WO2001032806A1 - Method and apparatus for selective deep catalytic cracking of hydrocarbons - Google Patents
Method and apparatus for selective deep catalytic cracking of hydrocarbons Download PDFInfo
- Publication number
- WO2001032806A1 WO2001032806A1 PCT/CA2000/001327 CA0001327W WO0132806A1 WO 2001032806 A1 WO2001032806 A1 WO 2001032806A1 CA 0001327 W CA0001327 W CA 0001327W WO 0132806 A1 WO0132806 A1 WO 0132806A1
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- WO
- WIPO (PCT)
- Prior art keywords
- zone
- temperature
- zeolite
- reactor
- catalyst
- Prior art date
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G2400/20—C2-C4 olefins
Definitions
- the present invention relates to a method and related apparatus for catalytic steam cracking of hydrocarbons.
- 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, usual ly in the presence of one or more catalysts.
- the reaction temperature usually ranges from 700 to 900°C according to the type of feedstock treated (the longer the hydrocarbon molecular structure, the lower the required temperature for cracking) while the residence time ranges from a few seconds to a fraction of second.
- the different resulting products, gaseous or liquid are then col lected and separated.
- product distribution depends on the nature of the initial hydrocarbon mixture and the reaction conditions.
- l ight olefins primarily ethylene and propylene
- the present invention provides a method and apparatus for selective deep catalytic cracking of petroleum naphthas or other hydrocarbon feedstocks.
- the invention provides an apparatus for catalytic steam cracking of hydrocarbons comprising a reactor having first and second main reaction zones.
- the first reaction zone being heated to a first temperature between 500 to 900°C, preferably between 660 and 720°C, comprises a low-surface area, porous and thermally resistant catalytic material.
- the second reaction zone being heated to a second temperature, being the same or different from the first temperature and also being between 500 to 900°C, preferably between 660 and 720°C, comprises a zeol ite-based catalyst.
- Also provided is a method for selective steam cracking of hydrocarbons comprising the steps of:
- Zone I contains beads of some catalytical ly mildly active porous material such as quartz or quartz doped with Cr-Al, is set at a temperature T ⁇
- Zone II contains a zeolite type catalyst, preferably ZSM5 zeolite or, most preferably, a hybrid zeolite catalyst.
- Figure 1 Flowchart schematically illustrating the method and apparatus of the present invention
- Figure 2 Graph showing the selectivity in light olefin output versus temperature in pre- catalytic Zone I of the steam cracking reactor apparatus used in the present invention (using n-hexane as a model hydrocarbon molecule).
- the method uses a tubular steam cracking reaction comprising two reaction zones: a pre-catalytic zone I containing a mildly active but robust catalyst and a catalytic zone II.
- Zone II contains a ZSM5 zeolite based catalyst, preferably of the hybrid configuration.
- Zone I a pre-catalytic zone located at the entrance of a tubular reactor (not shown).
- Zone I will advantageously contain a pre-catalyst composed of beads of some robust and mildly catalytic and porous material such as quartz, or quartz doped with Cr-Al.
- Zone I is set at a given temperature T, preferably between 500 to 900°C.
- Variations of the temperature of Zone I and the textural properties and/or the surface composition of the pre-catalyst are surprisingly used to achieve: (a) an increase the overal l conversion achieved by the method of the present invention, (b) an increase the propensity of the method towards the production of light olefins such as ethylene and propylene and (c) to vary the end product distribution, namely the ethylene/propylene ratio.
- the gas stream is partially cracked and surprisingly contains selectivity modifiers, i.e. compounds which wil l affect the end product distribution, namely the ethylene/propylene ratio. Therefore, the entire method will be more selective than that using only a catalyst bed as a reaction zone. In addition, under almost all operating conditions, the final conversion rate is increased owing to the partial conversion of the feed through Zone I.
- selectivity modifiers i.e. compounds which wil l affect the end product distribution, namely the ethylene/propylene ratio. Therefore, the entire method will be more selective than that using only a catalyst bed as a reaction zone.
- the final conversion rate is increased owing to the partial conversion of the feed through Zone I.
- Zone II which is set at temperature T 2 , contains a catalyst which is based on the ZSM5 zeolite or, preferably, a hybrid zeolite catalyst. Steam cracking in the presence of a zeol ite type catalyst is commonly referred to as deep cracking.
- the method of the present invention using a pre-catalyst system Zone I and a catalyst system Zone II, each having adjustable temperatures and properties, achieves dramatical ly higher conversion to commercial valuable products and greater flexibility and selectivity.
- the method of the present invention operates as a catalytic lever (hereinafter referred to as "CatLever" configuration) in which the operating conditions in Zone I can affect at will the composition of the products exiting Zone II.
- CatLever catalytic lever
- the cracking activity of the ZSM5 zeolite based catalysts on various petroleum feeds (the so-called deep catalytic cracking) is dramatically improved and a considerable production flexibility is obtained.
- the novel method can be described as selective deep catalytic cracking.
- ZSM5 zeolite materials is to be understood to encompass any such materials known to those ski lled in the art. Without restricting the foregoing, are envisaged any zeolite catalyst materials selected from the group of: microporous aluminosi cates, microporous silicoaluminophosphates and microporous aluminophosphates having the zeolite structure, and also mesoporous silica-containing materials. Also envisaged are desilicated and desi l icated/si lica-remserted zeolite materials as described in R. Le Van Mao, S.T. Le, D. Ohayon, F. Cail bot, L. Gelebart and G. Denes, Zeolites 1 9 (4) (1 997), 270-278 and R. Le Van Mao and D. Ohayon, Proceedings 12th International Zeolite Conference, Baltimore
- n-hexane used as a model molecule for petroleum naphthas.
- the present invention has been experimentally demonstrated based on n-hexane, this is an excellent model molecule for predicting the behaviour of other hydrocarbons, in particular longer chain hydrocarbons and their mixtures such as the ones found in petroleum naphthas, since the catalytic behaviors of these feeds are analogous.
- the products of this conversion include olefins and diolefins which are known to increase - by hydrogen transfer or olefin dissociation - the selectivity towards light olefins during the reaction over zeolite based catalysts
- the probable light olefin selectivity modifiers generated in Zone i and affecting the activity and selectivity of the zeolite catalysts of Zone II are presently identified as such:
- Aromatization olefins, diolefins and naphtene — » aromatics + nH 2
- Hydrogen transfer naphtene + olefins - aromatics + paraffins diolefins + paraffins — » olefins + olefins
- Olefin dissociation large olefins ⁇ ->• 2 small olefins + H 2
- Zone I contains a pre-catalyst porous material, preferably quartz having large pores and low surface area to avoid excessive coking.
- the surface of the porous material is used to enhance the contact effect and the pore system is used to lengthen the diffusion path of the feed in order to increase the steam-cracking conversion, thus, al lowing the reaction in Zone I to be carried out at relatively low temperatures.
- Zone I is different from the feed preheating zone which is used in the prior art in many chemical or catalytic processes. Indeed, i) the role of Zone I is well- defined : to produce some selectivity modifiers and to help increase the final total conversion obtained at the outlet of the catalytic reactor (Zone II), and ii) the temperature of Zone I is normal ly (but not always) higher (at least in the case of the present invention) than the temperature of the catalyst bed.
- Zone II contains a ZSM5 zeolite based catalyst or, preferably, a hybrid zeolite catalyst.
- the latter has been prepared by combining the ZSM5 zeolite with a Cr-Al containing cocatalyst in accordance with the method of formation of a pore continuum as described in US Patent 4,732,881 .
- the beneficial effects of the method based on two zones of conversion (with the parent ZSM5 zeol ite packed in Zone II) when compared to the conventional one-zone catalytic reaction (parent ZSM5 zeolite) are as follows : i) general ly higher total conversion and always higher selectivity to light olefins (and aromatics) as evidenced by the yield increases in light olefins and light olefins + aromatics of 24 % and 29 %, respectively; ii) a wide variation of the ethylene/propylene product ratio, depending on the temperature T1 of Zone I.
- the yield increases in light olefins and light olefins + aromatics reach the values of 35% and 41 %, respectively.
- the ethylene/propylene product ratio varies from 1 .0 (equal to the value for the parent ZSM5 zeolite, obtained using the conventional reactor) to 2.0. This is also shown in Figure 3.
- Quartz sicon oxide, fused from Aldrich, granules
- Hybrid catalyst containing the ZSM5 zeolite and the Cr-Al cocatalyst i)
- the ZSM-5 zeolite used was the Zeocat PZ-2/50, H-form, powder, purchased from
- the cocatalyst was prepared in the fol lowing way : the sol id material (20 g) obtained by drying the Col loidal silica Ludox AS-40 from Dupont and then activated in air at
- This cocatalyst is referred to as Cocat.
- Hyb. Cat. The final hybrid catalyst, referred to as Hyb. Cat., was obtained by extrusion with bentonite as follows : first, HZ and Cocat (70 wt % and 1 5 wt %, respectively) were careful ly mixed (a hour stirring in dry conditions); then, bentonite clay used as binder (1 5 wt %) was added to the previous sol id mixture and the all was stirred for another hour. Water was then added dropwise until a malleable paste was obtained. The resulting catalyst extrudates were dried at 1 20°C overnight and final ly activated in air at 700°C for 5 hours.
- TESTING PROCEDURE Liquids namely n-hexane and water, were injected into a vaporizer using two infusion pumps.
- nitrogen used as carrier gas was mixed with n-hexane vapors and steam.
- the gaseous stream was then sent into the tubular reactor, first in Zone I and then in Zone II.
- the testing conditions are as follows:
- weight of catalyst 5.0 g
- water/n-hexane molar ratio ca. 1 .0
- the total n-hexane conversion (mol % or wt %) is expressed as follows:
- Si 100 x (number of carbon atoms of product i / number of carbon atoms of converted products)
- Zone I Steam-cracking conversion of n-hexane in the non-catalytic zone, i.e. Zone I (Table 1): Runs were performed with the zone I set at various temperature T1 (660° - 720°C) which were slightly higher than the temperature T2 of the catalytic bed (650°C). In this series of runs, the catalyst bed was empty and Zone II was not heated. The results are reported in Table 1 .
- Zone I Zone II C t Y eth Y Pro Y but Y buta Y me Y p2 ⁇ Y Mq Y 0[e ' oie + aro ' y ° ⁇ ,(°c)
- the selectivity enhancers created in Zone I advantageously improve the performance of the catalyst in Zone II.
- the decrease of butadienes seen in the product stream was due to the hydrogen transfer within the zeolite network (Table 1 versus Table 2) : this is indicative of the role of these substances in the modification of the activity and selectivity of the zeolite based catalysts.
- the data obtained with the hybrid catalyst (Table 2) when compared to the HZSM5 normal conditions of testing, i.e. with no precatalytic zone, see Table 2), the increases in light olefins and light olefins + aromatics, are 35 % and 41 %, respectively.
- the apparatus of the present invention is not limited to a tubular reactor with two reaction zones.
- the catalytic zone (Zone II) may have another configuration such as that of a fluidized bed.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU13742/01A AU1374201A (en) | 1999-11-04 | 2000-11-03 | Method and apparatus for selective deep catalytic cracking of hydrocarbons |
EP00975698A EP1232230A1 (en) | 1999-11-04 | 2000-11-03 | Method and apparatus for selective deep catalytic cracking of hydrocarbons |
US10/129,577 US7135602B1 (en) | 1999-11-04 | 2000-11-03 | Method and apparatus for selective deep catalytic cracking of hydrocarbons |
CA002389536A CA2389536A1 (en) | 1999-11-04 | 2000-11-03 | Method and apparatus for selective deep catalytic cracking of hydrocarbons |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16345999P | 1999-11-04 | 1999-11-04 | |
US60/163,459 | 1999-11-04 |
Publications (1)
Publication Number | Publication Date |
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WO2001032806A1 true WO2001032806A1 (en) | 2001-05-10 |
Family
ID=22590099
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2000/001327 WO2001032806A1 (en) | 1999-11-04 | 2000-11-03 | Method and apparatus for selective deep catalytic cracking of hydrocarbons |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1232230A1 (en) |
AU (1) | AU1374201A (en) |
CA (1) | CA2389536A1 (en) |
WO (1) | WO2001032806A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003064039A1 (en) * | 2002-01-28 | 2003-08-07 | Concordia University | Hybrid catalysts for the deep catalytic cracking of petroleum naphthas and other hydrocarbon feedstocks |
US7456128B2 (en) | 2004-04-29 | 2008-11-25 | Valorbec, S.E.C., Represented By The Gestion Valeo, S.E.C. | Catalyst formulations for the thermo-catalytic cracking of naphthas and gas oils |
US8192591B2 (en) | 2005-12-16 | 2012-06-05 | Petrobeam, Inc. | Self-sustaining cracking of hydrocarbons |
EP2867339B1 (en) | 2012-08-09 | 2015-10-28 | Linde Aktiengesellschaft | Method for producing olefins through thermal water splitting |
US11066605B2 (en) | 2019-11-12 | 2021-07-20 | Saudi Arabian Oil Company | Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins |
US11066606B2 (en) | 2019-11-12 | 2021-07-20 | Saudi Arabian Oil Company | Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins with steam |
US11866397B1 (en) | 2023-03-14 | 2024-01-09 | Saudi Arabian Oil Company | Process configurations for enhancing light olefin selectivity by steam catalytic cracking of heavy feedstock |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2692193A (en) * | 1948-07-29 | 1954-10-19 | Inst Gas Technology | Method of preparing a gas interchangeable with coke oven gas, carbureted gas, or mixtures thereof |
EP0022883A1 (en) * | 1979-07-18 | 1981-01-28 | Exxon Research And Engineering Company | Catalytic cracking and hydrotreating process for producing gasoline from hydrocarbon feedstocks containing sulfur |
US4732881A (en) * | 1986-09-25 | 1988-03-22 | The Abestos Institute | Catalysts for up-grading steam-cracking products |
-
2000
- 2000-11-03 AU AU13742/01A patent/AU1374201A/en not_active Abandoned
- 2000-11-03 EP EP00975698A patent/EP1232230A1/en not_active Withdrawn
- 2000-11-03 WO PCT/CA2000/001327 patent/WO2001032806A1/en not_active Application Discontinuation
- 2000-11-03 CA CA002389536A patent/CA2389536A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2692193A (en) * | 1948-07-29 | 1954-10-19 | Inst Gas Technology | Method of preparing a gas interchangeable with coke oven gas, carbureted gas, or mixtures thereof |
EP0022883A1 (en) * | 1979-07-18 | 1981-01-28 | Exxon Research And Engineering Company | Catalytic cracking and hydrotreating process for producing gasoline from hydrocarbon feedstocks containing sulfur |
US4732881A (en) * | 1986-09-25 | 1988-03-22 | The Abestos Institute | Catalysts for up-grading steam-cracking products |
Non-Patent Citations (1)
Title |
---|
N.A. VASIL'EVA, R.A. BUYANOV AND I.N. KLIMIK: "The catalytic pyrolysis of hydrocarbons", KINETICS AND CATALYSIS., vol. 21, no. 1, 1980, CONSULTANTS BUREAU, NEW YORK, NY., US, pages 175 - 179, XP000987046, ISSN: 0023-1584 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003064039A1 (en) * | 2002-01-28 | 2003-08-07 | Concordia University | Hybrid catalysts for the deep catalytic cracking of petroleum naphthas and other hydrocarbon feedstocks |
US7026263B2 (en) | 2002-01-28 | 2006-04-11 | Valorbec, Société en commandite | Hybrid catalysts for the deep catalytic cracking of petroleum naphthas and other hydrocarbon feedstocks |
US7456128B2 (en) | 2004-04-29 | 2008-11-25 | Valorbec, S.E.C., Represented By The Gestion Valeo, S.E.C. | Catalyst formulations for the thermo-catalytic cracking of naphthas and gas oils |
US8192591B2 (en) | 2005-12-16 | 2012-06-05 | Petrobeam, Inc. | Self-sustaining cracking of hydrocarbons |
US8911617B2 (en) | 2005-12-16 | 2014-12-16 | Petrobeam, Inc. | Self-sustaining cracking of hydrocarbons |
EP2867339B1 (en) | 2012-08-09 | 2015-10-28 | Linde Aktiengesellschaft | Method for producing olefins through thermal water splitting |
US11066605B2 (en) | 2019-11-12 | 2021-07-20 | Saudi Arabian Oil Company | Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins |
US11066606B2 (en) | 2019-11-12 | 2021-07-20 | Saudi Arabian Oil Company | Systems and methods for catalytic upgrading of vacuum residue to distillate fractions and olefins with steam |
US11866397B1 (en) | 2023-03-14 | 2024-01-09 | Saudi Arabian Oil Company | Process configurations for enhancing light olefin selectivity by steam catalytic cracking of heavy feedstock |
Also Published As
Publication number | Publication date |
---|---|
AU1374201A (en) | 2001-05-14 |
EP1232230A1 (en) | 2002-08-21 |
CA2389536A1 (en) | 2001-05-10 |
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