CA2062947A1 - Low-aluminum boron beta zeolite - Google Patents

Abstract

A crystalline low-aluminum boron beta zeolite is prepared using a diquaternary ion as a template.

Description

-W O 91/00777 1 2 ~ 7 pC~/US90/0376 01 LOW-ALUMINUM ~ORON BETA ~EOLITE
~2 03 ~AC~GROUM~ OF T~E I~IV~N~ION

05 Natural and synthetic 2~011'-ic crYs~ i n ~ alu;r~ osilicat:~s 06 are u~eful as catalysts and adaor~nts. These 07 aluminosilicat~s have diati;lCt c.ry,tal structur~s which are 08 demonst~ated by X-ray dif~raction. The crystal structur~
09 defines cavities and por2s ~hica are c;~arac-coristic o^ t.ie different s~ecies. ,he a~.,orot~.ve ~nd c~ t~ r pro~ r~ies 11 of each crystallin- alu~ ^sil .a.e a-~ i~e e:-~l?.zd n par~ . :
12 by the dimensions o~ its ?ores and c;3vi~c12s~ Thus, ~he 13 utility o~ a partisular Z~011~2 ii- a parti~uldr appllcati on 14 depends at least partly on ita c~y.,.al ,tructure.
16 ~ecause of their unique mol~cular sieving characteristics, 17 as well as their catalytic properties, crystalline 18 alu~inosilicates are e~peei~l~y u~eful in such ~pplications 19 a5 gas drying and ~eparation and hydro~arbon conversion.
Although many di~ferent crystalline aluminosilicates and 21 silicates have been disclosed, ther~ is a continuing need 22 Xor new zeolites and silicates with desirable properties for 23 gas ~eparation and drying, hydr~carbon and chemical ; .

2~ conversions, and other applications.
~5 26 Cry5talline aluminosilicates are usually prepared from 27 a~ueous reaction mixtures containing alkali or alkaline 28 earth metal oxides, ilica, and alumina. "Nitrogenous 29 zeolites" have been prepared from reaction mixtures containing an organic templating agent, usually a . .
31 nitrogen-containing organic cation. By varying the :: 32 synthesis conditions and the composition of the reaction : 33 ~ mixtu~re,~different zeolites can be formed using the same :~ 34 ..
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WO 91tO0777 2 ~ ~ 2 ~ ~ ~ PCI/US9i~10:~76~

ûl templating agent. Use of N,M~N-trimethyl cyclopentyl-02 ammonium iodide in the preparatiorl of Zeolite SSZ-15 03 molecular sieve is disclosed in U.~. Patent No. 4,610,854;
use of l~azoniaspiro [4.4] nonyl bromide and N,N,N-trimethyl ,~5 neopentylamznoniu~ iodide in the preparation of a molecular 06 sieve te~med "Losod" is disclosed in Helv. ChimO Acta 07 (1974); Yol. 57, p. 1533 (~. Sieb r and W. M. Meier); Us2 O r 08 quinuclidinium co~pounds to pr2pare a zeolite termed "NU-3"
o9 is disclos~d in Europ2an Pate~t Publication No. 40016; use 1~ of 1,4-di(1~ onia bicy~lo~2.2.2~o~tan~) lo-~Y2r al~yl ll ~o~.pounds ~n.th- p.i~par~tion or ~201ite SiSZ-16 molecular 1~ si~v~ is disclos~d in U.S. Pa~s~ No. 4,508,837; use or 13 N,N,N-triai~yl-1-adaman,amine in the preparation of Z201ite 14 SSZ-13 mole~ular sieve is disclosed in U.S. Patent No.
4,54q,538, ~nd for SSz-24 in U.S. Patent No. 4,665,110.

17 ~eta zeolite is a known ~ynthetic ~ry~italline 18 alu~inosilicate oriqinally de~ierib@d in U.~. Patentsi Nos.
19 3,308,069 and Re 28,341 to whi~h reference ~s made for ~o further detail6 of this zeolite, it~ preparation and 21 properties.

23 Synthetic zeolitic crystalline borosilicates are useful as 24 ~atalysts. Meth~ds for preparing high silica content 25 zeolites that contain framework boron are known and 26 diiclosed in U.S. Patent No. 4,269 j813. The amount of boron 27 contained in the zeolite usually may be made to vasy by 28 incorporating different amounts of borate ion in the zeolite 29 forming solution.

3~ :
31 U.S. Patent No. 4,788,169 describes a method for preparing ~i2 beta zeolite containing boron. ~his boron beta zeolite 33 contains 7000 2art6 per million of aluminum according to the analyses given therein.

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i~' ~'"'' ' " ' " ';`"'' i '; ;' "' i~ ""..";i~ ':' , " , ~,.,. " ,, ,"" ,j ", ,, ,"" ,; ,, "~, ,jj, ~ " ",,, ,j,, W09~/nO777 3 ~ O S 2 9 ~ 1 Pcr/US90/0376 01 European Patent ~pplication No. 188,913 claims c~mpos~tions 02 f~r various intermediate pore boron-containing zoolite~ with ~ an aluminum cont~t of less than 0.05~ by weight.
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Q5 SUMMARY OF THE INV~NTION

07 ~e have pr~2ar~d a family of crystalline boro~ilicate 08 molecular ~ieYes with unique properties, ref~rred to herein ~9 as "Low-Aluminum Boron seta Z201ite" o~ si~ply ~s)~eta"~
1~ Thus, accor~ing to th~ pr2sent invention, a z201ite 1I composition, (~)Betar is provided. Al~o, advantageous uses 12 ha~e been discov~red. . .
13 :
14 ~s)seta has a mole ratio of an oxide selected from silicon oxide, ger~anium o~ide, and mixtures thereof to an oxide 16 selected from boron oxide or mixtures o boron 02ide with 17 aluminum, gallium, or iron oxide, greater than about 10:1 18 and wherein the amount of aluminum i6 le~s than 0.10% by l9 weight and h~ving the X-ray diffract;on lines o~ Table l(a) b~low. An ~luminu~-fre* boron beta zeol1te ca~ also be made 21 u~in~ the novel method disclosed herein. The amount of 22 aluminum contained in the zeolite depends si~ply upon the 23 aluminum impurity present in the ~ilica source.

2S Thi~ zeolite further ha~ a composition, as ~ynthesized and ~ in the anhydrous ~tate, in tcrm~ of mole ratios of oxides as 27 follows: (1.0 to 5~0)Q~0 (Ool to 2.0)M2o W203:(greater than ~ iO)YV2 wherein M is an alkali metal cation, W i~ ~elected 29 from boro~, Y is ~elected f~om ~ilicon, germanium and ~ixtures thereof, and Q is a diquaternary ammonium ion, or 31 mixtures of diquarternary ammonium cation, and 32 tetraethylammonium cation.

" ' :: ~ ~ : . r: . . .

2 0 6~9 pcrlus9o/o376a 01 ~B)~eta zeolites preferabl~l have a sili~a boria ratio 02 typically in the range of 10:1 to about lO0:1. Higher mole ~3 ratios can be o~tain~d by tr~ating th~ 2~01it~ ~ith 04 chelating agents or acld~ to ~x~ract boron f.o~ th2 zeolite 05 lattice. The sil~ o-~ ncl~ r~t o czn al~ b- ~ncreas~d o~ by ~sin~ silicon and carbon halides and other similar 07 compounds. Th~ boro~ in th2 c-vs~llin~ n~t~o~ .y also be 08 repl~ced by aluminum, galliu~ o~ ir~. Proc~ur~s fo~
09 inc~orporating alu;~ a - c~ e:~ in IJ.S. ?a~-nt Nos.

4,559,315 and 4,550,0~ hic~ a. 2 h~r?~ co-~r2~d hy 11 reference.

1~ A method for pre2arin~ _o-or. ~e ~_oll~e i~ descri~ed in 14 U.S. Patenc No. ~,7~,lj9. A te.raethyl ammonium template is used to make this z201ite which contains 7000 parts per 16 million of aluminum. Th~ methGd described in U.S. Patent 17 No. 4,788,169, however, cannot be used to make boron beta 18 zeolite co~taining less ~han 1000 part~ per million 19 alu~inum. Additionally, a low-alumi~um boron beta zeolite 2~ cannot be made by replacing the alumi~um with boron in the 21 synthesi2ed boron beta zeolite structure. Successful 22 preparation of the low-aluminum boron beta zeolite requires 23 using a new 8ynthe~is metho~ described herein.

Aocording to one ~mbodiment of the present invention, a 26 method is provided for making (B)beta zeolit~s, comprising 27 preparing an aqueous mixture containing sources of a 2~ diquaternary ammonium ion, an oxide selected from boron 29 oxide, and an oxide selected from sili~on oxide, germanium :~ :
oxi:de, and mixtures thereof, and having ~ ~omposi~ion, in 31 term6 of mole ratios of oxides, falling within the followinq ~32 range : YO2/W~O3,:10:1 to 100:1; wherein Y is ~elected from silicon, germanium, and mixtures thereof, W is ~elected from 3~

:

W~9~/00777 5 2 ~ ~ ~ 9 4 7 PCl/US90/03764 01 boron, and Q is a diquat~rnary ammonium ion; maintaining the 02 mixture at a t~mperature o~ at l-a~t 100C until the 03 ~rystals ~f said z~olite are ~orm~d; ilnd rlocovering 6aid 04 crystals.

06 Among other factors, the present invention is based on our 07 finding tha. low-aluminu.~ 'vo;on ~.a z~olite can be ~8 made using a diquat~rn_r~ ~m~onillm tetn~late. The structure og of this zeolit i, ~h2 S'7~'17 ~ h~ hvc.~n ~e~a ~ 7L2 structure ~yn.nesized using ~he ~.raethyl ammonium template 11 in U.S. Pat;ont ~o. i,733,1~3. ~ur~risin$1y, ~e haY~ found 12 that the amount o. alu~inum inco.~o.aLi~d in,o ~his s~~ucLure 13 cin be decreas2d by usinc a diff~r~nt to~olat~7 than the 14 tetraethyl ammonium tem21~o used in U.S. Paten~
15 No. 4,788,169. we have also found that thi~ zeolite hi~s 16 unexpectedly outstanding hydrocarbo~ conversion properties, ::

~7 particularly including refor~ing properties with high 6ul~ur 18 toleranc~.

DETAILED DESCR~PT~ON OF THE ~NVENTION

22 ~)Beta zeolites, as ~ynthesized, have a ~rystalline structure whose X-ray powaer dif~raction pattern shows the 24 following characteristic lines:

~8 : ~33 ' ~ ' : ~':
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WO 91/00777;, .,; ~ ~ PCl/VS90/0376'1 20~2~7 01 TABL~ l(a) 0~ 2 ~d~n100 x I/Io Shape O ~ __ , ,,,, 3~ 7 .711. 5 25 Broad 06 18 . 404 . 82 8 Yery Broad ~7 21 . ~4 .1~ 18 ~)8 22 . 533 . 95 100 ~9 27 . ~03 . 24 lO
28 . 923 . 10 ~ Broad 11 29 . ~02 . 97 9 1~ Typical (~ ta borosilicate and boroaluminosilicate zeolites have the x-ray diffraction pa~tern of Tables 2 and 16 4 below. The d-spacings are shown in Table 8 and 17 de~on trate framework ~ubstitution. Calcined (B)Beta has a 18 typical pattern as shown in Table l~b).
~ g TAE~L13 1 ~b) 22 ~ ~ d/n100 x I/Io Shape 7.7 11.5 85 Broad 26 13 . 5~6 . 52 9 :27 14.~75.g6 12 13road -20: ~ 18 . 50 4 . B0 3 Very Broad 2g ~21.834.07 15 2 2 . 8 73 . 8 9l O 0 B r o a d 31 ~ 27 . 3B~3 .~26 10 29 . 3:03 . 05 6 Broad : -33 ~ 30;. 0B ~ 2 .97 ~ ~ 8 34~

WO91/00777 ~CT/VS90/03764 0 6 2 9 ~ j~

01 The X-ray powder diffraction patterns were det~mined by 02 standard techniques. Th~ radiation was the K-alpha/doublet 03 of copper and a Ecintillation counter spectrometer with a 04 strip-chart p~n recorder was used. Th~ p~ak heights I and 05 the p~sitions, as a function of 2 e wh2r~ 0 i~ the Bragg 06 angle, were read from the Eipectrometer chart. ~rom these 07 mPasured values, the relative intensities, lOOI/Io, where Io 08 is the intensity (p~ak h2ight) of the ~trongest peak, and 09 d/n, related to int-rplanar spacings in Angstroms 10 eorr~sponding to the record2d pea~s, can b2 calculat~d. The 11 X-ray difrraction pattern of Table l(a3 is charaoteristic of ~2 (~)~eta zeolites. Th~ ~olite produc~d by exchan5ing the 13 metal or other cations pr~sent in the zeolite with various 14 other cations yields substantially the same diffraction pattern although there ean be minor ~hi f ts in interplanar 16 6p~cing and minor variations in relati~e int2nsity. Minor 17 variations in the dif~raction pattern can also re~ult from lB variations in the organic Gompound used in th~ preparation 19 and ~rom variations in th~ silica-to-boria mole ratio from ia~ple to ~iample. Calcination can al~io ~ause minor shift6 21 in the X-ray di~ra~tio~ patt~rn. Notwithatanding these 22 minor perturbations, th~ basic crystal lattice structure 2~ re~ains un~hanged.

(B)Beta zeolites can be suitably prepared from an aqueous ~6 solution containin~ 60urces of an alkali metal borate, a 27 bis~1-Azo~ia, bicyclo~2.2.2~ octane~ alkane diquat2rnary 2a ammonium ion, and an oxide o~ silicon or germanium, or 29 mixture of the two. Ths reaction mixture should have a composition in terms of mole ratios falling within the 3~ following ranges:

33 :
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WO 91/00777 ` r 8 PCr/U!~i901~3764 2~6~

01 ~road Preferred o~i ~ Y2/~23 10~ O 30-~00 ~4 OH/YO~ C.10-1.0 0.25 0.50 ~5 Q/~2 ~~-;~ 0.25-0.35 06 ~/YO2 ~.05-0.300.05-0.10 07 H2O/YC~ 15-300 25-50 08 Q/Q+~ 0.30-3.9~0.60-~.80 ~9 wherein Q i~ a dlyu~,aa{-i- a~ o~,iu.~ ion, or mi~ure with 11 tetramethyla~m3niuin Ca~io?., .~ ls silic~n, g~ nium or ~oth, 12 and w is ~oron. .M is ~ ~l,;ali ~z~7, pr2. erably aodium.
13 The organic comool~nd ~hich acts ~ a sourco c_ the 14 quaternarv ammonium ion employed can provide hydroxide ion.
16 When using the quaternary ammonium hydroxide co~pound as a 17 template, it has al~o been found that purer forms of (~)~eta 18 are prepared when there is an excess of compound present 19 relative to the amount of alkali metal hydroxide.
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2~ The bis(1-~zonia bicyclo~2.2.2]oct2ne) a' ~ alkane ~2 diquater~ary ammonium ion component Q/ of the 23 cry~ta~llization mixture, i~ derived from the quaternary 24 ~mmonium compound. Preferably, the diquaternary ammonium ion is.derived from a compound of the formula:

a ~ ~ N-~CH2)4 ~ N 2I o~ 20H

31~
~2~ ~ The:quaternary ammonium comDounds are prepared by methods 3:3 :~known in the art, an example of which can be found in U.S. ::~
34 ~:N:o- 4,508,837. ~ ;

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WO91/0~777 9 2 ~ ~ 2 9 ~ 7 PCT/Us90,0376~

Dl The r~action ~i~t~r~ is proparod using standard zeolitic 02 preparation techniqu~s. Sourcos oE bo~on for the reaction 03 mixture incl~d~ borosili~a,o gl~ss2a and most particularly, 04 ~ther reactive borat2s and bora.e zst-rs. Typical ~ources 05 of silicon o.~id~ i~clu~-- ài~ c~S, ~'lic2 h~-drcgPl, ~ilicic 06 acid, colloidal silic~ tra-alk~ rthosilicates, and 07 silica hydroxld;~s.
08 .
09 The reaction mi~ur2 :is ~ai.~ained at an el-~vat~d te~pera~l~rD un~ti~ .r~s~'; o~ t'~ ol~ r~
11 The t~mp2ra~u ~s ~uri.l~ h~ h~i_ c h~ a' _r~s~;alli~a'cion 12 ~tep arP typically ~alntain2d lro~ a~ 0~C to a~out 13 200C, pr~2ra~1y irO~1 d~Ou~ ~ ~O aDou~ 170~C and most 14 preferably rrom abou~ 13~'C ~O about lS~DC. The crystallization period is typically Sreater than ~ne day and 16 preferably from about three days to about ~even days.

18 The hydrothermal cry~tallization is conducted unde~ pressure 19 and u~ually in an autoclave 80 that the rea~tion ~ixture is 8ubje~t t~ autogano~s pressure. The reaction mixtur2 can be 21 stirred during crystallization.
2~ .
2~ Once the zeolit9 crystals h~vo for~ed, tha solid product is 24 separated from the r~action mixture by s~andard mechanical separation techni~ues suCh aQ filtration. The crystals are 26 water-washed and then dried~ e.g., at 90C to 150C from B
27 to 24 hours, to obtain the as synthesized, (B)~eta zeolite 28 crystals. The drying ~tep can be performed at atmospheric 29 or subatmospheric pressuces.
:
~; During the hydrothermal crystallization step, the (~)Beta ~2 crystals can be allowed to nucleate spontaneously ~rom the reaction mixture. The reaction mix~ure can also be seeded with (B)Beta crystals both to direct, and accelerate ~he ~: ' , ~

WO9l/00777 ~ 10 PCT/US90/0376 01 crystallization, as well as to ~i~lmize the formation of 02 undesir~d alumino~ilicate contaminants.

o~ The synthetic (B)Beta zeolites can be used as synthesized or 05 can be thermally trea~ed (calcined). Vsually, it i5 06 desirable to remove the alkali metal cati~n by ion exchange ~7 and replace it with hydrogen, ammonium, or any desired metal 08 ion. The zeolite can be leached with chelating agents, ~9 e~g., EDTA or dilute acid ~olutions, to increas~ the silica:bo~ia mole ratio. The zeolite can be used in 11 inti~ate combination with hydrogenatlng components, s~c~. as ~2 tungsten, vanadiu~, molybdenum, rhenium, nic'cel, ~o~al~, 13 chromiu~, mang2nes2, or a noble met~l, such as p~lladiu~ o~
1~ platinum, fo. tho~2 applications in whi~h a lS hydrogenation-dehydrogenation function is desir~d. Typical 16 replacing cations can include metal cations, e.g., rare earth, ~roup IIA and Group VI~I metals, as well as their 1~ ~ixt~res. Of ~he replacing metallic ~ations, cations of lg ~etals ~uch as rare earth, Mn, Ca, Mg, zn, Cd, Pt, Pd, Ni, C, Ti, Al, ~n, Fe, and Co are partic~llarly preferred.

22 The hydrogen, ammonium, and metal components can be 23 exchanged into the zeolite. The zeolite can also be 24 impregnated with the metals, or, the metals can be physically intimately admixed with the zeolite using 26 standard methods known to the art. And, the metals can be 27 occluded an the crystal lattice by having the desired metals 28 present as ions in the reaction mixture f rom whlch the 29 (~)3eta zeolite is prepared.
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31 Typical ion exchange techniques involve contacting the 32 synthetic ze~lite with a solution containing a salt of the 33 desired replacing cation or cations. Although a wide :~
3~ variety of salts can be employed, chlc,rides and other '~

WO 91100777 11 2 0 ~ ~ 9 ~ ~ P~/US90103764 o~ halides, nitrates, and sulfates are particularly preferred.
02 Representative ion exchange techniques are disclosed in a wide ~ariety of patents including U. S . Nos . 3 ,140, 249;
3,140,251; and 3,140,253.

oç Following contact with the sal~ solution of the desired ~7 replacing cation, the zeolite is typically washed with wa~er 08 and dried at temDeratures ranging from 6S0C to about ~9 315C. A~ter w~shing, the zeolite ca~ be cal~ined in air or 1~ inert gas at tem~eratures ranging from about 200C to 820C
11 for periods of ti~e ranging from 1 ~o 48 hours, or more, to 12 produce a catalytically active product ~specially use$ul i~
13 hydrocarbon conv~rsion processesO

15 Regardless of the cation~i present in the synthesized form of 16 the zeolite, the spatial arrangement of the atoms which form ~7 the basic crystal lattice of th~ zeolite remains esse~tially 18 unchanged. Th~? exchange of cations has little, if any, 19 ~fect on the zeolite lattice ~tructures.
2û
2~ The seta borosilicat~ ~nd sub~eque~t m~talloborosilicate can 22 be ~ormed into a wide variety of phycioal 6hapes. Generally 23 ~pea~ing, the zeolite can be in the form of a powder, a :~
24 granule, or a molded product, such as extrudate having particle ~ize ~iuffi~ient to pass through a 2-mesh ~Tyler) 26 screen and be retained on a 400-mesh (Tyler) screen. In 27 ca6es where the ~atalyst is molded, such as by extrusion 28 with an organir binder, the borosilicate can be extruded 29 before drying, or, dried or partially dried and then extruded. The zeolite ~an be ~o~posited with other 1 materials resi~tant to the temperatures and other c~nditions 2 employed in organic conversion processes~ Such matrix 33 materials include active and inactive materials ~.nd ynthetic or naturally occurring zeolites as well as .

W V 91/00777 ~ 12 PC~r/US90/~376~ -01 inorg~nic mate~ials su~h as ~12ys, 5ilicz~ and metal oxides.
02 The latter may occur natur~lly or may be in the form of 03 gelatinous pr~cipitat~s, ~ols, or s21s, including ~ixtur2s 04 of silica and metal o:~ides. U~ OL an active material in 05 conjunction wlth ';r.~ ,~n`_;l~_ e -~olic2, i.~., co~bin~d ~ith 06 it, tends to improve the eonversion and sel~ctivity of the 07 catalyst in certai:l or~ja.~ic c~nYersion processes. Inactive 08 materials can suita~lv serv~ as diluents to control the 09 amount OL conver~io~ irl a ai~;en oLoC~ss so that products can be o~taine~ r.~ J~ .g ~th~r ~o~nS ~or 11 controllins th.-~ o~ ^ac-'-~.. ? ~ c'l~ eolite ~ materials have ~e2n i.~co;?ora~ed i..~o naturall-~ occurring 13 clays, e.g.~ ~eiltoni.2 and `~aolia. ~es2 ma.~ials, i.e~, 14 clays, oxides, etc., runction, in par~, as binders for the catalyst. It is desirable to provide a catalyst having good 16 crush ~trength, bec~use in p~troleu~ refining the catalyst 17 is o~ten ~ubj~cted to rough handling. ~his tends ~o break 18 the catalyst down into powders which ca~se probl~ms in 19 processing, ~0 :
21 Naturally occurring clays which ean be composited with the 22 8ynthetic zeolites of this invention include the 23 ~ontmorillonite and k30l in f~lmilies, srhich fami~ies include 24 the sub-bentonite8 and the kaolins commonly known as Dixie, McNamee, Georgia, and Florida clays or others in which the 26 ~ain mineral constitu~nt is halloysite, ~aolinite, ~ickite, ~:
?7 ~acrite, or anauxite. Fibrous clays such as sepiolite and 28 attapulgite can also be us~d as supports. Such clays can be 29 u~ed in the raw ~tate as originally mined or can be 30 anitially ~ubjected to calcination, acid treatment or : ~:
31: chemi~al modification.
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WO91/00777 13 ~ ~ S 2 9 `~ 7 PCT/vs9olo376q ~1 In addition to the foregoing materials, the (B)Beta ~eolites 02 can be composited with porous matrix materials and mixtures ~3 of matrix materials su~h a~ silica, alumina, titania, 04 magnesia, silica:alumina, ~ gn~sia, silica-zirconia, ~5 silica-thoLia, ~ilica-~eryl~1.3, ~ilic~ a.~a, 06 titania-zirconia as w~ll as t2rnary compositions such as 07 silica-alumina-tho~ia, ,il ca-~lu~ - irc~ni~, -08 ~ilica-alumin~-magn~ , and ~ilic~-~ag~esia-~irconia. The Qg matrix ca~ b~ , n t~ 3rn ~ ~ co~

11 The (B)B~t~ æ~l t-~s -~e el~a ~ d ~ ~h vther ~2 zeolites such z~ synr:n-a~is ~nc~ r~ U j::lS' tQs ( c,g, ~ X
13 and Y)j 2rionit2s, a.. ~ m~ deni~ hey can also b~
14 composlt~d with purely synthe~ic z201ites such as those of the ZSM series. The combination o~ zeolites can also be 16 composited in a porous inorganic matrix.

18 (B)seta zeolites are useful an hydrocarbon con~er~ion 19 reactions. Hydrocarbon conversion reactions ~re chemical 2~ and catalytic process~s in which carbon containing compounds 21 are changed to dif~erent carbon-containing compounds.
22 Examples of hydrocarbon conversion reaçtions include 23 catalytic cracki~g, hydrocracking, and olefin and aromatics ~-24 formation reactions. The catalysts ar~ userul in other ~5 petroleum refining and hydrocarbon conversion reactions such 26 as i~o~erizing n-paraffins and naphthenes, polymerizing and 27 oligomerizing olefinic or acetylenic compounds such as 28 isobutylene and butPne-l, reforming, alkylating, isomerlzing 29 polyalkyl ~ubsti~u~ed aromatics ~e.g., or~ho xylene), and 3~ disproportionating aro~atic~ ~e.g., toluene) ~o provide 31 mixtures of benzene, xylenes, and higher methylbenzenes.
32 The (B)Beta catalysts have high selectivity, and under 33 hydrocarbon conversion conditions can provide a high 34 percentage of desirFd products relative to total products.
.

W091/00777 2 ~ 6 2 ~ ~ ~ 14 PCT/US90/0376' 01 ~B)Beta zeolites can be used in processing hydrocarbonac~ous 02 feedstock~. Hydrocarbonaceous feedstocks contain carbon Q3 compounds and can be ~ro~ many different sources, such as 04 virgin petroleu~ fractions, recycle petroleum fractions, 05 shale oil, liquefied coal, tar sand oil, and i~ generai, can 06 be any carbon containing fluid sl~sceptible to zeoliti~
07 catalytic r~actions. Dependi~s on t~ .ype of p~oc~ss~ng, 08 the hydrocarbonaceous feed is to undergo, the feed can og contain metal or bP frPe of ~t~ls, it can also have high ~r lD low nitrogen or ~ulfur impurities. It can be ~pproci~
11 however, that in ~ neral proc2ssing ~ more eL~i~'-' 12 (and the catalyst mor2 active) the lower the metal, 13 nitrogen, and sulfur content of the feedstock.
using a IB)Beta zeclite catalyst which contains boron and/or ~6 aluminum framework substitution and a hydrogenation 17 pro~oter, heavy petrol~um rcsidual feed~tocks, cyclic 18 ~tocks, and oth~r hydrocrack~te charge ~tock~ can be 19 hydrocraoked at hydrocracking conditions including a 2~ te~perature in the range of rom 175C to 485c, molar 21 ratios of hydrogen to hydrocarbon charge from 1 to 100, a 22 pressure in the range of from 0.5 to 350 bar, and a liquid 23 hourly space velocity ~L~SV) in the range of from o.l to 30. -~

The hydrocracking catalysts contain an effective amount of 2~ at least one hydrogenation catalyst tcomponent) of the type :-27 rommonly employed in hydrocracking ca~alyst~. The 28 hydrogenation component is generally selected from the group 29 of hydrogenation ~atalysts consisting of one or more metals of Group vIs and Group VIII, including the salts, complexes, 31 and 601utions containing such. The hydrogenation catalyst 32 is preferably selected from the group of metals, salts, and 33 complexes thereof of the group consisting of at least one of : :
34 platinum, palladium, rhodium, iridium, a~d mixtures thereof ; :~
,, . ;,, .

WO 91tO0777 ~ 9 d~ 7 PCr/U5901037~4 01 or the group consisting of at least one of nickel, 02 molybdenum, cobalt, tungsten, titanium, chromium, and 03 mixtures thereof. ReferF:nce 'co the catalytically active o~ metal or metals is intended to encompass ~iuch metal or metals in th~ çlemental sta~e or in some form such as an ~6 oxide, sulfide, halide, carboxylate, and the like.

oj~ The hydrogenation catalyst is pr~sent in an efifective a~ount gg to providP th~ hydrogenation function of the hydrocracking i~ c:i~talyst 2nd pr2 _ra~1y in t~ zang~ 9F f~ra 0.05~6 'co 256 ~y 11 ~eight.
~2 13 The catalyst may be employed in conjunction with traditional 14 hydrocracking oatalysts, e.g., any aluminosilicate heretofore employed as a component in hydrocracking 16 catalysts. Representative of the zeolitic aluminosilicates 17 disclosed heretofor~ as employable as ~omponent par~s of 1~ hydrocracking catalysts are Zeolite ~r ~ including steam 19 stabilized, e.g., ultra-stable sr), Zeolit~ X, Zeolite beta 2~ .~u~s. Pa~en~ No. 3,308,069), Zeolite Z~-20 (U.s. Patent No.
21 3,445,727), Zeolite ZSM-3 (U.S~ Pat~nt No. 3,415,736), ~2 faujasite, LZ-10 (U.R. Patent 2,014,970, June 9, lg82), 23 Z5M-5-type zeolites, e.g., ZSM-5, ZSM-ll, ZSM-12, ZSM-23, 24 ZSM-35, ZSM-38, ZSM-48, crystallin~ silicates such as silicalite (U.S. Patent No. 4,061,724), erionite, mordenite, 26 o~fretite, chabazite, FU-1-type zeolite, NU-type zeolite , 27 LZ-210-type zeolite, and mixtures thereof. ~Traditional 2~ hydrocracking catalysts Containing amoUntS of Na2O less ~han 29 about one percent by weight are generally preferred. The relative amounts of the (B~Beta component and traditional 31 hydrooracking component, if any, will depend at least in 3~ part, on the Eiele~ted hydrocarbon feedstock and cn the : 33 desired product distribution to be obt~ined thereErom, but 34 in all instances an effective amount of (B)Beta is employed.

: :

wogl/00777 æ~ 7 16 PCT/US90/037~ -01 The hydrocracking catalysts ~ro typlcally employ~d with an 02 inorganic o~ide matrix component which ~ay be any of the 03 inorganic oxide matrix compononLs ~.~hich have boen e~ploy2d 04 heretofore in the for~ula'ion of hydroc~a~ ing catalysts 05 includins: a~nor~;~ous c~ y~ic i~or~ c 0~ 5, o.g., 06 catalytically active silica-aluminas, clay~, silicas, 07 aluminas, silica-al~in~s, si7 ic~-~ircenias, 08 silica-magnesias, alumin~-bcrias, alu~ina-ti~anias, ~nd the og like and mi~tu.es ~'a~L ~OC. Th~ '.m~Jitior.ai hy.'rocrac'~ing 1~ catalyst comJonent (TC) 2.~d (~ota ~ e mi~;~d s~arately ~1 with the matri~ rs~.poaes.t ',.d th~?~ m.~.''d ~ T~ csmpon~nt 12 and (B)Beta ma~ b~ 5 _nd '~:~e~ T~ ~ t-i !C~ m-~cri~c 13 component.
1~ .
(s)seta can be u~ed to do~ax hydrocarbonac~ous feeds by 16 selectively r~oving or transformi~g straight chain 17 paraffins. ~he catalytic dewaxing conditions are dependent 18 in large ~easure on the feed used and upon the desired pour 19 point. ~enerally~ the temperature will be between about 200C and about 475C, preferably between about 250~C and 21 abo~t 450~C. Th~ pressure is typically between about lS
~2 psig and about 3000 psig, preferably between about ~00 psiy 23 and 3000 psig. The LHSV preferably will be from 0.1 to 20, 24 preferably between about 0.2 and about 10.
:
26 Hydrogen is pref~rably present in the reaction ~one during 2~ the catalytic dewaxing process. The hydrogen to feed ratio 28 is typically between about 500 and about 30,000 SCF/bbl 29 t~tandard cubic feet per barrel), preferably about 1,000 to ~bout 20,000 SCF/bbl. Generally, hydrogen will be separated 31 from the product and recycled to the reaction zone. Typical 32 feedstocks include light gas-oil, heavy gas-oils, and 33 reduced crudes boiling about 350F.

WO91~00777 17 2 ~ S 2 q I PCT/USgo/03764 01 The (B)~eta hydrodewaxing catalyst may optiorlally contain a 02 hydrogenation component of the 'cype commonly employed in ~3 dewaxing catalysts. Th~ hydrogenation component may be 04 6elected from the group of hydrogenation catalyst~
o~ consisting of one or ~or~ m2~ o~ Grou;~? YI~ and Grou~
06 VIII, including the salts, compl~,ces and ~olutions 07 containing such metals. The prererr~d hydrogonation ~B catalyst is at l-ast one OT the grcup o~ ~etals, salts, and og complexes ~electod ~rom tne grouo consi s~inr~ or at 1035t one 1~ of platinum, Dalladium, r~diu~, ixidium, and mixtu~es 11 thereof or at 12a6. ~ne: r~ tn2 ~,;rou~ ~on~is~ing oc nick~l, 12 ~olybdenum, cobalt, tun5ste~., t''L~.n~ n~ ch-3~iu~, and 13 mixtures thPr_of . ~e_~ ~n~ h~ ~aLal~'ica'ly activ~
14 metal or metals is in~ende~ tO 2aC0.~2SS ~u_h ~e;al o.
~5 metals in the elemental stare or in some sorm such as an 16 oxide, sulfide, halide, carboxylat2, and the like.

The hydrogenation component is pre~ent in an effective ~9 amount to proYide an ef~ective hydrodewaxing ~a~aly~t preferably in the rnnge of ~rom about 0O05 to 5~ by weight.

22 (B)Be~a c~n b~ u~ed to convert straigh~ ~un naphthas and 23 si~ilar mixtures to highly aromatic mix.ures. Thus, normal 24 and slightly branched chained hydrocarbons, preferably z5 having a boiling range above about 40C and less than about 26 200c, can be converted to products having a ~ubstantial 27 aromatics content by contacting .he hydrocarbon feed with 28 the zeolite at a temperature in the range of from about 29 400C to 600C, preferably 480C-550DC at pressures ranging from atmospheric to 10 bar, and L~V ranging ~rom 0.1 to 15.
31 The hydrogen to hydro~arbon ratio will range between 1 and ~2 10. (~)Beta can be used in a fix2d, Cluid o~ moving bed 33 r~for~er.

, 18 PCT/US90/0376~
9 ~

01 The conversion catalyst preferably ~ontain a Group VI~I
o~ metal compound to have sufficient activity for commercial use. By Group VIII ~etal compound as used herein is meant the metal itself or a compound thereof. The Group VIII
05 noble metals and th2ir compounds, platinum, palladium, a~
o~ iridium, or combinations theLeof can be used. The most 07 preIerred metal is platinum. The amount of ~roup VIII metal ~ present in the conversion catalyst ~hould ~e within the og normal range of use in reforming catalysts, from about O.OS
13 to 2.0 wt. %~ preferably 0.2 to 0.8 wt. %. ~he performance 1~ ~r the noble ~etal in ~B)Beta may be further enhanc~d by ihe 12 presen~e o~ oth~r ~tals as promotors for aromati2ation 13 5electi~
1~
The zeolite/Group VIII metal conv~rsion ratalyst can be used 16 without a binder or matrix. The preferred inorganic matrix, 17 where one is used, i8 a silica-based binder ~uch a~ :
18 Cab~O-Sil or Ludox~ Other matriees such a~ magnesia and 19 titania can be u~ed. ~he preferred inorganic matrix is ~o~aeidic.

22 It is critical to the selective production of aromatics in 23 useful quantities that the conversion catalyst be 24 substantially free of acidity, for example, by poisonins the zeolite with a basic metal, e.g., alkali metal, compound.
~6 The zeolite is usually prepared from mixtures containing ~-27 alkali metal hydroxides and thus, have alkali metal contents 28 of about 1-2 wt. ~. These hi~h levels of alkali metal, 29 usually ~odium or potassium, are ~nacceptable for most 30 catalyti~ applications because they greatly deactivate the ~.
31 catalyst fGr cracking reactions. Usually, the alkali metal 32 is removed to low l~vels by ion exchange with hydrogen or 33 ammonium ions. By alkali metal compound as used herein is 34 meant elemental or ionic alkali metals or their basic WO91/00777 :l9 2 ~ ~ 2 9 .~' 7 PCT/US9o,03764 ~1 compo~nds. Surprisingly, u~less the zeolit~ itsel is 02 substantially free of acidity, the baslc c~mpound lS
~3 required in the present process to direct the ~ynthetic o~ reactions to aromatics productlon. In the case o (B)~eta 05 the intrinsic c~ac~ing acidity is quitn lo~ and 06 neutralizatiorl is not usually required.

we have al~o ~ound ~ha~ seta is ~dvantageously u~ed to ~9 catalytically crac~ hydrocarbon feedstocks in ~he absence of hydro~en. 2referred conditions in~olve a fluidized ~1 catalytic cracking process ~hich consists of contacting a 12 hydroca~bcn f~edsto~ with a catalys, in a reaction zone in 13 the a~senc2 Os added hydrogen at average catalyst 14 t2mperatures ranging ~rom 800F to 1500F, separ~ting th-catalyst from the product efflu~nt, introducing the catalyst 1~ into a steam-stripping zone, and subsequently into ~
17 regeneration zone in the presence of ~team and free oxygen 18 containing ga~ where reactiorl coke deposi~ed on the catalyst ~9 ~s burned off at elevated te~np~ratures ranging ~rom 1000F
20 o 1550F, and then r~cyclinq the rea~tiYated catalyst to 21 the reaction zo~e.

23 For this purpo~e, the ~B)Beta can be employed in C~njunction 2~ with traditional cracking catalysts either as an incorporated con~tituent component or as a separate additive 26 particle, 28 The catalyst may be employed in conjunction with traditional 29 crac~ing catalysts, ~omprisin~ any aluminosilicat~
30 heretofore employed a~ a cQmponent in cracking catalysts.
1 Representative of the zeolitic aluminosilicates disclosed 32 he~retofore as employable as component parts of cracking catalysts are zeolite Y (including steam stabilized Y, rare 34 eerth Y, she~ically modified Y, ultra-stable Y or :' "".

~ , ' ' WO91/0~777 ~ 20 P~T/US90/037fif 01 combinations thereof), ~eoli~e X, Zeolite beta (U.s. Patent 02 No. 3,308,069), Zeolite z~ 20 ~u.S. Patent No. 3,445,727), ~3 Zeolit2 ZS~-3 (U.S. Paten~ ~lo. 3~915~736)~ faujasite, LZ-10 04 (U.K. Pat~nt 2,01q,970, J~:no 9, 19~2), ZS~-5-Typ~ Zeolites, 05 e.g., ZSM-~, ~S.~-ll, z5y_1~, 3~ 23, ~s.M-35, ZSM-38, 7sM-4a, 06 crystalline silicat-s such as silicalite (U~S. Patent No.
07 4,061,724), ~ri~nit~, ~ord-~it-~, oLfretite~ cha~a~ite, 08 FU-1-type z~olit~, ~u-~ype ~olit~, LZY~210 type zeolite or og other dealu~i lat ~ c7 ~ 21..5.i ~n~t c--~ll si~.~ or low~r, or ~eolite qro~n ;'in-situ~' in matrix materials (U.S. Patent 11 Nos. ~.,6~7,71~ -~no ~ 3~0/)! ~.C~ ~ho /~ turo~ the oo~.
1~ The term "~olit~" as u,~d h2r-7in eon~ ola~ea not only 13 alUminoSiliCa`~?s `~ll`C ~u~a~anl7Ds in ~hich silP al~minum is 14 replaced 'Dy gailium or Do~on and suos~ances in ~hicn silicon is replaced by germanium. Other re~resentative acidic 16 aluminosilicates also deemmed employable as component parts n 17 are amorphous &ilica-aluMina catalysts, ~ynthetic 1~ ~ic~-montmorillonite cataly~t~ ~as defined in U.5. Pa~ent 19 No- 3j252,889), cross-linked or pillared clays (as d~fin~d 20 in U.S. Patent Nos. 4,176t090; 4,248,73g; 4,238,364 and 21 4,216,188), and acid activated clays -- bentonite, 22 hectorite, saponite.

24 Traditional cracking ~atalysts containinq amounts of Na2O
less than about one percent by weight are generally 26 preferred. The relative amounts of the (B)Beta component 27 and traditional cracking component (TC), ir any, will depend 28 at least in part, on the selected hydrocarbon ~eedstock and ~g on the desired product distribution to be obtained therefrom, but in all instances, an effective amount of 31 (8)Beta is employed. When a TC component is employed, the 32 relative weight ratio of the TC to the (~)Beta is generally between about 1:10 and about 500:1, desirably between about WO~1/00777 21 2 ~ ~ ~ 9 ~ 7 PCT/US90/03764 01 1:10 and about 200:1, prefer~bly between about 1:2 and about 02 50:1, and most preferably is be~ween abou~ 1:1 and about 03 20:1.

05 The cracking c~t~ ar~ _~pic3'1y ~m3lo~e~ with ~
06 inorganic oxid~ ~a~ri~ compon2nt which may be any of the ~7 inorg~ic o~id~ ~2tLi~ c~L-~nenLa whieh hav2 been employed 08 heretofore i~ ~he ormulation of FCC catalysts in~luding:

og amorphous ca'alycic iho~e:nie ~d2s, e.g., cat~lyti~ally activa silic~-a'u~i~.~.,, Cl~vs! 5,7nt~.~tic or ~cid activ~ted 11 clay5~ SiliC~a, ~ .'na~ lu..~'na~, ~illca-~lreo~ias, 12 silica-ma~ngs11s, al'a~`na-`~'c_'2s, al~ ina-tit2nias, pillar~d 13 or cross-lin';~d cla~, a..~ the lik~ and ~ .ures thereof.

14 The TC componant and ~3)B~a ~ay be mixed separately with their respective matrix component and then mixed together or 16 the TC component and ~B)Beta may ~e mixed together and then 17 ~ormed with the matrix component.

19 The mixture of a traditional cracking cataly~t and (B)Beta may be ca~ried out n any manner which results in the 21 coincident pre~ence of ~uch in ~ontact with the crude oil 22 feedstock under catalytic ~racking conditions. For example, 23 a ~atalyst may be employed containing the traditional 2~ cracking catalyst component and (3)~etA in sin~le catalyst particles or ~B~Beta with or without a matrix component may 26 be added as a discrete component to a traditional crackin~
27 catalyst provided its particle has appropriate density and :
28 particle size distribution~ :

30 (B)~eta~ can al~o be u~ed to oligomerize straight and 31 branched chain olefins having from about 2-21 and preferably :
32 2-5 carbon atoms. The oligomers which are the products of -WO9~/0~777 2 0 6 2 9 Ll 7 PCT~VSgO/0376~

01 the process ~re medium to heavy olefi~s which are useEul for 02 both fuels, i.e., gasoline or a gasoline blending ~tock arld 03 chemicals.
0~ ' ~5 The oligomerization process comprises contacting the ole$in 06 feedstock in the gaseous ~tate phase with ~B)~eta at a ~7 temperature of from about 450~ ~o a~ou~ 1200F, a i?;~a~ o~
08 from about 0.2 ~o about 50 and a hydrooarbon partia:L
og pressure of f ro~ about 0 .1 to about 50 atmospher~s.
1~
11 Also, temperaturPs ~210w about 45~F m~y be used to 12 oligomerize the feedstock, when the ~eedstock is in ~h~
13 liq~id phase when con~acting the zeolite catalyst. Thus, 1~ when the olefin feedstock contacts the zeolite catalyst in 15 the liquid phase, te~peratures of from about 50F to about 16 450F, and p~eferably f~om 80-400F ~ay be used ~nd a WHSV
17 of from about 0.05 to 20 and preferably 0.1 to lû. It will 1~ be appre~ia'ced th~t the pressures employed illUSt be ~9 ~uffici~nt to maintaln the system in the liquid phase. As i~ known in the art, the pre~ure will be a function of the ~1 nu~ber o carbon atoms of the eed olefin and the 22 temperature. Suitable pres~ures include from about 0 psig 23 to about 3000 psig.
2~
25 The zeoli~e can have the original cations associat~d 26 therewith replaced by a wide variety of other cations : ;
according to techniques well known in the art. Typical 28 cation would include hydrogen, ammonium, and metal cations 29 including mixtures of the ~ame. Of the replaGing metallic ::
3~ cations, partiGular preference is given to cations of metals 31 such as rare earth metals, manganese, calcium, as well as 32 metals of Group II of the Periodic Table, e.g. r zinc, and 33~ Group V~II of the Periodic Table, e . q . . nickel . One of the 34 prime requisites is that the zeolite na~e a fairly 13w :; ' ' ,.

23 2~29~7 W O 91/00~77 PC~r/VS90/03764 01 aromatization activity, i.e., in which the amount of 02 aromatics produced i6 not more 'chan about 20 wt. %. This is 03 accomplished by using a zeolite with cont~oll~d acid 04 acti~ity [alpha v~lue] of from about 0.1 to about 120, 05 preferably from about 0.1 to a~o~t 100, ~s m~asiur~d ~y it~
06 iability to crack n-hexane.

o~ Alpha values are defined by a standard test known in th~
og art, e.g., as shown in U.S. Patent No. 3,9~0,918 which is 1~ incorporatod totally herein by reference. If roquir~d, suc~.
11 zeolites may be obtainPd by st~aming, ~y us~ in a canversion 12 process or by any other method which ~ay o~cur to one 13 skilled in tnis art.

lS (B)~eta can be used to convert light gas C2-C5 para~fins 16 and/or olefins to higher molecular weight hydrocarbons 17 including aromatic compounds. Operating temperatures of 18 100-700C, operating pressures of 0-1000 psig and ~pace 19 velocities of 0.5-40 hr 1 WHSV ~an be u~ed to convert the zo C2-C6 para~fin and/or ole~ins to aromatic compounds.
21 Preferably, the ze~lite will c~ntain a catalyst ~etal or :
22 metal oxide wherein ~aid metal is ~el~cted from the group 23 conslsting of Group IB, IIB, VIII, and ~XI~ of the Periodlc 2~ Table, and ~ost preferably ~allium or zinc and in the range ~ from about 0.05-5 wt. %.

27 (B)Beta can be used to condense lower aliphatic al~ohols .
28 having 1-10 carbon atoms to a gasoline boil~ng point 2~ hydrocarbon product comprising ~ixed aliphatic and aromatic :
hydroearbon. ~he condensation reaction proceeds at a 31 temperature of about 500-1000F, a pressure of about 32 0.5-1000 psig and a space velocity of about 0.5-50 WHSV.
33 The process disclosed in U.S. Patent No. 3,984,107 ~ore ~' ' 2 ~ ~2~ ~ PCT/US90/0376~

Ol ~pecifically describes the process conditions used in this 02 process, which patent is incorporated totally herein by 03 re~ere~ce.

05 The catalys~ ~ey be ~n ~ hvcl~o~en form or ~ay be base ~6 exchanged or impr2gnat~d ~o contain amonium or a metal 07 cation complem~nt, ~refera~ly in th~ range of from about o~ 0.05-5 wt. ~. The mocai ca-ions that may be present include og any of th~ ls of .he r-reu~5 I-VIII o th2 Periodic Tahle. However, in the oas~ o~ Grou? I~ metals, 'he cation 11 content ~;~ould in ~o o~se be s~ lar~,e as to o'L~ctively 12 inactivat~ the c~ta'-yst.

1~ The cataly~r .~a be Inade nighiy ac~ive and highly selective for iso~erizing C~ to C7 hydrocarbons. Thé activity means ~ that the catalyst can op~rate at relatively low temperatures 17 which thermodynamically favors highly branched paraffins.
18 Co~sequently, the catalyst can produce a high octane 19 product. ~he high selectivity means that a relatively high 2~ liquid yield can be achieved when the catalyst is r~n at a 21 high o~tane.

23 The present process compris~s contacting the isomeriz~tion 24 cataly~t with a hydrooarbon feed under isomerization conditions. ~he ~eed is preferably a light straiqht run 26 fraction, boiling within the range of 30-250F and ..
27 preferably Prom 60-200~F. Preferably, the hydrocarbon feed 28 for the process comprises a substantial amount of C4 to C7 29 normal and ~lightly branohed low oetane hydrocarbons, more preferably C5 and C6 hydrooarbons.

32 ~he pressure in ~he process is prererably between 50-1000 psig, more preferably between 100-500 psig. The LHSV is 34 preferably between about 1 to about 1- with a value in the ~. W091iO0777 25 2 ~ ~ 2 9 ~ I PCT/US90/03764 Ol rans~ of about 1 to about 4 b~ing ~oro preferred. It is 02 also preferable to carry out the isomerization reaction in 03 the presenc_ of hyd os~n. ~ref~r~bly, hyd~ogen is added to 04 give a hydrogen ~o hydrocarbon ratio (H2/~C) of betw~en 0.5 D5 and lO H2/~C, mo~ rab'l~ b~ ea 1 and a H2/HC. The 06 temperature is pref-erably bet~een about 200F and about 07 1000F, mor~ pr~:'era~'~ b2t~e~n ~00-600Fo ,~s is well known 08 to those s~illed in t`ne lsomerization art, ~he initial og selection OL- 'Cl1~ temPera~Ur~ hiï1 'chls `r~road range is made 1~ pri~arily as a ~~unct~on of th? de~iLed convPrsion 1eYe1 11 consid2ri..~ 'h~ cha-ae;~ ^s o~ ~h~ ~~eA ar,d of .h~
12 catalyst. The eaf~er. t3 ?r_~ide ~ re'atiYoli constant 13 value for c~n~-e;sio.., ,n~ mp~L~cure ~ay ~,ave to ~ slowly 14 increased du-ing th~ run to comp?nsat2 ~or any d&activation 1~ that occurs.

17 A low 6ulfur f~ed is e~pecially preferred in the present ~B pro~e~s. The feed prsfer~bly ~ont ins le~ than 10 pp~, 19 ~ore preferably less than 1 ppm, and ~ost prefcrably less 2~ than 0.1 ppm ~ulfur. In the case o~ a feed whieh i~ not 2~ already low in sulfur, aeceptable levels can be reached by 22 hydrogenating the feed in a presaturation zone with a 23 hydrogenating catalyst which is resistant ~o Eul~ur 24 poisoning. An example of a suitable catalyst ~or this hydrodesulfurization process is an alumina-containing 2~ ~upport and a minor catalytic proportion of molybdenum 27 oxide, cobalt oxide and/or nickel oxide. A platinum on 28 alumina hydrogenating catalyst can also work. In which 29 case, a 6ulfur sorber is preferably placed downstream of the hydrogenating catalyst, but upstzeam of the present 31 isomerization catalyst. Examples of sulfur sorbers are 32 alkali or alkaline earth metals on porous refractory ~4 ~0~ 26 PCI/US90/0376J

01 inorganic oxides, zinc, etc. Hydrodesulfurization is 02 typically conducted at 315-455~c, at 200-2000 psig, an~ at a 03 LHSV of 1 5.

o~ It is preferable to limit th2 nitrogen 12vel and tih~ ~7at~r 06 content of the eed. Catalysts and processes which are 07 suitable for the~e purposes are known to those s~illed in ~8 the art.
~9 Aft~r a p~ricd o~ operation, the cataIyst c~n ~co~a 11 deactivat2d b~ cokP. Coke can ~e removed ~y contaccing tha 12 catalyst ~ith an ovygen-containing gas at an eleYa~e~
13 temperatur~.

15 The isomerization catalyst preferably contains a Group VIII
16 metal ~ompound to have su~ficient acti~ity for commercial 17 use. By Group VIII metal co~pound as u~ed herein is ~eant 18 the metal it8elf or a compound thereo~. The Group VIII
19 noble metal~ and their co~pound~, platinum, palladiu~, and iridium, or combination~ thereof can be used. Rhenium and 21 tin may alBo be usd in conjunction with the noble metal.
~he most preferred metal is the amount of Group VI~I metal 23 present in the eonversion Gatalyst should be within the ::
24 normal ~ange of use in i~omerizing cataly~ts, from about 2S 0.05-2.0 wt. %.
2~ :
27 (B~eta can b~ converted to a catalyst for use in a procPss 28 ~or th~ alkylation or transal~ylation of an aromatic 2~ hydrocarbon. The proce~s comprises contacting the aromatic hydrocarbon with a C~ to C20 olefin alkylating agent or a 31 polyalkyl arômatic hydrocarbon transalkylating agent, under 32 at least partial liquid phase conditions, and in the 3 3: presence of a catalyst ~mprising ~)seta.

-2o~2~ 7 Wogl/00777 27 PCT/~S90/037~4 ~1 For high catalytic activity, the (s)Beta zeolite ~hould be 02 predominantly in its hydrogen ion form. Generally, th2 zeolite is converted to its hydrogen fo~m by ammonium o~ exchange followed by calcination. If the z~olite i5 05 synthesiæed with a high enough ratio of organo~itrogen oS cation to sodium ion, calcination alone may be sufficient~
07 It is preferred that, after calcination, at least 80~ of th2 oa cation sites ar~ occupied by hydrogen ions and/or rare ear'h ~9 ions.

~1 The pure ~B13eta z~olite may be us~d as a catalyst, ~ut 12 generally, i~ is preferr~d to mix tn2 zeolite powder with an 13 inorganic oxide binder such as alumina, silica, 14 silica/alumina, or naturally occurring clays and form the lS mixture into tablets or extrudates. The final catalyst may 16 contain from 1-99 wt. % (~)~eta zeolite. Usually the 17 zeolite content will range form 10-90 wt. %~ and more lB typioally from 60~80 wt. ~. The preferred inorganic binder 19 is alumina. The mixture may be fo~med into tablets or extrudates having the desi~ed shape by ~ethods we~l known in 2~ the art.
2~
~3 Examples of suitable aromatic hydrocarbon feedstocks which 24 may be alkylated or transalkylated by the process of the Z5 invention inelude aromatic compounds such as benzene, 26 toluene, and xylene. The preferred aromatic hydrocarbon is 27 benzene. Mixtures o~ aromatic hydrocarbons may also be : -28 emPloyed.
2g Suitable olefins for the alkylation of the aromatic 31 hydrocarbon are those containing 2-20 carbon atoms, such as 32 ethylene, propylene, butene-1, tran butene-2, and 33 cis-butene-2, and higher olefins or mixtures thereof. The 34 preferred olefin is propylene. These olefins may be present W~9l/~077~ 28 PCT/U~90/037~ -01 in admixtur~ wi-th th~ corresponding c~ to C20 paraffins, but 02 it is pr~ferablo to r-~ov~ 2n~,~ di_n~s, ~cetylenPs, sulfur 03 compounds or nitrogen compounds which may be prese~t in the 04 ol~fin f~edstock streain ~o ~reYa~t ra~id catalyst 05 deactivatio 07 When tr~nsal.~yiation is ~si red, the transalkylating agent 08 is a polyalkrl a!~a~ic hye.r~o~r~on eonta.ining two or more 09 alXyl group~ ~ha. ;-ac î ~ay ha~e from t~o te about four 10 carbon atom~. . or examDle, ~uitable polyalkyl aromatic 11 hydrocarbon~ inc' ~do ~ , tri-, and te.La-al)~yl aromatic 12 hydrocarbons, sucn as diechylbenzene, triYthylbenzene, 13 diethylme.h~ bon3-ne ~dtet~e~7ltol-l:en2!, ~i-iso~ro~r~yloenzene, 14 di-isoprop~1 to~uene, ~ibu~ enzen-, and the li~P.
Preferred poly~lkyl aromatic hydrocarbons are the dialkyl 16 benzenes. A particularly pr~f~rred polyalkyl aromatic 17 hydrocarbon i~ di-isopropylbenzene. .
~8 :
19 Reaction product~ which may be obtained include ethylbenzene .-from the reaction of bQnZene with either ethylene or ~1 polyethylbenzenes, cumene from the reaction of benzene with 22 propylene or polyi~opropylbenzenes, ~thyltoluene from the 23 reaction of toluQne with ethylene or polyethyltoluenes, 2~ ~ cymenes from the reaction of toluene with propylene or polyisopropyltoluenes, and secbutylbenzene from the reaction 26 of benzene and n-butene5 or polybutylbenze~es. The 27 production of cumene from the alkylation of benzene with 28 propylene or the transalkylation of benzene with 29 di~i~opropylben~ne is espe~ially preferred.
3~
31 Wh:en alkylation is the process conducted, reaction ~32 conditions are as follows. The aromatic hydrocar~on feed ~33 should be p~esent in stoichiometric excess. It is preferred 34 that molar ratio of aromatics to olef ns ~e greater than ~.
'' ~

' .
:' W~l/00777 29 ~ ~ ~ 2 9 ~ ~ PC~ 90/0376~
...

01 ~our-to-one tc pr~vent r~pid catalyst fouling. The reaction 02 temperature mav range Erom 100-600~F, preferably, 250-450F.
03 The reaction pressure should be sulricient to maintain at 04 least a partial llquld phase in order to retard catalyst 05 fouling. ~his is .ypically 50-1000 psig depending on the D6 ~eedstock and re~ction tDmper3ture. Contact time may ~ange 07 from lO ~eeond~ ~o 10 h~.s, ~u~ is u~ually ~rom five 08 minutes to an hour. ~:~e W'.~S~ ~n t-r~s of gra~s (pounds) of og aromati~ h~;d 3=.~ '~o~ a'~ ~ (pound~ of catalyst per hour, is g~n~rally ~ici~in ~n~ rang- o ~out 0.~ to 50.

12 When transalkyla-i~n is ~ proces~ conducted, the ~olar 13 ratio of arom~tic n~drocarbon will gen2rally range from 14 about 1:1 to 2~:1, and preferably fro~ about 2:1 to 20:1.
The reaction temperature may range from about 100-600~, but 16 it is preferably about ~SO-450~F. The reaction pressure 17 should be ~uffi~ient to maintain at 12ast ~ partial liquid pha~e, ~ypically in the range of ~bou~ 50-1000 psig, lg preferably 300-600 psig. The WHSY will range from a~out 2~ 0.1-10, 22 The conYersion of hydrocarbonaceous feeds can take place in 23 any convenient ~ode, for example, in fluidized bed, moving 24 bed, or fixed bed reactor~ depending on the types of process desired. The formulation of the catalyst particles will ~6 vary dependiny on the conversion process and method of 27 operation.

29 Other reactions which c~n be perfolmed using the catalyst of this inven~ion containing a metal, e.g., pla~inum, include 31 hydrogenation-dehydrogenation reactions, denitrogenation, ~2 and desulfurization reactions.

3~

: ~.

: ~.
', WO 91/00777 P~r/usso/03764 -01 Some hydrocarbon conversions can be carri~d out on ~8)Beta zeolites utilizing the large pore shape-selective behavior.
~3 For example, the ~ubstituted (B)Beta zeolite ~ay be used in o~ preparing cumene or other alkylbenzenes in proee~ses 05 utilizing propylene to alkylate aromatics.
~6 t)7 (B)Beta can be used in hydroca~bon conv~rsion r~actions wi~h 08 ac~i~e or inactive supports, with organic or inorganic ~9 binders, and with and without added metals. These rQactions 1~ are ~ell ~no~.~n to thP art, as ar~ the reac~ion conditions.

'~2 (~)ae~a can also be used as an adsorbont, as a fill2r in ~3 paper, paint, and toothpastes, and as a water-softe~ing 14 agent in detergents.
1~ The following examples illustrate the preparation and ~se of 17 ~ eta.

. . . _ 2~
21~xample 1 23 Synthesis of an ~ffective Diquaternary Ammonium Compound 24~ Boron ~eta Crystallization 26 48 grams of DABC0 (1,4 Diazabicyclo [2.2.2] octane) is 2~ stirred into 800 ml of Ethyl Acetate. 42 yrams of 1,4 2~ Dilodobutane is added dropwise and slowly while the reaction 29 is stirred. Allowing the reaction to run for a few days at room tQmperature produces a high yield of the precipitated .

2~ 9~7 Y~'V 9l/0~777 31 PCI/US9~/037~4 ; . . .

01 diquaternary compound, 0!~ N N-(CH2)~ il 2I

~9 The product is washed with THF and the~ ether and then 10 vacuum dried. Melting point ~ ~55C.
11 ' 12 The cry~t~lline salt is conv~ni2ntly con~rertad to the 13 hydroxide form by ~tirring overnight in water with AGI-X8 ~ 4 hydroxide ion exchange resin to achieve a solution ranging ~rom 0.25~ molar.
1~
~ 7 Example 2 19 10 ~ 85: g of a 0 . 90M ~olution of the tc~plate ~om 13xample 2~ ~iis:diluted wi~h 3.95 ml ~2- 0023 g of ~a2B407 18ff20 are : .
2~. di6solved in this ~olution and therl 1.97 g of Cabosil M5 are 22 blended in la~t. The reaction mixture is heated ~n a Parr ~:
23 4745 reactor at 150C and rc~tated at 43 rpm on a spit in a ; -:
24 I~lue M oven over a 9-day period. The ~olid component of the reacti~n i~ filtered, washed repeatedly, dried at 115C and 2~ analyzed by X-ray diffra~tion. The product is identified as 27 (B)Beta.

29 : ~ Example 3 .

: The same expe~iment is set up as in Example 2 except the :~
d;iquat~in Exa~.ple 2 is replaced by an equivalent amount of TEAO~ The experiment~:is run:under analogous conditions ;.
34~
:: ~ : ~ , .:

W~9l/n~777 ~C,T/US90/03764 .9 ~
nl although this time the cryst~llization is complete in 6 02 days. The product is ZSM - 5 by XRD . Thi s sho~s that TEAOH
03 doesn't hav2 en~ugh s~l~ctivity ~or ~2ta in the borosilicate 04 system. TEAOH is the te~olat2 used in the prior art for ~5 synthesis of ~et~.
OS
07 ~xamr~
0~ ' 09 ~02 g or a 0 . a~ olu.~ion o - ~h~ ?lat~ E-o~ E.cai~pl2 1 is 1~ mixed with 5~ 9~ ~2~ and 4.03 g or Na23,O7 10E~20. 35 g 11 of Cabosil MS ~~ bl~d~d i~ lasc and t:n~ reac-ion i s run in 12 a Parr 600-cc s~ir-~d ~.uto~~ i~v~ , lin~-~r ;Eo~ 6 days at 13 150C andstirr~d ~ 50 r~n. T~roduc~ is 14 well-cry~ -an 3';~12 pac~rn i~ aou~a~ed in 15 Table 2.

~8 19 2 ~ d/n_ __I n t .
21 7.7 11.5 28 B
22 18.40 4.828 VB
23 21.4~ 4.1~ 22 2~ 2?.53 3.95 120 : 25.50 3.49 7 ~6 26.08 3.42 3 B ~ .
27 27.50 3.24 11 2B 28 . 92 3 .109 B ::
~9~ 29.~0 2.g7 10 30.57 2.93 3 3l~ 31.15 2.852 VB
32 : : 33.62 ~ 2.~7 6 W~91/00777 33 2 ~ ~ 2 9 ~ ~ PCT/~'S90/0376~

01 TA~LE 2 (Co~t.) 0~ ..
03 2 e d/n Int . _ 0~
05 15 17 ^~.5, 2 06 36 . 32 2 . '17 2 08 ~ ~ ~road 09 ~13 ~i Y~r~ n_~

11 Examples 5-10 ar~ ~iven in T~DiP 3! d~cnst~t~ng ths 12 utility of the me~hod o~ inv~ tion. ~,~ampl~s 5-7 show i3 t~at (g)~ta can ~ m~ at V2~y lo~ ~lO2/~;2O3 values and 1~ that high2r ~alues eY~n~uc ily 1 ad ~o some Z~l;l 12 ror!nation 15 as well. Exampl~ ~ sho.~7s that th~ d~sired product can be 16 obtained usinq Ludo~ AS-30 as silica sourc_. Now the ;:
17 aluminum impurity has risen to 530 ppm. Examples 9 and 10 18 show that providing the diquat a~ a salt to ~uppl~men~ TEA0~ -19 can insure formation of pure Boron Beta. Example 9 shows ~Q that is the case even without seeding.
~1 22 Tab~ 4 show~ the XRD data ~or the product of Example 5 and :23 Table 5 is of x~mple 6, both in the a6-synthesized form.

2 7 ~ i ?' . '.

:2 3 ~

: : : ~ ~ :

WO 91/00777 3~i PCI/I~'S~0/~376'3 2~62~7 V t N
O 4~ V V J
c~ ~ 1~ Q Q a~
o~l o~ ~n n ~ O O
U~
~a aJ ~ 2 Z bO

O o X

O ~ o V~ U~ X ~

O o l- O r~ ~
~ O r-l ~ _~ ~o o ~ U~ o ~ ~
cq o ~ E
~4~ O O O ~ O ~ X

o o o er~

~¢ l ~ ~o E E a :
O O Ll ~ ~o o U~
,~ bo e 0 ~D ~ o ~ ~
o ~ U~ o ._ 0 ~ _I .o C

o~oo~oooo~

: :.

.

wo 91/00777 35 2 0 ~ 2 9 ~ 7 01 TA~LE 9 03 2 ~ d/n Int.

05 7.7 11.5 28 a 06 18.55 4.78 8 VB
37 21 . 55 4 . 12 ~!2 {18 22 . 60 3 . 93 110 og 25 . 60 3 . 48 4 26 . 00 3 . 43 3 B
11 27 . 5~ 3 . 24 8 :
1~ 29 . 00 3 . 08 6 B
13 25.9~3 2.98 6 :
14 30.65 2.92 2 31.15 2.87 1 VB ~.
16 33 . 67 2 .~6 4 B
17 35 .27 2 . 55 2 :
~ 8 36 . 50 2 . 47 2 B

B - Broad 21 VB ~ Very Broad :.
:: ~ 26 :2 7 - ::
:
28~
29~ : :

32~ ~ ;

34 ::

~ . ~

W~091/00777 r 29 ~r7 pcr/us9n~33764 ~2 03 ~ ~ d,'n Int 0~
05 7 . 7 11~ i 27 B
06 18 . 454 . 82 5 VB
,D7 2.~.47 ~.14 1~
08 22.56 3.94 1~8 0 9 .7 5 . S 3 3 . -- 3 ~6 . ~ '. 3 3 11 77 . 5~ 3, ~
12 2~ . 973 . ~79 7 3 1 ~ 2 9 . 9 _ 2 . 9 9 8 1 4 i O . ~ ~ 7 . 9 2 31. 20 2 . 83 2 VB
16 33.66 2.6~ 5 17 35.17 2.S5 2 .
18 36 . 352 . 47 2 B
19 .
B o Broad 21 VP,~ Very Broad ~3 XRD patterns for the calcine~ products o~ ~xamples 5 and 6 Z4 appear in Tables 6 and 7, respectively.
:
: 26 The presence of the boron in the framework of beta zeolite c~an be indi~-ated by changes in d-spacings. Table 8 compares ~28 the d-spacings before and a~ter calcination ~or ,~,ome of the 29 sharper peaks o~ the products of Examples 4, 5 and 6. Also ~hown are the values ~or an aluminum beta zeolite prepared 1 by the~ prior art ref~rence (Re 28,341). It ~-an be seen ~hat 2~ the ~oron Betas show d-spa_ings consistently smaller than 3~3 the aluminum Beta.
3 ~
:: :
:: :

:
~ .

:

9 ~ 7 wo sl/on777 37 P~/US9~10376~
~ . , n 1 TAs L E_ 6 0~ :
03 2 ~ d/n Int.
__ o~ :
05 7.7 ' 1 .5 3~ i3 06 13.58 6~53 3 07 l~.~a 5.~7 5 a ~8 18 . oO 4 . 77 2 VB
~9 21.a5 ~.Oo 10 3 10 22 . ~9 3, ~
11 25 . 30 3 . '5 ~ 3 1~ 27 . 3~ 3 ~5 5 13 2g . 35 3 . ~ 2 14 30.10 2.97 3 15 31.15 2 . 87 1 VB
16 34 . 00 2 . 64 1 VB
17 36 . 90 2 . 44 1 VB
1~3 " ' 19 s ~ sroad 20 VB 8 very aroad 23 : .
~ 4 2 e d~n I n t ._ 25: ~:
2:6 7.7 11.5 38 B
27 13 . 52 6 . 55 4 : ~:
14 . ~5 5 . 95 5 B
29 18 . 50 4 . 82 2 VB
3 0 : 21. ~0 ~4 . 08 5 B
31~ 22.82 3.90 50 : ~:
32~ :25 . 75 3 . 46 6 B ;~
33~ 27.35 : 3.26 5 , ~' 3~4 ~
~:

WO ~l/00777 38 Pcr/US90/0376d 2 ~ 7 01 TABLE 7 ( Cont .

03 2 ~ d/n Int.
~4 D5 29.27 ~.05 2 B
06 30 . ~0 2 . 98 4 07 31 0 00 2 . ~ 2 V~3 ~ 33,90 2.~ 2 V~3 og 36 . ao 2 . 44 1 VB
11 B = ~road 12 vs ~5 very sroad 14 TABLE 8 : :

16 Uncalc~ ned _ Calcined _ 17 d/n d/n_ d/n d/n d/n d/n : ::

l9 Al-B 3.97 3.30 3.03 3.97 3.30 3 03 21 ~Ex 4 0~07 E~-~3.95 3.24 2.99 3.89 3.26 2.97 22: ~ }3x 6 Q.10 B~B:3.94 3.24 2.99 3.gO 3.~6 2.98 2:3~ Ex 5 0.13 E~--B 3.93 3.24 2.98 3.88 3.26 2.97 25 Note: d/n spacinss for B-Betas are consistently less than 2 6 tho s e f o r Al -Be ta s .
:; :
27 ::
2~ ; Examp~

30 ~ The~produc~:~ of Example 4 was calcined as follows. ~he 3~ sa~ple ~was heated in a muffle furnace in nitrogen from room ~ -32~ tempe~ature up to ~540C:~ at a :steadily increasing ratç o~er a 33~ ~7-~ho~u~r p~r~iod.~ The ample was mai:ntained a~c ~40C f~r four :34~ ;mo~re ;~hours~ and ~then~ taken up to 600~C for an addi~cional four 39 20~9~7 WO 91/00777 ~PCIr/US90/03764 ... . .

01 hoursA Nitrogen was passed over the z?olite at a rate of 20 02 standard ~fm during heating. The calcined product had the 03 x-ray diffraction lines indicated in Table 9 below.
0~1 07 2 9 d/n Int.

39 7.7 11.5 58 B
lG 13. 5a 6.52 6 11 14.~7 5.g~ 8 B :
1~ 18.50 ~.80 2 VB
13 21. B34 . 07 10 B
1q 22.87 3.89 70 2~.75 3.46 7 16 27.3e 3.26 7 17 29.30 3.05 4 B
l~ 30.08 2.97 5 19 31.00 2.B8 3 B
33.95 2.64 2 v~ ~ .
21 :
22 B - Broad VB ~ Very Broad ~ ... ..
Example_12 27 Ion exchange of ~he calcined material from Example 4 was -:
28 carried out using N~4N03 to convert the ~eolites rom Na 29 form to N~4. Typically the same mass of NH4N03 as 2eolite 30 was slurried into ~2 at ratio of 50:1 ~2 zeolite. The 1 exchange solution was heated at 100C for two hours and then 2 filtered. This process was repeated two times, Finally, after the last exchange, the zeolite was washed ~e~eral 34 ti=es with H20 a~d dried. . ~ .

' '.': ' WO gl/00777 ` PCI`/US90/0376~1 2 0 ~ 7 01 Example I3 ~2 03 ~ rminat.ion o~ 0.53 g of t:~s hyd~og-n -~^o-~ o. ~he z-^lite or Exam~le 4 06 ~after treatme~t according to E,camples 11 and 12 was packed o~ into a 3/8-inch st~inless st~sl ~ bs ~-it~ alundum cn both 08 sides of the z'301it~ b2d. A ~indburg ~urnace ~as used to og he~t the re~c'.or ~U~3. ~`131iU~ .3 in~roàuced into ~he reactor tube at ;0 cc~inuto an~ a~mos~hQric prossurQ. ThQ

reactor was ta'.~en to 2~~' ~er ~0 ~.i~.u~es an~ th~n ~aisPd ~o ~2 BOOF. OncQ ~2~2ra.ur2 ~nuili~ra~i~n ~as achie~d a 50/50, 13 w/w f~ed of n-h~a~.3 an.d ~-~3t:hyl~e.-ta.,2 was introduced into ~ the reac~o~ a. a ra~ o~ 0.~2 cc/hour. Feed delivery was made via ~yringe pump. Di rect sampling onto a gas 16 chromatograph ~as begun after 10 minutes of feed 17 introduction. Constraint Index values were calculated from 1~ gas chromatographic data u~ing ~ethods known in the art.

19 ..

20 Example Conversion 21 No C.I~ at 10 Mi~.

23 13 -- 0 8~0 Example 14 27 The product of Exampie 4 a~ter treatment as in Examples 11 2B and 12 is refluxed overnight with Al(No3)3-gH2o with the 29~ latter being the same mass as the zeolite and usi~g the same dilution as in the ion exchange of Example 12. The product 31 is fiItered, wash*d, and calcined to 540C. After pell:etizing the zeolite powder and retaining the 20-40 mesh 33 fra:c~cion, the catalyst is tested as in Example 13. Data for .
.:
,, :~, .
., :. ~
~.

'~l 2~S2~
WO 9~/oo77~ P~r/US90/03764 ~ .
~ .. .
01 the reaction is git~en in TablP 10 along with a variety of 02 catalysts made f rom analogous treatments with other metal 03 salts.

o ~~ ~ a i~ o 1 a6 Q7 Please reE~r to ~r~ble 10 ~nd Ta~

UST~ L.~ 1 0 r~ ?.~ Y~d',' '`~ ,a~ion r ~t!~ rr 2~ B? ta . .

14Example.~eal Conversionr % Temp., :~
1~N o . S a l t C . I . _~ F
1~ . .
17 13 Nsx~e -- 0 800 18 14 Al(~03)3 1.0 35.0 600 19 15 GalN03)3 0.2~ 83.0 800 ; .
20 16 Sn(~C)2 0.70 1.0 ~00 : .
21 17 MgCL2 6~32O 2 . O O . 2 800 22 18 Co(N03)2 6H2o 1.0 5.0 800 ;~3 ;~4 ~able 11 shows the data for the treatment of the product of 25 Examples 4, 11, 12 with various quantities of Zn(Ac)2 2~20.
~6 31 ~
, : ~ 3~

: : :

: .
~ ~ , WO 91/00777 ~2 PC~ S90/03764 ~ ~2 ~ 4rl 03Example (B)Beta Zn(AC)2 2H20 Wt. % Zn after exch./calc.
04 No.

06 19 4.5 g 2.~ g 3012 ~7 20 4.5 g 1.10 9 1.95 o~ 21 ~.5 g û.55 g 1.38 og 27 4.5 g 0.25 ~ 0~7S

11 Example 20 gave 5~ conv2rsion a~ 800F for C.I. ~est 12 CI o 0,30.

1~ Exa~le 23 16 The borosilicate version of ~9)~eta was evaluated as a 17 re~orming cataly t. The zeolite powder was impregnated with 18 Pt(~3)q 2NO3 t~ give O.B wt. % Pt3 The material was 19 calcined up to ~50~F in air and ~ain~ ed at thi~
temperature for three hours~ The powder wa~ pelletized on a 2~ Carver press at 100~ psi and broken and meshed to 24 40.

23 The catalyst was evaluated at 900~ in hydrogen under the 24 following conditions:

26 psig ~ 200 27 H~/HC ~ 6~4 ~28 WHSV ~ 6 29 Temperature 8 900F
3~
31 The feed was an iC7 mixture (Philips Petroleum Company).
~
e 12 gives data at 800 and 900F and 50 and 200 psig.

, "
-~

::
-2~3~2~7 W~91/00777 P~T/VS90/~3764 , .

O1 ~ABLE 12( ) ~3 Temperature ~00F 8OO~F 9OOF
04 Pressure ( H2 ) 200 50 200 05 Conversion % B8.8 77.0100 ~6 A~om~tization Selectivity ~i 25.4 54.5 25.3 07 Product Toluene wt. ~i 19.1 39.316.9 ~ ~ Toluene in C5 Aromatics 84.9 93.767.8 og C5~ yield wt. % 46.9 77.430~2 C5-C8 RON 89.5 90.6104.3 12 (a)The Catalyst is quite sta~le and tha ~alui~ a~P av~r~ged 13 over at least 20 hours of ru~ time. :~

xample 24 17 The product of ~xample 18 now contained a hecond me'cial due ~ ~ to cobalt incorpo~ation. Th2 ca'caly6t was calcined to 19 1000F. Next, a reforming catalyst wis prepared as in 20 Example 23. The catalyst was evalua~ed under the following 21 conditio~ls 23 psig ~ 100, 200 24 H2/BC ~ 6.4 WHSV ~ 12 26 T~mperature - ~00~F

2B The feed has an iC7 mixture (Philips Petroleum Company).
29 The data for the run is given in Table 13. After 23 hours onstrea~, the pressure was dropped to 100 psig and thls data 31 also appears in the table. By comparison with Example 23, 32 the incorpor~tion of cobalt into the zeolite gives a more 33 C5~ selective reforming catalyst. The catalyst has good ..
5t-bility at 800~. :

. " ' WO91/U0777 ~4 PCT/U~90/~376~
9 ~

___ ~2 0~ Temperature 800F 8~0F
04 Pressure H2 200 100 ~5 Con~ersi~r- ~ 93.3 8~

06 ~romatizatio~ S~lectivity % 27 37 ~7 Product Tolu~n~ t. Q~ 18.~ 27.3 OB ~ Toluene in C~+ Ar~matics ~3.3 a5.9 09 C5~ yi~ld, ~ ~g.8 i~3.7 10 C5~C8 R0~l ~5.~ 90.3 l2 1~ A product was prepar?d a~ in Example 12. Next, the catalyst was dri~d at 600F, cooled in a closed system, and then 16 vacuum impr2g~ted with an aqueous ~olution of Pd(NH3)4 2N03 17 to give 0.5 wt. % loading of palladiumO The ~atalyst was 18 then calci~ed 610wly, Up to 900F in air and held there for 19 three hours. Table 14 gives run conditions and product data ~or the hydrocracking o~ hexadecane. The catalyst is quite 21 stable at the temperatures given.
~2 23 ~A~LE 14 .
2~
~5 Temperature, F 625 637 26 WHSV 1~55 1055 27 psig 1200 1200 2~ Conver~ion 85.1 37.8 29 Isom. Select. 94.5 69.9 30 Crack. Select. 5.6 30.1 31 c5+/c4 10.8 11.5 :
32 C5+C6/C5~ 17.8 17.1 '~:

.
- ~

WO 91/00, ï7 45 2 ~ ~ ~ 5 ~ 7 Pclr/us90/n376-1 01 The data sho~s that the ~atalyst has good isomerization 02 selectivity and that the li~uid yield is high compared with 03 the g~s ma!c~.
~4 05 ~ mol2 2~ :

07 The hydr~gen fori~ Oc ~ ?ta can b~ u~d in typical OB ~luidized catalytic crac~ing (~CC). (B)~eta, as prepared in og ~xa~ples 2, 11, 12 and r.~~lu~ad wlt~ Al(N03)3 9H~O as i~ -7o Exam~le 1 , w~ ~u'~ed ir~ - s~!ay dried FCC ~atalytic 11 octa~.~ a~ J~ 3n~ d i.o ~ d .luidiz~d cyclic 12 reactor- Fo- t."is 3~a~.~12~ ~2 ~C~ ca~alytic octane 13 additivP csn'ai~2d ~oi~inally 25~ Dy w~iyht (a)seta~ 32.5%
14 Kaolin and 42.5~ silica/alumina mat~ix. ~ixed fluidized cyclic testing wa~ conduct2d at 7 c~t/oil ratio, with a 16 1100F initial cataly~t temperature. ~ ~ubsequent gas 17 ch~omato~raphic analysi of the liquid product was made to d~termine cal~ulated octanes. The catalyst inventory durins 19 the fixed fluidized Gycl~c testing of the (B)~eta ~CC .:
2~ Gatalytic octane additive contained 90% ~t~amed rare ~arth 21 FCC c~talyst and 10~ of calcined (~)Beta FCC catalytic 22 octane additive. Feed properties o~ ~h~ gas oil used during 23 ~ixed fluidized cy~lic testing are ~ n in Table 1~.

27 API Gravity 27.43 28 ~niline Point 187.3 29 Total Nitrogen 1040 ppm ~:
: S i mu l a t e d D i s t i l l a t i o n ~31 ST 160C
3~2 : 5 Vol % ~ 256C
~;; 33 ~ 10% 2~7C :.:34 ~ : 30% 362C .
:: : , ` : -:: .

WO ~1/00777 , - ~6 P~/~'S90/03764 2~&2~ ~7 01 TABL~ 1$ ~Cont. ) 03 50% ~30C
04 70% 499C
05 90~i ~95Oc 06 95~ 630c 07 EP ~54 ~c og Table 16 shows calculated research anid mo~or octi r.s r.u~ r~
10 from the fixed ~luidized cyclic 'ces~s.

12 TP~BLE 16 14 Reference 25~ (B)~eta Plus Catalyst efe~ence Catalyst ~.8 RON ~5 . 6 87 . 8 19 MON 7509 76.8 21 C5-34~
22 RON 85.3 87.5 23 MON 75 . 6 7~, g 24 . `:
25~ :

3 ~ :
31 ~ :
32~
~3 ~ :

:

~: :

Claims (36)

WHAT IS CLAIMED IS:

1. A zeolite having a mole ratio of an oxide selected from silicon oxide, germanium oxide, and mixtures thereof to an oxide selected from boron oxide, or mixtures of boron oxide with aluminum oxide, gallium oxide or iron oxide, greater than 10:1 and wherein the amount or aluminum is less than 0.10% by weight and having the x-ray diffraction lines of Table 1(b).

2. A zeolite having a composition, as synthesized and in the anhydrous state, in terms of mole ratios of oxides as follows: (1.0 to 5)Q2O:(0.1 to 2.0)M2O:W2O3:-(greater than 10) YO2 wherein M is an alkali metal cation, W is selected from boron, Y is selected from silicon, germanium, and mixtures thereof, Q is a diquaternary ammonium ion and having the X-ray diffraction lines of Table 1(a).

3. A zeolite in accordance with Claim 1 having a mole ratio of an oxide selected from silicon oxide to boron oxide greater than 100:1.

4. A zeolite in accordance with Claim 1 wherein a portion of the boron in said zeolite is replaced by a first row transition metal or a Group IIIA metal.

5. A zeolite in accordance with Claim 4 wherein the replacing metal is aluminum, gallium, iron, silicon, zinc and mixtures thereof.

6. A zeolite prepared by thermally treating the zeolite of Claim 3 at a temperature from about 200°C to 820°C.

7. A zeolite in accordance with Claim 2 wherein the diquaternary ammonium ion is derived from a compound of the formula:

8. A zeolite in accordance with Claim 1 or 2 which has undergone ion exchange with hydrogen, ammonium, rare earth metal, Group IIA metal, or Group VIII metal ions.

9. A zeolite in accordance with Claim 1 or 2 wherein rare earth metals, Group IIA metal, or Group VIII metals are occluded in the zeolite.

10. A zeolite composition, comprising the zeolite of Claim 1 or 2 and an inorganic matrix.

11. A method for preparing the zeolite of Claim 1, comprising:
(a) preparing an aqueous mixture containing sources of a diquaternary ammonium ion, an oxide selected from boron oxide, and an oxide selected from silicon oxide, germanium oxide, and mixtures thereof;
(b) maintaining the mixture at a temperature of at least 140°C until the crystals of said zeolite form; and (c) recovering said crystals.

12. A method in accordance with Claim 11 wherein the aqueous mixture has a composition in terms of mole ratios of oxides falling in the ranges: YO2/W2O3, greater than 10; Q/YO2, 0.05:1 to 0.50:1; wherein Y is selected from silicon, germanium, and mixtures thereof, W is selected from boron, and Q is a bis (1-Azonia bicyclo[2.2.2]octane) .alpha.' .omega. alkane compound.

13. A method in accordance with Claims 11 and 12 wherein the diquaternary ammonium ion is derived from a compound of the formula:

14. A process for converting hydrocarbons comprising contacting a hydrocarbonaceous feed at hydrocarbon converting conditions with the zeolite of Claim 1 or 2.

15. The process in accordance with Claim 14 which is a hydrocracking process comprising contacting the hydrocarbon feedstock under hydrocracking conditions with the zeolite of Claim 1.

16. The process in accordance with Claim 14 which is a catalytic reforming process comprising contacting a hydrocarbonaceous feedstream under catalytic reforming conditions with the zeolite of Claim 1.

17. The process in accordance with Claim 14 which is a process for preparing a product having an increased aromatics content comprising:

(a) contacting a hydrocarbonaceous feed, which comprises normal and slightly branched hydrocarbons having a boiling range above about 40°C and less than about 200°C under aromatic conversion conditions with the zeolite of Claim 1, wherein said zeolite is substantially free of acidity; and (b) recovering an aromatic-containing effluent.

18. The process in accordance with Claim 17 wherein the zeolite contains a Group VIII metal component.

19. The process in accordance with Claim 14 which is a hydrocracking process comprising contacting the hydrocarbon feedstock under hydrocracking conditions with the zeolite of Claim 1.

20. The process in accordance with Claim 14 which is a catalytic cracking process comprising the step of contacting the hydrocarbon feedstock in a reaction zone under catalytic cracking conditions in the absence of added hydrogen with a catalyst comprising the zeolite of Claim 1.

21. A process in accordance with Claim 20 with a catalyst composition comprising a component which is the zeolite of Claim 1 and a large pore size crystalline aliminosilicate cracking component.

22. A process as defined in Claim 21 wherein the crystalline aluminosilicate cracking component has a pore size greater than 8.0 angstroms.

23. A process in accordance with Claim 21 wherein the catalyst composition comprise a physical mixture of the two components.

24. A process in accordance with Claim 21 wherein one of the components is the zeolite of Claim 1 incorporated in an inorganic oxide such as silica, alumina, amorphous silica-alumina, silica-magnesia, silica zirconia, alumina-boria, alumina-titanate, a synthetic clay such as synthetic mica-montmorillonite, natural clays such as kaolin, halloysite, montmorillonite, attapulgite, sepiolite, and saponite, acid activated clays, pillared or cross-linked clays, and mixtures thereof.

25. A process in accordance with Claim 21 wherein the two catalyst components are incorporated in an inorganic matrix comprised of the inorganic oxide of Claim 24.

26. The process in accordance with Claim 14 which is an isomerizing process for isomerizing C4 to C7 hydrocarbons, comprising contacting a catalyst, comprising at least one Group VIII metal and the zeolite of Claim 1, with a feed having normal and slightly branched C4 to C7 hydrocarbons under isomerization conditions.

27. A process in accordance with Claim 26 wherein the catalyst has been calcined in a steam/air mixture at an elevated temperature after impregnation of the Group VIII metal.

28. A process in accordance with Claim 26 wherein Group VIII metal is platinum.

29. The process in accordance with Claim 14 which is a process for alkylating an aromatic hydrocarbon which comprises contacting under alkylating conditions at least a mole excess of an aromatic hydrocarbon with a C2 to C20 olefin under at least partial liquid phase conditions and in the presence of a zeolite according to Claim 1.

30. The process in accordance with Claim 29 wherein the aromatic hydrocarbon and olefin are present in a molar ratio of about 4:1 to 20:1, respectively.

31. The process in accordance with Claim 29 wherein the aromatic hydrocarbon is a member selected from the group consisting of benzene, toluene and xylene, or mixtures thereof.

32. The process in accordance with Claim 14 which is a process for transalkylating an aromatic hydrocarbon which comprises contacting under transalkylating conditions an aromatic hydrocarbon with a polyalkyl aromatic hydrocarbon under at least partial liquid phase conditions and in the presence of a zeolite according to Claim 1.

33. The process in accordance with Claim 32 wherein said aromatic hydrocarbon and said polyalkyl aromatic hydrocarbons are present in a molar ratio of about 1:1 to about 25:1, respectively.

34. The process in accordance with Claim 32 wherein the aromatic hydrocarbon is a member selected from the group consisting of benzene, toluene and xylene, or mixtures thereof.

35. The process in accordance with Claim 32 wherein the polyalkyl aromatic hydrocarbon is dialkylbenzene.

36. The process in accordance with Claim 14 which is an oligomerization process comprising contacting an olefin feed under oligomerization conditions with the zeolite of Claim 1.