CA1297064C - Converting a stream containing heavy hydrocarbons into a stream containing hydrocarbons having a lower boiling range - Google Patents
Converting a stream containing heavy hydrocarbons into a stream containing hydrocarbons having a lower boiling rangeInfo
- Publication number
- CA1297064C CA1297064C CA000547709A CA547709A CA1297064C CA 1297064 C CA1297064 C CA 1297064C CA 000547709 A CA000547709 A CA 000547709A CA 547709 A CA547709 A CA 547709A CA 1297064 C CA1297064 C CA 1297064C
- Authority
- CA
- Canada
- Prior art keywords
- stream
- reactor
- hydrocarbons
- boiling range
- liquid
- 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 - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
Abstract
A B S T R A C T
CONVERTING A STREAM CONTAINING HEAVY HYDROCARBONS
INTO A STREAM CONTAINING HYDROCARBONS
HAVING A LOWER BOILING RANGE
Process for converting a stream containing heavy hydrocarbons comprising the steps of a) passing through a first conversion reactor (1) containing a conversion catalyst in the presence of hydrogen the stream at a temperature between 325 and 600 °C, a pressure between 1 and 30 MPa and at an hourly space velocity between 0.05 and 5 kg/1/hour to produce a primary converted stream;
b) passing the primary converted stream to a first gas/liquid separator (4) and removing from the first gas/liquid separator (4) a gaseous stream and a liquid stream:
c) passing the gaseous stream to a second conversion reactor (7); and d) passing through the second conversion reactor (7) containing a conversion catalyst in the presence of hydrogen the gaseous stream at a temperature between 325 and 600 °C, a pressure between 1 and 30 MPa and at an hourly space velocity between 0.1 and 10 kg/1/hour to produce a further converted stream having a lower boiling range.
(Figure 1) hsbff:k9773ff.txt
CONVERTING A STREAM CONTAINING HEAVY HYDROCARBONS
INTO A STREAM CONTAINING HYDROCARBONS
HAVING A LOWER BOILING RANGE
Process for converting a stream containing heavy hydrocarbons comprising the steps of a) passing through a first conversion reactor (1) containing a conversion catalyst in the presence of hydrogen the stream at a temperature between 325 and 600 °C, a pressure between 1 and 30 MPa and at an hourly space velocity between 0.05 and 5 kg/1/hour to produce a primary converted stream;
b) passing the primary converted stream to a first gas/liquid separator (4) and removing from the first gas/liquid separator (4) a gaseous stream and a liquid stream:
c) passing the gaseous stream to a second conversion reactor (7); and d) passing through the second conversion reactor (7) containing a conversion catalyst in the presence of hydrogen the gaseous stream at a temperature between 325 and 600 °C, a pressure between 1 and 30 MPa and at an hourly space velocity between 0.1 and 10 kg/1/hour to produce a further converted stream having a lower boiling range.
(Figure 1) hsbff:k9773ff.txt
Description
Hsb/Sb CONVERTING A STREAM CONTAINING HEAVY HYDRVCARBONS
INTO A STREAM CONTAINING HYDROCARBONS
HAVING A LOWER BOILING RANGE
The present invention relates to a process for converting a stream containing heavy hydrocarbons having a high boiling range into a stream containing hydrocarbons having a lower boiling range.
It is an object of the present invention to provide a process for converting in a first stage a substantially liquid stream and in a second stage a : substantially gaseous stream.
To this end the process for converting a stream containing heavy hydrocarbons having a high boiling ; range into a stream containing hydrocarbons having a lower boiling range according to the invPntion comprises the steps of ~ a) passing through a first conversion zone :~ 15 containing a conversion catalyst in the presence of - hydrogen the stream containing heavy hydrocarbons :~ having a high boiling range at a temperature between 325 and 600 C, a pressure between l and 30 MPa and at an hourly space veIccity between 0.05 and 5 kg~l/hour to produce a primary converted stream;
~ : b) passing the primary converted stream ~o a first :: separation zone and removing from the first separation zone a gaseous stream and a liquid stream;
:~ c) passing at least a part of the gaseous stream to a second conversion zone; and :
d) passing through the second conversion one containing a conversion catalyst in the presence of hydrogen the gaseous stream at a temperature between 325 and 600 oc, a pressure between l and 30 MPa and at . .. ..
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an hourly space velocity between 0.1 and 10.0 kg/l/hour to produce a further converted stream having a lower boiling range.
An advantage o~ the process according to the invention is that no fractional distillation is carried out between the first conversion zone and the second conversion zone. A further advantage i5 that the gaseous stream is maintained at a high pressure and at a high temperature.
Known is a process for hydrotreating pyrolysis gasoline, which is a hydrocarbon-containing stream having a boiling range between 180 and 205 C, comprising treating the stream in a ~irst reactor at a temperature between 80 and 130 C and a pxessure o~
about 6 MPa, separating the effluent from the first reactor into a gaseous stream and a liquid stream of which a part is returned to the first reactor, treating the gaseous stream and the remaining part of the liquid stream combined in a second reactor at a temperature between 230 and 280 C and a pressure between 4.5 and 6.5 MPa, and separating the e~fluent from the second reactor into a gaseous stream which is recycled to the second reactor and a liquid product stream.
; In the specification and in the claims the expression "heavy hydrocarbons having a high boiling range" is used to refer to hydrocarbons containing more than 70% by weight of hydrocarbons having a boiling range above 370 C. These hydrocarbons ~urther may con~ain sulphur~ for example between 0.05 and 8~ by weight, and heavy metals such as vanadium, for example between 0.5 and 2 000 ppm (parts per million). The ~` expression "hydrocarbons having a lower boiling range"
is used to refer to hydrocarbons which are liquid at normal conditions containing more than 40% by weight hydrocarbons having a boiling range below 370 C.
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In the speci~ication and in the claims the hourly space velocity is expressed as kg hydrocarbon-containing stream per liter of catalyst per hour (kg/l/hour).
The first conversion zone contains a ~irst conversion catalyst suitable l`or hydrocarbon conversion, for removal of asphaltenes, for producing hydrocarbons having a decreased amount of carbon residue left after evaporation and pyrolysis, and/or for demetallization. Examples of suitable catalysts are catalysts comprising an inorganic oxidic carrier, for example silica and/or alumina, containing one or more compounds of nickel, vanadium, molybdenum and tungsten.
The second conversion zone contains a second conversion catalyst suitable for desulphurization, hydrogenation and/or denitrogenation of a gaseous hydrocarbon stream. Examples of suitable catalysts are catalysts comprising an inorganic oxidic carrier, for example alumina and/or silica, containing either nickel and/or cobalt, or molybdenum and~or tungsten.
Heavy metals from the hydrocarbons having a high boiling range are deposited on the catalyst in the first conversion zone. Furthermore, in the separation zone heavy highly aromatic molecules, which are still present in the product from the first conversion zone, are separated from the gaseous stream. Therefore a stream substantially free of heavy metal~ and of heavy aromatic molecules is contacted with ths catalyst in the second conversion zone. This has a beneficial effect on the life of the catalyst in the second conversion zone.
The invention will now be described by way of example in more detail with reference to the drawings, wherein Figure 1 shows schematically a first embodiment of the invention:
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Figure 2 shows schematically a second embodiment o~ the invention;
Figure 3 shows schematically a third embodiment of the invention; and Figure 4 shows schematically a fourth embodiment of the invention.
Re~erence is made to Figure 1 showing an apparatus ~or carrying out the process according to the invention. The apparatus comprises a ~irst conversion zone in the ~orm of first reactor 1, a ~irst separation zone in the form of ~irst gas/liquid separator 4 and a second conversion zone in the form o~ second reactor 7.
To the first reactor 1 a hydrogen supply conduit 8 and a feed supply conduit 9 are connected. The first gas/liquid separator 4 is connected to the first reactor 1 by means of conduit 10. The upper zone of the first gas/liquid separator 4 is connPcted to the second reactor 7 by means of conduit 12, and a li~uid conduit 15 is connected to the lowar zone of the ~irst gas/liquid separator 4. To the second reactor 7 a second hydrogen supply conduit 17 is connected, and to the upper end of the second reactor 7 : an effluent removal conduit 18 is connected.
During normal operationt a preheated, ~ubstantially liquid stream containing hea~y hydrocarbons having a high boiling range is supplied to the first reactor 1 through the feed supply conduit 9, and hydrogen is supplied to the first reactor 1 through the hydrogen supply conduit 8. The temperature of the hydrocarbon-containing stream is between 325 and 600 C and suitably between 350 and 500 C, the pressure between 1 and 30 MPa and suitably between 2 and 25 MPa, and the rate at which the hydrocarbon-containing stream i~
supplied is selected such that in the first reactor 1 the hourly space velocity is between 0.05 and 5 .
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kg/1/hour and suitably between 0.1 and 2.5 kg/l/hour.
The amount of hydrogen is suitab]y between 250 and 2 ooO Nm3 per 1 000 kg hydrocarbon-containing stream. A
primary converted stream is removed from the first reactor 1 and is passed via conduit 10 to the first gas/liquid separator 4. From the first gas/liquid separator 4 a gaseous stream and a liquid stream are removed. Since the gas/liquid separation is carried out substantially at the same pr~ssures and temperatures as the conversions in the ~irst reactor and second reactor the gaseous stream, which contains hydrogen, is passed to the second reactor without substantially heating and/or pressurizing.
The gaseous stream is supp]ied via conduit 12 to the second reactor 7 at a temperature between 325 and 600 C and suitably between 350 and 500 C, a pressure between 1 and 30 MPa and suitably between 2 and 25 MPa.
The amount of catalyst in the second reactor 7 is such that at the rate at which the hydrocarbon~containing stream is supplied the hourly space velocity is between 0.1 and 10.0 kg/l/hour and suitably between 0.25 and 5.0 kg/l/hour. In addition hydrogen can be supplied to the second reactor 7, the amount of hydrogen being suitably up to 2 000 Nm3 per kg hydrocarbon-containing stream. A further converted stream containing hydro-carbons having a lower boiling range is withdrawn from the second reactor 7 through effluent removal conduit 18.
To control the pressurs in the first gas/li~uid separator 4 and in the second reactor 7, the conduits 10 and/or 12 may be provided with pressure control means (not shown)O
A liquid hydrocarbon-containing stream containing 93.5% by weight of hydrocarbons having a boiling range above 370 C`, 4~7~ by weight sulphur, and 84 ppm ' ,~ ' ~ ' ,~ .
vanadium is supplied to the first reactor l at an hourly space velocity of l kg/l/hour, a temperature of 440 oc and a pressure of 15 MPa. Hydrogen is supplied to the first reactor l at a rate of l 000 Nm3/l 000 kg S of liquid hydrocarbon-contain:ing stream. The ~irst reactor l is filled with a ca1:alyst comprising a silica-containing carrier and compounds of nickel and vanadium. The primary converted stream produced in the ~irst reactor 1 is passed to t:he first gas/liquid separator 4 and from the first: gas/liquid separator 4 a gaseous stream and a liquid st:ream are removed.
The liquid stream is removed from the first gas/liquid separator 4 through liquid conduit 15, and the amount of the liquid stream is 39% by weight of the liquid hydrocarbon-containing stream supplied to the first reactor. The liguid stream contains 53.47% by weight of hydrocarbons having a boiling range between 370 and 520 C and 46.53% by weight o~ hydrocarbons having a boiling range above 520 oc, and contains further 3.2%
by weight of sulphur and 4 ppm vanadium.
The gaseous stream removed from the first gas/liquid separator 4 through conduit 12 comprises hydrocarbons and hydrogen, the hydrocarbon content of this stream is 6~% by weight of the liquid hydrocarbon-containing stream supplied to the first reactor lo The hydrocarbon part o~ the gaseous stream comprises 83% by weight hydrocarbons having a boiling range below 370 C
and 0.8% by weight sulphur.
This gaseous stream is suppIied to the second reactor 7 at a temperature of 410 C and a pressure of 13 MPa. ~o extra hydrogen is supplied to the second reactor 7. The second reactor 7 is filled with a catalyst comprising an alumina-containing carrier and compounds of nickel and molybdenum. The volume of the reactor filled with catalyst is such that at the rate s ,.. ... . . .
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at which the stream to be treated is supplied the hourly space velocity is 0.5 kg/l/hour.
The further converted stream produced in the second reactor 7 contains hydrocarbons, hydrogen and gaseous contaminants such as H2S and NH3. The hydro-carbon content of the further converted stream e~lals 61% by weight of the licluid hydrocarbon-containing stream supplied to the first reactor 1, and it comprises 9.64~ by weight of hydrocarbons having l to 4 carbon atoms, 32.7B% by weight of hydrocarbons having more than 5 carbon atoms and a boiling range below 250 C, 49.61% by weight of hydrocarbons ha~ing a boiling range between 250 and 370 C, 7.98% by weight of hydrocarbons having a boiling range between 370 and 520 C, and 0.014% by weight o~ sulphur. It will be appreciated that hydrogen sulphide and hydrogen can be removed from the further converted stream in a conventional manner which is not described here, and that the separated hydrogen can be compressed and reused in the first or second conversion zone.
In the embodiment of the invention shown in Figure 2 liquid conduit 15 is connected by means of conduit 20 to the feed supply conduit 9. The parts of the apparatus shown in Figura 2 which are similar to the parts shown in Figure 1 have the same referenc~
numerals. This embodiment allows passing to the first reactor l a part of or substantially all lic~id separated from the primary converted stream tQ the first r~actor 1, so that the liquid stream can be further converted with the catalyst in the first reactor 1.
The hydrocarbon-containing stream of Example 1 is supplied uncler the same conditions to the first reactor 1 together with a recycle stream to be described hereinafter.
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The amount of liquid stream removed ~rom the first gas/liquid separator 4 is 106~ by weight of the liquid hydrocarbon-containing stream supplied to the first reactor 1. The liquid stream contains 61.03~ by weight of hydrocarbons having a boiling range between 370 and 520 C and 38.97~ by weight of hydrocarbons ha~ing a boiling range above 520 C, and contains further 2% by weight of sulphur and 2 ppm vanadium. From the liquid removed from the first gas/lic~id separator 4 an amount equal to ~0% by weight of the liquid hydrocarbon-containing stream supplied to the first reactor 1 is passed as the recycle stream to the first reactor 1 through conduit 20.
The amount of liquid stream removed from liquid conduit 15 downstream to the point where conduit Z0 is connected to conduit 15 is 46% by weight of the hydrocarbon-containing stream supplied to the first reactor 1, and this stream is removed as a bottom product.
The gaseous stream removed fxom the gas/liquid separator 4 through conduit 12 contains hydrocarbons and hydrogen, the hydrocarbon cont~nt of the gaseous stream is 54% by weight of the hydrocarbon-containing stream supplied to the first reactor 1. The hydrocarbon part of the gaseous stream comprises 73% by weight of hydrocarbons having a boiling range below 370 C and 0.9~ by weight sulphur. This gaseous stream is supplied to the second reactor 7 at a temperature of 410 C and a pressure of 13 MPa. No extra hydrogen is supplied to the second reactor 7. The second reactor 7 is filled with the same catalyst as in Example l. The volume of the reactor filled with catalyst is such that at the rate at which the stream ~o be treated is upplied the hourly space velocity is 0.5 kg/l/hour.
The further converted stream produced in the second reactor 7 contains hydrocarbons, hydrogen and -~ 9 -contaminants such as H2S and NH3. The hydrocarbon part of the further converted stream comprises 7.33~ by weight of hydrocarbons having 1 to 4 carbon atoms, 28.86% by weight of hydrocarbons having more than 5 carbon atoms and a boiling range below 250 C, 50.73 by weight of hydrocarbons having a boiling range between 250 and 370 C, and 13.08% by weight of hydrocarbons having a boiling range between 370 and 520 C and 0.021% by weight of sulphur. The amount of hydrocarbons in the range C1-C~ in the ~urther converted stream per unit of converted heavy hydrocarbon is less than in the further converted stream produced in h'xample l.
For some kinds of heavy hydrocarbons to be converted it would be more profitable to increase the upper limit of the boiling range of the gaseous skream supplied to the second reactor in order to improve the overall conversion of the hydrocarbons having a boiling range above 370 C.
To increase the upper limit of the boiling range of the gaseous stream liquid outlet 15 is connected to a second separation zone in the ~orm of second gas/-liquid separator 24 (see Figure 3). The gaseous hydrocarbons are removed from the second gas/liquid separator 24 and passed through conduit 25 to conduit 12 and into the second conversion reactor 7.
The liquid hydrocarbons are removed from the second gas/liquid separator 24 through conduit 26. If required a part of the liquid hydrocarbons may be added through conduit 27 to the stream containing heavy hydrocarbons having a high boiling range before this stream i.s passed through the first reactor 1.
A hydrocarbon-containing stream containing 90.5%
by weight o~ hydrocarbons having a boiling range above 370 C, 4.7% by weight sulphur, and 84 ppm vanadium is supplied to the first reactor 1 at an hourly space velocity of 1 kg/l/hour, a temperature of 440C and a pressure of 15 MPa, together with a recycle stream to be described hereinafter. Hydrogen is supplied to the first reactor 1 at a rate of 1 000 Nm3/1 000 kg of hydrocarbon-containing stream. The first reactor 1 is filled with a catalyst comprising a silica-containing carrier and compounds of nickel and vanadium. The primary converted stream produced in the first reactor 1 is passed to the first gas/liquid separator 4 and from the first separation zonle a gaseous stream and a liquid stream are removed.
The liquid stream is removed from the gas/liquid separator 4 through liquid conduit 15. The amount of this liquid stream is 77% by weight of the hydrocarbon-containing stream supplied to the first reactor 1, and the liquid stream does not contain hydrocarbons having a boiling range below 410 C, and contains 1.9~ by weight of sulphur and 4 ppm vanadium. The liquid stream is supplied to the second gas/liquid separator 24. In the second gas/liquid separator 24, operating at a pressure of 30 mm Hg, the stream is separated into a gaseous stream, corresponding to 28.4 % by weight of the hydrocarbon-containing stream supplied to the first reactor ~, and a liquid stream. The gaseous stream is supplied to the second reactor 7. The liquid stream contains 4.03% by weight of hydrocarbons having a boiling range between 370 and 520 C and 95.97% by weight of hydrocarbons having a boiling range above 520 CO A fraction of the liquid stream, corresponding to 30 % by weight of the hydrocarbon-containing stream supplied, is supplied as the recycle stream to the `~ first reactor 1 through conduit 27 to the first reactor 1, and the remaining part of the liquid stream, correspondin~ to 19 % by weight of the hydrocarbon-containing stream supplied to the flrst reactor 1, is , removed through conduit 26 downstream conduit 27 as a bottom product.
The gaseous stream removed from the gas/liquid separator 4 through conduit 12 contains hydrocarbons and hydrogen, the hydrocarbon content of the gaseous stream is 54~ by weight of the hydrocarbon-containing stream supplied to the first :reactor 1. The hydrocarbon part of the gaseous stream comprises 73% by weight o~
hydrocarbons having a boiling range below 370 C and 0.9% ~y weight of sulphur. Th.i~ gaseous stream is supplied to the second reactor 7.
The gaseous streams from the separators 4 and 24 are supplied to the second reactor 7 at a temperature o~ 410 oc and a pressure of 13 MPa. The total amount of the gaseous streams is 81% by weight o~ the hydro-carbon-containing stream supplied to the first reactor 1. No extra hydrogen is supplied to the second reactor 7. The second reactor 7 is Pilled with a catalyst comprising an alumina cont ining carrier and compounds of nickel and molybdenum. The volume of the reactor ~illed with catalyst is such that at the rate ak which the streams to be treated are supplied the hourly space velocity is 0.5 kg/l/hour.
The hydrocarbon content o~ the further converted : 25 stream produced in the second reactor 7 is 81% by weight o~ the hydrocarbon-containing stream supplied to the first reactor 1, and the further converted stream comprises 5.75% by weight of hydrocarbons having 1 to 4 carbon atoms, 25.90% by weight of hydrocarbons having more than 5 carbon atoms and a boiling range below 250 C, 42.34% by weight of hydrocarbons having a boiling range between 250 and 370 C, 25.74% by weight of hydrocarbons having a boiling range between 370 and 520 C, 0.26% by weight of hydrocarbons having a boiling range above 520 DC, and 0.032% by weight o~ sulphur~
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Reference is now ~ade to Figure 4, showing an embodimant of the invention wherein the liquid stream removed from the first gas/liquid separator 4 is passed through conduit 15 for further conversion to a third conversion zone in the form of third reactor 30. In the third reactor 30 the liquid stream is contacted in the presence of hydrogen with a conversion catalyst of the kind which is present in the second reactor 7 to produce a secondary converted stream.
This conversion catalyst is suitable for desulphurization, hydrogenation and/or denitrogenation o~ a gaseous hydrocarbon stream. Examples of suitable catalysts are catalysts comprising a carrier containing alumina or silica and alumina, and either nickel and/or cobalt, or molybdenum and/or tungsten.
The temperature of the liquid stream is between 325 and 600 C and suitably between 350 and 500 C, the ; pressure in the third reactor 30 is between 1 and 30 MPa and suitably between 2 and 25 MPa, and the volume o~ catalyst in the third reactor 30 i~ such that at the rate at which the liquid stream is supplied the hourly space velocity in the third reactor 30 is between 0.05 and 10 kg/l/hour and suitably between Ool and 5 kg/l/hour.
~ 25 If required hydrogen can be supplied to the third ; reactor through hydro~en supply conduit 31. The secondary converted stream is removed ~rom the third reactor 30 through outlet conduit 32.
To remove the gaseous components from the secondary converted stream this stream can be passed directly to the first gas/liquid separator (not shown), or the secondary converted stream can be passed to a third sep~ration zone in the form of third gas/liquid separator 35.
From the third gasJliquid separator 35 a gaseous straam is passed through conduit 36 to the second ..
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reactor 7. A liquid stream is removed from the third gas/liquid separator 35 through conduit 37. Xf required a part or all of the liquid stream can be passed through conduit 3g to the first reactor 1.
The hydrocarbon-containing stream of Example 1 is supplied under the same conditions to the first reactor 1 together with a recycle stream as hereinafter described.
The gaseous stream removed fxom the gas/liquid separator 4 through conduit 12 contains hydrocarbons and hydrogen, and the hydrocarbon content of the gaseous stream is 54% by weight of the hydrocarbon-containing stream supplied to the first reactor 1. The hydrocarbon part of the gaseous stream comprises 73% by : weight of hydrocarbons having a boiling range below 370 C, 0.9% by weight of sulphur. This gaseous stream is supplied to the second reactor 7 at a temperature o~
410 C and a pressure of 13 MPa.
The liquid stream is removed from liguid conduit 15. The amount of the liquid stream is 76% by weight of the hydrocarbon-containing stream supplied to the first reactor 1, and comprises 63% by weight having a boiling range above 52~ C and does not contain hydrocarbons 25 having a boiling range below 410 C, and 1.9% by weight of sulphur.
The liquid stream is passed to the third reactor ~ 30 which is filled with a catalyst comprising an : alumina-containing carxier and compounds of nickel and molybdenum. The volume of the reactor filled with catalyst is such that at the rate at which the stream to be treated i5 supplied the hourly space velocity is 2.7 kg/l/hour. The secondary converted stream produced in the third reactor 30 comprises 97~ by weight of hydrocarbons having a boiling range above 370 C and 58% by weight of hydrocarbons having a boiling range `:
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above 520 ~C, and 0.4% by weight of sulphur. This stream is passed through conduit 32 to the third gas/liquid separator 35, operating at 30 mm Hg.
The amount of liquid stream obtained in the third gas/liquid separator 35 is 45% by weight of the hydrocarbon-containing stream supplied to khe first reactor 1. The liquid stream contains 3.97% by weight of hydrocarbons having a boiling range between 370 and 520 C and 96.03% by weight O:e hydrocarbons having a boiling range above 520 C. A part of the liquid stream, corresponding to 15~ by weight of the hydrocarbon-containing stream as supplied to the first reactor 1, is removed through conduit 37 as a bottom product.
The remaining part of the liquid stream is passed through conduit 38 ~s the recycle stream to the first reactor 1, the amount of this stream is 30% by weight of the hydrocarbon-containing stream supplied to the first reactor 1.
The amount of the gaseous stream obtained in the third gas/liquid separator 35 equals 31% by weight of the hydrocarbon-containing stream supplied to the first reactor 1. The gaseous stream is passed through conduit 36 to the second reactor 7, where it is converted together with the gaseous stream from the first gas/liquid separator 4. No extra hydrogen is supplied to the second reactor. The second reactor 7 is ~illed with a catalyst comprising an alumina-containing carrier and compounds of nickel and molybdenum. The volume of the reactor filled with catalyst is such that at the rate at which the stream to be treated is supplied the hourly space velocity is 0.5 kg/l/hour.
The hydrocaxbon content of the further converted stream produced in the second reactor 7 is 84.90% by weight of the hydrocarbon-containing stream supplied to the first reactor 1, the further converted stream -- . :
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comprises 6.15% by weight of hydrocarbons having 1 to 4 carbon atoms, 24.50% by weight o~ hydrocarbons having more than 5 carbon atoms and a boiling range below 250 oc, 41.41% by weight of hydrocarbons having a boiling ranye between 250 and 370 C, 27.59% by weight of hydrocarbons having a boiling range between 370 and 520 C, 0.33% by weight of hydrocarbons having a boiling range above 520 C, and 0.020% by weight of sulphur.
A reactor as referred to in the Figures with reference numeral 1, 7 or 31 may be a packed bed reactor wherein the catalyst is arranged in a stationary bed, or a moving bed reactor wherein spent catalyst is continuously removed from the reactor at a predetermined rate and fresh catalyst is supplied to the reactor to replace spent catalyst, or a fluidized bed reactor wherein catalyst is fluidized by upwardly flowing fluid to be converted.
Each conversion zone may comprise a single reactor ~ or more than one, fox example three or four.
: 20 Hydrogen may be introduced as a separate stream into the reactor, or it may be mixed with the fluid to be converted before the fluid enters into the reactor.
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INTO A STREAM CONTAINING HYDROCARBONS
HAVING A LOWER BOILING RANGE
The present invention relates to a process for converting a stream containing heavy hydrocarbons having a high boiling range into a stream containing hydrocarbons having a lower boiling range.
It is an object of the present invention to provide a process for converting in a first stage a substantially liquid stream and in a second stage a : substantially gaseous stream.
To this end the process for converting a stream containing heavy hydrocarbons having a high boiling ; range into a stream containing hydrocarbons having a lower boiling range according to the invPntion comprises the steps of ~ a) passing through a first conversion zone :~ 15 containing a conversion catalyst in the presence of - hydrogen the stream containing heavy hydrocarbons :~ having a high boiling range at a temperature between 325 and 600 C, a pressure between l and 30 MPa and at an hourly space veIccity between 0.05 and 5 kg~l/hour to produce a primary converted stream;
~ : b) passing the primary converted stream ~o a first :: separation zone and removing from the first separation zone a gaseous stream and a liquid stream;
:~ c) passing at least a part of the gaseous stream to a second conversion zone; and :
d) passing through the second conversion one containing a conversion catalyst in the presence of hydrogen the gaseous stream at a temperature between 325 and 600 oc, a pressure between l and 30 MPa and at . .. ..
: ,~ , . :
~71D~
an hourly space velocity between 0.1 and 10.0 kg/l/hour to produce a further converted stream having a lower boiling range.
An advantage o~ the process according to the invention is that no fractional distillation is carried out between the first conversion zone and the second conversion zone. A further advantage i5 that the gaseous stream is maintained at a high pressure and at a high temperature.
Known is a process for hydrotreating pyrolysis gasoline, which is a hydrocarbon-containing stream having a boiling range between 180 and 205 C, comprising treating the stream in a ~irst reactor at a temperature between 80 and 130 C and a pxessure o~
about 6 MPa, separating the effluent from the first reactor into a gaseous stream and a liquid stream of which a part is returned to the first reactor, treating the gaseous stream and the remaining part of the liquid stream combined in a second reactor at a temperature between 230 and 280 C and a pressure between 4.5 and 6.5 MPa, and separating the e~fluent from the second reactor into a gaseous stream which is recycled to the second reactor and a liquid product stream.
; In the specification and in the claims the expression "heavy hydrocarbons having a high boiling range" is used to refer to hydrocarbons containing more than 70% by weight of hydrocarbons having a boiling range above 370 C. These hydrocarbons ~urther may con~ain sulphur~ for example between 0.05 and 8~ by weight, and heavy metals such as vanadium, for example between 0.5 and 2 000 ppm (parts per million). The ~` expression "hydrocarbons having a lower boiling range"
is used to refer to hydrocarbons which are liquid at normal conditions containing more than 40% by weight hydrocarbons having a boiling range below 370 C.
- . . .
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In the speci~ication and in the claims the hourly space velocity is expressed as kg hydrocarbon-containing stream per liter of catalyst per hour (kg/l/hour).
The first conversion zone contains a ~irst conversion catalyst suitable l`or hydrocarbon conversion, for removal of asphaltenes, for producing hydrocarbons having a decreased amount of carbon residue left after evaporation and pyrolysis, and/or for demetallization. Examples of suitable catalysts are catalysts comprising an inorganic oxidic carrier, for example silica and/or alumina, containing one or more compounds of nickel, vanadium, molybdenum and tungsten.
The second conversion zone contains a second conversion catalyst suitable for desulphurization, hydrogenation and/or denitrogenation of a gaseous hydrocarbon stream. Examples of suitable catalysts are catalysts comprising an inorganic oxidic carrier, for example alumina and/or silica, containing either nickel and/or cobalt, or molybdenum and~or tungsten.
Heavy metals from the hydrocarbons having a high boiling range are deposited on the catalyst in the first conversion zone. Furthermore, in the separation zone heavy highly aromatic molecules, which are still present in the product from the first conversion zone, are separated from the gaseous stream. Therefore a stream substantially free of heavy metal~ and of heavy aromatic molecules is contacted with ths catalyst in the second conversion zone. This has a beneficial effect on the life of the catalyst in the second conversion zone.
The invention will now be described by way of example in more detail with reference to the drawings, wherein Figure 1 shows schematically a first embodiment of the invention:
.
: ' , ' :
Figure 2 shows schematically a second embodiment o~ the invention;
Figure 3 shows schematically a third embodiment of the invention; and Figure 4 shows schematically a fourth embodiment of the invention.
Re~erence is made to Figure 1 showing an apparatus ~or carrying out the process according to the invention. The apparatus comprises a ~irst conversion zone in the ~orm of first reactor 1, a ~irst separation zone in the form of ~irst gas/liquid separator 4 and a second conversion zone in the form o~ second reactor 7.
To the first reactor 1 a hydrogen supply conduit 8 and a feed supply conduit 9 are connected. The first gas/liquid separator 4 is connected to the first reactor 1 by means of conduit 10. The upper zone of the first gas/liquid separator 4 is connPcted to the second reactor 7 by means of conduit 12, and a li~uid conduit 15 is connected to the lowar zone of the ~irst gas/liquid separator 4. To the second reactor 7 a second hydrogen supply conduit 17 is connected, and to the upper end of the second reactor 7 : an effluent removal conduit 18 is connected.
During normal operationt a preheated, ~ubstantially liquid stream containing hea~y hydrocarbons having a high boiling range is supplied to the first reactor 1 through the feed supply conduit 9, and hydrogen is supplied to the first reactor 1 through the hydrogen supply conduit 8. The temperature of the hydrocarbon-containing stream is between 325 and 600 C and suitably between 350 and 500 C, the pressure between 1 and 30 MPa and suitably between 2 and 25 MPa, and the rate at which the hydrocarbon-containing stream i~
supplied is selected such that in the first reactor 1 the hourly space velocity is between 0.05 and 5 .
, . .
, ~ ' '.... . ~ :
: . ' , ', ,; ' ' ' ~
kg/1/hour and suitably between 0.1 and 2.5 kg/l/hour.
The amount of hydrogen is suitab]y between 250 and 2 ooO Nm3 per 1 000 kg hydrocarbon-containing stream. A
primary converted stream is removed from the first reactor 1 and is passed via conduit 10 to the first gas/liquid separator 4. From the first gas/liquid separator 4 a gaseous stream and a liquid stream are removed. Since the gas/liquid separation is carried out substantially at the same pr~ssures and temperatures as the conversions in the ~irst reactor and second reactor the gaseous stream, which contains hydrogen, is passed to the second reactor without substantially heating and/or pressurizing.
The gaseous stream is supp]ied via conduit 12 to the second reactor 7 at a temperature between 325 and 600 C and suitably between 350 and 500 C, a pressure between 1 and 30 MPa and suitably between 2 and 25 MPa.
The amount of catalyst in the second reactor 7 is such that at the rate at which the hydrocarbon~containing stream is supplied the hourly space velocity is between 0.1 and 10.0 kg/l/hour and suitably between 0.25 and 5.0 kg/l/hour. In addition hydrogen can be supplied to the second reactor 7, the amount of hydrogen being suitably up to 2 000 Nm3 per kg hydrocarbon-containing stream. A further converted stream containing hydro-carbons having a lower boiling range is withdrawn from the second reactor 7 through effluent removal conduit 18.
To control the pressurs in the first gas/li~uid separator 4 and in the second reactor 7, the conduits 10 and/or 12 may be provided with pressure control means (not shown)O
A liquid hydrocarbon-containing stream containing 93.5% by weight of hydrocarbons having a boiling range above 370 C`, 4~7~ by weight sulphur, and 84 ppm ' ,~ ' ~ ' ,~ .
vanadium is supplied to the first reactor l at an hourly space velocity of l kg/l/hour, a temperature of 440 oc and a pressure of 15 MPa. Hydrogen is supplied to the first reactor l at a rate of l 000 Nm3/l 000 kg S of liquid hydrocarbon-contain:ing stream. The ~irst reactor l is filled with a ca1:alyst comprising a silica-containing carrier and compounds of nickel and vanadium. The primary converted stream produced in the ~irst reactor 1 is passed to t:he first gas/liquid separator 4 and from the first: gas/liquid separator 4 a gaseous stream and a liquid st:ream are removed.
The liquid stream is removed from the first gas/liquid separator 4 through liquid conduit 15, and the amount of the liquid stream is 39% by weight of the liquid hydrocarbon-containing stream supplied to the first reactor. The liguid stream contains 53.47% by weight of hydrocarbons having a boiling range between 370 and 520 C and 46.53% by weight o~ hydrocarbons having a boiling range above 520 oc, and contains further 3.2%
by weight of sulphur and 4 ppm vanadium.
The gaseous stream removed from the first gas/liquid separator 4 through conduit 12 comprises hydrocarbons and hydrogen, the hydrocarbon content of this stream is 6~% by weight of the liquid hydrocarbon-containing stream supplied to the first reactor lo The hydrocarbon part o~ the gaseous stream comprises 83% by weight hydrocarbons having a boiling range below 370 C
and 0.8% by weight sulphur.
This gaseous stream is suppIied to the second reactor 7 at a temperature of 410 C and a pressure of 13 MPa. ~o extra hydrogen is supplied to the second reactor 7. The second reactor 7 is filled with a catalyst comprising an alumina-containing carrier and compounds of nickel and molybdenum. The volume of the reactor filled with catalyst is such that at the rate s ,.. ... . . .
~ ' ' , . . .
: :
at which the stream to be treated is supplied the hourly space velocity is 0.5 kg/l/hour.
The further converted stream produced in the second reactor 7 contains hydrocarbons, hydrogen and gaseous contaminants such as H2S and NH3. The hydro-carbon content of the further converted stream e~lals 61% by weight of the licluid hydrocarbon-containing stream supplied to the first reactor 1, and it comprises 9.64~ by weight of hydrocarbons having l to 4 carbon atoms, 32.7B% by weight of hydrocarbons having more than 5 carbon atoms and a boiling range below 250 C, 49.61% by weight of hydrocarbons ha~ing a boiling range between 250 and 370 C, 7.98% by weight of hydrocarbons having a boiling range between 370 and 520 C, and 0.014% by weight o~ sulphur. It will be appreciated that hydrogen sulphide and hydrogen can be removed from the further converted stream in a conventional manner which is not described here, and that the separated hydrogen can be compressed and reused in the first or second conversion zone.
In the embodiment of the invention shown in Figure 2 liquid conduit 15 is connected by means of conduit 20 to the feed supply conduit 9. The parts of the apparatus shown in Figura 2 which are similar to the parts shown in Figure 1 have the same referenc~
numerals. This embodiment allows passing to the first reactor l a part of or substantially all lic~id separated from the primary converted stream tQ the first r~actor 1, so that the liquid stream can be further converted with the catalyst in the first reactor 1.
The hydrocarbon-containing stream of Example 1 is supplied uncler the same conditions to the first reactor 1 together with a recycle stream to be described hereinafter.
. .
g~
The amount of liquid stream removed ~rom the first gas/liquid separator 4 is 106~ by weight of the liquid hydrocarbon-containing stream supplied to the first reactor 1. The liquid stream contains 61.03~ by weight of hydrocarbons having a boiling range between 370 and 520 C and 38.97~ by weight of hydrocarbons ha~ing a boiling range above 520 C, and contains further 2% by weight of sulphur and 2 ppm vanadium. From the liquid removed from the first gas/lic~id separator 4 an amount equal to ~0% by weight of the liquid hydrocarbon-containing stream supplied to the first reactor 1 is passed as the recycle stream to the first reactor 1 through conduit 20.
The amount of liquid stream removed from liquid conduit 15 downstream to the point where conduit Z0 is connected to conduit 15 is 46% by weight of the hydrocarbon-containing stream supplied to the first reactor 1, and this stream is removed as a bottom product.
The gaseous stream removed fxom the gas/liquid separator 4 through conduit 12 contains hydrocarbons and hydrogen, the hydrocarbon cont~nt of the gaseous stream is 54% by weight of the hydrocarbon-containing stream supplied to the first reactor 1. The hydrocarbon part of the gaseous stream comprises 73% by weight of hydrocarbons having a boiling range below 370 C and 0.9~ by weight sulphur. This gaseous stream is supplied to the second reactor 7 at a temperature of 410 C and a pressure of 13 MPa. No extra hydrogen is supplied to the second reactor 7. The second reactor 7 is filled with the same catalyst as in Example l. The volume of the reactor filled with catalyst is such that at the rate at which the stream ~o be treated is upplied the hourly space velocity is 0.5 kg/l/hour.
The further converted stream produced in the second reactor 7 contains hydrocarbons, hydrogen and -~ 9 -contaminants such as H2S and NH3. The hydrocarbon part of the further converted stream comprises 7.33~ by weight of hydrocarbons having 1 to 4 carbon atoms, 28.86% by weight of hydrocarbons having more than 5 carbon atoms and a boiling range below 250 C, 50.73 by weight of hydrocarbons having a boiling range between 250 and 370 C, and 13.08% by weight of hydrocarbons having a boiling range between 370 and 520 C and 0.021% by weight of sulphur. The amount of hydrocarbons in the range C1-C~ in the ~urther converted stream per unit of converted heavy hydrocarbon is less than in the further converted stream produced in h'xample l.
For some kinds of heavy hydrocarbons to be converted it would be more profitable to increase the upper limit of the boiling range of the gaseous skream supplied to the second reactor in order to improve the overall conversion of the hydrocarbons having a boiling range above 370 C.
To increase the upper limit of the boiling range of the gaseous stream liquid outlet 15 is connected to a second separation zone in the ~orm of second gas/-liquid separator 24 (see Figure 3). The gaseous hydrocarbons are removed from the second gas/liquid separator 24 and passed through conduit 25 to conduit 12 and into the second conversion reactor 7.
The liquid hydrocarbons are removed from the second gas/liquid separator 24 through conduit 26. If required a part of the liquid hydrocarbons may be added through conduit 27 to the stream containing heavy hydrocarbons having a high boiling range before this stream i.s passed through the first reactor 1.
A hydrocarbon-containing stream containing 90.5%
by weight o~ hydrocarbons having a boiling range above 370 C, 4.7% by weight sulphur, and 84 ppm vanadium is supplied to the first reactor 1 at an hourly space velocity of 1 kg/l/hour, a temperature of 440C and a pressure of 15 MPa, together with a recycle stream to be described hereinafter. Hydrogen is supplied to the first reactor 1 at a rate of 1 000 Nm3/1 000 kg of hydrocarbon-containing stream. The first reactor 1 is filled with a catalyst comprising a silica-containing carrier and compounds of nickel and vanadium. The primary converted stream produced in the first reactor 1 is passed to the first gas/liquid separator 4 and from the first separation zonle a gaseous stream and a liquid stream are removed.
The liquid stream is removed from the gas/liquid separator 4 through liquid conduit 15. The amount of this liquid stream is 77% by weight of the hydrocarbon-containing stream supplied to the first reactor 1, and the liquid stream does not contain hydrocarbons having a boiling range below 410 C, and contains 1.9~ by weight of sulphur and 4 ppm vanadium. The liquid stream is supplied to the second gas/liquid separator 24. In the second gas/liquid separator 24, operating at a pressure of 30 mm Hg, the stream is separated into a gaseous stream, corresponding to 28.4 % by weight of the hydrocarbon-containing stream supplied to the first reactor ~, and a liquid stream. The gaseous stream is supplied to the second reactor 7. The liquid stream contains 4.03% by weight of hydrocarbons having a boiling range between 370 and 520 C and 95.97% by weight of hydrocarbons having a boiling range above 520 CO A fraction of the liquid stream, corresponding to 30 % by weight of the hydrocarbon-containing stream supplied, is supplied as the recycle stream to the `~ first reactor 1 through conduit 27 to the first reactor 1, and the remaining part of the liquid stream, correspondin~ to 19 % by weight of the hydrocarbon-containing stream supplied to the flrst reactor 1, is , removed through conduit 26 downstream conduit 27 as a bottom product.
The gaseous stream removed from the gas/liquid separator 4 through conduit 12 contains hydrocarbons and hydrogen, the hydrocarbon content of the gaseous stream is 54~ by weight of the hydrocarbon-containing stream supplied to the first :reactor 1. The hydrocarbon part of the gaseous stream comprises 73% by weight o~
hydrocarbons having a boiling range below 370 C and 0.9% ~y weight of sulphur. Th.i~ gaseous stream is supplied to the second reactor 7.
The gaseous streams from the separators 4 and 24 are supplied to the second reactor 7 at a temperature o~ 410 oc and a pressure of 13 MPa. The total amount of the gaseous streams is 81% by weight o~ the hydro-carbon-containing stream supplied to the first reactor 1. No extra hydrogen is supplied to the second reactor 7. The second reactor 7 is Pilled with a catalyst comprising an alumina cont ining carrier and compounds of nickel and molybdenum. The volume of the reactor ~illed with catalyst is such that at the rate ak which the streams to be treated are supplied the hourly space velocity is 0.5 kg/l/hour.
The hydrocarbon content o~ the further converted : 25 stream produced in the second reactor 7 is 81% by weight o~ the hydrocarbon-containing stream supplied to the first reactor 1, and the further converted stream comprises 5.75% by weight of hydrocarbons having 1 to 4 carbon atoms, 25.90% by weight of hydrocarbons having more than 5 carbon atoms and a boiling range below 250 C, 42.34% by weight of hydrocarbons having a boiling range between 250 and 370 C, 25.74% by weight of hydrocarbons having a boiling range between 370 and 520 C, 0.26% by weight of hydrocarbons having a boiling range above 520 DC, and 0.032% by weight o~ sulphur~
' ' .
Reference is now ~ade to Figure 4, showing an embodimant of the invention wherein the liquid stream removed from the first gas/liquid separator 4 is passed through conduit 15 for further conversion to a third conversion zone in the form of third reactor 30. In the third reactor 30 the liquid stream is contacted in the presence of hydrogen with a conversion catalyst of the kind which is present in the second reactor 7 to produce a secondary converted stream.
This conversion catalyst is suitable for desulphurization, hydrogenation and/or denitrogenation o~ a gaseous hydrocarbon stream. Examples of suitable catalysts are catalysts comprising a carrier containing alumina or silica and alumina, and either nickel and/or cobalt, or molybdenum and/or tungsten.
The temperature of the liquid stream is between 325 and 600 C and suitably between 350 and 500 C, the ; pressure in the third reactor 30 is between 1 and 30 MPa and suitably between 2 and 25 MPa, and the volume o~ catalyst in the third reactor 30 i~ such that at the rate at which the liquid stream is supplied the hourly space velocity in the third reactor 30 is between 0.05 and 10 kg/l/hour and suitably between Ool and 5 kg/l/hour.
~ 25 If required hydrogen can be supplied to the third ; reactor through hydro~en supply conduit 31. The secondary converted stream is removed ~rom the third reactor 30 through outlet conduit 32.
To remove the gaseous components from the secondary converted stream this stream can be passed directly to the first gas/liquid separator (not shown), or the secondary converted stream can be passed to a third sep~ration zone in the form of third gas/liquid separator 35.
From the third gasJliquid separator 35 a gaseous straam is passed through conduit 36 to the second ..
~' ' ' .
7a~
reactor 7. A liquid stream is removed from the third gas/liquid separator 35 through conduit 37. Xf required a part or all of the liquid stream can be passed through conduit 3g to the first reactor 1.
The hydrocarbon-containing stream of Example 1 is supplied under the same conditions to the first reactor 1 together with a recycle stream as hereinafter described.
The gaseous stream removed fxom the gas/liquid separator 4 through conduit 12 contains hydrocarbons and hydrogen, and the hydrocarbon content of the gaseous stream is 54% by weight of the hydrocarbon-containing stream supplied to the first reactor 1. The hydrocarbon part of the gaseous stream comprises 73% by : weight of hydrocarbons having a boiling range below 370 C, 0.9% by weight of sulphur. This gaseous stream is supplied to the second reactor 7 at a temperature o~
410 C and a pressure of 13 MPa.
The liquid stream is removed from liguid conduit 15. The amount of the liquid stream is 76% by weight of the hydrocarbon-containing stream supplied to the first reactor 1, and comprises 63% by weight having a boiling range above 52~ C and does not contain hydrocarbons 25 having a boiling range below 410 C, and 1.9% by weight of sulphur.
The liquid stream is passed to the third reactor ~ 30 which is filled with a catalyst comprising an : alumina-containing carxier and compounds of nickel and molybdenum. The volume of the reactor filled with catalyst is such that at the rate at which the stream to be treated i5 supplied the hourly space velocity is 2.7 kg/l/hour. The secondary converted stream produced in the third reactor 30 comprises 97~ by weight of hydrocarbons having a boiling range above 370 C and 58% by weight of hydrocarbons having a boiling range `:
, : " ' ' . ~ ~ ' -~l2~
above 520 ~C, and 0.4% by weight of sulphur. This stream is passed through conduit 32 to the third gas/liquid separator 35, operating at 30 mm Hg.
The amount of liquid stream obtained in the third gas/liquid separator 35 is 45% by weight of the hydrocarbon-containing stream supplied to khe first reactor 1. The liquid stream contains 3.97% by weight of hydrocarbons having a boiling range between 370 and 520 C and 96.03% by weight O:e hydrocarbons having a boiling range above 520 C. A part of the liquid stream, corresponding to 15~ by weight of the hydrocarbon-containing stream as supplied to the first reactor 1, is removed through conduit 37 as a bottom product.
The remaining part of the liquid stream is passed through conduit 38 ~s the recycle stream to the first reactor 1, the amount of this stream is 30% by weight of the hydrocarbon-containing stream supplied to the first reactor 1.
The amount of the gaseous stream obtained in the third gas/liquid separator 35 equals 31% by weight of the hydrocarbon-containing stream supplied to the first reactor 1. The gaseous stream is passed through conduit 36 to the second reactor 7, where it is converted together with the gaseous stream from the first gas/liquid separator 4. No extra hydrogen is supplied to the second reactor. The second reactor 7 is ~illed with a catalyst comprising an alumina-containing carrier and compounds of nickel and molybdenum. The volume of the reactor filled with catalyst is such that at the rate at which the stream to be treated is supplied the hourly space velocity is 0.5 kg/l/hour.
The hydrocaxbon content of the further converted stream produced in the second reactor 7 is 84.90% by weight of the hydrocarbon-containing stream supplied to the first reactor 1, the further converted stream -- . :
~29~
comprises 6.15% by weight of hydrocarbons having 1 to 4 carbon atoms, 24.50% by weight o~ hydrocarbons having more than 5 carbon atoms and a boiling range below 250 oc, 41.41% by weight of hydrocarbons having a boiling ranye between 250 and 370 C, 27.59% by weight of hydrocarbons having a boiling range between 370 and 520 C, 0.33% by weight of hydrocarbons having a boiling range above 520 C, and 0.020% by weight of sulphur.
A reactor as referred to in the Figures with reference numeral 1, 7 or 31 may be a packed bed reactor wherein the catalyst is arranged in a stationary bed, or a moving bed reactor wherein spent catalyst is continuously removed from the reactor at a predetermined rate and fresh catalyst is supplied to the reactor to replace spent catalyst, or a fluidized bed reactor wherein catalyst is fluidized by upwardly flowing fluid to be converted.
Each conversion zone may comprise a single reactor ~ or more than one, fox example three or four.
: 20 Hydrogen may be introduced as a separate stream into the reactor, or it may be mixed with the fluid to be converted before the fluid enters into the reactor.
':
:
- ~.
' ' ' ~ ' ' ' ~ ' :
~ ' . .
Claims (9)
1. Process for converting a stream containing heavy hydrocarbons having a high boiling range into a stream containing hydrocarbons having a lower boiling range comprising the steps of a) passing through a first conversion zone containing a conversion catalyst in the presence of hydrogen the stream containing heavy hydrocarbons having a high boiling range at a temperature between 325 and 600 °C, a pressure between 1 and 30 MPa and at an hourly space velocity between 0.05 and 5 kg/l/hour to produce a primary converted stream;
b) passing the primary converted stream to a first separation zone and removing from the first separation zone a gaseous stream and a liquid stream;
c) passing at least a part of the gaseous stream to a second conversion zone; and d) passing through the second conversion zone containing a conversion catalyst in the presence of hydrogen the gaseous stream at a temperature between 325 and 600 °C, a pressure between 1 and 30 MPa and at an hourly space velocity between 0.1 and 10.0 kg/l/hour to produce a further converted stream having a lower boiling range.
b) passing the primary converted stream to a first separation zone and removing from the first separation zone a gaseous stream and a liquid stream;
c) passing at least a part of the gaseous stream to a second conversion zone; and d) passing through the second conversion zone containing a conversion catalyst in the presence of hydrogen the gaseous stream at a temperature between 325 and 600 °C, a pressure between 1 and 30 MPa and at an hourly space velocity between 0.1 and 10.0 kg/l/hour to produce a further converted stream having a lower boiling range.
2. Process as claimed in claim 1, wherein a part of the liquid stream obtained in step b) is added to the stream containing heavy hydrocarbons having a high boiling range before this stream is passed in step a) through the first conversion zone.
3. Process as claimed in claim 2, wherein the liquid stream obtained in step b) is added to the stream containing heavy hydrocarbons having a high boiling range before this stream is passed in step a) through the first conversion zone.
4. Process as claimed in claim 1, further comprising passing the liquid stream obtained in step b) to a second separation zone, removing from the second separation zone a gaseous stream and a liquid stream, and adding the gaseous stream to the gaseous stream obtained in step b), before this gaseous stream is passed through the second conversion zone in step d).
5. Process as claimed in claim 4, wherein a part of the liquid stream removed from the second separation zone is added to the stream containing heavy hydrocarbons having a high boiling range before this stream is passed in step a) through the first conversion zone.
6. Process as claimed in claim l, further comprising passing through a third conversion zone containing a conversion catalyst in the presence of hydrogen the liquid stream obtained in step b) at a temperature between 325 and 600 °C, a pressure between 1 and 30 MPa and at an hourly space velocity between 0.05 and 10 kg/l/hour to produce a secondary converted stream.
7. Process as claimed in claim 6, further comprising passing a part of the secondary converted stream to the first separation zone.
8. Process as claimed in claim 6, further comprising passing the secondary converted stream to a third separation zone and removing from the third separation zone a gaseous stream and a liquid stream, and adding the gaseous stream to the gaseous stream obtained in step b) r before this gaseous stream is passed through the second conversion zone in step d).
9. Process as claimed in claim 8, further comprising adding a part of the liquid stream removed from the third separation zone to the stream containing heavy hydrocarbons having a high boiling range before this stream is passed in step a) through the first conversion zone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB868624952A GB8624952D0 (en) | 1986-10-17 | 1986-10-17 | Converting stream containing heavy hydrocarbons into stream |
| GB8624952 | 1986-10-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1297064C true CA1297064C (en) | 1992-03-10 |
Family
ID=10605932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000547709A Expired - Lifetime CA1297064C (en) | 1986-10-17 | 1987-09-24 | Converting a stream containing heavy hydrocarbons into a stream containing hydrocarbons having a lower boiling range |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0264158B1 (en) |
| JP (1) | JP2932182B2 (en) |
| CN (1) | CN1016966B (en) |
| AT (1) | ATE66485T1 (en) |
| AU (1) | AU593950B2 (en) |
| BR (1) | BR8705511A (en) |
| CA (1) | CA1297064C (en) |
| DE (1) | DE3772319D1 (en) |
| ES (1) | ES2024495B3 (en) |
| GB (1) | GB8624952D0 (en) |
| GR (1) | GR3002673T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8137531B2 (en) | 2003-11-05 | 2012-03-20 | Chevron U.S.A. Inc. | Integrated process for the production of lubricating base oils and liquid fuels from Fischer-Tropsch materials using split feed hydroprocessing |
| CN114350408A (en) * | 2014-12-22 | 2022-04-15 | 沙特基础工业全球技术有限公司 | Process for producing C2 and C3 hydrocarbons |
| WO2016102247A1 (en) | 2014-12-22 | 2016-06-30 | Sabic Global Technologies B.V. | Process for producing c2 and c3 hydrocarbons |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3506566A (en) * | 1968-05-20 | 1970-04-14 | Sinclair Research Inc | Conversion of clarified hydrocarbon oil to distillate hydrocarbon fuel oil of low pour point in two catalytic stages |
| BE793384A (en) * | 1971-12-27 | 1973-06-27 | Texaco Development Corp | HYDROCRACKING PROCESS FOR THE CONVERSION OF HEAVY HYDROCARBONS IN GASOLINE WITH LOW SULFUR CONTENT |
| US3992283A (en) * | 1974-09-23 | 1976-11-16 | Universal Oil Products Company | Hydrocracking process for the maximization of an improved viscosity lube oil |
| US4082647A (en) * | 1976-12-09 | 1978-04-04 | Uop Inc. | Simultaneous and continuous hydrocracking production of maximum distillate and optimum lube oil base stock |
| US4158622A (en) * | 1978-02-08 | 1979-06-19 | Cogas Development Company | Treatment of hydrocarbons by hydrogenation and fines removal |
| JPH0237389B2 (en) * | 1981-08-20 | 1990-08-23 | Jgc Corp | ITSURYUGATAKOATSUEKISOSUISOKATOKOATSUKISOSUISOKATONOCHOKURETSUKOTEINYORISOJUSHITSUYUKARAKEISHITSUYUOSEIZOSURUHOHO |
| EP0128250A1 (en) * | 1983-06-08 | 1984-12-19 | Mobil Oil Corporation | Catalytic dewaxing process |
| AU586980B2 (en) * | 1984-10-29 | 1989-08-03 | Mobil Oil Corporation | An improved process and apparatus for the dewaxing of heavy distillates and residual liquids |
-
1986
- 1986-10-17 GB GB868624952A patent/GB8624952D0/en active Pending
-
1987
- 1987-09-24 CA CA000547709A patent/CA1297064C/en not_active Expired - Lifetime
- 1987-10-14 CN CN87106905A patent/CN1016966B/en not_active Expired
- 1987-10-15 AU AU79791/87A patent/AU593950B2/en not_active Ceased
- 1987-10-15 BR BR8705511A patent/BR8705511A/en not_active IP Right Cessation
- 1987-10-15 JP JP62258500A patent/JP2932182B2/en not_active Expired - Lifetime
- 1987-10-16 ES ES87201992T patent/ES2024495B3/en not_active Expired - Lifetime
- 1987-10-16 AT AT87201992T patent/ATE66485T1/en not_active IP Right Cessation
- 1987-10-16 DE DE8787201992T patent/DE3772319D1/en not_active Expired - Fee Related
- 1987-10-16 EP EP87201992A patent/EP0264158B1/en not_active Expired - Lifetime
-
1991
- 1991-09-10 GR GR91401284T patent/GR3002673T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2932182B2 (en) | 1999-08-09 |
| DE3772319D1 (en) | 1991-09-26 |
| GB8624952D0 (en) | 1986-11-19 |
| EP0264158A1 (en) | 1988-04-20 |
| CN87106905A (en) | 1988-06-22 |
| ATE66485T1 (en) | 1991-09-15 |
| AU7979187A (en) | 1988-04-21 |
| GR3002673T3 (en) | 1993-01-25 |
| BR8705511A (en) | 1988-05-24 |
| ES2024495B3 (en) | 1992-03-01 |
| AU593950B2 (en) | 1990-02-22 |
| JPS63110286A (en) | 1988-05-14 |
| CN1016966B (en) | 1992-06-10 |
| EP0264158B1 (en) | 1991-08-21 |
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