CA1229353A - Catalytic conversion of methanol-containing feedstock to olefin-containing product - Google Patents
Catalytic conversion of methanol-containing feedstock to olefin-containing productInfo
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- CA1229353A CA1229353A CA000441681A CA441681A CA1229353A CA 1229353 A CA1229353 A CA 1229353A CA 000441681 A CA000441681 A CA 000441681A CA 441681 A CA441681 A CA 441681A CA 1229353 A CA1229353 A CA 1229353A
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- Prior art keywords
- zsm
- organic
- methanol
- zealot
- zeolite
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- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
CATALYTIC CONVERSION OF METHANOL-CONTAINING FEEDSTOCK
TO OLEFIN-CONTAINING PRODUCT
ABSTRACT
A process is provided for converting a feedstock comprising methanol and/or methyl ether to product comprising light olefins over a catalyst comprising a synthetic porous crystalline zeolite material designated zeolite ZSM-45 in the presence of a diluent selected from water, nitrogen, helium, carbon monoxide, carbon dioxide or mixtures of such diluents.
TO OLEFIN-CONTAINING PRODUCT
ABSTRACT
A process is provided for converting a feedstock comprising methanol and/or methyl ether to product comprising light olefins over a catalyst comprising a synthetic porous crystalline zeolite material designated zeolite ZSM-45 in the presence of a diluent selected from water, nitrogen, helium, carbon monoxide, carbon dioxide or mixtures of such diluents.
Description
F-2039 Canada -1 CANAL TIC CONVERSION OF METHANOL-CONTAINING FEED STOCK
TO OLEFIN-CONTAINING PRODUCT
. .
This invention relates to an improved process for converting methanol and/or methyl ether to light olefins over particular types of crystalline aluminosilicate zealot catalysts.
A remarkable growth in the production of synthetic fibers, plastics and rubber has taken place in recent decades. Such growth, to a large extent, has been supported and encouraged by an expanding supply of inexpensive petroleum raw materials such as ethylene and propylene. However, increasing demand for these light olefins has, from time to time, led to periods of shortage, either due to a diminished supply of suitable feed stocks or to limited processing capacity. In any event, it is now considered highly desirable to provide efficient means for converting raw materials other than US petroleum to light olefins.
One such non-petroleum source of light olefins is coal-derived methanol and methyl ether. In this respect, it is known -that methanol or methyl ether can be catalytically converted to olefin-containing hydrocarbon mixtures by contact under certain I conditions with particular types ox crystalline zealot catalyst materials. US. Patent 4,025,575, issued May 24, 1977, to Clang et at and US. Patent 49083,889, issued April 11, 1978 to Caesar et at, for example, both disclose processes whereby methanol and/or methyl ether can be converted to an olefin-containing product over a ZSM-5 type (constraint index 1-12) zealot catalyst. ZSM 5, in fact, converts methanol Andre methyl ether to hydrocarbons containing a relatively high concentration ox light (C2 and C3) olefins with prolonged catalyst lifetime before catalyst regeneration becomes necessary.
It is also known that other types ox zealot catalysts can be used to convert methanol and/or methyl ether to olefin-containing hydrocarbon products containing even higher proportions ox light olefins than can be realized by methanol methyl ether conversion over ZSM-5. For example, US. Patents 4,079,0g5 and ~,079,096~ both issued F 2039 Canada -2-March 14, 1978, to Gives, Plank and Rosin ski, disclose that zealots of the erionite-offretite type, and especially ZSM-34, can usefully be employed to promote conversion of methanol and/or methyl ether to products comprising a major amount of C2 and C3 light olefins.
However, while erionite-offretite type catalysts are highly selective to light olefins production, such smaller pore zealots tend to age rapidly in comparison to ZSM-5 when used for methanol/methyl ether conversion Thus in spite of the existence of methanol conversion processes utilizing a variety of zealot catalysts, there is a lug continuing need to develop new procedures suitable for selectively converting an organic charge comprising methanol and/or methyl ether over zealots catalysts to light Olin products with both high light olefin selectivity and prolonged catalyst lifetime.
Accordingly it is an object of the present invention to provide a process for converting methanol Andre methyl ether over a zeolite-based catalyst to olefin-containing products with high selectivity to production of light olefins.
It is a further object of the present invention to provide such a selective process wherein lifetime of the zealot catalyst is 2û enhanced for methanol/methyl ether conversion.
It is a Further object of the present invention to provide such a methanol/methyl ether conversion process employing a particular type of zealot catalyst, readily available reactants and delineates and commercially practical reaction conditions.
In accordance with the present invention, a process is provided for the catalytic conversion of an organic reactant feed comprising the organic reactants methanol and/or methyl ether to a hydrocarbon reaction product mixture containing light (C2-C4) olefins. The catalyst employed in such a process comprises at least some synthetic porous crystalline material designated as elite ZS~-45. Zealot ZSM-45 exhibits a characteristic X-ray powder diffraction pattern which distinguishes it from other known synthetic and naturally occurring zealots, and this distinctive x-ray diffraction pattern for ZSM-45 is shown hereinafter The porous crystalline Zealot ZSM-45 can be further identified, in terms of mole 35:3 F-2039 Canada -3-ratios of oxides, by the following formula:
TO OLEFIN-CONTAINING PRODUCT
. .
This invention relates to an improved process for converting methanol and/or methyl ether to light olefins over particular types of crystalline aluminosilicate zealot catalysts.
A remarkable growth in the production of synthetic fibers, plastics and rubber has taken place in recent decades. Such growth, to a large extent, has been supported and encouraged by an expanding supply of inexpensive petroleum raw materials such as ethylene and propylene. However, increasing demand for these light olefins has, from time to time, led to periods of shortage, either due to a diminished supply of suitable feed stocks or to limited processing capacity. In any event, it is now considered highly desirable to provide efficient means for converting raw materials other than US petroleum to light olefins.
One such non-petroleum source of light olefins is coal-derived methanol and methyl ether. In this respect, it is known -that methanol or methyl ether can be catalytically converted to olefin-containing hydrocarbon mixtures by contact under certain I conditions with particular types ox crystalline zealot catalyst materials. US. Patent 4,025,575, issued May 24, 1977, to Clang et at and US. Patent 49083,889, issued April 11, 1978 to Caesar et at, for example, both disclose processes whereby methanol and/or methyl ether can be converted to an olefin-containing product over a ZSM-5 type (constraint index 1-12) zealot catalyst. ZSM 5, in fact, converts methanol Andre methyl ether to hydrocarbons containing a relatively high concentration ox light (C2 and C3) olefins with prolonged catalyst lifetime before catalyst regeneration becomes necessary.
It is also known that other types ox zealot catalysts can be used to convert methanol and/or methyl ether to olefin-containing hydrocarbon products containing even higher proportions ox light olefins than can be realized by methanol methyl ether conversion over ZSM-5. For example, US. Patents 4,079,0g5 and ~,079,096~ both issued F 2039 Canada -2-March 14, 1978, to Gives, Plank and Rosin ski, disclose that zealots of the erionite-offretite type, and especially ZSM-34, can usefully be employed to promote conversion of methanol and/or methyl ether to products comprising a major amount of C2 and C3 light olefins.
However, while erionite-offretite type catalysts are highly selective to light olefins production, such smaller pore zealots tend to age rapidly in comparison to ZSM-5 when used for methanol/methyl ether conversion Thus in spite of the existence of methanol conversion processes utilizing a variety of zealot catalysts, there is a lug continuing need to develop new procedures suitable for selectively converting an organic charge comprising methanol and/or methyl ether over zealots catalysts to light Olin products with both high light olefin selectivity and prolonged catalyst lifetime.
Accordingly it is an object of the present invention to provide a process for converting methanol Andre methyl ether over a zeolite-based catalyst to olefin-containing products with high selectivity to production of light olefins.
It is a further object of the present invention to provide such a selective process wherein lifetime of the zealot catalyst is 2û enhanced for methanol/methyl ether conversion.
It is a Further object of the present invention to provide such a methanol/methyl ether conversion process employing a particular type of zealot catalyst, readily available reactants and delineates and commercially practical reaction conditions.
In accordance with the present invention, a process is provided for the catalytic conversion of an organic reactant feed comprising the organic reactants methanol and/or methyl ether to a hydrocarbon reaction product mixture containing light (C2-C4) olefins. The catalyst employed in such a process comprises at least some synthetic porous crystalline material designated as elite ZS~-45. Zealot ZSM-45 exhibits a characteristic X-ray powder diffraction pattern which distinguishes it from other known synthetic and naturally occurring zealots, and this distinctive x-ray diffraction pattern for ZSM-45 is shown hereinafter The porous crystalline Zealot ZSM-45 can be further identified, in terms of mole 35:3 F-2039 Canada -3-ratios of oxides, by the following formula:
2/n 203:x Sue wherein x is greater than 8, wherein M is an organic or metallic cation or is a combination of organic and metallic cations, and wherein n is the valence of each respective cation present.
Methanol/methyl ether conversion over such a Zealot ZSM-45-cnntaining catalyst occurs by contacting the organic reactant feed with the zealot based catalyst under conversion reaction conditions which are sufficient to produce a light olefin-containing product enriched in C2-C4 olefins, particularly ethylene. Such contacting further occurs in the presence of a gaseous delineate which can be water, nitrogen, helium, carbon monoxide, carbon dioxide or a mixture of such delineates.
The term "organic reactant feed" as used herein can comprise both the organic material used as reactants, i.e. the organic compounds such as methanol and methyl ether subjected to catalytic conversion to olefins, as well as additional components such as water or other delineates as described more fully hereinafter. Since methanol is miscible with water, the charge to the catalytic reaction zone may actually contain relatively large amounts of water, but only the methanol, methyl ether and associated organic compounds, constitute the reactant portion ox the organic reactant feed.
Any methanol product comprising at least 60 wt. of methanol may be used to provide methanol for the organic reactant feed in this invention. Substantially pure methanol, such as industrial grade an hydrous methanol is eminently suitable. Crude methanol, which usually contains from 12 to 20 wt. % water, or more dilute solutions, also may be used.
Small amounts of impurities such as higher alcohols, I aldehydes, or other oxygenated compounds in the organic reactant feedhave little effect on the conversion reaction of this invention. The organic reactant feed may also comprise methyl ether. When this component is present, it can comprise up to 100~ of the organic reactant feed or methyl ether can be admixed with methanol and/or water to form the organic reactant feed. For purposes of the present F-2039 Canada -4- ~L229~ 3 invention, it is contemplated to directly convert methanol and/or methyl ether in the feed to a hydrocarbon mixture characterized by a high content of light olefins, especially ethylene. Such amounts of methyl ether as may be formed concomitantly in the conversion reaction, however, may be recovered and recycled with fresh organic reactant feed.
The organic reactant feed as herein before described is catalytically converted to a light olefin containing hydrocarbon product enriched in ethylene by contact with a zeolite-based catalyst composition comprising a particular type of synthetic porous crystalline zealot material designated ZSM-45. The lattice of any crystalline zealot, including the particular ZSM-45 of the present invention, can be described as a rigid three~dimentional framework of Sue and Aye in which the tetrahedral are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedral containing aluminum is balanced by a cation, for example an alkali metal or alkaline earth metal cation. The ratio of cationic-valence/aluminum is thus unity. one cation may be exchanged mu for another in conventional manner. By means of such cation exchange it has been possible to vary the properties of a given zealot.
Since the cat ionic content of a zealot may thus be regarded as ephemeral, the only significant term in its compositional formula is the ratio of lattice silicon to aluminum, usually expressed as silica/alumina ratio. The Sue ratio of a given zealot is however often variable. For example, zealot X can be synthesized with Sue ratios of from 2 to 3; zealot Y, from 3 to about 6.. In some zealots, the upper limit of the Sue ratio is unbounded. ZSM-5 is one such example wherein the Sue ratio is at least 5 and up to infinity. U. S. Patent No. 3,941,871 discloses a zealot made from a reaction mixture containing no added alumina and exhibiting the X-ray diffraction pattern of zealot ZSM-5. U. S. Patent Nos. 4,061,724, 4,073,865 and 4,104,294 describe zealots of similar alumina and metal content.
~;~2~3~
F-2039 Canada -5-Synthetic zealots sometimes resemble naturally occurring zealots. Zealots ZSM~35 and ZSM-38 are, for instance, ferrierite-type zealots. Zealots ZK-20 (US.
Patent No. 3r459,676~ is described as being isostructural with the naturally occurring zealot levynite. European Patent Application No. POW 9 published November 18, 1981 describes synthetic elite Noah which is of the levynite type.
Zealot ZSM-45 is a high silica form of a levynite Allah of materials which exhibits a composition and properties which distinguish it from natural levynite. Zealot ZSM-45 exhibits a characteristic X-ray powder diffraction pattern which distinguishes it from other known synthetic and naturally occurring zealots. It may be said to be levynite-type, however.
ZSM-45 has the formula, on an an hydrous basis, in terms of mole ratios of oxides:
2/n Aye X Sue in which x is 8 or greater and M is an organic or metallic cation of valence n, which cation serves to balance the electrovalence of the tetrahedral aluminum atoms. Zealot ZSM-45 has an X-ray diffraction pattern containing the following significant lines:
InterplanarO
Spacing (A) Relative Into ye O
8.02 -I 0.14 Strong-Very Strong 5.07 0.09 Medium-Strong 254.21 0.08 Medium-Strong 4.01 + 0.07 Strong-Very Strong
Methanol/methyl ether conversion over such a Zealot ZSM-45-cnntaining catalyst occurs by contacting the organic reactant feed with the zealot based catalyst under conversion reaction conditions which are sufficient to produce a light olefin-containing product enriched in C2-C4 olefins, particularly ethylene. Such contacting further occurs in the presence of a gaseous delineate which can be water, nitrogen, helium, carbon monoxide, carbon dioxide or a mixture of such delineates.
The term "organic reactant feed" as used herein can comprise both the organic material used as reactants, i.e. the organic compounds such as methanol and methyl ether subjected to catalytic conversion to olefins, as well as additional components such as water or other delineates as described more fully hereinafter. Since methanol is miscible with water, the charge to the catalytic reaction zone may actually contain relatively large amounts of water, but only the methanol, methyl ether and associated organic compounds, constitute the reactant portion ox the organic reactant feed.
Any methanol product comprising at least 60 wt. of methanol may be used to provide methanol for the organic reactant feed in this invention. Substantially pure methanol, such as industrial grade an hydrous methanol is eminently suitable. Crude methanol, which usually contains from 12 to 20 wt. % water, or more dilute solutions, also may be used.
Small amounts of impurities such as higher alcohols, I aldehydes, or other oxygenated compounds in the organic reactant feedhave little effect on the conversion reaction of this invention. The organic reactant feed may also comprise methyl ether. When this component is present, it can comprise up to 100~ of the organic reactant feed or methyl ether can be admixed with methanol and/or water to form the organic reactant feed. For purposes of the present F-2039 Canada -4- ~L229~ 3 invention, it is contemplated to directly convert methanol and/or methyl ether in the feed to a hydrocarbon mixture characterized by a high content of light olefins, especially ethylene. Such amounts of methyl ether as may be formed concomitantly in the conversion reaction, however, may be recovered and recycled with fresh organic reactant feed.
The organic reactant feed as herein before described is catalytically converted to a light olefin containing hydrocarbon product enriched in ethylene by contact with a zeolite-based catalyst composition comprising a particular type of synthetic porous crystalline zealot material designated ZSM-45. The lattice of any crystalline zealot, including the particular ZSM-45 of the present invention, can be described as a rigid three~dimentional framework of Sue and Aye in which the tetrahedral are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedral containing aluminum is balanced by a cation, for example an alkali metal or alkaline earth metal cation. The ratio of cationic-valence/aluminum is thus unity. one cation may be exchanged mu for another in conventional manner. By means of such cation exchange it has been possible to vary the properties of a given zealot.
Since the cat ionic content of a zealot may thus be regarded as ephemeral, the only significant term in its compositional formula is the ratio of lattice silicon to aluminum, usually expressed as silica/alumina ratio. The Sue ratio of a given zealot is however often variable. For example, zealot X can be synthesized with Sue ratios of from 2 to 3; zealot Y, from 3 to about 6.. In some zealots, the upper limit of the Sue ratio is unbounded. ZSM-5 is one such example wherein the Sue ratio is at least 5 and up to infinity. U. S. Patent No. 3,941,871 discloses a zealot made from a reaction mixture containing no added alumina and exhibiting the X-ray diffraction pattern of zealot ZSM-5. U. S. Patent Nos. 4,061,724, 4,073,865 and 4,104,294 describe zealots of similar alumina and metal content.
~;~2~3~
F-2039 Canada -5-Synthetic zealots sometimes resemble naturally occurring zealots. Zealots ZSM~35 and ZSM-38 are, for instance, ferrierite-type zealots. Zealots ZK-20 (US.
Patent No. 3r459,676~ is described as being isostructural with the naturally occurring zealot levynite. European Patent Application No. POW 9 published November 18, 1981 describes synthetic elite Noah which is of the levynite type.
Zealot ZSM-45 is a high silica form of a levynite Allah of materials which exhibits a composition and properties which distinguish it from natural levynite. Zealot ZSM-45 exhibits a characteristic X-ray powder diffraction pattern which distinguishes it from other known synthetic and naturally occurring zealots. It may be said to be levynite-type, however.
ZSM-45 has the formula, on an an hydrous basis, in terms of mole ratios of oxides:
2/n Aye X Sue in which x is 8 or greater and M is an organic or metallic cation of valence n, which cation serves to balance the electrovalence of the tetrahedral aluminum atoms. Zealot ZSM-45 has an X-ray diffraction pattern containing the following significant lines:
InterplanarO
Spacing (A) Relative Into ye O
8.02 -I 0.14 Strong-Very Strong 5.07 0.09 Medium-Strong 254.21 0.08 Medium-Strong 4.01 + 0.07 Strong-Very Strong
3.78 OKAY Medium-Strong 3.11 0.06 Medium-Strong 2.751 0.05 Medium Strong The derivation of such lines in the X-ray pattern is described more sully hereinafter In the as-synthesised form, the zealot ZSM-45 usually conforms to the formula, on an an hydrous basis and in terms ox moles ratios of oxides:
(wrinkly xsio2 wherein R is a monovalent organic cation derived from a 2-(hydroxyalkyl~ trialkylammonium compound where alkyd is composed of one or two carbon atoms and x is greater khans 8, usually prom 8 to ~,~
Lo 3 F-2039 Canada -6-100. In such an empirical formula for the as synthesized zealot, it is understood that there must always be sufficient R, No and/or K
cations to completely balance the electrovalence of the lattice aluminum. In those instances wherein greater amounts of R, No and/or K are present than are necessary to balance the aluminum charge, the excess amount of R, No and/or K is present in the zealot in the form of occluded compounds formed from these cations.
The as-synthesized form of ZSM-45 has the X-ray diffraction pattern of Table 1 hereinbelow.
I
F-2039 Canada -7-InterplanarO
D-Spacing (A) Relet Ye Intensity I/In 10.16 0.18 Weak 8.02 + 0.14 Strong-Very Strong 7.56 + 0.14 Weak 6.55 + 0.12 Medium-Very Strong 5.66 + 0.10 Weak 5.50 + 0.10 Weak 5.07 + 0.09 Mediu~-Strong
(wrinkly xsio2 wherein R is a monovalent organic cation derived from a 2-(hydroxyalkyl~ trialkylammonium compound where alkyd is composed of one or two carbon atoms and x is greater khans 8, usually prom 8 to ~,~
Lo 3 F-2039 Canada -6-100. In such an empirical formula for the as synthesized zealot, it is understood that there must always be sufficient R, No and/or K
cations to completely balance the electrovalence of the lattice aluminum. In those instances wherein greater amounts of R, No and/or K are present than are necessary to balance the aluminum charge, the excess amount of R, No and/or K is present in the zealot in the form of occluded compounds formed from these cations.
The as-synthesized form of ZSM-45 has the X-ray diffraction pattern of Table 1 hereinbelow.
I
F-2039 Canada -7-InterplanarO
D-Spacing (A) Relet Ye Intensity I/In 10.16 0.18 Weak 8.02 + 0.14 Strong-Very Strong 7.56 + 0.14 Weak 6.55 + 0.12 Medium-Very Strong 5.66 + 0.10 Weak 5.50 + 0.10 Weak 5.07 + 0.09 Mediu~-Strong
4 95 jog Weak 4.21 + 0.08 Medium-Stronq 4.01 + 0.07 Strong-Very Strong 3.78 + 0.07 Medium-Strong 3.60 + 0.06 Weak 3.54 0.06 Weak-Medium 3.42 + 0.06 Weak 3.27 + 0.06 Medium 3.11 + 0.06 Medium-Strong 3.03 0.05 Weak 2.812 0.05 Weak 2.751 0.05 Medium-Strong 2.583 + 0.05 Weak 2.535 0.05 Weak I 2.521 0.05 Weak 2.475 0.04 Weak 2.405 0.04 Weak 2.362 0.04 Weak 2.251 0.04 Weak 2.181 + 0.04 Weak 2.133 -: 0.04 Weak 2.097 + 0.04 Weak 2.029 + 0.04 Weak 2.006 + 0.03 Weak 1.889 0.03 Weak 1.859 0.03 Weak 1.843 + 0.03 Weak 1.815 + 0.03 Weak 1.765 0.03 Weak 1.721 + 0.03 Weak 1.710 0.03 Weak 1.650 + 0.03 Weak 1.637 0.03 . Weak 1.617 I 0.03 Weak 1.606 0.03 Weak 1.559 0.03 Weak These values were determined by standard techniques. The radiation was the Caliph doublet of copper and a dif~ractometer F-2039 Canada I Lo 9 3 5~3 equipped with a scintillation counter and an associated computer was used. The peak heights, I, and the positions as a function of 2 theta, where theta is the Bragg angle, were determined using algorithms on the computer associated with the spectrometer. From these the relative intensities, 100 Rio where It is the intensity of the strongest line or peak, and d (orbs.) the inter planar spacing in Angstrom units (A), corresponding to the recorded lines, were determined. In Table 1, the relative intensities are given in terms of the strongest line being taken as 100Ø It should be lo understood that this X-ray diffraction pattern is characteristic of all the species of Zealot ZSM-45 compositions. The sodium form as well as other cat ionic forms reveal substantially the same pattern with some minor shifts in inter planar spacing and variation in relative intensity. Other minor variations can occur, depending on the silicon to aluminum ratio of the particular sample, as well as its degree of thermal and/or steam treatment.
The Zealot ZSM-45 used herein sorbs significant amounts of commonly used test adsorb ate materials, i.e. cyclohexane, Nixon and water, whereas naturally occurring levynite is not expected to adsorb cyclohexane due to its pore structure. Sorption capacities for Zealot ZSM-45 will range at room temperature as follows:
~dsortate Capacity, Wt. Percent Cyclohexane 2.2 7.0 Nixon - 12.9 Whetter - 22.9 The original organic and alkali metal cations o-f the as-synthesized ZSM-45 can be replaced at least in part in accordance with techniques well known in the art, with other cations. Such techniques include thermal treatment and ion exchange. Preferred replacing cations include metal ions, hydrogen ions hydrogen precursor, e.g. ammonium, ions and mixtures thereof Particularly preferred cations are those which render the ZS~-45 catalytically active for methanol conversion. These include hydrogen, anonym, rare earth metals and metals of Groups IA, IDA, IIIA, IVAN IBM JIB, III~, IVY and VIII of the Periodic Chart of the Elements The Zealot F-2039 Canada -9- Lo I 3 ZSM-45 is preferably employed in the methanol conversion process herein in either the ammonium or hydrogen form. The ZSM-45 zealot may also be utilized in a form wherein some of the active sites have been exchanged with alkali metal, alkaline earth metal or other metal cations. however, the zealot must contain some acid sites to be effectively utilized in -the process of the present invention.
Thermal treatment of the as-synthesized zealot is generally employed to remove all or part of the organic constituent. Such thermal treatment can for example be conducted at temperatures in lo excess of 250C or a period of time sufficient to remove the organic constituent to the desired extent. Following thermal treatment the zealot can then be subjected to ion exchange. A typical ion exchange technique would be to contact the synthetic ZSM-45 with a salt of the desired replacing cation or cations. Examples of such salts include the halides, e.g. chlorides, nitrates and sulfates.
The Zealot ZSM-45 useful in the methanol/methyl ether conversion process herein can advantageously be dehydrated, at least partially, prior to use. This can be done by heating the zealot to a temperature in the range of 200C to 595C in an inert atmosphere, I such as air, nitrogen, etc. and at atmospheric, sub atmospheric or super atmospheric pressures for between 30 minutes and 48 hours.
Dehydration can also be performed at room temperature merely by placing ZSM-45 in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
The Zealot ~SM-45 for use in the present process can be prepared from a reaction mixture containing sources of alkali metal ions (I and No), an oxide of aluminum, an oxide of silicon, an organic cation (R) derived from a 2-(hydroxyalkyl)trialkylammonium compound wherein alkyd is composed of of one or two carbon atoms and water and having a composition, in terms of mole ratios of oxides and cations, falling within the following ranges:
F-2039 Canada -10- ~L~293~3 Reactants Useful Preferred I.
Sue 10-150 15-80 OH Shea 0.~-1.0 0.3-0.8 IRK Nay 0.1-0.8 0.2-0.7 K/K+Na 0.0~0~8 0.05-0.3 wherein R is as above defined.
Crystallization of the Zealot ZSM-45 can be carried out at either static or stirred condition in a suitable reactor vessel, such as for example, polypropylene jars or Teflon lined or stainless steel autoclaves. A useful range of temperatures for crystallization is from about 80C to about 350C for a time of about 12 hours to about 200 days. Thereafter, the crystals can be separated from the liquid and recovered. The composition can be prepared utilizing materials which supply the appropriate oxides. Such compositions may include sodium silicate, silica hydrosol, silica gel, silicic acid sodium hydroxide, a source of aluminum, and an appropriate organic compound It should be realized that the reaction mixture component oxides can be supplied from more than one source. The reaction mixture can be prepared either bushes or continuously. Crystal size and crystallization time of the crystalline Zealot ZSM-4S will vary with the nature of the reaction mixture employed and the crystallization conditions.
In all cases, synthesis of the ZSM-45 crystals is facilitated by the presence of at least 0.01 %, preferably 0.10 and still more preferably 1 I, seed crystals (based on total weight) of crystalline product.
The 2 (hydroxyalkyl)trialkylammonium compound may be the hydroxide or halide, e.g. chloride, iodide or bromide. When the compound is 2-(hydroxyethyl)trimethylammonium chloride it is called choline chloride, a preferred source of organic cations (R) in the synthesis of Zealot ZSM-45.
The US 45 crystals so prepared can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder a granule, or a molded product, such as an F-2039 Canada 3l2~ 353 extradite having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a ~00 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion the crystals can be extruded before drying or partially dried and then extruded.
It may be desirable to incorporate the Zealot ZSM-45 with another material resistant to the temperatures and other conditions employed in the methanol/methyl ether conversion process embodiments of the present invention. Such materials include active and inactive material and synthetic or naturally occurring zealots as well as inorganic materials such as clays, silica and/or metal oxides, e.g.
alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material which is active in conjunction with the ZSM-45 crystal, i.e. combined therewith, may improve the conversion and/or selectivity of the catalyst in certain methanol conversion process embodiments Inactive materials suitably serve as delineates to control the amount of conversion in a given process so -that products can be obtained economically and orderly without employing other means for controlling -the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g.
bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e. clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst composite having good crush strength because in commercial use it is desirable to prevent the catalyst prom breaking down into powder-like materials. These clay binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays which can be composite with the ZSM-45 crystalline material include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolin commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is hollowest, coolant, Dakota, nacrite, or anxiety. Such clays can be used in the raw state as originally mined or initially subjected to calcination~ acid ~29~
F 2039 Canada -12-treatment or chemical modification. Binders useful for compositing with the ZSM-45 crystal also include inorganic oxides notably alumina.
In addition to the foregoing materials, the zealot ZSM-45 can be composite with a porous matrix material such as silica-alumina, silica magnesia silica-zirconia, silica-thoria, silica-Barlow, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-~lumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia. The relative proportions of finely divided crystalline material and inorganic oxide gel matrix vary widely, with the zealot content ranging from about 1 to about 90% by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight % of the composite.
As noted, the ZSM-45 zealot containing catalyst compositions as herein before described are especially useful for the selective conversion of methanol and/or methyl ether to a light olefin (C2-C4)-containing hydrocarbon product particularly enriched in ethylene By utilizing a selected combination of the particular ZSM-45 based catalyst along with particular methanol/methyl ether MU conversion reaction conditions including the presence of certain gaseous delineates, methanol/methyl ether conversion processes can be realized which are more selective to light olefin production than are similar processes employing other types of zealot catalysts.
Processes utilizing these particular ZSM-45 based catalysts and certain reaction conditions are also more resistant to catalyst aging or provide enhanced conversion of methanol and/or methyl ether-containing feed to olefins in comparison with other known zeolite-catalyzed methanol/methyl ether conversion processes. The process of the present invention can, in fact, yield a light olefin-containing product wherein ethylene is the major light olefin produced.
In accordance with the present process invention, a charge stock comprising methanol (methyl alcohol), methyl ether, methanol/methyl ether mixtures can be contacted in the vapor phase with the ZSM-45-based catalyst materials herein before described in a F-2039 Canada -13-reaction zone in the presence of a gaseous delineate and under reaction conditions suitable for effecting conversion of methanol and/or methyl ether to olefins. Such conditions include an operating temperature between about 260C (~V500F) and 540C (I 1000~), preferably 300C
and 450C; a pressure between about 104 Pa (0.1 atmosphere) and 3.0 x 106 Pa (300 atmospheres) preferably 5.0 x 105 Pa and 106 Pa;
and a weight hourly space velocity (WHSV) of the organic reactants between about 0.1 and 30, preferably 1 and 10.
The gaseous delineate is introduced into the reaction zone I along with the organic oxygenate reactant. Such delineates include, for example, nitrogen, helium, water, carbon monoxide, carbon dioxide, or mixtures of these gases. The preferred delineate is water. The gaseous delineate can be co-fed to the reaction zone using a weight hourly space velocity (WHSV) of from about 0.003 to 20, preferably from about 0.01 to 10. Generally the molar ratio of gaseous delineate to the organic reactants ranges from about 0.05:1 to 40:1, more preferably from about 0.1:1 to 20:1.
water (steam) is an especially useful delineate. Selectivity of the methanol conversion reaction for production of light (C2-C4) olefins can be improved for example by contacting the feed stock with the herein before described zealot based catalyst in the presence of up to about 20 moles, and preferably from about 1 to 10 moles of steam per mole of organic reactant. Such steam contact is made in the reaction zone under the methanol/methyl ether conversion conditions herein before described. Such steam may be provided directly by injecting the requisite amount of water or steam into the reaction zone. Alternatively, steam may be provided totally or in part by water present in the feed stock in a molar ratio of water to organic reactants of up to about 20:1, preferably from about 1:1 to about 10:1. Such water in the feed stock to the reaction zone, of course, forms steam in the reaction zone under the conversion conditions of the present invention. Steam can thus be passed to the reaction zone with a WHSV of from about 1 to 2û, more preferably of from about 2 to 10.
~%~
F-2039 Canada -14-Conversion reaction conditions, as well as the nature of the particular catalyst composition and delineate employed, can affect the selectivity of the present methanol/methyl ether conversion process to light olefin and ethylene production as well as percent conversion of organic reactants to hydrocarbon product and can also affect catalyst aging characteristics. However, it has been discovered that for a given set of reaction conditions the ZS~-45 based catalyst used in the present invention, and especially a ZSM-45 based catalyst used in combination with a gaseous delineate, will generally provide improved methanol conversion, light olefin selectivity and/or catalyst aging performance in comparison with similar prior art processes employing either other zealots or diluent-free reaction conditions.
The methanol and/or methyl ether conversion process described herein may be carried out as a batch-type, semi-continuous or continuous operation utilizing a fixed, fluidized or moving bed catalyst system. Q preferred embodiment entails use of a catalyst zone wherein the alcohol or ether charge optionally together with added water is passed concurrently or counter currently through a fluidized or moving bed of particle-form catalyst. The latter after use may be conducted to a regeneration zone wherein catalyst can be regenerated by any of the conventional regeneration methods known to the art and thereafter recycled to the conversion zone for further contact with the methanol and/or ether containing feed.
The product stream in the process of the invention contains steam and a hydrocarbon mixture of paraffins and olefins, which mixture can be substantially devoid of aromatics. As noted, the mixture is particularly rich in light olefins, and especially rich in ethylene. Thus, the predominant hydrocarbon product constitutes valuable petrochemicals. The steam and hydrocarbon products may be I separated from one another by methods well known in the art. In a preferred embodiment of the invention, the unconverted methanol and/or methyl ether, as well as at least part ox the water in the product, can be recycled to the reaction zone.
f-2039 Canada -15-In order to more fully illustrate the nature of the invention and the manner of practicing same, the following examples are presented. In the examples, whenever adsorption data are set forth For comparison of sorptive capacities of ZSM-45 for water, cyclohexane and/or Nixon, they were determined as follows:
A weighed sample of the calcined ZSM-45 adsorbent was contacted with the desired pure adsorb ate vapor in an adsorption chamber, evacuated to less than 133.22 Pa (1 mm Hug) and contacted with 1600 Pa (12 mm Hug) ox water vapor or 2666.55 Pa (20 mm Hug) of Nixon, or cyclohexane vapor! pressures less than the vapor-liquid equilibrium pressure of the respective adsorb ate at room temperature.
The pressure was kept constant (within about 66066 Pa) by addition of adsorb ate vapor controlled by a manostat during the adsorption period, which did not exceed about 8 hours. As adsorb ate was adsorbed by the zealot crystal, the decrease in pressure caused the manostat to open a valve which admitted more adsorb ate vapor to the chamber to restore the above control pressures. Sorption was complete when the pressure change was not sufficient to activate the manostat. The increase in weight was calculated as the adsorption capacity of the I sample in Lowe 9 of calcined adsorbent.
When Alpha Value For the ZSM-45 zealot is determined, it is noted that the Alpha Value is an approximate indication of the catalytic activity, e.g., cracking activity, of the catalyst compared to a standard catalyst and it gives the relative rate constant (rate ox normal hexane conversion per volume of catalyst per unit time). It is based on the activity of the highly active silica-alumina cracking catalyst taken as an Alpha Value of 1 (Rate Constant = 0.016 sea 1). The Alpha Test is described in US. Patent 3,354,078 and in The Journal of Catalysis, Vol. IV, pp. 522-529 (August 1965)~
Three separate components were prepared to comprise ingredients as follows:
. 15.45 grams of ASSAY 18H20 3.4~ grams of H2S0 90.2 grams of H20 F-2039 Canada -16-B. 135.4 grams of Q-Brand sodium silicate (28.5 wt. percent Sue) 8.8 wt. percent Noah and 62.7 wt.
percent H20) 2.0 grams of 86.4 wt. percent KOCH
11.0 grams of H20 C. 38.0 grams of choline chloride Component C was added to component B and A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 99C over 197 days. The crystalline product was separated, washed and dried and identified by X-ray diffraction analysis to be about 9û percent zealot ZSM-45 plus about 10 percent unidentified impurities. The complete X-ray pattern data for to s zealot is presented in Table 2, hereinafter.
Chemical analysis of the zealot product of this example proved it to have the following composition:
Component Wt. Percent N 2.07 No 0.28 K 0.35 Aye 7.40 Sue 89.90 Ash 80.50 Sue, molar 20.7 Sorption capacities of the zealot product of this example, calcined at 538C, were:
Adsorb ate Capacity Wt. Percent Cyclohexane, 20 Torn (pow) 3.5 Nixon, 20 Torn (2666.44 Pa) 12.
I Water, 12 Torn (1600 Pa) 18.3 The surface area of the zealot ZSM-45 product of this example was measured to be 514 m2/gram.
go F-2039 Canada -17-Degrees InterplanarO Relative Intensity, Two Theta D-Spacing (A) _ Rio 7.72 11.45 6 8.60 10.28 13 lo o 91 8.11 50 11.45 7.73 3 11.65 7,60 6 13.41 6.60 36 1015.60 5.68 6 16.00 5.54 9 17.38 5.10 81 17.84 4.97 12 20.98 4.23 51 1522.08 4.03 100 23.44 3.80 45 25.05 3.55 13 25.53 3.49 5 25.94 3.43 5 2027.12 3.29 20 28.53 .13 47 29.38 3.04 6 31.70 2. ~23 8 32.45 2.759 40
The Zealot ZSM-45 used herein sorbs significant amounts of commonly used test adsorb ate materials, i.e. cyclohexane, Nixon and water, whereas naturally occurring levynite is not expected to adsorb cyclohexane due to its pore structure. Sorption capacities for Zealot ZSM-45 will range at room temperature as follows:
~dsortate Capacity, Wt. Percent Cyclohexane 2.2 7.0 Nixon - 12.9 Whetter - 22.9 The original organic and alkali metal cations o-f the as-synthesized ZSM-45 can be replaced at least in part in accordance with techniques well known in the art, with other cations. Such techniques include thermal treatment and ion exchange. Preferred replacing cations include metal ions, hydrogen ions hydrogen precursor, e.g. ammonium, ions and mixtures thereof Particularly preferred cations are those which render the ZS~-45 catalytically active for methanol conversion. These include hydrogen, anonym, rare earth metals and metals of Groups IA, IDA, IIIA, IVAN IBM JIB, III~, IVY and VIII of the Periodic Chart of the Elements The Zealot F-2039 Canada -9- Lo I 3 ZSM-45 is preferably employed in the methanol conversion process herein in either the ammonium or hydrogen form. The ZSM-45 zealot may also be utilized in a form wherein some of the active sites have been exchanged with alkali metal, alkaline earth metal or other metal cations. however, the zealot must contain some acid sites to be effectively utilized in -the process of the present invention.
Thermal treatment of the as-synthesized zealot is generally employed to remove all or part of the organic constituent. Such thermal treatment can for example be conducted at temperatures in lo excess of 250C or a period of time sufficient to remove the organic constituent to the desired extent. Following thermal treatment the zealot can then be subjected to ion exchange. A typical ion exchange technique would be to contact the synthetic ZSM-45 with a salt of the desired replacing cation or cations. Examples of such salts include the halides, e.g. chlorides, nitrates and sulfates.
The Zealot ZSM-45 useful in the methanol/methyl ether conversion process herein can advantageously be dehydrated, at least partially, prior to use. This can be done by heating the zealot to a temperature in the range of 200C to 595C in an inert atmosphere, I such as air, nitrogen, etc. and at atmospheric, sub atmospheric or super atmospheric pressures for between 30 minutes and 48 hours.
Dehydration can also be performed at room temperature merely by placing ZSM-45 in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
The Zealot ~SM-45 for use in the present process can be prepared from a reaction mixture containing sources of alkali metal ions (I and No), an oxide of aluminum, an oxide of silicon, an organic cation (R) derived from a 2-(hydroxyalkyl)trialkylammonium compound wherein alkyd is composed of of one or two carbon atoms and water and having a composition, in terms of mole ratios of oxides and cations, falling within the following ranges:
F-2039 Canada -10- ~L~293~3 Reactants Useful Preferred I.
Sue 10-150 15-80 OH Shea 0.~-1.0 0.3-0.8 IRK Nay 0.1-0.8 0.2-0.7 K/K+Na 0.0~0~8 0.05-0.3 wherein R is as above defined.
Crystallization of the Zealot ZSM-45 can be carried out at either static or stirred condition in a suitable reactor vessel, such as for example, polypropylene jars or Teflon lined or stainless steel autoclaves. A useful range of temperatures for crystallization is from about 80C to about 350C for a time of about 12 hours to about 200 days. Thereafter, the crystals can be separated from the liquid and recovered. The composition can be prepared utilizing materials which supply the appropriate oxides. Such compositions may include sodium silicate, silica hydrosol, silica gel, silicic acid sodium hydroxide, a source of aluminum, and an appropriate organic compound It should be realized that the reaction mixture component oxides can be supplied from more than one source. The reaction mixture can be prepared either bushes or continuously. Crystal size and crystallization time of the crystalline Zealot ZSM-4S will vary with the nature of the reaction mixture employed and the crystallization conditions.
In all cases, synthesis of the ZSM-45 crystals is facilitated by the presence of at least 0.01 %, preferably 0.10 and still more preferably 1 I, seed crystals (based on total weight) of crystalline product.
The 2 (hydroxyalkyl)trialkylammonium compound may be the hydroxide or halide, e.g. chloride, iodide or bromide. When the compound is 2-(hydroxyethyl)trimethylammonium chloride it is called choline chloride, a preferred source of organic cations (R) in the synthesis of Zealot ZSM-45.
The US 45 crystals so prepared can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder a granule, or a molded product, such as an F-2039 Canada 3l2~ 353 extradite having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a ~00 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion the crystals can be extruded before drying or partially dried and then extruded.
It may be desirable to incorporate the Zealot ZSM-45 with another material resistant to the temperatures and other conditions employed in the methanol/methyl ether conversion process embodiments of the present invention. Such materials include active and inactive material and synthetic or naturally occurring zealots as well as inorganic materials such as clays, silica and/or metal oxides, e.g.
alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material which is active in conjunction with the ZSM-45 crystal, i.e. combined therewith, may improve the conversion and/or selectivity of the catalyst in certain methanol conversion process embodiments Inactive materials suitably serve as delineates to control the amount of conversion in a given process so -that products can be obtained economically and orderly without employing other means for controlling -the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g.
bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e. clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst composite having good crush strength because in commercial use it is desirable to prevent the catalyst prom breaking down into powder-like materials. These clay binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays which can be composite with the ZSM-45 crystalline material include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolin commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is hollowest, coolant, Dakota, nacrite, or anxiety. Such clays can be used in the raw state as originally mined or initially subjected to calcination~ acid ~29~
F 2039 Canada -12-treatment or chemical modification. Binders useful for compositing with the ZSM-45 crystal also include inorganic oxides notably alumina.
In addition to the foregoing materials, the zealot ZSM-45 can be composite with a porous matrix material such as silica-alumina, silica magnesia silica-zirconia, silica-thoria, silica-Barlow, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-~lumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia. The relative proportions of finely divided crystalline material and inorganic oxide gel matrix vary widely, with the zealot content ranging from about 1 to about 90% by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight % of the composite.
As noted, the ZSM-45 zealot containing catalyst compositions as herein before described are especially useful for the selective conversion of methanol and/or methyl ether to a light olefin (C2-C4)-containing hydrocarbon product particularly enriched in ethylene By utilizing a selected combination of the particular ZSM-45 based catalyst along with particular methanol/methyl ether MU conversion reaction conditions including the presence of certain gaseous delineates, methanol/methyl ether conversion processes can be realized which are more selective to light olefin production than are similar processes employing other types of zealot catalysts.
Processes utilizing these particular ZSM-45 based catalysts and certain reaction conditions are also more resistant to catalyst aging or provide enhanced conversion of methanol and/or methyl ether-containing feed to olefins in comparison with other known zeolite-catalyzed methanol/methyl ether conversion processes. The process of the present invention can, in fact, yield a light olefin-containing product wherein ethylene is the major light olefin produced.
In accordance with the present process invention, a charge stock comprising methanol (methyl alcohol), methyl ether, methanol/methyl ether mixtures can be contacted in the vapor phase with the ZSM-45-based catalyst materials herein before described in a F-2039 Canada -13-reaction zone in the presence of a gaseous delineate and under reaction conditions suitable for effecting conversion of methanol and/or methyl ether to olefins. Such conditions include an operating temperature between about 260C (~V500F) and 540C (I 1000~), preferably 300C
and 450C; a pressure between about 104 Pa (0.1 atmosphere) and 3.0 x 106 Pa (300 atmospheres) preferably 5.0 x 105 Pa and 106 Pa;
and a weight hourly space velocity (WHSV) of the organic reactants between about 0.1 and 30, preferably 1 and 10.
The gaseous delineate is introduced into the reaction zone I along with the organic oxygenate reactant. Such delineates include, for example, nitrogen, helium, water, carbon monoxide, carbon dioxide, or mixtures of these gases. The preferred delineate is water. The gaseous delineate can be co-fed to the reaction zone using a weight hourly space velocity (WHSV) of from about 0.003 to 20, preferably from about 0.01 to 10. Generally the molar ratio of gaseous delineate to the organic reactants ranges from about 0.05:1 to 40:1, more preferably from about 0.1:1 to 20:1.
water (steam) is an especially useful delineate. Selectivity of the methanol conversion reaction for production of light (C2-C4) olefins can be improved for example by contacting the feed stock with the herein before described zealot based catalyst in the presence of up to about 20 moles, and preferably from about 1 to 10 moles of steam per mole of organic reactant. Such steam contact is made in the reaction zone under the methanol/methyl ether conversion conditions herein before described. Such steam may be provided directly by injecting the requisite amount of water or steam into the reaction zone. Alternatively, steam may be provided totally or in part by water present in the feed stock in a molar ratio of water to organic reactants of up to about 20:1, preferably from about 1:1 to about 10:1. Such water in the feed stock to the reaction zone, of course, forms steam in the reaction zone under the conversion conditions of the present invention. Steam can thus be passed to the reaction zone with a WHSV of from about 1 to 2û, more preferably of from about 2 to 10.
~%~
F-2039 Canada -14-Conversion reaction conditions, as well as the nature of the particular catalyst composition and delineate employed, can affect the selectivity of the present methanol/methyl ether conversion process to light olefin and ethylene production as well as percent conversion of organic reactants to hydrocarbon product and can also affect catalyst aging characteristics. However, it has been discovered that for a given set of reaction conditions the ZS~-45 based catalyst used in the present invention, and especially a ZSM-45 based catalyst used in combination with a gaseous delineate, will generally provide improved methanol conversion, light olefin selectivity and/or catalyst aging performance in comparison with similar prior art processes employing either other zealots or diluent-free reaction conditions.
The methanol and/or methyl ether conversion process described herein may be carried out as a batch-type, semi-continuous or continuous operation utilizing a fixed, fluidized or moving bed catalyst system. Q preferred embodiment entails use of a catalyst zone wherein the alcohol or ether charge optionally together with added water is passed concurrently or counter currently through a fluidized or moving bed of particle-form catalyst. The latter after use may be conducted to a regeneration zone wherein catalyst can be regenerated by any of the conventional regeneration methods known to the art and thereafter recycled to the conversion zone for further contact with the methanol and/or ether containing feed.
The product stream in the process of the invention contains steam and a hydrocarbon mixture of paraffins and olefins, which mixture can be substantially devoid of aromatics. As noted, the mixture is particularly rich in light olefins, and especially rich in ethylene. Thus, the predominant hydrocarbon product constitutes valuable petrochemicals. The steam and hydrocarbon products may be I separated from one another by methods well known in the art. In a preferred embodiment of the invention, the unconverted methanol and/or methyl ether, as well as at least part ox the water in the product, can be recycled to the reaction zone.
f-2039 Canada -15-In order to more fully illustrate the nature of the invention and the manner of practicing same, the following examples are presented. In the examples, whenever adsorption data are set forth For comparison of sorptive capacities of ZSM-45 for water, cyclohexane and/or Nixon, they were determined as follows:
A weighed sample of the calcined ZSM-45 adsorbent was contacted with the desired pure adsorb ate vapor in an adsorption chamber, evacuated to less than 133.22 Pa (1 mm Hug) and contacted with 1600 Pa (12 mm Hug) ox water vapor or 2666.55 Pa (20 mm Hug) of Nixon, or cyclohexane vapor! pressures less than the vapor-liquid equilibrium pressure of the respective adsorb ate at room temperature.
The pressure was kept constant (within about 66066 Pa) by addition of adsorb ate vapor controlled by a manostat during the adsorption period, which did not exceed about 8 hours. As adsorb ate was adsorbed by the zealot crystal, the decrease in pressure caused the manostat to open a valve which admitted more adsorb ate vapor to the chamber to restore the above control pressures. Sorption was complete when the pressure change was not sufficient to activate the manostat. The increase in weight was calculated as the adsorption capacity of the I sample in Lowe 9 of calcined adsorbent.
When Alpha Value For the ZSM-45 zealot is determined, it is noted that the Alpha Value is an approximate indication of the catalytic activity, e.g., cracking activity, of the catalyst compared to a standard catalyst and it gives the relative rate constant (rate ox normal hexane conversion per volume of catalyst per unit time). It is based on the activity of the highly active silica-alumina cracking catalyst taken as an Alpha Value of 1 (Rate Constant = 0.016 sea 1). The Alpha Test is described in US. Patent 3,354,078 and in The Journal of Catalysis, Vol. IV, pp. 522-529 (August 1965)~
Three separate components were prepared to comprise ingredients as follows:
. 15.45 grams of ASSAY 18H20 3.4~ grams of H2S0 90.2 grams of H20 F-2039 Canada -16-B. 135.4 grams of Q-Brand sodium silicate (28.5 wt. percent Sue) 8.8 wt. percent Noah and 62.7 wt.
percent H20) 2.0 grams of 86.4 wt. percent KOCH
11.0 grams of H20 C. 38.0 grams of choline chloride Component C was added to component B and A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 99C over 197 days. The crystalline product was separated, washed and dried and identified by X-ray diffraction analysis to be about 9û percent zealot ZSM-45 plus about 10 percent unidentified impurities. The complete X-ray pattern data for to s zealot is presented in Table 2, hereinafter.
Chemical analysis of the zealot product of this example proved it to have the following composition:
Component Wt. Percent N 2.07 No 0.28 K 0.35 Aye 7.40 Sue 89.90 Ash 80.50 Sue, molar 20.7 Sorption capacities of the zealot product of this example, calcined at 538C, were:
Adsorb ate Capacity Wt. Percent Cyclohexane, 20 Torn (pow) 3.5 Nixon, 20 Torn (2666.44 Pa) 12.
I Water, 12 Torn (1600 Pa) 18.3 The surface area of the zealot ZSM-45 product of this example was measured to be 514 m2/gram.
go F-2039 Canada -17-Degrees InterplanarO Relative Intensity, Two Theta D-Spacing (A) _ Rio 7.72 11.45 6 8.60 10.28 13 lo o 91 8.11 50 11.45 7.73 3 11.65 7,60 6 13.41 6.60 36 1015.60 5.68 6 16.00 5.54 9 17.38 5.10 81 17.84 4.97 12 20.98 4.23 51 1522.08 4.03 100 23.44 3.80 45 25.05 3.55 13 25.53 3.49 5 25.94 3.43 5 2027.12 3.29 20 28.53 .13 47 29.38 3.04 6 31.70 2. ~23 8 32.45 2.759 40
5 34.57 1 2.595 10 35.25 2.546 2 35.46 2.531 2 38.08 2.363 2 3~.41 2.344 3039.80 2.265 3 40.50 2.227 41.25 2.189 3 42.2~ 2.14û 3 43.00 2.103 8 3544.52 2.035 2 45.10 2.010 4 46.89 1.93~ 1 47.32 1.921 48.02 1.895 6 48.90 1.863 6 49.40 1.845 3 50.10 1.821 7 51.61 1,771 12 52.42 1.745 5 53.00 1.7~8 2 53.50 1.713 54.10 1.695 55.00 1.670 55.58 1.653 3 3~3 allege F-2039 Canada 18-56.02 1.642 8 56.82 1.620 3 57.35 1.607 2 59.15 1.562 5 About 10 grams of the zealot ZSM-45 product of Example 1 was calcined in air at 5~8C for 10 hours and then contacted with 10 cc/gram zealot of 5 percent ammonium chloride solution at 85C five separate times The resulting zealot was then dried at about 110C
and calcined at 538C for 10 hours in air. It was then submitted for evaluation in the Alpha Test, described herein before. Its Alpha Value proved to be 14.
Three separate components were prepared to comprise ingredients as follows:
A. 15.45 grams of ASSAY 18H20 3.48 grams of H2SC4 90.2 grams of H20 B. 135.4 grams of Q-Brand sodium silicate (28.5 wt. percent Sue, 8.8 wt. percent Noah and 62.7 wt.
percent H20) 2.0 grams of 86.4 wt. percent KOCH
50.0 grams of H20 C. 38.0 grams of choline chloride Component C was added to component B and component A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 99C over 152 days. The crystalline product was separated, washed and dried and identified by X-ray diffraction analysis to be zealot ZSM-45.
Chemical analysis of the zealot product of this example proved it to have the following composition:
F-2039 Canada -19-Component Wt. Percent -N 2.25 No 0 43 K 0.25 Q123 7.60 Sue 89.00 Ash 78.90 Sorption capacities of the zealot product of this example, calcined at 538~C, were:
Adsorb ate Capacity_ Wit _ Percent . .
10Cyclohexane, 20 Torn (2666.44 Pa) 3.8 n Hexane, 2û Torn (2666.44 Pa) 11.3 Water, 12 Torn (1600 Pa) 16.2 The surface area of the zealot product of this example was measured to be 467 m gram.
About 10 grams of the zealot ZSM-45 product of Example 3 was calcined in air a-t 538C for 10 hours and then contacted with 5 percent ammonium chloride solution, dried and calcined as in Example 2. It was then submitted for evaluation in the Alpha Test Its Alpha Value proved to be 6.
Three separate components were prepared to comprise ingredients as follows:
A. 28.7 grams of sodium acuminate 36.0 grams of Nash 10.0 grams of 85 wt. percent KOCH
450.0 grams of H20 B. 650 0 grams of colloidal silica (30 wt. percent) C. 190.0 grams of choline chloride Component C was added to component A and component B was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 121C over 21 days. The crystalline product was separated, washed and dried and identified by it F-2039 Canada -20-X-ray diffraction analysis to be about 85 percent zealot ZSM-45 plus about 15 percent unidentified impurities. The complete Ray pattern data for this zealot is presented in Table 3, hereinafter.
5 Degrees InterplanarO Relative Intensity, Two Theta D-Spacin~ tax Rio 7.7~ 11.36 14 8.67 10.20 11 11.00 8.04 37 11.69 7.57 8 12.60 7-03 4 13.15 6.73 8 13.49 6.60 37 15.55 5.70 6 16.05 5.52 9 17.45 5.08 65 17.88 4.96 20 19.45 4 L 56 6 20.72 4.29 20 I 21.07 ~.22 47 22.12 4.02 100 23.49 3.79 62 25.~4 3.54 38 25.91 3.44 18 26.90 3.31 10 27.19 3.28 27 28.35 3.15 13 28.63 3.12 40 29.~0 3.04 7 31.54 2.~4 11 31.75 2.~19 10 32.51 2.754 35 34.65 2.589 6 35.50 2.529 2 36.25 2.478 5 38.10 2.362 3 39.80 2.265 2 41.25 2.189 2 42.28 2.138 3 I 43.05 2.101 7 45.17 2.007 3 48.11 1.891 5 48.90 1.863 4 ~9.45 1.843 3 50.1g 1.817 6 51.74 1.767 11 52.94 1.730 55.68 1.651 4 56.15 1.538 6 I
F-2039 Canada -21-56.94 1.617 59.26 1.559 3 Chemical analysis of the zealot product of this example proved it to have the following composition:
Component Wt. Percent N 2.34 No 0 49 K 0.58 Aye 6.90 Sue 72.60 Ash 81.5û
Sorption capacities of the zealot product of this example, calcined at 538CC, were:
Adsorb ate Capacity, Wt. Percent Cyclohexane, 20 Torn (2666.44 Pa) 5.0 Nixon, 20 Torn (2666.44 Pa) 11.0 Water, 12 Torn (1600 Pa) 14.5 The surface area of the zealot product of this example was measured to be 484 m2/gram.
About 10 grams of the zealot ZSM-45 product of Example 5 was calcined in air at 538C For 10 hours and then contacted with 5 percent ammonium chloride solution, dried and calcined as in Example 4. It was then submitted for evaluation in the Alpha Test. Its Alpha Value proved to be 27.
.
Three separate components were prepared to comprise ingredients as follows:
A. 23.2 grams ox Aye 18H20 5~2 grams of H2504 135 grams of H20 B.203.1 grams of Q-Brand sodium silicate (28.5 wt. percent Sue, 8.8 wt. percent Noah and 62.7 wt.
percent H20) F-2039 Canada -22-3.0 grams of 86.4 White percent KOCH
75.0 grams of H20 C. 57.0 grams of choline chloride Component C was added to component B and A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 100C over 151 days. The crystalline product was separated, washed and dried an identified by X-ray diffraction analysis to be 100 percent zealot ZSM-45. The complete X-ray pattern I data for this zealot is presented in Table 4, hereinafter.
Degrees InterplanarORelative Intensity 9 Two Theta D-Spacin9 tax Rio 7.77 11.38 4 15 8.71 10.15 10 11.04 8.û2 45 11.71 7.56 6 13.52 6.55 36 15.67 5.66 2 2016.11 5.50 10 17.49 5.07 76 17.93 4.95 13 19.57 ~.54 4 21.10 4.21 50 2522.18 4.01 100 23~54 3.78 47 23.80 3.74 8 25.16 3.54 15 26.08 3.42 5 3027.24 3.27 24 28.67 3.11 44 29.46 3-03 7 31.84 2.~10 7 32.55 2.750 38 3534.72 2.584 9 35.42 2.534 3 35.62 2.520 2 36.28 2.476 5 37.42 2.403 2 4038.22 2.~55 38.48 2.339 39.95 2.257 2 40.50 2.227 2 41.36 2.183 3 4542.40 2.132 3 43.12 2.098 7 F-2039 Canada -23~ 3~;3 44.70 2.027 6 45.22 2.0~5 4 47.35 1.920 2 48.16 1.889 5 49.03 1.858 4 49.50 1.841 3 50.23 1.316 6 51.7~ 1.766 11 53.01 1.727 2 53.75 1.705 2 55.68 1.651 3 56.15 1.638 6 56.99 1.616 2 57.39 1.605 59.30 1.558 4 Chemical analysis of the zealot product of this example proved it to have the following composition:
Component Wt. Percent N 2.26 No 0.37 K 0.79 Aye 7.48 sin 85.8 Ash 82.8 AYE molar 19.5 Sorption capacities of the zealot product of this example, calcined at 538C, were:
Adsorb ate amity, Wt. Percent Cyclohexane, 20 Torn (2666.44 Pa) 3.4 Nixon 20 Torn (2666.44 Pa 12.9 Water, 12 Torn (1600 Pa) 21.1 The surface area of the zealot product of this example was measured to be 471 m2/gram.
Two grams of zealot ZSM-45 product of Example 2 were dried by heating for 1 hour in air flowing at 10 cc/hour at 538~C. The zealot was mixed with an equal volume of quartz chips (both 14/25 mesh) and the mixture placed in a quartz micro reactor equipped with a thermocouple. The reactor was then flushed with air at 10 cc/minute it F-2039 Canada -24-for 105 minutes at 538C. The air flow was replaced with helium flow at 10 cc/minute while the reactor temperature was reduced to about 371C. Feed stock composed of 30 wt. % methanol and 70 wt. % water was then passed into the reactor at 3.4 cc/hour for 2 hours at atmospheric pressure. The weight hourly space velocity was 2.8_hr 1 and the temperature was maintained at about 371C. Product collected from the reactor was analyzed for chemical composition. Conversion of methanol was indicated to be 87 wt. %. The product hydrocarbon content comprised 39 wt. % ethylene and 16 wt. % C5 + components.
Two grams of zealot ZSM-45 prepared as in Example 4 were dried, mixed with quartz chips, placed in the micro reactor, air flushed and helium flushed as in Example 8. With the reactor temperature maintained at about 371C and the pressure at atmospheric, feed stock comprising 30 wt. methanol and 70 wt. % water was passed into the reactor at a WHSV of 2.4 hurl The molar ratio of water/methanol in the feed stock was 4/1. Product was collected and analyzed. Conversion of methanol proved to be 46 wt. %. Product hydrocarbon content comprised 44 wt. ethylene and nil C
components.
EXAMPLE Lo In this example, two grams of zealot ZSM-45 prepared as in Example 4 were dried, mixed with quartz chips, placed in the micro reactor, air and helium flushed as in Example 9. With the reactor maintained at from about 371C to about 379C and the pressure at atmospheric, feed stock of 100% methanol was passed into the reactor at a WHSV of 2.4 ho 1. Product was collected and analyzed, showing 79.7 wt. % conversion of methanol to product hydrocarbons comprising:
Component Wt. %
Ethylene 16.91 Propylene 39.46 Isobutane 11.68 Battalion 22.55 C5 Hydrocarbons 9.40
and calcined at 538C for 10 hours in air. It was then submitted for evaluation in the Alpha Test, described herein before. Its Alpha Value proved to be 14.
Three separate components were prepared to comprise ingredients as follows:
A. 15.45 grams of ASSAY 18H20 3.48 grams of H2SC4 90.2 grams of H20 B. 135.4 grams of Q-Brand sodium silicate (28.5 wt. percent Sue, 8.8 wt. percent Noah and 62.7 wt.
percent H20) 2.0 grams of 86.4 wt. percent KOCH
50.0 grams of H20 C. 38.0 grams of choline chloride Component C was added to component B and component A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 99C over 152 days. The crystalline product was separated, washed and dried and identified by X-ray diffraction analysis to be zealot ZSM-45.
Chemical analysis of the zealot product of this example proved it to have the following composition:
F-2039 Canada -19-Component Wt. Percent -N 2.25 No 0 43 K 0.25 Q123 7.60 Sue 89.00 Ash 78.90 Sorption capacities of the zealot product of this example, calcined at 538~C, were:
Adsorb ate Capacity_ Wit _ Percent . .
10Cyclohexane, 20 Torn (2666.44 Pa) 3.8 n Hexane, 2û Torn (2666.44 Pa) 11.3 Water, 12 Torn (1600 Pa) 16.2 The surface area of the zealot product of this example was measured to be 467 m gram.
About 10 grams of the zealot ZSM-45 product of Example 3 was calcined in air a-t 538C for 10 hours and then contacted with 5 percent ammonium chloride solution, dried and calcined as in Example 2. It was then submitted for evaluation in the Alpha Test Its Alpha Value proved to be 6.
Three separate components were prepared to comprise ingredients as follows:
A. 28.7 grams of sodium acuminate 36.0 grams of Nash 10.0 grams of 85 wt. percent KOCH
450.0 grams of H20 B. 650 0 grams of colloidal silica (30 wt. percent) C. 190.0 grams of choline chloride Component C was added to component A and component B was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 121C over 21 days. The crystalline product was separated, washed and dried and identified by it F-2039 Canada -20-X-ray diffraction analysis to be about 85 percent zealot ZSM-45 plus about 15 percent unidentified impurities. The complete Ray pattern data for this zealot is presented in Table 3, hereinafter.
5 Degrees InterplanarO Relative Intensity, Two Theta D-Spacin~ tax Rio 7.7~ 11.36 14 8.67 10.20 11 11.00 8.04 37 11.69 7.57 8 12.60 7-03 4 13.15 6.73 8 13.49 6.60 37 15.55 5.70 6 16.05 5.52 9 17.45 5.08 65 17.88 4.96 20 19.45 4 L 56 6 20.72 4.29 20 I 21.07 ~.22 47 22.12 4.02 100 23.49 3.79 62 25.~4 3.54 38 25.91 3.44 18 26.90 3.31 10 27.19 3.28 27 28.35 3.15 13 28.63 3.12 40 29.~0 3.04 7 31.54 2.~4 11 31.75 2.~19 10 32.51 2.754 35 34.65 2.589 6 35.50 2.529 2 36.25 2.478 5 38.10 2.362 3 39.80 2.265 2 41.25 2.189 2 42.28 2.138 3 I 43.05 2.101 7 45.17 2.007 3 48.11 1.891 5 48.90 1.863 4 ~9.45 1.843 3 50.1g 1.817 6 51.74 1.767 11 52.94 1.730 55.68 1.651 4 56.15 1.538 6 I
F-2039 Canada -21-56.94 1.617 59.26 1.559 3 Chemical analysis of the zealot product of this example proved it to have the following composition:
Component Wt. Percent N 2.34 No 0 49 K 0.58 Aye 6.90 Sue 72.60 Ash 81.5û
Sorption capacities of the zealot product of this example, calcined at 538CC, were:
Adsorb ate Capacity, Wt. Percent Cyclohexane, 20 Torn (2666.44 Pa) 5.0 Nixon, 20 Torn (2666.44 Pa) 11.0 Water, 12 Torn (1600 Pa) 14.5 The surface area of the zealot product of this example was measured to be 484 m2/gram.
About 10 grams of the zealot ZSM-45 product of Example 5 was calcined in air at 538C For 10 hours and then contacted with 5 percent ammonium chloride solution, dried and calcined as in Example 4. It was then submitted for evaluation in the Alpha Test. Its Alpha Value proved to be 27.
.
Three separate components were prepared to comprise ingredients as follows:
A. 23.2 grams ox Aye 18H20 5~2 grams of H2504 135 grams of H20 B.203.1 grams of Q-Brand sodium silicate (28.5 wt. percent Sue, 8.8 wt. percent Noah and 62.7 wt.
percent H20) F-2039 Canada -22-3.0 grams of 86.4 White percent KOCH
75.0 grams of H20 C. 57.0 grams of choline chloride Component C was added to component B and A was then added to the whole. The whole composition was then mixed and the mixture was transferred to a polypropylene jar. Crystallization occurred under static conditions at 100C over 151 days. The crystalline product was separated, washed and dried an identified by X-ray diffraction analysis to be 100 percent zealot ZSM-45. The complete X-ray pattern I data for this zealot is presented in Table 4, hereinafter.
Degrees InterplanarORelative Intensity 9 Two Theta D-Spacin9 tax Rio 7.77 11.38 4 15 8.71 10.15 10 11.04 8.û2 45 11.71 7.56 6 13.52 6.55 36 15.67 5.66 2 2016.11 5.50 10 17.49 5.07 76 17.93 4.95 13 19.57 ~.54 4 21.10 4.21 50 2522.18 4.01 100 23~54 3.78 47 23.80 3.74 8 25.16 3.54 15 26.08 3.42 5 3027.24 3.27 24 28.67 3.11 44 29.46 3-03 7 31.84 2.~10 7 32.55 2.750 38 3534.72 2.584 9 35.42 2.534 3 35.62 2.520 2 36.28 2.476 5 37.42 2.403 2 4038.22 2.~55 38.48 2.339 39.95 2.257 2 40.50 2.227 2 41.36 2.183 3 4542.40 2.132 3 43.12 2.098 7 F-2039 Canada -23~ 3~;3 44.70 2.027 6 45.22 2.0~5 4 47.35 1.920 2 48.16 1.889 5 49.03 1.858 4 49.50 1.841 3 50.23 1.316 6 51.7~ 1.766 11 53.01 1.727 2 53.75 1.705 2 55.68 1.651 3 56.15 1.638 6 56.99 1.616 2 57.39 1.605 59.30 1.558 4 Chemical analysis of the zealot product of this example proved it to have the following composition:
Component Wt. Percent N 2.26 No 0.37 K 0.79 Aye 7.48 sin 85.8 Ash 82.8 AYE molar 19.5 Sorption capacities of the zealot product of this example, calcined at 538C, were:
Adsorb ate amity, Wt. Percent Cyclohexane, 20 Torn (2666.44 Pa) 3.4 Nixon 20 Torn (2666.44 Pa 12.9 Water, 12 Torn (1600 Pa) 21.1 The surface area of the zealot product of this example was measured to be 471 m2/gram.
Two grams of zealot ZSM-45 product of Example 2 were dried by heating for 1 hour in air flowing at 10 cc/hour at 538~C. The zealot was mixed with an equal volume of quartz chips (both 14/25 mesh) and the mixture placed in a quartz micro reactor equipped with a thermocouple. The reactor was then flushed with air at 10 cc/minute it F-2039 Canada -24-for 105 minutes at 538C. The air flow was replaced with helium flow at 10 cc/minute while the reactor temperature was reduced to about 371C. Feed stock composed of 30 wt. % methanol and 70 wt. % water was then passed into the reactor at 3.4 cc/hour for 2 hours at atmospheric pressure. The weight hourly space velocity was 2.8_hr 1 and the temperature was maintained at about 371C. Product collected from the reactor was analyzed for chemical composition. Conversion of methanol was indicated to be 87 wt. %. The product hydrocarbon content comprised 39 wt. % ethylene and 16 wt. % C5 + components.
Two grams of zealot ZSM-45 prepared as in Example 4 were dried, mixed with quartz chips, placed in the micro reactor, air flushed and helium flushed as in Example 8. With the reactor temperature maintained at about 371C and the pressure at atmospheric, feed stock comprising 30 wt. methanol and 70 wt. % water was passed into the reactor at a WHSV of 2.4 hurl The molar ratio of water/methanol in the feed stock was 4/1. Product was collected and analyzed. Conversion of methanol proved to be 46 wt. %. Product hydrocarbon content comprised 44 wt. ethylene and nil C
components.
EXAMPLE Lo In this example, two grams of zealot ZSM-45 prepared as in Example 4 were dried, mixed with quartz chips, placed in the micro reactor, air and helium flushed as in Example 9. With the reactor maintained at from about 371C to about 379C and the pressure at atmospheric, feed stock of 100% methanol was passed into the reactor at a WHSV of 2.4 ho 1. Product was collected and analyzed, showing 79.7 wt. % conversion of methanol to product hydrocarbons comprising:
Component Wt. %
Ethylene 16.91 Propylene 39.46 Isobutane 11.68 Battalion 22.55 C5 Hydrocarbons 9.40
Claims (11)
1. A process for converting an organic reactant feed comprising the organic reactants methanol, methyl ether or mixtures thereof to a C2-C4 olefin-containing hydrocarbon reaction product, said process comprising contacting said organic reactant feed in a reaction zone under methanol or methyl ether conversion reaction conditions with a zeolite-based catalyst composition comprising a synthetic porous crystalline zeolite designated ZSM-45, said zeolite having the formula, on an anhydrous basis and in terms of mole ratio of oxides:
M2/nO:A12O3: x SiO2 wherein x is greater than 8, wherein M is an organic or metallic cation or is a combination of organic and metallic cations and wherein n is the valence of each respective cation present, and having an X-ray powder diffraction pattern containing the following significant lines:
said contacting of organic reactant feed with said catalyst occurring in the presence of a gaseous diluent selected from water, nitrogen, helium, carbon monoxide, carbon dioxide and mixtures of said diluents.
M2/nO:A12O3: x SiO2 wherein x is greater than 8, wherein M is an organic or metallic cation or is a combination of organic and metallic cations and wherein n is the valence of each respective cation present, and having an X-ray powder diffraction pattern containing the following significant lines:
said contacting of organic reactant feed with said catalyst occurring in the presence of a gaseous diluent selected from water, nitrogen, helium, carbon monoxide, carbon dioxide and mixtures of said diluents.
2. A process according to Claim 1 wherein, in the catalyst composition, the ZSM-45 zeolite component, in its as-synthesized form, has a composition on an anhydrous basis and in terms of moles of oxides per mole of alumina, expressed by the formula:
(0.8-1.8)R2O:(0.0-0.3)Na2O:(0.0-0.5)K2O:Al2O3:xSiO2 wherein R is a monovalent organic cation derived from a 2-(hydroxyalkyl) trialkylammonium compound where alkyl is composed of one or two carbon atoms and x is greater than 8, said ZSM-45 zeolite being further characterized by an X-ray diffraction pattern exhibiting values substantially as set forth in Table 1
(0.8-1.8)R2O:(0.0-0.3)Na2O:(0.0-0.5)K2O:Al2O3:xSiO2 wherein R is a monovalent organic cation derived from a 2-(hydroxyalkyl) trialkylammonium compound where alkyl is composed of one or two carbon atoms and x is greater than 8, said ZSM-45 zeolite being further characterized by an X-ray diffraction pattern exhibiting values substantially as set forth in Table 1
3. A process according to claim 2 wherein, in the formula for the zeolite, x is from greater than 8 to 100.
4. A process according to claim 2 wherein, in the formula for the zeolite, R is an organic cation derived from choline chloride.
5. A process according to claim 2 wherein said catalyst composition comprises the product of thermal treatment of the as-synthesized zeolite ZSM-45.
6. A process according to claim 1 wherein said catalyst comprises zeolite ZSM-45 having its ori-ginal cations replaced, at least in part, with a cation or a mixture of cations selected from hydrogen, ammonium, rare earth metals, and metals of Groups IA, IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII of the Periodic Table of the Elements.
7. A process according to claim 1, 2 or 5 wherein the gaseous diluent is co-fed to the reaction zone with the organic reactants using a weight hourly space velocity for the diluent of from 0.03 to 20 at a molar ratio of gaseous diluent to organic reactants of from 0.0501 to 40:1.
8. A process according to claim 1, 2 or 5 wherein a water diluent is co-fed to the reaction zone by utilizing an organic reactant feed comprising a methanol-water mixture.
9. A process according to claim 1, 2 or 5 wherein said conversion reaction conditions include a temperature from about 275°C to about 600°C, a pressure from 104 Pa to 3 x 106 Pa and a weight hourly space velocity of organic components of said feedstock from about 0.1 hr-1 to about 30 hr-1.
10. A process according to claim 1, 2 or 5 wherein said catalyst composition additionally comprises a binder for said ZSM-45 zeolite
11. A process according to claim 1, 2 or 5 wherein the zealite ZSM-45 component of said catalyst composition has a cyclohexane sorption capacity of 2.2 to 7.0 weight percent at 2666.44 Pa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44990982A | 1982-12-15 | 1982-12-15 | |
| US449,909 | 1982-12-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229353A true CA1229353A (en) | 1987-11-17 |
Family
ID=23785972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000441681A Expired CA1229353A (en) | 1982-12-15 | 1983-11-22 | Catalytic conversion of methanol-containing feedstock to olefin-containing product |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS59118723A (en) |
| CA (1) | CA1229353A (en) |
| ZA (1) | ZA839354B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005104912A (en) * | 2003-09-30 | 2005-04-21 | Jgc Corp | Method for manufacturing lower olefin |
| US7641999B2 (en) | 2004-08-27 | 2010-01-05 | Honda Motor Co., Ltd. | Fuel cell stack |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4086186A (en) * | 1976-11-04 | 1978-04-25 | Mobil Oil Corporation | Crystalline zeolite ZSM-34 and method of preparing the same |
| US4209499A (en) * | 1977-10-21 | 1980-06-24 | Mobil Oil Corporation | Crystalline zeolite ZSM-43 synthesis thereof |
| JPS5567521A (en) * | 1978-11-09 | 1980-05-21 | Mobil Oil | Crystalline aluminoosilicateezeolite catalyst* converting organic material by using same* and preparing same catalyst |
| DE3174798D1 (en) * | 1980-05-13 | 1986-07-17 | Ici Plc | Process for making olefins |
| EP0054387B1 (en) * | 1980-12-17 | 1985-09-18 | Imperial Chemical Industries Plc | Method for the preparation of hydrocarbons by using zeolite catalysts of the type nu-5. |
-
1983
- 1983-11-22 CA CA000441681A patent/CA1229353A/en not_active Expired
- 1983-12-15 JP JP58235243A patent/JPS59118723A/en active Granted
- 1983-12-15 ZA ZA839354A patent/ZA839354B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0379330B2 (en) | 1991-12-18 |
| ZA839354B (en) | 1985-08-28 |
| JPS59118723A (en) | 1984-07-09 |
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