CA1081151A - Process for the conversion of hydrocarbons - Google Patents
Process for the conversion of hydrocarbonsInfo
- Publication number
- CA1081151A CA1081151A CA223,008A CA223008A CA1081151A CA 1081151 A CA1081151 A CA 1081151A CA 223008 A CA223008 A CA 223008A CA 1081151 A CA1081151 A CA 1081151A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- larger
- catalysts
- desulphurization
- volume
- 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
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 128
- 239000003921 oil Substances 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical group CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B01J35/60—
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- B01J35/651—
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
Improved process for the hydrodesulphurization of vanadium and nickel-containing residual hydrocarbon oils by contacting the oils successively with two different catalysts each of which has a porosity and particle size within specified ranges depending on the porosity of the other catalyst in the combination and on the applied hydrogen partial pressure and that the catalysts are applied in a given volume ratio.
The improvement consists in the fact that the desulphurization is preceded by a hydrodemetallization over a catalyst having a porosity and particle size within specified limits depending among others on the porosity and particle size of the first desulphurization catalyst.
Improved process for the hydrodesulphurization of vanadium and nickel-containing residual hydrocarbon oils by contacting the oils successively with two different catalysts each of which has a porosity and particle size within specified ranges depending on the porosity of the other catalyst in the combination and on the applied hydrogen partial pressure and that the catalysts are applied in a given volume ratio.
The improvement consists in the fact that the desulphurization is preceded by a hydrodemetallization over a catalyst having a porosity and particle size within specified limits depending among others on the porosity and particle size of the first desulphurization catalyst.
Description
1~8~S~
Canadian ~atent application No. 220,643 relates to a process for the catalytic hydrode~ulphurization without catalyst replenishment cf vanadium and nickel-containine residual hydrocarbon oils. According to the ~aid Canadian patent application the desulphurization i~
carried out by contacting the oil at elevated temperature and pressure and in the presence of hydrogen successively with two different catalyst~, each of these t~o catalyst~ having a porosity and a particle size within specified limits depending on the poro~ity and particle size of the other catalyst in the combination and on the hydroeen partial pressure applied, while the two catalysts are applied in a specified v~lume ratio. As i8 shown in the said Canadian patent application, the life of 8 certain quantity by volume of such a catalyst combination in maintsining a certain desulphurization level is longer than that of an equal quantity by volume of either of the catalyst~ applied separately. It was already observed in the said Canadian patent application that the deactivation of the desulphurization catalyst combination can be suppressed and consequently its life prolonged, by preceding the desulphurization by Q cata~ytic demetallization. This observation implies that, if a feed that has previously been catalytically demetallized is processed over a certain quantity by volume of the catalyst combination, the life of the catalyst combination will be loneer than when the non-demetallized feed is processed over the same qu~1tity by volume of the catalyst combination.
Therefore, upon application of a catalytic demetallization as referred to hereinbefore, the feed wiIl be contacted with a larger quantity by volume of catalyst than when no demetallization i8 applied, since in the former case, besides a specific quantity by volume of the desulphurization catalyst combination, which is the same in both cases, a certain quantity by volume of demetallization catalyst i~ used in addition.
~, :
Upon contination of the studies concerning the catalytic hydrodemetallization of vanadium and nickel-containing residual hydrocarbon oils followed by catalytic hydrodesulphurization of the demetallized oil using a combination of two desulphurization catalysts according to the said Canadian patent application, it WQS found that the life of the desulphurization catalyst combination in maintaining a certain desulp~ urization level can be considerably prolonged, while keeping the total quantity by volume of catalyst constant, when part Or the desulphurization catalyst combination is replaced by a demetallization catalyst and when, in addition, the ~ollowing requirements are met, 1) The desulphuriz~tion catalyst combination, which according to the said Canadian patent application comprises a catalyst I containing one or more catalysts and a single catalyst II, is in the present patent application tsken to comprise only two single desulphurization cstalysts, of which the rirst is indicated as catalyst I and the second as catalyst II.
Canadian ~atent application No. 220,643 relates to a process for the catalytic hydrode~ulphurization without catalyst replenishment cf vanadium and nickel-containine residual hydrocarbon oils. According to the ~aid Canadian patent application the desulphurization i~
carried out by contacting the oil at elevated temperature and pressure and in the presence of hydrogen successively with two different catalyst~, each of these t~o catalyst~ having a porosity and a particle size within specified limits depending on the poro~ity and particle size of the other catalyst in the combination and on the hydroeen partial pressure applied, while the two catalysts are applied in a specified v~lume ratio. As i8 shown in the said Canadian patent application, the life of 8 certain quantity by volume of such a catalyst combination in maintsining a certain desulphurization level is longer than that of an equal quantity by volume of either of the catalyst~ applied separately. It was already observed in the said Canadian patent application that the deactivation of the desulphurization catalyst combination can be suppressed and consequently its life prolonged, by preceding the desulphurization by Q cata~ytic demetallization. This observation implies that, if a feed that has previously been catalytically demetallized is processed over a certain quantity by volume of the catalyst combination, the life of the catalyst combination will be loneer than when the non-demetallized feed is processed over the same qu~1tity by volume of the catalyst combination.
Therefore, upon application of a catalytic demetallization as referred to hereinbefore, the feed wiIl be contacted with a larger quantity by volume of catalyst than when no demetallization i8 applied, since in the former case, besides a specific quantity by volume of the desulphurization catalyst combination, which is the same in both cases, a certain quantity by volume of demetallization catalyst i~ used in addition.
~, :
Upon contination of the studies concerning the catalytic hydrodemetallization of vanadium and nickel-containing residual hydrocarbon oils followed by catalytic hydrodesulphurization of the demetallized oil using a combination of two desulphurization catalysts according to the said Canadian patent application, it WQS found that the life of the desulphurization catalyst combination in maintaining a certain desulp~ urization level can be considerably prolonged, while keeping the total quantity by volume of catalyst constant, when part Or the desulphurization catalyst combination is replaced by a demetallization catalyst and when, in addition, the ~ollowing requirements are met, 1) The desulphuriz~tion catalyst combination, which according to the said Canadian patent application comprises a catalyst I containing one or more catalysts and a single catalyst II, is in the present patent application tsken to comprise only two single desulphurization cstalysts, of which the rirst is indicated as catalyst I and the second as catalyst II.
2) The residual hydrocarbon oil that is used as the feed has a total vanadium and nickel content above 120 ppmw.
3) The demetallization catalyst, indicated as catalyst 0, meets : the following requirements a) the catalyst comprises one or more metals having hydrogenation activity on a carrier, b) p/d>3.5-0.02 v, in which v is the percentage of the total pore volume that consists of pores with a dia-meter larger than 100 nm, c) the total pore volume is larger than 0.40 ml/g, d) the specific surface area i8 larger than 100 m /g, but in cases where the catalyst has such a p and .
- , : , , , . : :
d that the quotient p/d is larger than 3.5-0.02 v, hut at most 10-0.15 v, the catalyst has to meet the following additional requirements: e) the nitrogen pore volume is larger than 0.60 ml/g, f) the specific surface area is larger than 150 m /g, and g) p is larger than 5nm.
- , : , , , . : :
d that the quotient p/d is larger than 3.5-0.02 v, hut at most 10-0.15 v, the catalyst has to meet the following additional requirements: e) the nitrogen pore volume is larger than 0.60 ml/g, f) the specific surface area is larger than 150 m /g, and g) p is larger than 5nm.
4. Catalyst 0 has a larger total pore volu~e than catalyst I.
5. Catalyst 0 and catalyst I have such a p, d and v that the following relation is met ~ cat.o~l 2X~ ~/(d) ] cat I-~.8(vo~vI))
6. l'he percentage of the joint cata]yst volume of catalysts 0, I and II that is occupied by catalyst 0 amo-mts to at least 10 %v.
The catalytic hydrodemetallization of residual hydrocarbon oils using a catalyst which meets the requirements given hereinbefole under a) to g) is described in Canadian patent applications No.'s ]72,04n, 212,547, 212,563 and 232,027.
The present inventioll therefore relates to an improved process for the catalytic hydrodesulphurization of vanadium and nic~el containing resid-ual hydrocarbon oils having a vanadium and nic~el content above 120 ppmw utilizing a desulphurization catalyst system comprising a single catalyst I
and a single catalyst II, which catalysts meet the following requirements:
(a) both catalysts have a total pore volume larger than 0.30 ml/g of which the percentage (v) that consists of pores with a diameter larger than 100 nm is less than 10, (b) catalyst II has such a specific average pore diameter (p) and a specific average particle diameter (d) that the quotient p/(d)0 9 meets the requirement 0.6x]0 4x(P~1 )2~ p/(d)0 9 cat II~3+6xlO x(P}I ) - (c) the percentage of the joint catalyst volume of catalysts I and II that is occupied by catalyst II (~OV cat. II) lies between 10 and 90% and meets the requirement ~Ox( rS rxlnO~2x(P}I )-2~ov cat. II~300x( ~ 100)2x(PIl )-2, ~ .
lOl~llSl in which SF is the sulphur content of the feed and Sp is the desired sulphur content of the desulphurized product (p in nm, d in mm, PH in bar, Sp and SF in %w, the improvement comprising prolonging the life of the desulphur-ization catalyst system by first hydrodemetallizing said vanadium and nickel containing residual hydrocarbon oil utilizing processing parameters compatible with and substantially identical to those for said hydrode-sulphurization step so that said catalytic hydrodemetallization step and said hydrodesulphurization step are conducted sequentially and continuously and utilizing a hydrodemetallization catalyst 0, providing the requirements given hereinbefore under 3) to 6) are met.
The present invention also provides in an apparatus for the hydrocracking of residual oil having a vanadium and nickel content of at least 120 ppmw and a sulphur content of about 2% w the improvement com-prising the use of a series of catalysts in the following order from the output to the infeed of the apparatus: (1) hydrodesulphurization catalysts comprising a single catalyst I and a single catalyst II, which catalysts ~
meet the following requirements: (a) both catalysts have a total pore volume ;
larger than 0.30 ml/g of which the percentage (v) that consists of pores with a diameter larger than 100 nm is less than 10, (b) catalysts II has such a specific average pore diameter (p) and a specific average particle diameter (d) that the quotient pt(d)0'9 meets the requirement (PH2) ~ ~/(d) ~cat II~3t6X10 4X(PH )2 (c) the percentage of the joint catalyst volume of catalysts I and II that is occupied by catalyst II (%v cat.II) lies between 10 and 90% and meets the requirement 40x~ xlO0) x~PH ) ~%v cat.II~300x( ~ H2 in which SF is the sulphur content of the feed and Sp is the desired sulphur content of the desulphurized product (p in nm, d in mm, PH in bar, Sp and SF in %w.
,, ~
.
~ ~ - 5 _ 1~81151 As demetallization catalysts preference is given to the catalysts described in above-ementioned Canadian patent applications No~s 172,040, 212,547, 212,563 and 232,027.
The invention will now be elucidated with the aid of the following example, EXAMPLE
Catalysts combinations consisting of a demetallization catalyst (catalysts 1,11 and 40), a first desulphurization catalyst (catalyst A) and a second desulphurization catalyst (catalyst D) were employed for hydrode-metallization followed by hydrodesulphurization without catalyst replenish-ment of two vanadium and nickel-containing residual hydrocarbon oils (oils D
and F). Moreover, catalyst combinations consisting of the two desulphur-ization catalysts A and D and also each of these two catalysts separately were employed for the hydrodesulphurization without catalyst replenishment ~ :
of the two oils.
, - 5a -~llSl Demetallization/desulphurization or only desulphurization of the oils was carried out by passing the oils together with hydrogen downwards through three cylindrical vertically disposed fixed catalyst beds at elevated temperature and pressure.
The experiments were carried out four by four. In each set of four experiments the same oil was desulphurized under the same conditions and with the same volume Or catalyst, down to the same sulphur content in the product. (In all the experiments Sp was 0.5 %w). In one of the four experiments the first catalyst bed contained the demetallization catalyst indicated hereinarter as catalyst 0, the second catalyst bed the desulphurization catalyst indicated hereinafter as catalyst I and the third catalyst bed the desulphurization catalyst indicated hereinafter ss catalyst II. In the three remaining experiments the three catalyst beds contained either a combination of catalyst I and catalyst II
successively or catalyst I exclusively or catalyst II exclusively.
The desulphurization experiments were carried out at an initial temperature of 36015C, a space velocity of 0.7 kg.l .h , a gas rate of 600 NlH2.kg and a hydrogen partial pressure of 100 or 150 bar. For the preparation of a product having constant sulphur content the temperature had to be gradually increased during the experiments. The desulphurization experiments were ended when ~ -a temperature of 420C had to be applied to prepare a product having the desired sulphur content.
The demetallization was carried out at a constant temperature Or 420 C and a hydrogen partial pressure and eas rate correspondine with those applied in the desulphurization. In case of demetallization followed by desulphurization the space velocity throuehout the catalyst system amounted to 0.7 kg.l .h Composition and properties Or the catalysts which were ap~lied in the form Or their ~ulphi~er. are aiven in Tables ~ and 13. For lV~llS~
information concerning the preparation of catalysts A and D reference is made to Canadian patent applicstion No. 220,643 and for information about the preparation Or cataly~ts 1 and 11 to Canadian patent ~pplication No. 172040 in which the preparation of these catalysts is described in detail. Catalyst 40 is a demetallization catalyst within the scope of Canadian patent application No. 172040, which catalyst was prepared by co-impre¢nation of an alumina carrier with an aqueous solution containing vanadyl oxalate and nickel nitrate, followed by drying and calcination of the composition.
The two re~idual oils used in the experiments are further de~cribed hereinafter. The results of the experiments are eiven in Table C.
OIL D
An oil havine a total vanadium and nickel content of 225 5 ppmw, and a sulphur content of 2.0 %w, which oil had been o~tained as a residue in the atmospheric distillation of a Caribbean crude oil.
OIL F
An oil having a total vanadium and nickel content of 410 ppmw and a sulphur content of 2.0 %w, which oil had been obtained as a residue in the atmospheric distillation of a Caribbean crude oil.
Table A
; Cat. Metal load, Carrier Pore Pore Specific % of % of v,% p,nm d,mm No. pbw per 100 vol., volume surface the the pbw of car- ml/g in pores area, pore pore rier with a m2/g volume volume ~ co ho diameter in in ~0.7xp pores pores and with with ~1.7xp, a dia- a dia-ml/e meter meter cO 7x~ >1.7x~
____ _____ ____ _______ ______ _______ _______ _:___ ______. .____ _____ ____ A 4,7 11,4 Al203 0,54 0,42 202 1~,7 5.f~ 1,3 14,1 1,5 3,8 9,5 Al203 0,50 0,47 303 2,8 3,2 ~,0 4,7 o,~
95_5~3~s~8-~53ns~3~s=~z=~===as==~3======55================-=-~5=======~==~
Table B
Cat Metal load, Carrier Pore Total Nitrogen v, ~ p, nm d, mm No. pbw per 100 vol., pore pore pbw of car- ml/z volume, volume, rier ml/e ml/g Nl V
____ _____ _____ _______ ______ ______ ________ ____ _____ _____1 _ 2,0 Al203 225 0,57 o,56 ~0,5 10,2 0,7 11 0,52,0SiO2 243 0,81 0,74 9 ~,0 2,2 40 0,52,0Al203 220 o,60 0,57 1,5 14,9 1,5 ============================
Table C
~xp. Oil PK , Cat.O ~v Cat.O %v Cat.I %v Cat.II Cat.life of No. No. 2 No. (Cat.No.A) (Cat.No.D) cat.or cat.
bar combination, _______________ _____ ________ _________ _________ _:__________ XVI' D150 - - 70 30 1000 XVI" D150 - - 100 ~ 425 XVI"' D150 - - - 100 600 XVII' D100 - - 60 40 2000 XVII" D100 - - 100 - 400 XVII"' D100 - - - 100 1300 XVIII' F150 - - 70 30 550 XVIII" F150 - - 100 - 200 XVIII"' F150 - - ~ 100 250 XIX' D150 - _ 7 30 1000 XIX" D150 - _ 100 _ 425 XIX"' D150 - - - 100 600 ====.,._.=.. ========.... ====.. =.. ====================================
Of the experiments eiven in Table C only experiments XVI-XVIII
are demetsllization/desulphurization experiments accordine to the present patent application. The other experiments have been included in the table for comparison.
In experiments XVI-XVIII catalyst combinations were applied in which each of the catalysts satisfied the requirements concerning porosity and particle size; the other requirements according to the present patent application were also satisfied in these experiments.
Comparison of the lives of each of the cntalyst combinations : ' ' :
1~8~
O/I/II given in the last column of Table C and applied in experiments XVI-XVIII with the lives of the catalyst combinations I/II applied in the associated experiments XVI'-XVIII' clearly shows the gain in catalyst life which is achieved upon a~plication of catalyst combinations according to the present patent application.
It is true that a suitable cntalyst combination I/II was applied in experiment XIX (and that this experiment therefore falls within the scope of Canadian patent application No. 220,643 , but the quotient p/(d)-9 of the catalyst O applied was too low to meet the requirements of the present patent application.
Experiments XVI'-XIX' are also experiments within the scope of Canadian patent application No. 220,643 It is pointed out that experiments XVI', XVI" and XVI"' given in Table C are identical with experiments XIX', XIX" and ~IX"' respectively, also in this table and that experiment~ XVI"', XVII" and XVII"' in Table C are identical with experiments IX", XIV' ~nd XIV" in Table B of C~adiun pateDt application 6'o. 220,643 .
The catalytic hydrodemetallization of residual hydrocarbon oils using a catalyst which meets the requirements given hereinbefole under a) to g) is described in Canadian patent applications No.'s ]72,04n, 212,547, 212,563 and 232,027.
The present inventioll therefore relates to an improved process for the catalytic hydrodesulphurization of vanadium and nic~el containing resid-ual hydrocarbon oils having a vanadium and nic~el content above 120 ppmw utilizing a desulphurization catalyst system comprising a single catalyst I
and a single catalyst II, which catalysts meet the following requirements:
(a) both catalysts have a total pore volume larger than 0.30 ml/g of which the percentage (v) that consists of pores with a diameter larger than 100 nm is less than 10, (b) catalyst II has such a specific average pore diameter (p) and a specific average particle diameter (d) that the quotient p/(d)0 9 meets the requirement 0.6x]0 4x(P~1 )2~ p/(d)0 9 cat II~3+6xlO x(P}I ) - (c) the percentage of the joint catalyst volume of catalysts I and II that is occupied by catalyst II (~OV cat. II) lies between 10 and 90% and meets the requirement ~Ox( rS rxlnO~2x(P}I )-2~ov cat. II~300x( ~ 100)2x(PIl )-2, ~ .
lOl~llSl in which SF is the sulphur content of the feed and Sp is the desired sulphur content of the desulphurized product (p in nm, d in mm, PH in bar, Sp and SF in %w, the improvement comprising prolonging the life of the desulphur-ization catalyst system by first hydrodemetallizing said vanadium and nickel containing residual hydrocarbon oil utilizing processing parameters compatible with and substantially identical to those for said hydrode-sulphurization step so that said catalytic hydrodemetallization step and said hydrodesulphurization step are conducted sequentially and continuously and utilizing a hydrodemetallization catalyst 0, providing the requirements given hereinbefore under 3) to 6) are met.
The present invention also provides in an apparatus for the hydrocracking of residual oil having a vanadium and nickel content of at least 120 ppmw and a sulphur content of about 2% w the improvement com-prising the use of a series of catalysts in the following order from the output to the infeed of the apparatus: (1) hydrodesulphurization catalysts comprising a single catalyst I and a single catalyst II, which catalysts ~
meet the following requirements: (a) both catalysts have a total pore volume ;
larger than 0.30 ml/g of which the percentage (v) that consists of pores with a diameter larger than 100 nm is less than 10, (b) catalysts II has such a specific average pore diameter (p) and a specific average particle diameter (d) that the quotient pt(d)0'9 meets the requirement (PH2) ~ ~/(d) ~cat II~3t6X10 4X(PH )2 (c) the percentage of the joint catalyst volume of catalysts I and II that is occupied by catalyst II (%v cat.II) lies between 10 and 90% and meets the requirement 40x~ xlO0) x~PH ) ~%v cat.II~300x( ~ H2 in which SF is the sulphur content of the feed and Sp is the desired sulphur content of the desulphurized product (p in nm, d in mm, PH in bar, Sp and SF in %w.
,, ~
.
~ ~ - 5 _ 1~81151 As demetallization catalysts preference is given to the catalysts described in above-ementioned Canadian patent applications No~s 172,040, 212,547, 212,563 and 232,027.
The invention will now be elucidated with the aid of the following example, EXAMPLE
Catalysts combinations consisting of a demetallization catalyst (catalysts 1,11 and 40), a first desulphurization catalyst (catalyst A) and a second desulphurization catalyst (catalyst D) were employed for hydrode-metallization followed by hydrodesulphurization without catalyst replenish-ment of two vanadium and nickel-containing residual hydrocarbon oils (oils D
and F). Moreover, catalyst combinations consisting of the two desulphur-ization catalysts A and D and also each of these two catalysts separately were employed for the hydrodesulphurization without catalyst replenishment ~ :
of the two oils.
, - 5a -~llSl Demetallization/desulphurization or only desulphurization of the oils was carried out by passing the oils together with hydrogen downwards through three cylindrical vertically disposed fixed catalyst beds at elevated temperature and pressure.
The experiments were carried out four by four. In each set of four experiments the same oil was desulphurized under the same conditions and with the same volume Or catalyst, down to the same sulphur content in the product. (In all the experiments Sp was 0.5 %w). In one of the four experiments the first catalyst bed contained the demetallization catalyst indicated hereinarter as catalyst 0, the second catalyst bed the desulphurization catalyst indicated hereinafter as catalyst I and the third catalyst bed the desulphurization catalyst indicated hereinafter ss catalyst II. In the three remaining experiments the three catalyst beds contained either a combination of catalyst I and catalyst II
successively or catalyst I exclusively or catalyst II exclusively.
The desulphurization experiments were carried out at an initial temperature of 36015C, a space velocity of 0.7 kg.l .h , a gas rate of 600 NlH2.kg and a hydrogen partial pressure of 100 or 150 bar. For the preparation of a product having constant sulphur content the temperature had to be gradually increased during the experiments. The desulphurization experiments were ended when ~ -a temperature of 420C had to be applied to prepare a product having the desired sulphur content.
The demetallization was carried out at a constant temperature Or 420 C and a hydrogen partial pressure and eas rate correspondine with those applied in the desulphurization. In case of demetallization followed by desulphurization the space velocity throuehout the catalyst system amounted to 0.7 kg.l .h Composition and properties Or the catalysts which were ap~lied in the form Or their ~ulphi~er. are aiven in Tables ~ and 13. For lV~llS~
information concerning the preparation of catalysts A and D reference is made to Canadian patent applicstion No. 220,643 and for information about the preparation Or cataly~ts 1 and 11 to Canadian patent ~pplication No. 172040 in which the preparation of these catalysts is described in detail. Catalyst 40 is a demetallization catalyst within the scope of Canadian patent application No. 172040, which catalyst was prepared by co-impre¢nation of an alumina carrier with an aqueous solution containing vanadyl oxalate and nickel nitrate, followed by drying and calcination of the composition.
The two re~idual oils used in the experiments are further de~cribed hereinafter. The results of the experiments are eiven in Table C.
OIL D
An oil havine a total vanadium and nickel content of 225 5 ppmw, and a sulphur content of 2.0 %w, which oil had been o~tained as a residue in the atmospheric distillation of a Caribbean crude oil.
OIL F
An oil having a total vanadium and nickel content of 410 ppmw and a sulphur content of 2.0 %w, which oil had been obtained as a residue in the atmospheric distillation of a Caribbean crude oil.
Table A
; Cat. Metal load, Carrier Pore Pore Specific % of % of v,% p,nm d,mm No. pbw per 100 vol., volume surface the the pbw of car- ml/g in pores area, pore pore rier with a m2/g volume volume ~ co ho diameter in in ~0.7xp pores pores and with with ~1.7xp, a dia- a dia-ml/e meter meter cO 7x~ >1.7x~
____ _____ ____ _______ ______ _______ _______ _:___ ______. .____ _____ ____ A 4,7 11,4 Al203 0,54 0,42 202 1~,7 5.f~ 1,3 14,1 1,5 3,8 9,5 Al203 0,50 0,47 303 2,8 3,2 ~,0 4,7 o,~
95_5~3~s~8-~53ns~3~s=~z=~===as==~3======55================-=-~5=======~==~
Table B
Cat Metal load, Carrier Pore Total Nitrogen v, ~ p, nm d, mm No. pbw per 100 vol., pore pore pbw of car- ml/z volume, volume, rier ml/e ml/g Nl V
____ _____ _____ _______ ______ ______ ________ ____ _____ _____1 _ 2,0 Al203 225 0,57 o,56 ~0,5 10,2 0,7 11 0,52,0SiO2 243 0,81 0,74 9 ~,0 2,2 40 0,52,0Al203 220 o,60 0,57 1,5 14,9 1,5 ============================
Table C
~xp. Oil PK , Cat.O ~v Cat.O %v Cat.I %v Cat.II Cat.life of No. No. 2 No. (Cat.No.A) (Cat.No.D) cat.or cat.
bar combination, _______________ _____ ________ _________ _________ _:__________ XVI' D150 - - 70 30 1000 XVI" D150 - - 100 ~ 425 XVI"' D150 - - - 100 600 XVII' D100 - - 60 40 2000 XVII" D100 - - 100 - 400 XVII"' D100 - - - 100 1300 XVIII' F150 - - 70 30 550 XVIII" F150 - - 100 - 200 XVIII"' F150 - - ~ 100 250 XIX' D150 - _ 7 30 1000 XIX" D150 - _ 100 _ 425 XIX"' D150 - - - 100 600 ====.,._.=.. ========.... ====.. =.. ====================================
Of the experiments eiven in Table C only experiments XVI-XVIII
are demetsllization/desulphurization experiments accordine to the present patent application. The other experiments have been included in the table for comparison.
In experiments XVI-XVIII catalyst combinations were applied in which each of the catalysts satisfied the requirements concerning porosity and particle size; the other requirements according to the present patent application were also satisfied in these experiments.
Comparison of the lives of each of the cntalyst combinations : ' ' :
1~8~
O/I/II given in the last column of Table C and applied in experiments XVI-XVIII with the lives of the catalyst combinations I/II applied in the associated experiments XVI'-XVIII' clearly shows the gain in catalyst life which is achieved upon a~plication of catalyst combinations according to the present patent application.
It is true that a suitable cntalyst combination I/II was applied in experiment XIX (and that this experiment therefore falls within the scope of Canadian patent application No. 220,643 , but the quotient p/(d)-9 of the catalyst O applied was too low to meet the requirements of the present patent application.
Experiments XVI'-XIX' are also experiments within the scope of Canadian patent application No. 220,643 It is pointed out that experiments XVI', XVI" and XVI"' given in Table C are identical with experiments XIX', XIX" and ~IX"' respectively, also in this table and that experiment~ XVI"', XVII" and XVII"' in Table C are identical with experiments IX", XIV' ~nd XIV" in Table B of C~adiun pateDt application 6'o. 220,643 .
Claims (2)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process for the catalytic hydrodesulphurization of vanadium and nickel containing residual hydrocarbon oils having a vanadium and nickel content above 120 ppmw utilizing a desulphurization catalyst system com-prising a single catalyst I and a single catalyst II, which catalysts meet the following requirements:
(a) both catalysts have a total pore volume larger than 0.30 ml/g of which the percentage (v) that consists of pores with a diameter larger than 100 nm is less than 10, (b) catalyst II has such a specific average pore diameter (p) and a specific average particle diameter (d) that the quotient p/(d)0.9 meets the requirement (c) the percentage of the joint catalyst volume of catalysts I and II
that is occupied by catalyst II (%v cat.II) lies between 10 and 90% and meets the requirement in which SF is the sulphur content of the feed and Sp is the desired sulphur content of the desulphurized product (p in nm, d in mm, pH2 in bar, Sp and SF in %w), the improvement comprising prolonging the life of the desulphur-ization catalyst system by first hydrodemetallizing said vanadium and nickel containing residual hydrocarbon oil utilizing processing parameters com-patible with and substantially identical to those for said hydrodesulphur-ization step so that said catalytic hydrodemetallization step and said hydro-desulphurization step are conducted sequentially and continuously and utilizing a hydrodemetallization catalyst O providing the follouing require-ments are met:
1) Catalyst 0 meets the following requirements (a) the catalyst comprises one or more metals having hydrogenation activity on a carrier, (b) p/d>3.5-0.02 v, (c) the total pore volume is larger than 0.40 ml/g, (d) the specific surface area is larger than 100 m2/g; but in cases where the catalyst has such a p and d that the quotient p/d is larger than 3.5 - 0.02 v, but at most 10-0.15 v, the catalyst has to meet the following additional requirements:
(e) the nitrogen pore volume is larger than 0.60 ml/g, (f) the specific surface area is larger than 150 m2/g, and (g) p is larger than 5 nm.
2) Catalyst 0 has a larger total pore volume than catalyst I.
3) Catalyst 0 and catalyst 1 have such a p, d and v that the follow-ing relation is met 4) The percentage of the joint catalyst volume of catalyst 0, I and II that is occupied by catalyst 0 amounts to at least 10%v.
(a) both catalysts have a total pore volume larger than 0.30 ml/g of which the percentage (v) that consists of pores with a diameter larger than 100 nm is less than 10, (b) catalyst II has such a specific average pore diameter (p) and a specific average particle diameter (d) that the quotient p/(d)0.9 meets the requirement (c) the percentage of the joint catalyst volume of catalysts I and II
that is occupied by catalyst II (%v cat.II) lies between 10 and 90% and meets the requirement in which SF is the sulphur content of the feed and Sp is the desired sulphur content of the desulphurized product (p in nm, d in mm, pH2 in bar, Sp and SF in %w), the improvement comprising prolonging the life of the desulphur-ization catalyst system by first hydrodemetallizing said vanadium and nickel containing residual hydrocarbon oil utilizing processing parameters com-patible with and substantially identical to those for said hydrodesulphur-ization step so that said catalytic hydrodemetallization step and said hydro-desulphurization step are conducted sequentially and continuously and utilizing a hydrodemetallization catalyst O providing the follouing require-ments are met:
1) Catalyst 0 meets the following requirements (a) the catalyst comprises one or more metals having hydrogenation activity on a carrier, (b) p/d>3.5-0.02 v, (c) the total pore volume is larger than 0.40 ml/g, (d) the specific surface area is larger than 100 m2/g; but in cases where the catalyst has such a p and d that the quotient p/d is larger than 3.5 - 0.02 v, but at most 10-0.15 v, the catalyst has to meet the following additional requirements:
(e) the nitrogen pore volume is larger than 0.60 ml/g, (f) the specific surface area is larger than 150 m2/g, and (g) p is larger than 5 nm.
2) Catalyst 0 has a larger total pore volume than catalyst I.
3) Catalyst 0 and catalyst 1 have such a p, d and v that the follow-ing relation is met 4) The percentage of the joint catalyst volume of catalyst 0, I and II that is occupied by catalyst 0 amounts to at least 10%v.
2. A process according to claim 1 wherein the hydrodesulphurization is carried out over an increasing temperature range from about 360°C to about 420°C with a hydrogen partial pressure of from about 100 to 150 bar.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7502490A NL7502490A (en) | 1975-03-03 | 1975-03-03 | Catalytic hydrodesulphurisn of metal-contg residua - after catalytic hydrodemetallation under specified conditions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1081151A true CA1081151A (en) | 1980-07-08 |
Family
ID=19823290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA223,008A Expired CA1081151A (en) | 1975-03-03 | 1975-03-25 | Process for the conversion of hydrocarbons |
Country Status (3)
| Country | Link |
|---|---|
| BE (1) | BE832104R (en) |
| CA (1) | CA1081151A (en) |
| NL (1) | NL7502490A (en) |
-
1975
- 1975-03-03 NL NL7502490A patent/NL7502490A/en not_active Application Discontinuation
- 1975-03-25 CA CA223,008A patent/CA1081151A/en not_active Expired
- 1975-08-04 BE BE1006813A patent/BE832104R/en active
Also Published As
| Publication number | Publication date |
|---|---|
| NL7502490A (en) | 1976-09-07 |
| BE832104R (en) | 1976-02-04 |
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