CA1198388A - Process for the production of hydrocarbon oil distillates - Google Patents
Process for the production of hydrocarbon oil distillatesInfo
- Publication number
- CA1198388A CA1198388A CA000416276A CA416276A CA1198388A CA 1198388 A CA1198388 A CA 1198388A CA 000416276 A CA000416276 A CA 000416276A CA 416276 A CA416276 A CA 416276A CA 1198388 A CA1198388 A CA 1198388A
- Authority
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- Canada
- Prior art keywords
- stream
- feed
- treatment
- product
- asphaltenes
- 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
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A B S T R A C T
PROCESS FOR THE PRODUCTION OF HYDROCARBON
OIL DISTILLATES
Distillates are produced from asphaltenes-containing hydro-carbon mixtures by a process comprising subjecting the hydrocarbon mixtures to a catalytic hydrotreatment, and subjecting the dis-tillation residue of the hydroconverted product to a combination of solvent deasphalting and thermal cracking.
PROCESS FOR THE PRODUCTION OF HYDROCARBON
OIL DISTILLATES
Distillates are produced from asphaltenes-containing hydro-carbon mixtures by a process comprising subjecting the hydrocarbon mixtures to a catalytic hydrotreatment, and subjecting the dis-tillation residue of the hydroconverted product to a combination of solvent deasphalting and thermal cracking.
Description
3~
PRQCESS FOR THE PRODUGTION OF HYDROCARBON
OIL DISTILLATES
The invention relates to a process for the production of hydrocarbon oil distillates from asphaltenes-containing hy-drocarbon mixtures.
In the atmospheric distillation of crude m~neral oil for the preparation of light hydrocarbon oil distillates, such as gas-oline, kerosene and gas oil, an asphaltenes-containing residue is formed as a by-product. In the beginning these atmospheric re-sidues (which in addition to asphaltenes5 u~ually contain a con-siderable percentage of sulphur and metals) were used as fuel oil.
In view of the growing demand for light hydrocarbon oil dis-tillates and the shrinking reserves of crude mineral oil, various treatments have already been proposed which aimed at converting atmospheric residues into light hydrocarbon oil distlllates. For instance, the atmospheric residue may be subjected to the~mal cracking. Further, the atmospheric residue may be separated by vacuum distillation into a vacuum distillate and a vacuum residue, the vacuum distillate may be subjected to therm 1 cracking or to catalytic cracking .n the presence or in the absence of hydrogen and the vacuum residue to thermal cracking. Finally, the vacuum residue may be separated by solvent deasphalting into a de-asphalted oil and an asphaltic bitumen, the deasphalted oil may be subjected to thermal cracking or to catalytic cracking in the presence or in the absence of hydrogen, and the asphaltic bitumen to thermal cracking.
Thermal cracking (TC) refers to a process wherein a heavy feedstock is converted into a product which contains less than 20% w C4 hydrocarbons and from which one or more distillate fractions may be separated as the desired light product and a heavy fraction as a by-product. TC has proved in actual practice to be a suitable treatment for the production of hydrocarbon oil distillates from a variety of asphaltenes-containing hydrocarbon mixtures.
38~3 It has now been investigated whether combining the TC treat-ment with pretreatment of the heavy feedstock and/or aftertreat-ment of the heavy fraction separated from the product of thermal cracking, and using at least part of the aftertreated heavy fraction as feed for the TC treatment, might yield a better result than employing nothing but the TC. In the assessment of the results the yield of light product is most important. The quali-ties of the light and heavy product are also of importance. In this context the quality of the light product is taken to be its suitability for processing into a valuable light fuel oil. This suitability will be greater according as the light product has, among other things, lower sulphur and olefin contents. In this context the quality of the heavy product is taken to be its suitability for use as a fuel oil component. This suitability will be greater according as the heavy product has among other things, lower metal and sulphur contents and lower viscosity and density.
As pretreatments for the feed of the TC treatment and as after-treatments for the heavy fraction of the TC product the following treatments were investigated: solvent deasphalting (DA) in which an asphaltenes-cont~;n;ng feed is converted into a product from which a deasphalted oil fraction and an asphaltic bitumen fraction are separated, and catalytic hydrotreatment ~HT) in which an asphaltenes-cont~in;ng feed is converted into a product having a reduced asphaltenes content from which can be separated one or more distillate fractions as the desired light product and a heavy fraction.
During the investigation a comparison was made between the results which can be obtained when equal quantities of an as-phaltenes-containing hydrocarbon mixture are used as the starting material in the preparation of a hydrocarbon oil distillate having a given boiling range and a heavy by-product by using a) nothing but TC, b) TC combined with DA, c) TC combined with HT and d) TC combined with both DA and ~T, the conditions of the various treatments being as similar as possible. In view of the quantity and quality of the hydrocarbon oil distillate and the quality of the heavy by-product to be obtained in each of the procedures, the various procedures may be arranged as follows:
Quantity of hydrocarbon oil distillate d >c >b >a Quality of hydrocarbon oil distillate c ,d >a >b Quality of hesvy by-product c >d ,a >b Taking into account the considerable difference in yield of hydrocarbon oil distillate obtained using procedures c) and d) and the no more than slight differences between the qualities of the hydrocarbon oil distillates and the heavy by-products obtained using procedures c) and d), a procedure in which a combination o~
a TC treatment, a DA treatment and a HT is used is much preferred.
As regards the order in ~hich the three treatments are carried out and also the feeds used for each of the three treat-ments, a number of embodiments may be considered. In all the embodiments the deasphalted oil fraction which is separated from the product of the DA treatment is used as the feed or a feed component for the TC treatment. Each of the embodiments may be placed in one of the following three classes:
I First, the asphaltenes-cont~in;np feed is subjected to a HT7 ;from the product thus formed a heavy fraction is separated and subjected to a combination of a DA treatment and a TC
treatment.
II First, the asphaltenes-containing feed is subje~ted to a DA
treatment, from the product thus obtained a deasphalted oil fraction and an asphaltic bitumen fraction are separated and these are both subjected to a combination of a TC treatment and a HT.
III First, the asphaltenes-containing feed is subjected to a TC
treatment, from the product thus obtained a heavy fraction is separated and subjected to a combination of a HT and a DA treatment.
The embodiments belonging to class I form the subject ma-tter of -the present patent application.
The embodiments to T~hich the present patent applic-ation relates may further be subdivided depending on whether the heavy frac-tion separated from the product from the HT is used as :LO Eeed for the DA treatment (class IA), or as a feed component for the TC (class IB). In the embodiments belonging to class IB the heavy fraction separated from the TC treatment is used as feed for the DA treatment.
The present patent application therefore relates to a process for the production of hydrocar~on oil distillates from asphaltenes-containing hydrocarbon mixtures, in which an asphal-tenes-containing hydrocarbon mixture (s-tream 1) is subjected to a catalytic hydro-treatment (HT) in which an asphal-tenes-containing feed is converted into a product having ~n a reduced asphal-tenes content from which one or more distillate fractions and a heavy fraction (stream 2) are separated, in which stream 2 is subjected to a combination of the following two treatments: solven-t deasphalting (DA) in which an asphaltenes-contain.ing :Eeed is converted into a product from which a deasphalted oil Eraction (stream 3) and an asphaltic bitumen Eraction (s-tream 4) are separated and thermal cracking (TC) in -4a-which one feed or two individual feeds are converted into a pro-duct which contains less than 20% w C4 hydrocarbons and from ~hich one or more distillate fractions and a heavy fraction (stream 5) are separated, in which stream 3 i5 used as the feed or as a feed component for the TC treatment and in which stream 2 is used either as a feed component for the TC
3~
treatment with stream 5 being used as the feed for the DA treat-ment, or as the feed for the DA treatment.
In the process according to the invention the feed used is an asphaltenes-containing hydrocarbon mixture. A suitable parameter S for the assessment of the asphaltenes content of a hydrocarbon mixtu~e as well as of the reduction of the asphaltenes content which appears when an asphaltenes-cont~;n;ng hydrocarbon mixture is subjected to a HT, is the Ramsbottom Carbon Test value (RCT).
The higher the asphaltenes content of the hydrocarbon mi~ture, the higher the RCT. Preferably, the process is applied to hydrocarbon mixtures which boil substantially above 350C and more than 35% w of which boils above 520C and which have an RCT of more than 7.5%
w. Examples of such hydrocarbon mixtures are residues obtained in the distillation of crude mineral oils and also heavy hydrocarbon mixtures obtained from shale and tar sand. If required, the process may also be applied to heavy crude mineral oils, residues obtained in the distillation of products formed in the thermal cracking of hydrocarbon mixtures and asphaltic bitumen obtained in the solvent deasphalting of aspha;tenes-cont?;ning hydrocarbon mixtures. The process according to the invention can very suitably be applied to residues obtained in the vacuum distillation of atmospheric distillation residues from crude mineral oils. If an atmospheric distillation residue from a crude mineral oil is available as feed for the process according to the invention, it is preferred to separate a vacuum distillate therefrom by vacuum distillation and to subject the resulting vacuum residue to the HT. The separated vacuum distillate may be subjected to thermal cracking or to catalytic cracking in the presence or in the absence of hydrogen to convert it into light hydrocarbon oil dis-3Q tillates. The separated vacuum distillate is very suitable for useas a feed component for the TC treatment, together with stream 3.
The process according to the invention is a three-step process in which in the first step an asphaltenPs-conta;n;ng feed tstream 1) is subjected to a HT for the production of a product 3~1~
with a reduced asphaltenes content from which one or more dis-tillate fractions and a heavy fraction (stream 2) are separated.
In the second and third steps of the process stream 2 is subjected to a combina~ion of a DA treatment and a TC treatment.
Asphaltenes-containing hydrocarbon mixtures usually include a considerable percentage of metals particularly vAnA~ m 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 first step of the process according to the invention, these metals are deposited on the catalyst used in the HT and thus shorten its effective life.
In view of this, asphaltenes-contA;ning hydrocarbon mixtures having a vanadium + nickel content of more than 50 parts per million by weight ~ppmw) should preferably be subjected to a demetallization treatment before they are contacted with the catalyst used in the HT. This demetalli7ation may very suitably be carried out by contacting the asphaltenes-cont~;n;ng hydrocarbon mixture, in the presence of hydrogen, with a catalyst consisting more than 80% w of silica. Bo,h catalysts completely consistin~ of silica and catalysts contAin;ng one or more metals having hydrogen-ating activity - in particular a combination of nickel and vana-dium - emplaced on a carrier substantially consisting of silica, are suitable for the purpose. When in the process according to the invention the asphaltenes-contAining ~eed is subjected to a catalytic demetAl1;7ation treatment in the presence of hydrogen, this demetAlli7Ation may be carried out in a separate reactor.
Since the catalytic demetAl1;7Ation and the HT for the reduceion of the asphaltenes content can be carried out under the same conditions, the two processes may very suitably be carried out in the same reactor contA;ning a bed of the demetallization catalyst and a bed of the catalyst used in the HT, successively.
Suitably catalysts ~or carrying out the HT are those con-taining ae least one metal chosen from the group for~ed by nickel and cobalt and in addition at least one metal chosen from the 3~
group formed by molybdenum and tungsten on a carrier, which carrier consists more than 40% w of ~lllmin~. Catalysts very suitable for use in the HT are those comprising the metal com-binations nickel/molybdenum or cobalt/molybdenum on alum;nA 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 from 50-300 bar and in particular of from 75-200 bar, a space velocity of from 0.02-lO g.g. 1.h 1 and in particular of from 0.1-2 g.g .h and a H2/feed ratio of Erom 100-5000 Nl.k~ and in particular of from 500-2000 Nl.kg . The conditions used in a catalytic demetal-lization treatment in the presence of hydlogen, to be carried out if required, are subject to the same preference as those for the HT for the reduction of the asphaltenes content stated herein-before.
The HT is preferably carried out in such a way that it yields a product the C5 fraction of which meets the following require-ments:
a) the RCT of the C5 fraction amounts to 20-70% of the feed (RCT), and b) the difference between the percentages by weight of hydrocarbon boiling below 350C present in the C5 fraction and in the feed is at most 40.
It should be noted that in the catalytic demetallization, apart from reduction of the metal content, there will be some reduction of the RCT and some formation of C5-350C product. A
similar phenomenon is seen in the HT, in which, apart from re-duction of the RCT and formation of C5-350C product, there will be some reduction of the metal content. The requirements mentioned under a) and b) refer to the total RCT reduction and the total formation of C5 350~C product (viz. including those occurring ln a catalytic demetallization treatment that may be carried out).
The first step of the process according to the invention yields a product having a reduced asphal~enes content from which one or more distillate fractions and a heavy fraction (stream 2) are separated. The distillate fractions separated from the product may be atmospheric distillates only, but it is preferred to separate a vacuum distillate from the product as well. This vacuum distillate may be converted into light hydrocarbon oil distillates in the ways stated hereinbefore.
In the process according to the invention the second or third step used is a DA trea~ment in which an asphaltenes-cont~;n;ng feed is converted into a product from which a deasphalted oil fraction (stream 3) and an asphaltic bitumen fraction (stream 4) are separated. Suitable solvents for carrying out the DA are paraffinic hydrocarbons having of from 3-6 carbon atoms per molecule, such as n-butane and mi~tures thereof, such as mixtures of propane and n-butane and mixtures of n-butane and n-pentane.
Suitable solvent/oil weight ratios lie between 7:1 and 1:1 and in particular between 4:1 and 1:1. The DA treatment is preferably 15 carried out at a pressure in the range of from 20 to 100 bar. When n-butane is used as the solvent, the deasphalting is preferably carried out at a pressure of from 35 45 bar and a ~emperature of from 100-150C.
In the process according to the invention the second or third step used is a TC treatment in which one feed or two separate feeds are 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 5) are separated. The way in which the TC
treatment is carried out is determined by the quality of the feeds available for the TC.
If the feed for the TC is composed of nothing but one or more streams having a relatively low asphaltenes content, such as stream 3 - optionally together with one or more vacuum distillates separated during the process - a TC treatment comprising a single cracking unit will be sufficient. From the product formed one or more distillate fractions and a heavy fraction (stream 5) are separated. The distillate fractions separated from the product may be atmospheric distillates only, but it is preferred to separate a vacuum distillate from the product as well. This vacuum distillate may be converted into light hydrocarbon oil distillates in the 3~
ways stated hereinbefore. If the feed for the TC treatment is composed of nothing but one or more streams having a relatively low asphaltenes content, and a TC treatment is used which com-prises only one cracking unit, then a heavy fraction of the cracked product is preferably recirculated to the cracking unit.
For instance, starting from strea~ 3 as the feed for the TC
treatment, a product may be prepared from which one or more atmos-pheric distillates are separated by distillation and subsequently part of the atmospheric residue may be recirculated to the cracking unit.
If the feed for the TC treatment is composed of both of one or more streams having a relatively low asphaltenes content, such as stream 3 - optionally together with one or more vacuum dis-tillates separated during the process - and of a relatively asphaltenes-rich stream, such as stream 4 or stream 2 obtained as vacuum residue, it is preferred to carry out a TC treatment comprising two cràcking units and to crack the two feeds se-parately to form products from which one or more distillate fractions and a heavy fraction (stream 5) are separated. The distillate fractions separated from the products may be atmos-pheric distillates only, but it is preferred to separate a vacuum distillate from the products as well. The separated vacuum dis-tillate may be converted into light hydrocarbon distillates in the manners described hereinbefore. ~s is the case when a TC treatment comprising a single cracking unit is used, so also when a TC
treatment comprising two cracking units is used, a heavy fraction from the cracked product from the cracking unit in which the relatively low asphaltenes feed is processed will preferably be recirculated to that cracking unit. When a TC treatment comprising two cracking units is used, a relatively low-asphaltenes heavy fraction may, if desired, be separated from the product obtained in the cracking unit in which the relatively asphaltenes-rich feed is cracked and be used as a feed component for the cracking unit in which the relatively low-asphaltenes feed is processed. When a TC treatment comprising two cracking units is used, it is not necessary for the distillation of the cracked products (atmos-pheric and, optionally, vacuum distillation) to be carried out in separate distillation units. If desired, the craGked products or fractions therefrom may be combined and dist;lled together.
The TC treatment both of relatively low-asphaltenes Eeeds and of relatively asphaltenes-rich feeds should preferably bc carried out a-t a tempera-ture of from 4~0-525C and a space velocity of Erom 0.01-5 kg fresh feed per litre cracking reactor volume per minute.
As has heen o~served hereinbefore, the embodiments to which the present patent application relates and which fall within class I may be subdivided depending on whether stream 2 is used as the feed for the DA treatment (class IAJ, or as a feed component for the TC treatment (class IB~. In the embodiments falling within class IB stream 5 is used as the feed Eor the DA
treatment.
The invention will now be described by way of reference to figures I to V in which:
Figure I represents various em~odiments falling
PRQCESS FOR THE PRODUGTION OF HYDROCARBON
OIL DISTILLATES
The invention relates to a process for the production of hydrocarbon oil distillates from asphaltenes-containing hy-drocarbon mixtures.
In the atmospheric distillation of crude m~neral oil for the preparation of light hydrocarbon oil distillates, such as gas-oline, kerosene and gas oil, an asphaltenes-containing residue is formed as a by-product. In the beginning these atmospheric re-sidues (which in addition to asphaltenes5 u~ually contain a con-siderable percentage of sulphur and metals) were used as fuel oil.
In view of the growing demand for light hydrocarbon oil dis-tillates and the shrinking reserves of crude mineral oil, various treatments have already been proposed which aimed at converting atmospheric residues into light hydrocarbon oil distlllates. For instance, the atmospheric residue may be subjected to the~mal cracking. Further, the atmospheric residue may be separated by vacuum distillation into a vacuum distillate and a vacuum residue, the vacuum distillate may be subjected to therm 1 cracking or to catalytic cracking .n the presence or in the absence of hydrogen and the vacuum residue to thermal cracking. Finally, the vacuum residue may be separated by solvent deasphalting into a de-asphalted oil and an asphaltic bitumen, the deasphalted oil may be subjected to thermal cracking or to catalytic cracking in the presence or in the absence of hydrogen, and the asphaltic bitumen to thermal cracking.
Thermal cracking (TC) refers to a process wherein a heavy feedstock is converted into a product which contains less than 20% w C4 hydrocarbons and from which one or more distillate fractions may be separated as the desired light product and a heavy fraction as a by-product. TC has proved in actual practice to be a suitable treatment for the production of hydrocarbon oil distillates from a variety of asphaltenes-containing hydrocarbon mixtures.
38~3 It has now been investigated whether combining the TC treat-ment with pretreatment of the heavy feedstock and/or aftertreat-ment of the heavy fraction separated from the product of thermal cracking, and using at least part of the aftertreated heavy fraction as feed for the TC treatment, might yield a better result than employing nothing but the TC. In the assessment of the results the yield of light product is most important. The quali-ties of the light and heavy product are also of importance. In this context the quality of the light product is taken to be its suitability for processing into a valuable light fuel oil. This suitability will be greater according as the light product has, among other things, lower sulphur and olefin contents. In this context the quality of the heavy product is taken to be its suitability for use as a fuel oil component. This suitability will be greater according as the heavy product has among other things, lower metal and sulphur contents and lower viscosity and density.
As pretreatments for the feed of the TC treatment and as after-treatments for the heavy fraction of the TC product the following treatments were investigated: solvent deasphalting (DA) in which an asphaltenes-cont~;n;ng feed is converted into a product from which a deasphalted oil fraction and an asphaltic bitumen fraction are separated, and catalytic hydrotreatment ~HT) in which an asphaltenes-cont~in;ng feed is converted into a product having a reduced asphaltenes content from which can be separated one or more distillate fractions as the desired light product and a heavy fraction.
During the investigation a comparison was made between the results which can be obtained when equal quantities of an as-phaltenes-containing hydrocarbon mixture are used as the starting material in the preparation of a hydrocarbon oil distillate having a given boiling range and a heavy by-product by using a) nothing but TC, b) TC combined with DA, c) TC combined with HT and d) TC combined with both DA and ~T, the conditions of the various treatments being as similar as possible. In view of the quantity and quality of the hydrocarbon oil distillate and the quality of the heavy by-product to be obtained in each of the procedures, the various procedures may be arranged as follows:
Quantity of hydrocarbon oil distillate d >c >b >a Quality of hydrocarbon oil distillate c ,d >a >b Quality of hesvy by-product c >d ,a >b Taking into account the considerable difference in yield of hydrocarbon oil distillate obtained using procedures c) and d) and the no more than slight differences between the qualities of the hydrocarbon oil distillates and the heavy by-products obtained using procedures c) and d), a procedure in which a combination o~
a TC treatment, a DA treatment and a HT is used is much preferred.
As regards the order in ~hich the three treatments are carried out and also the feeds used for each of the three treat-ments, a number of embodiments may be considered. In all the embodiments the deasphalted oil fraction which is separated from the product of the DA treatment is used as the feed or a feed component for the TC treatment. Each of the embodiments may be placed in one of the following three classes:
I First, the asphaltenes-cont~in;np feed is subjected to a HT7 ;from the product thus formed a heavy fraction is separated and subjected to a combination of a DA treatment and a TC
treatment.
II First, the asphaltenes-containing feed is subje~ted to a DA
treatment, from the product thus obtained a deasphalted oil fraction and an asphaltic bitumen fraction are separated and these are both subjected to a combination of a TC treatment and a HT.
III First, the asphaltenes-containing feed is subjected to a TC
treatment, from the product thus obtained a heavy fraction is separated and subjected to a combination of a HT and a DA treatment.
The embodiments belonging to class I form the subject ma-tter of -the present patent application.
The embodiments to T~hich the present patent applic-ation relates may further be subdivided depending on whether the heavy frac-tion separated from the product from the HT is used as :LO Eeed for the DA treatment (class IA), or as a feed component for the TC (class IB). In the embodiments belonging to class IB the heavy fraction separated from the TC treatment is used as feed for the DA treatment.
The present patent application therefore relates to a process for the production of hydrocar~on oil distillates from asphaltenes-containing hydrocarbon mixtures, in which an asphal-tenes-containing hydrocarbon mixture (s-tream 1) is subjected to a catalytic hydro-treatment (HT) in which an asphal-tenes-containing feed is converted into a product having ~n a reduced asphal-tenes content from which one or more distillate fractions and a heavy fraction (stream 2) are separated, in which stream 2 is subjected to a combination of the following two treatments: solven-t deasphalting (DA) in which an asphaltenes-contain.ing :Eeed is converted into a product from which a deasphalted oil Eraction (stream 3) and an asphaltic bitumen Eraction (s-tream 4) are separated and thermal cracking (TC) in -4a-which one feed or two individual feeds are converted into a pro-duct which contains less than 20% w C4 hydrocarbons and from ~hich one or more distillate fractions and a heavy fraction (stream 5) are separated, in which stream 3 i5 used as the feed or as a feed component for the TC treatment and in which stream 2 is used either as a feed component for the TC
3~
treatment with stream 5 being used as the feed for the DA treat-ment, or as the feed for the DA treatment.
In the process according to the invention the feed used is an asphaltenes-containing hydrocarbon mixture. A suitable parameter S for the assessment of the asphaltenes content of a hydrocarbon mixtu~e as well as of the reduction of the asphaltenes content which appears when an asphaltenes-cont~;n;ng hydrocarbon mixture is subjected to a HT, is the Ramsbottom Carbon Test value (RCT).
The higher the asphaltenes content of the hydrocarbon mi~ture, the higher the RCT. Preferably, the process is applied to hydrocarbon mixtures which boil substantially above 350C and more than 35% w of which boils above 520C and which have an RCT of more than 7.5%
w. Examples of such hydrocarbon mixtures are residues obtained in the distillation of crude mineral oils and also heavy hydrocarbon mixtures obtained from shale and tar sand. If required, the process may also be applied to heavy crude mineral oils, residues obtained in the distillation of products formed in the thermal cracking of hydrocarbon mixtures and asphaltic bitumen obtained in the solvent deasphalting of aspha;tenes-cont?;ning hydrocarbon mixtures. The process according to the invention can very suitably be applied to residues obtained in the vacuum distillation of atmospheric distillation residues from crude mineral oils. If an atmospheric distillation residue from a crude mineral oil is available as feed for the process according to the invention, it is preferred to separate a vacuum distillate therefrom by vacuum distillation and to subject the resulting vacuum residue to the HT. The separated vacuum distillate may be subjected to thermal cracking or to catalytic cracking in the presence or in the absence of hydrogen to convert it into light hydrocarbon oil dis-3Q tillates. The separated vacuum distillate is very suitable for useas a feed component for the TC treatment, together with stream 3.
The process according to the invention is a three-step process in which in the first step an asphaltenPs-conta;n;ng feed tstream 1) is subjected to a HT for the production of a product 3~1~
with a reduced asphaltenes content from which one or more dis-tillate fractions and a heavy fraction (stream 2) are separated.
In the second and third steps of the process stream 2 is subjected to a combina~ion of a DA treatment and a TC treatment.
Asphaltenes-containing hydrocarbon mixtures usually include a considerable percentage of metals particularly vAnA~ m 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 first step of the process according to the invention, these metals are deposited on the catalyst used in the HT and thus shorten its effective life.
In view of this, asphaltenes-contA;ning hydrocarbon mixtures having a vanadium + nickel content of more than 50 parts per million by weight ~ppmw) should preferably be subjected to a demetallization treatment before they are contacted with the catalyst used in the HT. This demetalli7ation may very suitably be carried out by contacting the asphaltenes-cont~;n;ng hydrocarbon mixture, in the presence of hydrogen, with a catalyst consisting more than 80% w of silica. Bo,h catalysts completely consistin~ of silica and catalysts contAin;ng one or more metals having hydrogen-ating activity - in particular a combination of nickel and vana-dium - emplaced on a carrier substantially consisting of silica, are suitable for the purpose. When in the process according to the invention the asphaltenes-contAining ~eed is subjected to a catalytic demetAl1;7ation treatment in the presence of hydrogen, this demetAlli7Ation may be carried out in a separate reactor.
Since the catalytic demetAl1;7Ation and the HT for the reduceion of the asphaltenes content can be carried out under the same conditions, the two processes may very suitably be carried out in the same reactor contA;ning a bed of the demetallization catalyst and a bed of the catalyst used in the HT, successively.
Suitably catalysts ~or carrying out the HT are those con-taining ae least one metal chosen from the group for~ed by nickel and cobalt and in addition at least one metal chosen from the 3~
group formed by molybdenum and tungsten on a carrier, which carrier consists more than 40% w of ~lllmin~. Catalysts very suitable for use in the HT are those comprising the metal com-binations nickel/molybdenum or cobalt/molybdenum on alum;nA 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 from 50-300 bar and in particular of from 75-200 bar, a space velocity of from 0.02-lO g.g. 1.h 1 and in particular of from 0.1-2 g.g .h and a H2/feed ratio of Erom 100-5000 Nl.k~ and in particular of from 500-2000 Nl.kg . The conditions used in a catalytic demetal-lization treatment in the presence of hydlogen, to be carried out if required, are subject to the same preference as those for the HT for the reduction of the asphaltenes content stated herein-before.
The HT is preferably carried out in such a way that it yields a product the C5 fraction of which meets the following require-ments:
a) the RCT of the C5 fraction amounts to 20-70% of the feed (RCT), and b) the difference between the percentages by weight of hydrocarbon boiling below 350C present in the C5 fraction and in the feed is at most 40.
It should be noted that in the catalytic demetallization, apart from reduction of the metal content, there will be some reduction of the RCT and some formation of C5-350C product. A
similar phenomenon is seen in the HT, in which, apart from re-duction of the RCT and formation of C5-350C product, there will be some reduction of the metal content. The requirements mentioned under a) and b) refer to the total RCT reduction and the total formation of C5 350~C product (viz. including those occurring ln a catalytic demetallization treatment that may be carried out).
The first step of the process according to the invention yields a product having a reduced asphal~enes content from which one or more distillate fractions and a heavy fraction (stream 2) are separated. The distillate fractions separated from the product may be atmospheric distillates only, but it is preferred to separate a vacuum distillate from the product as well. This vacuum distillate may be converted into light hydrocarbon oil distillates in the ways stated hereinbefore.
In the process according to the invention the second or third step used is a DA trea~ment in which an asphaltenes-cont~;n;ng feed is converted into a product from which a deasphalted oil fraction (stream 3) and an asphaltic bitumen fraction (stream 4) are separated. Suitable solvents for carrying out the DA are paraffinic hydrocarbons having of from 3-6 carbon atoms per molecule, such as n-butane and mi~tures thereof, such as mixtures of propane and n-butane and mixtures of n-butane and n-pentane.
Suitable solvent/oil weight ratios lie between 7:1 and 1:1 and in particular between 4:1 and 1:1. The DA treatment is preferably 15 carried out at a pressure in the range of from 20 to 100 bar. When n-butane is used as the solvent, the deasphalting is preferably carried out at a pressure of from 35 45 bar and a ~emperature of from 100-150C.
In the process according to the invention the second or third step used is a TC treatment in which one feed or two separate feeds are 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 5) are separated. The way in which the TC
treatment is carried out is determined by the quality of the feeds available for the TC.
If the feed for the TC is composed of nothing but one or more streams having a relatively low asphaltenes content, such as stream 3 - optionally together with one or more vacuum distillates separated during the process - a TC treatment comprising a single cracking unit will be sufficient. From the product formed one or more distillate fractions and a heavy fraction (stream 5) are separated. The distillate fractions separated from the product may be atmospheric distillates only, but it is preferred to separate a vacuum distillate from the product as well. This vacuum distillate may be converted into light hydrocarbon oil distillates in the 3~
ways stated hereinbefore. If the feed for the TC treatment is composed of nothing but one or more streams having a relatively low asphaltenes content, and a TC treatment is used which com-prises only one cracking unit, then a heavy fraction of the cracked product is preferably recirculated to the cracking unit.
For instance, starting from strea~ 3 as the feed for the TC
treatment, a product may be prepared from which one or more atmos-pheric distillates are separated by distillation and subsequently part of the atmospheric residue may be recirculated to the cracking unit.
If the feed for the TC treatment is composed of both of one or more streams having a relatively low asphaltenes content, such as stream 3 - optionally together with one or more vacuum dis-tillates separated during the process - and of a relatively asphaltenes-rich stream, such as stream 4 or stream 2 obtained as vacuum residue, it is preferred to carry out a TC treatment comprising two cràcking units and to crack the two feeds se-parately to form products from which one or more distillate fractions and a heavy fraction (stream 5) are separated. The distillate fractions separated from the products may be atmos-pheric distillates only, but it is preferred to separate a vacuum distillate from the products as well. The separated vacuum dis-tillate may be converted into light hydrocarbon distillates in the manners described hereinbefore. ~s is the case when a TC treatment comprising a single cracking unit is used, so also when a TC
treatment comprising two cracking units is used, a heavy fraction from the cracked product from the cracking unit in which the relatively low asphaltenes feed is processed will preferably be recirculated to that cracking unit. When a TC treatment comprising two cracking units is used, a relatively low-asphaltenes heavy fraction may, if desired, be separated from the product obtained in the cracking unit in which the relatively asphaltenes-rich feed is cracked and be used as a feed component for the cracking unit in which the relatively low-asphaltenes feed is processed. When a TC treatment comprising two cracking units is used, it is not necessary for the distillation of the cracked products (atmos-pheric and, optionally, vacuum distillation) to be carried out in separate distillation units. If desired, the craGked products or fractions therefrom may be combined and dist;lled together.
The TC treatment both of relatively low-asphaltenes Eeeds and of relatively asphaltenes-rich feeds should preferably bc carried out a-t a tempera-ture of from 4~0-525C and a space velocity of Erom 0.01-5 kg fresh feed per litre cracking reactor volume per minute.
As has heen o~served hereinbefore, the embodiments to which the present patent application relates and which fall within class I may be subdivided depending on whether stream 2 is used as the feed for the DA treatment (class IAJ, or as a feed component for the TC treatment (class IB~. In the embodiments falling within class IB stream 5 is used as the feed Eor the DA
treatment.
The invention will now be described by way of reference to figures I to V in which:
Figure I represents various em~odiments falling
2~ within class IA;
Figure II represents various embodiments falling within class IB;
Figure III represents a flow diagram based on embodiment IAS;
Figure IV represents a flow diagram based on embodimen-t IA6; and -lOa-Figure V represents a flow diagram based on embodiment IB2.
The various streams, fractions and ~eaction zones are indica-ted by three digit numbers, the first of which refers to the Figure concerned. Thus, the vacuum residue (302) for lnstance, refers to s-tream 2 as described hereinbefore in the context of Figure 3. According to Figure I the process is carried ou-t in an apparatus comprising a HT zone (106), a DA
zone (107) and a TC zone (108), successively. An asphaltenes-containing hydrocarbon mixture (101) is subjec-ted to a HT and -the hydrotreated product is separated into one or more distillate Eractions (109) and a residual fraction (102). Stream 102 is subjected to a DA treatment and the product is separated into a deasphalted oil (103) and an asphaltic bitumen (104). Stream 103 is subjected to a TC treatment and the cracked product is separated in-to one or more distilla-te fractions (110) and a residual fraction (105). In addition to this embodiment (IAl), in which streams 104 and 105 are not subjected to further pro-cessing, Figure I includes the following seven embodiments:
IA2 The use of at least part of stream 104 as a feed com-ponent for the HT. No further processing of stream 105.
IA3 The use of at least part of stream 104 as a feed com-ponent for the TC treatment. No further treatment of stream 105.
IA4 The use of part of stream 104 as a feed component for the HT and as a feed component for the TC treatment. No further processing of stream 105.
IA5-IA7 Embodiments substantially corresponding with those described under IA2-IA4, respectively, but with at least part of stream 105 being used as a feed component for the HT.
IA8 The use of at l~ast part of stream 105 as a feed com-ponent for t-ne HT. No further processing of stream 104.
]5 The various embodiments falling within class IB are represen-ted s~h- ~ically in Figure II. According to this Figure the process is carried out in an apparatus comprising a HT zone (206), a TC zone (207) and a DA zone (208). An asphaltenes-containing hydrocarbon mixture (201) is subjected to a HT and the hydro treated product is separated into one or more distillate fractions (209) and a residual fraction (202). Stream 202 is sub~ected to a TC treatment and the cracked product is separated into one or more distillate fractions (210) and a residual fraction (205). Stream 205 is subjected to a DA treatment and the product is separated 2S into a deasphalted oil (203) and an asphaltic bitumen ~204).
Stream 203 is used as a feed component for the TC treatment. In addition to this embodiment (IBl), in which stream 20~1 is not subjected to further processing Figure II includes another em-bodiment (IB2) in which at least part of stream 204 is used as a feed component for the HT.
3f~1~
In the embodiments where it is the object to achieve the most complete conversion possible of stream (201) into hydrocarbon oil distillates, a so-called "bleed stream" should preferàbly be separated from one of the heavy streams o~ the process. In this way the build-up of undesirable heavy components during the process can be obviated.
Three flow diagrams for the preparation of hydrocarbon oil distillates from asphaltenes-cont~in~ng hydrocarbon mixtures according to the invention will hereinafter be explained in more detail with the aid of Figures III-V.
Flow diagram A (based on embodiment IA5) See Figure III.
The process is carried out in an apparatus comprising, succes-sively a HT zone composed of a unit for catalytic hydrotreatment (306), a unit for atmospheric distillation (307) and a unit for vacuum distillation (308), a DA 70ne (309) and a TC zone composed of a thermal cracking unit (310), a second unit for atmospheric distillation (311) and a second unit for vacuum distillation ~312). An asphaltenes-containing hydrocarbon mixture (301) is 20 mixed with a reci}culation stream (313) and the mixture (314) is subjected together with hydrogen (315) to a catalytic hydrotreat-ment. The hydrotreatment product (316) is separated by atmospheric distillation into a gas fraction (317), an atmospheric distillate (318) and an atmospheric residue (319). The atmospheric residue (319) is separated by vacuum distillation into a vacuum distillate (320) and a varuum residue ~302). The vacuum residue (302) is separated by solvent deasphalting into a deasphalted oil (303) and an asphaltic bitumen (304). The deasphalted oil (303) is mixed with an atmospheric residue (321) and the mixture (322) is sub-30 ~ected to thermal cracking. The asphaltic bitumen (304) is dividedlnto two portions (323) and (324) and portion (324) is mixed with a vacuum residue (305) to form the recirculation stream (313). The thermally cracked product (325) is separat~d by atmospheric dis-tillation into a gas fraction (32S), an atmospheric distillate (327) and an a~mospheric residue (328). The atmospheric residue (328) is divided into two portions (321) and (329) and portion (329) is separated by vacuum distillation into a vacuum dlstillate (330) and a vacuum residue (305).
Flow diagram B (based on embodiment IA~) See Figure IV.
The process is carried out in an apparatus comprising, succes-sively, a HT zone composed of a unit for catalytic hydrotreatment l (40~), a unit for atmospheric distillation (407) and a unit for vacuum distillation (408), a DA zone (409) and a TC zone composed of a thermal cracking unit (410), a second unit for atmospheric distillation (411), a second thermal cracking unit (412), a third unit for atmospheric distillation (.413) and a second unit for vacuum distillation (414). An asphaltenes-cont~in;ng hydrocarbon mixture (401) is mixed with a vacuum residue (415) and the mixture (416) is subjected together with hydrogen (417) to a catalytic hydrotreatment. The hydrotreated product (418) is separated oy atmospheric distillation into a gas fraction (419), an atmospheric distillate (420) and an atmospheric residue (421). The atmospheric residue (421) is separated by vacuum distillation into a vacuum distillate (422) and a vacuum residue (402). The vacuum residue (402) is separated by solvent deasphalting into a deasphalted oil (403) and an asphaltic bitumen (404). The deasphalted oil (403) is mixed with atmospheric residue (4~3) and the mixture ~424) is converted in the second thermal cracking unit into a product (425) which is split up by atmospheric distillation into a gas fraction t426), an atmospheric distillate (427) and an atmospheric residue (428). The atmospheric residue (428) is divided into two portions (423) and (429). The asphaltic bitumen .(404) is converted in the first thermal cracking unit into a product (430) which i5 se-parated by atmospheric distillation into a gas fraction (431) an atmospheric distillate (432) and an atmospheric residue (433~. Gas fractions (426) and (431) are combined to form mixture (434).
Atmospheric distillates (427) and (432) are combined to form mixture (435). Atmospheric residues (429) and (433) are combined to form mixture (436) which is separated by vacuum distillation into a vacuum distillate (437) and a vacuum residue (405). Vacuum residue (405) is divided into two portions (415) and (438).
Flow diagram C (based on embodiment IB2) See Figure V.
The process is carried out in an apparatus comprising, succes-sively, a HT zone composed of a unit for catalytic hydrotreatment l (506), an atmospheric distillation unit (507) and a vacuum distillation unit (508), a TC zone composed of a thermal cracking unit (509), a second atmospheric distillation unit (510), a second thermal cracking unit (511), a third atmospheric distillation unit (512) and a second vacuum distillation unit (513), and a DA zone (514). An asphaltenes-containing hydrocarbon mixture ~501) is mixed with an asphaltic bitumen (515) and the mixture (516) is subjected, together with hydrogen (517) to a catalytic hydrotreat-ment. The hydrotreated product (518) is separated by atmospheric distillation iuto a gas fraction (519), an atmospheric distillate (520) and an atmospheric residue (521). The atmospheric residue (521) is separated by vacuum distillation into a vacuum distillate (522) and a vacuum residue (502). The vacuum residue (502~ is converted by thermal cracking into a product (523) which by atmospheric distillation is separated into a gas fraction (524), 25 an atmospheric distillate (525) and an atmospheric residue (52~).
The atmospheric residue (526) is mixed with an atmospheric residue (527) and the mixture (523) is separated by vacuum distillation into a vacuum distillate (529) and a vacuum residue (505). The vacuum residue (505) is separated by solvent deasphalting into a 30 deasphalted oil (503) and an asphaltic bitumen (504). The de-asphalted oil (503) is mixed with an atmospheric residue (530) and the mixture (531) is subjected to thermal cracking to form a product (532) which by atmospheric distillation is separated into a gas fraction (533), an atmospheric distlllate (534) and an 35 atmospheric residue (535). The atmospheric residue (535) is divided into two portions (527) and (530). Gas fractions (524) and (533) are combined to form mixture (536). Atmospheric distillates (525~ and (534) are combined to form mixture (537). Asphaltic bitumen (504) is divided into two portions (515) and (538).
The present patent application also includes apparatuses for carrying out the process according to the invention substantially corresponding with those schematically represented in ~igures I-V.
The invention is now elucidated with the aid of the following Examples.
The starting mixtures used in the process according to the invention were three asphaltenes-containing hydrocarbon mixtures obtained as residues in the vacuum distillation of atmospheric distillation residues from crude mineral oils from the Middle East. All three vacuum residues boiled substantially above 5~0C;
they had RCT's of 18.8, 14.5 and 17.1% w, respectively. The process was carried out according to flow diagrams A-C. The following conditions were used in th~ various zones:
In all the flow diagrams the unit for catalytic hydrotreat-ment comprised two reactors, thP first of which was filled with a Ni/V/Sio2 cztalyst conta;n~ng 0.5 parts by weight (pbw) of nickel and 2.0 pbw of vAn~ m per 100 pbw of silica, and the second of which was filled with a CofMo/A1203 catalyst containing 4 pbw of cobalt and 12 pbw of molybdenum per lO0 pbw of ~llm;n~. The catalytic hydrotreatment was carried out at a hydrogen pressure of 150 bar, a space velocity, measured for both the 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 all the flow dlagrams the DA treatment was carried out at a pressure of 40 bar using n-butane as solvent.
In all the flow diagrams the TC treatment was carried out in one or two cracking coils at a pressure of 20 har and a space velocity of 0.4 kg fresh feed per litre cracking coil volume per minute.
Further information concerning the conditions under which the DA treatment and the TC treatment were carried out is given in the Table.
TABLE
5 Example 1 2 3 Carried out according to flow diagram A B C
Flow diagram represented in Figure III IV V
DA
Solvent/oil weight ratio 3:1 3:1 2:1 Temperature, C 115 115 118 TC
Number of cracking units 1 2 2 15 Temperature in first cracking unit, C --- 460 490 Temperature in second cracking unit, C 480 490 500 Recirculation ratio in second 20 cracking unit (pbw residue per pbw fresh feed) 2 2 2 The cracking temperatures given were measured at ~he outlet of the cracking coils.
33~
-- 17 ~
Example 1 100 pbw 520C vacuum residue (3Ql) having an RCT of 18.8% w yielded the various streams in the following quan~ities:
130.3 pbw mixture (314) having an RCT of 23.8% w~ a product (316) 5 the C5 fraction of which had an RCT of 10.4% w, 17.1 pbw C5-350C atmospheric distillate (318), 106.0 1~ 350C atmospheric residue (319), 31.7ll 350-520C vacuum distillate (320) 74.3 1l 520C vacuum residue (302) 1053.5 ~ deasphalted oil (303) 20.8 1~ asphaltic bitumen (304) 6.0 " portion (323~, 14.8 1I portion (324) ~
20.0~ C5-350C atmospheric distillate (327), 56.0 " portion (323), 14.8 1~ portion (324) ~
20.0~ C5-350C atmospheric distillate (327), 30.1 ~ 350C atmospheric residue (329) ~
14. 6 " 350-520C vacuum distillate (330), 2015.5 I~ 520C vacuum residue (305) and 30.3 " recirculation stream (313).
Example 2 100 pbw 520C vacuum residue (401) having an RCT of 14.5% w yielded the various streams in the following quantities:
121.2 pbw mixture (416) having an RCT of 19.5% w~ a product (418) the C5 fraction of which had an RCT of 9.1% w, 18.7 pbw C5-350C atmospheric distillate (420) a 96.0 ~ 350C+ atmospheric residue (421), 28.1 ~ 350-520C vacuum distillate (420), 3067.9 ~ 520C vacuum residue (402) 9 46.2 ~I deasphalted oil (403) ~
21.7'1 asphaltic bitumen (404),
Figure II represents various embodiments falling within class IB;
Figure III represents a flow diagram based on embodiment IAS;
Figure IV represents a flow diagram based on embodimen-t IA6; and -lOa-Figure V represents a flow diagram based on embodiment IB2.
The various streams, fractions and ~eaction zones are indica-ted by three digit numbers, the first of which refers to the Figure concerned. Thus, the vacuum residue (302) for lnstance, refers to s-tream 2 as described hereinbefore in the context of Figure 3. According to Figure I the process is carried ou-t in an apparatus comprising a HT zone (106), a DA
zone (107) and a TC zone (108), successively. An asphaltenes-containing hydrocarbon mixture (101) is subjec-ted to a HT and -the hydrotreated product is separated into one or more distillate Eractions (109) and a residual fraction (102). Stream 102 is subjected to a DA treatment and the product is separated into a deasphalted oil (103) and an asphaltic bitumen (104). Stream 103 is subjected to a TC treatment and the cracked product is separated in-to one or more distilla-te fractions (110) and a residual fraction (105). In addition to this embodiment (IAl), in which streams 104 and 105 are not subjected to further pro-cessing, Figure I includes the following seven embodiments:
IA2 The use of at least part of stream 104 as a feed com-ponent for the HT. No further processing of stream 105.
IA3 The use of at least part of stream 104 as a feed com-ponent for the TC treatment. No further treatment of stream 105.
IA4 The use of part of stream 104 as a feed component for the HT and as a feed component for the TC treatment. No further processing of stream 105.
IA5-IA7 Embodiments substantially corresponding with those described under IA2-IA4, respectively, but with at least part of stream 105 being used as a feed component for the HT.
IA8 The use of at l~ast part of stream 105 as a feed com-ponent for t-ne HT. No further processing of stream 104.
]5 The various embodiments falling within class IB are represen-ted s~h- ~ically in Figure II. According to this Figure the process is carried out in an apparatus comprising a HT zone (206), a TC zone (207) and a DA zone (208). An asphaltenes-containing hydrocarbon mixture (201) is subjected to a HT and the hydro treated product is separated into one or more distillate fractions (209) and a residual fraction (202). Stream 202 is sub~ected to a TC treatment and the cracked product is separated into one or more distillate fractions (210) and a residual fraction (205). Stream 205 is subjected to a DA treatment and the product is separated 2S into a deasphalted oil (203) and an asphaltic bitumen ~204).
Stream 203 is used as a feed component for the TC treatment. In addition to this embodiment (IBl), in which stream 20~1 is not subjected to further processing Figure II includes another em-bodiment (IB2) in which at least part of stream 204 is used as a feed component for the HT.
3f~1~
In the embodiments where it is the object to achieve the most complete conversion possible of stream (201) into hydrocarbon oil distillates, a so-called "bleed stream" should preferàbly be separated from one of the heavy streams o~ the process. In this way the build-up of undesirable heavy components during the process can be obviated.
Three flow diagrams for the preparation of hydrocarbon oil distillates from asphaltenes-cont~in~ng hydrocarbon mixtures according to the invention will hereinafter be explained in more detail with the aid of Figures III-V.
Flow diagram A (based on embodiment IA5) See Figure III.
The process is carried out in an apparatus comprising, succes-sively a HT zone composed of a unit for catalytic hydrotreatment (306), a unit for atmospheric distillation (307) and a unit for vacuum distillation (308), a DA 70ne (309) and a TC zone composed of a thermal cracking unit (310), a second unit for atmospheric distillation (311) and a second unit for vacuum distillation ~312). An asphaltenes-containing hydrocarbon mixture (301) is 20 mixed with a reci}culation stream (313) and the mixture (314) is subjected together with hydrogen (315) to a catalytic hydrotreat-ment. The hydrotreatment product (316) is separated by atmospheric distillation into a gas fraction (317), an atmospheric distillate (318) and an atmospheric residue (319). The atmospheric residue (319) is separated by vacuum distillation into a vacuum distillate (320) and a varuum residue ~302). The vacuum residue (302) is separated by solvent deasphalting into a deasphalted oil (303) and an asphaltic bitumen (304). The deasphalted oil (303) is mixed with an atmospheric residue (321) and the mixture (322) is sub-30 ~ected to thermal cracking. The asphaltic bitumen (304) is dividedlnto two portions (323) and (324) and portion (324) is mixed with a vacuum residue (305) to form the recirculation stream (313). The thermally cracked product (325) is separat~d by atmospheric dis-tillation into a gas fraction (32S), an atmospheric distillate (327) and an a~mospheric residue (328). The atmospheric residue (328) is divided into two portions (321) and (329) and portion (329) is separated by vacuum distillation into a vacuum dlstillate (330) and a vacuum residue (305).
Flow diagram B (based on embodiment IA~) See Figure IV.
The process is carried out in an apparatus comprising, succes-sively, a HT zone composed of a unit for catalytic hydrotreatment l (40~), a unit for atmospheric distillation (407) and a unit for vacuum distillation (408), a DA zone (409) and a TC zone composed of a thermal cracking unit (410), a second unit for atmospheric distillation (411), a second thermal cracking unit (412), a third unit for atmospheric distillation (.413) and a second unit for vacuum distillation (414). An asphaltenes-cont~in;ng hydrocarbon mixture (401) is mixed with a vacuum residue (415) and the mixture (416) is subjected together with hydrogen (417) to a catalytic hydrotreatment. The hydrotreated product (418) is separated oy atmospheric distillation into a gas fraction (419), an atmospheric distillate (420) and an atmospheric residue (421). The atmospheric residue (421) is separated by vacuum distillation into a vacuum distillate (422) and a vacuum residue (402). The vacuum residue (402) is separated by solvent deasphalting into a deasphalted oil (403) and an asphaltic bitumen (404). The deasphalted oil (403) is mixed with atmospheric residue (4~3) and the mixture ~424) is converted in the second thermal cracking unit into a product (425) which is split up by atmospheric distillation into a gas fraction t426), an atmospheric distillate (427) and an atmospheric residue (428). The atmospheric residue (428) is divided into two portions (423) and (429). The asphaltic bitumen .(404) is converted in the first thermal cracking unit into a product (430) which i5 se-parated by atmospheric distillation into a gas fraction (431) an atmospheric distillate (432) and an atmospheric residue (433~. Gas fractions (426) and (431) are combined to form mixture (434).
Atmospheric distillates (427) and (432) are combined to form mixture (435). Atmospheric residues (429) and (433) are combined to form mixture (436) which is separated by vacuum distillation into a vacuum distillate (437) and a vacuum residue (405). Vacuum residue (405) is divided into two portions (415) and (438).
Flow diagram C (based on embodiment IB2) See Figure V.
The process is carried out in an apparatus comprising, succes-sively, a HT zone composed of a unit for catalytic hydrotreatment l (506), an atmospheric distillation unit (507) and a vacuum distillation unit (508), a TC zone composed of a thermal cracking unit (509), a second atmospheric distillation unit (510), a second thermal cracking unit (511), a third atmospheric distillation unit (512) and a second vacuum distillation unit (513), and a DA zone (514). An asphaltenes-containing hydrocarbon mixture ~501) is mixed with an asphaltic bitumen (515) and the mixture (516) is subjected, together with hydrogen (517) to a catalytic hydrotreat-ment. The hydrotreated product (518) is separated by atmospheric distillation iuto a gas fraction (519), an atmospheric distillate (520) and an atmospheric residue (521). The atmospheric residue (521) is separated by vacuum distillation into a vacuum distillate (522) and a vacuum residue (502). The vacuum residue (502~ is converted by thermal cracking into a product (523) which by atmospheric distillation is separated into a gas fraction (524), 25 an atmospheric distillate (525) and an atmospheric residue (52~).
The atmospheric residue (526) is mixed with an atmospheric residue (527) and the mixture (523) is separated by vacuum distillation into a vacuum distillate (529) and a vacuum residue (505). The vacuum residue (505) is separated by solvent deasphalting into a 30 deasphalted oil (503) and an asphaltic bitumen (504). The de-asphalted oil (503) is mixed with an atmospheric residue (530) and the mixture (531) is subjected to thermal cracking to form a product (532) which by atmospheric distillation is separated into a gas fraction (533), an atmospheric distlllate (534) and an 35 atmospheric residue (535). The atmospheric residue (535) is divided into two portions (527) and (530). Gas fractions (524) and (533) are combined to form mixture (536). Atmospheric distillates (525~ and (534) are combined to form mixture (537). Asphaltic bitumen (504) is divided into two portions (515) and (538).
The present patent application also includes apparatuses for carrying out the process according to the invention substantially corresponding with those schematically represented in ~igures I-V.
The invention is now elucidated with the aid of the following Examples.
The starting mixtures used in the process according to the invention were three asphaltenes-containing hydrocarbon mixtures obtained as residues in the vacuum distillation of atmospheric distillation residues from crude mineral oils from the Middle East. All three vacuum residues boiled substantially above 5~0C;
they had RCT's of 18.8, 14.5 and 17.1% w, respectively. The process was carried out according to flow diagrams A-C. The following conditions were used in th~ various zones:
In all the flow diagrams the unit for catalytic hydrotreat-ment comprised two reactors, thP first of which was filled with a Ni/V/Sio2 cztalyst conta;n~ng 0.5 parts by weight (pbw) of nickel and 2.0 pbw of vAn~ m per 100 pbw of silica, and the second of which was filled with a CofMo/A1203 catalyst containing 4 pbw of cobalt and 12 pbw of molybdenum per lO0 pbw of ~llm;n~. The catalytic hydrotreatment was carried out at a hydrogen pressure of 150 bar, a space velocity, measured for both the 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 all the flow dlagrams the DA treatment was carried out at a pressure of 40 bar using n-butane as solvent.
In all the flow diagrams the TC treatment was carried out in one or two cracking coils at a pressure of 20 har and a space velocity of 0.4 kg fresh feed per litre cracking coil volume per minute.
Further information concerning the conditions under which the DA treatment and the TC treatment were carried out is given in the Table.
TABLE
5 Example 1 2 3 Carried out according to flow diagram A B C
Flow diagram represented in Figure III IV V
DA
Solvent/oil weight ratio 3:1 3:1 2:1 Temperature, C 115 115 118 TC
Number of cracking units 1 2 2 15 Temperature in first cracking unit, C --- 460 490 Temperature in second cracking unit, C 480 490 500 Recirculation ratio in second 20 cracking unit (pbw residue per pbw fresh feed) 2 2 2 The cracking temperatures given were measured at ~he outlet of the cracking coils.
33~
-- 17 ~
Example 1 100 pbw 520C vacuum residue (3Ql) having an RCT of 18.8% w yielded the various streams in the following quan~ities:
130.3 pbw mixture (314) having an RCT of 23.8% w~ a product (316) 5 the C5 fraction of which had an RCT of 10.4% w, 17.1 pbw C5-350C atmospheric distillate (318), 106.0 1~ 350C atmospheric residue (319), 31.7ll 350-520C vacuum distillate (320) 74.3 1l 520C vacuum residue (302) 1053.5 ~ deasphalted oil (303) 20.8 1~ asphaltic bitumen (304) 6.0 " portion (323~, 14.8 1I portion (324) ~
20.0~ C5-350C atmospheric distillate (327), 56.0 " portion (323), 14.8 1~ portion (324) ~
20.0~ C5-350C atmospheric distillate (327), 30.1 ~ 350C atmospheric residue (329) ~
14. 6 " 350-520C vacuum distillate (330), 2015.5 I~ 520C vacuum residue (305) and 30.3 " recirculation stream (313).
Example 2 100 pbw 520C vacuum residue (401) having an RCT of 14.5% w yielded the various streams in the following quantities:
121.2 pbw mixture (416) having an RCT of 19.5% w~ a product (418) the C5 fraction of which had an RCT of 9.1% w, 18.7 pbw C5-350C atmospheric distillate (420) a 96.0 ~ 350C+ atmospheric residue (421), 28.1 ~ 350-520C vacuum distillate (420), 3067.9 ~ 520C vacuum residue (402) 9 46.2 ~I deasphalted oil (403) ~
21.7'1 asphaltic bitumen (404),
3~
20.2 pbw C5-350C atmospheric distillate (435), 44.3 " 350C atmospheric residue (436), 14.6 " 350-520C vacuum distillate (437), 29.7 " 520C vacuum residue (405), 5 8.5 " portion (438) and 21.2 " portion (415).
Example 3 100 pbw 520C vacuum residue (501) having an RCT of 17.1% w yielded the various streams in the following quantities:
lO 125.3 pbw mixture (516) having an RCT of 21.8% w, a product (5l8), the C5 fraction of which had an RCT of 9.8% w, 18.9 pbw C5-350C atmospheric distillate (520), 99.8 " 350C atmospheric residue (521), 28.4 " 350-520C vacuum distillate (522), 71.4 " 520C vacuum residue (502), 75.2 " 350C atmospheric residue (528), 14.7 " 350-520C vacuum distillate (529), 60.5 " 520C vacuum residue (505), 25.2 " deasphalted oil (503), 20 35.3 " asphaltic bitumen (504), 18.7 " C5-350~C atmospheric distillate (537), 25.3 " portion (515) and 10.0 " portion (538).
20.2 pbw C5-350C atmospheric distillate (435), 44.3 " 350C atmospheric residue (436), 14.6 " 350-520C vacuum distillate (437), 29.7 " 520C vacuum residue (405), 5 8.5 " portion (438) and 21.2 " portion (415).
Example 3 100 pbw 520C vacuum residue (501) having an RCT of 17.1% w yielded the various streams in the following quantities:
lO 125.3 pbw mixture (516) having an RCT of 21.8% w, a product (5l8), the C5 fraction of which had an RCT of 9.8% w, 18.9 pbw C5-350C atmospheric distillate (520), 99.8 " 350C atmospheric residue (521), 28.4 " 350-520C vacuum distillate (522), 71.4 " 520C vacuum residue (502), 75.2 " 350C atmospheric residue (528), 14.7 " 350-520C vacuum distillate (529), 60.5 " 520C vacuum residue (505), 25.2 " deasphalted oil (503), 20 35.3 " asphaltic bitumen (504), 18.7 " C5-350~C atmospheric distillate (537), 25.3 " portion (515) and 10.0 " portion (538).
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of hydrocarbon oil distillates from asphaltenes-containing hydrocarbon mixtures, characterized in that an asphaltenes-containing hydrocarbon mixture (stream 1) is subjected to 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, that stream 2 is subjected to a combination of the following two treatments: solvent deasphalting (DA) in which an asphaltenes-containing feed is converted into a product from which a deasphalted oil fraction (stream 3) and an asphaltic bitumen fraction (stream 4) are separated and thermal cracking (TC) in which one feed or two individual feeds are 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 5) are separated, that stream 3 is used as the feed or as a feed component for the TC treatment and that stream 2 is used either as a feed component for the TC treatment with stream 5 being used as the feed for the DA treatment, or as the feed for the DA treatment.
2. A process as claimed in claim 1, characterized in that stream 2 is used as the feed for the DA treatment and that at least part of stream 4 is used as a feed component for the HT
and/or as a feed component for the TC treatment and/or at least part of stream 5 is used as a feed component for the HT.
and/or as a feed component for the TC treatment and/or at least part of stream 5 is used as a feed component for the HT.
3. A process as claimed in claim 1, characterized in that stream 2 is used as a feed component for the TC treatment and that at least part of stream 4 is used as a feed component for the HT.
4. A process as claimed in claim 1, characterized in that the stream 1 used is a hydrocarbon mixture which boils sub-stantially 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 distillation of an atmospheric distillation residue from the crude mineral oil.
5. A process as claimed in claim 1, characterized in that one or more vacuum distillates separated from one or more of streams 1, 2 and 5 are used together with stream 3 as feed components for the TC treatment.
6. A process as claimed in claim 1, characterized in that in the HT for the reduction of the asphaltenes content of the feed a catalyst is used which comprises 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 on a carrier, which carrier consists more than 40% w of alumina.
7. A process as claimed in claim 1 or 6, 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.hour-1 and a H2/feed ratio of from 500-2000 N1.kg-1.
8. A process as claimed in claim 1 or 6, characterized in that the HT is carried out in such a manner that a product is obtained whose C5 + fraction 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 percentages by weight of hydro-carbons 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 percentages by weight of hydro-carbons boiling below 350°C present in the C5 + fraction and in the feed is at most 40.
9. 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.
10. A process as claimed in claim 1, characterized in that if the feed for the TC treatment is composed both of stream 3, if desired together with one or more vacuum distillates separated during the process, and of stream 2 or at least part of stream 4, a TC treatment is carried out which comprises two cracking units and that the two types of feed are cracked se-parately.
11. A process as claimed in claim 1, characterized in that in the TC of stream 3 a heavy fraction of the cracked product is recirculated to the cracking unit in which the cracking of stream 3 is carried out.
12. 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 of cracking reactor volume per minute.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8105560A NL8105560A (en) | 1981-12-10 | 1981-12-10 | PROCESS FOR PREPARING HYDROCARBON OIL DISTILLATES |
| NL8105560 | 1981-12-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1198388A true CA1198388A (en) | 1985-12-24 |
Family
ID=19838516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416276A Expired CA1198388A (en) | 1981-12-10 | 1982-11-24 | Process for the production of hydrocarbon oil distillates |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0082551B1 (en) |
| JP (1) | JPS58108295A (en) |
| AR (1) | AR247915A1 (en) |
| AU (1) | AU553542B2 (en) |
| CA (1) | CA1198388A (en) |
| DE (1) | DE3269261D1 (en) |
| ES (1) | ES517987A0 (en) |
| MX (1) | MX162957B (en) |
| NL (1) | NL8105560A (en) |
| SU (1) | SU1306479A3 (en) |
| ZA (1) | ZA829036B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8201233A (en) * | 1982-03-24 | 1983-10-17 | Shell Int Research | PROCESS FOR THE PREPARATION OF LOW ASPHALTENE HYDROCARBON MIXTURE. |
| CA2117571A1 (en) * | 1993-08-30 | 1995-03-01 | Junichi Kubo | Process for hydrotreating heavy hydrocarbon oil |
| FR2906812A1 (en) * | 2006-10-06 | 2008-04-11 | Inst Francais Du Petrole | Heavy oil feedstock e.g. atmospheric residue, converting method for producing e.g. petrol, involves distilling effluent to separate residue, and recycling part of residue during de-asphalting of feedstock by mixing part with feedstock |
| US20140221713A1 (en) * | 2013-02-04 | 2014-08-07 | Lummus Technology Inc. | Residue hydrocracking processing |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549517A (en) * | 1968-07-23 | 1970-12-22 | Hydrocarbon Research Inc | High conversion level hydrogenation of residuum |
| US3730875A (en) * | 1971-02-16 | 1973-05-01 | Universal Oil Prod Co | Combination process for black oil conversion |
| US3723297A (en) * | 1971-10-18 | 1973-03-27 | Universal Oil Prod Co | Conversion of asphaltene-containing charge stocks |
| NL7612960A (en) * | 1976-11-22 | 1978-05-24 | Shell Int Research | METHOD FOR CONVERTING HYDROCARBONS. |
| JPS541306A (en) * | 1977-06-07 | 1979-01-08 | Chiyoda Chem Eng & Constr Co Ltd | Hydrogenation of heavy hydrocarbon oil |
| GB2031011B (en) * | 1978-10-05 | 1983-01-06 | Chiyoda Chem Eng Construct Co | Processing heavy hydrocarbon oils |
-
1981
- 1981-12-10 NL NL8105560A patent/NL8105560A/en not_active Application Discontinuation
-
1982
- 1982-11-24 CA CA000416276A patent/CA1198388A/en not_active Expired
- 1982-12-07 ES ES517987A patent/ES517987A0/en active Granted
- 1982-12-07 DE DE8282201560T patent/DE3269261D1/en not_active Expired
- 1982-12-07 AR AR82291521A patent/AR247915A1/en active
- 1982-12-07 EP EP82201560A patent/EP0082551B1/en not_active Expired
- 1982-12-08 JP JP57216237A patent/JPS58108295A/en active Granted
- 1982-12-08 SU SU823520472A patent/SU1306479A3/en active
- 1982-12-08 AU AU91333/82A patent/AU553542B2/en not_active Ceased
- 1982-12-08 MX MX195508A patent/MX162957B/en unknown
- 1982-12-08 ZA ZA829036A patent/ZA829036B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES8308585A1 (en) | 1983-09-01 |
| EP0082551A1 (en) | 1983-06-29 |
| DE3269261D1 (en) | 1986-03-27 |
| EP0082551B1 (en) | 1986-02-19 |
| JPH0581636B2 (en) | 1993-11-15 |
| ES517987A0 (en) | 1983-09-01 |
| SU1306479A3 (en) | 1987-04-23 |
| ZA829036B (en) | 1984-05-30 |
| AU9133382A (en) | 1983-06-16 |
| AU553542B2 (en) | 1986-07-17 |
| AR247915A1 (en) | 1995-04-28 |
| JPS58108295A (en) | 1983-06-28 |
| MX162957B (en) | 1991-07-22 |
| NL8105560A (en) | 1983-07-01 |
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