CA1208150A - Process for the production of deasphalted oils and hydrocarbon oil distillates - Google Patents
Process for the production of deasphalted oils and hydrocarbon oil distillatesInfo
- Publication number
- CA1208150A CA1208150A CA000423237A CA423237A CA1208150A CA 1208150 A CA1208150 A CA 1208150A CA 000423237 A CA000423237 A CA 000423237A CA 423237 A CA423237 A CA 423237A CA 1208150 A CA1208150 A CA 1208150A
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- Prior art keywords
- feed
- stream
- treatment
- asphaltenes
- product
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A B S T R A C T
PROCESS FOR THE PRODUCTION OF DEASPHALTED OILS
AND HYDROCARBON OIL DISTILLATES
Deasphalted oils and distillates are produced from as-phaltenes-rich hydrocarbon mixtures by a process comprising either a catalytic hydrotreatment followed by solvent deasphalting and thermal cracking, or a catalytic hydrotreatment preceded by solvent deasphalting and thermal cracking.
PROCESS FOR THE PRODUCTION OF DEASPHALTED OILS
AND HYDROCARBON OIL DISTILLATES
Deasphalted oils and distillates are produced from as-phaltenes-rich hydrocarbon mixtures by a process comprising either a catalytic hydrotreatment followed by solvent deasphalting and thermal cracking, or a catalytic hydrotreatment preceded by solvent deasphalting and thermal cracking.
Description
~8~5~
PRDCES5 FOR T~E PRODUCTION OF DEASPHALl~D OILS
The invention relates to a process for the production of deasphalted oils and hydrw arbon oil distillates from asphaltenes-containing hydrocarbon mixtures.
The atmospheric distillation of crude mineral oil for the production of light hydrocarbon oil distillates, such as gasoline, kerosine and gas oil yields an asphaltenes-contaim ng residue as a by-product. Originally these residues (which usually in addition to asphaltenes also contain a considerable percentage of sulphur and metals) were used as fuel oil. In view of the growing demand of light hydrocarbon oil distillates and the shrinking reserves of crude mineral oil, several treatments aiming at the production of light hydrocarbon oil distillates from atm~spheric residues have already been proposed. For instance, a deasphalted oil may be separated fm m an atmospheric residue by solvent deasphalting and this deasphalted oil may be subjected to catalytic cracking in the presence or absence of hydrogen. Another option is to separate an atmospheric residue-into a vacuum distillate and a vacuum residue by vacuum distillation, to separate a deasphalted oil frcm the vacuum residue by solvent deasphalting and to subject both the vacuum distillate and the deasphalted oil to catalytic cracking in the presence or absence of hydrogen.
Solvent deasphalting (DA), a process in which an asphaltenes-containing feedstock is converted into a product from which a deasphalted oil can be separated as the desired main product and an asphaltic bitumen as a by-product, has proven in actual prac-tice to be a suitable treatment for ~he production of deasphalted oils from a variety of asphaltenes-containing hydrocarbon mlx-tures.
It has now been investigated whether combining the DA treat-ment with a pretreatment of the asphaltenes-containing feed and/or ,~7~
~ 8 ~ 5~
an aftertreatment of the asphaltic bitumen separated in the DA
treatment and using at least part of the asphaltic bitumen that has been subjected to the aftertreatment as the feed for the DA, might yield better results than employing nothing but the DA. In the assessment of the results the yields of deasphalted oil and light product(s) are most important. m e qualities of the de-asphalted oil and the light product(s) as well as the quality of the heavy by-product are also important. In this context the quality of the deasphalted oil is taken to be its sultability for co~lversion into hydrocarbon oil distillates by catalytic cracking in the presence or absence of hydrogen. This suitability is greater according as the deasphalted oil has, among other things, lcwer asphaltenes, metal and sulphur contents. In this context the quality of the light product is taken to be its suitability for processing into a valuable light fuel. m is suitability is greater according as the light product has, among other things, lower sulphur and olefins contents. In this context the quality of the heavy product is taken to be its suitability for serving as a fuel oil co~lponent. This suitability is greater according as the heavy product has, among other things, lcwer metal and sulphur contents and lower viscosity and density. For use as pretreatments of the feed for the DA and as aftertreatments of the asphaltic bitum~n separated in the DA, the follcwing treatments were investigatedo thermal cracking (TC) in which a heavy feed is converted into a product which contains less than 20 %w C4 hydrocarbons and from which one or more distillate fractions and a heavy fraction are separated and catalytic hydrotreatment (Hr~ in which an as-phaltenes-containing feed is converted into a product having a reduced asphaltenes content from which one or more distillate 3o fractions and a heavy fraction are separated.
During this investigation a ccmparison was made between the results that can be obtained when a deasphalted oil and possibly a hydrocarbon oil distillate having a given boiling xange as well as a heavy by-product are produced starting from equal quantities of ~z~s~
an asphaltenes-containing hydrocarbon mI~ture by using a) DA only, b) DA in ccmbination with TC, c) DA in ccmbination with HT and d) DA in combination with both TC and HT, the conditions of the various treatments being similar as much as possible. In view of quantity and quality of the deasphalted oil and the hydroc æbon oil distillate to be obtained in each of the procedures and the quality of the heavy by-product, the various procedures may be arranged as follcws:
Quantity of deasphalted oil d = c > b = a 10 Quality of the deasphalted oil d = c > b = a Quantity of hydrocarbon oil distillate d > c > b Quality of the hydrocarbon oil distillate c > d > b Quality of the heavy product c > d > a > b Taking into account the considerable difference in hydro-carbon oil distillate yields obtained according to procedures c) and d) and the no more than minor differences in quality between the hydrocarbon oil distillates and between the heavy by-products obtained according to procedures c) and d) a procedure in which a co~bination is used of a DA treatment, a TC treatment and a HT, is much preferred.
As regards the order in which the three treatments are carried out, a number of embodiments may be considered. Each of the embodiments may be placed in one of the two follcwing classes.
I. m e asphalte~es-containing feed is first subjected to a HT or a DA treatment and the heavy fraction or asphaltic bitumen separated from the respective products obtained, is subjected to a combination o a ~A treatrnent and a TC treatment or a combination of a TC treatment and a HT, respectively.
II. The asphaltenes-containing feed is first subjected to a TC
treatment and the heavy fraction separated from the product obtained is subjected to a combination of a D~ treatment and a HT.
The em~xx~ments belonging to class I constitute the subject matter of the present patent application.
iL2~ 5~
m e e~bodiments to which the present patent application relates, may be subdivided further depending on whether the asphaltenes-containing feed is used as a feed component for the HT
(class IA), or as a feed ccmponent for the DA treatment (class B).
In all the embodiments the asphaltic bitumen fraction which is separated from the product of the DA treatment is used as the feed for the TC treatment. In the embodiments belonging to class IA
the heavy fraction which is separated from the product of the TC
treatmPnt is used as a feed ccmponent for the HT and the heavy fraction which is separated frcm the product of the HT is used as the feed for the DA treatment. In the rmbodim nts belonging to class IB the heavy fraction which is separated from the product of the HT is used as a feed ccmponent for the DA treatment and the heavy fraction which is separated from the product of the TC
treatment is used as the feed for the HT.
The present patent application therefore relates to a process for the production of deasphalted oils and hydrocarbon oil distil-lates from asphaltenes-containing hydrocarbon mixtures, in which an asphaltenes-containing hydrocarbon mixture (stream 1) is subjected to a combination of the following three trea~ments: a catalytic hydrotreatment (HT) in which an asphaltenes-containing feed is converted into a product having a reduced asphaltenes content, from which one or more distillate fractions and a heavy fraction (stream 2) are separated, a solvent deasphalting (DA) treatment in which an asphaltenes-containing feed is converted into a prcxluct from which a deasphalted oil and an asphaltic bitumen (stre~m 3) are separated and a thermal cracking treatment (TC) in which a feed is converted into a product whi.ch conta.ins 3 less than 20 ~w C4 hydrocarbons and fro.m which one or more distillate fractions and a heavy fraction (stream 4) are se-parated, in which stream 3 is used as the feed for the TC treat-ment and stream 1 is used either 1) together with stream 4 as a feed component for the HT with stream 2 being used as the feed for the DA treatment, or ~ .
~ . . .
~~z~
-- 5 ~
PRDCES5 FOR T~E PRODUCTION OF DEASPHALl~D OILS
The invention relates to a process for the production of deasphalted oils and hydrw arbon oil distillates from asphaltenes-containing hydrocarbon mixtures.
The atmospheric distillation of crude mineral oil for the production of light hydrocarbon oil distillates, such as gasoline, kerosine and gas oil yields an asphaltenes-contaim ng residue as a by-product. Originally these residues (which usually in addition to asphaltenes also contain a considerable percentage of sulphur and metals) were used as fuel oil. In view of the growing demand of light hydrocarbon oil distillates and the shrinking reserves of crude mineral oil, several treatments aiming at the production of light hydrocarbon oil distillates from atm~spheric residues have already been proposed. For instance, a deasphalted oil may be separated fm m an atmospheric residue by solvent deasphalting and this deasphalted oil may be subjected to catalytic cracking in the presence or absence of hydrogen. Another option is to separate an atmospheric residue-into a vacuum distillate and a vacuum residue by vacuum distillation, to separate a deasphalted oil frcm the vacuum residue by solvent deasphalting and to subject both the vacuum distillate and the deasphalted oil to catalytic cracking in the presence or absence of hydrogen.
Solvent deasphalting (DA), a process in which an asphaltenes-containing feedstock is converted into a product from which a deasphalted oil can be separated as the desired main product and an asphaltic bitumen as a by-product, has proven in actual prac-tice to be a suitable treatment for ~he production of deasphalted oils from a variety of asphaltenes-containing hydrocarbon mlx-tures.
It has now been investigated whether combining the DA treat-ment with a pretreatment of the asphaltenes-containing feed and/or ,~7~
~ 8 ~ 5~
an aftertreatment of the asphaltic bitumen separated in the DA
treatment and using at least part of the asphaltic bitumen that has been subjected to the aftertreatment as the feed for the DA, might yield better results than employing nothing but the DA. In the assessment of the results the yields of deasphalted oil and light product(s) are most important. m e qualities of the de-asphalted oil and the light product(s) as well as the quality of the heavy by-product are also important. In this context the quality of the deasphalted oil is taken to be its sultability for co~lversion into hydrocarbon oil distillates by catalytic cracking in the presence or absence of hydrogen. This suitability is greater according as the deasphalted oil has, among other things, lcwer asphaltenes, metal and sulphur contents. In this context the quality of the light product is taken to be its suitability for processing into a valuable light fuel. m is suitability is greater according as the light product has, among other things, lower sulphur and olefins contents. In this context the quality of the heavy product is taken to be its suitability for serving as a fuel oil co~lponent. This suitability is greater according as the heavy product has, among other things, lcwer metal and sulphur contents and lower viscosity and density. For use as pretreatments of the feed for the DA and as aftertreatments of the asphaltic bitum~n separated in the DA, the follcwing treatments were investigatedo thermal cracking (TC) in which a heavy feed is converted into a product which contains less than 20 %w C4 hydrocarbons and from which one or more distillate fractions and a heavy fraction are separated and catalytic hydrotreatment (Hr~ in which an as-phaltenes-containing feed is converted into a product having a reduced asphaltenes content from which one or more distillate 3o fractions and a heavy fraction are separated.
During this investigation a ccmparison was made between the results that can be obtained when a deasphalted oil and possibly a hydrocarbon oil distillate having a given boiling xange as well as a heavy by-product are produced starting from equal quantities of ~z~s~
an asphaltenes-containing hydrocarbon mI~ture by using a) DA only, b) DA in ccmbination with TC, c) DA in ccmbination with HT and d) DA in combination with both TC and HT, the conditions of the various treatments being similar as much as possible. In view of quantity and quality of the deasphalted oil and the hydroc æbon oil distillate to be obtained in each of the procedures and the quality of the heavy by-product, the various procedures may be arranged as follcws:
Quantity of deasphalted oil d = c > b = a 10 Quality of the deasphalted oil d = c > b = a Quantity of hydrocarbon oil distillate d > c > b Quality of the hydrocarbon oil distillate c > d > b Quality of the heavy product c > d > a > b Taking into account the considerable difference in hydro-carbon oil distillate yields obtained according to procedures c) and d) and the no more than minor differences in quality between the hydrocarbon oil distillates and between the heavy by-products obtained according to procedures c) and d) a procedure in which a co~bination is used of a DA treatment, a TC treatment and a HT, is much preferred.
As regards the order in which the three treatments are carried out, a number of embodiments may be considered. Each of the embodiments may be placed in one of the two follcwing classes.
I. m e asphalte~es-containing feed is first subjected to a HT or a DA treatment and the heavy fraction or asphaltic bitumen separated from the respective products obtained, is subjected to a combination o a ~A treatrnent and a TC treatment or a combination of a TC treatment and a HT, respectively.
II. The asphaltenes-containing feed is first subjected to a TC
treatment and the heavy fraction separated from the product obtained is subjected to a combination of a D~ treatment and a HT.
The em~xx~ments belonging to class I constitute the subject matter of the present patent application.
iL2~ 5~
m e e~bodiments to which the present patent application relates, may be subdivided further depending on whether the asphaltenes-containing feed is used as a feed component for the HT
(class IA), or as a feed ccmponent for the DA treatment (class B).
In all the embodiments the asphaltic bitumen fraction which is separated from the product of the DA treatment is used as the feed for the TC treatment. In the embodiments belonging to class IA
the heavy fraction which is separated from the product of the TC
treatmPnt is used as a feed ccmponent for the HT and the heavy fraction which is separated frcm the product of the HT is used as the feed for the DA treatment. In the rmbodim nts belonging to class IB the heavy fraction which is separated from the product of the HT is used as a feed ccmponent for the DA treatment and the heavy fraction which is separated from the product of the TC
treatment is used as the feed for the HT.
The present patent application therefore relates to a process for the production of deasphalted oils and hydrocarbon oil distil-lates from asphaltenes-containing hydrocarbon mixtures, in which an asphaltenes-containing hydrocarbon mixture (stream 1) is subjected to a combination of the following three trea~ments: a catalytic hydrotreatment (HT) in which an asphaltenes-containing feed is converted into a product having a reduced asphaltenes content, from which one or more distillate fractions and a heavy fraction (stream 2) are separated, a solvent deasphalting (DA) treatment in which an asphaltenes-containing feed is converted into a prcxluct from which a deasphalted oil and an asphaltic bitumen (stre~m 3) are separated and a thermal cracking treatment (TC) in which a feed is converted into a product whi.ch conta.ins 3 less than 20 ~w C4 hydrocarbons and fro.m which one or more distillate fractions and a heavy fraction (stream 4) are se-parated, in which stream 3 is used as the feed for the TC treat-ment and stream 1 is used either 1) together with stream 4 as a feed component for the HT with stream 2 being used as the feed for the DA treatment, or ~ .
~ . . .
~~z~
-- 5 ~
2) together with stream 2 as a feed ccmponent for the DA treatment with stream 4 being used as the feed for the HT.
In the process according to the invention the feed used is an asphaltenes-containing hydroc æbon mlxture. A suitable parameter for assessing the asphaltenes content of a hydrocarbon mixture and the reduction of the asphaltenes content which occurs when an as-phaltenes-containing hydrocarbon muxture is subjected to a ~, is the Ramsbotb~m Carbon Test value ~RCT)~ m e higher the asphaltenes content of the hydrocarbon mixture, the higher the RfT. Preferably the process is applied to hydrocarbon muxtures which boil sub-stantially above 350C and more than 35 %w of which boils above 520C and which have an RCT higher than 7.5 %w. Examples of such hydrocarbon mixtures are residues obtained in the distillation of crude mineral oils and also heavy hydorcarbon mlxtures obtained f mm shale and tar sands. If desired, the process may also be applied ~o heavy crude mineral oils, residues obtained in the distillation of products formed in the thermal cracking of hydro-carbon mixtures and asphaltic bitumen obtained in the solvent de-asphalting of asphaltenes-containing hydroca~bon muxturesO The process according to the invention can very suitably be applied to residues obtained in the vacuum distillation of a~mospheric distillation residues from crude mineral oils. If the feed avail~-ble for the process according to the invention is an atmospheric distillation residue frcm a crude mineral oil, it is preferred to separate a vacuum distillate therefrQm by vacuum distillation and to subject the resulting vacuum residue to ~he process according to the invention. The separated vacuum distillate may he subjected to the~mal cracking or to catalytic cracking in the presence or absence of hydrogen to convert it into light hydrocarbon oil distillates.
The process according to the invention is a three-step process in which an asphaltenes-containing feed (stream 1) is subjected in the first step to a ~ or a DA treatment and in which the heavy fraction (stream 2) and the asphaltic bikumen (stream 3) 5~
separated frcm the product obtained by the respective treatments are subjected in the second and the third step of the process to a combination of a DA treatment and a TC treatment and a combination of a TC treatment and a HT, respectively.
Asphaltenes-containing hydrocarbon mLxtures usually include a considerable percentage of metals, particularly vanadium and nickel. When such hydrocarbon mixtures are subjected to a cata-lytic treatment, for instance a HT for the reduction of the asphaltenes content as is the case in the process according to the invention, these metals will be deposited on the catalyst used in the HT, thus shortening its useful lifeO In view of this, as-phaltenes-containing hydrocarbon mixtures having a vanadium +
nickel content higher than 50 parts per million by weight (ppmw) should preferably be subjected to a demetallization treatment before being contacted with the catalyst used in the HT. This demet~llization may very suitably be carried out by contacting the asphaltenes-containing hydrocarbon mixture in the presence of hydrogen with a catalyst more than 80 ~w of which consists of silica. Both catalysts consisting entirely of silica and catalysts containing one or more metals with hydrogenation activity - in particular a ccmbination of nickel and vanadium - supported on a carrier consisting substantially of silica, are suitable for the purp~se. When in the process according to the invention an as-phaltenes-containing feed is subjected to a catalytic demetal-lization treatment in the presence of hydrogen, this demetal-lization may be carried out in a separate reactor. Since the catalytic demetallization and the HT for the reduction of the asphaltenes content can be carried out under the same conditions, the two processes may also very suitably be carried out in the 3o same reactor, which successi~ely contains a bed of the demetalli-zation reactor and a bed of the catalyst used in the EIT.
Suitable catalysts for carrying out the ~T are those which contain at least one metal chosen from the group formed bv nickel and cobalt and in addition at least one metal chosen from the group formed by molybdenum and tungsten supported on a carrier, :~L26~8~5C~
which carrier conslsts more than 40 %w of alumina.
Very suitable catalysts for use in the HT are those which comprise the metal combination nickel/molybdenum or cobalt/molybdenum supported on alumina as the carrier. The HT is preferably carried out at a temperature of from 300-500C and in particular of from 350-450C, a pressure of fr~n 50-300 bar and in particular of from 75-200 bar, a space velocity of f m m 0.02-10 g.g 1.h 1 and in particular of from 0.1-2 g.g 1.h 1 and a H~/eed ratio of from 100-5000 Nl.kg 1 and in particular of from 500-2000 Nl.kg 1.
The same preference applies to the conditions which are used in a possible catalytic demetallization in the presence of hydrogen as to those given hereinbefore for the HT aiming at reduction of the asphaltenes content.
The HT is preferably carried out in such a manner that it yields a product, the C5+ fraction of which meets the follow-ing requirements:
a) the RCT of the C5 fraction amounts to 20-70% of the RCT of the feed, and b) the difference between the percentages by weight of hydro-carbons boiling below 350C present in the C5~ fraction and in the feed is at most 40.
I~ should be noted that in the catalytic demetallization the reduction of the metal content is accompanied by some reduction of the ~CT and some formation o C5-350C product. A similax pheno-menon occurs in the HT in which the reduction of the ~CT and the formation of C5-350C product are accompanied by some reduction of the met~l content. The requirements mentioned hereinbefore under a) and b) bear upon the overall reduction of R~T and for-mation of C5-350~C product (viz. including those occuring in a possible catalytic demetallization trPatment).
The HT yields a product with a reduced asphaltenes content fram which one or rnore distillate fractions and a heavy fraction (stream 2) are separated. The distillate fractions separated from the product may be only atmosph~ric distillates, but preferably a vacuum distillate should be separated from the product as well.
~2~S~
This vacuum distillate may be converted into light hydrocarbon oil distillates in the ways mentioned hereinbefore.
In the process according to the invention instead of a HT the first step applied may be a DA treatment in which an asphaltenes-containing feed is converted into a product from which a de-asphalted oil and an asphaltic bitumen (stream 3) are separated.
Suitable solvents for carrying out the DA treatment are paraffinic hydrocarbons having 3-6 carbon atcms per molecule, such as n-bu-tane and mixtures thereof, such as mixtures of propane and n-bu-tane and mixt~lres of n-butane and n-pentane. Suitable solvent/oil weight ratios lie in the range of from 7:1 to 1:1 and in par-ticular of from 4:1 to 1:1. m e ~A treatment is preferably carried out at a pressure in the range of from 20-100 bar. When n-butane is used as the solven~, the deasphalting is preferably carried out at a pres Æ e of frcm 35-45 b æ and a temperature of from 100-150C.
In the process according to the invention the second or thi~d step used is a TC treatment in which stream 3 is converted into a product which contains less than 20 %w C4 hydroc æbons and frcm which one or more distillate fractions and a heavy fraction (stream 4) are separated. The distillate fractions separated from the product may be only atmospheric distillates, but preferably a vacuum distillate should be separated frcm the product as well.
This vacuum distillate may be convert d into light h~droc æbon oil distillates in the manners indicated hereinbefore. The TC treat-ment is preferably carried out at a temperature of frcm 400~525C
and a space velocity of frcm 0.01-5 kg frebh feed per litre crack-ing reactor volume per munute.
As stated hexeinbefore, the embodiments belonging to class I
In the process according to the invention the feed used is an asphaltenes-containing hydroc æbon mlxture. A suitable parameter for assessing the asphaltenes content of a hydrocarbon mixture and the reduction of the asphaltenes content which occurs when an as-phaltenes-containing hydrocarbon muxture is subjected to a ~, is the Ramsbotb~m Carbon Test value ~RCT)~ m e higher the asphaltenes content of the hydrocarbon mixture, the higher the RfT. Preferably the process is applied to hydrocarbon muxtures which boil sub-stantially above 350C and more than 35 %w of which boils above 520C and which have an RCT higher than 7.5 %w. Examples of such hydrocarbon mixtures are residues obtained in the distillation of crude mineral oils and also heavy hydorcarbon mlxtures obtained f mm shale and tar sands. If desired, the process may also be applied ~o heavy crude mineral oils, residues obtained in the distillation of products formed in the thermal cracking of hydro-carbon mixtures and asphaltic bitumen obtained in the solvent de-asphalting of asphaltenes-containing hydroca~bon muxturesO The process according to the invention can very suitably be applied to residues obtained in the vacuum distillation of a~mospheric distillation residues from crude mineral oils. If the feed avail~-ble for the process according to the invention is an atmospheric distillation residue frcm a crude mineral oil, it is preferred to separate a vacuum distillate therefrQm by vacuum distillation and to subject the resulting vacuum residue to ~he process according to the invention. The separated vacuum distillate may he subjected to the~mal cracking or to catalytic cracking in the presence or absence of hydrogen to convert it into light hydrocarbon oil distillates.
The process according to the invention is a three-step process in which an asphaltenes-containing feed (stream 1) is subjected in the first step to a ~ or a DA treatment and in which the heavy fraction (stream 2) and the asphaltic bikumen (stream 3) 5~
separated frcm the product obtained by the respective treatments are subjected in the second and the third step of the process to a combination of a DA treatment and a TC treatment and a combination of a TC treatment and a HT, respectively.
Asphaltenes-containing hydrocarbon mLxtures usually include a considerable percentage of metals, particularly vanadium and nickel. When such hydrocarbon mixtures are subjected to a cata-lytic treatment, for instance a HT for the reduction of the asphaltenes content as is the case in the process according to the invention, these metals will be deposited on the catalyst used in the HT, thus shortening its useful lifeO In view of this, as-phaltenes-containing hydrocarbon mixtures having a vanadium +
nickel content higher than 50 parts per million by weight (ppmw) should preferably be subjected to a demetallization treatment before being contacted with the catalyst used in the HT. This demet~llization may very suitably be carried out by contacting the asphaltenes-containing hydrocarbon mixture in the presence of hydrogen with a catalyst more than 80 ~w of which consists of silica. Both catalysts consisting entirely of silica and catalysts containing one or more metals with hydrogenation activity - in particular a ccmbination of nickel and vanadium - supported on a carrier consisting substantially of silica, are suitable for the purp~se. When in the process according to the invention an as-phaltenes-containing feed is subjected to a catalytic demetal-lization treatment in the presence of hydrogen, this demetal-lization may be carried out in a separate reactor. Since the catalytic demetallization and the HT for the reduction of the asphaltenes content can be carried out under the same conditions, the two processes may also very suitably be carried out in the 3o same reactor, which successi~ely contains a bed of the demetalli-zation reactor and a bed of the catalyst used in the EIT.
Suitable catalysts for carrying out the ~T are those which contain at least one metal chosen from the group formed bv nickel and cobalt and in addition at least one metal chosen from the group formed by molybdenum and tungsten supported on a carrier, :~L26~8~5C~
which carrier conslsts more than 40 %w of alumina.
Very suitable catalysts for use in the HT are those which comprise the metal combination nickel/molybdenum or cobalt/molybdenum supported on alumina as the carrier. The HT is preferably carried out at a temperature of from 300-500C and in particular of from 350-450C, a pressure of fr~n 50-300 bar and in particular of from 75-200 bar, a space velocity of f m m 0.02-10 g.g 1.h 1 and in particular of from 0.1-2 g.g 1.h 1 and a H~/eed ratio of from 100-5000 Nl.kg 1 and in particular of from 500-2000 Nl.kg 1.
The same preference applies to the conditions which are used in a possible catalytic demetallization in the presence of hydrogen as to those given hereinbefore for the HT aiming at reduction of the asphaltenes content.
The HT is preferably carried out in such a manner that it yields a product, the C5+ fraction of which meets the follow-ing requirements:
a) the RCT of the C5 fraction amounts to 20-70% of the RCT of the feed, and b) the difference between the percentages by weight of hydro-carbons boiling below 350C present in the C5~ fraction and in the feed is at most 40.
I~ should be noted that in the catalytic demetallization the reduction of the metal content is accompanied by some reduction of the ~CT and some formation o C5-350C product. A similax pheno-menon occurs in the HT in which the reduction of the ~CT and the formation of C5-350C product are accompanied by some reduction of the met~l content. The requirements mentioned hereinbefore under a) and b) bear upon the overall reduction of R~T and for-mation of C5-350~C product (viz. including those occuring in a possible catalytic demetallization trPatment).
The HT yields a product with a reduced asphaltenes content fram which one or rnore distillate fractions and a heavy fraction (stream 2) are separated. The distillate fractions separated from the product may be only atmosph~ric distillates, but preferably a vacuum distillate should be separated from the product as well.
~2~S~
This vacuum distillate may be converted into light hydrocarbon oil distillates in the ways mentioned hereinbefore.
In the process according to the invention instead of a HT the first step applied may be a DA treatment in which an asphaltenes-containing feed is converted into a product from which a de-asphalted oil and an asphaltic bitumen (stream 3) are separated.
Suitable solvents for carrying out the DA treatment are paraffinic hydrocarbons having 3-6 carbon atcms per molecule, such as n-bu-tane and mixtures thereof, such as mixtures of propane and n-bu-tane and mixt~lres of n-butane and n-pentane. Suitable solvent/oil weight ratios lie in the range of from 7:1 to 1:1 and in par-ticular of from 4:1 to 1:1. m e ~A treatment is preferably carried out at a pressure in the range of from 20-100 bar. When n-butane is used as the solven~, the deasphalting is preferably carried out at a pres Æ e of frcm 35-45 b æ and a temperature of from 100-150C.
In the process according to the invention the second or thi~d step used is a TC treatment in which stream 3 is converted into a product which contains less than 20 %w C4 hydroc æbons and frcm which one or more distillate fractions and a heavy fraction (stream 4) are separated. The distillate fractions separated from the product may be only atmospheric distillates, but preferably a vacuum distillate should be separated frcm the product as well.
This vacuum distillate may be convert d into light h~droc æbon oil distillates in the manners indicated hereinbefore. The TC treat-ment is preferably carried out at a temperature of frcm 400~525C
and a space velocity of frcm 0.01-5 kg frebh feed per litre crack-ing reactor volume per munute.
As stated hexeinbefore, the embodiments belonging to class I
3 to which the present patent application relates are subdivided depending on whether stream 1 is used as a feed compo~ent for the (class IA) or as a feed ccmponent for the DA treabment (class IB).
5~
m e embodiment belonging to class IA is represented schema-tically in Figure I~ The various streams, fractions and reaction zones are indicated by three digit numbers, ~he first of which refers to the Figure concerned. m e vacuum residue ~302), for instance, refers to vacuum residue 2 in the context of Figure III.
According to Figure I the process is carried out in an ap-paratus comprising a HT zone (105), a DA zone (106) and a TC zone (107), successively. An asphaltenes-containing hydrocarbon mixture (101) and a residual fraction (104) are subjected to a ~ and the hydrotreated product is separated into one or more distillate fractions (108) and a residual fraction (102). Stream 102 is subjected to a DA treatment and the product is separated into a deasphalted oil (109) and an asphaltic bitumen (103). Stream 103 is suhjected to TC and the cracked product is separated into one or more distillate fractions (110) and a residual raction (104).
The embcdiment belonging to class IB is represented schema-tically in Figure II. According to this Figure the process is carried out in an apparatus consisting of a DA zone (2051, a TC
zone (206) and a ~ zone (207), successively. An asphaltenes-containing hydrocarbon mixture (201) and a residual fraction (202) are subjected to a DA treatment and the product is separated into a deasphalted oil (208) and an asphaltic bitumen (203). Stream 203 is subjected to a TC treatment and the cracked product is se-parated into one or more distillate fractions (209) and a residual fraction (204). Stream 204 is subjected to a HT and the hy~ro-treated product is separated into one or more distillate fractions (210) and a residual fraction (202).
In the enbodiments wher~ it is the object to achieve the cGmpletest possible ccnversion of stream (.01) into deasphalted 3o oil and hydrocarbon oil distillates, a so-called "bleed stream"
should preferably be separated from one of the heavy streams of the process. In this way the build-up of undesirable heavy compo, nents during the process can be obviated.
~2~8~56~
Two flow diagrams for the preparation of deasphalt.ed oil and hydrocarbon oil distillates from asphaltenes-containing hydro~
carbon muxtures according to the invention will hereinafter be explained in more detail with t,he aid of Figures III and IV.
Flow diagram A (based on embodiment IA) See Figure III.
The process is carried out in an apparatus ccmprising succesively, a HT zone camposed of a unit for catalytic hydrotreatment (305), a unit for atmospheric distillation (306) and a vacuum distillation unit (307), a DA zone (308) and a TC zone comp~sed of a ~hermal cracking unit (309), a second at~ ~p~er.ic distillation unit (310) and a second vacuum distillation Ullit ~311). A~ asphaltenes-containing hydrocarbon mlxture (3013 is ~xed with a recirculation stream (312) and the mlxture (313) is subjected together with hydrogen (314) to a catalytic hydrotreatment. The hydrotreated product (315) is separated by atmospheric distillation into a gas fraction (316), an atomospheric distillate (317) and an abmos-pheric residue (318)~ T.he atmospheric residue (318) is separated by vacuum distillation into a vacuum distillate (319) and a vacuum residue (302). m e vacuum residue (302) is separated by solvent deasphalting into a deasphalted oil (320) and an asphaltic bitumen (303). The asphaltic bitumen ~303) is subjected to thermal crack-ing and the thermally cracked product (321) is separated by atmospheric distillation into a gas fraction (322), an atmospheric distillate (323) and an atmospheric residue (324). The atmospheric residue (324) is separated by vacuum distillation into a vacuum distillate (325) and a vacuum residue (304). The vacuum residue (304) is divided into two portions (312) and (326).
Flow diagram B (based on embodiment IB) See Figure rv.
The process is carried out in an apparatus camprising, successive-ly, a DA zone (405), a TC zone composed of a thermal cracking unit (406), an abmospheric distillation unit (407) and a vacuum ~Z~5~
distillation unit (408) and a HT zone composed of a unit for catalytic hydrotreatment (409), a second atmospheric distillation unit (410) and a second vacuum distillation unit (411). An as-phaltenes-containing hydrocarbon mixture (401) is muxed with a vacuum residue (402) and the mixture (412) is separated by solvent deasphalting into a deasphalted oil (413) and an asphaltic bitumen (403). The asphaltic bitumen (403) is subjected to ther~al crack-ing and the thermally cracked product (414) is separated by atmospheric distillation into a gas fraction (415), an atmospheric distillate (416) and an atmospheric residue (417~. The atmospheric residue (417) is separated by vacuum distillation into a vacuum distillate (418) and a vacuum residue (404). The vacuum residue (404) is divided into two portions (419) and (420). Portion (420) is subjected together with hydrogen (421) to a catalytic hydro-treatm~nt. m e hydrotreated product (422) is separated by atmos-pheric distillation into a gas fraction (423), an atmospheric distillate (424) and an atmosph~ric residue (425). m e atmospheric residue (425) is separated by vacuum distillation into a vacuum distillate (426) and vacuum residue (402).
The present patent application also includes apparatuses for carrying out the process according to the invention substantially corresponding with those represented schematically in Figures I-IV.
The invention is now elucidated with the aid of the follcwing Examples.
In the process according to the invention two asphaltenes-containing hydrocarbon mlxtures obtained as residues in the vacuum distillation of atmospheric distillation residues frcm crude m m eral oils were used as the starting material~ m e two vacuum residues both boiled substantially above 520~ and they had RCT's of 19.1 and 15~8 %w, respectively. m e process was carried out according to flcw diagrams A and B. m e conditions used in the various zones were the follcwing.
m e unit for catalytic hydrotreatment as described in both the flow diagrams consisted of two reactors, the first of which was filled with a Ni/V/Sio2 catalyst containing 0.5 parts by weight (pbw) nickel and 2.0 pbw vanadium per 100 pbw silica and the second of which was filled with a Co/MD/A1203 catalyst containing 4 pbw cobalt and 12 pbw molybdenum per 100 pbw alumina.
m e catalysts were used in a 1:4 volume ratio. The HT was carried out at a hydrogen pressure of 150 bar, a space velocity (measured over the two reactors) of 0.5 kg feed per litre catalyst per hour, a H2/feed ratio of 1000 Nl per kg and an average temperature of 410C in the first reactor and 385C in the second reactor.
In both the flow diagrams the DA treatment was carried ou~
using n-butane as solvent, at a temperature of 115C, a pressure of 40 bar and a solvent/oil weight ratio of 3:1.
In both the flow diagrams the TC treatment was carried out in a cracking coil, at a pressure of 10 bar, a space velocity of 0.4 kg fresh fee~ per litre cracking coil volume per minute and a temperature of S00C (temperature measured at the outlet of the cracking coil~.
Example 1 This Example was carried out according to flow diagram A as represented by Figure III.
100 pbw ~acuum residue (301) having an RCT of 19.1 %w yielded the various streams in the follcwing ~uantities:
102.2 pbw mixture (313) having an ~CT of 19.5 %w, a product (315), the C5+ fraction of which had an RCT of g.4 %w, 20.7 pbw C5-350C atmospheric distillate ~317), 75.1 " 350C atmospheric residue (318), 30.1 " 350-520C vacuum distillate (319), 45 0 " 520C+ vacuum residue (302), 30.6 " deasphalted oil (320), 14.4 " asphaltic bitumen (303), 2.3 " C5-350C atmospheric distillate ~323), 11.7 " 350~ atmospheric residue (324), l5~
1.5 pbw 350-520C vacuum distillate (325), 10.2 " 520C~ vacuum .residue (304), 2.2 " portion (312) and 8.0 " portion (326).
Example 2 This Example was carried out according to f1GW diagram B as represented by Figure IV.
100 pbw Vacuum residue (401) having an RCT of 19.8 ~w yielded the various streams in the following quantities:
117.6 pbw mixture (412), 71.7 " deasphalted oil (413), 45.9 " asphaltic bitumen (403) 5.9 " C5-350C atm~spheric distillate (416), 31.9 " 350C abmospheric residue (417~,
5~
m e embodiment belonging to class IA is represented schema-tically in Figure I~ The various streams, fractions and reaction zones are indicated by three digit numbers, ~he first of which refers to the Figure concerned. m e vacuum residue ~302), for instance, refers to vacuum residue 2 in the context of Figure III.
According to Figure I the process is carried out in an ap-paratus comprising a HT zone (105), a DA zone (106) and a TC zone (107), successively. An asphaltenes-containing hydrocarbon mixture (101) and a residual fraction (104) are subjected to a ~ and the hydrotreated product is separated into one or more distillate fractions (108) and a residual fraction (102). Stream 102 is subjected to a DA treatment and the product is separated into a deasphalted oil (109) and an asphaltic bitumen (103). Stream 103 is suhjected to TC and the cracked product is separated into one or more distillate fractions (110) and a residual raction (104).
The embcdiment belonging to class IB is represented schema-tically in Figure II. According to this Figure the process is carried out in an apparatus consisting of a DA zone (2051, a TC
zone (206) and a ~ zone (207), successively. An asphaltenes-containing hydrocarbon mixture (201) and a residual fraction (202) are subjected to a DA treatment and the product is separated into a deasphalted oil (208) and an asphaltic bitumen (203). Stream 203 is subjected to a TC treatment and the cracked product is se-parated into one or more distillate fractions (209) and a residual fraction (204). Stream 204 is subjected to a HT and the hy~ro-treated product is separated into one or more distillate fractions (210) and a residual fraction (202).
In the enbodiments wher~ it is the object to achieve the cGmpletest possible ccnversion of stream (.01) into deasphalted 3o oil and hydrocarbon oil distillates, a so-called "bleed stream"
should preferably be separated from one of the heavy streams of the process. In this way the build-up of undesirable heavy compo, nents during the process can be obviated.
~2~8~56~
Two flow diagrams for the preparation of deasphalt.ed oil and hydrocarbon oil distillates from asphaltenes-containing hydro~
carbon muxtures according to the invention will hereinafter be explained in more detail with t,he aid of Figures III and IV.
Flow diagram A (based on embodiment IA) See Figure III.
The process is carried out in an apparatus ccmprising succesively, a HT zone camposed of a unit for catalytic hydrotreatment (305), a unit for atmospheric distillation (306) and a vacuum distillation unit (307), a DA zone (308) and a TC zone comp~sed of a ~hermal cracking unit (309), a second at~ ~p~er.ic distillation unit (310) and a second vacuum distillation Ullit ~311). A~ asphaltenes-containing hydrocarbon mlxture (3013 is ~xed with a recirculation stream (312) and the mlxture (313) is subjected together with hydrogen (314) to a catalytic hydrotreatment. The hydrotreated product (315) is separated by atmospheric distillation into a gas fraction (316), an atomospheric distillate (317) and an abmos-pheric residue (318)~ T.he atmospheric residue (318) is separated by vacuum distillation into a vacuum distillate (319) and a vacuum residue (302). m e vacuum residue (302) is separated by solvent deasphalting into a deasphalted oil (320) and an asphaltic bitumen (303). The asphaltic bitumen ~303) is subjected to thermal crack-ing and the thermally cracked product (321) is separated by atmospheric distillation into a gas fraction (322), an atmospheric distillate (323) and an atmospheric residue (324). The atmospheric residue (324) is separated by vacuum distillation into a vacuum distillate (325) and a vacuum residue (304). The vacuum residue (304) is divided into two portions (312) and (326).
Flow diagram B (based on embodiment IB) See Figure rv.
The process is carried out in an apparatus camprising, successive-ly, a DA zone (405), a TC zone composed of a thermal cracking unit (406), an abmospheric distillation unit (407) and a vacuum ~Z~5~
distillation unit (408) and a HT zone composed of a unit for catalytic hydrotreatment (409), a second atmospheric distillation unit (410) and a second vacuum distillation unit (411). An as-phaltenes-containing hydrocarbon mixture (401) is muxed with a vacuum residue (402) and the mixture (412) is separated by solvent deasphalting into a deasphalted oil (413) and an asphaltic bitumen (403). The asphaltic bitumen (403) is subjected to ther~al crack-ing and the thermally cracked product (414) is separated by atmospheric distillation into a gas fraction (415), an atmospheric distillate (416) and an atmospheric residue (417~. The atmospheric residue (417) is separated by vacuum distillation into a vacuum distillate (418) and a vacuum residue (404). The vacuum residue (404) is divided into two portions (419) and (420). Portion (420) is subjected together with hydrogen (421) to a catalytic hydro-treatm~nt. m e hydrotreated product (422) is separated by atmos-pheric distillation into a gas fraction (423), an atmospheric distillate (424) and an atmosph~ric residue (425). m e atmospheric residue (425) is separated by vacuum distillation into a vacuum distillate (426) and vacuum residue (402).
The present patent application also includes apparatuses for carrying out the process according to the invention substantially corresponding with those represented schematically in Figures I-IV.
The invention is now elucidated with the aid of the follcwing Examples.
In the process according to the invention two asphaltenes-containing hydrocarbon mlxtures obtained as residues in the vacuum distillation of atmospheric distillation residues frcm crude m m eral oils were used as the starting material~ m e two vacuum residues both boiled substantially above 520~ and they had RCT's of 19.1 and 15~8 %w, respectively. m e process was carried out according to flcw diagrams A and B. m e conditions used in the various zones were the follcwing.
m e unit for catalytic hydrotreatment as described in both the flow diagrams consisted of two reactors, the first of which was filled with a Ni/V/Sio2 catalyst containing 0.5 parts by weight (pbw) nickel and 2.0 pbw vanadium per 100 pbw silica and the second of which was filled with a Co/MD/A1203 catalyst containing 4 pbw cobalt and 12 pbw molybdenum per 100 pbw alumina.
m e catalysts were used in a 1:4 volume ratio. The HT was carried out at a hydrogen pressure of 150 bar, a space velocity (measured over the two reactors) of 0.5 kg feed per litre catalyst per hour, a H2/feed ratio of 1000 Nl per kg and an average temperature of 410C in the first reactor and 385C in the second reactor.
In both the flow diagrams the DA treatment was carried ou~
using n-butane as solvent, at a temperature of 115C, a pressure of 40 bar and a solvent/oil weight ratio of 3:1.
In both the flow diagrams the TC treatment was carried out in a cracking coil, at a pressure of 10 bar, a space velocity of 0.4 kg fresh fee~ per litre cracking coil volume per minute and a temperature of S00C (temperature measured at the outlet of the cracking coil~.
Example 1 This Example was carried out according to flow diagram A as represented by Figure III.
100 pbw ~acuum residue (301) having an RCT of 19.1 %w yielded the various streams in the follcwing ~uantities:
102.2 pbw mixture (313) having an ~CT of 19.5 %w, a product (315), the C5+ fraction of which had an RCT of g.4 %w, 20.7 pbw C5-350C atmospheric distillate ~317), 75.1 " 350C atmospheric residue (318), 30.1 " 350-520C vacuum distillate (319), 45 0 " 520C+ vacuum residue (302), 30.6 " deasphalted oil (320), 14.4 " asphaltic bitumen (303), 2.3 " C5-350C atmospheric distillate ~323), 11.7 " 350~ atmospheric residue (324), l5~
1.5 pbw 350-520C vacuum distillate (325), 10.2 " 520C~ vacuum .residue (304), 2.2 " portion (312) and 8.0 " portion (326).
Example 2 This Example was carried out according to f1GW diagram B as represented by Figure IV.
100 pbw Vacuum residue (401) having an RCT of 19.8 ~w yielded the various streams in the following quantities:
117.6 pbw mixture (412), 71.7 " deasphalted oil (413), 45.9 " asphaltic bitumen (403) 5.9 " C5-350C atm~spheric distillate (416), 31.9 " 350C abmospheric residue (417~,
4'7 " 350-520C vacuum distillate (418), 34.4 " 520C~ vac~um residue (404),
5.0 " portion (419), 29~4 " portion (420) having an R~T of 41.2 %w, a product (422~, the C5 fraction of which had an RCT of 18.5 %w, 4.1 pbw C5-350C atm3spheric distillate (424), 23.8 " 350C atm3sph~ric residue (425),
6.2 " 350-520C vacuum distillate (426) and 17.6 " 520C vacuum residue (402).
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of deasphalted oils and hydrocarbon oil distillates from asphaltenes-containing hydro-carbon mixtures, characterized in that an asphaltenes-containing hydrocarbon mixture (1) is subjected to a combination of the following three treatments:
- a catalytic hydrotreatment (HT) in which an asphaltenes-containing feed is converted into a product having a reduced asphaltenes content from which one or more distillate fractions and a heavy fraction (stream 2) are separated, - a solvent deasphalting (DA) treatment in which an asphaltenes-containing feed is converted into a product from which a de-asphalted oil and an asphaltic bitumen (stream 3) are separated and - a thermal cracking (TC) treatment in which a feed is converted into a product which contains less than 20 %w C4- hydrocarbons and from which one or more distillate fractions and a heavy fraction (stream 4) are separated, that stream 3 is used as the feed for the TC treatment and that stream 1 is used either 1) together with stream 4 as a feed component for the HT with stream 2 being used as the feed for the DA treatment, or 2) together with stream 2 as a feed component for the DA treat-ment, with stream 4 being used as the feed for the HT.
- a catalytic hydrotreatment (HT) in which an asphaltenes-containing feed is converted into a product having a reduced asphaltenes content from which one or more distillate fractions and a heavy fraction (stream 2) are separated, - a solvent deasphalting (DA) treatment in which an asphaltenes-containing feed is converted into a product from which a de-asphalted oil and an asphaltic bitumen (stream 3) are separated and - a thermal cracking (TC) treatment in which a feed is converted into a product which contains less than 20 %w C4- hydrocarbons and from which one or more distillate fractions and a heavy fraction (stream 4) are separated, that stream 3 is used as the feed for the TC treatment and that stream 1 is used either 1) together with stream 4 as a feed component for the HT with stream 2 being used as the feed for the DA treatment, or 2) together with stream 2 as a feed component for the DA treat-ment, with stream 4 being used as the feed for the HT.
2. A process as claimed in claim 1, characterized in that a hydrocarbon mixture which boils substantially above 350°C and more than 35 %w of which boils above 520°C and which has an RCT of more than 7.5 %w, such as a residue obtained in the vacuum distil-lation of an atmospheric distillation residue from the crude mineral oil is used as stream 1.
3. A process as claimed in claim 1, characterized in that one or more vacuum distillates are separated from one or more of streams 1, 2 and 4.
4. A process as claimed in claim 1, characterized in that the catalyst used in the HT aiming at the reduction of the asphaltenes content of the feed, is a catalyst containing at least one metal chosen from the group formed by nickel and cobalt and in addition at least one metal chosen from the group formed by molybdenum and tungsten supported on a carrier, which carrier consists more than 40 %w of alumina.
5. A process as claimed in claim 1, characterized in that the HT is carried out at a temperature of from 350-450°C, a pressure of from 75-200 bar, a space velocity of from 0.1-2 g.g-1.h-1 and a H2/feed ratio of from 500-2000 Nl.kg-1.
6. A process as claimed in claim 1, characterized in that the HT is carried out in such a way that it yields a product, the C5+ fraction of which meets the following requirements:
a) the RCT of the C5+ fraction is 20-70 % of the RCT of the feed and b) the difference between the weight percentages of hydrocarbons boiling below 350°C present in the C5+ fraction and in the feed is at most 40.
a) the RCT of the C5+ fraction is 20-70 % of the RCT of the feed and b) the difference between the weight percentages of hydrocarbons boiling below 350°C present in the C5+ fraction and in the feed is at most 40.
7. A process as claimed in claim 1, characterized in that the DA treatment is carried out using n-butane as the solvent at a pressure of from 35-45 bar and a temperature of from 100-150°C.
8. A process as claimed in claim 1, characterized in that the TC treatment is carried out at a temperature of from 400-525°C and a space velocity of from 0.01-5 kg fresh feed per litre cracking reactor volume per minute.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8201233A NL8201233A (en) | 1982-03-24 | 1982-03-24 | PROCESS FOR THE PREPARATION OF LOW ASPHALTENE HYDROCARBON MIXTURE. |
| NL8201233 | 1982-03-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1208150A true CA1208150A (en) | 1986-07-22 |
Family
ID=19839469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000423237A Expired CA1208150A (en) | 1982-03-24 | 1983-03-09 | Process for the production of deasphalted oils and hydrocarbon oil distillates |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0089707B1 (en) |
| JP (1) | JPS58173190A (en) |
| AU (1) | AU558158B2 (en) |
| CA (1) | CA1208150A (en) |
| DE (1) | DE3361373D1 (en) |
| ES (1) | ES520831A0 (en) |
| MX (1) | MX162276A (en) |
| NL (1) | NL8201233A (en) |
| ZA (1) | ZA831992B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60152594A (en) * | 1984-01-23 | 1985-08-10 | Kawasaki Heavy Ind Ltd | Desulfurization of residual oil from direct desulphurizer |
| CA2117571A1 (en) * | 1993-08-30 | 1995-03-01 | Junichi Kubo | Process for hydrotreating heavy hydrocarbon oil |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775293A (en) * | 1972-08-09 | 1973-11-27 | Universal Oil Prod Co | Desulfurization of asphaltene-containing hydrocarbonaceous black oils |
| US3859199A (en) * | 1973-07-05 | 1975-01-07 | Universal Oil Prod Co | Hydrodesulfurization of asphaltene-containing black oil |
| NL7512090A (en) * | 1975-10-15 | 1977-04-19 | Shell Int Research | PROCESS FOR CONVERTING HYDROCARBONS. |
| NL7610511A (en) * | 1976-09-22 | 1978-03-28 | Shell Int Research | METHOD FOR CONVERTING HYDROCARBONS. |
| NL7612960A (en) * | 1976-11-22 | 1978-05-24 | Shell Int Research | METHOD FOR CONVERTING HYDROCARBONS. |
| NL8105560A (en) * | 1981-12-10 | 1983-07-01 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBON OIL DISTILLATES |
| NL8105660A (en) * | 1981-12-16 | 1983-07-18 | Shell Int Research | PROCESS FOR PREPARING HYDROCARBON OIL DISTILLATES |
-
1982
- 1982-03-24 NL NL8201233A patent/NL8201233A/en not_active Application Discontinuation
-
1983
- 1983-03-04 DE DE8383200316T patent/DE3361373D1/en not_active Expired
- 1983-03-04 EP EP83200316A patent/EP0089707B1/en not_active Expired
- 1983-03-09 CA CA000423237A patent/CA1208150A/en not_active Expired
- 1983-03-22 ES ES520831A patent/ES520831A0/en active Granted
- 1983-03-22 AU AU12683/83A patent/AU558158B2/en not_active Ceased
- 1983-03-22 ZA ZA831992A patent/ZA831992B/en unknown
- 1983-03-22 JP JP58046126A patent/JPS58173190A/en active Pending
- 1983-03-23 MX MX196677A patent/MX162276A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL8201233A (en) | 1983-10-17 |
| DE3361373D1 (en) | 1986-01-16 |
| ES8401517A1 (en) | 1983-12-16 |
| EP0089707A2 (en) | 1983-09-28 |
| JPS58173190A (en) | 1983-10-12 |
| AU558158B2 (en) | 1987-01-22 |
| AU1268383A (en) | 1983-09-29 |
| EP0089707A3 (en) | 1983-10-26 |
| MX162276A (en) | 1991-04-19 |
| ZA831992B (en) | 1983-11-30 |
| ES520831A0 (en) | 1983-12-16 |
| EP0089707B1 (en) | 1985-12-04 |
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