Note: Descriptions are shown in the official language in which they were submitted.
-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
..
~: .
' ':
.
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.
16
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.
22
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.
'," ~' ' ' i. ' i ' i; : .'; " .:'; ' "'i " ':; ; ''' ' " i;i '' ,' ' '';i ' ~ '; ' '''`
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.
0~
Q5 SUMMARY OF THE INV~NTION
0
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.
24
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.
33
" ' :: ~ ~ : . 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.
12
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.
24
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.
05
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~.
19
DETAILED DESCR~PT~ON OF THE ~NVENTION
21
22 ~)Beta zeolites, as ~ynthesized, have a ~rystalline
structure whose X-ray powaer dif~raction pattern shows the
24 following characteristic lines:
26
27
~8
29
31
32
: ~33
34
' ~ '
: ~':
.
WO 91/00777;, .,; ~ ~ PCl/VS90/0376'1
20~2~7
01 TABL~ l(a)
02
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
12
13 -
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)
21
22 ~ ~ d/n100 x I/Io Shape
24
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.
24
(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:
32
33 :
3~ .
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.
~û
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:
26
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. ~ ;
:: :
: : . :
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.
17
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.
03
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.
21
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.
~ .
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.
05
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.
:-
32
33
:34
:
' ':
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.
17
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. -~
24
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.
C7
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.
34
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.
17
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.
21
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.
34
, 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.
21
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.
07
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.
22
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,
27
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.
23
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
34
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.
04
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~ :
29
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
33
34
-
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.
07
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.
14
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
34
~'
'
24
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.
0
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.
13
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.
22
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.
31
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.
16
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
33
~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.
04
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.
34
-
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
06
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.
11
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,
21
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.
28
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.
33
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.
9 EXAMPLES
. . . _
2~
21~xample 1
22
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
31
32
33
34
.
2~ 9~7
Y~'V 9l/0~777 31 PCI/US9~/037~4
; . . .
01 diquaternary compound,
02
03
0!~ N N-(CH2)~ il 2I
07
08
~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
18
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.
28
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.
16
17 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
34
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
07
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 4
2 7 ~ i ?' . '.
28
: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
11 11
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
PCT/US90/03764
01 TA~LE 9
02
03 2 ~ d/n Int.
0
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
1 9
B - Broad
21 VB ~ Very Broad
2 2
24
:.
:: ~ 26
:2 7 - ::
:
28~
29~ : :
32~ ~ ;
33
34 ::
~ . ~
W~091/00777 r 29 ~r7 pcr/us9n~33764
TABLE 5
~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
22
~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
2 1
Z 2 TAB L E 7
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 .
02
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
13
14 TABLE 8 : :
16 Uncalc~ ned _ Calcined _
17 d/n d/n_ d/n d/n d/n d/n : ::
18
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
2 4
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
05 TABLE 9
06
07 2 9 d/n Int.
08
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
26
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
04
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~.
22
23 13 -- 0 8~0
24
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
3 4
.
.:
,,
:~,
.
.,
:. ~
~.
'~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.
04
o ~~ ~ a i~ o 1
a6
Q7 Please reE~r to ~r~ble 10 ~nd Ta~
08
UST~ L.~ 1 0
r~ ?.~ Y~d',' '`~ ,a~ion
r ~t!~ rr 2~ B? ta
. .
13
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
27
28
29
31 ~
,
33
: ~ 3~
: : :
: .
~ ~ ,
WO 91/00777 ~2 PC~ S90/03764
~ ~2 ~ 4rl
01 TABLE 11
02
03Example (B)Beta Zn(AC)2 2H20 Wt. % Zn after exch./calc.
04 No.
05
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.
13
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.
22
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.
3 4
,
"
-~
::
-
2~3~2~7
W~91/00777
P~T/VS90/~3764
, .
O1 ~ABLE 12( )
02
~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
16
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
22
23 psig ~ 100, 200
24 H2/BC ~ 6.4
WHSV ~ 12
26 T~mperature - ~00~F
27
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 ~
01 TABLE 13
___
~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
11
l2
13
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
33
34
'~:
.
- ~
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~ :
06
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~.
24
TABLE 15
26
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. )
02
03 50% ~30C
04 70% 499C
05 90~i ~95Oc
06 95~ 630c
07 EP ~54 ~c
03
og Table 16 shows calculated research anid mo~or octi r.s r.u~ r~
10 from the fixed ~luidized cyclic 'ces~s.
11
12 TP~BLE 16
13
14 Reference 25~ (B)~eta Plus
Catalyst efe~ence Catalyst
16 -
17 C5-250
~.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~ :
26
27
28
29
3 ~ :
31 ~ :
32~
~3 ~ :
3 4
:
~: :
