CA1062642A - Process for the conversion of hydrocarbons - Google Patents
Process for the conversion of hydrocarbonsInfo
- Publication number
- CA1062642A CA1062642A CA219,667A CA219667A CA1062642A CA 1062642 A CA1062642 A CA 1062642A CA 219667 A CA219667 A CA 219667A CA 1062642 A CA1062642 A CA 1062642A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- desulphurization
- oil
- demetallization
- desulphurization catalyst
- 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
Abstract
A B S T R A C T
In a process for the catalytic hydrodesulphurization without catalyst replenishment of a vanadium- and nickel-containing residual oil, in which process a specified relation exists between the particle size and porosity of the catalyst and the applied hydrogen partial pressure, the lifetime of the catalyst is increased by partly demetallizing the oil prior to hydrodesulphurization in accordance with a specific equation which relates the extent of demetallization and the lifetime of the catalyst.
In a process for the catalytic hydrodesulphurization without catalyst replenishment of a vanadium- and nickel-containing residual oil, in which process a specified relation exists between the particle size and porosity of the catalyst and the applied hydrogen partial pressure, the lifetime of the catalyst is increased by partly demetallizing the oil prior to hydrodesulphurization in accordance with a specific equation which relates the extent of demetallization and the lifetime of the catalyst.
Description
The invention relates to a process for the catalytic hydro~
desulphurization witllout catalyst replenishment of a vanadium- and nickel-containing residual hydrocarbon oil. Process~s of this type are described in our Canadian Patent 985,651 and British Patent 1,406,804. According to these patents for this purpose catalysts are used the life and average activity of which exceed given minimum values, if they are used for the hydrodesulphurization of a residual hydrocarbon oil in a standard catalyst test. They have a total pore volume above 0.30 ml/g, less than 10% of which is present in pores with a diameter larger than 100 nm and such a specific average pore diameter tp) and specific average particle diameter (d) that the : quotient p~ (d) 9 fulfills the requirement 3 x 10-4 x (PH )2 c p/(d)0 9 s 17 x 10-4 x (PH ), where PH is the hydrogen partial pressure applied (p in nm, d in mm, PH in bar). In order to suppress the deactivation of the ; catalyst and thus extend the life, it was proposed in the saidpatent applications to precede the desulphurization by a demetallization treatment. This demetallization treatment is preferably conducted in the presence of hydrogen and a catalyst.
An investigation by Applicant into the effect of catalytic hydrodemetallization of residual hydrocarbon oils on the life of catalysts which are employed according to the said known processes for the hydrodesulphurization of the demetallized oils has brought ; to light some surprising facts, which can suitably be elucidated with the aid of the following general consideration which is based on experimental data.
If three vanadium- and nickel-containing residual hydrocarbon oils ~oils 1, 2, 3) obtained by distillation and having metal contents Ml, M2 and M3 respectively ~MlC M2 cM3), are subjected
desulphurization witllout catalyst replenishment of a vanadium- and nickel-containing residual hydrocarbon oil. Process~s of this type are described in our Canadian Patent 985,651 and British Patent 1,406,804. According to these patents for this purpose catalysts are used the life and average activity of which exceed given minimum values, if they are used for the hydrodesulphurization of a residual hydrocarbon oil in a standard catalyst test. They have a total pore volume above 0.30 ml/g, less than 10% of which is present in pores with a diameter larger than 100 nm and such a specific average pore diameter tp) and specific average particle diameter (d) that the : quotient p~ (d) 9 fulfills the requirement 3 x 10-4 x (PH )2 c p/(d)0 9 s 17 x 10-4 x (PH ), where PH is the hydrogen partial pressure applied (p in nm, d in mm, PH in bar). In order to suppress the deactivation of the ; catalyst and thus extend the life, it was proposed in the saidpatent applications to precede the desulphurization by a demetallization treatment. This demetallization treatment is preferably conducted in the presence of hydrogen and a catalyst.
An investigation by Applicant into the effect of catalytic hydrodemetallization of residual hydrocarbon oils on the life of catalysts which are employed according to the said known processes for the hydrodesulphurization of the demetallized oils has brought ; to light some surprising facts, which can suitably be elucidated with the aid of the following general consideration which is based on experimental data.
If three vanadium- and nickel-containing residual hydrocarbon oils ~oils 1, 2, 3) obtained by distillation and having metal contents Ml, M2 and M3 respectively ~MlC M2 cM3), are subjected
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- 3 to a hydrode~ulphurization treatment under identical condition~
with regard to c~lyst, pre~ure, maximu~ temperature, space ~elocity snd g~ throu4hput r~te, ~ccording to a proc~s a8 d~scribed in the said patent applications, the cst~lyst employed sho~s li~es o~ L1, L2 and L3 re~pectively (L1>L2>L3~. It turns out that in each ca~e the product of L and M i~ virtually constant (L1xM1~L2xM2~=L3xM3) or, in other words, the life of the cat~ly~t a~d the metal content of the feed are ~irtually inver~ely proportion~1.
Cat~lytic hydrodemetallization of the oils 2 and 3 offer~ a po~sibility of hydrodesulphurization of these feeds as well with the same cataly~t ~uch that the life L1 i~ attained. The question i~, howevcr, to what level the demetallization has tp be pur~ued to thi~ purpose. In view of the above-mentioned inver~e proportionality one miEht expect that dometallization o~ the oils 2 and 3 to a metal content M1 would bring about the de~ired extension of catalyst li~c. In point of fact, however, demetallization of ~ oil 2 to a metal content M1 (per cent by weight of metal removed :-............... M -M
V2 = ~ 1 x 100) and demetallization o~ oil 3 to a metal content M1 ~per cent by weight of metal removed V3~ ~ 100) lead to live~ of the desulphurization catalyst of L2~ a~d L31, respectively (L3~L2l~L1~. Evidently, the i~ver~e proportion~lity between cat~lyst lire and metal content Or the feed noted ~bove rOr the desulphurizQtion o~ re~idue~
obtained by distillation does not hold good for the de~ulphurizAtion such re~idues a~ter partial demetallization. For oil 2 a demet~llization to a met~l content M2'(M2'~M1) ~u~Pices to extend the lire o~
the de~ulphurization cstalyst from L2 to Ll. In ~iew of tho aforesaid.
on~ might expect that a demetall;zation of oil 3 ~gain to a metal content ~2~ ~ould al~o extend the lire of the dcsulphurization --3 ~
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catalyst for this feed to Ll. In actual fact, however, demetallization of oil 3 to a metal content M2' leads to a life L3" of the desulphurization catalyst (L3" > Ll). Evidently, the demetallization is still too deep.
For oil 3 a demetallization to a metal content M3' (M3' >M2') suffices to extend the life of ~he catalyst from L3 to Ll.
: In view of the foregoing consideration the following conclusions can be drawn with regard to the catalytic hydrodemetallization of residual hydrocarbon oils as a means of extending the life of the catalyst employed in a process according to our above-mentioned Canadian and British patents for the hydrodesulphurization of the demetallized oil. In order to increase the life of these catalysts to a certain fixed level it is :~
concluded:
` 1. that a demetallization which is far less deep than one would ;
expect on the basis of an assumed inverse proportionality : between the metal content of the feed and the life of the catalyst suffices tM2' >Ml;M3' >Ml).
. 2. that according as the feed has a higher metal content, a larger quantity of the metals should be removed (M3-M3'~M2-M2'), and 3. that according as the feed has a higher metal content, a less deep : 20 demetallization suffices (M3'> M2').
After continued research on this subject Applicant has succeeded :
in quantifying the aforesaid qualitative conclusions and formulating a relation between the metal content of a residual hydrocarbon oil before ; and after catalytic hydrodemetallization and the life of catalysts employed -. .
~ in a process according to the above known methods for the hydrodesulphurization :
of the residual hydrocarbon oil before and after demetallization. In the .:
formulation of this relation the following restrictions have been taken into account:
., .
.`, .
., .
~ - 4 -, 1. The metal content of the hydrocarbon oil before demetallization (Ml) may vary between 25 and 1500 ppmw.
2. The life of the desulphurization catalyst employed for the demetal-lized oil (L2) may vary between 2000 and 16000 hours.
3. The quotient of the metal contents of the hydrocarbon oil after and before the demetallization (M2 and Ml, respectively) may vary between 0.75 and 0.10.
with regard to c~lyst, pre~ure, maximu~ temperature, space ~elocity snd g~ throu4hput r~te, ~ccording to a proc~s a8 d~scribed in the said patent applications, the cst~lyst employed sho~s li~es o~ L1, L2 and L3 re~pectively (L1>L2>L3~. It turns out that in each ca~e the product of L and M i~ virtually constant (L1xM1~L2xM2~=L3xM3) or, in other words, the life of the cat~ly~t a~d the metal content of the feed are ~irtually inver~ely proportion~1.
Cat~lytic hydrodemetallization of the oils 2 and 3 offer~ a po~sibility of hydrodesulphurization of these feeds as well with the same cataly~t ~uch that the life L1 i~ attained. The question i~, howevcr, to what level the demetallization has tp be pur~ued to thi~ purpose. In view of the above-mentioned inver~e proportionality one miEht expect that dometallization o~ the oils 2 and 3 to a metal content M1 would bring about the de~ired extension of catalyst li~c. In point of fact, however, demetallization of ~ oil 2 to a metal content M1 (per cent by weight of metal removed :-............... M -M
V2 = ~ 1 x 100) and demetallization o~ oil 3 to a metal content M1 ~per cent by weight of metal removed V3~ ~ 100) lead to live~ of the desulphurization catalyst of L2~ a~d L31, respectively (L3~L2l~L1~. Evidently, the i~ver~e proportion~lity between cat~lyst lire and metal content Or the feed noted ~bove rOr the desulphurizQtion o~ re~idue~
obtained by distillation does not hold good for the de~ulphurizAtion such re~idues a~ter partial demetallization. For oil 2 a demet~llization to a met~l content M2'(M2'~M1) ~u~Pices to extend the lire o~
the de~ulphurization cstalyst from L2 to Ll. In ~iew of tho aforesaid.
on~ might expect that a demetall;zation of oil 3 ~gain to a metal content ~2~ ~ould al~o extend the lire of the dcsulphurization --3 ~
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catalyst for this feed to Ll. In actual fact, however, demetallization of oil 3 to a metal content M2' leads to a life L3" of the desulphurization catalyst (L3" > Ll). Evidently, the demetallization is still too deep.
For oil 3 a demetallization to a metal content M3' (M3' >M2') suffices to extend the life of ~he catalyst from L3 to Ll.
: In view of the foregoing consideration the following conclusions can be drawn with regard to the catalytic hydrodemetallization of residual hydrocarbon oils as a means of extending the life of the catalyst employed in a process according to our above-mentioned Canadian and British patents for the hydrodesulphurization of the demetallized oil. In order to increase the life of these catalysts to a certain fixed level it is :~
concluded:
` 1. that a demetallization which is far less deep than one would ;
expect on the basis of an assumed inverse proportionality : between the metal content of the feed and the life of the catalyst suffices tM2' >Ml;M3' >Ml).
. 2. that according as the feed has a higher metal content, a larger quantity of the metals should be removed (M3-M3'~M2-M2'), and 3. that according as the feed has a higher metal content, a less deep : 20 demetallization suffices (M3'> M2').
After continued research on this subject Applicant has succeeded :
in quantifying the aforesaid qualitative conclusions and formulating a relation between the metal content of a residual hydrocarbon oil before ; and after catalytic hydrodemetallization and the life of catalysts employed -. .
~ in a process according to the above known methods for the hydrodesulphurization :
of the residual hydrocarbon oil before and after demetallization. In the .:
formulation of this relation the following restrictions have been taken into account:
., .
.`, .
., .
~ - 4 -, 1. The metal content of the hydrocarbon oil before demetallization (Ml) may vary between 25 and 1500 ppmw.
2. The life of the desulphurization catalyst employed for the demetal-lized oil (L2) may vary between 2000 and 16000 hours.
3. The quotient of the metal contents of the hydrocarbon oil after and before the demetallization (M2 and Ml, respectively) may vary between 0.75 and 0.10.
4. The product of the metal content of the hydrocarbon oil before demetallization (Ml) and the life of the desulphurization catalyst employed for the demetallized oil SL2) may vary between 2x105 and 3xlO .
Taking into account the aforesaid restrictions 1-4, the relation reads as follows:
M2 = (1-05 + 0-20) x Ml x (Ll/L2)0-5, ~ where Ml and M2 represent the metal content of the hydrocarbon oil before `~ and after demetallization respectively, and Ll and L2 the lives of the desulphurization catalyst when employed for the non-demetallized and the demetallized oil respectively. This relation offers the possibility of establishing to what level the metal content of a residual hydrocarbon oil used as feedstock for the process according to the above-mentioned Netherlands patent applications should be lowered in order to extend the life of the desulphurization catalyst by a specific number of hours.
The present patent application therefore relates to a process for the catalytic hydrodesulphurization without catalyst replenishment of a vanadium- and nickel-containing residual hydrocarbon oil with the application of a catalyst having a total pore volume above 0.30 ml/g, less than 10% of which is present in pores with a diameter larger than lOQ nm and such a p and d that the quotient p/(d)0 9 fulfils the requirement ,: :
~ 3 x 10 4 x (rH )2 ~ p/(d) g ~ 17 x 10 x (PH ) - in which, to extend the life of the desulphurization ca~alyst, the desulphurization is preceded by a catQlytic hydrodemetallization in which the metal content of the oil is reduced from ~ll to M2, the degree of demetallization being chosen in dependence on the desired extension of the life of the desulphurization catalyst according to the above relation and in which the four requirements mentioned above under (1)-(4) are also fulfilled.
For the way in which p and d of the desulphurization catalyst were determined, reference is made to Canadian Paten~ No. 985,651 and British Patent 1J406J804 referred to above, in which the determination of these parameters is described in detail.
The catalysts which are used for the desulphurization according to the invention preferably have a total pore volume above 0.45 ml/g and a surface area in excess of 50 m2/g, in particular in excess of 100 m2/g. In the desulphurization according to the invention particular preference is given to the use of catalysts having a total pore volume above 0.45 ml/g, of which at least 0.4 ml/g is present in pores with a -~
diame~er of at least 0.7 x p and at most 1.7xp and a sharp pore diameter 20 distribution, characterized by: ;
a) the presence of less than 20% of the total pore volume in pores -having a diameter smaller than 0.7xp, and b) the presence of less than 20% of the total pore volume in pores having a diameter larger than 1.7xp.
, .
~he catalysts which are used according to the invention for desulphurization preferably contain 0.5-20 parts by weight, more preferably 0.5-10 parts by weight, of nickel and/or cobalt and 2.5-60 parts by weight, preferably 2.5-30 parts by weight, of molybdenum and/or tungsten per 100 parts by weight of carrler.
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The stomic ratio betw~n nick~l and/or cobalt on the one hand and ~olybdenum and/or tungaten on the other m4y v~ry widoly, but pre~rably liec b~tween 0.1 ~nd 5, Very 3uita~1~ met~l combin6tions ~or desulphurization CRtQly~t~ are nickel/tun~t~n, nickel/molybde~u~
Taking into account the aforesaid restrictions 1-4, the relation reads as follows:
M2 = (1-05 + 0-20) x Ml x (Ll/L2)0-5, ~ where Ml and M2 represent the metal content of the hydrocarbon oil before `~ and after demetallization respectively, and Ll and L2 the lives of the desulphurization catalyst when employed for the non-demetallized and the demetallized oil respectively. This relation offers the possibility of establishing to what level the metal content of a residual hydrocarbon oil used as feedstock for the process according to the above-mentioned Netherlands patent applications should be lowered in order to extend the life of the desulphurization catalyst by a specific number of hours.
The present patent application therefore relates to a process for the catalytic hydrodesulphurization without catalyst replenishment of a vanadium- and nickel-containing residual hydrocarbon oil with the application of a catalyst having a total pore volume above 0.30 ml/g, less than 10% of which is present in pores with a diameter larger than lOQ nm and such a p and d that the quotient p/(d)0 9 fulfils the requirement ,: :
~ 3 x 10 4 x (rH )2 ~ p/(d) g ~ 17 x 10 x (PH ) - in which, to extend the life of the desulphurization ca~alyst, the desulphurization is preceded by a catQlytic hydrodemetallization in which the metal content of the oil is reduced from ~ll to M2, the degree of demetallization being chosen in dependence on the desired extension of the life of the desulphurization catalyst according to the above relation and in which the four requirements mentioned above under (1)-(4) are also fulfilled.
For the way in which p and d of the desulphurization catalyst were determined, reference is made to Canadian Paten~ No. 985,651 and British Patent 1J406J804 referred to above, in which the determination of these parameters is described in detail.
The catalysts which are used for the desulphurization according to the invention preferably have a total pore volume above 0.45 ml/g and a surface area in excess of 50 m2/g, in particular in excess of 100 m2/g. In the desulphurization according to the invention particular preference is given to the use of catalysts having a total pore volume above 0.45 ml/g, of which at least 0.4 ml/g is present in pores with a -~
diame~er of at least 0.7 x p and at most 1.7xp and a sharp pore diameter 20 distribution, characterized by: ;
a) the presence of less than 20% of the total pore volume in pores -having a diameter smaller than 0.7xp, and b) the presence of less than 20% of the total pore volume in pores having a diameter larger than 1.7xp.
, .
~he catalysts which are used according to the invention for desulphurization preferably contain 0.5-20 parts by weight, more preferably 0.5-10 parts by weight, of nickel and/or cobalt and 2.5-60 parts by weight, preferably 2.5-30 parts by weight, of molybdenum and/or tungsten per 100 parts by weight of carrler.
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The stomic ratio betw~n nick~l and/or cobalt on the one hand and ~olybdenum and/or tungaten on the other m4y v~ry widoly, but pre~rably liec b~tween 0.1 ~nd 5, Very 3uita~1~ met~l combin6tions ~or desulphurization CRtQly~t~ are nickel/tun~t~n, nickel/molybde~u~
5 cobalt/molybdenum and nickel/cobalt/molybdenum, The metQl~ m~ybe pre~ent on th~ earrier in metallic or in their oxidic or sulphidie ~orm. In th~ proces~ according to the invention prerer~nCe i8 given to the use of desulphurization ca~aly~ts, in which the met~ls sre present on the carriers in their sulphidic form, In addition to the above mentioned eatalgtieally aetiYe metals~
the de3ulphurization eataly~t~ may also eontain other eat~lytieally aetive ~etal~ and promoter~, sueh as phosphorus, boron Qnd halogens, ~ueh a8 fluorin~ ~nd chlorine. Very suitable earriers ~or the desulphurizstion cQtalysts are oxides o~ element~ Or the Groups II, III and IV of the periodie sy~tem, such as siliea, alumina, magne~ia and zireonia, or mixture8 of the said oxides, ~ueh as silica-alumina, silica-magnesia, alu~ina-magnesia and siliea-~ireonia, Preference i8 gi~en to aluminas and ~ilica-aluminas as carriers ror the desulphurization catalyata~
The deaulphurization eatalysts used in the proee~s aeeording to the invention ean be prepsred by despo~iting the rolevant metal~ on a carrier with sueh a speei~ic average pore diameter : that ~Pter the deposition of the m~tsls thereon a eatalyst is obtsined which fulrils the requirem~nts of the invention, either às s wh or after the ~peeific average particle diameter has been increQsed or reduced. m e desulphurization catalysts used in : the proeess according to the invention are pre~ersbly pr~psred by eo-i~pregnatin6 ~ e~rrier in one or more ~tep~ with an a~ueous solution eontaining one or more nickel and/or cobalt compounds and one or more molybdenum snd/or tung~ten co~pounds, followed 1~6Z6~Z
by drying and calcining of the composition.
For information about methods which can be used to influence -~ the porosity of the carrier material or of the catalyst as well as for further details about preferred preparation routes for the desulphurization catalysts, reference can be made to the known processes described in Canadian Patent No. 985,651 and British Patent 1,406,804 referred to above in which these subjects are discussed in detail.
The catalytic hydrodesulphuriæation of residual hydrocarbon oils without catalyst replenishment is preferably carried out by passing the ln hydrocarbon oil at elevated temperature and pressure and in the presence of hydrogen in upward, downward or radial direction through one or more vertically arranged reactors containing a fixed catalyst bed. The hydro-carbon oil to be desulphurized may be fully or partially saturated with hydrogen, and apart from the hydrocarbon phase and the catalyst phase a hydrogen-containing gas phase may be present in the reactor.
The specific average particle diameter of the desulphurization catalyst used according to the invention is usually 0.5-2.5 mm and preferably 0.6-2.0 mm. If the value of d which is required according to the invention to obtain a good catalyst performance at a given p and PH , is too small for practical use, the desulphurization can be effected in the presence of porous agglomerates prepared from the small cata,yst particles in the way described in the above-mentioned Netherlands patent applications.
In the process according to the invention the residual hydrocarbon -~ oil is first catalytically hydrodemetallized before being desulphurized.
; Suitable demetallization catalysts are catalys~s which contain one or more ; metals with hydrogenative activity on a carrier. The demetalllzation of residual hydrocarbon oils is preferably carried out by passing oil at ~ elevated temperature and pressure and :' -:
1a~6264;~
g in the pre~enee of hyclro~-n in upw~rd, downw~rd or radi~l dir~ction throuEh one or mor~ vertic~lly arran~ed reactors containing a rixed or moving cataly~t bed. A very sttractive embodiment of the de~etallization proces~ i8 that in which the hydrocsrbon oil i8 pa~sed through a vertieally arr~nBed catalyst bed in whieh during operation fre~h cataly3t iB periodically introduced ~t ; the top of the bed and spent eataly3t withdrawn at the bottom thereof (demet~lization according to the '~unker ~low" principle).
Another very attractive embodi~ent of the demetallization process i8 that in which se~eral reactors containing a fixed cataly~t bed are present, whieh reactors are alternately u~ed for demetallization;
while the demetallization i9 being carried out in one or more of these reactors, the eatalyst i~ replenished in the other reactora (demetullization aceording to the "fixed bed swing" prineiple).
If desired, the demetallization may also be carried out by su~pending the eat~lyst in the oil to be demetallized (demetallization aceording to "slurry phase" principle).
In the process according to the invention the clemetalli~ation i~ preferQbly carried out according to the "bunker flow" principle or to the "fixod bed swing" principle and the de ulphurization ~ in a conventional fixed bed.
,, The reaction condition~ applied in the demet~llization and des-~lphurization aecording to the invention may vary widely.
Both the demetalliz~tion and the desulphurization are preferab}y earried out at a temperature of 390-475C, a hydrogen partial pre~sure of 50-250 bar, a space velocity of 0.1-25 part: by weight s of ~eed per part by volu~e o~ cat~lyst per hour hnd a hydrogen/feed ratio of 100-2000 Nl H2/kg of feed. In both proce~se~ partic~lar preference is given to a temperature of 350-450C, a hydro~en, 3 parti~l pressure of 75-200 bar, a space velocity of 0.5-10 parts by weight of ~eed per part by volume o~ catalyst per hour and ~ -9--.
L ~.0~ 642 _ lo -hydroe~:r~/l'e~cl r~tio o~ :~00-1000 Nl 112/ke Or feed.
~xa~ple~ of re~ds for which the proce~ uccordiDg to the in~ention c~n be u~ed are crude oil8 a~d residues obtained by di8tilling crude oil~ ~t atmospheric or reduced pre3~ure. Residu~
obtained in the distillstion o~ product~ o~ the thermal or cat~lytic cracking of heavy hydrocarbon 0;18 m~y al~o be p~oce~ed according to the invention.
The invention will now be further illustrated with re~erence ~o the following example.
EXAMPLE
Four vanadium- and nickel-containing re~idual hydrocarbon oils (oils 1-4) were desulphurized with or without preceding demetalli~ation. The desulph~rization o~ the oils w~s effected by psssing them at elevated temperature and pres~ure and in the presence of hydrogen in downward direction through a vertically arrangcd fixed bed of desulphurization catalyst The desulphuri~ation cataly~t contained 4.7 parts by weight Or cobalt and 11.4 part~ by weight of molybdenum per 100 parts by weight Or alumina carrier and had the rollowing properties:
speci~ic average pore diameter (p~: 14.1 nm specific averaga particle di~mer ~d): 1,5 m~
total pore volume: 0,54 ml/g B,E.T. specific surface: 202 m2/B
pore volume volume present in pores with a diameter o~ ~0.7xp and c1,7xp:o~42 ml the total pore volume pre~ent in pore~ with ~ di~eter of cO~7xp:16~7 ~ Or the totsl pore volume present in porea with a diamet~r o~ 7xp: 5.6%
3 and % of the total pore volume which i~
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present i.n pores with a diameter Or ~100 nm : 1,3%
The demetallization o~ the oils was effectea by psssin~
them at elevsted te~perature ~nd pressure and in the presence of hydrogen in down~ard direction through B ~ertiCBlly BrranBed rixed bed oP d demet~llization catalyst. The demetallization catsly~t contsined 0.5 pbw nickel and 2.0 pbw vanadium per 100 pbw silica carrier.
The Pour re~idual oils u~ed in the present experiments may be de3cribed a~ rollows.
. OIL 1 Oil h~ving a total vanadium and nickel content of 200 ppmY
and a sulphur content oP 2.0 %w, which oil had been obtained aB a residue in the atmospheric di~tillation of a Caribbe~n crude oil.
Oil ha~in~ B tot~l ~anadium and nickel content o~ 393 ppmw and a ~ulphur content of 2.ô ~w, which oil had been obtsined a8 A r~iaue in the ~tmospheric di~tillation oP B Caribbean crude oil.
OIL 3 .
Oil having ~ total vans,dium and nickel content oP 51 ppmw and a sulphur content of 4.0 %w, which oil hsd been obtained as a rc~idue in the ~tmospheric distill~tion o~ a Middle-East crudo oil .
Oil ha~ing a tQtal vanadium and ~ickel content of 100 ppmw nd a sulphur content Or 5.3 %w, which oil had been obtained a~ a residue in the distillation under reduced pre3sure of an ~tmosphoric distillation re~idue o~ a Middle-East crude oil.
In each of the experiments described hereinsrter one oP
'~ .
~062~Z
- ~2 -the oil~ a~ d2~ulphurized under speci~ic condition~ to a certain ~ulphur content (~xp~riment~ A-E~, ~heraupon that oAme oil w~ rir~t partinlly demctallized and subseguently desulphuri~cd ~nder the same condition~ ~nd to the ~mc sulphur conten~ ~experi~ent~
5 I-V), Thc starting temperature of the d~sulphurization e~periments w~ chosen a~ low ~8 possible, such that under the gi~en re~ction condition~ a product having the de~ired sulphur content could ~ -JUst be prepared. For the prep~ration of a product with a constcnt sulphur content it was necessary to rsi~e the temperature gradually during the experiments. The desulphuriiz~tion experiments were discontinued ~t the moment the temperature had to be raised above 420C in order to propare Q product having the de~ired ~ulphur content, ~he desulphuri~Qtion condition8 together with the resUlt~
of the experiments are collected in the t~ble below.
U~ I
o U~
o c~i o u~ c~ o o o 1-- ~ N U~ O ~
u~ -- N ~ ~oO N ~ D N t O U~ ~ _ O N O u~ O O O O
~3 --O U~ C~l o o C~ ~--`~t ~ ~ o. t o ~ _ U~ U~ _ o o o o C~ o o o~
~1 ~ O ~D~ O o u~ ~0 ~ o N ~1 V¦
~~r) O
O 1~ O O
al~o ~ o o O
O O O
- ~ I~ - o ~~ ~ o ~o~ ~ ' O o O
: ~ O 11~--O O
~ O O
., 0 0 O.
N N ~ N ~ O O O t--Cl -- O O
O~ ~O ~ O O ~ O O o ~ _ ~ ~ N N
a~ o o --,~1 I u~ o ~ , 8 u~ N O O t--~0 tr) t~l 8 o ' E~ I C~ J O ~ -- N Ir~
' O U~ O. o -- O N O ~ UN~ 8 u~ ~ 2 N ~ _ 3 ~3 ~ I
,~ 0 ~ ^ a~ ~ a ~ ^ ~ O A ~ a ' ~ ,~ ,3 ~ ~ ô ~ X ~
~ ~ ~ 8 ~ 3 h .~ O ,~ ~O .~ O ~O O ,N ~ "
~o~ ~ v ~ ~o ~o ~ ?1 ~ ~o~ x~
2; ~ ~ a ~ ~ ~ ~ $ ~ ~ u ~ o ~ ~ ~N
o ~1 ." bD ~ ~ S ~ h X ,~,~ h ~ O ~ h -- ¦
~ o c ~ ~ ~ x 3 ~ h ~ l u ~ ~ 60 ,~
h ~ ~ U~ d æ ~ o A ~
0 ~ ;~ Q ~Y ;~
--~3--.
... ~ .
.. .... .
106Z6~Z
qhe experim~nta 1-5 were experiments according to tho invention.
In the~e experiment~ the desu1phurization w~ cnrried out without catsly~t repleni~hment in the prcscnce Or ~ catalyst Or which the ~uotient p/(d~0'9 fulfilled the roquireme~t 3 x 10 x (PH )2 c p/(d)-9 < 17 x 10 4 x (PH )2, which catalyst hsd a total pore ~olume exceeding 0,30 ml/g, le~s th~n 10~ of which pore volume being pre~ent in pores hQving Q
diamcter larger than 100 mm. The desulphurization was applied to a vanadium- ~nd nickel-cont~ining residual hydrocarbon oil which hsd previously been catalyticslly hydrodemetallized to metsl content within the range given by the formula:
(1,05 + 0.20) x M1 x (L1/L2)0'5 In the experiments 1-5 the remaining four requirementa according to the invention ~or M1, L2, M2/M1 and M1 x L2 were al80 ~ulfilled.
The ex~eriments A-E lie outside the ~cope of the invontion, since in tho~e experiment~ the desulphurization wa~ ~pplied to a feed whioh h~d not previously been c~t~lytically hydrodemetallized.
The experiments ~-E ~re nevertheless related to the pre~ent invention becau~e i~ the calculation of N2 with the formula M2~ 05~0.20) x M1x¦Ll/L~)0'5 use is made of the L1 ~alue found in these experiments.
It should be realized that thc ~alue8 of L1, M2" and L2 ~tatad in the Table ~ere 08tabli~hed in the de~ulphurization ~nd aometallization experiment~ describad hereinbe~ore (in contr~t with ~he values ~entioned for M2, M21 and L2~l, which were calculated, and for M1 ~nd L2, which were ~iven).
, ~'~
_,~.c " . . ~ '
the de3ulphurization eataly~t~ may also eontain other eat~lytieally aetive ~etal~ and promoter~, sueh as phosphorus, boron Qnd halogens, ~ueh a8 fluorin~ ~nd chlorine. Very suitable earriers ~or the desulphurizstion cQtalysts are oxides o~ element~ Or the Groups II, III and IV of the periodie sy~tem, such as siliea, alumina, magne~ia and zireonia, or mixture8 of the said oxides, ~ueh as silica-alumina, silica-magnesia, alu~ina-magnesia and siliea-~ireonia, Preference i8 gi~en to aluminas and ~ilica-aluminas as carriers ror the desulphurization catalyata~
The deaulphurization eatalysts used in the proee~s aeeording to the invention ean be prepsred by despo~iting the rolevant metal~ on a carrier with sueh a speei~ic average pore diameter : that ~Pter the deposition of the m~tsls thereon a eatalyst is obtsined which fulrils the requirem~nts of the invention, either às s wh or after the ~peeific average particle diameter has been increQsed or reduced. m e desulphurization catalysts used in : the proeess according to the invention are pre~ersbly pr~psred by eo-i~pregnatin6 ~ e~rrier in one or more ~tep~ with an a~ueous solution eontaining one or more nickel and/or cobalt compounds and one or more molybdenum snd/or tung~ten co~pounds, followed 1~6Z6~Z
by drying and calcining of the composition.
For information about methods which can be used to influence -~ the porosity of the carrier material or of the catalyst as well as for further details about preferred preparation routes for the desulphurization catalysts, reference can be made to the known processes described in Canadian Patent No. 985,651 and British Patent 1,406,804 referred to above in which these subjects are discussed in detail.
The catalytic hydrodesulphuriæation of residual hydrocarbon oils without catalyst replenishment is preferably carried out by passing the ln hydrocarbon oil at elevated temperature and pressure and in the presence of hydrogen in upward, downward or radial direction through one or more vertically arranged reactors containing a fixed catalyst bed. The hydro-carbon oil to be desulphurized may be fully or partially saturated with hydrogen, and apart from the hydrocarbon phase and the catalyst phase a hydrogen-containing gas phase may be present in the reactor.
The specific average particle diameter of the desulphurization catalyst used according to the invention is usually 0.5-2.5 mm and preferably 0.6-2.0 mm. If the value of d which is required according to the invention to obtain a good catalyst performance at a given p and PH , is too small for practical use, the desulphurization can be effected in the presence of porous agglomerates prepared from the small cata,yst particles in the way described in the above-mentioned Netherlands patent applications.
In the process according to the invention the residual hydrocarbon -~ oil is first catalytically hydrodemetallized before being desulphurized.
; Suitable demetallization catalysts are catalys~s which contain one or more ; metals with hydrogenative activity on a carrier. The demetalllzation of residual hydrocarbon oils is preferably carried out by passing oil at ~ elevated temperature and pressure and :' -:
1a~6264;~
g in the pre~enee of hyclro~-n in upw~rd, downw~rd or radi~l dir~ction throuEh one or mor~ vertic~lly arran~ed reactors containing a rixed or moving cataly~t bed. A very sttractive embodiment of the de~etallization proces~ i8 that in which the hydrocsrbon oil i8 pa~sed through a vertieally arr~nBed catalyst bed in whieh during operation fre~h cataly3t iB periodically introduced ~t ; the top of the bed and spent eataly3t withdrawn at the bottom thereof (demet~lization according to the '~unker ~low" principle).
Another very attractive embodi~ent of the demetallization process i8 that in which se~eral reactors containing a fixed cataly~t bed are present, whieh reactors are alternately u~ed for demetallization;
while the demetallization i9 being carried out in one or more of these reactors, the eatalyst i~ replenished in the other reactora (demetullization aceording to the "fixed bed swing" prineiple).
If desired, the demetallization may also be carried out by su~pending the eat~lyst in the oil to be demetallized (demetallization aceording to "slurry phase" principle).
In the process according to the invention the clemetalli~ation i~ preferQbly carried out according to the "bunker flow" principle or to the "fixod bed swing" principle and the de ulphurization ~ in a conventional fixed bed.
,, The reaction condition~ applied in the demet~llization and des-~lphurization aecording to the invention may vary widely.
Both the demetalliz~tion and the desulphurization are preferab}y earried out at a temperature of 390-475C, a hydrogen partial pre~sure of 50-250 bar, a space velocity of 0.1-25 part: by weight s of ~eed per part by volu~e o~ cat~lyst per hour hnd a hydrogen/feed ratio of 100-2000 Nl H2/kg of feed. In both proce~se~ partic~lar preference is given to a temperature of 350-450C, a hydro~en, 3 parti~l pressure of 75-200 bar, a space velocity of 0.5-10 parts by weight of ~eed per part by volume o~ catalyst per hour and ~ -9--.
L ~.0~ 642 _ lo -hydroe~:r~/l'e~cl r~tio o~ :~00-1000 Nl 112/ke Or feed.
~xa~ple~ of re~ds for which the proce~ uccordiDg to the in~ention c~n be u~ed are crude oil8 a~d residues obtained by di8tilling crude oil~ ~t atmospheric or reduced pre3~ure. Residu~
obtained in the distillstion o~ product~ o~ the thermal or cat~lytic cracking of heavy hydrocarbon 0;18 m~y al~o be p~oce~ed according to the invention.
The invention will now be further illustrated with re~erence ~o the following example.
EXAMPLE
Four vanadium- and nickel-containing re~idual hydrocarbon oils (oils 1-4) were desulphurized with or without preceding demetalli~ation. The desulph~rization o~ the oils w~s effected by psssing them at elevated temperature and pres~ure and in the presence of hydrogen in downward direction through a vertically arrangcd fixed bed of desulphurization catalyst The desulphuri~ation cataly~t contained 4.7 parts by weight Or cobalt and 11.4 part~ by weight of molybdenum per 100 parts by weight Or alumina carrier and had the rollowing properties:
speci~ic average pore diameter (p~: 14.1 nm specific averaga particle di~mer ~d): 1,5 m~
total pore volume: 0,54 ml/g B,E.T. specific surface: 202 m2/B
pore volume volume present in pores with a diameter o~ ~0.7xp and c1,7xp:o~42 ml the total pore volume pre~ent in pore~ with ~ di~eter of cO~7xp:16~7 ~ Or the totsl pore volume present in porea with a diamet~r o~ 7xp: 5.6%
3 and % of the total pore volume which i~
106264;Z
present i.n pores with a diameter Or ~100 nm : 1,3%
The demetallization o~ the oils was effectea by psssin~
them at elevsted te~perature ~nd pressure and in the presence of hydrogen in down~ard direction through B ~ertiCBlly BrranBed rixed bed oP d demet~llization catalyst. The demetallization catsly~t contsined 0.5 pbw nickel and 2.0 pbw vanadium per 100 pbw silica carrier.
The Pour re~idual oils u~ed in the present experiments may be de3cribed a~ rollows.
. OIL 1 Oil h~ving a total vanadium and nickel content of 200 ppmY
and a sulphur content oP 2.0 %w, which oil had been obtained aB a residue in the atmospheric di~tillation of a Caribbe~n crude oil.
Oil ha~in~ B tot~l ~anadium and nickel content o~ 393 ppmw and a ~ulphur content of 2.ô ~w, which oil had been obtsined a8 A r~iaue in the ~tmospheric di~tillation oP B Caribbean crude oil.
OIL 3 .
Oil having ~ total vans,dium and nickel content oP 51 ppmw and a sulphur content of 4.0 %w, which oil hsd been obtained as a rc~idue in the ~tmospheric distill~tion o~ a Middle-East crudo oil .
Oil ha~ing a tQtal vanadium and ~ickel content of 100 ppmw nd a sulphur content Or 5.3 %w, which oil had been obtained a~ a residue in the distillation under reduced pre3sure of an ~tmosphoric distillation re~idue o~ a Middle-East crude oil.
In each of the experiments described hereinsrter one oP
'~ .
~062~Z
- ~2 -the oil~ a~ d2~ulphurized under speci~ic condition~ to a certain ~ulphur content (~xp~riment~ A-E~, ~heraupon that oAme oil w~ rir~t partinlly demctallized and subseguently desulphuri~cd ~nder the same condition~ ~nd to the ~mc sulphur conten~ ~experi~ent~
5 I-V), Thc starting temperature of the d~sulphurization e~periments w~ chosen a~ low ~8 possible, such that under the gi~en re~ction condition~ a product having the de~ired sulphur content could ~ -JUst be prepared. For the prep~ration of a product with a constcnt sulphur content it was necessary to rsi~e the temperature gradually during the experiments. The desulphuriiz~tion experiments were discontinued ~t the moment the temperature had to be raised above 420C in order to propare Q product having the de~ired ~ulphur content, ~he desulphuri~Qtion condition8 together with the resUlt~
of the experiments are collected in the t~ble below.
U~ I
o U~
o c~i o u~ c~ o o o 1-- ~ N U~ O ~
u~ -- N ~ ~oO N ~ D N t O U~ ~ _ O N O u~ O O O O
~3 --O U~ C~l o o C~ ~--`~t ~ ~ o. t o ~ _ U~ U~ _ o o o o C~ o o o~
~1 ~ O ~D~ O o u~ ~0 ~ o N ~1 V¦
~~r) O
O 1~ O O
al~o ~ o o O
O O O
- ~ I~ - o ~~ ~ o ~o~ ~ ' O o O
: ~ O 11~--O O
~ O O
., 0 0 O.
N N ~ N ~ O O O t--Cl -- O O
O~ ~O ~ O O ~ O O o ~ _ ~ ~ N N
a~ o o --,~1 I u~ o ~ , 8 u~ N O O t--~0 tr) t~l 8 o ' E~ I C~ J O ~ -- N Ir~
' O U~ O. o -- O N O ~ UN~ 8 u~ ~ 2 N ~ _ 3 ~3 ~ I
,~ 0 ~ ^ a~ ~ a ~ ^ ~ O A ~ a ' ~ ,~ ,3 ~ ~ ô ~ X ~
~ ~ ~ 8 ~ 3 h .~ O ,~ ~O .~ O ~O O ,N ~ "
~o~ ~ v ~ ~o ~o ~ ?1 ~ ~o~ x~
2; ~ ~ a ~ ~ ~ ~ $ ~ ~ u ~ o ~ ~ ~N
o ~1 ." bD ~ ~ S ~ h X ,~,~ h ~ O ~ h -- ¦
~ o c ~ ~ ~ x 3 ~ h ~ l u ~ ~ 60 ,~
h ~ ~ U~ d æ ~ o A ~
0 ~ ;~ Q ~Y ;~
--~3--.
... ~ .
.. .... .
106Z6~Z
qhe experim~nta 1-5 were experiments according to tho invention.
In the~e experiment~ the desu1phurization w~ cnrried out without catsly~t repleni~hment in the prcscnce Or ~ catalyst Or which the ~uotient p/(d~0'9 fulfilled the roquireme~t 3 x 10 x (PH )2 c p/(d)-9 < 17 x 10 4 x (PH )2, which catalyst hsd a total pore ~olume exceeding 0,30 ml/g, le~s th~n 10~ of which pore volume being pre~ent in pores hQving Q
diamcter larger than 100 mm. The desulphurization was applied to a vanadium- ~nd nickel-cont~ining residual hydrocarbon oil which hsd previously been catalyticslly hydrodemetallized to metsl content within the range given by the formula:
(1,05 + 0.20) x M1 x (L1/L2)0'5 In the experiments 1-5 the remaining four requirementa according to the invention ~or M1, L2, M2/M1 and M1 x L2 were al80 ~ulfilled.
The ex~eriments A-E lie outside the ~cope of the invontion, since in tho~e experiment~ the desulphurization wa~ ~pplied to a feed whioh h~d not previously been c~t~lytically hydrodemetallized.
The experiments ~-E ~re nevertheless related to the pre~ent invention becau~e i~ the calculation of N2 with the formula M2~ 05~0.20) x M1x¦Ll/L~)0'5 use is made of the L1 ~alue found in these experiments.
It should be realized that thc ~alue8 of L1, M2" and L2 ~tatad in the Table ~ere 08tabli~hed in the de~ulphurization ~nd aometallization experiment~ describad hereinbe~ore (in contr~t with ~he values ~entioned for M2, M21 and L2~l, which were calculated, and for M1 ~nd L2, which were ~iven).
, ~'~
_,~.c " . . ~ '
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the catalytic hydrodesulphurization without catalyst replenishment of a vanadium- and nickel-containing residual hydrocarbon oil with the application of a catalyst having a total pore volume above 0.30 ml/g, less than 10% of which is present in pores with a diameter larger than 100 nm and such a specific average pore diameter (p) and specific average particle diameter (d) that the quotient p/(d)0.9 fulfills the requirement 3 x 10 4 x (PH )2 ? p/(d)0.9 ? 17 x 10-4 x (PH)2, where PH is the hydrogen partial pressure applied, in which, to extend the life of the desulphurization catalyst, the desulphurization is preceded by a catalytic hydrodemetallization in which the metal content of the oil is reduced from M1 to M2, the degree of demetallization being chosen in dependence on the desired extension of the life of the desulphurization catalyst according to the relation M2=(1.05+0.20)x M1x(L1/L2)0.5, where L1 and L2 represent the lives of the desulphurization catalyst in the application to non-demetallized oil with a metal content M1 and demetallized oil with a metal content M2 respectively and in which furthermore the following requirements are fulfilled:
(1) 25 ? M1 ? 1500 (2) 2000 ? L2 ?16000 (3) 0.10 ? M2/M1 ? 0.75 and (4) 2 x 105 ? MlxL2 ? 3 x 106 (p in nm, d in mm, PH in bar, L1 and L2 in hours, M1 and M2 in ppmw).
(1) 25 ? M1 ? 1500 (2) 2000 ? L2 ?16000 (3) 0.10 ? M2/M1 ? 0.75 and (4) 2 x 105 ? MlxL2 ? 3 x 106 (p in nm, d in mm, PH in bar, L1 and L2 in hours, M1 and M2 in ppmw).
2. A process as claimed in claim 1, in which the desulphurization catalyst has a total pore volume above 0.45 ml/g.
3. A process as claimed in claim 1 in which the desulphurization catalyst has a surface in excess of 50 m2/g preferably in excess of 100 m2/g.
4. A process as claimed in claim 1 in which the desulphurization catalyst has a total pore volume above 0.45 ml/g, of which at least 0.4 ml/g is present in pores with a diameter of at least 0.7xp and at most 1.7xp and a sharp pore diameter distribution, characterized by:
(a) the presence of less than 20% of the total pore volume in pores with a diameter smaller than 0.7xp, and (b) the presence of less than 20% of the total pore volume in pores with a diameter larger than 1.7xp.
(a) the presence of less than 20% of the total pore volume in pores with a diameter smaller than 0.7xp, and (b) the presence of less than 20% of the total pore volume in pores with a diameter larger than 1.7xp.
5. A process as claimed in claim 1, in which the desulphurization catalyst contains 0.5-10 parts by weight, of nickel and/or cobalt and 2.5-30 parts by weight, of molybdenum ant/or tungsten per 100 parts by weight of carrier.
6. A process as claimed in claim 5, in which the atomic ratio in the desulphurization catalyst between nickel and/or cobalt on the one hand and molybdenum and/or tungsten on the other lies between 0.1 and 5.
7. A process as claimed in claim 1, in which the desulphurization catalyst is used in sulphidic form.
8. A process as claimed in claim 1, in which the desulphurization catalyst contains alumina or silica-alumina as carrier.
9. A process as claimed in claim 5, in which a desulphurization catalyst is used which is prepared by co-impregnating a carrier in one or more steps with an aqueous solution containing one or more nickel and/or cobalt compounds and one or more molybdenum and/or tungsten compounds, followed by drying and calcining of the composition.
10. A process as claimed in claim 1, in which the desulphurization is carried out by passing the demetallized oil at elevated temperature and pressure and in She presence of hydrogen in upward, downward or radial direction through one or more vertically arranged reactors containing a fixed catalyst bed.
11. A process as claimed in claim 1, in which the desulphurization catalyst has a specific average particle diameter of 0.6-2.0 mm.
12. A process as claimed in claim 1, in which the demetallization catalyst contains one or more metals having hydrogenative activity, on a carrier.
13. A process as claimed in claim 1, in which the demetallization is carried out by passing the residual hydrocarbon oil at elevated temperature and pressure and in the presence of hydrogen in upward, downward or radial direction through one or more vertically arranged reactors containing a fixed or moving catalyst bed.
14. A process as claimed in claim 1, in which demetallization of the residual hydrocarbon oil is carried out according to the "bunker flow"
principle or the "fixed bed swing" principle and that the desulphurization of the demetallized oil is carried out in a conventional fixed bed.
principle or the "fixed bed swing" principle and that the desulphurization of the demetallized oil is carried out in a conventional fixed bed.
15. A process as claimed in claim 1, in which both the demetallization and desulphurization are carried out at a temperature of 350-450°C, a hydrogen partial pressure of 75-200 bar, a space velocity of 0.5-10 parts by weight of feed per part by volume of catalyst per hour and a hydrogen/feed ratio of 200-1000 N1 of H2/kg of feed.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7404281A NL184479C (en) | 1974-03-29 | 1974-03-29 | PROCESS FOR THE CATALYTIC HYDROGENIZING DESULFULIFYING OF PRE-METALIZED HYDROCARBONS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1062642A true CA1062642A (en) | 1979-09-18 |
Family
ID=19821069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA219,667A Expired CA1062642A (en) | 1974-03-29 | 1975-02-10 | Process for the conversion of hydrocarbons |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS6027713B2 (en) |
| CA (1) | CA1062642A (en) |
| DE (1) | DE2513856C2 (en) |
| FR (1) | FR2265844B1 (en) |
| GB (1) | GB1505671A (en) |
| IT (1) | IT1034659B (en) |
| NL (1) | NL184479C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7607551A (en) * | 1976-07-08 | 1978-01-10 | Shell Int Research | METHOD FOR THE METALIZATION OF HYDROCARBON OILS. |
| NZ184200A (en) * | 1976-08-13 | 1979-11-01 | Mobil Oil Corp | Hydrometalation-desulfurization catalyst containing group vib and viii sulfide or oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1408759A (en) * | 1971-12-07 | 1975-10-01 | Shell Int Research | Catalytic hydrodesulphurisation process |
-
1974
- 1974-03-29 NL NL7404281A patent/NL184479C/en not_active IP Right Cessation
-
1975
- 1975-02-10 CA CA219,667A patent/CA1062642A/en not_active Expired
- 1975-03-26 JP JP50035660A patent/JPS6027713B2/en not_active Expired
- 1975-03-27 IT IT2176075A patent/IT1034659B/en active
- 1975-03-27 GB GB1292675A patent/GB1505671A/en not_active Expired
- 1975-03-27 FR FR7509645A patent/FR2265844B1/fr not_active Expired
- 1975-03-27 DE DE19752513856 patent/DE2513856C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2513856A1 (en) | 1975-10-02 |
| NL184479C (en) | 1989-08-01 |
| GB1505671A (en) | 1978-03-30 |
| NL7404281A (en) | 1975-10-01 |
| NL184479B (en) | 1989-03-01 |
| FR2265844B1 (en) | 1979-05-11 |
| JPS6027713B2 (en) | 1985-07-01 |
| IT1034659B (en) | 1979-10-10 |
| DE2513856C2 (en) | 1984-06-07 |
| FR2265844A1 (en) | 1975-10-24 |
| JPS50130805A (en) | 1975-10-16 |
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