EP0921176A1 - Production d'oléfines - Google Patents

Production d'oléfines Download PDF

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Publication number
EP0921176A1
EP0921176A1 EP97121376A EP97121376A EP0921176A1 EP 0921176 A1 EP0921176 A1 EP 0921176A1 EP 97121376 A EP97121376 A EP 97121376A EP 97121376 A EP97121376 A EP 97121376A EP 0921176 A1 EP0921176 A1 EP 0921176A1
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EP
European Patent Office
Prior art keywords
feedstock
catalyst
olefin
olefins
effluent
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.)
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EP97121376A
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German (de)
English (en)
Inventor
Jean-Pierre Dath
Luc Delorme
Jacques-François Grootjans
Xavier Vanhaeren
Walter Vermeiren
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.)
Total Research and Technology Feluy SA
Original Assignee
Fina Research SA
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.)
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Publication date
Application filed by Fina Research SA filed Critical Fina Research SA
Priority to EP97121376A priority Critical patent/EP0921176A1/fr
Priority to ZA9811082A priority patent/ZA9811082B/xx
Priority to TW087120161A priority patent/TW491889B/zh
Priority to EP98958122A priority patent/EP1036133B1/fr
Priority to ES98958122T priority patent/ES2202911T3/es
Priority to AT98958122T priority patent/ATE244288T1/de
Priority to PCT/BE1998/000187 priority patent/WO1999029802A1/fr
Priority to JP36197398A priority patent/JP4048458B2/ja
Priority to CNB988134624A priority patent/CN1170913C/zh
Priority to AU14302/99A priority patent/AU1430299A/en
Priority to DE69816114T priority patent/DE69816114T2/de
Priority to KR1020007006128A priority patent/KR20010032810A/ko
Publication of EP0921176A1 publication Critical patent/EP0921176A1/fr
Withdrawn legal-status Critical Current

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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
    • 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 process for cracking an olefin-rich hydrocarbon feedstock which is selective towards light olefins in the effluent.
  • olefinic feedstocks from refineries or petrochemical plants can be converted selectively so as to redistribute the olefin content of the feedstock in the resultant effluent.
  • zeolites to convert long chain paraffins into lighter products, for example in the catalytic dewaxing of petroleum feedstocks. While it is not the objective of dewaxing, at least parts of the paraffinic hydrocarbons are converted into olefins.
  • crystalline silicates for example of the MFI type, the three-letter designation "MFI" representing a particular crystalline silicate structure type as established by the Structure Commission of the International Zeolite Association. Examples of a crystalline silicate of the MFI type are the synthetic zeolite ZSM-5 and silicalite and other MFI type crystalline silicates are known in the art.
  • GB-A-1323710 discloses a dewaxing process for the removal of straight-chain paraffins and slightly branched-chain paraffins, from hydrocarbon feedstocks utilising a crystalline silicate catalyst, in particular ZSM-5.
  • US-A-4247388 also discloses a method of catalytic hydrodewaxing of petroleum and synthetic hydrocarbon feedstocks using a crystalline silicate of the ZSM-5 type. Similar dewaxing processes are disclosed in US-A-4284529 and US-A-5614079.
  • the catalysts are crystalline alumino- silicates and the above-identified prior art documents disclose the use of a wide range of Si/Al ratios and differing reaction conditions for the disclosed dewaxing processes.
  • GB-A-2185753 discloses the dewaxing of hydrocarbon feedstocks using a silicalite catalyst.
  • US-A-4394251 discloses hydrocarbon conversion with a crystalline silicate particle having an aluminium-containing outer shell.
  • Silicalite catalysts exist having varying silicon/aluminium atomic ratios and different crystalline forms.
  • EP-A-0146524 and 0146525 in the name of Cosden Technology, Inc. disclose crystalline silicas of the silicalite type having monoclinic symmetry and a process for their preparation. These silicates have a silicon to aluminium atomic ratio of greater than 80.
  • WO-A-97/04871 discloses the treatment of a medium pore zeolite with steam followed by treatment with an acidic solution for improving the butene selectivity of the zeolite in catalytic cracking.
  • EP-A-0305720 discloses the production of gaseous olefins by catalytic conversion of hydrocarbons.
  • EP-B-0347003 discloses a process for the conversion of a hydrocarbonaceous feedstock into light olefins.
  • WO-A-90/11338 discloses a process for the conversion of C 2 -C 12 paraffinic hydrocarbons to petrochemical feedstocks, in particular to C 2 to C 4 olefins.
  • US-A-5043522 and EP-A-0395345 disclose the production of olefins from paraffins having four or more carbon atoms.
  • EP-A-0511013 discloses the production of olefins from hydrocarbons using a steam activated catalyst containing phosphorous and H-ZSM-5.
  • US-A-4810356 discloses a process for the treatment of gas oils by dewaxing over a silicalite catalyst.
  • GB-A-2156845 discloses the production of isobutylene from propylene or a mixture of hydrocarbons containing propylene.
  • GB-A-2159833 discloses the production of a isobutylene by the catalytic cracking of light distillates.
  • Propylene is obtained from FCC units but at a relatively low yield and increasing the yield has proven to be expensive and limited. Yet another route known as metathesis or disproportionation enables the production of propylene from ethylene and butene. Often, combined with a steam cracker, this technology is expensive since it uses ethylene as a feedstock which is at least as valuable as propylene.
  • crystalline silicates of the MFI type are also well known catalysts for the oligomerisation of olefins.
  • EP-A-0031675 discloses the conversion of olefin-containing mixtures to gasoline over a catalyst such as ZSM-5.
  • the operating conditions for the oligomerisation reaction differ significantly from those used for cracking. Typically, in the oligomerisation reactor the temperature does not exceed around 400°C and a high pressure favours the oligomerisation reactions.
  • GB-A-2156844 discloses a process for the isomerisation of olefins over silicalite as a catalyst.
  • US-A-4579989 discloses the conversion of olefins to higher molecular weight hydrocarbons over a silicalite catalyst.
  • US-A-4746762 discloses the upgrading of light olefins to produce hydrocarbons rich in C 5 + liquids over a crystalline silicate catalyst.
  • US-A-5004852 discloses a two-stage process for conversion of olefins to high octane gasoline wherein in the first stage olefins are oligomerised to C 5 + olefins.
  • US-A-5171331 discloses a process for the production of gasoline comprising oligomerising a C 2 -C 6 olefin containing feedstock over an intermediate pore size siliceous crystalline molecular sieve catalyst such as silicalite, halogen stabilised silicalite or a zeolite.
  • US-A-4414423 discloses a multistep process for preparing high-boiling hydrocarbons from normally gaseous hydrocarbons, the first step comprising feeding normally gaseous olefins over an intermediate pore size siliceous crystalline molecular sieve catalyst.
  • US-A-4417088 discloses the dimerising and trimerising of high carbon olefins over silicalite.
  • US-A-4417086 discloses an oligomerisation process for olefins over silicalite.
  • GB-A-2106131 and GB-A-2106132 disclose the oligomerisation of olefins over catalysts such as zeolite or silicalite to produce high boiling hydrocarbons.
  • GB-A-2106533 discloses the oligomerisation of gaseous olefins over zeolite or silicalite.
  • the present invention provides a process for the catalytic cracking of an olefin-rich feedstock which is selective towards light olefins in the effluent, the process comprising contacting a hydrocarbon feedstock containing one or more olefins, with a MFI-type crystalline silicate catalyst having a silicon/aluminium atomic ratio of at least about 300 at an inlet temperature of from 500 to 600°C, at an olefin partial pressure of from 0.1 to 2 bars and the feedstock being passed over the catalyst at an LHSV of from 10 to 30h -1 , to produce an effluent with an olefin content of lower molecular weight than that of the feedstock.
  • the present invention can thus provide a process wherein olefin-rich hydrocarbon streams (products) from refinery and petrochemical plants are selectively cracked not only into light olefins, but particularly into propylene.
  • the olefin-rich feedstock may be passed over a MFI-type crystalline silicate catalyst with a particular Si/Al atomic ratio of at least about 300.
  • the catalyst is preferably a commercially available catalyst which has been prepared by crystallisation using an organic template and has been unsubjected to any subsequent steaming or de-alumination process.
  • the feedstock may be passed over the catalyst at a temperature ranging between 500 to 600°C, an olefin partial pressure of from 0.1 to 2 bars and an LHSV of from 10 to 30h -1 to yield at least 30 to 50% propylene based on the olefin content in the feedstock.
  • silicon/aluminium atomic ratio is intended to mean the Si/Al atomic ratio of the overall material, which may be determined by chemical analysis.
  • Si/Al ratios apply not just to the Si/Al framework of the crystalline silicate but rather to the whole material.
  • the feedstock may be fed either undiluted or diluted with an inert gas such as nitrogen.
  • an inert gas such as nitrogen.
  • the absolute pressure of the feedstock constitutes the partial pressure of the hydrocarbon feedstock in the inert gas.
  • Figure 1 shows the relationship between the amount of olefin feedstock conversion, the propylene yield, and the sum of the other components and the silicon/aluminium atomic ratio in a catalytic cracking process of the invention.
  • cracking of olefins is performed in the sense that olefins in a hydrocarbon stream are cracked into lighter olefins and selectively into propylene.
  • the feedstock and effluent preferably have substantially the same olefin content by weight.
  • the olefin content of the effluent is within ⁇ 15wt%, more preferably ⁇ 10wt%, of the olefin content of the feedstock.
  • the feedstock may comprise any kind of olefin-containing hydrocarbon stream.
  • the feedstock may typically comprise from 10 to 100wt% olefins and furthermore may be fed undiluted or diluted by a diluent, the diluent optionally including a non-olefinic hydrocarbon.
  • the olefin-containing feedstock may be a hydrocarbon mixture containing normal and branched olefins in the carbon range C 4 to C 10 , more preferably in the carbon range C 4 to C 6 , optionally in a mixture with normal and branched paraffins and/or aromatics in the carbon range C 4 to C 10 .
  • the olefin-containing stream has a boiling point of from around -15 to around 180°C.
  • the hydrocarbon feedstocks comprise C 4 mixtures from refineries and steam cracking units.
  • Such steam cracking units crack a wide variety of feedstocks, including ethane, propane, butane, naphtha, gas oil, fuel oil, etc.
  • the hydrocarbon feedstock may comprises a C 4 cut from a fluidized-bed catalytic cracking (FCC) unit in a crude oil refinery which is employed for converting heavy oil into gasoline and lighter products.
  • FCC fluidized-bed catalytic cracking
  • such a C 4 cut from an FCC unit comprises around 50wt% olefin.
  • the hydrocarbon feedstock may comprise a C 4 cut from a unit within a crude oil refinery for producing methyl tert-butyl ether (MTBE) which is prepared from methanol and isobutene.
  • MTBE methyl tert-butyl ether
  • Such a C 4 cut from the MTBE unit typically comprises around 50wt% olefin.
  • These C 4 cuts are fractionated at the outlet of the respective FCC or MTBE unit.
  • the hydrocarbon feedstock may yet further comprise a C 4 cut from a naphtha steam-cracking unit of a petrochemical plant in which naphtha, comprising C 5 to C 9 species having a boiling point range of from about 15 to 180°C, is steam cracked to produce, inter alia , a C 4 cut.
  • Such a C 4 cut typically comprises, by weight, 40 to 50% 1,3-butadiene, around 25% isobutylene, around 15% butene (in the form of but-1-ene and/or but-2-ene) and around 10% n-butane and/or isobutane.
  • the olefin-containing hydrocarbon feedstock may also comprise a C 4 cut from a steam cracking unit after butadiene extraction (raffinate 1), or after butadiene hydrogenation.
  • the feedstock may yet further alternatively comprise a hydrogenated butadiene-rich C 4 cut, typically containing greater than 50wt% C 4 as an olefin.
  • the hydrocarbon feedstock could comprise a pure olefin feedstock which has been produced in a petrochemical plant.
  • the olefin-containing feedstock may yet further alternatively comprise light cracked naphtha (LCN) (otherwise known as light catalytic cracked spirit (LCCS)) or a C 5 cut from a steam cracker or light cracked naphtha, the light cracked naphtha being fractionated from the effluent of the FCC unit, discussed hereinabove, in a crude oil refinery. Both such feedstocks contain olefins.
  • the olefin-containing feedstock may yet further alternatively comprise a medium cracked naphtha from such an FCC unit or visbroken naphtha obtained from a visbreaking unit for treating the residue of a vacuum distillation unit in a crude oil refinery.
  • the olefin-containing feedstock may comprise a mixture of one or more of the above-described feedstocks.
  • the use of a C 5 cut as the olefin-containing hydrocarbon feedstock in accordance with a preferred process of the invention has particular advantages because of the need to remove C 5 species in any event from gasolines produced by the oil refinery. This is because the presence of C 5 in gasoline increases the ozone potential and thus the photochemical activity of the resulting gasoline. In the case of the use of light cracked naphtha as the olefin-containing feedstock, the olefin content of the remaining gasoline fraction is reduced, thereby reducing the vapour pressure and also the photochemical activity of the gasoline.
  • C 2 to C 4 olefins may be produced in accordance with the process of the invention.
  • the C 4 fraction is very rich in olefins, especially in isobutene, which is an interesting feed for an MTBE unit.
  • C 2 to C 3 olefins are produced on the one hand and C 5 to C 6 olefins containing mainly iso-olefins are produced on the other hand.
  • the remaining C 4 cut is enriched in butanes, especially in isobutane which is an interesting feedstock for an alkylation unit of an oil refinery wherein an alkylate for use in gasoline is produced from a mixture of C 3 and C 5 feedstocks.
  • the C 5 to C 6 cut containing mainly iso-olefins is an interesting feed for the production of tertiary amyl methyl ether (TAME).
  • TAME tertiary amyl methyl ether
  • olefinic feedstocks can be cracked selectively so as to redistribute the olefinic content of the feedstock in the resultant effluent.
  • the catalyst and process conditions are selected whereby the process has a particular yield on an olefin basis towards a specified olefin in the feedstocks.
  • the catalyst and process conditions are chosen whereby the process has the same high yield on an olefin basis towards propylene irrespective of the origin of the olefinic feedstocks for example the C 4 cut from the FCC unit, the C 4 cut from the MTBE unit, the light cracked naphtha or the C 5 cut from the light crack naphtha, etc., This is quite unexpected on the basis of the prior art.
  • the propylene yield on an olefin basis is typically from 30 to 50% based on the olefin content of the feedstock.
  • the yield on an olefin basis of a particular olefin is defined as the weight of that olefin in the effluent divided by the initial total olefin content by weight.
  • the propylene yield on an olefin basis is 40%. This may be contrasted with the actual yield for a product which is defined as the weight amount of the product produced divided by the weight amount of the feed.
  • the paraffins and the aromatics contained in the feedstock are only slightly converted in accordance with the preferred aspects of the invention.
  • the catalyst for the cracking of the olefins comprises a crystalline silicate of the MFI family which may be a zeolite, a silicalite or any other silicate in that family.
  • the preferred crystalline silicates have pores or channels defined by ten oxygen rings and a high silicon/aluminium atomic ratio.
  • Crystalline silicates are microporous crystalline inorganic polymers based on a framework of XO 4 tetrahedra linked to each other by sharing of oxygen ions, where X may be trivalent (e.g. Al,B,...) or tetravalent ( e.g. Ge, Si,).
  • X may be trivalent (e.g. Al,B,...) or tetravalent (e.g. Ge, Si,).
  • the crystal structure of a crystalline silicate is defined by the specific order in which a network of tetrahedral units are linked together.
  • the size of the crystalline silicate pore openings is determined by the number of tetrahedral units, or, alternatively, oxygen atoms, required to form the pores and the nature of the cations that are present in the pores.
  • Crystalline silicates with the MFI structure possess a bidirectional intersecting pore system with the following pore diameters: a straight channel along [010]:0.53-0.56 nm and a sinusoidal channel along [100]:0.51-0.55 nm.
  • the crystalline silicate catalyst has structural and chemical properties and is employed under particular reaction conditions whereby the catalytic cracking readily proceeds. Different reaction pathways can occur on the catalyst. Under the process conditions, having an inlet temperature of around 500 to 600°C, preferably from 520 to 600°C, yet more preferably 540 to 580°C, and an olefin partial pressure of from 0.1 to 2 bars, most preferably around atmospheric pressure, the shift of the double bond of an olefin in the feedstock is readily achieved, leading to double bond isomerisation. Furthermore, such isomerisation tends to reach a thermodynamic equilibrium. Propylene can be, for example, directly produced by the catalytic cracking of hexene or a heavier olefinic feedstock. Olefinic catalytic cracking may be understood to comprise a process yielding shorter molecules via bond breakage.
  • the catalyst preferably has a high silicon/aluminium atomic ratio, greater than about 300, whereby the catalyst has relatively low acidity.
  • Hydrogen transfer reactions are directly related to the strength and density of the acid sites on the catalyst, and such reactions are preferably suppressed so as to avoid the formation of coke during the olefin conversion process, which in turn would otherwise decrease the stability of the catalyst over time.
  • Such hydrogen transfer reactions tend to produce saturates such as paraffins, intermediate unstable dienes and cyclo-olefins, and aromatics, none of which favours cracking into light olefins.
  • Cyclo-olefins are precursors of aromatics and coke-like molecules, especially in the presence of solid acids, i.e. an acidic solid catalyst.
  • the acidity of the catalyst can be determined by the amount of residual ammonia on the catalyst following contact of the catalyst with ammonia which adsorbs to the acid sites on the catalyst with subsequent ammonium desorption at elevated temperature measured by differential thermogravimetric analysis.
  • the silicon/aluminium ratio ranges from 300 to 1000, most preferably from 300 to 500.
  • One of the features of the invention is that with such high silicon/aluminium ratio in the crystalline silicate catalyst, a stable olefin conversion can be achieved with a high propylene yield on an olefin basis of from 30 to 50% whatever the origin and composition of the olefinic feedstock. Such high ratios reduce the acidity of the catalyst, thereby increasing the stability of the catalyst.
  • the propylene has a purity of at least 93%.
  • at least 85% by weight of the olefins in the feedstock are cracked into olefins or are present as the initial olefin.
  • the catalyst it is also preferred in accordance with the invention for the catalyst to have high stability int the cracking process in the sense that the catalyst is not reduced in activity as a result of coke being progressively deposited or formed on the catalyst.
  • Such coke formation has been found by the inventors to lead to a significant decrease of the ability of the catalyst to crack the olefins with a high propylene yield over time. All of these desired results in the cracking process may be achieved in accordance with the invention by providing a silicon/aluminium atomic ratio in the crystalline silicate catalyst of the MFI-type of at least about 300, in conjunction with the required process parameters of temperature and pressure.
  • the various preferred catalysts of the present invention have been found to exhibit high stability, in particular being capable of giving a stable propylene yield over several days, e.g. up to ten days. This enables the olefin cracking process to be performed continuously in two parallel "swing" reactors wherein when one reactor is operating, the other reactor is undergoing catalyst regeneration.
  • the catalyst of the present invention also can be regenerated several times.
  • the catalyst is also flexible in that it can be employed to crack a variety of feedstocks, either pure or mixtures, coming from different sources in the oil refinery or petrochemical plant and having different compositions.
  • the process conditions are selected in order to provide high selectivity towards propylene, a stable olefin conversion over time, and a stable olefinic product distribution in the effluent.
  • Such objectives are favoured by the use of a low acid density in the catalyst (i.e. a high Si/Al atomic ratio) in conjunction with a low pressure, a high inlet temperature and a short contact time, all of which process parameters are interrelated and provide an overall cumulative effect (e.g. a higher pressure may be offset or compensated by a yet higher inlet temperature).
  • the process conditions are selected to disfavour hydrogen transfer reactions leading to the formation of paraffins, aromatics and coke precursors.
  • the process operating conditions thus employ a high space velocity, a low pressure and a high reaction temperature.
  • the LHSV ranges from 10 to 30h -1 .
  • the olefin partial pressure ranges from 0.1 to 2 bars, more preferably from 0.5 to 1.5 bars.
  • a particularly preferred olefin partial pressure is atmospheric pressure ( i.e. 1 bar).
  • the hydrocarbon feedstocks are preferably fed at a total inlet pressure sufficient to convey the feedstocks through the reactor.
  • the hydrocarbon feedstocks may be fed undiluted or diluted in an inertgas, e.g. nitrogen.
  • the total absolute pressure in the reactor ranges from 0.5 to 10 bars.
  • the present inventors have found that the use of a low olefin partial pressure, for example atmospheric pressure, tends to lower the incidence of hydrogen transfer reactions in the cracking process, which in turn reduces the potential for coke formation which tends to reduce catalyst stability.
  • the cracking of the olefins is performed at an inlet temperature of the feedstock of from 500 to 600°C, more preferably from 520 to 600°C, yet more preferably from 540 to 580°C, typically around 560°C to 570°C.
  • the catalytic cracking process can be performed in a fixed bed reactor, a moving bed reactor or a fluidized bed reactor.
  • a typical fluid bed reactor is one of the FCC type used for fluidized-bed catalytic cracking in the oil refinery.
  • a typical moving bed reactor is of the continuous catalytic reforming type. As described above, the process may be performed continuously using a pair of parallel "swing" reactors.
  • the catalyst Since the catalyst exhibits high stability to olefinic conversion for an extended period, typically at least around ten days, the frequency of regeneration of the catalyst is low. More particularly, the catalyst may accordingly have a lifetime which exceeds one year.
  • the reactor effluent is sent to a fractionator and the desired olefins are separated from the effluent.
  • the C 3 cut containing at least 93% propylene, is fractionated and thereafter purified in order to remove all the contaminants such as sulphur species, arsine, etc..
  • the heavier olefins of greater than C 3 can be recycled.
  • the olefin conversion process can be controlled so as to produce selectively particular olefin distributions in the resultant effluents.
  • olefin-rich streams from refinery or petrochemical plants are cracked into light olefins, in particular propylene.
  • the light fractions of the effluent namely the C 2 and C 3 cuts, can contain more than 95% olefins.
  • Such cuts are sufficiently pure to constitute chemical grade olefin feedstocks.
  • the present inventors have found that the propylene yield on an olefin basis in such a process can range from 30 to 50% based on the olefinic content of the feedstock which contains one or more olefins of C 4 or greater.
  • the effluent has a different olefin distribution as compared to that of the feedstock, but substantially the same total olefin content.
  • the process of the present invention produces C 2 to C 3 olefins from a C 5 olefinic feedstock.
  • the catalyst is of crystalline silicate having a silicon/aluminium ratio of at least 300, and the process conditions are an inlet temperature of from 500 to 600°C, an olefin partial pressure of from 0.1 to 2 bars, and an LHSV of 10 to 30h -1 , yielding an olefinic effluent having at least 40% of the olefin content present as C 2 to C 3 olefins.
  • Another preferred embodiment of the present invention provides a process for the production of C 2 to C 3 olefins from a light cracked naphtha.
  • the light cracked naphtha is contacted with a catalyst of crystalline silicate having a silicon/aluminium ratio of at least 300, to produce by cracking an olefinic effluent wherein at least 40% of the olefin content is present as C 2 to C 3 olefins.
  • the process conditions comprise an inlet temperature of 500 to 600°C, an olefin partial pressure of from 0.1 to 2 bars, and an LHSV of 10 to 30h -1 .
  • a feedstock comprising 1-hexene was fed through a reactor at an inlet temperature of around 580°C, an outlet hydrocarbon pressure of atmospheric pressure and an LHSV of around 25 h -1 over ZSM-5 type catalysts available in commerce from the company CU Chemie Ueticon AG of Switzerland under the trade name ZEOCAT P2-2.
  • the catalysts being commercially available had been prepared by crystallisation using an organic template and had been unsubjected to any subsequent steaming or de-alumination process.
  • the catalysts had a varying silicon/aluminium atomic ratio of 50, 200, 300 and 490.
  • the crystal size of each catalyst was from 2 to 5 microns and the pellet size was from 35 to 45 mesh.
  • Figure 1 shows the yield of propylene in the effluent, the percentage conversion of the 1-hexene olefinic feedstock following the olefinic catalytic cracking process of the invention and the sum of the saturates, olefins and aromatics in the effluent.
  • both the yield of olefins in the effluent and the yield of propylene on an olefin basis are lower than the desired values of 85% and 30% respectively.
  • the propylene purity is also less than typical desired value commercially of 93%.
  • the resultant Si/Al ratio is preferably greater than only 180 in order to obtain the desired olefin content in the effluent, propylene yield on an olefin basis, and purity of propylene.
  • Si/Al atomic ratio of greater than about 300 in a commercially available catalyst which has not been pretreated by steaming and de-alumination at least about 85% of the olefins in the feedstock are cracked into olefins or are present as the initial olefin.
  • the feedstock and the effluent have substantially the olefin content by weight therein, to the extent that the olefin content by weight of the feedstock and the effluent are within ⁇ 15wt% of each other.
  • the yield of propylene is at least around 30% by weight on an olefin basis.
  • the olefin content of the effluent is greater than about 90% by weight of the olefin content of the feedstock and the propylene yield on an olefin basis approaches 40%.
  • the MFI silicates comprise zeolites of the ZSM-5 type, in particular zeolite sold in commerce under the trade name H-ZSM-5 available in commerce from the company PQ Corporation of Southpoint, P.O. Box 840, Valley Forge, PA 19482-0840, USA.
  • the crystalline silicates had a particle size of from 35-45 mesh and were not modified by prior treatment.
  • the crystalline silicates were loaded into a reactor tube and heated to a temperature of around 530°C. Thereafter, one gram of 1-hexene was injected into the reactor tube in a period of 60 seconds. The injection rate had a WHSV of 20h -1 and a catalyst to oil weight ratio of 3. The cracking process was performed at an outlet hydrocarbon pressure of 1 bar (atmospheric pressure).
  • Table 1 shows the yield in terms of wt% of various constituents in the resultant effluent and also the amount of coke produced on the catalyst in the reactor tube.
  • the propylene yield on an olefin basis is around 28.8 in the effluent, being significantly higher than the propylene yield of the two runs using the low Si/Al atomic ratios. It may be thus be seen that the use of a catalyst having a high silicon/aluminium atomic ratio increases the propylene yield on an olefin basis in the catalytic cracking of olefins to produce other olefins.
  • the butene-containing feedstock had the composition as specified in Tables 2a and 2b.
  • the catalytic cracking process was carried out at an inlet temperature of 545°C, an outlet hydrocarbon pressure of atmospheric pressure and at an LSHV of 30h -1 .
  • Tables 2a and 2b show the breakdown of the propylene, iso-butene and n-butene amounts present in the effluent.
  • the catalyst comprised a silicalite having a silicon/aluminium ratio of around 120, and having a crystallite size of from 4 to 6 microns and a surface area (BET) of 399m 2 /g.
  • BET surface area
  • the silicalite was pressed, washed and the 35-45 mesh fraction was retained. The catalyst had not been subjected to any steaming and alumination extraction process.
  • the catalyst comprised the same starting silicalite as in Comparative Example 1 which had been subjected to a steaming process in an atmosphere of 72vol% stream and 28vol% nitrogen at a temperature of 550°C at atmospheric pressure for a period of 48 hours, but not an aluminium extraction process.
  • Tables 2a and 2b The results are shown in Tables 2a and 2b respectively.
  • Comparative Example 1 and Comparative Example 2 the catalyst did not exhibit stability. In other words, the catalyst reduced its ability over time to catalyse the cracking process. It is believed that this is because of the formation of coke on the catalyst, which in turn results from the use of a low silicon/aluminium atomic ratio in the catalyst, leading to a relatively high acidity for the catalyst.

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
EP97121376A 1997-12-05 1997-12-05 Production d'oléfines Withdrawn EP0921176A1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP97121376A EP0921176A1 (fr) 1997-12-05 1997-12-05 Production d'oléfines
ZA9811082A ZA9811082B (en) 1997-12-05 1998-12-03 Production of olefins
TW087120161A TW491889B (en) 1997-12-05 1998-12-04 Production of olefins
EP98958122A EP1036133B1 (fr) 1997-12-05 1998-12-07 Production d'olefines
ES98958122T ES2202911T3 (es) 1997-12-05 1998-12-07 Produccion de olefinas.
AT98958122T ATE244288T1 (de) 1997-12-05 1998-12-07 Herstellung von olefinen
PCT/BE1998/000187 WO1999029802A1 (fr) 1997-12-05 1998-12-07 Production d'olefines
JP36197398A JP4048458B2 (ja) 1997-12-05 1998-12-07 オレフインの製造
CNB988134624A CN1170913C (zh) 1997-12-05 1998-12-07 烯烃的生产
AU14302/99A AU1430299A (en) 1997-12-05 1998-12-07 Production of olefins
DE69816114T DE69816114T2 (de) 1997-12-05 1998-12-07 Herstellung von olefinen
KR1020007006128A KR20010032810A (ko) 1997-12-05 1998-12-07 올레핀의 제조 방법

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JP (1) JP4048458B2 (fr)
KR (1) KR20010032810A (fr)
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AT (1) ATE244288T1 (fr)
AU (1) AU1430299A (fr)
DE (1) DE69816114T2 (fr)
ES (1) ES2202911T3 (fr)
TW (1) TW491889B (fr)
WO (1) WO1999029802A1 (fr)
ZA (1) ZA9811082B (fr)

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EP1061116A1 (fr) * 1999-06-16 2000-12-20 Fina Research S.A. Production d' oléfines
EP1365004A1 (fr) * 2002-05-23 2003-11-26 ATOFINA Research Production d'olefines
WO2004016572A1 (fr) * 2002-08-14 2004-02-26 Total Petrochemicals Research Feluy Production d'olefines
WO2006000449A1 (fr) * 2004-06-28 2006-01-05 Borealis As Catalyseurs zeolite
EP1837388A2 (fr) * 1999-06-17 2007-09-26 Total Petrochemicals Research Feluy Production d'oléfines
US8137631B2 (en) 2008-12-11 2012-03-20 Uop Llc Unit, system and process for catalytic cracking
US8246914B2 (en) 2008-12-22 2012-08-21 Uop Llc Fluid catalytic cracking system
US8889076B2 (en) 2008-12-29 2014-11-18 Uop Llc Fluid catalytic cracking system and process
CN111116289A (zh) * 2018-10-30 2020-05-08 中国石油化工股份有限公司 烯烃催化裂解装置扩能的方法
WO2021198172A1 (fr) * 2020-03-30 2021-10-07 Total Se Procédés de conversion de gaz en oléfines avec coproduction d'hydrogène

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EP0921180A1 (fr) * 1997-12-05 1999-06-09 Fina Research S.A. Production d'oléfines
JP4774812B2 (ja) * 2005-06-03 2011-09-14 三菱化学株式会社 プロピレンの製造方法
EA017251B1 (ru) * 2007-07-31 2012-11-30 Тотал Петрокемикалс Рисерч Фелюй Крекинг олефинов на модифицированных фосфором молекулярных ситах
US9035120B2 (en) 2007-07-31 2015-05-19 Total Research & Technology Feluy Use of phosphorus modified molecular sieves in conversion of organics to olefins
EP2039427A1 (fr) * 2007-09-12 2009-03-25 Total Petrochemicals Research Feluy Craquage d'oléfines sur des tamis moléculaires modifiés au phosphore
EP2082803A1 (fr) 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Procédé pour l'obtention de composites catalyseurs comprenant du MeAPO et leur utilisation dans la conversion de substances organiques en oléfines
EP2082802A1 (fr) 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Procédé pour l'obtention d'un composite catalyseur
EP2082801A1 (fr) 2008-01-25 2009-07-29 Total Petrochemicals Research Feluy Processus pour obtenir des tamis moléculaires modifiés
EP2108635A1 (fr) 2008-04-11 2009-10-14 Total Petrochemicals Research Feluy Processus de fabrication d'oléfines à partir d'éthanol
EP2108637A1 (fr) 2008-04-11 2009-10-14 Total Petrochemicals Research Feluy Processus de fabrication d'oléfines à partir d'éthanol
EP2143700A1 (fr) 2008-06-25 2010-01-13 Total Petrochemicals Research Feluy Procédé pour la fabrication d'oléfines à partir de composés oxygénés
EP2336272A1 (fr) 2009-12-15 2011-06-22 Total Petrochemicals Research Feluy Décongestionnement d'une unité de craquage à vapeur pour améliorer la production de propylène
EP2601160A1 (fr) 2010-08-03 2013-06-12 Total Research & Technology Feluy Procédé de fabrication d'oléfines à partir de méthanol et d'isobutanol
US9079813B2 (en) 2010-08-03 2015-07-14 Total Research & Technology Feluy Process to make propylene from isobutanol by dehydration and subsequent cracking
UA113632C2 (xx) 2011-08-03 2017-02-27 Спосіб приготування каталізатора на основі модифікованого фосфором цеоліту і застосування такого каталізатора
BR112014002583B1 (pt) 2011-08-03 2020-11-10 Total Research & Technology Feluy catalisador compreendendo uma zeólita modificada por fósforo, com uma estrutura parcialmente alpo
WO2018210827A1 (fr) 2017-05-17 2018-11-22 Total Research & Technology Feluy Procédé de valorisation de mto-ocp pour maximiser la sélectivité en propylène
CN114981212B (zh) 2019-11-22 2023-09-01 道达尔能源一技术 烷基卤化物向乙烯和丙烯的转化
CN115003647B (zh) 2019-11-22 2023-12-26 道达尔能源一技术 用于将一种或多种甲基卤化物转化为乙烯和丙烯的工艺
WO2021198175A1 (fr) 2020-03-30 2021-10-07 Total Se Procédé de conversion de gaz en oléfines avec coproduction d'hydrogène conjointement avec une section de réaction électrifiée
WO2021198166A1 (fr) 2020-03-30 2021-10-07 Total Se Procédé de conversion de gaz en oléfines avec coproduction d'hydrogène conjointement à un procédé d'intégration thermique
WO2021198479A1 (fr) 2020-04-03 2021-10-07 Total Se Production d'oléfines légères par oxychloration
WO2022023359A1 (fr) 2020-07-28 2022-02-03 Totalenergies Se Procédé pour produire une réaction de craquage catalytique endothermique dans un réacteur à lit fluidisé

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EP0109059A1 (fr) * 1982-11-10 1984-05-23 MONTEDIPE S.p.A. Procédé pour convertir des oléfines ayant de 4 à 12 atomes de carbone en propène
EP0135621A1 (fr) * 1983-07-12 1985-04-03 Mobil Oil Corporation Préparation de zéolite ZSM-12
EP0511013A2 (fr) * 1991-04-26 1992-10-28 ARCO Chemical Technology, L.P. Fabrication d'oléfines

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EP0109059A1 (fr) * 1982-11-10 1984-05-23 MONTEDIPE S.p.A. Procédé pour convertir des oléfines ayant de 4 à 12 atomes de carbone en propène
EP0135621A1 (fr) * 1983-07-12 1985-04-03 Mobil Oil Corporation Préparation de zéolite ZSM-12
EP0511013A2 (fr) * 1991-04-26 1992-10-28 ARCO Chemical Technology, L.P. Fabrication d'oléfines

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000077123A1 (fr) * 1999-06-16 2000-12-21 Atofina Research Production d'olefines
EP1061116A1 (fr) * 1999-06-16 2000-12-20 Fina Research S.A. Production d' oléfines
EP1837388A3 (fr) * 1999-06-17 2007-10-10 Total Petrochemicals Research Feluy Production d'oléfines
EP1857526A1 (fr) * 1999-06-17 2007-11-21 Total Petrochemicals Research Feluy Production d'oléfines
EP1840189A3 (fr) * 1999-06-17 2007-10-10 Total Petrochemicals Research Feluy Production d'oléfines
EP1837388A2 (fr) * 1999-06-17 2007-09-26 Total Petrochemicals Research Feluy Production d'oléfines
EP1840189A2 (fr) * 1999-06-17 2007-10-03 Total Petrochemicals Research Feluy Production d'oléfines
EP1365004A1 (fr) * 2002-05-23 2003-11-26 ATOFINA Research Production d'olefines
WO2003099964A1 (fr) * 2002-05-23 2003-12-04 Total Petrochemicals Research Feluy Production d'olefines
EP2267101A3 (fr) * 2002-05-23 2011-03-02 Total Petrochemicals Research Feluy Production d'oléfines
CN1329488C (zh) * 2002-05-23 2007-08-01 托塔尔石油化学产品研究弗吕公司 烯烃生产
EP1396481A1 (fr) * 2002-08-14 2004-03-10 ATOFINA Research Production d'oléfines
EA007767B1 (ru) * 2002-08-14 2006-12-29 Тотал Петрокемикалс Рисерч Фелюй Производство олефинов
WO2004016572A1 (fr) * 2002-08-14 2004-02-26 Total Petrochemicals Research Feluy Production d'olefines
WO2006000449A1 (fr) * 2004-06-28 2006-01-05 Borealis As Catalyseurs zeolite
US8137631B2 (en) 2008-12-11 2012-03-20 Uop Llc Unit, system and process for catalytic cracking
US8246914B2 (en) 2008-12-22 2012-08-21 Uop Llc Fluid catalytic cracking system
US8889076B2 (en) 2008-12-29 2014-11-18 Uop Llc Fluid catalytic cracking system and process
CN111116289A (zh) * 2018-10-30 2020-05-08 中国石油化工股份有限公司 烯烃催化裂解装置扩能的方法
CN111116289B (zh) * 2018-10-30 2022-12-09 中国石油化工股份有限公司 烯烃催化裂解装置扩能的方法
WO2021198172A1 (fr) * 2020-03-30 2021-10-07 Total Se Procédés de conversion de gaz en oléfines avec coproduction d'hydrogène
US11739035B2 (en) 2020-03-30 2023-08-29 Totalenergies Onetech Gas to olefins processes with coproduction of hydrogen

Also Published As

Publication number Publication date
AU1430299A (en) 1999-06-28
CN1170913C (zh) 2004-10-13
EP1036133B1 (fr) 2003-07-02
ATE244288T1 (de) 2003-07-15
KR20010032810A (ko) 2001-04-25
EP1036133A1 (fr) 2000-09-20
DE69816114T2 (de) 2004-07-15
ZA9811082B (en) 1999-06-07
TW491889B (en) 2002-06-21
ES2202911T3 (es) 2004-04-01
JP4048458B2 (ja) 2008-02-20
CN1284110A (zh) 2001-02-14
DE69816114D1 (de) 2003-08-07
WO1999029802A1 (fr) 1999-06-17
JPH11246869A (ja) 1999-09-14

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