CA1251133A - Method of recovering oil and gas from oil sand, oil chalk, and oil shale - Google Patents
Method of recovering oil and gas from oil sand, oil chalk, and oil shaleInfo
- Publication number
- CA1251133A CA1251133A CA000445624A CA445624A CA1251133A CA 1251133 A CA1251133 A CA 1251133A CA 000445624 A CA000445624 A CA 000445624A CA 445624 A CA445624 A CA 445624A CA 1251133 A CA1251133 A CA 1251133A
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- Canada
- Prior art keywords
- oil
- pyrolysis
- fluidized bed
- gas
- sand
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
Abstract of the Disclosure A method is disclosed for recovering oil and gas from oil sand, oil shale and/or oil chalk through pyrolysis in a pyrolysis fluidized bed which is indirectly heated to from 400 to 1000°C, and preferably from 500 to 750, the heating of the pyrolysis fluidized bed being effected through heating tubes.
Description
- \
~251~L33 The present invention relates to a method of recovering oil and gas from oil sand, oil chalk and/or oil shale by pyrolysis in a fluidized bed heated indirectly to from 400 to 1000C.
Amounts of oil bonded in oil sand and oil shale are known to be comparable to those present in the known places of mineral oil occurrences (Taylor, R.B.; Chemical Engineering, September 7, 1981, page 63). So, oils contained solely in the Canadian oil sands or the Alberta region covering about 48.000 km2 amount to more than 124 billion tons (Stausz, O.P. Lown, E.M.; Oil Sand a. Oil Shale Chemistry, Verlag Chemie, Weinheim-New York 1978).
The oil shale reserves in the world containing an oil proportion of more than 10 per cent are even estimated to comprise 2,550 billion tons oE bonded oil.
Oil sand and oil shale occurrences are distributed all over the world. The main occurrences are situated in the United States of America, Canada, Brazil, Australia, hlorocco, Jordan, USSR, and China. There are some smaller occurrences in the Federal Republic of Germany.
The exploitation of oil shale for the recovery of paraffins is older than the exploitation of mineral oil. However, in spite of the enormous reserves, no utilization worth mentioning has taken place to date. Altogether, only a few million tons of oil per annum are recovered from oil sand and oil shale according to the methods of recovery known to date (Grant, K.; Chemical Engineering, April 5, 1982, page 20E-20H). This is attributed to the fact that the economical and ecologically tolerable utilization of oil sand and oil shale poses considerably greater problems than the recovery of mineral oil. I~ith the methods known to date these problems consist, in the separation of the oil from the sand or shale with oil contents of only 7 to 15 per cent and, furthermore, in the high proportions of 8 to 25 per cent of asphalts, as well as in a ~25~33 sulphur content of from 3 to 7 per cent.
It is known that according to the method of the Syncrude L-td., as used in Alberta, Canada, oil may be recovered using superheated water vapour or hot water (Rammler, R.W.; Oil Shale Processing Technology, East Brunswick, New Jersey 1982, page 83). In this process, a residue will occur comprising the sand, largely freed of ~he oil but also still containing an oil/water sludge, which may result in too great an impairment of the environments. The thus recovered oil sand extract is not directly suited for use ~ithout any further after-treatment because it has too high a viscosity, too higll a pro-portion of asphalts, and too lligh a sulphur content. Therefore, the extract must be split into utilizable products in series-arranged hydro cracking plants.
Through this manner of processing, on the one hand, oil is lost and, on the other hand, the remainders of oil together with the simultaneously used large amounts of extraction water give rise to waste disposal problems. These dis-advantages have already led to closure of some of these plants.
It is furthermore known that oil shale is at the present time being utilized in sonne smaller plants such as the Lurgi-Ruhrgas process, the Kiviter process, the Tosco II process, and the Paraho process, as well as some other similar processes ~Allred V.D.; Oil Shale Processing Technology, The Center for Professional Advancement, East Brunswick, New Jersey 1982).
It is in addition known that in these processes use is made of circulating fluidizecl beds. Witll the Lurgi-Ruhrgas process, burnt hot sand which is circulated at temperatures of 630C serves to pyrolyze the oil shale.
The pyrolysis takes place in a mixer with one part of oil shale being mixed Witll 4 to 8 parts o:E sand. Thus, considerable amounts of hot sand must be transported. The same is equally applicable to processes in which burnt solid ~5~133 pyrolysis residues are circulated as heat carriers (United States patent letters 4,199,432, Tamm et al and 4,293,401, Sieg et al). ~ith the carrier process the oil shale is pyrolized by hot gas. The hot gas is produced in a retort by partial oxidation and introduction of vapour ~just as in United States patent 3,491,016). A portion o the oil is burnt in this manner.
In contrast to the above, the Tosco II process makes use of ceramic balls for the transfer of heat to the oil shale, the ceramic balls being moved in a rotary tube furnace. The ceramic balls are screened from the residue after pyrolysis and re-heated in a separate process step. The Paraho reactor consists of a vertically arranged, brick-lined shaft. The energy neces-sary for de-oiling is covered by additional supply of air and thus partial oxidation. Thereby, however, also the pyrolysis oils that have been ormed are partially oxidized.
For the supply of the necessary splitting energy, the known pro-cesses either use mechanically moved devices, circulating amounts of sand, or partial oxidation. But since the proportion of oil in the materials is at only 10 to 15 per cent, considerable masses must be moved in the mechanical pro-cesses. The partial oxidation, in particular, results in a drastic deteriora-tion of the oil qualities. Those processes working-with vapour, on the other hand, leave a residue which is hardly ecologically tolerable.
Through work performed at the University of Hamburg it became known that fluidi~ed beds which are indirectly heated by jet type heating tubes are suited to pyrolyze plastic wastes and old tires into aromatic carbon com-pounds~ e.g. reusable carbon black and gases rich in heating energy (German patent 26 58 371).
It is, therefore, the object of the invention to overcome the dis--- ~25~33 advantages of the prior art and provide a process renderlng possible the deoiling of oil sandr oil shale or oil chalk to form petrochemicals having properties superior to those provided by the prior art, with a far reaching desulphurization taking place during pyrolysis. It is a further object to produce a clean residue which may unobjectionably be disposed of.
These objects are accomplished according to the inven-tion using a process of the type indicated at the beginnin~, which is characterized in that the heating of the pyrolysis fluidized bed takes place indirectly through the use of heating tubes.
The present invention therefore provides a method of recovering oil and gas from oil sand, oil shale and/or oil chalk by pyrolysis in a fluidized bed heated indlrectly to a temperature of from 400 to 1000C, wherein either the fluidized bed is heated by preheated pyrolysis gas freed of oil which is combusted ln heating tubes, or the fluidized bed is heated by heating tubes containing waste gas as the heat carrier, and wherein the heat carrier waste gas is heated in a second fluidized bed in which the pyrolysis residue is burnt.
It is possible, according to the process of the invention, to pyrolyze oil sand, oil shale or oil chalk in indirectly heated fluidized beds without the known disadvantages of the prior art, with the pyrolysis oils formed exhibiting particularly superior properties, and with the pyrolysis residue being adapted to be converted into a clean sand or shale capable of being disposed of in a series-connected heat exchanger using air under generation of energy.
5~1.33 Using this process, the following advantages are obtained over the prior art:
(a) No mechanically moving parts are present in the hot zone;
(b) There is no need for any large amounts of sand or shale to be circulated;
(c) There is no partial oxidation of the starting material or products taking place in the fluidized bed reactor, owing to the preclusion of air;
(d) Aromatic compounds are predominantly ~ormed as the oils, which may be directly further processed without any after-treatment in hydrogenating or cracking plants;
4a ~25~33 ~ e) The resulting residues are solid, clean substances which are ecologically tolerable.
It is surprising that the fluidized bed does not become sticky even when the fine grained oil sand or ground oil shale is introduced and the layer is fluidized Wit}l the pyrolysis gas freed of the liquid products. This is all the more amazing since, in case of sewage sludge combustion, for example, which also moves a high proportion of inorganic solids, caking phenomena always occur in fluidized bed furnaces, although here the caked materials is partially burnt by partial oxidation.
With the process according to the invention such caking is pre-vented, as evidenced by examinations of individual sand grains or shale part-icles graphitizing in the reducing atmosphere and not sticking to one another.
Moreover, on the other hand, due to the lubricating effect of the graphite, there is no erosion in the fluidized bed reactor.
The invention will be explained in further detail with the aid of the attached drawing which schematically shows, by way of example, a plant suitable for practising the invention. With the process according to the invention, as will be seen in the drawing, the oil sand, oil shale and/or the oil chalk is preferably introduced into the fluidized bed in a heat exchanger where it is indirectly heated by jet type heating tubes to 400 to 1000C ~pre-ferably to 500 to 750C) through locks, screws or pneumatically.
Through an overflow pipe, or some other discharging device per-forming a metering action, just as much pyrolysis residue is dispensed per unit of time from the fluidized bed reactor as is formed through pyrolysis of the introduced oil sand, oil shale or oil chalk.
Surprisingly, the hot pyrolysis residue as withdrawn is self-burning ~Z5~33 upon supply of air in the heat exchanger 1 and covers the greatest proportion of the energy required for the pyrolysis in the fluidized bed reactor. Advan-tageously, the heat exchanger 1 is designed to provide a fluidized bed. Ilow-ever, rotary pipes or other solid heat exchangers may also be used for this purpose.
The pyrolysis gases leaving the fluidized bed reactor are largely freed of entrained solids particles in a separator such as a cyclone, for example, and then are decomposed according to ~he prior art in quenching coolers ~ld washers into oil .md gas which constitute valuable petrochemicals. Such a cyclone is shown labelled "Cyclone 1" in the drawing.
The burnt off pyrolysis sand and the used fluidized bed material leave the heat exchanger through an overflow pipe, thereby dispensing further heat in heat exchanger 2 to the required combustion air or, because exchange-able, to the pyrolysis gas ~hich has been freed of oils. T'ne residue is free of oil and carbon black remainders, and may, without any hesitation, be disposed of or used for other purposes.
The heating of the fluidized bed in the pyrolysis furnace is per-formed by reheating waste gases via heat exchanger pipes in the heat exchanger 1 and by passing them into pipes through the pyrolysis reactor. For initially heating the pyrolysis reactor, and for generating additional energy, jet type heating pipes may additionally be incorporated which are fired with the pyro-lysis gas as the latter is produced.
In a third heat excllallger, labelled 3 in the drawing, the gases required for fluidization are preheated using the waste gases. It is possible ~o incorporate further heat exchangers to improve the energy balance.
Through tlle arrangement according to -the invention of the pyrolysis fluidized bed, ancl the heat exchanger 1, etc., an optimal energy yield may be ~25~133 obtained, thereby minimizing the solids flow through absence of circulation of the pyrolysis residue.
It is surprising that over 90% of the pyrolysis oils are convert-ed into aromatic compounds in spite of the great proportion of solids in the starting material. In this connection, attention is drawn to Table 1 below.
PyRoLy SIS
In the p~roly~is of oil sand, oil shale or oil chalk according to the process of the invention, more than 75 per cent of the bonded oil is converted into utilizable products. Again, attention is drawn to Table 1.
It is also surprising that, in spite of the great proportion of solids in the starting material and the predominantly paraffinic structure of the bonded oil, and in contrast to the known processes, the pyrolysis oil formed is more than 90 per cent converted into aromatic compounds ~see Table 2 below).
Particularly high is the proportion of benzene and toluene. Fortunately, it is these BTX aromatic compounds that are the most sought after petrochemicals for fuels and for the chemical industry.
Moreover, the gas produced according to the process of the inven-tion exhibits some surprising properties (See Table 3 below). It contains high proportions (up to 22 weight per cent) of ethylene, and with more than 30.000 kJ/m , has so high a heating value that it may be compared to natural gas.
With regard to the high quality of the pyrolysis products formed, the process according to the invention will be seen to be superior to all the known processes discussed above.
The advantages of the process according to the invention are fur-ther enhanced by the fact that sulphur, WhiC}l occurs in all types of oil sands and oil shales, is transformed into inorganic salts by reactions with basic materials in the fluidized bed. Frequently these basic substances are already contained in a sufficient amount in the starting material. This is particular-ly true in the cases of oil chalks. In the absence of basic substances, the 25~L~L33 starting material may have chalk or dolomite added thereto in the required amounts. The pyrolysis products are then almost free of hydrogen sulphide.
Because of the high quality pyrolysis products it may also be reasonable to utiliæe, in the practising of the method of the invention, concentrates of oil sand or oil shale which have been produced according to known processes.
Products, in weight per cent, from the pyrolysis of oil sand and oi.l shale performed, according to the invention, at 740& .
Starting Material Oil Sand Oil Shale Oil Content Weight-O 13.5 15.0 Amount Employed ~kg) 380 3.5 Gas 5.3 10.5 Oil, thereof 5.2 6.9 Benzene fraction 0.8 1.1 Toluene fraction 2.6 3.2 Tar 1.8 2.6 Water 0.6 14.7 Residue ~Sand, Carbon Black) 88.9 67.5 , " . ! ~ ' ~25~133 TAB~E 2 Composition of the liquid products from the pyrolysis of oil sand perormed, according to the invention, at 740 C.
Benzene and Tar Weight-% Toluene Fraction Cyclopentadiene 1.8 Benzene 35.5 1.3 Toluene 20.7 0.2 ~thylbenzene/~ylene 6.9 0.1 Styrene 4.5 0.1 Indene 3.6 0.5 Naphthalene 4.3 2.i Methylnaphthalene 3.1 5.4 Diphenyl 0.1 1.5 Fluorene 3 3 Anthracene/Phenantrene - 3.2 Other aromatic compounds 19.5 82.3 `` ~25~33 Composition of the gases from the pyrolysis of oil sand and oil shale performed, according to the invention, at 740C.
Starting Material Oil Sand Oil Shale Plant Technical Plant Laboratory Plant Weight-% Vol-% Weight-% Vol-%
-Hydrogen 2.2 19.6 2.0 20.5 Methane 47.3 52.4 28.3 36.4 Ethane 12.1 7.2 7.4 5.1 10Ethylene 22.1 14.1 14.5 10.6 Propene 5.3 2.3 4.1 2.0 Butadiene 0.8 `0.3 1.1 0.4 Benzene 1.3 0.3 3.0 0.8 Toluene 0,4 0.1 0.1 0.02 Carbon dioxide 1.2 0.5 16.9 7.9 Carbon monoxide 1.3 0.8 21.6 15.9 Hydrogen sulphide 2.9 1.5 0.02 0.01 Other gases 3.1 0.9 0.98 0.37 Density at 20 C ~kg/m3) 0.742 0.856 20Heating value 37500 30500 ., , ~
~251~L33 The present invention relates to a method of recovering oil and gas from oil sand, oil chalk and/or oil shale by pyrolysis in a fluidized bed heated indirectly to from 400 to 1000C.
Amounts of oil bonded in oil sand and oil shale are known to be comparable to those present in the known places of mineral oil occurrences (Taylor, R.B.; Chemical Engineering, September 7, 1981, page 63). So, oils contained solely in the Canadian oil sands or the Alberta region covering about 48.000 km2 amount to more than 124 billion tons (Stausz, O.P. Lown, E.M.; Oil Sand a. Oil Shale Chemistry, Verlag Chemie, Weinheim-New York 1978).
The oil shale reserves in the world containing an oil proportion of more than 10 per cent are even estimated to comprise 2,550 billion tons oE bonded oil.
Oil sand and oil shale occurrences are distributed all over the world. The main occurrences are situated in the United States of America, Canada, Brazil, Australia, hlorocco, Jordan, USSR, and China. There are some smaller occurrences in the Federal Republic of Germany.
The exploitation of oil shale for the recovery of paraffins is older than the exploitation of mineral oil. However, in spite of the enormous reserves, no utilization worth mentioning has taken place to date. Altogether, only a few million tons of oil per annum are recovered from oil sand and oil shale according to the methods of recovery known to date (Grant, K.; Chemical Engineering, April 5, 1982, page 20E-20H). This is attributed to the fact that the economical and ecologically tolerable utilization of oil sand and oil shale poses considerably greater problems than the recovery of mineral oil. I~ith the methods known to date these problems consist, in the separation of the oil from the sand or shale with oil contents of only 7 to 15 per cent and, furthermore, in the high proportions of 8 to 25 per cent of asphalts, as well as in a ~25~33 sulphur content of from 3 to 7 per cent.
It is known that according to the method of the Syncrude L-td., as used in Alberta, Canada, oil may be recovered using superheated water vapour or hot water (Rammler, R.W.; Oil Shale Processing Technology, East Brunswick, New Jersey 1982, page 83). In this process, a residue will occur comprising the sand, largely freed of ~he oil but also still containing an oil/water sludge, which may result in too great an impairment of the environments. The thus recovered oil sand extract is not directly suited for use ~ithout any further after-treatment because it has too high a viscosity, too higll a pro-portion of asphalts, and too lligh a sulphur content. Therefore, the extract must be split into utilizable products in series-arranged hydro cracking plants.
Through this manner of processing, on the one hand, oil is lost and, on the other hand, the remainders of oil together with the simultaneously used large amounts of extraction water give rise to waste disposal problems. These dis-advantages have already led to closure of some of these plants.
It is furthermore known that oil shale is at the present time being utilized in sonne smaller plants such as the Lurgi-Ruhrgas process, the Kiviter process, the Tosco II process, and the Paraho process, as well as some other similar processes ~Allred V.D.; Oil Shale Processing Technology, The Center for Professional Advancement, East Brunswick, New Jersey 1982).
It is in addition known that in these processes use is made of circulating fluidizecl beds. Witll the Lurgi-Ruhrgas process, burnt hot sand which is circulated at temperatures of 630C serves to pyrolyze the oil shale.
The pyrolysis takes place in a mixer with one part of oil shale being mixed Witll 4 to 8 parts o:E sand. Thus, considerable amounts of hot sand must be transported. The same is equally applicable to processes in which burnt solid ~5~133 pyrolysis residues are circulated as heat carriers (United States patent letters 4,199,432, Tamm et al and 4,293,401, Sieg et al). ~ith the carrier process the oil shale is pyrolized by hot gas. The hot gas is produced in a retort by partial oxidation and introduction of vapour ~just as in United States patent 3,491,016). A portion o the oil is burnt in this manner.
In contrast to the above, the Tosco II process makes use of ceramic balls for the transfer of heat to the oil shale, the ceramic balls being moved in a rotary tube furnace. The ceramic balls are screened from the residue after pyrolysis and re-heated in a separate process step. The Paraho reactor consists of a vertically arranged, brick-lined shaft. The energy neces-sary for de-oiling is covered by additional supply of air and thus partial oxidation. Thereby, however, also the pyrolysis oils that have been ormed are partially oxidized.
For the supply of the necessary splitting energy, the known pro-cesses either use mechanically moved devices, circulating amounts of sand, or partial oxidation. But since the proportion of oil in the materials is at only 10 to 15 per cent, considerable masses must be moved in the mechanical pro-cesses. The partial oxidation, in particular, results in a drastic deteriora-tion of the oil qualities. Those processes working-with vapour, on the other hand, leave a residue which is hardly ecologically tolerable.
Through work performed at the University of Hamburg it became known that fluidi~ed beds which are indirectly heated by jet type heating tubes are suited to pyrolyze plastic wastes and old tires into aromatic carbon com-pounds~ e.g. reusable carbon black and gases rich in heating energy (German patent 26 58 371).
It is, therefore, the object of the invention to overcome the dis--- ~25~33 advantages of the prior art and provide a process renderlng possible the deoiling of oil sandr oil shale or oil chalk to form petrochemicals having properties superior to those provided by the prior art, with a far reaching desulphurization taking place during pyrolysis. It is a further object to produce a clean residue which may unobjectionably be disposed of.
These objects are accomplished according to the inven-tion using a process of the type indicated at the beginnin~, which is characterized in that the heating of the pyrolysis fluidized bed takes place indirectly through the use of heating tubes.
The present invention therefore provides a method of recovering oil and gas from oil sand, oil shale and/or oil chalk by pyrolysis in a fluidized bed heated indlrectly to a temperature of from 400 to 1000C, wherein either the fluidized bed is heated by preheated pyrolysis gas freed of oil which is combusted ln heating tubes, or the fluidized bed is heated by heating tubes containing waste gas as the heat carrier, and wherein the heat carrier waste gas is heated in a second fluidized bed in which the pyrolysis residue is burnt.
It is possible, according to the process of the invention, to pyrolyze oil sand, oil shale or oil chalk in indirectly heated fluidized beds without the known disadvantages of the prior art, with the pyrolysis oils formed exhibiting particularly superior properties, and with the pyrolysis residue being adapted to be converted into a clean sand or shale capable of being disposed of in a series-connected heat exchanger using air under generation of energy.
5~1.33 Using this process, the following advantages are obtained over the prior art:
(a) No mechanically moving parts are present in the hot zone;
(b) There is no need for any large amounts of sand or shale to be circulated;
(c) There is no partial oxidation of the starting material or products taking place in the fluidized bed reactor, owing to the preclusion of air;
(d) Aromatic compounds are predominantly ~ormed as the oils, which may be directly further processed without any after-treatment in hydrogenating or cracking plants;
4a ~25~33 ~ e) The resulting residues are solid, clean substances which are ecologically tolerable.
It is surprising that the fluidized bed does not become sticky even when the fine grained oil sand or ground oil shale is introduced and the layer is fluidized Wit}l the pyrolysis gas freed of the liquid products. This is all the more amazing since, in case of sewage sludge combustion, for example, which also moves a high proportion of inorganic solids, caking phenomena always occur in fluidized bed furnaces, although here the caked materials is partially burnt by partial oxidation.
With the process according to the invention such caking is pre-vented, as evidenced by examinations of individual sand grains or shale part-icles graphitizing in the reducing atmosphere and not sticking to one another.
Moreover, on the other hand, due to the lubricating effect of the graphite, there is no erosion in the fluidized bed reactor.
The invention will be explained in further detail with the aid of the attached drawing which schematically shows, by way of example, a plant suitable for practising the invention. With the process according to the invention, as will be seen in the drawing, the oil sand, oil shale and/or the oil chalk is preferably introduced into the fluidized bed in a heat exchanger where it is indirectly heated by jet type heating tubes to 400 to 1000C ~pre-ferably to 500 to 750C) through locks, screws or pneumatically.
Through an overflow pipe, or some other discharging device per-forming a metering action, just as much pyrolysis residue is dispensed per unit of time from the fluidized bed reactor as is formed through pyrolysis of the introduced oil sand, oil shale or oil chalk.
Surprisingly, the hot pyrolysis residue as withdrawn is self-burning ~Z5~33 upon supply of air in the heat exchanger 1 and covers the greatest proportion of the energy required for the pyrolysis in the fluidized bed reactor. Advan-tageously, the heat exchanger 1 is designed to provide a fluidized bed. Ilow-ever, rotary pipes or other solid heat exchangers may also be used for this purpose.
The pyrolysis gases leaving the fluidized bed reactor are largely freed of entrained solids particles in a separator such as a cyclone, for example, and then are decomposed according to ~he prior art in quenching coolers ~ld washers into oil .md gas which constitute valuable petrochemicals. Such a cyclone is shown labelled "Cyclone 1" in the drawing.
The burnt off pyrolysis sand and the used fluidized bed material leave the heat exchanger through an overflow pipe, thereby dispensing further heat in heat exchanger 2 to the required combustion air or, because exchange-able, to the pyrolysis gas ~hich has been freed of oils. T'ne residue is free of oil and carbon black remainders, and may, without any hesitation, be disposed of or used for other purposes.
The heating of the fluidized bed in the pyrolysis furnace is per-formed by reheating waste gases via heat exchanger pipes in the heat exchanger 1 and by passing them into pipes through the pyrolysis reactor. For initially heating the pyrolysis reactor, and for generating additional energy, jet type heating pipes may additionally be incorporated which are fired with the pyro-lysis gas as the latter is produced.
In a third heat excllallger, labelled 3 in the drawing, the gases required for fluidization are preheated using the waste gases. It is possible ~o incorporate further heat exchangers to improve the energy balance.
Through tlle arrangement according to -the invention of the pyrolysis fluidized bed, ancl the heat exchanger 1, etc., an optimal energy yield may be ~25~133 obtained, thereby minimizing the solids flow through absence of circulation of the pyrolysis residue.
It is surprising that over 90% of the pyrolysis oils are convert-ed into aromatic compounds in spite of the great proportion of solids in the starting material. In this connection, attention is drawn to Table 1 below.
PyRoLy SIS
In the p~roly~is of oil sand, oil shale or oil chalk according to the process of the invention, more than 75 per cent of the bonded oil is converted into utilizable products. Again, attention is drawn to Table 1.
It is also surprising that, in spite of the great proportion of solids in the starting material and the predominantly paraffinic structure of the bonded oil, and in contrast to the known processes, the pyrolysis oil formed is more than 90 per cent converted into aromatic compounds ~see Table 2 below).
Particularly high is the proportion of benzene and toluene. Fortunately, it is these BTX aromatic compounds that are the most sought after petrochemicals for fuels and for the chemical industry.
Moreover, the gas produced according to the process of the inven-tion exhibits some surprising properties (See Table 3 below). It contains high proportions (up to 22 weight per cent) of ethylene, and with more than 30.000 kJ/m , has so high a heating value that it may be compared to natural gas.
With regard to the high quality of the pyrolysis products formed, the process according to the invention will be seen to be superior to all the known processes discussed above.
The advantages of the process according to the invention are fur-ther enhanced by the fact that sulphur, WhiC}l occurs in all types of oil sands and oil shales, is transformed into inorganic salts by reactions with basic materials in the fluidized bed. Frequently these basic substances are already contained in a sufficient amount in the starting material. This is particular-ly true in the cases of oil chalks. In the absence of basic substances, the 25~L~L33 starting material may have chalk or dolomite added thereto in the required amounts. The pyrolysis products are then almost free of hydrogen sulphide.
Because of the high quality pyrolysis products it may also be reasonable to utiliæe, in the practising of the method of the invention, concentrates of oil sand or oil shale which have been produced according to known processes.
Products, in weight per cent, from the pyrolysis of oil sand and oi.l shale performed, according to the invention, at 740& .
Starting Material Oil Sand Oil Shale Oil Content Weight-O 13.5 15.0 Amount Employed ~kg) 380 3.5 Gas 5.3 10.5 Oil, thereof 5.2 6.9 Benzene fraction 0.8 1.1 Toluene fraction 2.6 3.2 Tar 1.8 2.6 Water 0.6 14.7 Residue ~Sand, Carbon Black) 88.9 67.5 , " . ! ~ ' ~25~133 TAB~E 2 Composition of the liquid products from the pyrolysis of oil sand perormed, according to the invention, at 740 C.
Benzene and Tar Weight-% Toluene Fraction Cyclopentadiene 1.8 Benzene 35.5 1.3 Toluene 20.7 0.2 ~thylbenzene/~ylene 6.9 0.1 Styrene 4.5 0.1 Indene 3.6 0.5 Naphthalene 4.3 2.i Methylnaphthalene 3.1 5.4 Diphenyl 0.1 1.5 Fluorene 3 3 Anthracene/Phenantrene - 3.2 Other aromatic compounds 19.5 82.3 `` ~25~33 Composition of the gases from the pyrolysis of oil sand and oil shale performed, according to the invention, at 740C.
Starting Material Oil Sand Oil Shale Plant Technical Plant Laboratory Plant Weight-% Vol-% Weight-% Vol-%
-Hydrogen 2.2 19.6 2.0 20.5 Methane 47.3 52.4 28.3 36.4 Ethane 12.1 7.2 7.4 5.1 10Ethylene 22.1 14.1 14.5 10.6 Propene 5.3 2.3 4.1 2.0 Butadiene 0.8 `0.3 1.1 0.4 Benzene 1.3 0.3 3.0 0.8 Toluene 0,4 0.1 0.1 0.02 Carbon dioxide 1.2 0.5 16.9 7.9 Carbon monoxide 1.3 0.8 21.6 15.9 Hydrogen sulphide 2.9 1.5 0.02 0.01 Other gases 3.1 0.9 0.98 0.37 Density at 20 C ~kg/m3) 0.742 0.856 20Heating value 37500 30500 ., , ~
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of recovering oil and gas from oil sand, oil shale and/or oil chalk by pyrolysis in a fluidized bed heated indirectly to a temperature of from 400° to 1000°C, wherein either the fluidized bed is heated by preheated pyrolysis gas freed of oil which is combusted in heating tubes, or the fluidized bed is heated by heating tubes containing waste gas as the heat carrier, and wherein the heat carrier waste gas is heated in a second fluidized bed in which the pyrolysis residue is burnt.
2. A method as defined in claim 1, in which the fluidized bed is heated to between 500 and 750°C.
3. A method according to claim 1, wherein the pyrolysis residue is withdrawn, while hot, from the pyrolysis reactor through a discharging device and transferred into the second fluidized bed.
4. A method according to claim 1, wherein the burnt-off pyrolysis residue exiting from the second fluidized bed preheats operating gases in another solid heat exchanger.
5. A method according to claim 1, wherein an inert gas is used to fluidize the pyrolysis fluidized bed.
6. A method according to claim 5, wherein the inert gas used for fluidizing the pyrolysis fluidized bed, is pyrolysis gas which has been preheated to from 200 to 500°C and which has been freed of oils.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3301765A DE3301765C2 (en) | 1983-01-20 | 1983-01-20 | Process for extracting oil and gas from oil sands, oil chalk and oil shale |
| DEP3301765.4 | 1983-01-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1251133A true CA1251133A (en) | 1989-03-14 |
Family
ID=6188734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000445624A Expired CA1251133A (en) | 1983-01-20 | 1984-01-19 | Method of recovering oil and gas from oil sand, oil chalk, and oil shale |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS59191794A (en) |
| AU (1) | AU574342B2 (en) |
| BR (1) | BR8400250A (en) |
| CA (1) | CA1251133A (en) |
| DE (1) | DE3301765C2 (en) |
| FR (1) | FR2539753B1 (en) |
| IT (1) | IT1173102B (en) |
| OA (1) | OA07639A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015053721A1 (en) * | 2013-10-11 | 2015-04-16 | Al Ahmad Trad | High range temperature thermal dismantling method in processing oil shale |
| WO2015053724A1 (en) * | 2013-10-11 | 2015-04-16 | Trad Al Ahmad | High range temperature thermal dismantling method in processing oil shale |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105907407A (en) * | 2016-06-17 | 2016-08-31 | 北京神雾环境能源科技集团股份有限公司 | Biomass pyrolysis system and method |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2735743A (en) * | 1956-02-21 | Temperature- xe | ||
| DE339787C (en) * | 1920-11-02 | 1921-08-11 | Georg Eduard Heyl | Process and apparatus for the exploitation of dumps and waste containing mineral oil |
| DE338115C (en) * | 1920-11-07 | 1921-06-11 | Georg Eduard Heyl | Device for separating petroleum from porous material or from oil sand |
| US2619415A (en) * | 1946-08-15 | 1952-11-25 | Standard Oil Dev Co | Supply of heat to fluidized solids beds for the production of fuel gas |
| US2680065A (en) * | 1948-05-26 | 1954-06-01 | Texas Co | Gasification of carbonaceous solids |
| US3491016A (en) * | 1967-07-18 | 1970-01-20 | Phillips Petroleum Co | Process for treating crushed oil shale |
| DE2432504B2 (en) * | 1974-07-04 | 1976-12-16 | Kiener, Karl, Dipl.-Ing., 7080 Goldshöfe | PROCESS AND SYSTEM FOR PRODUCING COMBUSTION GASES FROM COMPONENT DOMESTIC AND INDUSTRIAL MANUFACTURING ETC. |
| DE2658371C2 (en) * | 1976-12-23 | 1983-03-03 | Carl Robert Eckelmann AG, 2000 Hamburg | Process for pyrolyzing old tires |
| DE2713031C3 (en) * | 1977-03-24 | 1979-10-11 | Karl Dipl.-Ing. 7080 Goldshoefe Kiener | Smoldering drum |
| US4199432A (en) * | 1978-03-22 | 1980-04-22 | Chevron Research Company | Staged turbulent bed retorting process |
| DE2940387A1 (en) * | 1979-10-05 | 1981-04-16 | Deutsche Babcock Ag, 4200 Oberhausen | Low-temp. pyrolysis of oil shale - with indirect heat transfer from fluidised-bed combustion of pyrolysis residue |
| US4293401A (en) * | 1980-02-21 | 1981-10-06 | Chevron Research Company | Shale retorting with supplemental combustion fuel |
| DE3112708C2 (en) * | 1981-03-31 | 1985-06-13 | Bergwerksverband Gmbh, 4300 Essen | Process for generating H 2 and CO-containing gases from fine-grained fuel in the fluidized bed with heat exchangers immersed therein |
-
1983
- 1983-01-20 DE DE3301765A patent/DE3301765C2/en not_active Expired
-
1984
- 1984-01-18 AU AU23556/84A patent/AU574342B2/en not_active Ceased
- 1984-01-19 CA CA000445624A patent/CA1251133A/en not_active Expired
- 1984-01-19 BR BR8400250A patent/BR8400250A/en not_active IP Right Cessation
- 1984-01-20 JP JP59009395A patent/JPS59191794A/en active Pending
- 1984-01-20 FR FR8400850A patent/FR2539753B1/en not_active Expired
- 1984-01-20 IT IT19268/84A patent/IT1173102B/en active
- 1984-01-20 OA OA58211A patent/OA07639A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015053721A1 (en) * | 2013-10-11 | 2015-04-16 | Al Ahmad Trad | High range temperature thermal dismantling method in processing oil shale |
| WO2015053724A1 (en) * | 2013-10-11 | 2015-04-16 | Trad Al Ahmad | High range temperature thermal dismantling method in processing oil shale |
| CN105765051A (en) * | 2013-10-11 | 2016-07-13 | 油页岩技术投资有限公司 | High range temperature thermal dismantling method in processing oil shale |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8419268A0 (en) | 1984-01-20 |
| AU2355684A (en) | 1984-07-26 |
| DE3301765A1 (en) | 1984-08-30 |
| OA07639A (en) | 1985-05-23 |
| DE3301765C2 (en) | 1988-05-05 |
| JPS59191794A (en) | 1984-10-30 |
| FR2539753A1 (en) | 1984-07-27 |
| IT1173102B (en) | 1987-06-18 |
| FR2539753B1 (en) | 1987-03-20 |
| AU574342B2 (en) | 1988-07-07 |
| BR8400250A (en) | 1984-08-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |