GB2121698A - Catalyst based on gamma alumina - Google Patents
Catalyst based on gamma alumina Download PDFInfo
- Publication number
- GB2121698A GB2121698A GB08313562A GB8313562A GB2121698A GB 2121698 A GB2121698 A GB 2121698A GB 08313562 A GB08313562 A GB 08313562A GB 8313562 A GB8313562 A GB 8313562A GB 2121698 A GB2121698 A GB 2121698A
- Authority
- GB
- United Kingdom
- Prior art keywords
- moles
- sio2
- catalyst
- gamma alumina
- mexoy
- 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.)
- Granted
Links
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
- C07C5/2506—Catalytic processes
- C07C5/2512—Catalytic processes with metal oxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Catalysts based on gamma alumina, consisting of gamma alumina stabilised by silica and containing oxides of bivalent or trivalent metals chosen from those of Group 2a and/or Group 8 and/or Group 3b and/or the Lanthanide Series, are disclosed. The catalysts are particularly active in isomerisation reactions.
Description
SPECIFICATION
Catalyst based on gamma alumina
This invention relates to a catalyst based on gamma alumina, and its method of preparation.
Catalysts based on gamma alumina are known, but they have a too high acidity for certain reactions, and in particular for isomerisation reactions. Moreover, the acidity is increased when the gamma alumina is treated with silica in order to make it thermally stable, for example in accordance with the methods described in US-E-30668, US-A-4013590 and US-A-401 3589. On the other hand, stabilisation by means of silica is necessary in order to make the alumina suitable for high temperature regeneration without it losing its activity.
It has now been surprisingly found possible on the one hand to reduce the acidity of gamma alumina-based catalysts in such a manner as to make them suitable for isomerisation reactions, while on the other hand not reducing their thermal stability characteristics, by incorporating one or more oxides of the metals chosen from those of Group 2a (particularly calcium, strontium, and barium), and/or Group 8 (particularly iron), and/or
Group 3b (particularly lanthanum), and/or the
Lanthanide Series into the Silica-stabilised gamma alumina composition.
The catalyst based on gamma alumina according to the present invention has the general formula: aAI203.bSiO2 cMexOy where MexOy is the oxide of one or more of the aforesaid metals, and a, b and c are the number of moles of Awl203, SiO2 and MexOy respectively, b and c being related by the relationship: camb + B wherein B has a value greater than or equal to 0.01, and b has a value between 0.020 and 0.250, the ratio (b + c):a being between 0.01:1 and 9.0:1 and m being a number between 0.7 and 0.1.
The Periodic Table referred to herein is that published in "Handbook of Chemistry and
Physics", 55th edition, edited by Robert C.
Weast and published by CRC Press, Ohio.
In the specific case of calcium, the moles of
CaO are preferably related to the moles of
SiO2 by the relationship:
moles CaOaO500 (moles SiO2) + 0.030.
In the case of barium, the moles of BaO are preferably related to the moles of SiO2 by the relationship: moles BaOaO.500(moles SiO2) 0.020.
In the case of lanthanum, the moles of
La203 are preferably related to the moles of
SiO2 by the relationship: moles La2O30.257(moles SiO2) + 0.014.
In the case of iron, the moles of Foe203 are preferably related to the moles of SiO2 by the relationship: moles Fe203aO.290(moles SiO2) + 0.018.
In these four particular cases, the moles of
SiO2 and the ratio (b + c):a are as given above.
The catalyst according to the present invention is particularly useful in olefin isomerisation reactions, and in particular in the isomerisation of butene-2 to butene-1, as described and claimed in the British patent application filed by us on the same day as the present application and claiming priority from Italian
Patent Application No. 2151 1A/82.
In a preferred procedure for preparing a catalyst according to the invention, gamma alumina stabilised with silica, for example by any one of the procedures described in the aforesaid US Patents, is impregnated with aqueous solution or solutions of salt or salts of metal or metals of Groups 2a and/or Group 8 and/or Group 3b and/or the Lanthanide
Series, preferably aqueous solution of nitrate or acetate.
The invention will now be illustrated by the following Examples.
Example I 209 of gamma alumina (surface area 200 m2/g) are treated with 1 5 cc of an alcohol solution containing 0.75 9 of Dynasil A 40 (a 40% solution of ethylene orthosilicate). The mixture is allowed to react for two hours at 50"C. It is then drained off and treated with steam in order to hydrolyse the silanol groups.
It is dried and calcined at 500"C for 4 hours.
The material obtained in this manner, containing 1.5% of SiO2, is impregnated with 1 5 cc of an aqueous solution containing 5.90 g of lanthanum nitrate. The impregnated material is then dried and calcined at 500"C for 4 hours. A material is obtained, constituted by gamma alumina stabilised by 1.5% of SiO2, and containing 10% of La203.
This catalyst is fed into a reactor, in which trans-butene-2 is isomerised by reaction at a temperature of 470"C, at atmospheric pressure and at a weight hour space velocity (WHVS) of 6h - 1 The catalyst is able to produce butene-1 with an isobutene content of orily 140 ppm.
After thermal treatment for 24 hours at 1000"C, the catalyst has a surface area of 11 3 m2/g, and shows no loss of activity after 40 reaction cycles (332 hours in total) and 40 regeneration cycles (152 hours in total). The regeneration is carried out at a temperature of 540"C.
Example 2
Following the method described in Example 1, a catalyst is prepared constituted by 1.5% of SiO2 and 2.5% of CaO on gamma alumina.
The CaO is incorporated into the catalyst using an aqueous solution (15 cc) of calcium nitrate (2.40 g). Drying and calcining is again effected at 500"C for 4 hours.
The catalyst is fed into a reactor where transbutene-2 is isomerised by reaction at a temperature of 470"C, at atmospheric pressure and at a weight hourly space velocity (WHSV) at 6h-1. The catalyst is able to produce butene-1 with an isobutene content of only 150 ppm.
After thermal treatment for 24 hours at 1000"C, the catalyst has a surface area of 1 83 m2/g, and shows no loss of activity after 40 reaction cycles (332 hours in total) and 40 regeneration cycles (152 hours in total). Regeneration is effected at a temperature of 540"C.
Claims (7)
1. A catalyst based on gamma alumina and having the general formula: aAl2O3.bSiO2.cMeO wherein MexOy is the oxide of one or more of the metals of Groups 2a and/or Group 8 and/or Group 3b and/or the Lanthanide
Series, and a, b and c are the number of moles of Al2O3, SiO2 and MexOy respectively, b and c being related by the relationship: camb + B wherein B has a value greater than or equal to 0.01, b has a value of from 0.020 to 0.250, the ratio (b + c): a is from 0.01:1 to 9.0:1 and m is a number of from 0.1 to 0.7.
2. A catalyst as claimed in claim 1, wherein MexOy is La2O3, and wherein the number of moles of La2O3 is related to the number of moles of SiO2 by the relationship: moles La20320.257 (moles SiO2) + 0:014.
3. A catalyst as claimed in claim 1, wherein MexOy is Fe2O3, and wherein the number of moles of Fe2O3 is related to the number of moles of SiO2 by the relationship: moles Fe203a0.290(moles SiO2) + 0.018.
4. A catalyst as claimed in claim 1, wherein MexOy is CaO, and wherein the number of moles of CaO is related to the number of moles of SiO2 by the relationship: moles Ca030.500(moies SiO2) +0.030.
5. A catalyst as claimed in claim 1, wherein MexOy is BaO, and wherein the number of moles of BaO is related to the number of moles of SiO2 by the relationship: moles BaOaO.500(moles SiO2) + 0.020.
6. A catalyst as claimed in any of claims 1 to 5, prepared by impregnating gamma alumina stabilised by alumina with aqueous solution(s) of salt(s) of said metal(s).
7. A catalyst as claimed in claim 1, substantially as described in either of the foregoing Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21512/82A IT1152198B (en) | 1982-05-27 | 1982-05-27 | ALBUMINE RANGE CATALYST AND ITS PREPARATION METHOD |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8313562D0 GB8313562D0 (en) | 1983-06-22 |
| GB2121698A true GB2121698A (en) | 1984-01-04 |
| GB2121698B GB2121698B (en) | 1986-04-23 |
Family
ID=11182900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08313562A Expired GB2121698B (en) | 1982-05-27 | 1983-05-17 | Catalyst based on gamma alumina |
Country Status (29)
| Country | Link |
|---|---|
| JP (1) | JPS58216741A (en) |
| KR (1) | KR840004521A (en) |
| AU (1) | AU557471B2 (en) |
| BE (1) | BE896851A (en) |
| CA (1) | CA1193238A (en) |
| CS (1) | CS239938B2 (en) |
| DD (2) | DD228538A5 (en) |
| DE (1) | DE3319099A1 (en) |
| DK (1) | DK234483A (en) |
| EG (1) | EG16047A (en) |
| ES (1) | ES523075A0 (en) |
| FR (1) | FR2527941A1 (en) |
| GB (1) | GB2121698B (en) |
| GR (1) | GR78565B (en) |
| HU (1) | HU200709B (en) |
| IT (1) | IT1152198B (en) |
| LU (1) | LU84824A1 (en) |
| NL (1) | NL8301873A (en) |
| NO (1) | NO158485C (en) |
| NZ (1) | NZ204199A (en) |
| PH (1) | PH17970A (en) |
| PL (1) | PL140654B1 (en) |
| PT (1) | PT76765B (en) |
| RO (1) | RO86664B (en) |
| SE (1) | SE452954B (en) |
| SU (1) | SU1440330A3 (en) |
| YU (1) | YU44435B (en) |
| ZA (1) | ZA833399B (en) |
| ZW (1) | ZW11383A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187138A (en) * | 1991-09-16 | 1993-02-16 | Exxon Research And Engineering Company | Silica modified hydroisomerization catalyst |
| US5208200A (en) * | 1992-02-27 | 1993-05-04 | Exxon Research And Engineering Co. | Noble metal on rare earth modified silica alumina as hydrocarbon conversion catalyst |
| US5248409A (en) * | 1992-02-27 | 1993-09-28 | Exxon Research & Engineering Company | Metal on rare earth modified silica alumina as hydrocarbon conversion catalyst |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61157345A (en) * | 1984-12-28 | 1986-07-17 | Toyo C C I Kk | Carrier for catalyst |
| DE3839580C1 (en) * | 1988-11-24 | 1990-07-05 | Condea Chemie Gmbh, 2212 Brunsbuettel, De | |
| DE4445680A1 (en) * | 1994-12-21 | 1996-06-27 | Huels Chemische Werke Ag | Catalyst and process for the isomerization of aliphatic C¶4¶-C¶1¶¶¶ monoolefins |
| DE102013226370A1 (en) | 2013-12-18 | 2015-06-18 | Evonik Industries Ag | Production of butadiene by oxidative dehydrogenation of n-butene after prior isomerization |
| DE102015200702A1 (en) | 2015-01-19 | 2016-07-21 | Evonik Degussa Gmbh | Preparation of butadiene from ethene |
| JP6571392B2 (en) | 2015-05-29 | 2019-09-04 | Ｊｘｔｇエネルギー株式会社 | Isomerization catalyst, linear olefin production method and compound production method |
| JP6736017B2 (en) * | 2015-11-05 | 2020-08-05 | Ｅｎｅｏｓ株式会社 | Isomerization catalyst, method for producing linear olefin and method for producing compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2014057A (en) * | 1978-02-14 | 1979-08-22 | Engelhard Min & Chem | High temperature stabe catalyst composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461069A (en) * | 1944-06-10 | 1949-02-08 | Socony Vacuum Oil Co Inc | Simultaneous catalytic cracking and desulfurization of hydrocarbons |
| US3313858A (en) * | 1965-02-12 | 1967-04-11 | Phillips Petroleum Co | Isomerization of non-terminal olefins |
| US3925253A (en) * | 1973-03-19 | 1975-12-09 | Ethyl Corp | Catalysts |
| FR2424061A1 (en) * | 1978-04-25 | 1979-11-23 | Lyon Applic Catalytiques | NEW CONTACT MASS FOR HETEROGENOUS CATALYSIS |
| JPS6035174B2 (en) * | 1979-05-10 | 1985-08-13 | 株式会社日本触媒 | Catalyst for producing alkylene glycol ethers |
-
1982
- 1982-05-27 IT IT21512/82A patent/IT1152198B/en active
-
1983
- 1983-05-11 NZ NZ204199A patent/NZ204199A/en unknown
- 1983-05-11 ZA ZA833399A patent/ZA833399B/en unknown
- 1983-05-12 ZW ZW113/83A patent/ZW11383A1/en unknown
- 1983-05-17 YU YU1099/83A patent/YU44435B/en unknown
- 1983-05-17 GB GB08313562A patent/GB2121698B/en not_active Expired
- 1983-05-17 SE SE8302769A patent/SE452954B/en not_active IP Right Cessation
- 1983-05-18 PH PH28927A patent/PH17970A/en unknown
- 1983-05-18 KR KR1019830002174A patent/KR840004521A/en not_active Application Discontinuation
- 1983-05-19 GR GR71394A patent/GR78565B/el unknown
- 1983-05-20 AU AU14835/83A patent/AU557471B2/en not_active Expired - Fee Related
- 1983-05-24 RO RO111050A patent/RO86664B/en unknown
- 1983-05-25 EG EG323/83A patent/EG16047A/en active
- 1983-05-25 DK DK234483A patent/DK234483A/en not_active Application Discontinuation
- 1983-05-25 PL PL1983242188A patent/PL140654B1/en unknown
- 1983-05-25 FR FR8308649A patent/FR2527941A1/en not_active Withdrawn
- 1983-05-25 NO NO831848A patent/NO158485C/en unknown
- 1983-05-26 BE BE0/210854A patent/BE896851A/en not_active IP Right Cessation
- 1983-05-26 NL NL8301873A patent/NL8301873A/en not_active Application Discontinuation
- 1983-05-26 PT PT76765A patent/PT76765B/en unknown
- 1983-05-26 CA CA000428978A patent/CA1193238A/en not_active Expired
- 1983-05-26 SU SU833597798A patent/SU1440330A3/en active
- 1983-05-26 DE DE19833319099 patent/DE3319099A1/en active Granted
- 1983-05-26 LU LU84824A patent/LU84824A1/en unknown
- 1983-05-26 CS CS833718A patent/CS239938B2/en unknown
- 1983-05-26 HU HU831865A patent/HU200709B/en not_active IP Right Cessation
- 1983-05-27 ES ES523075A patent/ES523075A0/en active Granted
- 1983-05-27 JP JP58092564A patent/JPS58216741A/en active Pending
- 1983-05-27 DD DD83266938A patent/DD228538A5/en not_active IP Right Cessation
- 1983-05-27 DD DD83251339A patent/DD211720A5/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2014057A (en) * | 1978-02-14 | 1979-08-22 | Engelhard Min & Chem | High temperature stabe catalyst composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187138A (en) * | 1991-09-16 | 1993-02-16 | Exxon Research And Engineering Company | Silica modified hydroisomerization catalyst |
| US5208200A (en) * | 1992-02-27 | 1993-05-04 | Exxon Research And Engineering Co. | Noble metal on rare earth modified silica alumina as hydrocarbon conversion catalyst |
| US5248409A (en) * | 1992-02-27 | 1993-09-28 | Exxon Research & Engineering Company | Metal on rare earth modified silica alumina as hydrocarbon conversion catalyst |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940517 |