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Patent 2049928 Summary

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(12) Patent Application: (11) CA 2049928
(54) English Title: REFORMING NAPHTHA WITH BORON-CONTAINING LARGE-PORE ZEOLITES
(54) French Title: REFORMAGE DU NAPHTHA A L'AIDE DE ZEOLITES A LARGE PORES CONTENANT DU BORE
Status: Deemed Abandoned and Beyond the Period of Reinstatement - Pending Response to Notice of Disregarded Communication
Bibliographic Data
(51) International Patent Classification (IPC):
  • C10G 35/09 (2006.01)
  • C10G 35/06 (2006.01)
(72) Inventors :
  • RAINIS, ANDREW (United States of America)
  • ZONES, STACEY I. (United States of America)
  • HOLTERMANN, DENNIS L. (United States of America)
(73) Owners :
  • CHEVRON RESEARCH AND TECHNOLOGY COMPANY
(71) Applicants :
  • CHEVRON RESEARCH AND TECHNOLOGY COMPANY (United States of America)
(74) Agent: MARKS & CLERK
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 1990-07-03
(87) Open to Public Inspection: 1991-07-27
Examination requested: 1992-02-06
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US1990/003765
(87) International Publication Number: US1990003765
(85) National Entry: 1991-09-10

(30) Application Priority Data:
Application No. Country/Territory Date
471,256 (United States of America) 1990-01-26

Abstracts

English Abstract


ABSTRACT OF THE DISCLOSURE
Catalytic reforming processes using boron-containing
large-pore zeolites.
-25-


Claims

Note: Claims are shown in the official language in which they were submitted.


W091/11501
PCT/US90/03765
. -22-
WHAT IS CLAIMED IS:
l. A catalytic reforming process which comprises
contacting a hydrocarbonaceous feedstream under
catalytic reforming conditions with a composition
comprising large-pore borosilicats zeolites having
pore size greater than 6 and less than 8 angstroms.
2. A process in accordance with Claim 1 wherein said
large-pore borosilicate zeolites contain less than 1000
parts per million aluminum.
3. A process in accordance with Claim 2 wherein said
large-pore borosilicate zeolites are boron beta
zeolite, boron SSZ-24, boron SSZ-31, and SSZ-33.
4. A process in accordance with Claims l, 2 and 3 wherein
the boron in the large-pore borosilicate zeolites is
partially replaced by a Group IIIA metal, or a first
row transition metal.
5. A process in accordance with Claim 4 wherein the
replacing metal is cobalt, zinc, aluminum, gallium,
iron, nickel, tin and titanium.
6. A process in accordance with Claims l, 2, 3 and 4
wherein the hydrogenation/dehydrogenation component of
said large-pore borosilicate zeolites is a Group VIII
metal.
7. A process in accordance with Claim 6 wherein the
hydrogenation/dehydrogenation component of said
large-pore borosilicate zeolite comprises platinum.

WO91/11501 . PCT/US90/03765
-23-
8. A process in accordance with Claim 6 wherein said
large-pore borosilicate zeolite contains an alkali
metal component.
9. A process in accordance with Claims 1, 2, 3 and 4
wherein the hydrogenation/dehydrogenation component of
said large-pore borosilicate zeolite comprises rhenium
and platinum.
10. A process in accordance with Claims 1, 2, 3 and 4
wherein the hydrogenation/dehydrogenation component of
said large-pore borosilicate zeolites comprises
platinum and tin.
11. A process in accordance with Claim 1, 2 and 3
comprising using a fixed, moving or fluid bed reformer.
12. A process in accordance with Claims 1, 2 and 3 which is
a multi-stage catalytic reforming process.
13. A process in accordance with Claim 12 where the
large-pore borosilicate zeolite is used in the last
reactor to convert the remaining light paraffins not
converted by the Pt Re/Al2O3 or Pt Sn/Al2O3 catalysts
used in the upstream reactors.
14. A process in accordance with Claim 12 where the
large-pore borosilicate zeolite is used in the last
stage of a multi-stage catalytic reforming process
where the operating pressure of the last stage is much
lower than the upstream stage.

24
15. A process in accordance with claim 1 wherein the
feedstream contains less than 1 part per million sulfur.
16. A process in accordance with claim 1 wherein said
large-pore borosilicate zeolites comprise:
i) a Group VIII metal and a metal selected from
the group of metals consisting of Group IA metals and
Group IIA metals;
ii) said selected Group IA metals and/or Group IIA
metals reducing acidity of said catalyst.
17. A process in accordance with claim 16 wherein said
selected Group IA and/or Group IIA metals rendering said
catalyst substantially free of acidity without
introducing base poisoning to said catalyst.
18. A process of claim 16 wherein said selected metal is
a Group IA metal.
19. A process of claim 16 wherein said selected metal is
selected from the group consisting of sodium, potassium
and calcium.
20. A process of claim 19 wherein sufficient selected
metal is incorporated into said catalyst to neutralize
substantially all acid sites in said borosilicate
zeolites.
21. A process of claim 19 wherein said Group VIII metal
is selected from the group consisting of platinum,
palladium and iridium.
22. A process of claim 21 wherein said catalyst
comprises 0.05 to 2.0% by weight of said selected Group
VIII metal.

23. A process of claim 22 wherein said catalyst
comprises 0.2 to 0.8% by weight of said selected Group
VIII metal.
24. A process of claim 23 further comprising a binder
for said Group VIII metal selected from the group
consisting of a silica-based binder, alumina, magnesia
and titania.

Description

Note: Descriptions are shown in the official language in which they were submitted.


2~
01REFORMING NAPHT~A WI~H BORON-CONTAINING
02LARGE-PORE ZEOLITES
03
04BAC~GROUND OF THE_INVENTION
05
06 Catalytic reforming is a process for treating naphtha
07 fractions of petroleum di~tillates to improve their octane
OB rating by producin~ aromatic components and isomeriz~ng
~9 paraffins from component~ pre ent in naphtha feed~tocks.
Included among the hydrocarbon reactions occurring in
11 reforming processes are: dehydrogenation of naphthenefi to
12 aromaties, dehydrocyclization of parafins to aromatics, and
13 hydrocracking of paraffins to lighter gases with a lower
14 boiling point than gasoline. Hydrocracking reactions which
produce light paraffin gases are not desirable as they
16 reduce the yield of products in the gacoline range.
17
18 Natural and 6ynthe~ic zeolitic crystalline aluminosilicates
19 and borosilicates are useful as catalysts. The u6e of
ZSM-type catalysts and processes are described in U.S.
21 Patent Nos. 3,546,102, 3,679,575, 4,D18,711 and 3,574,092.
22 Zeolite L is also used ln reforming proce ses as described
23 in U.S. Patent Nos. 4,104,320, 4,447,316, 4,347,394 and
24 4,434,311.
2S 30rosilicate zecli~es are especially use~ul in catalytic
27 refor~ing. Methods for preparing high silica content
28 zeolites that contain framework boron are described i~ U.S.
29 Patent No. 4,269,313.
31 The use of int~rmediate pore borosilicate zeolite~ for
32 catalytic reforming is described in European Patent
33 Appl$cation No. 188,913. In this application, ZSM-5,
34
1-- ,

01 ZSM-ll, ZSM-12, ZSM-23, ZS~-35, ZSM-38, ZSM-48 and zeolite
02 beta have been identified as lntermedi~te pore boro~ilicate
03 zeOlites-
04
05 A method for controlling catalytic activity of large-pore
06 boron-containing zeolites i~ described in European Patent
07 Application No. 234,759-
08
09 SUMMARY OF INVENTIOI~
11 According to the present invention, a proce~s i~ provided
12 for catalytic reforming. The process compri~es contacting a
13 hydrocarbon feedstream under cataly~ic reforming conditions
14 with a composition comprising large-pore borosilicate
zeolites having ~ pore 8iZ~ b~tween 6 and 8 angstroms.
16 Preferably, th~ large-pore borosilicate zeolites ar~ boron
17 beta zeolite, (~)SSZ-24, SSZ-31 and SSZ-33.
18
19 Boron beta zeolite is described in co~monly assigned
co~pending applicatio~ U.S. Serial No. 377,359 ~Docket No.
21 B-3924~, filed concurrently herewith, and entitled
22 nLow-Aluminum ~oron aeta Zeolite", the di~closure of which
23 is incorporated herein by reference.
24
(B)SSZ-24 is de~cribed in commonly assigned co-pending
26 application U.S. Serial No. 377,357 (Docket No. B-3952),
27 filed concurrently herewith, and ~ntitled "Zeolite
28 (B)Ssz-24n~ the disclosure of which is incorporated herein
29 by reference.
31 SSZ-33 is described in commonly assigned co-pending
32 application U.S. Serial No. 377,358 (Docket No. B-3889),
33 filed concurrently herewlth, and entitled "Zeolite S5Z-33",
34 the disclosure of which is incorporated herein by reference.
--2--

01 SSZ-31 is described in commonly a~signed co-pending
02 application U.S. Serial ~o. _ (Docket No. 2-3986~,
03 filed concurrently herewith, and entitled "~ew Zeolite
04 SSZ-31", the disclosure of which is incorporated herein by
05 re~erence.
06
07 According to a pref~rred embodiment, the largs-pore
08 borosilicate zeolites may be used ln a multi-stage catalytic
09 reforming proce~s. These zeolites may be located in one or
more of the reactQrs, with conventional platinum and rhenium
11 catalyst located in the remaining reactors.
12
13 The reforming process may be acco~plished by using fixed
14 beds, fluid beds or moving beds ~or cGntacting the
hydrocarbon feedstream with the catalyst6.
16
17 Among other factors, the present invention is based on our
18 finding that large-pore borosilicates including boron beta
19 zeolite [(B)Betal, SSZ-33, (B)SSZ-24 and SSZ-31 have
unexpectedly outstanding reforming properties. These
21 include high sulfur tol~rance, high catalyst stability, and
22 high catalyst activity.
23
24 DETAIL15D DESCR~PTION OF THE INVENTION
26 The present invention relates ~o refor~ing processes
27 employinq large-pore borosilicate zeolites. A large-pore
~8 zeolite is defin~d herein as a zeolite having a poce ~ize
29 between 6 and 8 angstroms. A method of determining this
pore size is described in Journal o~ Catalysis (1986);
3~ Vol. 99, p. 335 (D. S. Santilli). A large-pore zeolite may
32 be identlfied by using the pnre probe technique de~crlbed in
33 Journal of Catalysis (1986); Vol. 99, p. 335 (D. S.
34 Santilli). This method allows measurement of the

01 steady-state concentrations of compounds within the pores of
02 materials. 2,2-dimethylbutane (22D~3~ enters the large
03 pores and the concentration in the pores i6 measured using
04 this technique.
05
06 According to preferred embodiments of our invention, SSZ-~3,
07 (B)SSZ-24, SSZ-31 and low-aluminum boron beta zeolite
08 I(B)betal are large-pore borosilioate æeolltes with high
09 catalyst activity in th@ reforming process.
11 SSZ-33 is defined as ~ zeolite having a mole ratio of an
12 oxide selected from silicon, germanium oxide and mixtures
13 thereof to an oxide selected from boron oxide or mixtures of
14 boron oxide with aluminum oxide, gallium oxide or iron
oxide, greater than about 20:1 and having the x-ray
16 diffraction lines of Table 1. The X-ray diffraction lines
17 of Table 1 correspond to the calcined SSZ-33.
18
19 Table 1
21 2 ~ d/n lO0 x I/Io
22 . 7 86 11.25 90
23. 20.48 4.336 100
24 21.47 4.139 40
22.03 4.035 90
26 23.18 3.837 64
27 ~6.83 3.323 40
28
(B)SSZ-24 is defined as a zeolite havin~ a mole ratio o~ an
oxide selected from silicon oxide, germanium oxide, and
mixtures thereof to an oxide selected from boron oxide or
mixtures of boron oxide with aluminum oxide, gallium oxide,
33
34

01 and iron oxide, between 20:1 and lQ0:1 and having the X-ray
02 diffraction lines of Table 2. The X-ray diffraction lines
03 of Table 2 correspond to the caleined (B)SSZ-24.
04
05 Table 2
06
0~ 2 ~ d/n 100 x I/Io
08
og 7.50 11.79 100
13.00 6.B1 16
11 15.03 5.~94 8
12 lg.93 4.455 35
13 21.42 4.148 48
14 22.67 3.922 60
lS 25.15 3.541 3
16 26.~0 3.401 22
17 29.38 3.040 12
18 30.43 2.947 12
lg
Boron beta zeolite is a zeolite having a mole ratio of an
21 oxide selected from silicon oxide, germanium oxide, and
22 mixtures thereof to an oxide selected from boron oxide, or
23 mixtures of boron oxide with aluminum oxide, gallium oxide
24 or iron oxide, greater than 10:1 and wherein the amount of
aluminum is less than 0.10% by weight and having the x-ray
26 diffraotion lines of Table 3. The x-ray diffraotion lines
27 of Table 3 correspond to the calcined boron beta zeolite.
28
29
31
32
33
34

01 Table 3
02
03 2 ~ d/n100 x I/I Shape
04 o
05 7.7 11.5 85 sroad
06 13.58 6.52 9
07 14.87 5.96 12 sroad
08 18.50 4.80 3 Very ~road
09 ~ 3 4.07 15
22.87 3.89 100 ~road
11 27.3~ 3.26 10
12 29.30 3.05 6 Broad
13 30.08 2.97 8
14
SSZ-31 is defined as a zeolite having a mole ratio of an
16 oxide selected from silicon oxide, germanium oxide, and
17 mixtures thereof to an oxide selected from aluminum oxide,
18 gallium oxide, iron oxide, and mixtures thcreof greater than
19 about 50:1, and having the X-ray diffraction lines of
Table 4. The X-ray diffraction lin~s of Table 4 correspond
21 to the calcined SSZ-31.
22
23 Table 4
24
2 ~ d/n100 x I/~o Shape
, ,,
26 6.08 14.54 9
27 7.35 12.03 9
28 a.oo 11.05 7 Broad
29 18.48 4.80 11
20.35 4.36 9 ~oad
31 21.11 4.21 100
32 22O24 4.00 56
33 24.71 3.60 21
34 30.R8 2.90 7
--6--
,

01 The large-pore borosilicates can be used as reforming
02 catalysts to convert light straight run naphtha6 and similar
03 mixtures to highly aromat~c mixtures. Thus, nor~al and
04 slightly branched chained hydrocarbons, preferably having a
05 boiling range above about 40C and less than about 250C,
06 can be converted to products having a subs~antial aromatics
07 content by contacting the hydrocarbon feed with the zeolite
08 at a temperature in the range of from about 400C to 600~C,
09 at pressures ranging from atmospheric to 20 atmosph2res,
10 LHSV ranging from 0.1 to 15, and a recycle hydrogen to
11 hydrocarbon ratio of about 1 to 10.
12
13 The reforming cataly6t preferably contains a ~roup YIII
14 metal compound to have suffioient activity for commercial
use. sy Group VIII metal compound as used herein is meant
16 the metal itself or a compound thereofO The Group VIII
17 noble metals and their compounds, platinum, palladium, and
18 iridium, or combinations thereof can be used. The most
19 preferred metal is platinum. The amsunt of Group VIII metal
present in the conversion catalyst should be within the
21 normal range of use in reforming catalysts, from about 0.05
22 to 2.0 wt. percent, preferably 0.2 to 0.~ wt. percent. In
23 addition, the catalyst can also contain a seoond Group VII
24 metal. Especially preferred is rhenium.
26 The zeolite/Group VIII metal cataly6t can be used with or
27 without a binder or matrix. The preferred inorganic matrix,
~8 where one is used, is a silica-based binder such as
29 Cab-O Sil or Ludox. Other matrices such as alumina,
magnesia and titania can be used. The preferred inorganic
31 matrix is nonacidic.
32
33
34

z~ Y3~,~
01 It is critical to the selective production of aromatics in
02 useful quantities that the conversion catalyst be
03 substanti~lly free of acidity, for example, by exchanging
04 the sites in the zeolite with metal ions, e.g., ~roup I and
05 Group II ions. The zeolite is usually prepared from
06 mixtures containing alkali metal hydroxides and thus, have
07 alkali metal contents o~ about 1-2 wt~ %. These high levels
~ of alkali metal, usually sodium or potassium, are
09 unacceptable for most other catalytic applications because
they greatly deactivate the catalyst for cracking reactions
11 by reducing catalyst acidity. Therefore, the alkali metal
12 is removed to low levels by ion exchange with hydrogen or
13 ammonium ions. ~y alkali metals as used herein is meant
14 ionic alkali metals or their basic compounds. Surprisingly,
unless the zeolite itself is substantially free of acidity,
16 the alkali metal is required in the present process to
17 reduce acidity and improve aromatics production. Alkali
18 metals are incorporated by impregnation or ion exchange
19 using nitrate, chloride or carbonate salts.
21 The amount of alkali metal necessary to render the zeolites
22 substantially free of acidity can be calculated using
23 standard techniques based on the aluminum, gallium or iron
24 content of the zeolites. If a zeolite free of alkali metal
is the ~tartin~ material, alkali metal ions can be ion
26 exchanged into the zeolite to substantially eliminate the
27 acidity of the zeolite. An alkali metal content of about
28 100%, or gr~ater, of the acid sites calculated on a molar
29 basis is suf~icient.
31 Where the metal ion content is less than 100% of the acid
32 sites on a molar basis, the test described in UOS. Patent
33 No. 4,34~,394, which patent is incorporated totally herein
34

01 by reference, can be used to determine if the zeolit~ is
02 substantially free of acidity.
03
04 The preferred alkali metals are sodium, potassium, and
05 ~esium, as well as other Groups IA and IIA metalR. The
06 zeolites can be substantially free of acidity only at very
07 high silica:alumina mole ratios; by "zeolite consisting
08 essentially of silica" i8 meant a zeolite which is
09 substantially free of acidity without base poisoning.
11 A low sulfur feed is preferred in the reforming pcocess; but
12 due to the sulfur tolerance of these catalysts, feed
13 desulfurization does not have to be as complete as with
14 conventional reforming catalysts. The feed shculd contain
less than 10 parts per million sulfur. In the case of a
16 feed which is not low enough in sulfur, acceptable levels
17 can be reached by hydrogenating the feed with a
18 hydrogenating catalyst which is resistant to sulfur
19 poisoning. An ex~mple of a suitable catalyst for this
hydrodesulfurization process is an alumina-containing
21 support and a minor catalytic proportion of molybdenum
22 oxide, cobalt oxide and/or nickel oxide. A platinum on
23 alumina hydrogenating catalyst can also work. In which
24 case, a sulfur fiorber is preferably placed downstream of the
hydrogenating catalyst, but upstream of the present
26 reforming catalyst. Examples of sulfur sorbers ar~ alkali
27 or alkaline earth metals on porous refractory inorganic
28 oxides, zin~, etc. Hydrodesulfur1zation is typically
29 conducted at 315-455C, at 200-2000 psig, and at a LHSV of
1-5.
31
32
33
34

01 It is preferable to limit the nitrogen level and the water
02 content of the feed. Catalysts and processes which are
03 suitable for these purposes are known to those skilled in
04 the art.
05
n6 After a period of operation, the catalyst oan become
07 deactivated by coke. Coke can be removed by contacting the
08 catalyst with an oxygen-containing gas at ~n elevated
09 temperature. If the Group VIII ~etal(~) have agglomerated,
then it can be redispersed by contacting the catalyst with a
11 chlorine gas under conditions effective to redisperse the
1~ metal(s). The method of regenerating the catalyst may
13 depend on whether there is a fixed bed, moving bed, or
14 fluidized bed operation. Regeneration methods and
conditions are well known in the art.
16
17 The reforming catalysts preferably contain a Group VIII
18 metal oompound to have su~ficient activity for commercial
19 use. ~y Group VIII metal ~ompound as used herein is meant
the metal it~elf or a compound thereof. The Group VIII
21 noble metals and their compounds, platinum, pallad~um, and
22 iridium, or oombinations~thereof can be used. Rhenlum and
23 tin may also be used in conjunction with the noble metal.
24 The most preferred metal is platinum. The amount of Group
VIII metal present in the conversion catalyst should be
26 within the normal range of use in reform~ng catalysts, from
27 about 0.05-2.0 wt~ %.
28
29 Example 1
31 Preparation of Platinum-(B)SSZ-24
32
33 The borosilicate version of (B)SSZ-24 was prepared for use
34 as a reforming catalyst. The zeolite powder was impregna~ed
--10--

01 with Pt~NH3)4-2No3 to give 0.8 wt. % Pt. ~he material was
02 calcined up to 550F in air and maintained at thi~
03 temperature for three hours. The powder was pelletized on a
04 Carver press at 1000 psi and broken and meshed to 24-40.
05
06 Example 2
07
08 Reforming Test_Results
09
(B)SSZ-24 from Example 1 was tested as a reforming catalyst.
11 The conditions for the re~orming tect were as follows.
12 The catalyst was prereduced for 1 hour in flowing hydrogen
13 at 950F and atmospheric pressure. Test conditions were:
14
Total Pressure ~ 200 psig
16 H2/HC Molar Ratio ~ 6.4
17 WHSV - 6 hr 1
18
19 The catalyst was initially tested at 800F and then at
900~F. The feed was an iC7 mixture supplied by Philips
21 Petroleum Company. The catalyst from Example 1 was ~ested
22 with these results.
23
24 Feed Products _
26 Temperature, F 800~F 900F
27 Con~ersion % 0 79.6 100
28 Toluene, wt. ~ 0.5 22.1 21.9
2Q C5-C8 Octane, RON 63.7 86.8 105.2
C5~ Yield, wt. % 100 54.9 35.
31 Aromatization
32 Selectivity, % 32.1 30.2
33 Toluene in the
34 C5+ ~romatics % 86.6 72.7

2~
01 As shown by the complete conversion, this catalyst is
02 capable of converting all types of feedstock molecule6.
03
04 Exam~le 3
05
06Preparation and Testing of a
07Neutralized Platinum-Aluminum-Boron SSZ-24
08
09 Aluminum was substituted into the borosilicate version of
(B)SSZ-24 by refluxing the zeolite with an equal mass o~
11 Al(NO3)3 9H2O overnight. Prior to use, the aluminum nitrate
12 was dissolved in H2O a~ a ratio of 50:1. The product
13 contained acidity due to the aluminum incorporation, and
14 this would lead to unacceptable cracking los~es. Two back
ion exchanges with KNO3 were performed and the catalyfit was
16 calcine~ to 1000F. Next, a re~orming catalyst was prepared
17 as in Example 1. It was tested as in Example 2.
18
19 Feed_ Products
21 Temperature, F 800 900
22 Conversion % 0 53O0 95.1
23 Toluene, wt. % 0.5 22.6 26.6
24 C5-C8 Octane, RON 63.7 78.1 99.6
C5~ Yield, wt. ~ 100 81.5 46.2
26 Aromatization
27 Selectivity, % 47.1 35.7
28 Toluene in the
29 C5~ Aromatics % 90.6 78.1
31 By comparison with Example 2, the incorporation of aluminum,
32 accompanied by its neutralization, gives a less active, but
33 more sel~ctive catalyst.
34

01 Example 4
02
03 Preparation and Testin~ of a Platinum-Boron-Bet
04
~5 The borosilicate version of boron beta was impregnated with
06 Pt(NH3)4'2NO3 to give 0.6 wt. ~ Pt. The material was
07 calcined up to 550~F in air ~nd maintained at this
08 temperature for three hours. The powder was pelletized on a
09 Carver press at 1000 psi and broken and meshed to 24-40.
The catalyst was te6ted as shown in Example 2 with the
11 exception that opera~ion at both 200 and 50 psig were
12 explored.
13
14 Pressure, psiq 200 50 200
Temperature, F 800 800 900
16 Conversion ~ 88.8 77.0 100
17 Toluene, wt. % 19.1 39.3 16.9
18 C5-C8 Octane, RON 89.5 90.S 104.3
19 C5+ Yield, wt. % 46.9 77.4 ~0.2
Aromatization
21 Selectivity, % 25.4 54.5 25.3
22 Toluene in the
23 C5+ Aromatics % 84.9 93.7 67.8
24
The catalyst is quite stable and the values are averaged
26 over at least 20 hours of run time.
2~
28
~9
30Preparation and Testing of a
31Platinum-Cobalt-Boron-Beta Catalyst
32
33 Cobalt was incorporated into the boron beta as described in
34 Exa~ple 3 with Co(NO3)2 6H2O as the cobalt source replacing

01 Al(NO3)3-9H2O as the aluminum source in Example 3. The
02 catalyst was cal~ined to 1000F, and a Platinum reforming
03 catalyst was prepared as described in ~xample 1. It was
04 tested as described in Example 2 except the wHsv was 12 and
05 operation at both 200 and 100 psig was evaluated.
06
07 Pressure, psig 200 100
08 Temperature, ~F 800 300
09 Conversion % 83.3 86.0
Toluene, wt. % 18.8 27.3
ll C5-C8 Octane, XON 85.3 90.3
12 C5~ Yield, wt. ~ 59~8 63.7
13 Aromatization
14 Selectivity, % 27 37
Toluene in the
16 C5+ Aromatics % 83.3 85.9
17
~8 By comparison with Example 4, the incorporating of cobalt
19 gives a more active catalyst. The catalyst has good
stability a~ 800F.
21
22 Example 6
2~
24 Preparation of Pt-SSZ-33
26 SSZ-33 was prepared for use as a reforming catalyst. The
27 zeolite powder was impregnated with Pt(NH3)4-2NU3 to give
2~ 0.8 wt. % Pt. The material was caleined up to 550~F in alr
29 and maintained at this temperature for three hours. The
powder was pelletized on a Carver press at 1000 psi and
31 broken and screened to 24-40 mesh.
32
33
34
-14-

01 Example 7
02
03 Preparation of Pt-Zinc-SSZ-33
04
05 Zinc was incorporated into the novel large-pore borosilicate
06 SSZ-33 by refluxing Zn(Ac)2 H2O as described in Example 3.
07 The product wa~ washed, dried, and calcined to 1000F, and
08 then impregnated with Pt~NH3)4 2NO3 to give 0.8 wt.% Pt.
09 The material was calcined up to 550F in air and maintained
at this temperature for three hours. The powder was
11 pelletized on a Carver press at 1000 psig, broken, and
12 meshed to 24-40. It was tested as described in Example 2.
13 Resul~s are as follows:
14
Pres ure, psig 200
16 Temperature, F 900
17 Conversion % 71.1
18 Toluene, wt. % 2~
19 C5-C~ Octane, RON 85
C5+ Yield, wt. % 74.2
21 Aromatization
22 Selectivity, ~ 44.5
23 Toluene in the
24 C5+ Aro~atics % 88.5
26
27
28
29
31
32
33
34
-15-

01 Example 8
02
03 Testing of Pt-SSZ-33 and Pt-Zinc-SSZ-3
04
05 The catalysts of ~xamples 6 and 7 were tested with a
06 partially reformed naphtha at:
07
08 Total Pressure - 50 psig
09 H2/~C Molar Ratio ~ 3
LHSV ~ 2 hr 1
11
12 These conditions simulate use of the catalyst in the last
13 reactor of a ~ulti-stage reforming process. An analysis of
14 the feed and products is shown below.
16 FeedProducts
17
18 Molecular Sieve Pt-SSZ-33 Pt-Zn-SSZ-33
19 ~emperature, F 780 860
21 Composition, wt. %
22 C4- 13.4 9.4
23 C5's Total 0 8.3 7.0
24 C6 Paraffins 8.7 8.3 7.7
C6 Naphthenes 1.0 0.9 0.9
~6 Benzene 1.6 3.5 2.6
27
28
2g
31
32
33
34

01 Feed Products
02
03 C7 Paraffins8.6 2.9 4.5
04 C7 Naphthenes 0.2 0.1 0
S Toluen~ 8.9 13.3 11.6
06
07 Ca Paraffins5.8 0.5 0
08 C8 Naphthenes 0.1 0 0
09 C8 Aromatics21.1 22.7 23.
11 Cg Paraffins2.1 0
12
13 Cg+ Aromatics 32.3 26.9 31.4
14
Octane, RON94.6 101.0 101.0
16
17 C5+ Yiqld, LV~ 100.0 86.0 89.0
18 of the Feed
19
These examples illustrate the ability of both cataly~t~ to
21 upgrade partially reformed naphtha. Incorporation of zinc
22 improves the liguid product selectivity, apparently by
2~ reducing dealkylation of exi~ing aromatlc~.
24
Example 9
26
2~Comparison of Unsulfided and Sulfided
28Platinum ~oron ~eta
29
The borosilicate version o~ Beta was impregnated with
31 Pt(NH3)4-2NO3 as in Example 4. The catalyst was ~ulfided at
32 950E for 1 hour in the presence of hydrogen.
33
34

01 Test conditions were:
02
03 Temperature ~ 800F
04 H2/HC Molar Ratio - 6.4
S WHSV ~ 6
06
07 U~sulfided Pt/tB)beta Sulfided Pt~(B)beta
08
09 Pressure, psig200 200 200 200
10 Time, hrs- 3 18 3 18
11 Feed ~onversion~ ~ 96.9 95.8 79.1 81.~
12 C5+ Yield, wt. % 37.6 40.2 59.4 57.0
13 Calculated RON93.0 92.8 87.5 88.4
14 Aromatization19.4 21.3 35.2 34.0
Selectivity,
16
17Example 10
18
l9Comparison of Sulfided Pt/~B)beta and
20Sulfided Pt/(B)beta with 52% SiO2 Binder
21
22800~, 200 psig, 6 WHSV, 6.4 ~l2:~C
23
24
Pt/(B)beta ~ound Pt/~B)beta
26
27 Time, hr~. 3 18 3 18
2a Feed Conversion, ~ 79.1 81.6 52.7 57.7
29 C5+ Yield, w~. %59.4 57.0 86.5 82.1
30 Calculated RON 87.5 88.4 79.5 80.2
31 Aromatization 35.2 34.0 52.9 47.0
32 Sele~tivity
33
34
-18-

01 800F, 50 psig, 6 WHSV, 6.4 H2:HC
02 - -
03
04 Pt/(B~beta Bound Pt/(B)beta
05
06 Time, hrs. 3 18 3 18
07 Feed Conversion, ~ 87.9 86.5 62.6 61.5
08 C5+ Yield, wt. % 64.3 66.0 84.4 85.0
09 Calcul~ted RO~97.8 96.5 84.4 83.7
Aromatiz~tion 50.8 Sl.S 56.3 55.5
11 Selectivity
l3 . Example 11
1~
15Comparison of 5ulfided Pt/(B~beta
16and Sulfided Pt/Cs-(Al)-(B)beta
18800F, 200 psig, 6 W~SV, 6.4 H2:HC*
19
Pt/tB?beta Pt/Cs-(Al)-~B)beta
21
22 Feed Convorsion, ~ 79.6 48.0
23 C5~ Yield, wt. % 59.7 93.7
24 Calculated RON 87.9 77.0
Propane ~ Butanes, 18.8 2.3
2~ wt. %
27 ~oluene, wt. % 25.6 ~5-9
2~ Aro~. Selectivity 35.7 56.0
29
30*Data averaged for first five hours.
31
32
33
34
-19-
.

2~
01800F, 50 psi~, 6 W~SV, 6.4 H2:HC~
02 _ __
03
Pt/~)Beta Pt/Cs-~Al)-~B)beta
O ~
05
06 Time, hrs. 3 18 3 lB
07 Feed Conversion, % 87.9 86.5 46.0 40.0
0~ C5+ ~ield, wt. %64.3 66.0 95.0 96.0
09 Calculated ~ON g7.8 96.5 77.0 74.5
Arom. Selectivity 50.R 51.5 59.5 58.0
11 Propane + ~utanes, 31.4 28.1 3.3 2.5
12 wt. %
l3 Toluene, wt. % 42.0 41.8 26.0 22.0
**Interpolated data.
16
17Example_12
18
Pre aration and Testin~ of P~-Boron-SSZ-31
19 P - - .
21 The borosilieate version of SSZ-31 was prepared for u~e as a
22 reforming catalyst. The zeolite powder was impregnated with
23 Pt(NH3)4'2NO3 to give 0.7 wt. ~ Pt. The material wa~
24 calcined up to 600~ in air and maintained at this
temperature for three hours. The powder was pelletized on a
26 Carver press at 1000 psi, broken, and ~creened ~o:24-40
27 mesh.
28
29 Pt-Boron-SSZ-31 wa~ tested for reforming using an iC7 feed
mixture (Ph$1ips Petroleum Company) as fol}ow~:
31
32
33
34
-20-

01 Reaction Conditions Run 1 Run 2
02 Temperature, F 800 800
03 Total pressure, psig 200 50
04 H2/Hydrocarbon Mole Ratio 6 . 4 6 . 4
05 Feed rate, WHSV, hr l 6 6
0~
07 Results Feed Run 1 Run 2
08 Conversion, % 0 68.1 69.7
09 Aromatization Select . 0 39 . 4 54 . 7
Toluene, wt . ~ 0 . 7 24 . 6 36 . 0
11 C5-C8 Octane, RON 6 3 . 9 B2 . B 87 . 6
12
13
14
16
17
18
19
21
22
23
24
26
27
28
29
31
32
33
34

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Administrative Status

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Event History

Description Date
Inactive: IPC from MCD 2006-03-11
Time Limit for Reversal Expired 1995-01-03
Application Not Reinstated by Deadline 1995-01-03
Inactive: Adhoc Request Documented 1994-07-04
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 1994-07-04
Request for Examination Requirements Determined Compliant 1992-02-06
All Requirements for Examination Determined Compliant 1992-02-06
Application Published (Open to Public Inspection) 1991-07-27

Abandonment History

Abandonment Date Reason Reinstatement Date
1994-07-04
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
CHEVRON RESEARCH AND TECHNOLOGY COMPANY
Past Owners on Record
ANDREW RAINIS
DENNIS L. HOLTERMANN
STACEY I. ZONES
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Claims 1991-07-26 4 101
Abstract 1991-07-26 1 6
Cover Page 1991-07-26 1 14
Drawings 1991-07-26 1 13
Descriptions 1991-07-26 21 561
Fees 1992-06-22 1 26
Fees 1993-06-13 1 29