CA2019713A1 - Process for the preparation of a presulfided and sulfided catalyst - Google Patents
Process for the preparation of a presulfided and sulfided catalystInfo
- Publication number
- CA2019713A1 CA2019713A1 CA002019713A CA2019713A CA2019713A1 CA 2019713 A1 CA2019713 A1 CA 2019713A1 CA 002019713 A CA002019713 A CA 002019713A CA 2019713 A CA2019713 A CA 2019713A CA 2019713 A1 CA2019713 A1 CA 2019713A1
- Authority
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- Canada
- Prior art keywords
- catalyst
- presulfided
- meaning
- carbon atoms
- different
- 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.)
- Abandoned
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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
- B01J37/20—Sulfiding
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
Abstract
PROCESS FOR THE PREPARATION
OF A PRESULFIDED AND SULFIDED CATALYST
ABSTRACT
Disclosed is a process for the ex situ presulfidation of hydrotreating catalysts employing organic sulfur compounds with a boiling point exceeding 100° C and satisfying the formula (I) wherein p = 0, 1 or 2, R1, R2, and R3 may be the same or different and represent alkylene groups having 1-4 carbon atoms, X and Y may be the same or different and have the meaning of -H, -OH, -OR44 or -C(O)OR5, wherein R4 has the meaning of an alkyl group or acyl group with 1-3 carbon atoms, and R5 has the meaning of -H, an ammonium group or an alkyl group with 1-3 carbon atoms.
Also disclosed is a process for activating the thus presulfided catalyst.
OF A PRESULFIDED AND SULFIDED CATALYST
ABSTRACT
Disclosed is a process for the ex situ presulfidation of hydrotreating catalysts employing organic sulfur compounds with a boiling point exceeding 100° C and satisfying the formula (I) wherein p = 0, 1 or 2, R1, R2, and R3 may be the same or different and represent alkylene groups having 1-4 carbon atoms, X and Y may be the same or different and have the meaning of -H, -OH, -OR44 or -C(O)OR5, wherein R4 has the meaning of an alkyl group or acyl group with 1-3 carbon atoms, and R5 has the meaning of -H, an ammonium group or an alkyl group with 1-3 carbon atoms.
Also disclosed is a process for activating the thus presulfided catalyst.
Description
PRQCESS FOR THE PREPARATION
OF A PRESULFIDED AND SULFIDED CATALYST
BACKGROUND OF THE INVENTION
The invention relates to a process for the ex situ preparation of a presulfided catalyst, a process for the preparation of a sulfided catalyst by activation of the presulfided catalyst, and the use of said sulfided catalyst in the catalytic hydrotreatment of hydrocarbon-containing feeds.
In the oil industry many processes are known in which hydrocarbon-containing feeds are catalytically treated with hydrogen, such as hydrodesulfurizing, hydrodenitrogenizing, and hydrocrac~ing. In such processes use is made of catalysts built up from a carri~r material, such as alumina, on which there are deposited one or more catalytically active metals or compounds thereof; examples of such metals are molybdenum, nickel, cobalt, and tungsten. It is common knowledge that optimum results are obtained in using such catalysts when the catalytically active metals are in their sulfided form.
In actual practice sulfidation is generally carried out in situ, i.e. in the reactor in which the final hydrotreatment of the hydrocarbon-containing feed is carried out. Having been introduced into the reactor, the fresh or regenerated catalyst during the start-up procedure is contacted at elevated temperature with a hydrogen gas stream mixed with a sulfiding agent, such as hydrogen sulfide, dimethyl disulfide, or carbon disulfide, or with a hydrogen gas stream combined with a hydrocarbon-containing feed containing either an added sulfiding agent (a so-called spiked feed) or natural sulfur compounds. In this connection see for instance H. Hallie's article in Oil & Gas Journal, Dec. 20, 1982, Technology, pp.
69-74.
A recent development in this field is so-called ex situ presulfidation. In this process the fresh or regenerated catalyst is treated (impregnated) with a sulfur compound, which may be in the dissolved state or not, outside the 201~713 reactor in which the final hydrotreatment of hydrocarbon-containing feed is carried out. Following optional drying to remove the solvent, the thus presulfided catalyst is activated, i.e. brought into the sulfided state, by being contacted at elevated temperature with hydrogen gas in the presence or not of a sulfiding agent or a sulfur-containing feed (spiked or non-spiked).
Proposals in the ex situ presulfidation field concentrate on the use of specific sulfur compounds. Thus Japanese Patent Application No. 63-302952 (published on 9 December, 1988) describes organic sulfur compounds containing at least one mercapto group and having a boiling point exceeding 10~ C; in the examples use is made, int. al., of diethylene thioether dithiol. European Patent Application No. 0,289,211 also describes mercapto group-containing organic compounds, viz.
mercapto-carboxylic acids, bivalent mercaptans, amino-substituted mercaptans, and thiocarboxylic acids. Compounds employed in the examples include 1,2-ethanedithiol and 1,4 butanedithiol. Finally, European Patent Application No.
0,352,851 recommends the use of organic sulfur compounds that preferably contain at least two sulfur atoms, while in the examples use is made of, int. al., 2,2'-dithiodiethanol.
However, there are drawbacks to the use of the sulfur compounds proposed so far. For instance, the mercapto groups (-SH) containing compounds have an objectionable odor, which renders their use on an industrial scale problematic. Also, it has been found that catalysts presulfided using the hitherto proposed sulfur compounds display undesired self-heating characteristics. The term self-heating is used to describe the phenomenon of a material acquiring a temperature in excess of the ambient temperature as a result of the spontaneous occurrence in it of exothermic processes. In the case of catalysts presulfided using organic sulfur compounds (and in that of many other materials) non-dissipation or insufficient dissipation of this heat will generate an uncontrolled rise in temperature that can objectionably affect 20197~3 the chemical composition of the material in an unpredictable way and, in the worst case, lead to spontaneous combustion.
SUMMARY OF THE INVENTION
The present invention envisages meeting the aforementioned drawbacks. To this end according to the invention use is made in the ex situ presulfidation of organic sulfur compounds with a boiling point exceeding 10~ C and satisfying the formula X - RI ~ S - R2 ~p S - R3 ~ Y ~I) wherein p = 0, 1 or 2, Rl, R2, and R3 may be the same or different and represent alkylene groups having 1-4 carbon atoms, X and Y may be the same or different and have the meaning of -~, -OH, -oR4 or -C(O) oR5 l wherein P~4 has the meaning of an alkyl group or an acyl group with 1-3 carbon atoms, and R5 has the meaning of -H, an ammonium group or an alkyl group with 1-3 carbon atoms.
This process makes it possible to have ex situ presulfidation employing compounds that do not cause odor nuisance, and presulfided catalysts are obtained which have a self-heating tendency within acceptable limits.
DETAILED DESCRIPTION OF THE INVENTION
The fresh or regenerated catalysts to be presulfided according to the process of the invention are those which are known in the prior art for use in the sulfided form in the catalytic hydrotreatment of hydrocarbon-containing feeds, for instance in hydrodesulfurizing, hydrodenitrogenizing, hydrodemetallizing, hydroreforming (which process in the present context is also considered to be a hydrotreatment of hydrocarbon-containing feeds), hydroisomerizing, hydrocracking, hydroalkylating, and hydrodealkylating. Such catalysts generally contain a carrier material, such as alumina, silica, silica-alumina, or crystalline aluminosilicate, with deposited thereon one or more metals or compounds of metals such as oxides, the metals being selected from the groups Ib, Vb, VIb, VIIb, and VIII of the Periodic System. Typical examples of these metals are iron, cobalt, nickel, tungsten, molybdenum, chromium, vanadium, copper, palladium, and platinum as well as combinations thereof.
Preference is given to molybdenum, tungsten, nickel, cobalt, and combinations thereof. The metal content of the catalysts generally is 0.1-50 wt.%, calculated on the weight of the total catalyst. In addition, the catalysts may contain other components, such as phosphorus, halogens, borium, zeolites, and clays including pillared clays.
The shape of the catalysts is dependent on the process in which they are employed. Most frequently used are extruded particles (cylindrical, polylobes) and fluidizable particles.
The sulfur compounds to be used in the presulfiding process should have a boiling point exceeding 10~ C and satisfy the aforementioned formula (I). As typical examples of such compounds may be mentioned 2,2'-thiodiethanol, thiodiglycolic acid, 3,3'-thiodipropanol, 3,3'-thiodipropanoic acid, the n-butyl ether of 2-(methylthio)ethanol, [2-(methylthio)ethyl]acQtate, 1,6-dihydroxy-2,5-dithiahexane, 3,6-dithiaheptanoic acid, and 1,9-dihydroxy-2,5,8-trithianonane.
Preferred compounds are those wherein (cf. formula (I)) p = o or 1, more particularly p = O, Rl, R2, and R3 are linear and, more particularly, have 1 or 2 carbon atoms, and/or X and Y have the meaning of -H or -OH, more particularly of -OH.
201~713 Also, combinations of sulfur compounds may be employed.
The amount of sulfur compound to be used in general is selected in such a way that there is deposited on the catalyst an amount of sulfur which, calculated on the sulfides that will finally be formed (e.g. MoS2, CogS8), is in the range of 0.5x to 1.5x the stoichiometrically required amount.
Usually, it is desired that the sulfur compound should be dissolved in, or mixed with, a solvent. Of course, the nature of the solvent is dependent on the type of sulfur compound employed. Both water and organic solvents may be used.
The sulfur compound can be deposited on the catalyst by means of conventional impregnating techniques, such as immersion, impregnation by spraying and pore volume saturation. If a solvent has been employed, there will have to be a drying step after the sulfur compound has been deposited on the fresh or regenerated catalyst, in order to remove the solvent or solvent remainders. To this end use may be made of conventional equipment, such as ovens, vacuum driers, and belt driers.
Next, the resulting presulfided catalyst should be activated in order to bring the catalyst into the sulfided form. Such activation is carried out by passing hydrogen gas, in combination or not with either a sulfiding agent or a sulfur-containing feed, (spiked or non-spiked) over the presulfided catalyst at a temperature in the range of 10~ C to 60~ C, preferably in the range of 10~ C to 40~ C, and a hydrogen pressure in the range of 1 to 300 bar, preferably of 1 to 100 bar. This process step may be carried out either ex situ, i.e. in a separate reactor, or in situ, i~e. in the reactor in which the catalyst will be used.
The catalyst thus prepared is suitable to be used in the catalytic hydrotreatment of hydrocarbon-containing feeds. The most significant of these processes are hydrodesulfurizing, hydrodenitrogenizing, hydrodemetallizing, hydroreforming, hydroisomerizing, hydrocracking, and mild hydrocracking. The process equipment to be used and the conditions under which the reactions are carried out ~ary with the process used and have been described in detail in the prior art. See for instance M. De Wind et al., Proceedings of symposium on catalyst performance testing, March 28/29, 1988, pp. 29-42;
published by Unilever ~esearch Laboratories, Vlaardingen, The Netherlands. Very generally, the following reaction conditions apply here: temperatures in the range of 20~ C to 55~ C, LHSV values in the range of 0.1 to 10 hours 1, partial hydrogen pressures in the range of 10 to 300 bar, and hydrogen/hydrocarbon ratios in the range of 50 to 5000 Nm3/m3.
The invention will be further described in the following examples.
20~713 Example 1 In a rotating impregnator 1700 g of fresh catalyst KF-165 CR~ (a commercial HDS catalyst ex Akzo Chemicals;
chemical composition: 15.5~ by weight of MoO3, 4.5% by weight of Coo, alumina carrier; PV (H2O): 0.5 ml/g) were treated at room temperature with a mixture (overall volume 850 ml) of water and 603 g of 2,2'-thiodiethanol, use being made of the pore volume saturation technique. After the product had ~een dried in air for 2 hours at 8~ C, the sulfur content of the presulfided catalyst was 7.3~ by weight.
EY~ample 2 In analogous manner to that described in Example 1 lS00 g of catalyst KF-165 ~ were impregnated with an aqueous solution of 528.4 g of 1,6-dihydroxy-2,5-dithiahexane ~overall volume 750 ml). After the whole had been dried under reduced pressure for 2 hours at 8~ C, the sulfur content of the pre~ulfided catalyst was 6.6% by weight.
ComParative Example 3 In analogous manner to that described in Example 1 1500 g of catalyst KF-165 ~ were impregnated with a mixture (overall volume 750 ml~ of ethanol and 186.7 g of 1,2-ethanedithiol.
After the whole had been dried under reduced pressure for 2 hours at 12~ C, the sulfur content of the presulfided catalyst was 7.1~ by weight.
20~713 Comparative Example 4 In analogous manner to that described in Example 1 1200 g of catalyst KF-165 ~R~ were impregnated with a mixture (overall volume 600 ml) of ethanol and 193.9 g of 1,4-butanedithiol.
After the whole had been dried under reduced pressure for 2 hours at 8~ C, the sulfur content of the presulfided catalyst was 7.1~ by weight.
Comparative Example 5 In analogous manner to that described in Example 1 1200 g of catalyst KF-165 ~ were impregnated with 237.7 g of diethylene thioether dithiol. The sulfur content of the presulfided catalyst was 7.7% by weight.
Comparative Example 6 In analogous manner to that described in Example 1 900 g of catalyst KF-165 ~ were impregnated with an aqueous solution of 261 g of 2,2'-dithiodiethanol (overall volume 450 ml). After the whole had been dried in air for 2 hours at 8~ C, the sulfur content of the presulfided catalyst was 7.9 by weight.
Comparative Example 7 In analogous manner to that described in Example 1 1700 g of catalyst KF-165 ~ were impregnated with a solution (overall volume 850 ml) of 306 g of 2,2'-trithiodiethanol in a mixture of water and ethanol (3:1 v/v). After the whole had been dried in air for 2 hours at 8~ C, the sulfur content of the presulfided catalyst was 8.3% by weight.
` 201~713 Self-heating Test The presulfided catalysts described above were examined with regard to self-heating characteristics along the lines of the description in the Recommendations on the transport of dangerous goods, 5th revised edition, United Nations Publications, Chapter 14, pp. 365-377, more particularly p.
375.
In the described test a cubic basket of stainless steel gauze having a mesh opening of 0.053 mm is filled with the material to be investigated and hung at the center of an oven.
By means of suitably placed thermocouples the temperature of the material and the temperature of the oven are recorded as a function of time. Use was made of a 10 cm x 10 cm x 10 cm basket filled with 1000 ml of catalyst material. The starting temperature of the oven was 14~ C. The basket was hung in the oven and the time and temperature were recorded. The following parameters were set for determining the self-heating characteristics:
tl: the time at which the temperature of the catalyst material exceeded the oven temperature;
t2: the time at which the temperature of the catalyst material exceeded the 20~ C limit.
The test results are given in the Table below. They show that catalysts presulfided according to the process of the invention (Examples 1 and 2) display more favorable self-heating characteristics than the catalysts of the comparative examples. This finding is remarkable, given the relatively small differences between the molecular structures of the used sulfur compounds. This is demonstrated most acutely by comparing the results of Example 1 with those of Comparative Examples 5 and 6. It might be concluded that a presulfiding process in which use is made of organic sulfur compounds containing one or more -SH groups and/or -S-S- groups will have a negative effect on the self-heating characteristics of the presulfided catalyst.
201~71~
The results in the Table further show that presulfiding according to the invention is preferably carried out using a sulfur compound which contains not more than one thioether group [-C-S-C-]: cf. Examples 1 and 2.
The functional importance of the parameters tl and t2 applied in the Table is that the greater the values found are, the less strict the precautions may be that are required for storing and transporting the catalyst in question, and for introducing it into the reactor.
20197~3 TABLE
Example Sulfur compound tl t2 (mln) fmln) 2 HO-C~2-S-C2H4-S-CH2-OH 360 430 3 (1)(2) HS-C2H4-SH 85 110 4 (1)(2) HS-C4H8-SH 65 105 5 (1)(3) HS-C2H4-S-C2H4-SH 120 240 6 (1)(4) HO-C2H4-S-S-C2H4-OH 240 300 7 (1) HO-C2H4-S-S-S-C2H4-OH 150 215 (1) Comparative examples (2) According to EP-A 0,289,211 (3) According to JA 63-302952 (4) According to EP-A 0,352,851
OF A PRESULFIDED AND SULFIDED CATALYST
BACKGROUND OF THE INVENTION
The invention relates to a process for the ex situ preparation of a presulfided catalyst, a process for the preparation of a sulfided catalyst by activation of the presulfided catalyst, and the use of said sulfided catalyst in the catalytic hydrotreatment of hydrocarbon-containing feeds.
In the oil industry many processes are known in which hydrocarbon-containing feeds are catalytically treated with hydrogen, such as hydrodesulfurizing, hydrodenitrogenizing, and hydrocrac~ing. In such processes use is made of catalysts built up from a carri~r material, such as alumina, on which there are deposited one or more catalytically active metals or compounds thereof; examples of such metals are molybdenum, nickel, cobalt, and tungsten. It is common knowledge that optimum results are obtained in using such catalysts when the catalytically active metals are in their sulfided form.
In actual practice sulfidation is generally carried out in situ, i.e. in the reactor in which the final hydrotreatment of the hydrocarbon-containing feed is carried out. Having been introduced into the reactor, the fresh or regenerated catalyst during the start-up procedure is contacted at elevated temperature with a hydrogen gas stream mixed with a sulfiding agent, such as hydrogen sulfide, dimethyl disulfide, or carbon disulfide, or with a hydrogen gas stream combined with a hydrocarbon-containing feed containing either an added sulfiding agent (a so-called spiked feed) or natural sulfur compounds. In this connection see for instance H. Hallie's article in Oil & Gas Journal, Dec. 20, 1982, Technology, pp.
69-74.
A recent development in this field is so-called ex situ presulfidation. In this process the fresh or regenerated catalyst is treated (impregnated) with a sulfur compound, which may be in the dissolved state or not, outside the 201~713 reactor in which the final hydrotreatment of hydrocarbon-containing feed is carried out. Following optional drying to remove the solvent, the thus presulfided catalyst is activated, i.e. brought into the sulfided state, by being contacted at elevated temperature with hydrogen gas in the presence or not of a sulfiding agent or a sulfur-containing feed (spiked or non-spiked).
Proposals in the ex situ presulfidation field concentrate on the use of specific sulfur compounds. Thus Japanese Patent Application No. 63-302952 (published on 9 December, 1988) describes organic sulfur compounds containing at least one mercapto group and having a boiling point exceeding 10~ C; in the examples use is made, int. al., of diethylene thioether dithiol. European Patent Application No. 0,289,211 also describes mercapto group-containing organic compounds, viz.
mercapto-carboxylic acids, bivalent mercaptans, amino-substituted mercaptans, and thiocarboxylic acids. Compounds employed in the examples include 1,2-ethanedithiol and 1,4 butanedithiol. Finally, European Patent Application No.
0,352,851 recommends the use of organic sulfur compounds that preferably contain at least two sulfur atoms, while in the examples use is made of, int. al., 2,2'-dithiodiethanol.
However, there are drawbacks to the use of the sulfur compounds proposed so far. For instance, the mercapto groups (-SH) containing compounds have an objectionable odor, which renders their use on an industrial scale problematic. Also, it has been found that catalysts presulfided using the hitherto proposed sulfur compounds display undesired self-heating characteristics. The term self-heating is used to describe the phenomenon of a material acquiring a temperature in excess of the ambient temperature as a result of the spontaneous occurrence in it of exothermic processes. In the case of catalysts presulfided using organic sulfur compounds (and in that of many other materials) non-dissipation or insufficient dissipation of this heat will generate an uncontrolled rise in temperature that can objectionably affect 20197~3 the chemical composition of the material in an unpredictable way and, in the worst case, lead to spontaneous combustion.
SUMMARY OF THE INVENTION
The present invention envisages meeting the aforementioned drawbacks. To this end according to the invention use is made in the ex situ presulfidation of organic sulfur compounds with a boiling point exceeding 10~ C and satisfying the formula X - RI ~ S - R2 ~p S - R3 ~ Y ~I) wherein p = 0, 1 or 2, Rl, R2, and R3 may be the same or different and represent alkylene groups having 1-4 carbon atoms, X and Y may be the same or different and have the meaning of -~, -OH, -oR4 or -C(O) oR5 l wherein P~4 has the meaning of an alkyl group or an acyl group with 1-3 carbon atoms, and R5 has the meaning of -H, an ammonium group or an alkyl group with 1-3 carbon atoms.
This process makes it possible to have ex situ presulfidation employing compounds that do not cause odor nuisance, and presulfided catalysts are obtained which have a self-heating tendency within acceptable limits.
DETAILED DESCRIPTION OF THE INVENTION
The fresh or regenerated catalysts to be presulfided according to the process of the invention are those which are known in the prior art for use in the sulfided form in the catalytic hydrotreatment of hydrocarbon-containing feeds, for instance in hydrodesulfurizing, hydrodenitrogenizing, hydrodemetallizing, hydroreforming (which process in the present context is also considered to be a hydrotreatment of hydrocarbon-containing feeds), hydroisomerizing, hydrocracking, hydroalkylating, and hydrodealkylating. Such catalysts generally contain a carrier material, such as alumina, silica, silica-alumina, or crystalline aluminosilicate, with deposited thereon one or more metals or compounds of metals such as oxides, the metals being selected from the groups Ib, Vb, VIb, VIIb, and VIII of the Periodic System. Typical examples of these metals are iron, cobalt, nickel, tungsten, molybdenum, chromium, vanadium, copper, palladium, and platinum as well as combinations thereof.
Preference is given to molybdenum, tungsten, nickel, cobalt, and combinations thereof. The metal content of the catalysts generally is 0.1-50 wt.%, calculated on the weight of the total catalyst. In addition, the catalysts may contain other components, such as phosphorus, halogens, borium, zeolites, and clays including pillared clays.
The shape of the catalysts is dependent on the process in which they are employed. Most frequently used are extruded particles (cylindrical, polylobes) and fluidizable particles.
The sulfur compounds to be used in the presulfiding process should have a boiling point exceeding 10~ C and satisfy the aforementioned formula (I). As typical examples of such compounds may be mentioned 2,2'-thiodiethanol, thiodiglycolic acid, 3,3'-thiodipropanol, 3,3'-thiodipropanoic acid, the n-butyl ether of 2-(methylthio)ethanol, [2-(methylthio)ethyl]acQtate, 1,6-dihydroxy-2,5-dithiahexane, 3,6-dithiaheptanoic acid, and 1,9-dihydroxy-2,5,8-trithianonane.
Preferred compounds are those wherein (cf. formula (I)) p = o or 1, more particularly p = O, Rl, R2, and R3 are linear and, more particularly, have 1 or 2 carbon atoms, and/or X and Y have the meaning of -H or -OH, more particularly of -OH.
201~713 Also, combinations of sulfur compounds may be employed.
The amount of sulfur compound to be used in general is selected in such a way that there is deposited on the catalyst an amount of sulfur which, calculated on the sulfides that will finally be formed (e.g. MoS2, CogS8), is in the range of 0.5x to 1.5x the stoichiometrically required amount.
Usually, it is desired that the sulfur compound should be dissolved in, or mixed with, a solvent. Of course, the nature of the solvent is dependent on the type of sulfur compound employed. Both water and organic solvents may be used.
The sulfur compound can be deposited on the catalyst by means of conventional impregnating techniques, such as immersion, impregnation by spraying and pore volume saturation. If a solvent has been employed, there will have to be a drying step after the sulfur compound has been deposited on the fresh or regenerated catalyst, in order to remove the solvent or solvent remainders. To this end use may be made of conventional equipment, such as ovens, vacuum driers, and belt driers.
Next, the resulting presulfided catalyst should be activated in order to bring the catalyst into the sulfided form. Such activation is carried out by passing hydrogen gas, in combination or not with either a sulfiding agent or a sulfur-containing feed, (spiked or non-spiked) over the presulfided catalyst at a temperature in the range of 10~ C to 60~ C, preferably in the range of 10~ C to 40~ C, and a hydrogen pressure in the range of 1 to 300 bar, preferably of 1 to 100 bar. This process step may be carried out either ex situ, i.e. in a separate reactor, or in situ, i~e. in the reactor in which the catalyst will be used.
The catalyst thus prepared is suitable to be used in the catalytic hydrotreatment of hydrocarbon-containing feeds. The most significant of these processes are hydrodesulfurizing, hydrodenitrogenizing, hydrodemetallizing, hydroreforming, hydroisomerizing, hydrocracking, and mild hydrocracking. The process equipment to be used and the conditions under which the reactions are carried out ~ary with the process used and have been described in detail in the prior art. See for instance M. De Wind et al., Proceedings of symposium on catalyst performance testing, March 28/29, 1988, pp. 29-42;
published by Unilever ~esearch Laboratories, Vlaardingen, The Netherlands. Very generally, the following reaction conditions apply here: temperatures in the range of 20~ C to 55~ C, LHSV values in the range of 0.1 to 10 hours 1, partial hydrogen pressures in the range of 10 to 300 bar, and hydrogen/hydrocarbon ratios in the range of 50 to 5000 Nm3/m3.
The invention will be further described in the following examples.
20~713 Example 1 In a rotating impregnator 1700 g of fresh catalyst KF-165 CR~ (a commercial HDS catalyst ex Akzo Chemicals;
chemical composition: 15.5~ by weight of MoO3, 4.5% by weight of Coo, alumina carrier; PV (H2O): 0.5 ml/g) were treated at room temperature with a mixture (overall volume 850 ml) of water and 603 g of 2,2'-thiodiethanol, use being made of the pore volume saturation technique. After the product had ~een dried in air for 2 hours at 8~ C, the sulfur content of the presulfided catalyst was 7.3~ by weight.
EY~ample 2 In analogous manner to that described in Example 1 lS00 g of catalyst KF-165 ~ were impregnated with an aqueous solution of 528.4 g of 1,6-dihydroxy-2,5-dithiahexane ~overall volume 750 ml). After the whole had been dried under reduced pressure for 2 hours at 8~ C, the sulfur content of the pre~ulfided catalyst was 6.6% by weight.
ComParative Example 3 In analogous manner to that described in Example 1 1500 g of catalyst KF-165 ~ were impregnated with a mixture (overall volume 750 ml~ of ethanol and 186.7 g of 1,2-ethanedithiol.
After the whole had been dried under reduced pressure for 2 hours at 12~ C, the sulfur content of the presulfided catalyst was 7.1~ by weight.
20~713 Comparative Example 4 In analogous manner to that described in Example 1 1200 g of catalyst KF-165 ~R~ were impregnated with a mixture (overall volume 600 ml) of ethanol and 193.9 g of 1,4-butanedithiol.
After the whole had been dried under reduced pressure for 2 hours at 8~ C, the sulfur content of the presulfided catalyst was 7.1~ by weight.
Comparative Example 5 In analogous manner to that described in Example 1 1200 g of catalyst KF-165 ~ were impregnated with 237.7 g of diethylene thioether dithiol. The sulfur content of the presulfided catalyst was 7.7% by weight.
Comparative Example 6 In analogous manner to that described in Example 1 900 g of catalyst KF-165 ~ were impregnated with an aqueous solution of 261 g of 2,2'-dithiodiethanol (overall volume 450 ml). After the whole had been dried in air for 2 hours at 8~ C, the sulfur content of the presulfided catalyst was 7.9 by weight.
Comparative Example 7 In analogous manner to that described in Example 1 1700 g of catalyst KF-165 ~ were impregnated with a solution (overall volume 850 ml) of 306 g of 2,2'-trithiodiethanol in a mixture of water and ethanol (3:1 v/v). After the whole had been dried in air for 2 hours at 8~ C, the sulfur content of the presulfided catalyst was 8.3% by weight.
` 201~713 Self-heating Test The presulfided catalysts described above were examined with regard to self-heating characteristics along the lines of the description in the Recommendations on the transport of dangerous goods, 5th revised edition, United Nations Publications, Chapter 14, pp. 365-377, more particularly p.
375.
In the described test a cubic basket of stainless steel gauze having a mesh opening of 0.053 mm is filled with the material to be investigated and hung at the center of an oven.
By means of suitably placed thermocouples the temperature of the material and the temperature of the oven are recorded as a function of time. Use was made of a 10 cm x 10 cm x 10 cm basket filled with 1000 ml of catalyst material. The starting temperature of the oven was 14~ C. The basket was hung in the oven and the time and temperature were recorded. The following parameters were set for determining the self-heating characteristics:
tl: the time at which the temperature of the catalyst material exceeded the oven temperature;
t2: the time at which the temperature of the catalyst material exceeded the 20~ C limit.
The test results are given in the Table below. They show that catalysts presulfided according to the process of the invention (Examples 1 and 2) display more favorable self-heating characteristics than the catalysts of the comparative examples. This finding is remarkable, given the relatively small differences between the molecular structures of the used sulfur compounds. This is demonstrated most acutely by comparing the results of Example 1 with those of Comparative Examples 5 and 6. It might be concluded that a presulfiding process in which use is made of organic sulfur compounds containing one or more -SH groups and/or -S-S- groups will have a negative effect on the self-heating characteristics of the presulfided catalyst.
201~71~
The results in the Table further show that presulfiding according to the invention is preferably carried out using a sulfur compound which contains not more than one thioether group [-C-S-C-]: cf. Examples 1 and 2.
The functional importance of the parameters tl and t2 applied in the Table is that the greater the values found are, the less strict the precautions may be that are required for storing and transporting the catalyst in question, and for introducing it into the reactor.
20197~3 TABLE
Example Sulfur compound tl t2 (mln) fmln) 2 HO-C~2-S-C2H4-S-CH2-OH 360 430 3 (1)(2) HS-C2H4-SH 85 110 4 (1)(2) HS-C4H8-SH 65 105 5 (1)(3) HS-C2H4-S-C2H4-SH 120 240 6 (1)(4) HO-C2H4-S-S-C2H4-OH 240 300 7 (1) HO-C2H4-S-S-S-C2H4-OH 150 215 (1) Comparative examples (2) According to EP-A 0,289,211 (3) According to JA 63-302952 (4) According to EP-A 0,352,851
Claims (5)
1. A process for the preparation of a presulfided catalyst which following activation is suitable for use in the catalytic hydrotreatment of hydrocarbon-containing feeds comprising providing ex situ a fresh or regenerated catalyst containing a carrier material and one or more catalytically active metals or metal compounds with an effective amount of an organic sulfur compound with a boiling point exceeding 100° C and having formula X - R1 ? S - R2 ?p S - R3 - Y (I) wherein p = 0, 1 or 2, R1, R2, and R3 may be the same or different and represent alkylene groups having 1-4 carbon atoms, X and Y may be the same or different and have the meaning of -H, -OH, -OR4 or -C(O)OR5, wherein R4 has the meaning of an alkyl group or acyl group with 1-3 carbon atoms, and R5 has the meaning of -H, an ammonium group or an alkyl group with 1-3 carbon atoms.
2. The process of claim 1, wherein X and Y may be the same or different and are -H or -OH.
3. The process of claim 1 wherein p = O.
4. The process of claim 1 wherein one or more catalytically active metals are selected from the groups VIb or VIII of the Periodic System.
5. A process for the preparation of a sulfided catalyst suitable for use in the catalytic hydrotreatment of hydrocarbon-containing feeds comprising contacting a presulfided catalyst prepared in accordance with the process of claim 1 at elevated temperature with hydrogen gas or hydrogen gas in combination with a sulfiding agent or a sulfur-containing feed.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/540,951 US5017535A (en) | 1990-06-20 | 1990-06-20 | Process for the preparation of a presulfided and sulfided catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2019713A1 true CA2019713A1 (en) | 1991-12-25 |
Family
ID=24157573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002019713A Abandoned CA2019713A1 (en) | 1990-06-20 | 1990-06-25 | Process for the preparation of a presulfided and sulfided catalyst |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5017535A (en) |
| EP (1) | EP0460300A1 (en) |
| JP (1) | JPH0457887A (en) |
| AU (1) | AU629944B2 (en) |
| CA (1) | CA2019713A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2623007A (en) * | 1949-08-30 | 1952-12-23 | Phillips Petroleum Co | Catalytic desulfurization of hydrocarbons |
| US4118342A (en) * | 1977-06-21 | 1978-10-03 | Labofina S. A. | Process for producing catalysts |
| US4213850A (en) * | 1978-06-29 | 1980-07-22 | Union Oil Company Of California | Hydrodesulfurization of oil feedstock with presulfided catalyst |
| FR2548205B1 (en) * | 1983-06-30 | 1985-11-29 | Eurecat Europ Retrait Catalys | PROCESS FOR PRESULFURIZING A HYDROCARBON PROCESSING CATALYST |
| DE3562987D1 (en) * | 1984-10-30 | 1988-07-07 | Eurecat Europ Retrait Catalys | Method for presulfiding a catalyst for the treatment of hydrocarbons |
| US4725569A (en) * | 1984-11-27 | 1988-02-16 | Tuszynski William J | Organopolysulfide-impregnated catalyst and methods of preparation and use |
| EP0289211B1 (en) * | 1987-04-22 | 1993-09-29 | Sumitomo Metal Mining Company Limited | Catalysts for hydrotreating hydrocarbons and method of activating the same |
| JP2577739B2 (en) * | 1987-06-03 | 1997-02-05 | 触媒化成工業株式会社 | Hydroprocessing catalyst for hydrocarbons |
| FR2627105B3 (en) * | 1988-02-16 | 1990-06-08 | Inst Francais Du Petrole | PROCESS FOR PRESULFURIZING A HYDROCARBON PROCESSING CATALYST |
| FR2627104B1 (en) * | 1988-02-16 | 1990-07-20 | Inst Francais Du Petrole | PROCESS FOR PRESULFURIZING A HYDROCARBON PROCESSING CATALYST |
| ATE81308T1 (en) * | 1988-07-29 | 1992-10-15 | Akzo Nv | METHOD FOR PREPARING A PRESULFIDATED CATALYST, METHOD FOR PREPARING A SULFIDED CATALYST AND USE OF SUCH CATALYST. |
| EP0357295B1 (en) * | 1988-08-19 | 1996-07-03 | Sumitomo Metal Mining Company Limited | Catalysts for hydrotreating of hydrocarbons and methods of preparing the same |
-
1990
- 1990-06-05 EP EP90201426A patent/EP0460300A1/en not_active Withdrawn
- 1990-06-12 AU AU57030/90A patent/AU629944B2/en not_active Ceased
- 1990-06-20 US US07/540,951 patent/US5017535A/en not_active Expired - Fee Related
- 1990-06-25 CA CA002019713A patent/CA2019713A1/en not_active Abandoned
- 1990-06-26 JP JP2165873A patent/JPH0457887A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0457887A (en) | 1992-02-25 |
| AU5703090A (en) | 1991-12-19 |
| US5017535A (en) | 1991-05-21 |
| EP0460300A1 (en) | 1991-12-11 |
| AU629944B2 (en) | 1992-10-15 |
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