[go: up one dir, main page]

WO1983000687A1 - Catalyseur de deshydrogenation calcine de maniere selective - Google Patents

Catalyseur de deshydrogenation calcine de maniere selective Download PDF

Info

Publication number
WO1983000687A1
WO1983000687A1 PCT/US1982/001120 US8201120W WO8300687A1 WO 1983000687 A1 WO1983000687 A1 WO 1983000687A1 US 8201120 W US8201120 W US 8201120W WO 8300687 A1 WO8300687 A1 WO 8300687A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
weight
dehydrogenation
steam
hours
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1982/001120
Other languages
English (en)
Inventor
David L Williams
George A Laufer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of WO1983000687A1 publication Critical patent/WO1983000687A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/862—Iron and chromium

Definitions

  • This invention relates generally to 5 catalysts particularly useful for the production of olefins by dehydrogenatin and more specifically to the composition and method of manufacture and use of improved dehydrogenation catalyst. 10 Considerable research has been directed in the past toward improving the production of olefins by dehydrogenation. Background Art
  • Steam active dehydrogenation catalysts 15 are widely used in the dehydrogenation to olefins and diolefins, e.g., butanes to butadienes; alkyl aromatics to alkenyl aromatics, e.g., ethylbenzene to styrene.
  • olefins and diolefins e.g., butanes to butadienes
  • alkyl aromatics to alkenyl aromatics, e.g., ethylbenzene to styrene.
  • Various catalysts and the dehydrogenation 20 conditions and other operating data are disclosed in Pitzer, U.S. Patent Nos. 2,866,790 and 2,866,781; Gutzeit, U.S. Patent No. 2,408,140, and Eggertsen, et al., U.S.
  • Patent No. 3,360,579 and Sie U.S. Patent
  • Pitzer discloses a catalyst where the catalyst which contains about 50% K-CO-., up to 10% Cr_0, and the balance Fe*® ? is heat treated at at least 1000 degrees or
  • the steam active alkalized iron dehydrogenation catalysts disclosed in these patents contain various amounts ' of iron oxide and potassium carbonate with a minor but effective amount of chromium oxide incorporated therein as a stablizer or structural promoter.
  • Facilities for dehydrogenation are advantageously operated at the highest practical throughput rates and small improvements in selectivity and activity of dehydrogenation catalyst can result in substantial savings.
  • SUBSTITUTE SHEET ⁇ IP high selectivity and high activity because generally, high selectivity is accompanied by low activity and vice versa.
  • Activity, of the catalyst is defined as the percent of the starting material, e.g., ethylbenzene, which is converted from the original state during the dehydrogenation process.
  • Selectivity of the catalyst is defined as the ratio of the amount of the desired product produced in the process, for example styrene, to the total feedstock converted.
  • a high conversion by catalytic dehydrogenation is generally favored by a high temperature and a low pressure.
  • dehydrogenation of ethylbenzene to styrene there are also undesirable side reactions which simultaneously occur to produce benzene and toluene.
  • the side reactions go to completion and are not limited by equilibrium considerations.
  • the benzene produced can be recycled for later processing but the toluene cannot and must be disposed of. Accordingly, in the evaluation of a system where the. by products are produced, the production of benzene as opposed to toluene is preferred.
  • the present invention provides a new and useful catalyst for the production of olefinic
  • the present invention also provides a method for production of a catalyst for the dehydrogenation of ethylbenzene to styrene at low steam to oil ratios where the catalyst maintains stability at lower steam/oil ratios and where, unexpectedly, the relative production of toluene is substantially diminished over a wide range of steam/oil weight ratios.
  • catalysts in accordance with the present invention provide longer operating periods between regeneration cycles even at lower steam/ oil ratios and reaction temperatures. It has been further found that catalysts provided by the present invention unexpectedly
  • SUE S T ⁇ TUTE SHEET provide good activity and selectivity in the dehydrogenation of diethylbenzene ethyltoluene, propylbenzene, butylbenzene and other alkyl substituted benzenes.
  • the present invention provides a catalyst found to be particularly effective in the dehydrogenation of ethylbenzene, diethylbenzene, and ethyltoluene, to olefinic compounds or
  • the catalysts includes iron oxide, at least 20% by weight alkali water gas promoter and at least 1.0% by weight chromium oxide where the catalyst is formed into pellets of selected configuration
  • Figure 1 is an illustration of a Mercury Porosimetry Evaluation of a catalyst within the scope of the present invention
  • FIG 2 is an illustration of the result of a Mercury Porose itry Evaluation of a comparison catalyst calcined in accordance with the present invention
  • Figure 3 is an illustration of the result of Mercury Porosimetry Evaluation of a catalyst within the scope of the present invention and one having the same composition but calcined for a different length of time
  • Figures 4a-4b are comparative illustrations of selectivity of a catalyst within the scope of the present invention and a prior art catalyst calcined for a longer time at higher temperatures
  • Figure 5 is a comparison of a catalyst shown in Figure 1 illustrating benzene/ toluene ratios in the effluent
  • Figure 6 is a graphic illustration of the conversion or activity of the catalysts of Figures 4a-4b over a period of time.
  • the method of the present invention provides a dehydrogenation catalyst including iron oxide, at least 25% by weight of potassium carbonate and at least 1.3% by weight chromium oxide.
  • the composition is formed into pellets of selected size and heat treated at 950 degrees to 1100 degrees for 15 minutes to 8 hours to provide the pore volume characteristics found to be beneficial in the subject invention, in that the catalyst unexpectedly yields excellent selectivity and longer catalyst life at lower steam to oil ratios, all as discussed hereinafter.
  • the iron oxide customarily is of pigmentary grade but may also be prepared by the thermal decomposition of ferric nitrate, ferric oxalate, ferrous sulfate and the like.
  • the iron oxide in the finished catalyst is usually in the alpha form.
  • the iron oxide may constitute up to 53.5% by weight of the catalyst but is preferably within the range from about 25% to about 45%.
  • One example of a catalyst of the present invention was prepared with the following analysis by dry mixing the necessary ingredients and calcining at 1000-1100 ⁇ F for 2 hours:
  • the concentration of alkali water gas promotor may vary from 20% to 55% and the proportion of chromium oxide may vary from 1.3% to 5.0% with the balance of the composition iron oxide.
  • FIG. 3 is an illustration of the pore volume distribution of two catalysts of similar composition in a Mercury Porosemetry evaluation, each catalyst including equivalent amounts of Fe ⁇ 0,, K-CO.. and Cr-O...
  • the catalyst represented by curve A was calcined in air at 1100 degrees for 24 hours.
  • the catalyst represented by curve 3 was calcined in accordance with the present invention at 15 900 degrees 1100 degrees for 2 hours.
  • a catalyst in accordance with the present invention as described above was placed in a reactor, for example a tubular reactor (in the following examples lOOcc of catalyst was used for each test in a 1" stainless steel reactor) where the feedstock, for example ethylbenzene, diethylbenzene, or ethlytoluene, was fed through the reactor with selected proportions of steam.
  • a reactor for example a tubular reactor (in the following examples lOOcc of catalyst was used for each test in a 1" stainless steel reactor) where the feedstock, for example ethylbenzene, diethylbenzene, or ethlytoluene, was fed through the reactor with selected proportions of steam.
  • the steam to oil (or feedstock) ratio was varied between 6:1 to 0.6:1 by weight as described hereinafter at liquid hourly space velocity (LHSV) of 1.0 to 2.0 as indicated hereinafter.
  • LHSV liquid hourly space velocity
  • TABLE I is a tabulation of the results of the dehydrogenation of ethyltoluene to vinyltoluene over the catalyst previously described at the conditions noted.
  • Table I illustrates that even in an extended heat run, reaction conditions can be modified then returned to initial conditions without adverse effect on catalyst performance.
  • Table II provides the results of tests to demonstrate performance of the invention catalyst and the aforementioned comparison catalyst in the dehydrogenation of diethylbenzene (DEB) to divinylbenze (DVB) and ethylvinyl benzene (EVB) at the indicated conditions.
  • DEB diethylbenzene
  • DVD divinylbenze
  • EVB ethylvinyl benzene
  • reaction temperature was varied stepwise between 1050°F; 1100° F; and 1150°F; steam/oil ratio varied from 2.5:1 to 6.0:1 and pressure varied from OPSIG to PSIG.
  • steam/oil ratio varied from 2.5:1 to 6.0:1
  • pressure varied from OPSIG to PSIG.
  • catalyst in accordance with the present invention is useful in dehydrogenation of ethylbenzene to styrene and unexpectedly provides improved characteristics as described hereinafter.
  • Table III is a tabulation of the results of the dehydrogenation of ethylbenzene to styrene over the invention catalyst previously described at the conditions noted.
  • Figure 4a graphically illustrates the selectivity of ethylbenzene conversion to styrene using the catalyst of the invention - at indicated steam/oil ratios by weight while Figure 4b indicates selectivity for the comparison catalyst.
  • Figures 4a and 4b illustrate that the selectivity of catalysts within the scope of the present invention is superior to the selectivity of the comparison catalyst.
  • the principal by-products are benzene and toluene.
  • the benzene is the more desirable by-product because it can be recycled whereas toluene cannot. Accordingly, the benzene/toluene distribution in the. dehydrogenation product is important as an indication of lost raw material, namely toluene.
  • Figure 5 is a graphic representation of the benzene/toluene ratio for selected conditions utilizing the catalyst of the
  • Figure 6 illustrates one of the unexpected advantages of the present invention; that is that the difference between the conversion rate of the catalyst diminishes with lower steam oil ratios and the catalyst of the present invention provides satisfactory and stable conversion at steam/oil ratios of 0.8 and 0.6 over an extended period of time where the comparison catalyst becomes unsatable at 1.0 S/O.
  • this advantage is important because the lower steam/oil ratios permit energy cost savings.
  • FIG. 6 illustrates that the conversion of ethylbenzene provided by the comparison catalyst diminishes to the point that the conversion provided by the catalyst of the invention catalyst at 0.8 steam/oil ratio is equivalent to the conversion provided by the comparison catalyst at 1.0 steam/oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

Un catalyseur est particulièrement efficace dans la déshydrogénation de l'éthylbenzène, du diéthylbenzène et de l'éthyltoluène en composés oléfiniques ou en substances aromatiques vinyliques, ce catalyseur comprenant de l'oxyde de fer, au moins 20 % en poids d'un activeur de gaz à l'eau d'alcali et au moins 1,3 % en poids d'oxyde de chrome, le catalyseur étant façonné en pastilles de configuration sélectionnée qui sont calcinées à une température comprise entre 900oF et 1110oF pendant une durée de temps allant de 15 minutes à 8 heures.
PCT/US1982/001120 1981-08-17 1982-08-17 Catalyseur de deshydrogenation calcine de maniere selective Ceased WO1983000687A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29329981A 1981-08-17 1981-08-17
US293,299810817 1981-08-17

Publications (1)

Publication Number Publication Date
WO1983000687A1 true WO1983000687A1 (fr) 1983-03-03

Family

ID=23128526

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1982/001120 Ceased WO1983000687A1 (fr) 1981-08-17 1982-08-17 Catalyseur de deshydrogenation calcine de maniere selective

Country Status (3)

Country Link
EP (1) EP0085718A4 (fr)
JP (1) JPS58501272A (fr)
WO (1) WO1983000687A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3319024A1 (de) * 1983-05-26 1984-11-29 Deggendorfer Werft Und Eisenbau Gmbh, 8360 Deggendorf Verfahren zur herstellung von styrol durch dehydrieren von aethylbenzol
US4496662A (en) * 1982-12-23 1985-01-29 Mobil Oil Corporation Catalysts for para-ethyltoluene dehydrogenation
US4503163A (en) * 1982-12-15 1985-03-05 Mobil Oil Corporation Catalysts for para-ethyltoluene dehydrogenation
US4504594A (en) * 1982-12-15 1985-03-12 Mobil Oil Corporation Catalysts for para-ethyltoluene dehydrogenation
US4593134A (en) * 1982-12-15 1986-06-03 Mobil Oil Corporation Process for para-ethyltoluene dehydrogenation
US4720604A (en) * 1982-12-15 1988-01-19 Mobil Oil Corporation Process for dehydrogenation of alkylaromatics
US4982030A (en) * 1985-07-26 1991-01-01 Mobil Oil Corporation Process for preparation of para-divinylbenzene

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2866790A (en) * 1957-02-18 1958-12-30 Phillips Petroleum Co Catalyst and dehydrogenation process
US2870228A (en) * 1956-12-24 1959-01-20 Shell Dev Dehydrogenation of hydrocarbons
US2916531A (en) * 1959-02-17 1959-12-08 Shell Dev Dehydrogenation of hydrocarbons
US3360579A (en) * 1965-05-21 1967-12-26 Shell Oil Co Catalytic dehydrogenation of alkylaromatics
US3849339A (en) * 1970-07-10 1974-11-19 Dow Chemical Co Method of preparing an improved dehydrogenation catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2870228A (en) * 1956-12-24 1959-01-20 Shell Dev Dehydrogenation of hydrocarbons
US2866790A (en) * 1957-02-18 1958-12-30 Phillips Petroleum Co Catalyst and dehydrogenation process
US2916531A (en) * 1959-02-17 1959-12-08 Shell Dev Dehydrogenation of hydrocarbons
US3360579A (en) * 1965-05-21 1967-12-26 Shell Oil Co Catalytic dehydrogenation of alkylaromatics
US3849339A (en) * 1970-07-10 1974-11-19 Dow Chemical Co Method of preparing an improved dehydrogenation catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0085718A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4503163A (en) * 1982-12-15 1985-03-05 Mobil Oil Corporation Catalysts for para-ethyltoluene dehydrogenation
US4504594A (en) * 1982-12-15 1985-03-12 Mobil Oil Corporation Catalysts for para-ethyltoluene dehydrogenation
US4593134A (en) * 1982-12-15 1986-06-03 Mobil Oil Corporation Process for para-ethyltoluene dehydrogenation
US4720604A (en) * 1982-12-15 1988-01-19 Mobil Oil Corporation Process for dehydrogenation of alkylaromatics
US4496662A (en) * 1982-12-23 1985-01-29 Mobil Oil Corporation Catalysts for para-ethyltoluene dehydrogenation
DE3319024A1 (de) * 1983-05-26 1984-11-29 Deggendorfer Werft Und Eisenbau Gmbh, 8360 Deggendorf Verfahren zur herstellung von styrol durch dehydrieren von aethylbenzol
US4982030A (en) * 1985-07-26 1991-01-01 Mobil Oil Corporation Process for preparation of para-divinylbenzene

Also Published As

Publication number Publication date
EP0085718A4 (fr) 1984-01-10
JPS58501272A (ja) 1983-08-04
EP0085718A1 (fr) 1983-08-17

Similar Documents

Publication Publication Date Title
US4486547A (en) Indium-containing dehydrogenation catalyst
US5593935A (en) Catalysts
CA1292248C (fr) Procede de deshydrogenation a la vapeur et de rechauffage oxydatif a l'aide d'un seul systeme catalyseur
US4404123A (en) Catalysts for para-ethyltoluene dehydrogenation
US5210357A (en) Composition of matter and method of oxidative conversion of organic compounds therewith
US3845156A (en) Processes for dehydrogenation of organic compounds
US4220560A (en) Spinel dehydrogenation catalyst
JPH01242535A (ja) アルケニル置換ベンゼン誘導体の製造方法
RU96107462A (ru) Способ каталитической конверсии алкилароматического углеводорода в алкенилароматический углеводород, способ регенерации и стабилизации активности катализатора дегидрирования и установка для конверсии алкилароматического углеводорода в алкенилароматический углеводород
US4551574A (en) Indium-containing dehydrogenation catalyst
CA1269222A (fr) Borate de cuivre et aluminium
US4467046A (en) Dehydrogenation catalyst
CA1318656C (fr) Catalyseur de desydrogenation
US3725493A (en) Oxidative dehydrogenation
US4310717A (en) Oxidative dehydrogenation and catalyst
US3784483A (en) Cobalt,iron,phosphorus and oxygen containing oxidatice dehydrogenation catalyst
US2870228A (en) Dehydrogenation of hydrocarbons
EP0085718A1 (fr) Catalyseur de deshydrogenation calcine de maniere selective
US3907916A (en) Dehydrogenation of alkyl aromatic hydrocarbons
EP0336622B1 (fr) Réaction pour la déshydrogénation d'hydrocarbures
US3793225A (en) Oxidative dehydrogenation catalyst
CA1212374A (fr) Agent catalyseur pour la dehydrogenation
US3626021A (en) Dehydrogenation of aliphatics over alkali metal oxide-chromia-zinc aluminate spinel catalyst
US3790500A (en) Oxidative dehydrogenation catalyst
EP0093518B1 (fr) Catalyseurs pour la déshydrogénation de para-éthyltoluéne

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): DE JP

AL Designated countries for regional patents

Designated state(s): BE DE

WWE Wipo information: entry into national phase

Ref document number: 1982903004

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1982903004

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1982903004

Country of ref document: EP