CA1148103A - Method of processing oil-shale or tar sand - Google Patents
Method of processing oil-shale or tar sandInfo
- Publication number
- CA1148103A CA1148103A CA000353431A CA353431A CA1148103A CA 1148103 A CA1148103 A CA 1148103A CA 000353431 A CA000353431 A CA 000353431A CA 353431 A CA353431 A CA 353431A CA 1148103 A CA1148103 A CA 1148103A
- Authority
- CA
- Canada
- Prior art keywords
- zone
- retorting
- shale
- oil
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/06—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of oil shale and/or or bituminous rocks
-
- 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
- C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Oil-shale or tar sand is subjected to hydrogenating carbonisation and the residue is passed into a combustion zone wherein residual coke in the residue is reacted with oxygen.
At least part of the heat produced in the combustion zone is used to heat the hydrogen to be used for the carbonisation step.
Oil-shale or tar sand is subjected to hydrogenating carbonisation and the residue is passed into a combustion zone wherein residual coke in the residue is reacted with oxygen.
At least part of the heat produced in the combustion zone is used to heat the hydrogen to be used for the carbonisation step.
Description
~48~(~3 1 The invention relates to a method of processing oil-shale or tar sand and more particularly, the hydrogenating carbonisation or distillation of oil-shale or tar sand.
A number of methods of carbonising or distilling oil-shale or tar sands in order to obtain the organic material therein have been put forward. Generally for example oil-shale is processed after preheating in a distillation or carbonation apparatus or retorting zone (in this specification the terms carbonisation and distillation are used interchangeably and such terms are also used interchangeably with the term "retorting").
In this operation, at temperatures of about 250 to 900C, besides fluid organic compounds and gaseous products, there are also formed carbon-bearing solid compounds (residual coke) which generally remain in the oil-shale after the carbonisation treatment, in amounts of from 5 to 10%. These substances are usually burnt and the waste heat obtained in this way is used in various ways in the process. Thus, all or part of the hot combustion gas may be passed as a heat-carrier agent into the retorting zone for direct heat exchange (as disclosed in U.S. patent 3,297,562 which issued January 10, 1967 to Biddick, et al~ or for indirect heat exchange ~see U.S. patent 3,384,569 which issued May 21, 1968 to Peet, or alternatively -used for preheating the oil-shale (see U.S. patent 3,475,319 which issued October 28, 1969 to Huntington~. The hot shale which has been burnt off and which is therefore substantially free from carbon can be used as a heat-carrier agent in the pro-cess ~see German laid-open application No. 2,429,767), but this requires correspondingly expensive equipment for separating it off. Therefore, it is frequently subjected to cooling, thereby regaining the heat content therefrom, and then removed from the process.
119~8103 1 Methods of producing shale-oil or oils from tar sand have also been disclosed, wherein the rotorting operation is performed in the presence o~ hydrogen. The oils produced in this way are of improved ~uality as they are more highly saturated and contain smaller amounts of sulphur and nitrogen compounds than oils which are produced without hydrogenation.
A particular advantage of such a hydrogenating carbonisation or distillation operation is that it makes it possible to produce a larger amount of the desired liquid products and a smaller amount of residual coke as, by virtue of the presence of hydrogen, the ~ormation of unsaturated hydrocarbon polymers and carbon residues is suppressed or reduced. Various modes of operation have been proposed for carrying out the hydrogenat-ing carbonisation or distillation step. Frequently, the method is performed using suspensions or slurries of the ground oil-shale in heavy oils resulting from the process ~U.S.pat~lts 3~65,751 which issued February 23, 1971 to Hoekstra and 3,617,469 which issued November 2, 1971 to Schlinger, et al). Catalytically effective compounds are also used in this operation (see above-mentioned U.S. patent 3,565,751). It has also been suggested that the hydrogenat~ng treatment of oil-shale should be per-formed with the addition of water (see U.S. patent 3,617,472 ~hich issued November 2, 1971 to Schlinger et al). This method provides a comparatively high yield in respect of the products desired and such a low residual carbon content, about 3%, in the processed shale, that it did not seem worthwhile to burn off the residual carbon content. It is therefore removed from the process after cooling.
It has now been found that the economic viability and efficiency of hydrogenating carbonation of oil-shale or 1~81~3 1 tar sand can be improved if the waste heat which is produced n the process is used in a certain manner.
Accordingly, the invention provides a method of pro-cessing oil-shale or tar sand wherein the oil-shale or tar sand is subjected to retorting in the presence of hydrogen, at a temperature of from 380 to 550C and a pressure of from 10 to 80 bars, with the exclusion of oxygen, in a retorting zone, wherein the residues of the oil-shape or tar sand are passed into a combustion zone in which residual coke remaining in the residues is reacted in the presence of oxygen, and wherein at least part of the heat produced in the combustion zone is used for heating the hydrogen introduced into the retorting zone.
The method according to the invention can be generally carried out in conventional retorting equipment, using known procedures.
In the method of the invention, the oil-shale is reduced to the desired particle size and introduced in known manner into the pressurised reaction zones which may be arranged in any suitable manner. If desired, the oil-shale may also be used in the form of a suspension or slurry in a high-boiling oil fraction which originates from the process. Generally, operation in the retorting process is at a temperature of from about 380 to 550 C, more particularly 430 to 500C, at a pressure of from about 10 to 80 bars, more particularly 30 to 40 bars, with the hydrogen partial pressure being selected at a sufficiently high level to produce the desired hydrogenation effect. The residence times in the retorting zone are generally up to about 60 minutes.
81{)3 1 It may be advantageous, in the carbonisation operation, to add water or water vapour, and optionally also carbon dioxide, in which case amounts of from about 0.05 to 0.~ tonne of water for each tonne of oil-shàle will generally be used.
In this way for example the liberation of carbon dioxide from inorganic carbonates can be reduced and thus it is possible to achieve a saving in respect of the hydrogen which otherwise would react with the carbon dioxide. It is then also possible to reduce the amount of hydrogen to be used as scavenge gas.
The carbonisation or distillation of oil-shale or tar sand is generally effected in such a way that the residual coke remaining in the processed residue is less than about 5~, preferably less than 3%. The combustion of this residual co~e in the reaction zone which can be operated at normal pressure or under an elevated pressure can be effected by means of an oxygen-bearing agent such as air. As in this case the waste gas contains considerable amounts of nitrogen, it will be taken off at the upper region of the reaction zone and will not be passed through the retorting zone. The heat of the waste gas which is for example at a temperature of 1000C is firstly utilised, at least in p~rt, for heating the hydrogen to be used in the distillation zone, preferably in an indirect heat-exchange mode, with the remaining heat being extracted and put to use in the usual way. It is advantageous however to use pure oxygen instead of air for reacting the residual coke. In this case the waste gas is also taken off at the top part of the combustion zone and used for heating the hydrogen. A part of the waste gas which is cooled in that manner is advantageously recycled to the combustion zone as a dilution and scavenge gas,as otherwise the temperature .,~$.,~ .
~1~8103 1 in that zone may rise to an undesirably high level. The shale or tar sand residue which is freed of residual coke is removed from the process, possibly after putting the residual heat still present therein to use, in known manner.
The operation of reacting the residual coke may also be effected in such a way that hydrogen which has possibly been preheated is introduced into the combustion zone, in addition to the pure oxygen, in which case operation in the combustion zone is.under.approximately the same pressure as the pressure in the distillation zone. In this operation, the amount of.oxygen is controlled.in.-such a way that a predetermlned part of the hydrogen reacts with the oxygen in the combustion.zone to form water. The heat which is produced in this exothermic reaction.is.used for heating the non-reacted h~drogen component which is introduced as a hydrogenating gas into the distillation zone. At the high temperatures in the combustion zone, the water formed is substantially reacted with the res.idual coke in water gas and conversion reactions, forming hydrogen, methane, carbon.monoxide and carbon dioxide, whereby the balance sheet, in regard to hydrogen, of the process is improved. By suitable adjustment of the amounts of hydrogen and oxygen supplied, and optionally by additionally supplying water or methane, it is possible to provide that the residual coke is virtually.completely reacted. The gas mixture produced in this way can be introduced directly into the distillation zone. The shale or tar sand residue is removed.from the process, possibly after making use of the heat in known manner.
~1481S~3 1 The distillation products obtained may be processed and used in the usual manner. Hydrogen and water vapour or water are separated off and recycled to the process. The fresh hydrogen required can be obtained for example by means of known processes from the flue gases. When the method uses pure oxygen in the combustion zone, it enjoys inter alia the advantage that the waste gas from the combustion zone has a relatively high sulphur content which makes it possible for the sulphur to be extracted for example by the usual Claus process. This is generally not possible when air is used as an oxygen carrier, as in that case the flue gas is excessively diluted or rarefied and thus desulphurisation must be carried out by means of a process in the nature of flue gas desulphurisation, which is less economically viable.
It may be advantageous for the high-boiling distillation or carbonisation products, for example with an initial boiling temperature of between 400 and 5~0C, to be recycled to the distillation zone. If this is done, it is no longer necessary for the fine shale particles which are entrained therewith to be separated to the maximum possible extent, before further processing.- The waste heat of the flue gas may be utilised in the usual manner, advantageously also for preheating the tar sand or oil-shale to be processed.
In this case for example the flue gas is cooled in a heat exchanger and the products which condense out are then separated off. A part of the residual gas produced in this way i5 taken off and circulated through the heat exchanger in which it absorbs heat from the hot flue gas which has not yet cooled down, and is then passed as a heat carrier agent through the preheating zone.
1148~3 1 The method according to the invention makes it possible for distillation or low-temperature carbonisation of oil-shale or tar sand to be carried ou-t in a particularly economic manner.
Reference will now be made to the accompanying drawing which shows the basic ~rinciple of an embodiment of the method of the invention, accessory equipment having been omitted from the drawing for the sake of enhanced clarity.
Crushed oil-shale is introduced into a preheating zone I
10 by way of conduit 1. After the oil-shale has been heated to about 100C, it passes by way of duct 2.into a retorting zone II which is operated at a temperature of about 450 C
and a pressure of about 30 bars. This zone II is supplied with water vapour and hydrogen required for the hydrogenation action, by way o conduit 3. The distillation or vaporous products, produced in zone II are taken off by way of conduit 5. The shale which has been substantially distilled off passes by way of conduit 6 into a combustion zone III.
In that zone, residual coke.which has remained in the shale is reacted with oxygen which is supplied by way of conduit -7, the temperature in combustion zone III rising to about lOOO~C. The residual shale which is thus virtually free of carbon is removed by way of conduit 8. The flue gas.formed in combustion zone III is taken off by way of conduit 9 and used in a heat exchanger V for heating the water vapour and hydrogen which are supplied to zone II by way of conduit lO.and conduit 4 respectively,and which are then passed at a temperature of about 900C by way of above-mentioned conduit 3 into zone II. A part of the waste gas from combustion zone III is removed by way of conduit 12.
.
.
~r 8~33 or v~ pO~d ~S
~`~ The distlIation~products which are taken from zone II
by way of conduit 5 are firstly cooled in heat exchanger IV
and then pas~ into separator VI where the gaseous conætltuents are ~eparated off. They are remo~ed by way of conduit 13, uDless they are passed by way of conduit 14 and, after being heated in heat exch~nger IV, by way of conduit 15, into the preheating zone I which they leave again by way of conduit 16. The excess gaseous products which are separated off in separator VI are fed to process~ng ~tep VII by way of conduit ~3 while the remaining products are pasæed to processing step VII by way of conduit 17. In proce~slng step VII, hydrogen which has not been consumed i~ recycled by way of conduit 18 and water or water ~apour is produced, for recycling by way of conduit 4. The distillation products are ~eparated into a high-boiling hea~y oil containing fine ~hale particles~ which i8 passed by way of conduit 19 into the preheating zone I, lower-boiling products in the gasoline and middle oil boiling range, which are passed by way of conduit 20 to a processing step (not shown) for processing to produce desired product qualities, and a heating or fuel gas which is taken off by way of conduit Zl and which can be put to any appropriate uses.
Although the above-given description relating to the drawing refers to oil-shale as the starting material, lt will be appreciated that the tar sand will be processed in corresponding fa~hion.
A more specific Example of the method will ~ow be described:
Exam~2ae An oll-shale comprising:
C 13.2% by weight H 1.9% by weight S 3.g% by weight ~81(~
Fischer o~ 1 content 7.1% by weight was crushed to a particle size of about 2 to 3 mm, and ~ub~ected to hydrogenating distillation or carboni6ation at a temperature o~ about 425 to 450co Result:
Di~tillation pre~sure bar 15 3 60 Yields of oil ~ by weight 9.0 10.7 11.1 gas n 3.4 2.9 3.1 water " 5.1 4.5 4.2 reæidual ~hale " 82.5 82.1 81.6 oil with respect to Fi~cher analysis n 111 151 156 C in the residual 6hale before reaction n 3. 3 2. 9 2. 7 C in the residual æhale after reaction " 0.2 0.1 0.1
A number of methods of carbonising or distilling oil-shale or tar sands in order to obtain the organic material therein have been put forward. Generally for example oil-shale is processed after preheating in a distillation or carbonation apparatus or retorting zone (in this specification the terms carbonisation and distillation are used interchangeably and such terms are also used interchangeably with the term "retorting").
In this operation, at temperatures of about 250 to 900C, besides fluid organic compounds and gaseous products, there are also formed carbon-bearing solid compounds (residual coke) which generally remain in the oil-shale after the carbonisation treatment, in amounts of from 5 to 10%. These substances are usually burnt and the waste heat obtained in this way is used in various ways in the process. Thus, all or part of the hot combustion gas may be passed as a heat-carrier agent into the retorting zone for direct heat exchange (as disclosed in U.S. patent 3,297,562 which issued January 10, 1967 to Biddick, et al~ or for indirect heat exchange ~see U.S. patent 3,384,569 which issued May 21, 1968 to Peet, or alternatively -used for preheating the oil-shale (see U.S. patent 3,475,319 which issued October 28, 1969 to Huntington~. The hot shale which has been burnt off and which is therefore substantially free from carbon can be used as a heat-carrier agent in the pro-cess ~see German laid-open application No. 2,429,767), but this requires correspondingly expensive equipment for separating it off. Therefore, it is frequently subjected to cooling, thereby regaining the heat content therefrom, and then removed from the process.
119~8103 1 Methods of producing shale-oil or oils from tar sand have also been disclosed, wherein the rotorting operation is performed in the presence o~ hydrogen. The oils produced in this way are of improved ~uality as they are more highly saturated and contain smaller amounts of sulphur and nitrogen compounds than oils which are produced without hydrogenation.
A particular advantage of such a hydrogenating carbonisation or distillation operation is that it makes it possible to produce a larger amount of the desired liquid products and a smaller amount of residual coke as, by virtue of the presence of hydrogen, the ~ormation of unsaturated hydrocarbon polymers and carbon residues is suppressed or reduced. Various modes of operation have been proposed for carrying out the hydrogenat-ing carbonisation or distillation step. Frequently, the method is performed using suspensions or slurries of the ground oil-shale in heavy oils resulting from the process ~U.S.pat~lts 3~65,751 which issued February 23, 1971 to Hoekstra and 3,617,469 which issued November 2, 1971 to Schlinger, et al). Catalytically effective compounds are also used in this operation (see above-mentioned U.S. patent 3,565,751). It has also been suggested that the hydrogenat~ng treatment of oil-shale should be per-formed with the addition of water (see U.S. patent 3,617,472 ~hich issued November 2, 1971 to Schlinger et al). This method provides a comparatively high yield in respect of the products desired and such a low residual carbon content, about 3%, in the processed shale, that it did not seem worthwhile to burn off the residual carbon content. It is therefore removed from the process after cooling.
It has now been found that the economic viability and efficiency of hydrogenating carbonation of oil-shale or 1~81~3 1 tar sand can be improved if the waste heat which is produced n the process is used in a certain manner.
Accordingly, the invention provides a method of pro-cessing oil-shale or tar sand wherein the oil-shale or tar sand is subjected to retorting in the presence of hydrogen, at a temperature of from 380 to 550C and a pressure of from 10 to 80 bars, with the exclusion of oxygen, in a retorting zone, wherein the residues of the oil-shape or tar sand are passed into a combustion zone in which residual coke remaining in the residues is reacted in the presence of oxygen, and wherein at least part of the heat produced in the combustion zone is used for heating the hydrogen introduced into the retorting zone.
The method according to the invention can be generally carried out in conventional retorting equipment, using known procedures.
In the method of the invention, the oil-shale is reduced to the desired particle size and introduced in known manner into the pressurised reaction zones which may be arranged in any suitable manner. If desired, the oil-shale may also be used in the form of a suspension or slurry in a high-boiling oil fraction which originates from the process. Generally, operation in the retorting process is at a temperature of from about 380 to 550 C, more particularly 430 to 500C, at a pressure of from about 10 to 80 bars, more particularly 30 to 40 bars, with the hydrogen partial pressure being selected at a sufficiently high level to produce the desired hydrogenation effect. The residence times in the retorting zone are generally up to about 60 minutes.
81{)3 1 It may be advantageous, in the carbonisation operation, to add water or water vapour, and optionally also carbon dioxide, in which case amounts of from about 0.05 to 0.~ tonne of water for each tonne of oil-shàle will generally be used.
In this way for example the liberation of carbon dioxide from inorganic carbonates can be reduced and thus it is possible to achieve a saving in respect of the hydrogen which otherwise would react with the carbon dioxide. It is then also possible to reduce the amount of hydrogen to be used as scavenge gas.
The carbonisation or distillation of oil-shale or tar sand is generally effected in such a way that the residual coke remaining in the processed residue is less than about 5~, preferably less than 3%. The combustion of this residual co~e in the reaction zone which can be operated at normal pressure or under an elevated pressure can be effected by means of an oxygen-bearing agent such as air. As in this case the waste gas contains considerable amounts of nitrogen, it will be taken off at the upper region of the reaction zone and will not be passed through the retorting zone. The heat of the waste gas which is for example at a temperature of 1000C is firstly utilised, at least in p~rt, for heating the hydrogen to be used in the distillation zone, preferably in an indirect heat-exchange mode, with the remaining heat being extracted and put to use in the usual way. It is advantageous however to use pure oxygen instead of air for reacting the residual coke. In this case the waste gas is also taken off at the top part of the combustion zone and used for heating the hydrogen. A part of the waste gas which is cooled in that manner is advantageously recycled to the combustion zone as a dilution and scavenge gas,as otherwise the temperature .,~$.,~ .
~1~8103 1 in that zone may rise to an undesirably high level. The shale or tar sand residue which is freed of residual coke is removed from the process, possibly after putting the residual heat still present therein to use, in known manner.
The operation of reacting the residual coke may also be effected in such a way that hydrogen which has possibly been preheated is introduced into the combustion zone, in addition to the pure oxygen, in which case operation in the combustion zone is.under.approximately the same pressure as the pressure in the distillation zone. In this operation, the amount of.oxygen is controlled.in.-such a way that a predetermlned part of the hydrogen reacts with the oxygen in the combustion.zone to form water. The heat which is produced in this exothermic reaction.is.used for heating the non-reacted h~drogen component which is introduced as a hydrogenating gas into the distillation zone. At the high temperatures in the combustion zone, the water formed is substantially reacted with the res.idual coke in water gas and conversion reactions, forming hydrogen, methane, carbon.monoxide and carbon dioxide, whereby the balance sheet, in regard to hydrogen, of the process is improved. By suitable adjustment of the amounts of hydrogen and oxygen supplied, and optionally by additionally supplying water or methane, it is possible to provide that the residual coke is virtually.completely reacted. The gas mixture produced in this way can be introduced directly into the distillation zone. The shale or tar sand residue is removed.from the process, possibly after making use of the heat in known manner.
~1481S~3 1 The distillation products obtained may be processed and used in the usual manner. Hydrogen and water vapour or water are separated off and recycled to the process. The fresh hydrogen required can be obtained for example by means of known processes from the flue gases. When the method uses pure oxygen in the combustion zone, it enjoys inter alia the advantage that the waste gas from the combustion zone has a relatively high sulphur content which makes it possible for the sulphur to be extracted for example by the usual Claus process. This is generally not possible when air is used as an oxygen carrier, as in that case the flue gas is excessively diluted or rarefied and thus desulphurisation must be carried out by means of a process in the nature of flue gas desulphurisation, which is less economically viable.
It may be advantageous for the high-boiling distillation or carbonisation products, for example with an initial boiling temperature of between 400 and 5~0C, to be recycled to the distillation zone. If this is done, it is no longer necessary for the fine shale particles which are entrained therewith to be separated to the maximum possible extent, before further processing.- The waste heat of the flue gas may be utilised in the usual manner, advantageously also for preheating the tar sand or oil-shale to be processed.
In this case for example the flue gas is cooled in a heat exchanger and the products which condense out are then separated off. A part of the residual gas produced in this way i5 taken off and circulated through the heat exchanger in which it absorbs heat from the hot flue gas which has not yet cooled down, and is then passed as a heat carrier agent through the preheating zone.
1148~3 1 The method according to the invention makes it possible for distillation or low-temperature carbonisation of oil-shale or tar sand to be carried ou-t in a particularly economic manner.
Reference will now be made to the accompanying drawing which shows the basic ~rinciple of an embodiment of the method of the invention, accessory equipment having been omitted from the drawing for the sake of enhanced clarity.
Crushed oil-shale is introduced into a preheating zone I
10 by way of conduit 1. After the oil-shale has been heated to about 100C, it passes by way of duct 2.into a retorting zone II which is operated at a temperature of about 450 C
and a pressure of about 30 bars. This zone II is supplied with water vapour and hydrogen required for the hydrogenation action, by way o conduit 3. The distillation or vaporous products, produced in zone II are taken off by way of conduit 5. The shale which has been substantially distilled off passes by way of conduit 6 into a combustion zone III.
In that zone, residual coke.which has remained in the shale is reacted with oxygen which is supplied by way of conduit -7, the temperature in combustion zone III rising to about lOOO~C. The residual shale which is thus virtually free of carbon is removed by way of conduit 8. The flue gas.formed in combustion zone III is taken off by way of conduit 9 and used in a heat exchanger V for heating the water vapour and hydrogen which are supplied to zone II by way of conduit lO.and conduit 4 respectively,and which are then passed at a temperature of about 900C by way of above-mentioned conduit 3 into zone II. A part of the waste gas from combustion zone III is removed by way of conduit 12.
.
.
~r 8~33 or v~ pO~d ~S
~`~ The distlIation~products which are taken from zone II
by way of conduit 5 are firstly cooled in heat exchanger IV
and then pas~ into separator VI where the gaseous conætltuents are ~eparated off. They are remo~ed by way of conduit 13, uDless they are passed by way of conduit 14 and, after being heated in heat exch~nger IV, by way of conduit 15, into the preheating zone I which they leave again by way of conduit 16. The excess gaseous products which are separated off in separator VI are fed to process~ng ~tep VII by way of conduit ~3 while the remaining products are pasæed to processing step VII by way of conduit 17. In proce~slng step VII, hydrogen which has not been consumed i~ recycled by way of conduit 18 and water or water ~apour is produced, for recycling by way of conduit 4. The distillation products are ~eparated into a high-boiling hea~y oil containing fine ~hale particles~ which i8 passed by way of conduit 19 into the preheating zone I, lower-boiling products in the gasoline and middle oil boiling range, which are passed by way of conduit 20 to a processing step (not shown) for processing to produce desired product qualities, and a heating or fuel gas which is taken off by way of conduit Zl and which can be put to any appropriate uses.
Although the above-given description relating to the drawing refers to oil-shale as the starting material, lt will be appreciated that the tar sand will be processed in corresponding fa~hion.
A more specific Example of the method will ~ow be described:
Exam~2ae An oll-shale comprising:
C 13.2% by weight H 1.9% by weight S 3.g% by weight ~81(~
Fischer o~ 1 content 7.1% by weight was crushed to a particle size of about 2 to 3 mm, and ~ub~ected to hydrogenating distillation or carboni6ation at a temperature o~ about 425 to 450co Result:
Di~tillation pre~sure bar 15 3 60 Yields of oil ~ by weight 9.0 10.7 11.1 gas n 3.4 2.9 3.1 water " 5.1 4.5 4.2 reæidual ~hale " 82.5 82.1 81.6 oil with respect to Fi~cher analysis n 111 151 156 C in the residual 6hale before reaction n 3. 3 2. 9 2. 7 C in the residual æhale after reaction " 0.2 0.1 0.1
Claims (20)
1. A method of retorting oil shale to produce shale oil in which crushed oil shale flows serially downward through at least a pre-heating zone, a retorting zone, and a combustion zone which comprises:
(a) generating flue gas at an elevated temperature by burning in said combustion zone carbonaceous material on the spent oil-shale from said retorting zone in the presence of an oxygen-containing gas introduced to said combustion zone;
(b) withdrawing the flue gas from said combustion zone and recycling at least a portion thereof to said combustion zone;
(c) introducing a hydrogen-containing gas to said retorting zone after heating same a sufficient amount to provide heat for retorting pre-heated oil shale at a temperature of from 380 to 550°C and a pressure of from 10 to 80 bars;
(d) said hydrogen-containing gas being heated by passage in indirect heat exchange with said flue gas withdrawn from said combustion zone;
(e) withdrawing vaporous product from said retorting zone and cooling and condensing it to separate therefrom a gaseous product, a light liquid product, and a heavy oil con-taining fine shale particles;
(f) introducing a portion of said gaseous product to said pre-heating zone after heating same a sufficient amount to pre-heat said oil-shale; and (g) recycling at least a portion of said gaseous product withdrawn from said pre-heating zone to said pre-heating zone.
(a) generating flue gas at an elevated temperature by burning in said combustion zone carbonaceous material on the spent oil-shale from said retorting zone in the presence of an oxygen-containing gas introduced to said combustion zone;
(b) withdrawing the flue gas from said combustion zone and recycling at least a portion thereof to said combustion zone;
(c) introducing a hydrogen-containing gas to said retorting zone after heating same a sufficient amount to provide heat for retorting pre-heated oil shale at a temperature of from 380 to 550°C and a pressure of from 10 to 80 bars;
(d) said hydrogen-containing gas being heated by passage in indirect heat exchange with said flue gas withdrawn from said combustion zone;
(e) withdrawing vaporous product from said retorting zone and cooling and condensing it to separate therefrom a gaseous product, a light liquid product, and a heavy oil con-taining fine shale particles;
(f) introducing a portion of said gaseous product to said pre-heating zone after heating same a sufficient amount to pre-heat said oil-shale; and (g) recycling at least a portion of said gaseous product withdrawn from said pre-heating zone to said pre-heating zone.
2. A method as set forth in claim 1 wherein the oil shale in the retorting zone is heated to a temperature from 430 to 500°C.
3. A method as set forth in claim 1 or 2 wherein the oil-shale in the retorting zone is under a pressure from 30 to 40 bars.
4. A method as set forth in claim 1 wherein the residence time of the oil-shale sand in the retorting zone is up to 60 minutes.
5. A method as set forth in claim 1 wherein water vapour or carbon dioxide is additionally introduced into the retorting zone.
6. A method as set forth in claim 1 wherein the products from the retorting zone which have a boiling point of above about 400°C are recycled to the retorting zone.
7. A method as set forth in claim 1 wherein a part of the flow of product gas from which condensate has been removed after cooling is passed from the retorting zone into a pre-heating zone for the oil-shale sand, and wherein the flow of product gas is heated by the hot gas by indirect heat exchange therewith, before said part flow is introduced into the pre-heating zone.
8. A method according to claim 1 in which said gaseous product prior to being introduced to said pre-heating zone is heated by indirect heat exchange with the vaporous product withdrawn from said retorting zone.
9. A method according to claim 1 in which said heavy oil containing fine shale particles is introduced to said retorting zone.
10. A method according to claim 1 in which said high-burning heavy oil containing fine shale particles is introduced to said pre-heating zone.
11. A method of retorting tar sand to produce sand oil in which tar sand flows serially downward through at least a pre-heating zone, a retorting zone, and a combustion zone which comprises:
(a) generating flue gast at an elevated temperature by burning in said combustion zone carbonaceous material on the spent tar sand from said retorting zone in the presence of an oxygen-containing gas introduced to said combustion zone;
(b) withdrawing the flue gas from said combustion zone and recycling at least a portion thereof to said combustion zone;
(c) introducing a hydrogen-containing gas to said retorting zone after heating same a sufficient amount to provide heat for retorting pre-heated tar sand at a temperature of from 380 to 550°C and a pressure of from 10 to 80 bars;
(d) said hydrogen-containing gas being heated by passage in indirect heat exchange with said flue gas withdrawn from said combustion zone;
(e) withdrawing vaporous product from said retorting zone and cooling and condensing it to separate therefrom a gaseous product, a light liquid product, and a heavy oil;
(f) introducing a portion of said gaseous product to said pre-heating zone after heating same a sufficient amount to pre-heat said tar sand; and (g) recycling at least a portion of said gaseous product withdrawn from said pre-heating zone to said pre-heating zone.
(a) generating flue gast at an elevated temperature by burning in said combustion zone carbonaceous material on the spent tar sand from said retorting zone in the presence of an oxygen-containing gas introduced to said combustion zone;
(b) withdrawing the flue gas from said combustion zone and recycling at least a portion thereof to said combustion zone;
(c) introducing a hydrogen-containing gas to said retorting zone after heating same a sufficient amount to provide heat for retorting pre-heated tar sand at a temperature of from 380 to 550°C and a pressure of from 10 to 80 bars;
(d) said hydrogen-containing gas being heated by passage in indirect heat exchange with said flue gas withdrawn from said combustion zone;
(e) withdrawing vaporous product from said retorting zone and cooling and condensing it to separate therefrom a gaseous product, a light liquid product, and a heavy oil;
(f) introducing a portion of said gaseous product to said pre-heating zone after heating same a sufficient amount to pre-heat said tar sand; and (g) recycling at least a portion of said gaseous product withdrawn from said pre-heating zone to said pre-heating zone.
12. A method as set forth in claim 11 wherein the tar sand in the retorting zone is heated to a temperature from about 430 to 500°C.
13. A method as set forth in claim 11 wherein the tar sand in the retorting zone is under a pressure from about 30 to 40 bars.
14. A method as set forth in claim 11 wherein the residence time of the tar sand in the retorting zone is up to about 60 minutes.
15. A method as set forth in claim 11 wherein the water vapour is additionally introduced into the retorting zone.
16. A method as set forth in claim 11 wherein carbon dioxide is additionally introduced into the retorting zone.
17. A method as set forth in claim 11 wherein the products from the retorting zone which have a boiling point of above about 400°C are recycled to the retorting zone.
18. A method according to claim 11 in which said gaseous product prior to being introduced to said pre-heating zone is heated by indirect heat exchange with the vaporous product withdrawn from said retorting zone.
19. A method according to claim 11 in which said heavy oil is introduced to said retorting zone.
20. A method according to claim 11 in which said high-burning heavy oil is introduced to said pre-heating zone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792923048 DE2923048C2 (en) | 1979-06-07 | 1979-06-07 | Process for smoldering oil shale or tar sand in the presence of hydrogen |
| DEP2923048.6 | 1979-06-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148103A true CA1148103A (en) | 1983-06-14 |
Family
ID=6072659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000353431A Expired CA1148103A (en) | 1979-06-07 | 1980-06-05 | Method of processing oil-shale or tar sand |
Country Status (3)
| Country | Link |
|---|---|
| BR (1) | BR8003485A (en) |
| CA (1) | CA1148103A (en) |
| DE (1) | DE2923048C2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3023670C2 (en) * | 1980-06-25 | 1982-12-23 | Veba Oel Entwicklungsgesellschaft mbH, 4660 Gelsenkirchen-Buer | Method and device for smoldering oil shale |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3922215A (en) * | 1973-06-01 | 1975-11-25 | American Gas Ass | Process for production of hydrocarbon liquids and gases from oil shale |
-
1979
- 1979-06-07 DE DE19792923048 patent/DE2923048C2/en not_active Expired
-
1980
- 1980-06-04 BR BR8003485A patent/BR8003485A/en unknown
- 1980-06-05 CA CA000353431A patent/CA1148103A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2923048A1 (en) | 1980-12-18 |
| BR8003485A (en) | 1981-01-05 |
| DE2923048C2 (en) | 1984-11-08 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |