INTEGRATED IONIC LIQUEFACTION PROCESS

Abstract: Improvements in liquefaction of carbonaceous materials in which methanol is employed for separating products and recycle solvents. The carbonaceous materials may include coal or other carbonaceous materials, or a mixture of coal and oil bearing materials including refinery bottoms, tar sands and oil shale. The figure (I) is a block diagram of the process, to include preparation area (A), liquefaction area (B), separation area (C), distillation (D), solid hydrogenation (E) with associated catalyst regeneration, further distillation (F) to produce recycle solvent, gas processing (I) to recover H2, gasification of solid rich stream (G), gas processing (H), and alkali recovery (J).

Description: INTEGRATED IONIC LIQUEFACTION PROCESS Field of the Invention This invention relates to the liquefaction of carbonaceous materials and more particularly to methods for producing useful products / including products which can be used directly in petroleum-like refining processes / or as a feed stock for further chemical synthesis / or as a low sulfur fuel or the like, or at ambient temperatures can be a pseudo-plastic or particulate solid or se i-solid product having a melting point range of from about 100°C to 200°C / or as a finely divided particulate can be burned in combustion engines / and are characterized by reduced sulfur and ash content. Background of the Invention One of the principal approaches to coal liquefaction and solvation in the past has employed reactions producing free radicals through thermal bond rupture. For many kinds of coal used this typically required temperatures above 350°C for enough free radicals to form through thermal bond rupture of carbon-carbon bonds, carbon-oxygen bonds, carbon-nitrogen bonds and carbon-sulfur bonds, to react with other compounds or hydrogen in order to form lower molecular weight compounds than the complex materials present in the coal. In some typical prior processes the free radicals formed were stabilized and hydrogenated by hydrogen atoms through hydrogen transfer from solvent donor molecules such as 1 / 2 , 3 / 4-tetrahydronaphthalene or 9, 10-di hydrophenanthrenβ / often used in the presence of minor amounts of coal solubilizing agents. After such reactions the solids are generally separated by distillation / or by solvent deashing. For such systems to be effective / it is important that the mixtures be suitable for either effective distillation or deashing without excessive coking. Another Liquefaction process termed ionic liquefaction, described in U.S. Patent No. 4,451,351, issued May 29, 1984, and Application Serial Nos. 471,731, filed March 3, 1983 and 564,223 filed December 27, 1983, the disclosures of which are incorporated herein by reference in their entirety, utilizes a high proportion of highly polar solvents. In processess where even minor amounts of highly polar solvents are employed either in a liquefaction reactor in subsequent processing, distillation problems are encountered and when alkali compounds are present which are difficult to remove, severe coking problems and product contamination can arise. Brief Summary of the Invention The present invention uses ethanol to precipitate or separate by partitioning solid products from liquefaction processes that utilize a mixture of carbonaceous material, polar solvent, and alkaline compounds, in order to produce a particulate solid product. The resulting products are then separated and the polar solvent recovered in various process embodiments described hereinafter. The use of a methanol precipitation or partitioning n ionic Liquefaction processes minimizes many of the deleterious effects normally encountered in the distillation, separation, and stabilization of mixtures containing polar organic Liquids and alkaline compounds and increases solvent recovery, thus improving recycle solvent balance and the economics attendant thereto, and simplifies downstream processing as will be described in detail hereafter. It is therefore an achievement of this invention to provide for the improved separation of solid products from Liquefied carbonaceous materials. The invention as described also provides an integrated process for the liquefaction of carbonaceous material separation of solid products derived therefrom / starting from the preparation of the feed material to the separation of solid particulate products / including the recovery and use of recycle streams r ch in phenolic solubilizing agents. The solid or pseudo-plastic material that is recovered is a finely divided solid at room temperature / which has reduced sulfur and ash content and which is useful as a fuel / coke or petrochem cal feedstock. Brief Description of the Drawings Fig. 1 is a schematic flow chart of a typical integrated ionic liquefaction process. Fig. 2 is a schematic flow chart of an integrated ionic Liquefaction process useful for the production of a fuel and coke substitute / and using methanol in an extraction process in accordance with one aspect of the present invention. Fig. 3 is a graph showing the e.ffect of water on the formation of two phases from a phenol ic /methanol mixture. Fig. 4 is a graph showing the effect of water in ratios of methanol and phenolics in the formation of two phases. Fig. 5 is a simplified schematic flow chart of an integrated ionic liquefaction process useful for the production of a fuel and coke substitute, and using methanol in a partition ng process in accordance with another aspect of the invention. Fig. 6 is a simplified schematic flow chart of an integrated ionic liquefaction process in accordance with yet another aspect of the invention. ■ Fig. 7 is a graph showing the effect of oil shale on CO consumption. Fig. 8 is a graph showing the effect of oil shale on hydrogen addition. Detailed Description of the Invention As used herein, the term carbonaceous material includes solid, semi-solid and liquid organic materials which are susceptible to the described treatment methods. Examples of solid carbonaceous materials which may be used in connection with the practice of the present invention include coal, such as anthracite, bituminous, subbitum nous, and lignite coals, solid, semi-solid and liquid products derived from coal such as coal tars, and derived liquids and the like, as well as other solid, semi-solid and liquid carbonaceous materials, such as wood, Lignin, peat / solid petroleum residuals / tar sand, asphalt / oil shale, heavy petroleum oiLs, light petroleum oils, petroleum residuals and the Like. Ionic Liquefaction as used herein is intended to mean the chemical process described in previously described ionic liquefaction processes which are characterized by the use of polar solvent solubi Li zat on of the polymeric structure of carbonaceous materials susceptible to the described treatment methods, in the presence of alkali and alkaline earth compounds in amounts which favor ionic reactions involving the solubilized carbonaceous material and ionic species such as phenoxide, hydroxide, and formate ions, and favor stabilization of the ionic species to produce distillable products, low-sulfur products, and low-ash reduced-sulfur pseudo-plastic, normally solid products useful as fuel, coke or petrochemical feedstocks. In addition to ionic reactions, it is believed that ionic Liquefaction, as described, may change the apparent molecular weight and other physical properties of the solubilized carbonaceous material by reducing the extent of hydrogen bonding between the molecules present in carbonaceous materials. Because of the reactive nature of ionic species remaining after solubi Li zation and ionic reaction, the resultant product mixture after liquefaction must be further processed in order to remove gases, to remove insoluble solid impurities, and to precipitate solid product and stabilize the reaction products and reactants to be able to recover usable products including a recycle stream rich in phenolics which can again be used in the ionic Liquefaction reactions. This processing includes using a methanol-water mixture to solubilize the Light phenolics and alkali ions into a distinct phase which can be separated from insoluble phases, and subsequently distilled to recover the recyclable phenolic solvents. Or using methanol to partition the product mixture to remove the solid product as finely divided particles, and distilling the resulting Liquid phase to recover the recyclable phenolic solvents and recycle partitioning solvent, i.e. methanol. The amount of methanol required is dependent on the water content of the solution to be extracted or partitioned. Likewise, the amount of water present in the solution is dependent on the nature of the gas/liquid phase separation and the water in the reaction mixture. The relationships necessary for the formation of a single phase of methanol and light phenolics are shown in Figs. 3 and 4. In view of these relationships it can be determined whether it is necessary or desirable to adjust, in a predetermined manner the amounts of water and/or methanol that are required, in a given system, to produce the formation of a single methanol soluble and methanol insoluble phase. The remaining process steps are further described hereinafter. The term alkaline as used is synonymous with basic which includes, without limitation, alkali metal and alkaline earth compounds. A base can be an aqueous solution which contains OH ions, or any substance which accepts protons, or any substance which is an electron pair donor. Typical cations are the light metals of groups IA and IIA. Preferred cations are Na and K . Typical anions include OH , nic liquefaction a polar solvent or polar solvents means a solubilizing agent selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols / and mixtures thereof. Typically / such solvents do not have an α hydrogen. Liquid mixtures of solubi lizing polar solvents used in the ionic liquefaction process of the present invention typically will contain greater than 50% by weight of such polar solvents. Synthesis gas / as that term is used herein, means a gas primarily comprised of carbon monoxide and hydrogen. Other gaseous components present in small concentrations can include carbon dioxide, light hydrocargon gases, and some impurities such as nitrogen and still be effective in the process described herein. In addition, small amounts of water vapor may also be present. The higher yields of products achieved in the present invention through the synergistic effect in a Liquefaction reactor of a solvent/solute system combining a phenolic solvent, water and added amounts of an alkali or alkaline-earth metal compound, and the use of methanol to recover solid products by precip tation or partitioning, without or without the addition of synthesis gas, depending on the reactants selected will be more fully described hereinafter. In summary / the prior ionic Liquefaction process for coal or other carbonaceous material can be substantially improved by the use of an organic solvent containing greater than about 50% by weight of phenolic compounds in amounts between about 1.5 and 3.5 times the weight of carbonaceous materials / in combination with between about 25 to about 400 parts by weight of alkali for every 1000 parts by weight of carbonaceous material / and between about 25 to about 400 parts by weight of water for every 1000 parts by weight of carbonaceous material; when the carbonaceous material, the organic solvent and the solvent /solute pair are reacted together at temperatures less than about 360 and pressures between about 100 to about 2500 psig. Further improvement can be obtained by the presence of synthesis gas, having an H 2 /C0 ratio between about 0.5 and about 2.0 in amounts between about 0.16 to about 1.25 m /Kg of carbonaceous material in the reaction step when combined with gas and solid separations prior to the formation of distinct phases using methanol extraction of the phenolics and alkali ions followed by separation and recovery of recycle methanol extraction solvent and recycle of a high phenolics stream containing alkali and water, or by partitioning of the reaction products with ethanoL whereby to separate solid product followed by distillation of the liquid phase to recover light oil distillate product / a high phenolics stream recycle solvent containing alkali and water / and recycle parti ioning solvent. As will be described in detail hereinafter, the extraction or partitioning with methanoL in accordance with the teachings of the present invention reduces problems associated with prior art liquefaction processes, simplifies the recovery of recycle solvent and improves materials balance. The ionic Liquefaction described herein, at the conditions employed, will produce methanol extractable or parti tionable polar solvent recycle streams having desirable Low molecular weights. The presence of highly polar phenolic compounds, alkali compounds, and the ionic forms thereof, along with the oxygenated compounds derived from the carbonaceous material, during the ionic liquefaction processes can, as described, Lead to potential processing problems downstream from the Liquefaction reactor. Some oxygenated compounds, including many phenols, are often unstable, especially in the presence of coking promoters such as ionic alkaline species. These compounds are concentrated in the bottoms during distillation operations. It is, therefore, important to either minimize the amount of alkaline compound present in the distillate feed stream and/or reduce the severity of distillation conditions to minimize coking. Typically, the major quantity of alkaline compounds were removed before distillation s begun because of the severity of the conditions required for recycle solvent recovery. Regardless, it has been shown that a portion of the phenolics becomes adducted during distillation which adversely affects the quality of the recycle solvent. The present invention substantially reduces or eliminates these prior problems. Under the conditions typically used in ionic Liquefaction, i.e., relatively low temperature and low pressure, quantities of coal-derived phenolics are produced, but because of adduction, the amount of phenolics recovered is Limited. Therefore, to regenerate solvent and obtain additional product, a portion of the liquefaction product liquids should preferably undergo further reaction in the presence of hydrogen under conditions which will break the bond between the phenolics and the coal derived organic species. The reaction may be performed at conditions which are severe enough to break the bond / but are not severe enough to saturate the aromatic ring / or remove the oxygen atom as water. The use of methanol as an extraction solvent for the phenolics and alkali ions or as a partioning solvent as described herein helps to recover the light phenolics prior to adduction in a manner to make the subsequent solvent recovery and stabilization more efficient. Because the ionic liquefaction products produced by the Liquefaction processes described are typically high in reactive oxygenated species there can be a tendency for the products to oxidize and polymerize with time or with severe thermal treatment. In the case where additional solvent recovery and product upgrading are desired, specific sequential processing steps are then needed. A typical process ncorporating these necessary steps is shown in Fig. 1 / which is modified according to the present invention as further described herein. Referring to the schematic diagram in Fig. 1 / the feed preparation at ( A ) , comminutes the carbonaceous material / stream (1) / by conventional means such as hammermi I Is or ball mills or comparable equipment; and adds a water-alkali mixture stream (4); and recycle polar solvent streams ( 2 ) and (3), preferably containing greater than about 50% by weight of phenolic compounds. The comminution process may be accomplished either dry or wet. If performed wet / then the recycLe polar solvent may be used as the wetting agent / if proper precautions are taken. The carbonaceous feed is preferably comminuted to 100 percent minus 74 micron (200 mesh) particle size, more preferably to 100 percent minus 147 microns (100 mesh) particle size, the most preferably to 100 percent minus 350 microns ( 40 mesh) particle size but in any event must be in a form which will enable the requisite so lubi Li zati on for the ionic Liquefaction to proceed. Using 1000 parts by weight of stream ( 1 ) carbonaceous material as an example, the preferred amount of polar recycle solvent for the required solubi Lization to proceed / streams (2) plus (3 ) is between about .1500 and about 3500 parts by weight depending on the prepared form of the carbonaceous material / with about 2000 parts by weight of solvent the most preferred amount. The polar recycle solvent contains preferably greater than about 50% by weight of phenolic compounds / and more preferably greater than 60% by weight phenolic compounds. The preferred amount of alkaline material in streams (2) and (4) is selected to be enough to produce the desired results. It has been found under the conditions disclosed herein that between about 25 parts and about 400 parts by weight per 1000 parts by weight of material is effective with the more preferred amount being between about 25 and about 150 parts by weight / and depending on the kinds and amounts of phenolic compounds employed / the preparation of the carbonaceous material and the conditions selected / the most preferred amount is about 50 parts. The amount of water in streams (2) and (4) should preferably be sufficient to maintain the alkaline material in the ionic form in solution at the herein described ionic liquefaction conditions, and sufficient to allow the water gas shift reaction, to produce the hydrogen required for solvent regeneration and ionic species - II - stab lization in the hydrogenation (E) step. The amount of water in streams (2) and (4) is between about 25 and about 400 parts by weight, more preferably between about 50 and about 250 parts by weight, and most preferably between about 100 and 200 parts by weight. The water content can be controlled during pressure let down of the reactor after liquefaction. The reaction products exiting the reactor (B) (B1), stream (7) of Figs. 1 and 2, are then separated into component streams in the separation systems, process (C) of Fig. 1. Leaf filters, candle filters, hydroclones, centrifuges or comparable equipment can be used for solids separation. Solids also may be separated by processes such as solvent deashing or the like. The purpose of the solids separation step is to separate unreacted carbonaceous material and insoluble alkaline salts from the ionic liquefaction product liquids. Due to the hygroscopic nature of the alkaline salts, some of the water present also typically will be separated with the filter cake. The preferred temperature for filtration is preferably between about 150 and about 100°C (302 and 212 F) . The pressure is maintained at a sufficient Level to obtain efficient filtration / preferably between about 0.34 and about 1.03 MPA (50 psia to 150 psia ) . In the filtration step, the pressure is let down to control the amount of water in the phase separation, and the solids content of the Liquid is typicalLy reduced to Less than about 1.0 percent by weight, the mineral matter content to less than about 0.5 percent by weight, and the alkaline species content to less than about 0.25 percent by weight. The values obtained are dependent upon factors such as the degree of comminution used in feed preparation, the ionic liquefaction conditions selected, and the design of the filter equipment. The separation train should preferably be operated to reduce the water content of the filtrate stream ( 10 ) of Fig. 1, below about 20 percent by weight, and most 5. preferably below about 10 percent by weight. Water concentrations above this level are not desirable since that can lead to increased methanol use, as wi ll be described hereinafter, and the undesirable potential for forming two phases, as well as creating additional 10 distillation requirements in downstream processing steps. Liquids, stream (10) of Fig. 1, with alkaline compounds contents of about 0.25 percent by weight and phenolic content greater than about 50 percent by weight may successfully be further processed by 15 distiLlation (D), although the upper limit is dependent upon the exact nature of the product. The solids rich filter cake, and stream (8) of Fig. 1, are used as feed to a gasification system (G) for production of synthesis gas and recovery of alkaline compounds (J ) . 20 The gas stream, stream (9) of Fig. 1, is sent to gas processing (I) for upgrading before use as a hydrogen rich gas in subsequent hydrogenati on (E) operations. When methanol partitioning is employed the liquids from the separation system are sent, stream (10) of 25 Fig. 1, to a distillation tower where the methanol containing recycle stream is fractionally distilled. The products from the distillation are methanol, stream ( M) of Fig. 1, and a polar recycle solvent stream, stream (2) of Fig. 1. 30 The distillation operation has two primary purposes. First, methanol is recovered for- recycle. Second, a polar recycle solvent stream rich in phenolics material is recovered. After the solution of the carbonaceous material in 35 an ionic liquefaction reactor, the slurry is removed and the temperature and pressure reduced. The slurry is filtered to remove the ash and undissolved organic materials that have not dissolved in the solvent /so Lute system. A large portion of the ash will be removed in this step including a majority of the inorganic sulfur. The filtrate in other embodiments (Fig. 2 ) is then transferred to a Liquid extraction stream to remove dissolved ash components and alkali. The ash and alkali are removed by contacting the filtrate with a methanoL and water, or the like. The present invention eliminates the liquid-liquid extraction step previously utilized in onic liquefaction. More particularly, the use of a methanol-water mixture in accordance with one aspect of the invention precipitates particulate solids produced from the de-gassed /de-ashed liquefaction reactor product stream. The separated liquid stream containing the phenolic solvent, alkali ions and methanol is then distilled to recover the phenolic solvent and alkali ions. The overheads from the distillation tower contain methanol and a lower cut provides improved recovery of recycle phenolic solvent. The distillation temperature is selected to accomplish this result. The foregoing may be further understood in connection with the following examples. Coal obtained from the Indian Head Mine of North Dakota was ground to a top size of 100 mesh. The coal was mixed 1 part coal to 2 parts process derived recycle solvent which contained greater than 50% phenolics and the alkali and water content adjusted to about 15% added water and about 10% sodium hydroxide. The slurry was pumped through a preheater, reactor and pressure let down continuous flow system in the presence of carbon monoxide. The de-gassed reactor product was de-ashed in a continuous basket centrifuge and samples A and B collected. Sample B containing coal derived liquid products was treated with formic acid. The aqueous phase containing water, alkali, and residual phenolics was removed. The organic phase containing recycle solvent and coal derived products was collected and distilled. The non-di st I Lable fraction was coLlected and analyzed, Sample A containing as above, was contacted with an equal volume of a methanol-water solution. An insoluble phase was recovered and analyzed as B above. Thermogravimeteric analysis and C13 in NMR was performed on samples A and B above. Sample B contained an average of 15.8 weight percent phenolics of whirh 12.0 weight percent was tightly bound and could not be removed by heat treatment. Sample A contained an average 1.1 weight percent which could not be recovered by heat. Further, the non-di sti I Lable solid from sample B was collected as a residual mass from the distillation. Sample A was produced as a precipitated material and collected by filtration. The particle size of sample A was 100 percent minus 200 mesh. As can be seen from the foregoing, the use of a methanol-water precipitation process step in an ionic Liquefaction process train can provide an improved particulate solid product and improved phenolic recycle solvent recovery. The separation of particulate solids is accomplished by the use of sufficient methanol added to the liquid product stream to precipitate the solid product desired. An alternative processing system employing methanoL partitioning in accordance with the present • invention is shown in Fig. 5. Referring to Fig. 5, the carbonaceous feed material is comminuted as before by conventional means, and the comminuted feed stream is slurried at AA with a recycle phenolics stream 3A containing alkali as before. Particle size, material balance and make-up, and processing conditions are all as previously described. The slurry is heated as before, and the slurry is then treated with synthesis gas at BB to produce the desired ionic liquefaction products as before. The reaction products stream fr.om Liquifaction unit BB is then filtered to remove unreacted solids, as before, and the filtrate is then treated with methanol at partitioning unit CC. The methanol acts to partition solid reaction products in finely divided form and insoluble alkaline salts from the light oi l products (distillate product), phenolics recycle solvent and water. The solids from partitioning unit CC are resuspended in a fresh aqueous acid wash at FF. The aqueous acid wash separates the finely divided solid reaction products from the alkaline salts which dissolve in the aqueous acid wash. The finely divided solids product remaining was then washed to produce a clean finely divided ionic liquefaction solid product. The methanol extract stream from CC is then passed to a distillation column I where a clean recycle methanol stream is removed as overhead. The bottoms from column I are passed to a second distillation column II where the phenolics solvent and light oil distillate are separately recovered / light oil distillates recovered as product / and the phenolics recycled to AA for reslurring new feed materials. If desired the insoluble filter cake materials from CC and the solid wash solutions from FF also can be added to the distillation column FF. Alternatively, the insoluble filter cake materials from CC and the solid wash solutions from FF may be returned directly to AA. As will be seen from the foregoing the use of methanol partitioning solvent provides a number of significant advantages. For one, dist llation of the methanol stream may be accomplished under less severe distillation conditions. More particularly, the operating temperatures of distillation column I, are reduced from about by 250 C as was required in conventional processing, to about 100 C. Moreover, the heat of vaporization for methanol is substantially less than water or the phenolic recycle stream. Thus the overall energy requirements for the distillation tr^in wherein methanol is employed as a partitioning solvent as described herein are substantially reduced as compared to conventional separation schemes. Additionally, sodium inclusion and phenolics recycled solvent adduction into the solid product is substantially reduced using methanoL partitioning in accordance with the present invention. For example, solid products produced using a conventional separations process as set forth in Fig. 1 may contain approximately twelve percent by weight of adducted recycled solvent derived phenolics, while solid products separated by methanol partitioning in accordance with the process set forth in Fig. 5 typically will contafn Less than about one to about three percent by weight of adducted recycle solvent derived phenolics and only trace amounts, e.g. about 20 to about 100 parts per million of sodium. Moreover, the solid product separated by methanoL partitioning is of higher purity in ash content, and the product is finely divided. This permits the solid product produced in accordance with the present invention to be used directly as a fuel oil or diesel fuel extender. Depending on particle size up to about 50 weight percent blend of solids produced in accordance with the present invention may be directly employed as a fuel oil, diesel fuel or coal/water extender. Yet another alternative to the present invention is shown in Fig. 6. Referring to Fig. 6, the carbonaceous feed material at (AAA) comprises a mixture of comminuted solid carbonaceous material such ' as coal and oil bearing products such as refinery bottoms, tar sands, oil shale and the like. Typically, the coal will comprise from about 10 to about 90% by weight of the carbonaceous material feed mixture, more preferably about 30 to about 70% by weight, and most preferably about 50% by weight. A reaction solvent comprising a watei—alkaline mixture and a phenolics solvent stream are added as before. Particle size, material balance and make-up, and processing conditions are all as previously described. The slurry is heated as before, and the slurry treated with synthesis gas at BBB to produce the desired ionic liquefaction products as before. The reaction products stream from Liquefaction reactor (BBB) may then be filtered to remove unreacted solids, as before, and the filtrate is then treated with methanoL at partitioning unit CCC as before. The methanoL acts to partition solid reaction products in finely divided form and insoluble alkaline salts from the Light oil products, phenolics recycle solvent and water. The solids from partitioning unit CCC may then be treated with a fresh aqueous acid wash as described previously with reference to Fig. 5. Alternati ely, as shown in Fig. 6, the methanol insoluble fraction may be passed to an extraction unit DDD as will be described in detail hereinafter. The methanol extraction stream from CCC is then passed to a vacuum distillation column I where methanoL, water, and a -225 F distillate product are recovered as overheads, and a +225 F bottom which is passed to extraction unit DDD. The methanol overheads are recycled to separation unit CCC, while the +225 F distillate product is passed to a distillation unit II where the phenolics solvent and light oil distillate are separately recovered, Light oil distillates recovered as product, and the phenolics recycled to AAA or BBB for reslurrying new feed material and ionic liquefaction. The methanoL insoluble fraction from CCC is extracted at DDD using conventional extraction techniques with toluene or cyclohexane. Extraction produces three phases, an ash phase, an alkali-aqueous phase, which is recycled to AAA, and a solid p roduct. As can be seen from Figs. 7 and 8, when coal and shale are processed together, solid product yield and total conversion is increased. The foregoing may be further understood in connection with the following examples: Kentucky 9 Bituminous Coal from Fies Mine, Kentucky, ground to a top size of 100 mesh, and Cleveland Member Shale from Montgomery County, Kentucky, also ground to a top size of 100 mesh, were subjected to ionic liquefaction in the presence of process derived recycle solvent comprising greater than about 50% phenolics, alkali and water as above described (Examples 1 to 3) and a synthesized solvent containing a nitrogen-containing heterocyclic (Example 4) / and analyzed as set forth in Table II. TABLE I REACTION CONDITIONS AND RESULTS OF COPROCESSING STUDY REACTION INITIAL CO REACTION FEED FEED TEMP PRESSURE TIME RUN COAL SHALE** FEED SOLVENT cAIALYsi (oc) l E iia) iiiαi 3.5g 3.5g Solvent -14. Og NaOH-0.35g 335 1500 45 Water-1. Og I 7.0g Solvent -14. Og NaOH-0.35g 335 1500 45 Water-1. Og 7.0g Solvent -14. Og NaOH-0.35g 335 1500 45 Water-1. Og 7.0 Cresylic Acid-10.5g NaO-0.35g 335 1500 45 Pi peri di nopy r i di ne-3.5g Water-1. Og TABLE II RESULTS SOLID C.-650 F CHEMICAL YIELD H 2 CO CONV YIELD YIELD BASIS ADDED RUN (wt%MAF COAL) (wt%MAF COAL) (wt%MAF COAL) CONV (wt%MAF COAL) Coal 8 Shale 40.19 38.59 65.20 103.79 2.17 o | Coal Only 24.63 26.62 54.12 80.74 1.50 Shale Only 3* 45.95 16.45 22.37 38.82 0.76 • COAL Only 29.99 29.83 64.63 94.46 1.56 * Yields Based on MAF Shale WhiLe not wishing to be bound by theory, it is believed the positive effect of the oil shale on coal conversion may be due to the presence of the nitrogen-containing heterocyc l cs (kerogen) in the oil shale. And, while the presence of nitrogen-conta ning heterocyc lies appears to increase distillate and solid product yield, the presence of the nitrogen-conta ning heterocyclics does appear to significantly and beneficially effect hydrogenation. Examples 4A and 4B run under identical reaction conditions to Example 4 illustrate the advantages of methanol partitioning as earlier described, as can be seen in Table III. TABLE III RESULTS C 4 -650 F SOLID YIELD CO CONV YIELD CHEMICAL BASIS H 4-PP 2 RUN (wt%MAF COAL) (wt%MAF COAL) CONV. CONV ADDED RECOVERY W/CH 3 OH 4A 29.99 29.83 64.63 94.46 1.55 104.09 WO/CH-.OH 4B 28.62 23.42 57.00 80.42 1.56 64.13 In Run 4A, the distillate, solid product and total conversion are higher. The difference in added hydrogen is not significant. In Run 4A the methanol extract was distilled to recover methanol and a recycle solvent. In Run 4B the product slurry was distilled to recover product. The 350 - 650 F fraction from the distillations were recovered and analyzed by GC/MS for the meta-cresol and piperi di nopyridi ne ( 4-PP). A material balance was calculated as follows: RUN M-CRESOL 4-PP NUMBER METHANOL RECOVERY RECOVERY 4A W 89.22 104.09 4B W0 107.53 64.13 We have found the use of methanol partitioning prior to distillation in accordance with the present invention substantially increases recovery of the nitrogen-containing heterocyc li cs. And, methanol partitioning prior to distillation also reduces or eliminates adduction of the nitrogen-con aining heterocyc l cs into the solid product. Attempts to process the reaction products using conventional distillation prior to removal of non-di sti I lable products produces significant nitrogen-compound heterocyclic adduction. The present invention is susceptible to modification. For example, increased product yield and conversion may be achieved by adding one or a mixture of heterocyc li cs such as 4-piperid inopyr di ne or a kerogen directly to a coal carbonaceous feed as an ionic liquefaction pro otor so as to enhance process performance. Methanol partitioning of ionic liquefaction reaction stream prior to distillation in accordance with the present invention also may advantageously be employed in a conventional ionic Liquefaction process. Still other changes may be made in accordance with the foregoing teachings and the scope of the claimed invention is to be limited only by the prior art as applied to the claims.

Claims: WHAT IS CLAIMED IS: 1. A method of regenerating the solubilizing agent from the process stream of a single stage ionic coal Liquefaction process wherein said coal liquefaction is accomplished by reaction of the coal with a polar solvent solubilizing agent and an aqueous solution containing inorganic ionic species where major amounts of the solubilizing agent are selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p-cresol, catechol, resorcinoL, naphthoL and mixtures and derivative thereof; and minor amounts of polycyclic aromatic hydrocarbons, parti aI Ly-hydrogenated polycyclic aromatic hydrocarbons and fully hydrogenated polycycLic aromatic hydrocarbons having from 1 to 4 carbon rings such as naphthalene, anthracene, phenanthrene, acenaphtha lene, 1-methyInaphtha Lene, 2-methyl naphtha Lene, tetraline, gammapicoli ne, i soqu noli ne, dihydronaphtha Lene, decaline, 9, 10-dihydroanthracene, 9,10 di Kydrophenanth rene and mixtures and derivatives thereof, as well as carbonaceous material-derived solvents; and (b) the inorganic ionic species are dissolved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metals comprising the steps after ionic liquefaction of: ( 1) removing non-condensible gases from said process stream; ( 2) removing immiscible water from said process stream; (3 ) . removing alkaline compound containing solids from said process stream; (4 ) removing carbonaceous products from said process stream by the use of methanol; (5) separately hydrot reating said carbonaceous products; and (6) recovering regenerated solubilizing agent capable of being used directly n a single stage ionic coal liquefaction process. 2. A method of recovering solid product from a carbonaceous liquefaction process stream after ionic liquefaction in which a polar solvent or mixtures thereof have been utilized for liquefaction together with alkali metal or alkaline earth compounds or mixtures thereof comprising the steps of: ( 1 ) removing non-condensible gases from said process stream; ( 2 ) removing alkaline containing solids from said process stream; (3) recovering solid and liquid products from said process stream by the introduction of methanol into said process stream to separate solid precipitates and volatile liquid products; and (4) distilling the volatile Liquid products to recover phenolic rich recycle solvents. 3. The process of claim 2 wherein the recycle process stream recovered comprises aromatic polar solvents suitable for use in subsequent ionic Liquefaction processes. 4. A method of producing a pseudo-plastic soLid product which is solid at room temperature from an ionic coal Liquefaction process wherein said coal Liquefaction is accomplished by reaction of the coal with a polar solvent solubilizing agent and an aqueous solution containing inorganic ionic species where major amounts of the solubilizing agent are selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p-cresol, catechol, resorcinoL, naphthoL and mixtures and derivatives thereof; and minor amounts of polycyclic aromatic hydrocarbons, parti a I Ly-hydrogenated polycyclic aromatic hydrocarbons and fully hydrogenated polycyclic aromatic hydrocarbons having from 1 to 4 carbon rings such as naphthalene, anthracene, phenanthrene, acenaphtha lene, 1 -methyInaphtha Lene, 2-methyInaphtha lene, tetraline, gamma-pi coLi ne, soquinol i ne, di hydronap tha lene, decalin, 9,10-dihydroanthracene, 9, 10-dihydrophenanthrene and mixtures and derivatives thereof, as well as carbonaceous material-derived solvents; and (b) the inorganic ionic species are dissoLved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metals comprising the steps after ionic Liquefaction of ( 1 ) removing non-condens ble gases from said process stream; (2) removing alkaline compound containing solids from said process stream; (3) precipitating solubilized carbonaceous materials from said process stream; ( 4 ) distilling said process stream to provide recycle agent capable of being used directly in an ionic coal liquefact on process and a pseudo-plasti c product useful as a fuel or coke substitute. 5. The solid product obtained from a carbonaceous Liquefaction process stream after ionic Liquefaction in which a polar solvent or mixtures thereof have been util zed for liquefaction together with alkali metaL or alkaline earth compounds or mixtures thereof where: non-condensible gases have been removed from said process stream; alkaline containing solids have been removed from said process stream; solid products have been recovered from said process stream by a precipitation with methyl alcohol. 6. The product of clai 5 wherein the recycle process stream recovered comprises aromatic polar solvents suitable for use in subsequent ionic liquefaction processes. 7. A pseudo-pLasti c product which is solid at room temperature which is obtained from an ionic coal liquefaction process wherein said coal liquefaction is accomplished by reaction of the coal with a polar solvent solubilizing agent and an aqueous solution containing inorganic species where major amounts of the solubilizing agent are selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p-cresol, catechol, resorcinoL, naphthoL and mixtures and derivatives thereof; and minor amounts of polycyclic aromatic hydrocarbons, partia L Ly-hydrogenated polycycLic aromatic hydrocarbons and fully hydrogenated polycyclic aromatic hydrocarbons having from 1 to 4 carbon rings such as naphthalene, anthracene, phanathrene, acenaphthalene, 1-methy Lnapht ha lene, 2-methyLnaphthaLene, tetraline, gammapi coli ne, soqui noli ne, di hydronaphtha Lene, decaline, 9, 10-dihydroanthroacene, 9, 10-di hydrophenanthrene and mixtures and derivatives thereof, as well as carbonaceous material-derived solvents; and (b) the inorganic ionic species are dissolved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metals where after ionic liquefaction: non-condensible gases are removed from said process stream; and alkaline compound containing solids are removed from said process stream; and methanoL is applied to precipitate carbonaceous materials and the remaining process stream is distilled to produce recyclable solubilizing agent which is capable of being used directly in an ionic coal liquefaction process to product, upon precipitation, a pseudo-plastic product useful as a fuel or coke substi tute. 8. A method of regenerating the soLubiLizing agent from the process stream of a single stage ionic coal liquefaction process wherein said coal Liquefaction is accomplished by reaction of the coal with a polar solvent solubilizing agent and an aqueous solution containing inorganic ionic species where major amounts of the solubilizing agent are selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p-cresol, catechol, resorcinoL, naphthoL and mixtures and derivative thereof; and minor amounts of polycyclic aromatic hydrocarbons, partial Ly-hydrogenated polycyclic aromatic hydrocarbons and fully hydrogenated polycyclic aromatic hydrocarbons having from 1 to 4 carbon rings such as- naphthalene, anthracene, phenanthrene, acenaphthalene, 1-methy lnaphtha lene, 2-methy lnaphtha lene, tetraline, gammapi coli ne, i soqui noLine, dihydronaphthalene, decaline, 9,10-di hydroanthracene, 9,10 di hydrophenanth rene and mixtures and derivatives thereof, as well as carbonaceous material-der ed solvents; and (b) the inorganic ionic species are dissolved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metaLs comprising the steps after ionic Liquefaction of: ( 1) removing non-condensible gases from said process stream ; (2) removing immiscible water from said process stream; (3) removing alkaline compound containing solids and reaction products solids from said process stream by treating with methanol; (4) hydrotreating said reaction products solids from step (3); (5) recovering alkaline compound containing solids and reaction product solids; and (6) separately recovering regenerated solubilizing agent capable of being used directly in a single stage ionic coal liquefaction process, and recycle methanol . 9. A method of recovering solid product from a carbonaceous liquefaction process stream after ionic liquefaction in which a poLar solvent or mixtures thereof have been utilized for liquefaction together with alkali metal or alkaline earth compounds or mixtures thereof comprising the steps of: (1) removing non-condens ble gases from said process stream; (2) removing alkaline containing solids and reaction product solids from said process stream by the introduction of methanol into said process stream to separate solid precipitates and volatile liquid products; ( 3) washing the solid precipitates to recover reaction product solids; and (4) distilling the volatile liquid products to recover phenolic rich recycle solvents and methanoL 10. . The process of claim 9 wherein the recycle process stream recovered comprises aromatic polar solvents suitable for use in subsequent ionic Liquefaction processes, and separately recovered methanoL suitable for use in subsequent separations. 11. A method of producing a pseudo-plastic solid product which is solid at room temperature from an ionic coal liquefaction process wherein said coal liquefaction is accomplished by reaction of the coal with a polar solvent solubilizing agent and an aqueous solution containing inorganic ionic species where major amounts of the solubilizing agent are selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p-cresol, catechol, resorcinoL, naphthoL and mixtures and derivatives thereof; and minor amounts of polycyclic aromatic hydrocarbons, part ia ILy-hydrogenated polycyclic aromatic hydrocarbons and fully hydrogenated polycyclic aromatic hydrocarbons having from 1 to 4 carbon rings such as naphthalene, anthracene, phenanthrene, acenaphthalene, 1 -methyLnaphtha Lene, 2-methylnaphtha Lene, tetraline, gammapicoli ne, soquinoline, dihydronaphtha lene, decalin, 9, 10-dihydroanthracene, 9, 10-dihydrophenanthrene and mixtures and derivatives thereof, as well as carbonaceous material-de ived solvents; and ( b) the inorganic ionic species are dissolved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metals comprising the steps after ionic Liquefaction of (1) removing non-condensible gases from said process stream; ( 2) removing alkaline compound containing solids and pseudo-plastic reaction product solids from said process stream by treating with methanoL; ( 3) hydrotreating said solids from step (2); ( 4) recovering alkaline compound containing solids suitable for use in subsequent ionic liquefaction process, and pseudo-plastic reaction product; and (5) distilling said process stream to provide recycle agent capable of being used directly in an ionic coal Liquefaction process and a recycle methanol . 12. The solid product obtained from a carbonaceous liquefaction process stream after liquefaction where: non-condensible gases have been removed from said process stream; solid products have been recovered from said process stream by a precip tation with methyl alcohol. 13. The product of claim 12 wherein the recycle process stream recovered comprises aromatic polar solvents suitable for use in subsequent ionic liquefaction processes. 14. A pseudo-plastic product which is solid at room temperature which is obtained from an ionic coal liquifaction process wherein said coal liquefaction is accomplished by reaction of the coal with a polar solvent solubilizing agent and an aqueous solution containing inorganic species where major amounts of the solubilizing agent are selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p-cresol, catechol, resorcinoL, naphthol and mixtures and derivatives thereof; and minor amounts of polycyclic aromatic hydrocarbons, partial Ly-hydrogenated polycyclic aromatic hydrocarbons and fully hydrogenated polycyclic aromatic hydrocarbons having from 1 to 4 carbon rings such as naphthalene, anthracene, phanathrene, acenaphthaLene, 1-methylnaphthalene, 2-methy Lnaphthalenβ / tetralinβ / gammapicoLi nβ / i soquinolinβ / dihydronaphtha Lenβ / decalinβ / 9, 10-dihydroanthroacenβ / 9 / 10-di hydrophenanthrene and mixtures and derivatives thereof / as well as carbonaceous material-derived solvents; and (b) the inorganic ionic species are dissolved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metals where after ionic liquefaction: non-condensible gases are removed from said process stream; and methanol is applied to precipitate carbonaceous materials and alkaline compound containing solids which are further separated and recovered by hydrotreat ng; and the remaining process stream is distilled to produce recyclable solubi lizing agent which is capable of being used directly in an ionic coal liquefaction process to product, upon precipitation / a pseudo-plastic product useful as a fuel or coke substitute / and recycle methanol. 15. A method of regenerating the solubi lizing agent from the process stream of a single stage ionic coal liquefaction process wherein said coal liquefaction is accomplished by reaction of the coal and oi l shale with a polar solvent solubilizing agent and an aqueous solution containing inorganic ionic species where major amounts of the solubilizing agent are selected from the group consisting of aromatic alcohols, phenols, po lycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p cresol, catechol, resorcinoL, naphthol and mixtures and derivative thereof; and minor amounts of polycyclic aromatic hydrocarbons, partial ly-hydrogenated polycyclic aromatic hydrocarbons and fully hydrogenated polycyclic aromatic hydrocarbons having from 1 to 4 carbon rings such as naphthaLene, anthracene, phenanthrene, acenaphthaLene, 1-methy Lnaphthalene, 2-methyLnaphtha lene, tetraline, gammapi coline, soquinoLi ne, dihydronaphtha Lene, decaline, 9, 10-di hydroanth racene, 9,10 dihydrophenanthrene and mixtures and derivatives thereof, as well as carbonaceous material-derived solvents; and (b) the inorganic ionic species are dissolved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metals comprising the steps after ion c liquefaction of : (1) removing non-condensible gases from said process stream; (2 ) removing immiscible water from said process st ream; (3) removing alkaline compound containing solids and reaction products solids from said process stream by treating with methanol; (4) hydrot reating said solids from step (3); (5) recovering alkaline compound containing solids and reaction product solids; and (6) separately recovering regenerated solubilizing agent capable of being used directly in a single stage ionic coal liquefaction process, and recycle methanol. 16. A method of recovering solid product from a carbonaceous liquefaction process stream after ionic Liquefaction of a carbonaceous material in ' the presence of a nitrogen-containing organic compound in which a polar solvent or mixtures thereof have been utilized for liquefaction together with alkali metaL or alkaline earth compounds or mixtures thereof comprising the steps of: ( 1 ) removing non-condensible gases from said process stream; (2) . removing aLkaline containing solids and reaction product solids from said process stream by the introduction of methanoL into said process stream to separate solid precipitates and volatile I iquid products; (3) wash ng the solid precip tates to recover reaction product solids; and (4) distilling the volatile liquid products to recover phenolic rich recycle solvents and methanol. 17. The process of claim 16 wherein the recycle process stream recovered comprises aromatic polar solvents suitable for use in subsequent ionic Liquefaction processes, and separately- recovered methanol suitable for use in subsequent separations. 18. A method of producing a pseudo-plastic solid product which is solid at room temperature from an ionic coal liquefaction process wherein said coal liquefaction is accomplished by reaction of the coal and oil shale with a poLar solvent solubilizing agent and an aqueous solution conta ning inorganic ionic species where ma or amounts of the solubilizing agent are selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p-cresol, catechol, resorcinoL, naphthoL and mixtures and derivatives thereof; and minor amounts of polycyclic aromatic hydrocarbons, pa rtia Lly-hydrogenated polycyclic aromatic hydrocarbons and fully hydrogenated polycyclic aromatic hydrocarbons having from 1 to 4 carbon rings such as naphthalene, anthracene, phenanthrene, acenaphthaLene, 1-methy Lnaphtha Lene, 2-methyLnaphtha lene, tetraLine, gamma-picoline, i soquinoLine, dihydronaphtha lene, decalin, 9, 10-dihydroanth racene, 9,10-dihydrophenanthrene and mixtures and derivatives thereof, as well as carbonaceous material-derived solvents; and (b ) the inorganic ionic species are dissolved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metals comprising the steps after ionic liquefaction of (1) removing non-condensi ble gases from said process stream; (2) removing alkaline compound containing solids and pseudo-pLasti c reaction product solids from said process stream by treating with methanol; (3) hydrotreating said solids from step (2); (4) recovering alkaline compound containing solids suitable for use in subsequent ionic liquefaction process, and pseudo-plastic reaction product; and (5) distilling said process stream to provide recycle agent capable of being used directly in an ionic coal Liquefaction process and a recycle methanol . 19. The solid product obtained from a carbonaceous liquefaction process stream after ionic Liquefaction of a carbonaceous material in the presence of a nitrogen-containing organic compound in which a polar solvent or mixtures thereof have been utilized for liquefaction together with alkali metaL or alkaline earth compounds or mixtures thereof where: non-condensible gases have been removed from said process stream; solid products have been recovered from said process stream by a precip tation with methyl alcohol. 20. The product of claim 19 wherein the recycle process stream recovered comprises aromatic polar solvents suitable for use in subsequent ionic Liquefaction processes. 21. A pseudo-plastic product which is solid at room temperature which is obtained from an ionic coal liquefaction process wherein said coaL Liquefaction is accomplished by reaction of the coaL and oil shale with a polar solvent solubilizing agent and an aqueous solution containing inorganic species where major amounts of the solubi lizing agent are selected from the group consisting of aromatic alcohols, phenols, polycyclic phenols and substituted phenols; such as o-cresol, m-cresol, p-cresol, catechol, resorcinoL, naphthol and mixtures and derivatives thereof; and minor amounts of polycyclic aromatic hydrocarbons / parti al ly-hydrogenated polycyclic aromatic hydrocarbons and fully hydrogenated polycyclic aromatic hydrocarbons having from 1 to 4 carbon rings such as naphthalene / anthracene / phenathrene, acenaphthalene, 1-methyInaphthalene, 2-methyInaphthalene, tetraline, gammapicoline, i soquinoli ne, di hydronaphtha Lene, decaline, 9, 10-dihydroanthroacene, 9, 10-di hydrophenanthrene and mixtures'and derivatives thereof, as well as carbonaceous material-derived solvents; and (b) the inorganic ionic species are dissolved in water and include a compound having a cation selected from the group consisting of alkali and alkaline-earth metals where after ionic Liquefaction: non-condensi ble gases are removed from said process stream; and methanol is applied to precipitate a solid product and alkaline compound containing solids are further separated and recovered by hydrotreati ng; and the remaining process stream is distilled to produce recyclable solubilizing agent which is capable of being used directly in an ionic coal liquefaction process to produce, upon precipitation, a pseudo-plastic product useful as a fuel or coke substitute, and recycle methanoL. 22. . A method of improving the yield in an ionic coal liquefaction process wherein said coal Liquefaction is accomplished by reaction of the coal with a polar solvent soLubilizing agent and an aqueous solution containing inorganic ionic species, which comprises conducting said ionic Liquefaction in the presence of a nitrogen-containing organic compound. 23. A method according to claim 22 wherein said nitrogen-containing organic compound comprises oil shale 24. A method according to claim 22 wherein said nitrogen-containing organic compound comprises oil shale derived kerogen.

Inventors: FARNUM SYLVIA A, KAESZ HERBERT D, KNUDSON CURTIS L, MILLER RONALD L, PORTER CLIFFORD R, RINDT JOHN R, FARNUM, SYLVIA, A., KAESZ, HERBERT, D., KNUDSON, CURTIS, L., MILLER, RONALD, L., PORTER, CLIFFORD, R., RINDT, JOHN, R.
Applicants: CARBON RESOURCES INC, CARBON RESOURCES, INC.
Application year: 1987
Main classification: C10G1
IPC codes: C10G1