OIL PRODUCTS DERIVED FROM DILUTED PYROLYSIS GAS BY CONTINUOUS MILD-TEMPERATURE PYROLYSIS COAL-TAR SEPARATION PROCESS

Abstract

The present invention pertains to the recovery, separation and the unique product mixtures obtained by recovery and separation of coal-tar oils produced from low-rank-coal by a novel mild-temperature pyrolysis [MTP] process originating at the point where the vapor phase exits the pyrolysis reactor. Mild-temperature pyrolysis [MTP] takes place below 1200 F. in contrast to the high-temperature pyrolysis [HTP] that is operated at 1600-2000 F. for coke oven processing of metallurgical coke. The yield and composition of coal-tar-oil recovered from MTP are quite different from HTP coal-tar. In order to optimize the oil recovery process, the most appropriate recovery and separation processes therefore also will be different. The MTP process produces coal-tar containing a major fraction of strongly polar compounds mixed with non-polar compounds that separates into several liquid phases and overlap in their distillation ranges. This invention addresses the distinct product fractions obtained from MTP and the integrated multi step oil recovery and product separation process, which is designed with the objective to improve and facilitate the product separation, decrease the required amount of energy for separation and equipment cost for downstream processing.

Claims

1-29. (canceled)

30. A process for recovering oil from pyrolysis vapor phase produced during mild temperature pyrolysis of a low rank coal by simultaneous fractionation of coal-tar-oil liquids, the method comprising: extracting the coal-tar-oil in vapor phase as one of the end-product of mild temperature pyrolysis process of a low rank coal using a sweeping gas; optimizing the recovered coal-tar-oil from the vapor phase and reduced the amounts of non-condensing gas compounds by sequentially passing the high temperature vapor phase through a plurality of vapor condensing unit such that each vapor condensing unit operates at a defined temperature which is lower than the temperature in preceding vapor condensing unit to condense a fraction of coal-tar-oil liquid; wherein each sequential vapor condensing unit separates a different fraction of the coal-tar-oil liquid which has a condensing point within the operating temperature range of corresponding vapor condensing unit.

31. The process of claim 30, wherein the vapor phase is recovered and condensed into several fractions by means of contacting the uncondensed vapors sequentially with product condensate-recycle streams cooled stepwise to a lower temperature in order to obtain in each step a predetermined condensation temperature and liquid product quality, and where the condensation temperatures are in the ranges of 750-850 F., 625-700 F., 425-675 F., 235-265 F. and 110-145 F.; and preferentially 825-850 F., 645-665 F., 440-460 F., 245-255 F. and 110-130 F., or more preferentially 845 F., 650 F., 450 F., 250 F. and 120 F.

32. The process of claim 30, wherein the mild temperature pyrolysis is conducted at a temperature below 1150 F. in the presence of the sweeping gas.

33. The process of claim 30, wherein the coal-tar-oil vapor phase contains the volatile material which is then recovered and simultaneously fractionated into the plurality of oil fractions.

34. The process of claim 30, wherein in each of the vapor condensing unit, the vapor phase is contacted with a condensed liquid material in a quench column followed by a surface-contact packing for condensation and droplet agglomeration.

35. The process of claim 34, wherein the condensed liquid material is circulated through a heat exchanger where it is cooled to attain the temperature of the corresponding vapor condensing unit and is recycled back into the quench column.

36. The process of claim 34, wherein the condensed fraction of coal-tar oil is removed from the vapor condensing unit for downstream processing.

37. The process of claim 30, wherein one of the plurality of vapor condensing unit operates at temperature above 650 F.

38. The process of claim 30, wherein one of the plurality of vapor condensing unit operates at temperature within range of 450 F. to 650 F.

39. The process of claim 30, wherein one of the plurality of vapor condensing unit operates at temperature within range of 250 F. to 450 F.

40. The process of claim 30, wherein one of the plurality of vapor condensing unit operates at temperature within range of 130 F. to 250 F.

41. The process of claim 38, wherein the fraction of coal-tar-oil condensed form the vapor condensing unit operating at temperature within 450 F. to 650 F., is further treated to remove coal fines by using cyclone separators, filtration or a combination thereof.

42. The process of claim 30, wherein the different fraction of coal-tar-oil derived from each of the plurality of vapor condensing unit are further fractionated into separate sub-fractions of polar compounds and non-polar compounds and wherein the non-polar compounds are refined into a synthetic crude oil refinery feedstock fraction, one or more wax fractions, and an electrode-binder-pitch feedstock fraction.

43. A system for recovering oil fractions from pyrolysis vapor effluent produced during mild temperature pyrolysis of a low rank coal, the system comprising: a pyrolysis system for producing a coal-tar-oil vapor effluent phase as one of the end-product of mild temperature pyrolysis process of a low rank coal using a sweeping gas; a plurality of vapor condensing unit arranged sequentially for optimizing the recovered coal-tar-oil from the vapor phase and reducing the amounts of non-condensing gas compounds in the vapor effluent, each of the said plurality of vapor condensing unit operates at a temperature lower than the preceding vapor condensing unit; wherein the vapor condensing unit comprises a condensed liquid material that when contacts with the vapor effluents condensed the uncondensed vapor present in the vapor effluent which has a condensation point equivalent to the corresponding vapor condensing unit.

44. The system of claim 43, wherein the mild temperature pyrolysis is conducted at a temperature below 1150 F. in the presence of the sweeping gas.

45. The system of claim 43, wherein in each of the vapor condensing unit, the vapor phase is contacted with a condensed liquid material in a quench column followed by a surface-contact packing for condensation and droplet agglomeration.

46. The system of claim 43, wherein the condensed liquid material is circulated through a heat exchanger where it is cooled to attain the temperature of the corresponding vapor condensing unit and is recycled back into the quench column.

47. The system of claim 43, wherein the condensed fraction of coal-tar oil is removed from the vapor condensing unit for downstream processing.

48. The system of claim 43, where the condensation temperatures are in the ranges of 750-850 F. 625-700 F., 425-675 F., 235-265 F. and 110-145 F.; and preferentially 825-850 F., 645-665 F., 440-460 F., 245-255 F. and 110-130 F., or more preferentially 845 F., 650 F., 450 F., 250 F. and 120 F.

49. The system of claim 43, wherein the different fraction of coal-tar-oil derived from each of the plurality of vapor condensing unit are further fractionated into separate sub-fractions of polar compounds and non-polar compounds and wherein the non-polar compounds are refined into a synthetic crude oil refinery feedstock fraction, one or more wax fractions, and an electrode-binder-pitch feedstock fraction.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0038] As can be readily understood by those skilled in the art, the process vessels used in the pyrolysis effluent oil-recovery condensation process herein described may be separate units or joined together in a single segmented shell unit depending on the plant design capacity, the equipment dimensions and the installed cost. The schematic drawings presented as FIGS. 1, 2, 3, and 4 illustrate one embodiment of the process equipment and mass flows.

[0039] FIG. 1 shows a Mild Temperature Pyrolysis process for converting a low ranking coal into a coal-char product, a coal-tar-oil (vapor phase) and pyrolysis gas in accordance with an embodiment of the present invention.

[0040] FIG. 2 illustrates a process flow diagram showing mass flow of coal-tar-oil vapor phase through a plurality of vapor condensing unit, for recovering fractions of oil, in accordance with an embodiment of present invention.

[0041] FIG. 3 is a schematic illustration of a vapor condensing unit showing flow of coal-tar-oil vapor phase in a vapor condensing unit in accordance with an embodiment of present invention.

[0042] FIG. 4 illustrates a plurality of vapor condensing unit processing the coal-tar-oil liquid in stepwise manner, in accordance with an embodiment of present invention.

[0043] FIG. 5 illustrates a multiple fraction vapor condensing unit having two units of quench separation, in accordance with an embodiment of present invention.

[0044] FIG. 6 illustrates the recovery process for recovering coal-tar oil fractions for downstream processing of different fractions obtained from coal-tar-oil or entire coal-tar-oil in accordance with an embodiment of present invention.

[0045] FIG. 7 illustrates a hydrotreating process for downstream processing of different fractions obtained from coal-tar-oil or entire coal-tar-oil in accordance with an embodiment of present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0046] In the following detailed description of embodiments of the invention, numerous specific details such as specific process steps, processing conditions, processing equipment, apparatus, and operating features are set forth in order to provide a systematic understanding of the invention. However, it is to be clearly understood by those skilled in the art that these are merely exemplary of the invention and are given to disclose the invention in the best embodiment presently contemplated by the inventor, and do not in any sense constitute a limitation upon the invention. This is particularly so with respect to the equipment and apparatus, since many functional variations can be used to carry out the invention, as will be appreciated by those skilled in the art.

[0047] Furthermore, it will be clear that the invention is not limited to these embodiments only. Numerous modifications, changes, variations, substitutions and equivalents will be apparent to those skilled in the art, without parting from the spirit and scope of the invention.

[0048] In order to overcome the disadvantages associated with prior art, the present invention provides a multi-step coal-tar-oil recovery process. The recovery process for the coal-tar gas and liquid fractions is specially designed with the following goals in mind: (a) Optimize the recovered coal-tar-oil from the pyrolysis vapor effluent and reduce the amounts of non-recovered condensable compounds in the gas; (b) Produce several separate liquid fractions during the recovery process; (c) In order to avoid deposits of high-viscosity wax and pitch material on the colder heat exchange surfaces required for condensation of the lower boiling hydrocarbon compounds, the high boiling compounds need to be recovered and separated at higher temperatures; (d) Optimize the temperature and heat content of recoverable waste heat for process utilization; (e) Reduction and optimization of operating cost including downstream processing cost and minimization of the overall capital cost; (f) Separation of coal-fines from the condensed coal-tar liquid fractions that contain reactive compounds that have affinity for activated carbon catalyzed polymerization at ambient temperature. The preferred process configuration and operating conditions are described in the following without limiting the present invention to the specific examples used to illustrate the process design.

[0049] The present invention is directed specifically to oil products derived from a mild temperature pyrolysis process for treating a low rank coal. As can be appreciated by those skilled in the art of coal pyrolysis, the mild temperature pyrolysis [MTP] gasification process for the formation of char and pyrolysis oil starts with a non-caking, non-coking coal and differs substantially from a process utilized for the formation of metallurgical coke. An important difference of this invention is the operability of a mild temperature pyrolysis process with the ability to control the temperature and composition of the pyrolysis gas in order to also provide precise control over the residual volatile content of the coal-char formed.

[0050] Although, high-temperature pyrolysis is widely used to produce metallurgical coke and coal-tar, these processes differ significantly from mild-temperature pyrolysis in design, operating conditions, coke product properties, coal-tar yield, composition and properties, and feedstock criteria. The yield and composition of high-temperature coal-tar have limited its value so that it has remained confined to being a byproduct. In contrast, due to the higher oil yield and quality, the coal-tar-oil product from mild-temperature pyrolysis [MTP] of low rank coal (LRC) can become the economic justification for development of commercial scale coal conversion projects based on the subject invention. By utilizing the present invention, the development of a coal conversion industry producing coal-char fuel, coal-tar-syncrude and coal-tar chemicals becomes technical feasible and economically viable. The present invention is useful because it provides a means whereby more than 75%, 85% or even 95% of the condensable coal-tar-oil contained in the diluted pyrolysis gas effluent from the mild-temperature pyrolysis reactor can be recovered in liquid form. The liquid oil can then be subjected to downstream processing and utilization instead of defaulting to fuel gas use. The economic value is potentially significant because the yield of recovered oil determines the economic viability of mild-temperature pyrolysis processing on low-rank coal.

[0051] FIG. 1 shows a Mild Temperature Pyrolysis process for converting a low ranking coal into a coal-char product, a coal-tar-oil (vapor phase) and pyrolysis gas in accordance with an embodiment of the present invention. The feedstock preparation unit [30] provides for screening, milling and weighing of feedstock [37] before it is conveyed into the drier [2] where it is heated and most of the water is vaporized [10] using steam [23] recovered from the downstream process units that exits as recycle condensate [47]. The dried feedstock [3] is fed into the preheater-pyrolysis kiln [31] which is heated in part with indirect heating medium [48, exiting 49] provided to the outside of the kiln, and in part with a direct-contact hot gas stream [39] that flows through the kiln and exits as process off-gas [41]. This process off-gas [41] contains some amount of coal-fines and most of the mercury in the coal, and it is therefore passed through a cyclone [32] for coal-fines separation and recycle [42] and an absorber [45] for recovery of mercury [38] before the off-gas [11] flows to gas treatment. The preheated feedstock [54] exiting the pre-heater pyrolysis kiln [31] feeds into the high temperature pyrolysis kiln [33] which is heated in part with indirect heating medium [50, exiting 51] provided to the outside shell of the kiln, and in part with a direct-contact hot gas stream [40] that flows through the kiln and exits as high-temperature pyrolysis gas [43]. The pyrolysis gas [43] is passed through a cyclone [34] for separation of recycle coal-fines [44] and pyrolysis gas [5] that flows to the oil recovery unit. The hot coal-char [55] exiting the pyrolysis kiln [33] feeds directly into the char cooler [36] that is provided with indirect cooling medium [52, exits 53] for heat recovery and cools the coal-char product [16] for pyrite removal [17] and stabilization [19]. The mild temperature pyrolysis process is described in details in co-pending non-provisional application that contain priority from provisional application No. 62/601,521, the content of which is hereby incorporated in reference to its entirety.

[0052] In the MTP process the coal-tar-oil compounds are produced by mild-temperature pyrolysis and volatilized by the interaction between the elevated operating temperature, reaction residence time at temperature and the amount and space velocity of a sweeping gas. The pyrolysis takes place at 450-1200 F. with 15-45-minutes residence time. The sweeping gas has several separate and important functions in the process, since it is used simultaneously as a heating medium for the pyrolysis, to decrease the partial pressures of the compounds and help vaporize the coal-tar-oil, to help dilute the vapor phase and thereby decreasing the polymerization of reactive coal-tar compounds, and to help transport the coal-tar vapors out of the reactor. Sweeping gas must be inert, containing nitrogen, carbon dioxide, carbon monoxide, water and argon, but less than 1.5-vol % oxygen, preferably less than 0.5 w %; however, it also may contain traces of light hydrocarbons. It is desirable that the ratio of coal-tar-oil to sweeping gas is larger than 10-w %, preferably larger than 20%, although 4.5-6.5% is still operable, but less desirable because the lower concentration inhibits the recovery process and increases its efficiency and cost. Substituting part of the direct heating of the pyrolysis reactor with indirect heating results in decreased heating-gas requirements and higher coal-tar-oil concentration in the effluent.

[0053] The pyrolysis vapor phase effluent contains non-condensing gas compounds, including H2S, COS, CH4, C2H6 and homologues hydrocarbons together with sweeping gas and condensable oil compounds. The condensable fraction of the crude coal-tar has a boiling range of 200 F.-1400 F. The volatilization of compounds boiling above the 1200 F. upper pyrolysis temperature is due to the relatively low partial pressure of the individual components, the presence of sweeping gas and the effect of co-distillation with other compounds.

[0054] The present invention provides a method and a system for recovering different fractions of syncrude oil from the coal-tar-oil derived from the mild temperature pyrolysis process. The method involves utilizing several sequential coal-tar recovery process steps that separate the pyrolysis vapor effluent into three or more separate process streams including a non-condensed gas stream. The pyrolysis vapor effluent stream coming from the MTP process is at temperature above 1100 F., in which the oil vapors are present with different gases due to high temperature of effluent gas. The coal-tar oil contains different fractions that can be used for extracting the coal tar products which have variable economic importance. These fractions have different condensation point, which means the vapor phase can be condensed at different temperature to extract different fractions of coal-tar-oil. The present invention utilizes a plurality of vapor condensing unit arranged sequentially such that the pyrolysis vapor effluent from MTP first enters into a first vapor condensing unit operating at a specified temperature range. The fraction of oil which has a condensation point in this range get condensed in the first vapor condensing unit. The vapor effluent is then passed into a second vapor condensing unit operating at a second temperature range which is lower than the first vapor condensing unit. The fraction of coal-tar-oil which has condensation point in this range gets condensed and is then separated from the vapor effluent. This method is then performed in stepwise manner, such that each succeeding vapor condensing unit is operating at a temperature which is lower than the preceding vapor condensing unit.

[0055] The following example illustrates the process design, without thereby intending in any way to limit the number of separate liquid fractions that can be obtained. In this example the pyrolysis vapor is recovered and separated into five fractions: [1] Fraction-A, 650+ F.; [2] Fraction-B, 450-650 F.; [3] Fraction-C, 250-450 F.; [4] a mostly water Fraction-D at 135 F., [5] and a gas stream E, as described below.

[0056] Condensation of Fraction A, 650+ F.: The vapor phase effluent from pyrolysis is contacted with a recycle of the condensed liquid material in a quench column containing a combination of one or several spray-decks for initial gas/liquid contact followed by a surface-contact packing for condensation and droplet agglomeration. The recycle liquid exits the bottom of the quench column, passes through a heat exchanger where it is cooled so that the resulting vapor quench temperature is reached, passes through the recycle pump, and a side stream removes product [with level control from the column bottoms]. The recycle is then split into two, one going to the spray-deck sections and the other going to the top of the top of the contact-packing section. The 650+ F. fraction comprises approximately 45-55 w % of the condensable recovered pyrolysis coal-tar oil yield.

[0057] Recovery of Fraction B, 450-650 F.: The process is as described above for the gas-quench, except that the operating temperatures are 200 F. lower in order to condense the 450 F. fraction, which comprise 25-35 w % of the total recovered oil yield.

[0058] Recovery of Fraction C, 250-450 F.: The process is as described above, except that the operating temperatures are 200 F. lower in order to condense the 250 F. fraction, which comprise 5-15 w % of the total recovered oil yield.

[0059] Gas scrubbing to 135 F. [nominal temperature]: Recovery and separation of Fractions D, 135-250 F. and gas stream E. The vapor phase from the 250 F.-quench is cooled and water washed in a water-scrubbing column to recover water and any condensable material. The bottom liquid separates into an oil phase and a water phase that are withdrawn separately for further processing. Only the water phase is used as recycle to the gas scrubber. The gas phase exiting the top of the wash column is a lean fuel gas that will be used as process recycle sweeping gas [see above] and, after cleaning to remove source emissions, as fuel for the process heaters. For example, a plurality of vapor condensing unit are arranged sequentially such that the vapor condensing unit is operated in any of the following temperature range: 750-850 F., 625-700 F., 425-675 F., 235-265 F. and 110-145 F.; and preferentially 825-850 F., 645-665 F., 440-460 F., 245-255 F. and 110-130 F., or more preferentially 845 F., 650 F., 450 F., 250 F. and 120 F.

[0060] In an embodiment of present invention, the Coal-fines are removed from coal-tar-oil fractions to help the downstream processing of coal tar fraction. The removal of coal-fines, which essentially comprise activated carbon with catalytic properties, from the 450-650 F. oil fraction is important to prevent polymerization and instability of the chemically reactive polar compounds. This can be accomplished by several means, including using cyclone separators for the incoming vapor phase, cyclone separation or filtration of the condensed liquid, or a combination thereof. When gas-phase cyclone separation is used, sufficient pressure to overcome the associated pressure drop will have to be provided by means of higher upstream operating pressure or using a low-pressure compressor. When coal-fines removal from the liquid oil phase is employed a combination of cyclone separation and a series of filters of decreasing fineness may be most suitable and cost effective depending of the MTP design and the characteristics of the feed-coal.

[0061] FIG. 2 illustrates a process flow diagram showing mass flow of coal-tar-oil vapor phase through a plurality of vapor condensing unit, for recovering fractions of oil, in accordance with an embodiment of present invention. There are four vapor condensing unit (VCU) that are arranged sequentially to recover a fraction of coal-tar-oil. The high temperature vapor effluent from pyrolysis unit is passed through a first vapor condensing unit. The vapor effluent from the pyrolysis unit is at high temperature, which is in range of 950-1050 F. Due to the high temperature, the coal-tar-oil is in vapor phase intermixed with different gases. The first vapor condensing unit is operating at a temperature which is lower than the vapor effluent stream. A condensing liquid or gas is present in the first condensing unit, such that the vapor effluent from the pyrolysis kiln is contacted with the condensing liquid or gas at a heat exchanger surface, and on the contact with heat exchanger at a lower temperature, a fraction of coal-tar-oil gets condensed which can then be recovered from the bottom of the first vapor condensing unit. For illustration purpose, the first vapor condensing unit of FIG. 1 is operating at a temperature above 600 F. The condensate from the first vapor condensing unit is then pumped to a system where the downstream processing of this fraction condensate is performed to sub-fractionate and refinement of the first condensate fraction.

[0062] The remaining vapor effluent is then passed through a second vapor condensing unit, which also contains a condensate liquid or gas, a heat exchanger. The second vapor condensing unit is operating at a temperature lower than the first vapor condensate. For example, in case of FIG. 1, the second vapor condensing unit is design to condensate the fraction within a temperature range of 450-600 F. The temperature of the second condensing unit is lower than the first condensing unit, therefore, when the vapor effluent from the first vapor condensing unit passes through the second condensing unit, the fraction of oil which has a condensing point within the operating temperature range of 450-600 F. gets condensed and then collected through the bottom of the second vapor condensing unit. The second condensate fraction is then pumped to undergo downstream processing for sub-fractionation and refining.

[0063] The vapor effluent from the second condensing unit is then passed through a third vapor condensing unit which is similar in structure to the first vapor condensing unit and the second vapor condensing unit. The operating temperature of the third vapor condensing unit is lower than the first vapor condensing unit and the second vapor condensing unit. The vapor effluent when contacted with the condensing media, results in the condensation of oil fraction which has a condensation point within the operating range of the third vapor condensing unit. For illustration purpose, the third vapor condensing unit is operating at a temperature range of 300-450 F. The condensed fraction is collected from the bottom of the third vapor condensing unit.

[0064] The vapor effluent from the third vapor condensing unit is then passed through a fourth vapor condensing unit, which is operating at a temperature lower than the third vapor condensing unit. For illustration, the fourth vapor condensing unit is operating at a temperature range of 135-300 F. The vapor phase contacting the quench get cooled and withdrawn from bottom for further processing. The gas phase exiting the top of the wash column is a lean fuel gas that will be used as process recycle sweeping gas and, after cleaning to remove source emissions, as fuel for the process heaters

[0065] FIG. 3 is a schematic illustration of a vapor condensing unit showing flow of coal-tar-oil vapor phase in a vapor condensing unit in accordance with an embodiment of present invention. The vapor condensing unit comprises a Venturi gas/liquid mixer [5], a quench vessel [6], a packed section [7], a plurality of spray deck [8], a recycle pump [9], a first heat exchanger [10] and a second heat exchanger [11]. In an embodiment, each of the plurality of vapor condensing unit may be schematically identical or different, depending on the viscosity of the individual oil fractions separated by the particular vapor condensing unit. In another embodiment, the dimensions of equipments of each of the vapor condensing unit are different among vapor condensing unit, depending on the difference in temperature, gas volume being processed and liquid product collected.

[0066] In the Venturi gas/liquid mixture [5], the pyrolysis gas and vapor effluent coming from the pyrolysis kiln is mixed with a stream of condensed liquid such that the mixture of vapor effluent and liquid stream reach the desired condensing temperature. The desired temperature stream of condensed liquid by cooling the liquid stream by the first heat exchanger [10] to a lower temperature so that the mixture of vapor effluent and the liquid reach the desired condensing temperature. The condensing stream of liquid is pumped through the recycle pump 9. The quenching of vapor effluent and liquid mixture will take place at the quench vessel [6]. The quench vessel [6] has a plurality of spray decks [8] through which condensed liquid is sprayed on the vapor effluent/condensed liquid mixture coming from the Venturi gas/liquid mixture. The upper part of quench vessel [6] has a packed section [7] that serves as a thermal stabilizer and a means to coalesce escaping droplets. The packed section [7] is at a sufficient height from the plurality of spray decks [8] such that the highest boiler fractions get condensed en route between the Venturi mixer and the plurality of spray decks, which prevent the upper packed section to get clogged by condensed particles. The spray decks are in relatively open configuration that also prevents the clogging of packed section.

[0067] The process flow in the vapor condensing unit starts with mixing of vapor effluents with the liquid condensed material which drops the temperature of vapor effluent to condensation point. The resulting mixture then travels to quench vessel [6] where the condensed liquid is sprayed over the incoming mixture to help condensation of fraction of coal-tar-oil. The remaining vapor pass form the top of quench vessel [6] to next vapor condensing unit for further processing. The condensed fraction of coal-tar-oil along with the condensed liquid passed through the bottom of quench vessel. The recycle pump [9] pumps the condensed fraction and liquid to the first heat exchanger [10] where the fraction is cooled to the desired temperature and thus recycling of condensed liquid takes place. The cooled condensed liquid and fraction of coal-tar oil is then used for cooling the incoming vapor effluents in Venturi mixer and plurality of spray deck. From this recycle stream, a side stream of product is withdrawn and cooled by the second heat exchanger [11]. This is the fraction of oil that is recovered from the vapor condensing unit. The recovered oil fraction is then stored in a storage tank [12] which is then pumped by a pump [13] for downstream processing. The heat generated by the first heat exchanger [10] and the second heat exchanger [11] can be utilized for heating process either in mild temperature pyrolysis or other process. Thus, by using the process of present invention, it is possible to recover heat from the first heat exchanger [10] and the second heat exchanger [11].

[0068] In an embodiment, the present invention utilizes a plurality of vapor condensing unit operating at different temperature range for condensing oil fraction, wherein each sequential vapor condensing unit is operation at a temperature lower than the previous vapor condensing unit.

[0069] FIG. 4 illustrates a plurality of vapor condensing unit processing the coal-tar-oil liquid in stepwise manner, in accordance with an embodiment of present invention. FIG. 4 shows a first vapor condensing unit [14], a second vapor condensing unit [15], a third vapor condensing unit [16] and a fourth vapor condensing unit [17] arranged in a sequence to process the vapor effluent stream coming from the pyrolysis kiln. The operating condensing temperature of the fourth vapor condensing unit is lower than the operation condensing temperature of the third vapor condensing unit, which in turn is lower than the operating condensing temperature of the second vapor condensing unit, which in turn is lower than the operating condensing temperature of the first vapor condensing unit. Due to the difference in operating condensing temperature, the rating of equipments and the design of these vapor condensing units may be identical or different. The vapor effluent from the pyrolysis kiln is entered into the first vapor condensing unit [14]. The vapor effluent is mixed with the condensed liquid in the Venturi mixer of the first vapor condensing unit and is then passed through the quench vessel, where the condensed liquid is sprayed on the vapor effluent/condensed liquid mixture. The condensation takes place and the condensed mixture is collected from the bottom of the first vapor condensing unit. A stream of product is removed from the condensed liquid obtained from the first vapor condensing unit and is transported to a storage tank for storing first fraction. The rest of the condensed liquid/fraction mixture is recycled to use for next stream of vapor effluent. In the first vapor condensing unit only that fraction of coal-tar-oil that has a condensation point within the operating range of the first condensing unit gets condensed, and the remaining vapor effluent pass from the top of the first vapor condensing unit to the second condensing unit. In the second condensing unit, same process is repeating and a second fraction of oil is recovered from the vapor effluent that has condensation temperature lower than the first vapor condensing unit. The second fraction of recovered coal-tar-oil is then stored in a second storage tank.

[0070] The remaining vapor effluent from the second condensing unit then passes to the third vapor condensing unit which condenses the fraction of coal-tar-oil that has condensation temperature lower than the second vapor condensing unit. The fraction obtained from the third vapor condensing unit is stored in a third storage tank.

[0071] The remaining vapor effluents from the third vapor condensing unit [16] is then passed to the fourth condensing unit [17], where the fourth fraction of coal-tar-oil is recovered and stored in a fourth storage tank. The remaining vapor effluent contains primarily contain non-condensable gas fraction which can then either be used as a fuel or in the pyrolysis process itself.

[0072] The example in FIG. 4 is for mere illustrative purpose, whereas in embodiment, the present invention utilizes a plurality of vapor condensing unit, which may be two to more than six vapor condensing units.

[0073] In an embodiment of present invention, it is envisioned that the design of a vapor condensing unit used in the present invention can be modified to include one or more vapor condensing unit in a single vessel. The two or more vapor condensing units are connected by a chimney tray that allows the vapor effluent in gas phase to flow up from the lower quench vessel to the next upper quench vessel. The vapor effluents from pyrolysis kiln enter into a Venturi mixer where it is mixed with a liquid condensed material and enters into the vessel. The vessel in FIG. 5 contains two vapor condensing unit stacked one over another separated by a chimney tray. The mixture of vapor effluent and the condensed liquid enter into the first vapor condensing unit where condensation of first fraction of coal-tar oil takes place. The remaining vapor effluents then enter into the second vapor condensing unit which is present in the same vessel. The condensation of second fraction of coal-tar-oil is recovered from the second vapor condensing unit.

[0074] FIG. 5 illustrates how the stacking of one vapor condensing unit on top of the next can provide savings in equipment and piping cost. In an embodiment, any reasonable number of VCUs can be joined in this manner depending on cost limitations associated with the vessel dimensions, except if vapor cyclones are installed between quench vessels to separate gas from coal-fines and/or oil droplets.

[0075] FIG. 6 illustrates the recovery process for recovering coal-tar oil fractions for downstream processing of different fractions obtained from coal-tar-oil or entire coal-tar-oil in accordance with an embodiment of present invention. The vapor condensing unit comprises a hot pyrolysis gas and oil vapor stream [5] exiting the pyrolysis unit at 900-1100 F. flows into a Venturi-mixing quench device [60] and mixes with two cooled recycle oil streams [97 and 98] from the first absorber vessel [61], reducing the temperature of the gas/oil mixture [95] to below the oil cracking range as it exits the quench device and enters the absorber vessel [61]. The uncondensed gas/vapor pass upward through a quench spray-deck section [91] in contact with downwards flow of oil pumped from the vessel bottom through a pump [79] and heat exchanger cooler [69] to spray nozzles placed above the spray-deck and mixing with oil from the mid-section of the vessel flowing through a pump [80] and heat exchanger cooler [68] to spray nozzles placed above the spray-deck. Two similar absorber sections [92 and 93] are placed above the first with separate coolers [67 and 68] to control the operating temperatures as required to obtain the desired composition of the exit gas/vapor phase stream [105]. The condensed oil fraction [96] exiting at the bottom of the first absorber vessel [61] flows through a cooler [69] to a pump [79] and splits into a first recycle stream [97] going to the gas-quench mixer [60], a second recycle stream [103] going to the first spray-deck, and a third stream [104] passing through a heat exchanger cooler [78] and joining with the other oil fractions going to hydrotreating [7]. The overhead gas phase [105] from the absorber vessel [61] flows to the second absorber vessel [62] where the oil condensation and fractionation process is repeated at lower temperatures employing two cooled oil recycle loops [106 and 108] with a pump [81] and two heat exchanger coolers [70 and 71] to produce a second condensed oil fraction [109] that is cooled in heat exchange [125] and then joins the oil feed stream [7] going to hydrotreating. The uncondensed gas phase [110] exiting from the top of the absorber vessel [62] flows through a partial condenser [72], an electrostatic separator [67] for coalescing of oil-mist and a phase separation vessel [63] from where the third condensed oil fraction [111] flows through a pump [82] and a cooler [85] joining the oil feed stream [7] going to hydrotreating. The gas phase [112] flows to the third absorber vessel [64] where an oil fraction [113] is separated at the bottom and a gas stream [122] is removed at the top and conducted to the downstream gas and water separation and treatment unit. The condensed oil fraction [113] from the bottom of the vessel [64] flows through a pump [83] and a heat exchanger [74] to a distillation column [65] that is provided with a reboiler [75], condenser [77] and overhead separation vessel [66] where the non-condensable gas [116] is separated from the condensed light-end oil fraction [117] and flows to gas treatment [26], while the condensed oil fraction is pumped via pump [85] in part back as reflux [118] for vessel [65] and in part [119] joins the oil feed stream [7] going to hydrotreating. From the bottom of the distillation column [65] the oil fraction product [120] flows through a pump [84] and heat-exchanger [74], and then is split into a recycle stream [123] going to the top of the absorber vessel [64] and an oil stream [121] passing through a cooler [76] and joining the other recovered oil fractions [7] on the way to hydrotreating. The recovered oil fractions generally are not mixed until entering hydrotreating processing due to their different compositions, polarity, viscosity, density and solubility that in some cases may cause phase separation.

[0076] In an embodiment of present invention, the coal tar fractions is converted to synthetic crude oil by fixed bed catalytic hydrotreating process. FIG. 7 illustrates a hydrotreating process for downstream processing of different fractions obtained from coal-tar-oil or entire coal-tar-oil in accordance with an embodiment of present invention. FIG. 7 shows a preferred version of the oil hydrotreating section that reflects the large hydrogen demand by pyrolysis oil in the range of 55-kg/ton-oil (3000-SCF/bbl), the attendant large heat release and the need for stepwise reaction temperature increases for better control of the conversion of olefins, oxygenated compounds, aromatics and high molecular weight hydrocarbons. The reactor configuration features three ebullient-bed reactors [132, 136 and 140] in series. The oil feedstock [7] is comprised of the condensed oil fractions from the oil recovery and gas separation section and is introduced into the first reactor vessel [132] through a high-pressure pump [130] and heat exchanger [131]. The reactors are provided with a hydrogen supply [160] entering through a primary compressor unit [151] with inter-cooler [152] and a water separation vessel [153] that feeds into a secondary recycle compressor unit [154] with condenser [155] and separator vessel [156]. The high-pressure hydrogen [161] is delivered to the reactors [132, 136 and 140] through internal nozzles ensuring good internal mixing [ebullience] and circulation. The reactor [132] is cooled by means of recycle cooling media in contact with internal and external cooling surface areas as well as a process-oil recycle loop [cooler 134 and pump 135] providing temperature control and waste-heat recovery. The reactor effluent [163] is heated in a heat-exchanger [133] to the higher reaction temperature required in the next down-stream reactor. This sequence is repeated for the other reactors [136 and 140]. Fresh catalyst slurry [157] is introduced through a pump [158] into the catalyst recycle loop [167]. The effluent [165] from the last reactor [140] is separated into a liquid oil fraction and a hydrogen gas fraction through several steps of cooling [144, 146] and phase separations with pressure reduction and vapor/liquid-flash separations [145, 147, 148] of which two are shown schematically in this design case. The gas phase is further treated in a gas separation unit [150] to recover a fuel gas stream [170] and a hydrogen rich recycle stream [162] that returns back to the hydrogen recycle compressor [154]. The recovered oil phase [166] from separation vessel [148] contains catalyst slurry and is in part recycled through a pump [149] back to the hydrotreating reactor [132]. The balance of the oil is clarified in a filter [159] and exported as synthetic crude oil product [9] while the spent catalyst [168] is removed for disposal.

[0077] In an embodiment of present invention, the removal of the polar compounds [catechol, cresylic acid and N-bases fractions] from the coal-tar feedstock before undergoing mild temperature pyrolysis, results in significant savings in hydrogen consumption in the order of 15-30-%. Removal of the 900+ F. high boiling coal-tar-pitch fraction, which may have better use as electrode binder pitch or delayed-coke feedstock, also decreases the hydrotreating cost and increases the yields of desirable hydrocarbons. The coking process yields a light-cycle-oil that can be used as feedstock in the hydrotreater.

[0078] In another embodiment, an alternative to hydroterating at the above mentioned operating conditions, is applying a high-pressure process such as the HTI hydrotreating designed for coal conversion and using a homogeneous slurry catalyst and 3000-psia pressure of higher. In this case the presence in the recovered coal-tar-oil of 900+ F.-HT-pitch and coal-fines that tend to form deposits on fixed-bed catalysts, do not present unusual problems. Several similar alternative hydrotreating process are in operation on feedstock derived from tar-sand oil extraction, oilshale and coal-to-liquid, and the choice of process is an economic decision based on the cost, experience, feedstock quality, product slate and commercial warranties provided for each site specific project.

[0079] In an embodiment of present invention, the condensate from coal-tar-oil produced during the mild temperature pyrolysis of low-rank coal can be used to produce a wax. The high boiling condensate is collected and vacuum distilled to yield a bottoms material with a boiling point in excess of +550 F. This bottoms material is then diluted with N-Methylpyrrolidone (NMP) at ratios of 1:1 and 2:1 NMP to 550+ boiling fraction of the condensed material. While the 550+ bottoms material remains solid at 150 F. initially, with the addition of both 1:1 and 2:1 NMP to bottoms render it free flowing at temperatures as low as room temperature, transforming it into a useful low temperature extraction feed material, useful for counter current extraction.

[0080] This feed material is then extracted against various ratios of heptane to feed of 2:1 to 5:1, resulting in heptane soluble wax yields of 22% to 39% when extracted at 110 F., and wax yields of 26% to 44% when extracted at 160 F. The heptane is then stripped from the wax products by vacuum distillation and all of the resulting properties is found to be miscible with molten paraffin wax. The NMP diluant get mixed with the raffinate and does not contaminate the heptane extract or the wax, allowing for more than 99% recovery of the NMP from the raffinate, resulting in a commercially viable coal tar pitch.

[0081] In another embodiment, the 550+ bottoms feed is diluted with 2 parts NMP to 1 part of 550+ fraction condensate material and is then subsequently extracted against an excess of heptane 5 times, collecting the resulting wax materials with each extraction step. The properties of each sample are measured using Iatroscan, which reports the constituents in the broad categories of Saturates, Aromatics, Polars A and Polars B, which represent two molecular weight ranges of polar materials. Extractions is carried out at 110 F. and 160 F. with the wax yield data for each extraction appearing in the table A below, where the first 2 lines of data, SGITC 550+ and D100-1-4-T1-BT being feed materials, NMP being the diluant for the feed materials and almost totally polar, sample labels ending in C being extracted at 110 F. and those with labels ending in D being extracted at 160 F. and the last two lines being the wax products.

TABLE-US-00001 TABLE A Satu- Aro- Sample rates matics Polars A Polars B (S + A): P SGITC 550+ 10 16 46 28 0.35 D100-1-4-T1-BT 8 16 51 25 0.32 NMP 0 0 93 7 0.00 EX-1C 21 35 32 12 1.27 EX-2C 13 40 38 9 1.13 EX-3C 7 42 40 11 0.96 EX-4C 4 40 43 13 0.79 EX-5C 0 35 51 14 0.54 EX-1D 22 37 31 10 1.44 EX-2D 16 43 32 9 1.44 EX-3D 9 35 42 14 0.79 EX-4D 2 43 41 14 0.82 EX-5D 3 42 40 15 0.82 D100-1-6-BT-4A 21 35 33 11 1.27 D100-1-6-BT-4B 21 37 33 9 1.38 SGI Wax B 19 31 43 7 1.00 SGI Wax B Bau 12 47 36 5 1.44

[0082] As can be seen by inspection of Table-A below, the extraction process results in a 3-4 fold increase in the (Saturates+Aromatics): Polars ratio, to the range of 1:1, creating a product with a high boiling point, and an almost equal affinity for polar and non-polar materials, and surprisingly, rendering it compatible with both. This material is tested and found to be commercially viable in a hard board manufacturing operation, having a lower emission profile during the high temperature press cure cycle than paraffin or slack wax, due to its higher boiling point. The coal derived wax was also shown, both in the laboratory and in the manufacturing operation to be completely miscible with petroleum waxes, so that it could be used in any ratio in the formulation. The properties of commercial waxes and this coal-derived wax are compared in Table-B below. This coal derived wax, +550 F waxTreated and +550 F. waxUn-Treated, is unique in as a coal derived wax in its difference from and compatibility with petroleum waxes and also, by inspection of the above table unique from the only known coal extracted wax which is Montan wax, and which is 99% polar in nature and not miscible with paraffin wax.

TABLE-US-00002 TABLE B ADHESIVE WAX PROPERTIES +550 F. WAX +550 F. WAX COMMERCIAL WAXES TEST METHOD TREATED UN-TREATED PARAFFIN MONTAN Softening Point (deg. F.) ASTM Ring & Ball 86-99 71 124 167-176 Acid Number Proprietary 8.1 11.0-16.1 <0.5 22-36 Saponification No. Proprietary 99.7 40.3-00.4 7.7 75-100 Iodine No. Proprietary 79.3 63.0-75.3 16 Boiling Range (% @ 550 deg. F.) Proprietary >90 >90 >90 Oxygen (% w/w) By difference 4.39 3.56-5.15 <0.5 6.8 Saturates (% w/w) latroscan 12 15-20 93 <1 Aromatics (% w/w) latroscan 47 34-39 2 1 Polars (% w/w) latroscan 41 43-51 5 99 Miscable with molten Paraffin Proprietary YES YES YES NO

[0083] The balance in polar and non-polar properties suggest that this wax may form stable mixtures with adhesives, and may be formulated to chemically react with adhesives during the cure cycle as well, due to its reactivity which arises from the characteristics of mild temperature pyrolysis liquids, creating an new category of reactive waxes which function like reactive diluents imparting properties such as fracture toughness or surface sheen, and reduced cost to adhesive and coating formulations.

[0084] The following examples and numeric data are provided for the purpose of illustration and information without implying any limitations as to the process invention, the equipment or any other limitation with respect to the invention. The downstream processing of the recovered oil fractions will depend on market conditions including the relative values of the compounds contained in the oil. The pre-fractionation accomplished in the multi-stage quench-condensation process described herein facilitates the downstream processing and eliminates the need for a crude coal-tar-oil distillation plant. The following examples and data illustrate the range of compositions of the MTP coal-tar-oil, recovered oil fractions and functionality resulting from the process.

Example-01 LRC MTP Crude Coal-Tar Properties

[0085] The vapor effluent from MTP processing was collected and condensed, and the vapor phase and liquid phase were analyzed by GC and converted to a single material balance. The material balance provides an example of the process when indirect heating with inert-gas recycle is provided as 100% of the thermal energy for pyrolysis. As demonstrated, this results in rather low concentration of condensable coal-tar-oil, in this example to just 4.7 w % organic material and 95.3 w % recycle-gas plus non-condensable fuel gas [note use of decimal rounding].

TABLE-US-00003 Component Lb/h Wt % Non-condensable CO 487 0.23 compounds CO2 30,728 14.63 H2 2 0.001 H2S 71 0.03 N2 119,341 56.83 NH3 241 0.11 Water 46,649 22.2 SO2 138 0.07 Methane 1579 0.75 Ethane 386 0.18 C-3 283 0.13 C-4 210 0.1 C-5 130 0.06 Subtotal 200,245 95.35 w % Condensable C-6 111 0.053% Oils compounds C-7 15 0.007% C-8 and C-9 30 0.014% C-10 and C-11 35 0.017% C-12 15 0.007% C-13 38 0.018% C-14 130 0.062% C-15 180 0.086% C-16 220 0.105% C-17 270 0.129% C-18 275 0.131% C-19 304 0.145% C-20 306 0.146% Phenol 168 0.080% p-Cresol 239 0.114% Et-phenol 260 0.124% Pr-phenol 210 0.100% Bu-phenol 227 0.108% Naphthol 115 0.055% Dibenzofurane 15 0.007% Recisorcinol 199 0.095% Ethylbenzene 42 0.020% Me-naphthalene 86 0.041% Et- naphthalene 168 0.080% Benzol-naphthal. 258 0.123% Phenanthrene 115 0.055% Benzothiaphene 21 0.010% Me-pyridine 15 0.007% Indole 157 0.075% BP-fraction 582-693 F. 1,827 0.870% BP-fraction 693-783 F. 1,764 0.840% BP-fraction 783-1303 F. 1,936 0.922% Subtotal Liquid material 9,755 4.7 w % Total gas and oil 210,000 100.0%

Example-02, LRC MTP Crude Coal-Tar Properties

[0086] Sample of coal-tar-oil recovered from Wyoming sub-bituminous LRC MTP was fractionated by distillation and inspected for physical properties. The data indicates that at the pyrolysis operating conditions 15-20% of the light-end materials were not recovered because of low partial pressure and a low oil/inert-gas ratio of 4.5-6.0-w %. At room temperature the material separates into three separate liquid phases.

TABLE-US-00004 Total Oil Fraction Sample #1 #2A #2B #3 #4 Physical properties Distillation yield, w % 100.00 9.4 3.2 28.7 16.6 42.1 Boiling Range, F. 185-1150 IBP-450 450-550 550-650 650-900 900+ Specific gravity, g/ml 1.081 N/A 0.938 1.046 1.049 1.09 API Gravity, 60 F. 1-3 19.4 3.4 3.4 ~1.5 Acid number, mgKOH/g N/A 0.6 3.2 1.3 5.1 Elemental analysis: wt % Carbon 79.5 N/A 82.7 78.3 83.4 83.2 Hydrogen 8.62 10.5 8.6 9.7 7.8 Oxygen (diff.) 9.79 4.2 11.2 6.1 7.4 Nitrogen 0.54 0.22 0.49 0.35 0.47 Sulfur 0.52 0.26 0.31 0.32 0.33 Ash nil H/C-molar-ratio 8.62/[79.50/12] = 1.30 Viscosity, 122 F., CS 280 Pour Point, F. 66-90 Flash Point, F. 170-240 Water, wt % 1-2 Sediment, wt % 1-3 Heating value, Btu/gal 140,000

Example-03, LRC MTP Crude Coal-Tar Distillation Fractions

[0087] Two different samples of coal-tar-oil recovered from Wyoming sub-bituminous LRC MTP was fractionated by distillation and inspected.

TABLE-US-00005 I Distillation Fractions: wt % Sp. Gr. Flash point 1 IBP-450 F. 9.4 g/ml COC, C 2 450-650 31.9 1.090 171 3 650-900 16.6 1.117 237 4 901+ 42.1 1.122 316 Total 100.00 II Distillation Fractions: Fraction IBP - 662 F. w % Compounds Saturated HC Aliphatic paraffins 4.5 Other saturated HC 2.8 Aromatics Monocyclic aromatics 2.2 Bicyclic aromatics 3.2 Tricyclic aromatics 0.5 Tetracyclic aromatics 13.1 Polar Phenol 1.5 compounds Cresols 2.7 Other phenols 4.1 Naphthols 1.2 Benzenediols 7.8 Subtotal 43.6 = 43.60 Residual Fraction 662+ F. Toluene-insoluble fraction 14.63 Toluene-soluble fraction 41.77 Total 100.00

Example-04, Oil Fractions, Yields and Potential Downstream Processing

[0088] The fractionation provided as an integral part of the coal-tar-oil recovery process is motivated by the need for downstream separation into marketable fractions and the desire to decrease the cost of this separation. The following example serves to illustrate the pre-fractionation of pyrolysis effluent into 4 fractions, numerical examples of oil yields, the potential downstream separations into sub-fractions and their potential application as refinery syncrude oil, electrode binder pitch, feed for wax products and coal-tar chemicals. As can be appreciated by those skilled in the art, this example illustrates a preferred application of the process without limiting its applicability in any way as to the number of fractions, yields, temperatures or downstream processing or disposition of the products. In this example the multi-step recovery process results in the separation of four liquid fractions and a gas-phase. This separation is useful because these fractions are designated for different downstream processing. The oil yields are typical ranges for Western low-rank-coals. TABLE showing coal-tar-oil fractions, yields and prospective sub-fractions:

TABLE-US-00006 Oil-Yield Examples Temperature Range, Feedstock Downstream Fraction # Degrees, F. wt % wt % wt % Fraction Processing 1 A 850+ 16-24 18 syncrude hydrocracking A-1 18 syncrude delayed coking A-2 15 binderpitch visbreaking 2 B 650-850 28-38 31 syncrude hydrocracking B-1 15 waxes extraction B-2 15 binderpitch visbreaking 3 C 450-650 25-40 28 syncrude hydrotreating C-1 14 waxes extraction 4 D 250-450 15-25 23 D-1 10 syncrude refining, HT D-1 10 cresylics extraction D-2 3 pyridines extraction Total A-D 250-900+ 100 100 4 E 135-250 1-2 0.5 naphtha range hydrocarbons Water 135-212 5 F Non-condensable gasses - - - reports to fuel gas

Example-05, Fractions 650+ F. and 850+ F.

[0089] A sample of coal-tar-oil was fractionated by distillation and the 650+ F. fraction was separated by short-path wiped-film vacuum distillation into a lower boiling wax fraction [650-900 F.] and a residual pitch fraction [850+ F.] that may have considerable higher value than as refinery feedstock for motor fuel. The wax and pitch fractions also can be separated by solvent extraction as is practiced for extraction of Montan wax from coal. The wax fraction was separated into various fractions with characteristics that match market specifications. After separation, the pitch fraction can be thermally treated at 1400-1500 F. to convert it into higher value electrode-binder pitch. Material not converted into specialty product can report to the syncrude pool for use as feedstock for oil refinery processing with visbreaking, delayed coking, hydrocracking or hydrotreating.

Example-06, Fraction 450-650 F.

[0090] A sample of coal-tar-oil was fractionated by distillation and the composition determined by GC. This fraction contains valuable chemical compounds that are highly polar in nature in addition to non-polar hydrocarbons. Depending on the feed-coal and MTP operation, the weight ratio of polar compounds to non-polar hydrocarbons is 0.10-0.25. The following table shows a typical example for illustration. The composition of the 450-650 F. coal-tar-oil fraction was identified as follows. Sub-fractions from 450-650 F. Fraction [ref.: BDM 9/20/97]

TABLE-US-00007 Acids Bases Neutrals Total Wt % wt % wt % wt % Sub-fraction Extraction 47.7 6.6 45.7 100.0 Sub-fraction, of total Analysis 15.2 2.1 14.6 31.9 C 74.3 76.9 85.7 H 7.5 8.2 11.2 O 17.9 9.6 2.2 N 0.03 4.6 0.5 S 0.3 0.7 0.4 Total 100.0 100.0 100.0 Ratio H/C 1.57 SpGr., g/ml 0.814 Composition: [phenol-free basis] Aromatics 51.0 n-paraffins 3.8 iso-parasffins 13.9 naphthenes 7.4 olefins 19.9 others 4.0 Total 100.0

Example-07, Fraction 450-650 F.

[0091] A sample of recovered coal-tar-oil was fractionated by distillation and the composition determined by GC. The composition of the 450-650 F. coal-tar-oil fraction was identified as follows.

TABLE-US-00008 Composition basis: Total 450-650 Coal-tar F. fraction Compound Group: wt % wt % Alkyl-phenolics, cresylic acids 7.1 23 Alkyl-indanols, naphthols and byphenylols 3.5 12 Alkyl-pyridines, quinolines, amine-bases 2.6 9 Alkyl-naphthalenes 0.5 2 Non-polar hydrocarbons 14.8 49 Other compounds 1.5 5 Total 30.0 100

Example-08, Fraction-D, 206-480 F.

[0092] A sample of coal-tar-oil was fractionated by distillation to identify the low boiling fraction from the initial boiling point [IBP] to 482 F. [bottom temperature]. The yield of this fraction was 1.0-w % of the total recovered coal-tar-oil. The distillation range of this fraction at normal pressure was as follows. Composition of the recovered distillate was 50/50 oil/water. As expected the oil is mostly low boiling C-5-C-7 hydrocarbons that co-distil together with water at 97-110 C.

TABLE-US-00009 Distilled Volume Wt-% Condensation Bottoms of total oil Temperature Temperature IBP 101 C. 214 F. 154 C. 309 F. 0.25 98 208 174 345 0.50 97 206 193 379 0.75 98 208 220 428 1.00 110 230 250 482

Example-09, Coal-Tar-Oil Compound Group Identification

[0093] Several samples from coal-tar-oil recovered from MTP were inspected to determine variations in composition over time [approximately the same process conditions as per the previous coal-tar-oil example]. More than 165 individual compounds were identified out of more than 1000+ present.

TABLE-US-00010 Number of Sample # 1 2 3 Identified Compound Group w % w % w % Compounds Methyldichloride Cresylic acids, phenols 6.2 5.94 6.9 18 soluble Catechols 4.7 4.69 3.5 24 fraction: Neutral HC oils 74.11 incl 74.1 86 N-bases 2.65 incl 3.5 24 Ether-extract of 5.24 incl 5.3 13 900 + F. fract. Methyldichloride insoluble 7.09 incl 6.7 15+ Other nil 86.11 nil + Total 100 100 100 165+

Example-10, PHENOLIC FRACTION COMPOUND YIELD IDENTIFICATION

[0094] The cresylic acid fraction containing phenols, cresols and catechol compounds was separated from the 450-650 F. fraction and the compounds were identified with GC/MS assay.

TABLE-US-00011 w % of w % Compound: fraction of total I. Cresylic acid fraction: Phenol 15.0 0.88 5.9-w % of total 0-cresol 9.0 0.53 coal-tar oil m/p-cresol 30.5 1.83 2,4/2.5-xylenol 7.0 0.41 p-ethyl-phenol 8.0 0.47 MeEt-phenol 8.6 0.51 Identified others 11.5 0.68 Unidentified others 10.0 0.59 Total 100.0 5.90 II. Catechol fraction: Catechol 38.4 1.79 4.67-w % of total 3-m-catechol 10.5 0.49 coal-tar oil 4-m-catechol 30.8 1.44 Others 20.3 0.95 Total 100.0 4.67

Example-11, Comparison of Coal-Tar Pitch Fractions

[0095] Samples of pitch fractions from coal-tar-oil recovered from MTP and HTP were prepared by distillation under vacuum. The characteristics were analyzed and the results are compared below.

TABLE-US-00012 High-temperature Mild-pyrolysis Coal-tar type process Coke-oven-pitch 950-1100 F. Characteristic: typical spec Fraction Fraction Fraction 700+ F. 650-900 F. 900+ F. [a] Softening point* 88-121 C. 48 C. 65-91 C. Sp. Gr., at 25 C., g/ml >1.32 1.117 1.122 Flash point, COC 254 C. Atomic ratio, H/C >1.75 1.175 Coking value* .sup.55-60% 25% 36% Ash 0.25% nil nil Sulfur <0.6 0.3 0.3 Distillation to 680 F. 2.5 <3.8 <1.0 Toluene insoluble, w %* 26-32 7.7 Quinoline insoluble, w % 8-15 Total soluble in CS2 - 70% [a] Pitch fraction Distillation bottoms, 250 C., 20-mm Hg abs. *Certain minimum requirements for use as eletrode binder pitch

Example-12, Hydrotreating of Coal-Tar-Oil

[0096] Conversion of coal-tar fraction 450-650 F. to syncrude oil was conducted by fixed bed catalytic hydrotreating at 675 F., 900-psia, 1600 2100 SCF/bbl at 2-4 LHSV, with Topsoe Ni/Mo catalyst TK-555 [Ref. BDM Phase-1 Final Report, 9/10/97] producing 21-25 API syncrude oil. Conversion was 85-90-%, and the product is a suitable feedstock for naphtha [gasoline fraction] and light-atmospheric gas-oil [diesel fuel fraction] processing. Removal of the polar compounds [catechol, cresylic acid and N-bases fractions] from the coal-tar feedstock results in significant savings in hydrogen consumption in the order of 15-30-%. Removal of the 900+ F. high boiling coal-tar-pitch fraction, which may have better use as electrode binder pitch or delayed-coke feedstock, also decreases the hydrotreating cost and increases the yields of desirable hydrocarbons. The coking process yields a light-cycle-oil that can be used as feedstock in the hydrotreater. An alternative to hydroterating at the above mentioned operating conditions, is applying a high-pressure process such as the HTI hydrotreating designed for coal conversion and using a homogeneous slurry catalyst and 3000-psia pressure of higher. In this case the presence in the recovered coal-tar-oil of 900+ F.-HT-pitch and coal-fines that tend to form deposits on fixed-bed catalysts, do not present unusual problems. Several similar alternative hydrotreating process are in operation on feedstock derived from tar-sand oil extraction, oilshale and coal-to-liquid, and the choice of process is an economic decision based on the cost, experience, feedstock quality, product slate and commercial warranties provided for each site specific project. The data from hydrotreating to produce synthetic crude oil exemplefies the acheivable product quality (see attachment 1 and 2).

Example-13, Coking of Heavy Fractions After Distillation

[0097] A sample of coal-tar-oil was fractionated by vacuum distillation into a 650-900 F. fraction and a 900+ F. fraction, and each fraction was subjected to delayed coke processing at two different conditions, as shown below. The recovery yield of distillates is 52-61 w %, coke 32-42-w % and fuel gas 3.5-4.3-w %.

TABLE-US-00013 Coal-tar fraction: [650-900 F.] [900+ F.] Yield range on total coal-tar [16-24-w %] [28-38-w %] Coking Test # A B C D Temperature, avg., C. 505 535 515 540 Deg. F. 941 993 959 1004 Mass balance: w % w % w % w % Gas 3.5 4.2 3.7 4.3 Distillates: Gasoline fraction 6.6 7.8 7.2 7.3 Diesel fraction 13.1 13.3 13.3 13.8 Heavy Gas oil fraction 43.8 40.6 31.6 31.3 Sub-total distillates 63.5 61.7 52.1 52.4 Coke 31.9 31.8 42.3 41.4 Total recovery 98.9 97.8 98.1 98.1 Distillates wt % of coal-tar Yield [10-15] [15-20]

Example-14, Electrode Binder Pitch

[0098] Electrode-binder pitch for electrode manufacturing is made from high-temperature coke-oven tars. However, the 650+ F. fraction of MTP coal-tar-oil can serve the same purpose after undergoing thermal cracking at 1300-1500 F. Depending on the LRC feedstock quality, the MTP process temperature and residence time, and the selected coal-tar fraction, a suitable electrode-binder pitch can be produced. Samples of 650+ F. and 900+ F. fractions distilled from MTP coal-tar-oil were processed and tested in mixtures for this purpose.

Example-15, Coal-Fines Removal Form Coal-Tar-Oil

[0099] The 450-650 F. fraction was filtered to remove active carbon coal-fines material immediately after condensation. This is important to prevent polymerization and instability of the chemically reactive polar compounds. Increasingly finer filters were tested to determine throughput versus carbon retention down to micron particle size. It was found that essentially all coal-fine material can be removed with a single 5-micron filter, but that several filters of decreasing fineness accelerates the filtration process and decrease the pressure drop of the overall process. Specific filtration rates were not determined because the scale-up to larger capacity will be defined by pilot operation in commercial vendor testing equipment.