CA1067845A

CA1067845A - Process for the upgrading of heavy hydrocarbon oils

Info

Publication number: CA1067845A
Application number: CA232,457A
Authority: CA
Inventors: Frans Goudriaan; Karel M.A. Pronk
Original assignee: Shell Canada Ltd
Current assignee: Shell Canada Ltd
Priority date: 1974-09-27
Filing date: 1975-07-29
Publication date: 1979-12-11
Also published as: DE2542878A1; MX3110E; FR2286186A1; FR2286186B1; JPS5160206A; NL7412761A; GB1523343A

Abstract

A B S T R A C T
A process for reducing the C5-asphaltenes content and the Vk210 of a heavy hydrocarbon oil by contacting the oil at elevated temperature and pressure and in the presence of hydrogen with a catalyst which satisfies a number of requirements with respect to particle size and porosity.

Description

~678~L~
` .

The present invention relates to a process for the up~rading of he-a~y hydrocarbon oils by contactillg these oils with a catal~st at elevated temperature and pressure and in the presence of hydrogen.
j ~igh-boilin~ hydrocarbon oils, such as residual oils obtained in the di~tillation of orude oils at atmospherio or reduced pressurel as well as certain heavy crude oil~, in particu].ar those originating from South America~ contain ConBiderable amoUntB of aæphaltenes and haYe a high viæcosity.
~o reduce the asphaltenes content and the viscosity these oils may be contactcd with a suitable cataly~t at elevated temperature and pressure and in the presence of hydrogen.
In ~uch prooe~ses, which are often referred to as processes fcr the upgrading of hea~y oil~, oils having a C5-asphaltenes i 15 content above 5y2w and a Vk above 30 cSt are contacted with a oatal~st at a temperatur210 Or at lea6t 400C~ a hydrogen partiaI pressure of at least 100 bar and a Bpace velocity of at most 2.0 l.l 1.h 1, in order to reduoe the C5-asphaltenes content by at least 30% and the Vk by at least 50%
(C5-asphaltenes content and ~k 2f0the feed compared with that of the liquid reaction 210 product obtained). Suitable catalyst~ for thi~ purpose are catalyst~ oompri ing one or more metals ha~ing hydrogenation activity on a carrier.
An in~estigation by the Applioant into the upgrading Or heavy oilc with the aid of cataly~ta aompri~in~ one or more metals having hydrogenation activity on a carrier, has revealed that optimum catalyst~ for thia purpose should ~eet a nuMber of requirementæ with regard to their particle diameter and porosity. An optimum catalyst for the up~rading of heavy hydrocarbon oils should be taken to mean in this patent application a catalyst whose activity as well as ~tability are of a aufficiently hi~h level for this purpose.
It has been found that for the upgrading of heavy ,,~J;

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hydrocarbon oil~ the requirements with respect to particle diameter and poro~ity which an optimum catalyst f~hould meet are as Pollows. In the first place the cataly6ts should have a total pore voll~e above 0.40 ml/g, while the percentage of the total pore volume that consists of pores with a diameter above 100 nm(~) should be srnaller than 50.
~he cataly~ts 6hould further have sush a specific average pore diameter (p in nm) and ~pecific average partiole diameter (d in mm~ that the quotient p/d meet~ the requirements p/d ~ 3.5 - 0.02 v. ~inally, the catalysts flhould have a specifi¢ surface area larger than 100 m2/g.
In ca~es where the oatalysts have such 8 p and d that the quoti~nt p/d iB larger than 3.5-0.02 v, but i8 at most 10.0-0~15 v~ the catalysts have to meet the following addit~onal requirements:
(1) the nitrogen pore volume should be larger than 0.60 ml/g,

(2) the specific surface area should be larger than 150 ~2/g, and

(3) p 6hould be larger than 5 nm.
~he above-mentioned values of p and d ha~e been defined as ~ollows on the basis of their method of determination.
The way in which d is determined depends on the shape oP the catalyst particles. If the shape i~ such that the particle diameter distribution of the catalyst can be determined with the aid of a sieve analy3is, d is determined a~ follows. A~ter a complete sieve analy~is of a repre~entative catalyst sample has been carried out, d i~
read from a graph in which Por each ~uc¢essive sieve ~raction thè percentage by weight, based on the total weight of the catalyst sample, has been cumulatively plotted as a Punction of the linear average particle diameter oP the relevant sleve fraction; d is the particle diameter corresponding to 50~ of the total weight. ~hi~ method can be used to determine d of spherical and granular materials and of materials with a similar shape, such as extrudates 1~i7845 and pellets having a length/diameter ratio between 0.9 and 1.1. ~he determination of d of extr~date~ and pell~t~ having a length/diameter ratio smaller than 0.9 or larger than 1.1 and of similar cylindric~lly ~haped materials, whose particle diameter distribution cannot be determined with the aid of a sieve analysis, i5 carried out as follows. After a complete length distribution analysis (if the length/
diamster ratio is smaller than O.9) or after a complete diameter distribution analysis (i~ the length/diameter ratio i lar~er than 1.1) o~ a representative catalyst ple has been carried out, d is read from a graph in whioh for each succes3ive length and diameter fraction, re~peotively, the percentage by weight, based on the total ~`
weight of the catalyst ~ample, has been cumulatively plotted a~ a function of the linear a~erage size of the relevant fraction; d is the ~alue corresponding to 50,~ of the total weight.
After the complete pore diameter distribution of a cataly6t sample ha6 been determined, p is read from a ; 20 graph in which for the pore diameter range of 0-100 nm, ~or each successive pore ~olume increment smaller than or equal to 10% of the pore volume, the quotient of the pore yol~me increment and the corresponaing pore diameter ~nterYal has been cumulatively plotted as a function of the linear average pore diameter over the rele~ant pore diameter interval; p i~ the pore diameter corresponding to 50% of the total quotient at 100 nm.
A determination of the complete pore diameter distribution of the ¢atalyst may very ~uitably be carried out with the aid of the nitrogen adsorption/desorption method (as described by E.V. ~allou and O.K. Doolen in Analytical Chemistry 32t 532 (1960)) combined with the mercury penetration method (as described by H.L. Ritter and L.C. Drake in Industrial and En~ineering Chemistry, Analytical Edition ~1L 787 (1945)), applying mercury ~L~67~4S

pressures of 1-2000 bar. In this case, the pore diameter distribution of the catalyst in the pore diameter range below and including 7.5 ~m is calculated from the nitrogen desorption isotherm (assuming cyli~drical pores) according to the method described by J.C.P. ~roekhoff and J.H. de ~oer in Journal of Catalysi~ 10~ 377 (1968) and the pore diameter distribution of the catalyet in the pore diameter range above 7.5 nm i~ calculated with the aid of the formula:
pore diameter (in nm) = ~ 000 absolute mercury pressure (in bar) The nitrogen pore volume and the total pore volume mentioned in this patent application are determined a~
follows. ~he nitrogen pore volume of a catalyst ls the pore volume determined with the aid of` the above-mentioned nitrogen adeorption/desorption method. ~he total pore volume of a catàlyst i~ the sum of the nitrogen pore volume pre~ent in pore~ with a diameter below and including 7.5 nm (determined ~ith the aid of the above-mentioned nitrogen adsorption/
desorption method) and the mercury pore volume present in pores with a diameter abo~e 705 nm (determined with the ald of the above-mentioned mercury penetration method). ~he ~pecific surface areas mentioned in this patent application have been determined according to the ~.E.T. method.
~ he present patent appllcation therefore relate~ to a proce s for the upgrading of a heavy hydrocarbon oil 9 in wbich proce~ the C5-asphaltenes content and the Vk of an oil with a C5-asphaltenes content above 5yw and a V21 above 30 cSt, are reduced by at least 30% and at least 50~2,1 respectively, by contacting the oil, at a temperature of at lea~t 400Cj a hydro~en partial pres~ure of at least 100 bar and a space velocity of at most 2.0 1.1 1. h 1, with a cataly6t compri~in~ one or more metals having hydrogenation activity on a carrier, which cataly~t meets the followin~
requirement 6: .
(1) p/d ~3.5 0.02 v, in which p is the specific average pore diametex in nm, d i8 the specific average particle 7~

diameter in mm and v i~ the percentage of the total pore volume that consi~ts of pore`s with a diameter lar~er t}lan 100 nm, (2) the total pore volume is larger than 0.40 ml/g, (3) v i~ smaller than 50, and

(4) the specific surface area i~ larger than 100 m2~g;
if the cataly~t has such a p and d that the quotisnt p/d i~ larger than ~.5-0.02 v, but at most 10-0.15 v~ the cataly~t ha~ to meet the ~ollowing additional requirementæ:
(a) the nitrogen pore volume is lar~er than 0.60 ml/~, (b~ the ~pecific ~urfaoe area is larger than 150 m2/g, and (o) p i~ larger than 5 nm.
~ he catalysts applied according to the invention are charaoterized, among-other thing~, by a given relation between their~average pore diameter and average particle diameter. It iæ esaential that the a~erage pore diameter and the average particle diameter used for the characterization of the oatalysts should be determined accordin~ to the method~ specified above for the ~pecific average pore diameter and ~pecific average particle diameter, because, i~ for the characterization of the catalysts u~e is made of an average pore diameter or an average particle diameter determined by a method other than those one speci~ied above for the specific average pore diameter and ~pecific average particle diameter (for example an avera~e pore diameter caloulated a~ four timea the quotient of the pore volume and the speoific ~urface area or an a~erage particle diameter caloulated as the linear average), entirely different results may be obtained.
~he relatien between p and d makes it possible at a given d of the catalyst particle~ to determine a minimum value above whi¢h the p of the catalyst particles ~hould be selected to obtain an optimum oatalyst. Consequently, it is al~o possible to derive from the relation found the maximum value bslow whi¢h the d Or ¢atalyst particles havine a ~L0~;78~5 - certain p should be ~elected to obtain an optimum catalyst.
~he most suitable values for p and d, re~pectively, within the ranges found are deterrnined by, among other factors, the compo6ition of the hydrocarbon oil to be treated.
Ac¢ordin~ as the hydrocarbon oil to be treated has a higher C5-asphaltenes content, a catalyst with a higher p/d i~ preferred.
; The upgrading of hea~y hydrocarbon oil~ accordin~ to the in~ention is preferably carried out in the pre~ence of a catalyst compri~in~ 0.1-15 pbw metal~ having hydro~enation activity per 100 pbw carrier. ~he metal~ ha~ing hydrogenation a¢tivity are preferably seleoted from the group consi~ting of nickel, cobalt, molybdenum, vanadium and tun~sten. It is further preferred that the catalyst ~hould comprise at least one metal selected from the group consisting of nickel and cobalt and at least one metal seleoted from the group consisting of molybdenum, vanadium and tungsten and further that the atomic ratio between nickel and/or cobalt on the one hand and molybdenuml vanadium and/or tungsten on the other hand iB between 0.05 and 3Ø Suitable metal oombinations are nickel-vanadium7 oobalt-molybdenum, niokel-molybdenum and nickel-tungsten~
~he metal load of the catalysts applied acooraing to the inYention prererably amount~ to 0~5-10 pbw and in particular 2.0-7.5 pbw per 100 pbw carrier. Especially preferred catalysts accordin~ to the in~ention are catalysts comprisin~
about 1/2 pbw nickel and about 2 pbw vanadium per 100 pbw oarrier, a~ well a~ cataly~t~ compri~ing about 1 pbw nickel or cobalt and about 4 pbw molybdenum per 100 pbw carrier. The metal~ may be present on the carrier in the metallic form or in the form of their oxides or sulphides. Preference is gi~en to cataly~ts in which the metals are present on the carriers in the form of their ~ulphides. Sulphidation of the present satalyst~ may be carried out by any technique for the sulphidation of ~0678~5 catalysts known in the art. Sulphidation may9 for instance, be carried out ~y contactin~ the catalysts with a sulphur-containing gas~ 6uch a~ ~ mixture of hydro~en and hydrogen ~ulphlde, a mixture of hydrogen and carbon diæulphide, or a mixture of hydrogen and a mercaptan such as butyl meroaptan.
Sulphidation may al~o be carried out by contacting the catalystc with hydrogen and with a ~ulphur-containing hydrocarbon oil, such as a ~ulphur~oontaining kerosine or ga~ oil. In addition to the above-mentioned catalytioally active metal~, the cataly~ts may oontain other catalytically a¢tive metals and promoters such a~ pho~phorus 9 boron and halogen~, such as fluorine and chlorine. Very suitable carriers for the catalysts are oxides o~ the elements of Group II, III or IV of the Periodic ~able of Elements or mixture~ of the said oxides, such as silica, alumlna, magnesia, zirconia, thoria, boria, hafnia, silica-alumina, ilica-ma~neæia and alumina-magne~ia.
Another type of material that i8 very suitable to aerve as the carrier for the present catalysts i8 soot, i~
paxticular a 600t obtainèd as by-product of the partial oxidation of hydrocarbons with air~ oxygen or mixtures o~
air and oxygen, either in the pre~ence or in the absence Or ~team. ~paxt from the fact that 800t i8 a suitable carrier ~or the pre~ent oataly~ts, its u~e for this pu~po e ha~ an additional advantage when the catalyst~ are employed for the upgrading of hydrooarbon oils having a high metal oontent, which advantage i8 not aohieved when any of the oxidi¢ oarriers mentioned hereinbefora i~ employed. ~his oan be eluoidated a~ followR. Although the pre~ent catalysts show a long life when applied in the process according to the invention to hydrocarbon oils having a high metal ~ontent, even these catalysts are in the long run deaotivated as ~ result of the deposition of large amounts of metal~, in particular vanadium and nickel, and therefore, after a certain time of operation, they hare to be replaced. If it i~ intended ,7~

g to recover the deposited metals from the deactivated catalyst, the use of a catalyst on soot as the carrier offers the considerable advantage over catalysts on other carrier materials that the carrier can æimply be removed from the deactivated cataly~t by combustion, after which a mixture of the metal~ concerned i~ left behind in the form of their oxides for further working up.
The prepar~tion Or the catalysts may be ¢arried out by depositing the metals concerned on a carrier ha~ing such a pore diameter distribution and specific average pore diameter that after depo~ition of the metal~ thereon a catalyst i~ obtained which meets the requirement~ of the invention, either as such or after the 6pecific average catalyst particle diameter has been decreased.
~he porosity of the finished catalyst depends to a ~ertain extent on the~metal load applied. In general, it is true to say that when starting from a carrier with a ~iven porosity, the poro~ity of the finished catalyst will be lower accordin~ as the metal load i8 higher. ~hi~
phenomenon play9 only a minor role when relatively low metal loads are applied. ~his meanæ that at the relati~ely low metal loads which are preferred for th~ catalysts a¢cordin~ to the invention, the porosity of the finished oatalyst is mainly determined by the poro~ity of the 2S carrier applied, so that for the preparation of these cataly~t~ carriers should be selected having a porosity which diff~rs only little from the desired porosity of the finishea catalyst. ~he porosity of a carrier may also be influenced by means of a high-temperature treatment, either in the presence or in the abæenoe of ~team.
~ he porosity of a carrier i~ mainly dete~ined by the way in whioh the carrier has been prepared. Catalyst carriers Or the m~tal-oxide type are usually prepared by adding to one or more aqueous solutions of the salts of the metals concerned one or more ~elating agents, as a 1~:1 E;7~

.
result of which the metal~ are precipitated in the form of metal hydro~ide gels, which are subQequently shaped and calcined. ~sually, before being shaped the metal hydroxide ~els are allowed to age for some time. During the preparation of the carrier there i~ ample opportunity to influen¢e the porosity of the carrier. The poro6ity of the final carrier ;~ depend6, among other factors, on the rate of addition of the gelating agent~, and on the temperature and p~ applied during the formation of the gel. ~he poroaity of the final oarrier may also be influenced by addition of certain chemical~ to the gel, such a~ phosphorus oompounds and/or halogen compounds. If agein~ i~ applied, the porosity of the final carrier also depends on the a~eing time and on the temperature and p~ applied during a~eing. In the preparation of mixed metal oxide carrier~ a further aapect of importance for the porosity of the final carrier i~ the way in which the metal hydroxide gel6 are precipitated:
simultaneouQly or separately, e~g. one ~el on top of the other. The poro~ity of the final carrier further depends on the way ln which the carrier particles ha~e been shaped, on ~ the conditions applied during shaping, and on the temperature `~ ~pplied during calcination.
During shaping the porosity Or the carrier particle~ i8 influenced, for e~ample, by the type and amount of peptizing agents and binder~ which are usually added during thi~ 6tage o~ carrier preparation, by the addition of certain chemicals, and by the addition of amali amount~ of inert materials. If the ¢arrier particles are ~haped by extrucion or tablettin~, ;
the porosity of the final carrier i8 influenced by the extxuaion or tabletting pressure applied. If UBe i~ made of the spray-drying technique, the porosity Or the oarrier i8 influenced by the spraying temperature and spraying pressure applied.
The catalysts may be prepared by any tech~ique for the preparation of ~upported cataly~ts known in the art. It iB

:~L0678~5 not necessary for the catalytically acti~e metals to be deposited on a finished carrier. ~hey may alæo be incorporated into the carrier material during the preparation thereof, for example, prior to shaping. Incorporating the catalytically active metals into the carrier at an early stage of catalyst preparation may al~o have a considerable influence on -the porosity of the finished catalyst.
~ n attracti~e way in which the present catalyst~ may be prepared is by single or multistep coimpregnation of a carrier with an aqueous solution compriaing one or more nickel and/or cobalt compounds and one or more molybdenum, ~anadium and/or tungsten compounds, followed by drying and calcining. If the impregnation is carried out in several ~teps, the material may be dried and calcined, if desired, between the successive ~teps of impregnation. Drying and calcining are preferably carried out at temperatures between 50 and 150 C and between 150 and 550C, respectively.
Example~ of quitab1e water-soluble compounds of nickel, cobalt, ~anadium, molybdenum and tungsten which may be applied in the preparation of the present catalystRare nitrates, chlorides, formates and acetates of niokel and cobalt, vanadyl oxalate, vanadyl sulphate, ammonium vanadate and vanadyl acetyl acetonate, ammonium molybdate and ammonium tungstate. In order to inorea~e the ~olubility of these oompounds and to stabilize the solutions, certain oompounds,such as ammonium hydroxide, monoethanolamine a~d eorbitol~may be added to the solutions.
~ As carriers for the present catalysts aluminas, Hilicas and ~ilica-aluminas are preferred. Very suitable carriers are alumina particles or silica particles prepared by ~pray-drying Or an alumina or silica gel, followed by ~haping Or the spray-dried micro particles into larger particles, e.g. by extrusion, and spherical alumina particles or silica particles obtained by the well-known oil drop method. The latter method comprises formation of an alumina 84~

or silica hydxosol, combining the hydro~o] with a æuitable gelating agent and disperRing the mi~ture as droplets into an oil which ma~ be kept at an elevated temperature the droplets are allowed to remain in the oil until they have solidified to spherical hydrogel particles, which are subsequently isolated, washed, dried and calcined. Very ~ suitable silica-alumina carriers for the present catalystæ
; are cogels of aluminium hydroxide gel on silica hydrogel.
In addition to extrusion and tabletting,which ha~e already been mentioned hereinbefore as attractive shapin~
techniques for the preRent catalyct~ and catalyst carriers, another attxacti~e ~haping technique i8 the well-known nodulizing technique. Acoording to this method catalyst particles or catalyst-carrier particles having a diameter ~ 15 of at most 0.1 mm are agglomerated with the aid of a ; ~ranulation liquid to particle~ having a diameter of at least 1.0 mm. In actual practice oatalyst preparation aocording to the nodulizing technique usually takes place as follows. Catalyst-carrier material having a diameter of at most 0.1 mm is placed on a rotatin~ disc provided with a raised edge and a scraping device. ~he disc i8 disposed at a specific angle to the horizontal plane. A granulation Iiquid is sprayed onto the carrier mater:ial, which i8 in continuous motion on the disc. In praotice, when alumina i~
u~ed a~ the carrier, a dilute aqueous solution of acetic ~cid or citric acid iR usually employed as the granulation liquid. During the residence of the small particle~ on the disc, larger paxticles are formed from the small ones by agglomeration. The nodulizing technique may be oarried out either batchwise or continuou~ly. When the continuous proce~ is u~ed finely divided material ia continuously 6upplied to the rotating disc and agglomerated material continuou~ly leaves the disc via the top of the raised edge when this is in its lo~rest position. After the agglomerated particle~ have left the disc a sieve fraction ~O~i7~345 with the desired diameter is separated from it. Particles with a diameter smaller than that of the desired s;eve fraction may be recycled to the disc.
If the agglomerated material con~ains particles with a diameter larger than that of the desired sieve fraction, these particles, after reduction of the particle size, for instance by grinding, may also be recycled to the disc.
The conversion of the agglomerated material with the desired particle size into a suitable carrier material takes place by drying and calcination.
The emplacement of one or more metals with hydrogenation activity on the - carrier material thus prepared is usually effected by impregnation with an aqueous solution of compounds of the respective meta]s, followed by drying and calcination of the impregnated material.
If in the process according to the invention use is ~ade of a catalyst prepared according to the nodulizing technique, preference is given to a catalyst that meets one or more of the following conditions.
~1) The pore volume of the catalyst that consists of pores with a diameter larger than 50 nm should be at least 0.2 ml/g and preferably at least 0.3 ml/g.
(2) The ca~alyst comprises alumina as the carrier and has been prepared using dilute nitric acid as the granulation liquid.
(3) In the preparation of the catalyst the starting material from whlch larger particles are formed by nodulizing, has been mixed with a certain amount of glass powder, prefera`bly 0.5-15%w based on the amount of starting material with which it is mixed, and the particles formed by nodulizing are subjected to a calcination at a temperature above the softening temperature of glass.
(4) The catalyst comprises phosphorus, preferably in an amount of 0.5-5 pbw per 100 pbw carrier material.
~5) In the preparation of the catalyst the particles formed ~)678~5 have been rotated for some time after they have left the rotating di~c, but before drying and calcination ana prefexabl~ for a period of time at least equal ~ to the residence time of the materi.al on the rotating :~ 5 disc.
(6) In the preparation of the catalyst a granulat.ion liquid has been applled into whi.ch one or more compounds of metals with hydrogenation activity have been incorporated.
The relationship found between p and d makes it possible to prepare catal~sts having optimum properties for the ; upgrading of heavy hydrocarbon oils. If a catalyst or catalyst carrier is available of which d is too large in relation to p, it is possible to prepare therefrom an optimum catalyst or catalyst carrie~ by adapting d to p.
This can be effected in a simple way by reducing the particle size of the catalyst or catalyst carrier, for example bygrindin~ the particles.
~he process according to the inv~ntion i9 preferably carried out by passing the hydrocarbon o:Lls together with hydrogen in upward, downward or radial direction through one or more vertically disposed reactors containing a fixed or moving bed of the cataly~t particle3 concerned.
The process may, for instance, be carried out by passing the hydrocarbon olls together with hydro~en throu~h a verticall~ disposed catalyst bed in the upwara direction, the liquid and gas velocity used being such that expansion af the catalyst bed occurs (processing in ebullated bed operation). If several reactors are used in series for the process, the catalysts present in these reactors may differ from each other, for instance with resepct to their p, d and/or chemical composition. A very attractive embodiment Or the present process is one in which the hydrocarbon oil ia passed through a vertically disposed catalyst bed in which during operation fresh catalyst is periodically introduced at the top of the catalyst bed and spent ~0~ 5 - 15 ~
catalyst i8 withdrawn at the bottom thereof (processing in bunker flow operation). Another very attxactive embodiment of the present proce~s is one in which several reactors containing a fixed cataly~t bed are used, which reac-tor~
are alternately used for the process; while the process i~
carried out in one or more of the~e reactors, the catalyst in the other reactors iB replenished (processing in fixed-bed swing operation). If desired, the process may also be carried out by suspending the catalyst in the hydrocarbon oil to be demetallized (prooessing in slurry phase operation).
Por the upgrading of heavy hydrocarbon oils use iB
generall~ ~ade of catalyst particle~ having a d of 0.~-5.0 mm.
Catalyst particles having a d of 0.5-4.0 mm and in particular of o.6-3.0 mm are preferred for this purpose.
~he catalyst particles preferably have a total pore volume of at least 0.50 ml/g, while the ~pecific surface area is above 150 m2/g.
The process according to the invention is preferably carried out at a temperature of 400-500C, a hydrogen partial pre~sure of 100-300 bar and a space velocity of 0.2-2.0 l.l 1,h 1.
Example~ of heavy hydrooarbon oils which can be upgraded by application of the prooess according to the lnvention are crude oils and residues obtained from the distillation of crude oils at atmospheric or reduced pressure,suoh as topped crude oils and long and short residue~.
The invention will now be further eluciaated with the aid of the following example.
Exam~le Seven catalysts were tested for the upgrading of a re~idual hydrocarbon oil having a C5-asphaltenes content of 11.0%w and a V} of 183 cSt, which oil had been obtained as residue in the 21 atmospheric distillation of a crude oil originating from South America. ~o this end the oil, together ~OG784S
.

with hydrogen, was passed dowrlward~ through a cylindrical~
vertically diRposed fixed cataly~t bed at a temperature of 410C, a hydxogen partial pressure of 125 bar, a space velocity of 0.4 1.1 1.h 1 and an exit gas rate of 250 Nl/kg of feed. ~he catalyst~ were applied in the form of their sulphides. The preparation of the seven catalysts is described hereinafter. The results of the upgrading experiments as well as the properties of the catalysts ha~e been collected in the table.
Catal~st_A
As starting material u~e was made of an alumina obtained by spray-drying with a d smaller than 0.09 ~m, thi~ alumina having a pore vol~ulZe of 1.2 ml/~ consisting of pore~ with a diameter larger than 50 nm. Of this alumina 100 g was mixed with 2 g glass powder with a d smaller than 0.09 mm; the ` mixture was put on a rotating disc and 100 ml of an aqueous ; solution containing 3.5 g citric acid was ~radually sprayed onto ito The rotating disc, which was provided with a raised edge of 10 cm high, had a diameter of 40 cm. ~he disc made 40 revolutions per minute and was disposed at an angle of 45 to the horizontal plane~ After 15 minutes' residence time the nodules formed were removed from the disc. After drying at 120C a sieve ~raction with a d of 2.0 mm was isolated from the dried material. After 1 hour's calcination at 600C followed by calcination for 1 hour at 800C the particles were impre~nated with an aqueous solution containing nickel nitrate, ammonium molybdate and ~4H2P04. Finally, the impregnated material was dried at 120C and calcined for 1 hour at 500C. The catalyst thus prepared contained 1 pbw nickel, 4 pbw molybdenum and 1 pbw phosphorus per 100 pbw alumina.
Ca_alyst ~
~he starting material was a soot with a d smaller than 0.1 mm, which soot had a pore volume of 0.58 ml/g consisting : ' .

~o~ s _ 17 _ of pores with a diameter larger than 50 nm. ~he soot had been obtained as a by-product of the partial oxidation of hydrocarbons with air. ~he soot, being available in the form of a slurry in water, ~12S isolated from it by filtration, drying of the filter cake and grinain~ of the dried material to the particle size mentioned. ~ro~ the ~oot nodules were prepared. ~he preparation of the nodules from the soot was carried out in substantially the same way as that of the nodules from alumina a~ described for cataly~t A, the difference being, however, that in the pre~ent case no glas~ powder was used and that an aqueou~
~olution of ligno 6ulphonate was used as the granulation liquid. After 15 minutes' re~idence time the nodules formed were removed from the disc. After diying at 120C a sieve fraction with a d of 1.8 ~m was isolated from the dried material. After 1 hour'~ calcination in a nitrogen strea~
at 700C these particleæ were impregnated with an aqueous solution containing nickel nitrate and vanadyl oxalate.
Finall~, the impregnated material was d~ied at 120C and calcined for 1 hour at 500 C in a nitrogen stream. ~he oatalyst thus prepared contained 0.5 pbw nickel and 2 pbw vanadium per 100 pbw 800$.
Catalyst C
This cataly~t, which comprised 0.5 pbw nickel and 2.0 pbw ~anadium per 100 pbw alumina carrier was prepared by impregnation of an alumina with an aqueou6 solution containing ~anadyl oxalate and nickel nitrate, followed by drying and calcination of the composition.
Cataly~t D
~his catalyst, which comprised 0.5 pbw nickel and 2.0 pbw vanadium per 100 pbw silica carrier was prepared in subst~ntially the same way as catalyst C, the differen¢e being, howe~er, that in the present case a silica instead Or an alumina was u~ed as the carrier.

~6'7~3~S

Catal;rst 13 ~ his catalyst, which comprised 4.0 pbw cobalt and 11.0 pbw molybdenum per 100 pbw alumina carrier wa6 prepaxed by impreg~ation of an alumina with an aqueous

5 ~olution conl;aining cobalt nitrate, ammonium molybdate and hydrogen peroxide, followed by dry~ng and calcination of the compo~ition.
Catal~st F
~his catalyst, which comprised 2.5 pbw cobalt and 10 6.0 pbw molybdenum per 100 pbw alumina carrier, was prepared in ~ubstantially the came way as cataly6t E.
Catalyst G
Thi~ catalyst, which comprised 1.0 pbw nickel and 8.0 pbw molybdenum per 100 pbw alumina carrier, waæ
15 prepared in sub~tantially the 6ameway a~ catalyst E, the differellce being, however, that in the present case an impregnation liquid was used containing nickel nitrate in~tead of cobalt nitrate.
Table ` 20 Cataly~t No. A :E~ C D E ~ a Specific urface 264 450 236 272 353 303 210 ~otal pore volume- 1.39 1,50 0.86 o.94 -74 045 078 25 Nitrogen pore0.74 0. ao0.72 0.89 0.59 0.45 0.55 Pore volume consisting of pore~ with a 30 diameter larger than 50 nm,ml/g 0.800.36 v, % 47 8 20 5 25 c0.5 22 d, mm 2.9 1.8 ~.o 1.8 1.0 1.5 1.5 p, nm 9 38 14.6 9.4 9.4 4.8 7.6 35 Experiment No. 1 2 3 4 5 6 7 Reduction in C -asphaltenes co~tent af ter proces~ing 2 tons feed/kg 40 catalyst, ~ 47 33 34 38 43 15 6 ~06'i'~3~5 -- 19 -~
~ble oo~t'd Catalyat ~o. A ~ C D E E G
Reduction in Vk after 210 pxocessing 2 tons feed/kg catalyst, =============_..================_======_==_================
A cataly~t i~ optimum under the conditions applied durin~ these up~rading experiments when the criterion is met that the catalyst is still capable of reducin~ the C5-asphaltenes c~ntent a~d the Vk of the oil by at least - 30% and at least 50~0, respective~10after two tons of the oil have been processed over the catalyst.
Experiments 1-5 (in which catalyst~ were applied which met the above-mentioned requirements concerning the reduction ; 15 of asphaltenes content and vi6cosity) are upgrading experiments within the scope of the present invention.
In experiments 1, 2, 3 and 5, in which catalysts were applied with p/d ~10.0-0.15 v, these cataly~ts al50 satisfied the further requirements of the invention concerning v(<50%), total pore volume (>0.40 ml/g) and ~pecific surface area (~100 m2/g). In experiment 4, in which a catalyst was applied with 10.0-0.15 v ~p/d ~3.5-0.02 ~, this oataly~t also eatisfied the further requirements of the invention concerning - v(~50%), p(~5nm), nitrogen pore volume (~o.60 ml/g) and ~pecific urface area ~150 m2/g).
Experiments 6 and 7 (in which the catalyst~ did not meet the above re~uirements concerning the reduction of a~phaltenes content and viscosity) are experiment~ outside the 6cope o~ the pre~ent invention. In experiment 6 a catalyst was applied with p/d ~3.5-0.02 v. In experiment 7 a catalyst was applied with 10.0-0.15 v ~p/d ~3.5-0.02 v, but with a nitrogen pore volume smaller than 0.60 ml/~.
.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the upgrading of a heavy hydrocarbon oil, in which process the C5-asphaltenes content and the Vk210 of an oil with a C5-alphal-tenes content above 5%w and a Vk210 above 30 cSt are reduced by at least 30%
and at least 50%, respectively, by contacting the oil, at a temperature of at least 400°C, a hydrogen partial pressure of at least 100 bar and a space velo-city of at most 2.0 1.1-1.h-1, with a catalyst comprising one or more metals having hydrogenation activity on a carrier, which catalyst meets the following requirements:

(1) p/d>3.5-0.02 v, in which p is the specific average pore diameter in nm, d is the specific average particle diameter in mm and v is the percentage of the total pore volume that consists of pores with a diameter larger than 100 nm, (2) the total pore volume is larger than 0.40 ml/g, (3) v is smaller than 50, and (4) the specific surface area is larger than 100 m2/g; if 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 re-quirements:
(a) the nitrogen pore volume is larger than 0.60 ml/g, (b) the specific surface area is larger than 150 m2/g, and (c) p is larger than 5 nm.

2. A process according to claim 1, which process is carried out in the presence of a catalyst comprising 0.1-15 pbw metals having hydrogenation activity per 100 pbw carrier.

3. A process according to claim 2, which process is carried out in the presence of a catalyst comprising 0.5-10 pbw metals having hydrogenation activity per 100 pbw carrier.

4. A process according to claim 2, which process is carried out in the presence of a catalyst comprising 2.0-7.5 pbw metals having hydrogenation activity per 100 pbw carrier.

5. A process according to claims 2, 3 or 4, which process is carried out in the presence of a catalyst of which the metals having hydrogenation activity are selected from the group consisting of nickel, cobalt, molybdenum, vanadium and tungsten.

6. A process according to claim 3, which process is carried out in the presence of a catalyst comprising at least one metal selected from the group consisting of nickel and cobalt and at least one metal selected from the group consisting of molybdenum, vanadium and tungsten.

7. A process according to claim 6, which process is carried out in the presence of a catalyst in which the atomic ratio between nickel and/or cobalt on the one hand and molybdenum, vanadium and/or tungsten on the other hand is between 0.05 and 3Ø

8. A process according to claim 7, which process is carried out in the presence of a catalyst comprising either about 1/2 pbw nickel and about 2 pbw vanadium, or about 1 pbw nickel or cobalt and about 4 pbw molybdenum per 100 pbw carrier.

9. A process according to claim 8, which process is carried out in the presence of a catalyst containing the metals with hydrogenation activity in the form of their sulphides.

10. A process according to claim 8, which process is carried out in the presence of a catalyst containing a carrier selected from the group consisting of silica, alumina, silica-alumina and soot.

11. A process according to claim 10, which process is carried out in the presence of a catalyst containing soot as the carrier, which soot has been obtained as by-product of the partial oxidation of hydrocarbons with air, oxygen or mixtures of air and oxygen, either in the presence or in the absence of steam.

12. A process according to claim 10 which process is carried out in the presence of a catalyst that comprises alumina as the carrier and has been prepared using dilute nitric acid as the granulation liquid.

13. A process according to claim 11 or 12, which process is carried out in the presence of a catalyst prepared according to the nodulizing technique.

14. A process according to claim 11, which process is carried out in the presence of a catalyst whose pore volume that consists of pores with a diameter larger than 50 nm should at least be 0.2 ml/g.

15. A process according to claim 12, which process is carried out in the presence of a catalyst whose pore volume that consists of pores with a diameter larger than 50 nm should at least be 0.2 ml/g.

16. A process according to claim 15, which process is carried out in the presence of a catalyst in the preparation of which the starting material from which larger particles are formed by the nodulizing technique has been mixed with from about 0.5 to 15% by weight based on the starting material of glass powder, and in which the particles formed by the nodulizing technique are subjected to a calcination at a temperature above the softening temperature of glass.

17. A process according to claim 16, which process is carried out in the presence of a catalyst comprising phosphorus, in an amount of 0.5-5 pbw per 100 pbw carrier material.

18. A process according to claim 17, which process is carried out in the presence of a catalyst in the preparation of which the particles formed are rotated for some time after they have left the rotating disc, but before drying and calcination, and preferably for a period of time at least equal to the residence time of the material on the rotating disc.

19. A process according to any one of claim 16, 17 or 18, which process is carried out in the presence of a catalyst in the preparation of which a granulation liquid is applied into which one or more compounds of metals with hydrogenation activity have been incorporated.

20. A process according to claim 10, which process is carried out in the presence of a catalyst comprising as the carrier alumina particles or silica particles prepared by spray-drying of an alumina or silica gel, followed by shaping of the spray-dried micro particles into larger particles.

21. A process according to claim 10, which process is carried out in the presence of a catalyst comprising as the carrier spherical alumina particles or silica particles prepared with the aid of the oil drop method.

22. A process according to claim 10, which process is carried out in the presence of a catalyst comprising as the carrier a cogel of aluminium hydroxide gel on silica hydrogel.

23. A process according to claim 22, which process is carried out by passing the hydrocarbon oil in the presence of hydrogen in upward, downward or radial direction through one or more vertically disposed reactors containing a fixed or moving bed of the catalyst particles concerned.

24. A process according to claim 23, which process is carried out by passing the hydrocarbon oil through a vertically disposed catalyst bed in which during operation fresh catalyst is periodically introduced at the top of the catalyst bed and spent catalyst is withdrawn at the bottom thereof (processing in bunker flow operation).

25. A process according to claim 23, which process is carried out in several reactors containing a fixed catalyst bed, which reactors are alternately used for the process; while the process is carried out in one or more of these reactors, the catalyst in the other reactors is replenished (processing in fixed-bed swing operation).

26. A process according to claim 25, which process is carried out in the presence of a catalyst having a d of 0.4 - 5.0 mm.

27. A process according to claim 26, which process is carried out in the presence of a catalyst having a d of 0.5-4.0 mm and preferably of 0.6-3.0 mm.

28. A process according to claim 27, which process is carried out in the presence of a catalyst having a total pore volume of at least 0.50 ml/g.

29. A process according to claim 28, which process is carried out in the presence of a catalyst having a specific surface area above 150 m2/g.

30. A process according to claim 29, which process is carried out at a temperature of 400-500°C, a hydrogen partial pressure of 100-300 bar and a space velocity of 0.2-2.0 1.1-1.h-1.

31. A process according to claim 14, 15 or 16 which process is carried out in the presence of a catalyst whose pore volume that consists of pores with a diameter larger than 50 nm should at least be 0.3 ml/g.

32. A process according to claim 17 or 18 which process is carried out in the presence of a catalyst whose pore volume that consists of pores with a diameter larger than 50 nm should at least be 0.3 ml/g.