GB1574389A - Catalyst activation process - Google Patents
Catalyst activation process Download PDFInfo
- Publication number
- GB1574389A GB1574389A GB2974/77A GB297477A GB1574389A GB 1574389 A GB1574389 A GB 1574389A GB 2974/77 A GB2974/77 A GB 2974/77A GB 297477 A GB297477 A GB 297477A GB 1574389 A GB1574389 A GB 1574389A
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- Prior art keywords
- catalyst
- process according
- temperature
- nickel
- partially
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 97
- 238000001994 activation Methods 0.000 title description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- -1 silicate ions Chemical class 0.000 claims description 2
- 241000286904 Leptothecata Species 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 230000004913 activation Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000015096 spirit Nutrition 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000007591 Tilia tomentosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008096 xylene Substances 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J23/755—Nickel
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(54) CATALYST ACTIVATION PROCESS
(71) We, EXXON RESEARCH AND
ENGINEERING COMPANY, a Corporation duly organised and existing under the laws of the State of Delaware, United States of
America, of Linden, New Jersey, 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 :- The present invention relates to a process for activating a catalyst by reduction. The invention relates more particularly, but not exclusively, to the activation of catalysts comprising nickel, e. g. massive nickel catalysts.
Massive nickel hydrogenation catalysts having high nickel surface areas, for example, more than 70 m2/g, are known in the art. U. S.
Patent 3,868,332 teaches such a catalyst characterised as having a low sodium content, i. e. less than 0.2 wt. % based on total weight of catalyst. In U. S. Patent 3,859,370 the use of this catalyst in hydrogenation processes is claimed.
The present invention provides a process for activating a catalyst by reduction comprising the following steps in sequence:
(a) reducing said catalyst by heating in the
presence of hydrogen at a tempera
ture sufficient partially to activate the
catalyst; (b) contacting said partially activated
catalyst in the presence of hydrogen
with a reactive feed which undergoes
exothermic reaction in the presence
of said partially activated catalyst at
conditions whereby said exothermic re
action occurs, said conditions including
a temperature greater than the
temperature in step (a) at which the
said catalyst is partially activated; and
(c) continuing said contacting for a time
sufficent to convert said partially acti
vated catalyst to a more highly acti
vated catalyst than the partially acti
vated catalyst of step (a).
The catalyst may comprise nickel and may also comprise silica. The catalyst may comprise nickel and silica and have a nickel surface area in the range of from 50 to 100 m2/g and a total surface area in the range of from 150 to 300 m2/g.
The process of the invention may be employed for activating catalysts which are commonly activated by reduction at elevated temperatures, for example, at least 150 C.
The catalyst prior to this activation step may be prepared by any method known in the art.
For example, in preparing a supported catalyst which comprises a metal supported on an inert, porous support, a catalyst metal precursor will be impregnated or precipitated onto the support or, alternatively, the supported catalyst may be formed by coprecipitation, from solution, of the precursors of both the metal and the support. The solution may comprise any solvent in which the catalyst metal precursors are soluble, i. e., the solvent may be aqueous or nonaqueous. For example, a catalyst comprising nickel, copper and silica may be prepared by contacting a porous support (e. g. silica or kieselguhr), preferably a particulate support, with a solution of nickel, copper and silicate ions at such conditions that said ions are co-precipitated onto said support to yield a composite comprising nickel, copper and silica precursors supported on said porous support. The excess solvent is removed by methods known in the art, including heating and/or use of a vacuum. After solvent removal, if desirable, a calcination in air or an inert gas may be carried out.
The process of the invention is especially suitable for preparing hydrogenation catalysts which are activated by reduction at high temperature. Most especially, the process of the invention is useful for activating the massive nickel hydrogenation catalysts des cribed in the U. S. mentioned above. In its most preferred embodiment, the process of the invention is utilized to activate the catalysts which comprise nickel, copper and silica coprecipitated onto a porous support.
In one preferred embodiment, the importance of the invention arises from the fact that many commercial hydrogenation units are limited to a maximum temperature at the inlet of from 200 C to 250 C. It is noted that there are commercial hydrogenation units wherein a furnace is used to preheat the feed at the inlet. However, these units must be designed for temperatures of from 350 C to 400 C, since the nickel-silica catalyst must be reduced at a temperature of at least about 350 C for complete activation. Thus the catalyst is generally reduced and stabilized by the manufacturer. This requirement, however, increases the cost of the catalyst and makes in situ activation more attractive. Because of the above limitation on inlet temperature, prior to the discovery of the process of the instant invention, in situ techniques were not commonly available to the commercial users of nickel-silica hydrogenation catalysts.
In a preferred embodiment of the process of the instant invention the massive nickel catalyst, which is a high surface area nickel catalyst preferably containing copper, is charged into the hydrogenation reactor in a manner designed to minimize absorption of water from the atmosphere. The reactor may be purged with dry air or a dry inert gas to remove traces of water from both the reactor and the catalyst. The reactor is closed and then purged with an inert gas to remove oxygen.
When the oxygen level is sufEiciently low, i. e. less than 1%, the purge gas is terminated and a reducing gas, preferably a hydrogen-rich gas is passed over the catalyst at a flow rate of from 1,000 V/Hr/V to 50, 000 V/Hr/V, pre- ferably 5, 000 V/Hr/V. The reducing gas is bled into the reactor with steadily increasing flow up until the point where full flow has been obtained. Then the temperature at the inlet is increased in increments of 10 C to 30 C at thirty minute intervals until a temperature of from 210 to less than 235 C is achieved within the catalyst bed. This temperature is maintained for a time sufficient to provide a partially activated catalyst composite, e. g., with 1v75% of the activity of a fully activated catalyst. The catalyst at this point is an active catalyst, although, due to the fact that much of the nickel exists in the nonmetallic (noncatalytically active) state, the catalyst is characterized as being partially activated. However, as will be further described below, it is critical that sufficient nickel exist in the metallic, i. e. catalytically active, state to yield a composite having some catalytic activity. The temperature at the inlet is then lowered to from about 100 C to 125 C and the flow of a reactive feed through the catalyst bed is commenced. The reactive feed when a hydrogenation catalyst is being activated by the process o, the instant invention is conveniently an unsaturated hydrocarbon, i. e., either an aromatic or olefinic hydrocarbon; or oxygenated derivatives thereof, e. g. alcohols, ethers, etc.
Examples of reactive feed which are useful in the process of the instant invention include: C2 to Czo olefins, C6 to Czo aromatic hydrocarbons, e. g. benzene, toluene, xylene hexene, butadiene, styrene, inter alia. The reactive feed may be 100% olefinic or aromatic or comprise mixtures of olefins and aromatics. Nonreactive components such as paraffins may also make up a portion of the reactive feedstream. Hydrogen is provided with the reactive feed since it is necessary as a reactant and to reduce the nickel to the metal. It is critical to the process of the instant invention that the reaction used to activate the partially activated catalyst composite must be exothermic since the purpose in contacting the catalyst with a reactive feed, at this point, is to utilize the heat of reaction to obtain a higher temperature at the surface of the catalyst than is available at the inlet or in the catalyst bed. Thus, the skilled artisan would adjust the reactive feed accordingly to obtain sufficient heat of reaction to convert the partially activated catalyst into a high activity catalyst, e. g., a catalyst with more than 75% of the activity of a fully activated catalyst.
The temperature during the contacting of the partially activated massive nickel hydrogenation catalyst with the reactive feed is raised, in increments of 10 C to 30 C per thirty minute interval, until the maximum temperature in the catalyst bed exceeds 235 C, preferably the temperature is raised to between 235 C and 275 C.
The ratio of the reactive fed to hydrogen and flow rates of both are adjusted to achieve a sufficient exotherm to raise the temperature of the catalyst in the bed to a level of 250- 275 C or more. The catalyst will be maintained at this temperature by means of the reaction occurring for a time sufficient to achieve, preferably full, i. e., 100%, activation of the catalyst, in approximately 2 to 20 hours.
The massive nickel catalysts activated by the process of the invention are useful in hydrogenation and may be used to hydrogenate aromatics, aldehydes, alcohols, olefins, including both straight and branched chain, and the various hydrocarbon double bonds found in edible fats and oils.
EXAMPLES
The following examples best illustrate the process of the instant invention. The catalyst used in all the tests was prepared according to the following method: 8.75 gm of
Cu (NO.,),. 3HO and 112 gm. of
Ni (NO,),. 6H, O were dissolved in 500 ml of distilled water, then 39 gm. of Na2SiOs. 9H20 was dissolved ir. another 500 ml of water and 5 gm. ot acid washed kieselguhr was slurried in this second solution. The second solution with the kieselguhr slurried therein was stirred vigorously while the first solution containing the copper and nickel salts was added at a uniform rate over a 20 minute period. This mixture was then heated to the boiling point and 80 gm. of NH, HCO3 was added at a uniform rate over a 20 minute period. The mixture was kept at the boiling point for 3 hours while stirring continued. It was then filtered and washed 5 times with boiling water, each wash consisting of 500 ml of water. The filtercake was then dried at 120 C and calcined in air for 4 hours at 400 C. The catalyst contained by weight 45.0% nickel, 5.0% copper, and 50% silica (the impurities present in the acid washed kieselguhr being included in the weight of silica given).
In Example A the catalyst was activated in
H2, at a catalyst bed temperature of 245 C, with a nonreactive feed flow. In Example B, the catalyst was activated in H2, at a catalyst bed temperature of 245 C, with a reactive feed which contained 22.3% aromatics. In
Example C, the catalyst was activated in H2, at a catalyst bed temperature of 245 C, with a reactive feed which contained 21.7% aromatics. In Example D, the catalyst was activated first with H2 at a catalyst bed temperature of 232 C, then with a reactive feed which contained 21.7% aromatics at 245 C.
TABLE I
Example A Example B
Conversion of aromatics at 100 hours on oil 60% 80%
Run Conditions:
Space Velocity-10-Volume feed/Hr/Volume Catalyst
Pressure-600 psig Temperature-160 C H2-1000 Standard Cubic Feet/Barrel
Feed-Mineral spirits*
22. 3% aromatics
TABLE II
Example C Example D
Conversion of aromatics at
75 hours on oil 24% 34% Run :
Space Velocity-30 Volume feed/Hr SVolume Catalyst
Pressure-600 psig
Temperature-160 C Ho-1000 Standard Cubic Feed/Barrel Feed spirits*
21.7% aromatics * The mineral spirits used was VARSOLTM ~3, from Exxon Chem. Co. U. S. A. which
is a naphtha fraction with a boiling range of 310 F to 341 F, aromatics content of
from about 21 to 23% on a wt. basis and 1.5 ppm sulfur or less."VARSOL"is a
trade mark for the foregoing product.
In Table I, Example B shows significantly higher conversion than Example A. The data in
Table II show how the added improvement obtained by the activation procedure described ir. this application. Example D shows sub santially more conversion than Example C which did not include a treatment with H2 prior to the high temperature activation with the reactive feed. Thus, the data in Tables I and II demonstrate the criticality of the two step activation process of the instant invention.
It should be noted, for purposes of definition,
Example D represents a fully active catalyst composite, while Examples A, B and C, represent partially active catalyst composites, i. e., they have an activity (as measured by the reaction described in Example D and defining the catalyst activity of said catalyst composite as 10 ()/) from from to 75/,.
Claims (18)
1. A process for activating a catalyst by reduction comprising the following steps in sequence:
(a) reducing said catalyst by heating in the
presence of hydrogen at a temperature
sufficient partially to activate the cata lyst ; (b) contacting said partially activated cata
lyst in the presence of hydrogen with
a reactive feed which undergoes exo
thermic reaction in the presence of
said partially activated catalyst at
conditions whereby said exothermic
reaction occurs, said conditions includ
ing a temperature greater than the
temperature in step (a) at which the
said catalyst is partially activated ; and (c) continuing said contacting for a time
sufficient to convert said partially acti
vated catalyst to a more highly acti
vated catalyst than the partially acti
vated catalyst of step (a).
2. A process according to claim 1 in which the catalyst comprises nickel.
3. A process according to claim 2 in which the catalyst comprises silica.
4. A process according to claim 3 in which the catalyst has a nickel surface area in the range of from 50 to 100m 2/g and a total surface area in the range of from 150 to 300 m'/g.
5. A process according to claim 3 or claim 4 in which the catalyst comprises copper.
6. A process according to claim 5 in which said catalyst is prepared by contacting a porous support with a solution of nickel, copper and silicate ions at conditions whereby said ions are co-precipitated onto said support to yield a composite comprising nickel, copper and silica precursors supported on said porous support.
7. A process according to claim 6 in which the said porous support is a particulate support.
8. A process according to claim 6 or claim 7 in which the said support is silica or kieselguhr.
9. A process according to any one of claims 1 to 8 in which the temperature in step (a) is less than 235 C and the temperature em ployed in step (b) is in the range of from 235 C to 275 C.
10. A process according to any one of claims 1 to 9 in which the temperature of the catalyst surface during step (b) exceeds the temperature of the catalyst bed.
11. A process according to any one of claims 1-10 in which step (a) is continued for a time sufficient to yield a catalyst with an activity of from 10 to 75% of the fully activated catalyst.
12. A process according to any one of claims 1-11 in which steps (b) and (c) are carried out at conditions sufficient to yield a catalyst with an activity of greater than 75% of the fully activated catalyst.
13. A process according to any one of claims 1 to 12 in which the said reactive feed comprises an unsaturated hydrocarbon or oxygenated derivative thereof.
14. A process according to claim 13 in which the said unsaturated hydrocarbon is a C4 to C2 aromatic hydrocarbon.
15. A process according to claim 13 in which the said unsaturated hydrocarbon is Cz to C20 olefinic hydrocarbon.
16. A process for activating a catalyst according to any one of claims 1 to 15 substantially as hereinbefore described.
17. A process for activating a catalyst sub stantially as hereinbefore described with reference to Example D.
18. A catalyst whenever activated in accordance with the process of any one of claims 1 to 17.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US65469376A | 1976-02-02 | 1976-02-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1574389A true GB1574389A (en) | 1980-09-03 |
Family
ID=24625877
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB2974/77A Expired GB1574389A (en) | 1976-02-02 | 1977-01-25 | Catalyst activation process |
Country Status (10)
Country | Link |
---|---|
JP (1) | JPS5939182B2 (en) |
AU (1) | AU514928B2 (en) |
BE (1) | BE850966A (en) |
BR (1) | BR7700626A (en) |
CA (1) | CA1080685A (en) |
DE (1) | DE2702327A1 (en) |
FR (1) | FR2339432A1 (en) |
GB (1) | GB1574389A (en) |
IT (1) | IT1080316B (en) |
NL (1) | NL7701077A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2280618A (en) * | 1993-07-28 | 1995-02-08 | Exxon Chemical Patents Inc | Activating catalysts |
EP2380953A1 (en) * | 2010-04-22 | 2011-10-26 | BASF Corporation | Hydrogenation of fatty acids using a promoted supported nickel catalyst |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU774584A1 (en) * | 1978-01-05 | 1980-10-30 | Предприятие П/Я А-7531 | Catalyst activating method |
DK144996C (en) * | 1980-05-19 | 1982-12-20 | Haldor Topsoe As | PROCEDURE FOR CARRYING OUT THE CATALYTIC EXOTHERMY GAS PHASE PROCESS AND PROCEDURE FOR THE PREPARATION OF A CATALYST |
KR20210001784A (en) | 2019-06-28 | 2021-01-06 | 한화솔루션 주식회사 | Catalyst for nickel-based hydrogenation reaction, and preparation method thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3868332A (en) * | 1970-10-26 | 1975-02-25 | Exxon Research Engineering Co | Massive nickel catalysts |
AU511696B2 (en) * | 1975-05-14 | 1980-09-04 | Exxon Research And Engineering Company | Supported Cuni-Sio2 catalyst for hydrogenation |
-
1977
- 1977-01-18 CA CA269,936A patent/CA1080685A/en not_active Expired
- 1977-01-20 AU AU21494/77A patent/AU514928B2/en not_active Expired
- 1977-01-21 DE DE19772702327 patent/DE2702327A1/en active Granted
- 1977-01-25 GB GB2974/77A patent/GB1574389A/en not_active Expired
- 1977-01-28 JP JP52008596A patent/JPS5939182B2/en not_active Expired
- 1977-02-01 BE BE174555A patent/BE850966A/en not_active IP Right Cessation
- 1977-02-01 FR FR7702761A patent/FR2339432A1/en active Granted
- 1977-02-01 IT IT19855/77A patent/IT1080316B/en active
- 1977-02-01 BR BR7700626A patent/BR7700626A/en unknown
- 1977-02-02 NL NL7701077A patent/NL7701077A/en not_active Application Discontinuation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2280618A (en) * | 1993-07-28 | 1995-02-08 | Exxon Chemical Patents Inc | Activating catalysts |
EP2380953A1 (en) * | 2010-04-22 | 2011-10-26 | BASF Corporation | Hydrogenation of fatty acids using a promoted supported nickel catalyst |
WO2011133037A1 (en) | 2010-04-22 | 2011-10-27 | Basf Corporation | Hydrogenation of fatty acids using a promoted supported nickel catalyst |
US8884042B2 (en) | 2010-04-22 | 2014-11-11 | Basf Corporation | Hydrogenation of fatty acids using a promoted supported nickel catalyst |
Also Published As
Publication number | Publication date |
---|---|
JPS5294890A (en) | 1977-08-09 |
BE850966A (en) | 1977-08-01 |
NL7701077A (en) | 1977-08-04 |
FR2339432B1 (en) | 1983-10-07 |
CA1080685A (en) | 1980-07-01 |
AU514928B2 (en) | 1981-03-05 |
AU2149477A (en) | 1978-07-27 |
FR2339432A1 (en) | 1977-08-26 |
DE2702327C2 (en) | 1987-07-30 |
IT1080316B (en) | 1985-05-16 |
JPS5939182B2 (en) | 1984-09-21 |
BR7700626A (en) | 1977-10-04 |
DE2702327A1 (en) | 1977-08-04 |
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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 |
Effective date: 19940125 |