CA1082630A - Process for the preparation of light hydrocarbon fractions - Google Patents
Process for the preparation of light hydrocarbon fractionsInfo
- Publication number
- CA1082630A CA1082630A CA236,702A CA236702A CA1082630A CA 1082630 A CA1082630 A CA 1082630A CA 236702 A CA236702 A CA 236702A CA 1082630 A CA1082630 A CA 1082630A
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- CA
- Canada
- Prior art keywords
- stage
- oil
- hydrocracked
- residual
- residual fraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A B S T R A C T
Process for the preparation of light hydrocarbon fractions by hydrocracking of a heavy hydrocarbon oil, in which a heavy hydrocarbon oil that consists at least partly of a deasphalted oil, is hydro-cracked. The hydrocracked product is separated by distillation into one or more light hydrocarbon fractions and a residual fraction.
The residual fraction is divided into two portions having the same composition but differing in size and the larger portion is recirculated to the hydrocracker.
Process for the preparation of light hydrocarbon fractions by hydrocracking of a heavy hydrocarbon oil, in which a heavy hydrocarbon oil that consists at least partly of a deasphalted oil, is hydro-cracked. The hydrocracked product is separated by distillation into one or more light hydrocarbon fractions and a residual fraction.
The residual fraction is divided into two portions having the same composition but differing in size and the larger portion is recirculated to the hydrocracker.
Description
~ he invention relates to a process for the preparation of light hydrocarbon fractions by hydrocracking of a heavy hydrocarbon oil.
Hydrocracking of heavy hydrocarbon oils for the preparation of light hydrocarbon fractions, such as gasoline, kerosine and gas oil fractions, is applied on a large scale in the oil industry. From the product obtained in hydrocracking the desired light hydrocarbon frac-tions are separated by distillation and the residue obtained in the distillation is recycled to the hydrocracker.
The heavy hydrocarbon oil that is used as the feed for the hydro-cracker is often prepared from an atmospheric distillation residue ofa crude oil (called a long residue) by distillation at reduced pressure.
In addition to a heavy distillate that is used as the ~eed for the hydrocracker this distillation yields a residual fraction tcalled a "
short residue).
To obtain from a certain long residue a higher yield of light hydrocarbon fractions than is possible in the process described here-inbefore, one might think of subjecting a larger proportion of the long residue to hydrocracking. ~o this end the long residue may be de-asphalted and the deasphalted oil thus obtained may be hydrocracked or the short residue may be deasphalted, the deasphalted oil thus obtained be mixed with the heavy distillate from the long residue and the mixture be hydrocracked. Attempts to increase the yield of light hydrocarbon frac-tions in this way have been rather unsuccessful up to now, because when using these heavy feeds a very rapid deactivation of the hydrocracking catalyst occurs.
It has now been found that hydrocracking such heavy feeds according ; to the process described hereinbefore presents no problems if from the residue obtained in the distillation of the hydrocracked product a quantity ;;less than half is separated before this residue is recirculated to the hydrocracker.
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The invention therefore relates to a process for ~he prepara-tion of light hydrocarbon fractions, in which a heavy hydrocarbon oil that consists at least pa~tly of a deasphalted oil is hydroc~acked, the hydro-cracked product being separated by distillation into one or more light hydro-carbon fractions and a residual ~raction, the residual fraction being divided into two portions having the same composition but differing in size, the larger portion being recirculated to the hydrocracker.
Thus this invention provides a process for the preparation of light hydrocarbon fractions by hydrocracking of a heavy hydrocarbon oil, characterized in that a heavy hydrocarbon oil that consists at least partly of a deasphalted oil~ is hydrocracked in one stage, or the hydrocracking of the heavy hydrocarbon oil in the first stage and the hydrocracking of the distillation residue in the second stage3 when carrying out the process ac-cording to the invention in two stages, is effected by contacting the feeds concerned together with hydrogen at elevated temperature and pressure with a suitable hydrocracking catalyst at a temperature of from 250 to 450C, a pres-sure of from 50 to 200 bar, a hydrogen/feed ratio of from 250 to 4000 Nl hy-drogen/kg feed and a space velocity of from 0.2 to 5.0 1 of feed per litre of catalyst per hour in the presence of an acid catalyst comprising one or more me~als of Group VI and one or more metals of Group VIII ciron group~ on a carrier, in that the hydrocracked product is separa~ed by distillation into one or more light hydrocarbon fractions and a residual fraction, in that the residual fraction is divided into two portions having the same composition but difering in size and in that the larger portion is recirculated to the hydro~
cracker.
The division of the residual fraction into two unequal portions is preferably carried out in such a way that the smal]er portion corresponds in quantity with 1 25 %w of the heavy hydrocarbon oil to be hydrocracXed.
The process according to the invention not only offers the pos_ 3Q sibility of hydrocracking the said heavy hydrocarbon oils to light hydro~
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car~on fractions without this leading to a very rapid deactlvation of the catalyst~ but, in addition, yields as a useful by-product a residual hydro-carbon oil tha~ can very suitably be used as a high-viscosity-index lubri-cating oil, as a low~sulphur residual fuell or as a blending component for the preparation of a lubricating oil or a residual fuel, The process according to the invention can very suitably be used for hydrocracking heavy hydrocarbon oils in one stage. The process according to the invention can also very suitably be used as the second stage o~ a two~stage hydrocracking process, In hydrocracking of heavy hydrocarbon oils in two stages for the preparation of light hydrocarbon ractions the hydrocracked products of the first and the second stage may be distilled separately or jointly, Both in one-stage and in two-stage hydrocracking a gas containing hydrogen is separated from the crude hydro-cracking products, before the cracking prod~cts are separated into the de-sired light hydrocarbon fractions and ~ residual ~raction. After purifi cation this gas is preferably recycled to the first and/or the second hydro-cracker, - 3a , -~ hen the process according to the invention is carried out as the second stage of a two-stage hydrocracking process for the preparation of light hydrocarbon fractions from a heavy hydrocarbon oil, the hydro-cracked products of the ~irst and of the second stage being distilled separately, the process is carried out as ~ollows. A heavy hydrocarbon oil consisting at least partly o~ a deasphalted oil is hydrocracked in the first stage and from the hydrocracked product the desired light hydrocarbon fractions are separated by distillation. The residue ob-tained in this distillation is subsequently hydrocracked in the second stage and from the hydrocracked product the desired light hydrocarbon frsctions are separated in a separate distillation unit. The residue obtained in this second distillation is divided into two unequal por-tions, the smaller portion in quantity preferably corresponding with 1-25 %w of the heavy hydrocarbon oil that is used as the feed for the first hydrocracker and the larger portion is recirculQted to the second hydrocracker.
When the process according to the invention is carried out as the second stage of a two-stage hydrocracking process for the preparation of light hydrocarbon fractions from a heavy hydrocarbon oil, the hydro-cracked products of the first and of the second stage being distilledjointly, the process is carried out as follows. A heavy hydrocarbon oil consisting at least partly of a deasphalted oil, is hydrocracked in the ~irst stage, the hydrocracked product of the first stage is mixed with the hydrocracked product of the second stage and from the mixture the desired light hydrocarbon fractions are separated by distillation.
The residue obtained in this aistillation is divided into two unegual portions, the smaller portion in quantity preferably corresponding with 1_25 %w of the heavy hydrocarbon oil that is used as the feed for the first hydrocracker while the larger portion is used as the ~eed for the second hydrocracker.
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In the process according to the invention a heavy hydrocarbon oil consisting at least partly o~ a deasphalted oil should be used as the feed, for example a deasphalted distillation residue of a crude oil.
This distillation residue may have been obtained in the distillation at atmospheric pressure or in the distillation at a reduced pressure. Al-though it is in principle possible in the process according to the in-vention to use as the starting material a ~eed entirely consisting of a deasphalted oil, for example a deasphalted long or short residue, preference is given to a feed consisting of a mixture of a distillate obtained in the distillation at a reduced pressure of a long residue with a deasphalted short residue. A very suitable ~eed ~or the process accord- i~
ing to the invention can be prepared by splitting up a long residue by distillation at reduced pressure into a distillate and a short residue, deasphalting the short residue and blending the distillate with the de-asphalted oil, pre~erably in production ratio. When in the process according to the invèntion one o~ the feed components is a distillate obtained in the distillation at reduced pressure of a long residue, a flashed distillate of a long residue is preferred ~or this purpose.
In the process according to the invention the feed must consist at least partly of a deasphalted oil, The deasphalting of the oil is pre~erably carried out at elevated temperature and pressure and in the ~ `
presence of an excess of a lower hydrocarbon, such as propane, butane or pentane or a mixture thereof, as the solvent.
The hydrocracking of the heavy hydrocarbon oil, when carrying out the process according to the invention in one stage9 or the hydrocracking of the heavy hydrocarbon oil in the first stage and the hydrocracking o~
the distillation residue in the second stage, when carrying out the process according to the invention in two stages, is ef~ected by con-tacting the ~eeds concerned together with hydrogen at elevated tempe-rature and pressure with a suitable hydrocracking catalyst. Suitable ;
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hydrocracking conditions are a temperature of from 250 to 450 C, a pressure of from 50 to 200 bar, a hydrogen/feed ratio of from 250 to 4000 Nl hydrogen/kg feed and a space velocity of from 0.2 to 5.0 1 of feed per litre of catalyst per hour. In hydrocracking the ~ollowing conditions are preferably applied: a temperature of ~rom 300 to 425 C, a pressur~ o~ from 75 to 175 bar, a hydrogen/feed ratio of from 750 to 2500 ~1 hydrogen/kg feed and a space velocity of from 0.5 to 3.0 1 of feed per litre of catalyst per hour.
The catalysts preferably used are acid catalysts comprising one or more metals o~ Group VI and one or more metals of Group VIII (iron group) on a carrier. Examples of suitable metal combinations are cobalt-molybdenum, nickel-molybdenum and nickel-tungsten. E~amples o~ suitable carriers are silica, alumina, magnesia9 and æirconia, as well as com-binations of these such as silica-alumina and silica-zirconia. Zeolites are also eligible for use as carriers for the present hydrocracking cata-lysts, Besides the above-mentioned metals the catalysts preferably also ~;
contain one or more promoters, such as phosphorus and/or halogens9 in particular fluorine. The metals may be present on the carriers as such or in the form of their oxides or sulphides. Preference is given to the application of catalysts in which the metals are present on the carrier in the form of their sulphides.
Very favourable results can be achieved by application of the process according to the invention to the hydrocracking o~ a heavy hydro-carbon oil in one StQge using a catalyst containing nickel sulphide, 25 molybdenum sulphide and fluorine on alumina, as well as to the hydro- i~
crscking of a heavy hydrocarbon oil in two stages using a catalyst con-taining nickel sulphide, molybdenum sulphide and fluorine on alumina in `the first stage and a catalyst containing nickel sulphide, tungsten sulphide and fIuorine on silica-alumina in the second stage.
; 30 The preparation of light hydrocarbon fractions by hydroaracking . ' ' . ' - ' ' , ~ .
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a hea~y hydrocarbon oil can be effected in the vapour phase, in the liquid phase or partly in the vapour phase and partly in the liquid phase. Preferably a ~ixed catalyst bed is used. A very suitable em- --bodiment is the one in which the feed to be converted, which is partly in the liquid phase and partly in the gas phase, is passed over a fixed catalyst bed, the so-called trickle phase method.
As was already stated hereinbe~ore, the process according to the invention yields as a useful by-product a residual hydrocarbon oil that is very suitable to be used as a high-viscosity-index lubricating oil, as a low-sulphur residual fuel or as a blending component for the preparation of a lubricating oil or a residual fuel.
If the residual hydrocarbon oil obtained as a by-product in the - process according to the invention is intended for use as a high-viscosity-index lubricating oil or as a blending component ~or the preparation of a lubricating oil by blending with other components having 8 viscosity in the lubricating oil range, the residual hydro-carbon oil is preferably dewaxed. For dewaxing the usual techniques can be applied3 such as cooling in the presence of a solvent. As a solvent a mixture of methyl ethyl ketone and toluene is very suitable~ ~he sepa-rated paraffin wax can be further processed separately, but can also very suitably be recycled in the hydrocracking process. ; -I~ the residual hydrocarbon oil that is obtained as by-product in the process according to the invention is used as low-sulphur blending component for the preparation of a residual fuel, distillate as well as residual components can be used as the other components in the blend. A
very suitable blending component ~or the residual hydrocarbon oil for the preparation of a residual fuel is the asphalt obtained in the pre-paration of the deasphalted oil that is used as the feed for the process according to the invention.
The invention will now be elucidated with the aid of the following ~xa~ple.
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AMPLE
As starting material was used an atmospheric distillation residue originating rrOm a Middle East crude, which residue had the following properties:
initial boiling point 370 C
Vk (kinematic viscosity at 210 F) 15.6 cSt sulphur content 3.3 ~w 100 pbw of this long residue were split up by rlashing into 47 pbw rlashed distillate and 53 pbw short residue. The short residue was deasphalted with n-butane as the solvent at an avera~e temperature Or 125 C, a pressure Or 40 bar and a solvent/oil weight ratio of 4:1.
In this way 33 pbw deasphalted oil and 20 pbw butane asphalt ha~ing a sulphur content of 6 ~w were obtained ~rom the short residue. The `
rlashed distillate was blended in production ratio with the deasphalted oil to 80 pbw Or a heavy hydrocarbon oil which was used in the hydro-cracking experiments mentioned hereinarter.
EXPERIMENT A - `~
The heavy hydrocarbon oil described hereinbe~ore was hydrocracked in a one-stage process at an initial temperature of 400 C, a hydrogen partial pressure o~ 123 bar, a hydrogen/feed ratio of 1000 ~l H2/kg fresh ~eed and a space ~elocity of 0.5 l o~ ~resh`~eed per litre o~
catalyst per hour. As the catalyst a composition was used containing nickel sulphide, molybdenum sulphide and ~Iuorine on alu~ina (3.? Yw Ni/
11,8 gw Mo/6.4 %w F). The hydrocracked product was split up by diQ-tillation st atmospheric pressure into a C4 fraction, a~C5-150 C-~
fraction, ~ 150-370 C fraction and a 370 C residue, which residue was recycled completely to the hydrocracker~ using a recycle ratio~
(pbw recycled product: pbw fresh ~eed? o~ 0.5. In this way-10 pbw o~ a C4 rrsctiOn, 23 pbw of a C5-150 C fraction and 47 pbw of a 150-370 C ~raction were obtained ~rom 80 pbw~or the heavy hydrocarbon , .
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, .. .. : `"' oil. The 150-370 C ~raction had a pour point of -12 C and a cetane number of 50. The duration of the experiment was 1000 h. To compensate for the catalyst deactivation the temperature had to be increased by 1.5 C every 100 h.
This experiment was carried out in substantially the same way as experiment A, the difference being, however, that in the present case a space velocity of C.8 l of fresh feed per litre of catalyst per hour was applied and that from the 370 C residue a quantity was se-parated corresponding with 32 %w of the residue before this was recycled to the hydrocracker. In this way 8 pbw of a C4 fraction, 18 pbw of a C5-150 C fraction, 38 pbw o~ a 150-370 C fraction and 16 pbw of a 370 C
residue were obtained from 80 pbw of the heavy hydrocarbon oil. The 150-370 C fraction had a pour point of -12 C and a cetane number of 50. The 370 C residue had a sulphur content of 0.1 ~w and a Vk of 7.4 cSt. To compensate for the catalyst deactivation, in the pre2sent case the temperature needed to be increased by only 0.2 C every 100 h.
A stable residual fuel was prepared by blending 16 pbw of the 370 C residue obtained according to experiment 1 with 2.9 pbw of the butane asphalt obtained in the deasphalting of the short residue.
; The fuel had a sulphur content of 1.0 ~w and a Vk of 22 cSt.
EXPERIME~T 3 A bigh-viscosity-index lubricating oil was prepared by dewaxing the 370 C residue obtained according to experiment 1. The dewaxing was carried out by mixing the residue with a solvent consisting of 60 %v methyl ethyl ketone and 40 %v toluene using a solvent/oil ratio ; of 2.5 l per kg and by cooling the mixture to -30 C. In this way 14 pbw lubricating oil and 2 pbw slack wax were obtained from 16 pbw of the residue. The lubricating oil had a VI of 120, a Vk of 7.8 cSt and a pour point of -25 C. 210 . .
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EXPERIMENT B
The heavy hydrocarbon oil described hereinbefore was hydrocracked in two stages. The first stage of the process was carried out at a temperature of 385 C, a hydrogen partial pressure of 123 bar, a hydrogen/
feed ratio of 1000 Nl H2/kg feed and a space velocity of 0.5 l feed per litre catalyst per hour. The second stage of the process was carried out at an initial temperature of 310 C, a hydrogen partial pressure of 123 bar, a hydrogen/feed ratio of 1700 Nl H2/kg feed and a space velo-city of 0.7 l of feed per litre of catalyst per hour. In the first stage of the process a composition containing nickel sulphide, molyb-denum sulphide and fluorine on alumina (3.2 ~w Ni/11.8 ~w Mo/6.4 ~w F) was used as the catalyst. In the second stage of the process a composi-tion containing nickel sulphide, tungsten sulphide and fluorine on silica-alumina (3.5 %w Ni/2.6 %w W/2.6 %w F) was used as the catalyst.
The volume ratio of the catalysts in the first and in the second stage of the process was 1:1. The hydrocracked products of the first and of the second stage were blended and the blend was split up by distillation at atmospheric pressure into a C~ fraction9 a C5-150 C fraction, a 150-370 C fraction and a 370 C residue, which residue was used completely as the feed for the second stage. The recycle ratio was 0.40 in this case. In this way 8 pbw of a C4 fraction, 20 pbw of a C5-150 C
fraction and 52 pbw of a 150-370 C fraction were obtained from 80 pbw of the heavy hydrocarbon oil. The 150-370 C fraction had a pour point of -30 C and a cetane number of 54. m e duration of the experiment was 1000 h. To compensate for the catalyst deactivation in the second stage the temperature in the second stage had to be increased by 1.2 C
every 100 h.
This experiment was carried out in substantially the s&me way as experiment B, the difference being, however, that in the present case a space velocity of 1.2 l of ~eed per litre of catalyst per hour was used i3~
in the second stage and a volume ratio o~ the catalysts ~ 2:1 in the ~irst stage and in the second stage of the process and that from the 370 C residue a quantity was separated corresponding with 33 %w of the residue before this was used as the ~eed for the second stage. In this way 6 pbw of a C4 fraction, 14 pbw of a C~-150 C fraction, 44 pbw of a 150-370 C fraction and 16 pbw o~ a 370 C residue were obtained ; ~rom 80 pbw of the heavy hydrocarbon oil. The 150-370 C fraction had a pour point of -25 ~C and a cetane number of 53. The 370 C residue had a sulphur content of less than 0.01 %w and a Vk of 7.2 cSt. To compensate for the catalyst deactivation in the secon~ stage, in the present case the temperature in the second stage needed to be increased by only 0.2 C every 100 h.
EXPE~IMENT 5 A stable residual fuel was prepared by blending 16 pbw of the 37 ~C residue obtained according to experiment 4 with 3.1 pbw o~
the butane asphalt obtained in the deasphalting of the short residue.
The fuel had a sulphur content of 1 %w and a Vk of 23 cSt.
A high-viscosity-index lubricating oil was prepared by dewaxing the 370 C residue obtained according to experiment ~. The dewaxing was carried out in the same way as described under experiment 3. From 16 pbw o~ the residue 13 pbw lubricating oil and 3 pbw slack wax were obtained. The lubricating oil had a VI of 123, a Vk of 7.8 cSt and a pour point of -23 C. 210 The following observation can be made with regard to the above example. Experiments 1-6 are experiments according to the invention.
Experiments A and B fàll outside the scope of the invention and have been included for comparison. Comparison o~ the results of experiments 1 and A shows that application of the invention in a one-stage hydro-crackinJ proce~s 1 ds to : conslder~ble decre~ss of the c~t~lyst de-'. . '' ', ":
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~Z630 activation (from 1.5 C/100 h to 0.2 C/100 h). Comparison of the re-sults of experiment 4 and B shows that application o~ the invention in the second stage of a two-stage hydrocracking process also leads to a considerable decrease of the catalyst deactivation in this stage (from ; 5 1.2 C/100 h to 0.2 C/100 h). In experiment 1 as well as in experiment 4 a residual hydrocarbcn oil is obtained as by-product, which as such is suitable as a low-sulphur residual fuel (sulphur content 0.1 %w and 0.01 %w, respectively). As is seen from experiments 2 and 5, the re-sidual hydrocarbon oil obtained as by-product c~n also very suitably be used as a blending component ~or the preparation of a stable residual ~uel by blending the oil with asphalt obtained in the deasphalting of the short residue. Finally, experiments 3 and 6 show that the residual hydrocarbon oil obtained as by-product can suitably be used for the preperet~on o~ e high-viscosity-index lubrio~ting oil by dev ing.
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Hydrocracking of heavy hydrocarbon oils for the preparation of light hydrocarbon fractions, such as gasoline, kerosine and gas oil fractions, is applied on a large scale in the oil industry. From the product obtained in hydrocracking the desired light hydrocarbon frac-tions are separated by distillation and the residue obtained in the distillation is recycled to the hydrocracker.
The heavy hydrocarbon oil that is used as the feed for the hydro-cracker is often prepared from an atmospheric distillation residue ofa crude oil (called a long residue) by distillation at reduced pressure.
In addition to a heavy distillate that is used as the ~eed for the hydrocracker this distillation yields a residual fraction tcalled a "
short residue).
To obtain from a certain long residue a higher yield of light hydrocarbon fractions than is possible in the process described here-inbefore, one might think of subjecting a larger proportion of the long residue to hydrocracking. ~o this end the long residue may be de-asphalted and the deasphalted oil thus obtained may be hydrocracked or the short residue may be deasphalted, the deasphalted oil thus obtained be mixed with the heavy distillate from the long residue and the mixture be hydrocracked. Attempts to increase the yield of light hydrocarbon frac-tions in this way have been rather unsuccessful up to now, because when using these heavy feeds a very rapid deactivation of the hydrocracking catalyst occurs.
It has now been found that hydrocracking such heavy feeds according ; to the process described hereinbefore presents no problems if from the residue obtained in the distillation of the hydrocracked product a quantity ;;less than half is separated before this residue is recirculated to the hydrocracker.
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The invention therefore relates to a process for ~he prepara-tion of light hydrocarbon fractions, in which a heavy hydrocarbon oil that consists at least pa~tly of a deasphalted oil is hydroc~acked, the hydro-cracked product being separated by distillation into one or more light hydro-carbon fractions and a residual ~raction, the residual fraction being divided into two portions having the same composition but differing in size, the larger portion being recirculated to the hydrocracker.
Thus this invention provides a process for the preparation of light hydrocarbon fractions by hydrocracking of a heavy hydrocarbon oil, characterized in that a heavy hydrocarbon oil that consists at least partly of a deasphalted oil~ is hydrocracked in one stage, or the hydrocracking of the heavy hydrocarbon oil in the first stage and the hydrocracking of the distillation residue in the second stage3 when carrying out the process ac-cording to the invention in two stages, is effected by contacting the feeds concerned together with hydrogen at elevated temperature and pressure with a suitable hydrocracking catalyst at a temperature of from 250 to 450C, a pres-sure of from 50 to 200 bar, a hydrogen/feed ratio of from 250 to 4000 Nl hy-drogen/kg feed and a space velocity of from 0.2 to 5.0 1 of feed per litre of catalyst per hour in the presence of an acid catalyst comprising one or more me~als of Group VI and one or more metals of Group VIII ciron group~ on a carrier, in that the hydrocracked product is separa~ed by distillation into one or more light hydrocarbon fractions and a residual fraction, in that the residual fraction is divided into two portions having the same composition but difering in size and in that the larger portion is recirculated to the hydro~
cracker.
The division of the residual fraction into two unequal portions is preferably carried out in such a way that the smal]er portion corresponds in quantity with 1 25 %w of the heavy hydrocarbon oil to be hydrocracXed.
The process according to the invention not only offers the pos_ 3Q sibility of hydrocracking the said heavy hydrocarbon oils to light hydro~
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....... . ........ . ,, . ..... i ..... .: .. .. . .. , . . . ~ .. . . ...
car~on fractions without this leading to a very rapid deactlvation of the catalyst~ but, in addition, yields as a useful by-product a residual hydro-carbon oil tha~ can very suitably be used as a high-viscosity-index lubri-cating oil, as a low~sulphur residual fuell or as a blending component for the preparation of a lubricating oil or a residual fuel, The process according to the invention can very suitably be used for hydrocracking heavy hydrocarbon oils in one stage. The process according to the invention can also very suitably be used as the second stage o~ a two~stage hydrocracking process, In hydrocracking of heavy hydrocarbon oils in two stages for the preparation of light hydrocarbon ractions the hydrocracked products of the first and the second stage may be distilled separately or jointly, Both in one-stage and in two-stage hydrocracking a gas containing hydrogen is separated from the crude hydro-cracking products, before the cracking prod~cts are separated into the de-sired light hydrocarbon fractions and ~ residual ~raction. After purifi cation this gas is preferably recycled to the first and/or the second hydro-cracker, - 3a , -~ hen the process according to the invention is carried out as the second stage of a two-stage hydrocracking process for the preparation of light hydrocarbon fractions from a heavy hydrocarbon oil, the hydro-cracked products of the ~irst and of the second stage being distilled separately, the process is carried out as ~ollows. A heavy hydrocarbon oil consisting at least partly o~ a deasphalted oil is hydrocracked in the first stage and from the hydrocracked product the desired light hydrocarbon fractions are separated by distillation. The residue ob-tained in this distillation is subsequently hydrocracked in the second stage and from the hydrocracked product the desired light hydrocarbon frsctions are separated in a separate distillation unit. The residue obtained in this second distillation is divided into two unequal por-tions, the smaller portion in quantity preferably corresponding with 1-25 %w of the heavy hydrocarbon oil that is used as the feed for the first hydrocracker and the larger portion is recirculQted to the second hydrocracker.
When the process according to the invention is carried out as the second stage of a two-stage hydrocracking process for the preparation of light hydrocarbon fractions from a heavy hydrocarbon oil, the hydro-cracked products of the first and of the second stage being distilledjointly, the process is carried out as follows. A heavy hydrocarbon oil consisting at least partly of a deasphalted oil, is hydrocracked in the ~irst stage, the hydrocracked product of the first stage is mixed with the hydrocracked product of the second stage and from the mixture the desired light hydrocarbon fractions are separated by distillation.
The residue obtained in this aistillation is divided into two unegual portions, the smaller portion in quantity preferably corresponding with 1_25 %w of the heavy hydrocarbon oil that is used as the feed for the first hydrocracker while the larger portion is used as the ~eed for the second hydrocracker.
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3~
In the process according to the invention a heavy hydrocarbon oil consisting at least partly o~ a deasphalted oil should be used as the feed, for example a deasphalted distillation residue of a crude oil.
This distillation residue may have been obtained in the distillation at atmospheric pressure or in the distillation at a reduced pressure. Al-though it is in principle possible in the process according to the in-vention to use as the starting material a ~eed entirely consisting of a deasphalted oil, for example a deasphalted long or short residue, preference is given to a feed consisting of a mixture of a distillate obtained in the distillation at a reduced pressure of a long residue with a deasphalted short residue. A very suitable ~eed ~or the process accord- i~
ing to the invention can be prepared by splitting up a long residue by distillation at reduced pressure into a distillate and a short residue, deasphalting the short residue and blending the distillate with the de-asphalted oil, pre~erably in production ratio. When in the process according to the invèntion one o~ the feed components is a distillate obtained in the distillation at reduced pressure of a long residue, a flashed distillate of a long residue is preferred ~or this purpose.
In the process according to the invention the feed must consist at least partly of a deasphalted oil, The deasphalting of the oil is pre~erably carried out at elevated temperature and pressure and in the ~ `
presence of an excess of a lower hydrocarbon, such as propane, butane or pentane or a mixture thereof, as the solvent.
The hydrocracking of the heavy hydrocarbon oil, when carrying out the process according to the invention in one stage9 or the hydrocracking of the heavy hydrocarbon oil in the first stage and the hydrocracking o~
the distillation residue in the second stage, when carrying out the process according to the invention in two stages, is ef~ected by con-tacting the ~eeds concerned together with hydrogen at elevated tempe-rature and pressure with a suitable hydrocracking catalyst. Suitable ;
i., ,...i, .
, ;~
~ .
hydrocracking conditions are a temperature of from 250 to 450 C, a pressure of from 50 to 200 bar, a hydrogen/feed ratio of from 250 to 4000 Nl hydrogen/kg feed and a space velocity of from 0.2 to 5.0 1 of feed per litre of catalyst per hour. In hydrocracking the ~ollowing conditions are preferably applied: a temperature of ~rom 300 to 425 C, a pressur~ o~ from 75 to 175 bar, a hydrogen/feed ratio of from 750 to 2500 ~1 hydrogen/kg feed and a space velocity of from 0.5 to 3.0 1 of feed per litre of catalyst per hour.
The catalysts preferably used are acid catalysts comprising one or more metals o~ Group VI and one or more metals of Group VIII (iron group) on a carrier. Examples of suitable metal combinations are cobalt-molybdenum, nickel-molybdenum and nickel-tungsten. E~amples o~ suitable carriers are silica, alumina, magnesia9 and æirconia, as well as com-binations of these such as silica-alumina and silica-zirconia. Zeolites are also eligible for use as carriers for the present hydrocracking cata-lysts, Besides the above-mentioned metals the catalysts preferably also ~;
contain one or more promoters, such as phosphorus and/or halogens9 in particular fluorine. The metals may be present on the carriers as such or in the form of their oxides or sulphides. Preference is given to the application of catalysts in which the metals are present on the carrier in the form of their sulphides.
Very favourable results can be achieved by application of the process according to the invention to the hydrocracking o~ a heavy hydro-carbon oil in one StQge using a catalyst containing nickel sulphide, 25 molybdenum sulphide and fluorine on alumina, as well as to the hydro- i~
crscking of a heavy hydrocarbon oil in two stages using a catalyst con-taining nickel sulphide, molybdenum sulphide and fluorine on alumina in `the first stage and a catalyst containing nickel sulphide, tungsten sulphide and fIuorine on silica-alumina in the second stage.
; 30 The preparation of light hydrocarbon fractions by hydroaracking . ' ' . ' - ' ' , ~ .
:
a hea~y hydrocarbon oil can be effected in the vapour phase, in the liquid phase or partly in the vapour phase and partly in the liquid phase. Preferably a ~ixed catalyst bed is used. A very suitable em- --bodiment is the one in which the feed to be converted, which is partly in the liquid phase and partly in the gas phase, is passed over a fixed catalyst bed, the so-called trickle phase method.
As was already stated hereinbe~ore, the process according to the invention yields as a useful by-product a residual hydrocarbon oil that is very suitable to be used as a high-viscosity-index lubricating oil, as a low-sulphur residual fuel or as a blending component for the preparation of a lubricating oil or a residual fuel.
If the residual hydrocarbon oil obtained as a by-product in the - process according to the invention is intended for use as a high-viscosity-index lubricating oil or as a blending component ~or the preparation of a lubricating oil by blending with other components having 8 viscosity in the lubricating oil range, the residual hydro-carbon oil is preferably dewaxed. For dewaxing the usual techniques can be applied3 such as cooling in the presence of a solvent. As a solvent a mixture of methyl ethyl ketone and toluene is very suitable~ ~he sepa-rated paraffin wax can be further processed separately, but can also very suitably be recycled in the hydrocracking process. ; -I~ the residual hydrocarbon oil that is obtained as by-product in the process according to the invention is used as low-sulphur blending component for the preparation of a residual fuel, distillate as well as residual components can be used as the other components in the blend. A
very suitable blending component ~or the residual hydrocarbon oil for the preparation of a residual fuel is the asphalt obtained in the pre-paration of the deasphalted oil that is used as the feed for the process according to the invention.
The invention will now be elucidated with the aid of the following ~xa~ple.
;
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~i5 2~
- .:
AMPLE
As starting material was used an atmospheric distillation residue originating rrOm a Middle East crude, which residue had the following properties:
initial boiling point 370 C
Vk (kinematic viscosity at 210 F) 15.6 cSt sulphur content 3.3 ~w 100 pbw of this long residue were split up by rlashing into 47 pbw rlashed distillate and 53 pbw short residue. The short residue was deasphalted with n-butane as the solvent at an avera~e temperature Or 125 C, a pressure Or 40 bar and a solvent/oil weight ratio of 4:1.
In this way 33 pbw deasphalted oil and 20 pbw butane asphalt ha~ing a sulphur content of 6 ~w were obtained ~rom the short residue. The `
rlashed distillate was blended in production ratio with the deasphalted oil to 80 pbw Or a heavy hydrocarbon oil which was used in the hydro-cracking experiments mentioned hereinarter.
EXPERIMENT A - `~
The heavy hydrocarbon oil described hereinbe~ore was hydrocracked in a one-stage process at an initial temperature of 400 C, a hydrogen partial pressure o~ 123 bar, a hydrogen/feed ratio of 1000 ~l H2/kg fresh ~eed and a space ~elocity of 0.5 l o~ ~resh`~eed per litre o~
catalyst per hour. As the catalyst a composition was used containing nickel sulphide, molybdenum sulphide and ~Iuorine on alu~ina (3.? Yw Ni/
11,8 gw Mo/6.4 %w F). The hydrocracked product was split up by diQ-tillation st atmospheric pressure into a C4 fraction, a~C5-150 C-~
fraction, ~ 150-370 C fraction and a 370 C residue, which residue was recycled completely to the hydrocracker~ using a recycle ratio~
(pbw recycled product: pbw fresh ~eed? o~ 0.5. In this way-10 pbw o~ a C4 rrsctiOn, 23 pbw of a C5-150 C fraction and 47 pbw of a 150-370 C ~raction were obtained ~rom 80 pbw~or the heavy hydrocarbon , .
. .
. .
,: .' ,:
, .. .. : `"' oil. The 150-370 C ~raction had a pour point of -12 C and a cetane number of 50. The duration of the experiment was 1000 h. To compensate for the catalyst deactivation the temperature had to be increased by 1.5 C every 100 h.
This experiment was carried out in substantially the same way as experiment A, the difference being, however, that in the present case a space velocity of C.8 l of fresh feed per litre of catalyst per hour was applied and that from the 370 C residue a quantity was se-parated corresponding with 32 %w of the residue before this was recycled to the hydrocracker. In this way 8 pbw of a C4 fraction, 18 pbw of a C5-150 C fraction, 38 pbw o~ a 150-370 C fraction and 16 pbw of a 370 C
residue were obtained from 80 pbw of the heavy hydrocarbon oil. The 150-370 C fraction had a pour point of -12 C and a cetane number of 50. The 370 C residue had a sulphur content of 0.1 ~w and a Vk of 7.4 cSt. To compensate for the catalyst deactivation, in the pre2sent case the temperature needed to be increased by only 0.2 C every 100 h.
A stable residual fuel was prepared by blending 16 pbw of the 370 C residue obtained according to experiment 1 with 2.9 pbw of the butane asphalt obtained in the deasphalting of the short residue.
; The fuel had a sulphur content of 1.0 ~w and a Vk of 22 cSt.
EXPERIME~T 3 A bigh-viscosity-index lubricating oil was prepared by dewaxing the 370 C residue obtained according to experiment 1. The dewaxing was carried out by mixing the residue with a solvent consisting of 60 %v methyl ethyl ketone and 40 %v toluene using a solvent/oil ratio ; of 2.5 l per kg and by cooling the mixture to -30 C. In this way 14 pbw lubricating oil and 2 pbw slack wax were obtained from 16 pbw of the residue. The lubricating oil had a VI of 120, a Vk of 7.8 cSt and a pour point of -25 C. 210 . .
.. . .
~8~;3~
EXPERIMENT B
The heavy hydrocarbon oil described hereinbefore was hydrocracked in two stages. The first stage of the process was carried out at a temperature of 385 C, a hydrogen partial pressure of 123 bar, a hydrogen/
feed ratio of 1000 Nl H2/kg feed and a space velocity of 0.5 l feed per litre catalyst per hour. The second stage of the process was carried out at an initial temperature of 310 C, a hydrogen partial pressure of 123 bar, a hydrogen/feed ratio of 1700 Nl H2/kg feed and a space velo-city of 0.7 l of feed per litre of catalyst per hour. In the first stage of the process a composition containing nickel sulphide, molyb-denum sulphide and fluorine on alumina (3.2 ~w Ni/11.8 ~w Mo/6.4 ~w F) was used as the catalyst. In the second stage of the process a composi-tion containing nickel sulphide, tungsten sulphide and fluorine on silica-alumina (3.5 %w Ni/2.6 %w W/2.6 %w F) was used as the catalyst.
The volume ratio of the catalysts in the first and in the second stage of the process was 1:1. The hydrocracked products of the first and of the second stage were blended and the blend was split up by distillation at atmospheric pressure into a C~ fraction9 a C5-150 C fraction, a 150-370 C fraction and a 370 C residue, which residue was used completely as the feed for the second stage. The recycle ratio was 0.40 in this case. In this way 8 pbw of a C4 fraction, 20 pbw of a C5-150 C
fraction and 52 pbw of a 150-370 C fraction were obtained from 80 pbw of the heavy hydrocarbon oil. The 150-370 C fraction had a pour point of -30 C and a cetane number of 54. m e duration of the experiment was 1000 h. To compensate for the catalyst deactivation in the second stage the temperature in the second stage had to be increased by 1.2 C
every 100 h.
This experiment was carried out in substantially the s&me way as experiment B, the difference being, however, that in the present case a space velocity of 1.2 l of ~eed per litre of catalyst per hour was used i3~
in the second stage and a volume ratio o~ the catalysts ~ 2:1 in the ~irst stage and in the second stage of the process and that from the 370 C residue a quantity was separated corresponding with 33 %w of the residue before this was used as the ~eed for the second stage. In this way 6 pbw of a C4 fraction, 14 pbw of a C~-150 C fraction, 44 pbw of a 150-370 C fraction and 16 pbw o~ a 370 C residue were obtained ; ~rom 80 pbw of the heavy hydrocarbon oil. The 150-370 C fraction had a pour point of -25 ~C and a cetane number of 53. The 370 C residue had a sulphur content of less than 0.01 %w and a Vk of 7.2 cSt. To compensate for the catalyst deactivation in the secon~ stage, in the present case the temperature in the second stage needed to be increased by only 0.2 C every 100 h.
EXPE~IMENT 5 A stable residual fuel was prepared by blending 16 pbw of the 37 ~C residue obtained according to experiment 4 with 3.1 pbw o~
the butane asphalt obtained in the deasphalting of the short residue.
The fuel had a sulphur content of 1 %w and a Vk of 23 cSt.
A high-viscosity-index lubricating oil was prepared by dewaxing the 370 C residue obtained according to experiment ~. The dewaxing was carried out in the same way as described under experiment 3. From 16 pbw o~ the residue 13 pbw lubricating oil and 3 pbw slack wax were obtained. The lubricating oil had a VI of 123, a Vk of 7.8 cSt and a pour point of -23 C. 210 The following observation can be made with regard to the above example. Experiments 1-6 are experiments according to the invention.
Experiments A and B fàll outside the scope of the invention and have been included for comparison. Comparison o~ the results of experiments 1 and A shows that application of the invention in a one-stage hydro-crackinJ proce~s 1 ds to : conslder~ble decre~ss of the c~t~lyst de-'. . '' ', ":
. _ _ ...... . , :
', ~ . . .. , ., ~
~Z630 activation (from 1.5 C/100 h to 0.2 C/100 h). Comparison of the re-sults of experiment 4 and B shows that application o~ the invention in the second stage of a two-stage hydrocracking process also leads to a considerable decrease of the catalyst deactivation in this stage (from ; 5 1.2 C/100 h to 0.2 C/100 h). In experiment 1 as well as in experiment 4 a residual hydrocarbcn oil is obtained as by-product, which as such is suitable as a low-sulphur residual fuel (sulphur content 0.1 %w and 0.01 %w, respectively). As is seen from experiments 2 and 5, the re-sidual hydrocarbon oil obtained as by-product c~n also very suitably be used as a blending component ~or the preparation of a stable residual ~uel by blending the oil with asphalt obtained in the deasphalting of the short residue. Finally, experiments 3 and 6 show that the residual hydrocarbon oil obtained as by-product can suitably be used for the preperet~on o~ e high-viscosity-index lubrio~ting oil by dev ing.
' ' ~.'~,',:
' "'' '-'' '.
' :'.'.'`"
'. .
.. . .
,:
. .
' .''' .
' :'
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of light hydrocarbon fractions by hydrocracking of a heavy hydrocarbon oil, characterized in that a heavy hydrocarbon oil that consists at least partly of a deasphalted oil, is hydrocracked in one stage, or the hydrocracking of the heavy hydrocarbon oil in the first stage and the hydrocracking of the distillation residue in the second stage, when carrying out the process according to the invention in two stages, is effected by contacting the feeds concerned together with hydrogen at elevated temperature and pressure with a suitable hydrocracking catalyst at a temperature of from 250 to 450°C, a pressure of from 50 to 200 bar, a hydrogen/feed ratio of from 250 to 4000 Nl hydrogen/kg feed and a space velocity of from 0.2 to 5.0 l of feed per litre of catalyst per hour in the presence of an acid catalyst comprising one or more metals of Group VI and one or more metals of Group VIII (iron group) on a carrier, in that the hydrocracked product is separated by distillation into one or more light hydrocarbon fractions and a residual fraction, in that the residual fraction is divided into two portions having the same composition but differing in size and in that the larger portion is recirculated to the hydrocracker.
2. A process according to claim 1, characterized in that the division of the residual fraction into two unequal portions is carried out in such a way that the smaller portion corresponds in quantity with 1-25 %w of the heavy hydrocarbon oil to be hydrocracked.
3. A process according to claim 1 or 2, characterized in that it is carried out as the second stage of a two-stage hydrocracking process for the preparation of light hydrocarbon fractions from a heavy hydrocarbon oil.
4. A process according to claim 1, characterized in that the heavy hydrocarbon oil is hydrocracked in the first stage, in that the hydrocracked product is separated by distillation into one or more light hydrocarbon fractions and a residual fraction, in that the residual fraction is subsequently hydrocracked in the second stage, in that the hydrocracked product is separated in a separate distillation unit into one or more light hydrocarbon fractions and a residual fraction, in that the residual fraction, is divided into two unequal portions, the smaller portion in quantity pre-ferably corresponding with 1-25 %w of the heavy hydrocarbon oil that is used as the feed for the first hydrocracker and that the larger portion is recir-culated to the second hydrocracker.
5. A process according to claim 1, characterized in that the heavy hydrocarbon oil is hydrocracked in the first stage, in that the hydrocracked product of the first stage is mixed with the hydrocracked product of the second stage, in that the mixture is separated by distillation into one or more light hydrocarbon fractions and a residual fraction, in that the re-sidual fraction is divided into two unequal portions, the smaller portion in quantity is used as the feed for the first hydrocracker while the larger portion is used as the feed for the second hydrocracker.
6. A process according to claim 5 characterized in that the division of the residual fraction into two unequal portions is carried out in such a way that the smaller portion corresponds in quantity with 1-25 %w of the residual fraction.
7. A process according to any one of claims 1, 4 or 5, characterized in that from the smaller portion obtained in the division of the residual fraction into two unequal portions, a lubricating oil or lubricating oil blending component is prepared by dewaxing this portion.
8. A process according to any one of claims 1, 4 or 5, characterized in that from the smaller portion obtained in the division of the residual fraction into two unequal portions, a residual fuel is prepared by mixing this portion with one or more distillate components or residual components,
9. A process according to any one of claims 1, 4 or 5, characterized in that from the smaller portion obtained in the division of the residual fraction into two unequal portions, a residual fuel is prepared by mixing this portion with one or more distillate components or residual components, one of which is the asphalt obtained in the preparation of the deasphalted oil which is present in the feed to be hydrocracked.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7416169 | 1974-12-12 | ||
| NL7416169A NL7416169A (en) | 1974-12-12 | 1974-12-12 | PROCESS FOR THE PREPARATION OF LIGHT CARBON-HYDROGEN FRACTIONS. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1082630A true CA1082630A (en) | 1980-07-29 |
Family
ID=19822634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA236,702A Expired CA1082630A (en) | 1974-12-12 | 1975-09-30 | Process for the preparation of light hydrocarbon fractions |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5183604A (en) |
| CA (1) | CA1082630A (en) |
| DE (1) | DE2555625A1 (en) |
| FR (1) | FR2294226A1 (en) |
| GB (1) | GB1525478A (en) |
| IT (1) | IT1054436B (en) |
| NL (1) | NL7416169A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3778841B1 (en) * | 2019-08-15 | 2021-11-24 | Infineum International Limited | Method for reducing piston deposits in a marine diesel engine |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3245900A (en) * | 1963-12-26 | 1966-04-12 | Chevron Res | Hydrocarbon conversion process |
| US3287254A (en) * | 1964-06-03 | 1966-11-22 | Chevron Res | Residual oil conversion process |
| DE1228738B (en) * | 1966-01-07 | 1966-11-17 | Basf Ag | Process for the production of lower-boiling hydrocarbons from crude oils or crude oil residues by catalytic hydrogenation |
| 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 |
-
1974
- 1974-12-12 NL NL7416169A patent/NL7416169A/en not_active Application Discontinuation
-
1975
- 1975-09-30 CA CA236,702A patent/CA1082630A/en not_active Expired
- 1975-12-10 IT IT3017475A patent/IT1054436B/en active
- 1975-12-10 JP JP14645575A patent/JPS5183604A/en active Pending
- 1975-12-10 GB GB5059775A patent/GB1525478A/en not_active Expired
- 1975-12-10 FR FR7537779A patent/FR2294226A1/en active Granted
- 1975-12-10 DE DE19752555625 patent/DE2555625A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB1525478A (en) | 1978-09-20 |
| DE2555625A1 (en) | 1976-06-16 |
| JPS5183604A (en) | 1976-07-22 |
| NL7416169A (en) | 1976-06-15 |
| IT1054436B (en) | 1981-11-10 |
| FR2294226A1 (en) | 1976-07-09 |
| DE2555625C2 (en) | 1987-05-27 |
| FR2294226B1 (en) | 1979-08-31 |
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