EP0093476B1 - Conversion de certaines hydrocarbures utilisant des catalyseurs à base de silicates-TEA calcinés - Google Patents

Conversion de certaines hydrocarbures utilisant des catalyseurs à base de silicates-TEA calcinés Download PDF

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Publication number
EP0093476B1
EP0093476B1 EP19830200611 EP83200611A EP0093476B1 EP 0093476 B1 EP0093476 B1 EP 0093476B1 EP 19830200611 EP19830200611 EP 19830200611 EP 83200611 A EP83200611 A EP 83200611A EP 0093476 B1 EP0093476 B1 EP 0093476B1
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Prior art keywords
stream
range
product effluent
diluent
tea
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EP19830200611
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German (de)
English (en)
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EP0093476A1 (fr
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Daniel Christopher Garska
Edith Marie Flanigen
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • This invention relates to the preparation of streams containing recoverable benzene, toluene, and xylenes ("BTX") from initial by-product effluent streams that contain other components, notably monoolefins and diolefins.
  • the invention concerns the removal by conversion of these other components which ordinarily prevent recovery by distillation or solvent extraction of benzene-toluene-xylenes aromatics from the streams.
  • it concerns a low severity process for treating the by-product streams with a specified catalyst, and under defined reaction conditions, both to produce benzene-toluene-xylenes from the initial stream and to reduce or eliminate those components that otherwise would interfere with the economic recovery of these aromatics from the streams.
  • the total reactor effluent will contain not only the desired olefin or diolefin, but a variety of other components, ranging from methane gas to high boiling polycyclic hydrocarbons.
  • These by-products are conventionally separated, usually by distillation and/or absorption, so as to concentrate the main desired products for ultimate recovery, and to produce one or more by-product effluent streams.
  • the by-product effluents contain a mixture of hydrocarbon types, including paraffins, monoolefins, diolefins, aromatics, cyclics, and various substituted and polynuclear aromatics. Unless the by-product effluent stream or streams contains a particularly valuable or desirable component, making removal economical, the by-product effluent streams are of only limited utility.
  • the lighter gases are useful only as fuel, while the heavier, normally liquid, components usually termed "dripolene", if not hydrogenated and then subjected to BTX extraction, are customarily either burned locally as fuel or else hydrogenated to saturate the unstable diolefins, and then blended with other gasoline fractions as motor fuel.
  • a further object is to provide a process for treating such by-product effluent stream in a simplified, low severity, operation so as both to produce benzene-toluene-xylenes (BTX), and, simultaneously, to decrease the content of interfering components.
  • Still another object is to remove those monolefins and diolefins which have heretofore interfered with the solvent extraction of BTX from dripolene and the like.
  • a stream from which benzene, toluene, and xylenes may be recovered readily is prepared by contacting a pyrolitic hydrocarbon cracking by-product effluent stream, containing substantial amounts of interfering monolefins and diolefins, calcined with a TEA-silicate molecular sieve catalyst under low severity hydrocarbon processing conditions.
  • a pyrolitic hydrocarbon cracking by-product effluent stream containing substantial amounts of interfering monolefins and diolefins, calcined with a TEA-silicate molecular sieve catalyst under low severity hydrocarbon processing conditions.
  • One of the remarkable aspects of the invention is that the same low severity conditions of temperature, pressure, and space velocity, which are suitable for hydrogenation with a TEA-silicate catalyst, are also suitable for the dehydrogenation reaction involved in aromatization.
  • a simple processing scheme with only a single reactor stage, is often adequate both to reduce to a minimal content, or eliminate the olefinic constituents that would interfere with the economic recovery of aromatics, and to produce benzene-toluene-xylenes from the feed stream.
  • a further important advantage of the invention resides in its ability to process any of a variety of the byproduct effluent streams from pyrolitic cracking processes.
  • these by-product effluent streams customarily include a C 4 fraction composed predominantly of butanes, butenes, and butadiene; a C 5 fraction composed mainly of pentanes, pentenes, pentadienes and cyclic C s compounds; a C 6 -C 8 "dripolene" fraction containing BTX aromatics together with interfering olefins (i.e., having a similar boiling range); and a Cg-plus fraction, including some BTX along with higher alkylated benzenes and polynuclear aromatics and aliphatics.
  • Each of these streams, plus others that may be present in a particular plant may be processed according to the invention.
  • TEA-silicate catalyst for use with the present invention, to be identified more fully below, is described in Grose et al. U.S. 4,104,294. It is believed to be isostructural with zeolite ZSM-12; see Rosinski et al. U.S. 3,832,449.
  • TEA-silicates are crystalline metal organosilicates having identifiable X-ray diffraction characteristics and other properties that have been described in the reference above.
  • the thermal pyrolysis, or cracking, of petroleum fractions may utilize as feed stocks hydrocarbons such as ethane, LPG (liquefied petroleum gas, chiefly propane with a few percent butanes), naphtha, heavy gas oil, or crude petroleum oil. These are subjected to controlled high temperature, low pressure, short time, pyrolitic cracking to produce the desired product or products. Thereafter the reactor effluent is subjected to a combination of condensation, fractional distillation, absorption, and perhaps other unit operations, to segregate various effluent streams enriched in one or more desirable components.
  • the precise arrangement of product recovery streams forms no part of the present invention, and indeed it is probable that no two pyrolitic cracking plants utilize the same recovery scheme.
  • the reactor effluent liquid may be subjected to fractional distillation to separate one or more fractions rich in benzene (B.P. 80.103°C.), toluene (B.P. 110.623°C.), and/or the xylenes, namely ethylbenzene (B.P. 136.187°C.), p-xylene (B.P. 138.348°C.), m-xylene (B.P. 139.102°C.), and o-xylene (B.P. 144.414°C.).
  • This fraction, or fractions is desirably solvent extracted, as for example by the Udex or solfolane process, to recover the BTX aromatic/aromatics.
  • solvent extraction is ineffective to extract the aromatics from the remaining aliphatics, inasmuch as solvents selective for aromatics will also extract many olefins and diolefins.
  • the diolefins and the aromatics cannot be separated by fractional distillation; for example, benzene, with a boiling point of 80.103°C., is not easily distilled from the 2,4-hexadienes, which boil at about 80.0°C.
  • the various dimethylpentenes boil within a range of 72.2°C. to 85.0°C.
  • the total reactor effluent may be segregated into a predominantly gaseous fraction including recoverable ethylene and propylene; a crude C 4 fraction, a distillation cut which includes hydrocarbons with primarily four carbon atoms each; a crude C 5 fraction, another distillation cut which primarily contains hydrocarbon molecules with five carbon atoms each, and generally containing a large quantity of unsaturated and cyclic compounds, including olefins and lesser amounts of C 4 's and lighter C 6 's and heavier; a C 6 ⁇ C 8 fraction, sometimes referred to as pyrolysis gasoline or dripolene; and a Cg plus fraction, a heavier distillation cut which primarily includes hydrocarbons with at least nine carbon atoms, along with lesser amounts of C 5 ⁇ C 8 hydrocarbons.
  • the C 9 fraction generally is produced as the distillation bottoms from the processing of dripolene to remove pyrolysis gasoline, and contains components as widely varying as styrene, ethyltoluenes, and trimethylbenzenes, to heavier compounds including ethyl naphthalene, diphenyl, and dimethyl naphthalene.
  • compositions may vary quite widely, depending upon the initial feed to the pyrolitic cracking unit, the type of pyrolitic cracking unit, conditions, in the pyrolitic unit, and the type and conditions of the product recovery section.
  • the by-product effluent streams may likewise be blended with each other where this is desired, or may include recycle components from elsewhere in the product recovery section.
  • the catalyst used in the present process in commonly termed calcined TEA-silicate, a newly discovered crystalline silica polymorph described in Grose et al. U.S. 4,104,294.
  • the class of crystalline metal organisilicates are synthesized from reaction systems essentially free of aluminum-containing reagents and are either entirely free of framework AI0 4 -tetrahedra or contain no crystallographically significant amounts thereof.
  • These compositions, as a class, are called TEA-silicates and have the following as-synthesized composition in terms of moles of oxides: wherein R represents the tetraethylammonium cation, M represents an alkali metal cation, and x has a value of from 0 to 15 depending upon the degree of hydration of the composition.
  • TEA-silicates possess a definite crystal structure whose X-ray powder diffraction pattern shows the following significant lines:
  • the crystalline metal organosilicates can be suitably synthesized by preparing a reaction system which in terms of moles of oxides has a composition within the range: wherein R represents the tetraethylammonium cation and M represents an alkali metal cation, preferably sodium, potassium or lithium, said reaction mixture having a pH of greater than 12.
  • the reaction mixture is preferably formed from the hydroxide of the alkali metal employed and the tetraethylammonium cation can be provided from an appropriate salt or base thereof such as tetraethylammonium bromide and tetraethylammonium hydroxide.
  • Any reactive source of Si0 2 such as silica sols, gels, solid amorphous silicas or alkali metal silicates can be utilized in the same manner as Si0 2 is conventionally supplied to reaction mixtures in the preparation of synthetic zeolites.
  • the reaction system is maintained at a temperature within the range of 125° to 150°C. until crystals of TEA-silicate are formed, usually a period of from about 70 to 250 hours. Thereafter the crystals are separated from the mother liquor and recovered by filtration or other conventional means. After washing with water, the TEA-silicate crystals are dried either in vacuum or an inert atmosphere such as air at moderate temperatures, 100°-110°C.
  • the crystalline organosilicates described herein are substantially free of alumina, but may contain very minor amounts thereof due to the presence of alumina as an impurity in the reactants employed, principally the silica source. Accordingly, the molar ratio of alumina to silica will be in the range of zero to less than 0.005.
  • Neither the tetraethylammonium nor the alkali metal cations of the TEA-silicates can be removed by ion-exchange techniques.
  • the organic cations can be decomposed thermally by calcination at temperatures of 400°C. or higher in an oxidizing or inert atmosphere such as air or nitrogen, respectively. Thermal decomposition of the organic cations does not affect the essential crystalline structure of the composition and the X-ray powder diffraction pattern is essentially unaltered.
  • Calcination to thermally decompose the TEA cations produces an apparent pore diameter of greater than 6.2 Angstroms. Thereafter, the calcined TEA-silicate is desirably washed to remove any metals or trace contaminants.
  • calcined TEA-silicate When used in the present process, calcined TEA-silicate may be employed either alone or in intimate admixture with independently active catalytic components, as for example the noble metals such as platinum, or other catalytically active metals such as molybdenum, vanadium, zinc, etc.
  • independently active catalytic components as for example the noble metals such as platinum, or other catalytically active metals such as molybdenum, vanadium, zinc, etc.
  • the techniques of introducing catalytically active metals to a molecular sieve zeolite are disclosed in the literature, and preexisting metal incorporation techniques are suitable. See, for example, Rabo et al. U.S. 3,236,761 and U.S. 3,236,762.
  • the physical form of the calcined TEA-silicate catalyst depends on the type of the catalytic reactor being employed. Calcined TEA-silicate by itself is a fine-grain granule or powder, and is desirably compacted into a more readily usable form (e.g., larger agglomerates), usually with a silica or alumina binder for fluidized bed reactions, or pills, prills, spheres, extrudates, or other shapes of controlled size to accord adequate catalyst-reactant contact. As indicated, the catalyst may be employed either as a fluidized catalyst, or in a fixed or moving bed, and in one or more reaction stages.
  • reaction conditions are low severity as compared with many preexisting processes.
  • conversion parameters while broad, may be selected to provide a high degree of versatility, depending upon the feed composition and on the desired product quality.
  • the pressure almost uniquely, is desirably quite low. Atmospheric pressure operation has been used successfully in the laboratory, but under specific conditions may be as high as 10.1x10 6 Pa or more. A desirable range is from atmospheric pressure to about 0.7 ⁇ 10 6 Pa. High pressures facilitate hydrogenation; lower pressures facilitate dehydrocyclization. The optimum pressure will therefore depend on process economics, considering whether it is more desirable to hydrogenate olefins than to produce a high yield of BTX aromatics.
  • Process stream flow rate as expressed in units of weight hourly space velocity (WHSV), or weight of hydrocarbon feed per unit weight of catalyst, is suitably within the range of 0.1 to 20, more desirably 0.5-5.0.
  • WHSV weight hourly space velocity
  • High WHSV's permit more economic plant construction, while lower WHSV's permit more complete reaction at given temperature pressure conditions.
  • a gaseous or gasifiable diluent may be introduced along with the hydrocarbon feed to the silicalite catalyst.
  • This diluent may be inert, typified by steam, nitrogen or a low boiling paraffin, or may be reactive with the feed under catalysis conditions (e.g., hydrogen).
  • Hydrogen is particularly desirable as it minimizes coke formation and deposition on the catalyst, with resulting premature deactivation, and also facilitates hydrogenation. As demonstrated below, however, the technique of the present invention need not utilize hydrogen.
  • diluent/hydrocarbon molar (gas volume) ratios optimally, of from 0.1 to 10 may be employed.
  • the catalyst be regenerated, either periodically or continuously, to remove the carbonaceous coke-like deposits from the catalyst.
  • a portion of the catalyst is continuously withdrawn from the reactor and then subjected to regeneration by combustion with air or other oxygen containing gas, after which it is continuously recycled to the reactor.
  • the removal of catalyst followed by regeneration may be effected either continuously or periodically.
  • a fixed bed operation it is generally desirable that two or more reactors be used in parallel, so that when one is processing the hydrocarbon feed, the other is out of service and being regenerated. Regeneration conditions of approximately 450-650°C, preferably 500 ⁇ 600°C. may be employed.
  • a Cg plus by-product hydrocarbon effluent from the thermal pyrolysis unit was reacted over 37g of 15.9 mm extrudates of TEA-silicate with a 15% alumina binder.
  • the reaction vessel was 1.91 cm OD stainless steel tubular reactor.
  • the reaction pressure was ambient; the reaction temperature was approximately 450°C.; and the space velocity of the feed varied from 0.7-0.8 g feed/g catalyst/hr.
  • the molar ratio of Si02 to-AI203 in the catalyst was 377:1.
  • the feed had the following analysis:
  • the gas samples were analyzed on a Hewlett Packard 5830A gas chromatograph equipped with a thermal conductivity detector.
  • a forty foot stainless steel column with an OD of 31.8 mm packed with 20% tributylphosphate on 35-80 mesh Chromasorb P (acid washed) was used.
  • the thermal conductivity detector temperature was set at 250°C., and the column temperature was ambient (approximately 2D-22°C.).
  • Gas samples were injected into the column off-line, through an eight port gas switching value, via a gas syringe.
  • the sample gas volume was approximately 0.3 cc; the carrier gas rate was 30 cc/min of helium.
  • Liquid samples for both product and feed were analyzed on a Hewlett Packard 5730A gas chromatograph, using a 5705A thermal conductivity detector.
  • the detector temperature was set at 250°C.
  • the column was maintained in an oven, with a temperature programmed from 55°C. to 190°C. at 4°C./min; the injector temperature was 250°C.
  • a sample size of approximately 2 ml. was used, and the helium carrier gas rate was 30 cc/min.
  • a crude butadiene by-product hydrocarbon from an olefins production unit was reacted over 0.25 g of powdered catalyst (TEA-silicate) in a thermal chromatograph microreactor at 450°C. Crude butadiene flow rate was 5 cc/min at ambient pressure. The molar ratio of SiO 2 ⁇ to ⁇ Al 2 O 3 in the catalyst was 377:1.
  • the reaction products were collected in a liquid nitrogen trap and then were allowed to purge into a gas chromatograph OV-101 column with a helium carrier gas. Analyses were run on both a flame detector and a thermal conductivity detector.
  • Example II The extrudate catalyst used in Example I was tested in the microreactor for the conversion of crude butadiene byproduct. All conditions and the amount of catalyst were the same as in Example II.

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

Claims (10)

1. Procédé à faible sévérité pour la préparation d'un produit enrichi en benzène-toluène-xylènes à teneur minimale en mono-oléfines et en dioléfines à partir d'un courant de charge comprenant un effluent de sous-produits d'un procédé de craquage pyrolytique d'hydrocarbures pour former des oléfines ou des dioléfines légères, le courant d'effluent de sous-produits contenant des oléfines et des dioléfines, procédé qui consiste à faire entrer en contact ledit courant effluent de sous-produits, dans des conditions de faible sévérité comprenant une température dans l'intervalle d'environ 300 à 700°C, une pression dasn l'intervalle d'environ 0 à 10,1 x 106 Pa et une vitesse spatiale horaire en poids dans l'intervalle d'environ 0,1 à 20, avec un catalyseur essentiellement formé d'un TEA-silicate calciné.
2. Procédé suivant la revendication 1, dans lequel lesdites conditions impliquent une température dans l'intervalle d'environ 350 à 600°C, une pression dans l'intervalle d'environ 350 à 600°C, une pression dans l'intervalle d'environ 0,1 à 0,7x106 Pa et une vitesse spatiale horaire en poids dans l'intervalle de 0,5 à 5,0.
3. Procédé suivant la revendication 1, dans lequel ledit effluent de sous-produits est un courant en C4.
4. Procédé suivant la revendication 1, dans lequel ledit effluent de sous-produits comprend un courant en Cs.
5. Procédé suivant la revendication 1, dans lequel ledit effluent de sous-produits comprend un courant de dripolène entier ou fractionné.
6. Procédé suivant la revendication 1, dans lequel lediq courant de charge est mélange avec un diluant.
7. Procédé suivant la revendication 6, dans lequel ledit diluant est de la vapeur.
8. Procédé suivant la revendication 6, dans lequel ledit diluant est de l'hydrogène.
9. Procédé suivant la revendication 6, dans lequel ledit diluant est une paraffine de bas point d'ébullition.
10. Procédé suivant la revendication 6, dans lequel ledit diluant est un mélange d'une paraffine de bas point d'ébullition, d'hydrogène et/ou de vapeur.
EP19830200611 1982-04-30 1983-04-29 Conversion de certaines hydrocarbures utilisant des catalyseurs à base de silicates-TEA calcinés Expired EP0093476B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US37372982A 1982-04-30 1982-04-30
US373729 1999-08-13

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EP0093476A1 EP0093476A1 (fr) 1983-11-09
EP0093476B1 true EP0093476B1 (fr) 1985-09-04

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EP (1) EP0093476B1 (fr)
JP (1) JPS58203921A (fr)
CA (1) CA1199647A (fr)
DE (1) DE3360711D1 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104294A (en) * 1977-11-10 1978-08-01 Union Carbide Corporation Crystalline silicates and method for preparing same
US4235701A (en) * 1979-03-30 1980-11-25 Atlantic Richfield Company Aromatics from dripolene
US4247386A (en) * 1979-08-06 1981-01-27 Mobil Oil Corporation Conversion of hydrocarbons to olefins
AU540104B2 (en) * 1980-01-10 1984-11-01 Mobil Oil Corp. Calytic reforming
US4341622A (en) * 1980-12-04 1982-07-27 Mobil Oil Corporation Manufacture of benzene, toluene and xylene

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Publication number Publication date
DE3360711D1 (en) 1985-10-10
JPS58203921A (ja) 1983-11-28
EP0093476A1 (fr) 1983-11-09
CA1199647A (fr) 1986-01-21

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