CA1157412A - Process and apparatus for the demetallization of a hydrocarbon oil - Google Patents
Process and apparatus for the demetallization of a hydrocarbon oilInfo
- Publication number
- CA1157412A CA1157412A CA000358662A CA358662A CA1157412A CA 1157412 A CA1157412 A CA 1157412A CA 000358662 A CA000358662 A CA 000358662A CA 358662 A CA358662 A CA 358662A CA 1157412 A CA1157412 A CA 1157412A
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- Canada
- Prior art keywords
- catalyst
- hydrocarbon oil
- demetallization
- hydrogen
- beds
- 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.)
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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
-
- 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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A B S T R A C T
PROCESS AND APPARATUS FOR THE DEMETALLIZATION OF A HYDROCARBON OIL
A process for the demetallization of a hydrocarbon oil by passing said oil together with hydrogen over one or more fixed beds (1-6) of a demetallization catalyst, in which process whenever that catalyst portion which is first contacted with the hydrocarbon oil is deactivated, the point of supply of the hydrocarbon oil is moved downstream, at least part of the original supply of hydrogen (7) being maintained over the entire catalyst.
PROCESS AND APPARATUS FOR THE DEMETALLIZATION OF A HYDROCARBON OIL
A process for the demetallization of a hydrocarbon oil by passing said oil together with hydrogen over one or more fixed beds (1-6) of a demetallization catalyst, in which process whenever that catalyst portion which is first contacted with the hydrocarbon oil is deactivated, the point of supply of the hydrocarbon oil is moved downstream, at least part of the original supply of hydrogen (7) being maintained over the entire catalyst.
Description
~157~2 PRQCESS AND APPA~ATUS FOR T~IE DEMETALLIZATION OF A H~DROCARBON OIL
The invention relates to a process for the demetalliza-tion of a hydrocarbon oil by passing said oil together with hydrogen over one or more fixed beds of a demetallization catalyst.
When refining hydrocarbon oils, such as mineral oils and in particular petroleum, the light products are usually first removed by distillation at atmospheric pressure, subsequently heavier fractions are separated off by means of vacuum distillation and the remaining residue (short residue) is deasphalted, in which process deasphalted vacuum residue of a mineral oil (also referred to as DAO below) and asphalt are obtained. The heavier fractions obtained in the vacuum distillation (also referred to as vacuum distillate fractions) and the residual fractions, in particular DAO, can be used as heavy fuel or as feedstock for catalytic cracking. In order -to discharge the smallest possible quantity of sulphur compounds into the atmosphere during the combustion of heavy fuel, it is necessar-y that the sulphur content of oils to be used as heavy fuel should be as low as possible. To this end the sulphur is very suitably removed with catalysts suitable therefor in the presence of hydrogen. Said catalysts are deactivated rapidly if the fraction to be desulphurized contains a considerable quan-tity of metal.
If the DAO and/or vacuum distillate fractions are to be used as feed for a catalytic cracking reaction~ the metal conten-t and the tendency to coke deposition of the feed -to be used must be as low as possible in order to prevent rapid deactivation of the cracking catalyst.
In order to meet the requirements set for the metal content, at least part of -the metals, which occur in larger quantities in residual fractions than in the vacuum distillate fractions, must therefore in many cases be removed both from vacuum distillate fractions and from residual fractions (by which are meant fractions which have remained behind as residue in the vacuum distillation of a mineral oil or have been obtained from such a residue, for example short residue, DAO, asphalt). Said metals consist for the greater part of nickel and vanadium, which may occur in considerable quantities in mineral oils.
- ~k q~-4 ~ ~
Removal of me-tals, which need not be complete, is referred to as demetallization in the present application.
The usual catalysts for catalytic hydrodesulphuriza-tion are not resistant to quan-tities of metals in -the feed in excess of about 20 ppmw, since in the case of larger quantities of metal unaccep-table pressure drop across the catalyst occurs after a relatively short time.
For this reason hydrocarbon oils having a metal content higher than about 20 ppm canno-t be desulphurized with said catalysts in an economically justified manner.
~0 In a number of cases it is therefore aclvisable that prior to desulphurization a hydrocarbon oil to be desulphurized should be demetallized -to a metal content below about 20 ppm, and this applies in particular to residual fractions, since the latter usually have metal contents which are considerab]y higher than 20 ppm.
~5 For the deme-tallization o~ hydrocarbon oils in the presence of hydrogen (hydrodemetallization) specific ca-talysts exist which posess a high activi-ty for demetallization but only a low capacity ~or desulphurization. Consecuently, the hydrocarbon oil obtained in the demetallization will in many cases still have to be desulphurized, in order to obtain the desired demetallized and desulphurized hydrocarbon oils. The hydrodesulphurization is very suitably carried out by ~eans of catalysts suitable therefore which as stated above, are not resistant to quantities of metal in the feed of about 20 ppm or more.
If no special measures are taken, demetallization catalysts have a relatively short life, since after a relatively short -time, as a result of the cluantities of metals and coke which originate ~rom the hydrocarbon oil and have been deposited on the catalyst, the ca-talyst is deactivated and such a high pressure drop across the demetallization catalyst occurs that said catalyst cannot be used further and must be removed and/or regenera-ted.
It is possible to use a -fresh cluantity of dematallization catalyst which is contained, for example, in a different parallel-1~57412 ~ 3 --connected reactor than the deactiva-ted catalyst and to regenerate and/or remove the deactivated deme-tallization catalyst.
However~ this method, has the drawback that ~or the regeneration and/or removal from the reactor o~ the deactiYated demetallizati`on 5 catalyst this reactor must be opened or at least the hydrogen present therein must be replaced by air. On a site where a number o~ reactors are located in which hydrotreatments at high pressure and temperature are carried out, it is, ~or sa~ety reasons, undesirable to shut down one o~ the reactors separately and replace the hyarogen therein by an oxygen-containing gas. The aim will be to close down the whole plant simultaneousl~ for the regeneration andlor remoYal of the demetalliza-tion catalyst.
The invention provides a process ~or the hydrodemetallization o~ a hydrocarbon o;l~ in which process the time during which~a J5 demetallization catalyst can be used without it being necessary to be removed and/or regenerated, is prolonged considerably.
Accordingly, the invention relates to process ~or the demetallization o~ a hydrocarbon oil by passing said oil together with hydrogen over one~or more ~ixed beds o~ a demetallization catalyst, which process is characterized in that whenever that catalyst portion which is first contacted with the hydrocarbon oil is deactivated the point o~ supply o~ the hydrocarbon oil is moved downstream, at least part of the original supply o~ hydrogen belng main-tained over the~entire catalyst.
It is essential that at least part of the hydrogen stream should be maintained over the entire catalyst. A~ter the supply~ o~
the hydrocarbon oil to be demetallized has been movea to a point located further downstream, a quantit~ o~ oil învariably remains present on the deactivatea part o~ the catalyst. This oil may exhibit undesired decomposi:tion reactions with heat production, as a result o~ which local oYerheating o~ the deactivated catalyst may occur. By maintaining a hydrogen stream over the entire catalyst such reactions are largely suppressed and if they nevertheless occur, removal o~ the ieat produce is ensurea.
. ~ :
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.
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~ ~L57~2 In addition -to the hydrogen s-tream maintained over the en-tire catalyst it is as a matter of course, possible to introduce hydrogen in one or more downstream places if desired. The moment when -the catalys-t portion which is first contacted with the oil to be deme-tallized is considered deactiva-ted, is determined by the pressure drop occurring across the catalyst. Depending on the conditions a not excessive pressure drop may be permitted before the supply of hydrocarbon oil is removed. When under the prevailing conditions the period of time elapsing between the supply of hydrocarbon oil to a certain part of the catalyst and the deactivation thereof has become known, it is of course also possible on the basis of said period to move -the supply of hydrocarbon oil to a point located further down-stream a short time before the pressure drop across the catalyst becomes unacceptable.
Any hydrocarbon oil to be demetalli~ed can serve as feed for the 15 process according to the invention. As examples may be mentioned crude oil, oil from which the volatile products are removed (topped crude oil), oil from which light products are removed by distillation at atmospheric pressure (so-called long residue), shale oils, oils obtained from tar sands. Preference is given to residual fractions, as defined 20 above Deme-tallization catalysts are known; they usually consist of oxidic carriers on which one or more metals with hydrogenation activity (or compounds of said metals) are optionally deposited. In the process according to the invention use is very suitably made of catalysts of the 25 type described in the Dutch patent application 7309387. Said catalysts contain one or more metals with hydrogenation activity on a carrier and fulfil the following requirements:
1~ p/d ~ 3.5 - Q.02 v, in which p represents the specific average pore diameter in nm, d represents the specific average par-ticle diameter in mm and v is the percentage of the total pore volume consisting of pores having a diameter above 100 nm,
The invention relates to a process for the demetalliza-tion of a hydrocarbon oil by passing said oil together with hydrogen over one or more fixed beds of a demetallization catalyst.
When refining hydrocarbon oils, such as mineral oils and in particular petroleum, the light products are usually first removed by distillation at atmospheric pressure, subsequently heavier fractions are separated off by means of vacuum distillation and the remaining residue (short residue) is deasphalted, in which process deasphalted vacuum residue of a mineral oil (also referred to as DAO below) and asphalt are obtained. The heavier fractions obtained in the vacuum distillation (also referred to as vacuum distillate fractions) and the residual fractions, in particular DAO, can be used as heavy fuel or as feedstock for catalytic cracking. In order -to discharge the smallest possible quantity of sulphur compounds into the atmosphere during the combustion of heavy fuel, it is necessar-y that the sulphur content of oils to be used as heavy fuel should be as low as possible. To this end the sulphur is very suitably removed with catalysts suitable therefor in the presence of hydrogen. Said catalysts are deactivated rapidly if the fraction to be desulphurized contains a considerable quan-tity of metal.
If the DAO and/or vacuum distillate fractions are to be used as feed for a catalytic cracking reaction~ the metal conten-t and the tendency to coke deposition of the feed -to be used must be as low as possible in order to prevent rapid deactivation of the cracking catalyst.
In order to meet the requirements set for the metal content, at least part of -the metals, which occur in larger quantities in residual fractions than in the vacuum distillate fractions, must therefore in many cases be removed both from vacuum distillate fractions and from residual fractions (by which are meant fractions which have remained behind as residue in the vacuum distillation of a mineral oil or have been obtained from such a residue, for example short residue, DAO, asphalt). Said metals consist for the greater part of nickel and vanadium, which may occur in considerable quantities in mineral oils.
- ~k q~-4 ~ ~
Removal of me-tals, which need not be complete, is referred to as demetallization in the present application.
The usual catalysts for catalytic hydrodesulphuriza-tion are not resistant to quan-tities of metals in -the feed in excess of about 20 ppmw, since in the case of larger quantities of metal unaccep-table pressure drop across the catalyst occurs after a relatively short time.
For this reason hydrocarbon oils having a metal content higher than about 20 ppm canno-t be desulphurized with said catalysts in an economically justified manner.
~0 In a number of cases it is therefore aclvisable that prior to desulphurization a hydrocarbon oil to be desulphurized should be demetallized -to a metal content below about 20 ppm, and this applies in particular to residual fractions, since the latter usually have metal contents which are considerab]y higher than 20 ppm.
~5 For the deme-tallization o~ hydrocarbon oils in the presence of hydrogen (hydrodemetallization) specific ca-talysts exist which posess a high activi-ty for demetallization but only a low capacity ~or desulphurization. Consecuently, the hydrocarbon oil obtained in the demetallization will in many cases still have to be desulphurized, in order to obtain the desired demetallized and desulphurized hydrocarbon oils. The hydrodesulphurization is very suitably carried out by ~eans of catalysts suitable therefore which as stated above, are not resistant to quantities of metal in the feed of about 20 ppm or more.
If no special measures are taken, demetallization catalysts have a relatively short life, since after a relatively short -time, as a result of the cluantities of metals and coke which originate ~rom the hydrocarbon oil and have been deposited on the catalyst, the ca-talyst is deactivated and such a high pressure drop across the demetallization catalyst occurs that said catalyst cannot be used further and must be removed and/or regenera-ted.
It is possible to use a -fresh cluantity of dematallization catalyst which is contained, for example, in a different parallel-1~57412 ~ 3 --connected reactor than the deactiva-ted catalyst and to regenerate and/or remove the deactivated deme-tallization catalyst.
However~ this method, has the drawback that ~or the regeneration and/or removal from the reactor o~ the deactiYated demetallizati`on 5 catalyst this reactor must be opened or at least the hydrogen present therein must be replaced by air. On a site where a number o~ reactors are located in which hydrotreatments at high pressure and temperature are carried out, it is, ~or sa~ety reasons, undesirable to shut down one o~ the reactors separately and replace the hyarogen therein by an oxygen-containing gas. The aim will be to close down the whole plant simultaneousl~ for the regeneration andlor remoYal of the demetalliza-tion catalyst.
The invention provides a process ~or the hydrodemetallization o~ a hydrocarbon o;l~ in which process the time during which~a J5 demetallization catalyst can be used without it being necessary to be removed and/or regenerated, is prolonged considerably.
Accordingly, the invention relates to process ~or the demetallization o~ a hydrocarbon oil by passing said oil together with hydrogen over one~or more ~ixed beds o~ a demetallization catalyst, which process is characterized in that whenever that catalyst portion which is first contacted with the hydrocarbon oil is deactivated the point o~ supply o~ the hydrocarbon oil is moved downstream, at least part of the original supply o~ hydrogen belng main-tained over the~entire catalyst.
It is essential that at least part of the hydrogen stream should be maintained over the entire catalyst. A~ter the supply~ o~
the hydrocarbon oil to be demetallized has been movea to a point located further downstream, a quantit~ o~ oil învariably remains present on the deactivatea part o~ the catalyst. This oil may exhibit undesired decomposi:tion reactions with heat production, as a result o~ which local oYerheating o~ the deactivated catalyst may occur. By maintaining a hydrogen stream over the entire catalyst such reactions are largely suppressed and if they nevertheless occur, removal o~ the ieat produce is ensurea.
. ~ :
.. . .
.
: , , , ' '' ~ .
~ ~L57~2 In addition -to the hydrogen s-tream maintained over the en-tire catalyst it is as a matter of course, possible to introduce hydrogen in one or more downstream places if desired. The moment when -the catalys-t portion which is first contacted with the oil to be deme-tallized is considered deactiva-ted, is determined by the pressure drop occurring across the catalyst. Depending on the conditions a not excessive pressure drop may be permitted before the supply of hydrocarbon oil is removed. When under the prevailing conditions the period of time elapsing between the supply of hydrocarbon oil to a certain part of the catalyst and the deactivation thereof has become known, it is of course also possible on the basis of said period to move -the supply of hydrocarbon oil to a point located further down-stream a short time before the pressure drop across the catalyst becomes unacceptable.
Any hydrocarbon oil to be demetalli~ed can serve as feed for the 15 process according to the invention. As examples may be mentioned crude oil, oil from which the volatile products are removed (topped crude oil), oil from which light products are removed by distillation at atmospheric pressure (so-called long residue), shale oils, oils obtained from tar sands. Preference is given to residual fractions, as defined 20 above Deme-tallization catalysts are known; they usually consist of oxidic carriers on which one or more metals with hydrogenation activity (or compounds of said metals) are optionally deposited. In the process according to the invention use is very suitably made of catalysts of the 25 type described in the Dutch patent application 7309387. Said catalysts contain one or more metals with hydrogenation activity on a carrier and fulfil the following requirements:
1~ p/d ~ 3.5 - Q.02 v, in which p represents the specific average pore diameter in nm, d represents the specific average par-ticle diameter in mm and v is the percentage of the total pore volume consisting of pores having a diameter above 100 nm,
2) the total pore vol~e is above 0.40 ml/g,
3) v is below 50 and 1 157~1~
4) the specific surface area is above 100 m !g;
in case -the catalyst has such a p and d that the quotient p/d is higher than 3.5-0.02 v, but at most 10-0.~5 v, the catalyst must fulfil the following additional requirements:
a¦ the nitrogen pore volume is above Q.60 ml/g, b) -the speeific surface area is above 150 m /g and cl p is above 5 nm.
The values to be used for p, d, v, the total pore volume, the nitrogen pore ~olume and the specific surface area must be deter-mined as descrihed in -the Dutch patent application 7309387.
The catalyst contains Yery suitably, metals with hydrogenation activity selected from the group consisting of nickel, eobalt, molybdenum, vanadium and tungsten, and particular preference is given to catalysts which contain at least one metal o~ the group 15 consisting of nickel and cobalt and at least one metal of the group eonsisting of molybdenum, vanadium and tungsten.
Catalysts containing niekel and vanadium are particularly suitable.
~he metals are preferably present as their oxides or sulphides.
Alumina and silica-alumina are very suitable as carriers.
20 Preference is given to carriers completely or substantially completely consisting o~ silica.
Yery suitable catalysts for -the hydrodemetallization according to the invention are those described in the Dutch patent application 7316396. Said catalysts eontain 0.1-15 parts by weight of the metal combination nickel-vanadium per ~00 parts by weight of a silica carrier and have a loss on ignition, determined under standard conditions, of less than 0. 5% by weight.
Catalysta as described in the Dutch patent application 7412155 are also very suitable. The latter catalysts ~ulfil the above-mentioned requirements and are obtained by the nodulizing technique;they have a pore volume, present in pores having a diameter above 50 nm, of at least 0. 2 ml/g.
If the hydrocarbon oil to be demetallized has a high metal eontent, it is also possible to use as eatalyst silica on whieh 35 no metals with hydrogenation aetivity have been deposited, as described in the Dutch patent applieation 7607552.
t~7~
The process according to the invention is carried out under conditions which are usual for hydrodeme-tallization. The hydrocarbon oil to be demetalliæed (which in most cases is for at least 80 vol.% in the liquid phase) together with hydrogen is very suitably passed in downward direction over the ca-talyst at a temperature between 300 and 450C
~preferably between 350 and 425C), a total pressure between 75 and 250 bar (preferably between 100 and 200 bar), a hydrogen partial pressure between 35 and 120 bar (preferably between 50 and 100 bar~, a space velocity of 0.~-25 parts by volume of fresh feed per part by volume of 10 catalyst per hour and a hydrogen/feed ratio of 100-2000 (preferably 200-1500) Nl of H2/kg of feed.
The hydrogen required for the hydrodeme-tallization may be a hydrogen containing gas s-tream, such as a reformer off-gas stream, or a mainly pure hydrogen. The hydrogen-containing gases preferably contain 35 at least 60% by volume of hydrogen.
The demetallization catalyst may be present in one fixed bed, but is preferabl~ present in several serially connected fixed beds. The fixed beds can be located in one or more reactors. The size of the catalyst beds is very suitably so chosen that the supply point of 20 hydrocarbon oil to be demetallized is in all cases moved to a place between two catalyst beds.
After the furthest downstream portion of the catalyst is also deactivated7 the catalyst must be taken out of service and can be regenerated and~or removed. During regeneration the coke deposits and 25 the metal deposits (which in many cases mainly consist of vanadium and to a lesser e~tent of nickell must be at least partly removed. The regeneration is ver~ suitably carried out b~ the methods described in the Dutch patent applications 75~1993, 7703181 and 7703380. In these methods, the deactivated catalyst is extracted with an aqueous solution 30 Of a mineral acid (for example sulphuric acid~, which extraction is very suitably preceded by a treatment with a reducing agent or is carried out in the presence of a reducing agent. Sulphur dioxide is very suitable as reducing agen-t.
In order to remove also the coke and sulphur deposits it is 1~57~2 advisable, before -the extraction with an aqueous solution of a mineral acid (and the optional trea-tment with a reducing agent), to subject the deactivated catalys-t to a treatment with steam, and/or an oxygen-containing gas such as air, and/or with a mixture of steam and air, at a temperature above 250 C at atmospheric or a higher pressure.
If the carrier of -the ca-talys-t is resistant to an aqueous solu-tion of mineral acid (i.e. consists of~ for example, silica) the ca-talyst can be reused after removal of the coke, sulphur and metals, op-tionally after application O-r the abovementioned metals wi-th hydrogena-tion activity.
If the carrier is not resistant to an aqueous solution of a m;neral acid (i.e. consists, for example, of alumina) regeneration in the above-mentioned manner is impossible. In that case it is also possible, however, to carry out the treatment with mineral acid in order to recover the metals deposited from the hydrocarbon oil. Said metals can of course also be recovered from the extract obtained in the treatment with an aqueous mineral acid solution of deactivated catalys-ts, the carriers of which are resis-tan-t to a treatment of this type.
The demetallized hydrocarbon oil obtained in the process accord-ing to the invention can be used for any desired purpose.The demetallization need of course not be complete and a quantity of metal may still be present in -the demetallized product.
~ s stated above~ it is in many cases at-tractive to subject the resultan-t demetallized hydrocarbon oil to a hydrodesulphurization treatment and it is advantageous to carry out the deme-tallization and desulphurization in one continuous treatment without intermediate isolation and!or purification of the deme-tallized hydrocarbon oil and of the hydrogen-containing gas becoming available from the final reactor bed of demetallization catalyst.
For the hydrodesulphurization of heavy hydrocarbon fractions, such as residual fractions, specific catalysts are known which can be used for a long time without replacement or regeneration of -the ca-talyst being necessary as a result of deposition of coke and high-molecl1lar components (such as resins, polyaroma-tics and asphaltenes) from the feed. Catalysts as described in the Dutch paten-t application 7010427 are very sui-table. The particles of said catalysts have a pore volume above 0.30 ml/g, of which pore ~1574:1~
volume less than 10% is present in pores having a diameter above ~00 nm, and the catalyst ~articles have a speci~ic pore diameter expressed in nm ~rom 7.5 x d-9 to 17 x d 9, in which d represents the spec;fic particle diameter in ~.
Said catalysts very sui-tably contain a carrier on which one or more metals chosen ~rom the group consisting of nickel, cobalt, tungsten and molybdenum, and in particular one metal o~ the group consisting o~
nickel and cobalt and one metal o~ the group consisting o~ tungsten and molybdenum, are deposited. Catalysts containing nickel or cobalt 10 together with molybdenum are particularly suitable. The metals are preferably present as their oxides or sulphides. Very sui-table carriers are silica, silica-alumina and in particular alumina.
The hydrodesulphurization is carried out under the usual conditions.
The demetallized hyclrocarbon oil to be desulphurized together wi-th the hydrogencontaining gas obtained in the demetallization (to which extra hydrogen is added, i~ desired~ is very suitably passed in downward direction over the catalyst at a temperature between 350 and 475 C
(preferably between 385 and 4~5C), a total pressure between 75 and 250 bar (pre~erably between 100 and 225 bar), a hydrogen partial pressure 20 between 35 and 120 bar (preferably between 50 and 100 bar), a space velocity o~ 0.1-25 (pre~erably 0.2-5~ parts by volume of ~eed per part by volume o~ catalyst and a hydrogen/feed ratio o~ 150-2000 (preferably 250-1500) Nl o~ II2/kg o~ ~eed.
The desulphurization catalyst is very suitably contained in one or 25 more fixed beds which, i~ desired, are located in several serially connected reactors.
When the demetalli~ation catalyst or the desulphurization catalyst is deactivated, the whole plant is closed down and the demetallization catalyst and desulphurization ca-talyst are both removed and/or 30 regenerated. For economic reasons the aim will be to choose the quantities of demetallization catalyst and desulphurization catalyst in such a manner tha-t both are deac-tivated about simu]taneously, since in -that manner no or only a small portion o~ active catalyst is removed and/or subjected to a regeneration process.
~ ~57~2 ~o The product ob-tained after the desulphurization is sepera-ted from the hydrogen-containing gas in the usual manner; if desired, said gas can be recycled -to the process after complete or partial removal of H2S and any other impurities. ~ r~Jn~
The inven-tion also relates to an apparatus ~r~e~a-~ one or more serially connected reac-tors each o which can be filled with one or more fixed catalyst beds, the first bed of the first reactor having an inlet for a gas and an inlet for a hydrocarbon oil~ characterized in that one or more inlets for hydrocarbon oil is/are present downs-tream, and that each hydrocarbon oil inlet can be separa-tely connected or closed.
The invention will now be illus-trated with reference to the following diagrammatic figure. Each of the reactors R1, R2 and R3 contains two ~ixed beds of demetallization catalyst (1, 2, 3, 4, 5 and 6~. Hydrogen is supplied to the bed 1 in reactor R1 through a line 7, passes the beds 2, 3, 4, 5 and 6 consecutively and leaves reactor R3 through a line 8 toge-ther with demetallized hydrocarbon oil. Fresh hydrocarbon oil is supplied -through a line 9 and is initially supplied to bed 1 via an open valve 10 and passes through the beds 1, 2, 3, 4, 5 and 6 consecutively. ~alves 11, 12, 13, 14 and 15 are closed. After the demetallization catalyst in bed 1 is deactivated, valve 11 is opened and valve 10 is closed. The hydro-carbon oil to be demetallized is then supplied to bed 2 and passes through the beds 2, 3, 4, 5 and 6 consecutively. When bed 2 is de-activated, valve 12 is opened and valve ~1 is closed and the hydro-carbon oil to be demetallized is supplied to bed 3. In a similar manner the hydrocarbon oil to be demetallized is supplied to the beds 4, 5, and 6 whenever the preceding bed is deactivated. After bed 6 is also deactivated, the hydrocarbon oil and hydrogen streams are interrup-ted and the catalyst in reactors R1, R2 and R3 is replaced or regenerated. ln the figure -the resul-tan-t demetallized hydrocarbon oil and -the hydrogen containing gas which become available -through a line o from reactor R3 are passed without further purification through the reactors R4 and R5, each containing two beds of a desulphurization ca-ta~ys-t.
_ _ .... _ _ _ _ . . . .
~:lS7~L~2 The desulphurized and demetallized hydrocarbon oil and the hydrogen-containing gas becoming available from reactor R5 through a line 16 can be separated and purified by conventional methods. As regards pressure, temperature and space velocity, conditions suitable for demetallization are maintained in reactors R1, R2 and R3 and con-ditions suitable for desulphurization are maintained in reactors R
and R5.
EX~PLE
In an apparatus as described in the figure, beds-1-6in the reactors R1, R2 and R3 are filled with a demetallization catalyst.
Said catalyst contains o.6% by weight of nickel (as oxide) and 1.9%
by weight of vanadium (as oxide~ on silica as carrier, has a specific average pore diameter of 13.6 nm, a specific average particle dia-meter of 2.2 mm, a specific surface area of 262 m /g and a pore volume of o.78 ml/g, of which pore volume 0.3% consists o~ pores having a diameter above 100 nm. Before use the catalyst is sulphided by passing over it a gasoil containing ~.6% by weight of sulphur, at a space velocity of 1 kg/litre of catalyst/h, a temperature of 350 C
and a hydrogen pressure of 50 bar. The reactors R4 and R5 are filled with a desulphurization catalyst. This catalyst contains 3.6% by weight of nickel (as oxide~ and 8.9% by weight of molybdenum (as oxide) on alumina as carrier, and has a specific average pore dia-meter of 20.2 nm, a specific average particle diameter of 1.5 mm, a specific surface area of ~83 m /g and a pore volume of o.54 ml/g, of 25 which less than 0.4% is present in pores h~ving a diameter above 100 nm. Before use this desulphurization ca-talyst is sulphided in the same way as the demetallization catalyst.
A deasphalted vacuum residue of a mineral oil (DA0) containing 40 ppm of vanadium and 2.7~ by weigh-t o~ sulphur, is subsequently 30 passed through the reactors R1-R5 at a space velocity of 0.29 kg/l o~ catalyst/h both ~or the demetal.lization catalyst and -the desulphur-ization catalyst, at a temper-ature o~ 390 C, a hydrogen partial pressure o~ 70 bar and a gas space velocity of 1000 Nl/kg of feed.
Whenever the pressure drop increases rapidly, the feed inlet is moved -to the nex-t bed of demetallization catalyst, the hydrogen stream being maintained over all the beds.
1 1 5 ~
The test is interrup-ted after unaccep-table pressure drop occurs while the feed is being supplied to bed 6; this is 12,000 hours after -the start of the test. The product obtained con-tains 1 ppm of vanadium and 0.5% by weight of sulphur.
For the sake of comparison an experir~ent is carried ou-t in which the feed inlet is not moved downstream. After only 2000 hours such a pressure drop occurs that the experiment must be interrupted.
-
in case -the catalyst has such a p and d that the quotient p/d is higher than 3.5-0.02 v, but at most 10-0.~5 v, the catalyst must fulfil the following additional requirements:
a¦ the nitrogen pore volume is above Q.60 ml/g, b) -the speeific surface area is above 150 m /g and cl p is above 5 nm.
The values to be used for p, d, v, the total pore volume, the nitrogen pore ~olume and the specific surface area must be deter-mined as descrihed in -the Dutch patent application 7309387.
The catalyst contains Yery suitably, metals with hydrogenation activity selected from the group consisting of nickel, eobalt, molybdenum, vanadium and tungsten, and particular preference is given to catalysts which contain at least one metal o~ the group 15 consisting of nickel and cobalt and at least one metal of the group eonsisting of molybdenum, vanadium and tungsten.
Catalysts containing niekel and vanadium are particularly suitable.
~he metals are preferably present as their oxides or sulphides.
Alumina and silica-alumina are very suitable as carriers.
20 Preference is given to carriers completely or substantially completely consisting o~ silica.
Yery suitable catalysts for -the hydrodemetallization according to the invention are those described in the Dutch patent application 7316396. Said catalysts eontain 0.1-15 parts by weight of the metal combination nickel-vanadium per ~00 parts by weight of a silica carrier and have a loss on ignition, determined under standard conditions, of less than 0. 5% by weight.
Catalysta as described in the Dutch patent application 7412155 are also very suitable. The latter catalysts ~ulfil the above-mentioned requirements and are obtained by the nodulizing technique;they have a pore volume, present in pores having a diameter above 50 nm, of at least 0. 2 ml/g.
If the hydrocarbon oil to be demetallized has a high metal eontent, it is also possible to use as eatalyst silica on whieh 35 no metals with hydrogenation aetivity have been deposited, as described in the Dutch patent applieation 7607552.
t~7~
The process according to the invention is carried out under conditions which are usual for hydrodeme-tallization. The hydrocarbon oil to be demetalliæed (which in most cases is for at least 80 vol.% in the liquid phase) together with hydrogen is very suitably passed in downward direction over the ca-talyst at a temperature between 300 and 450C
~preferably between 350 and 425C), a total pressure between 75 and 250 bar (preferably between 100 and 200 bar), a hydrogen partial pressure between 35 and 120 bar (preferably between 50 and 100 bar~, a space velocity of 0.~-25 parts by volume of fresh feed per part by volume of 10 catalyst per hour and a hydrogen/feed ratio of 100-2000 (preferably 200-1500) Nl of H2/kg of feed.
The hydrogen required for the hydrodeme-tallization may be a hydrogen containing gas s-tream, such as a reformer off-gas stream, or a mainly pure hydrogen. The hydrogen-containing gases preferably contain 35 at least 60% by volume of hydrogen.
The demetallization catalyst may be present in one fixed bed, but is preferabl~ present in several serially connected fixed beds. The fixed beds can be located in one or more reactors. The size of the catalyst beds is very suitably so chosen that the supply point of 20 hydrocarbon oil to be demetallized is in all cases moved to a place between two catalyst beds.
After the furthest downstream portion of the catalyst is also deactivated7 the catalyst must be taken out of service and can be regenerated and~or removed. During regeneration the coke deposits and 25 the metal deposits (which in many cases mainly consist of vanadium and to a lesser e~tent of nickell must be at least partly removed. The regeneration is ver~ suitably carried out b~ the methods described in the Dutch patent applications 75~1993, 7703181 and 7703380. In these methods, the deactivated catalyst is extracted with an aqueous solution 30 Of a mineral acid (for example sulphuric acid~, which extraction is very suitably preceded by a treatment with a reducing agent or is carried out in the presence of a reducing agent. Sulphur dioxide is very suitable as reducing agen-t.
In order to remove also the coke and sulphur deposits it is 1~57~2 advisable, before -the extraction with an aqueous solution of a mineral acid (and the optional trea-tment with a reducing agent), to subject the deactivated catalys-t to a treatment with steam, and/or an oxygen-containing gas such as air, and/or with a mixture of steam and air, at a temperature above 250 C at atmospheric or a higher pressure.
If the carrier of -the ca-talys-t is resistant to an aqueous solu-tion of mineral acid (i.e. consists of~ for example, silica) the ca-talyst can be reused after removal of the coke, sulphur and metals, op-tionally after application O-r the abovementioned metals wi-th hydrogena-tion activity.
If the carrier is not resistant to an aqueous solution of a m;neral acid (i.e. consists, for example, of alumina) regeneration in the above-mentioned manner is impossible. In that case it is also possible, however, to carry out the treatment with mineral acid in order to recover the metals deposited from the hydrocarbon oil. Said metals can of course also be recovered from the extract obtained in the treatment with an aqueous mineral acid solution of deactivated catalys-ts, the carriers of which are resis-tan-t to a treatment of this type.
The demetallized hydrocarbon oil obtained in the process accord-ing to the invention can be used for any desired purpose.The demetallization need of course not be complete and a quantity of metal may still be present in -the demetallized product.
~ s stated above~ it is in many cases at-tractive to subject the resultan-t demetallized hydrocarbon oil to a hydrodesulphurization treatment and it is advantageous to carry out the deme-tallization and desulphurization in one continuous treatment without intermediate isolation and!or purification of the deme-tallized hydrocarbon oil and of the hydrogen-containing gas becoming available from the final reactor bed of demetallization catalyst.
For the hydrodesulphurization of heavy hydrocarbon fractions, such as residual fractions, specific catalysts are known which can be used for a long time without replacement or regeneration of -the ca-talyst being necessary as a result of deposition of coke and high-molecl1lar components (such as resins, polyaroma-tics and asphaltenes) from the feed. Catalysts as described in the Dutch paten-t application 7010427 are very sui-table. The particles of said catalysts have a pore volume above 0.30 ml/g, of which pore ~1574:1~
volume less than 10% is present in pores having a diameter above ~00 nm, and the catalyst ~articles have a speci~ic pore diameter expressed in nm ~rom 7.5 x d-9 to 17 x d 9, in which d represents the spec;fic particle diameter in ~.
Said catalysts very sui-tably contain a carrier on which one or more metals chosen ~rom the group consisting of nickel, cobalt, tungsten and molybdenum, and in particular one metal o~ the group consisting o~
nickel and cobalt and one metal o~ the group consisting o~ tungsten and molybdenum, are deposited. Catalysts containing nickel or cobalt 10 together with molybdenum are particularly suitable. The metals are preferably present as their oxides or sulphides. Very sui-table carriers are silica, silica-alumina and in particular alumina.
The hydrodesulphurization is carried out under the usual conditions.
The demetallized hyclrocarbon oil to be desulphurized together wi-th the hydrogencontaining gas obtained in the demetallization (to which extra hydrogen is added, i~ desired~ is very suitably passed in downward direction over the catalyst at a temperature between 350 and 475 C
(preferably between 385 and 4~5C), a total pressure between 75 and 250 bar (pre~erably between 100 and 225 bar), a hydrogen partial pressure 20 between 35 and 120 bar (preferably between 50 and 100 bar), a space velocity o~ 0.1-25 (pre~erably 0.2-5~ parts by volume of ~eed per part by volume o~ catalyst and a hydrogen/feed ratio o~ 150-2000 (preferably 250-1500) Nl o~ II2/kg o~ ~eed.
The desulphurization catalyst is very suitably contained in one or 25 more fixed beds which, i~ desired, are located in several serially connected reactors.
When the demetalli~ation catalyst or the desulphurization catalyst is deactivated, the whole plant is closed down and the demetallization catalyst and desulphurization ca-talyst are both removed and/or 30 regenerated. For economic reasons the aim will be to choose the quantities of demetallization catalyst and desulphurization catalyst in such a manner tha-t both are deac-tivated about simu]taneously, since in -that manner no or only a small portion o~ active catalyst is removed and/or subjected to a regeneration process.
~ ~57~2 ~o The product ob-tained after the desulphurization is sepera-ted from the hydrogen-containing gas in the usual manner; if desired, said gas can be recycled -to the process after complete or partial removal of H2S and any other impurities. ~ r~Jn~
The inven-tion also relates to an apparatus ~r~e~a-~ one or more serially connected reac-tors each o which can be filled with one or more fixed catalyst beds, the first bed of the first reactor having an inlet for a gas and an inlet for a hydrocarbon oil~ characterized in that one or more inlets for hydrocarbon oil is/are present downs-tream, and that each hydrocarbon oil inlet can be separa-tely connected or closed.
The invention will now be illus-trated with reference to the following diagrammatic figure. Each of the reactors R1, R2 and R3 contains two ~ixed beds of demetallization catalyst (1, 2, 3, 4, 5 and 6~. Hydrogen is supplied to the bed 1 in reactor R1 through a line 7, passes the beds 2, 3, 4, 5 and 6 consecutively and leaves reactor R3 through a line 8 toge-ther with demetallized hydrocarbon oil. Fresh hydrocarbon oil is supplied -through a line 9 and is initially supplied to bed 1 via an open valve 10 and passes through the beds 1, 2, 3, 4, 5 and 6 consecutively. ~alves 11, 12, 13, 14 and 15 are closed. After the demetallization catalyst in bed 1 is deactivated, valve 11 is opened and valve 10 is closed. The hydro-carbon oil to be demetallized is then supplied to bed 2 and passes through the beds 2, 3, 4, 5 and 6 consecutively. When bed 2 is de-activated, valve 12 is opened and valve ~1 is closed and the hydro-carbon oil to be demetallized is supplied to bed 3. In a similar manner the hydrocarbon oil to be demetallized is supplied to the beds 4, 5, and 6 whenever the preceding bed is deactivated. After bed 6 is also deactivated, the hydrocarbon oil and hydrogen streams are interrup-ted and the catalyst in reactors R1, R2 and R3 is replaced or regenerated. ln the figure -the resul-tan-t demetallized hydrocarbon oil and -the hydrogen containing gas which become available -through a line o from reactor R3 are passed without further purification through the reactors R4 and R5, each containing two beds of a desulphurization ca-ta~ys-t.
_ _ .... _ _ _ _ . . . .
~:lS7~L~2 The desulphurized and demetallized hydrocarbon oil and the hydrogen-containing gas becoming available from reactor R5 through a line 16 can be separated and purified by conventional methods. As regards pressure, temperature and space velocity, conditions suitable for demetallization are maintained in reactors R1, R2 and R3 and con-ditions suitable for desulphurization are maintained in reactors R
and R5.
EX~PLE
In an apparatus as described in the figure, beds-1-6in the reactors R1, R2 and R3 are filled with a demetallization catalyst.
Said catalyst contains o.6% by weight of nickel (as oxide) and 1.9%
by weight of vanadium (as oxide~ on silica as carrier, has a specific average pore diameter of 13.6 nm, a specific average particle dia-meter of 2.2 mm, a specific surface area of 262 m /g and a pore volume of o.78 ml/g, of which pore volume 0.3% consists o~ pores having a diameter above 100 nm. Before use the catalyst is sulphided by passing over it a gasoil containing ~.6% by weight of sulphur, at a space velocity of 1 kg/litre of catalyst/h, a temperature of 350 C
and a hydrogen pressure of 50 bar. The reactors R4 and R5 are filled with a desulphurization catalyst. This catalyst contains 3.6% by weight of nickel (as oxide~ and 8.9% by weight of molybdenum (as oxide) on alumina as carrier, and has a specific average pore dia-meter of 20.2 nm, a specific average particle diameter of 1.5 mm, a specific surface area of ~83 m /g and a pore volume of o.54 ml/g, of 25 which less than 0.4% is present in pores h~ving a diameter above 100 nm. Before use this desulphurization ca-talyst is sulphided in the same way as the demetallization catalyst.
A deasphalted vacuum residue of a mineral oil (DA0) containing 40 ppm of vanadium and 2.7~ by weigh-t o~ sulphur, is subsequently 30 passed through the reactors R1-R5 at a space velocity of 0.29 kg/l o~ catalyst/h both ~or the demetal.lization catalyst and -the desulphur-ization catalyst, at a temper-ature o~ 390 C, a hydrogen partial pressure o~ 70 bar and a gas space velocity of 1000 Nl/kg of feed.
Whenever the pressure drop increases rapidly, the feed inlet is moved -to the nex-t bed of demetallization catalyst, the hydrogen stream being maintained over all the beds.
1 1 5 ~
The test is interrup-ted after unaccep-table pressure drop occurs while the feed is being supplied to bed 6; this is 12,000 hours after -the start of the test. The product obtained con-tains 1 ppm of vanadium and 0.5% by weight of sulphur.
For the sake of comparison an experir~ent is carried ou-t in which the feed inlet is not moved downstream. After only 2000 hours such a pressure drop occurs that the experiment must be interrupted.
-
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the demetallization of a hydrocarbon oil by passing said oil together with hydrogen over one or more fixed beds of a demetallization catalyst, characterized in that whenever that catalyst portion which is first contacted with the hydrocarbon oil is deactivated, the point of supply of the hydrocarbon oil is moved downstream, at least part of the original supply of hydrogen being maintained over the entire catalyst.
2. A process as claimed in claim 1, characterized in that the demetal-lization catalyst is contained in several serially connected beds.
3. A process as claimed in claim 2, characterized in that the point of supply of the hydrocarbon oil to be demetallized is in all cases moved to a point between two catalyst beds.
4. A process as claimed in claim 1, 2 or 3, characterized in that the hydrocarbon oil is a residual fraction.
5. A process as claimed in claim 1, 2 or 3, characterized in that the demetallization catalyst contains at least one metal of the group consisting of nickel and cobalt, at least one metal of the group consisting of molybdenum, vanadium and tungsten, supported on a carrier, and fulfils the following require-ments:
1) p/d > 3.5-0.02 v, where p represents the specific average pore diameter in nm, d represents the specific average particle diameter in mm and v is the percentage of the total pore volume consisting of pores having a dia-meter above 100 nm, 2) the total pore volume is above 0.40 ml/g, 3) v is below 50 and 4) the specific surface area is above 100 m2/g; in case the catalyst has such a p and d that the quotient p/d is above 3.5-0.02 v, but at most 10-0.15 v, the catalyst must fulfil the following additional requirements:
a) the nitrogen pore volume is above 0.60 ml/g, b) the specific surface area is above 150 m2/g and c) p is above 5 nm.
1) p/d > 3.5-0.02 v, where p represents the specific average pore diameter in nm, d represents the specific average particle diameter in mm and v is the percentage of the total pore volume consisting of pores having a dia-meter above 100 nm, 2) the total pore volume is above 0.40 ml/g, 3) v is below 50 and 4) the specific surface area is above 100 m2/g; in case the catalyst has such a p and d that the quotient p/d is above 3.5-0.02 v, but at most 10-0.15 v, the catalyst must fulfil the following additional requirements:
a) the nitrogen pore volume is above 0.60 ml/g, b) the specific surface area is above 150 m2/g and c) p is above 5 nm.
6. A process as claimed in claim 1, 2 or 3, characterized in that the demetallization is carried out at a temperature between 350 and 425°C, a total pressure between 100 and 200 bar, a hydrogen partial pressure between 50 and 100 bar, a space velocity of 0.1-25 parts by volume of fresh feed per part by volume of catalyst per hour and a hydrogen/feed ratio of 200-1500 N1 of 112/kg of feed.
7. A process as claimed in claim 1, characterized in that the demetal-lized hydrocarbon oil is subjected to a hydrodesulphurization treatment.
8. A process as claimed in claim 7, characterized in that the demetal-lization and desulphurization are carried out in one continuous treatment with-out intermediate isolation and/or purification of the demetallized hydrocarbon oil and of the hydrogencontaining gas becoming available from the final reactor bed of demetallization catalyst.
9. An apparatus comprising one or more serially connected reactors each of which can be filled with one or more fixed catalyst beds, the first bed of the first reactor having an inlet for a gas and an inlet for a hydrocarbon oil, characterized in that one or more hydrocarbon oil inlets are present downstream and that each hydrocarbon oil inlet can be separately connected or closed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7907142 | 1979-09-26 | ||
| NL7907142A NL191763C (en) | 1979-09-26 | 1979-09-26 | Method of demetallizing a hydrocarbon oil. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1157412A true CA1157412A (en) | 1983-11-22 |
Family
ID=19833914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000358662A Expired CA1157412A (en) | 1979-09-26 | 1980-08-20 | Process and apparatus for the demetallization of a hydrocarbon oil |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0026508B1 (en) |
| JP (1) | JPS5655489A (en) |
| AU (1) | AU538217B2 (en) |
| CA (1) | CA1157412A (en) |
| DE (1) | DE3064280D1 (en) |
| MX (1) | MX155344A (en) |
| NL (1) | NL191763C (en) |
| NZ (1) | NZ195045A (en) |
| SG (1) | SG32384G (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2570385B1 (en) * | 1984-09-14 | 1987-08-21 | Raffinage Cie Francaise | PROCESS FOR HYDROPROCESSING HYDROCARBON CHARGES AND CATALYST FOR CARRYING OUT SAID METHOD |
| FR2650759B1 (en) * | 1989-08-08 | 1991-10-31 | Inst Francais Du Petrole | NICKEL-BASED CAPTATION MASS FOR THE ELIMINATION OF ARSENIC AND PHOSPHORUS CONTAINED IN LIQUID HYDROCARBON CUTS, ITS PREPARATION AND ITS USE |
| FR2686617B1 (en) * | 1992-01-28 | 1994-03-18 | Institut Francais Petrole | PROCESS FOR SELECTIVE HYDROGENATION OF HYDROCARBON CHARGE WITH CATALYTIC LETS CARRIED OUT SUCCESSIVELY. |
| EP0712922B1 (en) | 1994-11-16 | 2000-02-23 | Shell Internationale Researchmaatschappij B.V. | Process for improving lubricating base oil quality |
| AU688610B2 (en) * | 1994-11-16 | 1998-03-12 | Shell Internationale Research Maatschappij B.V. | Process for improving lubricating base oil quality |
| US20060070918A1 (en) * | 2004-10-01 | 2006-04-06 | Mayis Seapan | Method to extend the utilization of a catalyst in a multistage reactor system |
| DE102007059243A1 (en) * | 2007-12-07 | 2009-06-10 | Uhde Gmbh | Process for the desulfurization of olefin-containing starting materials |
| DE102009032802A1 (en) * | 2009-07-10 | 2011-01-13 | Uhde Gmbh | Process for the desulfurization of olefin-containing feedstocks by controlling the olefin content |
| FR2970260B1 (en) * | 2011-01-10 | 2014-07-25 | IFP Energies Nouvelles | METHOD FOR HYDROTREATING HEAVY HYDROCARBON LOADS WITH PERMUTABLE REACTORS INCLUDING AT LEAST ONE SHORT-CIRCUIT STEP OF A CATALYTIC BED |
| FR3015514B1 (en) * | 2013-12-23 | 2016-10-28 | Total Marketing Services | IMPROVED PROCESS FOR DESAROMATIZATION OF PETROLEUM CUTTERS |
| WO2017014947A1 (en) * | 2015-07-17 | 2017-01-26 | Exxonmobil Research And Engineering Company | Production of low sulfur gasoline |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3206395A (en) * | 1963-01-21 | 1965-09-14 | Pullman Inc | Desulfurization product recovery process |
| US3563887A (en) * | 1968-10-25 | 1971-02-16 | Gulf Research Development Co | Asphaltene hydrodesulfurization with small catalyst particles disposed in a guard chamber-main reactor system |
| GB1388714A (en) * | 1971-04-01 | 1975-03-26 | Exxon Research Engineering Co | Process for the conversion of metal-contaminated hydrocarbon feedstocks |
| NL175732C (en) * | 1972-07-07 | Shell Int Research | PROCEDURE FOR THE CATALYTIC DEMETALLIZATION OF RESIDUAL HYDROCARBON OILS AND THE FURTHER CATALYTIC CONVERSION OF THE OIL OBTAINED THEREIN. | |
| DE2329700C3 (en) * | 1973-06-09 | 1982-04-15 | Basf Ag, 6700 Ludwigshafen | Process for the hydrogen refining and / or hydrogen cracking of hydrocarbonaceous feedstock |
| US4017382A (en) * | 1975-11-17 | 1977-04-12 | Gulf Research & Development Company | Hydrodesulfurization process with upstaged reactor zones |
-
1979
- 1979-09-26 NL NL7907142A patent/NL191763C/en not_active IP Right Cessation
-
1980
- 1980-08-20 CA CA000358662A patent/CA1157412A/en not_active Expired
- 1980-08-28 DE DE8080200807T patent/DE3064280D1/en not_active Expired
- 1980-08-28 EP EP19800200807 patent/EP0026508B1/en not_active Expired
- 1980-09-24 MX MX18406280A patent/MX155344A/en unknown
- 1980-09-24 AU AU62664/80A patent/AU538217B2/en not_active Ceased
- 1980-09-24 JP JP13179680A patent/JPS5655489A/en active Granted
- 1980-09-24 NZ NZ19504580A patent/NZ195045A/en unknown
-
1984
- 1984-04-23 SG SG32384A patent/SG32384G/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0138157B2 (en) | 1989-08-11 |
| AU6266480A (en) | 1981-04-09 |
| DE3064280D1 (en) | 1983-08-25 |
| EP0026508B1 (en) | 1983-07-20 |
| AU538217B2 (en) | 1984-08-02 |
| NL7907142A (en) | 1981-03-30 |
| NZ195045A (en) | 1983-02-15 |
| SG32384G (en) | 1985-06-07 |
| MX155344A (en) | 1988-02-19 |
| NL191763B (en) | 1996-03-01 |
| JPS5655489A (en) | 1981-05-16 |
| NL191763C (en) | 1996-07-02 |
| EP0026508A1 (en) | 1981-04-08 |
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