CA1249573A - Method for preparing silica supported hydrotreating catalysts and catalysts thus prepared - Google Patents
Method for preparing silica supported hydrotreating catalysts and catalysts thus preparedInfo
- Publication number
- CA1249573A CA1249573A CA000491645A CA491645A CA1249573A CA 1249573 A CA1249573 A CA 1249573A CA 000491645 A CA000491645 A CA 000491645A CA 491645 A CA491645 A CA 491645A CA 1249573 A CA1249573 A CA 1249573A
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- catalyst
- catalysts
- silica
- prepared
- nickel
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and 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
- 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
Abstract
A B S T R A C T
METHOD FOR PREPARING SILICA SUPPORTED HYDROTREATING
CATALYSTS AND CATALYSTS THUS PREPARED
Silica supported hydrotreating catalysts are prepared by impregnating a dry silica support with a hydrogenation metals-containing solution obtained by reacting a molybdenum halide and/or a nickel and/or cobalt halide in the presence of a nitrile and heating the mixture formed to between 25 and 80 °C until most of the metal compounds have reacted and/or dissolved followed by removal of undissolved solids from the solution, and drying the impregnated silica support at elevated temperature.
METHOD FOR PREPARING SILICA SUPPORTED HYDROTREATING
CATALYSTS AND CATALYSTS THUS PREPARED
Silica supported hydrotreating catalysts are prepared by impregnating a dry silica support with a hydrogenation metals-containing solution obtained by reacting a molybdenum halide and/or a nickel and/or cobalt halide in the presence of a nitrile and heating the mixture formed to between 25 and 80 °C until most of the metal compounds have reacted and/or dissolved followed by removal of undissolved solids from the solution, and drying the impregnated silica support at elevated temperature.
Description
'`73 METHOD FOR PREPARING SILICA SUPPORTED HYDROTREATING
~ATALYSTS AND CATALYSTS T~US PREPARED
The invention relates to a method for preparing silica supported hydrotreating catalysts and to catalysts thus prepared.
Silica supported hydrotreating catalysts, when prepared by conventional aqueous porefilling impregnation with catalytically active metals, tend to have very poor activity compared to corresponding alumina based catalysts. This is thought to be because the metal oxides (MoO3, NiO, CoO) react very weakly with the support, and thus are very poorly dispersed on the support.
Potentially, silica based hydrotreating catalysts should perform well in treating residual oll feedstocks. Silica based catalysts should be less prone to coke formation than alumina based catalysts because of the lower acidity of silica. Since coke deposition is a ma~or catalyst deactivator in such applications, an active and stable silica based catalyst could have an enormous impact on hydrotreating such feedscocks.
In U.S. patent specifications 3,167,496 and 3,167,497 processes have been disclosed for hydrogenating olefins and aromatics in the presence of catalysts comprising molybdenum and nickel in a particular atomic ratio supported on silica. These catalysts are prepared by aqueous impregnation, preferably with the precursor of the molybdenum catalytic agent prior to impregnation with the precursor of the nickel catalytic agent. The molybdenum compound content ranges between about 12 and about 35%w (as MoO3), based on total weight of the catalyst. The nickel compound is preferably present in an amount to provide an atomic ratio of molybdenum to nickel between about 2-3.
In U.S. patent specification 3,420,771 a process has been disclosed for hydrorefining an asphaltenic hydrocarbonaceous charge stock containing either sulphurous or nitrogeneous compounds in 5'~3 contact with a catalyst prepared by impregnating hydrated silica which has not been calcined (5-15%w water) with from about 4-30%w of aqueous molybdenum compounds prior to calcining. Preferably the catalyst also contains from about 1-6%w nickel. Nickel nitrate hexahydrate and phosphomolybdic acid are suggested as the source of catalytically active metals.
These prior art methods of preparing silica supported catalysts all suffer from the disadvantage of poor catalytic metals distribution on the support. A non-aqueous method for preparing silica based hydrotreating catalysts has now been found which overcomes this disadvantage by improvin& the dispersion of metals on the support, thereby greatly increasing catalyst activity.
The present invention relates to a method for preparing a silica supported hydrotreating catalyst containing from about 10-25%w molybdenum and from about 1-5%w nickel and/or cobalt as hydrogenation metals, which comprises impregnating a dry silica support in one or more steps with a hydrogenation metals-containing solution obtained by reacting a molybdenum halide and/or a nickel and/or cobalt halide in the presence of a nitrile and heating the mixture formed to between 25 and 80 C until most of the metal compounds have reacted and/or dissolved followed by removal of undissolved solids from the solution, and drying the impregnated silica support at elevated temperature.
Suitably, molybdenum chlorides and bromides can be used advantageously in the process according to the present invention.
Good results have been obtained using molybdenum pentachloride.
Suitable nickel and/or cobalt halides comprise the chlorides and the bromides, in particular nickel chloride hexahydrate.
Acetonitrile (a member of the class of nitriles having at least one alpha-hydrogen atom attached to the carbon atom next to the nitrile group) i8 the preferred nitrile to be used in the process according to the present invention. If desired, additional non-aqueous solvents such as methylene dichloride or chloroform may be present as well.
~95'~3 The present invention relates in particular to a process wherein the hydrogenation metals-containing solution is obtained by reacting a mixture of MoCl5 and of Ni(H20)6Cl2 and/or Co(H20)6Cl~
in amounts to provide a desired catalytic metals concentration on a support in the presence of a solubilizing amount of acetonitrile and heating the mixture to between about 25 and 80 C until most of the metal compounds have reacted and/or dissolved and removing any undissolved solids from the solution.
It has been reported (R. Fricke, W. Hanke and G. Ohlmann, J. Catal., 79, 1, (1983)) from experiments in preparing supported metal halides that the strong support-metal interactlon resulting from the dehydrohalogenation reaction between metal halide and support hydroxyl (reaction I) could yield well dispersed catalytic precursors.
Cl Cl Cl MoCl5 + OH \ / OH Mo ~ + 2HCl (I) si si si Similarly, it was felt that the oxophilic nature of MoCl5 would permit the formation of stable oxo or hydroxy linkages between Ni and Mo in the preparative solution that could yield a catalyst precursor that would sulphide to a mixed metal sulphide phase in the final catalyst. Such phases have been postulated as ~he active phase in hydrotreating catalysts. These goals have been realized to a varying extent by the method of the invention.
The preferred catalyst according to the invention is prepared by reacting MoCl5 and Ni(H20)6Cl2 and/or Co(H20)6Cl2 in the presence of acetonitrile. The Ni--Mo or Co-Mo solution, thus prepared, is then used to impregnate a suitable dried silica support. The impregnated support is then dried, but need not be calcined. The resulting catalyst has more than 90% of the hydrodenitrification (HDN) activity of a high activity commercially available alumina-based hydrotreating catalyst with comparable ~z~s~
metals content. Furthermore, is has greatly increased hydrogenation and hydrosulphurization (H2 HDS) activities over a silica-based hydroconversion catalyst containing comparable metals contents, but prepared in a manner similar to that of a commercial alumina-based hydrotreating catalyst, i.2., by aqueous metal impregnation of the support.
Full characterization of the impregnation solution used in the experiment has not been made. However, the reaction between MoCl5 and Ni(H20)6C12 or Co(H20)6Cl2 proceeds with great vigour and the release of HCl gas. Based on this observation and elemental analysis data, a reasonable guess as to the reaction path in acetonitrile/trichloromethane appears below (reaction II). The reaction product is very soluble in acetonitrile and can be impregnated directly into a support. The impregnated support is then dried, preferably under a vacuum. Calcination is not required.
2MoC15 -~ Ni(H20)6C12 > H4~(C13MoO2)2Ni] + 4 HCl (II) Suitable hydrotreating catalysts according to the invention generally contain from about 10-25%w molybdenum and from about 1-5%w nickel and/or cobalt on a dried silica support. Preferably, the catalysts will contain from about 10-20% molybdenum and from about 2-4%w nickel and/or cobalt. Of the latter metals, nickel is the most preferred.
The activity testing of the catalysts according to this invention was done in microreactor systems. These units are of conventional, fixed-bed, downflow design. Each unit consists of a reactor (1.27 cm O.D.) with a preheat section, a phase separator and a large product tank. Unit pressure is controlled by a motor valve on the outlet gas line and inlet H2 rate is malntained by pressure drop across a length of capillary tubing. LAPP pumps are used for charging liquid feed. Emergency circuitry automatically shut5 down the unit in the event of fire, high reactor temperature, high or low unit pressure or loss of instrument air.
5'73 Catalysts were crushed, screened to 3 O. 3-1 mm and dried at 482 C for testing. To facilitate control of the reactor temperature the catalyst was diluted 1-1 by volume with a high-density alumina or silicon carbide ground to ~ 0.3-1 mm. Prior to processing hydrocarbon feed, the catalyst was presulphided at atmospheric pressure with 5% H2S in H2. The temperature program Eor the presulphiding was 2 hours at 204 C, 1 hour at 316 C and 2 hours at 371 C. Depending upon the metals content, the catalyst will contain from about 10-20%w sulphur.
Elemental composition of the catalyst prepared in accordance with the invention before and after sulphiding appears in Table 1.
%w Mo %w Ni ¦ %w S %w C1 I
Before Sulphidlng 13.4 2.5 1 0 13.0 After Sulphiding 17.2 3.1 ¦ 16.3 0.3 The most noteworthy feature of these data is that the total metal:sulphur ratio (metal - Mo+Ni) is 1 to 2.1. This is sulphur-rich relative to the expected MoS2/NiS system. Additionally, a thermogravimetric analysis clearly indicated that the sulphur was chemisorbed or structurally absorbed rather than merely physisorbed.
In a typical conventional Ni/Mo or Co/Mo hydrotreating catalyst preparation method catalytically active metals are deposited on a support by a dry (pore volume) impregnation technique. In this method, the support i5 impregnated with a quantity of metal-salt solution that is just sufficient to be absorbed in the pore volume of the support. The impregnating solution is generally prepared in two parts initially. One part contains the molybdenum salt and most of the water that can be used. After most of the molybdenum sslt has dissolved (with heating and stirring), H202 (30%w) is added (about 0.4 cc/g of Mo) to aid S'73 solubilization. The other part of the solution con~ains the Ni and/or Co salt(s) and sufficient phosphoric acid (85%w) to aid the solubility and stability of the solution and to include about 3%w P
in the catalyst. When both solutions are clear and cool, the Mo solution is added slowly (with vigorous stirring) to the Ni-P or Co-P solution. The combined solution is then diluted to the proper volume and added slowly, usually ln one or more steps, to the support. The impregnated catalyst is dried at 121 C for about 2 hours and then calcined in air at 482 C for about 2 hours.
A substantial increase in the hydrodenitrification (HDN) activity, relative to existing commercial catalysts, is required to commercialize a new hydrotreating catalyst. In an effort to develop such an improved catalyst, a standard 72 hour HDN activity test was used to evaluate the various catalysts. In this test the HDN and HDS activities of a cat cracked heavy gas oil were evaluated at 344 C and 58.6 bar H2 partial pressure. Activities were compared based on observed rate constants for HDN and on plug flow kinetics for HDS.
Suitable hydroconversion conditions for the processes using catalysts according to the invention are as Eollows:
a temperature of 350-420 C;
a total pressure of 75-200 bar;
a partial hydrogen pressure of 50-200 bar;
a space velocity of 0.4-1.5 kg oil/1 catalyst/hour; and a hydrogen feed rate of 250-2500 N1/kg oil feed.
The hydrodenitrification of heavy oil feeds according to the present process is preEerably carried out under the following conditions:
a temperature of 360-410 C;
a total pressure of 100-150 bar;
a partial hydrogen pressure of 80-150 bar;
a space velocity oE 0.4-1.0 kg oil/1 catalyst/hour; and a hydrogen feed rate of 500-1500 N1/kg oil Eeed.
The hydrogen applied can be pure hydrogen of a hydrogen-con-taining gas, preferably one comprising more then 70% hydrogen. The hydrogen-containing gas may also contain up to about 10% of hydrogen sulphide.
The invention will now be illustrated by the following Examples:
Two catalysts, A (alumina based) and B (silica based) were prepared by a conventional aqueous impregnation Method for comparative purposes.
Catalyst A was a standard commercial hydrotreating catalyst (available from Shell Chemical Company) which was prepared by using a dry (pore volume) metals aqueous impregnation technique to impart metals onto a gamma alumina support. This catalys~ was prepared by the typical aqueous impregnation method described hereinabove. The composition of this alumina based catalyst is given in Table 2. The various hydrotreating activities of this catalyst were taken as l.0 for comparison.
Catalyst B was prepared by impregnating a dried Grade 57 silica(from Davison Chemical, a division of W. R. Grace Co.) with the same metals solution and dry (pore volume) ~echnique used for Catalyst A. The composition of this silica based catalyst is also given in Table 2.
A silica based catalyst, C, was prepared by the method according to the invention by mixing 55.3 g MoC15 and 23.8 g Ni(H20)6C12 in a 250 ml round bottom flask with a condenser. 100 ml acetonitrile were then added slowly through the condenser. The MoC15 reacted vigorously with the Ni(H20)6C12 liberating HCl gas.
Upon completion of the addition, the mixture was heated at acetonitrile reflux temperature (~ 78 C) for 1 hour, cooled, filtered and diluted to 140 ml with acetonitrile. 70 g dry (120 C) grade 57 Davison silica (~ 0.5-0~85 mm) were then impregnated with 80 ml of this solution, dried under vacuum at 80 C, and then impregnated with the remaining solution. The resulting catalyst was 5'~3 then dried overnight at 80 C under reduced pressure (about
~ATALYSTS AND CATALYSTS T~US PREPARED
The invention relates to a method for preparing silica supported hydrotreating catalysts and to catalysts thus prepared.
Silica supported hydrotreating catalysts, when prepared by conventional aqueous porefilling impregnation with catalytically active metals, tend to have very poor activity compared to corresponding alumina based catalysts. This is thought to be because the metal oxides (MoO3, NiO, CoO) react very weakly with the support, and thus are very poorly dispersed on the support.
Potentially, silica based hydrotreating catalysts should perform well in treating residual oll feedstocks. Silica based catalysts should be less prone to coke formation than alumina based catalysts because of the lower acidity of silica. Since coke deposition is a ma~or catalyst deactivator in such applications, an active and stable silica based catalyst could have an enormous impact on hydrotreating such feedscocks.
In U.S. patent specifications 3,167,496 and 3,167,497 processes have been disclosed for hydrogenating olefins and aromatics in the presence of catalysts comprising molybdenum and nickel in a particular atomic ratio supported on silica. These catalysts are prepared by aqueous impregnation, preferably with the precursor of the molybdenum catalytic agent prior to impregnation with the precursor of the nickel catalytic agent. The molybdenum compound content ranges between about 12 and about 35%w (as MoO3), based on total weight of the catalyst. The nickel compound is preferably present in an amount to provide an atomic ratio of molybdenum to nickel between about 2-3.
In U.S. patent specification 3,420,771 a process has been disclosed for hydrorefining an asphaltenic hydrocarbonaceous charge stock containing either sulphurous or nitrogeneous compounds in 5'~3 contact with a catalyst prepared by impregnating hydrated silica which has not been calcined (5-15%w water) with from about 4-30%w of aqueous molybdenum compounds prior to calcining. Preferably the catalyst also contains from about 1-6%w nickel. Nickel nitrate hexahydrate and phosphomolybdic acid are suggested as the source of catalytically active metals.
These prior art methods of preparing silica supported catalysts all suffer from the disadvantage of poor catalytic metals distribution on the support. A non-aqueous method for preparing silica based hydrotreating catalysts has now been found which overcomes this disadvantage by improvin& the dispersion of metals on the support, thereby greatly increasing catalyst activity.
The present invention relates to a method for preparing a silica supported hydrotreating catalyst containing from about 10-25%w molybdenum and from about 1-5%w nickel and/or cobalt as hydrogenation metals, which comprises impregnating a dry silica support in one or more steps with a hydrogenation metals-containing solution obtained by reacting a molybdenum halide and/or a nickel and/or cobalt halide in the presence of a nitrile and heating the mixture formed to between 25 and 80 C until most of the metal compounds have reacted and/or dissolved followed by removal of undissolved solids from the solution, and drying the impregnated silica support at elevated temperature.
Suitably, molybdenum chlorides and bromides can be used advantageously in the process according to the present invention.
Good results have been obtained using molybdenum pentachloride.
Suitable nickel and/or cobalt halides comprise the chlorides and the bromides, in particular nickel chloride hexahydrate.
Acetonitrile (a member of the class of nitriles having at least one alpha-hydrogen atom attached to the carbon atom next to the nitrile group) i8 the preferred nitrile to be used in the process according to the present invention. If desired, additional non-aqueous solvents such as methylene dichloride or chloroform may be present as well.
~95'~3 The present invention relates in particular to a process wherein the hydrogenation metals-containing solution is obtained by reacting a mixture of MoCl5 and of Ni(H20)6Cl2 and/or Co(H20)6Cl~
in amounts to provide a desired catalytic metals concentration on a support in the presence of a solubilizing amount of acetonitrile and heating the mixture to between about 25 and 80 C until most of the metal compounds have reacted and/or dissolved and removing any undissolved solids from the solution.
It has been reported (R. Fricke, W. Hanke and G. Ohlmann, J. Catal., 79, 1, (1983)) from experiments in preparing supported metal halides that the strong support-metal interactlon resulting from the dehydrohalogenation reaction between metal halide and support hydroxyl (reaction I) could yield well dispersed catalytic precursors.
Cl Cl Cl MoCl5 + OH \ / OH Mo ~ + 2HCl (I) si si si Similarly, it was felt that the oxophilic nature of MoCl5 would permit the formation of stable oxo or hydroxy linkages between Ni and Mo in the preparative solution that could yield a catalyst precursor that would sulphide to a mixed metal sulphide phase in the final catalyst. Such phases have been postulated as ~he active phase in hydrotreating catalysts. These goals have been realized to a varying extent by the method of the invention.
The preferred catalyst according to the invention is prepared by reacting MoCl5 and Ni(H20)6Cl2 and/or Co(H20)6Cl2 in the presence of acetonitrile. The Ni--Mo or Co-Mo solution, thus prepared, is then used to impregnate a suitable dried silica support. The impregnated support is then dried, but need not be calcined. The resulting catalyst has more than 90% of the hydrodenitrification (HDN) activity of a high activity commercially available alumina-based hydrotreating catalyst with comparable ~z~s~
metals content. Furthermore, is has greatly increased hydrogenation and hydrosulphurization (H2 HDS) activities over a silica-based hydroconversion catalyst containing comparable metals contents, but prepared in a manner similar to that of a commercial alumina-based hydrotreating catalyst, i.2., by aqueous metal impregnation of the support.
Full characterization of the impregnation solution used in the experiment has not been made. However, the reaction between MoCl5 and Ni(H20)6C12 or Co(H20)6Cl2 proceeds with great vigour and the release of HCl gas. Based on this observation and elemental analysis data, a reasonable guess as to the reaction path in acetonitrile/trichloromethane appears below (reaction II). The reaction product is very soluble in acetonitrile and can be impregnated directly into a support. The impregnated support is then dried, preferably under a vacuum. Calcination is not required.
2MoC15 -~ Ni(H20)6C12 > H4~(C13MoO2)2Ni] + 4 HCl (II) Suitable hydrotreating catalysts according to the invention generally contain from about 10-25%w molybdenum and from about 1-5%w nickel and/or cobalt on a dried silica support. Preferably, the catalysts will contain from about 10-20% molybdenum and from about 2-4%w nickel and/or cobalt. Of the latter metals, nickel is the most preferred.
The activity testing of the catalysts according to this invention was done in microreactor systems. These units are of conventional, fixed-bed, downflow design. Each unit consists of a reactor (1.27 cm O.D.) with a preheat section, a phase separator and a large product tank. Unit pressure is controlled by a motor valve on the outlet gas line and inlet H2 rate is malntained by pressure drop across a length of capillary tubing. LAPP pumps are used for charging liquid feed. Emergency circuitry automatically shut5 down the unit in the event of fire, high reactor temperature, high or low unit pressure or loss of instrument air.
5'73 Catalysts were crushed, screened to 3 O. 3-1 mm and dried at 482 C for testing. To facilitate control of the reactor temperature the catalyst was diluted 1-1 by volume with a high-density alumina or silicon carbide ground to ~ 0.3-1 mm. Prior to processing hydrocarbon feed, the catalyst was presulphided at atmospheric pressure with 5% H2S in H2. The temperature program Eor the presulphiding was 2 hours at 204 C, 1 hour at 316 C and 2 hours at 371 C. Depending upon the metals content, the catalyst will contain from about 10-20%w sulphur.
Elemental composition of the catalyst prepared in accordance with the invention before and after sulphiding appears in Table 1.
%w Mo %w Ni ¦ %w S %w C1 I
Before Sulphidlng 13.4 2.5 1 0 13.0 After Sulphiding 17.2 3.1 ¦ 16.3 0.3 The most noteworthy feature of these data is that the total metal:sulphur ratio (metal - Mo+Ni) is 1 to 2.1. This is sulphur-rich relative to the expected MoS2/NiS system. Additionally, a thermogravimetric analysis clearly indicated that the sulphur was chemisorbed or structurally absorbed rather than merely physisorbed.
In a typical conventional Ni/Mo or Co/Mo hydrotreating catalyst preparation method catalytically active metals are deposited on a support by a dry (pore volume) impregnation technique. In this method, the support i5 impregnated with a quantity of metal-salt solution that is just sufficient to be absorbed in the pore volume of the support. The impregnating solution is generally prepared in two parts initially. One part contains the molybdenum salt and most of the water that can be used. After most of the molybdenum sslt has dissolved (with heating and stirring), H202 (30%w) is added (about 0.4 cc/g of Mo) to aid S'73 solubilization. The other part of the solution con~ains the Ni and/or Co salt(s) and sufficient phosphoric acid (85%w) to aid the solubility and stability of the solution and to include about 3%w P
in the catalyst. When both solutions are clear and cool, the Mo solution is added slowly (with vigorous stirring) to the Ni-P or Co-P solution. The combined solution is then diluted to the proper volume and added slowly, usually ln one or more steps, to the support. The impregnated catalyst is dried at 121 C for about 2 hours and then calcined in air at 482 C for about 2 hours.
A substantial increase in the hydrodenitrification (HDN) activity, relative to existing commercial catalysts, is required to commercialize a new hydrotreating catalyst. In an effort to develop such an improved catalyst, a standard 72 hour HDN activity test was used to evaluate the various catalysts. In this test the HDN and HDS activities of a cat cracked heavy gas oil were evaluated at 344 C and 58.6 bar H2 partial pressure. Activities were compared based on observed rate constants for HDN and on plug flow kinetics for HDS.
Suitable hydroconversion conditions for the processes using catalysts according to the invention are as Eollows:
a temperature of 350-420 C;
a total pressure of 75-200 bar;
a partial hydrogen pressure of 50-200 bar;
a space velocity of 0.4-1.5 kg oil/1 catalyst/hour; and a hydrogen feed rate of 250-2500 N1/kg oil feed.
The hydrodenitrification of heavy oil feeds according to the present process is preEerably carried out under the following conditions:
a temperature of 360-410 C;
a total pressure of 100-150 bar;
a partial hydrogen pressure of 80-150 bar;
a space velocity oE 0.4-1.0 kg oil/1 catalyst/hour; and a hydrogen feed rate of 500-1500 N1/kg oil Eeed.
The hydrogen applied can be pure hydrogen of a hydrogen-con-taining gas, preferably one comprising more then 70% hydrogen. The hydrogen-containing gas may also contain up to about 10% of hydrogen sulphide.
The invention will now be illustrated by the following Examples:
Two catalysts, A (alumina based) and B (silica based) were prepared by a conventional aqueous impregnation Method for comparative purposes.
Catalyst A was a standard commercial hydrotreating catalyst (available from Shell Chemical Company) which was prepared by using a dry (pore volume) metals aqueous impregnation technique to impart metals onto a gamma alumina support. This catalys~ was prepared by the typical aqueous impregnation method described hereinabove. The composition of this alumina based catalyst is given in Table 2. The various hydrotreating activities of this catalyst were taken as l.0 for comparison.
Catalyst B was prepared by impregnating a dried Grade 57 silica(from Davison Chemical, a division of W. R. Grace Co.) with the same metals solution and dry (pore volume) ~echnique used for Catalyst A. The composition of this silica based catalyst is also given in Table 2.
A silica based catalyst, C, was prepared by the method according to the invention by mixing 55.3 g MoC15 and 23.8 g Ni(H20)6C12 in a 250 ml round bottom flask with a condenser. 100 ml acetonitrile were then added slowly through the condenser. The MoC15 reacted vigorously with the Ni(H20)6C12 liberating HCl gas.
Upon completion of the addition, the mixture was heated at acetonitrile reflux temperature (~ 78 C) for 1 hour, cooled, filtered and diluted to 140 ml with acetonitrile. 70 g dry (120 C) grade 57 Davison silica (~ 0.5-0~85 mm) were then impregnated with 80 ml of this solution, dried under vacuum at 80 C, and then impregnated with the remaining solution. The resulting catalyst was 5'~3 then dried overnight at 80 C under reduced pressure (about
2.6 x 10 5 bar). Calcining the catalyst was not required. The composition of catalyst C is also given in Table 2.
_ _ _ .
Composition Surface Area Relative Activity Catalyst/ _ (Support) %wMo %wNi m2/g H2 HDN HDS
_ _ ( 2 3) 13.2 2.71601.00~.031.00+.10 1.00+.10 8 (SiO2) 15.0 3.0 - 0.71 0.17 0.20 C (SiO2) 13.4 2.5163 0.92 0.92 0.75 The three catalysts (A, B, C) were heated to about 200 C, presulphided and compared to determine their relative hydrotreating activities (H2 ~ hydrogenation; HDN - hydrodenitrification; HDS -hydrodesulphuri~ation) over a standard cat cracked heavy gas oil feed under first stage hydrocracking conditions. (Feed properties:
88.99%C; 9.68~H2; 1.28%S; 482 ppm N). For these tests, 10,4 ml of catalyst (~ 0.3-1 mm) were placed in a microreactor and used to contact the feed at 344 C, 58.6 bar H2 partial pressure, H2/oil ratio - 4/1 and LHSV = 2Ø Results of these tests are shown in Table 2.
The relative activity of the commercial alumina based catalyst A, was taken as 1.00 by definition. As can be seen from Table 2, the activity of the silica based catalyst B, prepared in the same manner as that conventionally used for a commercial alumina based hydrotreating catalyst gave very poor results for all three (H2, HDN, HDS) hydrotreating activities. However, the activity of the silica based catalyst C, prepared by the method according to the 95'73 g invention is within experimental error of the activity of a top quality commercial alumina based hydrotreating catalyst, A, and nearly six times as active as a conventionally prepared silica based catalyst.
_ _ _ .
Composition Surface Area Relative Activity Catalyst/ _ (Support) %wMo %wNi m2/g H2 HDN HDS
_ _ ( 2 3) 13.2 2.71601.00~.031.00+.10 1.00+.10 8 (SiO2) 15.0 3.0 - 0.71 0.17 0.20 C (SiO2) 13.4 2.5163 0.92 0.92 0.75 The three catalysts (A, B, C) were heated to about 200 C, presulphided and compared to determine their relative hydrotreating activities (H2 ~ hydrogenation; HDN - hydrodenitrification; HDS -hydrodesulphuri~ation) over a standard cat cracked heavy gas oil feed under first stage hydrocracking conditions. (Feed properties:
88.99%C; 9.68~H2; 1.28%S; 482 ppm N). For these tests, 10,4 ml of catalyst (~ 0.3-1 mm) were placed in a microreactor and used to contact the feed at 344 C, 58.6 bar H2 partial pressure, H2/oil ratio - 4/1 and LHSV = 2Ø Results of these tests are shown in Table 2.
The relative activity of the commercial alumina based catalyst A, was taken as 1.00 by definition. As can be seen from Table 2, the activity of the silica based catalyst B, prepared in the same manner as that conventionally used for a commercial alumina based hydrotreating catalyst gave very poor results for all three (H2, HDN, HDS) hydrotreating activities. However, the activity of the silica based catalyst C, prepared by the method according to the 95'73 g invention is within experimental error of the activity of a top quality commercial alumina based hydrotreating catalyst, A, and nearly six times as active as a conventionally prepared silica based catalyst.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method for preparing a silica supported hydrotreating catalyst containing from about 10-25%w molybdenum and from about -5%w nickel and/or cobalt as hydrogenation metals which comprises impregnating a dry silica support in one or more steps with a hydrogenation metals-containing solution obtained by reacting a molybdenum halide and/or a nickel and/or cobalt halide in the presence of a nitrile and heating the mixture formed to between about 25 and 80 °C until most of the metal compounds have reacted and/or dissolved, followed by removal of undissolved solids from the solution, and drying the impregnated silica support at elevated temperature.
2. A method according to claim 1, wherein the hydrogenation metals-containing solution is obtained by reacting a mixture of MoCl5 and of Ni(H2O)6Cl2 and/or Co(H2O)Cl2 in amounts to provide a desired catalytic metals concentration on a support in the presence of a solubilizing amount of acetonitrile and heating the mixture to between about 25 and 80 °C until most of the metal compounds have reacted and/or dissolved and removing any undissolved solids from the solution.
3. A method according to claim 1 , wherein the hydrogenation metals-containing solution contains an amount of hydrogenation metals to impregnate from about 10-20%w molybdenum and from about 2-4%w nickel into the support.
4. A method according to claim 1, wherein the mixture formed is heated at nitrile reflux temperature.
5. A method according to claim 1, wherein the catalyst obtained is sulphided before being used in a hydrotreating process.
6. A hydrotreating catalyst comprising from about 10-25%w molybdenum and from about 1-5%w nickel and/or cobalt as hydrogenation metals supported on silica, which catalyst has been prepared by a method according to claim 1.
7. A hydrotreating catalyst comprising from about 10-20%w molybdenum and from about 2-4%w nickel as hydrogenation metals supported on silica, which catalyst has been prepared by a method according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US660,624 | 1984-10-15 | ||
| US06/660,624 US4574120A (en) | 1984-10-15 | 1984-10-15 | Method for preparing high activity silica supported hydrotreating catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1249573A true CA1249573A (en) | 1989-01-31 |
Family
ID=24650283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000491645A Expired CA1249573A (en) | 1984-10-15 | 1985-09-26 | Method for preparing silica supported hydrotreating catalysts and catalysts thus prepared |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4574120A (en) |
| EP (1) | EP0178711B1 (en) |
| JP (1) | JPS6197036A (en) |
| CA (1) | CA1249573A (en) |
| DE (1) | DE3563420D1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108067271A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | The preparation method of sulfurized hydrogenation catalyst |
| CN108067256A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of sulfurized hydrogenation catalyst |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5336654A (en) * | 1990-12-24 | 1994-08-09 | Exxon Research And Engineering Company | Method for the preparation of supported hydrogenation and hydrotreating catalysts |
| US6218333B1 (en) | 1999-02-15 | 2001-04-17 | Shell Oil Company | Preparation of a hydrotreating catalyst |
| US6281158B1 (en) | 1999-02-15 | 2001-08-28 | Shell Oil Company | Preparation of a co-containing hydrotreating catalyst precursor and catalyst |
| US6333016B1 (en) * | 1999-06-02 | 2001-12-25 | The Board Of Regents Of The University Of Oklahoma | Method of producing carbon nanotubes |
| US20030091496A1 (en) * | 2001-07-23 | 2003-05-15 | Resasco Daniel E. | Method and catalyst for producing single walled carbon nanotubes |
| US7816709B2 (en) * | 1999-06-02 | 2010-10-19 | The Board Of Regents Of The University Of Oklahoma | Single-walled carbon nanotube-ceramic composites and methods of use |
| US6919064B2 (en) * | 2000-06-02 | 2005-07-19 | The Board Of Regents Of The University Of Oklahoma | Process and apparatus for producing single-walled carbon nanotubes |
| US6413487B1 (en) * | 2000-06-02 | 2002-07-02 | The Board Of Regents Of The University Of Oklahoma | Method and apparatus for producing carbon nanotubes |
| US7829622B2 (en) * | 2002-06-19 | 2010-11-09 | The Board Of Regents Of The University Of Oklahoma | Methods of making polymer composites containing single-walled carbon nanotubes |
| US7153903B1 (en) | 2002-06-19 | 2006-12-26 | The Board Of Regents Of The University Of Oklahoma | Carbon nanotube-filled composites prepared by in-situ polymerization |
| CA2549428A1 (en) * | 2003-12-15 | 2005-07-21 | Daniel E. Resasco | Rhenium catalysts and methods for production of single-walled carbon nanotubes |
| EP1748837A4 (en) * | 2004-01-09 | 2009-11-11 | Olga Matarredona | Carbon nanotube pastes and methods of use |
| CN101365830B (en) | 2005-06-28 | 2013-06-12 | 俄克拉荷马州大学评议会 | Methods for growing and harvesting carbon nanotubes |
| FR3004968B1 (en) | 2013-04-30 | 2016-02-05 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF A TUNGSTEN CATALYST FOR USE IN HYDROTREATMENT OR HYDROCRACKING |
| FR3004967B1 (en) | 2013-04-30 | 2016-12-30 | Ifp Energies Now | PROCESS FOR THE PREPARATION OF A MOLYBDENE CATALYST FOR USE IN HYDROTREATMENT OR HYDROCRACKING |
| FR3013720B1 (en) * | 2013-11-28 | 2015-11-13 | IFP Energies Nouvelles | METHOD FOR HYDROPROCESSING VACUUM DISTILLATES USING A CATALYST SURFACE |
| CN116139873A (en) * | 2022-11-30 | 2023-05-23 | 中国石油大学(华东) | Preparation method of space-limited nickel-molybdenum diesel hydrogenation catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2813837A (en) * | 1954-06-16 | 1957-11-19 | Universal Oil Prod Co | Manufacture of purification catalysts |
| US3167496A (en) * | 1959-08-11 | 1965-01-26 | Pullman Inc | Hydrogenation catalyst and process |
| US3420771A (en) * | 1966-03-17 | 1969-01-07 | Universal Oil Prod Co | Hydrorefining asphaltenic petroleum charge stocks |
| US4424141A (en) * | 1981-01-05 | 1984-01-03 | The Standard Oil Co. | Process for producing an oxide complex catalyst containing molybdenum and one of bismuth and tellurium |
-
1984
- 1984-10-15 US US06/660,624 patent/US4574120A/en not_active Expired - Lifetime
-
1985
- 1985-09-25 DE DE8585201544T patent/DE3563420D1/en not_active Expired
- 1985-09-25 EP EP85201544A patent/EP0178711B1/en not_active Expired
- 1985-09-26 CA CA000491645A patent/CA1249573A/en not_active Expired
- 1985-10-14 JP JP60227064A patent/JPS6197036A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108067271A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | The preparation method of sulfurized hydrogenation catalyst |
| CN108067256A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of sulfurized hydrogenation catalyst |
| CN108067271B (en) * | 2016-11-15 | 2019-07-12 | 中国石油化工股份有限公司 | The preparation method of sulfurized hydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6197036A (en) | 1986-05-15 |
| EP0178711A1 (en) | 1986-04-23 |
| DE3563420D1 (en) | 1988-07-28 |
| US4574120A (en) | 1986-03-04 |
| EP0178711B1 (en) | 1988-06-22 |
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