US3456026A - Sulfur dehydrogenation of organic compounds - Google Patents

Sulfur dehydrogenation of organic compounds Download PDF

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Publication number
US3456026A
US3456026A US679667A US3456026DA US3456026A US 3456026 A US3456026 A US 3456026A US 679667 A US679667 A US 679667A US 3456026D A US3456026D A US 3456026DA US 3456026 A US3456026 A US 3456026A
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sulfur
dehydrogenation
catalyst
mole
reaction
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Abraham David Cohen
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/46—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with sulfur or a sulfur-containing compound as an acceptor

Definitions

  • the invention relates to the vapor phase dehydrogenation of organic compounds. More particularly, this invention relates to a process for effecting the dehydrogenation of hydrocarbon by reaction with sulfur in the presence of an inert diluent. In a preferred embodiment, the invention relates to a catalytic process, wherein the yield of unsaturated products may be substantially enhanced.
  • inert diluents inert diluents in oXidative dehydrogenation reactions
  • U.S. 3,210,436 The use of inert diluents has been directed towards the removal of heat in these exothermic reaction systems.
  • the wellknown halogen promoted oxidative dehydrogenation systems as well as sufur promoted oxidative dehydrogenation systems utilize inert diluents to absorb the heat of reaction and thereby maintain, as nearly as possible, isothermal reaction conditions so that burning of the hydrocarbon feed to CO CO and H 0 is minimized.
  • the present invention does not utilize oxygen but utilizes sulfur only ice and is, therefore, an endothermic dehydrogenation reaction. Consequently, the function of the inert diluent is not to provide a better control of an exotherim reaction, but to increase the rate of the dehydrogenation reaction relative to the rate of the undesirable side reactions.
  • reaction (1) is about 45 kcal./ mole endothermic.
  • the significantly lower endothermicity of reaction (1) shows the greater efficacy of S as a dehydrogenation agent.
  • the overall sulfur dehydrogenation reaction involving S and the hydrocarbon feed always produce more molecules in the product than were originally present. For example in the balanced equation:
  • the process of this invention can be applied to a great variety of organic compounds to obtain the unsaturated derivatives thereof.
  • such compounds will contain about 2-20 carbon atoms and have at least one l grouping, i.e., adjacent carbon atoms singly bonded to each other and each attached to at least one hydrogen atom.
  • these compounds may also contain oxygen, halogens, nitrogen, and sulfur.
  • Illustrative applications include: ethylbenzene to styrene, isopropyl benzene to ot-methyl styrene, cyclohexane to benzene, ethane to ethylene, n-butane to butenes and butadiene, isobutane to isobutylene, methyl butene to isoprene, propionaldehyde to acrolein, ethyl chloride to vinyl chloride, propionitrile to acrylonitrile, methyl isobutyrate to methyl methacrylate, propionic acid to acrylic acid, ethyl pyridine to vinyl pyridine, and the like.
  • Preferred feedstocks are the C -C hydrocarbons, i.e., paraflins, alkyl benzenes, and monoolefins. Particularly preferred, however, are C to C parafiins, C to C monoolefins, and C to C alkyl benzenes. Particularly effective as feedstocks are the olefinic hydrocarbons or alkyl benzenes which may be dehydrogenated to provide a product wherein the major unsaturated product has the same number of carbon atoms at the feed hydrocarbon.
  • the inert gas which may be employed to reduce the partial pressure of the sulfur vapor may be any gas normally inert under the conditions of the reaction.
  • gases that may be employed are: helium, notrogen, carbon monoxide, carbon dioxide, steam, hydrogen sulfide, etc. as well as methane, waste gases containing methane, and mixtures of the foregoing.
  • the molar ratio of inert diluent to sulfur is not critical and may vary over a wide range as long as at least about two moles of diluent are present. This value, however, is merely an arbitrary limit at which the yield of dehydrogenated product becomes practical and economical.
  • Molar ratios below this value will also show increases in yield, generally the conversion and yield increasing with increased dilution of the sulfur.
  • the upper limit is not at all critical and larger amounts of diluent will only serve to further reduce the sulfur vapor partial pressure.
  • a molar ratio of 2 to 30, more preferably 6 to 14, of diluent to sulfur is employed.
  • the partial pressure of the reactants can be partially or wholly reduced by use of a vacuum so that the inert diluent may be partially or wholly dispensed with, respectively.
  • this method is not preferred.
  • reaction conditions under which this process is carried out are not critical and may vary widely. Temperatures should be such that the reaction is effected in the vapor phase. Normally, however, temperatures in excess of about 800 F. and preferably ranging from about 8001400 F., more preferably 1050-1300 F., e.g., 1200 F. may be employed.
  • the space velosity of the reaction is normally dependent upon reaction temperature, i.e., higher temperatures corresponding to shorter contact times. However, space velocities usually range from about 0.15 to 1.15 grams per hour of feed per gram of catalyst (w./w./hr.), preferably about 0.30- 0.75 w./w./hr., e.g., 0.50 w./w./hr.
  • Reaction pressures are not critical and may also vary over a wide range. Pressures from less than one atmosphere to about 50 atmospheres, preferably 0.7 to 7 atmospheres, e.g., 1 atmosphere, may be successfully employed in the process.
  • the molar ratio of sulfur to feed material is dependent upon the degree of unsaturation required in the end product.
  • butane may be dehydrogenated to produce butene or butadiene according to the following equations:
  • the active sulfur is believed to be S Theoretically, therefore, one-half mole of S is necessary to produce one mole of a monounsaturate from a saturated compound.
  • significant yields may be expected when as little as 0.1 mole of [S per mole of feed is employed.
  • S is written as [8 Thus, in this process at least about 0.1 moles [S per mole of feed should be employed.
  • While the process of this invention may be conducted without a catalyst, it is generally preferable, in order to achieve optimum conversion and yields, to employ catalytic agents.
  • Various catalyst systems can be employed herein; however, a crtical requirement of the catalyst is that it not only catalyzes the desired reaction but also inhibits undesirable side reactions such as cracking and/ or tar formation, thereby permitting the most effective use of the hydrocarbon feed. Cracking and/or tar formation may be inhibited by various techniques, such as impregnating large surface area materials with inert materials to effectively reduce the surface area, adjusting catalyst pore sizes, e.g., as in molecular sieves, so as to preclude the admittance of the feedstocks, or preferably, the use of low surface area catalysts.
  • Preferred catalysts are those that are or could be used as catalyst support materials. More specifically, these catalysts may be described as difficulty reducible oxides or refractory oxides which are selected from the oxides of the metals of Groups II, III, IV, V, and VI-B of the Periodic Chart of the Elements, though the oxides of Groups II, III-A, and V-B are preferred. Suitable examples of these oxides are: magnesia, barium oxide, thoria, alumina, boria, alundum, vanadia, chromia, titania, silica, silica-alumina, tungsten oxide, and the like.
  • silica and Group II-B oxides are most preferred, particularly aluminum oxide in its various forms, e.g., alumina, alundum.
  • common supports as silicon carbide; carbon, e.g., coke, activated carbon, graphite; diatomaceous earths, e.g., kieselguhr; clays both natural and synthetic, e.g., attapulgite clays, magnesium silicates; phosphates, e.g., calcium nickel phosphate, aluminum phosphate, calcium aluminum phosphate; and zeolites, etc. may also be employed. Of these latter materials phosphates are generally preferred.
  • the surface area of high surface area materials may be reduced by any of the techniques mentioned above.
  • it is also possible to reduce surface area by heat treating, for example, a 265 m. /g. alumina heated for several hours at about 2000 F., will result in a catalyst of optimum surface area that will give excellent conversions and yields in sulfur dehydrogenation.
  • metals their salts, oxides and hydroxides, preferably the oxides, can be used for this purpose and in fact suitable metals or mixtures of metals can be selected from Group I-A through Group VIII of the Periodic Chart of Elements. Examples of these metals are: potassium, calcium, magnesium, titanium, chromium, manganese, iron, copper, zinc, tin, antimony, cerium, uranium, tungsten and the like.
  • the weight ratio of metal to support may vary from 0.001 to 1.0, preferably from 0.01 to 0.25.
  • the metals or metal compounds are preferably solid at reaction temperatures, but they may be molten, e.g., antimony. Metals such as mercury which are gaseous at reaction temperatures are not suitable and are therefore excluded from use.
  • the metals or metal compounds can be deposited onto the support in any known manner, e.g., impregnation from dilute solutions, etc.
  • the reactor input consists of two streams: firstly, a stream consisting of inert diluent and sulfur vapor and, secondly, a stream consisting of hydrocarbon feed which may or may not contain inert diluent. Both streams are preheated but the first one is preheated to a higher temperature, e.g., about 300 F. greater, than the second one.
  • the preheating operation is so controlled that when the two gas streams are mixed at the top of the reactor vessel they attain the requisite reaction temperature and their components are in the appropriate mole ratio.
  • the reactor contains a catalyst, which may be utilized in a fixed, fluidized or moving bed, wherein the desired dehydrogenation takes place.
  • the product stream which mostly consists of styrene, H 8 and inert diluent (or diluents) together with any unconverted sulfur and ethylbenzene is then rapidly quenched. It is convenient for some or all of the inert diluent to be steam since on cooling the reactor efiluent an aqueous layer would be obtained that would contain most of the unreacted sulfur in colloidal form suitable for recycle to the reactor.
  • the gas eflluent can be treated in a conventional sulfur plant to oxidize the H 8 back to sulfur for recycle to the reactor.
  • the liquid product is subjected to standard distillation procedures now employed in ethylbenzene thermal dehydrogenation units. This allows the separation of styrene from the liquid product, and also recovers unreacted ethylbenzene for recycle to the reactor.
  • the reactor feed ethylbenzene and gases were accurately metered by the use of rotameters.
  • the reactor consisted of a 1 inch diameter Vycor tube which could be conveniently filled with a catalyst.
  • the reactor was heated in a temperature controlled furnace to the desired temperature.
  • Part of the reactor served to preheat the sulfur vapor and ethylben zene separately to a temperature near that of the reaction zone of the reactor.
  • the reactor efiluent was rapidly quenched by passing it through a water cooled condenser placed immediately after the reactor. Both the gas and liquid reactor effluent were weighed and then subjected to gas chromatographic analysis.
  • the sulfur in the reactor feed was omitted.
  • Example 1 Table I below gives data for the thermal dehydrogenation of ethylbenzene to styrene with and without a catalyst at various temperatures.
  • This table shows the relatively poor conversions achieved with ethylbenzene by thermal dehydrogenation with or Without a catalyst of 4.75 mP/g. surface area alumina.
  • Example 2 Table 11 below gives data for the sulfur dehydrogenation of ethylbenzene with and without a catalyst.
  • Example 3 Table III below gives data on the effect the inert diluent mole ratio to ethylbenzene has on the sulfur dehydrogenation of ethylbenzene to styrene.
  • Example 4 Table IV below gives data on the effect of sulfur concentration on the sulfur dehydrogenation of ethylbenzene to styrene.
  • Example 5 Table V below gives data of the effect of temperature on sulfur dehydrogenation of ethylbenzene to styrene.
  • Table V shows that there is an optimum temperature range for best styrene yield. Under the conditions employed in Table V the optimum temperature was about 1300 F.
  • Example 6 Table VI below gives data on different sulfur dehydrogenation catalysts for the conversion of ethylbenzene t0 styrene.
  • a process for the dehydrogenation of organic feedstocks containing at least one l l grouping which comprises reacting, in the vapor phase, a C C organic feedstock and at least about 0.1 mole [S per mole of feed, the reaction being conducted at a temperature of at least about 800 F., and in the presence of an inert diluent.
  • a support material selected from the group consisting of oxides of metals of Groups II, III, IV, V, and VI-B, silicon carbide, carbon, diatomaceous earths, clays, phosphates, and zeolites is employed as a catalyst and has a surface area below about mF/gm. is employed.
  • a process for the dehydrogenation of a C C feed hydrocarbon having at least one H II I l grouping which comprises reacting, in the vapor phase, the feed hydrocarbon with at least about 0.1 moles [S per mole of feed hydrocarbon, at a temperature ranging from about 800 F. to 1400 F., in the presence of at least about 2 moles of inert diluent per mole of feed hydrocarbon, and in the presence of a support material 9 selected from the group consisting of oxides of metals of Groups II, III, IV, V, and VI-B, silicon carbide, carbon, diatomaceous earths, clays, phosphates, and zeolites having a surface area below about 100 m. gm.
  • hydrocarbon feed is selected from the group consisting of C -C paraffins, C C monoolefins, and C C alkyl benzenes.
  • the support material is selected from the group consisting of silica, alumina, and phosphates.
  • the support is alumina of a surface area ranging from 0.5 to 20 mF/gm.
  • catalyst is selected from the group consisting of oxides of metals of Group II, III, IV, V, and VIB.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US679667A 1967-11-01 1967-11-01 Sulfur dehydrogenation of organic compounds Expired - Lifetime US3456026A (en)

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JP (1) JPS5026522B1 (de)
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4291183A (en) * 1980-01-29 1981-09-22 El Paso Products Company Production of tertiary-butylstyrene
US4393263A (en) * 1980-01-29 1983-07-12 El Paso Products Company Tertiary-butylstyrene production
US4568783A (en) * 1985-06-24 1986-02-04 The Standard Oil Company Indenes by catalytic dehydrogenation of indanes
US5341405A (en) * 1991-06-11 1994-08-23 Digital Equipment Corporation Data recovery apparatus and methods
US5436383A (en) * 1992-03-02 1995-07-25 Institut Francais Du Petrole Process for the dehydrogenation of aliphatic hydrocarbons saturated into olefinic hydrocarbons
US6258992B1 (en) * 1999-09-17 2001-07-10 Saudi Basic Industries Corporation Gas phase catalytic oxidation of hydrocarbons to carboxylic acids and dehydrogenated products
EP1136467A1 (de) * 2000-03-24 2001-09-26 Aventis Animal Nutrition S.A. Verfahren zur katalytischen Umsetzung von Alkanen in Alkenen
CN103861619A (zh) * 2012-12-11 2014-06-18 江苏省海洋石化股份有限公司 一种烷烃脱氢硫化物催化剂及烷烃脱氢的方法
WO2019034987A1 (en) * 2017-08-14 2019-02-21 Sabic Global Technologies B.V. PROCESSES FOR PRODUCING 1,3-BUTADIENE FROM ETHYLENE AND SULFUR
CN114749191A (zh) * 2022-03-24 2022-07-15 淮阴工学院 一种Ni/P-凹凸棒石粘土催化剂及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4559714B2 (ja) * 2003-06-19 2010-10-13 独立行政法人科学技術振興機構 アルケンの製造方法、硫化水素の製造方法、アルカンの脱水素方法、および触媒

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2392289A (en) * 1943-09-08 1946-01-01 Monsanto Chemicals Process for producing styrene
US3247278A (en) * 1963-03-21 1966-04-19 Socony Mobil Oil Co Inc Catalytic reactions of sulfur with organic compounds
US3344201A (en) * 1965-06-07 1967-09-26 Seymour C Schuman Production of styrene
US3373213A (en) * 1965-07-29 1968-03-12 Exxon Research Engineering Co Process for dehydrogenating hydrocarbons
US3387054A (en) * 1965-06-07 1968-06-04 Seymour C. Schuman Conversion of c4, c5 hydrocarbons with elemental sulfur and metal sulfide catalyst

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2197872A (en) * 1938-09-23 1940-04-23 Universal Oil Prod Co Treatment of hydrocarbons
US3344203A (en) * 1965-06-07 1967-09-26 Seymour C Schuman Production of methyl acetylene and propylene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2392289A (en) * 1943-09-08 1946-01-01 Monsanto Chemicals Process for producing styrene
US3247278A (en) * 1963-03-21 1966-04-19 Socony Mobil Oil Co Inc Catalytic reactions of sulfur with organic compounds
US3344201A (en) * 1965-06-07 1967-09-26 Seymour C Schuman Production of styrene
US3387054A (en) * 1965-06-07 1968-06-04 Seymour C. Schuman Conversion of c4, c5 hydrocarbons with elemental sulfur and metal sulfide catalyst
US3373213A (en) * 1965-07-29 1968-03-12 Exxon Research Engineering Co Process for dehydrogenating hydrocarbons

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4291183A (en) * 1980-01-29 1981-09-22 El Paso Products Company Production of tertiary-butylstyrene
US4393263A (en) * 1980-01-29 1983-07-12 El Paso Products Company Tertiary-butylstyrene production
US4568783A (en) * 1985-06-24 1986-02-04 The Standard Oil Company Indenes by catalytic dehydrogenation of indanes
US5341405A (en) * 1991-06-11 1994-08-23 Digital Equipment Corporation Data recovery apparatus and methods
US5436383A (en) * 1992-03-02 1995-07-25 Institut Francais Du Petrole Process for the dehydrogenation of aliphatic hydrocarbons saturated into olefinic hydrocarbons
US6258992B1 (en) * 1999-09-17 2001-07-10 Saudi Basic Industries Corporation Gas phase catalytic oxidation of hydrocarbons to carboxylic acids and dehydrogenated products
EP1136467A1 (de) * 2000-03-24 2001-09-26 Aventis Animal Nutrition S.A. Verfahren zur katalytischen Umsetzung von Alkanen in Alkenen
WO2001070655A1 (en) * 2000-03-24 2001-09-27 Aventis Animal Nutrition S.A. Catalytic conversion of alkanes to alkenes
US20040092784A1 (en) * 2000-03-24 2004-05-13 Olivier Legendre Catalytic conversion of alkanes to alkenes
CN103861619A (zh) * 2012-12-11 2014-06-18 江苏省海洋石化股份有限公司 一种烷烃脱氢硫化物催化剂及烷烃脱氢的方法
WO2019034987A1 (en) * 2017-08-14 2019-02-21 Sabic Global Technologies B.V. PROCESSES FOR PRODUCING 1,3-BUTADIENE FROM ETHYLENE AND SULFUR
CN114749191A (zh) * 2022-03-24 2022-07-15 淮阴工学院 一种Ni/P-凹凸棒石粘土催化剂及其制备方法和应用
CN114749191B (zh) * 2022-03-24 2023-06-30 淮阴工学院 一种Ni/P-凹凸棒石粘土催化剂及其制备方法和应用

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DE1806255A1 (de) 1969-06-12
GB1236622A (en) 1971-06-23
NL6815621A (de) 1969-05-05
FR1590431A (de) 1970-04-13
JPS5026522B1 (de) 1975-09-01

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