+

WO1993003116A1 - Deshydrogenation et isomerisation/oligomerisation de charges d'alimentation composees de paraffine legere - Google Patents

Deshydrogenation et isomerisation/oligomerisation de charges d'alimentation composees de paraffine legere Download PDF

Info

Publication number
WO1993003116A1
WO1993003116A1 PCT/US1992/006267 US9206267W WO9303116A1 WO 1993003116 A1 WO1993003116 A1 WO 1993003116A1 US 9206267 W US9206267 W US 9206267W WO 9303116 A1 WO9303116 A1 WO 9303116A1
Authority
WO
WIPO (PCT)
Prior art keywords
zsm
acidic catalyst
dehydrogenation
product
metal
Prior art date
Application number
PCT/US1992/006267
Other languages
English (en)
Inventor
Werner Otto Haag
Mohsen Nadimi Harandi
Hartley Owen
Original Assignee
Mobil Oil Corporation
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
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to JP5503693A priority Critical patent/JPH06509382A/ja
Priority to EP19920917263 priority patent/EP0610218A4/fr
Publication of WO1993003116A1 publication Critical patent/WO1993003116A1/fr

Links

Classifications

    • 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
    • C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
    • C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only

Definitions

  • This invention relates to a dual catalyst process for increasing the production fo the total olefin and 5 iso-olefin derivatives in the conversion of alkane-containing feeds
  • the present invention provides a process for converting a C.-c.- paraffin-containing feed to effluents which contain substantially less paraffins 0 comprising: contacting the feed comprising an alkane under dehydrogenation conditions, with a non-acidic catalyst comprising a dehydrogenation metal in an amount from 0.01 to 20 wt %, and a non-acidic microporous crystalline material containing a modifier selected from indium, thallium, lead, tin and iridium, the modifier being present in an amount of from 0.01 to 20 wt % to produce a product in which the alkane has been converted to alkene; wherein the alkane and alkene contain 4 to 10 carbon atoms and each of the alkane and the alkene are normal or branched chain; contacting the product with an acidic catalyst composition comprising a zeolite selected from ZSM-5, ZSM-23, ZSM-22, ZSM-35 and ZSM-48 and admixtures thereof, under
  • the present inventi-.-. also provides a process for converting a C.-C.. paraffin-containing feed to effluents which contain substantially less paraffins comprising: contacting the feed comprising an alkane under dehydrogenation conditions, with a non-acidic catalyst comprising a dehydrogenation metal in an amount from 0.01 to 20 wt %, and a non-acidic microporous crystalline material containing a modifier selected from indium, thallium, lead, tin and iridium, the modifier being present in an amount of from 0.01 to 20 wt % to produce a product in which the alkane has been converted to alkene; wherein the alkane and alkene contain 4 to 10 carbon atoms; and each of the alkane and the alkene are normal or branched chain; contacting the product with an acidic catalyst composition comprising a zeolite selected from ZSM-5, ZSM-23, ZSM-22, ZSM-35 and ZSM-48 and
  • the present invention further provides a process for converting a C 4 ⁇ C 10 paraffin-containing feed to an effluent which is an aromatic C_+ product stream comprising: contacting the feed comprising an alkane under dehydrogenation conditions, with a non-acidic catalyst comprising a dehydrogenation metal in an amount from 0.01 to 20 wt %, and a non-acidic microporous crystalline material containing a modifier selected from indium, thallium, lead, tin and iridium, the modifier being present in an amount of from 0.01 to 20 wt % to produce a product in which the alkane has been converted to alkene; contacting the product with an acidic catalyst composition, under conditions effective to aromatize the product including a temperature ranging from 400° to 700°C, a pressure ranging from 0 to 1000 psig, hydrogen to hydrocarbon ratios from 0-20 and HSV of
  • an acidic catalyst comprising a zeolite or a metal impregnated zeolite selected from ZSM-5, ZSM-23, ZSM-22, ZSM-35 and ZSM-48 and admixtures thereof, and producing the aromatic C ⁇ + product stream.
  • the four C. mono-olefins, 1-butene, cis-2-butene, trans-2-butene and 2-methylpropene, are collectively called butylenes.
  • the term isobutylene is by established usage interchangeable with the nomenclature 2-methylpropene, while the other three isomers are n-butenes. Often they are treated collectively because the four mono-olefins are obtained as mixtures, from various processes.
  • olefins are often contained in mixtures of C.-C 's, which include both alkanes and alkenes.
  • Isobutylene is a desirable reactant for the production of alkylate, an oligomer of petroleum refinery C ⁇ -C ⁇ off gases, which includes high octane gasoline components, and for the production of methyl-t-butyl ether, when isobutylene is reacted with methanol.
  • the drawing is a graph of the plot of the selectivity of the production to iso-olefin vs. conversion of n-butenes.
  • the drawing illustrates the effect of catalyst on iso-butene selectivity, of 1-butene conversion at 450 ⁇ C and one atmosphere.
  • the process of the invention comprises catalytic production of the C. olefin(s) from feeds containing C. alkanes which olefins are selected from the group • consisting of 1-butene, cis-2-butene, and trans-2-butene and contact of the C. olefin(s) with a catalyst which will convert at least one of these butenes to an isobutylene product, optionally, relatively free of oligomers of any of the C monoolefins.
  • the class of reactant feeds includes alkanes of C.-C. Q carbon atoms including n-butane, n-pentane and n-hexane.
  • the class of reactant feeds may come from catalytic cracking of a higher molecular weight paraffin feed, over a catalyst in the vapor phase.
  • the C. fraction may be separated from C 5 hydrocarbons, which may also be effected, by conventional pressure distillation. However, this separation is not essential and is not necessarily preferred. Catalyst contact with the feed can be undertaken in a fixed bed, moving bed or fluidized system.
  • 2-methylpropene is undertaken, under catalytic dehydrogenation conditions, in the presence of a non-acidic catalyst.
  • catalytic dehydrogenation comprises contacting a paraffin, with the dehydrogenation catalyst, preferably a non-acidic catalyst composition, to produce the corresponding unsaturated analog together with H_.
  • the catalytic dehydrogenation exhibits high selectivity with respect to production of the unsaturated analog, with substantially little, if any, selectivity for hydrogenolysis (cracking) and with substantially little, if any, selectivity for isomerization.
  • the feed can comprise at least one unsubstituted chain paraffinic compound in which the paraffinic moiety has four to ten carbon atoms.
  • dehydrogenation of the paraffinic moiety occurs to yield the unsaturated analog.
  • Preferred pressures for catalytic dehydrogenation range from 0.1 to 3 atmospheres. However, pressures up to 500 psig can be employed, particularly if a light olefin is co-fed for transhydrogenation.
  • the catalytic dehydrogenation is conducted at elevated temperatures ranging from 400° to 700*C and, most preferably, from 400° to 600 ⁇ C.
  • Reactor inlet H_/feed ratios are 5 or less; even at reactor inlet ratios of zero (0) , there will be a hydrogen partial pressure in the reactor because hydrogen is a by product of dehydrogenation.
  • the liquid hourly space velocity of 0.1 to 50, preferably 0.5 to 10.
  • the unsaturated product of this stage of the process invention can be characterized as substantially free (preferably less than 5%) of molecular products of less (fewer number) carbon atoms than the reactants and as substantially free of isomers of the reactant or of isomers of its unsaturated analogs of the reactant.
  • This stage of the process can be conducted in the presence or absence of added hydrogen and in the presence or absence of diluents inert to conditions of the catalytic dehydrogenation such as steam, nitrogen, and methane.
  • dehydrogenation can be advantageously conducted at low hydrogen partial pressure.
  • the dehydrogenation catalyst comprises a dehydrogenation metal and a non-acidic microporous crystalline material.
  • crystalline used to refer to these materials relates to the ordered definite crystalline structure of the material which is unique and thus identifiable by a characteristic X-ray diffraction pattern.
  • microporous relates to pores or channels, with diameters of less than 20 Angstroms.
  • microporous crystalline materials include crystalline silicates, crystalline alumino-silicates (zeolites) , crystalline ALPOs, crystalline SAPO and related compositions and intercalated pillared materials derived from clays, layered silicates and titanates.
  • the crystalline silicate, alumino silicate (zeolites) , ALPOs and SAPOs have pores of uniform size and channel systems which are uniquely determined by unit structure of the material.
  • the uniform pore size and/or channel systems allow such a material to selectively absorb molecules of certain dimensions and shapes.
  • microporous material having pores or channels of less than 20 Angstroms can be divided into small, medium and large pore by the diameters of those pores, or channels.
  • the pores of the small pore material have an average diameter of less than 5 Angstroms; medium size pores range from an average diameter of 5 to 7 Angstroms, and large pore silicates indicates a diameter of greater than 7.
  • the demarcation between small, medium, and large pore materials can be based on the following sorption properties (measured at room temperature for crystallites having a minimum dimension of 0.1 micron):
  • n-C /i-C sorption ratio greater than approximately 10.
  • Medium pore n-C 6 /i-C 8 is less than 10 and n-C_/Mesitylene sorption ratio greater than approximately 5.
  • zeolites are a subclass of crystalline microporous silicates. Zeolites can contain aluminum as well as silicon. In some zeolites, the upper limit of the silicon/aluminum atomic ratio is unbounded.
  • ZSM-5 is one such example wherein the silica/alumina mole ratio is at least 12 and up to infinity.
  • RE 29,948 discloses a porous crystalline silicate made from a reaction mixture containing no deliberately added aluminum and exhibiting the X-ray diffraction pattern characteristic of ZSM-5 zeolites; in certain examples tin is deliberately added to the silicate synthesis mixture.
  • Zeolites can be acidic or non-acidic, depending on the framework aluminum content and on the amount of compensating cations, such as Na +, K+ , etc.
  • ALPOs described in U.S. Patent No. 4,310,440 are neutral.
  • 4,440,871 can be acidic or non-acidic depending on the ratio of framework A1:P therein and the compensating cation, such as Na , K (other than proton species and other than proton forming species such as NH +.) .
  • the microporous crystalline materials of the non-acidic catalyst preferably contain a modifier which is tin, iridium, thallium, lead or iridium.
  • the modifier content of the crystalline microporous materials can range from 0.01 to 20 wt %. Practically, the modifier content will range from 0.1 to 10 wt %.
  • the crystalline microporous modifier containing materials of the invention are characterized by Si/Al ratios of at least 2. However, the silica:alumina ratio of the zeolite can be up to 1000, or greater.
  • the aluminum content of these materials is less than 0.1 wt % and, more preferably, less than 0.02 wt %.
  • the crystalline microporous modifier containing material of the invention can contain other elements including boron, iron, chromium and gallium.
  • the content of these other elements in the crystalline modifier containing silicates can range from 0 to 10 wt %.
  • the modifier containing crystalline materials of the invention described herein are crystalline in the sense that they are identifiable as isostructural with zeolites by X-ray powder diffraction pattern.
  • the crystalline microporous modifier containing material has an X-ray diffraction pattern which corresponds to a zeolite, SAPO, ALPO, etc.
  • the pore size of the microporous crystalline modifier-containing silicates ranges from 5 to 8 Angstroms.
  • the microporous crystalline material containing modifier exhibits the structure of ZSM-5, by X-ray diffraction pattern. The X-ray diffraction pattern of ZSM-5 has been described in U.S. Patent No. 3,702,886 and RE 29,948.
  • the amount of dehydrogenation metal in the catalyst can range from 0.01 to 30 wt % and, preferably, 0.1 to 10 wt % of the crystalline modifier containing material.
  • platinum is the hydrogenation/ dehydrogenation metal.
  • the hydrogenation/ dehydrogenation metal can be any Group VIII metal including those of the platinum group, chromium and vanadium.
  • compositions comprising hydrogenation/ dehydrogenation metal combined with the crystalline modifier containing silicates do not exhibit any appreciable acid activity. These catalysts would meet the criteria of non-acidic catalysts described by Davis and Venuto, J. CATAL. Vol. 15, p.363 (1969).
  • the crystalline modifier dehydrogenation metal containing material exhibits an X-ray diffraction pattern of a zeolite
  • at least some of the dehydrogenation metal may be intrazeolitic, that is, some of that metal is within the pore structure of the crystal, although some of that metal can be on the surface of the crystal.
  • a test for determining whether, for example, Pt is intrazeolitic or extrazeolitic in the case of ZSM-5 is reported by R. M. Dessau, J. CATAL. Vol. 89, p. 520 (1984) . The test is based on the selective hydrogenation of olefins.
  • compositions of the invention used in catalysis decrease the hydrogen content of the reactant to produce a product having the same number of carbon atoms as the number of carbon atoms in the reactant.
  • modifier-free counterparts of those compositions catalyzed also hydrogenolysis of paraffins, e.g., to methane, as a major competing side reaction; and, accordingly, the latter compositions exhibit decreased selectivity for the aromatization of paraffins but increased selectivity for C.-C 8 paraffin production.
  • One way of incorporating modifier into the composition of this invention is by incorporation during the synthesis of the non-acidic crystalline microporous material.
  • modifier can be incorporated with the crystalline composition post-synthesis of the microporous crystalline material.
  • the dehydrogenating metal can be incorporated during or after synthesis of the microporous crystalline material.
  • the dehydrogenating metal can be incorporated before, simultaneously with or after modifier incorporation.
  • Stepwise preparation includes techniques of cocrystallization, impregnation, or exchange.
  • Simultaneous incorporation includes the combination of modifier with the dehydrogenation/hydrogenation function during synthesis (i.e., crystallization) or simultaneously after synthesis of the crystalline material.
  • a modifier-free material can be treated with modifier compounds at elevated temperatures. Such treatments can be conducted so that the source of modifier is either in the gaseous or the liquid phase including the aqueous phase (such as modifier II) .
  • a modifier-free crystalline reactant can simply be impregnated with modifier source and then calcined at temperatures above 400°C.
  • the modifier-free catalyst can have high silica:alumina ratios or contain other elements such as boron, chromium, iron, and gallium. Silicates containing 0.1 wt % or less aluminum are preferred. In materials of the invention, all cation-exchangeable sites are occupied by non-hydrogen (non-proton) and by non-hydrogen precursors, such as NH. .
  • alkali metals serve to neutralize any acidity due to framework aluminum.
  • the source of alkali metal cation can derive from cations incorporated during synthesis, in excess of the aluminum content thereof.
  • the non-acidic crystalline microporous modifier containing silicates of the invention are treated with Pt(NH_) 4 Cl in aqueous solution which has a pH of at least 7 to incorporate the necessary platinum for catalyst composition formulation.
  • the non-acidic, crystalline, microporous, modifier or iridium modifier and dehydrogenation metal containing materials of the invention can be combined with a matrix or binder material to render them attrition resistant and more resistant to the severity of the conditions to which they will be exposed during use in hydrocarbon conversion applications.
  • the combined compositions can contain 1 to 99 wt . of the materials of the invention based on the combined weight of the matrix (binder) and material of the invention.
  • the material of the invention When used in dehydrogenation and/or dehydrocyclization, the material of the invention will preferably be combined with non-acidic matrix or binder materials.
  • a preferred matrix or binder material would be silica, when the materials of the invention are used in dehydrogenation/hydrogenation.
  • the binder or matrix material can be inactive material and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Use of a material in conjunction with the new composition i.e.
  • Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction.
  • These materials may be incorporated into naturally occurring clays, e.g. bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions.
  • Said materials, i.e. clays, oxides, etc. function as binders for the catalyst. It may be desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials.
  • These clay binders have been employed normally only for the purpose of improving the crush strength of the overall catalyst.
  • Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with the present crystal also include inorganic oxides, notably alumina.
  • the crystalline tin material can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • the relative proportions of finely divided crystalline material and inorganic oxide gel matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of 2 to 80 wt % of the composite.
  • dehydrogenation catalysts which can be employed are oxides of chromium, molybdenum, palladium, platinum, or admixtures thereof on alumina (e.g. gamma-or eta- alumina).
  • alumina e.g. gamma-or eta- alumina.
  • the olefin content of the feed is increased.
  • the acidic catalyst also employed in the process of the invention, the olefinic components of the feed are isomerized and/or converted to oligomers.
  • a single reactor in which the concentration of the acidic catalyst in the reactor is at least 1 to 100 times less than the dehydrogenation catalyst concentration is used.
  • the dehydrogenation non-acidic catalyst converts alkanes to olefins which undergo oligomerization and/or isomerization over the acidic catalyst which shifts alkane dehydrogenation equilibrium toward completion.
  • the oligomers can undergo aromatization to produce C g aromatic rich effluent.
  • the acidic catalyst may be in the form of a powder, spheres, beads or extrudates.
  • Supports, matrix and binder materials for the acidic catalyst can be those described above.
  • the C4. olefins produced in the dehydrogenation reaction can be contacted with ZSM-35, in the acidic form, to increase the isobutylene content of the composition, and to decrease the content of the C.s other than isobutylene, while maintaining the total C. isomers substantially constant, without substantial oligomerization thereof.
  • the product of the process of the invention is substantially free of oligomerization products of the any one of the C. mono-olefins, when the acidic catalyst is ZSM-5, ZSM-23, ZSM-22, ZSM-34, ZSM-35, ZSM-48 and zeolites of similar structure and the proposed operating conditions are used.
  • ZSM-5 is described in U.S. Patent No. 3,702,886; ZSM-23 in U.S. Patent No. 4,076,842; ZSM-22 in U.S. Patent No. 4,556,477; ZSM-23 in U.S. Patent No. 4,076,842; ZSM-34 in U.S. Patent No. 4,086,186; ZSM-35 in U.S. Patent No. 4,016,245; and, ZSM-48 in U.S. Patent No. 4,375,573.
  • the ZSM-23 containing catalyst may be unsupported or supported on a matrix or may be in the form of a powder, spheres, beads or extrudates. Supports for the zeolites are described above.
  • Catalyst contact with the C . mono-olefin feed can be undertaken in a fixed bed, moving bed or fluidized bed.
  • the physical conditions of the vapor phase catalysis includes a temperature within the range of from 427° to 621 ⁇ C (800° to 1150 ⁇ F) , preferably from 538" to 593"C (1000 to 1100'F) .
  • the operating pressure is preferably equal or close to the dehydrogenation step.
  • WHSV range from 10 to 1000, preferably from 50 to 150 for butene isomerization.
  • n-butene to iso-butene over ZSM-23 at atmospheric pressure, high WHSV, and 538°c (1000 ⁇ F) occurs with no significant oligomerization to heavier molecules.
  • the ZSM-23 isomerization of n-butene(s) is favored by low reactant partial pressure and high operating temperature in the dehydrogenation process.
  • the ZSM-5 can be used in olefin isomerization at essentially the same operating range as ZSM-23.
  • the isomerization catalyst may follow the dehydrogenation catalyst in a separate reactor or in the same reactor. It is preferred, however, to mix the two catalysts or provide the two components in a single binder. This can result in a higher conversion of n-paraffins, since the equilibrium is shifted by the isomerization reaction.
  • the ZSM-5 can be used in olefin isomerization at temperatures between 427° and 593'C (800* and 1100 ⁇ F) , at weight hourly space velocities between 10 and 200.
  • the ZSM-5 containing catalyst can be used for olefin oligomerization under olefin oligomerization conditions, e.g., at a temperature of 232° to 649°C
  • the hydrocarbon partial pressure ranges between 0.5 to 40 atmospheres, preferably between 1 and 20 atmospheres and a WHSV of from 0.2 to 50, preferably
  • the oligomerization feed can be pure C 2 "" 5 olefin, or it may be prepared by forming mixtures thereof and mixtures with Ci,-C c _>.
  • the product of that oligomerization is a gasoline blending stock. Under the preferred conditions, the gasoline fraction contains predominantly higher olefins.
  • the acidic zeolite catalyst containing, for example, ZSM-5 can be used to aromatize the olefins produced as a result of the first stage of the process.
  • Temperatures of aromatization range from 400° to 700°C, pressure ranging from 0 to 1000 psig, hydrogen to hydrocarbon ratios are from 0 to 20 and WHSV from 0.1 to 500.
  • Preferred conditions are temperatures of from 400° to 650°C, atmospheric to 500 psig, absence of hydrogen and WHSV of from 0.5 to 10. The foregoing condition relate to conditions for separate reactors containing separate catalyst beds.
  • the temperature conditions of dehydrogenation per se may be constructively reduced.
  • the temperature can range from 399° to 677°c (750° to
  • WHSV for dehydrogenation can range from 1-100 preferably from 3-10
  • WHSV for isomerization can range from 5-200, preferably from 10-30
  • WHSV for oligomerization can range from 1-40, preferably from 3-8 r
  • WHSV for aromatization can range from 0.5-20, preferably from 1-5.
  • EXAMPLES The tin containing microporous crystalline materials can be formed as in Examples 1-6.
  • Tin ZSM-5 silicate was synthesized in a static system at 149°C (300°F) . 400 g 28.5% sodium silicate (Q-brand) was added to a solution of 60 g 50% tetramethy1ammonium chloride, 15 g SnC1..5H-0, 30 g 98% H 2 S0., and 60g TPA+Br- in 2250 g water. The mixture was stirred and then placed in a polypropylene bottle in an autoclave for 5 days. The product was 85% crystalline ZSM-5 and consisted of large 5-10 micron crystals.
  • the zeolitic silicates produced were characterized as having at least one crystal dimension which was at least 0.5 microns; it analyzed for 80.4% Si0 2 , 0.30% A1,0 , 3.78% Sn, 2.00% Na, 7.70% C, and 1.05% N.
  • Example 2
  • Another tin containing ZSM-5 sample was synthesized by employing 0.69 g Sn(II)SO. to form a hydrogel reaction mixture which is described by the following mole ratios: Si0 2 /Sn : H 2 0/Sn : OH-/SiO- : Na+/SiO_ : TPA+/SiO_ 75 : 40 : 0.30 : 0.35 : 0.10
  • the hydrogel was reacted at 160°C for 5 days with stirring (400 rpm) before quenching.
  • the resulting crystalline product was processed in the usual manner by filtering, washing, and drying. X-ray diffraction analysis of the product zeolite showed it to be 100% crystalline ZSM-5.
  • Example 3 A tin containing ZSM-5 sample was synthesized in a similar manner except that the Si0 2 /Sn ratio was 150 and the Na+/SiO_ was 0.31.
  • the crystalline ZSM-5 product contained 1.36% Sn, 0.0025% Al, 0.93% Na, and 89.31% Ash.
  • Example 4
  • a tin containing ZSM-5 sample was synthesized in a similar manner except that the Si0 2 /Sn ratio was 50, the Na+/Si0 2 was 0.38, and the synthesis time was 4 days.
  • a tin containing ZSM-5 sample was synthesized at a Si0 2 /Sn ratio of 38, a Na+/Si0 2 ratio of 0.40, and a synthesis time of 3 days. Tin incorporation was achieved during the zeolite synthesis, i.e., tin salts were added directly to the high silica ZSM-5 synthesis mixture. SEM data suggests that a significant portion of the tin is located outside of the large crystals formed ( Figure 1) . Nevertheless, some tin must be inside the ZSM-5 crystals, since it modifies the selectivity of the platinum, which itself is intracrystalline.

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention se rapporte à un procédé à double catalyseur servant à augmenter la production totale de dérivés d'iso-oléfine et d'oléfine dans la conversion de charges d'alimentation contenant un alcane.
PCT/US1992/006267 1991-07-31 1992-07-28 Deshydrogenation et isomerisation/oligomerisation de charges d'alimentation composees de paraffine legere WO1993003116A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP5503693A JPH06509382A (ja) 1991-07-31 1992-07-28 軽質パラフィンフィードの脱水素および異性化／オリゴマー化方法
EP19920917263 EP0610218A4 (fr) 1991-07-31 1992-07-28 Deshydrogenation et isomerisation/oligomerisation de charges d'alimentation composees de paraffine legere.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US73836991A 1991-07-31 1991-07-31
US738,369 1991-07-31

Publications (1)

Publication Number Publication Date
WO1993003116A1 true WO1993003116A1 (fr) 1993-02-18

Family

ID=24967704

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/006267 WO1993003116A1 (fr) 1991-07-31 1992-07-28 Deshydrogenation et isomerisation/oligomerisation de charges d'alimentation composees de paraffine legere

Country Status (5)

Country Link
EP (1) EP0610218A4 (fr)
JP (1) JPH06509382A (fr)
AU (1) AU2419692A (fr)
CA (1) CA2112119A1 (fr)
WO (1) WO1993003116A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0770666A1 (fr) * 1995-10-28 1997-05-02 Uop Procédé en deux étapes pour revaloriser les naphtes cycliques
WO1998005738A1 (fr) * 1996-08-06 1998-02-12 Phillips Petroleum Company Procede de production d'olefines et de composes aromatiques a partir de composes non aromatiques
RU2165913C2 (ru) * 1998-08-04 2001-04-27 Общество с ограниченной ответственностью "Нефтехимстарт" Способ получения изоалкенов и их смесей из нормальных алканов
WO2001030942A1 (fr) * 1999-10-28 2001-05-03 Mobil Oil Corporation Processus de purification de btx (benzene, toluene et xylene)
EP1233050A1 (fr) * 1999-03-15 2002-08-21 Uop Llc Valorisation de naphte par un procédé combiné de formation d'oléfines et d'aromatisation
US7517824B2 (en) 2005-12-06 2009-04-14 Exxonmobil Chemical Company Process for steam stripping hydrocarbons from a bromine index reduction catalyst
CN102061195A (zh) * 2009-11-13 2011-05-18 Ifp新能源公司 从饱和轻馏分生产优质煤油和柴油燃料和联产氢的方法
US9024100B2 (en) 2007-07-19 2015-05-05 China Petroleum & Chemical Corporation Process for producing olefins
WO2019040481A1 (fr) * 2017-08-23 2019-02-28 Phillips 66 Company Procédés de reformage sélectif de naphta

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4324940A (en) * 1980-04-09 1982-04-13 Mobil Oil Corporation Shape selective acid catalyzed reactions of olefins over crystalline zeolites
US4990710A (en) * 1988-06-24 1991-02-05 Mobil Oil Corporation Tin-containing microporous crystalline materials and their use as dehydrogenation, dehydrocyclization and reforming catalysts

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859308A (en) * 1988-01-19 1989-08-22 Mobil Oil Corporation Two-stage process for conversion of alkanes to gasoline
US4968401A (en) * 1988-06-27 1990-11-06 Mobil Oil Corp. Aromatization reactor design and process integration
US4956509A (en) * 1989-10-16 1990-09-11 Mobil Oil Corp. Integrated paraffin upgrading and catalytic cracking processes
US5037529A (en) * 1989-12-29 1991-08-06 Mobil Oil Corp. Integrated low pressure aromatization process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4324940A (en) * 1980-04-09 1982-04-13 Mobil Oil Corporation Shape selective acid catalyzed reactions of olefins over crystalline zeolites
US4990710A (en) * 1988-06-24 1991-02-05 Mobil Oil Corporation Tin-containing microporous crystalline materials and their use as dehydrogenation, dehydrocyclization and reforming catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0610218A4 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0770666A1 (fr) * 1995-10-28 1997-05-02 Uop Procédé en deux étapes pour revaloriser les naphtes cycliques
WO1998005738A1 (fr) * 1996-08-06 1998-02-12 Phillips Petroleum Company Procede de production d'olefines et de composes aromatiques a partir de composes non aromatiques
RU2165913C2 (ru) * 1998-08-04 2001-04-27 Общество с ограниченной ответственностью "Нефтехимстарт" Способ получения изоалкенов и их смесей из нормальных алканов
EP1233050A1 (fr) * 1999-03-15 2002-08-21 Uop Llc Valorisation de naphte par un procédé combiné de formation d'oléfines et d'aromatisation
WO2001030942A1 (fr) * 1999-10-28 2001-05-03 Mobil Oil Corporation Processus de purification de btx (benzene, toluene et xylene)
US6500996B1 (en) 1999-10-28 2002-12-31 Exxonmobil Oil Corporation Process for BTX purification
US7517824B2 (en) 2005-12-06 2009-04-14 Exxonmobil Chemical Company Process for steam stripping hydrocarbons from a bromine index reduction catalyst
US9024100B2 (en) 2007-07-19 2015-05-05 China Petroleum & Chemical Corporation Process for producing olefins
CN102061195A (zh) * 2009-11-13 2011-05-18 Ifp新能源公司 从饱和轻馏分生产优质煤油和柴油燃料和联产氢的方法
FR2952646A1 (fr) * 2009-11-13 2011-05-20 Inst Francais Du Petrole Procede de production de carburants kerosene et diesel de haute qualite et de coproduction d'hydrogene a partir de coupes saturees legeres
EP2333031A1 (fr) * 2009-11-13 2011-06-15 IFP Energies nouvelles Procédé de production de carburants kérosène et diesel de haute qualité et de coproduction d'hydrogène à partir de coupes saturées légères
US8470165B2 (en) 2009-11-13 2013-06-25 IFP Energies Nouvelles Process for the production of high-quality kerosene and diesel fuels for the coproduction of hydrogen from saturated light cuts
WO2019040481A1 (fr) * 2017-08-23 2019-02-28 Phillips 66 Company Procédés de reformage sélectif de naphta

Also Published As

Publication number Publication date
JPH06509382A (ja) 1994-10-20
EP0610218A4 (fr) 1994-10-26
CA2112119A1 (fr) 1993-02-18
EP0610218A1 (fr) 1994-08-17
AU2419692A (en) 1993-03-02

Similar Documents

Publication Publication Date Title
US5192728A (en) Tin-colating microporous crystalline materials and their use as dehydrogenation, dehydrocyclization reforming catalysts
US4990710A (en) Tin-containing microporous crystalline materials and their use as dehydrogenation, dehydrocyclization and reforming catalysts
US4962250A (en) Process for the conversion of paraffins to olefins and/or aromatics and non-acidic zeolite catalyst therefor
AU628031B2 (en) A dehydrogenation and dehydrocyclization catalyst, its synthesis and use
US4886926A (en) Catalytic dehydrogenation of hydrocarbons over tin-containing crystalline microporous materials
US5019664A (en) Process for the conversion of paraffins to olefins and/or aromatics and low acidity zeolite catalyst therefor
US5177281A (en) Double bond isomerization of 1-olefin containing feeds using ZSM-22, ZSM-23 or ZSM-35
US4451685A (en) Process to convert C2 -C3 olefins to a gasoline blending stock
US5108969A (en) Low acidity catalyst for conversion of paraffins to olefins and/or aromatics
US4433190A (en) Process to convert linear alkanes
US5396016A (en) MCM-36 as a catalyst for upgrading paraffins
US5237120A (en) Double bond isomerization of olefin-containing feeds with minimal oligomertization using surface acidity deactivated zeolite catalysts
WO1993003116A1 (fr) Deshydrogenation et isomerisation/oligomerisation de charges d'alimentation composees de paraffine legere
EP1127039A1 (fr) Procede de preparation de propylene et d'ethylene
US4910357A (en) Alkylate upgrading
US4849567A (en) Catalytic dehydrogenation of hydrocarbons over indium-containing crystalline microporous materials
US5107054A (en) Zeolite MCM-22 based catalyst for paraffin isomerization
US5146029A (en) Olefin interconversion by shape selective catalysis
US5122489A (en) Non-acidic dehydrogenation catalyst of enhanced stability
US4499325A (en) Alkene conversion using AMS-1B crystalline borosilicate
US5124497A (en) Production of mono-substituted alkylaromatics from C8 +N-paraffins
US5220089A (en) Olefin upgrading by selective catalysis
US4931416A (en) Thallium or lead-containing microporous crystalline materials and their use as dehydrogenation dehydrocyclization and reforming catalysts
US5475175A (en) Process for the production of alkylate gasoline from FCC light aliphatics
US5147837A (en) Titania containing dehydrogenation catalysts

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2112119

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1992917263

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1992917263

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1992917263

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载