CA1060370A - Process for the conversion of hydrocarbons - Google Patents
Process for the conversion of hydrocarbonsInfo
- Publication number
- CA1060370A CA1060370A CA220,643A CA220643A CA1060370A CA 1060370 A CA1060370 A CA 1060370A CA 220643 A CA220643 A CA 220643A CA 1060370 A CA1060370 A CA 1060370A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- catalysts
- cat
- combination
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT
Life of a combination of two or more catalysts in a hydrodesulphurization process without catalyst replenishment of a residual oil is longer than that of each of the catalysts if applied separately, provided that each of the catalysts has a porosity and particle size within specified ranges depending on the porosity and particle size of the applied hydrogen partial pressure combination and on the applied hydrogen partial pressure and that the catalysts are applied in a given volume ratio.
Life of a combination of two or more catalysts in a hydrodesulphurization process without catalyst replenishment of a residual oil is longer than that of each of the catalysts if applied separately, provided that each of the catalysts has a porosity and particle size within specified ranges depending on the porosity and particle size of the applied hydrogen partial pressure combination and on the applied hydrogen partial pressure and that the catalysts are applied in a given volume ratio.
Description
10~ 70 The invention relates to a process for the catalytic hydrodesulphur-ization of vanadium- and nickel-containing residual hydrocarbon oils without catalyst replenishment. Processes of this type have been described in our Canadian patent application 985,651 and applicants'British Patent Specification 1,406,804. According to these patent applications, catalysts are used for this purpose showing a life and average activity which exceed established minimum values if they are used for residue desulphurization in a standard catalyst test. They have a total pore volume of more than 0.30 ml/g of wllich less than 10% is present in pores having a diameter of more than 100 nm and they have a specific average pore diameter (p) and a specific average 1~ particle diameter ~d) such that the quotient p/(d)0 9 satisfies the require-mcnt:
3 x 10 4 x ~PH )2 < p/(d)0 9 < 17 x 10 4 x (PH )2, where PH represents the hydrogen partial pressure used (p in nm, d in mm, PH in bar). As is demon-strated in the above-mentioned patent applications, catalysts having a quot-ient p/(d)0 9 of less than 3 x 10 4 x (PH )2 or larger than 17 x 10 x (PH )show a life in the stardard catalyst test which is too short and/or an average activity which is too low to satisfy the minimum requirements in respect of life and average activity stated in the patent applications.
iO;~70 Since the life of a catalyst for the hydrodesulphuri zation of vanadium- and nickel-containing residual hydrocarbon oils without catalyst replenishment is shorter according as the catalyst displays a higher average desulphurization activity, the aforesaid Canadian Patent Application and British Patent Specification are in fact based on a compromise between these two catalyst properties.
Continued research by applicant into this subject has shown that considerably better results can be obtained if the residual hydrocarbon oil is successively contacted with two or more different catalysts as compsred with a process in which only one catalyst is used. The use of a suitable com-bination of two or more different catalysts produces an improvement in activity and/or life of the combination in respect of each of the catalyst individually, i.e. by retaining the same conditions a more thorough desulphurization is effect-ed or by maintaining a certain desulphurization level (as is customary in practice~ the catalyst life is prolonged. However, these better results are only achieved if the catalysts used satisfy a number of re~uirements in respect of their porosity, particle ~ize and volumetric ratio.
For the sake of simplicity a combination of two or more catalysts will in this patent application be considered as consisting of a catalyst I and a catalyst II, 10~;0370 the designation ~'catalyst II~' referring to the second catalyst when using a combination of two catalysts, or to the last catalyst when using a combination of more than two catalysts and the designation "catalyst I" referring to the first catalyst when using a combination of two catalysts, or to the combination of all catalysts with the exception of the last one when using a combination of more than two cata-lysts t"first", "second" and "last" as seen in the direction of the liquid floN over the catalyst combination).
When a combination of two catalysts is used, the requirements in respect of porosity, particle size and volumetric ratio of the catalysts are as follows:
~a) in respect of the total pore volume and the percentage thereof present in pores having a diameter in excess of 100 nm the same require-ments apply to catalyst I and catalyst II as to the catalysts according to the aforesaid Canadian Patent Application and British Patent Specifica-tion, i.e~ they should have a total pore volume of more than 0.3Q ml/g of which less than 10% is present in pores having a diameter in excess of 100 nm;
') ~060370 (b) catalyst II should haYe a p and d such that the quotient ~p/(d) ]cat II satisfies the requirement:
~PH2) <[p/(d) ]cat II< 3 ~ 6 x IO 4X(PH )2 (c) catalyst I should have a p and d such that the quotient ~p/~d) ]cat I satisfies the requirement:
~P/( ) ~cat~ p/~d) ]cat I~ 5+30x10-4x(pH )2 ~d) the percentage of the total catalyst volume taken up by catalyst II (~ vol. of catalyst II) should lie between 10 and 90% and should satisfy the follow-ing requirement:
40x( ~ x100)2x (PH ) 2~ %vol.cat.II<300x( ~ xlOO) x~PH ) where SF represents the sulphur content of the feed and Sp the desired sulphur content of the desulphurized product, expressed in percentage by weight.
When a combination of more than two catalysts is used, the requirements in respect of porosity, particle size and volumetric ratio of the catalysts are essentially in agreement with those mentioned above under (a)-(d) for a combination of two catalysts, with the pro~iso that:
te) the requirements mentioned under (a) in respect of the total pore volume and the percentage thereof in pores having a diameter in excess of 100 nm now apply to each of the individual catalysts of which the combination of catalyst I
and _ 5 _ ~0~;0370 catalyst II is composed, (f) the requirement mentioned under ~e) in respect of [p/~d) 9] t I now applies to the average P/td) 9 of catalyst I, determined as the weight average of the values p/~d)0 9 of each of the individual catalysts of which catalyst I is composed, and tg) each of the individual catalysts of which catalyst I is composed has a p and d such that the quotient p/~d)0 9 of each of these catalysts exceeds ~p/(d) ] cat. II-The present patent application therefore provides a process forthe catalytic hydrodesulphurization of vanadium- and nickel-containing residual 1~ hydrocarbon oils without catalyst replenishment, the hydrocarbon oil being consecutively contacted with a catslyst I and 8 catalyst II which satisfy the following requirements:
ta) each of the individual catalysts of which the combination of catalyst I
and catalyst II is composed has a total pore volume in excess of 0.30 ml/g of which less than 10% is present in pores having a diameter in excess of 100 nm, (b) catalyst II has a specific average pore diameter (p) and a specific average particlediameter (d) such that the quotient p/(d)- of catalyst II sat-isfies the requirement:
( H2) < [p/(d) ] cat II < 3 + 6 x 10 4x(PH )2~
c) if the combination of catalyst I and catalyst II is composed of two cata-lysts, catalyst I has a p and d such that the quotient p/~d)0 9 of catalyst I satisfies the requirement:
[P ( ) ] cat. II < [p/(d) ] cat I < 5+30xlO 4x(PH )2, while if the combination of catalyst I and catalyst II is composed of more than two catalysts, the above requirement in respect of [p/(d)0 9] t applies to the average p/~d) 9 of catalyst I which is determined as the weight average of the values of p/(d)0 9 of each of the individual catalysts of which catalyst I is composed, y, -6-,~
10~0370 ~d) The percentage of the total catalyst Yolume which is taken up by catalyst ~ ovOl. of catalyst II~ is between 10 and 90% and satisfies the require-ment:
40x( 5 xlO0) x(PH ) <~O vol. cat. II < 300x( 5 xlO0~ x(PH ) wherein SF represents the sulphur content of the feed and Sp the required sulphur content of the desulphurized product, and (e) if the combination of catalyst I and catalyst II is composed of more than two catalysts, each of the individual catalysts of which catalyst I is composed has a p and d such that the quotient p/(d)0 9 of each of these catalyst is greater than [P/td) ] cat. II ~P H2 bar, Sp and SF in percentage by weight).
~ hen the requirements which are now made of the quotient p/(d)0 9 of catalyst I and catalyst II are compared with those which were made in the past of this quotient of the catalysts applicable according to the aforesaid Canadian patent application and British Patent Specification, it is found that a number of the catalysts which were rejected in the past are now eligible for application in the catalyst combination according to the invention.
-6a-~0~0370 Catalysts outside the scope of the aforesaid Canadian Patent Application and British Patent Specification which are now eligible for application are:
(a) As catalyst II, a catalyst having a p and d such that the quotient /~d) ]cat II satisfies the requirement:
( H2) ~ [p/ld) ]cat IIC3xlo 4x(PH )2 tb) As catalyst II, a catalyst having a p and d such that the quotient lP/td~ ]cat II satisies the requirement:
17xlO x ~PI~ ) <[P/td) ~cat II< 3~6xlO 4XtPH )2 tThis situation occurs when hydrogen partial pre-sures of less than approx. 52 bar are used).
tc) When using one catalyst as catalyst I, a c,atalyst I having a p and d such that the quotient lP/ld) ]cat I satisfies the requirement:
1.2XO.6X10 4X (PH )2<1P/ ~d)0'9]cat I<3X10 4x (PH ) (d) When using one catalyst as catalyst I, a catalyst I having a p and d such that the quotient ~ [P/(d)o 9~cat I satisfies the requirement:
tPH2) ~p/~d) ]cat I< 5~30xlO 4x ~PH )2 In addition to an extension in respect of the afore-said Canadian PatentApplication and British Patent Specification as regards the applicable catalysts, the present invention also entails limitations.
Catalysts usable according to the aforesaid Canadian Patent Application and British Patent Specification which are not eligible for application in the present case are inter alia:
(a) as catalyst II, a catalyst having a p and d such that the quotient P/(d) ~cat II satisfies the requirement:
tPH2) > ~P/ (d) ~cat II>3~6XlO 4x ~PH )2 tThis situation occurs when hydrogen partial pressures of more than approx. 52 ba~r are used.) tb) When using one catalyst as catalyst I, a catalyst I having a p and d such that the quotient [p/Cd) ]cat I satisfies the requirement:
(PH2) ~lp/td) ~cat I <l~2xlp/(d)o~9] II' (This situation occurs if as catalyst II a catalyst is used haYing a p and d such that the quotient [p/(d) ]cat II satisfies the requirement:
lP/Cd) ]cat II >2-5 x 10 x CPH ) ) For the way in which p and d are determined, reference is made to the aforesaid Canadian~Patent Application and British Patent Specification, wherein the determination of these parameters has been described in detail.
The catalysts which are used in the process accordin~ to the invention as catalyst II preferably have a total pore volume in excess of 0.45 ml/g and a surface 1(P~i0370 g in excess of 100 ~2/g and in particular a surface in excess of 150 m2/g. In addition, they preferably have a p and d such that the quotient _ p/(d) -7cat II satisfies the requirement:
5 _ p/(d) -7cat II ' 10 x (PH )2-In the hydrodesulphurization according to the invention there is particular preference for using a catalyst II which has a p and d such that the auotient / P/(d) -7cat.II satisfies the requirement x (PH2) ~ / p/(d) -7cat.II '3 ~6xlO x(PH )2, which catalyst also has a total pore volume in excess o~ 0.45 ml/g of which at least 0.4 ml/g is present in pores having a diameter o~ at least 0.7 x p and at most 1.7 x p and a sharp pore diameter distribution characterized in that (a) less than 20% of the total pore volume is present in pores having a diameter s~aller than 0.7 x p and (b) less than 20% of the total pore volume is present in the pores having a diameter greater than 1.7 x p.
As has already been noted above, one single catalyst or a combination of two or more catalysts can be used as catalyst I in the process according to the invention.
The process is preferably carried out us`ing one single catalyst as catalyst I. If use is made of a combination of two or more catalysts as catalyst I, the catalysts of which catalyst I is composed ~ay occur in t~e desulphuriz3~iGn reactor both mixed with each other and separated from each other (for example in separate beds or layers).
When a combination of two or more catalysts is used as catalyst I, preference is given to a process in which the catalysts of which catalyst I is composed occur in the reactor separated from each other, in particular in such a sequencethat the quotient p/(d)-9 of each of the catalysts of which catalyst I is composed is smaller than that of the preceding catalyst, i,e.
that the quotient p/(d)'9 decreases in the direction o~ the liquid flow over the catalyst combination, When one single catalyst is used as catalyst I and also when a combination of two or more catalysts are used as catalyst I, catalysts having a total pore volume in excess of 0,40 ml/g are preferred, It is also preferred that a catalyst I is used with a p and d such that the quotient ~ p/(d)'97Cat I satisfies the requirement:
~ /(d) -7cat,I >1-4 x /P/(d) 97cat II
with the proviso that when a combination of two or more catalysts is used as catalyst I, this preference in respect of ~ ~(d)'97Cat I applies to the average p~(d)-9 of catalyst I, which is determined as the weight average of the values p/(d)-9 of each of the individual catalysts of which catalyst I is composed.
Catalysts which are used according to the inven~ion preferably contain 0.5-20 parts by weight and in particular 0.5-10 parts by weight of nickel and/or cobalt and
3 x 10 4 x ~PH )2 < p/(d)0 9 < 17 x 10 4 x (PH )2, where PH represents the hydrogen partial pressure used (p in nm, d in mm, PH in bar). As is demon-strated in the above-mentioned patent applications, catalysts having a quot-ient p/(d)0 9 of less than 3 x 10 4 x (PH )2 or larger than 17 x 10 x (PH )show a life in the stardard catalyst test which is too short and/or an average activity which is too low to satisfy the minimum requirements in respect of life and average activity stated in the patent applications.
iO;~70 Since the life of a catalyst for the hydrodesulphuri zation of vanadium- and nickel-containing residual hydrocarbon oils without catalyst replenishment is shorter according as the catalyst displays a higher average desulphurization activity, the aforesaid Canadian Patent Application and British Patent Specification are in fact based on a compromise between these two catalyst properties.
Continued research by applicant into this subject has shown that considerably better results can be obtained if the residual hydrocarbon oil is successively contacted with two or more different catalysts as compsred with a process in which only one catalyst is used. The use of a suitable com-bination of two or more different catalysts produces an improvement in activity and/or life of the combination in respect of each of the catalyst individually, i.e. by retaining the same conditions a more thorough desulphurization is effect-ed or by maintaining a certain desulphurization level (as is customary in practice~ the catalyst life is prolonged. However, these better results are only achieved if the catalysts used satisfy a number of re~uirements in respect of their porosity, particle ~ize and volumetric ratio.
For the sake of simplicity a combination of two or more catalysts will in this patent application be considered as consisting of a catalyst I and a catalyst II, 10~;0370 the designation ~'catalyst II~' referring to the second catalyst when using a combination of two catalysts, or to the last catalyst when using a combination of more than two catalysts and the designation "catalyst I" referring to the first catalyst when using a combination of two catalysts, or to the combination of all catalysts with the exception of the last one when using a combination of more than two cata-lysts t"first", "second" and "last" as seen in the direction of the liquid floN over the catalyst combination).
When a combination of two catalysts is used, the requirements in respect of porosity, particle size and volumetric ratio of the catalysts are as follows:
~a) in respect of the total pore volume and the percentage thereof present in pores having a diameter in excess of 100 nm the same require-ments apply to catalyst I and catalyst II as to the catalysts according to the aforesaid Canadian Patent Application and British Patent Specifica-tion, i.e~ they should have a total pore volume of more than 0.3Q ml/g of which less than 10% is present in pores having a diameter in excess of 100 nm;
') ~060370 (b) catalyst II should haYe a p and d such that the quotient ~p/(d) ]cat II satisfies the requirement:
~PH2) <[p/(d) ]cat II< 3 ~ 6 x IO 4X(PH )2 (c) catalyst I should have a p and d such that the quotient ~p/~d) ]cat I satisfies the requirement:
~P/( ) ~cat~ p/~d) ]cat I~ 5+30x10-4x(pH )2 ~d) the percentage of the total catalyst volume taken up by catalyst II (~ vol. of catalyst II) should lie between 10 and 90% and should satisfy the follow-ing requirement:
40x( ~ x100)2x (PH ) 2~ %vol.cat.II<300x( ~ xlOO) x~PH ) where SF represents the sulphur content of the feed and Sp the desired sulphur content of the desulphurized product, expressed in percentage by weight.
When a combination of more than two catalysts is used, the requirements in respect of porosity, particle size and volumetric ratio of the catalysts are essentially in agreement with those mentioned above under (a)-(d) for a combination of two catalysts, with the pro~iso that:
te) the requirements mentioned under (a) in respect of the total pore volume and the percentage thereof in pores having a diameter in excess of 100 nm now apply to each of the individual catalysts of which the combination of catalyst I
and _ 5 _ ~0~;0370 catalyst II is composed, (f) the requirement mentioned under ~e) in respect of [p/~d) 9] t I now applies to the average P/td) 9 of catalyst I, determined as the weight average of the values p/~d)0 9 of each of the individual catalysts of which catalyst I is composed, and tg) each of the individual catalysts of which catalyst I is composed has a p and d such that the quotient p/~d)0 9 of each of these catalysts exceeds ~p/(d) ] cat. II-The present patent application therefore provides a process forthe catalytic hydrodesulphurization of vanadium- and nickel-containing residual 1~ hydrocarbon oils without catalyst replenishment, the hydrocarbon oil being consecutively contacted with a catslyst I and 8 catalyst II which satisfy the following requirements:
ta) each of the individual catalysts of which the combination of catalyst I
and catalyst II is composed has a total pore volume in excess of 0.30 ml/g of which less than 10% is present in pores having a diameter in excess of 100 nm, (b) catalyst II has a specific average pore diameter (p) and a specific average particlediameter (d) such that the quotient p/(d)- of catalyst II sat-isfies the requirement:
( H2) < [p/(d) ] cat II < 3 + 6 x 10 4x(PH )2~
c) if the combination of catalyst I and catalyst II is composed of two cata-lysts, catalyst I has a p and d such that the quotient p/~d)0 9 of catalyst I satisfies the requirement:
[P ( ) ] cat. II < [p/(d) ] cat I < 5+30xlO 4x(PH )2, while if the combination of catalyst I and catalyst II is composed of more than two catalysts, the above requirement in respect of [p/(d)0 9] t applies to the average p/~d) 9 of catalyst I which is determined as the weight average of the values of p/(d)0 9 of each of the individual catalysts of which catalyst I is composed, y, -6-,~
10~0370 ~d) The percentage of the total catalyst Yolume which is taken up by catalyst ~ ovOl. of catalyst II~ is between 10 and 90% and satisfies the require-ment:
40x( 5 xlO0) x(PH ) <~O vol. cat. II < 300x( 5 xlO0~ x(PH ) wherein SF represents the sulphur content of the feed and Sp the required sulphur content of the desulphurized product, and (e) if the combination of catalyst I and catalyst II is composed of more than two catalysts, each of the individual catalysts of which catalyst I is composed has a p and d such that the quotient p/(d)0 9 of each of these catalyst is greater than [P/td) ] cat. II ~P H2 bar, Sp and SF in percentage by weight).
~ hen the requirements which are now made of the quotient p/(d)0 9 of catalyst I and catalyst II are compared with those which were made in the past of this quotient of the catalysts applicable according to the aforesaid Canadian patent application and British Patent Specification, it is found that a number of the catalysts which were rejected in the past are now eligible for application in the catalyst combination according to the invention.
-6a-~0~0370 Catalysts outside the scope of the aforesaid Canadian Patent Application and British Patent Specification which are now eligible for application are:
(a) As catalyst II, a catalyst having a p and d such that the quotient /~d) ]cat II satisfies the requirement:
( H2) ~ [p/ld) ]cat IIC3xlo 4x(PH )2 tb) As catalyst II, a catalyst having a p and d such that the quotient lP/td~ ]cat II satisies the requirement:
17xlO x ~PI~ ) <[P/td) ~cat II< 3~6xlO 4XtPH )2 tThis situation occurs when hydrogen partial pre-sures of less than approx. 52 bar are used).
tc) When using one catalyst as catalyst I, a c,atalyst I having a p and d such that the quotient lP/ld) ]cat I satisfies the requirement:
1.2XO.6X10 4X (PH )2<1P/ ~d)0'9]cat I<3X10 4x (PH ) (d) When using one catalyst as catalyst I, a catalyst I having a p and d such that the quotient ~ [P/(d)o 9~cat I satisfies the requirement:
tPH2) ~p/~d) ]cat I< 5~30xlO 4x ~PH )2 In addition to an extension in respect of the afore-said Canadian PatentApplication and British Patent Specification as regards the applicable catalysts, the present invention also entails limitations.
Catalysts usable according to the aforesaid Canadian Patent Application and British Patent Specification which are not eligible for application in the present case are inter alia:
(a) as catalyst II, a catalyst having a p and d such that the quotient P/(d) ~cat II satisfies the requirement:
tPH2) > ~P/ (d) ~cat II>3~6XlO 4x ~PH )2 tThis situation occurs when hydrogen partial pressures of more than approx. 52 ba~r are used.) tb) When using one catalyst as catalyst I, a catalyst I having a p and d such that the quotient [p/Cd) ]cat I satisfies the requirement:
(PH2) ~lp/td) ~cat I <l~2xlp/(d)o~9] II' (This situation occurs if as catalyst II a catalyst is used haYing a p and d such that the quotient [p/(d) ]cat II satisfies the requirement:
lP/Cd) ]cat II >2-5 x 10 x CPH ) ) For the way in which p and d are determined, reference is made to the aforesaid Canadian~Patent Application and British Patent Specification, wherein the determination of these parameters has been described in detail.
The catalysts which are used in the process accordin~ to the invention as catalyst II preferably have a total pore volume in excess of 0.45 ml/g and a surface 1(P~i0370 g in excess of 100 ~2/g and in particular a surface in excess of 150 m2/g. In addition, they preferably have a p and d such that the quotient _ p/(d) -7cat II satisfies the requirement:
5 _ p/(d) -7cat II ' 10 x (PH )2-In the hydrodesulphurization according to the invention there is particular preference for using a catalyst II which has a p and d such that the auotient / P/(d) -7cat.II satisfies the requirement x (PH2) ~ / p/(d) -7cat.II '3 ~6xlO x(PH )2, which catalyst also has a total pore volume in excess o~ 0.45 ml/g of which at least 0.4 ml/g is present in pores having a diameter o~ at least 0.7 x p and at most 1.7 x p and a sharp pore diameter distribution characterized in that (a) less than 20% of the total pore volume is present in pores having a diameter s~aller than 0.7 x p and (b) less than 20% of the total pore volume is present in the pores having a diameter greater than 1.7 x p.
As has already been noted above, one single catalyst or a combination of two or more catalysts can be used as catalyst I in the process according to the invention.
The process is preferably carried out us`ing one single catalyst as catalyst I. If use is made of a combination of two or more catalysts as catalyst I, the catalysts of which catalyst I is composed ~ay occur in t~e desulphuriz3~iGn reactor both mixed with each other and separated from each other (for example in separate beds or layers).
When a combination of two or more catalysts is used as catalyst I, preference is given to a process in which the catalysts of which catalyst I is composed occur in the reactor separated from each other, in particular in such a sequencethat the quotient p/(d)-9 of each of the catalysts of which catalyst I is composed is smaller than that of the preceding catalyst, i,e.
that the quotient p/(d)'9 decreases in the direction o~ the liquid flow over the catalyst combination, When one single catalyst is used as catalyst I and also when a combination of two or more catalysts are used as catalyst I, catalysts having a total pore volume in excess of 0,40 ml/g are preferred, It is also preferred that a catalyst I is used with a p and d such that the quotient ~ p/(d)'97Cat I satisfies the requirement:
~ /(d) -7cat,I >1-4 x /P/(d) 97cat II
with the proviso that when a combination of two or more catalysts is used as catalyst I, this preference in respect of ~ ~(d)'97Cat I applies to the average p~(d)-9 of catalyst I, which is determined as the weight average of the values p/(d)-9 of each of the individual catalysts of which catalyst I is composed.
Catalysts which are used according to the inven~ion preferably contain 0.5-20 parts by weight and in particular 0.5-10 parts by weight of nickel and/or cobalt and
2.5-60 parts by weight and in particular 2.5-30 parts by weight of molybdenum and/or tungsten per 100 parts by weight of carrier. The atomic ratio between nickel and/or cobalt on the one hand, and molybdenum and~or tun~sten on the other, may vary within wide limits, but is preferably between 0.1 and 5. Examples of very suitable metal combinations for the present catalysts are nickel~tungsten, nickel/molybdenum, cobalt/molybdenum and nickel/cobaltimolybdenum. The metals may be present on the carrier in metallic form or in the form of their oxides or sulphides. It is preferred to use the catalysts accordin~ to the invention in which the metals are present on the carrier in the form of their sulphides. In addition to the catalytically active metals mentioned above, the catalysts may also contain other catalytically active metals and promoters such as phosphorus, boron and halogens, such as fluorine and chlorine. Very suitable carriers for the present catalysts are oxides of elements of the Groups II, III and IV of the periodic system, such as silica, alumina, magnesia and zirconia, or mixtures of the said oxides, such as silica-alumina, silica-magnesia, alumina-magnesia and silica-zirconia. Aluminas and silica-aluminas are preferred as carriers for the pre-sent catalysts.
The metal loads of most commercial catalysts which contain the cobalt/molybdenum metal combination supported on alumina or silica-alumina as carrier and which are recommended for the treatment of hydrocarbons with hydrogen as a rule amount to approx. 15 parts by weight of metal per 100 parts by weight of carrier.
In the experimental work upon which the aforesaid Canadian Patent Application and British Patent Specifi-cation are based, which applications refer to the relationship between porosity and particle size of catalysts and the hydrogen partial pressures used on the one hand, and the suitability of these catalysts for hydro-desulphurization of vanadium- and nickel-containing residual hydrocarbon oils without catalyst replenishment on the other, it was assumed that also for this application the above metal load produces the most attractive results. As can be seen from the examples of these patent applications, the metal load of the cobalt-molybdenum catalyst is only varied between 13.3 and 16.1 parts by weight per 100 parts by weight of carrier. Continued research has now shown that the metal load of these catalysts can be greatly reduced without impairing their suitability ~;06037~
for the desulphurization of residual hydrocarbon oils.
Thus, for example, it was found that a catalyst which contained 2.0 psrts by weight of cobalt and 5.5 parts by weight of molybdenum per lOO parts by weight of alumina possessed the same excellent suitability for the desulphurization of residual hydrocarbon oils as a catalyst which contained 4.3 psrts by weight of cobalt and 10.9 parts by weight of molyW enum per 100 parts by weight of alumina, p, d and PH remaining the same. The discovery of the fact that a lower metal load can be used than had been assumed until recently is of course very important with a view to the cost of catalyst preparation. A lower metal load saves metals and may result in a simplification in the catalyst preparation. If use is made in the process according to the invention of a catalyst which contains cobalt and molyW enum supported on alumina or silica-alumina as a carrier, it is preferred, in view of the above, to select a catalyst which contains 5-10 parts by weight of metal per lQ0 parts by weight of carrier.
This preference for a low metal load of course also applies if in the process according to the aforesaid Canadian Patent Application and British Patent Specification a catalyst is used which contains cobalt and molybdenum supported on alumina or silica-alumina.
~OfàO370 The catalysts which are applicable according to the invention may be prepared by supporting the relevant metals on a carrier having such a specific average pore diameter that after the metals have been supported thereon, a catalyst is obtained which satisfies the requirements of the invention, either as such or after the specific average particle diameter has been increased or reduced. The catalysts which are applicable according to th0 invention are preferably prepared by co-impregnat-ing a carrier in one or more steps with an aqueous solution containing one or more nickel and/or tungsten compounds, followed by drying and calcining of the com-position.
For information on methods which can be used to influence the porosity of the carrier material of the catalyst and for further particulars of preferred methods of preparation for the present catalysts, reference is made to the aforesaid Canadian Patent Application and British Patent Specification, wherein th0se subjects are discussed in detail.
The catalytic hydrodesulphurization of residual hydrocarbon oils without catalyst replenishment is preferably carried out by passing the hydrocarbon oil at elevated temperature and pressure and in the presence of hydrogen in an upward, downward or radial direction through two or more vertically arranged 1~0370 fixed catalyst beds. The hydrocarbon oil to be desulphurizedmay be completely or partly saturated with hydrogen and a hydrogen-containing gaseous phase may be present in the reactor in addition to the hydrocarbon phase and the catalyst phase.
The hydrodesulphurization according to the invention may be carried out in one single reactor or in two or more reactors. If the process according to the invention is carried out in one reactor, it should ~0 at least contain two catalyst beds, the first catalyst bed of which (viewed in the direction of the liquid flow) and possibly one or more immediately subsequent beds contain a catalyst or combination of catalysts designated hereinbefore as catalyst I and the final catalyst bed (viewed in the direction of the liquid flow) and possibly one or more immediately preceding beds contain a catalyst designated hereinbefore as catalyst II. If the process according to the invention is carried out in two or more reactors, the first reactor and possibly one or more immediately subsequent reactors should contain catalyst I and the final reactor and possibly one or more immediately preceding reactors should contain catalyst II. The catalysts which are applied in the individual catalyst beds and~or individual reactors may difrer from each other as regards their chemical composition.
:~060370 The specific average particle diameter of the catalysts which are used according to the invention is as a rule 0.5-2.5 mm and preferably 0.6-2.0 mm. If the value d which is required according to the invention to achieve a good catalyst performance at a given p and P~l is too small for practical application, the desulphuri-zation may be carried out in the presence of porous agglomerates prepared from the small catalyst particles in a manner as described in the aforesaid Canadian Patent Application and British Patent Specification.
The reaction conditions used in the hydro-desulphurization according to the invention may vary between wide limits. The hydrodesulphurization is preferably car-ried out at a temperature between 300G and 475C, a hydro-gen partial pressure of 5Q-200 bar, a space velocity of Q.l-10 parts by weight of fresh feed per part by vol~me of catalyst per hour and a hydrogen/feed ratio of 150 -2000 Nl of H2/kg of feed. Special preference is given to a temperature of 350C-445C, a hydrogen partial pressure 2n of 70-1~0 bar, a space velocity of 0.2-5 parts by weight of fresh feed per part by volume of catalyst per hour and a hydrogen/feed ratio of 250-1000 Nl of ~l2/kg of feed.
The hydrodesulphurization according to the inven-tion may very suitably be preceded by a demetallization (3370 treatment. As a result of the demetallization the deactivation of the desulphurization catalyst combination is suppressed and its life is consequently prolonged.
The demetalliaation of residual hydrocarbon oils is preferably carried out in the presence of hydrogen and a catalyst. Demetallization may very suitably be effected by passing the hydrocarbon oil at elevated temperature and pressure and in the presence of hydrogen in an upward, downward or radial direction through one or more vertically arranged reactors which cvntain a fixed or moving catalyst bed. In a very attractive embodiment of the demetallization, the hydrocarbon oil is passed through a vertically arranged catalyst bed into which, during operation, fresh catalyst is intermittently introduced at the top of the bed and spent catalyst is withdrawn from the lower part thereof (demetallization according to the bunker flow principle).
In another very attractive embodiment of the demetallization treatment several reactors containing a fixed catalyst 2~ bed are present, which reactors are alternately used for the demetallization treatment. ~lile demetallization is carried out in one or more of these reactors, the catalyst is replenished in the remaining reactors ~demetallization according to the fixed bed swing ~5 principle). If desired, demetallization can also l(N~0370 be carried out by suspending the catalyst in the hydrocarbon oil to be demetallized (demetallization accordinF
to the slurry phase principle). Suitable catalysts for the demetallization of residual hydrocarbon oils are catalysts which contain one or more metals havin~
hydrogenating activity, supported on a carrier.
If the desulphurization according to the invention is preceded by a demetallization treatment, the demetallization i3 pre~erably carried out according to the bunker ~0 flow principle or according to the fixed bed swing principle and the desulphurization is effected over two or more conventional fixed catalyst beds.
As has been noted above, the demetallization of a vanadium- and nickel-containing residual hydrocarbon oil results in a prolonged life of the catalyst combination which is used for the hydrodesulphurization of the demetallized oil. For the catalytic hydrodemetallization of a vanadium- and nickel-containing residual hydrocarbon oil followed by desulphurization of the demetallized oil according to the present invention, applicant has derived the following equation:
M2 = (l,n5+0,20)xMlx(Ll/L2)0'5, wherein M1 and M2 represent t.he metal contents of the non-demetallized and the demetallized oil respectively and L1 and L2 represent the lives of the desulphurization catalyst combination when used for the non-demetallized and the demetallized oil respectively. In drawing up this equation the following limitations have been taken into account:
(1) The metal content of the hydrocarbon oil before demetallization (M1) may vary between 25 and 1500 ppmw (parts by weight per million).
(2) The life of the desulphurization catalyst combination used for the demetallized oil (L2) may vary between 2000 and 16,000 hours.
~3) The quotient of the metal contents of the hydrocarbon oil after and before demetallization (M2 and M1) may vary between 0.75 and 0.10 and (4) the product of the metal content of the hydrocarbon oilbefore demetallization (M1) and the life of the desulphurization catalyst combination used for the demetallized oil (L2) may vary between 2 x 105 and 3 x 106.
The abovementioned relationship between L1, L2, Ml and M2 offers the possibility, during the hydrodesulphurizatio~
Or a residual hydrocarbon oil according to the present invention, using prior catalytic hydrodemetallization ,Or the feed, to establishto what value the metal content of the feed has to be reduced in order to prolong the life of the desulphurization catalyst combination by a certain number of hours.
`` 1(~0~70 Examples of reeds to which the process accordin~
to the invention can be applied are crude oils and residues obtained by distillation of crude oils at atmospheric or reduced pressure. Residues obtained durin~ the distillation of products originating from thermal or catalytic cracking of heavy hydrocarbon oils may also be treated in accordance with the invention.
The invention will now be elucidated with reference to the following Example.
EXAMPLE
Eleven combinations of two different catalysts as well as each of these catalysts separately (catalysts A-M) were used for the hydrodesulphurization of five vanadium- and nickel-containing residual hydrocarbon oils (oils A-E) without catalyst replenishment. Desulphurization o~ the oils was effected by passin~ these oils at elevated temperature and pressure and in the presence of hydrogen in a downward direction through two cylindrical ~ixed catalysts beds.
The experiments were carried out in series of three. Per series of three experiments the same oil was desulphurized under the same conditions and with the same volume of catalyst to the same sulphur content in the product (Sp). In one of the three experiments the first catalyst bed contained the catalyst referred to below as catalyst I and the second bed the catalyst 10f~037o referred to below as catalyst II. In the two remaining experiments both catalyst beds contained either exclusively catalyst I or exclusively catalyst II.
The de~ulphurization experiments were carried out at an initial temperature of 360 +5C, a space velocity of 0.7 kg.l 1.h l, a ~as velocity Or 600 Nl o~ H2/k~ l and a hydrogen partial pressure varyinE
rrOm 75 to 150 bar. To prepare a product havin~ a constant sulphur content the temperature had to be gradually increased during the experiments. The desulphurization experiments were terminated at the moment when a temperature in excess of 420C had to be used in order to prepare a product with the desired sulphur content.
The composition and properties o~ the catalysts, which were used in the form Or their sulphides, are stated in Table A. For information on the preparation Or the nine catalysts used in the present experiments C~
D reference is made to the examples of our Metherlends patent application 7 ~4397, wherein the preparation o~ these catalysts has been described in detail. The preparation Or the catalysts B* and D* was ef~ected in the same manner as described for the catalysts B and D~ with the proviso that a lower metal load was used in the preparation of the catalyst B* and D~. ~he rive residual oils involved in the investi~ation ~iO3'70 are described in greater detail below. The results of the desulphurization experiments are stated in Table B.
OIL A
Oil having a total vanadium and nickel content of 75 ppmw and a sulphur content of 4.0% by weight, obtained as residue in the distillation at atmospheric pressure of a Middle East crude oil.
OIL B
~0 Oil having a total vanadium and nickel content of 64 ppmw and a sulphur content of 4.0% by weight, obtained as residue in the distillation at atmospheric pressure of a Middle East crude oil.
OIL C
Oil having a total vanadium and nickel content of 110 ppmw and a sulphur content of 5.2% by weight, obtained as residue in the distillation at reduced pressure of an atmospheric distillation residue of a Middle East crude oil.
OIL _ Oil having a total vanadium and nickel content o~ 225 ppmw and a sulphur content of 2.0% by weight, obtained as residue in the distillation at atmospheric pressure of a Caribbean crude.
~0~0370 OIL E
Oil having a total vanadium and nickel content of 130 ppmw and a sulphur content of 1.9% by weight, obtained by demetallization of oil D. The demetallization of oil D was carried out by passing it at elevated temperature and pressure and in the presence of hydrogen in a downward direction through a vertically arranged fixed bed of a demetallization catalyst. The demetallization catalyst contained 0.5 parts by weight of nickel and 2~0 parts by weight of vanadium per 100 parts by weight of silica carrier.
~()60370 E; I . . . . . . . . . , C) o ~ CO ~ ~ ~ ~ ~D O ~
S:: ~ . . . . I
d) U~ ~ I I
~ ~ I ~ o ~1 ~ o ~o ~ ao ~ I
O ~ O I
O O S~
~p.~
~ ~ ~ , ~ o ~ x t ~o ~ a~ ~ ~ ~ u~ o ~
P.S
O O
O ~ ~ X ~ ~ ~ ~ o o ~
o o ~ rl o v ~ l l CC C~ bO I N ~ O1~1~ 0 ~D CJ~ ~ I
O~ h ~ ~ I o ~ D ~ o ocu ~~ 3 S~J ~~, ~, ~ ~, .D
E~
~ o a~ X X I ~ c~ ~ ~ ~ r--r~
OO~O~IOOOOOOOOO
h ~1~ 1 o o o c; o o o o o o 0~
IOOOOOOOOO
5-1 I N N (~
~ I ¢ ": '1: ~ 'C '5 ~: ~ ¢
C~ I I
o c) o O
~01 ~d~~ I I I I I I I . . . I
I
~ ICl m m ~
o ~z - 25 ~ 03~70 Table B
Exp. Jil SF~ Sp, PH , Cat.I Cat.II, %v Life of the No. No. 2 No. No.Cat.II c~t. or cat.
%w %w bar combination, hours _______________ ______ _____ ~____ _______ ______ ____________ I A4.00.5 150 M D 50 2400 I' A 4.0 0.5 15C M - 0 400 I~ A 4.0 0.5 150 - D 100 1600 II A 4.0 1.0 150 B* D* 30 4800 II' A4.0 1.() 150 B* - 0 3400 ~ A4.01.0 150 - D* 100 3000 III R4.0 1.0 125 M D 30 4500 III~ B4.0 1.0 125 M - 0 500 B 4.0 1.0 125 - D 100 3500 IV B4.0 1.0 125 K D 20 4600 IV~ B4.0 1.0 125 K - 0 800 IVI' B4.0 l.0 125 - D 100 3500 V A4.01.0 100 M H 70 4200 V~ A 4.0 1.0 100 M - 0 300 V~ A 4.0 1.0 100 - H 100 3400 VI A4'n ~ 5 100 B D 80 3000 VI~ A4.0 0.5 100 B - 0 400 VII' A4. 0~5 100 - D 100 2500 VII B4.0 1.0 100 C D 40 6400 VII' B4.0 1.0 100 C - 0 600 VII" B 4.0 1.0 100 - D100 4000 VIII C 5.2 1.3 125 C D 30 1600 VIII~ C 5.2 1.3 125 C - 0 600 VIII" C 5.2 1.3 125 - D100 250 IX D 2.0 0.5 150 M D 40 1100 IX~ D 2.0 0.5 150 M - 0 500 IX~' D 2.0 0.5 150 - D100 600 X E 1.9 0.5 150 M D 50 3600 X' E 1.9 0.5 150 M - 0 1200 X~' E 1.9 0.5 150 - D100 2300 XI D 2.0 0,5 100 B D 40 2000 XI' D 2.0 0.5 100 B - 0 600 XI" D 2.0 0.5 100 - D100 1301~
XII E 1.9 0.5 100 B D 50 4500 XII' E 1.9 0.5 100 B - 0 1350 XII" E 1.9 0.5 100 - D100 4000 XIII A 4.0 1.0 100 A D 50 5000 XIII' A 4.0 1.0 100 A - 0 2500 XIII" A 4.0 1,0 100 - D100 3900 XNr D 2.0 0.5 100 A D70 1500 XIV' D 2.0 0.5 100 A - 0 400 XIV~' D 2.0 0.5 100 - D 100 1300 XV A 4.0 .5 150 B* D*40 2400 XV~ A 4.0 0.~ 150 B* - 0 400 XV" A 4,0 0,5 150 - D*1001600 A A 4.0 0.5 150 A H40 1200 A' A 4.0 0.5 150 A - 0 80G
A" A 4.0 .5 150 - H100 1800 B A 4.0 1.0 150 D* B~70 3300 B' A 4,0 1.0 150 D* - 0 3000 B" A 4.0 1,0 150 - B~1003400 C A 4.0 0.5 150 D M50 1000 C' A 4.0 0.5 150 D - 0 1600 C" A 4.0 0.5 150 ~ M100 400 D A 4.0 1.0 75 C H50 250 D' A 4.0 1.0 75 C - 0 200 D" A 4.0 1.0 75 - H100 300 _______________________________________________________________________ ~0~0370 Of the experiments stated in Table B, only experiments I-XV are desulphurization experiments according to the invention. The remaining experiments have been incorporated in the Table for the purpose of comparison.
In the experiments I-XV, catalyst combinations were used of which each catalyst satisfied the requirements made in respect of porosity and particle size; in these experiments the requirements made in respect of "~vol.
o~ catalyst II" were also satisfied~ When the life of each o~ the catalyst combinations used in the experiments I-~V stated in the final column of Table II is compared with the life of the individual catalysts used in the relevant experiments I'-XV' and I"-XV", the improvement in catalyst life which is achieved by usin~ the catalyst i5 combinations of the invention is clearly demonstrated.
The experiments A-D, A'-D' and A"-D" have also been incorporated in table B for the purpose of comparison.
Although a combination of two catalysts was used in the experiments A-D, it did not satisfy the requirements set. In the experiments A, B and C a catalyst was used as catalyst I of which the quotient p/(d)0 9 was too small, in experiment D a catalyst was used as catalyst II of which the quotient p/(d)'9 was too large. I~hen the life of each of the catalyst combinations used in ~5 the experiments A-D and stated in the final column of table B is compared with the life of the individual - 27 - iO~?370 catalysts used in the relevant experiments A'-D' and A"-D", it is found that although applicationof these catalyst combinations produces an improvement in catalyst life in respect of individual application of one of the two catalysts of the combination, it produces a loss in catalyst life in respect of separate application of the other catalyst of the combination.
When the life of the catalyst combinations used in the experiments I and II and stated in the final ~0 column of table B is compared with that of the catalyst combinations used in the experiments C and B, respectively the large influence of the sequence in which catalyst I and catalyst II are used is clearly demonstrated.
The metal loads of most commercial catalysts which contain the cobalt/molybdenum metal combination supported on alumina or silica-alumina as carrier and which are recommended for the treatment of hydrocarbons with hydrogen as a rule amount to approx. 15 parts by weight of metal per 100 parts by weight of carrier.
In the experimental work upon which the aforesaid Canadian Patent Application and British Patent Specifi-cation are based, which applications refer to the relationship between porosity and particle size of catalysts and the hydrogen partial pressures used on the one hand, and the suitability of these catalysts for hydro-desulphurization of vanadium- and nickel-containing residual hydrocarbon oils without catalyst replenishment on the other, it was assumed that also for this application the above metal load produces the most attractive results. As can be seen from the examples of these patent applications, the metal load of the cobalt-molybdenum catalyst is only varied between 13.3 and 16.1 parts by weight per 100 parts by weight of carrier. Continued research has now shown that the metal load of these catalysts can be greatly reduced without impairing their suitability ~;06037~
for the desulphurization of residual hydrocarbon oils.
Thus, for example, it was found that a catalyst which contained 2.0 psrts by weight of cobalt and 5.5 parts by weight of molybdenum per lOO parts by weight of alumina possessed the same excellent suitability for the desulphurization of residual hydrocarbon oils as a catalyst which contained 4.3 psrts by weight of cobalt and 10.9 parts by weight of molyW enum per 100 parts by weight of alumina, p, d and PH remaining the same. The discovery of the fact that a lower metal load can be used than had been assumed until recently is of course very important with a view to the cost of catalyst preparation. A lower metal load saves metals and may result in a simplification in the catalyst preparation. If use is made in the process according to the invention of a catalyst which contains cobalt and molyW enum supported on alumina or silica-alumina as a carrier, it is preferred, in view of the above, to select a catalyst which contains 5-10 parts by weight of metal per lQ0 parts by weight of carrier.
This preference for a low metal load of course also applies if in the process according to the aforesaid Canadian Patent Application and British Patent Specification a catalyst is used which contains cobalt and molybdenum supported on alumina or silica-alumina.
~OfàO370 The catalysts which are applicable according to the invention may be prepared by supporting the relevant metals on a carrier having such a specific average pore diameter that after the metals have been supported thereon, a catalyst is obtained which satisfies the requirements of the invention, either as such or after the specific average particle diameter has been increased or reduced. The catalysts which are applicable according to th0 invention are preferably prepared by co-impregnat-ing a carrier in one or more steps with an aqueous solution containing one or more nickel and/or tungsten compounds, followed by drying and calcining of the com-position.
For information on methods which can be used to influence the porosity of the carrier material of the catalyst and for further particulars of preferred methods of preparation for the present catalysts, reference is made to the aforesaid Canadian Patent Application and British Patent Specification, wherein th0se subjects are discussed in detail.
The catalytic hydrodesulphurization of residual hydrocarbon oils without catalyst replenishment is preferably carried out by passing the hydrocarbon oil at elevated temperature and pressure and in the presence of hydrogen in an upward, downward or radial direction through two or more vertically arranged 1~0370 fixed catalyst beds. The hydrocarbon oil to be desulphurizedmay be completely or partly saturated with hydrogen and a hydrogen-containing gaseous phase may be present in the reactor in addition to the hydrocarbon phase and the catalyst phase.
The hydrodesulphurization according to the invention may be carried out in one single reactor or in two or more reactors. If the process according to the invention is carried out in one reactor, it should ~0 at least contain two catalyst beds, the first catalyst bed of which (viewed in the direction of the liquid flow) and possibly one or more immediately subsequent beds contain a catalyst or combination of catalysts designated hereinbefore as catalyst I and the final catalyst bed (viewed in the direction of the liquid flow) and possibly one or more immediately preceding beds contain a catalyst designated hereinbefore as catalyst II. If the process according to the invention is carried out in two or more reactors, the first reactor and possibly one or more immediately subsequent reactors should contain catalyst I and the final reactor and possibly one or more immediately preceding reactors should contain catalyst II. The catalysts which are applied in the individual catalyst beds and~or individual reactors may difrer from each other as regards their chemical composition.
:~060370 The specific average particle diameter of the catalysts which are used according to the invention is as a rule 0.5-2.5 mm and preferably 0.6-2.0 mm. If the value d which is required according to the invention to achieve a good catalyst performance at a given p and P~l is too small for practical application, the desulphuri-zation may be carried out in the presence of porous agglomerates prepared from the small catalyst particles in a manner as described in the aforesaid Canadian Patent Application and British Patent Specification.
The reaction conditions used in the hydro-desulphurization according to the invention may vary between wide limits. The hydrodesulphurization is preferably car-ried out at a temperature between 300G and 475C, a hydro-gen partial pressure of 5Q-200 bar, a space velocity of Q.l-10 parts by weight of fresh feed per part by vol~me of catalyst per hour and a hydrogen/feed ratio of 150 -2000 Nl of H2/kg of feed. Special preference is given to a temperature of 350C-445C, a hydrogen partial pressure 2n of 70-1~0 bar, a space velocity of 0.2-5 parts by weight of fresh feed per part by volume of catalyst per hour and a hydrogen/feed ratio of 250-1000 Nl of ~l2/kg of feed.
The hydrodesulphurization according to the inven-tion may very suitably be preceded by a demetallization (3370 treatment. As a result of the demetallization the deactivation of the desulphurization catalyst combination is suppressed and its life is consequently prolonged.
The demetalliaation of residual hydrocarbon oils is preferably carried out in the presence of hydrogen and a catalyst. Demetallization may very suitably be effected by passing the hydrocarbon oil at elevated temperature and pressure and in the presence of hydrogen in an upward, downward or radial direction through one or more vertically arranged reactors which cvntain a fixed or moving catalyst bed. In a very attractive embodiment of the demetallization, the hydrocarbon oil is passed through a vertically arranged catalyst bed into which, during operation, fresh catalyst is intermittently introduced at the top of the bed and spent catalyst is withdrawn from the lower part thereof (demetallization according to the bunker flow principle).
In another very attractive embodiment of the demetallization treatment several reactors containing a fixed catalyst 2~ bed are present, which reactors are alternately used for the demetallization treatment. ~lile demetallization is carried out in one or more of these reactors, the catalyst is replenished in the remaining reactors ~demetallization according to the fixed bed swing ~5 principle). If desired, demetallization can also l(N~0370 be carried out by suspending the catalyst in the hydrocarbon oil to be demetallized (demetallization accordinF
to the slurry phase principle). Suitable catalysts for the demetallization of residual hydrocarbon oils are catalysts which contain one or more metals havin~
hydrogenating activity, supported on a carrier.
If the desulphurization according to the invention is preceded by a demetallization treatment, the demetallization i3 pre~erably carried out according to the bunker ~0 flow principle or according to the fixed bed swing principle and the desulphurization is effected over two or more conventional fixed catalyst beds.
As has been noted above, the demetallization of a vanadium- and nickel-containing residual hydrocarbon oil results in a prolonged life of the catalyst combination which is used for the hydrodesulphurization of the demetallized oil. For the catalytic hydrodemetallization of a vanadium- and nickel-containing residual hydrocarbon oil followed by desulphurization of the demetallized oil according to the present invention, applicant has derived the following equation:
M2 = (l,n5+0,20)xMlx(Ll/L2)0'5, wherein M1 and M2 represent t.he metal contents of the non-demetallized and the demetallized oil respectively and L1 and L2 represent the lives of the desulphurization catalyst combination when used for the non-demetallized and the demetallized oil respectively. In drawing up this equation the following limitations have been taken into account:
(1) The metal content of the hydrocarbon oil before demetallization (M1) may vary between 25 and 1500 ppmw (parts by weight per million).
(2) The life of the desulphurization catalyst combination used for the demetallized oil (L2) may vary between 2000 and 16,000 hours.
~3) The quotient of the metal contents of the hydrocarbon oil after and before demetallization (M2 and M1) may vary between 0.75 and 0.10 and (4) the product of the metal content of the hydrocarbon oilbefore demetallization (M1) and the life of the desulphurization catalyst combination used for the demetallized oil (L2) may vary between 2 x 105 and 3 x 106.
The abovementioned relationship between L1, L2, Ml and M2 offers the possibility, during the hydrodesulphurizatio~
Or a residual hydrocarbon oil according to the present invention, using prior catalytic hydrodemetallization ,Or the feed, to establishto what value the metal content of the feed has to be reduced in order to prolong the life of the desulphurization catalyst combination by a certain number of hours.
`` 1(~0~70 Examples of reeds to which the process accordin~
to the invention can be applied are crude oils and residues obtained by distillation of crude oils at atmospheric or reduced pressure. Residues obtained durin~ the distillation of products originating from thermal or catalytic cracking of heavy hydrocarbon oils may also be treated in accordance with the invention.
The invention will now be elucidated with reference to the following Example.
EXAMPLE
Eleven combinations of two different catalysts as well as each of these catalysts separately (catalysts A-M) were used for the hydrodesulphurization of five vanadium- and nickel-containing residual hydrocarbon oils (oils A-E) without catalyst replenishment. Desulphurization o~ the oils was effected by passin~ these oils at elevated temperature and pressure and in the presence of hydrogen in a downward direction through two cylindrical ~ixed catalysts beds.
The experiments were carried out in series of three. Per series of three experiments the same oil was desulphurized under the same conditions and with the same volume of catalyst to the same sulphur content in the product (Sp). In one of the three experiments the first catalyst bed contained the catalyst referred to below as catalyst I and the second bed the catalyst 10f~037o referred to below as catalyst II. In the two remaining experiments both catalyst beds contained either exclusively catalyst I or exclusively catalyst II.
The de~ulphurization experiments were carried out at an initial temperature of 360 +5C, a space velocity of 0.7 kg.l 1.h l, a ~as velocity Or 600 Nl o~ H2/k~ l and a hydrogen partial pressure varyinE
rrOm 75 to 150 bar. To prepare a product havin~ a constant sulphur content the temperature had to be gradually increased during the experiments. The desulphurization experiments were terminated at the moment when a temperature in excess of 420C had to be used in order to prepare a product with the desired sulphur content.
The composition and properties o~ the catalysts, which were used in the form Or their sulphides, are stated in Table A. For information on the preparation Or the nine catalysts used in the present experiments C~
D reference is made to the examples of our Metherlends patent application 7 ~4397, wherein the preparation o~ these catalysts has been described in detail. The preparation Or the catalysts B* and D* was ef~ected in the same manner as described for the catalysts B and D~ with the proviso that a lower metal load was used in the preparation of the catalyst B* and D~. ~he rive residual oils involved in the investi~ation ~iO3'70 are described in greater detail below. The results of the desulphurization experiments are stated in Table B.
OIL A
Oil having a total vanadium and nickel content of 75 ppmw and a sulphur content of 4.0% by weight, obtained as residue in the distillation at atmospheric pressure of a Middle East crude oil.
OIL B
~0 Oil having a total vanadium and nickel content of 64 ppmw and a sulphur content of 4.0% by weight, obtained as residue in the distillation at atmospheric pressure of a Middle East crude oil.
OIL C
Oil having a total vanadium and nickel content of 110 ppmw and a sulphur content of 5.2% by weight, obtained as residue in the distillation at reduced pressure of an atmospheric distillation residue of a Middle East crude oil.
OIL _ Oil having a total vanadium and nickel content o~ 225 ppmw and a sulphur content of 2.0% by weight, obtained as residue in the distillation at atmospheric pressure of a Caribbean crude.
~0~0370 OIL E
Oil having a total vanadium and nickel content of 130 ppmw and a sulphur content of 1.9% by weight, obtained by demetallization of oil D. The demetallization of oil D was carried out by passing it at elevated temperature and pressure and in the presence of hydrogen in a downward direction through a vertically arranged fixed bed of a demetallization catalyst. The demetallization catalyst contained 0.5 parts by weight of nickel and 2~0 parts by weight of vanadium per 100 parts by weight of silica carrier.
~()60370 E; I . . . . . . . . . , C) o ~ CO ~ ~ ~ ~ ~D O ~
S:: ~ . . . . I
d) U~ ~ I I
~ ~ I ~ o ~1 ~ o ~o ~ ao ~ I
O ~ O I
O O S~
~p.~
~ ~ ~ , ~ o ~ x t ~o ~ a~ ~ ~ ~ u~ o ~
P.S
O O
O ~ ~ X ~ ~ ~ ~ o o ~
o o ~ rl o v ~ l l CC C~ bO I N ~ O1~1~ 0 ~D CJ~ ~ I
O~ h ~ ~ I o ~ D ~ o ocu ~~ 3 S~J ~~, ~, ~ ~, .D
E~
~ o a~ X X I ~ c~ ~ ~ ~ r--r~
OO~O~IOOOOOOOOO
h ~1~ 1 o o o c; o o o o o o 0~
IOOOOOOOOO
5-1 I N N (~
~ I ¢ ": '1: ~ 'C '5 ~: ~ ¢
C~ I I
o c) o O
~01 ~d~~ I I I I I I I . . . I
I
~ ICl m m ~
o ~z - 25 ~ 03~70 Table B
Exp. Jil SF~ Sp, PH , Cat.I Cat.II, %v Life of the No. No. 2 No. No.Cat.II c~t. or cat.
%w %w bar combination, hours _______________ ______ _____ ~____ _______ ______ ____________ I A4.00.5 150 M D 50 2400 I' A 4.0 0.5 15C M - 0 400 I~ A 4.0 0.5 150 - D 100 1600 II A 4.0 1.0 150 B* D* 30 4800 II' A4.0 1.() 150 B* - 0 3400 ~ A4.01.0 150 - D* 100 3000 III R4.0 1.0 125 M D 30 4500 III~ B4.0 1.0 125 M - 0 500 B 4.0 1.0 125 - D 100 3500 IV B4.0 1.0 125 K D 20 4600 IV~ B4.0 1.0 125 K - 0 800 IVI' B4.0 l.0 125 - D 100 3500 V A4.01.0 100 M H 70 4200 V~ A 4.0 1.0 100 M - 0 300 V~ A 4.0 1.0 100 - H 100 3400 VI A4'n ~ 5 100 B D 80 3000 VI~ A4.0 0.5 100 B - 0 400 VII' A4. 0~5 100 - D 100 2500 VII B4.0 1.0 100 C D 40 6400 VII' B4.0 1.0 100 C - 0 600 VII" B 4.0 1.0 100 - D100 4000 VIII C 5.2 1.3 125 C D 30 1600 VIII~ C 5.2 1.3 125 C - 0 600 VIII" C 5.2 1.3 125 - D100 250 IX D 2.0 0.5 150 M D 40 1100 IX~ D 2.0 0.5 150 M - 0 500 IX~' D 2.0 0.5 150 - D100 600 X E 1.9 0.5 150 M D 50 3600 X' E 1.9 0.5 150 M - 0 1200 X~' E 1.9 0.5 150 - D100 2300 XI D 2.0 0,5 100 B D 40 2000 XI' D 2.0 0.5 100 B - 0 600 XI" D 2.0 0.5 100 - D100 1301~
XII E 1.9 0.5 100 B D 50 4500 XII' E 1.9 0.5 100 B - 0 1350 XII" E 1.9 0.5 100 - D100 4000 XIII A 4.0 1.0 100 A D 50 5000 XIII' A 4.0 1.0 100 A - 0 2500 XIII" A 4.0 1,0 100 - D100 3900 XNr D 2.0 0.5 100 A D70 1500 XIV' D 2.0 0.5 100 A - 0 400 XIV~' D 2.0 0.5 100 - D 100 1300 XV A 4.0 .5 150 B* D*40 2400 XV~ A 4.0 0.~ 150 B* - 0 400 XV" A 4,0 0,5 150 - D*1001600 A A 4.0 0.5 150 A H40 1200 A' A 4.0 0.5 150 A - 0 80G
A" A 4.0 .5 150 - H100 1800 B A 4.0 1.0 150 D* B~70 3300 B' A 4,0 1.0 150 D* - 0 3000 B" A 4.0 1,0 150 - B~1003400 C A 4.0 0.5 150 D M50 1000 C' A 4.0 0.5 150 D - 0 1600 C" A 4.0 0.5 150 ~ M100 400 D A 4.0 1.0 75 C H50 250 D' A 4.0 1.0 75 C - 0 200 D" A 4.0 1.0 75 - H100 300 _______________________________________________________________________ ~0~0370 Of the experiments stated in Table B, only experiments I-XV are desulphurization experiments according to the invention. The remaining experiments have been incorporated in the Table for the purpose of comparison.
In the experiments I-XV, catalyst combinations were used of which each catalyst satisfied the requirements made in respect of porosity and particle size; in these experiments the requirements made in respect of "~vol.
o~ catalyst II" were also satisfied~ When the life of each o~ the catalyst combinations used in the experiments I-~V stated in the final column of Table II is compared with the life of the individual catalysts used in the relevant experiments I'-XV' and I"-XV", the improvement in catalyst life which is achieved by usin~ the catalyst i5 combinations of the invention is clearly demonstrated.
The experiments A-D, A'-D' and A"-D" have also been incorporated in table B for the purpose of comparison.
Although a combination of two catalysts was used in the experiments A-D, it did not satisfy the requirements set. In the experiments A, B and C a catalyst was used as catalyst I of which the quotient p/(d)0 9 was too small, in experiment D a catalyst was used as catalyst II of which the quotient p/(d)'9 was too large. I~hen the life of each of the catalyst combinations used in ~5 the experiments A-D and stated in the final column of table B is compared with the life of the individual - 27 - iO~?370 catalysts used in the relevant experiments A'-D' and A"-D", it is found that although applicationof these catalyst combinations produces an improvement in catalyst life in respect of individual application of one of the two catalysts of the combination, it produces a loss in catalyst life in respect of separate application of the other catalyst of the combination.
When the life of the catalyst combinations used in the experiments I and II and stated in the final ~0 column of table B is compared with that of the catalyst combinations used in the experiments C and B, respectively the large influence of the sequence in which catalyst I and catalyst II are used is clearly demonstrated.
Claims (20)
1. A process for the catalytic hydrodesulphurization of vanadium- and nickel-containing residual hydrocarbon oils without catalyst replenishment, in which the hydrocarbon oil is consecutively contacted with a catalyst I and a catalyst II which satisfy the following requirements:
(a) each of the individual catalysts of which the combination of catalyst I and catalyst II is composed has a total pore volume in excess of 0.30 ml/g of which less than 10% is present in pores having a diameter in excess of 100 nm, (b) catalyst II has a specific average pore diameter (p) and a specific average particlediameter (d) such that the quotient p/(d)0.9 of catalyst II
satisfies the requirement:
(e) if the combination of catalyst I and catalyst II
is composed of two catalysts, catalyst I has a p and d such that the quotient p/(d)0.9 of catalyst I satisfies the requirement:
while if the combination of catalyst I and catalyst II is composed of more than two catalysts, the above requirement in respect of cat.I
applies to the average p/(d)0.9 of catalyst I
which is determined as the weight average of the values of p/(d)0.9 of each of the individual catalysts of which catalyst I is composed, (d) the percentage of the total catalyst volume which is taken up by catalyst II (%vol. of catalyst II) is between 10 and 90% and satisfies the requirement:
wherein SF represents the sulphur content of the feed and Sp the required sulphur content of the desulphurized product, and (e) if the combination of catalyst I and catalyst II is composed of more than two catalysts, each of the individual catalysts of which catalyst I is composed has a p and d such that the quotient p/(d)0.9 of each of these catalystsis greater than [p/(d)0.9]cat II[p in nm, d in mm, PH2 in bar, Sp and SF in percentage by weight).
(a) each of the individual catalysts of which the combination of catalyst I and catalyst II is composed has a total pore volume in excess of 0.30 ml/g of which less than 10% is present in pores having a diameter in excess of 100 nm, (b) catalyst II has a specific average pore diameter (p) and a specific average particlediameter (d) such that the quotient p/(d)0.9 of catalyst II
satisfies the requirement:
(e) if the combination of catalyst I and catalyst II
is composed of two catalysts, catalyst I has a p and d such that the quotient p/(d)0.9 of catalyst I satisfies the requirement:
while if the combination of catalyst I and catalyst II is composed of more than two catalysts, the above requirement in respect of cat.I
applies to the average p/(d)0.9 of catalyst I
which is determined as the weight average of the values of p/(d)0.9 of each of the individual catalysts of which catalyst I is composed, (d) the percentage of the total catalyst volume which is taken up by catalyst II (%vol. of catalyst II) is between 10 and 90% and satisfies the requirement:
wherein SF represents the sulphur content of the feed and Sp the required sulphur content of the desulphurized product, and (e) if the combination of catalyst I and catalyst II is composed of more than two catalysts, each of the individual catalysts of which catalyst I is composed has a p and d such that the quotient p/(d)0.9 of each of these catalystsis greater than [p/(d)0.9]cat II[p in nm, d in mm, PH2 in bar, Sp and SF in percentage by weight).
2. A process as claimed in claim 1, in which catalyst II has a total pore volume in excess of 0.45 ml/g.
3. A process as claimed in claim 2, in which catalyst II has a surface in excess of 150 m2/g.
4. A process as claimed in claim 3, in which catalyst II has a p and d such that the quotient [p/(d)0.9]cat II satisfies the requirement:
[p/(d)0.9]cat.II?10-4x(PH2)2.
[p/(d)0.9]cat.II?10-4x(PH2)2.
5. A process as claimed in claim 4, in which catalyst II has a total pore volume in excess of 0.45 ml/g of which at least 0.4 ml/g is present in pores having a diameter of at least 0.7xp and at most 1.7xp and a sharp pore diameter distribution, characterized in that (a) less than 20% of the pore volume is present in pores having a diameter smaller than 0.7xp (b) less than 20% of the pore volume is present in pores having a diameter greater than 1.7xp.
6. A process as claimed in claim 5, which process is carried out using one single catalyst as catalyst I.
7. A process as claimed in claim 6, in which the catalyst used as catalyst I has a total pore volume in excess of 0.40 ml/g.
8. A process as claimed in claim 6 or 7, in which the catalyst used as catalyst I has a p and d such that the quotient [p/(d)0.9]cat.I satisfies the requirement: [p/(d)0.9]cat.I?1.4x[p/(d)0.9]cat.II.
9. A process as claimed in any one of claims 1, 4 or 5 which process is carried out using a combination of two or more catalysts as catalyst I, which catalysts occur in the reactor separated from each other and in such a sequence that the quotient p/(d)0.9 of each of the catalysts of which catalyst I is composed is smaller than that of the preceding catalyst.
10. A process as claimed in any one of claims 1, 4 or 5 which process is carried out using a combination of two or more catalysts as catalyst I, which catalysts have a total pore volume in excess of 0.40 ml/g.
11. A process as claimed in claim 5, which process is carried out using a combination of two or more catalysts as catalyst I, which catalysts have a p and d such that the average p/(d)0.9 of catalyst I, which is determined as the weight average of the values of p/(d)0.9 of the individual catalysts of which catalyst I is composed, is at least 1.4x[p/(d)0.9]cat.II.
12. A process as claimed in claim 11, in which catalysts are used which contain 0.5-10 parts by weight of nickel, cobalt or a mixture thereof and 2.5-30 parts by weight of molybdenum, tungsten or a mixture thereof per 100 parts by weight of carrier.
13. A process as claimed in claim 12, in which catalysts are used wherein the atomic ratio between nickel, cobalt or a mixture thereof on the one hand and molybdenum, tungsten or a mixture thereof on the other, is between 0.1 and 5.
14. A process as claimed in claim 13, in which the catalysts are used in sulphidic form.
15. A process as claimed in claim 14, in which the catalysts contain alumina, or silica-alumina as carrier.
16. A process as claimed in claim 15, in which catalysts are used which contain the cobalt-molybdenum metal combination supported on alumina or silica-alumina as carrier and which contain 5-10 parts by weight of metal per 100 parts by weight of carrier.
17. A process as claimed in claim 16, in which catalysts are used which have been prepared by co-impregnating a carrier in one or more steps with an aqueous solution containing one or more compounds of nickel, tungsten or a mixture thereof, followed by drying and calcining of the composition.
18. A process as claimed in claim 17, in which the catalysts have a specific average particle diameter of 0.6-2.0 mm.
19. A process as claimed in claim 18, which process is carried out by passing the hydrocarbon oil to be desulphurized at elevated temperature and pressure and in the presence of hydrogen in an upward, downward or radial direction through two or more vertically arranged fixed catalyst beds, the hydrocarbon oil first coming into contact with one or more catalyst beds which contain catalyst I and subsequently with one or more catalyst beds which contain catalyst II.
20. A process as claimed in claim 19, which process is carried out at a temperature between 350°C and 445°C, a hydrogen partial pressure of 70-180 bar, a space velocity of 0.2-5 parts by weight of fresh feed per part by volume of catalyst per hour and a hydrogen/feed ratio of 250-1000 Nl of H2/kg of feed.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NLAANVRAGE7404948,A NL187641C (en) | 1974-04-11 | 1974-04-11 | PROCESS FOR CATALYTIC HYDROGENIZING DESULFULIFYING WITHOUT CATALYST REPLACEMENT OF RESIDUAL HYDROCARBON OILS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1060370A true CA1060370A (en) | 1979-08-14 |
Family
ID=19821155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA220,643A Expired CA1060370A (en) | 1974-04-11 | 1975-02-24 | Process for the conversion of hydrocarbons |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS6027714B2 (en) |
| BE (1) | BE827492A (en) |
| CA (1) | CA1060370A (en) |
| DE (1) | DE2512294A1 (en) |
| DK (1) | DK129375A (en) |
| ES (1) | ES435948A1 (en) |
| FR (1) | FR2267359B1 (en) |
| GB (1) | GB1504586A (en) |
| IT (1) | IT1034407B (en) |
| NL (1) | NL187641C (en) |
| NO (1) | NO144424C (en) |
| SE (1) | SE408431B (en) |
| ZA (1) | ZA751655B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11136513B2 (en) | 2017-02-12 | 2021-10-05 | Magëmä Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| US11203722B2 (en) | 2017-02-12 | 2021-12-21 | Magëmä Technology LLC | Multi-stage process and device for treatment heavy marine fuel oil and resultant composition including ultrasound promoted desulfurization |
| US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
| US12025435B2 (en) | 2017-02-12 | 2024-07-02 | Magēmã Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US12071592B2 (en) | 2017-02-12 | 2024-08-27 | Magēmā Technology LLC | Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6215231U (en) * | 1985-07-11 | 1987-01-29 | ||
| JPH0311812U (en) * | 1989-06-21 | 1991-02-06 | ||
| US5492684A (en) * | 1993-07-06 | 1996-02-20 | Mobil Oil Corporation | Graded-bed system for improved separations |
| JP3802106B2 (en) | 1995-06-08 | 2006-07-26 | 日本ケッチェン株式会社 | Hydrocarbon oil hydrotreating catalyst, production method thereof and activation method thereof |
-
1974
- 1974-04-11 NL NLAANVRAGE7404948,A patent/NL187641C/en not_active IP Right Cessation
-
1975
- 1975-02-24 CA CA220,643A patent/CA1060370A/en not_active Expired
- 1975-03-13 GB GB10508/75A patent/GB1504586A/en not_active Expired
- 1975-03-13 NO NO750853A patent/NO144424C/en unknown
- 1975-03-14 SE SE7502921A patent/SE408431B/en not_active IP Right Cessation
- 1975-03-18 IT IT21422/75A patent/IT1034407B/en active
- 1975-03-18 ZA ZA00751655A patent/ZA751655B/en unknown
- 1975-03-20 DE DE19752512294 patent/DE2512294A1/en active Granted
- 1975-03-24 ES ES435948A patent/ES435948A1/en not_active Expired
- 1975-03-26 DK DK129375A patent/DK129375A/da not_active IP Right Cessation
- 1975-03-26 FR FR7509481A patent/FR2267359B1/fr not_active Expired
- 1975-04-02 JP JP50039308A patent/JPS6027714B2/en not_active Expired
- 1975-04-03 BE BE1006570A patent/BE827492A/en unknown
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11136513B2 (en) | 2017-02-12 | 2021-10-05 | Magëmä Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| US11203722B2 (en) | 2017-02-12 | 2021-12-21 | Magëmä Technology LLC | Multi-stage process and device for treatment heavy marine fuel oil and resultant composition including ultrasound promoted desulfurization |
| US11345863B2 (en) | 2017-02-12 | 2022-05-31 | Magema Technology, Llc | Heavy marine fuel oil composition |
| US11441084B2 (en) | 2017-02-12 | 2022-09-13 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US11447706B2 (en) | 2017-02-12 | 2022-09-20 | Magēmā Technology LLC | Heavy marine fuel compositions |
| US11492559B2 (en) | 2017-02-12 | 2022-11-08 | Magema Technology, Llc | Process and device for reducing environmental contaminates in heavy marine fuel oil |
| US11530360B2 (en) | 2017-02-12 | 2022-12-20 | Magēmā Technology LLC | Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit |
| US11560520B2 (en) | 2017-02-12 | 2023-01-24 | Magēmā Technology LLC | Multi-stage process and device for treatment heavy marine fuel oil and resultant composition and the removal of detrimental solids |
| US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
| US11795406B2 (en) | 2017-02-12 | 2023-10-24 | Magemä Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| US11884883B2 (en) | 2017-02-12 | 2024-01-30 | MagêmãTechnology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US11912945B2 (en) | 2017-02-12 | 2024-02-27 | Magēmā Technology LLC | Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit |
| US12025435B2 (en) | 2017-02-12 | 2024-07-02 | Magēmã Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US12071592B2 (en) | 2017-02-12 | 2024-08-27 | Magēmā Technology LLC | Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil |
Also Published As
| Publication number | Publication date |
|---|---|
| NO144424B (en) | 1981-05-18 |
| DE2512294C2 (en) | 1987-08-27 |
| JPS50136302A (en) | 1975-10-29 |
| FR2267359B1 (en) | 1982-03-19 |
| ES435948A1 (en) | 1976-12-16 |
| AU7921175A (en) | 1976-09-23 |
| DK129375A (en) | 1975-10-12 |
| FR2267359A1 (en) | 1975-11-07 |
| IT1034407B (en) | 1979-09-10 |
| NO144424C (en) | 1981-08-26 |
| DE2512294A1 (en) | 1975-10-23 |
| JPS6027714B2 (en) | 1985-07-01 |
| SE408431B (en) | 1979-06-11 |
| SE7502921L (en) | 1975-10-13 |
| NL7404948A (en) | 1975-10-14 |
| ZA751655B (en) | 1976-02-25 |
| BE827492A (en) | 1975-10-03 |
| NL187641C (en) | 1991-12-02 |
| GB1504586A (en) | 1978-03-22 |
| NO750853L (en) | 1975-10-14 |
| NL187641B (en) | 1991-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5389595A (en) | Hydroprocessing catalyst, its use, and method of preparation | |
| US4886594A (en) | Hydrotreating catalyst and process | |
| US4066574A (en) | Hydrocarbon hydrotreating catalyst composition | |
| US4016067A (en) | Process for demetalation and desulfurization of petroleum oils | |
| US4374020A (en) | Catalytic hydroconversion process with catalyst retainer | |
| US4549957A (en) | Hydrotreating catalyst and process | |
| CA1249541A (en) | Single-stage hydrotreating process | |
| US4404097A (en) | Residua demetalation/desulfurization catalyst and methods for its use | |
| US5514274A (en) | Process for the use of a phosphorus-containing hydroprocessing catalyst | |
| EP0464931A1 (en) | Aromatics saturation process for diesel boiling-range hydrocarbons | |
| US4454026A (en) | Hydrotreating catalyst and process | |
| CA1060370A (en) | Process for the conversion of hydrocarbons | |
| CA1187468A (en) | Hydrotreating catalyst and process | |
| US4776945A (en) | Single-stage hydrotreating process | |
| CA2190392A1 (en) | Stacked bed catalyst system for deep hydrosulfurization | |
| CA1071561A (en) | Process for the conversion of hydrocarbons | |
| EP0203228B1 (en) | Single-stage hydrotreating process | |
| CA1074717A (en) | Process for the desulphurization of hydrocarbon oils | |
| GB1560599A (en) | Process for demetallizing hydrocarbon oils | |
| EP0024199B1 (en) | Catalyst having low volume of large pores and hydrocarbon hydroconversion process using same | |
| EP0159097B1 (en) | Process for the catalytic conversion of heavy hydrocarbon oils | |
| EP0112667B1 (en) | Hydrotreating catalyst and process | |
| SE461336B (en) | PROCEDURES FOR DEMETALIZATION AND HYDROOM CONVERSION OF METAL containing hydrocarbon feed oils REFERRED TO SYNTHETIC CATALYSTER INTENDED TO BE USED IN THE PROCEDURE | |
| CA1038789A (en) | Hydrocarbon conversion process | |
| CA1295964C (en) | Process for the catalytic conversion of hydrocarbon oils |