EP0262049B1 - Process for up-grading steam-cracking products - Google Patents

Process for up-grading steam-cracking products Download PDF

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Publication number
EP0262049B1
EP0262049B1 EP19870402135 EP87402135A EP0262049B1 EP 0262049 B1 EP0262049 B1 EP 0262049B1 EP 19870402135 EP19870402135 EP 19870402135 EP 87402135 A EP87402135 A EP 87402135A EP 0262049 B1 EP0262049 B1 EP 0262049B1
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EP
European Patent Office
Prior art keywords
steam
zeolite
cracking
zsm
catalyst
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EP19870402135
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German (de)
English (en)
French (fr)
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EP0262049A3 (en
EP0262049A2 (en
Inventor
Raymond Le Van Mao
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L'INSTITUT DE L'AMIANTE
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L'INSTITUT DE L'AMIANTE
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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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
    • C10G63/04—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only including at least one cracking step
    • 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
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • Steam-cracking is one of the most widely used basic petrochemical processes. It is used by industries to produce light olefins such as ethylene, propylene, butenes and butadiene and it is also relied upon for the production of aromatics such as benzene, toluene and xylenes.
  • steam-cracking comprises a step in which the hydrocarbon mixture to be transformed is mixed with steam and submitted to elevated temperatures in a tubular reactor.
  • the different resulting products, gaseous and liquid hydrocarbons are then collected and separated.
  • product distribution depends on the nature of the initial hydrocarbon mixture as well as experimental conditions.
  • C2-C4 light olefins as well as benzene, toluene, ethylbenzene and xylenes have the highest commercial values and since enormous quantities are processes throughout the world, even small yield improvements lead to substantial profit increases.
  • ZSM-5 zeolite catalysts have drawn considerable attention because of their ability to increase selectivity in a variety of industrial processes such as xylene isomerization, toluene disproportionation, aromatic alkylation, methanol conversion and conversion of synthesis gas to ethane.
  • US 4 472 535 discloses a method of converting a synthesis gas mixture comprising hydrogen and carbon monoxide to a hydrocarbon product, with improved selectivity for the production of ethane, which comprises contacting the synthesis gas under conversion conditions with a conversion catalyst comprising a crystalline zeolite component having acidic functionality and a metal component impregnated into the zeolite from a liquid ammonia solution wherein said metal component comprises a metal or metals which are an effective catalyst for the conversion of synthesis gas to methanol.
  • modifications of the catalyst can also lead to highly efficient production of light olefins resulting from methanol conversion.
  • modified zeolite catalysts have the possibilities to present very interesting properties for enhancing yields in petrochemical reactions.
  • the present invention relates to a process for up-grading products resulting from the steam-cracking of hydrocarbons which comprises bringing the steam-cracking reaction products in contact with a multifunctional Zn-ZSM-5 zeolite/Cr2O3/Al2O3 catalyst comprising of a mixture of from 2.5 to 7.5% wt of Cr2O3, 5 to 17.5% wt of Al2O3 and 75 to 85% wt of a Zn-ZSM-5 zeolite or a Zn-ZSM-5 zeolite/asbestos.
  • a multifunctional Zn-ZSM-5 zeolite/Cr2O3/Al2O3 catalyst comprising of a mixture of from 2.5 to 7.5% wt of Cr2O3, 5 to 17.5% wt of Al2O3 and 75 to 85% wt of a Zn-ZSM-5 zeolite or a Zn-ZSM-5 zeolite/asbestos.
  • the main feature of the present invention resides in the presence of a catalytic reactor at the outlet of the steam-cracking reactor.
  • This catalytic reactor contains a multifunctional catalyst which comprises a zeolite of the ZSM-5 type coupled with metallic oxides.
  • These oxides can either be coupled to the zeolite by being directly deposited on the zeolite or mechanically mixed with the zeolite.
  • the metallic oxides can be selected from oxides such as Cr2O3, Al2O3, or from any metallic oxide having a hydrogenating/dehydrogenating function.
  • catalytic reactor used in the present invention was a fixed-bed reactor, it will be understood that any suitable design commonly used for catalytic reactions could have been chosen.
  • the starting hydro-carbon material 2 is first mixed with a stripping gas 4. It is to be noted, however, that the use of a stripping gas is optional. In the context of the actual experiments, a stripping gas was used only for convenience.
  • the resulting mixture is then forwarded to a vaporizer-mixer 6, in which steam is injected by means of an infusion pump 8.
  • the gaseous mixture thus obtained enters a steam-cracking tubular reactor 10 heated at a temperature ranging between 760° and 860°C.
  • products coming out of the steam-cracking tubular reactor 10 are sent into a catalytic reactor 12 heated at a temperature ranging between 450° and 550°C.
  • the resulting products are then cooled by a series of condensers 14 (water-cooling condensers and ice bath).
  • the liquid and gaseous phases are separated.
  • the liquids are first collected in a liquid-collector cylinder 16 while the gases flow through the liquid-collector cylinder to be collected for on line analysis in a dynamic sampler cylinder 18 located at a higher position than the liquid collector cylinder.
  • Propane is the starting hydrocarbon material on which the steam-cracking process was performed. It was introduced into the system at a flow rate of 45 ml/min. or 4.95 g/hour. It was first mixed with helium acting as a stripping gas. After having been flown through the vaporizer-mixer, in which steam was injected at a rate of 1.7 g/hour, the gaseous mixture was then sent into the steam-cracking reactor whose internal temperature had been set to 780°C at atmospheric pressure. The residence time of the starting material in the steam-cracking reactor was approximately 1 second.
  • the resulting product was then separated into its liquid and the gaseous phases.
  • the liquid fraction was analyzed by GC using a capillary column (length: 50 m, PONA® type, fused silica coated with a cross-linked polymer).
  • the gases were analyzed on line by gas chromatography.
  • a column having a length of 3.5 m packed with Chromosorb® P coated with 20% by weight of Squalane® was used for the analysis.
  • the GC used was a dual FID Hewlett-Packard Model 5790 equipped with a 3392A Model integrator. Results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was repeated the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 1.
  • Example 5 The same procedure as in Example 1 was repeated the only modification being the internal temperature of the steam-cracking reactor which was set at 835°C. Results are shown in Table 5.
  • propane was chosen as the starting hydrocarbon material. It was mixed with helium and flown through the vaporizer-mixer. The gaseous mixture was then forwarded through the steam-cracking reactor whose internal temperature had been set to 780°C. The resulting products were then sent to the catalytic reactor which had been previously embedded with 4 g of a Zn-Mn-ZSM-5 zeolite which was prepared according to the procedure described in Can. Pat. Appl. S.N. 471,463 (US-A-4 615 995). The temperature of the catalytic reactor had been previously set at 500°C, with a pressure of 1 atmosphere and a W.H.S.V. (weight hourly space velocity) of 1 h ⁇ 1. The final products were analyzed using the techniques discussed in Example 1. Results are shown in Table 2.
  • Example 2 The same procedure as in Example 4 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 2.
  • Example 4 The same procedure as in Example 4 was repeated, except for the following modifications: the catalytic reactor was embedded with 4 g of a Zn-Mn-ZSM-5 zeolite/asbestos catalyst prepared according to the procedure described in Can. Pat. Appl. S.N. 471,463 (US-A- 4 615 995). Results are shown in Table 3.
  • Example 6 The same procedure as in Example 6 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results are shown in Table 3.
  • Example 4 The same procedure as in Example 4 was repeated, except for the following modification: the catalytic reactor was embedded with a Zn-ZSM-5 zeolite/ asbestos/Cr2O3/Al2O3 catalyst.
  • the Zn-ZSM-5 zeolite/ asbestos catalyst was prepared according to the method described in Can. Pat. Appl. S.N. 471,463. Then, 4.5 g of the Zn-ZSM-5 zeolite/asbestos catalyst obtained were wet with a solution prepared from 0.3 g of Cr2O3 and 0.4 g of sodium aluminate dissolved in 5 ml of distilled water. The resulting multifunctional catalyst was dried at 120°C for 12 hours and actuated at 500°C for another 12 hour period. Finally, the catalyst was reduced in hydrogen at 350°C for at least 1 hour. Results are shown in Table 4.
  • Example 8 The same procedure as in Example 8 was repeated, the only modification being the internal temperature of the steam-cracking reactor which was set at 800°C. Results were shown in Table 4.
  • Example 3 a run without catalyst was performed at 835°C. This temperature was fairly close to temperatures used in industrial steam-cracking facilities using propane as a starting hydrocarbon material.
  • the product distribution of such a run is compared to the run performed in presence of the Zn-ZSM-5 zeolite/asbestos/Cr2O3/Al2O3 catalyst and with the steam-cracking reactor temperature set at 800°C, as described in Example 9, it can be seen, as it is shown in Table 5, that in the presence of the multifunctional catalyst and with a much lower steam-cracking temperature, higher yields in ethylene and propylene were obtained.
  • the propylene yield was nearly doubled (due mainly to a lower steam-cracking temperature) and the ethylene yield was increased by 5 wt percentage points while methane formation was significantly lower.
  • the liquid yield was much lower for the run performed at a lower steam-cracking temperature in the presence of the multifunctional catalyst.
  • the BTX aromatics benzene, toluene, ethylbenzene and xylenes
  • the total "ethylene + propylene" yield can be increased by 10 wt percentage points and the ethylene/propylene wt ratio can be decreased to a very large extent (see Table 5).

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  • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP19870402135 1986-09-25 1987-09-24 Process for up-grading steam-cracking products Expired EP0262049B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA519081 1986-09-25
CA000519081A CA1270240A (en) 1986-09-25 1986-09-25 Process for up-grading steam-cracking products

Publications (3)

Publication Number Publication Date
EP0262049A2 EP0262049A2 (en) 1988-03-30
EP0262049A3 EP0262049A3 (en) 1989-03-22
EP0262049B1 true EP0262049B1 (en) 1992-03-11

Family

ID=4134019

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870402135 Expired EP0262049B1 (en) 1986-09-25 1987-09-24 Process for up-grading steam-cracking products

Country Status (4)

Country Link
EP (1) EP0262049B1 (ja)
JP (1) JPS6397233A (ja)
CA (1) CA1270240A (ja)
DE (1) DE3777305D1 (ja)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0275930B1 (en) * 1987-01-23 1992-01-02 Mobil Oil Corporation Upgrading diene-containing hydrocarbons
DE69016904T2 (de) * 1989-09-26 1995-07-06 Shell Int Research Verfahren zur Verbesserung eines Schwefel enthaltenden Einsatzmaterials.
GB9218346D0 (en) * 1992-08-28 1992-10-14 Bp Chem Int Ltd Process
US6033555A (en) * 1997-06-10 2000-03-07 Exxon Chemical Patents Inc. Sequential catalytic and thermal cracking for enhanced ethylene yield
AU2001279519A1 (en) * 2000-07-31 2002-02-13 Concordia University Catalysts for deep catalytic cracking of hydrocarbon feedstocks for the selective production of light olefins and its preparation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097367A (en) * 1977-07-25 1978-06-27 Mobil Oil Corporation Conversion of olefinic naphtha
US4188336A (en) * 1977-08-18 1980-02-12 Mobil Oil Corporation Conversion of synthesis gas to aromatic hydrocarbons
US4472535A (en) * 1982-11-22 1984-09-18 Mobil Oil Corporation Conversion of synthesis gas to ethane
EP0131975B1 (en) * 1983-07-14 1988-08-24 Shell Internationale Researchmaatschappij B.V. Process for upgrading a gasoline
US4615995A (en) * 1985-01-03 1986-10-07 The Asbestos Institute Zeolite catalysts

Also Published As

Publication number Publication date
DE3777305D1 (de) 1992-04-16
JPS6397233A (ja) 1988-04-27
EP0262049A3 (en) 1989-03-22
CA1270240A (en) 1990-06-12
EP0262049A2 (en) 1988-03-30

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