CN101230283A - Oil shale retorting process reclaiming method - Google Patents
Oil shale retorting process reclaiming method Download PDFInfo
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- CN101230283A CN101230283A CN 200810010311 CN200810010311A CN101230283A CN 101230283 A CN101230283 A CN 101230283A CN 200810010311 CN200810010311 CN 200810010311 CN 200810010311 A CN200810010311 A CN 200810010311A CN 101230283 A CN101230283 A CN 101230283A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
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Abstract
The invention discloses an oil forming shale retorting technique recovery method. Cyclone oil trapping, indirect cooling, heavy oil washing, electricity trapping tar, and other washing techniques and related equipment are introduced into the oil recovery process of the product of retorting. Firstly, shale oil and dust are separated from the product of retorting by direct washing via a gas collecting groove; after oil drips and dust are removed by a cyclone trapping tower, the product of retorting enters into an indirect cooling tower; after further cooling, a majority of shale oil and dust are condensed off. The gas coming out from the indirect cooling tower enters into an oil washing tower, the light oil in the retorting gas can be collected by the shale oil which is self-produced by the technique. Oil steam existing in gas form is collected in the electricity trapping tar tower. Finally, the retorting gas is sent into the system by a gas fan for recycling, the washing water circulates in closed loop in the system. The invention can improve the oil recovery rate by 10-15 percentage points; reduces the emission of pollutants; improves the automation degree of the overall operation; and reduces the contents of impurities in the oil.
Description
One, technical field
The present invention utilizes the oil shale resource to produce the complete processing of shale oil, is the upgrading that is carried out at existing distillation process recovery system.
Two, background technology
What the recovery system of existing distillation process adopted is three grades of water wash systems, the destructive distillation product that promptly comprises shale oil, water and dry distillation gas, respectively in collecting tubule, washing tower, cooling tower, with recirculated water and destructive distillation product directly contact cool off with the washing, shale oil is taken away by water, gets the finished product shale oil again through oil-water separation system.The washing water of sloughing behind the shale oil use at system's internal recycle.
Dry distillation gas after the washing is divided into three parts: a part is sent the recuperative heater heating, as the thermal barrier of shale retorting heat supply; A part is as the fuel of recuperative heater; Remainder then uses for gas fired-boiler and generating set.
There is following shortcoming in three grades of washing recovery systems:
A, dry distillation gas outlet temperature after three grades of washings is 55 ℃, also has the part lightweight oil not to be recovered (it is upright to be about 10 gram/marks) under this temperature in the coal gas, has reduced the oil recovery rate.
The process of B, refiltered oil is directly washed by water and is finished, and every cover destructive distillation device per hour can produce 23-25 ton retort sewage, and to the improvement complex process of retort sewage, cost is very high.
What C, three grades of water wash systems used is recirculated water, and the recycle system is huge, and power consumption is also big.
Pump and groove in D, the system, jar more, the adjustment of liquid level all need by manually carrying out, and level of automation is low.
The diffusing discharge point of each tower, groove, jar is more in E, the system, and on-the-spot irritating smell is big, and operating environment is poor.
Three, summary of the invention
The purpose of this invention is to provide a kind of oil shale retorting process reclaiming method,, alleviate labor intensity of operating personnel, reduce the generation of all contaminations in the production process, improve the operating environment of production scene to improve the oil recovery rate.
The technical solution used in the present invention is: the production equipment of oil shale retorting process is made up of distillation system, heating system and recovery system three parts, recovery technology of the present invention has been used for reference the purification process of town gas, use therein whirlwind is caught in the recovery of oil process of washing process such as oil, indirectly cooling, heavy oil washing, electrically trapped tar oil and relevant device introducing dry distillation gas.
The destructive distillation product is directly washed cooling through pneumatic trough earlier, and temperature is dropped to 55 ℃-70 ℃, isolates shale oil and dust.Enter whirlwind and catch after oily tower removes oil droplet and dust, enter indirect cool tower.In indirect cool tower, the destructive distillation product does not directly contact with recirculated water, and gas-liquid two-phase is an indirect heat transfer and mass transfer process does not take place.In this process, dry distillation gas is further cooled to about 40 ℃, and shale oil and water vapor major part all are condensed, thereby make dry distillation gas obtain purification.The gas that indirect cool tower comes out enters the oil wash tower, and the shale oil that utilizes technology self to produce washs dry distillation gas, to collect wherein contained lightweight oil.In the electrically trapped tar oil tower, collect the oil vapour that exists with gas form then.Last dry distillation gas is made thermal barrier and fuel gas respectively in gas fan is delivered to process furnace.
Pneumatic trough, whirlwind are caught shale oil and the phlegma that equipment such as oily tower, indirect cool tower, oil wash tower, electrically trapped tar oil tower are discharged, sedimentation layering in gun barrel, cyclic ammonia water groove respectively, the shale oil of gained flows automatically to the shale oil groove, and washing water then carry out closed cycle in system uses.
The contrast prior art, the present invention has following advantage and positively effect:
1. the oil recovery rate can be improved 10-15 percentage point, and then increase economic efficiency.
This kind recovery system can be brought up to 80%-85% by 70% of original system with the oil recovery rate, the lightweight oil content in the dry distillation gas be controlled at 1 gram/mark upright below.Can overcharge 5.4 tons of oil every day than three grades of every covering devices of washing process, can reclaim 1900 tons of shale oil more every year, year can be created 7,770,000 yuan of economic benefits more.
2. reduced the discharging of pollutent.
Because of having only the direct water washing process of one-level, and washing water use at totally-enclosed system internal recycle and do not efflux, and all recovery systems do not have retort sewage to produce, and greatly reduce to handle the required cost of retort sewage.
Each tower in the recovery system, groove, jar data such as temperature, liquid level monitor automatically by the DCS system, all realize not having the uncontrollable discharge phenomenon by closed operations in on-the-spot, in-situ production environment be improved significantly.
Dry distillation gas has been adopted dry desulfurizing process, made H
2The content of S drops to the emission standard that country allows, and has reduced SO after the gas-fired
2Quantity discharged.
3. adopt the DCS Controlling System, control becomes centralized Control by disperseing manually.
In system, pneumatic trough is directly washed, the indirect refrigerative water yield of indirect cool tower has formed interlocked control with the temperature of dry distillation gas respectively.When oxygen level surpassed the higher limit of setting in the dry distillation gas, static was caught oily device and is cut off the power supply automatically, has improved the level of automation of integrated operation and the safety coefficient of system.
4. the dry distillation gas calorific value after purifying is that 2300-2500 kilojoule/mark is upright, and still incendivity is the shale retorting heat supply.
5. the lightweight fraction in the gained shale oil increases, and well cuts content reduces.
Two kinds of recovery system gained of table 1 oil quality index contrast table
| Project name | Unit | Analytical results | ||
| Former water wash system | New recovery system | |||
| Density | D 20 4 | 0.8890 | 0.8859 | |
| Condensation point | ℃ | 36 | 34 | |
| Calorific value | KJ/kg | 45980 | 43778.75 | |
| Flash-point | ℃ | 138 | 122 | |
| Mechanical impurity | ％ | 0.8 | 0.462 | |
| Boiling range | Initial boiling point | ℃ | 216 | 215 |
| 10% recovered temperature | ℃ | 264 | 262 | |
| 20% recovered temperature | ℃ | 293 | 272 | |
| 30% recovered temperature | ℃ | 318 | 310 | |
| 40% recovered temperature | ℃ | 343 | 322 | |
From the table shale oil analytical results as can be seen, the upgrading, improved recovery system gained shale oil, quality is better than former washing recovery system, helps the scavenging process of shale oil.
Four, description of drawings
Fig. 1 is three grades of washings of existing distillation process recovery system schematic diagram, and pecked line is a water pipeline among the figure, and long dotted line is a gas line, and solid line is an oil pipeline;
Fig. 2 is a technical process schematic diagram of the present invention, and pecked line is a circulating water pipework among the figure, and long dotted line is a gas line, and solid line is an oil pipeline.
Five, embodiment
What the recovery system of prior art distillation process adopted is three grades of water wash systems, the destructive distillation product that promptly comprises shale oil, water and dry distillation gas is after gas retort 1 outlet derivation, respectively in collecting tubule 2, washing tower 5, cooling tower 9, cool off and washing with direct contact of recirculated water, formed three grades of water wash systems with the destructive distillation product.
One-level water wash system: form by collecting tubule 2, collection mud jar 3, collection dredge pump 4.Circulation cleaning water is sent in the collecting tubule 2 by collection dredge pump 4, and 90-100 ℃ destructive distillation product is carried out spray washing, and wherein contained 60% shale oil is washed down.Shale oil is brought in the collection mud jar 3 by water, and profit carries out layering by the proportion difference in collection mud jar 3.The water of lower floor is sent into collecting tubule 2 internal recycle by collection dredge pump 4 and is used.The oil on upper strata is delivered to oil-water separation system and is got the finished product shale oil.
Secondary water wash system: form by washing saturator 5, wash trough 6, washing pump 7.Washing saturator 5 is the equipment of two towers unification, and top is washing tower, and the bottom is a saturator.Destructive distillation product temperature after one-level washing still has about 85 ℃, and after entering from wash tower bottoms, contained 30% oil wash is wherein got off in the washing water countercurrent flow of sending into washing pump 7.Dry distillation gas after the washing is derived from cat head, is divided into two parts behind gas dispatch machine 8: a part is sent into process furnace as cold circulating gas, and some sends into three grades of water wash systems.After the washing water of band oil enter the saturator of bottom, at the bottom of tower, enter wash trough 6.In wash trough 6, oil, water carry out layering by the proportion difference, and the washing water of lower floor are sent into washing tower 5 by washing pump 7 and recycled, and the oil on upper strata is delivered to oil-water separation system and got the finished product shale oil.
Three grades of water wash systems: form by cooling tower 9, cooling pool 10, cooling pump 13, water cooling tower 11, cooling pond 12, cold water pump 14.Dry distillation gas temperature after the two-stage washing still has about 80 ℃, need be dropped to 55 ℃ to satisfy processing requirement in this system.The reverse contact of washing water that the dry distillation gas that enters from cooling tower 9 bottoms and cat head cold water pump 14 are sent into and being lowered the temperature derived by cat head again.The oil-containing washing water enter cooling pool 10 by tower bottom, in cooling pool 10, oil, water carry out layering by the proportion difference, the washing water of lower floor are sent in the water cooling tower 11 by cooling pump 13, borrow natural wind to lower the temperature after the cooling, enter in the cooling pond 12 of water cooling tower 11 bottoms, send into cooling tower 9 tops by cold water pump 14 again and recycle.The oil on cooling pool 10 upper stratas is delivered to oil-water separation system and is got the finished product shale oil.
Cooling tower 9 outlet dry distillation gases are divided into two parts: a part is as the fuel of recuperative heater; A part is then used for gas fired-boiler and generating set.
The destructive distillation product of the inventive method gas retort 1 outlet is directly washed cooling through pneumatic trough 15 earlier, and temperature is dropped to 55 ℃-70 ℃, isolates shale oil and dust.Entering whirlwind catches oily tower 16 and removes oil droplet and dust.In indirect cool tower 17, the destructive distillation product does not directly contact with recirculated water, and gas-liquid two-phase is an indirect heat transfer and mass transfer process does not take place.In this process, dry distillation gas is further cooled to about 40 ℃, and shale oil and water vapor major part all are condensed, thereby make dry distillation gas obtain purification.The gas that inter cooler 17 comes out enters oil wash tower 18, and the shale oil that utilizes technology self to produce washs dry distillation gas, to collect wherein contained lightweight oil.In electrically trapped tar oil tower 19, collect the oil vapour that exists with gas form then.The last H that sloughs in the coal gas at two-step desulfurization tower 20,21
2Behind the S, deliver to through gas fan 22 and to make thermal barrier and fuel gas in the process furnace respectively.
Major equipment in this recovery system has:
1. pneumatic trough 15: directly wash the destructive distillation product with cyclic ammonia water, wherein most of oil and greasy filth are washed down, be recycled ammoniacal liquor and bring gun barrel 29 into, in jar after the sedimentation layering, the oil spill on top flow in the shale oil groove 32, and the water of bottom is sent into pneumatic trough 15 internal recycle with cyclic ammonia water pump 31 and used.Quantity of circulating water can be adjusted automatically according to the amount and the temperature variation of dry distillation gas.
2. whirlwind is caught oily tower 16: in whirlwind is caught oily tower 16, the destructive distillation product with the speed of 15-25m/s by down from pass through, water droplet wherein, oil droplet get off by gravity is separated, also enter after the cone tank at the bottom of the tower compiles and carry out oily water separation in the gun barrel 29.Cat head is provided with spray header,, can spray into cyclic ammonia water and lower the temperature when too high as gas temperature.
3. indirect cool tower 17: the cooling water purification is walked tube side, and dry distillation gas is walked shell side.Dry distillation gas is reduced to about 40 ℃ at this, and wherein a spot of lightweight oil and water smoke are condensed, and flows into certainly in the phlegma groove 27, and after this standing separation, the oil on upper strata is sent into gun barrel 29 with condensate pump 28.Cat head also is provided with spray header, and when the water-cooled tube outer wall hung up grease and influences heat-transfer effect, the available heat cyclic ammonia water cleaned.
Water purification water pump 23, water purification cold water jar 24, water purification water cooling tower 25 have formed the cooling water purifying recycle system.
4. the oil wash tower 18: utilize " similar mixing " principle, the shale oil that utilizes system self to reclaim to get off is delivered to cat head with oil pump 26, spray in the tower by shower nozzle, dry distillation gas countercurrent flow with the bottom feeding, dry distillation gas is carried out circulation cleaning, absorb the lower organic hydrocarbon of coal gas Semi-polarity, with further raising oil recovery rate.The tower body bottom is small-sized oil tank, oil is measured back oil can flow automatically in the shale oil groove 32.
5. the electrically trapped tar oil tower 19: feed high voltage direct current in this device, make negative electrode, anode in this device form high-voltage electric field.When voltage increases to a certainly when critical, the negative electrode in the device produces corona discharge, makes ionization of air produce a large amount of positive and negative ion and electronics.Grit in the dry distillation gas that feeds and be vaporific profit, because charged with ion or electronic impact, under the effect of electric field Coulomb's force, charged particle, water, mist of oil drip each and fly to and be captured to heteropole, and off-load flows down automatically, and aggregation is discharged in the oil pooling dipper of device bottom.
Tower outlet gas line is provided with oxygen on-line monitoring instrument, and when oxygen level in the coal gas surpassed 1%, equipment can cut off the power supply automatically.Cat head is provided with explosion trap, can play the effect of pressure release.
6. thionizer 20,21: dry distillation gas is adopted two-step desulfurization, and the dress sweetening agent adopts dry desulfurization (dry desulfurization is smart desulfurization) in the thionizer, can slough the H in the coal gas
2S, it is upright to make its content be lower than 200 milligrams/mark, reaches the emission standard that country allows.When using that for some time, sweetening effectiveness weakened, can feed steam sweetening agent is regenerated.
The reactive desulfurizing agent principle is as follows:
Fe(OH)
3+3H
2S→Fe
2S
3+6H
2O
2Fe(OH)
3+H
2S→2Fe(OH)+2H
2O+S
Fe(OH)
2+3H
2S→FeS+2H
2O
Sweetening agent regenerative response principle is as follows:
Fe
2S
3+6H
2O+3O
2→4Fe(OH)
3+6S
4FeS+3O
2+6H
2O→4Fe(OH)
3+4S
1, through nearly trimestral experiment operation, test data is as follows in the small test device of Fushun Mining Group Engineering Technical Research Centre for recovery method of the present invention:
(1) each equipment of recovery system is caught oily efficiency test result
Pneumatic trough: catching oily efficient is 60%;
Whirlwind is caught oily tower: catching oily efficient is 29%;
Indirect cool tower: catching oily efficient is 100%;
The electrically trapped tar oil tower: catching oily efficient is 32%.
(2) each equipment efficiency of dust collection test result of recovery system
Each equipment efficiency of dust collection test result of table 2
| Gas dustiness (milligram/mark is upright) | Efficient (%) | |
| The gas retort outlet | 1931 | --- |
| The pneumatic trough outlet | 519 | 73 |
| Whirlwind is caught oily tower outlet | 16.6 | 96.8 |
| The indirect cool tower outlet | 0.88 | 95 |
| The outlet of electrically trapped tar oil tower | 0.11 | 87.5 |
(3) dry desulfurization efficiency test result
Table 3 two-step desulfurization tower desulfuration efficiency test result
| Hydrogen sulfide content in the gas (milligram/mark is upright) | Efficient (%) | |
| The thionizer inlet | 1295 | --- |
| 1 #The thionizer outlet | 1246 | 3.8 |
| 2 #The thionizer outlet | 676 | 45.7 |
2, recovery method of the present invention is on small test device is achieved success empirical basis, carried out industrialization promotion in the newly-built E part device of Fushun Mining Group shale refinery, the operation of will going into operation in August, 2008 of this reconstruction and extension project.
The E part device will build 40 of gas retorts and two cover heating systems, are overlapped recovery system and supporting desulphurization system.Year handling the oil shale amount is 2,000,000 tons, year produces 8.017 ten thousand tons of shale oil, contrasts 60,000 tons/year of the designed capacitys of former technology, can increase production 2.017 ten thousand tons every year, year can create nearly 80,000,000 yuan of economic benefit more.Not only economic benefit is improved, and the level of automation of the environment of production scene, system also will be greatly improved.
Recovery system mainly is made up of three parts, and designing treatment coal gas amount is 140000m
3/ h.
First part: dry distillation gas cooling, purification, recovery shale oil part;
Second section: dry distillation gas desulfurization after the purification and sulphur product recovery part;
Third part: air pressurized, humidification, warming portion are formed.
This process characteristic:
(1) the destructive distillation product that 40 gas retorts are produced focuses on the recovery product, has improved plant factor and recycling effect, has reduced construction land, has saved investment;
(2) effective than the existing direct process for cooling gas purification of this factory, shale oil recovery efficient height, good operational environment, environmental benefit is obvious;
(3) adopt new and effective transverse tube type inter cooler, cooling water amount is few, has saved water resources;
(4) adopt new and effective electrically trapped tar oil tower, the shale mist of oil can be controlled in 20mg/m behind the tower
3Below, help the production operation of follow-up desulfurization unit and process furnace circulating gas;
(5) adopt the gas fan of band fluid-flywheel clutch easy to operate, the efficient height, reduced investment, energy-conservation;
(6) each storage tank dispersing gas discharging after the tower washing is cleaned in exhaust has reduced objectionable impurities to atmospheric pollution;
(7) the shale dregs of fat regularly send the boiler house, allocate in the bunker coal, have avoided secondary pollution.
(8) utilize saturated circulating gas of hot ammoniacal liquor and main air, reduced steam consumption.
Claims (7)
1. oil shale retorting process reclaiming method, it is characterized in that: whirlwind is caught in the recovery of oil process of washing process such as oil, indirectly cooling, heavy oil washing, electrically trapped tar oil and relevant device introducing dry distillation gas, the destructive distillation product is earlier after pneumatic trough (15) is directly washed cooling, temperature is dropped to 55 ℃-70 ℃, isolates shale oil and dust simultaneously; Entering whirlwind again catches and enters indirect cool tower (17) after oily tower (16) is removed oil droplet and dust; In indirect cool tower (17), the destructive distillation product does not directly contact with recirculated water, and gas-liquid two-phase is an indirect heat transfer and mass transfer process does not take place, in this process, dry distillation gas is further cooled to about 40 ℃, and the shale oil major part all is condensed, thereby makes dry distillation gas obtain purification; The gas that indirect cool tower (17) comes out enters oil wash tower (18), and the shale oil that utilizes technology self to produce washs dry distillation gas, to collect wherein contained lightweight oil; In electrically trapped tar oil tower (19), collect the oil vapour that exists with gas form; Last dry distillation gas is delivered to through gas fan (22) and is made thermal barrier and fuel gas in the process furnace respectively; Pneumatic trough (15), whirlwind are caught the shale oil and the phlegma of oily tower (16), indirect cool tower (17), oil wash tower (18), the discharge of electrically trapped tar oil tower equipment such as (19), sedimentation layering in gun barrel (28), cyclic ammonia water groove (30) respectively, the shale oil of gained flows automatically to shale oil groove (32), and washing water then carry out closed cycle in system uses.
2. oil shale retorting process reclaiming method according to claim 1, it is characterized in that: said pneumatic trough (15) washing is directly to wash the destructive distillation product with cyclic ammonia water, wherein most of oil and greasy filth are washed down, be recycled ammoniacal liquor and bring gun barrel (29) into, in jar after the sedimentation layering, the oil spill on top flow in the shale oil groove (32), and the water of bottom is sent into pneumatic trough (15) internal recycle with cyclic ammonia water pump (31) and used.
3. oil shale retorting process reclaiming method according to claim 1, it is characterized in that: in whirlwind is caught oily tower (16), the destructive distillation product with the speed of 15-25m/s by down from pass through, water droplet wherein, oil droplet get off by gravity is separated, also enter after the cone tank at the bottom of the tower compiles in the gun barrel (29) and carry out oily water separation; Cat head is provided with spray header,, can spray into cyclic ammonia water and lower the temperature when too high as gas temperature.
4. oil shale retorting process reclaiming method according to claim 1, it is characterized in that: in indirect cool tower (17), the cooling water purification is walked tube side, dry distillation gas is walked shell side, wherein a spot of lightweight oil and water smoke are condensed, in flowing into phlegma groove (27), behind this standing demix, the oil on upper strata is sent into gun barrel (29) with condensate pump (28); The indirect cool tower cat head also is provided with spray header, and when the water-cooled tube outer wall hung up grease and influences heat-transfer effect, the available heat cyclic ammonia water cleaned; Water purification water pump (23), water purification cold water jar (24), water purification water cooling tower (25) have formed the cooling water purifying recycle system.
5. oil shale retorting process reclaiming method according to claim 1, it is characterized in that: oil wash tower (18) utilizes " similar mixing " principle, the shale oil that utilizes system self to reclaim to get off is delivered to cat head with oil pump (26) and is sprayed in the tower, dry distillation gas countercurrent flow with the bottom feeding, dry distillation gas is carried out circulation cleaning, absorb the lower organic hydrocarbon of coal gas Semi-polarity, with further raising oil recovery rate; The tower body bottom is small-sized oil tank, oil is measured back oil can lean on from baric flow in shale oil groove (32).
6. oil shale retorting process reclaiming method according to claim 1, it is characterized in that: in electrically trapped tar oil tower (19), feed high voltage direct current, make negative electrode, anode in this device form high-voltage electric field, when voltage increases to a certain when critical, negative electrode in the device produces corona discharge, makes ionization of air produce a large amount of positive and negative ion and electronics; Grit in the dry distillation gas that feeds and be vaporific profit, because charged with ion or electronic impact, under the effect of electric field Coulomb's force, charged particle, water, mist of oil drip each and fly to and be captured to heteropole, and off-load flows down automatically, and aggregation is discharged in the oil pooling dipper of device bottom; Tower outlet gas line is provided with oxygen on-line monitoring instrument, and when oxygen level in the coal gas surpassed 1%, equipment can cut off the power supply automatically; Cat head is provided with explosion trap, can play the effect of pressure release.
7. oil shale retorting process reclaiming method according to claim 1 is characterized in that: dry distillation gas is adopted thionizer (20), (21) two-step desulfurization, sweetening agent is housed in the thionizer, adopt dry desulfurization, can slough the H in the coal gas
2S, it is upright to make its content be lower than 200 milligrams/mark, reaches the emission standard that country allows; When using that for some time, sweetening effectiveness weakened, can feed steam sweetening agent is regenerated.
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| CN102010732A (en) * | 2010-12-13 | 2011-04-13 | 华东理工大学 | Method and device for condensing and recovering shale oil in gas tower section of oil shale distillation system |
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| US3954597A (en) * | 1974-03-27 | 1976-05-04 | Morrell Jacque C | Process for the production of distillate fuels from oil shales and by-products therefrom |
| BR8606369A (en) * | 1986-12-22 | 1988-07-12 | Petroleo Brasileiro Sa | IMPROVEMENT IN EQUIPMENT AND PROCESS FOR OBTAINING OIL, GAS AND BY-PRODUCTS FROM PIROBETUMINOUS SHALES AND OTHER MATERIALS IMPREGNATED WITH HYDROCARBONS |
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