CA1101633A

CA1101633A - Crystalline borosilicate (ams-1b) and process use

Info

Publication number: CA1101633A
Application number: CA288,362A
Authority: CA
Inventors: Marvin R. Klotz
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1976-10-18
Filing date: 1977-10-07
Publication date: 1981-05-26
Also published as: FR2367701A1; IN146957B; CS676977A2; PT67167B; LU78338A1; JPS6054243B2; NL187236C; DK153134B; NL7711239A; IT1090043B; IN148719B; IE46162B1; DE2746790A1; YU250377A; DK461477A; JPS5355500A; DE2746790C2; PT67167A; IE46162L; DK153134C

Abstract

CRYSTALLINE BOROSILICATE (AMS-1B) AND PROCESS USE
ABSTRACT OF THE DISCLOSURE
A new crystalline borosilicate composition of matter and process using it wherein the composition is expressed as mole ratios of oxides as follows:
0.9 ? 0.2 M2/nO : B2O3 : YSiO2 : ZH2O
wherein M is at least one cation, n is the valence of the cation, Y is generally a value of from about 4 to about 500 or higher, and Z is a value of from 0 to about 160, and characterized by a specified X-ray powder diffraction pattern as is described herein. Catalytic conversion including processes such as isomerization, disproportionation, or trans-alkylation are also disclosed.

Description

BACXG_OUND~ OF ~E I~VEN~ION
Field of the lnv~ntlon ,~-Thi8 inventlon relates to novel cry~talllne borosilicate~ and to their u~e. More partlcularly, thl~ lnvention relstes to novel boro~
silicate crystalline molecular sieve ~ater~als having c~talytic propertle~ and ~o ~riou~ hydrocarbon conver~ion prDces~ u~i~g such crystalline boro~ilicates. Relevant patent art c~n be found in U.S. .;
Patent Class 423-326~ 252-458 ant 260-668.
Descrlptlon of the Prior Art j.
Zeolitic 3atcrial~, both natural and synthetlc, have baen demon~
strated ln the p88t to have catalytic capabilities for msny hydrocarbon proces~e~. The zeolltic materlsls are ordered porous crystalline l- l~lllc-t~o h-vi~g definite ttructtre wlth large ~d =oLl ~, - 1 - . ;
~; ' .:

:- .

: . . .
::: - -.
., .. ~ . .. . . .

.,: .; : .
- ,: ;-~: : ..
. : ;. : , .
;: . , . . :
. . ., ,, ;~ ~ : .
., . .
..
: ' , ' : , ~. ~
i33 cavlties interconnected by channels. Th~ caviti~ and ch~els through-out the cry~talline materlal are gener~ 7 uniform ln slze allowing selective separation o~ hydroearbon~. Consequently9 the~ materlal~ in many instances have come to be cla~sifled in the art at m~lecular sleves and are utilized, in addl~ion to ~he ad~orptlve seleetiYe proce~ses, for certain catalytic propertle~. Th~ cataly~ic propQr~ies of the3e ~sterials are also ~ffected to ~o~e extent by the siz~ of the molecules which ars Allowad ~Qlactlvely to penetrate the cry~tal s~ructure presumsbly to be co~tacted with activ~ catalytlc sites ~l~hin the ordered st~ucture of these mat~rials.
Generally the term "molecular sieve" lnclude~ a wide variety of posltive lon c~ntainlng cry~talline materials of both natural and synthetic var1~tia~. They are generally characteriæed a~ crystalline alumlnosllicate~, although other cry~talllne materlals are included in the broad defini~ion. The cry~talline aluminosilicate~ are made up o net~70rks of tetrshedra of S104 and A104 moieties in ~7hich the sllicon ; and ~lumi~um ~toms are cros~ linked by the sharing of oxy~e~ ~toms. The electrovalence of the alumlnum atom is balanced by the use o~ a positive ion, for example alkali metals or alkallne earth me~als.

Prior art developments have result~d ln the formation of ma~y synthetic cry~tslline materisls. Crystalline aluminosillcates are ~he most prevalent ~nd as described in the paten~ litersture ~nd in the publlshed ~ourn~l~ are desi8nated by letters or other con~enient symbols.

P~emplary of these mater1~1s ar~ 7.eolite A (U.S. Patent 2,882,243), ~ 25 Zeollte X (U.S. Patent 2,882,244), Zeolite Y (U.S. Patent 3,130,007), ~ Zeolite ZSM-5 (U.S. Paten~ 3,702,~86~, Zeolite ZSM~ll (U.S. Patent `- 3,709,979), Ze~lite ZSM-12 (U.S. Patent 3,832,449) ~nd other~.
~elevant art 18 the above U.S. Patent 3,702,886, claimln~ the crystalllne alumino~illcate Zeollte ZSM-5 and the method for making the 6~3 same. Thl~ pAtent 1~ limitad to the productlon o~ a zeolit~ wherein aluminum or galllum o~id~ ar~ pre~ent in the crys~alline structure along with silicon or germanium o~ides. A ~peclflc ratio o~ the latter to the former are reacted to produce a cla~s of zeolites designated ZSM-S which i~ llmited ~o c~ystalline alumlno or gallo ~illcates or ger~anates and having a ~p~cified X-ray diP~rac~lon patt~rn. The above ZS~S-ll and ZSM-12 patent~ are similsrly limited to cry~talline alumino or gallo silicate or germanates also having ~pecified X-ray diffractlon patterns.
Manu~actur~ of the Z~l materlal~ utilizes a mixed bs~Qd sy te~ in which sodium alu~inate, and a silicon containing material are mixed together wlth ~odium hydro~ide and an organic ba~e such a~ tetra propyl~
a~monium hydro~ide or tetra propylam~onium bromide under spectfled reactio~ condition~ to ~onm tha dQsired crystalline aluminosilicate.
U.S. Paten~ 3,941,871 clalms and teaches an orgsnosilicate having ~,~
; very ll~tle aluminum in its cry~talllne etructure and posse~sing a~X-ray di~fractlon pat~ern ~lmilar to the ZS~1-5 compositlon. Thi~ patent is con~idered relev~nt art.
Other relevant art includes U.S. Patent~ 3,329,480 and 3,329,481 : 20 which r~late to "zircono-~il.tc~te~" and "titano-silicste~", respectively.
The pre~ent invention, however, relat~s to a novel family of ~table synthet~c cry~talline materials characterized as boroRilicates identlfied a~ AMS-lB kavi~g a specifled X-ray dl~r~ctio~ pattern. The clsimed : A~IS-lB cry~talline boro~llicates are form~d by reacting a boron ~alt : 25 and 8 ~ilicon containing material in a baaic medium.
SUMMARY OF TH~ IIWENTION
In a broad embodiment my inve~tlon relates to a cry~talllne boro-silicate having a composition ln term~ of mole ratio~ of oxide~ a~
follo~s:
~: 30 0.9 ~ 0.2 M2/nO B203 YS102 ZH20 where M iB at lea t one cation havlng a valence n, Y ls between 4 and about 500 snd z 1~ between 0 and about 160~ ~aid borosillcate ~howing thc interplanar spaclng~ and ae~lgned ~trengtha as descrlbed ln Table I
of the opeciflcation.
In a more preferred ambod$ment Y i~ a value between about 40 and about 500 and Z i~ a value between 0 and about 40.
In a~other broad e~bodiment my inventlon relates to a cry~talli~e borosilicate having a compo~ltlon in tcrms of oxides as follo~a:
to ~9 + Z t~R2) ~ tl-W) M2/n0 : B203 : YSiO2 : Z~2 whereln R i~ ~etrsalkyl~mmoniu~, M i~ an alkali metal catlon, W 1B
greater tha~ 0 and le~s than or eq wl to 1, Y ic between 4 and 500, Z is between 0 and about 160 and showi~g ~he interplan~r spacings and a~signed strength~ ~8 described ln Table II of the ~pecificatio~.
` In a more preferred ~bodiment W i8 a ~alue between about 0~6 and : about 0.9, Y 18 a value between about 20 and about 500 and Z 1B a value : betwee~ 0 and about 40.
`:"
`~ In another embodiment my invention relates to a procQs~ for con-version of a hydrocarbon which comprises contactlng sald hydrocarbon at ~ 20 ;-` converslon co~dltion~ wlth a crystalline borosllicate hav~ng a co~positio~
;
in terms of mole ratio~ of oxide~ a~ follows:
o,9 + 0,2 M2/nO : B203 : YSiO2 ZH20 ;~ wherein M 1~ at lea~t one cation having a valence n, Y 1~ in the range ~ of ~rom about 4 to about 500, and Z lo in the range of from 0 to sbout -:~; 25 160, and sald boroollicate ~howlng the lntsrplsn~r ~pacings snd as~lgned ~trength~ a~ de~crlbed in Table I of the ~pecifica~lon.
In ~noeher ~mbotiment ~y inventlon relate~ to a proces~ for c~talytic i~sm~rlzat10n of a xylene feed which comprlses contacting ~aid feed at isomerlzation condltlono wlth a cry~talline boro~lllcate having a ~`

compo~itlon in terms of mole ratios of oxlde~ a~ follaws:
0.9 ~ 0,2 M2/nO : B203 : ~Si02 ZH20 wherein M i~ at lea~t one cation having a val¢nce 1l, Y 1~ in the range of from about 4 ~o about 500 and Z i~ in the range of from about 0 to about 40, said cry~talline boro~lllcate show:LIlg ~he interplanar spacings ; and a~igned strengths as described in Iable I o the specificatlon.
D~SC~IPTIO~l ~F THE SP~CIFIC E~ODIMENT
The present invention relate6 to a novel ~ynthetic ~MS-lB crys-talline borosilicate. This family of ~S-lB cry~talline boro~ilicate materials ha~ a specified X~ray diffraction pattern as is shown in the ; Tables below. ~he AMS-lB cry~talline borosilicates can generally be characterized, in terms of the mole ratio of oxide~, as follow~ in equation I:
0.9 + 0.2 M2/n0 : B203 : YSiO2 ZH20 (I) wherein M i~ at lea~t one cation, n i~ the balence of the cation, Y is a value of from 4 to about 500, and Z representing the water present in such material as having a value of from 0 up to about 160 or more, In another instance, the claimed ~MS-lB crystalline borosillcate can be represented in term~ of mole ratio~ of oxide~ for the crystalline material not yet activated or calcined at high temperatures as follo~s in equatio~
0-9 ~ 0-2 (~2 ~ W) M2/no~ : B203 : YSiO2 ZH20 (II) where R is tetrapropylammonium, ~ i~ at lea~t ona catlon, n i~ the valence of the cation, Y is a value ~rom about 4 to 500, Z i~ a value from about 0 to about 160 and W i8 a value greater than 0 ~nd le~s than l.
The origlnal catlon, "M" in the above formulations, can be replaced ln accordance with technique~ well-known in the art, at lea~t ln part by ion exchange with other cation~. Preferred replacing cations include tetraalkylammonium catlons, metal ions, ammonium ions, hydrogen ions, and mixture~ of the above. Particularly preferred cation~ are tho~e which render the AMS-lB cry~talline boro~ cate ca~alytically actlve especially for hydrocarbon conversion. These materials include hydrogen, rare earth metal~, aluminum, metals of Groups IB, IIB and VIII of the 5 Period$c Table, noble metal6, manganese, etc. and other catalytically active material~ and meeal~ kno~m to the art. The catalytic~lly actlve components c~n be pre~ent anywhere from about 0.05 to about 25 weight percent of the AMS~lB cry~talline borosilicate.
Members o~ the family of AMS-lB crystalline borosllicates pos~ess ~o a specified and distinguishlng crystalline structure. The reported x-ray dlffraction patternR generated by these materlal~ were obtained using standard powder diffraction techniques. The X-ray diPfractometer Wa8 8 Phillips instrument which utilized copper K slpha r~diation ln COD~u~ctiOn wlth an AMR focusing monochromet~r and ~ thata compen~ating 15 sllt, in which its aperture varies with the theta nngle.
ThQ output from the diffractometer wa~ proces6ed through a Canberra hardware/~oftw~re package and reported by way of a strip char~ and tabular printout. The co~pensating ~lit and the Canberra p~ckage tend to increase the peak/background ratio~ ~hile redueing the peak int~nsities at low theta angles [high d (A)] and inereA~ing ~he peak inten~itie6 at high theta anglej [low d (A)J. All of the X-ray pa~erns reported hereln used the above analytical techniques.
;~ The relat~ve lnten~ities reportQd were calculated as (100 I/Io~
~` where Io i~ the lnten~ity of the s~rongest recorded peak and I i8 the 25 value actually read for the particular interplanar spacing.
`~ For ease ~f reporting the relatlve lntensitie~ were arbitrarily - as~igned the f~llowing values:

: ` `

Assi~ned Stren~th le~s than 10 ~ VW
10-19 ~ W
20-39 ~ M
40-70 ~ MS
gre~ter ~han 70 ~ VS
5A eypical X-ray diffractlorl patt~rn dl~pl~ying the aigniicant line~
which have~ rel~ti~e inten~ o~ 11 or hlgh0r ~orl~n AMS-lB cry~t~lllne boro~illcat~ after c~lclnation at 1000F. (535C.) i~ ~howrl in Table I
belo~:
TABLE I
Inte~pla~ar Spacing Rela~cive As~lgned d tA) Intens~ty Strength : 11.3 + 0.2 38 M
`~ 10.1 + 0.2 30 M
`` 6.01 t 0,07 14 ~ 4.35 + 0.05 11 W
: 4.26 ~ 0.05 14 W
`~ 3.84 + û.û5 100 VS

~ 153 65 + 0 05 31 ~l `~ 3.44 + 0.05 14 W
3.33 ~ 0.05 16 W
3.04 + 0.05 16 W
: 2.97 ~ 0.02 22 M

2.48 ~ 0.02 11 W
1.99 + 0.02 20 M
1.66 + 0.02 12 20AI1 ~S-lB boro~ilicate wh~ch ha~ been only subJacted to mild drying at 165C (a~ produced mat2r~Lal) p0~13e9~3e8 an X-ray dlffraction pattern havlng the following signi~lcant line~:
TABL~ II
:
Interpla~ar Spaclng Relative Ass$gned d (A) Inten~lty S'crength 2511.4 + 0.2 lg W
10.1 + 0.2 17 W

3.84 + 0.05 100 VS
3.73 ~ 0.05 43 ~IS
: 3.66 ~ 0.05 26 M
3.45 ~ 0.05 11 W
3.32 ~ ~),.05 13 W
3.05 ~ 0.05 12 W
2.g8 + 0.02 16 W
301.99 t 0.0~ 10 W
1.66 ~ 0.02 20 M

rip ch~rt ~æcordlngs of th~ ealcined boro~lllc~t~ r~ported ln Tabl~ I above ~how~d ~ha~ ~hl6 ~terl~l had thQ followlng X-r~y dl~2r~ctlon line~ .
T~L~. III
Interplan~r Spaclng d (A~
Run 1 ~tun 2 11.3 11~2 10.2 10.0 7.4~ 7.37 6.70 6.7û
.~1 6.36 6.02 5.98 5.71 5.67 5 6~ 5.57 5 01 5.34

4.62 5.01 ~ . 62 4.27 6,~35 4.00 4.25 3.85 4.00 3.72 3.85 3.64 3070 3.48 3.~4 3 44 3.46 3 30 3.42 3.14 3.30 3 04 3.25 2 98 3.12 2.~96 3.04 2 . 71 2 . ~7 2.60 2.86 2.t~8 2.71 2.39 2.32 2.22 2.00 l~g 1.g5 1. 86 1.75 1.66 : O
run t~rmlnat~t ~ 2. 71 d (A) ~ c A~S-lB crystalllne borosilicate~ are U8efUl in the catalytic cracklng and hydrocrackin~ proce~se~ ThQY appear to h~ve relatively useful catalytic properties ln other petrolellm refini~g processe3 ~uch as the isomeri~atlon of normal paraffins and naphthenes, the reforming of certain feedstocks, the l~omerizatlon o~ aromAtics especlally the isomeri~ation ~f polyalXyl sub~titued aromatics such as ortho~ylene, the disproportionation of arDmatlcs ~uch as toluene to form mixture~ of other more valuable products including benzene, xylene and other hi~her methyl substit~ted ben~enes and hydrodealkylation. ~en u~ed as a ; lO catalyst ln isomerization processes with suitable cations placed on the lon exchangeable sites within the. A~S~lB crystalline boroslllcate, reasonably high ~electivlt-les for p~oduction of de~lred i~omer~ are obtained.
The activlty for these material~ ~o be ~tahle under high temparR~
ture6 or in the presence oE other normal deactivatlng a~ents appears ~o make this class of crys~all$ne material~ relatively valuable for high tempera~ure operations lncluding the cyclical types of fluidized cata-lytic cracking or other processing.

The hMS-lB crys~alline borosilicate~ can be u~ad AS catalysts or a~
ad~orbent~ l~hether in the al~ali metal forms, the ammonium or~, the hydrogen form or any other univalent or multiYalent ca~i~nic form.
Mlxtures o cations may be employed. Ihe ~IS-lB cry6talllne borosilicate~
can also be u~ed ln intlmate combination with a hydrogenatln~ co~ponent such a~ tungRten, vanadiu~, molybdenum~ rhenium, nickel, cobalt, chromium9 manganese, or a noble metal 8uch as platinu~ or palladium or rare earth metals where a hydrogeDation-d~hydrogenation function i~ to be performed~
Such components can be e~changed into the co~po~ltion at the catlonlc slte~, represented by the te-rm "M" in the above fGrmula~, impregIlated therein or physically intimately admixed therewith. In one example, ~o platinum can be placed on the borosillcate with a platlnum metal con-tainlng ion.
The original catlon a~sociated wlth the AMS-lB crystslline boro-sillcate can be replaced a~ mentloned above by a wlde variety of other cstlon~ according to techniques whlch are known ln the art. Ion e~chan~e technlq~es known in the a~t are disclosed ln many pate~t~ in-; cludln~ U.S. Patent 3,140,249, U.S. Patent 3,140,251 and ~IS. PateDt 3,140,253.
~ ' !~ Pollowing lon exchange, impregnation or contact with another msterlal to place catalytlcally actl~e material~ wl~hin or on the `~ boroallicate structure, the ~aterial can be waahcd and then drled at temperatuses ln the range of about 150 to Absut 600F. It can then be calcined in air or nitrogen or combination~ of both at cloaely regulated temperaeures in a range rom about S00 to about 1500~ for various periods of time.
Iv~ ~xchange within the cationlc ~lte wi~hin the crystallinematerial ~ enerally have a relati~ely inRignificant effect o~ the overall X-ray dlffractlon pat~ern that the crystalllne borosillcate ~at~rial gen~rates. S~all vari~tlons ~ay occur at varlous spaclngs o~
the X-ray pattern but the overall pattern remain~ es~ent~ally th~ sa~e.
Sm211 change~ ln the X~rny diffraction patt~rns may al~o be the result of proce~ing d~fferences durin~ msnufacture of the boroslllcaee, how-ever, the ~aterlal wlll ~till fall wlthin the generlc class of AMS-18 crystalline borosllicate~ deflned in terms of thelr ~-ray dlf~ractlon pattor~6 as ~hown in Table~ I, II and III or in the Exampl~s that ~ollow.
The clalm~d crystalline boro~lllcate may be incorporated a~ a pur~
boro~llicate in a cataly~t or ad~orbent or may be admixed with ~arlous ' .

, , ~ , .: , .

binder~ or base~ depending upon the lntended proce~s u~. In ~any lnsta~c~, the cryatalline boro~ilicate can be pelletized or extruded.
The crystalline borosilica~e can be combined with actlve or inactive material~, ~ynthetic or na~urally occurring ~eolites a~ wQll a~ ln-organic or organlc m&terials which would be u~eful for blnding the : borosilicate. Other well-known materiala include ~lxtures of ~ilica, silica-alumina~ alumins ~ol~5 clays such ~ bentonite or kaolin or other binder~ well known in the art. The crystalllne boro~ cate can al~o be mi~ed intimately with porou~ matrix materlals such aa silica-z~xconia, silica-~gne~la, 8illca-alumi~a~ ~tlica~ thoria~ ~ilica-beryl-lia, allica-titania as well as three compo~en~ composition~ including but not limited to sillca-alumlns-thoria and m~ny other materlal~ well known in the ar~. Th~ crystalline borosilicate con~nt c~n vary any-wh~re from a ~ew up to 100 per cent of the total finl0hed product.
The A~fS-lB crystalline boro~ilieats can be g~nerally prepared by ml~ln~ in an aqueous medlum oxide~ o~ boron, sodium or any other alkali ~etal ant ~ilicon9 and a tetraalkyl~m~onium compound. The le ra~ios oE the vsriou~ reactan~ can be vari~d con~lderably to produce the AMS-lB cry~talline boro~llicates. In particular, r~actan~ mol~ ratios ln texmA of the variou~ o~ide~ for producing the borosill te can vary as i8 lndicated in Tsble IV below.
TABLE IY
Mol~ Ratios Si2tB~3 5 600 (or higher) R4N~/(R4N + Na ~ 0.1-1 OH /SiO2 0~01-10 where R i8 alkyl ~nd pre~erably propyl. The above quan~iti~s can be var~ed in concentrstlon ln the aqueous medlum. It 1~ generally pre-ferred th~t the mole ratio of water to thQ hydroxyl lon vary ~nywh~re from about 10 to about 500 or higher.

By simple regulation of the q~antity of boron ~a3 B20~3 ln the reactlon mixtur~, it i8 possible to vary ~he SiO~/B2O3 molar ratio in the final product in a range of from about 40 to about 500 or mor~. In instances where a deliberate effort i~ made to eliminate aluminu~ r~ the boro-; 5 silicate crystal ~tructure becau~e of lts sdverse influence on psrticular conversion processes the molar ratios of SiO2/A1203 can ea~ily exceed 2000-3000, This ratio ~8 generally only limited by the av~llablllty of aluminu~-free raw material6.
MolAr ratios of S1021B~03 ~n the f~nal cry~talline produc~ can vary ,~ lO from about 4 to about 500 or more. Ac~ual laboratory preparatlons under the general conditions described hereln produce SiO2/B203 molar ratlo~
starting around 40 or lowes~ Lower ratio~ can generally be produced u8ing production m~thod~ which ~till are ln ~he 8cope of ~he teaching~
of thl~ speci~ication~
Bas~d on known propert~es o mordenite and ~errleritQ alumlnosillcatea, the present cry~talllne borosilicates will have about 4.5 B04 tetrahedra pcr unit cell at SiO2/B2O3 molar ratios around 80. In ~iew of this it ; would sppear that a ~lngl~ BO4 exi8t8 at S102/B203 ratio~ around 500.
A~ove thi~ ratio there would be many unit cells which did not contain a ~04 tetrshedro~ and the resultlng cry~talllne ~tructure mi8ht not be considsred a borosilicate. There sre no e~a~liahed crlteria for establl~hlng at what SiO2/B203 molar ratlo the crystallin~ material cease~ to be a borosilicata. It s~e~ sa~e to as~ume that at hlgh SiO2/B~03 value~ (above 1000 or more) ~he influence of the B04 tetrahedra in the cry~talline ~trueture b~csm~ ~omewhat dlmlnlshed and the crystalllne materlal would no long~r be re~erred to a~ a boro~lllcate.
Under rea~onably controlled condltion~ using the above lnformatlon the claimed AMS-lB cry~talllne boro~ilicate wlll be produced. Typical reaction condition~ include heating the r~act~nt~ to a ~emperature of .

3~63~

anywhere from about 90 to about 250C or higher for ~ perlod of time of anywhere from about ~ few hours to a few wcek~ or more. Preferred temperature rsnge~ are an~where from abou~ 150 to abont 180C with an smount of time neces~ary for the preclpitatlon of the ~ ~-lB cry~talline borosllica~e. Ebpeclally preferred condition~ lnclude a tQmperature around 165C for a perlod of about 7 tays.
The material thus for~ed can be separ~ted and recovered by well-known means such as fll~ration. Thl~ materlal can be mildly dried for snywher~ from a few hours to a few days at varying temperatures to form to a dry c~ke which lt~elf ca~ then be cru~hed to a powder or to ~mall particles sud extruded, pelletlzed or Lade into forms cu~table for it~
intended use. Typlcally the mQterial prepared after the mild drying conditions wlll contain the'tetraalkylsmmonlum ion within the ~olid ma6s and a ~ubsequent actlvatlon or calcination procedure 18 neces~ary i~ it i8 de~lred to remove thls materlal from the formed product.
Typically the high t~perature calcinatlon condltlous wlli take plac~ ~t temperatures anywhere from about 800 to about 1600-F or higher.
Extreme calclna~lon temperatures may prove dctrim~ntal to the crys~al atructur~ or ~ay totally destroy it. There iP gen¢rally no need for goiDg beyond about 1700F in order to remove the tetraalkylammonlum ca~lon from the origlnal crystalline material formed.
When the AMS-lB crystalllne borosilicate i8 u~ed a8 a hydrocracking catalyst, hydrocracking charge stock~ can pa88 over thc catalyst at ~emper~turca anywhere from about 450 to About 900F or hlghor u~ing known mola~ r~tio~ o~ hydrocarbon to hydrogen in the range of 1 to 100 and varying pressures anywhere from 20 up to 2500 pounds per square inch or higher. The liquid hourly space velocity may be in the range of from about 0.1 to about 50, and other process parameters can be varied consistent with the well-known teachings of the art.

~1~3L633 In employing the borosilicate for fluidi7ed catalytic cracking processing, well known operating conditions can be used including temperatures anywhere from about 500 to about 1200F in the reaction zone and temperatures anywhere from about 800 to about 1300F in the regeneration zone. Contact times, feedstocks and other process conditions are known in the art. The pressure may in certain embodiments be in the range of from about atmospheric to about 2500 psig and a liquid hourly space velocity in the range of from about 0.1 to about 75.
The specified AMS-lB crystalline borosilicate is also suitable as a reforming catalyst to be used with the appropriate hydrogenation components at well known reforming conditions including temperatures of anywhere ~rom ` about 500 to 1050F or more, pressures anywhere from a few up to 300 to `` 1000 psig and liquid hourly space velocities and hydrocarbon to hydrogen mole ratios consistent with those well known in the reforming art.
; The present composition is also suitable for hydrocarbon isomeriza- ;
tion and disproportionation. Suitable isomerization conditions include a temperature in the range of about 200F to about 1000F, a pressure in the range of atmospheric to about 3000 psig, a liquid hourly space velocity in the range of 0.1 to about 50, and a molar ratio of hydrogen to hydrocarbon in the range of 0 to about 20. It is especially useful for liquid or vapor phase isomerization of xylenes and especially the isomerization of mixed xylenes to predominately paraxylene products. Xylene isomerization conditions include temperatures of anywhere from about 250F to about 990F, hydrogen to hydrocarbon mole ratios of from about 0, to about 20, and a pressure in the range of about zero to about 1000 psig, a weight hourly space velocity in the range of 1 to about 20, and a pressure in the range of a~out zero to about 1000 psig. The choice of catalytically active metals to be placed on the AMS-lB crystalline borosilicate can be selected from any of those well known in the art. Nickel seems to be especially appropriate for i60merization of aromatics.
The claimed AMS-lB crystalline borosilicate can also be used as absorbents to selectively adsorb specific isomers or hydrocarbons in general from a liquid or vapor stream.
~ 14 -The follQwing example~ are presented ~8 speclfic e~bodlment~ of the pre~ent inventlon and should not be read to unduly li~lt or ~estrict the ,~ scope of the app~ded c~alms.

';`

: 10 ~ ` :

2s ` 30 -` EXA~LE I
An AMS-lB crystalline boroslllcate wa~ prepared by dis~ol~ing 0.25 gm of B3B03 snd 1.6 g~ of NaOH in 60 gm of diatilled H20. Then 9.4 jgmB of tetra-n-propyl~mmonium bro~ide (TPABr~ were added and again di~sol~red. Finally, 12.7 8m of Ludox-AS (30% solid6) were added with vigorou6 ~tirring. The atdition o Ludox ga~e a curdy, gelatinous, milky solution. Thls solu~ion was placed in a reactlon bomb and sealed.
The bomb was placed in a 165C oven ~nd left there for 7 days. At the ent of ~his tlme lt was opened and lt~ content~ were filtered. The reco~ered cry~t~lline materlal was washed wlth copious qu~ntities of H20 and was ~hen drled at 165-C ln a forced air oven. The drlet material wa~ ldentified by X-ri~y diffra~tion a~ a crystalllne ~terial h~vlng ~he typical AMS-lB pattern with 100% cry~tallinlty. The yleld wa~

approxlmately 2 griams.

*Trade Mark .
: 20 ~ :
::

~X~PLE II
In thl~ ~a~ple the ASkl-lB crystalline boro~$1icate of Example I
wa8 URed to produce a catalyst having l~omerlzation capabllitie~.
The materlal fro~ ~mpla I was calci~ed a~ 1100~ (535C) in air ~or 4 hours to remove the or~anic ba~e. The calclned ~ievc was e~changsd one time with a ~olution o 20 gm of NH4N03 in 200 ml o~ EI20 and then a ~econd time with 20 gm of NH40Ac ln 200 ~1 of H20 at l90~F for 2 hourM.
Th~ exchanged borosilicate wa~ dried and calcined ln alr by heating it to 900F in 4 hours5 main~aining the boro~llicate at 900F for 4 hours and then cooling to 100F in 4 hours. The calcined materlsl wa~ ex-changed wi~h 100 ml of a 5% ~ N03)2 . 6H20 ~olution for 2 hours at 190~. The sieve wa~ wa~hed wlth ~2 a~d the Ni~ wa~ completely washed out of the 6ie~e. The sleve ~3~ drled and calcined agal~ u~ing the above procedure. About 2 gram~ of th~ boroailicate wao di~per~ed in 16.9 g~ of P~-A1203 hydrosol ~8.970 ~olids~ and mixed thoroughly. One ~illillter of di~tllled 1120 and 1 ml of conc. N~ OH were ml~ed ~nd added to the slurry wlth int2nsive mixing. The AKS-lB-A1203 mlx wa~ placed i~
a drying oven at 165C for 4 hour3. The dried material wa6 a8ain cal-2Q clned u~lng th~ above procedure. The calclned c~taly~t wa~ c~ushed30-50 me~h and lmpreg~ated wlth 2 ml of a 5~0 (Ni(N03)2 . 6H20 ln d~otilled H20. The catalyst wa~ again d~ied and activated by a fourth prog~ammed calcinatlon.
The calcined catAlyst contalned 65 welght percent boroailicate and 35 weight perc~nt amorphous alu~ina with approximately 0.5 ~ight per-cent of th~ total solld a~ nickel.
One gr~m of the siæed and activated c~t~ly~t wa~ placed in th~
microreac~or a~d ~ul~lded wlth ~I2S or 20 minute~ a~ room tempQratUre.
The cataly~t was then pl~ced under ~I2 pre~sure and heat~d to 6004F.

Af~er 1 hour feed wa~ p~ffsed through the ~icrore~ctor under the following o~e-through condition~:

;
Temperature 800F

Pressure 150 psig WHSV 6.28 hrs.

; H/HC, mole ratio 7 ':
The liquid feed and effluent streams for this operation are shown below. Because of the equipment limitations on the screening unit, only analysis on liquid streams were performed and reported. The light-end production over this catalyst was low from the gas chromatographic analysis made on the off-gas -~
stream from the unit. The volume of off-gas was determined to not su~stantially reduce overall liquid yields over the catalyst.

Component Liquid Feed, wt.% Liquid Product, wt.

Paraffins and .03 .08 naphthenes Benzene -- 1.51 Toluene .077 .26 Ethylbenzene 19.71 17.35 paraxylene -- 19.43 metaxylene 79.80 46.40 orthoxylene ~38 14.96 C9+* -- 1.*
~.
* Approximate values only ~18-X~ LE III
A 801utio~ of 600 gm 1120, 2.5 gm ~I3B~3 aQd 7.5 ~n o~ ~AOH wa~
prepared~ 94.3 ~ of TPABr was added to the original mi~ture and dl~-~olved, Then 114.5 gm of Ludox-~S ~30 wt.~ ~olids) were added to the originsl llquid m~xture with vigorous ~kirrlng.
The re~ultlng mix~ure wa~ placed in a reaction bomb and sealed.
The bomb was plsced ln an oven at 165C for 7 day~.
After washlng and drying of the reco~ered solid~ a~ descrlbed in Example I. The cry~talline boro~ilicate was iden~ified a~ ~IS-lB

a~d ohow~d an X-ray diffraction pattern similar to ~hat of Table II.

_ 19 -.~

EXAMPLE IV
A borosilicate similar to that prepared in Example I was calcined at about 1100F and then analyzed to determine its over-all composition. The results are shown below.
Component SiO2, wt.% 94.90 B2O 1.06 " Na2 ; ~123 0 057 Fe23 0.029 Volatiles* 2.984 Total 100.000 ' :
Mole Ratios Si2/B23 104.5 Na20/B203 1. 0 :
SiO2/A12O3 2824.4 SiO2/Fe2O3 8787.0 SiO2/(A12O3 + Fe2O3) 2146.2 * Assumed value to total 100~

Other borosilicates were produced as generally described in Example I except that the H3BO4 content ratio was varied resulting in SiO3/B2O3 molar ratios varying from 50 to 160 or higher before the borosilicate was calcined or exchanged.
After exchange with suitable catalytic materials the Sio2/B2O3 molar ratio generally increased to a value of 80-100 for an as prepared borosilicate which had a Sio2/B2o3 molar ratio of around 50.

.

'EX'AMPL~ V
Three borosilicate materials were prepared similar to the method described in Example I. The recovered materials were calcined at 1000F (535C) and then analyzed for boron and silicon as reported below.

Wt. % Molar Ratio Borosilicate Boron SiO2/B2O3 A 0.66 47.4 B 0.64 49.1 C 0.71 44.5 After ion exchange with ammonium acetate the borosilicate was calcined at 535C. The following was then determined:

Molar Ratio Boros-ilicate SiO2/B203 A 75.1 B 71.2 C 64.2 Powder X-ray diffraction analysis was performed on samples of the above borosilicates after they had been calcined at 1000F but prior to ion exchange. The reported patterns are shown below for relative intensities (I/Io) of 10 or greater.
Table III above shows the interplanar spacings indicated from a strip chart for two runs of borosilicate A after 1000F (535C) calcination but before ion exchange.

TABLE V
(Borosilicate A) , ~
Interplanar Spacing d (A) Relative Intensit~ (I/Io) 11.34 38 10.13 30 6.01 14 4.26 14 3.84 100 TABLE` V ~continued) ~Borosilicate A) : Interplanar Spacing d (A) Relative Intensity (I/Io) 3.72 52 : 3.65 31 3.44 14 2.97 22 :
2.48 11 1.99 20 1.66 12 TABLE VI
(Borosilicate B) Interplanar Spacing d (A) Relative Intensity (I/Io) `~
11.35 41 10.1~ 31 6.02 15 4.26 15 3.8~ 100 3.72 52 -3.65 33 3.4~ 13 3.32 15 2.97 22 2.48 11 1.99 20 1.66 12 ,~
! .

~' -22-:

. `

TAr,LE VII
(13orosilicate C) Interplanar Spacing d (1~)Relative Intensity (I/Io) 511 . 40 33 - 10 . 17 29 6.03 13

5.62 10 4,27 14 3 . ~4 100 3 . 73 51 3 . 65 30 3 . 44 13 3 . 32 16 3 . 05 16 2 . 98 21 1.99 19 1 . 66 12 ;

~' -- ~3 --

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A crystalline borosilicate having a composition in terms of mole ratios of oxides as follows:

0.9 ? 0.2 M2/nO : B2O3 : YSiO2 : ZH2O
where M is at least one cation having a valence n, Y is between 4 and about 500 and Z is between 0 and about 160, said borosilicate showing the X-ray diffraction lines of Table I of the specifications.

2. The composition of Claim 1 further characterized in that Y is a value in the range of from about 4 to about 200.

3. The composition of Claim 1 further characterized in that M is selected from the group consisting of alkylammonium, ammonium, hydrogen, metal cations or mixtures thereof.

4. The composition of Claim 3 further characterized in that M comprises nickel.

5. The composition of Claim 1 further characterized in that M comprises hydrogen, nickel and an alkali metal.

6. The composition of Claim 1 further characterized in that M comprises hydrogen and nickel.

7. The composition of Claim 2 further characterized in that Z is in the range of from 0 to about 40.

8. The composition of Claim 1 further characterized in that Z is in the range of from 0 to about 40.

9. The composition of Claim 8 further characterized in that Y is in the range of from about 50 to about 160.

10. The composition of Claim 1 further characterized in that said borosilicate also shows the X-ray diffraction lines of Table III (Run 1) of the specification.

11. A crystalline borosilicate having a composition in terms of mole ratios of oxides as follows:

0.9 ? 0.2 M2/nO : B2O3 : YSiO2 : ZH2O
where M is at least one cation having a valence n, Y is between 4 and about 500 and Z is between 0 and about 160, said borosili-cate showing the X-ray diffraction lines and assigned strength substantially as described in Table I of the specification.

12. The composition of Claim 11 further characterized in that Y is a value in the range of from about 4 to about 200.

13. The composition of Claim 11 further characterized in that M is selected from the group consisting of alkylammonium, ammonium, hydrogen, metal cations or mixtures thereof.

14. The composition of Claim 13 further characterized in that M comprises nickel.

15. The composition of Claim 11 further characterized in that M comprises hydrogen, nickel and an alkali metal.

16. The composition of Claim 11 further characterized in that M comprises hydrogen and nickel.

17. The composition of Claim 12 further characterized in that Z is in the range of from 0 to about 40.

18. The composition of Claim 11 further characterized in that Z is in the range of from 0 to about 40.

19. The composition of Claim 18 further characterized in that Y is in the range of from about 50 to about 160.

20. A crystalline borosilicate having a composition in terms of oxides as follows:
0.9 ? 0.2 (WR2O + (1-W) M2/nO) : B2O3 : YSiO2 : ZH2O
wherein R is tetrapropylammonium, M is an alkali metal cation, is greater than 0 and less than or equal to 1, Y is between about 4 and about 500, Z is between 0 and about 160, said boro-silicate showing the X-ray diffraction lines and assigned strengths substantially as described in Table II of the specification.

21. The composition of Claim 20 further characterized in that Y is a value in the range of from about 4 to about 200.

22. A process for conversion of a hydrocarbon which comprises contacting said hydrocarbon at conversion conditions with a crystalline borosilicate having a composition in terms of mole ratios of oxides as follows:
0.9 ? 0.2 M2/NO: B2O3 : YSiO2 : ZH2O

wherein M is at least one cation having a valence n, Y is in the range of from about 4 to about 500, and Z is in the range of from 0 to about 160, said borosilicate showing the X-ray diffrac-tion lines and assigned strengths as described in Table I of the specification.

23. The process of Claim 22 further characterized in that Y is in the range of from 4 to about 200.

24. The process of Claim 22 further characterized in that Y
is in the range of from about 4 to about 200 and Z is in the range of from 0 to about 40.

25. The process of Claim 22 further characterized in that Y is in the range of from about 50 to about 160 and Z is in the range of from 0 to about 40.

26. The process of Claim 22 further characterized in that said borosilicate shows X-ray diffraction lines and relative intensities as described in Table I of the specification.

27. The process of Claim 22 further characterized in that the conversion is cracking and said conversion conditions in-clude a temperature in the range of from about 500°F to about 1200°F, a pressure in the range of from about atmospheric to about 2500 psig and a liquid hourly space velocity in the range of from about 0.1 to about 75.

28. The process of Claim 22 further characterized in that the conversion is hydrocracking and said conversion conditions include a temperature in the range of from about 450 to about 900°F, a mole ratio of hydrogen to hydrocarbon in the range of from about 1 to about 100, a pressure in the range of from about 20 psig to about 2500 psig and a liquid hourly space velocity in the range of from about 0.1 to about 50.

29. The process of Claim 22 further characterized in that the conversion is isomerization and said conversion conditions include a temperature in the range of from about 200°F to about 1000°F, a pressure in the range of from about atmospheric to about 3000 psig, a liquid hourly space velocity in the range of from about 0.1 to about 50 and a molar ratio of hydrogen to hydrocarbon in the range of from zero to about 20.

30. A process for catalytic isomerization of a xylene feed which comprises contacting said feed at isomerization conditions with a crystalline borosilicate having a composition in terms of mole ratios of oxides as follows:
0.9 ? 0.2 M2/nO : B2O3 : YSiO2 : ZH2O
wherein M is at least one cation having a valence n, Y is in the range of from about 4 to about 500 and Z is in the range of from 0 to about 160, said crystalline borosilicate showing X-ray diffraction lines and assigned strengths as described in Table I
of the specification.

31. The process of Claim 30 further characterized in that Y is in the range of from about 4 to about 200 and Z is in the range of from 0 to about 40.

32. The process of Claim 30 further characterized in that said isomerization conditions include a temperature in the range of from about 250°F to about 900°F, a pressure in the range of from about zero psig to about 1000 psig, a mole ratio of hydrogen to hydrocarbon in the range of from about 0 to about 20 and a weight hourly space velocity in the range of from about 1 to about 20.

33. The process of Claim 32 further characterized in that Y is in the range of from about 4 to about 200 and Z is in the range of from about 0 to about 40.

34. The process of Claim 30 further characterized in that Y is within the range of 4 to about 200.