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• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• • 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
  • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
  • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/62—Catalyst regeneration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/37—Acid treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• • 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
  • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• • 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
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
  • C10G2300/1092—C2-C4 olefins
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/40—Ethylene production

Definitions

• This invention relates to improved zeolite catalysts, to methods of producing such catalysts, and to their use in the conversion of ethanol and ethylene to liquid and aromatic hydrocarbons, including the conversion of ethanol to ethylene. More particularly this invention relates to the use of zeolite catalysts of high SiO 2 :Al 2 O 3 ratios such as the ZSM and related types in the conversion reaction of aqueous and anhydrous ethanol to ethylene, of aqueous ethanol to higher hydrocarbons, and of ethylene into liquid and aromatic hydrocarbons.
• Zeolites of the ZSM type, in particular ZSM-5 are known to be of value as catalysts for the conversion of a range of gaseous and liquid organic materials such as olefins or oxygen containing compounds into hydrocarbons, including both liquid and aromatic hydrocarbons. See for example the following references,
• the value of the catalysts used in such conversion reactions derives firstly from the selectivity with which hydrocarbons containing 5 or more carbon atoms are formed, and more so from the selectivity with which benzenoid hydrocarbons of the benzene, toluene, xylene and tri-methylbenzene series are formed.
• the catalysts are suitable for the manufacture of gasoline and aromatics from starting materials which include the lower olefins, alcohols and other oxygenated compounds.
• high conversions of such compounds are obtained by passing the vapour of the compounds with pr without diluent gas over catalysts at a temperature generally in the range 350 to 400°C.
• Methanol for example, can be converted to hydrocarbons quite readily by passing it as a vapour with or without diluent gas over a ZSM catalyst at a temperature of about 340 to 400°C.
• methanol can be produced from synthesis gas by well established and relatively simple technology, and as synthesis gas is readily obtained by steam reforming of methaneor by the action of steam and oxygen on coal or coke, the combination of these processes with catalytic conversion of the methanol provides an attractive route for production of high octane motor spirit.
• methanol is not a particularly desirable fuel for direct use as motor spirit because it has relatively low calorfic vaiue and poor miscibility with petrol at low temperatures and in moist conditions.
• reaction (c) was uncommon and could not be reliably reproduced after regenerating the catalyst in oxygen or hydrogen or in " both.
• reaction (c) can be promoted by first activating the ZSM-5 catalyst by treatment with hydrogen halides, organic halides or aqueous mineral acids.
• hydrogen halides organic halides
• aqueous mineral acids Those skilled in the art would appreciate that other zeolites of high SiO 2 :Al 2 O 3 ratio might be likewise activated.
• Ethylene which may be produced by the dehydrogenation of ethanol, also does not undergo ready conversion to C 6 to C 10 aromatics over the proton form of ZSM-5 zeolite obtained by way of the ammonium form but the conversion can be promoted by the use of zeolite catalyst activated in the same manner as described above in relation to the conversion of ethanol.
• a further object is to provide a method of making the improved zeolite catalyst.
• a still further object is to provide methods of use of the improved catalyst whereby anhydrous or aqueous ethanol may- be converted to ethylene and whereby aqueous ethanol and ethylene may be converted to hydrocarbons.
• a zeolite catalyst for use in the conversion of ethanol to ethylene and higher hydrocarbons and of ethylene to higher hydrocarbons, characterized in that it comprises a zeolite having a SiO 2 to Al 2 O 3 ratio greater than 10 and being of the ZSM or a related type, which has been treated with a hydrogen halide, an organic halide capable of elimination of hydrogen halide or a mineral acid to improve the catalytic properties of the zeolite.
• a second aspect of the present invention provides a method of preparing a zeolite catalyst for use in the conversion of ethanol to ethylene and higher hydrocarbons and of ethylene to higher hydrocarbons, characterised in that a zeolite having a SiO 2 to Al 2 O 3 ratio greater than 10 and being of the ZSM or related type is treated with a hydrogen halide, an organic halide capable of elimination of hydrogen halide or a mineral acid to improve the catalytic properties of the zeolite.
• a third aspect of the present invention provides a method of converting ethanol and ethylene to higher hydrocarbons and/or of converting ethanol to ethylene wherein the ethanol or ethylene is contacted with a zeolite- catalyst, characterized in that the catalyst comprises a zeolite having a SiO 2 to Al 2 O 3 ratio greater than 10 and being of the ZSM or related type and which prior to or simultaneously with contact with the ethanol or ethylene, is treated with a hydrogen halide, an organic halide capable of elimination of hydrogen halide or a mineral acid to improve the catalytic performance of the zeolite.
• Zeolites used in accordance with the present invention are those with SiO 2 to Al 2 O 3 ratios greater than 10 of the ZSM and related types including ZSM-5, ZSM-8, ZSM-11, ZSM-12 and zeolite ⁇ .
• the zeolites include all those made by the action of tetraalkyl ammonium bases having alkyl groups of 2 or more carbon atoms upon starting material containing the elements of alumina and silica.
• zeolites When used as catalysts, according to the prior art, such zeolites are converted, most commonly by cation exchange techniques, to forms which display or develop Brönsted acidity under the conditions of catalysts. Most commonly the zeolite, freed of organic matter is exchanged with a solution of an ammonium salt to give the ammonium form of the zeolite which is decomposed to the proton form by heating.
• the method of the present invention applies not only to the ammonium and proton forms of the appropriate zeolites prepared as above, but to these forms however prepared and to forms of the zeolite in combination with multivalent cations which confer Brönsted acidity such as for example the rare earth cations.
• the method of the invention is not limited to zeolites which are completely exchanged into the cation or Brönsted acidity but also applies to incompletely exchanged forms.
• a preferred form of the invention utilizes as the starting material a zeolite which is largely in the hydrogen form but with some residual sodium, which is then activated according to the method of this invention.
• a particularly preferred form of the invention uses
• ZSM-5 zeolite activated with 0.1 to 1.0 molar mineral acid at 20° to 200°C for 20 to 70 hours.
• the second aspect of the present invention which is the method of treating the zeolite so as to improve its catalytic properties, will now be discussed in more detail.
• the zeolite is treated with dilute aqueous mineral acid preferably at a temperature between 0°C and 100°C for a period of 1-48 hours prior to use as a catalyst.
• the mineral acid is preferably hydrochloric acid but may be any other strong mineral acid.
• the proton form of ZSM-5 zeolite is treated with 0.5 to 1.0 molar hydrochloric acid at 20 to 40°C for 20 to 40 hours.
• the zeolite is treated with the vapour of a hydrogen halide or of an aqueous hydrogen halide.
• Such treatment of the zeolite by the hydrogen halide may be effected prior to the use of the zeolite as a catalyst, or may be effected during the use of the zeolite catalyst in the conversion process by introducing the hydrogen halide into the ethylene or ethanol feed, either continuously or intermittently.
• the untreated proton form of the ZSM-5 type zeolite is employed as a catalyst for the conversion of a 2% w/w solution of HCl in ethanol.
• the zeolite is heated with an organic halide either prior to the use of the zeolite as a catalyst, or during such use of the zeolite.
• Suitable organic halides are all those hydrocarbon halides containing from 1 to 20 carbon atoms excluding perhalogenated compounds, such as carbon tetrachloride, which cannot undergo elimination of hydrogen halide.
• 1,2-dichloroetha in an amount from 0.1% to 5.0% v/v is added to the ethanol and this solution is then contacted with the proton form of the ZSM-5 type zeolite at a reaction temperature of 300 to 450°C, to convert the ethanol in accordance with the third aspect of the present invention.
• the hydrogen halide and the organic halides may be generated and applied to the treatment of the zeolites according to the method of the invention in diverse ways , it is not intended that the invention be restricted only to those forms of halide generation described herein. Any method of producing halogencontaining compounds or other compounds suitable for treating zeolites of the type described herein may be used.
• zeolite is also encompassed by this invention. Also encompassed by this invention is the incorporation of the zeolite into any suitable matriz or support medium which may then be used as a catalyst.
• the zeolite may be combined with, dispersed in, or otherwise admixed with a porous matrix or other suitable support media. It should be understood that the method of this invention, whereby the zeolite is treated with a halogen containing compound or mineral acid may be applied to either zeolite itself or to any such zeolitecontaining admixture.
• the third aspect of the present invention that is the conversion of ethanol and ethylene into higher hydrcarbons such as liquid and aromatic hydrocarbons and the conversion of ethanol into ethylene, will now be described in more detail.
• hydrocarbons which are produced by the conversion of ethanol and ethylene comprise hydrocarbons containing more than 2 carbon atoms and are most usually hydrocarbons containing from 3 to 12 carbon atoms.
• Such hydrocarbons include saturated and unsaturated hydrocarbons usually containing from 3 to 6 carbon atoms, benzene, toluene, xylene, tri-methylbenzenes and other aromatic hydrcarbons containing 12 or less carbon atoms, all of which are useful components for motor spirit and chemical feedstuffs.
• Whether the product of the conversion of ethanol will be predominantly ethylene or higher hydrocarbons or a mixture thereof depends on a number of reaction variables which include catalytic activity, temperature, water content of the ethanol and ethanol feed rate. For example, a decrease in the treatment temperature promotes the formation of ethylene while an increase in the temperature promotes the formation of higher hydrocarbons. For a given reaction temperature, the more "active" the catalyst, the more likely it is that the products will, be higher hydrocarbons rather than ethylene.
• the activity of the catalyst depends on such factors as composition, method of preparation and activation. The importance of such factors is well known to those skilled in the art and the conditions are selected with regard to the products desired taking into account such known factors.
• hydrocarbons with carbon numbers greater than two including liquid and aromatic hydrocarbons are produced by conversion of aqueous ethanol (4-96 volume % ethanol) with the activated zeolite at relatively Jhigh temperatures (about 250 to 500°C).
• the activated form of ZSM-5 is treated with 0.2 to 50 parts by weight of aqueous ethanol per part by weight of catalyst per hour at a pressure of one to 10 atmospheres.
• ethylene is produced by conversion of aqueous ethanol (4-96 volume % ethanol) with the activated zeolite at relatively low temperatures (about 150 to 300°C).
• the activated form of ZSM-5 is treated with 0.2-50 parts by weight of aqueous ethanol per part by weight of catalyst per hour at a pressure of 1 to 10 atmospheres.
• ethylene is produced by conversion of anhydrous ethanol with the activated zeolite at relativel low temperatures (about 150° to 300 C).
• the activated form of ZSM-5 is treated with 0.2 to 50 parts by weight of anhydrous ethanol per part by weight of catalyst per hour at a pressure of 1 to 10 atmospheres.
• the water content of the ethanol may cover a wide range (4 to 96 volume % water). For economic reasons a range with lower water contents may be preferred.
• Aqueous or anhydrous ethanol can be brought into contact with the activated zeolite in diverse ways, for instance, the ethanol in vapour form may be brought into contact alone or may be carried by an inert gas or recycled gas into contact with the catalyst which can be used as a fixed or fluidised bed. It is not intended that the invention be restricted only to the forms of treatment described herein.
• the performance of zeolite catalysts change with time during the catalytic conversion.
• the initial activity can, however, be restored by regeneration of the catalyst.
• One such regeneration treatment involves exposing ZSM-5 in a stream of oxygen for 16 hours at 500°C (ref. 4.).
• the catalysts can be regenerated by a similar high temperature treatment in oxygen.
• other regeneration procedures may be applied, for instance, exposure to a stream of air at high temperature.
• Advantage may also attach to an additional periodic reactivation if the feed material for catalytic conversion is aqueous or anhydrous ethanol originating from a fermentation process containing dissolved mineral matter.
• C 3 hydrocarbons e.g. propane
• C 4-5 hydrocarbons e.g. isobutane and n-butane
• the present invention may be used in combination with such known processes, to produce hydrocarbons having the required number of carbon atoms.
• Zeolite catalyst was prepared by the following method: 90 parts by weight of sodium silicate solution having the composition 27.9 wt.% SiO 2 , 8.7 wt.% Na 2 O and 63.4 wt.% H 2 O was mixed with 110 parts of water and 10 parts of n-propanol. A second solution containing 3 parts of aluminium sulphate hydrate (AI 2 (SO 4 ) 3 .18H 2 O), seyen and one half parts of 98 wt.% sulphuric acid and 150 parts of water was rapidly mixed with the first solution. The mixture was shaken yigorously for 5 minutes to produce a firm gel which was heated in a clean, closed stainless steel pressure vessel at 175°C for 24 hours.
• AI 2 (SO 4 ) 3 .18H 2 O aluminium sulphate hydrate
• the white crystalline product was activated as follows: It was first calcined in air at 500°C, then refluxing gently with 150 parts of 0.3 molar hydrochloric acid for 24 hours. It was finally filtered, washed copiously with distilled water, and then dried in air at 120°C.
• the X-ray diffraction pattern of the final catalyst was similar to that reported for orthorhombic ZSM-5 by E L Wu etal, in 83 J Phys.Chem (1979) 2777 and did not indicate the presence of any other compounds.
• 0.15g of the catalyst was packed into a quartz microreactor tube, pre-treated with oxygen at 500°C, and fed with dry ethanol at a rate of 0.8g/hour and nitrogen at a rate of 2.2ml/minute at a reactor temperature of 280°C under a pressure of 1-2 atmospheres. Complete conyersion of the ethanol to hydrocarbons and water occurred. Initially the organic product contained 45% of aromatic hydrocarbons of carbon number 6-9 (particularly toluene and xylenesl and 2% ethylene. Most of the balance of the organic products consisted of aliphatic hydrocarbons of carbon numbers 3-6.
• Zeolite catalyst was prepared by . the following method: A mixed solution of 90 parts by weight of sodium silicate having the composition 27.9 wt% SiO 2 , 8.7 wt% Na 2 O and 63.4% H 2 O was mixed with 110 parts of water and 10 parts of n-propanol. A second solution containing 9 parts of aluminium sulphate hydrate, 4.5 parts of 98% sulphuric acid and 150 parts of water was rapidly mixed with the first solution. The mixture was shaken vigorously for 5 minutes to give a gel which was heated in a clean, closed stainless steel pressure vessel for 48 hours at 177°C. The heating was interrupted after the first two hours to shake the vessel vigorously for two minutes. After 48 hours the product was filtered, washed for two minutes.
• the product was filtered, washed copiously with, distilled water, dried at 120°C for 4 hours and calcined at 500°C. It then had the mole ratio composition Na 2 O:Al 2 O 3 :SiO 2 of 1:1:22 and had a diffraction pattern similar to -that of the material produced by the method of example 1. 1 part of the calcined zeolite was refluxed with 150 parts of 0.3 molar hydrochloric acid for 24 hours, then filtered, washed copiously with water and dried at 120°C. The product was of unchanged crystallinity and had a mole ratio composition Na 2 O:Al 2 O 3 :SiO 2 of 0.01:1:22.
• the catalyst was pelleted. 0.15g of broken pellets of
• Example 4 An experiment was carried out just like that of Example 4 except in that the microreactor temperature was 291°C. Complete conversion of ethanol to water and hydrocarbons occurred. Less than 2% of the product was ethylene, 40% was hydrocarbons of carbon numbers 3-4 and 44% was aromatic hydrocarbons of carbon numbers 6-9 (mainly toluene and xylenes).
• Zeolite catalyst was prepared by the following method: 90 parts by weight of sodium silicate solution having the composition 27.9 wt.% SiO 2 , 8.7%wt.% Na 2 O and 63.4 wt.% water was mixed with 80 parts water, 20 parts of n-propanol and 40 parts of 25 wt.% ammonia solution. A second solution containing 3 parts of aluminium sulphate hydrate (Al 2 (SO 4 ) 3 .18H 2 O), 7.5 parts of 98 wt. % sulphuric acid and 150 parts of water was rapidly mixed with the first solution. The resulting mixture was heated in a clean, closed stainless steel pressure vessel according to the method of example 1.
• the product was washed and dryed in accordance with example 1 and had a diffraction pattern similar to that of the material produced by the method of example 1.
• the product was calcined and treated with aqueous hydrochloric acid according to the method of example 1. 0.15g of the catalyst so produced and activated was packed into a quartz microreactor. Dry ethanol was fed to the reactor at a rate of 0.8g/hour and nitrogen at a rate of 2.2ml/minute at a reactor temperature of 290°C and a pressure of 1-2 atmospheres. 100% dehydration of the ethanol to ethylene occurred a,nd was maintained for a period of 1 hour. The catalyst discoloured slightly but was restored to its original condition and activity by regeneration in a stream of oxygen at 500°C for 1 hour.
• Example 7 The experiment of Example 7 was repeated at a reactor temperature of 290°C. The ethanol was completely converted to hydrocarbons and water and the hydrocarbon product consisted of 50-605 ethylene and 40-50% higher hydrocarbons.
• Ethanol containing 4w/w 1,2-dichloroethane was fed at a rate of 0.7g/hr via a preheater coil to a microreactor containing O.lg of the proton form ZSM-5 catalyst, prepared and activated as described in Example 1 at a temperature of 400°C and a total pressure of 1 atmosphere, During the first three hours of reaction, ethanol conversion was greater than 95%, and more than 80%w/w of the organic product consisted of aromatic products in the C 6 -C 10 molecular size range, with less than 20% in the greater than C 10 size range. After 5 hours ethanol conversion was still more than 95%, but approximately 50%w/w of the product was in the greater than C 10 size range.
• Example 9 The experiment of example 9 was repeated but with an ethanol feed containing 2%w/w hydrogen chloride.
• the desirable behavious observed during the first 3 hours in example.9. was obseryed during a period of 4 hours at a reactor temperature of 400°C.
• ZSM-5 catalyst which had been treated with ethanol containing 4% w/w 1,2-dichloroethane according to the method of Example 9, was fed with a mixture of ethylene (30%) and hydrogen (70%) at a gaseous feed rate of 8.5cc/min.
• the conversion of ethylene was 80-90% at a reactor temperature of 400°C.
• 50%w/w of the product consisted of aromatic hydrcarbons of C 6 to C 10 molecular size, 2% consisted of aromatic hydrocarbons of greater molecular size, and most of the balance consisted of C 3 and C 4 hydrocarbons.
• the selectivity for formation of C 8 -C 10 hydrocarbons increased to 80%, and this selectivity was then maintained for at least 4 hours. Similar results were obtained when the ethylene feed was admixed with nitrogen.
• ZSM-5 catalyst was treated with ethanol containing hydrogen chloride according to the method of Example 10. Ethylene was then fed to the catalyst at 400°C according to the method of Example 13. The conversion and selectivity were similar to those observed in Example 12.
• ZSM-5 catalyst activated using aqueous nitric acid according to the method of Example 11 was treated with an ethylene containing feed according to the method of Example 13.
• the conversion and selectivity were similar to those observed in Example 13.
• ZSM-5 catalyst activated using aqueous hydrochloric acid according to the method of example 12 was treated with an ethylene containing feed according to the method of Example 13.
• the conversion and selectivity were similar to those observed in Example 13.

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• Silicates, Zeolites, And Molecular Sieves (AREA)

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• 1980
  • 1980-07-01 JP JP50142380A patent/JPS56500877A/ja active Pending
  • 1980-07-01 WO PCT/AU1980/000026 patent/WO1981000062A1/en not_active Ceased
  • 1980-07-02 EP EP80302241A patent/EP0022640A1/en not_active Withdrawn

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