CA1088448A - Process for the conversion of hydrocarbons - Google Patents
Process for the conversion of hydrocarbonsInfo
- Publication number
- CA1088448A CA1088448A CA261,785A CA261785A CA1088448A CA 1088448 A CA1088448 A CA 1088448A CA 261785 A CA261785 A CA 261785A CA 1088448 A CA1088448 A CA 1088448A
- Authority
- CA
- Canada
- Prior art keywords
- residue
- vacuum
- hydrocracking
- atmospheric
- distillation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/0463—The hydrotreatment being a hydrorefining
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
Landscapes
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Abstract of the Disclosure Process for the preparation of one, or more, atmospheric hydro carbon oil distillates from an atmospheric hydrocarbon oil residue, utilizing a hydrocracking process in combination with a catalytic hydrotreatment, deasphalting, gasification and thermal cracking or coking as supplementary processes. This process converts the residue in to useable distillate frac-tions, such as gasolines.
Description
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The invention relates to a process for the production of one or more atmospheric hydrocarbon oil distillates from an atmospheric hydrocarbon oil residue.
During the atmospheric distillation of crucLe oil, as employed on a large scale in the refineries for the production of light hydrocarbon oil distillates, a residual oil is obtained as a by-product.
In some cases this residual oil is suitable to serve as base material for the production o~ lubricating oil, but often the residual oil, which as a rule contains considerable quantities of sulphur, metals and asphal~enes, only qualifies for use as fuel oil.
In view of the growing need for atmospheric hydrocarbon oil distillates various processes have been proposed over the years which aimèd at the conversion of the residual oils into lieht distillQtes. Examples of such processes are catalytic cracking, ther~al cracking, gasirication in combination with hydrocarbon synthesis, coking and hydrocracking. The use o~ the residual oils &B such as feed ~or each o~ these processes has considerable disadvantages, which seriously hQmper their Qpplication on a commercial scale.
~or instance, the catalytic cracking of these residu~l oils has the serious drawbacks that cataiyst consumption is very high and that owing to the high coke and gas production only a low yield of the d;-sired atmospheric distillates is obtained. The thermal cracking of these residual oils for the production of atmospheric distillates is not attractive either, because the stability of the cracked product pe i ts only a low conversion to desired atmospheric distillates. Coking of the residual oils yields a considerable quantity of coke as product and this coke production occurs at the expen~e of bhe yield of desired atmospheric distillates.
Gasirication Or the residual oils in co~bination with hydroc~rbon synthesis i8 rather expensive and moreover nob very attractive because in this way first the too heavy molecules are cr~cked to form too light molecules, the latter subsequently being recombined to form heavier one~. ~he hyclrocracking of the residual oils is accompanied by a rapid catalyst deactivation, a high gas production and a hiBh consumption of hydrogen.
In view of the above and taking into account the fact that in the atmospheric distillation of crude oil about half of the crude oil is left behind as distillation residue, it will be ~.
. . .
~18849~8 .
- -clear that there is a pressing need for a process which oifers the possibility of converting in an economically justified way atmospheric hydrocarbon oil residues into atmosplleric hydrocarbon oil distillates such as gasolines.
As in practice hydrocracking has proved to be an excellent process for the conversion of heavy hydrocarbon oil distillates such as gas oils into light hydrocarbon oil distillates such as ; gasolines, the Applicant has carried out an investigation in order to find out what use could be made of hydrocracking for the conversion of atmospheric hydrocarbon oil residues into atmospheric distillates.
It has been found that by a correct combination o~ hydrocracking as the main process with a catalytic hydrotreatment, deasphalting, -~
gasificQtion and thermal cracking or coking as supplementary processes, a process can be realised which is highly suitable for this purpose.
The present patent application relates to such a process.
In the proc2s~ according to the invention an atmospheric hydrocarbon oil residue (AR) and/or an atmospheric residue obtained therefrom by catalytic hydrotreatment and distillation of the hydrotreated product, is split, ~y vacuum distillation, into a vacuum distillate (VD) and a vacuum residue (VR). The vacuum residue and/or a vacuum residue obtained therefrom by catalytic hydrotreatment and distillation o~ the hydrotreated product, is split, by deasphalting, into a deasphalted oil and asphalt. The ,deasphalted oil and the ~acuum distillate (VD) are hydrocracked and the cracked product is separated by atmospheric distilla~ion into one or more light ditillates as end products, and, if desired, a middle distillate (M1) as end product, and a residue of which at lea~t a part is again subjected to hydrocracking. The Qsphalt and/or a residue or asphalt fraction of this residue obtained therefrom by cat~lytic hydrotreatment and distillation of the hydrotreated product, is subjected to thermal crackine or coking and the liquid product so obtained is split by distillation into one or more light distillates as end products, an intermediate fraction as end product or as intermediate product and a residual fraction , The coke or the residual fraction obtained in the distil-lation of the thermally cracked product is gasified for the pro-duotion o~ hydrogen ~or both the cntnlytio hydrotrentment nnd '. " ''' .. ..
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the hydrocracking. '~he catalytic hydrotreatment is applied either to at least part of the atmospheric distillation residue (AR), or to at least'part of the vacuum residue (VR), or to at lea6t part of the asphalt obtained from the vacuum residue (VR) by deasphalting.
In the process according to the invention hydrocracking is employed as the main process. In the hydrocracking process a considerable part of the heavy feed is converted into lighter products. '~he desired end products are separated from the cracked product by atmospheric distillation.
If it is the intention to prepare only one or more light distillates as end products, further processing of the residue may take place in the following ways.
1. The entire residue i8 again subjected to hydrocracking.
2. '~he re~idue is split into two portions of the same composition and one of these portions is again subjected to hydrocracking, whereas the other portion is removed from the process and may be used, ~or instance, as blending component ~or ~uel oil,
The invention relates to a process for the production of one or more atmospheric hydrocarbon oil distillates from an atmospheric hydrocarbon oil residue.
During the atmospheric distillation of crucLe oil, as employed on a large scale in the refineries for the production of light hydrocarbon oil distillates, a residual oil is obtained as a by-product.
In some cases this residual oil is suitable to serve as base material for the production o~ lubricating oil, but often the residual oil, which as a rule contains considerable quantities of sulphur, metals and asphal~enes, only qualifies for use as fuel oil.
In view of the growing need for atmospheric hydrocarbon oil distillates various processes have been proposed over the years which aimèd at the conversion of the residual oils into lieht distillQtes. Examples of such processes are catalytic cracking, ther~al cracking, gasirication in combination with hydrocarbon synthesis, coking and hydrocracking. The use o~ the residual oils &B such as feed ~or each o~ these processes has considerable disadvantages, which seriously hQmper their Qpplication on a commercial scale.
~or instance, the catalytic cracking of these residu~l oils has the serious drawbacks that cataiyst consumption is very high and that owing to the high coke and gas production only a low yield of the d;-sired atmospheric distillates is obtained. The thermal cracking of these residual oils for the production of atmospheric distillates is not attractive either, because the stability of the cracked product pe i ts only a low conversion to desired atmospheric distillates. Coking of the residual oils yields a considerable quantity of coke as product and this coke production occurs at the expen~e of bhe yield of desired atmospheric distillates.
Gasirication Or the residual oils in co~bination with hydroc~rbon synthesis i8 rather expensive and moreover nob very attractive because in this way first the too heavy molecules are cr~cked to form too light molecules, the latter subsequently being recombined to form heavier one~. ~he hyclrocracking of the residual oils is accompanied by a rapid catalyst deactivation, a high gas production and a hiBh consumption of hydrogen.
In view of the above and taking into account the fact that in the atmospheric distillation of crude oil about half of the crude oil is left behind as distillation residue, it will be ~.
. . .
~18849~8 .
- -clear that there is a pressing need for a process which oifers the possibility of converting in an economically justified way atmospheric hydrocarbon oil residues into atmosplleric hydrocarbon oil distillates such as gasolines.
As in practice hydrocracking has proved to be an excellent process for the conversion of heavy hydrocarbon oil distillates such as gas oils into light hydrocarbon oil distillates such as ; gasolines, the Applicant has carried out an investigation in order to find out what use could be made of hydrocracking for the conversion of atmospheric hydrocarbon oil residues into atmospheric distillates.
It has been found that by a correct combination o~ hydrocracking as the main process with a catalytic hydrotreatment, deasphalting, -~
gasificQtion and thermal cracking or coking as supplementary processes, a process can be realised which is highly suitable for this purpose.
The present patent application relates to such a process.
In the proc2s~ according to the invention an atmospheric hydrocarbon oil residue (AR) and/or an atmospheric residue obtained therefrom by catalytic hydrotreatment and distillation of the hydrotreated product, is split, ~y vacuum distillation, into a vacuum distillate (VD) and a vacuum residue (VR). The vacuum residue and/or a vacuum residue obtained therefrom by catalytic hydrotreatment and distillation o~ the hydrotreated product, is split, by deasphalting, into a deasphalted oil and asphalt. The ,deasphalted oil and the ~acuum distillate (VD) are hydrocracked and the cracked product is separated by atmospheric distilla~ion into one or more light ditillates as end products, and, if desired, a middle distillate (M1) as end product, and a residue of which at lea~t a part is again subjected to hydrocracking. The Qsphalt and/or a residue or asphalt fraction of this residue obtained therefrom by cat~lytic hydrotreatment and distillation of the hydrotreated product, is subjected to thermal crackine or coking and the liquid product so obtained is split by distillation into one or more light distillates as end products, an intermediate fraction as end product or as intermediate product and a residual fraction , The coke or the residual fraction obtained in the distil-lation of the thermally cracked product is gasified for the pro-duotion o~ hydrogen ~or both the cntnlytio hydrotrentment nnd '. " ''' .. ..
' ~
~844~ :
:
the hydrocracking. '~he catalytic hydrotreatment is applied either to at least part of the atmospheric distillation residue (AR), or to at least'part of the vacuum residue (VR), or to at lea6t part of the asphalt obtained from the vacuum residue (VR) by deasphalting.
In the process according to the invention hydrocracking is employed as the main process. In the hydrocracking process a considerable part of the heavy feed is converted into lighter products. '~he desired end products are separated from the cracked product by atmospheric distillation.
If it is the intention to prepare only one or more light distillates as end products, further processing of the residue may take place in the following ways.
1. The entire residue i8 again subjected to hydrocracking.
2. '~he re~idue is split into two portions of the same composition and one of these portions is again subjected to hydrocracking, whereas the other portion is removed from the process and may be used, ~or instance, as blending component ~or ~uel oil,
3. In the atmo~pheric distillQtion of the cracked product, besid~s one or more light distillatea, an atmospheric middle '~ dist~llate M1 is separated which is again subjected to hydro-cracking. The residue obtained in this atmospheric distillation may be processed further in the following ways.
a) '~he entire residue is removed from the process.
b) 'rhe residue is split into two portions of the same composition and one of these portions i~ again subjected to hydrocracking, whereas the other portion i8 removed from the process.
c) From the resiaue a distillate is separated by vacuum dis-~illation, which distillate i9 again ~ubjected to hydrocracking.
'~he residue obtained by this vacuum distillQtion is removed from the process or is split into two portions of the same composition, of which one is again subjected to hydrocracking, whereas the other portion is removed from the process.
If it i~ the intention to prepare, besides one or more light distillates, also an atmospheric middle distillate M1 a8 end pro-duct, ~urther processing of the residue 80 obtained may take place in the same way as indicated hereinbefore under 1., 2. and -~ 3.c).
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, If in the further processing o~ a residue obtained by dis-tillation of the hydrocracked product use is made of a process in which the residue is divided into two portions of the same composition of which one is again subjected to hydrocracking, whereas the other portion is removed ~rom the process, the quantity of material that is recirculated is preferably more than 25 ~Ow of the available quantity of residue and this quantity is preferably chosen higher according as the residue concerned has a lower initial boiling point.
The hydrocracking used as the main treatment in the process according to the invention takes place by contacting the feed at elevated temperature and pressure and in the presence of hydrogen with a suitable hydrocracking catalyst. Preferably the hydro-cracking is carried out as a two-step process, the hydrocracking proper, which takes place in the second step, being preceded by a catalytic hydrotreatment with the main object of reducine the nitroge~ and polyaromatics contents of the feed to be hydrocracked. i~
Suitable cataly~ts for uae in the one-step hydrocracking process as well as for use in the second step of the two-step hydrocracking 1 20 process are moderately acidic and strongly acidic catalysts which i contain one or more mètals with hydrogenating acti~ity on a carrier.
! Examples of suitable catalysts for use in the one-step hydro-cracking process are fluorine-containing Yulphidic catalysts comprising nickel and/or cobalt and in addition molybdenum and/or tungsten on alumina or amorphou~ silica-alumina as carrier, Examples of `i suitable catalysts for use in the second ~tep of the two-step hydrocracking process are fluorine-containing sulphidic catalysts ccmprising nickel and/or cobalt and in addition molybden~m and/or tungsten on amorphous silica-alumina as carrier, sulphidic cata-lysts containing or not containing fluorine, and comprising nickel and/or cobalt and in addition molybdenum and/or tungsten on crystalline silica-alumina as carrier, and catalysts, containing or not con-taining fluorine and comprising one or more noble metals from Group VIII and in particular palladium on crystalline silica-alumina as carrier. Suitable catalysts for use in the first step of the two-step hydrocracking process are weakly acidic and moderately ~ ~ acidic catalysts comprising one or more metals with hydrogenating ;
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. '..' ; '.' : .' 8~413 ; activity on a carrier, such as fluorine-containing sulphidic cata-lysts comprising nickel andjor cobalt and in addition molybdenum and/or tungsten on alumina or amorphous silica-alumina as carrier.
If in the process according to the in~ention the hydrocracking is carried out in onelstep preferably the following reaction con-ditions are applied: a temperature of from 350 to 425C a~d in particular of from 375 to 410C, a hydrogen partial pressure of from 5~ to 300 bar and in particular of from 75 to 150 bar, a space velocity of from 0.25 to 5 kg.l .hour and in particular of fro~ 0.25 Ito 2 kg.l 1.hour 1 and a hydrogen/feed ratio o~ from 500 to 3000 Ml.kg and in psrticular of from 1000 to 2500 Nl.kg If in the process according to the invention the hydrocracking ~;~
is carried out in two steps preferably the following reaction cQnditions are applied in the first step: a temperature o~ from 325 to 425C and in particular of from 350 to 410C, a hydrogen partial pressure of from 50 to 300 bar and in particular o~ from 75 to 150 bar, a space ~elocity of from 0.1-5 kg.l .hour 1 and in particular o~ from 0.5 to 1,5 kg.l 1.hour and Q hyarogetl/feed ratio of from 500 to 3000 Nl.kg 1, In the second step preferably substantially the same conditions are applied as indicated here-inbefore for the one-step process, with the e~ception o~ the temperature, which in this case preferably should be 300-400C
and in particular 320-380C, ~hen the hydrocracking is carried out according to the two-step process preferably the whole reaction product from the first step (without ammonia, hydrogen sulphide or other volatile components being separated therefrom) is used a9 ~eed ~or the second step.
In the process according to the invention a catal~tic hydro-treatment i8 applied as supplementQry process, be it to an atmo-spheric residue, or to a vacuum residue or to an ~sphalt. In this treatment compounds whose presence in the feed for a hydrocracker is not very desirable are converted into compounds more suitable - ~ -for this purpose. In this treatment at the same time a small quan-tity of atmospheric hydrocarbon oil distillate is formed, which is isolated as end product, The hydrotreated product is split into one or more 1ight at=ospheric distillatee as end products, ', ~' ' ' .
101~1~44~ ; ~
an atmospheric middle distillate M2 and an atmospheric residue, which canbe further split by vacuum distillation into a vacuum distillate and a vacuum residue.
If the catalytic hydrotreatment is applied to asphalt, the above-mentioned vacuum distillation of the atmospheric residue of the hydrotreated product can be replaced very suitably with deasphelting. ~he de~sphalted oil obtained from this deasphalting of the atmospheric residue is used as a feed co~ponent for the hydrocracker and the asphalt is subjected to thermal cracking or coking.
If it is the intention to prepare only one or more light distillates as end products by the process according to the invention, the atmospheric middle distillate M2 is used as a feed component for the hydrocracker. If, however, it is the intention to prepare, besides one or more light distillates, also an atmospheric middle distillate M2 as end product, fraction M2 is removed from the procesa as end product.
The catalytic hydrotreatment which in the process according to the invention is applied as supplementary treatment takes place by contacting the feed at elevated temperature and pressure and in the presence of ydrogen to a non-acidic or weakly acidic catalyst. In the catalytic hydrotreatment the following reaction ; conditions are prefer~bly applied: a temperature of from 380 to 500C and in particular of from 380 to 4600C, a hydrogen partial pressure of from 50 to 300 bar and in particular of from 75 to 200 bar, a space velocity of from 0.1 to 5 kg.l 1.hour 1 and in particular of from 0.1 to 1 kg.l 1.hour 1 and a hydrogen/feed ratio of from 200 to 2000 Nl.kg 1 and in particular of from 500 to 2000 Nl.kg 1 In the catalytic hydrotreatment preferably a temperature is applied which is at least 10C and in particular at least 20C higher than the hydrocracking temperature applied.
(If the hydrocracking is carried out in two steps then in this -context the hydrocracking temperature should be understood to be the temperature in the second step). Examples of suitable catalysts for carrying out the catalytic hydrotreatment are alumina~ silica, sulphidic catalysts containing or not containing fluorine and comprisin~ nickel and/or cobalt and in addition molybdenum, tungsten ' , , and/or vanadium on alu~ina as carrier, and sulphidic catalysts comprising nickel and/or cobalt and in addition molybdenum, tungsten and/or vanadium on silica or silica-alumina as çarrier.
The process according to the invention further comprises deasphalting as a supplementary process. lhis deasphalting is preferably carried out at elevated temperature and pressure and in the presence of an excess of a lower hydrocarbon such as propane, butane or pentane as solvent.
The process according to the invention further comprises thermal cracking or coking as supplementary processes. In these processes a considerable proportion of the residual feed is converted into distillate. From the product obtained by thermal cracking or coking one or more light distillates can be separated as end products by distillation, as well as a middle distillate M3 as end product or as a feed component for the hydrocracker. The ^oke or the residual fraction which i9 left after working up of the product obtained by ther~al cracking serves a~ feed for the gasification ; unit. If in the procea~ according to the invention thermal cracking is applied, this is preferably carried out at a temperature of from 400 to 525C, a pressure of from 2.5 to 25 bar and a residence time of from 1 to 25 minutes. Special preference exists for carrying out the thermal cracking at a temperature of from 425 to 500C, a pressure of from 5 to 20 bar and a residence time of from 5 to 20 r~inutes. If in the process according to the invention coking is employed, this i8 preferably carried out at a temperature o~
from 400 to 600C, a pressure of from 1 to 25 bar and Q residence time of from 5 to 50 hours. Special preference exists for carrying out the coking at a temperature of from 425 to 550C, a pressure of from 2.5 to 20 bar and a residence time of from 10 to 40 ~our8.
Finally, the process according to the invention comprises ga~ification as a supplementary process. As feed for the gasification unit coke or the residual fraction which i8 left after working up of the product obtained by thermal cracking is used. The easi-fication is carried out by incomplete combustion of the feed with oxygen. Preferably steam is added to the mixture as moderator.
In the incomplete combustion a crude gas is obtained consisting substantially of carbon monoxide and hydrogen and containing ' ".
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a) '~he entire residue is removed from the process.
b) 'rhe residue is split into two portions of the same composition and one of these portions i~ again subjected to hydrocracking, whereas the other portion i8 removed from the process.
c) From the resiaue a distillate is separated by vacuum dis-~illation, which distillate i9 again ~ubjected to hydrocracking.
'~he residue obtained by this vacuum distillQtion is removed from the process or is split into two portions of the same composition, of which one is again subjected to hydrocracking, whereas the other portion is removed from the process.
If it i~ the intention to prepare, besides one or more light distillates, also an atmospheric middle distillate M1 a8 end pro-duct, ~urther processing of the residue 80 obtained may take place in the same way as indicated hereinbefore under 1., 2. and -~ 3.c).
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, If in the further processing o~ a residue obtained by dis-tillation of the hydrocracked product use is made of a process in which the residue is divided into two portions of the same composition of which one is again subjected to hydrocracking, whereas the other portion is removed ~rom the process, the quantity of material that is recirculated is preferably more than 25 ~Ow of the available quantity of residue and this quantity is preferably chosen higher according as the residue concerned has a lower initial boiling point.
The hydrocracking used as the main treatment in the process according to the invention takes place by contacting the feed at elevated temperature and pressure and in the presence of hydrogen with a suitable hydrocracking catalyst. Preferably the hydro-cracking is carried out as a two-step process, the hydrocracking proper, which takes place in the second step, being preceded by a catalytic hydrotreatment with the main object of reducine the nitroge~ and polyaromatics contents of the feed to be hydrocracked. i~
Suitable cataly~ts for uae in the one-step hydrocracking process as well as for use in the second step of the two-step hydrocracking 1 20 process are moderately acidic and strongly acidic catalysts which i contain one or more mètals with hydrogenating acti~ity on a carrier.
! Examples of suitable catalysts for use in the one-step hydro-cracking process are fluorine-containing Yulphidic catalysts comprising nickel and/or cobalt and in addition molybdenum and/or tungsten on alumina or amorphou~ silica-alumina as carrier, Examples of `i suitable catalysts for use in the second ~tep of the two-step hydrocracking process are fluorine-containing sulphidic catalysts ccmprising nickel and/or cobalt and in addition molybden~m and/or tungsten on amorphous silica-alumina as carrier, sulphidic cata-lysts containing or not containing fluorine, and comprising nickel and/or cobalt and in addition molybdenum and/or tungsten on crystalline silica-alumina as carrier, and catalysts, containing or not con-taining fluorine and comprising one or more noble metals from Group VIII and in particular palladium on crystalline silica-alumina as carrier. Suitable catalysts for use in the first step of the two-step hydrocracking process are weakly acidic and moderately ~ ~ acidic catalysts comprising one or more metals with hydrogenating ;
! ~
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. '..' ; '.' : .' 8~413 ; activity on a carrier, such as fluorine-containing sulphidic cata-lysts comprising nickel andjor cobalt and in addition molybdenum and/or tungsten on alumina or amorphous silica-alumina as carrier.
If in the process according to the in~ention the hydrocracking is carried out in onelstep preferably the following reaction con-ditions are applied: a temperature of from 350 to 425C a~d in particular of from 375 to 410C, a hydrogen partial pressure of from 5~ to 300 bar and in particular of from 75 to 150 bar, a space velocity of from 0.25 to 5 kg.l .hour and in particular of fro~ 0.25 Ito 2 kg.l 1.hour 1 and a hydrogen/feed ratio o~ from 500 to 3000 Ml.kg and in psrticular of from 1000 to 2500 Nl.kg If in the process according to the invention the hydrocracking ~;~
is carried out in two steps preferably the following reaction cQnditions are applied in the first step: a temperature o~ from 325 to 425C and in particular of from 350 to 410C, a hydrogen partial pressure of from 50 to 300 bar and in particular o~ from 75 to 150 bar, a space ~elocity of from 0.1-5 kg.l .hour 1 and in particular o~ from 0.5 to 1,5 kg.l 1.hour and Q hyarogetl/feed ratio of from 500 to 3000 Nl.kg 1, In the second step preferably substantially the same conditions are applied as indicated here-inbefore for the one-step process, with the e~ception o~ the temperature, which in this case preferably should be 300-400C
and in particular 320-380C, ~hen the hydrocracking is carried out according to the two-step process preferably the whole reaction product from the first step (without ammonia, hydrogen sulphide or other volatile components being separated therefrom) is used a9 ~eed ~or the second step.
In the process according to the invention a catal~tic hydro-treatment i8 applied as supplementQry process, be it to an atmo-spheric residue, or to a vacuum residue or to an ~sphalt. In this treatment compounds whose presence in the feed for a hydrocracker is not very desirable are converted into compounds more suitable - ~ -for this purpose. In this treatment at the same time a small quan-tity of atmospheric hydrocarbon oil distillate is formed, which is isolated as end product, The hydrotreated product is split into one or more 1ight at=ospheric distillatee as end products, ', ~' ' ' .
101~1~44~ ; ~
an atmospheric middle distillate M2 and an atmospheric residue, which canbe further split by vacuum distillation into a vacuum distillate and a vacuum residue.
If the catalytic hydrotreatment is applied to asphalt, the above-mentioned vacuum distillation of the atmospheric residue of the hydrotreated product can be replaced very suitably with deasphelting. ~he de~sphalted oil obtained from this deasphalting of the atmospheric residue is used as a feed co~ponent for the hydrocracker and the asphalt is subjected to thermal cracking or coking.
If it is the intention to prepare only one or more light distillates as end products by the process according to the invention, the atmospheric middle distillate M2 is used as a feed component for the hydrocracker. If, however, it is the intention to prepare, besides one or more light distillates, also an atmospheric middle distillate M2 as end product, fraction M2 is removed from the procesa as end product.
The catalytic hydrotreatment which in the process according to the invention is applied as supplementary treatment takes place by contacting the feed at elevated temperature and pressure and in the presence of ydrogen to a non-acidic or weakly acidic catalyst. In the catalytic hydrotreatment the following reaction ; conditions are prefer~bly applied: a temperature of from 380 to 500C and in particular of from 380 to 4600C, a hydrogen partial pressure of from 50 to 300 bar and in particular of from 75 to 200 bar, a space velocity of from 0.1 to 5 kg.l 1.hour 1 and in particular of from 0.1 to 1 kg.l 1.hour 1 and a hydrogen/feed ratio of from 200 to 2000 Nl.kg 1 and in particular of from 500 to 2000 Nl.kg 1 In the catalytic hydrotreatment preferably a temperature is applied which is at least 10C and in particular at least 20C higher than the hydrocracking temperature applied.
(If the hydrocracking is carried out in two steps then in this -context the hydrocracking temperature should be understood to be the temperature in the second step). Examples of suitable catalysts for carrying out the catalytic hydrotreatment are alumina~ silica, sulphidic catalysts containing or not containing fluorine and comprisin~ nickel and/or cobalt and in addition molybdenum, tungsten ' , , and/or vanadium on alu~ina as carrier, and sulphidic catalysts comprising nickel and/or cobalt and in addition molybdenum, tungsten and/or vanadium on silica or silica-alumina as çarrier.
The process according to the invention further comprises deasphalting as a supplementary process. lhis deasphalting is preferably carried out at elevated temperature and pressure and in the presence of an excess of a lower hydrocarbon such as propane, butane or pentane as solvent.
The process according to the invention further comprises thermal cracking or coking as supplementary processes. In these processes a considerable proportion of the residual feed is converted into distillate. From the product obtained by thermal cracking or coking one or more light distillates can be separated as end products by distillation, as well as a middle distillate M3 as end product or as a feed component for the hydrocracker. The ^oke or the residual fraction which i9 left after working up of the product obtained by ther~al cracking serves a~ feed for the gasification ; unit. If in the procea~ according to the invention thermal cracking is applied, this is preferably carried out at a temperature of from 400 to 525C, a pressure of from 2.5 to 25 bar and a residence time of from 1 to 25 minutes. Special preference exists for carrying out the thermal cracking at a temperature of from 425 to 500C, a pressure of from 5 to 20 bar and a residence time of from 5 to 20 r~inutes. If in the process according to the invention coking is employed, this i8 preferably carried out at a temperature o~
from 400 to 600C, a pressure of from 1 to 25 bar and Q residence time of from 5 to 50 hours. Special preference exists for carrying out the coking at a temperature of from 425 to 550C, a pressure of from 2.5 to 20 bar and a residence time of from 10 to 40 ~our8.
Finally, the process according to the invention comprises ga~ification as a supplementary process. As feed for the gasification unit coke or the residual fraction which i8 left after working up of the product obtained by thermal cracking is used. The easi-fication is carried out by incomplete combustion of the feed with oxygen. Preferably steam is added to the mixture as moderator.
In the incomplete combustion a crude gas is obtained consisting substantially of carbon monoxide and hydrogen and containing ' ".
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a considerable quantity of sulphur. The hydrogen content of this cruae gas is increased by subjecting it to the water gas shift reaction in which carbon monoxide i8 converted into carbon dioxide and hydrogen by reaction with steam. The water gas shift resction
a considerable quantity of sulphur. The hydrogen content of this cruae gas is increased by subjecting it to the water gas shift reaction in which carbon monoxide i8 converted into carbon dioxide and hydrogen by reaction with steam. The water gas shift resction
5 i9 preferably carried out by passing the gas to be converted at a temperature of bet*een 325 and 400C through two or more reactors containing a high-temperature water gas shift catalyst and subsequently passing the partly converted gas mixture at a temperature of between 200 and 275C through a reactor containing a low-temperature water gas shift catalyst. As high-temperature water gas shift catalysts iron-chromium catalysts are very suitable.
Effective low-temperature water gas shift catalysts are copper-zinc catalysts. In view of the rapid contamination of the catalysts by soot, this must, at least when use is made of conventional reactors, be removed from the gQS before it is subjected to the catalytic water gas shi~t reaction. I~ use is made o~ sulphur-sensitive catalysts, such as the above-mentioned iron-chromium and copper-zinc catalysts, sulphur must also be removed from the gas be~ore it I is subjected to the catalytic water gas shift reaction. Re~oral : 20 of the sulphur from the crude gas may be omitted if use is msde of sulphur-insensitive catalysts such as the Ni/Mo/Al203 or Co/Mo/Al203 catalysts according to Netherlands patent application 7304793 ! or the Ni/Mo/Al/Al203 or Co/Mo/Al/A1203 catalysts according to ~etherlands patent application 7305340. The water ~as shift reaction i9 preferably carried out at a pressure of between 10 and 100 bar and in particul&r between 20 and 80 bar. The quantity o~ bteam which is present in the 8as mixture that is subjected to the water
Effective low-temperature water gas shift catalysts are copper-zinc catalysts. In view of the rapid contamination of the catalysts by soot, this must, at least when use is made of conventional reactors, be removed from the gQS before it is subjected to the catalytic water gas shi~t reaction. I~ use is made o~ sulphur-sensitive catalysts, such as the above-mentioned iron-chromium and copper-zinc catalysts, sulphur must also be removed from the gas be~ore it I is subjected to the catalytic water gas shift reaction. Re~oral : 20 of the sulphur from the crude gas may be omitted if use is msde of sulphur-insensitive catalysts such as the Ni/Mo/Al203 or Co/Mo/Al203 catalysts according to Netherlands patent application 7304793 ! or the Ni/Mo/Al/Al203 or Co/Mo/Al/A1203 catalysts according to ~etherlands patent application 7305340. The water ~as shift reaction i9 preferably carried out at a pressure of between 10 and 100 bar and in particul&r between 20 and 80 bar. The quantity o~ bteam which is present in the 8as mixture that is subjected to the water
6~8 ~hif~ reaction preferably amounts to 1-50 mol per mol carbon monoxide. After completion of the water gas shift reaction the 3~ hydrogen-rich 8as still has to be purified so as to obtain pure hydrogen, Insofar as removal of soot and sulphur has not already been effected prior to the water gas shift reaction, it has to take place now. The purification of the hydrogen-rich gas ~urther ; comprises, inter aIia, the removal of the carbon dioxide formed and of unconverted carbon monoxide.
;¦ The hydrogen which in the process according to the invention l is produced by gasi~ication is primarily intended for use in i; ~
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~ 10 -the catalytic hydrotreatment and the hydrocracking. ~he process is preferably carried out in such a way that the quantity of hydrogen produced by gasification is st least sufficient to satisfy fully ~ -the hydrogen requirement of the catalytic hydrotreatment ana the hydrocracking. Ifthe gasification yields more hydrogen thEln i8 needed for the catalytic hydrotreatment and the hydrocracking, the extra quantity of hydrogen may be used for an application beyond the scope of the process. If the quantity of hydrogen prepared by gasification is insufficient to cover the complete hydrogen requirement of the catalytic hydrotreatment and the hydro- -crackin~, the additional quantity of hydrogen needed should be ;~
fed in from outside the process. The quantity of hydrogen obtained in the gasification i9 determined mainly by the quantity of f-ed which is supplied to the gasification section. The latter quantity -can to a certain extent be controlled by variation of the conditions under which the catalytic hydrotreatment, the deasphalting and the thermal cracking or coking are carried out. More effective means o~ controlling the quantity of feed which is offered to the gasification section ara:
a) The use of part of the residue from the product obtained by hydrocracking as a feed component for the therma1 cracking, coking or gasification; ~ -b) a repeated catalytic hydrotreatment of a heavy fraction of the product which has already undergone such a treatment;
c) application of the catalytic ffl drotreatment to only a part of the eligible material instead of to all the material con-cernedtand d) combinations of the measure5 mentioned under a-c.
In the application of variant c only a part of the atmospheric distillation re~idue which serves as feed for the process, or of the vacuum residue obtained therefrom by vacuum distillation, or of the asphait obtained from the vacuum residue by deasphalting , ........... ......................................................................... ..
is ~ubjected to catalytic hydrotreatment, the remainder being mixed with the hydrotreated product. Since in each of the three embodiments of the process accordin~ to the invention briefly described hereinbefore under variant c) the asphalt and/or a residue obtained there~rom by catalytic hydrotreatment and distillation .
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~08~4L13 of the hydrotreated product may be converted by thermal cracking or coking, these three embodiments correspond with six process schemes. These six process schemes will be explained in more detail below by reference to the accompanying drawings.
Process scheme I (see Fig. I) The process is carried out in a plant which comprises a catalytic hydrotreating unit (1), a first atmospheric distillation unit (2), a vacuum distillation unit (3), a deasphalting unit (4), a thermal cracking unit (5), a gecond atmospheric distillation unit (6), a gasification unit (7), a catalytic hydrocracking unit (8), and a third atmospheric distillation unit (9); An atmospheric hydrocarbon oil residue (10) is divided into two portions (11) and (12). Portion (11) is subjected to a catalytic hydrotreatment and the hydrotreated product (13) is split, by atmospheric d;stillation, ~- ;
into a C4 ~raction (14), a gasoline ~raction (15), a middle distillate fraction (16) and a residue (17). The residue (17) is mixed with portion (12) o~ the atmospheric residue (10) and the mixture is split by vacuum distillation into a vacuum distillate (1B) and a vacuum residue (19). The residue (19) is split by deasphalting into a deasphalted oil (20) and an asphalt (21). The asphalt (21) is thermally cracked and the thermally cracked product (22) ~ ~
is split by atmospheric distillation into a C4 fraction (23)~ - -a gasoline fraction (2~), a middle distillate fraction (25) and a residue (26). The residue (26) is Easified and the gas obtained i8 converted, by means of the water gas shift reaction and puri~ica~ion, into hydrogen (27) and a waste gas (28) which substantially consists of carbon dioxide. The hydrogen (27) is split into two portions, of which one (29) is fed to the catalytic hydrotreating unit and the other (30) to the catalytic hydrocracking unit. 'rhe vacuum distillate (18) is hydrocracked together with the deas~halted oil (20). The hydrocracked product (31) is split by atmospheric distillation into a C4 fraction (32), a gasoline fraction (33), a middle distill~te fraction (34) and a residue (35). The residue (35) is di~ided into two~portions, of which one (36) is ag~in subjected to hydrocracking while the other (37) is used as a feed component ~or the gasification unit.
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1(~88~1L8 Process scheme_ I (see Fig. II) The process is cQrried out in a plant substantiall~ equal to the one described under process scheme I, thle difference being that now instead of the thermal cracking unit (5), a coking unit (5) is present. The processing of the atmospheric hydrocarbon oil residue (10), up to and including the splitting of the residue ?
(19) by deasphalting int8 a deasphalted oil ~20) and an asphalt (21), takes place in sub~tantially the same way as described under process scheme I. Now the asphalt (21) is converted by coking into a distillate (22) and coke (23). The distillate (22) is split by atmospheric distillation into a C4 fraction (24), a gasoline fraction (25), a middle distillate fraction (26) and a residue (27) that is removed from the process. The coke (23) is gQsified and the eas obtained i9 converted by means of the water gas shift reaction Qnd purification into hydrogen (28) and a waste gas (29) which substQntiQlly consists o~ carbon d;oxide. The hydro~en (28) i8 split into two portions, o~ which one (30) is ~ed to the catalytic hydrotreating unit and the other (31) to the catalytic hydrocracking unit, The vacuum distillate (18) ~gether with the deasphalted oil (20) is hydrocracked, in which, besides the hydrogen stream (31), an additional hydrogen stream (32) is fed to the hydrocracking unit. The hydrocracked product ~33) is split by atmospheric distillation in~ Q C4 fraction (34), a gasoline fraction (35), a middle distillate fraction (36) and a residue (37), which is again subjected to , hydrocracking.
Process scheme III (see Fig, III) The process is cQrried out in a plant which comprises a first ~acuum distillation unit (1), a catalytic hydrotreating unit (2), a first atmospheric distillation unit (3), a second vacuum distillation unit (4), Q deQsphalting unit (5), a thermal cracking unit (6), a second atmospheric distillQtion unit (7), ~-a gasificQtion unit (8), a catalytic hydrocracking unit (93 and a third atmospheric distillation uni~ (10), An atmospheric hydroearbon oil residue (11) is split by vacuum distillation into Q vacuum distillate ~12) and a vacuum residue (13), The vacuum residue (13) is di~ided into two portions (14) and (15). Portion (14) l is subjected to a cabalytic hydrotreatment and the hydrotreated `. : "
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, product ( 16) is split by atmospheric distillation into a C4 fraction (17), a gasoline fraction (18), a middle distillate fraction .:
(19) and a residue (20). The residue (20) is split by vacuum distil-lstion into a vacuum distillate (21) and a vacuum residue (22).
The vacuum residue (22) is mixed with portion (15) of the vacuum :.
residue (13) and th~ mixture is split by deasphal.ting into a deasphalted oil (23) and an asphalt (24) . ~he asphalt (24) is thermally cracked and the thermally cracked product (25) is split by atmospheric distillation into a C4 fraction (26), a gasoline fraction (27), a middle distillate fraction (28) and a residue (29). The residue (29) is gasified and the gas obtained is converted by means of the water gas shift reaction and purification into hydrogen (30) .:
and a waste gas (31) which substantially consists of carbon diox;de. -~
The hydrogen (30) is split into two portions, of which one (32) i8 fed to the catalytic hydrotreating unit and the other (33) : :
to the catalytic hydrocracking unit. The vacuum distillates (12) and (21) together with the deasphalted oil (23) are hydrocracked7 The hydrocracked product (34) is split by atmospheric distill.ation into Q C4 fraction (35), a gasoliné fraction (36), a middle distillate fraction (37) and a residue (38). The residue (38) is divided into two portions, of which one (39) is again subjected to hydrocrackig and the other (40) is removed from the process.
I Process scheme IV (see Fig. IV) jl The process is carried out in a plant which is substanti311y ~5 equal to the one described under process scheme III, the difference being that now instead of the thermal cracking unit (6), a coking unit (6) i~ present. The processing of the atmospheric hydrocarbon oil residue (11), up to and including the splitting of the mixture of (15) and (22) by dea~phalting into a deasphalted oil (23) ~ 30 and an QsphQlt (24), takes place in substantiQlly the same way i as described under process scheme III. Now the asphalt (24) is converted by coking into a distillate (25) and coke (26). The distillate (25) is split by atmospheric distillation into a C4 fraction (27), a gasoline fraction (28), a middle distillate fraction (29) and a residue (30) which is removed from the process.
The coke (26) is gasified and the gas obtained is converted, ~by means of the water gas shift reaction and purification, into ~ :-: .: .
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hydrogen (31) and a wal;te gas (32) which substantially consists o~ carbon dioxide. The hydrogen ~31) is split into two portions, of which one (33) is fed to the catalytic hydrotreating unit and -the other (34) to the catalytic hydrocracking unit. The vacuum -~
distillat~s (12) and (21) together with a deasphalted oil (23) are hydrocracked. The hydrocracked product (35) is split by atmospheric dstillation into a C4 fraction (36), a gasoline ~raction (37), a middle distillate fraction (38) and a residue (39), which ls again subjected to hydrocracking.
Process scheme ~ (see Fig. V) The proces~ is carried out in a plant which comprises a first vacuum diætillation unit (1~, a deasphalting unit (2), a catalytic hydrotreating unit (3), a first atmospheric distillation unit (4), a second vacuum distillation unit (5), a thermal cracking unit (6), a second atmospheric distillation unit (7), a gas;~ication ; unit (8), a catalytic hydrocracking unit (9) and a third Qtmosphericdistillation unit (10). An atmospheric hydrocarbon oil res;due (11) is split by vacuu~ distillakion into a vacuum distill~te (12) and a vacuum residue (13). The vacuum residue (13) is aplit by deasphalting into a'deasphalted oil (14) and an asphalt (15).
The asphalt (15) is divided into two portions (16) and (17). Portion (16) i~ subJected to a catalytic hydrotreatment and the hydro-treated product (18) is split by atmospheric distillation into a C4 fraction (19), a gasoline ~raction (20), a middle distillate fraction (21) and a residue (22). The residue (22) is split by vacuum distillation into a vacuum distillate (23) and a vacuum residue (24). The vacuum residue (24) is mixed with portion (17) o~ the asphalt (15) and the mixture iB thermally cracked, The thermally cracked product (25) is split by atmospheric distillation into a C4 ~raction (26), a gasoline fracbion (27), a middle distillate fraction (28) and a residue (29). The residue (29) is gasified ; -and the gas obtained is converted by means of the water gas shift - -~
reaction and purification into hydrogen (30) and a wa~te gas (31) which substantially consists of carbon dioxide. The hydrogen (30) is divided into two portions, of which one (32) is fed to the catalytic hydrotreating unit and the other (33) to the catalytic .
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hydrocracking unit. The vacuum distillates (12) and (23) together with the deasphalted oil (14) are hydrocracked. The hydro~racked product (34) is split by atmospheric distillation into a C4 fraction (35), a gasoline fraction (36), a middle distillate fraction (37) and a residue (38). ~he residue (38) is split into two portions, of which one ~39) is again subjected to hydrocracking while the Other (40) is removed from the process.
Process scheme VI (see Fig. VI) ~he process is carried out in a plant which is substantially equal to the one describedunder process scheme V, the differences being that now the second vacuum distillation unit (5) is absent and that instead of the thermal cracking unit (6), a coking unit (5) is present. An atmospheric hydrocarbon oil residue (10) is split by vacuum distillation into a vacuum distillate (11) and a vacuum residue (12). The vacuum residue (12) i8 divided by deasphalting into a deasphalted oil (13) and an aaphalt (14). The asphalt (14) is divided into two portions (15) and (16). Portion (15) i8 sub-jected to catalytic hydrotreatment and the hydrotreated product (17) is split by atmo~pheric distillation into a C4 fraction 1 20 (18), a gasoline fraction (19), a middle distillate fraction (20) ;! and a residue (21). The residue (21) is mixed with portion (16) of the asphalt (14) and the mixture is converted by coking into a distilla~te (22) and coke (23). The distillate (22) is split by atmospheric digtillation into a C4 fraction (24), a gasoline fraction (25), a middle distillate fraction (26) and a residue (27) which is removed from the process. The coke (23) is gasified and the gas obtained is oonverted, by means of the water gas shift reaotion and purification, into hydrogen (28) and a waste gas (29) which substantially consists of carbon dioxide. The hydrogen (28) is divided into two portions, of which one (30) is fed to the catalytic hydrotreating unit and the other (31) to the catalytic hydrocracking unit. The vacuum distillate (11) together with the deasphalted oil (13) are hydrocracked, in which, besides the hydrogen stream (31), an additional hydro~en stream (32) i~ fed to the hydrocracking unit. The hydrocracked product (33) is separated by atmospheric distillation into a C4 fraction (3~), a gasoline fraction;(35), a middle distillate fraction (36) and ~-: ~ '' ':, .
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a residue (37). The residue (37) is split into two portions, of which one (38) is again subjected to hydrocracking while the other (39) is removed from the process.
The present patent application also comprises plants for carrying out the process according to the invention &S schematically represented in figures I-VI.
The invention will now be elucidated by reference to the following examples.
The process according to the invention was applied to an atmospheric distillation residue from a crude oil originating ~rom the Middle East. The atmospheric distillation residue had an initial boiling point of 350C, a sulphur content of 4 7w and a C4 asphaltenes content of 23 %w. The process was carried out according to process schemes I-VI. In the various units the following conditions were employed.
With all process schemes a sulphidic Co/Mo/~l203 catalysk containing 5 part~ by weight cobalt and 10 parts by weight molybdenum per 100 parts by weight alumina was employed for the catalytic hydrotreatment. When proce~s schemes I-IV were used the catalytic hydrotreatment took place at an average temperature of 390C, a hydrogen partial pressure of 100 bar and a hydrogen/oil ratio of 1000 Nl/Xg. When process schemes I and II were used the catalytic hydrotreatment took place at a space velocity of 0.75 kg oil per litre of catalyst per hour and, when process schemes III and IV were used, at a space velocity of 0.4 kg oil per litre of catalyst per hour. When process schemes V and VI were used the catalytic ~ ~-hydrotreatment took place at an average temperature of 450C, a hydrogen partial pressttre of 150 bar, a space velocity of 0.2 kg oil per litre of catalyst per hour and a hydrogen/oil ratio of 1500 ~l/kg.
With all process schemes deasphalting was carried out with liquid butane as the solvent and using a solvent/oil weight ratio .. . .
varying between 3.5:1 and 4.5:1O When process schemes I-III, V
- and VI were ~sed the deasphalting temperature was 120C and when process scheme IV was used this temperature was 140C.
When process scheme6 I, III and V were used thermal cracking !~ was carried out at a pressure of 10 bar, a residence time of;15 minutes and a temperature varying between 450 and 470C.
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~1hen process schemes II, [V and VI were used cokin~s ~ras carried out at a pressure of 3.5 bar, a temperature of 470C and a residen-ce time varying from 20 to 24 hours.
With all process schemes gasification was carried out at a temperature of 1300C, a pressure of 30 bara~d both a steam/feed Weight ratio and an oxygen/feed weight ratio of 0.8:1. The water gas shift reaction was carried out in succession over an iron-chromium catalyst at a temperature of 350C and a pressure of 30 bar and over a copper-zinc catalyst at a temperature of 250C and a pressure of 30 bar.
With all process schemes the catalytic hydrocracking was carried out in two steps in which the total reaction product from the first step was used as feed for the second step; part of the cracked product was recycled to the first step. With all process schemes for the first step of the catalytic hydrocracking use was made of a sulphidic Ni/Mo/F/Al203 catalyst co~taining 5 parts by weight nickel, 20 parts by weight molybdenum and 15 parts by weight fluorine per 100 part~ by weight alumina and for the second step of a sulphidic Ni/W/F/fau3asite catalyst which contained 3 parts by weight nickel, 10 parts by weight tungsten and 5 parts by weight fluorine per 100 parts by weight faujasite.
With all process schemes the first step of the catalytic hydrocracking was carried out at an average temperature of 390C, ~ pressure of 120 bar, a hydrogenfoil ra~io of 2000 Nl.kg 1 and a spsce velocity of 0.75 l.l l.hour and the second step at ~n average temperature of 365C, a pressure of 120 bar, a hydrogen/oil ratio Or 2000 Nl.kg 1 and a space velocity of 1.5 l.l 1.hour 1.
EXAI~I,E I '''.' q'his example was carried out according to process acheme ;; 30 I. Starting from 100 parts by weight of the 350C atmo~pheric distillQtion residue (10) the following quantities of the~ various streQms were obtained: ~
49.0 parts by welght portion (11), ~;
51.0 " " " portion (12), 2.1 ~' " " C4 fraction (14), 0.4 ~ " " C5-200C gasoline fraction (15), 2.4 " ~ n 200-350C middle distillate fraction (l6), 44.7 " " " 350C atmospheric residue (17), , ~ , t !
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" ' 50.9 parts by weight 350-520C vacuum distillate (18), 44.8 " ~' " 520C vacuum residue (19), 30.8 " " " deasphalted oil (20), 14.0 " " " asphalt ( 21), 0.1 " " " C4 fraction (23), 1.1 " " " C5-200C gasoline fraction ( 24), 1.5 ~ ~ ~ 200-350C middle distillate fraction (25), 11.3 350C atmospheric distillate (26) 2.6 " " " hydrogen ( 27), o.6 " " " portion (29), 2.0 " " " portion (30), 4.4 " " " al~ fraction ~32), 53.9 " " " C5-200C gasoline fraction (33), ~ `23.4 " " " 200-350C middle distil1ate fraction (34), 6.4 " " ~ 350C Qtmospheric residus (35), 4.4 n ~ portion ( 36), and 2.0 ~ portion ( 37) .
~XAMPL~ II
~his example was carried out according to process scheme II. StQrting from 100 parts by weight of the 350C atmospheric :~.
distillation residue (10) the following quantities of-the vQrious streams were obtained:
27.2 parts by weight portion (11), 72.8 ~ portion ( 12), 1.1 ~ ' C4 fraction (14), : .
0.2 ~ " " C5-200C gasoline fraction (15), n 200-350C middle,di~tillate fraction ( 16), 24.9 350C atmo~pheric residue ( 17), 47.9 " " " 350-520C vacuum distillate (18), 30 49.8 ~' ~' " 520C vacuum residue (19), 32.1 " " ~ deasphalted oil (20), 17.7 " " " asphalt (21), 8.2 " " " ~ distillate (22), 9.5 ~' " " coke ( 23), 2.2 ~ " C4 fraction ( 24), - ~ -1.8 " " " C5-200C gasoline fraction (25), 2.2 " " " 200-350C middle distillate fraction (26), ' .
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2.0 parts by weight 350C atmospheric residue (27), 1.6 " " " hydrogen (28)? ~ ~ -0.4 " " " portion ( 3C ), 1.2 " " " portion (31), 1.2 " " ~ hydrogen ( 32), 4.5 " " " C4 fraction ( 34), 53. ô " " " C5-200C gasoline fraction (35), 24~1 " 200-300C middle distillate :Eraction (36)~ and 8,1 " " " 350C atmospheric residue (37).
EXAMPLE III
~I~his example was carried out accordine to process scheme III. Starting from 100 parts by weight of the 350C atmospheric distillation residue (11) the following quantities of the v~rious stream~ were obtained: : :
15 44.0 parts by weight 350-520C vacuum distillate (12), 56,o " " ~ 520C vacuum residue (13), 23,8 ~ " portion (14), 32,2 " " " portion ( 15), 1.6 " C4 fraction ( 17), 1.3 ~ ~ ~ C5-200C gasoline fraction (18), 3.3 " " " 200-350C middle distillate fraction (19), ! 18.2 " " " 350C atmospheric residue (20), 8.4 " " 350-520C vac~.ura distillate (21), 9.8 " " " 520C vacuum residue (22), 25 27.5c ~ deasphalted oil (23), 14.5 " " " a~phalt (24), 0.2 ~ ' C4- fraction ( 26), 1.0 " C5-200C gasoline ïraction (27), 1.4 " " " 200-350C rliddle distillate fraction (28), 30 ~1.9 " ~ n 350C atmospheric residue (29), 2.3 " " " hydrogen (30), : ~ .
0.6 " " " portion ( 32), 1.7 " " " : portion (33), 4.1 ~ " " C4 fraction ( 35), 35 48.6 ~ " " C5-200C gasoline fraction (36), ` 21.4 " " ~ 200-350C middle distillate fraction (37), ;, ~0.5 " " " 350C atmospheric residue (38), ` -~
3.0 " " " portion ( 39), and
;¦ The hydrogen which in the process according to the invention l is produced by gasi~ication is primarily intended for use in i; ~
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~ 10 -the catalytic hydrotreatment and the hydrocracking. ~he process is preferably carried out in such a way that the quantity of hydrogen produced by gasification is st least sufficient to satisfy fully ~ -the hydrogen requirement of the catalytic hydrotreatment ana the hydrocracking. Ifthe gasification yields more hydrogen thEln i8 needed for the catalytic hydrotreatment and the hydrocracking, the extra quantity of hydrogen may be used for an application beyond the scope of the process. If the quantity of hydrogen prepared by gasification is insufficient to cover the complete hydrogen requirement of the catalytic hydrotreatment and the hydro- -crackin~, the additional quantity of hydrogen needed should be ;~
fed in from outside the process. The quantity of hydrogen obtained in the gasification i9 determined mainly by the quantity of f-ed which is supplied to the gasification section. The latter quantity -can to a certain extent be controlled by variation of the conditions under which the catalytic hydrotreatment, the deasphalting and the thermal cracking or coking are carried out. More effective means o~ controlling the quantity of feed which is offered to the gasification section ara:
a) The use of part of the residue from the product obtained by hydrocracking as a feed component for the therma1 cracking, coking or gasification; ~ -b) a repeated catalytic hydrotreatment of a heavy fraction of the product which has already undergone such a treatment;
c) application of the catalytic ffl drotreatment to only a part of the eligible material instead of to all the material con-cernedtand d) combinations of the measure5 mentioned under a-c.
In the application of variant c only a part of the atmospheric distillation re~idue which serves as feed for the process, or of the vacuum residue obtained therefrom by vacuum distillation, or of the asphait obtained from the vacuum residue by deasphalting , ........... ......................................................................... ..
is ~ubjected to catalytic hydrotreatment, the remainder being mixed with the hydrotreated product. Since in each of the three embodiments of the process accordin~ to the invention briefly described hereinbefore under variant c) the asphalt and/or a residue obtained there~rom by catalytic hydrotreatment and distillation .
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~08~4L13 of the hydrotreated product may be converted by thermal cracking or coking, these three embodiments correspond with six process schemes. These six process schemes will be explained in more detail below by reference to the accompanying drawings.
Process scheme I (see Fig. I) The process is carried out in a plant which comprises a catalytic hydrotreating unit (1), a first atmospheric distillation unit (2), a vacuum distillation unit (3), a deasphalting unit (4), a thermal cracking unit (5), a gecond atmospheric distillation unit (6), a gasification unit (7), a catalytic hydrocracking unit (8), and a third atmospheric distillation unit (9); An atmospheric hydrocarbon oil residue (10) is divided into two portions (11) and (12). Portion (11) is subjected to a catalytic hydrotreatment and the hydrotreated product (13) is split, by atmospheric d;stillation, ~- ;
into a C4 ~raction (14), a gasoline ~raction (15), a middle distillate fraction (16) and a residue (17). The residue (17) is mixed with portion (12) o~ the atmospheric residue (10) and the mixture is split by vacuum distillation into a vacuum distillate (1B) and a vacuum residue (19). The residue (19) is split by deasphalting into a deasphalted oil (20) and an asphalt (21). The asphalt (21) is thermally cracked and the thermally cracked product (22) ~ ~
is split by atmospheric distillation into a C4 fraction (23)~ - -a gasoline fraction (2~), a middle distillate fraction (25) and a residue (26). The residue (26) is Easified and the gas obtained i8 converted, by means of the water gas shift reaction and puri~ica~ion, into hydrogen (27) and a waste gas (28) which substantially consists of carbon dioxide. The hydrogen (27) is split into two portions, of which one (29) is fed to the catalytic hydrotreating unit and the other (30) to the catalytic hydrocracking unit. 'rhe vacuum distillate (18) is hydrocracked together with the deas~halted oil (20). The hydrocracked product (31) is split by atmospheric distillation into a C4 fraction (32), a gasoline fraction (33), a middle distill~te fraction (34) and a residue (35). The residue (35) is di~ided into two~portions, of which one (36) is ag~in subjected to hydrocracking while the other (37) is used as a feed component ~or the gasification unit.
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1(~88~1L8 Process scheme_ I (see Fig. II) The process is cQrried out in a plant substantiall~ equal to the one described under process scheme I, thle difference being that now instead of the thermal cracking unit (5), a coking unit (5) is present. The processing of the atmospheric hydrocarbon oil residue (10), up to and including the splitting of the residue ?
(19) by deasphalting int8 a deasphalted oil ~20) and an asphalt (21), takes place in sub~tantially the same way as described under process scheme I. Now the asphalt (21) is converted by coking into a distillate (22) and coke (23). The distillate (22) is split by atmospheric distillation into a C4 fraction (24), a gasoline fraction (25), a middle distillate fraction (26) and a residue (27) that is removed from the process. The coke (23) is gQsified and the eas obtained i9 converted by means of the water gas shift reaction Qnd purification into hydrogen (28) and a waste gas (29) which substQntiQlly consists o~ carbon d;oxide. The hydro~en (28) i8 split into two portions, o~ which one (30) is ~ed to the catalytic hydrotreating unit and the other (31) to the catalytic hydrocracking unit, The vacuum distillate (18) ~gether with the deasphalted oil (20) is hydrocracked, in which, besides the hydrogen stream (31), an additional hydrogen stream (32) is fed to the hydrocracking unit. The hydrocracked product ~33) is split by atmospheric distillation in~ Q C4 fraction (34), a gasoline fraction (35), a middle distillate fraction (36) and a residue (37), which is again subjected to , hydrocracking.
Process scheme III (see Fig, III) The process is cQrried out in a plant which comprises a first ~acuum distillation unit (1), a catalytic hydrotreating unit (2), a first atmospheric distillation unit (3), a second vacuum distillation unit (4), Q deQsphalting unit (5), a thermal cracking unit (6), a second atmospheric distillQtion unit (7), ~-a gasificQtion unit (8), a catalytic hydrocracking unit (93 and a third atmospheric distillation uni~ (10), An atmospheric hydroearbon oil residue (11) is split by vacuum distillation into Q vacuum distillate ~12) and a vacuum residue (13), The vacuum residue (13) is di~ided into two portions (14) and (15). Portion (14) l is subjected to a cabalytic hydrotreatment and the hydrotreated `. : "
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, product ( 16) is split by atmospheric distillation into a C4 fraction (17), a gasoline fraction (18), a middle distillate fraction .:
(19) and a residue (20). The residue (20) is split by vacuum distil-lstion into a vacuum distillate (21) and a vacuum residue (22).
The vacuum residue (22) is mixed with portion (15) of the vacuum :.
residue (13) and th~ mixture is split by deasphal.ting into a deasphalted oil (23) and an asphalt (24) . ~he asphalt (24) is thermally cracked and the thermally cracked product (25) is split by atmospheric distillation into a C4 fraction (26), a gasoline fraction (27), a middle distillate fraction (28) and a residue (29). The residue (29) is gasified and the gas obtained is converted by means of the water gas shift reaction and purification into hydrogen (30) .:
and a waste gas (31) which substantially consists of carbon diox;de. -~
The hydrogen (30) is split into two portions, of which one (32) i8 fed to the catalytic hydrotreating unit and the other (33) : :
to the catalytic hydrocracking unit. The vacuum distillates (12) and (21) together with the deasphalted oil (23) are hydrocracked7 The hydrocracked product (34) is split by atmospheric distill.ation into Q C4 fraction (35), a gasoliné fraction (36), a middle distillate fraction (37) and a residue (38). The residue (38) is divided into two portions, of which one (39) is again subjected to hydrocrackig and the other (40) is removed from the process.
I Process scheme IV (see Fig. IV) jl The process is carried out in a plant which is substanti311y ~5 equal to the one described under process scheme III, the difference being that now instead of the thermal cracking unit (6), a coking unit (6) i~ present. The processing of the atmospheric hydrocarbon oil residue (11), up to and including the splitting of the mixture of (15) and (22) by dea~phalting into a deasphalted oil (23) ~ 30 and an QsphQlt (24), takes place in substantiQlly the same way i as described under process scheme III. Now the asphalt (24) is converted by coking into a distillate (25) and coke (26). The distillate (25) is split by atmospheric distillation into a C4 fraction (27), a gasoline fraction (28), a middle distillate fraction (29) and a residue (30) which is removed from the process.
The coke (26) is gasified and the gas obtained is converted, ~by means of the water gas shift reaction and purification, into ~ :-: .: .
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hydrogen (31) and a wal;te gas (32) which substantially consists o~ carbon dioxide. The hydrogen ~31) is split into two portions, of which one (33) is fed to the catalytic hydrotreating unit and -the other (34) to the catalytic hydrocracking unit. The vacuum -~
distillat~s (12) and (21) together with a deasphalted oil (23) are hydrocracked. The hydrocracked product (35) is split by atmospheric dstillation into a C4 fraction (36), a gasoline ~raction (37), a middle distillate fraction (38) and a residue (39), which ls again subjected to hydrocracking.
Process scheme ~ (see Fig. V) The proces~ is carried out in a plant which comprises a first vacuum diætillation unit (1~, a deasphalting unit (2), a catalytic hydrotreating unit (3), a first atmospheric distillation unit (4), a second vacuum distillation unit (5), a thermal cracking unit (6), a second atmospheric distillation unit (7), a gas;~ication ; unit (8), a catalytic hydrocracking unit (9) and a third Qtmosphericdistillation unit (10). An atmospheric hydrocarbon oil res;due (11) is split by vacuu~ distillakion into a vacuum distill~te (12) and a vacuum residue (13). The vacuum residue (13) is aplit by deasphalting into a'deasphalted oil (14) and an asphalt (15).
The asphalt (15) is divided into two portions (16) and (17). Portion (16) i~ subJected to a catalytic hydrotreatment and the hydro-treated product (18) is split by atmospheric distillation into a C4 fraction (19), a gasoline ~raction (20), a middle distillate fraction (21) and a residue (22). The residue (22) is split by vacuum distillation into a vacuum distillate (23) and a vacuum residue (24). The vacuum residue (24) is mixed with portion (17) o~ the asphalt (15) and the mixture iB thermally cracked, The thermally cracked product (25) is split by atmospheric distillation into a C4 ~raction (26), a gasoline fracbion (27), a middle distillate fraction (28) and a residue (29). The residue (29) is gasified ; -and the gas obtained is converted by means of the water gas shift - -~
reaction and purification into hydrogen (30) and a wa~te gas (31) which substantially consists of carbon dioxide. The hydrogen (30) is divided into two portions, of which one (32) is fed to the catalytic hydrotreating unit and the other (33) to the catalytic .
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hydrocracking unit. The vacuum distillates (12) and (23) together with the deasphalted oil (14) are hydrocracked. The hydro~racked product (34) is split by atmospheric distillation into a C4 fraction (35), a gasoline fraction (36), a middle distillate fraction (37) and a residue (38). ~he residue (38) is split into two portions, of which one ~39) is again subjected to hydrocracking while the Other (40) is removed from the process.
Process scheme VI (see Fig. VI) ~he process is carried out in a plant which is substantially equal to the one describedunder process scheme V, the differences being that now the second vacuum distillation unit (5) is absent and that instead of the thermal cracking unit (6), a coking unit (5) is present. An atmospheric hydrocarbon oil residue (10) is split by vacuum distillation into a vacuum distillate (11) and a vacuum residue (12). The vacuum residue (12) i8 divided by deasphalting into a deasphalted oil (13) and an aaphalt (14). The asphalt (14) is divided into two portions (15) and (16). Portion (15) i8 sub-jected to catalytic hydrotreatment and the hydrotreated product (17) is split by atmo~pheric distillation into a C4 fraction 1 20 (18), a gasoline fraction (19), a middle distillate fraction (20) ;! and a residue (21). The residue (21) is mixed with portion (16) of the asphalt (14) and the mixture is converted by coking into a distilla~te (22) and coke (23). The distillate (22) is split by atmospheric digtillation into a C4 fraction (24), a gasoline fraction (25), a middle distillate fraction (26) and a residue (27) which is removed from the process. The coke (23) is gasified and the gas obtained is oonverted, by means of the water gas shift reaotion and purification, into hydrogen (28) and a waste gas (29) which substantially consists of carbon dioxide. The hydrogen (28) is divided into two portions, of which one (30) is fed to the catalytic hydrotreating unit and the other (31) to the catalytic hydrocracking unit. The vacuum distillate (11) together with the deasphalted oil (13) are hydrocracked, in which, besides the hydrogen stream (31), an additional hydro~en stream (32) i~ fed to the hydrocracking unit. The hydrocracked product (33) is separated by atmospheric distillation into a C4 fraction (3~), a gasoline fraction;(35), a middle distillate fraction (36) and ~-: ~ '' ':, .
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a residue (37). The residue (37) is split into two portions, of which one (38) is again subjected to hydrocracking while the other (39) is removed from the process.
The present patent application also comprises plants for carrying out the process according to the invention &S schematically represented in figures I-VI.
The invention will now be elucidated by reference to the following examples.
The process according to the invention was applied to an atmospheric distillation residue from a crude oil originating ~rom the Middle East. The atmospheric distillation residue had an initial boiling point of 350C, a sulphur content of 4 7w and a C4 asphaltenes content of 23 %w. The process was carried out according to process schemes I-VI. In the various units the following conditions were employed.
With all process schemes a sulphidic Co/Mo/~l203 catalysk containing 5 part~ by weight cobalt and 10 parts by weight molybdenum per 100 parts by weight alumina was employed for the catalytic hydrotreatment. When proce~s schemes I-IV were used the catalytic hydrotreatment took place at an average temperature of 390C, a hydrogen partial pressure of 100 bar and a hydrogen/oil ratio of 1000 Nl/Xg. When process schemes I and II were used the catalytic hydrotreatment took place at a space velocity of 0.75 kg oil per litre of catalyst per hour and, when process schemes III and IV were used, at a space velocity of 0.4 kg oil per litre of catalyst per hour. When process schemes V and VI were used the catalytic ~ ~-hydrotreatment took place at an average temperature of 450C, a hydrogen partial pressttre of 150 bar, a space velocity of 0.2 kg oil per litre of catalyst per hour and a hydrogen/oil ratio of 1500 ~l/kg.
With all process schemes deasphalting was carried out with liquid butane as the solvent and using a solvent/oil weight ratio .. . .
varying between 3.5:1 and 4.5:1O When process schemes I-III, V
- and VI were ~sed the deasphalting temperature was 120C and when process scheme IV was used this temperature was 140C.
When process scheme6 I, III and V were used thermal cracking !~ was carried out at a pressure of 10 bar, a residence time of;15 minutes and a temperature varying between 450 and 470C.
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~1hen process schemes II, [V and VI were used cokin~s ~ras carried out at a pressure of 3.5 bar, a temperature of 470C and a residen-ce time varying from 20 to 24 hours.
With all process schemes gasification was carried out at a temperature of 1300C, a pressure of 30 bara~d both a steam/feed Weight ratio and an oxygen/feed weight ratio of 0.8:1. The water gas shift reaction was carried out in succession over an iron-chromium catalyst at a temperature of 350C and a pressure of 30 bar and over a copper-zinc catalyst at a temperature of 250C and a pressure of 30 bar.
With all process schemes the catalytic hydrocracking was carried out in two steps in which the total reaction product from the first step was used as feed for the second step; part of the cracked product was recycled to the first step. With all process schemes for the first step of the catalytic hydrocracking use was made of a sulphidic Ni/Mo/F/Al203 catalyst co~taining 5 parts by weight nickel, 20 parts by weight molybdenum and 15 parts by weight fluorine per 100 part~ by weight alumina and for the second step of a sulphidic Ni/W/F/fau3asite catalyst which contained 3 parts by weight nickel, 10 parts by weight tungsten and 5 parts by weight fluorine per 100 parts by weight faujasite.
With all process schemes the first step of the catalytic hydrocracking was carried out at an average temperature of 390C, ~ pressure of 120 bar, a hydrogenfoil ra~io of 2000 Nl.kg 1 and a spsce velocity of 0.75 l.l l.hour and the second step at ~n average temperature of 365C, a pressure of 120 bar, a hydrogen/oil ratio Or 2000 Nl.kg 1 and a space velocity of 1.5 l.l 1.hour 1.
EXAI~I,E I '''.' q'his example was carried out according to process acheme ;; 30 I. Starting from 100 parts by weight of the 350C atmo~pheric distillQtion residue (10) the following quantities of the~ various streQms were obtained: ~
49.0 parts by welght portion (11), ~;
51.0 " " " portion (12), 2.1 ~' " " C4 fraction (14), 0.4 ~ " " C5-200C gasoline fraction (15), 2.4 " ~ n 200-350C middle distillate fraction (l6), 44.7 " " " 350C atmospheric residue (17), , ~ , t !
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" ' 50.9 parts by weight 350-520C vacuum distillate (18), 44.8 " ~' " 520C vacuum residue (19), 30.8 " " " deasphalted oil (20), 14.0 " " " asphalt ( 21), 0.1 " " " C4 fraction (23), 1.1 " " " C5-200C gasoline fraction ( 24), 1.5 ~ ~ ~ 200-350C middle distillate fraction (25), 11.3 350C atmospheric distillate (26) 2.6 " " " hydrogen ( 27), o.6 " " " portion (29), 2.0 " " " portion (30), 4.4 " " " al~ fraction ~32), 53.9 " " " C5-200C gasoline fraction (33), ~ `23.4 " " " 200-350C middle distil1ate fraction (34), 6.4 " " ~ 350C Qtmospheric residus (35), 4.4 n ~ portion ( 36), and 2.0 ~ portion ( 37) .
~XAMPL~ II
~his example was carried out according to process scheme II. StQrting from 100 parts by weight of the 350C atmospheric :~.
distillation residue (10) the following quantities of-the vQrious streams were obtained:
27.2 parts by weight portion (11), 72.8 ~ portion ( 12), 1.1 ~ ' C4 fraction (14), : .
0.2 ~ " " C5-200C gasoline fraction (15), n 200-350C middle,di~tillate fraction ( 16), 24.9 350C atmo~pheric residue ( 17), 47.9 " " " 350-520C vacuum distillate (18), 30 49.8 ~' ~' " 520C vacuum residue (19), 32.1 " " ~ deasphalted oil (20), 17.7 " " " asphalt (21), 8.2 " " " ~ distillate (22), 9.5 ~' " " coke ( 23), 2.2 ~ " C4 fraction ( 24), - ~ -1.8 " " " C5-200C gasoline fraction (25), 2.2 " " " 200-350C middle distillate fraction (26), ' .
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2.0 parts by weight 350C atmospheric residue (27), 1.6 " " " hydrogen (28)? ~ ~ -0.4 " " " portion ( 3C ), 1.2 " " " portion (31), 1.2 " " ~ hydrogen ( 32), 4.5 " " " C4 fraction ( 34), 53. ô " " " C5-200C gasoline fraction (35), 24~1 " 200-300C middle distillate :Eraction (36)~ and 8,1 " " " 350C atmospheric residue (37).
EXAMPLE III
~I~his example was carried out accordine to process scheme III. Starting from 100 parts by weight of the 350C atmospheric distillation residue (11) the following quantities of the v~rious stream~ were obtained: : :
15 44.0 parts by weight 350-520C vacuum distillate (12), 56,o " " ~ 520C vacuum residue (13), 23,8 ~ " portion (14), 32,2 " " " portion ( 15), 1.6 " C4 fraction ( 17), 1.3 ~ ~ ~ C5-200C gasoline fraction (18), 3.3 " " " 200-350C middle distillate fraction (19), ! 18.2 " " " 350C atmospheric residue (20), 8.4 " " 350-520C vac~.ura distillate (21), 9.8 " " " 520C vacuum residue (22), 25 27.5c ~ deasphalted oil (23), 14.5 " " " a~phalt (24), 0.2 ~ ' C4- fraction ( 26), 1.0 " C5-200C gasoline ïraction (27), 1.4 " " " 200-350C rliddle distillate fraction (28), 30 ~1.9 " ~ n 350C atmospheric residue (29), 2.3 " " " hydrogen (30), : ~ .
0.6 " " " portion ( 32), 1.7 " " " : portion (33), 4.1 ~ " " C4 fraction ( 35), 35 48.6 ~ " " C5-200C gasoline fraction (36), ` 21.4 " " ~ 200-350C middle distillate fraction (37), ;, ~0.5 " " " 350C atmospheric residue (38), ` -~
3.0 " " " portion ( 39), and
7.5 " " " portion (40).
~)81~44~ ~
AMPLE IV
This exam~le was carried out according to process scheme : ~;
IV. Starting from 100 parts by weight of the 350C atmospheric :
distillation residue (11) the following quantities of the various streamæ were obtained:
44.0 parts b~ weight 350-520C vacuum distillate (12), 56,o " " n 520C+ vacuum residue (13), 11.8 " " " portion (14), 44.2 " " " portion (15), 0.8 " " " C4 fraction (17), :
0.7 " " " C5-200C gasoline fraction (18), 1~5 " " " 200-350C middle distillate fraction (19), ;~:
9.0 " " " 3~;0C atmospheric residue (20), , ~ :~
4.2 " 350-520C vacuum distillate (21), '!.
4.8 ~ 520C vacuum residue (22), 23,5 ~ deasphalted oil (23), 25,5 " ~ a3phalt (24), 11,7 ~ distillate (25), :~:
13.8 " " ~ coke (26), ~ ~ :
3.2 " " ll C4 Praction (27), :;
2,6 " " " C5-200C gasoline fraction (28), 3.1 " ~' " 200-350C middle distillate fraction (29), 2.8 " " " 350C atmospheric residue ~30), 2,5 " n n hydrogen (31), 0,2 " " " portion (33), 2.3 " " " portion (34), 4.0 ~ C4 Praction (36), 50.0 " " ~' C5-200C easoline fraation (37), 20.0 ~ ~ " 200-350C middle distillate fraotion (38), and ; 30 7.3 " ~' " 350C atmospheric reæidue (39). :: ` -EXAMPLE V
This example waæ carried out according to process scheme: -~- V. Starting from 100 parts by weight of the 350C atmoæpheric distillation residue (11) the~following quantitieæ of the variouæ
streams were obtained:
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~ - 21 -, 44~0 parts by weight 350-520C vacuum distillate (12)~ -56~o ~ n ~ 520C vacuum residue (13)~ -33~0 ~ n deasphalted oil (14)~
23~0 ~ asphalt ( 15)~
ii 5 10.0 " " " portion (16), ~:
13~0 ~ portion (17), 1~3 It n ~ C4 fraction ( 19)~ -0~9 ~ Cs~200C gasoline fraction (20)~
3~9 ~ 200-350C middIe distillate fraction (21)~ -4~4 ~ 350C atmospheric residue (22)~ 1 2~3 ~ 3350-520C vacuum distillate (23)~
2~ 520C vacuum residue (24)~
0~2 ~ C4~frl3ction(26), 1~2 ~ n Cs-200C gasoline fraction (27), 1~6 ~ 200-350C middle distillate ~raction (28), 12~ 350C atmospheric residue (29)~
2.4 ~ hydrogen (30), ..
0-5 ~ portion (32)~
1,9 " ~ ~ portion (33)~
4.3 ~ ' C4 fraction ( 35)~
52~4 ll ~ Cs-200C gasoline fraction (36)~
22~8 ~ 200-350C middle distillate ~raction (37)~
6.o " " " 350C atmo~pheric residue (38), 4~3 ~ portion (39)~ and 1~7 l~ n ~ portion (40)~
! EXAMPLE VI
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;I This example was c~rried out according to proces~ scheme VI, 8tartinB from 100 parts ~ weight of the 350C atmospheric ¦ distillation residue (10) the fol~owing qu~ntities o~ the var;ous Btreams were obtained:
44~0 parts by weight 350-520C vacuum distillate (11), ; 56~o llfl ~ 520C vacuum residue (12), ~ :
32~9 ~ deasphalted oil (13)~
23~ n ii asphalt (14)~
11~2 ~ 7 portion ~ 15)~
:1 ~ 11.9 " ~ " : portion (16), i 1~5 C4 fraction (18)~
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~)81~44~ ~
AMPLE IV
This exam~le was carried out according to process scheme : ~;
IV. Starting from 100 parts by weight of the 350C atmospheric :
distillation residue (11) the following quantities of the various streamæ were obtained:
44.0 parts b~ weight 350-520C vacuum distillate (12), 56,o " " n 520C+ vacuum residue (13), 11.8 " " " portion (14), 44.2 " " " portion (15), 0.8 " " " C4 fraction (17), :
0.7 " " " C5-200C gasoline fraction (18), 1~5 " " " 200-350C middle distillate fraction (19), ;~:
9.0 " " " 3~;0C atmospheric residue (20), , ~ :~
4.2 " 350-520C vacuum distillate (21), '!.
4.8 ~ 520C vacuum residue (22), 23,5 ~ deasphalted oil (23), 25,5 " ~ a3phalt (24), 11,7 ~ distillate (25), :~:
13.8 " " ~ coke (26), ~ ~ :
3.2 " " ll C4 Praction (27), :;
2,6 " " " C5-200C gasoline fraction (28), 3.1 " ~' " 200-350C middle distillate fraction (29), 2.8 " " " 350C atmospheric residue ~30), 2,5 " n n hydrogen (31), 0,2 " " " portion (33), 2.3 " " " portion (34), 4.0 ~ C4 Praction (36), 50.0 " " ~' C5-200C easoline fraation (37), 20.0 ~ ~ " 200-350C middle distillate fraotion (38), and ; 30 7.3 " ~' " 350C atmospheric reæidue (39). :: ` -EXAMPLE V
This example waæ carried out according to process scheme: -~- V. Starting from 100 parts by weight of the 350C atmoæpheric distillation residue (11) the~following quantitieæ of the variouæ
streams were obtained:
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~ - 21 -, 44~0 parts by weight 350-520C vacuum distillate (12)~ -56~o ~ n ~ 520C vacuum residue (13)~ -33~0 ~ n deasphalted oil (14)~
23~0 ~ asphalt ( 15)~
ii 5 10.0 " " " portion (16), ~:
13~0 ~ portion (17), 1~3 It n ~ C4 fraction ( 19)~ -0~9 ~ Cs~200C gasoline fraction (20)~
3~9 ~ 200-350C middIe distillate fraction (21)~ -4~4 ~ 350C atmospheric residue (22)~ 1 2~3 ~ 3350-520C vacuum distillate (23)~
2~ 520C vacuum residue (24)~
0~2 ~ C4~frl3ction(26), 1~2 ~ n Cs-200C gasoline fraction (27), 1~6 ~ 200-350C middle distillate ~raction (28), 12~ 350C atmospheric residue (29)~
2.4 ~ hydrogen (30), ..
0-5 ~ portion (32)~
1,9 " ~ ~ portion (33)~
4.3 ~ ' C4 fraction ( 35)~
52~4 ll ~ Cs-200C gasoline fraction (36)~
22~8 ~ 200-350C middle distillate ~raction (37)~
6.o " " " 350C atmo~pheric residue (38), 4~3 ~ portion (39)~ and 1~7 l~ n ~ portion (40)~
! EXAMPLE VI
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;I This example was c~rried out according to proces~ scheme VI, 8tartinB from 100 parts ~ weight of the 350C atmospheric ¦ distillation residue (10) the fol~owing qu~ntities o~ the var;ous Btreams were obtained:
44~0 parts by weight 350-520C vacuum distillate (11), ; 56~o llfl ~ 520C vacuum residue (12), ~ :
32~9 ~ deasphalted oil (13)~
23~ n ii asphalt (14)~
11~2 ~ 7 portion ~ 15)~
:1 ~ 11.9 " ~ " : portion (16), i 1~5 C4 fraction (18)~
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1(~88~
- 22 ~ :
, - I .
I 1.0 psrts by weight C5-200C gasoline fraction (19), 4.4 " " " 200-350C middle distillate fraction t20), : 4.9 " " " 350C atmospheric residue ~21),
8.5 " " " distillate (22), ~ :~
8.3 " " " coke (23), ,-~
2,3 " "- C4 fraction (24), 1.9 " " " C5-200C gasoline fraction (25), 2.3 ~ " " 200-350C middle distillate fraction (26), - 2.0 " " " 350C atmospheric residue (27), 1.5 " " " hydrogen (28), o.6 " " " portion (30), 0.9 " " " portion (31), :
1.0 ~' " " hydrogen (32), -4.1 " " " C4- ~raction (34), 50.8 " " " C5-200C gasoline ~raction (35), .
I 22.2 " " ~ 200-350C middle di~tillate fraction (36), ,;.:
! 5.8 1I 1l ~ 350C atmospheric residue (37), ,~ 4,1 ~ portion (38), and 1.7 ~ portion (39).
: -1, ~ ., ,',.:
' ;,' , '.
.1 .
~ ~ .
- , . ...
~'1 ' ':
f : , ~` ' ~'~` . i ''', ~: ~ ' , , , : ~ ! .
"
' ' :,.
i , . ,. ,:
8.3 " " " coke (23), ,-~
2,3 " "- C4 fraction (24), 1.9 " " " C5-200C gasoline fraction (25), 2.3 ~ " " 200-350C middle distillate fraction (26), - 2.0 " " " 350C atmospheric residue (27), 1.5 " " " hydrogen (28), o.6 " " " portion (30), 0.9 " " " portion (31), :
1.0 ~' " " hydrogen (32), -4.1 " " " C4- ~raction (34), 50.8 " " " C5-200C gasoline ~raction (35), .
I 22.2 " " ~ 200-350C middle di~tillate fraction (36), ,;.:
! 5.8 1I 1l ~ 350C atmospheric residue (37), ,~ 4,1 ~ portion (38), and 1.7 ~ portion (39).
: -1, ~ ., ,',.:
' ;,' , '.
.1 .
~ ~ .
- , . ...
~'1 ' ':
f : , ~` ' ~'~` . i ''', ~: ~ ' , , , : ~ ! .
"
' ' :,.
i , . ,. ,:
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of one or more atmospheric hydrocarbon oil distillates from an atmospheric hydrocarbon oil residue (AR), characterised in that the preparation takes place using hydrocracking as the main process in combination with a catalytic hydrotreatment, deasphalting, gasification, and thermal cracking or coking as supplementary processes, in that the atmo-spheric residue (AR) and/or an atmospheric residue obtained therefrom by catalytic hydrotreatment and distillation of the hydrotreated product, is split by vacuum distillation into a vacuum distillate (VD) and a vacuum residue (VR), in that the vacuum residue and/or a vacuum residue obtained therefrom by catalytic hydrotreatment and distillation of the hydrotreated product, is split by deasphalting into a deasphalted oil and asphalt, in that the deasphalted oil and the vacuum distillate are hydrocracked, in that the cracked product is split by atmospheric distillation into one or more light distillates as end products, and, if desired, an intermediate distillate as end product and a residue of which at least a part is again subjected to hydrocracking, in that the asphalt and/or a residue or asphalt fraction of this residue obtained therefrom by catalytic hydrotreatment and distillation of the hydrotreated product, is subjected to thermal cracking or coking, in that the liquid product thus obtained is split by distillation into one or more light distillates as end products, an intermediate fraction as end product or as intermediate product, and a residual fraction, that the coke or the residual fraction obtained in the distillation of the thermally cracked product is gasified for the production of hydrogen for both the catalytic hydrotreatment and the hydro-cracking and in that the catalytic hydrotreatment is applied either to at least part of the atmospheric distillation residue (AR), or to at least part of the vacuum residue (VR), or to at least part of the asphalt obtained from the vacuum residue (VR) by deasphalting.
2. A process according to claim 1, characterised in that the product obtained by hydrocracking is split by atmospheric distillation into one or more light distillates as end products, a middle dis-tillate M1 and a residue, in that the middle distillate M1 is again subjected to hydrocracking and in that the residue a) is removed from the process, or b) is divided into two portions of the same composition, of which one is again subjected to hydrocracking, whereas the other portion is removed from the process, or c) is split by vacuum distillation into a vacuum distillate which is again subjected to hydrocracking and a vacuum residue which is either removed from the process or divided into two portions of which one is again subjected to hydrocracking, whereas the other portion is removed from the process.
3. A process according to claim 1, characterised in that the product obtained by hydrocracking is split by atmospheric distillation into one or more light distillates and a middle distillate M1 as end products and a residue which is split further by vacuum distillation into a vacuum distillate and a vacuum residue, in that the vacuum distillate is again subjected to hydrocracking and in that the vacuum residue is either removed from the process or divided into two portions of the same composition of which one is again subjected to hydrocracking, whereas the other portion is removed from the process.
4. A process according to claim 1, characterised in that a process is used in which a residue originating from the hydrocracked product is divided into two portions of the same composition of which one is again subjected to hydrocracking, whereas the other portion is removed from the process and in that the quantity of material which is recirculated is more than 25 %w of the available quantity of residue.
5. A process according to claim 1 characterised in that the hydro-cracking is carried out as a one-step process using a moderately acidic or strongly acidic catalyst comprising one or more metals with hydrogenating activity on a carrier.
6. A process according to claim 1 characterised in that the hydro-cracking is carried out as a two-step process using a weakly acidic or moderately acidic catalyst comprising one or more metals with hydrogenating activity on a carrier in the first step and a moderately acidic or strongly acidic catalyst comprising one or more metals with hydrogenating activity on a carrier in the second step.
7. A process according to claim 6, characterised in that the entire reaction product from the first step is used as feed for the second step.
8. A process according to claim 1 characterised in that the catalytic hydrotreatment is carried out using a non-acidic or weakly acidic catalyst.
9. A process according to claim 1 characterised in that in the catalytic hydroteatment a temperature is applied which is at least 10°C and preferably 20°C higher than the temperature applied in the hydrocracking.
10. A process according to claim 1 characterised in that the catalytic hydrotreatment is applied to at least part of the asphalt obtained from the vacuum residue (VD) by deasphalting, in that the hydrotreated product is split by atmospheric distillation into one or more light distillates as end products, a middle distillate fraction M2 and an atmospheric residue and in that the atmospheric residue is split by deasphalting into a deasphalted oil which serves as a feed component for the hydrocracker and an asphalt which is subjected to thermal cracking or coking.
11. A process according to claim 1 characterised in that it is carried out under such conditions that the quantity of hydrogen obtained by gasification is at least sufficient to fully meet the hydrogen requirement of both the catalytic hydrotreating unit and the hydrocracking unit.
12. A process according to claim 1 characterised in that part of the residue obtained by the distillation of the hydrocracked product is used as a feed component for the thermal cracking, the coking or the gasification.
13. A process according to claim 1 characterised in that a heavy fraction of the product obtained in catalytic hydrotreatment is again subjected to this treatment.
14. A process according to claim 1 characterised in that only part of the feed eligible for the catalytic hydrotreatment is subjected to this treatment and in that the rest is mixed with the hydrotreated product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7512090A NL7512090A (en) | 1975-10-15 | 1975-10-15 | PROCESS FOR CONVERTING HYDROCARBONS. |
| NL7512090 | 1975-10-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1088448A true CA1088448A (en) | 1980-10-28 |
Family
ID=19824670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA261,785A Expired CA1088448A (en) | 1975-10-15 | 1976-09-22 | Process for the conversion of hydrocarbons |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS607678B2 (en) |
| CA (1) | CA1088448A (en) |
| DE (1) | DE2646220A1 (en) |
| FR (1) | FR2328033A1 (en) |
| GB (1) | GB1546960A (en) |
| IT (1) | IT1068909B (en) |
| NL (1) | NL7512090A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7702161A (en) * | 1977-03-01 | 1978-09-05 | Shell Int Research | METHOD FOR CONVERTING HYDROCARBONS. |
| EP0068543B1 (en) * | 1981-06-25 | 1988-09-21 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of a hydrocarbon mixture |
| NL8105660A (en) * | 1981-12-16 | 1983-07-18 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBON OIL DISTILLATES |
| NL8201233A (en) * | 1982-03-24 | 1983-10-17 | Shell Int Research | PROCESS FOR THE PREPARATION OF LOW ASPHALTENE HYDROCARBON MIXTURE. |
| NL8201243A (en) * | 1982-03-25 | 1983-10-17 | Shell Int Research | PROCESS FOR THE PREPARATION OF LOW ASPHALTANE HYDROCARBON MIXTURE. |
| DE3479225D1 (en) * | 1983-04-18 | 1989-09-07 | Shell Int Research | A process for the production of low-asphaltenes hydrocarbon mixtures |
| ITMI20042446A1 (en) * | 2004-12-22 | 2005-03-22 | Eni Spa | PROCEDURE FOR CONVERSION OF PESANTYI CHARGES SUCH AS HEAVY CRATES AND DISTILLATION RESIDUES |
| FR2933710B1 (en) * | 2008-07-10 | 2012-12-07 | Inst Francais Du Petrole | CONVERSION PROCESS COMPRISING DESASPHALTAGE AND RESIDUAL CONVERSION |
| FR2933711B1 (en) * | 2008-07-10 | 2010-08-27 | Inst Francais Du Petrole | CONVERSION PROCESS COMPRISING VISCOREDUCTION OF RESIDUE, THEN DESASPHALTAGE AND HYDROCONVERSION |
-
1975
- 1975-10-15 NL NL7512090A patent/NL7512090A/en not_active Application Discontinuation
-
1976
- 1976-09-22 CA CA261,785A patent/CA1088448A/en not_active Expired
- 1976-10-13 DE DE19762646220 patent/DE2646220A1/en active Granted
- 1976-10-13 IT IT2827976A patent/IT1068909B/en active
- 1976-10-13 JP JP12196576A patent/JPS607678B2/en not_active Expired
- 1976-10-13 GB GB4252976A patent/GB1546960A/en not_active Expired
- 1976-10-13 FR FR7630765A patent/FR2328033A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT1068909B (en) | 1985-03-21 |
| FR2328033A1 (en) | 1977-05-13 |
| GB1546960A (en) | 1979-05-31 |
| DE2646220C2 (en) | 1987-05-27 |
| FR2328033B1 (en) | 1982-06-11 |
| DE2646220A1 (en) | 1977-04-28 |
| JPS5249202A (en) | 1977-04-20 |
| NL7512090A (en) | 1977-04-19 |
| JPS607678B2 (en) | 1985-02-26 |
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| MKEX | Expiry |