US 4,375,402 AGrant
Pyrolysis Process
Issue Date:1983-03-01
•21 Claims
•5 Drawing Sheets
Abstract
In a process for recovery of values contained in solid carbonaceous material, the solid carbonaceous material is comminuted (10) and then subjected to pyrolysis, in the presence of a solid particulate source of heat in a pyrolysis zone, to form a pyrolysis product stream (24). The pyrolysis product stream contains a gaseous mixture and particulate solids. The solids are separated from the gaseous mixture to form a substantially solids-free gaseous stream (28) which comprises volatilized hydrocarbon free radicals newly formed by pyrolysis. The solid particulate source of heat is formed by oxidizing part of the separated particulate solids (32). Condensed stabilized hydrocarbons are obtained by quenching the gaseous mixture stream with a quench fluid (76) which contains a capping agent for stabilizing and terminating newly formed volatilized hydrocarbon free radicals. The capping agent is partially depleted of hydrogen by the stabilization and termination reaction. Hydrocarbons of four or more carbon atoms in the gaseous mixture stream are condensed. A liquid stream (64) containing the stabilized liquid product is then treated or separated into various fractions. A liquid containing the hydrogen depleted capping agent is hydrogenated to form a regenerated capping agent. At least a portion of the regenerated capping agent is recycled to the quench zone (34) as the quench fluid. In another embodiment capping agent is produced by the process, separated from the liquid product mixture, and recycled.
Metadata
Assignee
- Occidental Research Corporation
Inventor
- Kandaswamy Durai-Swamy
Application Information
Application Number:US 2958910
Filing Date:1981-08-25
Priority Date:1981-08-06
Art Unit:116
Classifications
IPC:
C10G 100
Field of Search:
2088 R;8 LE;11 R;11 LE
Patent Drawings (5 sheets)
Description
Technical Field
The technical field of the invention relates to the production of condensed stabilized hydrocarbons from solid particulate carbonaceous material, such as, but not limited to, coal, especially bituminous coal, gilsonite, tar sands, oil shale, and the organic portion of solid waste. The invention is particularly useful for the production of tar bases comprising amines, tar acids comprising phenols, and neutral tar liquids from bituminous coal.
Background Art
The present invention is directed to a process for producing condensed stabilized hydrocarbons by pyrolysis of solid particulate carbonaceous material.
Fluid fossil fuels, such as oil and natural gas, are becoming scarce as these fuels are consumed by a world whose population is continually growing. As a consequence, considerable attention is being directed toward pyrolyzing solid carbonaceous materials such as coal to useful liquid and gaseous hydrocarbon products. A problem exists in maximizing the yield of liquid hydrocarbons having molecular weights useful for conversion to more valuable end products because of the presence of newly formed volatilized hydrocarbon free radicals in the volatilized pyrolytic vapor.
One of the first steps in the pyrolysis of carbonaceous material is the thermal generation of hydrocarbon free radicals via homolytic bond scission of the coal. The hydrocarbon free radicals will combine with each other to produce undesirable heavy molecules such as heavy viscous tars having high boiling points. These hydrocarbon free radicals will also combine with carbon sites, such as present on char, to form more char or coke.
A technique that has been used to upgrade tar liquids and improve middle distillate tar liquid yield, is the addition of gaseous hydrogen directly to the pyrolysis reactor. By hydrogenating volatilized hydrocarbons directly in the pyrolysis reaction zone, sulfur and nitrogen are removed as hydrogen sulfide and ammonia. Hydrogenation directly in the pyrolysis zone also reduces the viscosity and lowers the average boiling point of the subsequently condensed volatilized hydrocarbons by terminating some hydrocarbon free radicals before they are allowed to polymerize to heavy tar liquids.
Processes involving hydrogenation are disclosed in U.S. Pat. Nos. 4,162,959 and 4,166,786. These patents disclose a process wherein a carbonaceous material feed, hot heat supplying carbon-containing residue, and hydrogen gas are reacted in a transport flash pyrolysis reactor. Pyrolysis and hydrogenation of the pyrolysis products occur simultaneously.
The effectiveness of hydrogen gas in terminating hydrocarbon free radicals is directly related to the hydrogen partial pressure. The pyrolysis reactor is preferably operated at pressures slightly greater than ambient, although pressures up to about 10,000 psig may also be used. An increase in hydrogen partial pressure increases free radical termination. High pressures, however, increase both the capital and operational cost of pyrolysis. Therefore, the preferred hydropyrolysis pressure for economical operation is from atout 1 psig to about 1000 psig.
Tar polymerization and cracking occur rapidly at pyrolysis temperatures. To minimize cracking pyrolysis vapors are rapid cooled and condensed by either direct or indirect heat exchange. Rapid cooling and condensation, although preventing some tar from cracking, are still not satisfactory in preventing a significant portion of the tar from polymerizing by free radical recombination in the liquid state.
A pyrolysis process is therefore needed which substantially eliminates undesirable volatilized hydrocarbon free radical reactions early in the formation of pyrolysis products, thereby increasing the yield of desirable lower molecular weight tar liquids having relatively low boiling points and decreasing the yield of undesirable heavy viscous tars having relatively high boiling points.
Summary and Disclosure of the Invention
This invention relates to a process for recovery of values produced from a solid particulate carbonaceous material containing bound hydrogen atoms. In general a solid particulate carbonaceous feed material containing bound hydrogen atoms is pyrolyzed under conditions of time and elevated temperature sufficient to pyrolyze the solid particulate carbonaceous feed material. The heat required to pyrolyze the solid particulate carbonaceous material is supplied principally by a solid particulate source of heat which contacts the solid particulate carbonaceous feed material in the pyrolysis zone. The pyrolysis products comprise particulate solids and a gaseous mixture. The particulate solids comprise a carbon-containing solid residue produced from the solid particulate carbonaceous feed material. The gaseous mixture comprises pyrolytic product vapors produced from the solid particulate carbonaceous feed material. The pyrolytic product vapors comprise hydrocarbons which comprise newly formed volatilized hydrocarbon free radicals. At least a portion of the hydrocarbons comprise four or more carbon atoms.
The particulate solids are separated from the gaseous mixture to form a substantially solids-free gaseous mixture stream which is then immediately contacted with a quench fluid which comprises at least one capping agent capable of stabilizing newly formed volatilized hydrocarbon free radicals contained in the gaseous mixture stream. Such free radicals are stabilized by the transfer of hydrogen from the capping agent to the free radicals thereby forming stabilized radicals and a hydrogen depleted capping agent. At least a major portion of the volatilized hydrocarbon free radicals contained in the gaseous mixture stream are stabilized and at least a major portion of the hydrocarbon vapors having four or more carbon atoms in the gaseous mixture stream are condensed. A gaseous residue and a liquid mixture are then formed. The liquid mixture comprises a hydrocarbon condensate, the quench fluid, a portion of the capping agent, and a hydrogen depleted capping agent. Values are recovered from the gaseous residue. Condensed stabilized hydrocarbons are recovered from the liquid mixture.
This invention therefore relates to a process for recovery of condensed stabilized hydrocarbons produced by pyrolysis of solid particulate carbonaceous materials and, more particularly, to a process for terminating free radicals by quenching with a capping agent, or a fluid containing a capping agent, a pyrolytic vapor mixture removed from a pyrolysis zone.
In practicing this invention, a solid particulate carbonaceous feed material containing bound hydrogen atoms, a transport gas, and a solid particulate source of heat are fed to a pyrolysis zone for pyrolyzing the feed solid particulate carbonaceous feed material. A pyrolysis product stream is formed which contains particulate solids and a vapor mixture comprising pyrolytic product vapors which comprise hydrocarbons. The hydrocarbons formed include larger hydrocarbons having four or more carbon atoms. The hydrocarbons formed also include volatilized hydrocarbon free radicals including volatilized hydrocarbon free radicals having four or more carbon atoms. The pyrolysis product stream passes from the pyrolysis reactor to a separation zone where at least a major portion of the particulate solids are separated from the gas-solid mixture, to form a substantially solids-free gaseous mixture stream.
A portion of the separated particulate solids is recovered as char product and a remainder is recycled, after heating, to the transport flash pyrolysis reactor as the solid particulate source of heat.
The solids-free gaseous mixture stream is then contacted in a quench zone with a quench fluid which comprises at least one capping agent for terminating or stabilizing at least a major portion of the newly formed hydrocarbon free radicals contained in the gaseous mixture stream. While we do not wish to be bound by theory, the capping agent terminates, i.e., stabilizes the newly formed hydrocarbon free radicals by providing active hydrogen atoms to react with and terminate the free radicals. In one embodiment the capping agent is added initially to the system and is regenerated by the process. Make-up capping agent can be added if required. In another embodiment the process produces a capping agent in the hydrocarbon product stream. In either case, the quench fluid is provided under conditions sufficient to condense at least a major portion of the hydrocarbon vapors having four or more carbon atoms thereby forming a hydrocarbon condensate and a gaseous residue. The hydrocarbon condensate in admixture with the quench fluid forms a liquid mixture. At least a portion of the capping agent is partially depleted of hydrogen atoms in the quench zone and passes with any unconsumed capping agent in the liquid mixture to a liquid product separation zone for separation and recovery of liquid products.
A neutral tar liquid stream which comprises tar liquids and at least a portion of the capping agent and hydrogen depleted capping agent is separated from the liquid mixture in the liquid product separation zone. In one embodiment at least a portion of the neutral tar liquid stream is hydrogenated to upgrade the tar liquids and to regenerate capping agent from the depleted capping agent so that it is suitable for reuse in the process as a capping agent for terminating hydrocarbon free radicals. In one embodiment at least a portion of the hydrogenated neutral tar liquid stream is utilized as a quench liquid. In another embodiment the regenerated capping agent and any unconsumed capping agent are separated from the hydrogenated neutral tar liquid stream and that combination is recycled as the quench liquid. In the latter embodiment the quench liquid has a higher concentration of capping agent than in the former embodiment.
In still another embodiment at least a portion of the depleted capping agent and any unconsumed capping agent are separated directly from the liquid mixture and hydrogenated to regenerate a capping agent suitable for terminating hydrocarbon free radicals. This steam is then recycled to the quench zone as at least a portion of the quench fluid. In a preferred embodiment, especially after steady state is reached, the capping agent is principally a liquid produced by the pyrolysis process.
Capping agents useful in accordance with the practice of this invention include hydrogen donor solvents, hydrogen transferring or shuttling agents, and/or free radical trapping agents, mixtures thereof and the like.
Hydrogen donor solvents are those solvents which can donate hydrogen to tar free radicals to prevent recombination or polymerization of tar liquids by free radical mechanisms in the vapor or liquid state. Examples of hydrogen donor solvents are hydroaromatic compounds, such as tetrahydronaphthalene, dihydronaphthalene, partially hydrogenated phenanthrenes, partially hydrogenated anthracenes, alkyl substituted compounds of the above, mixtures thereof, and the like, which comprise multi-ring structures wherein one of the rings is aromatic. Also useful as hydrogen donor solvents are fully saturated aromatic compounds or alicyclics, such as decahydronaphthalene, perhydroanthracene, perhydrophenanthrene, or alkyl substituted compounds of the above, or mixtures thereof or the like. Hydroaromatic compounds are preferred capping agents with tetrahydronaphthalene being especially preferred.
Hydrogen transferring or shuttling agents do not have donatable hydrogen but can accept hydrogen from other sources and transfer the hydrogen to the hydrocarbon free radicals. Examples of hydrogen transferring or shuttling agents are naphthalene, anthracene, creosote oil, and the like.
Capping agents can also be free radical trapping agents, such as thiols, phenols, amines, and the like which can act either as hydrogen donor solvents and/or as hydrogen transferring or shuttling agents.
Regardless of the particular capping agent utilized, the quench liquid preferably contains a sufficient amount of the capping agent or agents to terminate substantially all of the volatilized hydrocarbon free radicals newly formed by pyrolysis and contained in the substantially solids-free gaseous mixture stream. By "substantially all of the volatilized hydrocarbon free radicals", it is meant that at least about 95% and preferably greater than about 99% of the volatilized hydrocarbon free radicals newly formed by pyrolysis and contained in the pyrolytic vapor stream are terminated.
In carbonaceous materials such as coal or the like there are many large and relatively stable free radicals initially present before pyrolysis which, it is believed, are not terminated in the process. These radicals, of course, are not newly formed and are believed to be large free radicals that have multiple ring structures, having unpaired electrons which are highly stabilized by resonance and therefore are less reactive with capping agents. Steric hindrance factors in such large radicals can also retard the free radical-capping agent interaction.
As the percentage of volatilized hydrocarbon free radicals that are terminated increases, the average molecular weight of the tar liquid products decreases, providing for a higher yield of the desirable lower molecular weight tar liquids. It takes one reactive hydrogen atom to stabilize each volatilized hydrocarbon free radical produced, for example, tetrahydronaphthalene can donate four hydrogen atoms for capping or terminating four volatilized hydrocarbon free radicals. In one embodiment, at least a molar amount of tetrahydronaphthalene is utilized in the quench fluid which is equal to one fourth the number of moles of newly formed hydrocarbon free radicals. In a preferred embodiment excess capping agent is used.
The quench liquid containing capping agent is introduced at a temperature and at a flow rate which will provide for condensation of at least a major portion and preferably substantially all of the vaporized hydrocarbons having four or more carbon atoms. By "substantially all of the vaporized hydrocarbons having four or more carbon atoms", it is meant that at least about 95% and preferably greater than about 99% of the vaporized hydrocarbons having four or more carbon atoms in the gaseous mixture stream are condensed by direct heat exchange with the quench fluid.
Temperature reduction of the pyrolytic vapors should also be sufficiently rapid to hinder recombination of desirable lighter hydrocarbon molecules into less desirable heavier molecules. Generally, the temperature of the product vapor can be reduced sufficiently rapidly by using a ratio of about 0.1 to about 100 pounds of quench liquid per pound of substantially solids-free vapor mixture. Preferably the ratio is from about 1 to about 10 pounds of quench liquid per pound of vapor mixture.
The temperature of the substantially particulate solids-free gaseous mixture stream is usually in the range of the desired pyrolysis temperature, i.e., from about 800.degree. to about 2000.degree. F. and preferably from about 900.degree. to about 1400.degree. F. It has been found desirable to provide the quench liquid at a temperature and flow rate sufficient for rapidly reducing the temperature of the gaseous mixture to less than about 700.degree. F., preferably to less than about 200.degree. F. for substantially eliminating recombination of lighter hydrocarbon molecules.
The solid carbonaceous material from which values may be recovered in accordance with this invention include coals, gilsonite, tar sands, oil shale, the organic portion of solid waste and the like. Since the process is especially useful for coals, the process will be described for the processing of coals and particularly agglomerative coals. All the various types of coal or coal-like substances can be pyrolyzed. Coals include anthracite coal, bituminous coal, subbituminous coal, lignite, peat, and the like.
Brief Description of the Drawings
These and other features and advantages of the present invention will become better understood with reference to the following description, accompanying drawings and appended claims.
FIG. 1 schematically illustrates the overall process of the invention.
FIG. 2 schematically illustrates the operation of a quench zone.
FIG. 3 shows a schematic of a quench and oil recovery section of a commercial size plant.
FIG. 4 is a flow sheet of a unit used to demonstrate features of this invention.
FIG. 5 shows molecular weight gel permeation chromatograms of two hydrocarbon product liquids.
Best Mode for Carrying Out the Invention
With reference now to FIG. 1, the coal to be pyrolyzed is introduced into a coal preparation zone 10 where it is initially comminuted to a suitable particle size for pyrolysis. A suitable particle size has been found to be less than about 1000 microns.
When an agglomerative coal is used, preferably the particle size is less than about 250 microns to enable the coal to be rapidly heated through the plastic state of the coal before the coal contacts the walls of a pyrolysis reactor in order to prevent the coal from agglomerating and plugging the reactor. The desired coal particle size will depend on the size and configuration of the pyrolysis reactor.
In general the coal is preferably comminuted to as small a size as practical for facilitating its rapid heating in the pyrolysis reactor. However, it is important to minimize the production of fines, e.g., particles having a size less than about 10 microns, in order to facilitate subsequent gas-solid separation operations as described later herein. Fines which are produced can be removed in a cyclone separation zone (not shown) designed for separation of the fines smaller than a predetermined particle size. Fine removal minimizes particle carry-over and contamination of pyrolysis liquid products.
The coal can be fully dried or preferably only partially dried thereby allowing steam to be produced in the pyrolysis zone which serves to inhibit active sites on char solids, as will be explained further below. It has been found that a high hydrocarbon product yield is obtained by leaving about 15% by weight water in subbituminous coal feeds. The coal can be dried fully or partially with flue gas, or effluent gas from a flare, or the like. Additional details of the preparation of coal for pyrolysis can be found in U.S. Pat. No. 4,145,274.
The comminuted coal can be combined with a non-deleterious reactive carrier or transport gas and is passed through line 12 to pyrolysis zone 14. Little if any transport gas is required if the pyrolysis zone comprises a mixer having a double shaft which rotates in the same sense as shown in U.S. Pat. Nos. 4,038,045, 4,230,528 and 4,054,492. However, if it is desirable to very rapidly pyrolyze the coal, or other aromatic feed material, such as can be realized in a flash pyrolysis process utilizing a transport reactor, then relatively large amounts of transport gas is required and the reactivity of the transport gas becomes more serious. By a "non-deleterious reactive carrier or transport gas", is meant a gas substantially free of free oxygen, but which may contain constituents which react to upgrade product quality. In one embodiment recycle product gas can be used as the carrier gas. Nitrogen could be used as a carrier gas in experimental or developmental studies but nitrogen as a carrier gas in a commercial process is not thought to be economical. The carrier gas may also contain carbon dioxide and/or steam as char deactivators or may be a synthesis gas or methane.
The solid particulate carbonaceous feed material is combined, in pyrolysis zone 14, with a solid particulate source of heat which is preferably a portion of the solid residue of pyrolysis or char heated in oxidation zone 16 by partial oxidation to a temperature sufficient for direct use as a solid particulate source of heat in pyrolysis zone 14. Pyrolysis zone 14 is operated at temperatures from about 900.degree. to about 2000.degree. F. at residence time sufficient to complete the desired pyrolysis, which generally is between about 0.1 seconds and about 30 minutes to maximize the yield of volatilized hydrocarbons. Longer residence times at lower pyrolysis temperatures are preferred because cracking of volatile pyrolysis vapors is minimized while the desired degree of devolatilization is still achieved. In one embodiment, not shown in the figures, the pyrolysis zone comprises a double shaft mixer having two shafts which rotate in the same sense. The pyrolytic products from the mixture are introduced into a degasification zone where additional gasification of the feed carbonaceous material occurs. Gaseous products from the degasification zone will be free from tar if sufficiently high temperatures are maintained in the mixer. In some embodiments it is preferred to have the degasification operated at a higher temperature and pressure and for a longer solids residue time than that in the mixer. To effect pyrolysis, the weight ratio of the solid particulate source of heat to the solid particulate carbonaceous feed material will range from about 2:1 to about 40:1. These weight ratios require the temperature of the solid particulate souce of heat to be about 25.degree. to about 500.degree. F. higher than the pyrolysis zone temperature. Pyrolysis operations to which this invention is adapted are described in U.S. Pat. Nos. 3,736,233, 4,085,030 and 4,145,274. When the embodiment using the double shaft mixer and degasification zone is used the solid particulate source of heat can be divided between the mixer and the degasification zone.
The coal or solid particulate carbonaceous feed material, the non-deleteriously reactive transport gas if used, and the solid particulate source of heat are combined in pyrolysis reactor 14. The solid particulate source of heat is fed to the pyrolysis zone at a rate sufficient to maintain the pyrolysis reaction zone at the desired pyrolysis temperature. Therefore the solid particulate carbonaceous feed material or coal feed, the solid particulate souce of heat, and, in some embodiments, the substantially non-deleteriously reactive transport gas are introduced into the pyrolysis reaction zone under conditions sufficient to pyrolyze the solid particulate carbonaceous feed material. Pyrolysis product stream 24 contains as particulate solids, the solid particulate source of heat and a carbon-containing solid residue of pyrolysis; and a gaseous mixture comprising the substantially non-deleteriously reactive transport gas if such was employed, and pyrolytic product vapors which comprise hydrocarbons some of which have four or more carbon atoms and newly formed volatilized hydrocarbon free radicals.
Pyrolysis product stream 24 from pyrolysis reactor 14 is introduced into a separation zone 26. In separation zone 26, which can comprise cyclone separators or the like, at least a major portion of the solids are separated from the gas-solid mixture to form a substantially solids-free gaseous mixture stream 28. It is desirable to separate substantially all, i.e., about 99% or higher, of the solids from the gas-solid mixture to form the substantially solids-free gaseous mixture stream. Removing substantially all of the solids from the gas-solid mixture provides a gaseous mixture stream which can be handled in various downstream equipments without fouling or plugging.
A portion of the carbon-containing solid residue and spent solid particulate source of heat is withdrawn from separation zone 26 and conveyed in conduit 32 to oxidation zone 16 for partial oxidation with a source of oxygen, such as air, to produce a solid particulate source of heat and a combustion gas. Another portion of the separated solids is withdrawn as product char in stream 30. The flue gas from the oxidation zone 16 contains oxidation products of the char such as carbon monoxide, carbon dioxide, water vapor and sulfur dioxide. In this embodiment, oxidation of the char, which is exothermic, generates essentially all of the heat required for pyrolysis of the coal. Other means of heating can be used however.
The hot particulate char is then separated from the combustion gas by means (not shown) such as one or more centrifugal separation stages in series, or a baffled collection vessel as in U.S. Pat. No. 4,038,045. In one embodiment, oxidation zone 16 is a cyclone oxidation-separation reactor designed so that the char can be both heated and separated from the gaseous combustion products in a single unit with attendant savings in capital and operating costs.
The separated, heated char particles can then be reacted with steam or with a mixture of steam and carbon dioxide to form hydrogen gas according to the following reactions:
As seen by these reactions, the gas produced comprises hydrogen, carbon monoxide, steam, and some carbon dioxide and is a mixture of water gas and combustion gas. The extent of char gasification to produce hydrogen and carbon monoxide is controlled by the amount of steam used and the temperature and pressure of the hot char steam mixture. The greater the amount of steam used, the greater the amount of hydrogen generated. While we do not wish to be bound by theory, the newly formed hydrogen, or nascent hydrogen, is believed to be very reactive in stabilizing or capping hydrocarbon free radicals, thereby improving the quality of the condensed stabilized hydrocarbons produced by this process; or stated another way, the effectiveness of nascent hydrogen permits the use of a lower hydrogen partial pressure for the same degree of hydrogenation.
The heated char is conveyed in char transport line reactor 31 to pyrolysis reactor 14 and utilized therein as the solid particulate source of heat. In this embodiment oxygen is used instead of air as the combustion gas and the flue gas from the oxidation zone is used as the non-deleteriously reactive transport gas which is also introduced into the pyrolysis reactor.
The substantially solids-free gaseous mixture stream 28 from the separation zone 26 comprises non-deleteriously reactive transport gas, if such were employed, and volatilized hydrocarbons. The volatilized hydrocarbons include condensible hydrocarbons having four or more carbon atoms, a portion of which are free radicals. The condensible hydrocarbons are recovered as condensate in quench zone 34 by direct contact with a quench fluid containing the capping agent to stabilize and terminate the free radicals, including the newly formed free radicals, aided, if desired, by indirect cooling, such as a heat exchanger. In addition, the volatilized hydrocarbons comprise normally noncondensible gases, such as methane and other lower molecular weight hydrocarbon gases which are not recoverable by condensation means which are not very low temperature or cryogenic. These gases are conveyed through conduit 60 to gas recovery zone 36.
The substantially solids-free gaseous mixture stream 28, which comprises newly formed volatilized hydrocarbon free radicals which have not been terminated in the pyrolysis zone, is introduced into the quench zone 34 wherein the newly formed volatilized hydrocarbon free radicals are stabilized and terminated by contacting with a capping agent. Quench zone 34 is a gas-liquid contacting zone and for example can comprise a spray tower, a Venturi contactor, a gas absorption tower, or the like, or combinations thereof.
As indicated, in order to stabilize or terminate free radicals, a quench fluid is provided which consists essentially of hydrocarbons and includes at least one capping agent. In this embodiment, the quench fluid is a hydrogenated neutral tar liquid recovered from the condensate. The quench fluid contains, in this embodiment, at least one regenerative capping agent which is formed during pyrolysis or hydrogenation of liquid pyrolysis products. In another embodiment the capping agent is added initially and when depleted of hydrogen atoms can be regenerated by hydrogenation. In either case it is convenient to add the capping agent at start up. Where the capping agent is produced by the process it can be different than the start-up capping agent in which case the capping agent becomes essentially process produced capping agent after steady state is reached.
The capping agents are hydrogen donor solvents, hydrogen transferring or shuttling agents, and/or free radical trapping agents, mixtures thereof, and the like. The amount of quench fluid, which contains a capping agent or agents for terminating substantially all of the free radicals newly formed in pyrolysis and present in the pyrolytic gaseous mixture stream, is sufficient to rapidly cool the gaseous mixture stream and to form a condensate which contains the condensed stabilized hydrocarbons and unconsumed and spent capping agent.
Use of a quench fluid comprising a capping agent causes stabilizing and terminating of tar free radicals of constituents of the treated hydrocarbon vapors and cooling and condensing of a substantial portion of the hydrocarbon vapors having four or more carbon atoms. This process utilizing a quench fluid with a capping agent increases the yield of lower molecular weight tar liquids.
In one preferred embodiment a multiple stage quench is used rather than a single stage quench. The advantage of a multiple stage quench is that during pressure upsets or other malfunctions, solids which enter the quench zone can be handled without rendering the quench recirculation system inoperative as is likely to result if only a single stage is used. A two stage quench provides enough system flexibility and time to take corrective action by automatic or manual control procedures. For example in one embodiment the first quench stage is designed so as not to plug with mixtures containing entrained particulates by providing a quench fluid flow rate sufficient to simultaneously scrub and flush out any entrained particulates. This is an important embodiment because the higher molecular weight viscous tars when condensed are sticky and will form an agglomerative mass with any entrained particulates. Examples of a suitable first stage are non-plugging means such as spray wash towers or loose packed towers. However, a wash tower or loose packed tower which is satisfactory for a first stage generally is not efficient by itself as a scrubbing device when high volatile coal is rapidly pyrolyzed because entrained liquids and aerosols are generally found in the first quench stage effluent. This is especially true in embodiments where substantial amounts of transport gas are employed. A second stage contacting means therefore is beneficial to separate and recover any entrained liquids and aerosols. The second stage must have a higher contacting efficiency than normally available in a wash tower. A high efficiency Venturi scrubber is an example of a suitable second stage contactor. A two stage quench system, consisting of a wash tower as a first stage followed by a Venturi scrubber as a second stage, has been found to be effective. The wash tower first stage provides for most of the free radical termination, temperature reduction and removal of the bulk of any entrained solids. The Venturi second stage effectively collects the remainder of the entrained liquids and aerosols. An electrostatic precipitator can also be used for collecting entrained liquids and aerosols.
Referring now to FIG. 2, a preferred system includes wash tower 38 as a first quench stage, having a condensation section 40 and a liquid collection section 42. A first quench fluid stream 44 comprising a capping agent, provided in an amount sufficient for stabilizing and terminating substantially all of the newly formed hydrocarbon free radicals contained in the substantially solids-free gaseous mixture stream, is introduced into the condensation section 40 of the wash tower. The substantially solids-free gaseous mixture stream 28 of FIG. 1 comprising volatilized hydrocarbons having four or more carbon atoms and volatilized hydrocarbon free radicals is also introduced into the condensation section 40. The first quench fluid stream 44 contacts the substantially solids-free gaseous mixture stream 28 in the condensation section, thereby stabilizing and terminating the vaporized free radicals and condensing at least a major portion of the larger hydrocarbons which contain four or more carbon atoms per molecule in the gaseous mixture stream. Preferably the first quench fluid stream is introduced into the quench zone at a temperature and at a flow rate sufficient to reduce the temperature of the substantially solids-free gaseous stream to less than about 700.degree. F. and especially preferably to less than about 200.degree. F. A condensate is formed which comprises the stabilized and terminated hydrocarbon free radicals. A gaseous residue stream 46 then remains which comprises those portions of the gaseous mixture stream 28, such as non-condensible gases, lighter hydrocarbons, which have not condensed, the lighter molecular weight portion of the quench fluid which has been vaporized and entrained liquids, and aerosols. The condensate and the bulk of the first quench fluid flow down into liquid collection section 42 of wash tower 38 and combine to form a first liquid mixture. Any remaining tar free radicals that were not terminated in the gaseous state but were condensed will be terminated by contact with the capping agent in the quench fluid in liquid collection section 42. The liquid mixture containing the condensate is removed from the wash tower and conveyed in conduit 48 to a solids removal zone 50.
A residual gaseous residue stream is removed from the top portion of the condensation section of the wash tower and conveyed in conduit 46 to Venturi scrubber 52. A second portion of the quench fluid stream is introduced into the Venturi scrubber through conduit 54 and contacts the residual gaseous residue stream 46 to terminate any remaining volatilized hydrocarbon free radicals and to scrub entrained hydrocarbons in the form of aerosols or vapors from the gaseous residue stream. The scrubbed gaseous residue stream and the second portion of the quench fluid are combined and removed from the Venturi scrubber through conduit 56. The remaining gas phase is separated from the liquids by introducing stream 56 into separator vessel 58. The separated gas is removed through conduit 60.
The second portion of the quench fluid and the separated entrained tars are removed from separator vessel 58 as a liquid mixture in conduit 62 and combined with the liquid mixture in stream 48 to form a combined liquid mixture in stream 64. Combined liquid mixture stream 64 is conveyed to liquid product separation zone 66 of FIG. 1.
A portion of the volatilized hydrocarbons produced by pyrolysis of coal comprise heavy tars having boiling points above the boiling points of middle distillate tar liquids. These heavy viscous tars have a high carbon-hydrogen atomic ratio and frequently contain heterocyclic compounds such as organic sulfur and nitrogen compounds. By hydrogenating volatilized hydrocarbons in the pyrolysis reaction zone using hydrogen gas, the value of the volatilized hydrocarbons can be increased by sulfur and nitrogen removal as hydrogen sulfide and ammonia. Vapor phase hydrogenation with hydrogen directly in the pyrolysis reactor will reduce the viscosity and lower the average boiling point of the volatilized hydrocarbons by terminating some free radicals, but hydrogenation at pyrolysis temperatures is not as effective in stabilizing and terminating volatilized free radicals as contacting with a quench fluid containing a capping agent and terminating the newly formed free radicals in the vapor state as described herein. Nevertheless, since some free radicals can be terminated in the pyrolysis zone by hydrogenation, in this embodiment, the gas produced in oxidation zone 16 which comprises hydrogen can be introduced into pyrolysis reactor 14 as a carrier or flush gas, if desired, along with the solid particulate source of heat to terminate at least a portion of the free radicals directly in the pyrolysis zone by hydrogen reaction. In another embodioment a hydrogen or synthesis, or methane-containing gas stream can be fed separately into the pyrolysis reactor for this purpose.
The pyrolysis reaction zone is preferably operated at pressures slightly greater than ambient, although pressures up to about 10,000 psig may also be used. An increase in pressure increases the hydrogen partial pressure in the pyrolysis zone and increases the hydrogenation of the volatilized hydrocarbons. However, as the pressure in the pyrolysis reaction zone increases, the capital and operating costs of the process also increase. Therefore, the preferred operating pressure range for the pyrolysis reaction zone for economical reasons is from about 1 psig to about 1000 psig.
It is known that the char produced by rapid heating of coal, as in pyrolysis or dry distillation, is very porous, has a large or open pore volume, and a high surface area. These characteristics result in a higher char reactivity than chars produced by slow heating. High reactivity of these chars is largely attributed to their high internal surface area. The char produced from pyrolysis of coal, as described herein, is also very reactive.
It has been determined that the presence of carbon dioxide and steam in the pyrolysis zone increases the yield of condensible hydrocarbons by neutralizing active sites on the char produced during pyrolysis. Char which has not been so neutralized tends to catalyze the formation of high molecular weight hydrocarbons by promoting polymerization and/or cracking at such active char sites.
While not wishing to be bound by theory, it is believed that the hydrocarbon vapors produced by pyrolysis or dry distillation of coal occupy the reactive sites on the hot char used as a heating medium and are polymerizedto heavy tar liquids, char, or coke by free radical mechanisms. This has the result of reducing the yield of middle distilate tar liquids, a desired product. It is also believed that the char reactions with CO.sub.2 or steam involve an oxygen transfer step from these gases to the char, followed by a gasification step in which the oxygen-carbon complex is released as CO. These reactions are believed to take place on the reactive sites on the char, and in so doing reduce the availability of these reactive sites for tar adsorption, polymerization, and cracking. Therefore, hydrogen, steam, carbon dioxide, or mixtures thereof introduced into the pyrolysis zone or used as a carrier gas for hot char, in combination with a subsequent capping agent quench, immediately after pyrolysis increases the yield of lower molecular weight hydrocarbons, decreases the average molecular weight of condensible liquid product, and minimizes hydrocarbon yield loss.
Referring again to FIG. 1, combined liquid mixture stream 64, which comprises the liquid mixture from the first stage of the quench zone and the liquid mixture from the second stage of the quench zone, is sent to a liquid product separation zone 66.
In the embodiment shown in FIG. 1, which is particularly useful when the feed coal or solid carbonaceous feed material has a high oxygen and nitrogen content, at least several liquid hydrocarbon fractions are recovered from the combined liquid mixture stream in liquid product separation zone 66. These fractions are the light low boiling hydrocarbon fraction comprising C.sub.4 's to C.sub.8 's, tar acids comprising phenols, tar bases comprising amines, and a neutral tar liquid fraction comprising C.sub.9 's and higher and the heavy tar product.
The neutral tar liquid fraction comprises hydrocarbon liquids which comprise consumed and unconsumed capping agents from the quench zone 34. The neutral tar liquid fraction can be upgraded by hydrogenation. A fluidized or fixed bed hydrogenation process is useful for this purpose. A suitable hydrogenation process comprises hydrogenation at least a portion of the neutral tar liquid stream to produce a hydrogenated neutral tar liquid stream comprising a regenerated capping agent capable of terminating free radicals. The hydrogenation process in the embodiment shown in FIG. 1 involves the removal of contaminants, such as sulfur as hydrogen sulfide and nitrogen as ammonia, from the liquid, thereby resulting in a more environmentally attractive fuel product. Water is also removed. Conventional processes may be employed for these removal steps. This embodiment will enhance the chemical stability of the product and form products with improved handling and storage chracteristics. In another embodiment at least a portion of the liquids are hydrocracked to form lower molecular weight hydrocarbons suitable for use in such products as gasoline.
Suitable hydrogenation conditions are a hydrogenation temperature from about 700.degree. to about 900.degree. F., hydrogen partial pressures of from about 1000 to about 3000 psia, a hydrogen volume between about 1000 to about 5000 standard cubic feet per barrel of feed of neutral tar liquid to be treated, and an amount of catalyst of from about 0.2 to about 3 volumes of neutral tar liquid per hour per volume of catalyst. Suitable hydrogenation catalysts are for example metals in the sulfide form, such as nickel, molybdenum, tungsten, and cobalt which can be supported on alumina or silica-aluminum base. Hydrogenation can also be conducted at elevated temperatures and pressures in the absence of a catalyst.
As shown in FIG. 1, neutral tar liquid stream 68 is introduced into hydrogenation zone 70 and contacted with a stream of hydrogen gas introduced into the hydrogenation zone through conduit 69. The hydrogenated neutral tar liquids thusly produced are then conveyed through conduit 72 to tar separation zone 74. The hydrogenated neutral tar liquids are separated by conventional distillation processes in the tar separation zone 74 into at least a hydrogenated tar product fraction comprising hydrogenated heavy tars and a hydrogenated liquid fraction comprising regenerated capping agent and any unconsumed capping agent. At least a portion of the hydrogenated liquid fraction is utilized as quench fluid stream 76 to quench zone 34. It is preferred that the liquid separations are conducted so that the recycle quench fluid stream comprises tar liquids having a boiling point range between about 350.degree. and about 650.degree. F.
In still another embodiment of this invention, at least a portion of the consumed capping agent, i.e. the hydrogen depleted capping agent, and any unconsumed capping agent, are separated directly from the combined liquid mixture stream. The mixture of hydrogen depleted and unconsumed capping agent is then hydrogenated to form a regenerated capping agent mixture at least a portion of which is then recycled to the quench zone as the quench fluid.
In an alternate embodiment at least a portion of the unconsumed and consumed capping agent are separated from the neutral tar liquid stream prior to hydrogenation of the neutral tar liquid stream. The consumed and unconsumed capping agent mixture is then hydrogenated separately to form a regenerated capping agent mixture at least a portion of which is recycled to the quench zone as the quench fluid.
In the embodiment shown in FIG. 2, recycle quench fluid stream 76 is split to form quench fluid stream 44 and quench fluid stream 54. It is to be understood that stream 44 and 54 do not have to be identical in chemical composition and can be tailored to the duty required of each quench zone.
At least a portion of the phenols from liquid product separation zone 66, FIG. 1, can, if desired, be added to the quench fluid as additional capping agent for enhancing the free radical termination ability of the quench fluid. Phenols are good solvents for tar liquids and will improve the miscibility of hydrocarbon condensate in combined liquid mixture stream 64. Since phenols are also capping agents their inclusion in the quench fluid will improve hydrocarbon free radical termination capability of the quench fluid.
At least a portion of the heavier tar liquid products having a boiling point of from above about 650.degree. to about 950.degree. F. can be recycled back to the pyrolysis zone for further cracking if desired, or blended with light oil to produce a fuel oil.
The remainder of gaseous residue stream is removed from quench zone 34 through conduit 60 and introduced into gas recovery zone 36 for recovery of light hydrocarbon such as methane, butane, propane, and other low molecular weight hydrocarbons. Preferably sulfur and nitrogen compounds are also removed enabling recovery of hydrogen, hydrogen sulfide, ammonia, and the like. For example gas recovery zone 36 can be a conventional acid gas removal unit where the hydrogen sulfide is separated and removed. After removal of the hydrogen sulfide, the remaining gas can be compressed and utilized in coal preparation operations or as a transport gas. Any surplus gas can be used as a fuel gas, or as a feed gas for conversion to pipeline quality natural gas or ammonia. The hydrogen sulfide-rich stream from the acid gas removal unit can be sent to a Claus unit for sulfur recovery.
In a commercial size operation sized coal is transferred to a pyrolysis section of a commercial plant where it is contacted with a circulating stream of hot char in a pyrolysis reactor. Coal reacts at a temperature of about 900.degree. to about 1750.degree. F., producing oil, gas and char. Oil and gas products are separated from the char and sent to a quench and oil recovery section. A portion of the char product is heated or burned in a transfer line combustor to reheat it and use it as the circulating char stream. The flue gas from the char burner is sent to a heat recovery section. Energy is recovered from the flue gas which is then used to dry the coal. The net char product is conveyed directly to a char handling and cooling section from where it is transported to a power plant.
Hot vapors from the pyrolysis section are line quenched with a quench fluid containing the capping agent and further quenched and cooled to obtain oil and gas fractions.
The oil fraction that contains the quench fluid and capping agent is held in a soaking drum for a period of about 1 to 60 minutes in order to allow for the desulfurization and stabilization of the product oils. Hydrogen is transferred from the capping agent to the product oils in the soaking drum. The oil fraction is then transferred to a distillation column where light, medium and heavy oil products are obtained.
The quench fluid and capping agent are recovered from the column as a side stream and subsequently hydrotreated to replace the donated hydrogen. The capping agent is then recycled for contacting additionally produced pyrolysis vapors, thereby stabilizing additionally produced newly formed free radicals in the vapor state.
Dry gas is compressed, purified of sulfur compounds, and used partly as feedstock for hydrogen production by steam reforming, and partly as plant fuel, with the remainder being pipelined to the power plant for boiler fuel and/or for gas turbine fuel.
The commercial size quench and oil recovery section is shown in FIG. 3.
In this commercial section pyrolysis gas 201 is contacted with stream 204 of quench fluid containing a capping agent and undergoes two successive quenching steps followed by a distillation step.
Light, medium and heavy oil products are obtained together with a fuel gas.
The quench fluid and capping agent are recovered as a middle cut from the distillation tower and recycled, after a hydrotreating step. to replace the hydrogen donative capability of the capping agent, to the quench zone.
In first quench tower 210, which is equipped with shed trays, the vapor is quenched with cooled tower-bottoms-recycle stream 212. Tower 210 operates at pressures of about 1 to 35 psia and the products leave at 400.degree. ; F. Heavy oil 216 from the bottom of the tower flows to settling sludge drum 220, where any gross char carry-over that might occur at upstream upset conditions is collected. Any sludge that may be present is withdrawn from settler 220 and recycled to the pyrolysis section of the commercial plant.
Overhead gas stream 214, at about 400.degree. F., is quenched in medium oil quench tower 230 with cooled-recycled-bottoms stream 232.
Tower 230 operates at pressures of about 1 to about 32 psia and produces a medium oil bottoms, which will become part of the distillation tower feed.
Overhead gas stream 234 from tower 230, at about 240.degree. F., is cooled in air cooler 236 to about 150.degree. F. followed by cooling in water cooled trim cooler 238 to bring down its temperature to about 105.degree. F.
Vapor, light oil and the condensed water are separated in separator drum 240.
Vapor stream 242 flows to gas compression section 310 and water to phenol recovery section 320. Light oil from separator drum 240 and the medium oil product 239 from last quench stage 230 are combined in surge drum 250.
The combined stream from surge drum 250 is then combined with heavy-oil bottoms product stream 224 from first stage quench 210, and after being heated by indirect heat exchange with product streams 284 and 286 in heat exchangers 226 and 228, is further heated to about 650.degree. F, in heater 260 and transferrred to soaking drum 262 for a soaking residence time of about 1 to about 60 minutes.
Most of the hydrogen transfer, after free radical stabilization in the vapor state, to the product oils takes place in soaking drum 262.
Soaked-liquid stream 263 is then fed to distillation tower 270, after being partially vaporized in fired heater 264.
The distillation tower's oil-bottom-product stream 272, after being cooled in air cooler 280 to about 300.degree. F., is sent via stream 282 to storage.
Practically all of the char that was not removed as sludge in settling drum 220 is contained in heavy oil product 282.
Middle cut 274 from distillation tower 270 provides the quench fluid-spent capping agent mixture, which is sent to the hydrotreating section 300.
A light oil product obtained as overhead distillate stream 276 is sent to storage via conduit 296.
Noncondensables in stream 278 from overhead stream 276 are combined with the gases separated in separator drum 240 and sent to gas compression section 310.
Water stream 279 condensed out of distillation tower 270 overhead is sent to the phenol recovery section 320.
Foul water stream 244 recovered from this quench and oil recovery section is treated to remove and recover phenols. The treated water is steam stripped to remove acid gases and ammonia. Stripped water is sent to a water treatment section for purification prior to discharge. Sour water from hydrotreatring is also steam stripped and sent to the water treatment section. Gases containing ammonia are treated to recover anhydrous ammonia and the residual gas is combined with other H.sub.2 S-bearing gases and sent to a sulfur recovery section where elemental sulfur is produced.
This process, therefore, uses a quench fluid with a capping agent to stabilize the liquid vapors from the pyrolysis reactor in the vapor state. Additional hydrogen transfer to liquid product occurs by in-sity transfer in the soaking drum. The capping agent in this commercial embodiment contains compounds with carbon numbers ranging from 6 to 16 and with normal boiling points ranging from 358.degree. to 670.degree. F. One compound for example is dihydrophenanthrene.
In one embodiment the capping agent properties are:
Example
The following example demonstrates the value of this invention.
These tests demonstrated that utilization of a capping agent as a quenching agent for pyrolysis product vapors reduces the average molecular weight of the tar liquid product.
The pyrolsis unit shown in FIG. 4 comprises a fluidized char feeder 80 for feeding char through char feed valve 82 to transfer line char heater 84. The external wall of char heater 84 was heated by electrical heating elements. Char feeder 80 was also used as a receiver vessel for product char.
Wyoming subbituminous coal was fed to the pyrolysis reactor 86 at a rate of about 3 lb/hr using fluidized coal feeder 88. Nitrogen, as a transport gas, was fed to the coal feeder at a flow rate of about 0.3 SCFM (standard cubic feet per minute) to fluidize and transport the coal through coal transport line 90 and into pyrolysis reactor 86. Additional transport gas was introduced into char heater 84 at a flow rate of 2.7 SCFM to convey the hot char into the pyrolysis reactor. The external wall of the reactor was heated by electrical heating elements, which in conjunction with the heated char causes the coal to be heated to about 1200.degree. F. thereby effecting pyrolysis of the coal. A product stream comprising hydrocarbon vapors and solids, was treated in series connected primary centrifugal separator 92 and secondary centrifugal separator 94 to separate solids from gases. Separated solids from the primary separator dropped into a stand leg 96 and then into char feeder 80. Solids separated by secondary separator 94 were collected in char drum 98.
Hot gases from the secondary separator were conveyed to quench scrubber 100 and contacted therein with tetrahydronaphthalene as a capping agent and quench fluid to stabilize the pyrolytic vapors in the vapor phase. At least a portion of the pyrolytic product vapors were condensed as liquid product and collected along with the quench liquid in primary quench tank 102. Hot pyrolytic product vapors which were not condensed in quench scrubber 100 and uncondensed gas, containing CH.sub.4, CO.sub.2, H.sub.2, C.sub.2 H.sub.4, and CO flowed from primary quench tank 102 to secondary quench scrubber 104 where it was contacted with more quench fluid. Condensate and quench fluid were collected in secondary quench tank 106. Quench liquid flow rates to the primary and secondary scrubbers were maintained at about 10 gph (gallons per hour) each. The quench fluid temperature was about 30.degree. to about 40.degree. F. Liquid was pumped out of the bottom of secondary quench tank 106 by pump 108, then through heat exchanger 110, and then into both the primary and secondary quench scrubbers.
The cooled gases and any condensate in the form of an aerosol passed from the top of secondary quench tank 106 to electrostatic precipitator 112 which separated and recovered the aerosols. The remaining cooled gas at a temperature of about 50.degree. to about 80.degree. F. was then passed through activated charcoal bed 114 to remove remaining trace amounts of light hydrocarbons. The cooled gas then passed from activated charcoal bed 114 through the vent line 116, flow meter 118, drierite bed 119 for removal of water vapor, and lastly through flow meter 120 before being vented to the atmosphere.
A second test was conducted using a bench scale unit similar to the bench scale unit of FIG. 4. In the second test, the vapors from the pyrolysis unit described in U.S. Pat. No. 4,162,959, were cooled and condensed using indirect cooling, i.e., heat exchangers, rather than by being cooled directly with a quench liquid comprising a capping agent as in the first described test.
Gel permeation chromatograms of the liquid product of the first and second tests are shown in FIG. 5. FIG. 5 shows the molecular weight profile of the two liquid products. Curve A is a curve of the molecular weight distribution of the liquid produced in the second test where the pyrolysis vapors were cooled indirectly without a capping agent. Curve B is a curve of molecular weight distribution of the liquid produced in the first test where the pyrolysis vapors were cooled directly using the capping agent, tetrahydronaphthalene.
The gel permeation gas chromatograms of FIG. 5 show that when a pyrolysis vapor is quenched with a capping agent the concentration of high molecular weight species is markedly decreased, while the concentration of lower molecular weight species is markedly increased.
The advantage of this invention is that pyrolytic hydrocarbon liquid product recovered using a quench liquid comprising a capping agent has a much lower average molecular weight than the hydrocarbon liquid product recovered when product vapors are condensed without the use of a capping agent.
This invention can be used with many types of pyrolysis, carbonization or gasification processes such as the Lurgi-Ruhrgas process, the COED process, the TOSCO and TOSCOAL processes, the hydrocarbonization process of Union Carbide (CoalCon), and the hydrocarbonization process of Consul of Scientific and Industrial Research Organization of Australia (CSIRO).
Although this invention has been described in considerable detail with reference to certain embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of this invention as described above and defined in the appended claims.
Industrial Applicability
Condensed stabilized hydrocarbons produced by pyrolysis of solid particulate carbonaceous material can be used as fuels, refinery feedstock, and for the recovery therefrom of chemical values such as phenols, benzenes, toluenes, and xylenes.
Claims
What is claimed is:
1. A continuous process for producing condensed stabilized hydrocarbons from a solid particulate carbonaceous material comprising: (a) heating a solid particulate carbonaceous material in a pyrolysis zone with a solid particulate source of heat to a first temperature between about 900.degree. and about 2000.degree. F. for a period of time between about 0.5 seconds to about 2 hours to produce from said solid carbonaceous material a pyrolysis product comprising particulate product solids and pyrolytic product vapors which comprise hydrocarbons which comprise newly formed volatilized hydrocarbon free radicals, a portion of said hydrocarbons containing larger hydrocarbons, said larger hydrocarbons being all the hydrocarbon vapors in said pyrolytic product vapors containing four or more carbon atoms, a portion of said hydrocarbons comprising a product agent suitable for use as a capping agent either directly or after hydrotreatment of said product agent; (b) separating solids which comprise said particulate product solids and said solid particulate source of heat from a gaseous mixture which comprises said pyrolytic product vapor to form a substantially solids-free gaseous mixture stream; (c) contacting said substantially solids-free gaseous mixture stream with a quench fluid comprising a capping agent suitable for stabilizing said newly formed volatilized hydrocarbon free radicals, under predetermined conditions of temperature and flow rate of capping agent sufficient for substantially simultaneously stabilizing at least a major portion of said newly formed volatilized hydrocarbon free radicals by the transfer of hydrogen from said capping agent to said newly formed volatilized hydrocarbon free radicals, and substantially simultaneously condensing at least a major portion of said larger hydrocarbons, thereby forming a gaseous residue and a liquid mixture comprising condensed stabilized hydrocarbons, a hydrogen depleted capping agent, and said product agent; (d) separating said liquid mixture from said gaseous residue; (e) introducing said separated solids and a gas comprising molecular oxygen into one end of a transfer line combustion zone under conditions sufficient to heat said separated solids to a second temperature between about 925.degree. to about 2100.degree. F., said second temperature being higher than said first temperature, thereby producing heated solids; (f) introducing said heated solids from said transfer line combustion zone into said pyrolysis zone as said solid particulate source of heat; (g) separating said liquid mixture, after separation from said gaseous residue, in a distillation zone into a light oil stream, a medium oil stream, and a heavy oil stream; (h) hydrogenating at least a portion of said medium oil stream thusly separated in said distillation zone to product hydrogenated medium oil comprising a hydrogenated capping agent suitable for stabilizing said newly formed volatilized hydrocarbon free radicals, at least a major portion of said hydrogenated capping agent being produced from said product agent; (i) utilizing said hydrogenated medium oil as at least a major portion of said capping agent contained in said quench fluid used for contacting said substantially solids-free gaseous mixture stream; and (j) recovering said light oil stream and said heavy oil stream at least one of which comprises condensed stabilized hydrocarbons.
2. The process of claim 1 wherein said quench fluid used for contacting said substantially solids-free gaseous mixture stream has a boiling point range between about 350.degree. and about 650.degree. F. for about 90 weight percent of said quench fluid.
3. The process of claim 1 wherein said solid particulate carbonaceous feed material is selected from the group consisting of coal, agglomerative coal, gilsonite, tar sands, oil shale, and the organic portion of solid waste.
4. The process of claim 1 wherein said solid particulate carbonaceous feed material is selected from the group consisting of coal and agglomerative coal.
5. The process of claim 1 wherein the amount of said capping agent contained in said quench fluid used for contacting said substantially solids-free gaseous mixture stream is sufficient to terminate substantially all of said newly formed volatilized hydrocarbon free radicals.
6. The process of claim 1 wherein the amount of said capping agent contained in said quench fluid used for contacting said substantially solids-free gaseous mixture stream is sufficient to terminate 95 percent of said newly formed volatilized hydrocarbon free radicals.
7. The process of claim 1 wherein the amount of said capping agent contained in said quench fluid used for contacting said substantially solids-free gaseous mixture stream is sufficient to terminate 99 percent of said newly formed volatilized hydrocarbon free radicals.
8. The process of claim 1 wherein at least a portion of said capping agent is selected from the group consisting of tetrahydronaphthalene, decahydronaphthalene, dihydronaphthalene, hydrogenated phenanthrenes, hydrogenated anthracenes, alkyl substituted tetrahydronaphthalene, alkyl substituted decahydronaphthalene, alkyl substituted dihydronaphthalene, alkyl substituted hydrogenated phenanthrenes, alkyl substituted hydrogenated anthracenes, naphthalene, anthracene, creosote oil, thiols, phenols, amines, and mixtures thereof.
9. The process of claim 1 further comprising adding at least a portion of said tar acids to said quench fluid.
10. The process of claim 1 further comprising separating at least a portion of said phenols from said tar acids and adding at least a portion of said phenols thusly separated to said quench fluid.
11. The process of claim 1 wherein said contacting of said substantially solids-free gaseous mixture stream is in a quench system comprising a first stage and a second stage, said second stage having a higher contacting efficiency than said first stage.
12. The process of claim 1, 9 or 10 wherein said pyrolysis zone comprises a double-shaft mixing zone having two shafts which rotate in the same sense, wherein said pyrolytic product vapors and a solid particulate residue are produced in said mixing zone, wherein said solid particulate residue is introduced into a degasification zone wherein additional gaseous product is produced therefrom and a solid particulate residue is formed, and wherein said separated solids comprise said solid particulate residue.
13. A continuous process for producing condensed stabilized hydrocarbons from a solid particulate carbonaceous material comprising: (a) pyrolyzing a solid particulate carbonaceous feed material under conditions of time and elevated temperature sufficient to produce therefrom a pyrolysis product comprising particulate product solids and pyrolytic product vapors which comprise hydrocarbons which comprise newly formed volatilized hydrocarbon free radicals, a portion of said hydrocarbons containing larger hydrocarbons, said larger hydrocarbons being all the hydrocarbon vapors in said pyrolytic product vapors containing four or more carbon atoms, a portion of said hydrocarbons comprising a product agent suitable for use as a capping agent either directly or after hydrotreatment of said product agent; (b) separating solids which comprise said particulate product solids from a gaseous mixture which comprises said pyrolytic product vapor to form a substantially solids-free gaseous mixture stream; (c) contacting said substantially solids-free gaseous mixture stream with a quench fluid comprising a capping agent suitable for stabilizing said newly formed volatilized hydrocarbon free radicals, under predetermined conditions of temperature and flow rate of capping agent sufficient for substantially simultaneously stabilizing at least a major portion of said newly formed volatilized hydrocarbon free radicals by the transfer of hydrogen from said capping agent to said newly formed volatilized hydrocarbon free radicals, and substantially simultaneoulsy condensing at least a major portion of said larger hydrocarbons, thereby forming a gaseous residue and a liquid mixture comprising condensed stabilized hydrocarbons, a hydrogen depleted capping agent, and said product agent; (d) separating said liquid mixture after separation from said gaseous residue into at least (i) light aromatics comprising liquids of from about four to about eight carbon atoms per molecule, (ii) tar bases comprising amines, (iii) tar acids comprising phenols, and (iv) neutral tar liquids comprising at least a major portion of said hydrogen depleted capping agent, said product agent, and heavy tars of said liquid mixture; (e) hydrogenating at least a portion of said neutral tar liquids thusly separated to produce hydrogenated neutral tar liquids comprising a hydrogenated capping agent suitable for stabilizing said newly formed volatilized hydrocarbon free radicals, and hydrogenated heavy tars comprising at least a portion of said condensed stabilized hydrocarbons, at least a major portion of said hydrogenated capping agent being produced from said product agent; (f) separating said hydrogenated neutral tar liquids into at least a recycle stream comprising at least a major portion of said hydrogenated capping agent, and a heavy tar stream comprising at least a major portion of said hydrogenated heavy tars; (g) utilizing at least a portion of said recycle stream as at least a major portion of said capping agent contained in said quench fluid used for contacting said substantially solids-free gaseous mixture stream; and (h) recovering at least a portion of said light aromatics, said tar bases, said tar acids and said heavy tar stream.
14. The process of claim 13 wherein said quench fluid used for contacting said substantially solids-free gaseous mixture stream has a boiling point range between about 350.degree. and about 650.degree. F. for about 90 weight percent of said quench fluid.
15. The process of claim 13 wherein said solid particulate carbonaceous feed material is selected from the group consisting of coal, agglomerative coal, gilsonite, tar sands, oil shale, and the organic portion of solid waste.
16. The process of claim 13 wherein the amount of said capping agent contained in said quench fluid used for contacting said substantially solids-free gaseous mixture stream is sufficient to terminate substantially all of said newly formed volatilized hydrocarbon free radicals.
17. The process of claim 13 wherein the amount of said capping agent contained in said quench fluid used for contacting said substantially solids-free gaseous mixture stream is sufficient to terminate 95 percent of said newly formed volatilized hydrocarbon free radicals.
18. The process of claim 13 wherein the amount of said capping agent contained in said quench fluid used for contacting said substantially solids-free gaseous mixture stream is sufficient to terminate 99 percent of said newly formed volatilized hydrocarbon free radicals.
19. The process of claim 13 further comprising adding at least a portion of said tar acids to said quench fluid.
20. The process of claim 13 further comprising separating at least a portion of said phenols from said tar acids and adding at least a portion of said phenols thusly separated to said quench fluid.
21. The process of claim 13 wherein said contacting of said substantially solids-free gaseous mixture stream is in a quench system comprising a first stage and a second stage, said second stage having a higher contacting efficiency than said first stage.