CA1183098A - Hydrogenation of carbonaceous material - Google Patents
Hydrogenation of carbonaceous materialInfo
- Publication number
- CA1183098A CA1183098A CA000422172A CA422172A CA1183098A CA 1183098 A CA1183098 A CA 1183098A CA 000422172 A CA000422172 A CA 000422172A CA 422172 A CA422172 A CA 422172A CA 1183098 A CA1183098 A CA 1183098A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- hydrogenation
- hydrogen
- bitumen
- carbonaceous material
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Abstract
ABSTRACT OF THE DISCLOSURE
Discloses that in the hydrogenation of liquid, carbonaceous crude material such as bitumen and other heavy oils, a catalyst derived from the addition of Fe2(CO)9 is advantageously used to provide a superior yield of distillable oils compared to prior practice.
Discloses that in the hydrogenation of liquid, carbonaceous crude material such as bitumen and other heavy oils, a catalyst derived from the addition of Fe2(CO)9 is advantageously used to provide a superior yield of distillable oils compared to prior practice.
Description
'7A ~h~(3~
2~4 The Hydrogenation of Carbonaceous_Material The present lnvention relates to the hydro-genation of liquid carbonaceous ma~erial, e.g. para~finic crudes, for e~ample bitum~n, heavy oil,petroleum pitch, oil shale and conventional crudP vacuum residues, and paxticularly to ~.he hydrogenak~on of such material in the presence of a catalyst.
A great deal of efort has gone into developing eatalysts that can tolerate bitumen and heavy ~il hydro-cracking condikions. These effoxts have mainly drawn on the experience of petroleum hydro-treating and us~d ~upported heterogeneous catalysts which inerease the yield of llght, distillable hydro-carbons. However~ the use of such catalys~, e.g. Co-Mo supported on sn alumina base, has gi~en rise to many pro~lems: Il) the si~e of some molecules in pitch and other similar ear~onaceous materials is too large in relation to the pore slze of ~upported catalysts to be hydrogenated and these molecules are therefore left unreacted, (2) under the conditions necessary to hydrogenate bitumen etc. coke forms, which blinds the supported catalyst,, (3) the presence of impurities in the carbonaceous material e.g. Ni, V, Fe, clay and sil~ca foul the catalyst and 60 deactivate lt.
There have been ~any attempts to overcome the above problems but none has met with complete successD
~or example, it has been reported that alkali metal promoters decrease catalyst coking and extend catalyst life. It has also been suggested that a Co-Mo catalyst on a coke support reduces ooking and liabllity to fouling, but some coke is still formedO
The use of unsupported heterogeneous catalysts and of homogeneou~ catalys~s has not been so generally studied because of the difficulty in recovering the ~atalyst from the hydrogenation prDduct~ and also because many homogeneous and unsupported heterogeneous ~atalysts are unstable und~er the rigorous hydrogenatlon .,,~ ,~,
A great deal of efort has gone into developing eatalysts that can tolerate bitumen and heavy ~il hydro-cracking condikions. These effoxts have mainly drawn on the experience of petroleum hydro-treating and us~d ~upported heterogeneous catalysts which inerease the yield of llght, distillable hydro-carbons. However~ the use of such catalys~, e.g. Co-Mo supported on sn alumina base, has gi~en rise to many pro~lems: Il) the si~e of some molecules in pitch and other similar ear~onaceous materials is too large in relation to the pore slze of ~upported catalysts to be hydrogenated and these molecules are therefore left unreacted, (2) under the conditions necessary to hydrogenate bitumen etc. coke forms, which blinds the supported catalyst,, (3) the presence of impurities in the carbonaceous material e.g. Ni, V, Fe, clay and sil~ca foul the catalyst and 60 deactivate lt.
There have been ~any attempts to overcome the above problems but none has met with complete successD
~or example, it has been reported that alkali metal promoters decrease catalyst coking and extend catalyst life. It has also been suggested that a Co-Mo catalyst on a coke support reduces ooking and liabllity to fouling, but some coke is still formedO
The use of unsupported heterogeneous catalysts and of homogeneou~ catalys~s has not been so generally studied because of the difficulty in recovering the ~atalyst from the hydrogenation prDduct~ and also because many homogeneous and unsupported heterogeneous ~atalysts are unstable und~er the rigorous hydrogenatlon .,,~ ,~,
3~
- 2 - PC-2~.~4 conditions. No satisfactory method ~or catalyst recovery has hitherto been found.
The present invention cixcumven~s the need to recover the catalyst by u~ing a cheap and readily available substance as a ~atalyst which can be discarded without making the hydrogenation process uneconomic, Cheap materials, e,g.
Fe23, ~1203 and Ti02, have been replaced commercially by supported Co-Mo catalysts despite the problems outlined above.
The present invention is based on the discovery that ~e2(C93g as a source of catalyst ~a~ is effective in catalysing the hydrogenation of bitumen, (b) is not poisoned by impurities in the feed bitumen and (c~ because it is composed of cheap components, iron and carbon monoxide, it can be discarded without substantially prejudicing the economics of the hydrogenation process.
According to the presen invention, there is provided a process of hydrogenating liquid carbonaceous crude material, which process comprises heating the material in 2n contact with a catalyst derived from Fe2(CO)g in the presence of a hydrogen-containing gas.
The process of the present invention is especially useful in the hydrogenation of bitumen, particularly Athabasca bitumen.
The reactions that occur in the hydrogenation of carbonaceous material are complex. It may be that the Fe2(C0)9 does not itself act a~ a catalyst but that it is convexted under the conditions prevailing during hydrogenation into a different chemical ~pecies and it is that different species that acts as a catalyst~ ~hether that is the case or not, we have found that the addition of Fe2(CO)g to the hydrogenation reaction mass of beneficial.
An advantage of Fe~(CO)g as a source of catalyst is that it produces a ~uperior yield of distillable oils, which are the most valuable product of hydrotreating bitumen and other heavy oils. A further advantage is that Fe~iCO)g reduces coking compared to uncatalys~d reactions and, under some conditions, can eliminate coking altogether. This is particularly advantageous in that after one hydrogenation ¢~44t,~
step, the products can be distilled and the still bottoms, which contain the catalyst, can be recirculated to catalyse a further hydrogenation stage. When no coke is formed during hydrogenation, there is no coke build-up in such a cyclical operation, as a res~lt of which the operation of the equipment is much easier. Fresh catalyst may optionally be added before each hydrogenation step in which case a portion of the still bottoms should occasionally be bled off to prevent a build-up of iron. The bleed portion may be coked ~o to recover its content o valuable volatile oils and the iron values in the coke residue may be discarded because they have no commercial value.
Fe2(CO)g is cheap and readily available, It can be produced by exposing Fe~CO~s to ultra violet light in glacial acetic acid or petroleum.
The hydrogenation is preferably carried out at a temperature of from 400 to 500C, more preferably from 425 to 475C, at a hydrogen partial pressure of from 500 to 5000 pounds per square inch ~psi3, which corresponds to 3,450 to 34,500 kN/m2, more preferably from 2,500 to 3,500 psi (17,000 to 24,000 kN/m2). The hydrogen-containing gas used in the hydrogenation may be pure hydrogen or a carbon monoxide-hydrogen mixture.
Three Examples of processes in accordance with the present invention will now be given.
400 9 of Athabasca bitumen havins the following composition:
in welght pe~cent C~ ~2,.7 lO o 41 N 0. 4 ;9 S 4,,~3 Ash 1 and in parts pex milllon:
Ni 77 Fe 40B
and a onradson Carbon Resldu of 1~ 6~ was mixed with
- 2 - PC-2~.~4 conditions. No satisfactory method ~or catalyst recovery has hitherto been found.
The present invention cixcumven~s the need to recover the catalyst by u~ing a cheap and readily available substance as a ~atalyst which can be discarded without making the hydrogenation process uneconomic, Cheap materials, e,g.
Fe23, ~1203 and Ti02, have been replaced commercially by supported Co-Mo catalysts despite the problems outlined above.
The present invention is based on the discovery that ~e2(C93g as a source of catalyst ~a~ is effective in catalysing the hydrogenation of bitumen, (b) is not poisoned by impurities in the feed bitumen and (c~ because it is composed of cheap components, iron and carbon monoxide, it can be discarded without substantially prejudicing the economics of the hydrogenation process.
According to the presen invention, there is provided a process of hydrogenating liquid carbonaceous crude material, which process comprises heating the material in 2n contact with a catalyst derived from Fe2(CO)g in the presence of a hydrogen-containing gas.
The process of the present invention is especially useful in the hydrogenation of bitumen, particularly Athabasca bitumen.
The reactions that occur in the hydrogenation of carbonaceous material are complex. It may be that the Fe2(C0)9 does not itself act a~ a catalyst but that it is convexted under the conditions prevailing during hydrogenation into a different chemical ~pecies and it is that different species that acts as a catalyst~ ~hether that is the case or not, we have found that the addition of Fe2(CO)g to the hydrogenation reaction mass of beneficial.
An advantage of Fe~(CO)g as a source of catalyst is that it produces a ~uperior yield of distillable oils, which are the most valuable product of hydrotreating bitumen and other heavy oils. A further advantage is that Fe~iCO)g reduces coking compared to uncatalys~d reactions and, under some conditions, can eliminate coking altogether. This is particularly advantageous in that after one hydrogenation ¢~44t,~
step, the products can be distilled and the still bottoms, which contain the catalyst, can be recirculated to catalyse a further hydrogenation stage. When no coke is formed during hydrogenation, there is no coke build-up in such a cyclical operation, as a res~lt of which the operation of the equipment is much easier. Fresh catalyst may optionally be added before each hydrogenation step in which case a portion of the still bottoms should occasionally be bled off to prevent a build-up of iron. The bleed portion may be coked ~o to recover its content o valuable volatile oils and the iron values in the coke residue may be discarded because they have no commercial value.
Fe2(CO)g is cheap and readily available, It can be produced by exposing Fe~CO~s to ultra violet light in glacial acetic acid or petroleum.
The hydrogenation is preferably carried out at a temperature of from 400 to 500C, more preferably from 425 to 475C, at a hydrogen partial pressure of from 500 to 5000 pounds per square inch ~psi3, which corresponds to 3,450 to 34,500 kN/m2, more preferably from 2,500 to 3,500 psi (17,000 to 24,000 kN/m2). The hydrogen-containing gas used in the hydrogenation may be pure hydrogen or a carbon monoxide-hydrogen mixture.
Three Examples of processes in accordance with the present invention will now be given.
400 9 of Athabasca bitumen havins the following composition:
in welght pe~cent C~ ~2,.7 lO o 41 N 0. 4 ;9 S 4,,~3 Ash 1 and in parts pex milllon:
Ni 77 Fe 40B
and a onradson Carbon Resldu of 1~ 6~ was mixed with
4 ., 36 g o:E Fe2 (CO) g and charged ~nto a feed pot in whlch the mixture wa heated to about 1 50C~ The feed pot was then pres~urised wi1:h nitrogen to 200 psi (1380 kN/m2 ) and when ~he charge had reached temperature t it was txansferred to a pump feed pot,leaving that vessel with an overpressure o:E 40 psi. (275 kN/m23, ~ high pressure 13ran & :Luebbe pu~np was then used to ~ransfer the slurry iErom the feed pot, throuyh 0. 64 cm SS slurry transfer l~nes to a high pressure 1 litre AutoclaYe Engineers bolt and closure autocla~e. The autoclave was then pressurized to lt~0 - 2000 psi (6,~90 - 13~780 kN/m2 ) with hydrogen, sealed and he2ted to the reac:ti~n temperature ~4UO - 500C), Once at temperatuxe, the pressuxe of the vessel ~as "~opped Dffll at ~he requixed pre:ssuxe. Pxes~ur~ and temperature were maintained for a hal~ hour and the autoclave was then cooled to about 150C~ ll but .500 psi ~3,450 kN/m2) of the over-pressure was discharged through gas t~ansfer lines through a~ ~till head~ a high temperature eonderlser ( ~5~C~ d a low te~n~erature condenser C-20C~ and collec~ed in 40 litre ~ample ~anks ~or gas chrom~to-graphic analysi~. The contents o~ lthe autoclave were ~en discharged into a still ~ich was h~ated. An abr~spheric 3~) distillatiD~ was carrled out in ~ closed systern with reduced pressure in th~ low temperatuxe condenser be~ng used to adjust the pressure in the still and high temperature condenser to between O and 1 psig (between O and 7 kN/m ~O The ~tlll bottoms ~ere heated to ~bou$
350C, distillate wa~ collected from the high temperature condenser9 and condensate was obtalned fxom the low temperature condenser. The stlll bottoms were then allowed to drain lnto the pump feed pot. A fresh bitumen~catalyst ~lurry equal in welght to the distillate, condensate and hydrocarbon gases collected was then charged to the ~eedpot and transferred to the pump feed po~ as dPscribed abo~e. The mixture in the pump feed pot was then pumped ~o the high pressure autoclave and the above steps repeated. Testing continued for 6 complete cycles or until the still hottoms were too viscous to handlec The results o$ this process and of similar processes using no catalyst and using ~arshaw CoMo-0402T 1/8 catalyst, which is a Co-Mo catalyst supported on an alumina base, are shown in accompanying Table 1~
- 6 ~ 214 ,~ 'i ~;3 C U~ D M ~'1 t`l 9 ~ t`~
Y N ~ 8 N a~ D O ;1~ S~ 11 ~ - l ~
N~
8 ~ ~ 8 ~ ~ ~ y ~A yA ~
~ 7 ~ PC-2~4~
It can be seen from the results given in Table 1 that, under the prevailing conditions, the catalyst derived from Fe~(co~9 suppresses all coke production and th~ it gives about the same yield of the desirable distillate fraction as a fresh supported Co-Mo catalyst, which can be expected ~o poison readily.
Processes similar to those described in Example 1 were performed except the numbers of cycles were not limiked to 6 but the processes were continued until a st~ady state was reachedO The product slate is shown in Table 2 for processes using Fe2(~0~9 as a source of catalyst, and Harshaw CoMo-0204T 1,/8 catalysts and no catalyst. The Table also shows the percen~age of the hydrogenation product that must be recycled after distillation~
T 5C) 450 450 450 Catalyst Fe2(C039 none Harshaw CoMo Concentration 1.09 0 1.0 (g/100 g bitumen) Net Product Slate (wt %) CH4 4~03 6.82 6.08 C ~ 5 hydrocarbons 10.7 15.9 10.1 Condensate 8~05 12.7 10.8 Distillate 73.8 36.3 67.6 ~2S ~ C~S 3.3~ 2.27 5J4 Coke o 2 5 8 0 3~ To~al 100 100 100 .. .. ... ..
% Recycle 62 45 Ç2 It can be seen that the process employing an Fe2(CO~g derived catalyst gives a much better yield of the valuable distillate fraction than the process employing ~ 8 - PC-214 no catalyst and an approximately equal yield of that f~action compared to a process employ~ng the readily-poi~soned supported Co~Mo catalyst.
Three sets oX tests sim.ilar to those de.scxibed in Example 1 were performed in the presence of catalysts derived from ~a) Fe(C0~ and (b) Fe2(CO)g and (c) no catalyst. The results of these tests can be compared directly because they were al~ performed on Athab~sca bitumen from the same batch. The conditions used in the tests are set out in Table 3:
Test 384-3~9371 37S 390=395 Catalyst None~e(Co35 ~e,~C0)9 Catalyst addition -continuous continuous Catalyst conc.
(g/100 g bitumen) ~ 0.99 0.99 Gas H~ H~ H2 Total pressure ~kN/m2) 20,700 aO,700 ao,700 Partial p~essure ~Ha) ao,700 2D,700 ~C97CD
T~C) 450 450 450 Residence tlme (h~ 0.5 ~.5 0~5 ~ycles 6 6 The compositlon of the bitumen feed and the hydrogenation products for the three sets of tests are shown ln Tables 4, 5 a~d 6~ The product ~lates for the three ~ets of tests are given in Table 7.
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T~LE 7 Test 3~4-3B7 371-376 390~395 Catalyst Source norAe Fe [co3 5 ~Fe2 lC0) g Canvexsion* (%3 80.1 87 . 3 92 . B
H2 C~ns~ption ~g/100 g blt~T~) 1.37 2.~ 2~83 -~ Proauct Slate (g/100 ~-~t~nen) (X),C~ 0.~3 l.lï 0.66 S 3.~4 4.11 ~.39 ~0~ 0.0 ~.0 ~.0 C~ 4.~i7 2.7 ;2.6g Ca 4 .11 2 . 95 2 ~ 56 C3 ~ . !90 ~ .07 3 . 8~
.79 0. 69 0. 43 . nC4 3.02 2.39 2.19 ~ 5 1.49 1.16 1.12 nC5 3029 2.51 2.32 Condensate 3.87 4.33 4.2&
Dis~illate 34 . 94 47 ~ 81 51.01 Bottoms 17 . 57 27 . 98 30 . 22 Coke 13 . 30 6 0 79 0 DO
Total 96 .00 108 . 60105 . 68 Unac~untel9 ~5 . 87 ~6 . 20 -2 . 85 Bitumen ~ H2 101 . 87102 . 40 102 . 83 * Conversion = (L wt 1 ~ /
bitumen ~ WtcOke ~ x ll/wtbi~umen Wtcokel, tcoke ~ rWtbol:toms x CCRb~t,~Ds ~
~ l h~(3~
- 13 ~ PC-21~4 It can be seen by comparlng the lron ~ontents ~f the condPnsate, the distillate and the bottoms given in ~ables 5 ~nd 6 tha~, ln the case of Fe~CO)5s iron reports to the valuable hydrogenation products and i~ may well be necessary to include an additional process ~tep ts remove ~his iron from the products~ On ~he other hand, ln the case o~ ~e,(CO)g t ~ ron repor~s primarily to the still bottoms which has two advantages, (a3 ~he catalyst is recycled in a contlnuous operation in which the bottoms are mixed wi~h further bitumen and su~jected to further hydrogenation, and thus the consumption of catalyst is lower than in the case ~f Fe(CO35 and tb~ the hydrogenation products contain less iron impurity than the products of hydrogenation with Fe(CO)5-With reference to Table 7, it can be seen thatcatalysts derived from both Fe(CO)s and Fe2(co)g catalyse hydrogenation in that they both increase the yield of the distillate and condensate fractions as compared to the uncatalysed reaction, howev2r Fe2(co)g as a catalyst source is the more effective of the two. Furthermore, it can be seen that Fe2(co)g completely eliminates coke formation, which is highly advan~ageous, whereas ~e CO)5 does not.
350C, distillate wa~ collected from the high temperature condenser9 and condensate was obtalned fxom the low temperature condenser. The stlll bottoms were then allowed to drain lnto the pump feed pot. A fresh bitumen~catalyst ~lurry equal in welght to the distillate, condensate and hydrocarbon gases collected was then charged to the ~eedpot and transferred to the pump feed po~ as dPscribed abo~e. The mixture in the pump feed pot was then pumped ~o the high pressure autoclave and the above steps repeated. Testing continued for 6 complete cycles or until the still hottoms were too viscous to handlec The results o$ this process and of similar processes using no catalyst and using ~arshaw CoMo-0402T 1/8 catalyst, which is a Co-Mo catalyst supported on an alumina base, are shown in accompanying Table 1~
- 6 ~ 214 ,~ 'i ~;3 C U~ D M ~'1 t`l 9 ~ t`~
Y N ~ 8 N a~ D O ;1~ S~ 11 ~ - l ~
N~
8 ~ ~ 8 ~ ~ ~ y ~A yA ~
~ 7 ~ PC-2~4~
It can be seen from the results given in Table 1 that, under the prevailing conditions, the catalyst derived from Fe~(co~9 suppresses all coke production and th~ it gives about the same yield of the desirable distillate fraction as a fresh supported Co-Mo catalyst, which can be expected ~o poison readily.
Processes similar to those described in Example 1 were performed except the numbers of cycles were not limiked to 6 but the processes were continued until a st~ady state was reachedO The product slate is shown in Table 2 for processes using Fe2(~0~9 as a source of catalyst, and Harshaw CoMo-0204T 1,/8 catalysts and no catalyst. The Table also shows the percen~age of the hydrogenation product that must be recycled after distillation~
T 5C) 450 450 450 Catalyst Fe2(C039 none Harshaw CoMo Concentration 1.09 0 1.0 (g/100 g bitumen) Net Product Slate (wt %) CH4 4~03 6.82 6.08 C ~ 5 hydrocarbons 10.7 15.9 10.1 Condensate 8~05 12.7 10.8 Distillate 73.8 36.3 67.6 ~2S ~ C~S 3.3~ 2.27 5J4 Coke o 2 5 8 0 3~ To~al 100 100 100 .. .. ... ..
% Recycle 62 45 Ç2 It can be seen that the process employing an Fe2(CO~g derived catalyst gives a much better yield of the valuable distillate fraction than the process employing ~ 8 - PC-214 no catalyst and an approximately equal yield of that f~action compared to a process employ~ng the readily-poi~soned supported Co~Mo catalyst.
Three sets oX tests sim.ilar to those de.scxibed in Example 1 were performed in the presence of catalysts derived from ~a) Fe(C0~ and (b) Fe2(CO)g and (c) no catalyst. The results of these tests can be compared directly because they were al~ performed on Athab~sca bitumen from the same batch. The conditions used in the tests are set out in Table 3:
Test 384-3~9371 37S 390=395 Catalyst None~e(Co35 ~e,~C0)9 Catalyst addition -continuous continuous Catalyst conc.
(g/100 g bitumen) ~ 0.99 0.99 Gas H~ H~ H2 Total pressure ~kN/m2) 20,700 aO,700 ao,700 Partial p~essure ~Ha) ao,700 2D,700 ~C97CD
T~C) 450 450 450 Residence tlme (h~ 0.5 ~.5 0~5 ~ycles 6 6 The compositlon of the bitumen feed and the hydrogenation products for the three sets of tests are shown ln Tables 4, 5 a~d 6~ The product ~lates for the three ~ets of tests are given in Table 7.
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p~ 2144 u~ I ~ o o ~ r~
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dP
t~ N ~ C~ ~ r~
~ ~ ,~ ..... O ... O ., ro ~4 s~ll ~ N ~l r~ ~ tY O
~r ~
tl ~D ¦ Q ~ ~ ~ ~ ~ t~ `1 N t'~l t`J e~l C~ CO
E ~ ~`J v v v v v v v v v v v Y r~
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T~LE 7 Test 3~4-3B7 371-376 390~395 Catalyst Source norAe Fe [co3 5 ~Fe2 lC0) g Canvexsion* (%3 80.1 87 . 3 92 . B
H2 C~ns~ption ~g/100 g blt~T~) 1.37 2.~ 2~83 -~ Proauct Slate (g/100 ~-~t~nen) (X),C~ 0.~3 l.lï 0.66 S 3.~4 4.11 ~.39 ~0~ 0.0 ~.0 ~.0 C~ 4.~i7 2.7 ;2.6g Ca 4 .11 2 . 95 2 ~ 56 C3 ~ . !90 ~ .07 3 . 8~
.79 0. 69 0. 43 . nC4 3.02 2.39 2.19 ~ 5 1.49 1.16 1.12 nC5 3029 2.51 2.32 Condensate 3.87 4.33 4.2&
Dis~illate 34 . 94 47 ~ 81 51.01 Bottoms 17 . 57 27 . 98 30 . 22 Coke 13 . 30 6 0 79 0 DO
Total 96 .00 108 . 60105 . 68 Unac~untel9 ~5 . 87 ~6 . 20 -2 . 85 Bitumen ~ H2 101 . 87102 . 40 102 . 83 * Conversion = (L wt 1 ~ /
bitumen ~ WtcOke ~ x ll/wtbi~umen Wtcokel, tcoke ~ rWtbol:toms x CCRb~t,~Ds ~
~ l h~(3~
- 13 ~ PC-21~4 It can be seen by comparlng the lron ~ontents ~f the condPnsate, the distillate and the bottoms given in ~ables 5 ~nd 6 tha~, ln the case of Fe~CO)5s iron reports to the valuable hydrogenation products and i~ may well be necessary to include an additional process ~tep ts remove ~his iron from the products~ On ~he other hand, ln the case o~ ~e,(CO)g t ~ ron repor~s primarily to the still bottoms which has two advantages, (a3 ~he catalyst is recycled in a contlnuous operation in which the bottoms are mixed wi~h further bitumen and su~jected to further hydrogenation, and thus the consumption of catalyst is lower than in the case ~f Fe(CO35 and tb~ the hydrogenation products contain less iron impurity than the products of hydrogenation with Fe(CO)5-With reference to Table 7, it can be seen thatcatalysts derived from both Fe(CO)s and Fe2(co)g catalyse hydrogenation in that they both increase the yield of the distillate and condensate fractions as compared to the uncatalysed reaction, howev2r Fe2(co)g as a catalyst source is the more effective of the two. Furthermore, it can be seen that Fe2(co)g completely eliminates coke formation, which is highly advan~ageous, whereas ~e CO)5 does not.
Claims (10)
1. A process of hydrogenating liquid carbonaceous material, which process comprises heating the material in contact with a catalyst derived from Fe2(CO)9 in the presence of a hydrogen-containing gas.
2. A process as claimed in claim 1, wherein the hydrogenation is carried out at a temperature of from 400 to 500°C.
3. A process as claimed in claim 2, wherein the temperature is from 425 to 475°C.
4. A process as claimed in claim 1, wherein the hydrogenation is carried out at a hydrogen partial pressure of from 3,450 to 34,500 kN/m2.
5. A process as claimed in claim 4, wherein the hydrogen partial pressure is from 17,000 to 24,000 kN/m2.
6. A process as claimed in claim 1, wherein the hydrogen-containing gas is selected from the group of hydrogen and a hydrogen/carbon monoxide mixture.
7. A process as claimed in claim 1, wherein the carbonaceous material is bitumen.
8. A process as claimed in claim 1, wherein the hydrogenation products are distilled and the still residue is mixed with a fresh batch of liquid carbonaceous material and subjected to a further hydrogenation step.
9. A process as claimed in claim 8, wherein fresh catalyst is mixed with the said fresh batch of liquid carbonaceous material prior to the further hydrogenation step.
10. A process as claimed in claim 8, wherein a portion of the still residue is bled off, coked and the catalyst is not recovered from the residue.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8205496 | 1982-02-24 | ||
| GB82/05496 | 1982-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1183098A true CA1183098A (en) | 1985-02-26 |
Family
ID=10528585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000422172A Expired CA1183098A (en) | 1982-02-24 | 1983-02-23 | Hydrogenation of carbonaceous material |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4455218A (en) |
| EP (1) | EP0087324A1 (en) |
| CA (1) | CA1183098A (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4502941A (en) * | 1982-02-24 | 1985-03-05 | Inco Limited | Non-aqueous hydrogenation of solid carbonaceous material |
| US4591430A (en) * | 1984-05-18 | 1986-05-27 | Exxon Research And Engineering Co. | Process for the denitrogenation of nitrogen-containing hydrocarbon compounds |
| US4608153A (en) * | 1984-07-30 | 1986-08-26 | Exxon Research And Engineering Co. | Process for the removal of polynuclear aromatic hydrocarbon compounds from admixtures of liquid hydrocarbon compounds |
| US4839326A (en) * | 1985-04-22 | 1989-06-13 | Exxon Research And Engineering Company | Promoted molybdenum and tungsten sulfide catalysts, their preparation and use |
| US4693752A (en) * | 1986-04-17 | 1987-09-15 | Owens-Corning Fiberglas Corporation | Coating grade asphalt |
| CA1300068C (en) * | 1988-09-12 | 1992-05-05 | Keith Belinko | Hydrocracking of heavy oil in presence of ultrafine iron sulphate |
| US5578197A (en) * | 1989-05-09 | 1996-11-26 | Alberta Oil Sands Technology & Research Authority | Hydrocracking process involving colloidal catalyst formed in situ |
| US6799615B2 (en) * | 2002-02-26 | 2004-10-05 | Leslie G. Smith | Tenon maker |
| MXPA06012528A (en) | 2004-04-28 | 2007-08-02 | Headwaters Heavy Oil Llc | Ebullated bed hydroprocessing methods and systems and methods of upgrading an existing ebullated bed system. |
| US10941353B2 (en) | 2004-04-28 | 2021-03-09 | Hydrocarbon Technology & Innovation, Llc | Methods and mixing systems for introducing catalyst precursor into heavy oil feedstock |
| BRPI0510346A (en) * | 2004-04-28 | 2007-10-30 | Headwaters Heavy Oil Llc | fixed bed hydroprocessing methods and systems for upgrading an existing fixed bed system |
| EP1753844B1 (en) * | 2004-04-28 | 2016-06-08 | Headwaters Heavy Oil, LLC | Hydroprocessing method and system for upgrading heavy oil |
| US8034232B2 (en) | 2007-10-31 | 2011-10-11 | Headwaters Technology Innovation, Llc | Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker |
| US8142645B2 (en) * | 2008-01-03 | 2012-03-27 | Headwaters Technology Innovation, Llc | Process for increasing the mono-aromatic content of polynuclear-aromatic-containing feedstocks |
| MX2008006051A (en) * | 2008-05-09 | 2009-11-09 | Mexicano Inst Petrol | Liquid ionic catalyst for the improvement of heavy crude and vacuum residues. |
| KR101917198B1 (en) | 2010-12-20 | 2019-01-24 | 셰브런 유.에스.에이.인크. | Hydroprocessing catalysts and methods for making thereof |
| US9790440B2 (en) | 2011-09-23 | 2017-10-17 | Headwaters Technology Innovation Group, Inc. | Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker |
| US9644157B2 (en) | 2012-07-30 | 2017-05-09 | Headwaters Heavy Oil, Llc | Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking |
| US11414607B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor with increased production rate of converted products |
| US11414608B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor used with opportunity feedstocks |
| US11421164B2 (en) | 2016-06-08 | 2022-08-23 | Hydrocarbon Technology & Innovation, Llc | Dual catalyst system for ebullated bed upgrading to produce improved quality vacuum residue product |
| US11118119B2 (en) | 2017-03-02 | 2021-09-14 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor with less fouling sediment |
| US11732203B2 (en) | 2017-03-02 | 2023-08-22 | Hydrocarbon Technology & Innovation, Llc | Ebullated bed reactor upgraded to produce sediment that causes less equipment fouling |
| CA3057131A1 (en) | 2018-10-17 | 2020-04-17 | Hydrocarbon Technology And Innovation, Llc | Upgraded ebullated bed reactor with no recycle buildup of asphaltenes in vacuum bottoms |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US390979A (en) * | 1888-10-09 | Rail for street-railways | ||
| US3231488A (en) * | 1963-10-28 | 1966-01-25 | Universal Oil Prod Co | Process for hydrorefining heavy hydrocarbon charge stocks and catalyst therefor |
| US3702874A (en) * | 1970-12-07 | 1972-11-14 | Texaco Inc | Hydrocarbon conversion process |
| US3711399A (en) * | 1970-12-24 | 1973-01-16 | Texaco Inc | Selective hydrocracking and isomerization of paraffin hydrocarbons |
| US4003850A (en) | 1971-10-04 | 1977-01-18 | United States Steel Corporation | Novel iron oxide catalysts |
| US4152248A (en) * | 1978-05-02 | 1979-05-01 | The United States Of America As Represented By The United States Department Of Energy | Hydrogenation of coal liquid utilizing a metal carbonyl catalyst |
| US4325802A (en) * | 1980-11-17 | 1982-04-20 | Pentanyl Technologies, Inc. | Method of liquefaction of carbonaceous materials |
-
1983
- 1983-02-23 CA CA000422172A patent/CA1183098A/en not_active Expired
- 1983-02-24 EP EP83300971A patent/EP0087324A1/en not_active Ceased
- 1983-02-24 US US06/469,440 patent/US4455218A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0087324A1 (en) | 1983-08-31 |
| US4455218A (en) | 1984-06-19 |
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