EP0591504A1 - Verfahren zur herstellung von olefinen - Google Patents
Verfahren zur herstellung von olefinenInfo
- Publication number
- EP0591504A1 EP0591504A1 EP93909070A EP93909070A EP0591504A1 EP 0591504 A1 EP0591504 A1 EP 0591504A1 EP 93909070 A EP93909070 A EP 93909070A EP 93909070 A EP93909070 A EP 93909070A EP 0591504 A1 EP0591504 A1 EP 0591504A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zeolite
- process according
- member channel
- alkyl
- tertiary butyl
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
Definitions
- the present invention relates to a process for the production of olefins by utilising a zeolite catalyst in the conversion of an oxygenate feed.
- Olefins in particular, branched olefins such as isobutene are valuable industrial products and are often used as the starting materials for the production of other desirable chemicals.
- Isobutene may be polymerised to provide polyisobutene which is a valuable chemical in the detergents and fuel industry.
- polyisobutene is used as a fuel additive and a lubricant.
- Isobutene may be produced via various reaction schemes including the catalytic conversion of oxygenates such as methanol as disclosed in our European Patent Applications 485145 and 489497.
- isobutene may be produced from the cracking of the petroleum additive tertiary butyl alcohol (TBA) . This may be achieved using an alumina catalyst.
- TSA tertiary butyl alcohol
- the present invention provides a process for the production of olefins which comprises passing a feed containing an oxygenate of the general formul I
- the present invention provides a method of producing olefins from an oxygenate containing feed which requires a lower operating temperature than known prior art processes. Furthermore, by-product yield is minimised,thus providing an improvement in the selectivity to the desired product.
- the process of the present invention provides a method of cracking an oxygenate to produce an olefin.
- the oxygenate is of general formula R-O-R ⁇ -.
- R of general formula I is an alkyl of 4 or 5 carbon atoms and is preferably a secondary or tertiary alkyl. It is especially preferred that R is tertiary butyl.
- ⁇ - of general formula. I is H or alkyl optionally substituted with an ether group.
- ⁇ is C ⁇ to C alkyl, especially methyl or ethyl.
- R 1 is -(CH2-) n -O 2 where R 2 is C2 to C4 alkyl
- the process of the present invention is particularly suitable for the production of isobutene from methyl tertiary butyl ether
- MTBE 2-methoxy butane
- TSA tertiary butyl alcohol
- SBA secondary butyl alcohol
- the feed may be obtained from any suitable source and may be fed into the reaction chamber either with or without a diluent.
- suitable diluents include steam or an inert gas, e.g. nitrogen, hydrogen, or an alkane.
- the mole 1 of the diluent gas present may suitably be, for example, up to 50X, preferably up to 25Z, especially from 5 to 10X.
- the feed contains an alcohol, for example TBA.
- the percent weight of water present in the feed will affect the selectivity to isobutene.
- the feedstream may contain from up to 30X weight of water, preferably up to 20X weight and especially up to 10X weight water.
- Zeolites which may be used in the present invention include TON (Theta-1, Nu-10, ZSM-22, KZ-2, ISI-1) , MTT (ZSM-23, EU-13, ISI-4, KZ-1), ZSM-48, FER (FU-9, Nu-23, ISI-6, ZSM-35) and EUO (EU-1, TPZ-3, ZSM-50), all of which contain a 10- membered channel that is not intersected by another 10- or 12- membered channel.
- MTW ZSM-12, CZH-5, Theta-3, TPZ-12
- MOR mordenite
- MTW ZSM-12, CZH-5, Theta-3, TPZ-12
- MOR memory
- MTW ZSM-12, CZH-5, Theta-3, TPZ-12
- MOR memory
- MTW ZSM-12, CZH-5, Theta-3, TPZ-12
- MOR memory
- MTW ZSM-12, CZH-5, Theta-3, TPZ-12
- MOR memory
- the preferred zeolite is TON. Information on zeolite structures is given in the Atlas of Zeolite Structure Types by Meier WM and Olsen DH, 1987, distributed by Polycrystal Book Service, Pittsburgh, USA. All of these known zeolite structure types can be prepared by published literature methods.
- the synthetic zeolite immediately after synthesis contains cations which, depending upon the precise synthesis method used, may be hydrogen, aluminium, alkali metals, organic nitrogen containing cations or any combination thereof.
- the zeolite is preferably used in the present process in the hydrogen form.
- the hydrogen form may be achieved by, in the case of organic containing zeolite, calcination to remove the organics followed by either ammonium ion exchange followed by calcination, proton exchange with an acid solution or a combination of both.
- the hydrogen form could, if desired, be prepared by either direct ammonium exchange followed by calcination or proton exchange with acid solution or a combination of both.
- the hydrogen form of the zeolite also may be partially exchanged or impregnated with a metal such as Ga or Mg and used in the present process.
- the zeolite may be modified to alter its acidity or shape selectivity in such a way to improve the catalytic performance.
- the modifications may include a calcination regime, steam treatment, chemical treatment, e.g. with a dealu inating agent such as SiCl , EDTA, etc or an aluminating agent such as sodium aluminate, AICI3 inclusion of phosphorus compound, Lewis base, HF etc.
- a combination of treatments may also be carried out.
- the treatment step may be carried out during the preparation of the H-form or be carried out after preparation of the H-form.
- the zeolite may be bound in a suitable binding material.
- the binder may suitably be one of the conventional alumina, silica, clay or aluminophosphate binders or a combination of binders.
- the process according to the invention may suitably be carried out at a temperature of from 100 to 400 ⁇ C, preferably 150 to 300"C, especially 150 - 200'C, and is preferably carried out at atmospheric pressure, although other pressures may be used if desired, eg up to 15 barg.
- the oxygenate feed may be fed into the reaction chamber either with or without diluents at a rate of suitably 0.1 to 50, preferably 0.9 to 10, especially 0.9 to 4.5 liquid hourly space velocity (LHSV) .
- LHSV liquid hourly space velocity
- liquid hourly space velocity is defined as the volume of feed fed per volume of catalyst per hour.
- the process of the present invention may be carried out in any suitable reactor, for example a fixed bed, fluid bed, a reactive distillation column, a slurry reactor or a continuous catalyst regeneration reactor.
- the preferred reactor is a fixed bed reactor.
- the reactor may be made from any suitable material, e.g. steel or quartz.
- the product of the process of the present invention will, of course, be dependent upon the feed.
- R is butyl
- the product comprises butenes, e.g. n-butene and iso-butene.
- R is pentyl
- the product comprises pentenes, e.g. n-pentene and iso-pentene.
- the product stream will also comprise water. Additionally, small amounts of other alkenes such as ethene, propene, hexene, octene, and the corresponding alcohols may also be present.
- Theta-1 was synthesised using ammonia as the templating agent.
- Sodium aluminate (19.67g, 61wtX AI2O3, 38wtX a2 ⁇ ) and sodium hydroxide (17.58g ex BDH) were dissolved in distilled water (240g) .
- Ammonia solution (1400g, SG 0.90° containing 25% ammonia) was added with gentle mixing.
- Ludox AS40 (Trade Mark) (1200g) silica gel which contained 40wtZ silica was added over 20 minutes with stirring to maintain a homogeneous hydrogel.
- the molar composition of the hydro el was:
- Example 1 The Theta-1 as synthesised in Example 1 which contained both Na + and H4 + ions was directly ion exchanged in order to remove the Na + ions.
- the zeolite was mixed for 1 hour at room temperature with an aqueous ammonium nitrate solution (1M, zeolite to solution weight ratio of 1:20).
- the zeolite was filtered, washed and the ion exchange treatment repeated twice.
- the ammonium form of the zeolite was then dried at 100 ⁇ C and calcined overnight in air at 550°C to convert it to the hydrogen form.
- the X-ray diffraction pattern of the H-form is shown in Table 1.
- the zeolite powder (H-form) was pressed into tablets at 10 tonnes. The tablets were broken and sieved into granules to pass through 850 micron but not 600 micron sieves.
- An 7.8ml volume of the catalyst weight 3.15 was loaded into a quartz reactor with a 35ml preheater zone in an isothermal Carbolite furnace, activated in air at a rate of 600ml per hour following the temperature profile: room temperature l°C/minutev 120°C (2 hours) l°C/minute. 500C° (14- hours.-10°C/minute-.150°C initial test temperature.
- TBA Tertiary butyl alcohol
- the zeolite powder (H-form) was pressed into tablets at 10 tonnes. The tablets were broken and sieved into granules to pass through 850 micron but not 600 micron sieves.
- An 8.2ml volume of the catalyst weight 4.34g was loaded into a quartz reactor with a 25ml preheater zone in an isothermal Carbolite furnace, activated in air at a rate of 600ml per hour following the temperature profile: room temperature 2°C/minute 300 ⁇ C (12 hours)-10°C/hour >. 175°C.
- Methyl tertiary butyl ether was pumped into the reactor using a perfusor syringe driver fitted with a 50ml syringe. On entering the reactor, the MTBE was vapourised and mixed with nitrogen (gas flow of 680ml per hour). Table 3 provides the product stream analyses obtained for the reaction. Comparative Example 1
- Example 3 The process of Example 3 was repeated using a commercial alumina catalyst of surface area 184 ⁇ 4m'/g and mean pore volume of 19nm. A 7.8ml volume of the catalyst (weight 5.13g) was used.
- the catalyst was purchased from ARCO under the trade name of UOP CAB 2L and came in the form of 3mm spheres. Table 3 provides the product stream analysis obtained for the reaction. It can be seen that conversion of tertiary butyl alcohol is considerably less when an alumina catalyst is used in the process. Selectivity to isobutene is also less than in the corresponding process using the zeolite catalyst. Comparative Example 2
- Comparative Example 1 The process of Comparative Example 1 was repeated using methyl tertiary butyl ether as the feed.
- the product stream analysis is given in Table 4. It can be seen that conversion of MTBE is considerably less when an alumina catalyst is used in the process. Selectivity to dimethyl ether is also greater than in the corresponding process using the zeolite catalyst.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB929208739A GB9208739D0 (en) | 1992-04-22 | 1992-04-22 | Process for the production of isobutene |
GB9208739 | 1992-04-22 | ||
GB9210548 | 1992-05-18 | ||
GB929210560A GB9210560D0 (en) | 1992-05-18 | 1992-05-18 | Process for the production of isobutene |
GB9210560 | 1992-05-18 | ||
GB929210548A GB9210548D0 (en) | 1992-05-18 | 1992-05-18 | Process for the production of isobutene |
GB9210918 | 1992-05-22 | ||
GB929210918A GB9210918D0 (en) | 1992-05-22 | 1992-05-22 | Process for the production of isobutene |
PCT/GB1993/000823 WO1993021139A1 (en) | 1992-04-22 | 1993-04-20 | Process for the production of olefins |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0591504A1 true EP0591504A1 (de) | 1994-04-13 |
Family
ID=27450861
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93909070A Withdrawn EP0591504A1 (de) | 1992-04-22 | 1993-04-20 | Verfahren zur herstellung von olefinen |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0591504A1 (de) |
JP (1) | JPH06508640A (de) |
CA (1) | CA2110904A1 (de) |
WO (1) | WO1993021139A1 (de) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10327215A1 (de) | 2003-06-17 | 2005-01-13 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von Isobuten aus tert.-Butanol |
EP1790627A1 (de) | 2005-11-29 | 2007-05-30 | BP Chemicals Limited | Verfahren zur Herstellung von Olefinen |
WO2012143564A1 (en) | 2011-04-21 | 2012-10-26 | Shell Internationale Research Maatschappij B.V. | Process for converting a solid biomass material |
US9169444B2 (en) | 2011-04-21 | 2015-10-27 | Shell Oil Company | Liquid fuel composition |
CN103597056A (zh) | 2011-04-21 | 2014-02-19 | 国际壳牌研究有限公司 | 转化固体生物质材料的方法 |
US8927794B2 (en) | 2011-04-21 | 2015-01-06 | Shell Oil Company | Process for regenerating a coked catalytic cracking catalyst |
US8779226B2 (en) | 2011-09-07 | 2014-07-15 | Shell Oil Company | Process for preparing ethylene and propylene |
US20130245221A1 (en) * | 2011-09-07 | 2013-09-19 | Shell Oil Company | Process for preparing ethylene and propylene |
SG11201400359XA (en) * | 2011-09-07 | 2014-04-28 | Shell Int Research | Process for preparing ethylene and propylene |
CN104125859A (zh) * | 2011-12-27 | 2014-10-29 | 国际壳牌研究有限公司 | 分子筛催化剂、其配制和使用方法 |
EP2841536A1 (de) | 2012-04-23 | 2015-03-04 | Shell Internationale Research Maatschappij B.V. | Verfahren zur umwandlung eines festen biomassematerials |
US10513472B2 (en) * | 2017-10-26 | 2019-12-24 | Lyondell Chemical Technology, L.P. | Methods of producing propylene and ethylene |
CN111116282B (zh) * | 2018-10-30 | 2022-07-08 | 中国石油化工股份有限公司 | 叔丁醇制烯烃的方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4359595A (en) * | 1980-04-28 | 1982-11-16 | Mobil Oil Corporation | Selective production of olefins |
DE3048084A1 (de) * | 1980-12-19 | 1982-07-15 | EC Erdölchemie GmbH, 5000 Köln | Verfahren zur herstellung von tertiaeren olefinen |
EP0055529B2 (de) * | 1980-12-19 | 1990-09-19 | Imperial Chemical Industries Plc | Zeolithe |
EP0065400B1 (de) * | 1981-05-20 | 1986-03-05 | Imperial Chemical Industries Plc | Zeolithe |
NZ207523A (en) * | 1983-04-22 | 1986-03-14 | Mobil Oil Corp | Catalytic production of olefin mixtures from alcohols and/or ethers |
US4476338A (en) * | 1983-06-02 | 1984-10-09 | Mobil Oil Corporation | Olefins from methanol and/or dimethyl ether |
US5157192A (en) * | 1991-11-12 | 1992-10-20 | Mobil Oil Corporation | Conversion of tertiary alcohols to C8+ olefins |
-
1993
- 1993-04-20 EP EP93909070A patent/EP0591504A1/de not_active Withdrawn
- 1993-04-20 JP JP5518149A patent/JPH06508640A/ja active Pending
- 1993-04-20 CA CA 2110904 patent/CA2110904A1/en not_active Abandoned
- 1993-04-20 WO PCT/GB1993/000823 patent/WO1993021139A1/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9321139A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1993021139A1 (en) | 1993-10-28 |
CA2110904A1 (en) | 1993-10-28 |
JPH06508640A (ja) | 1994-09-29 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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17P | Request for examination filed |
Effective date: 19931129 |
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Kind code of ref document: A1 Designated state(s): BE DE ES FR GB IT NL |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 19951101 |