirit of the invention.
  • the temperature rise in the second stage was greater.
  • Samples C and D had 84% and 75% aromatic parting from the spirit of the invention.
  • undealkylated alkylnaphthalenes can be recycled to the process to effect greater yields.
  • a two-stage process for making naphthalene from a sulfur-containing petroleum fraction boiling mainly within the range of 400* F. to 550 F. and composed of at least 50% aromatic hydrocarbons comprising mainly alkylnaphthalenes and the remainder comprising mainly non-aromatic hydrocarbons which comprises subjecting said petroleum fraction to conditioning treatment in the presence of a desulfurization catalyst and added hydrogen under reaction conditions including a temperature between 800 and 980 F.
  • a two-stage process according to claim 4 where-in said petroleum fraction is selected from the group consisting of aromatic. concentrates separated from cracked gas oil and aromatic concentrates separated from straight run petroleum fractions.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (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)
US25531A 1960-04-29 1960-04-29 Production of naphthalene Expired - Lifetime US3177262A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US25531A US3177262A (en) 1960-04-29 1960-04-29 Production of naphthalene
DE1443096A DE1443096C3 (de) 1960-04-29 1961-04-17 Verfahren zur Herstellung von Naphthalin aus Alkylnaphthallne enthaltenden Kohlenwasserstoffen
LU40049D LU40049A1 (forum.php) 1960-04-29 1961-04-22

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3260765A (en) * 1965-05-25 1966-07-12 Universal Oil Prod Co Treatment of alkyl-substituted aromatic compounds
US3284527A (en) * 1963-12-31 1966-11-08 Monsanto Co Dealkylation of alkyl-substituted aromatics
US3483266A (en) * 1966-12-20 1969-12-09 Monsanto Co Thermal dealkylation of alkyl aromatic compounds employing a hydrogen donor and molecular hydrogen
US3485883A (en) * 1966-12-27 1969-12-23 Monsanto Co Dealkylation of alkyl aromatics using a hydrogenated aromatic hydrogen donor
US3548019A (en) * 1968-04-22 1970-12-15 Sun Oil Co Process for the production of naphthalene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1999738A (en) * 1928-01-13 1935-04-30 Ig Farbenindustrie Ag Purification of polynuclear aromatic hydrocarbons
US2423176A (en) * 1945-01-26 1947-07-01 Shell Dev Production of aromatic hydrocarbons
US2577788A (en) * 1949-07-26 1951-12-11 Standard Oil Dev Co Concurrent dealkylation of aromatic hydrocarbons and dehydrogenation of naphthenic hydrocarbons
US3001932A (en) * 1959-07-15 1961-09-26 Exxon Research Engineering Co Treatment of hydrocarbon oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1999738A (en) * 1928-01-13 1935-04-30 Ig Farbenindustrie Ag Purification of polynuclear aromatic hydrocarbons
US2423176A (en) * 1945-01-26 1947-07-01 Shell Dev Production of aromatic hydrocarbons
US2577788A (en) * 1949-07-26 1951-12-11 Standard Oil Dev Co Concurrent dealkylation of aromatic hydrocarbons and dehydrogenation of naphthenic hydrocarbons
US3001932A (en) * 1959-07-15 1961-09-26 Exxon Research Engineering Co Treatment of hydrocarbon oils

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3284527A (en) * 1963-12-31 1966-11-08 Monsanto Co Dealkylation of alkyl-substituted aromatics
US3260765A (en) * 1965-05-25 1966-07-12 Universal Oil Prod Co Treatment of alkyl-substituted aromatic compounds
US3483266A (en) * 1966-12-20 1969-12-09 Monsanto Co Thermal dealkylation of alkyl aromatic compounds employing a hydrogen donor and molecular hydrogen
US3485883A (en) * 1966-12-27 1969-12-23 Monsanto Co Dealkylation of alkyl aromatics using a hydrogenated aromatic hydrogen donor
US3548019A (en) * 1968-04-22 1970-12-15 Sun Oil Co Process for the production of naphthalene

Also Published As

Publication number Publication date
DE1443096C3 (de) 1975-06-12
DE1443096A1 (de) 1968-12-19
LU40049A1 (forum.php) 1961-06-22

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