GB1589661A - Hydrogen mordenite loaded with rhodium or with rhodium and palladium suitable for use as a hydrocracking catalyst - Google Patents
Hydrogen mordenite loaded with rhodium or with rhodium and palladium suitable for use as a hydrocracking catalyst Download PDFInfo
- Publication number
- GB1589661A GB1589661A GB21035/78A GB2103578A GB1589661A GB 1589661 A GB1589661 A GB 1589661A GB 21035/78 A GB21035/78 A GB 21035/78A GB 2103578 A GB2103578 A GB 2103578A GB 1589661 A GB1589661 A GB 1589661A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydrogen mordenite
- rhodium
- weight
- elemental
- palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052680 mordenite Inorganic materials 0.000 title claims description 26
- 239000010948 rhodium Substances 0.000 title claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 22
- 239000001257 hydrogen Substances 0.000 title claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 22
- 229910052703 rhodium Inorganic materials 0.000 title claims description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052763 palladium Inorganic materials 0.000 title claims description 19
- 238000004517 catalytic hydrocracking Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 title description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
Description
(54) HYDROGEN MORDENITE LOADED WITH RHODIUM OR WITH
'RHODIUM AND PALLADIUM, SUITABLE FOR USE AS A HYDROCRACKING
CATALYST
(71) We, NORTON COMPANY, of 1 New Bond Street, Worcester 6, Massachusetts,
United States of America, a corporation organized under the laws of the State of
Massachustts, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to hydrocracking employing noble metal loaded hydrogen mordenite as hydrocracking catalyst.
The patent literature contains references to the use of noble metal loaded hydrogen mordenite in the field of hydrotreatment of hydrocarbons. For example U.S. Patent 3,544,451 discloses the use of platinum, palladium or rhodium in combination with rhenium on mordenite and alumina (with no more than 20 weight % mordenite present) as a hydrotreatment catalyst both for hydroisomerization and at higher temperatures, 800 to 1050"F, for hydrocracking combined with isomerization. The object of isomerization is to convert straight chain hydrocarbons to branched chain hydrocarbons. The object of hydrocracking is to produce gas and/or the conversion of higher boiling feeds to the gasoline range, desirably with the concurrent isomerization of the hydrocarbons.
According to a first aspect of the present invention, there is provided hydrogen mordenite having a silica to alumina mole ratio from 13/1 to 20/1, at least 0.4 meq. per gram of acidity greater than that of 48 weight % sulphuric acid, and having deposited thereon at least 0.2 weight % of elemental rhodium.
According to a second aspect of the present invention, there is provided a process for hydro cracking hydrocarbons to produce predominantly gaseous hydrocarbon products, comprising contacting at a temperature below 700"F, a hydrocarbon stream with hydrogen mordenite according to said first aspect of the present invention.
Preferably, said hydrogen mordenite according to said first aspect of the present invention also contains elemental palladium deposited thereon, said palladium being in a ratio of up to 9 parts by weight of elemental palladium per one part by weight of said elemental rhodium, for example in a weight ratio of (0.1 to 9.0)/1.0. The combined weights of said elemental rhodium and said elemental palladium are preferably from 0.2 to 1.0 weight %.
Said acidity requirement of at least 0.4 meq. per gram of acidity can be determined by titration with n-butyl amine in benzene using a Hammet indicator (see Benesi, H.J. Catalysis, 61, 970, 1957; and Johnson, O.J. Phys. Chem., 59, 827, 1955).
In carrying out said process according to said second aspect of the present invention, the hydrogen mordenite according to said first aspect of the present invention can be used in the form of pellets or other shapes. For example, the shapes (for instance pellets) can comprise binding material, for example alumina or organic binding material (see Example 1 later below). Preferably, said hydrocarbon stream is an n-pentane feed or a hydrotreated gas oil feedstock.
The effectiveness of the process according to said second aspect of the present invention is surprising in view of Examples 1 and 2 given later below; and particularly in view of the literature teaching that rhodium by itself is less effective in cracking or isomerization than is palladium, when supported on an acid type catalyst (see Bond, G.C., Catalysis by Metals, p.442, published by Academic Press, N.Y. 1962).
The present invention is illustrated by the following Examples.
EXAMPLE 1
This Example illustrates the product distribution achieved in accordance with the present invention.
Na Zeolon 100 powder (a zeolite) was ammonium exchanged until the sodium content of the zeolite was reduced to 0.02 weight % anhydrous, and thereafter was treated with boiling dilute (0.35N) nitric acid for 3 hours. The resultant zeolite was ion exchanged with a solution of Pd(NH3)4C12 and Rh(NH3)5CI until the zeolite contained 0.44 and 0.37 weight % of palladium and rhodium respectively, calculated on the basis of the elemental metals. The resultant mordenite loaded with palladium and rhodium was subsequently mixed with a binding material, extruded into 1/16" pellets, and calcined at 5500C, to give hydrogen mordenite loaded with elemental palladium and elemental rhodium. 15 weight % alumina can be used as the binding material. Generally, not more than 20 weight % alumina should be used. Instead of alumina, organic binders may be employed which are burned out after formation of pellets or other shapes in the green state. For example 1/8" pellets were formed employing an organic binder. The hydrocracking activity of the hydrogen mordenite loaded with elemental palladium and elemental rhodium was evaluated according to Table I given later below. The results of the evaluation appear at Sample 3 in Table I.
Samples containing elemental palladium alone and elemental rhodium alone are given at
Samples 1 and 2 respectively in Table I. Samples 1 and 2 were prepared in a similar manner to the preparation of Sample 3.
TABLE I normal pentane hydrocracking activity
Sample Pd Rh Pd/Rh Conversion Yield weight % n-C5 Cracked to
Selectivity
Weight % < C5 i-C5 C1 C2 C3 C4 1 0.60 0.00 56 1.3 98.7 0.12 0.12 0.18 0.32 2 0.00 0.27 0 65 89.4 10.6 18.99 14.96 11.88 6.55 3 0.44 0.37 1.2 58 34.0 66.0 3.82 4.63 5.80 5.29
Reaction Conditions
Temperature, F. 480
Pressure, psig 450
LHSV, hr-1 1.00
H2/C5 1.81
Catalyst Vol, cc 20.0 As illustrated by the above results (Table I), the use of the hydrogen mordenite loaded with palladium and rhodium results in a unique product distribution which is characterized by a balance between cracked and isomerized n-pentane products. Such a product distribution is only achievable when said loaded hydrogen mordenite is utilized. Rhodium, alone, has unexpectedly high cracking utility.
EXAMPLE 2
Samples 2 and 3 of Example 1 were further evaluated using a hydrotreated gas oil feedstock. Process conditions, conversions and product compositions are listed in Table II. It is evident from Table II that of the gas oil converted, 42% weight percent was a liquid with a boiling point less than 400"F. and the remainder was LPG. Table II also refers to sample 4, which was prepared as described in Example 3.
TABLE II
GAS OIL HYDROCRACKING ACTIVITY
Metal Weight
% Selectivity, weight
Temp. Outlet Liquid, gms Outlet Gas Total % to Liq
Sample Pd Rh F. Total BP > 400 F. BP < 400 F. gms Conversion % < 400 F To Gas 2 0.00 0.27 599 73.01 30.27 42.49 13.13 46 63 37 3 0.44 0.37 590 65.13 22.41 42.72 20.76 46 42 58 4 0.42 0.60 600 71.87 26.48 45.39 13.94 42 58 42
Reaction Conditions
H2/HC, SCF/BBL 5079
LHSV, cc/cc hr 1.00
Pressure, psig 700
Feed - Hydrotreated Gas Oil
Composition: % of feed with BP # 400 F. 8.7
% of feed with BP > 400 F. 91.3 EXAMPLE 3
Another catalyst, Sample 4, was prepared in a similar manner as in Example 1. The catalytic behavior of this sample is summarized in Table II. As shown from these results, the ratio of Pd/Rh may be varied in accordance with the present invention.
In all cases, before use, the palladium or rhodium component on the mordenite is subjected to reducing conditions to reduce the metal to its elemental form. Before reduction the metal may be in various oxidized and/or complexed forms. The quality of metal as referred to herein is calculated on the basis of the elemental metal.
Claims (15)
1. Hydrogen mordenite having a silica to alumina mole ratio from 13/1 to 20/1, at least 0.4 meq. per gram of acidity greater than that of 48 weight % sulphuric acid, and having deposited thereon at least 0.2 weight % of elemental rhodium.
2. Hydrogen mordenite as in claim 1, also containing elemental palladium deposited thereon, said palladium being in a ratio of up to 9 parts by weight of elemental palladium per one part by weight of said elemental rhodium.
3. Hydrogen mordenite as in claim 2, wherein the combined weights of said elemental rhodium and said elemental palladium are from 0.2 to 1.0 weight %.
4. Hydrogen mordenite as in claim 1, substantially as hereinbefore described.
5. Hydrogen mordenite as in claim 1, substantially as described in Example 1.
6. Hydrogen mordenite as in claim 1, substantially as described in Example 3.
7. A process for hydrocracking hydrocarbons to produce predominantly gaseous hydrocarbon products, comprising contacting at a temperature below 700"F, a hydrocarbon stream with hydrogen mordenite according to any one of claims 1 to 6.
8. A process as in claim 7, wherein said hydrogen mordenite is shaped said hydrogen mordenite.
9. A process as in claim 8, wherein said shaped hydrogen mordenite comprises not more than 20 weight % alumina as binding material.
10. A process as in any one of claims 7 to 9, wherein said hydrocarbon stream is an n-pentane feed.
11. A process as in any one of claims 7 to 9, wherein said hydrocarbon stream is a hydrotreated gas oil feedstock.
12. A process as in claim 7, substantially as hereinbefore described.
13. A process as in claim 7, substantially as described in Example 1.
14. A process as in claim 7, substantially as described in Example 2.
15. A predominantly gaseous hydrocarbon product produced by a process as in any one of claims 7 to 14 - .. . 14.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80308577A | 1977-06-03 | 1977-06-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1589661A true GB1589661A (en) | 1981-05-20 |
Family
ID=25185539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB21035/78A Expired GB1589661A (en) | 1977-06-03 | 1978-05-22 | Hydrogen mordenite loaded with rhodium or with rhodium and palladium suitable for use as a hydrocracking catalyst |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5433890A (en) |
| DE (1) | DE2822730A1 (en) |
| FR (1) | FR2393050A1 (en) |
| GB (1) | GB1589661A (en) |
| IT (1) | IT1159691B (en) |
| NL (1) | NL7805560A (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3544451A (en) | 1968-04-24 | 1970-12-01 | Universal Oil Prod Co | Conversion of hydrocarbons with a catalyst containing platinum and rhenium combined with a carrier material containing alumina and mordenite |
| US3775298A (en) * | 1968-11-25 | 1973-11-27 | Texaco Inc | Hydroconversion process for production of lpg in presence of mordenite aluminosilicate |
| US3878125A (en) * | 1972-09-08 | 1975-04-15 | Universal Oil Prod Co | Multimetallic catalyst composite |
| US3847796A (en) * | 1973-03-15 | 1974-11-12 | Universal Oil Prod Co | Hydrocracking process for the production of lpg |
| GB1499622A (en) * | 1975-06-30 | 1978-02-01 | Elf Aquitaine | Method of production of ethane by selective hydrogenolysis of alkanes |
-
1978
- 1978-05-22 GB GB21035/78A patent/GB1589661A/en not_active Expired
- 1978-05-23 NL NL7805560A patent/NL7805560A/en not_active Application Discontinuation
- 1978-05-24 DE DE19782822730 patent/DE2822730A1/en not_active Withdrawn
- 1978-05-24 FR FR7815411A patent/FR2393050A1/en active Granted
- 1978-05-24 IT IT68188/78A patent/IT1159691B/en active
- 1978-05-25 JP JP6279378A patent/JPS5433890A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IT7868188A0 (en) | 1978-05-24 |
| DE2822730A1 (en) | 1978-12-14 |
| JPS5433890A (en) | 1979-03-12 |
| FR2393050B1 (en) | 1984-09-14 |
| IT1159691B (en) | 1987-03-04 |
| NL7805560A (en) | 1978-12-05 |
| FR2393050A1 (en) | 1978-12-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |