CA1139733A - Form of zeolite zsm-11, preparation thereof and catalytic conversion therewith - Google Patents

Abstract

NEW FORM OF ZEOLITE ZSM-11, PREPARATION THEREOF
AND CATALYTIC CONVERSION THEREWITH

ABSTRACT

A new and highly siliceous form of zeolite ZSM-11, ways of synthesising it and its use in conversions of organic compounds such as cracking, reforming and alcohol aromatization.
Synthesis is effected in the absence of added alumina. The product manifests the x-ray diffraction pattern characteristic of zeolite ZSM-11.

F-CO14 Canada

Description

1~39733 NE~ FOR~ OF ZEOLITE ZSM-11, PREPARATION THEREOF
AND CATALYTIC CONVERSION THEREWIT~

~ his invention relates to a new form of tha zeolite ZSM/11, to a method for its preparation and to its u~e in catalytio conversion of organic ¢ompounds.

Prior art techniquas have resulted in the formation of a great variety of synthetio aluminoailioates. 'rhese aluminosilLcates have com0 to be designated by letter or other convenient symbolsl as illu~trated by zeolite A tU.S. Patent 2,882,243), zeolite X (U.S.
Patent 2,882,244)~ zeolite Y (U.S. Patent 3,130,007), zeolite ZK-5 (U.S. Patent 3,247,195), zeolite Z~-4 (U.S. Patent 3,314,752), zeolite ZSM 5 ~.S. Patent 3,702,886), and zeolite ZSM-11 (U.S.
Patent 3,709,979), merely to name a few.

The SiO2/A1203 ratlo oP a given zeolite i~ often ~arlable.
For example, zeollte X oan be synthesiz2d with SiO2/A1203 ratio of from 2 to 3; zeollte Y, from 3 to about 6. In aome zeolites the upper limit of SiO2/A1203 ratio 19 unbounded. ZSM-5 19 one suoh example wherein S102~A1203 ratio i9 at least five. U.S.
Patent 3,941,871 discloses a crystalllne metal organosllicate essentially free of aluminium and exhibiting an X-ray diffration pattern characteristic of ZSM-5 type aluminosllicates. U.S. Patents 4,061,724, 4,073,865 and 4,104, 294 describe microporous, crystalline silioaq or or~anosilicates. The present invention iq directed to a form of zeolite ZS~-11 having silica to alumina ratio higher than previously disclosed and indeed attaining an effectively alumina-free condition.

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i~39733 .

The composition of the new form of ZSM-11 can be identlfied, in terms Or mole ratios o~ oxides as ~ollows:

(0-10)M2/nO : (0-0.5~A1203 : (100)SiO2 where M i9 at least one cation havlng a valenoe n. In the as syn-the3ized for~, the zeolite has a rormula, after clehydration, in terms o~ moles of oxides, per 100 moles of silloa, as ~ollows:

(0-10)R20 : (0-10)M2/nO : (0-0.5)A1203 : ~100)SiO2 wherein M i9 an alkali or alkaline earth metal, R2 is an organic co~pound cr Group 5A element of the Periodic Table, preferably nitrogen or phosphorou~, containin~ at least one alkyl or aryl group having between 1 and 7 carbon atoms, preferably between 2 and 5, carbon atom3, prePerably containln~ at leaat one ethyl or butyl sroup and still mors preferably X20 i9 a quaternary ammonium co~pound.

In a ravoured embodlment the zeolite oontains iron and/or ohromium and it~ composition can be identlfled, terms o~ mole ratios oP aAhydrous oxides per 100 miles oP sil~oa as ~ollow~:

2~r. ~(a)Cr23 ~ (b)Fe203 ~ (c)A1203]
100 SiO2, wherein M is at lea~t one catlon having a valence n, asO-4, b,0-5, c=0.001-0.5, with the proviso that a and b cannot both be equal to 0 at the 9ame ti~e; when one equal~ 0 the other must be zreater than the value of c. The ohro~ium and lron oxide need not ocour as Cr203 or Fe203 but are 90 calculated in the ~ormula.

' ' ' ` ~139q33 In the as-syntheslzed form, this embodiment of the zeolite has the formula after dehydration, in terms o~ moles o~ oxides, per 100 moles of silica, as follows:

3 2 ~ ) 2/n ~ ) 2 3 ~ ) Fe203 ~ (c)A1203] : 100 SiO2, ~hereln M i9 an alkali or alkaline earth metal, R~0 i9 an organic compound of Grcup 5A element of the Periodic Table, preferably nitroeen or phosphorou~, containin3 at least one alky} or aryl group having between 1 and 7 carbon atoms, ~preferably between 2 and 5, carbon atoms) preferably containing at least one butyl group and still more pre~erably R20 is a quaternary ammonium compound oontaining at least one butyl group, a=0-4, b=0-5, and c-0.001-0.4.
~o~ever, a and b cannot both be equal to 0 at tha same time ~hen one equal~ 0 the other mu~t be greater than 0 and 8reater than the value o~ c.

The n~w ~or~ of the zeolite may have small amountq of A1, Fe and/or Cr in positions o~ tetrahedral substltution withln ~he silica lattlce To thls extent, tha latter poqse~ses a negat1Ye change1 one excess electron for each atom substitutlon, whlch is balanced by oatlon~. These catlon~ may be replaced at least in part, by other ions using conYentional ion exchange techniques. Due to pore blocka~e, in some cases, by the R20 species it may be necessary to pre-calclne the zeollte prior to ion-exchange. Ion~ introduced to replace the original alkali, alkaline earth and/or organic cation may be any that are desired 30 long aY they can paqs through the channels within the lattice. Especially de~ired replacing ions are those of hydrogen9 ammonium ahd metals Or Grcups I through ~III
o~ the Periodic Table. Among the metals those particularly preferred are rare earth metals, manganese, zinc and those o~ Group ~III o~ the Periodic Table.

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~39~33 ZSM-11 ha~ a characteristic X-ray dif~raction pattern which distin3uishes it from other crystalline materials and by which it is defined for the purpose3 o~ this qpeci~ication.

me X-ray diffraction pattern o~ the zeolite has the ~ol}owlng values:

~ABLE 1 Interplanar Spacing D (A~) Relative Intensity 11.2 + .2 -~ m.
10.1 ' .2 -~ - m.
6.73 + .2 _______ w.
5.75 ~ .1 _________ w.
5.61 ~ --- N.
5.03 ~ .1 _ ____~__ w.

4.62 ~ .1 ~ -~ w.
4.39 ~ .08 --------- w.
3.a6 ~ .07 _________ V9-3.73 ~ .07 --------- m~
3.49 ~ .or ~ ---- w~ ~
(3.07, 3.00) ~ .05 -- ~ --- w.
2.01 ~ .02 ~ --- w.

The parenthesis around line~ 3.07 and 3.00 indicate that they are separata and distinct line~, but are often superimposed. These value~ were determined by standard techniques. The radiation was the K alpha doublet of copper, and a Gei8er counter ~pectrometer with a strip chart pen rec~rder was used. Peak heights and their positions as a funotion of 2 tLmes theta, where theta is the Bragg angle, were read from the spectrometer chart. From these, the relative Lnten-sities, 100I/Io, where Io is the intensity Or the qtrongest line .
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, ~3~'~33 or peak, and D the Lnterplanar spaoing in A, correqponding to the recorded line~, were estimated. The intensity in the table above i9 expre~sed as follows:

m - medium, w = weak and vs a very strong ZSM=11 l~ similar to ZSM-5 with the notable exceptioa that whereas the ZSM-5 zeolite contalns a doublet at about 10.1, 3073, 3.00 and 2.01, A. interplaning spacing, ZSM-11 shows a s~nglet at these valuss. Thi~ means that the cry~tal class of the ZSM-11 is different ~rom that of the other zeolite. ZSM-11 is tatragonal whereaY ZSM-5 tend3 to ba orthorhombic.

Different cationic form3 reveal substantially the same pattern with minor shi~ts in interplanar spacing and ~ariation of relative int~nslty.

Zeolite ZSM-11 can be used either in the alkali metal Porm, e.~. the sodium form, the ammonium ~orm, the hydrogen form or ~nother univalent or multivalent cationia ~orm. When used as a oatalyst lt will usually ~lrst be sub~ectad to thermal treatment tQ remove part or all of the organic constituent. It can alao be uaed as a catalyst in intimate combination with a hydrogenatin~ component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal quch as platinum or palladium where a hydrogenation-dehydrogenation function iq to be performed. Such component can be exchanged into the composition to the extent Al is in the structure, impregnated therein or phyqically intimately admixed therewith. Such component can be impregnated in or on to it by, in the case of platinum, treating the zeolite with a solution contalning a platinum metal-containlng ion. Thus, suitable platinum compoundq include chloroplatinic acid, platinous chloride and various compounds containing the platinum ~mine complex.

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The ammonium, alkylammonium and arylammonium forms can be converted to another Porm by thermal treatment, at a temperature of at least 700F for at least 1 minute and not greater than 20 hour3.
~hlla 3ubatmo~pheric pressure can be employed for the thermal treat-ment, atmospheric pressure i9 desired Por reason~ oP convenience.
The thermal treatment can be performed a~ a temperature up to about 1700-F. The thermally treated product i9 particularly useful in the cataly~i~ of certain hydrocarbon conversion reaction~.

~ hen employed either as an absorbent or as a catalyst the zeollte should be dehydrated, at lea3t partially. Thia can be done by heating to a temperature in the range of 200 to 600~C in an atmosphere, su~h as air, nitrogen~ etc. and at atmo~pherio, sub-atmo~pheric or 3uperatmospheric pre~sure~ ~or between 1 and 48 hours.
Dehydration can also be performed at room temperature merely by placin6 the ZSM-11 in a vacuum, but a longer time i~ required to obtain a ~ufPiqient amount Or dehydration.
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Z$M-11 according to the present invention can be prepaqred Prom a reaotion mixture qontainin~ a souroe oP sllica, R20, an alkali metal oxide, e.g. sodium, water, and no added alumnina, and having a compo3ition, in terms o~ mole ratio~ o~ oxides, falling wlthln the Pollowlng range~:

REACTANTS BROAD PREFERRED

2 2 _ 5 to 30 1O to 20 0~R20 = 0.Q to 6 0.09 to 3.0 B20.~R20 = 100 to 500 3OO to 400 wherein R20 i9 the oxide form of an organic compound of an element of Group 5-A oP the P~riodic Table and can be a compound containing ~ , :

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one butyl group, M i9 an alkali or alkaline earth metal, and main-taininS the mixture, at crystallization temperatures, untll crystals are ~ormed. No alumina i9 added, the only aluminium present occuring a~ an impurity in ~oms other component of the crystallization medium.

The chromium and/or iron ¢ontaining form of the zeolite can be prepared from a reaction mixture containing a ~ource Or silica, R20, an al~ali metal oxide, e.~. sodium, a chromium or iron compound, water, and no added alumina, and havin~ a composition, in terms of mole ratios of oxides, falling within the followin~ ratios:

REACTANTS ~ROAD P~EFE~ED
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2/ 2 = 5 to 30 lO to 20 M20/R20 , O to 6 0.9 to 3.0 Cr203 ~
2 3) 2 ~ 0.2 to l.O 0.2 to 0.4 H20~R20 = 100 to 500 300 to 400 whereln R20 i~ the oxide form of an organic compound Or an element o~ Group 5-A Or the Periodic Tabla and can be a compound contalning one butyl group, and M is an alkali or alkaline earth metal, and maintaining the mixture until crystal~ are ~ormed. A3ain, no alumina 19 added.

Preferably, crystallization is performed under pressure in an autoclave or static bomb reactor but can be carried out in polypro-pylene ~ar~ at 100C. The temperature may range ~rom 80C to 250'C, preferably 100-C to 200C, but at lower temperatures e.g. about 100C, crystallization time i~ longer. These times vary from about 6 hrs to 90 days. Thereafter, the crystals are separated from the liquid and recovered. m e composition can be prepared utilizing materials which ~upply the appropriate oxide. Such compo~itions .

1~3g`733 include 30dium 3ilioate, siliaa hydrosol, ~ilica ~el, qilicic aoid, sodium hydroxide, chromic potas~ium sulphate and ferrio ammonium sulphate. The organic compound~ can be any elemsnt o~ Group S-A such as nitrogen, phosphorus, arsenic, antimony. The preferred compounds are quaternary compound generally expre~qed by the following ~ormula:

R ~ +

R L -R ) or R4L

R

wherein L is an element oP Group 5-A of the Periodic Table, and each R i3 an alkyl or aryl ~roup havin~ between I and 7 (preParably.2 - 5) carbon atoms. Prererably at least one R group is butyl. ~hil~
normally each alkyl or aryl group will be the same, it is not necessary that each sroup havs the same number of carbon atom~ ir. the chain. In preparing an ammonium species, the organic substituted ammounium chlorlde or less preferably, hydroxide i3 u3eiul. In preparin~ the phosphonium species of the zeolite tetrabutylphQsphonium chloride i~ particularly de3irable as a means of incorporating the quaternary metal compound in the zeolite. In preparing an anmonium sp0cias tetrabutylammonium chloride or bromide or, less preferably, hydroxide is ussful. The other elements of Group 5-A behave similarly and thus the zeolite containln6 the same can be prepared by the same manipulative procedure ~ubstitutin~ the other Croup 5-A
metal for phosphorous. It 3hould be realized that the oxide can be supplied from more than one source. The reaction mixture can be prepared either batchwise or continuously. Crystal 3ize and crystalllzation time will vary with the nature of the reaction mixture employed and the crystallization conditionq.

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The quaternary compounds need not be used a3 such. They may be produced in situ by the addition of the appropriate precursors.
These precursors comprise a compound characterized by the formula R1~2R3L where R1~ R2 and R3 are 9elected from alky}~
3ubstituted alkyl, aryl substituting aryl, cycloalkyl, sub~tituted cycloalkyl and hydrogen and L i9 an element of group 5-A and a compound of the formula R4L where R~ 19 alkyl, sub~tituted alkyl, cycloalkyl, substituting cycloalkyl, aryl and substltuted aryl and L
i9 an electronegative group. According to a speoial ambodi~ent of the invention, the method o~ the invention can be praoticed u~ing the compound R1R~3L alone. In this case it i9 assumed that quaternary compound~ are not formed. m u9, in specific embodiments one may u~e as the source o~ R20, amines or phosphine3 either primary, seoondary or tertiary as well as diamines witout addition of any R4X.

Synthe3i~ can be ~acilitated by the presenae o~ at least O.OOt, preferably at least 0.01, more pre~erably at least 0.1 percent by weight (based on total crystalline product) oP seed ary~tals. The zeolite may be formed in a wide variety o~ partloular sizes.
Generally speaXing, the partlcles oan be in the form of a powder, a granule, or a moldedproduct, such as an extrudate having particle slze suf~ioient to pass through a 2 mesh~(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In ca3es where a catalyst is molded, such as by extrusion, the zeolite can be extruded before drylng or dried partially dried and then extruded.

~ hen used as a catalyst ZS~-ll according to the invention may be compos~ted with a matrix, as described in relation to zeolite ZS~-43 in our European speci~ication 0,001,695.

~ ~39~ 3 Employing the zeolite of this invention as a ca~alyqt, wAich may contain additional hydrogenation componentsl heavy p~troleum re~idual ~toc~s, cycle stocks, and other hydrocrackable charge stocks can ba hydrocracked at temperatureq between 400F and 815F u~in~
molar ratios of hydrogen to hydrocarbon c~.ar~e in the range between 2 and 80. The pre~qure employed will vary between 10 and 2,500 pqig and the liquid hourly spaoe velocity between 0.1 and 10.

Hydrocarbon crackin~ stocks can be cracked at a liquid hourly space veloaity betwesn about 0.5 and 50, a temp~rature between about 550F and 1100F, a pressure bstween about subatmospheric and several hundred atmospheres.

Reformin6 stock3 can be reformed employing a temperature betNeen 700-F and IOOO-F. The pressure can be between 100 and 1000 psi~ but iq preferably between 200 and 700 psig. The llquid hourly spacc velooity 19 generally between 0~1 and 10, preferably betwe~n 0.4 and 4 and the hydro~en to hydrocarbon mole ratio is generally between 1 and 20 preferably botween 4 and 12.

The zeollte can al~o be used Por hydroisomerizatioan o~ nor~al parafrins, when provided with a hydrogenation component, e.g., platinum. Hydroi~omerization is carried out at a temperature between 200- and 700F, preferably 300- to 550F, with a liquid hourly space velocity 0.01 and 2, preferably between 0.25 and 0.50 employing hydro~en 3uch that the hydFogen to hydrocarbon molc ratio i9 between 1:1 and 5:1. Additionally, the catalyst can be u~ed for olefin isomerization employing temperatures between 30-F and 700F.

Other reactions which can be accomplished employing the catalyst of this invention containing a metal, e.~., platinum, include hydrogenation~dehydrogenation reactions and desulfurization reactions, .
, ' . ` , ' ~ 39~33 olefin polymerization (oll~omerization) and other organic compound conversion such as the conversion of alcohols (e.g. methanol to hydrocarbon).

In the Examples whlch ~ollow adsorption data were determined as rOllOws:

A weighed sample of the aalcined zeollta was contacted with the deslred pura adsorbate vapor in an adsorptlon chambar, evacuated to <1 mm and contacted with 12 ~m Hs of water vapor and 20 mm ~g of cyclohexane and n-hexane vapor, pressures les3 than the vapor-liquid ~quillbrium pre~ ure of the respecti~e adsorbate at room temp~rature.
The pre ~ure was ~ept constant (wlthin about ~ 0.5 mm~ by addition o~ adsorbate vapor controlled by a mano~tat durin~ the adsorption period, which did not exceed about elght hour~. As the adsorbate was adsorbæd the decrease in prsssure caused the manostat to open a valve whlch admltted more adsorbate vapor to the chamber to restore ths above control pressures. Sorptlon was complete when the pres~ure chan~e was not su~lcient to activate the manostat. The increase in woight was calculated as the ad~orption capaclty o~ the sample in g~100g of calcined adsorbant.

Examples 1-4 A ~tarting gel reactlon mixture was prepared from sodium silicate (28.a% SiO2, 8.9S Na20, 62% H20), obtained commercially as "Q-brand,~
tetrabutylammonium bromide, sulfuric acid and water. Crystalllzation was carried ou~ in polypropylene ~ars at 210-F or in 2 litre qtainless ~teel pressure vessqls ~250~F). After crystallization, the solids were separated from any unreacted components by filtration and then water washed followed by drying at 230~F. The a~ountq o~ starting materials, identification of same, product compositions, and adsorption data are listed in Table 2.

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~397~3 Examples 5-15 .~ ~.. _ A starting ~el mixture was prepared from colloidal silica, tstrabutylammonium bromide, sodium hydroxide and water. Crystal-lization was carried out in propylene ~ars at 210~F or in 2 litre stainless steel pre~ure vessel~ (300F). After crystallization, the solid~ were separated from any unreacted components by filtration and then water washed followed by dryin~ at 230-F. The a~ount3 o~
starting materlals, identlfication Or same, product composltions, adsQrption data, and catalytic data are listed in Tables 3 (Ex~mpleq

5-8) and 3A (Examples 9-15 and 18).

Example 16 A startlng gel mixture was prepared from fume sll$ca (91.3%
S102), tetrabutylammonlum bromide, sodium hydroxide and watar.
Cryqtalllzatlon was carriod out in propylene ~ars at 210~. After ory~tallization, the solids were separated ~rom any unreaated components by filtration and then water washed followed by drying at 230-F. The amounts of startin~ materlals, identlflcation o~ same, product compo~itlon, and catalytlc data ars listed in Table 4.

Example 17 _ ;

A tartlng gel mixture was prepared from colloidal sillca, tetrabutyla~onium hydroxlde (40~) and water. Crystallization wa~ carrled out in propylene ~ar3 at 210-F. After crystallization the solld~ were separated rrom any unreacted components by ~iltration and then water washed followed by drying at 230F. The amounts o~
startin~ materials, identi~ication o~ same, product composition, and catalytic data are listed in Table 5.

~' ~ 1 3 9 ~ ~3 The data in Tables 2-5 show that the A1203 content (after drying) of the as-3ynthesized materials varied from 0.04 (Example 18) to 0.64 (Example 16). Most, however, ran8ed rrom 0.4 to 0.2 (Examples 1-3, 5-10, 12 and 14-17). It was also found that 3ynthesis in the pre3ence o~ ZSM-11 ~eed3 ylelded produots of hi~h crystallinity, as hi~h as 130~ in three days (Example 14).

amples 19-22 These examples illustrate the u~e of tetrabutylphosphonium chloride as the the source of the alkyl Group 5-A cation, and one example (22) addltionally incorporates triethanol amlne (to promote larger crystal growth) into the starting mixture, which i~ otherwise the same as that of Examples 1-5. me amounts of starting materials, identification o~ same, produot composition, adsorption data, and catalytlo data are llsted in Tablc 6.

The data presented in Table 6 show that the A1203 aont~nt (after dryin~) o~ the as~synthasized materials wa3 negll~ible. It is to be noted, with respcct to Example 22, that not onLy was triethanol aml~e introducsd to promote larger orystal growth, but orystalllzation was allowed to procaed for 50 days. X-ray ana}ysis was about 100%
ZSM-1t type zeolite.

Examples 23-34 A starting gel reaction mixture was prepared from sodium si}icate (28.8% SiO2, 8.9% Na20, 62S H20), tetrabutylammonium bromida, chromic potassium sulfate, sulfuric acid and water. Crystallization was carried out in polypropylene jars at 210~F, glass-lined stainlass steel autoclaves (300~F) or in stirred 2 1itar stainlesq steel pressure vessels at 250-300~F. After crystallization the solids were separated by filtration, water washed, and dried at 230F. m e amounts of starting material, identi~ication of same, product compo-sitions and adsorption data are listed in Table 7.

l~L39>;1'3d3 Examples 35-36 A ~tarting gel mixtura was prepared from sodlum silicate (28.0 SiO2m 8.~% Na20, 62% H20) tetrabutylam~onium bromide, ferric ammonium sulrata, sulfuric acid and water. Crystallization W29 carriad out in polypropyLene Jars at 210-F or in stirred 2 liter staiDless steel pres3ure vessela (300F). After cryatallization the solids were filtered, water washed, and dried at 230-F~ The amounts of startin~ materials, identification of same, produot compositions and adsorption data are listed in Table 8.

ample 37 This sxample illustrates its preparation oP a low alumi~a ZSU-11 through the use of a speoially prepared hi~h purity sllloa hydrogel. The silica hydrogel usad as a souroe of silica was prepared as ~ollows:

A. 2479 0c of tetraethylorthosilioate Si(OCH2CH3)4 782 cO ethanol 178~7 cc 4N HN03 Allowed to age for 1~2 hour at room temperature, then cooled to 38-43 F.

B. 233.3 cc NH40H~ cooled ~o 38-43Fo Solution B is added to A and mixed for 30 seconds. The resultant 6el is water washed and has 17.0~ solids.

Preparational detaila are ~i~en in Table 9.

, : ~ ' :~ ~1397~3 , rhe data in Table~ 7, 8 and 9 show that the A1203 oontent (after drying) of the as-synthe~ized material~ varied from 370 ppm (Example 37) to 0.30~ (Example 31). Most, however, ranged between 0.2 to 0.3 (Example~ 23-30, 32, 33 and 34). It was al30 ~ound that synthesis in tha pre~ence of ZSM-11 seed yielded product3 of high cr~F~tallinity, as hi~h a_ 115% in riYe days (Example 36).

Examples 38-44 Aliquots o~ the products of some o~ the previou~ Examples ~ere calcined at 1000~F and then ion exchanged with a solution o~ NH4Ct, rollowed by recalcination of the NH4 ZSM-11 to the H-~orm, of which the ~odium content was:

~a~e Material Na content, _ample(Mater1al o~ t ~) 38 Example 7 0.02 39 Example 15 0.02 Example 9 <0.01 41 Example 6 <0.01 42 Example 3 <0.01 43 Example 14 0.02 44 Example 12 .034 A 1.0 cc sample o~ each of the aliquot3 waq teqted for cracking of n-hexane at a liquid hourly 3pace velocity of 1.0 and a temperature of 1000-F. The S n-hexane converslon and the calculated relative cracking activity of the catalysts after 5 minutes on stream were:

ExampleConverqion 38 2.3 0.4 39 3.1 0.6 ~0 1.6 0.3 41 3.6 0.7 42 10.3 2.1 43 2.9 0.6 44 0.9 0.3 L39~733 The C~ -te~t is de3cribed in a letter to the editor entitled Superactive Crystalline Alumino~ilioate Hydrocarbon Cracking Catalystqn by P.B. ~eis~ and J.N. Miale, Journal of Catalyqt~, Vol.
4, pp. 527-529 (Augu3t 1965).

Mo~t of the aliquot~ were also testsd for oligomerization o~
propylene. In thi~ teqt propylene was paqsed over either a 0. 25g or a 0.5~ ~ample of the catalyst at a desi~n ~low ratlo o~ 100Q c¢/hr and a nominal temperature o~ 700~F. The re~ulting wei~ht haurly ~pace veloclty was about 3.5 for the 0.50 5 loadlng and 7 ~or the 0.25g loadlng. The actual ~HSV and catalytic data calculated on a total recoYery basi~ ware:

Conversion Selectivity Example WHS~ wt ~ ~ on C3 Converted C4, C5~ C6~-38 3.8 93.2 94.8 68.5 48.1 39 3.7 91.5 95.5 70.3 47.3 3.7 90.4 96.0 70.8 47.8 41 3.7 92.8 93.6 69.7 50.8 42 7.5 91.8 93.4 64.9 43.8 43 7.4 85.4 96.9 62.9 36.8 ampleq 45-50 Allquot3 o~ the producta o~ Example~ 23, 26, 27, 31 and 36 were sub~ected to the C~ test for cracking activity. In addition, the products of Examples 23 and 26 ware te~ted for propylene oligomeri-zation. ~oth teqtq were those employed in Examples 38 to 44, all pertinent detailq, i.e. condition~ o~ treatment of the catalyst, compo~itions after treatment and calcination, test reqult~ and the like, are set ~orth in Table 10.

~39~3;3 The data ~et forth in Table 10 reveals that n-Hexane conversion after 5 minute~ ranged ~rom 0.3 (Example 48) to 17.1 (Example 46) wt per cent. C~values ranged after 5 minutes ~rom 0.06 ~Exa~ple 48~
to 3.6 (Example 46). The best n-hexane conversion and c~ -valuea were obtained ~rom the product o~ ori~inal Examp:Le 26.

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1139~33 Starting materials, gms A. Sodium Silicate 70.0 140 455 70.0 (28.8~ SiO2, 8.9% Na O, 2~
H2O 80.0 160 520 80.0 Colloidal SiO2 (3~% SiO2) NaOH
B. Tetrabutyl-ammonium bromide 17.4 34.8113.1 17.4 H2SO4 7.2 14.4 46.8 3.6 H2O 80.0 160 530 80.0 C. ZSM-ll Seeds (82.9%) Starting Co~)ositions, moles (TBA)20 1.0 1.0 1.01.0 Na2O 1.0 1.0 1.02.28 Na SO4 2.57 2.57 2.57 1.28 Si~2 12.0 12.0 12.012.0 Crystallization Conditions Stirred Temp F 210 210 250210 Time, days 15 15 5 16 X-Ray Analysis ZSM-ll ZSM-ll ZSM-ll ZSM-ll 105~ 105% 150%110%
Product Compositions wt. %
C 8.97 N 0.89 0.66 0.650.67 Na 1.36 1.30 1.402.15 SiO2 81.04 80.07 82.179.8 Ash 85.9 83.4 84.984.5 A123 0.18 0.21 0.160.33 Molar Ratio SiO2/A12O3 765 648 872411 Adsorption wt ~ (1000F Calcination) Cyclohexane 7.1 6.2 3.8 3.7 n-Hexane 10.0 9.5 8.2 8.4 H2O 13.5 14.4 8.411.8 Surface Area m /gm 327 328 256 (1) TBA = Tetrabutylammonium+

~ , :1~3g`733 Example 5 6 7 8 Starting Materials, gms A. Sodium Silicate (28.8~ SiO2, 8.9% Na2O, 62% H2O) H O 50.0 100 50.0 280 Colloidal SiO2O
(30% SiO ) 190 380 190 1064 NaOH 2 14.629.2 14.6 81.76 B. Tetrabutylammonium Bxomide 19.038.0 19.0 106.4 H2O 24.048.0 24.0 134 CO ZSM-ll Seeds (82.9~) 9.6 0.5 1.68 Starting Co ~sitions, moles (TBA)20 1.0 1.0 1.0 1.0 Na2O 6.2 6.2 6.2 6.2 Na2 4 Sio2 32.2 32.2 32.2 32.2 Crystallization Conditions Temp F 210 210 210 250 Time, days 11 12 18 7 X-Ray Analysis ZSM-ll ZSM-ll ZSM-ll ZSM-ll 135% 135% 120% 145%
Product Compositions wt %
C 7.90 N 0.660.851.16 0.57 Na 1.331.751.70 2.0 SiO2 78.782.080.45 83.2 Ash 85.585.3 85.2 85.9 A123 0.100.10 0-09 0.12 Molar Ratio SiO2/A12O3 1338 1394 1520 1176 Adsorption wt ~ (1000 F Calcination) Cyclohexane 5.9 7,0 3.4 n-Hexane 10.0 10.6 7.3 H2O 13.3 13.2 9.4 Surface Area m /gm 336 367 227 (1) TBA = Tetrabutylammonium~

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~1 0 u~ h 1~L3~733 Example Starting Materials, gms A. H2O 195 Colloidal SiO2 (30~ SiO2) NaOH 5.04 Fume Silica (91.3~) 48.0 B. Tetrabutylammonium Bromide13.1 H2O 48.0 C. ZSM-ll Seeds (82.9~) Starting Co~)osition, moles (TBA)2o 1.0 Na O 3.1 SiO2 36.0 Crystallization Conditions Temp F 210 Time, days 41 X-ray Analysis ZSM-ll 100%
Product Compositionl wt %
N 0.63 Na 1.29 Si2 77.09 Ash 83.13 A123 0.64 Molar Ratio SiO2/A12O3 205 Adsorption, wt ~ (1000F Calcination) Cyclohexane 6.4 n-Hexane 8.1 H2O 4.2 Surface Area, m /gm 312 (1) TBA = Tetrabutylammonium ~139`~33 .

Example 17 Starting Materials, gms A. H2O
Colloidal SiO2(30% SiO2) 132.8 NaOH '2`
Fume Silica (91.3~) 40% TBAOH
B. Tetrabutylammonium Bromide 64.8 H2O 34.2 C. ZSM-ll Seeds (82.9~) 0.3 Starting Co ~ ~sition , moles (TBA)2O 1.0 Na20 0 . O
SiO 13.3 H2o2 180 Crystallization Conditions Temp F 210 Time, days 9 X-Ray Analysis ZSM-ll Product Composition, wt %
N 1.27 Na 0.16 SiO2 78.1 Ash 80.7 2 3 0.09 Molar Ratio SiO2/A12O3 1475 Adsorption, wt % (1000F Calcination) Cyclohexane 13.8 n-Hexane 14.3 H2O 29.1 Surface Area, m2/gm 522 (1) TBA = Tetrabutylammonium (2) TBAOH = Tetrabutylammonium hydroxide solution (40~) i~39733 Examples _ 20 21 22_ Starting Materials, gms A. Sodium Silicate 50 150 300 50 (28~8~ SiO2, 8.9~ Na O, 62~ H20)2 B. Tetrabutylphos-phonium chloride 25 75 150 25 H2S~4 (96~) 5 15 30 4.8 C. Triethanol Amine 100 Starting Co~Josition, moles (TBP)2O .0424 .1272 .2544 .0424 Na O .0718 .2154 .4308 .0718 Si~2 .2396 .7188 1.4376 .2396 H2O 15.61 46.83 93.6~ 35.06 X-Ray Analysis ZSM-ll ZSM-ll2SM-ll ZSM-ll 95% 90~ 105~ 100%
Crystallization Conditions Temp F 212 212 212 212 Time, days 19 10 11 50 Product Composition, wt ~
P 54 .50 .44 .22 Na 1.1 1.79 .39 SiO 96.4 99.5 94.3 93.7 A12~3 .14 .15 .13 .17 Molar Ratio SiO2/A12O3 1169 1069 1257 949 (1) TBP = Tetrabutylphosphonium +

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~:~3g7~3 Examples 35 36 Starting Materials, gms A. Na Silicate (28.8% SiO2, 8.9% Na O 62% H O) 74.6 484.9 B. FeNH4(So4)2 l2H2o 2 1 13 65 H2O 105 682.5 C. Tetrabutylammonium bromide 20.5 133.25 D. ZSM-ll Seeds (gms, solids) 2.0 Starting com~ition, moles ~TBA)20 1.0 1.0 Na2O 1.51 1.50 Na254 1.86 1.86 Fe O3 0.30 0.30 SiO2 11.26 11.26 Crystallization Conditions Stirred Temp F 210 300 Days 104 5 X-Ray Analysis ZSM-ll ZSM-ll 75% 115 Product Composition, wt % 1000F
N - 0.55 Na 2.98 2.27 Fe 5.2 5.2 SiO ~5.0 86.22 A h2 99.5 98.4 A123 0.16 0.27 Product Composition, moles(2) R2O - 1.37 Na2O 4.57 3.44 3 3.24 Al O3 0.11 0.18 Si~2 100 100 Sio2/A12O3 909 555 Adsorption wt ~ 1000F 1000F
Cy-C 5.1 6.2 n-c66 9.1 H2O 3.8 18.3 Surface Area m /gm 275 Molar Ratio SiO2/A12O3 903 543 (1) TBA = Tetra~utylammonium (2) Calculated as 100% anhydrous solids il39~33 Example 37 Starting Materials, gms A. FeNH4(SO4)2-12H2O 59.8 H2SO4 13.6 ~2 68~.5 B. Tetrabutylammonium bromide133.25 C. (ETO)4Si Gel (17.0~ SiO2)821.47 NaO~ 55.68 H2O 35.97 D. ZSM-ll Seeds (gms, solids) 2.0 Starting Composition, moles (TBA)2o 1.0 Na~O 1.51 Na SO4 1.86 Fe2O 0.30 sio23 11.~6 Crystallization Conditions Stirred Temp F 300 Days 5 X-Ray Analysis ZSM-ll 125%
Product Composition, wt ~
N 0.55 Na 1.4 Fe SiO 76.0 Ash2 85.0 A123 (1) 370 ppm Product Composition, moles R2O 1.55 NazO 2.41 2 3 3.04 2 3 0.03 SiO2 100 Molar Ratio SiO2/A12O3 3.333 Adsorption, wt % 1000F
Cyclohexane 6.9 n-Hexane 10.4 Watsr 16.2 Surface Area, m2/gm 306 (1) Calculated as 100% anhydrous solids 1139~7~3 Examples 45 46 47 Base Description material of material of material of Ex. 23 Ex. 26 Ex. 27 Pre-Treat TlO-1000F TlO-1000F TlO-1000F
10~ NH4Cl Treat 190-195F 4xl hr 3xl hr 3xl hr lx2 hrs lx2 hrs 10% NH4Cl Treat 16 hrs 160F (120F) 16 hrs 16 hrs Composition, wt %
Na 0.14 0.33 0.10 Cr 1.9 2.0 0.15 SiO2 92.9 91.3 95.8 Ash 98.1 98.1 100 A123 0.23 0.55 0.22 Product Composition, moles(l) R20 - _ _ Na2O 0.19 0.46 0.14 Cr2O3 1.18 1.26 0.09 Fe23 A123 0.15 0.35 0.14 SiO2 100 100 100 Molar Ratio SiO2/Al~O~ 667 286 714 ~- Test lOaOF
n-Hexane Conv. wt %
5 min. 7.7 17.1 0.7 25 min. 5.4 14.4 0.5 -Value 5 min. 1.5 3.6 0.13 25 min. 1.1 3.0 0.10 Propylene Conv. wt %
700F 31.1 71.0 Selectivity C4= 19.7 31.7 C5+ 75.2 64.0 (1) Normalized to 100% solids ~ , . . .

~39`~33 TABLE 10 Continued .....
Examples 48 49 50 Base Description material o~ material of material of Ex. 31 Ex. 35 Ex.36 Pre-Treat TlO-1000F TlO-1000F TlO-1000F
(185-190F) (185-190F) 10~ NH Cl Treat 190-1~5F 3x2 hrs. 3xl hr lxl hr ` lx2 hrs 2~2 hrs 10% NH Cl Treat 160~ 16 hrs 18 hrs 16 hrs (145F) (142F) Composition, wt %
Na 0.20 0.22 0.34 Cr 0.79 ~e 5.4 Fe 5.1 SiO2 91.3 87.1 89.2 Ash 99.8 99~5 99.0 A123 0.36 0.18 0.24 Product Composition, moles (1) Na2O 0.28 0.33 0.49 Cr203 0 . 09 23 ~ 3.34 3.07 A123 0.23 0.12 0.16 SiO2 100 100 100 Molar Ratio SiO2/

~-Test 1000F
n-Hexane Conv. wt ~
5 min. 0.3 1.8 8.7 25 min. 0.2 0.7 3.8 -Value 5 min. 0.06 0.34 1.73 25 min. 0.04 0.13 0.75 Propylene Conv. wt %

Selectivity c5+

(1) Normalized to 100% solids ~ . ~

Claims (11)

Claims:

1. Zeolite ZSM-11 having the composition, in terms of moles of oxides:
(0 - 10) M2/nO : (0 to 0.5) A12O3 : 100 SiO2 in which M is at least one cation of valence n.

2. A zeolite according to claim 1 which contains at least 0.001 moles of A12O3 per 100 moles of SiO2.

3. A zeolite according to claim 2 having the composition:
(0 - 10) R2O : (0 - 10) M2/nO : (0 - 0.5) A12O3 : 100 SiO2 in which R2O is the oxide form of an organic compound containing an element of Group 5A of the Periodic Table, said compound comprising an alkyl or an aryl group having from 1 to 7 carbon atoms at least one of which is ethyl or butyl, and M is an alkali or alkaline earth metal.

4. A zeolite according to claim 3 wherein R is tetra-butylammonium and M is sodium.

5. A zeolite according to claim 1, 2 or 3 wherein M is hydrogen, ammonium and/or rare earth.

6. A method for preparing zeolite ZSM-11 as claimed in claim 1 which comprises preparing a reaction mixture containing a source of an alkali metal oxide, an oxide of silicon, R2O and water and having a composition, in terms of mole ratios of oxides, falling within the following ranges:
SiO2/R2O = 5 to 30 M2O/R2O = 0.0 to 6 H2O/R2O = 100 to 500 wherein R2O is the oxide form of an organic compound of an element of Group 5A of the Periodic Table, said organic compound comprising an alkyl or aryl group having between 1 and 7 carbon atoms, M is an alkali or alkaline earth metal, and maintaining the mixture until crystals of said zeolite are formed.

7. A method according to claim 6 wherein R2O comprises at least one ethyl or butyl radical.

8. A method according to claim 6 wherein the reaction mixture has the composition:
SiO2/R2O = 10 to 20 M2O/R2O = 0.09 to 3.0 H2O/R2O = 300 to 400

9. A method according to claim 6, 7 or 8 wherein R2O
is a quaternary compound.

10. A method according to claim 6, 7 or 8 wherein R is a tetrabutylammonium or tetrabutylphosphonium.

11. A method of converting an organic charge which comprises contacting the same under conversion conditions with a catalyst comprising zeolite ZSM-11 as claimed in claim 1, 2 or 3.