CA1236815A - Preparation of modified zeolites and their utilization - Google Patents
Preparation of modified zeolites and their utilizationInfo
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- CA1236815A CA1236815A CA000474415A CA474415A CA1236815A CA 1236815 A CA1236815 A CA 1236815A CA 000474415 A CA000474415 A CA 000474415A CA 474415 A CA474415 A CA 474415A CA 1236815 A CA1236815 A CA 1236815A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
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- 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
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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
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- 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
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/271—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with inorganic acids; with salts or anhydrides of acids
- C07C5/2718—Acids of halogen; Salts thereof; complexes thereof with organic compounds
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- 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
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- 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
- B01J2229/36—Steaming
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
- C07C2527/1213—Boron fluoride
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- 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
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
PREPARATION OF MODIFIED ZEOLITES AND THEIR UTILIZATION
ABSTRACT
A method for modifying the catalytic activity of a crystalline zeolite having a constraint index of 1 to 12 and a silica-to-alumina ratio of 30 to no greater than 300, comprises contacting said zeolite with gaseous boron trifluoride under conditions effective to reduce the alpha activity of the zeolite.
ABSTRACT
A method for modifying the catalytic activity of a crystalline zeolite having a constraint index of 1 to 12 and a silica-to-alumina ratio of 30 to no greater than 300, comprises contacting said zeolite with gaseous boron trifluoride under conditions effective to reduce the alpha activity of the zeolite.
Description
~12368~5 PREPARATIQ~ EDIFIED ZE;Or.ITES AND THEIR UTTL~$ION
This invention is concerned with the catalytic corlver-soon of hydrocarbons and other organic compound over crystalline alumlnosilicate zealot of the ZSM-5 type which have been modified by treatment with ~F3, to provide enhanced selectivity, activity, or both, and with the method or preparing such catalysts.
Zeolltlc materials, both natural and synthetic, have been demonstrated in the past to have catalytic prapertles for various type of conversion. One such conversion which has generated considerable interest it the production of hydrocarbons, including olefins and gasoline from alcohols and ethers.
U.S. 4,025,575 describes a process by which lower alcohol and/or their eighth are converted to a mixture of C2-C5 olefins by contact at subatmo~pheric inlet partial pressure with a crystalline aluminosilicate zealot of the ZSM-5 type.
l~Z368~5 U.S. 3,931,349, issued January 9, 1976, also disk closes a process for the conversion of methanol to gasoline utilizing a ZSM-5 type catalyst.
U.S. 4,083,888, issued on April 11, 1978, discloses a process for the manufacture of hydrocarbons by the catalytic conversion of methanol in the presence of a substantially an hydrous delineate and a ZSM-5 type zealot.
There are many other patents and publications which describe the conversion of methanol to hydrocarbons, including gasoline, such as U.S. 3,931,349; 3,969,426;
3,899,544; 3,894,104; 3,904,916; and 3,894,102. Other conversions include, for example, propylene oligomeri-ration, Tulane disproportionation, zillion isomerization, alkylation of aromatics with alcohol or olefins, such as Tulane + ethylene -- p-ethyltoluene, and dew axing, i.e., shape-selective cracking of wax molecules.
U.S. 4,163,028 discloses the isomerization of a feed stock containing zillion in the presence of ZSM-5.
U.S. 4,268,420 describes a crystalline borosilicate AMS-lB (ZSM-5) which can be used as a catalyst in the isomerization of zillion.
U.S. 4~292,457 discloses the alkylation of aromatic hydrocarbons in the presence of a borosilicate AMS-lB (ZSM-5) catalyst. U.S. 4,269,813 discloses the use of this gala-lust in disproportionation and transalkylation processes as well as in zillion isome~ization. Similar processes in %;~;815 the presence of ZSM-4 and ZSM-5 catalysts are also disclosed in U.S. 4,377,502.
U.S. 4,208,305 and U.S. 4,238,318 disclose, in add-lion to the above catalytic processes, upgrading cracked gasoline and naphtha, preparation of olefins from Alcoa hots, preparation of olefinic gasoline, alkylation of olefins, separation of hydrogen mixtures, and catalytic hydrodewaxing of hydrocarbon oils in the presence of zealot catalysts.
The present invention is directed to a method for modifying the catalytic activity of a crystalline zealot having a constraint index of 1 to 12 and a silica-to-alumina ratio of 30 to no greater than 300, which method comprises contacting said zealot with gaseous boron trifluoride under conditions effective to reduce the alpha activity of the zealot.
A ZSM-5 type zealot is advantageously modified by contacting the zealot with gaseous an hydrous boron trifluoride at moderately elevated temperature, such as 150C, and for a relatively short time, such as 30 minutes, as more fully described hereinbelow. Surprise tingly, the novel product exhibits reduced activity for cracking a refractory hydrocarbon such as normal hexane, as measured by the alpha test conducted at 538C, but it exhibits enhanced activity for the conversion of methanol to hydrocarbons, as more fully described hereinbelow.
Furthermore, as will be shown by example, the novel modified zealot catalysts in general show a much higher catalytic activity for conversions of less refractory feed stocks than normal hexane than would be expected from their alpha values. Such catalytic conversions of organic compounds include olefin oligomerization, Tulane Diaspora-lZ36815 portionation, zillion i30merization, catalytic dew axing, and the cavern of methanol to hydrocarbons, including olefin~
and/or guy line.
The boron trifluoride treated zealot catalyst make it possible to use lower operating temperature or, quite obviously, to use the same temperatures as generally employed in the prior art but at higher Race velocities.
It is immediately apparent that having a catalyst of enhanced activity has the potential for lowering operating costs due to the fact that lower temperatures can be used and allowing for a greater throughput due to the fact that higher space velocities can be employed.
The treatment with boron trlfluoride by the method described also imparts change in chemical composition and physical properties as well as catalytic properties. These ware illustrated by Example 21. This example suggest that a reaction occurs between the zealot and BF3. It also demonstrates that the modified zealots have somewhat smaller pores and therefore will favor formation of thinner molecules such as ethylene yin methanol con-version) and para-xylene (in zillion isomerization).
¦ The novel catalyst of this invention is prepared simply by treating a ZSM-5 type zealot at least partially yin the acid form, preferably HZSM-5, with boron in-fluoride. The treated zealot preferably is purged to remove any excess BF3 that may be present. The method of ~236t3~S
treatment is not narrowly critical and typical conditions utilize boron trifluoride flowing at 30 cc/mln. through 1 gram catalyst bed maintained at 150 C. However, it it noted that flow rates of 1 to 600 cc/min. through 1 gram of catalyst bed maintained at a temperature of from 25 to 500 C are also operable to produce the enhanced catalyst of this invention. The time at which the boron trifluoride is contacted with the catalyst is also not narrowly critical and activation can be obtained at period of lime ranging from 0.01 hour to 10 hours and preferably from about 0.1 to 2.0 hours. Following treatment with boron trifluoride, the catalyst is ready for use, but it may be air calcined, if desired. Contacting with boron trifluoride it highly effective at atmospheric prosier, but suba~mospheric or elevated pressure may be used.
¦ The conversion of lower alcohols, their ether, or mixtures thereof to C2-C5 olefins and to heavier hydrocarbons Rand the conversion of methanol to olefin~, to gasoline, and to other hydrocarbon with ZSM-5 type catalyst it well known. The conditions for these reactions are well documented in the patents incorporated herein by reference.
the modified zealots of this invention are advantageously used in these conversions. Other conversions in which the modified zealots are advantageously used will now be described.
¦ Oligomerlzation and polymerization involve the linking of similar molecules in the presence of heat and a catalyst S
. , It form bigger molecule. Ollgomerization involves the forming of divers, trimmers and quatramer8, whereas a typical polymerization concern the joining of light olefins to form pa very long chain olefin. Olefin oligomerizat~on and polyp ¦merizatlon condition include a temperature of from about 950 to about 935 F, preferably form about 390 F to about 810 F, a pressure of from about atmospheric to about 10,000 prig, preferably from about atmospheric to about 2,000 prig, a WHSV (when a flow operation) of from about 0.1 Harley to about 50 Harley, preferably from about 0.5 Harley to about 10 Harley, and a contact time (when a batch operation) of from about 0.1 hour to about 48 hours, preferably from about 0.5 hour to about 24 hours and a hydrogen/olefin mole ratio of from about 0 to about 20, preferably from about 0 to 10.
l Olefin oligomerizatlon, e.g., propylene may be carried tout at temperatures below 525 C and preferably at about 13000 C, at WHSV's from 0.1 to 50, preferably at about 30, at pressures from 350 prig to 550 prig.
l Tulane disproportionation is carried out at temperatures from 90 C to 550 C, preferably at about 500 I at pressures from 0 prig to 3000 prig, at WHSV's from ¦0.01 Harley to 90 Harley, preferably at about 10.
l Zillion isomerization may be carried out at temperature from 230 C to 540 C, more preferably from 230 C to 300 C, at pre9sureg up to 1500 prig, preferably from 20 to 400 slug, at WHSV's from 0.1 to 200, preferably from 0.5 to 50, and more preferably from 5 to 25, and even :1236815 more preferably at about 10.
¦ A it known in the art, Z~M-5 type zeolitic materials ware member of a novel class of zealots that exhibit unusual propertle~. Although these zealots have unusually slow alumina contents, i.e. high silica to alumina ratio, they are very active even when the silica to alumina ratio exceeds 30. the activity it surprising since catalytic activity is generally attributed to framework aluminum atoms Andre cations associated with these aluminum atom. These solute retain their cry~tallin~ty for long periods in spite of the presence of steam at high temperature which induces irreversible collapse of the framework of other solutes, e.g. of the X and A type.
An important characteristic of the crystal structure of thus class of zeollteg it that it provide constrained axis to and egress from the intracrystalline free space by virtue of having an effective pore size intermediate between the small pore Line A and the large pore Line X, i.e. the spore windows of the structure have about a size such as would be provided by 10-membered rings of oxygen atoms. It is to be understood, of course, that these ring are those formed by the regular disposition of the tetrahedral making p the anionic framework of the crystalline aluminosilicate, the oxygen atoms themselves being bonded to the silicon or aluminum atom at the centers of the tetrahedral Briefly, the preferred type zeoliteg useful in this invention obsess, in combination: a silica to alumina mole ratio of ~368~5 it least about 12s and a structure providing constrained access to the crystalline free space.
¦ The silica to alumina ratio referred to may be deter-wined by conventional analyst. This ratio I meant to represent, as closely as possible, the ratio in the rigid anionic framework of the zealot crystal and to exclude aluminum in the binder or in cationlc or other loam within the channels. Although zealots with a silica to alumina ratio of at least 12 are useful, it is preferred to use solutes having higher ratios of at least about 30. Such solutes, after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e. they exhibit hydrophobic properties.
Kit is believed that this hydrophobic character is ad van-¦tageous in the present invention.
¦ The preferred zealots useful in this invention have an effective pore size such as to freely sorb normal hexane.
yin addition, the structure must provide constrained access to larger molecules. It is sometime possible to judge from a known crystal structure whether such constrained access exits. For example, if the only pore window in a crystal no formed by 8-membered rings of oxygen atoms, then access to molecules of larger cross-section than normal hexane it excluded and the zealot is not of the desired type. Win-owe of 10-membered ring are preferred, although in some intones excessive puckering of the ring or pore blockage Jay render these zealots ineffective. 12-membered rings ~236~31S
usually do not offer sufficient constraint to produce the advantageous conversions, although the puckered 12-ring structure of TEA offretite show constrained access. Other wrung structures may exist which, due to pore blockage or to other cause, may be operative.
¦ Father than attempt to judge from crystal structure whether or not a zealot possesses the necessary constrained access to molecules larger than normal paraffins, a simple determination of the constraint Index or KIWI., as herein defined may be made by passing continuously a mixture of an equal weight of normal hexane and 3-methylpentane over a small sample, approximately one gram or less, of zealot at atmospheric pressure according to the following procedure.
PA sample of the zealot, in the form of pellets or extra-date, is crushed to a particle size about that of coarse sand and mounted in a glass tube. Prior to testing, the zealot is treated with a stream of air at 1000 for at least 15 minute. The zealot is then flushed with helium and the temperature is adjusted between 550 and 950 F to give an overall convection between 10~ and 60%. The mixture of hydrocarbon it pasted at 1 liquid hourly space velocity (i.e. 1 volume of liquid hydrocarbon per volume of zealot or hour) over the zealot with a helium dilution to give a ilium to total hydrocarbon mole ratio of sly. After 20 inures on stream, a sample of the effluent is taken and analyzed, most conveniently by gag chromatography, to deter-mine the fraction remaining unchanged for each of the two lZ3G815 ¦ hydrocarbon The KIWI. is calculated a follows:
KIWI. = KIWI (fra~lQn of Nixon ~emalninqL
logl~fraction of 3-methylpentane remaining) l The Constraint Index approximates the ratio of the ¦ cracking rate constants for the two hydrocarbon. Zealots ¦ suitable for the prevent invention are those having a Con-¦ strait Index of 1 to 12. KIWI. values for Rome typical ¦ zealot are:
~2368~5 ZSM-5 By ZSM-ll 8.7 ZSM-23 9.1 TEA Offretlte 3.7 Beta 0.6 H-Zeolon (mordant) 0.4 Amorphous Silica-Alumlna 0.6 Erlonlte 38 The above-described Constraint Index I an important and even critical deflnltlon of those zealots which are useful in the ln~thnt invention. The very nature of this parameter and the recited technique by which it it deter-mined, however, admit of the posalblllty that a given zoo-lute can be tested under somewhat different conditions and thereby have different Constraint Indexes. Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders. There-fore, it will be appreciated that it may be possible to a select text conditions to establish more than one value in ~lZ368~5 the range of 1 to 12 for the Constraint Index of a part-cuter zealot. Such a zealot exhibits the constrained access as herein defined and is to be regilded as having a Constraint Index of 1 to 12. Also contemplated herein as having a Constraint Index of 1 to 12 and therefore within the scope of the novel class of highly siliceous zealots are those zealots which, when tested under two or more sets ox conditions within the above-specified ranges of temperature and conversion, produce a value of the Constraint Index slightly less than 1, e.g. 0.9, or somewhat greater than 12, e.g. 14 or 15, with at least one other value of 1 to 12. Thus, it should be under-stood that the Constraint Index value as used herein is an inclusive rather than an exclusive value. That is, a zealot when tested by any combination of conditions within the testing definition set forth hereinabove and found to have a Constraint Index of 1 to 12 is intended to be included in the instant catalyst definition regard-less that the same identical zealot tested under other defined conditions may give a Constraint Index value outside of 1 to 12.
Tune class of zealots defined herein is example-fled by ZSM-5, ZSM-ll, ZSM-12, ZSM-21, ZSM-23, ZSM-35, ZSM-38, ZSM-48, and other similar materials. U.S. Patent 3,702,886 describes and claims ZSM-5.
ZSM-ll is more particular lye described in U.S. Patent 3,709,979.
,,.
1Z;36815 ZSM-12 is more particularly described in U.S. Patent 3,832,449.
ZSM-21 is more particularly described in U.S. Patent 4,046,859.
ZSM-23 is more particularly described in U.S. Patent 4,076,842.
ZSM-35 is more particularly described in U.S. Patent 4,016,245.
ZSM-38 is more particularly described in U.S. Patent 4,046,859.
Natural zealots may sometimes be converted to this type zealot catalyst by various activation prove-dunes and other treatments such as base exchange, steaming, alumina extraction and calcination, in come binations. Natural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite, and clinoptilolite. The pro-furred crystalline zealots are ZSM-5, ZSM-ll, ZSM-12, ZSM-21, %SM-23, ZSM-35, ZSM-38 and ZSM-48, with ZSM-5 and ZSM-11 particularly preferred. In some instances, it is advantageous to steam the frost zealot to no-dupe its activity and thereby improve its selectivity ,.~
:~Z368~5 prior to use. Such improvement has been noted with steamed ZSM-5.
In a preferred aspect of this invention, the zealots selected are those having a crystal framework density, in the dry hydrogen form, of not less than about 1.6 grams per cubic centimeter. It has been found that zealots which satisfy all three of these criteria are most desired. Therefore, the preferred zealots of this invention are those hosing a Constraint Index as defined above of about 1 to 12 and a dried crystal density of not less than about 1.6 grams per cubic centimeter. The dry density for known structures may be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on Page 19 of the article on elite Structure by WOMB. Meter. This paper is included in "Proceedings of the Conference on Molecular Sieves, London, April 1967," published by the Society of Chemical Industry, London, 1968. When the crystal structure is unknown, the crystal framework density may be determined by classical pyknometer techniques. For example, it may be determined by immersing the dry hydrogen form of the zealot in an organic solvent not sorbed by the crystal.
Or, the crystal density may be determined by mercury porosimetry, since mercury will fill the interstices between crystal but will not penetrate the intracry-stalling free space. It is possible that the unusual sustained activity and stability of this class of ,~;;
~23681S
solutes is associated with its high crystal anionic frame-work density of not less that about 1.6 grams per cubic centimeter. This high density must necessarily be also-shouted with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, it important was the locus of catalytic activity.
~236~31S
Crystal framework densities of some typical zealot ¦ including some which are not within the purview of they'll ¦ invention are:
Void Framework Zealot Volume Density Ferrlelrite 0.28 cc/cc 1.76 g/cc Morden:lte aye 1 .7 ZSM-5, 11 .29 1.79 ZSM-12 - 1.8 ZSM-23 - 2.0 Dachia:cdite .32 1.72 L .32 1.61 Cllnoptllollte .34 1.71 Laminate .34 1,77 ZSM-4, Omega .38 1.65 Heulandlte .39 1.69 P .41 1.57 Offret.Ite .40 1.5S
Levynite .40 1.54 Erionilte ,35 1.51 Gmelin.ite ,44 1.46 Chabaz:Lte ,47 1,45 A ,5 1.3 Y .48 1.27 ~Z36815 When sinusoid in the alkali metal form, the ZSM-5 type zealot before treatment with BF3 is conveniently con-vented to the hydrogen form, generally by intermediate formation of the ammonlum form a a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form, i.e. HZSM-5. In addition to the hydrogen loam, other form of the zealot wherein the original alkali metal has been reduced to lets than about 1.5 percent by weight may be used.
In practicing the desired conversion process, it may be desirable to incorporate the above-described crystalline alumlnosilicate in another matrix resistant to temperature and other conditions employed in the process. However, it has been found that such incorporation preferably should not take place until after the Zulu ha been treated with boron trifluoride since the presence of some matrices, for reasons which are not completely understood, interferes with the activation procedure This is particularly true for alumina or alumina-contalnlng) matrices. Silica matrices Jay not be detrimental to the activation procedure and could be composite with the zealot prior to activation with boron trifluoride.
The modified zealot, if treated with 8F3 in the absence of binder, may be incorporated with any conventional matrix material. Such matrix maternal include synthetic or naturally occurring substances a well a inorganic materials such as clay, silica Andre metal oxides. Natural clays lZ36815 which can be compocited with the zealot include those of the montmorlllonite and kaolin families, which families include the sub-bentonitea and the kaolin commonly known as Dixie, McNamee-Georgia and Florida clay or others in which the main mineral constituent Lo hollowest, coolant, Dakota, nacrite or Anita.
In addition to the foregoing maternal the zealots employed herein may be composite with a porous matrix material, such as alumina, silica-alumina, ailicA-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titanic as well as ternary compositions, such a silica-alumlna-thorla, ~ilica-alumina-zlrconla, ~lllca-alumina-magnesia and ~ilica-magnesia-zirconla, The matrix may be in the form of a Vogel. The relative proportions of zealot component and inorganic oxide gel matrix on an anhydrouc basis may vary widely with the zealot content ranging from between about 1 to about 99 percent by weight and more usually in the range of about 5 to about 80 percent by weight of the dry composite.
Although there to generally come type of correlation between alpha value and catalytic activity in the convert Sweeney contemplated in twig invention, the alpha activity of the boron trifluoride treated catalyst way much reduced by the treatment, but the conversion of methanol went up (Table 1). This is a surprising and unexpected result which it not understood.
The following examples will illustrate the best mode lZ36815 contemplated for carrying out the invention.
A sample of HZSM-5 having a silica-to-alumina ratio of 70:1 and without binder was treated with boron trifluoride by contacting it at 150 C and at atmospheric pressure with boron trifluoride flowing at 30 cc/min. through a 1 gram catalyst bed for approximately 10 minute, after which the zealot way cooled in a steam of dry nitrogen.
The boron trifluoride modified catalyst of Example 1 was then tested for conversion of methanol to hydrocarbons along with an HZSM-5 type zealot which had not been boron trifluoride modified. The following Table 1 compares data from the catalyst of this invention with the catalyst of the prior art:.
.. -V (I I L') X t) Jo I I I I
I I I I I L'-r I_ Jo V
V
I Jo W ,_ I O ED In Us I I
O do cry I
,,~ I
r I Cc . us o I
_ V I o o 'I I
or ¦ ; r; an Al I
o o o I
O I cut = I Al Lo I
n rJ~ r 1 Lo r.
Jo n I
I
to -- I: m rod lo I, I I
~23~815 A can be seen from the above table, a space velocity f approximately 0.5 is required to achieve loo methanol onverslon at 300 c for an untreated HZSM-5. For the boron trifluoride modified catalyst, a space velocity of 9.0 chives loo methanol conversion. This corresponds to an increase in catalyst activity by a factor of approximately 15-20. Even at 280 C, the BF3 modlf$ed catalyst is four to five times as active as the unmodified catalyst at 300 C.
SXAMPLEi~ 13 A swirls of experiments were carried out in order to remonstrate the uniqueness of the novel activation procedure f this invention.
In each of Examples 7-13c HzsM-5 having a lookout-lumlna ratio of 70:1 was employed. In Examples 7 Anglo, he conventional HZSM-5 catalyst of the prior art was employed. In Examples 8 and if, and HZSM-5 treated with Ron fluoride in the manner set forth in Example 2-6 was mployedc In Example 9, an ammonlum fluoride treated catalyst as employed. This catalyst was prepared by m~xlng 0.46 ram of ammonlum fluoride with lo gram of ~ZSM-5 (no lender) and healing at 150 C for 10 minutes with argon flowing at 30 cc/min. These conditions simulate those used for the preparation of sF3 catalyst. The catalyst of sample 9 was then calcined in air at 500 C overnight to overt it to the hydrogen form. In Example 12, a mixture f HZSM-5 with alumina was treated with BF3 in the manner previously described. In Example 13, a hydrogen fluoride treated catalyst was used. This catalyst way prepared by flowing a mixture of 3 cc of hydrogen fluoride and 27 cc of Ron at 300 cc/min. over 1 gram of HZSM-5 (no binder) at 150 C for 15 minutes. The result obtained for methanol inversion as well as alpha values of the various catalyst no given in Table 2.
123683.S
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This invention is concerned with the catalytic corlver-soon of hydrocarbons and other organic compound over crystalline alumlnosilicate zealot of the ZSM-5 type which have been modified by treatment with ~F3, to provide enhanced selectivity, activity, or both, and with the method or preparing such catalysts.
Zeolltlc materials, both natural and synthetic, have been demonstrated in the past to have catalytic prapertles for various type of conversion. One such conversion which has generated considerable interest it the production of hydrocarbons, including olefins and gasoline from alcohols and ethers.
U.S. 4,025,575 describes a process by which lower alcohol and/or their eighth are converted to a mixture of C2-C5 olefins by contact at subatmo~pheric inlet partial pressure with a crystalline aluminosilicate zealot of the ZSM-5 type.
l~Z368~5 U.S. 3,931,349, issued January 9, 1976, also disk closes a process for the conversion of methanol to gasoline utilizing a ZSM-5 type catalyst.
U.S. 4,083,888, issued on April 11, 1978, discloses a process for the manufacture of hydrocarbons by the catalytic conversion of methanol in the presence of a substantially an hydrous delineate and a ZSM-5 type zealot.
There are many other patents and publications which describe the conversion of methanol to hydrocarbons, including gasoline, such as U.S. 3,931,349; 3,969,426;
3,899,544; 3,894,104; 3,904,916; and 3,894,102. Other conversions include, for example, propylene oligomeri-ration, Tulane disproportionation, zillion isomerization, alkylation of aromatics with alcohol or olefins, such as Tulane + ethylene -- p-ethyltoluene, and dew axing, i.e., shape-selective cracking of wax molecules.
U.S. 4,163,028 discloses the isomerization of a feed stock containing zillion in the presence of ZSM-5.
U.S. 4,268,420 describes a crystalline borosilicate AMS-lB (ZSM-5) which can be used as a catalyst in the isomerization of zillion.
U.S. 4~292,457 discloses the alkylation of aromatic hydrocarbons in the presence of a borosilicate AMS-lB (ZSM-5) catalyst. U.S. 4,269,813 discloses the use of this gala-lust in disproportionation and transalkylation processes as well as in zillion isome~ization. Similar processes in %;~;815 the presence of ZSM-4 and ZSM-5 catalysts are also disclosed in U.S. 4,377,502.
U.S. 4,208,305 and U.S. 4,238,318 disclose, in add-lion to the above catalytic processes, upgrading cracked gasoline and naphtha, preparation of olefins from Alcoa hots, preparation of olefinic gasoline, alkylation of olefins, separation of hydrogen mixtures, and catalytic hydrodewaxing of hydrocarbon oils in the presence of zealot catalysts.
The present invention is directed to a method for modifying the catalytic activity of a crystalline zealot having a constraint index of 1 to 12 and a silica-to-alumina ratio of 30 to no greater than 300, which method comprises contacting said zealot with gaseous boron trifluoride under conditions effective to reduce the alpha activity of the zealot.
A ZSM-5 type zealot is advantageously modified by contacting the zealot with gaseous an hydrous boron trifluoride at moderately elevated temperature, such as 150C, and for a relatively short time, such as 30 minutes, as more fully described hereinbelow. Surprise tingly, the novel product exhibits reduced activity for cracking a refractory hydrocarbon such as normal hexane, as measured by the alpha test conducted at 538C, but it exhibits enhanced activity for the conversion of methanol to hydrocarbons, as more fully described hereinbelow.
Furthermore, as will be shown by example, the novel modified zealot catalysts in general show a much higher catalytic activity for conversions of less refractory feed stocks than normal hexane than would be expected from their alpha values. Such catalytic conversions of organic compounds include olefin oligomerization, Tulane Diaspora-lZ36815 portionation, zillion i30merization, catalytic dew axing, and the cavern of methanol to hydrocarbons, including olefin~
and/or guy line.
The boron trifluoride treated zealot catalyst make it possible to use lower operating temperature or, quite obviously, to use the same temperatures as generally employed in the prior art but at higher Race velocities.
It is immediately apparent that having a catalyst of enhanced activity has the potential for lowering operating costs due to the fact that lower temperatures can be used and allowing for a greater throughput due to the fact that higher space velocities can be employed.
The treatment with boron trlfluoride by the method described also imparts change in chemical composition and physical properties as well as catalytic properties. These ware illustrated by Example 21. This example suggest that a reaction occurs between the zealot and BF3. It also demonstrates that the modified zealots have somewhat smaller pores and therefore will favor formation of thinner molecules such as ethylene yin methanol con-version) and para-xylene (in zillion isomerization).
¦ The novel catalyst of this invention is prepared simply by treating a ZSM-5 type zealot at least partially yin the acid form, preferably HZSM-5, with boron in-fluoride. The treated zealot preferably is purged to remove any excess BF3 that may be present. The method of ~236t3~S
treatment is not narrowly critical and typical conditions utilize boron trifluoride flowing at 30 cc/mln. through 1 gram catalyst bed maintained at 150 C. However, it it noted that flow rates of 1 to 600 cc/min. through 1 gram of catalyst bed maintained at a temperature of from 25 to 500 C are also operable to produce the enhanced catalyst of this invention. The time at which the boron trifluoride is contacted with the catalyst is also not narrowly critical and activation can be obtained at period of lime ranging from 0.01 hour to 10 hours and preferably from about 0.1 to 2.0 hours. Following treatment with boron trifluoride, the catalyst is ready for use, but it may be air calcined, if desired. Contacting with boron trifluoride it highly effective at atmospheric prosier, but suba~mospheric or elevated pressure may be used.
¦ The conversion of lower alcohols, their ether, or mixtures thereof to C2-C5 olefins and to heavier hydrocarbons Rand the conversion of methanol to olefin~, to gasoline, and to other hydrocarbon with ZSM-5 type catalyst it well known. The conditions for these reactions are well documented in the patents incorporated herein by reference.
the modified zealots of this invention are advantageously used in these conversions. Other conversions in which the modified zealots are advantageously used will now be described.
¦ Oligomerlzation and polymerization involve the linking of similar molecules in the presence of heat and a catalyst S
. , It form bigger molecule. Ollgomerization involves the forming of divers, trimmers and quatramer8, whereas a typical polymerization concern the joining of light olefins to form pa very long chain olefin. Olefin oligomerizat~on and polyp ¦merizatlon condition include a temperature of from about 950 to about 935 F, preferably form about 390 F to about 810 F, a pressure of from about atmospheric to about 10,000 prig, preferably from about atmospheric to about 2,000 prig, a WHSV (when a flow operation) of from about 0.1 Harley to about 50 Harley, preferably from about 0.5 Harley to about 10 Harley, and a contact time (when a batch operation) of from about 0.1 hour to about 48 hours, preferably from about 0.5 hour to about 24 hours and a hydrogen/olefin mole ratio of from about 0 to about 20, preferably from about 0 to 10.
l Olefin oligomerizatlon, e.g., propylene may be carried tout at temperatures below 525 C and preferably at about 13000 C, at WHSV's from 0.1 to 50, preferably at about 30, at pressures from 350 prig to 550 prig.
l Tulane disproportionation is carried out at temperatures from 90 C to 550 C, preferably at about 500 I at pressures from 0 prig to 3000 prig, at WHSV's from ¦0.01 Harley to 90 Harley, preferably at about 10.
l Zillion isomerization may be carried out at temperature from 230 C to 540 C, more preferably from 230 C to 300 C, at pre9sureg up to 1500 prig, preferably from 20 to 400 slug, at WHSV's from 0.1 to 200, preferably from 0.5 to 50, and more preferably from 5 to 25, and even :1236815 more preferably at about 10.
¦ A it known in the art, Z~M-5 type zeolitic materials ware member of a novel class of zealots that exhibit unusual propertle~. Although these zealots have unusually slow alumina contents, i.e. high silica to alumina ratio, they are very active even when the silica to alumina ratio exceeds 30. the activity it surprising since catalytic activity is generally attributed to framework aluminum atoms Andre cations associated with these aluminum atom. These solute retain their cry~tallin~ty for long periods in spite of the presence of steam at high temperature which induces irreversible collapse of the framework of other solutes, e.g. of the X and A type.
An important characteristic of the crystal structure of thus class of zeollteg it that it provide constrained axis to and egress from the intracrystalline free space by virtue of having an effective pore size intermediate between the small pore Line A and the large pore Line X, i.e. the spore windows of the structure have about a size such as would be provided by 10-membered rings of oxygen atoms. It is to be understood, of course, that these ring are those formed by the regular disposition of the tetrahedral making p the anionic framework of the crystalline aluminosilicate, the oxygen atoms themselves being bonded to the silicon or aluminum atom at the centers of the tetrahedral Briefly, the preferred type zeoliteg useful in this invention obsess, in combination: a silica to alumina mole ratio of ~368~5 it least about 12s and a structure providing constrained access to the crystalline free space.
¦ The silica to alumina ratio referred to may be deter-wined by conventional analyst. This ratio I meant to represent, as closely as possible, the ratio in the rigid anionic framework of the zealot crystal and to exclude aluminum in the binder or in cationlc or other loam within the channels. Although zealots with a silica to alumina ratio of at least 12 are useful, it is preferred to use solutes having higher ratios of at least about 30. Such solutes, after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e. they exhibit hydrophobic properties.
Kit is believed that this hydrophobic character is ad van-¦tageous in the present invention.
¦ The preferred zealots useful in this invention have an effective pore size such as to freely sorb normal hexane.
yin addition, the structure must provide constrained access to larger molecules. It is sometime possible to judge from a known crystal structure whether such constrained access exits. For example, if the only pore window in a crystal no formed by 8-membered rings of oxygen atoms, then access to molecules of larger cross-section than normal hexane it excluded and the zealot is not of the desired type. Win-owe of 10-membered ring are preferred, although in some intones excessive puckering of the ring or pore blockage Jay render these zealots ineffective. 12-membered rings ~236~31S
usually do not offer sufficient constraint to produce the advantageous conversions, although the puckered 12-ring structure of TEA offretite show constrained access. Other wrung structures may exist which, due to pore blockage or to other cause, may be operative.
¦ Father than attempt to judge from crystal structure whether or not a zealot possesses the necessary constrained access to molecules larger than normal paraffins, a simple determination of the constraint Index or KIWI., as herein defined may be made by passing continuously a mixture of an equal weight of normal hexane and 3-methylpentane over a small sample, approximately one gram or less, of zealot at atmospheric pressure according to the following procedure.
PA sample of the zealot, in the form of pellets or extra-date, is crushed to a particle size about that of coarse sand and mounted in a glass tube. Prior to testing, the zealot is treated with a stream of air at 1000 for at least 15 minute. The zealot is then flushed with helium and the temperature is adjusted between 550 and 950 F to give an overall convection between 10~ and 60%. The mixture of hydrocarbon it pasted at 1 liquid hourly space velocity (i.e. 1 volume of liquid hydrocarbon per volume of zealot or hour) over the zealot with a helium dilution to give a ilium to total hydrocarbon mole ratio of sly. After 20 inures on stream, a sample of the effluent is taken and analyzed, most conveniently by gag chromatography, to deter-mine the fraction remaining unchanged for each of the two lZ3G815 ¦ hydrocarbon The KIWI. is calculated a follows:
KIWI. = KIWI (fra~lQn of Nixon ~emalninqL
logl~fraction of 3-methylpentane remaining) l The Constraint Index approximates the ratio of the ¦ cracking rate constants for the two hydrocarbon. Zealots ¦ suitable for the prevent invention are those having a Con-¦ strait Index of 1 to 12. KIWI. values for Rome typical ¦ zealot are:
~2368~5 ZSM-5 By ZSM-ll 8.7 ZSM-23 9.1 TEA Offretlte 3.7 Beta 0.6 H-Zeolon (mordant) 0.4 Amorphous Silica-Alumlna 0.6 Erlonlte 38 The above-described Constraint Index I an important and even critical deflnltlon of those zealots which are useful in the ln~thnt invention. The very nature of this parameter and the recited technique by which it it deter-mined, however, admit of the posalblllty that a given zoo-lute can be tested under somewhat different conditions and thereby have different Constraint Indexes. Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders. There-fore, it will be appreciated that it may be possible to a select text conditions to establish more than one value in ~lZ368~5 the range of 1 to 12 for the Constraint Index of a part-cuter zealot. Such a zealot exhibits the constrained access as herein defined and is to be regilded as having a Constraint Index of 1 to 12. Also contemplated herein as having a Constraint Index of 1 to 12 and therefore within the scope of the novel class of highly siliceous zealots are those zealots which, when tested under two or more sets ox conditions within the above-specified ranges of temperature and conversion, produce a value of the Constraint Index slightly less than 1, e.g. 0.9, or somewhat greater than 12, e.g. 14 or 15, with at least one other value of 1 to 12. Thus, it should be under-stood that the Constraint Index value as used herein is an inclusive rather than an exclusive value. That is, a zealot when tested by any combination of conditions within the testing definition set forth hereinabove and found to have a Constraint Index of 1 to 12 is intended to be included in the instant catalyst definition regard-less that the same identical zealot tested under other defined conditions may give a Constraint Index value outside of 1 to 12.
Tune class of zealots defined herein is example-fled by ZSM-5, ZSM-ll, ZSM-12, ZSM-21, ZSM-23, ZSM-35, ZSM-38, ZSM-48, and other similar materials. U.S. Patent 3,702,886 describes and claims ZSM-5.
ZSM-ll is more particular lye described in U.S. Patent 3,709,979.
,,.
1Z;36815 ZSM-12 is more particularly described in U.S. Patent 3,832,449.
ZSM-21 is more particularly described in U.S. Patent 4,046,859.
ZSM-23 is more particularly described in U.S. Patent 4,076,842.
ZSM-35 is more particularly described in U.S. Patent 4,016,245.
ZSM-38 is more particularly described in U.S. Patent 4,046,859.
Natural zealots may sometimes be converted to this type zealot catalyst by various activation prove-dunes and other treatments such as base exchange, steaming, alumina extraction and calcination, in come binations. Natural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite, and clinoptilolite. The pro-furred crystalline zealots are ZSM-5, ZSM-ll, ZSM-12, ZSM-21, %SM-23, ZSM-35, ZSM-38 and ZSM-48, with ZSM-5 and ZSM-11 particularly preferred. In some instances, it is advantageous to steam the frost zealot to no-dupe its activity and thereby improve its selectivity ,.~
:~Z368~5 prior to use. Such improvement has been noted with steamed ZSM-5.
In a preferred aspect of this invention, the zealots selected are those having a crystal framework density, in the dry hydrogen form, of not less than about 1.6 grams per cubic centimeter. It has been found that zealots which satisfy all three of these criteria are most desired. Therefore, the preferred zealots of this invention are those hosing a Constraint Index as defined above of about 1 to 12 and a dried crystal density of not less than about 1.6 grams per cubic centimeter. The dry density for known structures may be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on Page 19 of the article on elite Structure by WOMB. Meter. This paper is included in "Proceedings of the Conference on Molecular Sieves, London, April 1967," published by the Society of Chemical Industry, London, 1968. When the crystal structure is unknown, the crystal framework density may be determined by classical pyknometer techniques. For example, it may be determined by immersing the dry hydrogen form of the zealot in an organic solvent not sorbed by the crystal.
Or, the crystal density may be determined by mercury porosimetry, since mercury will fill the interstices between crystal but will not penetrate the intracry-stalling free space. It is possible that the unusual sustained activity and stability of this class of ,~;;
~23681S
solutes is associated with its high crystal anionic frame-work density of not less that about 1.6 grams per cubic centimeter. This high density must necessarily be also-shouted with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, it important was the locus of catalytic activity.
~236~31S
Crystal framework densities of some typical zealot ¦ including some which are not within the purview of they'll ¦ invention are:
Void Framework Zealot Volume Density Ferrlelrite 0.28 cc/cc 1.76 g/cc Morden:lte aye 1 .7 ZSM-5, 11 .29 1.79 ZSM-12 - 1.8 ZSM-23 - 2.0 Dachia:cdite .32 1.72 L .32 1.61 Cllnoptllollte .34 1.71 Laminate .34 1,77 ZSM-4, Omega .38 1.65 Heulandlte .39 1.69 P .41 1.57 Offret.Ite .40 1.5S
Levynite .40 1.54 Erionilte ,35 1.51 Gmelin.ite ,44 1.46 Chabaz:Lte ,47 1,45 A ,5 1.3 Y .48 1.27 ~Z36815 When sinusoid in the alkali metal form, the ZSM-5 type zealot before treatment with BF3 is conveniently con-vented to the hydrogen form, generally by intermediate formation of the ammonlum form a a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form, i.e. HZSM-5. In addition to the hydrogen loam, other form of the zealot wherein the original alkali metal has been reduced to lets than about 1.5 percent by weight may be used.
In practicing the desired conversion process, it may be desirable to incorporate the above-described crystalline alumlnosilicate in another matrix resistant to temperature and other conditions employed in the process. However, it has been found that such incorporation preferably should not take place until after the Zulu ha been treated with boron trifluoride since the presence of some matrices, for reasons which are not completely understood, interferes with the activation procedure This is particularly true for alumina or alumina-contalnlng) matrices. Silica matrices Jay not be detrimental to the activation procedure and could be composite with the zealot prior to activation with boron trifluoride.
The modified zealot, if treated with 8F3 in the absence of binder, may be incorporated with any conventional matrix material. Such matrix maternal include synthetic or naturally occurring substances a well a inorganic materials such as clay, silica Andre metal oxides. Natural clays lZ36815 which can be compocited with the zealot include those of the montmorlllonite and kaolin families, which families include the sub-bentonitea and the kaolin commonly known as Dixie, McNamee-Georgia and Florida clay or others in which the main mineral constituent Lo hollowest, coolant, Dakota, nacrite or Anita.
In addition to the foregoing maternal the zealots employed herein may be composite with a porous matrix material, such as alumina, silica-alumina, ailicA-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titanic as well as ternary compositions, such a silica-alumlna-thorla, ~ilica-alumina-zlrconla, ~lllca-alumina-magnesia and ~ilica-magnesia-zirconla, The matrix may be in the form of a Vogel. The relative proportions of zealot component and inorganic oxide gel matrix on an anhydrouc basis may vary widely with the zealot content ranging from between about 1 to about 99 percent by weight and more usually in the range of about 5 to about 80 percent by weight of the dry composite.
Although there to generally come type of correlation between alpha value and catalytic activity in the convert Sweeney contemplated in twig invention, the alpha activity of the boron trifluoride treated catalyst way much reduced by the treatment, but the conversion of methanol went up (Table 1). This is a surprising and unexpected result which it not understood.
The following examples will illustrate the best mode lZ36815 contemplated for carrying out the invention.
A sample of HZSM-5 having a silica-to-alumina ratio of 70:1 and without binder was treated with boron trifluoride by contacting it at 150 C and at atmospheric pressure with boron trifluoride flowing at 30 cc/min. through a 1 gram catalyst bed for approximately 10 minute, after which the zealot way cooled in a steam of dry nitrogen.
The boron trifluoride modified catalyst of Example 1 was then tested for conversion of methanol to hydrocarbons along with an HZSM-5 type zealot which had not been boron trifluoride modified. The following Table 1 compares data from the catalyst of this invention with the catalyst of the prior art:.
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~23~815 A can be seen from the above table, a space velocity f approximately 0.5 is required to achieve loo methanol onverslon at 300 c for an untreated HZSM-5. For the boron trifluoride modified catalyst, a space velocity of 9.0 chives loo methanol conversion. This corresponds to an increase in catalyst activity by a factor of approximately 15-20. Even at 280 C, the BF3 modlf$ed catalyst is four to five times as active as the unmodified catalyst at 300 C.
SXAMPLEi~ 13 A swirls of experiments were carried out in order to remonstrate the uniqueness of the novel activation procedure f this invention.
In each of Examples 7-13c HzsM-5 having a lookout-lumlna ratio of 70:1 was employed. In Examples 7 Anglo, he conventional HZSM-5 catalyst of the prior art was employed. In Examples 8 and if, and HZSM-5 treated with Ron fluoride in the manner set forth in Example 2-6 was mployedc In Example 9, an ammonlum fluoride treated catalyst as employed. This catalyst was prepared by m~xlng 0.46 ram of ammonlum fluoride with lo gram of ~ZSM-5 (no lender) and healing at 150 C for 10 minutes with argon flowing at 30 cc/min. These conditions simulate those used for the preparation of sF3 catalyst. The catalyst of sample 9 was then calcined in air at 500 C overnight to overt it to the hydrogen form. In Example 12, a mixture f HZSM-5 with alumina was treated with BF3 in the manner previously described. In Example 13, a hydrogen fluoride treated catalyst was used. This catalyst way prepared by flowing a mixture of 3 cc of hydrogen fluoride and 27 cc of Ron at 300 cc/min. over 1 gram of HZSM-5 (no binder) at 150 C for 15 minutes. The result obtained for methanol inversion as well as alpha values of the various catalyst no given in Table 2.
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As can be seen from the above table, thy catalyst of Example 8 had a ~ubstantlally lower alpha activity than the catalyst of Example 7, yet it had enhanced activity for the conversion of methanol. The same is equally true with regard It the catalyst of Simple 11 as compared to the catalyst of Example 10. Please note that treatment with ammonium fluoride, i.e. Example 9, and hydrogen fluoride, it Example 13 did not result in enhancement of methanol conversion activity and, in fact, Example 13 shows an actual decline relative to the untreated material.
Example 12 depict the results of incorporating an ~ZSM-5 into an alumina binder prior to treatment with boron trlfluoride and, as can be seen, a catalyst was obtained with an alpha of 6 and only slightly enhanced activity at 300 C. The BF3 appears to react much more rapidly with the alumina binder than with the ZSM-5.
EXAMPLES 14-l7 These examples will illustrate the criticality of the silica-to alumina ratio of the ZSM-5 type zealot. In Examples 14 and 15, a crystalline ZSM-5 zealot having a silica-to-alumina ratio of 800:1 was employed. In Examples 16 and 17, a similar material but having a silica-to-alumina ratio of 1600:1 was employed. The method of activation with boron trifluoride wag the game a previously described. The results are shown in Table 3.
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l A can be seen from the table, treatment with boron ¦trifluorlde did not enhance the methanol conversion activity of either of these two ZSM-5's simply because the sllica-to-alumina ratio was too high.
¦ Therefore, the novel process of this invention it applicably to ZSM-5 type zealots having a slllca-to-alumina ratio of 30 to no greater than about 3~0 and, more preferably, no greater than 100 and, even more desirably, availing a sillca-to-alumina ratio of from about 30 to 80.
¦ Eye lo A Cockney trifluoride modified catalyst prepared as in example 1 was tested for propylene conversion ¦~oligomerizatlon) at 300 C and 30 WHSV. Table 4 compare the data obtained with the boron trlfluorlde modified catalyst with data obtained using HZSM-5 of similar activity alphabet at the same operation conditions.
As can be seen from Table 4, propylene conversion way approximately 16 time higher for the boron trlfluoride treated catalyst compared to untreated HZSM-5. on addition, the boron trifluor~de treated catalyst produced more of desirable C6+ gasoline range hydrocarbons. Other olefins would be expected to react similarly to propylene.
6tl15 -I
¦ Swahili HZSI~-5 I
. I
temperature, C 300 300 so 30 30 ¦~talysl~ Activity 0.14 0.16 conversion, Kit 99 6 Product disttihution, wit ¦ 11ethane no own I thin no 0. n I ~I:hylnnla n . 2 n. o IPro~ane 3,3 1.0 I En p Y l. Q
nlltnnle foe I.
n-Rutane 3.1 2.0 I Olefin~s 11.3 17.0 Us Olefins foe 15.5 C6 Oleelns 13.8 30.2 C7 Olefins lows 10.4 I Olefln~ 33.4 8.4 . Cog Olefin~ 11.5 12.4 Coo Oleflns 2.3 0.2 99.9 100.0 SLUICE
I supply 19 ¦ A boron trifluoride catalyst prepared as in Employ 1 wow tested for Tulane disproportionation at 500 C and 10 ¦WHSV. Table 2 summarizes the data and compares them with data obtained using ~2SM-5 of similar activity alphabet ¦ A can be seen from Table I at the same operating conditions and using catalysts of the same alpha-activity, the boron trifluorlde catalyst showed approximately 18 tome higher conversion compared to untreated 82SM-5.
¦ TABLE
l BF3-HZSM-5 HZSM-5 I_______________________________ Temperature C 500 500 Catalyst Activity ¦ alphabet 2.2 2.2 . conversion, White 5.07 0.28 ~2368i5 ¦ AMPLE 20 ¦ A boron trifluorlde catalyst prepared as in Example l WEBB tested for zillion isomerizatlon at lo WHSV and various temperatures. Table 6 ~ummarizeg the data and compares them with Dwight obtained UB1n9 ~ZSM-5 of similar activity alpha-test).
¦ As can be seen from Table 6, at 300 C and using catalyst of the tame alpha activity the boron trifluoride catalyst showed approximately four times higher conversion compared to untreated HZSM-5. In order to obtain equivalent conversancy, the temperature of the boron trifluoride catalyst had to be significantly lowered to 230- C.
I
l BF3-HZSM-5 HZSM-5 I __________ ______ . temperature, C 300 230 300 WHSV lo lo lo Catalyst Activity alpha test 2.2 2.2 2.2 ~onvec~l~n, it 16.3 4.3 I
~236~1S
For the conversion contemplated heroin, it it referred to use ZSM-5 type zealots having a silica-to-alumina ratio no greater than 300 and, more preferably, no treater than loo and, even more de~lr~bly, having a silica-to alumina ratio of from about 30 to 80.
¦ In audition to the above examples, the catalysts of the invention may also be used in a wide variety of acid catalyzed reactions. Dewaxlng, i.e., the selective cracking of wax molecules, can be carried out at temperature greater than 175c C ~347 F), more preferably at temperatures from OWE C (392 F) to 430 C (806 F), and even more preferably Nat temperature from 260 C (500 P) to 360 C (680 F1.
the dew axing reaction can be carried out at space velocities ¦(LHSV) from 0.1 to lo, more preferably from 0.1 to 50 and it pressures up to 3000 prig, more preferably from 25 to 1500 p819.
The alkylation of aromatics with alcohols or olefin~
may be carried out at temperatures for 150 C to 750 C, Gore preferably from 2Z5 C to 600 C, at pressures up to p500 slug, more preferably from 20 prig to 500 prig, at ~SV's form Owl to 400, more preferably from 3 to 30.
alcohols or oleflns such as methyl alcohol, ethyl alcohol, ripen, ethylene, butane, l-butene, l-propene, l-dodecene, can be used ¦ EXAMPLE 21 l Several preparations were made by the method used in example l and were evaluated for physical properties, 12368~5 ¦ including selectivity log ethylene produced when converting ¦ methanol. at 100~ conver~lon. The royalty are summarized in ¦ Table 7.
¦ TABLE 7 ¦ Physic]. HZSM-5 Range for I Property 3-HZSM-5 ¦ Alpha Value 150 typical 0 to 29 ¦ Crystalllnity, 100 90 to 95 ¦ O-xylene sorption) ¦ Capacity, mug ) 50 19 Diffusion time for 30~ of capacity ) 270 900 I for O-xylene, minutes) ¦ White Boron 0 0.1 - 0.5 ¦ White Fluorine 0 5 to 10 ¦ Ethylene selectivity,) ¦ 100~ Methanol ) 8 18 I Conversion, White ) ¦ Although this invention is described particularly with ¦ reference to 8F3, it 18 contemplated to employ other Lewis ¦ acid fluorides such a PF3, AsF3, SbF5 and Bits in place of ¦ BF3-
in fC '3 I O Lo aye .
no o v v I
En .
O n I I
us ? Ye o o o o _ us Jo , , , . . I
o O
.,, Us O Jo ,. o o C o o o , --. co o o Jo E N I o Jo Jo _ O O Jo O CUD I
Us I_ a In V V
I Us Us V _ O
Us Us I q I V
Jo 1 I V
I
a 1 V I
D I U
r I ox o 2 'I
Jo ~236~31S
As can be seen from the above table, thy catalyst of Example 8 had a ~ubstantlally lower alpha activity than the catalyst of Example 7, yet it had enhanced activity for the conversion of methanol. The same is equally true with regard It the catalyst of Simple 11 as compared to the catalyst of Example 10. Please note that treatment with ammonium fluoride, i.e. Example 9, and hydrogen fluoride, it Example 13 did not result in enhancement of methanol conversion activity and, in fact, Example 13 shows an actual decline relative to the untreated material.
Example 12 depict the results of incorporating an ~ZSM-5 into an alumina binder prior to treatment with boron trlfluoride and, as can be seen, a catalyst was obtained with an alpha of 6 and only slightly enhanced activity at 300 C. The BF3 appears to react much more rapidly with the alumina binder than with the ZSM-5.
EXAMPLES 14-l7 These examples will illustrate the criticality of the silica-to alumina ratio of the ZSM-5 type zealot. In Examples 14 and 15, a crystalline ZSM-5 zealot having a silica-to-alumina ratio of 800:1 was employed. In Examples 16 and 17, a similar material but having a silica-to-alumina ratio of 1600:1 was employed. The method of activation with boron trifluoride wag the game a previously described. The results are shown in Table 3.
~Z3~}15 .,, ,, V , . .,. , . .
,.~ , I, , Lo V
Jo I, .,~ I 0 I
t, X . . .
o , s n o to I on UP Jo ED
to Al) Jo o , o o .0 owe to o to o o e E I
to I o I
, US o , v in Jo on us n O O
I I I I I
." Jo to to o o I
Jo or us ED t` ^ ^
Jo . owe :~Z36~S
l A can be seen from the table, treatment with boron ¦trifluorlde did not enhance the methanol conversion activity of either of these two ZSM-5's simply because the sllica-to-alumina ratio was too high.
¦ Therefore, the novel process of this invention it applicably to ZSM-5 type zealots having a slllca-to-alumina ratio of 30 to no greater than about 3~0 and, more preferably, no greater than 100 and, even more desirably, availing a sillca-to-alumina ratio of from about 30 to 80.
¦ Eye lo A Cockney trifluoride modified catalyst prepared as in example 1 was tested for propylene conversion ¦~oligomerizatlon) at 300 C and 30 WHSV. Table 4 compare the data obtained with the boron trlfluorlde modified catalyst with data obtained using HZSM-5 of similar activity alphabet at the same operation conditions.
As can be seen from Table 4, propylene conversion way approximately 16 time higher for the boron trlfluoride treated catalyst compared to untreated HZSM-5. on addition, the boron trifluor~de treated catalyst produced more of desirable C6+ gasoline range hydrocarbons. Other olefins would be expected to react similarly to propylene.
6tl15 -I
¦ Swahili HZSI~-5 I
. I
temperature, C 300 300 so 30 30 ¦~talysl~ Activity 0.14 0.16 conversion, Kit 99 6 Product disttihution, wit ¦ 11ethane no own I thin no 0. n I ~I:hylnnla n . 2 n. o IPro~ane 3,3 1.0 I En p Y l. Q
nlltnnle foe I.
n-Rutane 3.1 2.0 I Olefin~s 11.3 17.0 Us Olefins foe 15.5 C6 Oleelns 13.8 30.2 C7 Olefins lows 10.4 I Olefln~ 33.4 8.4 . Cog Olefin~ 11.5 12.4 Coo Oleflns 2.3 0.2 99.9 100.0 SLUICE
I supply 19 ¦ A boron trifluoride catalyst prepared as in Employ 1 wow tested for Tulane disproportionation at 500 C and 10 ¦WHSV. Table 2 summarizes the data and compares them with data obtained using ~2SM-5 of similar activity alphabet ¦ A can be seen from Table I at the same operating conditions and using catalysts of the same alpha-activity, the boron trifluorlde catalyst showed approximately 18 tome higher conversion compared to untreated 82SM-5.
¦ TABLE
l BF3-HZSM-5 HZSM-5 I_______________________________ Temperature C 500 500 Catalyst Activity ¦ alphabet 2.2 2.2 . conversion, White 5.07 0.28 ~2368i5 ¦ AMPLE 20 ¦ A boron trifluorlde catalyst prepared as in Example l WEBB tested for zillion isomerizatlon at lo WHSV and various temperatures. Table 6 ~ummarizeg the data and compares them with Dwight obtained UB1n9 ~ZSM-5 of similar activity alpha-test).
¦ As can be seen from Table 6, at 300 C and using catalyst of the tame alpha activity the boron trifluoride catalyst showed approximately four times higher conversion compared to untreated HZSM-5. In order to obtain equivalent conversancy, the temperature of the boron trifluoride catalyst had to be significantly lowered to 230- C.
I
l BF3-HZSM-5 HZSM-5 I __________ ______ . temperature, C 300 230 300 WHSV lo lo lo Catalyst Activity alpha test 2.2 2.2 2.2 ~onvec~l~n, it 16.3 4.3 I
~236~1S
For the conversion contemplated heroin, it it referred to use ZSM-5 type zealots having a silica-to-alumina ratio no greater than 300 and, more preferably, no treater than loo and, even more de~lr~bly, having a silica-to alumina ratio of from about 30 to 80.
¦ In audition to the above examples, the catalysts of the invention may also be used in a wide variety of acid catalyzed reactions. Dewaxlng, i.e., the selective cracking of wax molecules, can be carried out at temperature greater than 175c C ~347 F), more preferably at temperatures from OWE C (392 F) to 430 C (806 F), and even more preferably Nat temperature from 260 C (500 P) to 360 C (680 F1.
the dew axing reaction can be carried out at space velocities ¦(LHSV) from 0.1 to lo, more preferably from 0.1 to 50 and it pressures up to 3000 prig, more preferably from 25 to 1500 p819.
The alkylation of aromatics with alcohols or olefin~
may be carried out at temperatures for 150 C to 750 C, Gore preferably from 2Z5 C to 600 C, at pressures up to p500 slug, more preferably from 20 prig to 500 prig, at ~SV's form Owl to 400, more preferably from 3 to 30.
alcohols or oleflns such as methyl alcohol, ethyl alcohol, ripen, ethylene, butane, l-butene, l-propene, l-dodecene, can be used ¦ EXAMPLE 21 l Several preparations were made by the method used in example l and were evaluated for physical properties, 12368~5 ¦ including selectivity log ethylene produced when converting ¦ methanol. at 100~ conver~lon. The royalty are summarized in ¦ Table 7.
¦ TABLE 7 ¦ Physic]. HZSM-5 Range for I Property 3-HZSM-5 ¦ Alpha Value 150 typical 0 to 29 ¦ Crystalllnity, 100 90 to 95 ¦ O-xylene sorption) ¦ Capacity, mug ) 50 19 Diffusion time for 30~ of capacity ) 270 900 I for O-xylene, minutes) ¦ White Boron 0 0.1 - 0.5 ¦ White Fluorine 0 5 to 10 ¦ Ethylene selectivity,) ¦ 100~ Methanol ) 8 18 I Conversion, White ) ¦ Although this invention is described particularly with ¦ reference to 8F3, it 18 contemplated to employ other Lewis ¦ acid fluorides such a PF3, AsF3, SbF5 and Bits in place of ¦ BF3-
Claims (14)
1. A method for modifying the catalytic activity of a crystalline zeolite having a constraint index of 1 to 12 and a silica-to-alumina ratio of 30 to no greater than 300, which method comprises contacting said zeolite with gaseous boron trifluoride under conditions effective to reduce the alpha activity of the zeolite.
2. The method described in claim 1 wherein said contacting is effected at a temperature of 25° to 500°C
and a pressure of 0.1 to 500 psig for from about 0.01 hour to about 10 hours.
and a pressure of 0.1 to 500 psig for from about 0.01 hour to about 10 hours.
3. The method of claim 2 including the step of purging said contacted zeolite with an inert gas.
4. The method of claim 1 wherein said crystalline zeolite is free of alumina binder.
5. The method described in claim 1, 2 or 3 wherein said crystalline zeolite is ZSM-5.
6. A process for converting a catalytically con-vertible organic compound feed, which process comprises contacting said feed under conversion conditions with a crystalline zeolite modified by the method of claim 1.
7. The process of claim 6 wherein said feed comprises a lower alcohol, an olefin, an aromatic hydro-carbon, a normal paraffin having at least 10 carbon atoms or a singly methyl branched paraffin having at least 10 carbon atoms.
8. The process of Claim 6 wherein said convertible feed is an olefin and said conversion is oligomerization.
9. The process of Claim 8 wherein said olefin is propylene.
10. The process of Claim 6 wherein said convertible feed comprises an alkyl aromatic hydrocarbon and said conversion is disproportionation.
11. The process of Claim 10 wherein said alkyl aromatic is toluene.
12. The process of Claim 6 wherein said convertible feed comprises an alkyl aromatic hydrocarbon and said conversion is isomerization.
13. The process of Claim 6 wherein said convertible feed comprises a waxy petroleum oil and said conversion is dewaxing.
14. The process of Claim 6 wherein said convertible feed comprises alkyl alcohol having up to four carbon atoms or an ether derived therefrom and the alcohol or ether is converted into hydrocarbons.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58148149A JPS6040194A (en) | 1983-08-15 | 1983-08-15 | Improvement for converting lower alcohol/ether to hydrocarbon |
| US52676483A | 1983-08-26 | 1983-08-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1236815A true CA1236815A (en) | 1988-05-17 |
Family
ID=26478461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000474415A Expired CA1236815A (en) | 1983-08-15 | 1985-02-15 | Preparation of modified zeolites and their utilization |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS61187935A (en) |
| AU (1) | AU574428B2 (en) |
| CA (1) | CA1236815A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU601803B2 (en) * | 1987-02-17 | 1990-09-20 | Mobil Oil Corporation | Dealumination of aluminosilicate zeolites |
| BR112015002175B1 (en) * | 2012-08-10 | 2021-03-16 | Asahi Kasei Chemicals Corporation | method for converting an olefin or an alcohol to produce propylene or an aromatic compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0062123B1 (en) * | 1981-04-08 | 1986-07-02 | Mobil Oil Corporation | De-aluminization of aluminosilicates |
-
1985
- 1985-02-14 AU AU38713/85A patent/AU574428B2/en not_active Ceased
- 1985-02-15 CA CA000474415A patent/CA1236815A/en not_active Expired
- 1985-02-15 JP JP60026636A patent/JPS61187935A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61187935A (en) | 1986-08-21 |
| AU574428B2 (en) | 1988-07-07 |
| AU3871385A (en) | 1986-08-21 |
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