CA1242751A - Small olefin interconversions - Google Patents

Abstract

SMALL OLEFIN INTERCONVERSIONS
ABSTRACT
The process for the interconversion of "small olefins" selected from the class consisting of ethylene, propylene, butenes and mixtures thereof comprising contacting said small olefin(s) with non-zeolitic molecular sieves.

Description

SMALL OLEFIN INTERCONVERSIONS
_ _, FIELD OF INVENTION
The instant invention relates to the use of specific new non-zeolitic molecular sieves for the interconversion of C2 to C4 olefins whereby feedstocks containing a given molar amount of ethylene, propylene, butenes and derivatives thereof or mixtures thereof and are converted to an olefinic mixture having substantially different molar amounts of ethylene, propylene or butenes.
BACKGROUND OF THE INVENTION
.
Processes for various conversions of low molecular weight olefins are well known in the prior art. Representative of such general conversion processes are U.S. Patent Nos.: 3,140,249;
3,140,251; 3,140,253; 3,140,322; and 2,9~2,643.
The conversion of paraffins, olefins and/or naphthenes to aromatics using a ZSM-5 catalyst is disclosed in U.S. Patent No. 3,756,942. The conversion of olefins to aromatics by use of ZSM-5 and ZSM-8 is disclosed in U.S. Patent No. 3,760,024.
The prior art relating to olefin conversion over ZSM-type catalysts also includes numerous process related patents including: U.S. Patent No. 3,775,501 (co-feed air with olefins over ZSM-5); U.S. Patent No. 3,827,968 (ZSM-5 in a two step process); U.S.
Patent No. 3,960,978 (ion-exchange and/or steamed ZSM-5 or ZSM-ll~, U.S. Patent No. 4,021,502 (olefin conversion using ZSM-5, ZSM-12, ZSM-18, chabazite and beta zeolite under controlled process conditions);
U.S. Patent No. 4,150,062 (use of co--fed water with olefins over D-14,234 -: r~ ~

ZSM-5); U.S. Patent No. 4,227,992 (ethylene/
propylene conversion over ZSM-12 employing controlled process conditions?.
The above processes employ the aluminosilicates generally kno~n as "ZSM-type"
aluminosilicates. (The term "ZSM-type" is generally employed in the literature to denominate the aluminosilicates assigned a "ZSM-n" name where "n"
is an integer.) Accordingly, such processes do not relate to a process or processes not employing aluminosilicate molecular sieves.
The use of certain novel non-zeolitic molecular sieves as "polymerization" catalysts to produce high boiling polymerization products is disclosed in: Canadian Patent No. 1,202,016, issued March 18, 1986, Canadian Application No. 450,65~, filed March 28, 1984; Canadian Application No.
458,495, filed July 10, 1984; and Canadian Application No. 458,914, filed July 13, 1984. The interconversion of C2, C3 and C~ olefins using certain non-zeolitic molecular sieves is not disclosed in the aforementioned applications. U.S.
Patent No. 4,310,440, discloses that aluminophosphates ~AlPO4) may be employed as polymerization catalysts.
A process for the oligomerization olefins to hydrocarbon fuels is disclosed in commonly assigned Canadian Application No. 467,476, filed on November 9, 1984. The instant invention is to be distinguished from the aforementioned oligomerization process by the selection of specific non-zeolitic molecular sieves for the instant olefin interconversion whereby less than 20 mole percent of D-14,234-C
~, ,,;

the C2 to C4 olefins are converted to products containing greater than five carbons.
SUMMARY OF THE INVENTION
The instant process relates to the "interconversion" of ethylene, propylene and/or butenes using a non-zeolitic molecular sieves ~"NZ~MS") as disclosed in U.S. Patent No. 4,310,440 or a "N2-MS" having a framework structure of MO2, AlO2 and PO2 tetrat ~dra and having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR: (MXAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (MXAlyPz)O~, "M" represents specific elements present other than aluminum and phosphorus in the form o a tetrahedral oxide, as hereinafter discussed, "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.
The non-zeolitic molecular sieves employed in the instant process are those disclosed in:
Canadian Paten-t No. 1,202,016, issued March 18, 1986 (SAPOs wherein "M" is silicon); Canadian Application No. 450,658, filed March 28, 1984 (TAPOs wherein "M"
is titanium); Canadian Application No. 458,4g5, filed Jul.y 10, '984 (MeAPOs wherein "Me" is at least one of magnesium, manganese, cobalt and zinc); and U. S. Patent No. 4,310,440; Canadian Application No.
458,914, filed July 13, lg84 (FAPOs wherein "M" is iron). The acronyms "AlPO4" "SAPO", "TAPO", D-14,234-C

~24~7~5~

"MeAPO" and "FAPO" and etc. ~re explained in the aforementioned patents and patent applications and are briefly discussed hereinafter in the "DETAILED
DESCRIPTION OF THE INVENTION" section.
The instant process comprises contacting an initial mixture containing at least one of ethylene, propylene and butenes wi~h at least one of the aforementioned non-zeolitic molecular sieves at effective olefin interconversion conditions. The NZ-MSs employed in the ins-tant process are further characterized by an adsorption for n-hexane of more than 2 percent by weight at a pressure of ~00 torr and a temperature of 24.0C and by an adsorption for isobutane of less than 2 percent by ~eight at a pressure of 100 torr and a temperature of 24QC. The preferred molecular non-zeolitic sieves of this invention are characterized by specific x-ray powder difraction data as set forth hereinafter.
DETAILED DESCRIPTION OF THE INVENTION
The instant process relates to the interconversion of at least one small olefin of the group consisting of ethylene, propylene, and but~nes to one of the other olefins in the group.
Accordingly, the invention relates to six olefin interconversions which may be carried out singularly or in combination, although in most instances more than one such interconversion will occur concurrently. The following conversions are those which define the term "olefin interconversion" as D-14,234-C

7~

that term is employed herein:
1) ethylene to propylene;

2) ethylene to butenes;

3) propylene to ethylene;

4) propylene to butenes;

5) butenes to ethylene; and

6) butenes to propylene.
Further, the terms "small olefins" or "olefins" are employed herein to refer to ethylene, propylene, butenes, derivatives thereof and mixtures thereof.
The term "butenes" is employed herein -to refer to all butenes and butadienes. The derivatives of the "small olefins" may include functional groups which do not interfere with the interconversion to small olefins and derivatives thereof and may include substitution by functional groups such as halogen, cyanide, carboxylic acid, aldehyde and the like.
The process involves contacting such small olefins at effective olefin interconversion conditions with at least one "non-æeolite molecular sieve", ("NZ-MS"), as disclosed in U.S. Paten-t No.
4,310,440 or a "NZ-MS" having a framework structure of MO2, AlO2 and PO2 tetrahedra and having an empirical chemical composition on an anhydrous basis expressed by ~he f ormula:
MR: (MXAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (MXAlyPz)O2, "M" represents silicon~
iron, titanium or at least one o magnesium, manganese, cobalt and zinc, such being D-14,234 ,.
~.

present in the form of a tetrahe~ral oxide; and "x", "y" and "z" represent the mole fractions of "m", aluminum and ?hosphorus, respectively, present as tetrahedral o~ides.
The term "non-zeolitic molecular sie~e" or the abbreviation "NZ-~S" is employed herein -to denominate the molecular sieve compositions described in Canadian Patent No. 1,202,016 and Canadian Patent Applications Serial Nos. 450,658, 458,495 and 458,914, and in U.S. Patent No.
4,310,440. These non-zeolitic molecular sieves are employed herein to provide the instant interconversion of ethylene propylene and butenes.
The NZ~MS employed in the instant process are further characterized by an adsorption for n-hexane of more than 2 percent by weight at a pressure of 400 torr and a temperature of 24.0C and by an adsorption for isobutane of less than 2 percent by weight at a pressure 100 torr and a temperature of 24C. The preferred non-zeolitic molecular sieves for use in the instant process are characterized b~ x-ray diffraction patterns as set forth in Table A, Table B or Table C or Table D, or Table E or Table F:
TABLE A
d(A) Relative Intensit~

7.70 - 7.75 11.5 - 11.~ vs ~ .61 s - vs 15.5 - 15.55 5.72 - 5.70 s 1~.65 - 19.7 4.52 - 4.51 w - s 20.5 - 20.6 4.33 - 4.31 vs 31.8 - 32.00 2.812 - 2.7g7 w - s D-14,234-C

TA~LE B
d(A) Relative ~ntensity 9.60 - 9.65 9.21 - 9.16 vs 15.5 - 15.55 5.72 - 5.70 m 16~9 - 17.1 5.25 - 5.19 m 20.15 - 20.25 4.41 - 4.39 m 20.95 - 21.05 4.24 4.22 m 31.8 - 32.5 2.814 - 2.755 m TABLE C
2e ~ (A) Relative Intensity 9.9 - 9.65 9.41 - 9.17 s - vs 15.9 - 16.2 5.57 - 5.47 vw - m 17.85 - 18.4 4.97 - 4.~2 w - s 20.3 - 20.9 4.37 - 4.25 m - vs 24.95 - 25.4 3.57 - 3.51 vw - s 30.3 - 30.8 2.95 - 2.90 w - s TABLE D
d(A) Relative Inten 10.8 - 11.1 8.19 - 7.97 m 17.2 - 17.4 5.16 - 5.10 s - vs 21.0 - 21.25 4.23 - 4.18 m - s 21.8 - 22.0 4.08 - 4.04 vs 31.8 - 32.2 2.814 - 2.788 m TABLE E
d(A) Relative Intensity 9.4 - 9.5~ 9.41 - 9.26 vs 13.0 - 13.1 6.81 - 6.76 w - m 16.0 - 16.2 5.54 - 5.47 w - m 20.6 - 20.85 4.31 - 4.26 s - vs 24.3 - 24.q 3.66 - 3.65 w - vs 30.7 - 30.95 2.9~2 - 2.88~ w - s D-~4,234 ..~"

'7~

Table F
2~ d(A) Relative Intensity 9.4 9.41 vs 15.9 - 16.0 5.57 - 5.54 w - m ~0.5 - 20.6 4.33 - 4.31 s 24.5 - 24.7 3.63 - 3.60 w 25.8 - 25.9 3.45 - 3.44 w 30.4 - 30.5 2.9~0 - 2.931 w The class members of the molecular sieves set forth in the above identifled copending applications are referred to therein by a series of abbreviations. These abbreviations include:
AlPO4, SAPO, FeAPO, CoAPO, MAPO, MnAPO, TAPO, and ZAPO where each acronym is as defined in the above referenced applications. The members of each class, e.g., the members of the SAPO class, MAPO class or ZAPO class, are characterized by referring to class members as a "-n" member, e.g., as SAPO-5, MnAPO-ll, ZAPO-34 and etc., wherein the "n" designation is a number specific to a given class member as its preparation is reported in the aforementioned copanding applications. For the sake of convenient reference the aforementioned non-zeolitic molecular sieves, i.e. those disclosed in the above copendin~
patent applications, will be generally referred to herein as the "NZ-MS" molecular sieves. Individual members of the class of "NZ-~Ss" will be referred to by the nomenclature assigned to that class member as such is denominated in a particular referenced application.

D-14,234 '7~
g The effective olefin intercon~ersion conditions employed in the instant process, such as temperature, pressure, space velocity and molar ratio of any co-fed diluent to the small olefin, will have an affect on the process. ~n general the process is carried out at effective interconversion conditions such that interconversion of said starting olefin occurs and such that less than 20 mole percent, preferably less than 10 mole percen~, of the starting small olefin(s) is converted to products having a carbon number greater than five (5).
The instant small olefin interconversion process may be carried out in either the liquid-phase or the vapor-phase by contacting the NZ-M~ and the small olefin(s) in a reaction zone, such as, for example, a fixed bed of catalyst, under effectlve olefin interconversion conditions. The process may be conducted in either batch or fluid bed operation with attendant benefits of either operation readily obtainable.
The effective olefin interconversion conditions employed in carrying out the instant process include an effective temperature(s), pressure(s), weight hourly space velocity, contact time(s) and, if employed, an effective amount of diluent. The process is generally carried out at an effective temperature between about 150C and about 600C, preferably between about 200C and about 550C, and at effective pressures ranging between about 0.1 atmosphere ~14.7 psia) up to about 100 atmospheres or higher, although subatmospheric pressures may be employed. The pressure is D-14,234 .

preferably between about 1 and about 50 atmospheres.
The weight hourly space velocity (WHSV) of the olefins is generally maintained at between about 0.01 hr and about 100 hr 1 and is preferably between about 0.1 hr 1 and about 40 hr 1.
The instant olefin interconversion process may employ an effective amount of diluent in the process, including, but not limited to: Cl-C4 paraffins; methane; ethane; propane; isobutane and n-butane; inert gases, such as nitrogen, carbon dioxide; water (and/or steam); and hydrogen.
The effective amount of diluent which may be employed in the instant process is not narrowly critical, although specific effec.ive amounts of some diluents may exist, e.g., water. The amount of diluent may vary within the range of from O to about 99 weight percent, more preferably between about 1 and about 95 weight percent, based on the total weight of small olefin(s) and diluent. The amount of diluent is more preferably within the range between about 10 and about 70 weight percent~ The NZ-MS catalysts, as above defined for use herein, may be particularly benefited by co-fed water which may aid in resisting coking and aging of the NZ-MS
containing catalyst.
It has been found that the NZ-MS class of non-zeolitic molecular sieves can be employed in the present process to provide for the selective interconversion of small olefins selected from the gro~p consisting of ethylene, propylene, butenes and mixtures thereof to one of the other olefins of the D-14,234 7~ ~

aforementioned group. The products of the present process contain primarily small olefins and generally contain less than 20 percent by weight of products containing five carhons or greater.
The NZ-MS catalysts employed in the instant invention may have a certain proportion of the original cations associated therewith replaced by a wide variety of ~ther cations according to techniques well known in the art. Typical replacing cations include hydrogen, ammonium and alkali and alkaline earth metal cations, incl~ding mixtures of the same.
Typical ion exchange techniques invo've contacting the particular non-zeolitic molecular sieve (NZ-MS) with a salt of the desired replacing cation or cations. Although a wide variety of soluble salts can be employed, particular preference is given to chlorides, nitrates and sulfates owing to their solubility in water since water is the preferred solvent for such ion exchange techniques.
Representative ion exchange techniques are disclosed in a wide variety of patents including U.S. Pat. No.
3,140,249; 3,140,251; and 3,140,253.
Following contact with the ion exchange solution of the desired replacing cation, the N2-MS may be washed with water and dried .
One embodiment of this invention resides in the use of a poro~s matrix with the NZ-MS ca~alysts previously described. The NZ-MS can be combined, dispersed or otherwise intimately admixed with a poro~s matrix in such proportions that the res~lting product contains from 1% to 95~ by weight, and D-14,234 Z75~

preferably from 20% to 80% by weight, of the NZ-MS in the final catalyst composite. The catalysts may be formed by standard catalyst forming techniques including spray-drying, pelleting, extrusion and other suitable conventional means.
The term "porous matrix" includes active or inactive inorganic compositions with which the NZ-MS
can be combined, dispersed or otherwise intimately admixed. It is to be ~mderstood that the porosity of the composltions employed as a matrix can either be inherent in the particular material or it can be introduced by mechanical or chemical means.
Representative matrices which can be employed include metals and alloys thereof, sintered metals and sintered glass, asbestos, silicon carbide aggregates, pumice, firehrick, diatomaceous earths, aluminosilicates and inorganic oxides. Inorganic compositions especially those o~ a siliceous nature are preferred. Of these matrices, inorganic oxides such as clay, chemically treated clay, silica, silica-alumina, etc., are particularly preferred because o~ their superior porosity, attrition resistance and stability.
The inorganic oxide may also consist of raw clay or a clay mineral which has been treated with an acid medium to render it active. The NZ-MS may be incorporated with the clay simply by blending the two and fashioning the mixture into desired shapes.
Suitable clays include attapulgite, kaoline, sepiolite, poly-garskite, kaoline, halloysite, plastic ball clays, kentonite, montmorillonite, illite, chlorite, etc. Other useful matrices D-14,23~

-~'2~

include powders of refractory oxides, such as alumina, alpha alumina, etc., having very low internal pore volume. Preferably, these materials are inert with respect to the instant reactions, having substantiall~ no inherent catalytic activity of their own.
Final catalysts comprising at least one NZ-MS may be heated in steam or in other atmospheres, e.g., air, at the temperature contemplated for conversion or may be heated to operating temperatures initially during use in the process or may be calcined in air, steam, nitrogen, helium, flue gas, or other gases not harmful to the catalyst product, at temperatures ranginy from about 500F to 1600F
and for periods of time ranging from 1 to 48 hours or more. It is to be understood that the NZ~MS may also be calcined prior to incorporation with a matrix. It is to be further understood that the ~Z-MS need not be ion exchanged prior to incorporation into a matrix but can be so treated during or after such incorporation.

EXPERIMENTAL PROCEDURE
The olefin interconversion set forth in the examples were carried out b~ mixing about 0.4 to 0.5 grams of a selected NZ-~S with about 0.75 to 2.5 grams o~ quartz chips (20-30 U.S. Standard mesh).
The resulting mixture was then placed in a 1/4 inch (outside diameter) No. 304 stainless steel tubular reactor having a wall ~hickness of 0.035 inch. The tubular reactor was immersed in a fluidized heated sand bath having electrical resistance heaters D-14,234 provided for maintaining the sand bath and the tubular reactor at the desired temperature.
Thermocouples were provided for measurement of the reactor temperature.
A selected small olefin was introduced to the tubular reactor either alone or concurrently with a stream of a diluent. The pressure employed in the examples was the autogenous pressure (about one ~1) to about three (3) atmospheres unless otherwise noted. The flow rates of the small olefin(s) and diluent are set forth in each example in cubic centimeters per minute (crn3~min). The effluent from the tubular reactor (the reaction products) was analyzed.
The conversion to products is based on the small olefin~s) present in the final reaction mixture with the yield to a particular small olefin being given as the mole percentage of that small olefin in the final reaction mixture. When a product was not detected or if the amount was not capable of ~eing yuantitatively detected such is reported as zero.
The following examples are provided to exemplify the invention and are not meant to be limiting i.n any way.
Examples 1 to 9 SAPO-34 was evaluated according to the EXPERIMENTAL PROCEDUkE for the interconversion of ethylene, propylene and butenes. Th~ SAPO-34 was prepared according to the disclosure of Canadian Patent No. 1,202,016, issued March 18, 1986, had an D-1~,234-C

adsorption of n-hexane of greater than 2 percent by weight at a pressure of 400 torr and a temperat~re of 24C and an adsorption of isobutane of less than 2 percent by weight at a pressure of 100 torr and a temperature of 24~C and was characterized by t~e x-ray diffraction pattern of Table C. The feed for each interconversion and the process conditions are identified in Tables I to IX. The percent of each component in the feed is based on a vol~me percent and the product analysis is based on a mole percent.
The results in Tables I to IX demonstrate that SAPO-34 provides for the interconversion of ethylene to propylene and butenes with less than 20 mole percent prod~cts containing greater than five carbons.

D-14,234 TABLE ~ (Examp~e 1)1 Methane 0.00 0.00 0.00 Ca.bon Dioxide0.44 0.15 0.05 Ethylene 22.93 10.18 15.60 Ethane 1.78 2.52 4.01 Propylene 18.56 20.60 37.85 Propane 35.68 42.90 16.92 Butenes 16.92 18.11 19.83 C5 2.98 4.70 g.90 C6 0.73 0.83 0.80 Run Times, HrsØ5 1.25 2.08 The feed was a mixture of 85 vo'ume perce~t nitrogen and 15 volume percent ethylene. The total flow rate was 5 cm3/min, the temperature was 375C
and the pressure was the autogenous pressure.

D-~4,234 ~L~Li~t~

TA~LE ~l (Example 2) Run a Run b Methane 0.50 0.17 0.190.000.06 0.00 Carbon Dioxide0.62 0.260.220.07 0.03 0.02 Ethylene13.4944.00 51.6569.0678.1782.92 Ethane 4.44 2.79 2.491.301.22 1.00 Propylene37.4443.81 38.9927.2618.8215.05 Propane12.79 0.00 0.000.000.00 0.00 Butenes23.19 8.43 5.762.001.63 0.94 Cs 5.41 0.85 0.610.300.06 0.08 C6 0.83 0.12 0.090.000.00 0.00 Run Times, HrsØ75 1.422.0 0.5 1.25 2.0 lThe feed was a mixture of 50 percent ethylene and 50 - percent nitrogen; the total flow rate was S cm3/min in "Run a" and 10 cm3/min in "Run b", the temperature in "Run a" and "Run b" was 375~C; and the same catalyst charge was employed in "Run a" and "Run b". This catalyst was treated at 500C in air for 3 hours prior to "Run a".

D-~4,234 '7Si~

TABLE ~l (Example 3)1 Methane 0.00 0 00 Q-00 Carbon Dioxide0.00 0.00 0.00 Ethylene 1.78 1.07 0.85 Ethane 0.03 0.02 0.0' Propylene 11.77 6.20 4.33 Propane 0.75 0.16 0.05 Butenes 83.87 91.50 94.22 Cs 1.66 0.71 0.48 C6 0.11 0.32 0.04 Run Times, HrsØ5 1.41 2.25 The feed was mixture of 1-butene and nitrogen each provided at a flow rate of 5 cm3/min for a total flow rate of 10 cm3/min. and the temperature was 375C. This catalyst was treated at 500C in air for 2 hours prior to use.

~-~4,234 '7~

TABLE JV (Example 4)1 Methane 0.13 0.00 O_OQ
Carbon Dioxide 0.04 0.00 0.03 ~thylene 6.36 3.63 2.92 Ethane 0.08 0.02 0.00 Propylene '62.9088.60 93.14 Propane 5.61 0.00 0.00 Butenes 25.71 6.69 3.48 Cs 4.99 0.63 0.20 C6 0.79 0.43 0.23 Run Times, Hrs. 0.5 1.25 2.0 The feed was a mixture of: a)50/50 percent mixture of propylene and nitrogen and b) water;
where the flow rate of propylene/nitrogen was 10 cm3/min. and of water was 1.6 cm3/hr.; and the temperature was 375~C. This catalyst wa.s trea;ed at 500C in air for 2 hours prior to use.

D-~4,234 7~

TABLE V (Example 5)1 Methane 0.14 0.00 0.00 Carbon Dioxide0.02 0.00 0.00 Ethylene 7.49 6.62 4.31 Ethane 0.31 0.10 0.02 Propylene 64.42 85.92 92.28 Propane 0.00 0.00 0.00 Butenes 17.20 6.44 2.91 c5 2.33 0.48 o,?0 C6 0.76 0.42 0.25 Run Times, Hrs.n.s 1.33 2.5 .
The feed was a mixture of 50 percen. propylene and 50 percent nitrogen; the temperature was 375~C; and the flow rate was 10 cm3/min. This ca~alyst was treated at 500C in air for 2 hours prior to use.

3~

TABLE Vl (ExamPle 6)1_ Run a Methane 0.82 0.49 - 0.37 Carbcn Dioxide0.08 0.04 0.03 Ethylene 36.03 59.53 71.39 Ethane 3.80 2.66 2.08 Propylene 50.54 33.80 23~88 Propane 0.00 0.00 0.00 Butenes 7.43 3.10 1.97 ~5 0.90 0.29 0.21 C6 0.39 0.10 0.08 Run Times, Hrs.1.00 1.75 2.5 The feed was ethylene in "Run a" and propylene in "Run b";
the flow rate was 5 cm3/min in "Run a" and 4.4 cm3/min in nRun b"; the temperature was 375C in each run; and the same catalyst charge was employed in each run. The catalyst was treated at 500C in air for 3.5 hours prior to use in each run.

D-l4,234 , ,~

7~
~2 -BLE Vl (Example 6)1 R~n b Methane 0.76 0.34 0.2 Carbon Dioxide0.05 0.05 0.04 Ethylene 11.02 8.35 6.25 Ethane 0.67 0.23 Q.13 Propylene 77.08 86.94 90.75 Propane 0.00 0.00 ~.00 Butenes 8.25 3.01 1.72 C5 0.98 0.30 0.23 C6 1.19 0.78 0.64 Run Times, Hrs.1.00 1.8 2.5 _ The feed was e.hylene in "Run a" and propylene in "Xun b~ the flow rate was 5 cm3/min in "Run a" and 4.4 cm3/min in "Run b"; the temperature was 375C in ~ach run; and the same catalyst charge was employed in each. The catalyst was treated at 500C in air for 3.5 hours prior to use in each run.

D-14,234 '7~
~ 23 -TABLE VII (Example 7)1 Methane 0.00 -Carbon Dioxide 0.03 0.02 Ethylene 1.20 0.68 Ethane 0.02 0.01 Propylene 0.76 0.36 Propane 0.55 0.18 B~tenes 97.41 98.41 C5 0.00 0.00 C6 o. oo o. oo Run Time, Hrs. 0.5 1.33 The feed was a mixture of 1,3 butadiene and nitrogen formed by mixing each a~ a flow rate of 5 cm3/min. for a total flow rate of 10 cm3/min.; and the temperature was 375C.

D-l4,234 '~ 5 TABLE V~ Example 8)1 Methane 0.12 0.01 0.00 Carbon Dioxide0.00 0~00 0.00 Ethylene 2.18 0.56 0.31 Ethane 0.51 0.00 0.00 Propylene 6.47 1.11 0.80 Propane 0.20 0.04 0.00 Butenes 89.29 97.9098.29 C5 0.75 0.10 0.05 C6 0.10 0.1~ 0.00 Run Times, HrsØ5 1.75 2.75 -The feed wa.s a mixt~re of l-butene and nitrogen formed by mixing each at a flow rate of 5 cm3/min~ for a total flow rate of 10 cm3/min.;
and the temperatl~re was 425C. The catalyst was treated at 500C in air for 6 hours prior to use.

D-]4,234 7S~L

TABLE IX (Examp~e gjl Methane 1.22 0.11 0.~00 Carbon Dioxide0O02 0.00 0.00 Ethylene 12.57 9.~6 5.38 Ethane 1.08 0.17 0.03 Propylene 57.98 83.42 90.76 Propane 3.58 0.00 0.00 Butenes 19.33 5.87 3.15 Cs 3.08 0.32 0.11 C6 1.15 0.65 0.56 Run Times, HrsØ5 1.33 2.5 The feed was a mixture of 50 volume percent propylene and 50 volume percent nitrogen; the flow rate was 10 cm3/min.; and the temperature was 425C. The catalyst was treated at 500C in air for 4 hours prior to use.

D-14,234 L,2L~ jJ~

Examples 10 and 11 MAPO 34 (where "M" is Mg) was employed for the interconversion of propylene to ethylene and butylene ~Example 10) and of Pthylene to propylene and butenes ~Example 11). MAPO-34 was prepared in accordance with the disclosure of Canadian Application No. 458,495, filed July 10, 1984, was characterized by the same n-he~ane and isobutane adsorption observed for the SAPO-34 of examples 1 to 9 and was characterized by the x-ray diffraction pattern of Table C.
MAPO-34 formed no C5 or C6 products but did form mixtures of small olefins from the starting small olein.

TABLE X (Example 10)1 Methane 0.04 0.00 0_00 Carbon Dioxide0.00 0.00 0.00 Ethylene 2.24 1.16 0.~9 Ethane 0.45 0.21 0.13 Propylene 96.30 9B.38 98.94 Propane 0.00 0.00 0.00 Butenes 1.00 0.20 0.14 Cs 0.00 0.00 0.00 C6 0.00 0.00 0.00 Run Times, HrsØ5 1.3 2.0 .
The feed was a mixture of 50 percent propylene and 50 percent nitrogen; the flow rate was 10 cm3/min.; and the temperature was 375C.

D-l4,234 - 28 ~
~Z~

Methane 0.00 0.00 0.00 Carbon Dioxide0.00 0.03 0~3 Ethylene 33.5797.53 97.67 Ethane 0.48 0.18 0.14 Propylene 4.68 1.65 1.68 Propane 0.92 0.4S 0.40 Butenes 0.28 0.79 0.05 C5 0.00 0.00 0.00 C6 0.00 0.00 0.00 Run Times, HrsØ5 1.25 2.0 The feed mixture was a mixture of 50 percent ethylene and 50 percent nitrogen; the flow ra'e was 10 cm3/min.; and the temperature was 375C. The catalyst was treated at 500C in air for 2 hours prior to use.

D-l4,234 Exam~les 12 to 14 AlPO4-17, as disclosed in U. S. Patent No. 4,310,440, was evaluated for: the inter-conversion of propylene to ethylene and butenes (Example 12); the interconversion of ethylene to propylene and butenes (Example 13); and the interconversion of l-butene to ethylene and propylene (Example 14).

D-'4,234 75~

TABLF. X~J (Example 12)1 Methane 0.35 0.55 0~26 Carbon Dioxide1.77 1.78 1.14 Ethylene 0.03 0.04 0.02 Ethane 0.00 0.00 0-00 Propylene 96.98 96.81 98O00 Propane 0.00 0.00 0.00 Butenes 0.31 0.19 0.10 CS 0.03 0.10 0.07 C6 O.S0 0.49 0.38 Run Times, HrsØ5 1.16 2.0 __ _ The feed was a mixture of 50 perçent propylene and 50 percen~ nitrogen; the flow rate was 10 cm3/min.; and the temperature was 425C. The catalyst was treated at 500C in air for one hour prior to use.

D-14,234 7~

TABLE XIII ~Examp~e 13)1 Methane 0.40 0.00 0.~0 Carbon Dioxide 1.93 0.25 0.11 Ethylene 94.42 98.35 95.06 Ethane 0.09 0.00 0.00 Propylene 2.15 1.40 1.33 Propane 0.00 0.00 0.00 Bu~enes 1.00 0.00 0.00 C5 0 . 00 O. 00 O. 00 C~ 0. 00 O. 00 O. 00 Run Times, Hrs. 0.5 1.5 2.16 -The feed was a mixture of 50 percent ethylene and 50 percent nitrogen; the flow rate was 10 cm3/min.; and the temperature was 425C.
- The catalyst was treated at 500C in air for one hour p~ior to use.

D-14,234 32 ~'~

TABLE X~V (Example 14)1 Methane 0.03 0.00 Carbon Dioxide 0O13 0.08 Ethylene 0.16 0.13 Ethane 0.00 0.00 Propylene 0.26 0.32 Propane 0.00 0.00 B~tenes 99.42 99.47 C5 0.00 0.02 C6 o. oo o. oo Run Time, Hrs. 0.5 1.41 The feed was a mixture of 50 percent l-butene and 50 percent nitrogen; the flow rate was 5 cm3/ min.; and the temperature was 375C.
The catalyst was treated at 500C in air for two hours prior to use.

D-~4,234

Claims (30)

-33-

1. Process for the interconversion of ethylene, propylene and butenes comprising contacting an olefin feed containing at least one of ethylene, propylene and butenes with a non-zeolitic molecular sieve, NZ-MS, characterized by an adsorption for n-hexane of more than 2 percent by weight at 400 torr and at 24.0°C and by an adsorption for isobutane of less than 2 percent by weight at a pressure of 100 torr and a temperature of 24°C, at effective olefin interconversion conditions for forming small olefin products.

2. The process of claim 1 wherein said "NZ-MS" is a silicoaluminophosphate (SAPO).

3. The process of claim 1 wherein said "NZ-MS" is a ferroaluminophosphate (FAPO).

4. The process of claim 1 wherein said "NZ-MS" is a titanium aluminophosphate (TAPO).

5. The process of claim 1 wherein said "NZ-MS" is a methal aluminophosphate (MeAPO) in which the metal is at least one of magnesium, manganese, cobalt and zinc.

6. The process of claim 1 wherein said "NZ-MS" is a manganese aluminophosphate (MnAPO).

7. The process of claim 1 wherein said "NZ-MS" is a cobalt aluminophosphate (CoAPO).

8. The process of claim 1 wherein said "NZ-MS" is a metal aluminophosphate (MAPO) in which the metal is one of a mixture of two or more divalent metals selected from magnesium, manganese, zinc and cobalt.

9. The process of claim 1 wherein said "NZ-MS" is a zinc aluminophosphate (ZnAPO).

10. The process of claims 1 or 2 or 3 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table A as follows:

11. The process of claims 1 or 2 or 3 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table B as follows:

12. The process of claims 1 or 2 or 3 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table C as follows:

13. The process of claims 1 or 2 or 3 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table D as follows:

14. The process of claims 1 or 2 or 3 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table E as follows:

15. The process of claims 1 or 2 or 3 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table F as follows:

16. The process of claim 1 wherein less than 20 percent by weight of the small olefins is converted to products having a carbon number greater than five.

17. The process of claims 1 or 2 or 3 wherein said olefin feed consists essentially of at least one of ethylene, propylene and butenes.

18. The process of claim 1 wherein the process is carried out in the vapor phase.

19. The process of claim 1 wherein the process is carried out in the liquid phase.

20. The process of claim 1 wherein said process is carried out in the presence of a diluent.

21. The process of claim 20 wherein the diluent is selected from the class consisting of C1 to C4 paraffins, nitrogen, carbon dioxide, water and mixtures thereof.

22. The process of claim 21 wherein the diluent is water.

23. The process of claim 21 wherein the diluent is nitrogen.

24. The process of claims 4 or 5 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table A as follows:

25. The process of claims 4 or 5 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table B as follows:

26. The process of claims 4 or 5 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table C as follows:

27. The process of claims 4 or 5 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table D as follows:

28. The process of claims 4 or 5 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table E as follows:

29. The process of claims 4 or 5 wherein said "NZ-MS" has an x-ray diffraction pattern characterized by Table F as follows:

30. The process of claims 4 or 5 wherein said olefin feed consists essentially of at least one of ethylene, propylene and butenes.