CA1100068A - Coal conversion using rocket engine type injector device - Google Patents
Coal conversion using rocket engine type injector deviceInfo
- Publication number
- CA1100068A CA1100068A CA277,052A CA277052A CA1100068A CA 1100068 A CA1100068 A CA 1100068A CA 277052 A CA277052 A CA 277052A CA 1100068 A CA1100068 A CA 1100068A
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- CA
- Canada
- Prior art keywords
- reaction
- hydrogen
- coal
- carbonaceous material
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/003—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor in a downward flow
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Abstract of the Disclosure Disclosure is made of a method and apparatus for reacting carbonaceousmaterial such as pulverized coal with heated hydrogen to form hydrocarbon gases and liquids suitable for conversion to fuels wherein the reaction involves injection of pulverized coal entrained in a minimum amount of gas and mixing theentrained coal at ambient temperature with a separate source of heated hydrogen.The heated hydrogen and entrained coal are injected through a rocket engine typeinjector device. The coal particles are reacted with hydrogen in a reaction chamber downstream of the injector. The products of reaction are rapidly quenched as they exit the reacting chamber and are subsequently collected.
Description
1100(~68 ` Background of the Invention 1. Field of the Invention This invention relates to the field of coal conversion to form hydrocarbon gases and liquids suitable for conversion to fuels.
More particularly, this invention relates to reacting carbonaceous material such as pulverized coal with heated hydrogen to form hydrocarbon gases and liquids suitable for conversion to fuels or for use as a chemical feedstock.
DescriPtion of the Prior Art The problem is to react coal directly with hydrogen in such a way as to maximize the yield of liquid products. A
number of researchers have shown that at the beginning of coal pyrolysis a transient period exists for a few tenths of a second where the coal is highly reactive toward hydrogen. If excess hydrogen is not available during this period, some of the free-radical pyrolytic fragments will strip molecular hydrogen from the aromatic groups while other fragments will polymerize to form unreactive char. The overall effect is a limited yield of liquid and gaseous hydrocarbons, and a large yield of char. If instead, excess hydrogen is present during the critical transient period, many more hydrogenated fragments that are amenable to still further hydrogenation are produced. The ove~all effect of pyrolysis in hydrogen is a much larger yield of li~uids and gases, and a lower char yield.
It is generally well known the conversion of coal to liquid or gaseous fuels is achieved by the addition of hydrogen.
This may be accomplished by the direct contact of coal with hydrogen as in the ~ureau of Mines Hydrane proces.s to produce methane; by a cata~yzed liquid-phase reaction with hydrogen to
More particularly, this invention relates to reacting carbonaceous material such as pulverized coal with heated hydrogen to form hydrocarbon gases and liquids suitable for conversion to fuels or for use as a chemical feedstock.
DescriPtion of the Prior Art The problem is to react coal directly with hydrogen in such a way as to maximize the yield of liquid products. A
number of researchers have shown that at the beginning of coal pyrolysis a transient period exists for a few tenths of a second where the coal is highly reactive toward hydrogen. If excess hydrogen is not available during this period, some of the free-radical pyrolytic fragments will strip molecular hydrogen from the aromatic groups while other fragments will polymerize to form unreactive char. The overall effect is a limited yield of liquid and gaseous hydrocarbons, and a large yield of char. If instead, excess hydrogen is present during the critical transient period, many more hydrogenated fragments that are amenable to still further hydrogenation are produced. The ove~all effect of pyrolysis in hydrogen is a much larger yield of li~uids and gases, and a lower char yield.
It is generally well known the conversion of coal to liquid or gaseous fuels is achieved by the addition of hydrogen.
This may be accomplished by the direct contact of coal with hydrogen as in the ~ureau of Mines Hydrane proces.s to produce methane; by a cata~yzed liquid-phase reaction with hydrogen to
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1~0~
produce liquid products as in the Synthoil process; or in-directly by reacting coal with steam. Many different processes have been proposed and are under development. These schemes vary in the method of contacting coal and hydrogen or steam, and in the type of coal feed utilized. A solid such as coal can be contacted with a gas in three basically different ways.
In the first, gas is forced through a fixed or slowly moving bed of solid.
- 2a -11~68 76R18 Another method of contact is by use of a fluidized bed. With sufficiently small solid particles and a sufficiently high gas velocity in vertical upward flow the air dynamic drag forces on the individual particles begin to approach the gravitational forces and the par~icles themselves begin to move about.
The bulk properties of the gas solid mixture then become those of a fluid.
Because of the improved heat and mass transfer characteristics in a fluidi2ed bed as opposed to a fixed bed, most coal gasification processes now are the fluidized bed variety. Yet another basic category of gas solid contacting is entrained f1OW as in the Bigas process. In this regime gas velocities are high enough and particle sizes low enough that the solid particles are carried along with the gas stream. An advantage of the entrained flow processes is the ability to utilize any grade or class of coal. Caking coals will agglo-merate causing difficult problems when fed to fluidized or fixed bed systems.
Further advantages of entrained flow with respect togas production include operation at high temperatures so that tar production is kept to a minimum, adaptability to slagging conditions and high energy production per unit volume. The present invention utilizes this type of entrained flow coal con-version process. Heretofore no large scale attempt to use this approach for direct hydrogenation of coal has been made.
A patent issued to W. C Schroeder, No. 3,030,297, describes a process which comprises heating dry particles of coal entrained in a heated stream of hydrogen at total pressure of about 500-6000 psig from a temperature below about 300C to a reaction temperature in the range of from about 600C to about 1000C. Two minutes are required to heat the coal particles to about 600C and then two to twenty seconds time at temperature for hydrogenation.
The slow heat-up results from the main hydrogen stream being utilized to carry the coal into the reactor. The products of reaction are then cooled below reaction temperature to provide a product comprised of light oil, pre-dominantly aromatic in nature, and hydrocarbon gases, primarily methaneh, ethane, and carbon monoxide.
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This process i5 disadvantaged in that the coal particles entrained in the hydrogen are preheated prior to introduction into a heating chamber thus the reaction process is started upstream of the reaction chamber which will cause agglomeration and plugging within the conduit carrying the entrained coal. The present invention overcomes this agglomeration problem by pro-viding two sources of gas, one source of gas such as hydrogen brings entrained coal into an injector at ambient temperature, and a separate source provides heated hydrogen to an injector which contacts the entrained dense phase coal downstream of an injector within a reaction zone thereby starting the hydro-genation process within the reaction chamber and not upstream of the chamber.
Schroeder is further disadvantaged in that he attempts to heat the en-trained coal particles through a tube wall. At the mass throughputs specified in the example, it is doubtful that enough heat could be transferred through the tube wall in a reasonable length to sufficiently heat the coal and, at the same time, use the tube wall to contain the system pressure. This type of reactor does not scale to the necessary larger diameters for commercial coal conversion reasonably because the heat transfer surface-to-volume ratio decreases rapidly with an lncrease in size~
Schroeder is still further disadvantaged in that the mixing and the heating takes place in minutes and seconds whereas the present invention ac-complishes the hydrogenation of the entrained coal in milliseconds and if a uniform flow pattern can be maintained (to avoid back mixing which will cause longer residence time and gas production instead of liquids) and if the coal can be dispersed uniformly even on a microscopic scale (to minimize gas dif-fusion limitations), and if rapid and efficient quenching can be achieved (Schroeder carries the hydrogenated products through a conduit towards a separate quenching chamber whereas the present invention ~uenches the re-AC ~
~ products immediately upon exiting the end of the reaction chamber), llOQ~8 then it should be possible to hydrogenate d substantial fraction of the coal to liquid products. The utilization of rocket engine type injector principles in a coal liquefaction plant as described in the present invention is believed to be unique and is one of the principal objects of the invention.
Another patent issued to Schroeder et al, 3,152,063, teaches a process which comprises dispersing pulverized and catalyzed coal, in the absence of a pasting oil, in hydrogen under a pressure of about 500 to 4000 psig, react-ing the mixture of coal and hydrogen at a temperature in the range of about 450 to 600C, for a gas residence time of less than about 200 seconds, cool-ing the reaction products and recovering liquid and gas hydrocarbon products therefrom.
Schroeder teaches passing of catalyzed coal and hydrogen into a two-stage reactor that consists of a multiplicity of parallel tubes axially extending within the reactor. The tubes are heated by a source of hot gas to start the reaction within the tubes. Vaporized oil and gas products are drawn off as wel1 as unused hydrogen to a cooling device. The residual heavier oil and tar products are collected in the bottom of the reactor and a source of hydrogen may then be brought in to further hydrogenate these heavier products.
This invention is disadvantaged in that the pulverized coal must be passed through a catalyzing process, sent through a dryer and grinder and finally separated into minute particles by passing the coal through a screen-ing process. The present invention utilizes finely-divided pulverized coal directly without the foregoing pre-treatment process.
Schroeder's invention is further disadvantaged in that it also utilizes the carrier hydrogen in the coal passages as the main source of hydrogen.
The heat-up process then takes considerable time as compared to the present invention in that the carrier gas cannot be pre-heated prior to entering into a reaction charnber.
l~OQ~68 Additionally, the invention is disadvantaged in that the coal particles are heated through a tube or a series of tubes thereby seriously affecting the ability to scale-up the process to commercial production proportions. A
comrnercial unit would necessarily have to process in the neighborhood of 1000 tons/hour. The Schroeder patents teach a mass throuyhput Ot approximately 145 lbs/hr ft.2, a very low process rate. For example, in a commercial re-actor using the Schroeder process, each reactor being 15 feet in diameter, 82 reactors would be needed to process 1000 tons/hr of coal. In addition, be-cause of the small surface-to-volume ratio the reactors would have to be on the order of one hundred feet long to transfer sufficient heat through the wall transporting the entrained coal particles. One of the most important advantages of the high throughput of dense phase coal particles through the reactor of the present invention (33,000 lbs/hr ft.2) is that it is scaleable to a commercial size. Two reactors utilizing the principles set forth in the following specificaticns, 6-feet in diameter would process 1000 tons/hr of coal. The heat is supp1ied directly in the hydrogen so that vessel surface-to-volume ratio is not a limiting factor.
Although the chemistry of coal pyrolysis and hydrogenation has been ap-parent for some time, no well-developed reactor exists which efficiently utilizes the rapid-reaction regime. Some of the basic reasons for this appear to be a lack of adequate gas/solid injection and mixing technology, difficulty in meeting chemistry and residence time requirements, and agglomeration and plugging of the reactor. Hydrogenation of raw bituminous coal usually re-sults in agglomeration, so that typical fluidized bed or moving bed reactors cannot be used as heretofore described. In addition, the requirement of short residence time (less than 1 sec) necessarily restricts the reactor to an entrained flow type. By maintaining rapid mixing, heat-up, and reaction of the coal near the point of injection and hot reactor walls, the agglomera-tion problem can be avoided. The uniform and precise mixing of extremely l~O~Q68 large feed streams in time of a few milliseconds is the special accomplish-ment of large rocket engine injectors and one of the principal objects of the present invention.
Summary of the Invention It is an object of this invention to convert coal particles entrained in a gas in a dense phase to hydrocarbon liquids and gases by hydrogenating the coal particles.
More particularly, it is an object of this invention to utilize rocket engine injection and mixing techniques in an entrained flow reactor to rapidly mix and react a separate stream of heated hydrogen with a dense phase stream of pulverized coal at ambient temperature to produce liquid and gaseous hydro-carbons.
It is yet another object of this invention to build and operate a high-temperature, coal liquefaction reactor which minimizes secondary oil and tar decomposition reactions by optimum control of gas-phase residence time, and prevents reactor plugging from coal agglomeration by very rapid dispersion and reaction of the coal while maintalning the internal reactor wall at high temperature.
A coal liquefaction method and apparatus to produce hydrocarbon liquids and gases by hydrogenating pulverized coal with hydrogen by flowing pulverized coal particles entrained in a gas such as hydrogen in a dense phase in a coal flow conduit at ambient temperature toward an injector adjacent to a reaction chamber and a heating means is provided for heating a separate source of hydrogen. The dense phase pulverized coal is injected through the injector into the reaction chamber followed by injecting the heated separate source of hydrygen gas through the injector into the reaction chamber and means to separate the ambient temperature dense phase coal particles and the heated hydrogen prior to injection of the dense phase coal and the heated hydrogen llOQ~68 into the reaction chamber to prevent premature hydrogenation of the pulverized coal. A quenching means is provided adjacent the reaction chamber to rapidly arrest the hydrogenation process at a predetermined ti~e period when the re-action products exit the reaction chamber, and a collecting means is provided for collecting the reaction products.
The coal is fed to the reactor at nearly its bulk density so that the quantity of entrained gas is minimized, and the heated hydrogen brought in separately provides the heat source needed to raise the coal rapidly to re-action temperatures.
An entrained flow reactor using rocket engine injection and mixing tech-niques to react a stream of hot hydrogen with a stream of pulverized coal was designed, built, and operated. As an example only, typical reactor operating conditions were 1000 psig, 1100F, ~150 milliseconds residence time, and 0.36 lb H2/lb coal. Approximately 19% of the coal carbon was converted to a synthetic crude oil having a boiling range of 200-350C and a heating value of 15,800 8TU/lb, 9% to gas containing methane, ethane, and carbon oxides, and 3~,' to organic compounds in the quench water. The coal throughput rate WdS approximately 33,000 lbs/hr ft2 reactor cross section or 11,000 lbs/hr ft3 reactor volume. The products of reaction were rapidly quenched to 220F
in a distance of 1 ft using large flowrates of water through spray nozzles.
Thus, an advantage over the prior art is the use of rocket engine in-jection and mixing techniques to rapidly mix and react a stream of entrained coal with hot hydrogen to produce liquid and gaseous hydrocarbons.
Another advantage of the present invention over the prior art is the minimization of secondary oil and tar decomposition reaction by aptimum con-trol of gas-phase residence time by very rapid coal partic1e dispersion and reaction of the coal while maintaining the internal reactor wall at high temperature.
00~68 76Rl8 Yet another advantage over the prior art is the prevention of coal ag-glomeration upstream of the reaction chamber by transporting the entrained dense phase coal in a gas at ambient temperature.
Still another advantage over the prior art is the ability to use a carrier gas other than hydrogen for transporting the coal partic1es in a dense phase to the injector thus minimizing explosion hazards in the coal feed sys-tem due to hydrogcn leakage to the atmosphere from moving mechanical parts such as valves buildup of explosive mixtures of hydrogen and air in the coal containing vessels and loss of hydrogen through venting when lock hoppers are used.
A still further advantage over the prior art is the immediate quenching of the hydrogenated coal particles as they exit the end of the reaction cham-ber thereby maximizing the product yield of liquid and gaseous hydrocarbons Another advantage over the prior art is the direct hydrogenation of coal particles in a reacticn chamber as opposed to heating the exterior wall of a tube surrounding the hydrogen and coal particles contained within the tube.
The above-noted objects and advantages of the present invention will be more fully understood upon the study of the following description in con-junction with the detailed drawings.
Brief Description of the Drawing FIG. 1 is a fl~lsheet schematic of the coal liquefaction apparatus;
FIG. 2 is a detailed cross-section of the principal elements of the in-vention;
FIG. 3 is an enlarged partially cross-sectioned view of the hot hydrogen and t~e coal flo~ coupling upstream ~ the injector;
FIG. 4 is an enlarged cross-section of the concentric injector;
FIG. 5 is a view of the heater coil element and electrical coupling ad-jacent the reaction chamber and coal flow tubes;
FIG. 6 is an alternative view of the reaction chamber illustrating di-~be verging walls from the injector fdce to the exit plane of the reactor~;
l~OOQ68 FIG. 7 is an alternative view of an injector illustrating a four-on-one injection pattern; and FIG. 8 is a view taken along lines 8-8 of FIG. 7.
Description of the Preferred Embodiments Referring now FIG. 1, a coal liquefaction unit generally designated as 10 consists of a nitrogen supply system generally designated as 12 that serves as a purge supply source as well as a pressurizing source for a quench water tank system generally designated as 14.
A high pressure coal feeder generally designated as 16 comprises a cylindrical vessel 18 suspended from a load cell 20.
The coal feeder 16 is charged by flowing coal from a low pressure conical tank 22 through a tube 24. To charge the high pressure coal feeder 16, the conical tan~ 22 is pressurized to about 55 psig with nitrogen from supply system 12, a ball valve 26 at the conical tank bottom is quickly opened wide, and the coal flows in a dense phase through the tu~e 24 to the coal feeder 16.
The excess nitrogen vents out of the coal feeder through a dust filter 28. After the coal feeder 16 is charged, the tu~e 24 is disconnected and capped as shown at 27, and the dust filter 28 is disconnected and the pressure relief line 32 connected in its place as shown in FIG. 1. A hopper hydrogen feed line 30 from a hydrogen source 48 or inert gas from an inert gas source 50 is opened for subsequent operation. Load cell 20 readings before and after charging indicate the quantity of coal in the feeder. The bottom 19 of the coal feeder 16 is conically shaped with a 30 included angle to provide smooth discharging of coal. Coal is fed to the reactor assembly by opening a ball valve 34 and flowing in a dense phase through a feed line 36. The hydrogen or inert gas pressure in the coal feeder is maintained, for example, about 60 to 70 psi higher than in the reactor assembly generally designated as 38 so as to provide the driving force for feeding the coal to the llOOQ6~ ' reactor assembly 38. The weight of hydrogen carried in the coal as a percent of the coal flowrate is about 0.5% when the reaction chamber pressure is 1000 psig. In the case of inert transport gas, the weight percent transport gas will vary according to gas density. The flowrate of coal is about .15 pound per second and the flowrate of hydrogen is about .0075 pound per second where hydrogen is used as the carrier gas.
Load cell readings are printed during a test so that the coal feed rate can be continuously monitored (not shown). When the 10feeder ball valve 34 is in a closed position, nitrogen from nitrogen supply system 12 flowing through a line 4~ is purged through the feed line 36 to keep it clear and to prevent the coal side of the injector ~FIG. 4) from overheating. The portion of the coal feed line passing through a top flange 37 and making up part of an injector assembly 92 ~FIG. 3) is typically fabricated from stainless steel. Details of the r injector assembly 92 are shown in FIGS. 3 and 4.
Pressurized water for a quench system generally designated as 42 is supplied by, for example, a 150 gallon pressurized 20quench water tank system 14. The flow of water can ~e accurately measured continuously during tests and is varied by changing the pressure on the water tank from nitrogen supply system 12.
AccuratP flow control is possible because the pressure drop across spray nozzles 106 CFIG. 2) is normally a~out 180 psi. In addition, there is about another 130 psi in pressure drop ahead of the spray nozzles.
It would be obvious to use fluid other than water to quench the hydro-genated products as they exit the reaction chamber such as steam, oil or cold gas ~hydrogen).
There are three gas supply systems, one for nitrogen, one for hydrogen and one for an inert gas The nitrogen supply system 12 supplies the nitrogen bleed to a preheater assembly 39 through a conduit 31 and reactor pressure shells 53, and for 13`00Q68 purging the coal feed line through line 40. The flows are controlled by using sonic nozzles (not shown) and varying the pressure upstream of the nozzles to obtain various flowrates.
The hydrogen source 48 supplies the high pressure coal feeder 16 and the preheater assembly 39. The hydrogen flow to the coal feeder 16 is on demand and is only measured with an orifice (now shown). The gas supplied to the coal feeder 16 need not be hydrogen from hydrogen source 48 but may be an inert gas such as nitrogen, carbon dioxide or mixture thereof from inert gas source 50. The hydrogen flow to the preheater assembly 39 is controlled by a sonic nozzle an-d upstream pressure regulator (not shown). The hydrogen system may be set up so that nitrogen can be used in place of hydrogen for purging and leak checks(not shown).
Product gas from a spherical catch tank 52 flows through a conduit 54 to a liquid separator tank 56 and then through a back pressure regulator system. After the product gas is let down in pressure, the flowrate is measured using an orifice and then the gas goes to a burn~tack 58 through a tu~e 60. A
gas sample bottle system generally designated as 62 is connected to the high pressure side through a line 64 of the gas sample bottle system 62 and is vented back into the system t~rough a line 66 to burnstack 58. The sample ~ottle valves 68 are automated to open in sequence a~out every 30 to 60 seconds during a test.
The liquia product letdown is controlled by a tank liquid level control system generally designated as 70 that actuates an on-o~f valve 72. The flow out of catch tank 52 is regulated ~y a linear plug valve 74. The linear plug valve 74 is basically a variable orifice that is used to prevent the liquid from surging out of catch tank 52 so fast that pressure control in the reactor assembly 38 is upset. A header of three valves 76 is used to select which of drums 78 is to receive the liquid product.
A more detailed drawing of the hydrogen preheater assembly generally designated as 39 is presented in FIGS. 2 and 5 and of the reactor assembly generally designated as 38 is presented in FIG. 2. The hydrogen preheater assembly is contained within a pressure shell 41 and the preheater coil 43 is a stainless steel tube through which an electric current is passed as hydrogen passes through it. The preheater coil 43 is thin walled and small in diameter at end 45 and heavy walled and larger in diameter at end 47. As the hydrogen enters end 45 it is relatively cool and as it progresses down through helical-shaped preheater coil 43 it heats up and expands. The variable I.D. and wall thickness of the coil compensates for this expansion of hydrogen. Seven motor-generator sets [not shown) supply about 600-800 amps to copper stud conductors 77 and 79 connected to plate 80 through the wall 49 with a power input up to 150 Kw. The heat transfer from the resistively-heated wall 49 to the pressurized hydrogen entering end 45 o preheater coil 43 through hydrogen feed line 30 is excellent and has demonstrated efficiencies of about 99%. Since the tube wall strength is very low at the heater operating temperatures (the wall is about 200~F hotter than the hydrogen at the exit 47 of the tube 43), the preheater coil 43 is contained in a pressure shell 41 made from, for example, carbon-steel pipe and 600 lb flanges 82 and 84. The void space 86 in the pressure shell 41 is stuffed with, for example, a very low thermal conductivity insulation 87 such as ~ibrefrax, a product of Carborundum Corporation, Refractories and Insulation Division, Fibrefrax Branch,Niagara Falls, New York, and is purged continuously with about 5 SCFM of nitrogen at about 1000 psig.
The copper stud conductors 77 and 7g, plate 80, and inlet end 45 of the preheater coil 43 are electrically isolated from the pressure shell 41 and serve as the positive connection to the motor 1100(~68 generator sets, The ground connection is made to another end 51 of the pressure shell 41 through the blind stainless steel flange 88 that is sandwiched between the two carbon steel, weld-neck flanges 84 and 85. A thermocouple 90 is immersed in the gas exiting the preheater assembly 39, and a pressure transducer (not shown) is connected to a similar port in the flange.
In a similar fashion, referring to FIG. 2, the reactor tube 98 and injector assembly generally designated as 92 are enclosed in a pressure shell 53 so that the hot reactor tube walls 94 experience very little stress while at high temperature.
The reactor tube is supported by the insulation 87 and slip fits through a hole in the insulation support plate 96 so that thermal elongation of the reactor tube 98 is allowed. The preheater assembly 39 is connected to the in~ector assembly 92 via a stainless steel coiled tube 100. This tube is coiled so that it can thermally elongate without applying a force against the injector assembly 92, possibly bowing the reactor tube 98. The reactor tube 98 and injector assem~ly 92 can easily be removed from the pressure shell 53 by removing the top flange 37 and a small amount of insulation 87. Several bosse~ 102 along the side of the pressure shell 53 permit thermocouple measurements along the reactor outside wall, and one directly inside the bottom of the reactor tube 98 near exit plane 99.
The quench zone lQ4 consists, for example, o~ 3 rows of 4 full-cone spray nozzIes lQ6 that screw into the quench zone pipe wall 108 from the outside. As the reaction products exit the reactor tube 98, they are quenched immediately with water sprays supplying water at about 3 to 6 gpm. Enough spray water is used to reduce the product temperature to about 200 ~F.
The li~uid, gas, and solids are forced down into spherical catch tank 52 (FIG. 1~ where the gas separates and exits. The iioo~68 liquid level control system 70 (FIG. 1) is used to maintain a liquid level in the spherical catch tank 52 and to let down the slurry product into drums 78 ~FIG. 1). Vent line 71 connects to the liquid level control system 70.
FIGS. 3 and 4 illustrate in more detail the injector assembly 92 and reactor tube 98 combination wherein a stream of hot (1500-2000F) hydrogen is reacted with a stream of pulverized coal. The injector assembly generally designated as 92, for example, consists of a housing body 110 that is separable from a coal feed line assembly 112 and the reactor tube 98 by a pair of, for example, AN type nuts 114 and 116.
The coal feed line assembly 112 consists of 3 tubes, an outer shell tube 130, an insulation tube 118, and a post tube 120.
The post tube 120 is 3/8 inch O.D. (Dimension "D" FIG. 4) x 0.083 inch wall, 321 stainless steel. A 0.55 inch length of end 121 of the post tube 120 is machined to form end 121 to 0.254 inch O.D. (Dimension "I" FIG. 4) x 0.020 inch wall. The entire injector assembly 92 is contained within the pre~sure shell 53 (FIG. 2). The pos* tube 120 extends through top flange 37 via a packing gland fitting such as a 3/8 inch Conax fitting 105 made by Conax Corporation of Buffalo, New York, and is coupled with coal feed line 36 outside of the pressure shell 53. End 121 of the post tube 120 extends concentrically within a separate cone 122 that is connected to housing body 110 by AN nut 116. An annulus 124 (FIG 4) is defined between inner wall 123 of cone 122 and outer surface 125 of end 121 of post tube 120. Annulus 124 is 0.350 inch O.D. with a gap of 0.048 inches (Dimension "G" FIG. 4) to the outer surface 125 of end 121 of the post tube 120. End 121 is recessed 0.212 inch (Dimension "F"). Three wire spacers 117 are brazed to end 121 to center the post tube 120 and end 121 in the annulus 124.
The post tube 120 is supported as it passes through a plate 115 by a 3/8 inch Conax fitting 135 that is screwed into plate 115.
110~6~ ' The insulation tube 118 is 1 inch O.D. x .049 inch wall, 321 stainless steel and terminates at end 119 in a cone that diverges toward but is not affixed to the outer wall of the post tube 120 near end 121. End 113 of tube 118 is affixed to plate 115. An annulus 126 is defined by an outer surface 127 of tube 120 and an inner surface 128 of tube 118. The annulus 126 is filled with insulation material 87. The outer shell tube 130 is a structural member that houses concentric tubes 118 and 120 and connects at a first end 132 to plate 115 and at the other end 134 to housing body 110 by nut 114. Tube 130 is 1.5 inch O.D. x .049 inch wall, 321 stainless steel. An annulus 136 is defined by an outer surface 138 of tube 118 and an inner surface 140 of housing body 110. The annulus 136 serves to direct a hot hydrogen exterior port 111 toward annulus 124 and out injector assembly 92 (FIG. 4). An annulus 131 is defined by outer surface 138 of tube 118 and inner surface 129 of tube 130 and is filled with insulation 87 that is kept from falling in annulus 136 by a sleeve 133. The reactor tube 98 (FIG. 3) is 1.5 inch O.D. x .049 inch wall (Dlmension "B'~, 321 stainless steel tube, is 3 feet long (,Dimension "A"), and i$ connected to the housing body 110 by nut 116. The overall injector assembly 92 is about 1 ft long (Dimension "C").
In operation, the coal liquefaction plant functions in the following manner: A pulverized bituminous coal such as Kentucky hvAb may be utilized. Other types of pulverized coal such as lignite and sub-bituminous may also be used. The coal is typically 70% less than 74 microns in size ~200 mesh coal) and is fed into high pressure coal feeder 16. The average coal particle size is 40 to 50 microns. A quarter inch line approxi-mately 20 feet long directs dense phase coal from valve 34 into post tube 120 outside of top flange 37 towards the injector assembly 92. The pressure shells 41 and 53 are pressurized 1~0~68 with nitrogen to approximately 1000 psig from nitrogen supply system 12. Typically, a 70 psi differential between coal feeder 16 and the pressure shells 41 and 53 is maintained to encourage coal flow in a dense phase through feed line 36 into the injector assembly 92. In other words, the pressure within the coal feeder is approximately 1070 psig during operation.
In this specific example hydrogen from hydrogen source 48 is directed towards the coal feeder 16 through hydrogen feed line 30 and the ratio of hydrogen to coal is about 0.005 lbs of hydrogen per pound of coal. Obviously, an inert gas may be utilized in place of the hydrogen with the pulverized coal from inert gas source 50 to the coal feeder 16. Hydrogen is additionally fed from hydrogen source 48 through a conduit 29 into the hydrogen preheater assembly 39. The hydrogen is directed into a 321 stainless steel preheater coil 43 at end 45. The coil 43 at end 45 is 1/4 inch O.D. x .035 inch wall and as the helix progresses down the coil 43 it transitions into a 5/16 inch O.D. x .049 inch wall coil and from there into a 3/8 inch O.D. x .083 inch wall coil. The hydrogen exits coil 43 at end 47 towards coiled tube 100 which directs hot hydrogen into the injector assembly 92. The hydrogen flowrate is 10 to 50 percent of the flowrate of dense phase coal. The coil is about 260 inches long in this example. The hydrogen is typically fed into coil 43 at the rate of .025 lbs per second. At startup the dense phase coal is flowed through feed line 36 into the post tube 120 outside top flange 37 and into the injector assembly 92 followed by introduction of hot hydrogen through the preheater coil 43. The hydrogen exits the heated coil in a temperature range between 150Q and 2000F (a typical tempera-ture is 1~50F~ adjacent the injector assembly 92. Typically, in the foregoing example the reaction temperature within the chamber by reactor tube 98 is found to be about 1100F with a residence time of the pulverized coal within the reactor tube 98 ~1001~68 of about 150 milliseconds when the hot hydrogen flowrate is 0.36 lbs of hydrogen per pound of coal. The reaction time in reactor tube 98 may be between 10 and 500 milliseconds for the hydrogenation process. As can be seen from the above, with a typical reaction temperature of about 1100F and a hydrogen temperature range of 1500-2000F, the hydrogen temperature is from 400 to 900F in excess of the typical reaction temperature.
It i9 desirable to promote better mixing to assure that hot hydrogen moves past the coal particles within the reactor tube 98. For example, the hot hydrogen velocity exiting the injector assembly 92 is approximately 1000 ft/ second while the velocity of the dense phase entrained coal exiting the injector is about 7 ft~second. Within these parameters approximately 19 to 20 of the coal carbon is converted into a synthetic crude oil having a boiling range of about 200-350C and a heating value of 15,800 BTU per lb, 9% to gas containing methane, ethane, and carbon oxides, and about 3% to organic compounds in the quench water. The coal throughput rate is approximately 33,000 lbs per hour ft reactor cross-section or 11, ooa lbs per hour ft3 reactor volume. The products of reaction are rapidly quenched to about 225F downstream of exit plane 99 of reactor tube 98 in a distance of about 1 ft, the reaction products passing by water spray nozzles 106 in the quench zone below the reaction chamber defined by reactor tube 98. The water flowrate through the multiplicity of water spray nozzles is from 2 to 6 gallons per minute. The products are then moved into the catch tank 52 and from there to the various drums 78 where the solids are collected the ga~ and by-products being directed into separator tank 56 and the by-products being directed through burnstack 58.
It would be obvious to use other means to heat the hydrogen being separately directed to the injector assembly 92 other than use of high electrical current to heat up a coil which is trans-porting the hydrogen. For example, a conventional fuel fired furnace or heater could be utilized to heat up a coil tube containing hot hydrogen. Many other methods to heat hot hydrogen are within the state of the art.
Turning now to FIG. 6 an alternative reactor tube 141 is illustrated wherein one end of the reaction chamber connected to the injector assembly 92 at end 142 begins a diverging wall section which diverges towards end 144 adjacent plate 146.
The diverging walls defining a reaction chamber 150 tend to discourage sticking of the partially hydrogenated products passing through the reactor tube 141, thus minimizing any tendency to plug.
FIGS. 7 and 8 disclose a different type of injector commonly known in the rocket engine field as a four-on-one injector. The injector consists of a center post 154 which transports dense phase coal particles and is supported within an upper plate 156 and a bottom injector plate 160. The inner face 157 of plate 156 and the inner face 158 of injector plate 160 define an annular chamber 162 which directs hot hydrogen entering a conduit 164 from the preheater assembly into the chamber. A
thermal insulator 159 is provided around the post center 154 so that coal particle~ transported within center post 154 are not prematurely heated. The injector plate 160 has drilled therein a series of four orificés 166 equidistantl~ spaced around the injector ~FIG. 8) each of the orifices having an impingement angle with respect to the center line of the center post 154 of approximatély 30 which facilitates greater mixing of the minute coal particles exiting center post 154 with the - impinging hot hydrogen downstream of the injector face. FIG. 8 better depicts the xelationship of the orifices with respect to the center post 154.
It would be obvious to configure any num~er of gas streams on the central coal stream with different impingement angles, all of which are well within the state-of-the-art particularly in the rocket engine field.
It will, of course, be realized that various modifications can be made in the design and operation of the present invention without departing from the spirit thereof. Thus, while the principal preferred construction and mode of operation of the invention have been explained and what is now considered . to represent its best embodiment has been illustrated and described, it should be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically illustrated and described.
1~0~
produce liquid products as in the Synthoil process; or in-directly by reacting coal with steam. Many different processes have been proposed and are under development. These schemes vary in the method of contacting coal and hydrogen or steam, and in the type of coal feed utilized. A solid such as coal can be contacted with a gas in three basically different ways.
In the first, gas is forced through a fixed or slowly moving bed of solid.
- 2a -11~68 76R18 Another method of contact is by use of a fluidized bed. With sufficiently small solid particles and a sufficiently high gas velocity in vertical upward flow the air dynamic drag forces on the individual particles begin to approach the gravitational forces and the par~icles themselves begin to move about.
The bulk properties of the gas solid mixture then become those of a fluid.
Because of the improved heat and mass transfer characteristics in a fluidi2ed bed as opposed to a fixed bed, most coal gasification processes now are the fluidized bed variety. Yet another basic category of gas solid contacting is entrained f1OW as in the Bigas process. In this regime gas velocities are high enough and particle sizes low enough that the solid particles are carried along with the gas stream. An advantage of the entrained flow processes is the ability to utilize any grade or class of coal. Caking coals will agglo-merate causing difficult problems when fed to fluidized or fixed bed systems.
Further advantages of entrained flow with respect togas production include operation at high temperatures so that tar production is kept to a minimum, adaptability to slagging conditions and high energy production per unit volume. The present invention utilizes this type of entrained flow coal con-version process. Heretofore no large scale attempt to use this approach for direct hydrogenation of coal has been made.
A patent issued to W. C Schroeder, No. 3,030,297, describes a process which comprises heating dry particles of coal entrained in a heated stream of hydrogen at total pressure of about 500-6000 psig from a temperature below about 300C to a reaction temperature in the range of from about 600C to about 1000C. Two minutes are required to heat the coal particles to about 600C and then two to twenty seconds time at temperature for hydrogenation.
The slow heat-up results from the main hydrogen stream being utilized to carry the coal into the reactor. The products of reaction are then cooled below reaction temperature to provide a product comprised of light oil, pre-dominantly aromatic in nature, and hydrocarbon gases, primarily methaneh, ethane, and carbon monoxide.
~0~6B
This process i5 disadvantaged in that the coal particles entrained in the hydrogen are preheated prior to introduction into a heating chamber thus the reaction process is started upstream of the reaction chamber which will cause agglomeration and plugging within the conduit carrying the entrained coal. The present invention overcomes this agglomeration problem by pro-viding two sources of gas, one source of gas such as hydrogen brings entrained coal into an injector at ambient temperature, and a separate source provides heated hydrogen to an injector which contacts the entrained dense phase coal downstream of an injector within a reaction zone thereby starting the hydro-genation process within the reaction chamber and not upstream of the chamber.
Schroeder is further disadvantaged in that he attempts to heat the en-trained coal particles through a tube wall. At the mass throughputs specified in the example, it is doubtful that enough heat could be transferred through the tube wall in a reasonable length to sufficiently heat the coal and, at the same time, use the tube wall to contain the system pressure. This type of reactor does not scale to the necessary larger diameters for commercial coal conversion reasonably because the heat transfer surface-to-volume ratio decreases rapidly with an lncrease in size~
Schroeder is still further disadvantaged in that the mixing and the heating takes place in minutes and seconds whereas the present invention ac-complishes the hydrogenation of the entrained coal in milliseconds and if a uniform flow pattern can be maintained (to avoid back mixing which will cause longer residence time and gas production instead of liquids) and if the coal can be dispersed uniformly even on a microscopic scale (to minimize gas dif-fusion limitations), and if rapid and efficient quenching can be achieved (Schroeder carries the hydrogenated products through a conduit towards a separate quenching chamber whereas the present invention ~uenches the re-AC ~
~ products immediately upon exiting the end of the reaction chamber), llOQ~8 then it should be possible to hydrogenate d substantial fraction of the coal to liquid products. The utilization of rocket engine type injector principles in a coal liquefaction plant as described in the present invention is believed to be unique and is one of the principal objects of the invention.
Another patent issued to Schroeder et al, 3,152,063, teaches a process which comprises dispersing pulverized and catalyzed coal, in the absence of a pasting oil, in hydrogen under a pressure of about 500 to 4000 psig, react-ing the mixture of coal and hydrogen at a temperature in the range of about 450 to 600C, for a gas residence time of less than about 200 seconds, cool-ing the reaction products and recovering liquid and gas hydrocarbon products therefrom.
Schroeder teaches passing of catalyzed coal and hydrogen into a two-stage reactor that consists of a multiplicity of parallel tubes axially extending within the reactor. The tubes are heated by a source of hot gas to start the reaction within the tubes. Vaporized oil and gas products are drawn off as wel1 as unused hydrogen to a cooling device. The residual heavier oil and tar products are collected in the bottom of the reactor and a source of hydrogen may then be brought in to further hydrogenate these heavier products.
This invention is disadvantaged in that the pulverized coal must be passed through a catalyzing process, sent through a dryer and grinder and finally separated into minute particles by passing the coal through a screen-ing process. The present invention utilizes finely-divided pulverized coal directly without the foregoing pre-treatment process.
Schroeder's invention is further disadvantaged in that it also utilizes the carrier hydrogen in the coal passages as the main source of hydrogen.
The heat-up process then takes considerable time as compared to the present invention in that the carrier gas cannot be pre-heated prior to entering into a reaction charnber.
l~OQ~68 Additionally, the invention is disadvantaged in that the coal particles are heated through a tube or a series of tubes thereby seriously affecting the ability to scale-up the process to commercial production proportions. A
comrnercial unit would necessarily have to process in the neighborhood of 1000 tons/hour. The Schroeder patents teach a mass throuyhput Ot approximately 145 lbs/hr ft.2, a very low process rate. For example, in a commercial re-actor using the Schroeder process, each reactor being 15 feet in diameter, 82 reactors would be needed to process 1000 tons/hr of coal. In addition, be-cause of the small surface-to-volume ratio the reactors would have to be on the order of one hundred feet long to transfer sufficient heat through the wall transporting the entrained coal particles. One of the most important advantages of the high throughput of dense phase coal particles through the reactor of the present invention (33,000 lbs/hr ft.2) is that it is scaleable to a commercial size. Two reactors utilizing the principles set forth in the following specificaticns, 6-feet in diameter would process 1000 tons/hr of coal. The heat is supp1ied directly in the hydrogen so that vessel surface-to-volume ratio is not a limiting factor.
Although the chemistry of coal pyrolysis and hydrogenation has been ap-parent for some time, no well-developed reactor exists which efficiently utilizes the rapid-reaction regime. Some of the basic reasons for this appear to be a lack of adequate gas/solid injection and mixing technology, difficulty in meeting chemistry and residence time requirements, and agglomeration and plugging of the reactor. Hydrogenation of raw bituminous coal usually re-sults in agglomeration, so that typical fluidized bed or moving bed reactors cannot be used as heretofore described. In addition, the requirement of short residence time (less than 1 sec) necessarily restricts the reactor to an entrained flow type. By maintaining rapid mixing, heat-up, and reaction of the coal near the point of injection and hot reactor walls, the agglomera-tion problem can be avoided. The uniform and precise mixing of extremely l~O~Q68 large feed streams in time of a few milliseconds is the special accomplish-ment of large rocket engine injectors and one of the principal objects of the present invention.
Summary of the Invention It is an object of this invention to convert coal particles entrained in a gas in a dense phase to hydrocarbon liquids and gases by hydrogenating the coal particles.
More particularly, it is an object of this invention to utilize rocket engine injection and mixing techniques in an entrained flow reactor to rapidly mix and react a separate stream of heated hydrogen with a dense phase stream of pulverized coal at ambient temperature to produce liquid and gaseous hydro-carbons.
It is yet another object of this invention to build and operate a high-temperature, coal liquefaction reactor which minimizes secondary oil and tar decomposition reactions by optimum control of gas-phase residence time, and prevents reactor plugging from coal agglomeration by very rapid dispersion and reaction of the coal while maintalning the internal reactor wall at high temperature.
A coal liquefaction method and apparatus to produce hydrocarbon liquids and gases by hydrogenating pulverized coal with hydrogen by flowing pulverized coal particles entrained in a gas such as hydrogen in a dense phase in a coal flow conduit at ambient temperature toward an injector adjacent to a reaction chamber and a heating means is provided for heating a separate source of hydrogen. The dense phase pulverized coal is injected through the injector into the reaction chamber followed by injecting the heated separate source of hydrygen gas through the injector into the reaction chamber and means to separate the ambient temperature dense phase coal particles and the heated hydrogen prior to injection of the dense phase coal and the heated hydrogen llOQ~68 into the reaction chamber to prevent premature hydrogenation of the pulverized coal. A quenching means is provided adjacent the reaction chamber to rapidly arrest the hydrogenation process at a predetermined ti~e period when the re-action products exit the reaction chamber, and a collecting means is provided for collecting the reaction products.
The coal is fed to the reactor at nearly its bulk density so that the quantity of entrained gas is minimized, and the heated hydrogen brought in separately provides the heat source needed to raise the coal rapidly to re-action temperatures.
An entrained flow reactor using rocket engine injection and mixing tech-niques to react a stream of hot hydrogen with a stream of pulverized coal was designed, built, and operated. As an example only, typical reactor operating conditions were 1000 psig, 1100F, ~150 milliseconds residence time, and 0.36 lb H2/lb coal. Approximately 19% of the coal carbon was converted to a synthetic crude oil having a boiling range of 200-350C and a heating value of 15,800 8TU/lb, 9% to gas containing methane, ethane, and carbon oxides, and 3~,' to organic compounds in the quench water. The coal throughput rate WdS approximately 33,000 lbs/hr ft2 reactor cross section or 11,000 lbs/hr ft3 reactor volume. The products of reaction were rapidly quenched to 220F
in a distance of 1 ft using large flowrates of water through spray nozzles.
Thus, an advantage over the prior art is the use of rocket engine in-jection and mixing techniques to rapidly mix and react a stream of entrained coal with hot hydrogen to produce liquid and gaseous hydrocarbons.
Another advantage of the present invention over the prior art is the minimization of secondary oil and tar decomposition reaction by aptimum con-trol of gas-phase residence time by very rapid coal partic1e dispersion and reaction of the coal while maintaining the internal reactor wall at high temperature.
00~68 76Rl8 Yet another advantage over the prior art is the prevention of coal ag-glomeration upstream of the reaction chamber by transporting the entrained dense phase coal in a gas at ambient temperature.
Still another advantage over the prior art is the ability to use a carrier gas other than hydrogen for transporting the coal partic1es in a dense phase to the injector thus minimizing explosion hazards in the coal feed sys-tem due to hydrogcn leakage to the atmosphere from moving mechanical parts such as valves buildup of explosive mixtures of hydrogen and air in the coal containing vessels and loss of hydrogen through venting when lock hoppers are used.
A still further advantage over the prior art is the immediate quenching of the hydrogenated coal particles as they exit the end of the reaction cham-ber thereby maximizing the product yield of liquid and gaseous hydrocarbons Another advantage over the prior art is the direct hydrogenation of coal particles in a reacticn chamber as opposed to heating the exterior wall of a tube surrounding the hydrogen and coal particles contained within the tube.
The above-noted objects and advantages of the present invention will be more fully understood upon the study of the following description in con-junction with the detailed drawings.
Brief Description of the Drawing FIG. 1 is a fl~lsheet schematic of the coal liquefaction apparatus;
FIG. 2 is a detailed cross-section of the principal elements of the in-vention;
FIG. 3 is an enlarged partially cross-sectioned view of the hot hydrogen and t~e coal flo~ coupling upstream ~ the injector;
FIG. 4 is an enlarged cross-section of the concentric injector;
FIG. 5 is a view of the heater coil element and electrical coupling ad-jacent the reaction chamber and coal flow tubes;
FIG. 6 is an alternative view of the reaction chamber illustrating di-~be verging walls from the injector fdce to the exit plane of the reactor~;
l~OOQ68 FIG. 7 is an alternative view of an injector illustrating a four-on-one injection pattern; and FIG. 8 is a view taken along lines 8-8 of FIG. 7.
Description of the Preferred Embodiments Referring now FIG. 1, a coal liquefaction unit generally designated as 10 consists of a nitrogen supply system generally designated as 12 that serves as a purge supply source as well as a pressurizing source for a quench water tank system generally designated as 14.
A high pressure coal feeder generally designated as 16 comprises a cylindrical vessel 18 suspended from a load cell 20.
The coal feeder 16 is charged by flowing coal from a low pressure conical tank 22 through a tube 24. To charge the high pressure coal feeder 16, the conical tan~ 22 is pressurized to about 55 psig with nitrogen from supply system 12, a ball valve 26 at the conical tank bottom is quickly opened wide, and the coal flows in a dense phase through the tu~e 24 to the coal feeder 16.
The excess nitrogen vents out of the coal feeder through a dust filter 28. After the coal feeder 16 is charged, the tu~e 24 is disconnected and capped as shown at 27, and the dust filter 28 is disconnected and the pressure relief line 32 connected in its place as shown in FIG. 1. A hopper hydrogen feed line 30 from a hydrogen source 48 or inert gas from an inert gas source 50 is opened for subsequent operation. Load cell 20 readings before and after charging indicate the quantity of coal in the feeder. The bottom 19 of the coal feeder 16 is conically shaped with a 30 included angle to provide smooth discharging of coal. Coal is fed to the reactor assembly by opening a ball valve 34 and flowing in a dense phase through a feed line 36. The hydrogen or inert gas pressure in the coal feeder is maintained, for example, about 60 to 70 psi higher than in the reactor assembly generally designated as 38 so as to provide the driving force for feeding the coal to the llOOQ6~ ' reactor assembly 38. The weight of hydrogen carried in the coal as a percent of the coal flowrate is about 0.5% when the reaction chamber pressure is 1000 psig. In the case of inert transport gas, the weight percent transport gas will vary according to gas density. The flowrate of coal is about .15 pound per second and the flowrate of hydrogen is about .0075 pound per second where hydrogen is used as the carrier gas.
Load cell readings are printed during a test so that the coal feed rate can be continuously monitored (not shown). When the 10feeder ball valve 34 is in a closed position, nitrogen from nitrogen supply system 12 flowing through a line 4~ is purged through the feed line 36 to keep it clear and to prevent the coal side of the injector ~FIG. 4) from overheating. The portion of the coal feed line passing through a top flange 37 and making up part of an injector assembly 92 ~FIG. 3) is typically fabricated from stainless steel. Details of the r injector assembly 92 are shown in FIGS. 3 and 4.
Pressurized water for a quench system generally designated as 42 is supplied by, for example, a 150 gallon pressurized 20quench water tank system 14. The flow of water can ~e accurately measured continuously during tests and is varied by changing the pressure on the water tank from nitrogen supply system 12.
AccuratP flow control is possible because the pressure drop across spray nozzles 106 CFIG. 2) is normally a~out 180 psi. In addition, there is about another 130 psi in pressure drop ahead of the spray nozzles.
It would be obvious to use fluid other than water to quench the hydro-genated products as they exit the reaction chamber such as steam, oil or cold gas ~hydrogen).
There are three gas supply systems, one for nitrogen, one for hydrogen and one for an inert gas The nitrogen supply system 12 supplies the nitrogen bleed to a preheater assembly 39 through a conduit 31 and reactor pressure shells 53, and for 13`00Q68 purging the coal feed line through line 40. The flows are controlled by using sonic nozzles (not shown) and varying the pressure upstream of the nozzles to obtain various flowrates.
The hydrogen source 48 supplies the high pressure coal feeder 16 and the preheater assembly 39. The hydrogen flow to the coal feeder 16 is on demand and is only measured with an orifice (now shown). The gas supplied to the coal feeder 16 need not be hydrogen from hydrogen source 48 but may be an inert gas such as nitrogen, carbon dioxide or mixture thereof from inert gas source 50. The hydrogen flow to the preheater assembly 39 is controlled by a sonic nozzle an-d upstream pressure regulator (not shown). The hydrogen system may be set up so that nitrogen can be used in place of hydrogen for purging and leak checks(not shown).
Product gas from a spherical catch tank 52 flows through a conduit 54 to a liquid separator tank 56 and then through a back pressure regulator system. After the product gas is let down in pressure, the flowrate is measured using an orifice and then the gas goes to a burn~tack 58 through a tu~e 60. A
gas sample bottle system generally designated as 62 is connected to the high pressure side through a line 64 of the gas sample bottle system 62 and is vented back into the system t~rough a line 66 to burnstack 58. The sample ~ottle valves 68 are automated to open in sequence a~out every 30 to 60 seconds during a test.
The liquia product letdown is controlled by a tank liquid level control system generally designated as 70 that actuates an on-o~f valve 72. The flow out of catch tank 52 is regulated ~y a linear plug valve 74. The linear plug valve 74 is basically a variable orifice that is used to prevent the liquid from surging out of catch tank 52 so fast that pressure control in the reactor assembly 38 is upset. A header of three valves 76 is used to select which of drums 78 is to receive the liquid product.
A more detailed drawing of the hydrogen preheater assembly generally designated as 39 is presented in FIGS. 2 and 5 and of the reactor assembly generally designated as 38 is presented in FIG. 2. The hydrogen preheater assembly is contained within a pressure shell 41 and the preheater coil 43 is a stainless steel tube through which an electric current is passed as hydrogen passes through it. The preheater coil 43 is thin walled and small in diameter at end 45 and heavy walled and larger in diameter at end 47. As the hydrogen enters end 45 it is relatively cool and as it progresses down through helical-shaped preheater coil 43 it heats up and expands. The variable I.D. and wall thickness of the coil compensates for this expansion of hydrogen. Seven motor-generator sets [not shown) supply about 600-800 amps to copper stud conductors 77 and 79 connected to plate 80 through the wall 49 with a power input up to 150 Kw. The heat transfer from the resistively-heated wall 49 to the pressurized hydrogen entering end 45 o preheater coil 43 through hydrogen feed line 30 is excellent and has demonstrated efficiencies of about 99%. Since the tube wall strength is very low at the heater operating temperatures (the wall is about 200~F hotter than the hydrogen at the exit 47 of the tube 43), the preheater coil 43 is contained in a pressure shell 41 made from, for example, carbon-steel pipe and 600 lb flanges 82 and 84. The void space 86 in the pressure shell 41 is stuffed with, for example, a very low thermal conductivity insulation 87 such as ~ibrefrax, a product of Carborundum Corporation, Refractories and Insulation Division, Fibrefrax Branch,Niagara Falls, New York, and is purged continuously with about 5 SCFM of nitrogen at about 1000 psig.
The copper stud conductors 77 and 7g, plate 80, and inlet end 45 of the preheater coil 43 are electrically isolated from the pressure shell 41 and serve as the positive connection to the motor 1100(~68 generator sets, The ground connection is made to another end 51 of the pressure shell 41 through the blind stainless steel flange 88 that is sandwiched between the two carbon steel, weld-neck flanges 84 and 85. A thermocouple 90 is immersed in the gas exiting the preheater assembly 39, and a pressure transducer (not shown) is connected to a similar port in the flange.
In a similar fashion, referring to FIG. 2, the reactor tube 98 and injector assembly generally designated as 92 are enclosed in a pressure shell 53 so that the hot reactor tube walls 94 experience very little stress while at high temperature.
The reactor tube is supported by the insulation 87 and slip fits through a hole in the insulation support plate 96 so that thermal elongation of the reactor tube 98 is allowed. The preheater assembly 39 is connected to the in~ector assembly 92 via a stainless steel coiled tube 100. This tube is coiled so that it can thermally elongate without applying a force against the injector assembly 92, possibly bowing the reactor tube 98. The reactor tube 98 and injector assem~ly 92 can easily be removed from the pressure shell 53 by removing the top flange 37 and a small amount of insulation 87. Several bosse~ 102 along the side of the pressure shell 53 permit thermocouple measurements along the reactor outside wall, and one directly inside the bottom of the reactor tube 98 near exit plane 99.
The quench zone lQ4 consists, for example, o~ 3 rows of 4 full-cone spray nozzIes lQ6 that screw into the quench zone pipe wall 108 from the outside. As the reaction products exit the reactor tube 98, they are quenched immediately with water sprays supplying water at about 3 to 6 gpm. Enough spray water is used to reduce the product temperature to about 200 ~F.
The li~uid, gas, and solids are forced down into spherical catch tank 52 (FIG. 1~ where the gas separates and exits. The iioo~68 liquid level control system 70 (FIG. 1) is used to maintain a liquid level in the spherical catch tank 52 and to let down the slurry product into drums 78 ~FIG. 1). Vent line 71 connects to the liquid level control system 70.
FIGS. 3 and 4 illustrate in more detail the injector assembly 92 and reactor tube 98 combination wherein a stream of hot (1500-2000F) hydrogen is reacted with a stream of pulverized coal. The injector assembly generally designated as 92, for example, consists of a housing body 110 that is separable from a coal feed line assembly 112 and the reactor tube 98 by a pair of, for example, AN type nuts 114 and 116.
The coal feed line assembly 112 consists of 3 tubes, an outer shell tube 130, an insulation tube 118, and a post tube 120.
The post tube 120 is 3/8 inch O.D. (Dimension "D" FIG. 4) x 0.083 inch wall, 321 stainless steel. A 0.55 inch length of end 121 of the post tube 120 is machined to form end 121 to 0.254 inch O.D. (Dimension "I" FIG. 4) x 0.020 inch wall. The entire injector assembly 92 is contained within the pre~sure shell 53 (FIG. 2). The pos* tube 120 extends through top flange 37 via a packing gland fitting such as a 3/8 inch Conax fitting 105 made by Conax Corporation of Buffalo, New York, and is coupled with coal feed line 36 outside of the pressure shell 53. End 121 of the post tube 120 extends concentrically within a separate cone 122 that is connected to housing body 110 by AN nut 116. An annulus 124 (FIG 4) is defined between inner wall 123 of cone 122 and outer surface 125 of end 121 of post tube 120. Annulus 124 is 0.350 inch O.D. with a gap of 0.048 inches (Dimension "G" FIG. 4) to the outer surface 125 of end 121 of the post tube 120. End 121 is recessed 0.212 inch (Dimension "F"). Three wire spacers 117 are brazed to end 121 to center the post tube 120 and end 121 in the annulus 124.
The post tube 120 is supported as it passes through a plate 115 by a 3/8 inch Conax fitting 135 that is screwed into plate 115.
110~6~ ' The insulation tube 118 is 1 inch O.D. x .049 inch wall, 321 stainless steel and terminates at end 119 in a cone that diverges toward but is not affixed to the outer wall of the post tube 120 near end 121. End 113 of tube 118 is affixed to plate 115. An annulus 126 is defined by an outer surface 127 of tube 120 and an inner surface 128 of tube 118. The annulus 126 is filled with insulation material 87. The outer shell tube 130 is a structural member that houses concentric tubes 118 and 120 and connects at a first end 132 to plate 115 and at the other end 134 to housing body 110 by nut 114. Tube 130 is 1.5 inch O.D. x .049 inch wall, 321 stainless steel. An annulus 136 is defined by an outer surface 138 of tube 118 and an inner surface 140 of housing body 110. The annulus 136 serves to direct a hot hydrogen exterior port 111 toward annulus 124 and out injector assembly 92 (FIG. 4). An annulus 131 is defined by outer surface 138 of tube 118 and inner surface 129 of tube 130 and is filled with insulation 87 that is kept from falling in annulus 136 by a sleeve 133. The reactor tube 98 (FIG. 3) is 1.5 inch O.D. x .049 inch wall (Dlmension "B'~, 321 stainless steel tube, is 3 feet long (,Dimension "A"), and i$ connected to the housing body 110 by nut 116. The overall injector assembly 92 is about 1 ft long (Dimension "C").
In operation, the coal liquefaction plant functions in the following manner: A pulverized bituminous coal such as Kentucky hvAb may be utilized. Other types of pulverized coal such as lignite and sub-bituminous may also be used. The coal is typically 70% less than 74 microns in size ~200 mesh coal) and is fed into high pressure coal feeder 16. The average coal particle size is 40 to 50 microns. A quarter inch line approxi-mately 20 feet long directs dense phase coal from valve 34 into post tube 120 outside of top flange 37 towards the injector assembly 92. The pressure shells 41 and 53 are pressurized 1~0~68 with nitrogen to approximately 1000 psig from nitrogen supply system 12. Typically, a 70 psi differential between coal feeder 16 and the pressure shells 41 and 53 is maintained to encourage coal flow in a dense phase through feed line 36 into the injector assembly 92. In other words, the pressure within the coal feeder is approximately 1070 psig during operation.
In this specific example hydrogen from hydrogen source 48 is directed towards the coal feeder 16 through hydrogen feed line 30 and the ratio of hydrogen to coal is about 0.005 lbs of hydrogen per pound of coal. Obviously, an inert gas may be utilized in place of the hydrogen with the pulverized coal from inert gas source 50 to the coal feeder 16. Hydrogen is additionally fed from hydrogen source 48 through a conduit 29 into the hydrogen preheater assembly 39. The hydrogen is directed into a 321 stainless steel preheater coil 43 at end 45. The coil 43 at end 45 is 1/4 inch O.D. x .035 inch wall and as the helix progresses down the coil 43 it transitions into a 5/16 inch O.D. x .049 inch wall coil and from there into a 3/8 inch O.D. x .083 inch wall coil. The hydrogen exits coil 43 at end 47 towards coiled tube 100 which directs hot hydrogen into the injector assembly 92. The hydrogen flowrate is 10 to 50 percent of the flowrate of dense phase coal. The coil is about 260 inches long in this example. The hydrogen is typically fed into coil 43 at the rate of .025 lbs per second. At startup the dense phase coal is flowed through feed line 36 into the post tube 120 outside top flange 37 and into the injector assembly 92 followed by introduction of hot hydrogen through the preheater coil 43. The hydrogen exits the heated coil in a temperature range between 150Q and 2000F (a typical tempera-ture is 1~50F~ adjacent the injector assembly 92. Typically, in the foregoing example the reaction temperature within the chamber by reactor tube 98 is found to be about 1100F with a residence time of the pulverized coal within the reactor tube 98 ~1001~68 of about 150 milliseconds when the hot hydrogen flowrate is 0.36 lbs of hydrogen per pound of coal. The reaction time in reactor tube 98 may be between 10 and 500 milliseconds for the hydrogenation process. As can be seen from the above, with a typical reaction temperature of about 1100F and a hydrogen temperature range of 1500-2000F, the hydrogen temperature is from 400 to 900F in excess of the typical reaction temperature.
It i9 desirable to promote better mixing to assure that hot hydrogen moves past the coal particles within the reactor tube 98. For example, the hot hydrogen velocity exiting the injector assembly 92 is approximately 1000 ft/ second while the velocity of the dense phase entrained coal exiting the injector is about 7 ft~second. Within these parameters approximately 19 to 20 of the coal carbon is converted into a synthetic crude oil having a boiling range of about 200-350C and a heating value of 15,800 BTU per lb, 9% to gas containing methane, ethane, and carbon oxides, and about 3% to organic compounds in the quench water. The coal throughput rate is approximately 33,000 lbs per hour ft reactor cross-section or 11, ooa lbs per hour ft3 reactor volume. The products of reaction are rapidly quenched to about 225F downstream of exit plane 99 of reactor tube 98 in a distance of about 1 ft, the reaction products passing by water spray nozzles 106 in the quench zone below the reaction chamber defined by reactor tube 98. The water flowrate through the multiplicity of water spray nozzles is from 2 to 6 gallons per minute. The products are then moved into the catch tank 52 and from there to the various drums 78 where the solids are collected the ga~ and by-products being directed into separator tank 56 and the by-products being directed through burnstack 58.
It would be obvious to use other means to heat the hydrogen being separately directed to the injector assembly 92 other than use of high electrical current to heat up a coil which is trans-porting the hydrogen. For example, a conventional fuel fired furnace or heater could be utilized to heat up a coil tube containing hot hydrogen. Many other methods to heat hot hydrogen are within the state of the art.
Turning now to FIG. 6 an alternative reactor tube 141 is illustrated wherein one end of the reaction chamber connected to the injector assembly 92 at end 142 begins a diverging wall section which diverges towards end 144 adjacent plate 146.
The diverging walls defining a reaction chamber 150 tend to discourage sticking of the partially hydrogenated products passing through the reactor tube 141, thus minimizing any tendency to plug.
FIGS. 7 and 8 disclose a different type of injector commonly known in the rocket engine field as a four-on-one injector. The injector consists of a center post 154 which transports dense phase coal particles and is supported within an upper plate 156 and a bottom injector plate 160. The inner face 157 of plate 156 and the inner face 158 of injector plate 160 define an annular chamber 162 which directs hot hydrogen entering a conduit 164 from the preheater assembly into the chamber. A
thermal insulator 159 is provided around the post center 154 so that coal particle~ transported within center post 154 are not prematurely heated. The injector plate 160 has drilled therein a series of four orificés 166 equidistantl~ spaced around the injector ~FIG. 8) each of the orifices having an impingement angle with respect to the center line of the center post 154 of approximatély 30 which facilitates greater mixing of the minute coal particles exiting center post 154 with the - impinging hot hydrogen downstream of the injector face. FIG. 8 better depicts the xelationship of the orifices with respect to the center post 154.
It would be obvious to configure any num~er of gas streams on the central coal stream with different impingement angles, all of which are well within the state-of-the-art particularly in the rocket engine field.
It will, of course, be realized that various modifications can be made in the design and operation of the present invention without departing from the spirit thereof. Thus, while the principal preferred construction and mode of operation of the invention have been explained and what is now considered . to represent its best embodiment has been illustrated and described, it should be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically illustrated and described.
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process of reacting a pulverized carbonaceous material with hydrogen at a desired hydrogenation reaction temperature in a single reaction zone to form desired gaseous and liquid hydrocarbon reaction products comprising:
introducing thermally separated streams of gas-entrained pulverized carbonaceous material and of hot hydrogen into the single reaction zone, the hot hydrogen stream being injected at a high velocity of at least several hundred feet per second in excess of that of the carbonaceous material stream so as to provide an intimately mixed reaction mixture having a high entrained flow cross-sectional throughput through said reaction zone of pulverized carbonaceous material in said hydrogen stream, said carbonaceous material and hydrogen having a residence time in the reaction zone substantially equal to the reaction time, said introduced hot hydrogen stream prior to contact with the carbonaceous material being at a temperature several hundred degrees Fahrenheit above that of the carbonaceous material and that of the desired hydrogenation reaction temperature and in an amount sufficient to raise the temperature of said intimately mixed reaction mixture to said desired hydrogenation reaction temperature, maintaining said high velocity entrained flow reaction mixture at said desired reaction temperature for a residence-reaction time of about 10 to 500 milliseconds whereby desired gaseous and liquid hydrocarbon reaction products are formed, and immediately thereafter quenching the products of said reaction and collecting said reaction products.
introducing thermally separated streams of gas-entrained pulverized carbonaceous material and of hot hydrogen into the single reaction zone, the hot hydrogen stream being injected at a high velocity of at least several hundred feet per second in excess of that of the carbonaceous material stream so as to provide an intimately mixed reaction mixture having a high entrained flow cross-sectional throughput through said reaction zone of pulverized carbonaceous material in said hydrogen stream, said carbonaceous material and hydrogen having a residence time in the reaction zone substantially equal to the reaction time, said introduced hot hydrogen stream prior to contact with the carbonaceous material being at a temperature several hundred degrees Fahrenheit above that of the carbonaceous material and that of the desired hydrogenation reaction temperature and in an amount sufficient to raise the temperature of said intimately mixed reaction mixture to said desired hydrogenation reaction temperature, maintaining said high velocity entrained flow reaction mixture at said desired reaction temperature for a residence-reaction time of about 10 to 500 milliseconds whereby desired gaseous and liquid hydrocarbon reaction products are formed, and immediately thereafter quenching the products of said reaction and collecting said reaction products.
2. The process of Claim 1 wherein said pulverized carbonaceous material is coal and is introduced at sub-stantially ambient temperature.
3. The process of Claim 1 wherein the flow cross-section of the reaction products being quenched is expanded to reduce the flow velocity.
4. The process of Claim 1 wherein said introduced hot hydrogen stream is at a temperature in the range of 1500°F
to 2000°F.
to 2000°F.
5. The process of Claim 4 wherein said pulverized carbonaceous material is coal and is introduced at sub-stantially ambient temperature.
6. The process of Claim 5 wherein the flow cross-section of the reaction products being quenched is expanded to reduce the flow velocity.
7. The process of Claim 4 wherein the desired hydro-genation temperature of said reaction mixture is about 1100°F.
8. The process of Claim 1 wherein said hot hydrogen is introduced at a temperature of from 400° to 900°F above the desired hydrogenation reaction temperature.
9. A hydrogenation apparatus having a single reaction chamber for reacting hydrogen and a pulverized carbonaceous material at a desired hydrogenation reaction temperature to form desired gaseous and liquid hydrocarbon reaction products, said apparatus comprising:
a source of hydrogen;
heating means for heating said hydrogen to a temperature several hundred degrees Fahrenheit above that of the carbonaceous material and that of the desired hydrogenation reaction temperature;
an unimpeded flow-through single reaction chamber defining a single reaction zone, said reaction zone providing for the unimpeded high-velocity entrained flow therethrough of said hot hydrogen and carbonaceous material and reaction products formed therefrom, said chamber having opposite ends and having a length sufficient to provide for a residence time of said hot hydrogen and pulverized carbonaceous material in said reaction zone substantially equal to a reaction time of up to about 500 milliseconds and having a cross-sectional area sufficient to provide a high entrained flow cross-sectional throughput through said reaction zone of pulverized carbonaceous material in said hot hydrogen;
injector means adjacent one end of said reaction chamber, said injector means including (a) means for introducing said pulverized carbonaceous material into said reaction zone, (b) means for introducing said heated hydrogen into said reaction zone in an amount sufficient to rapidly heat said carbonaceous material to the desired hydrogenation reaction temperature in said reaction zone and at a high velocity of at least several hundred feet per second in excess of that of said carbonaceous material to ensure rapid and uniform mixing with said carbonaceous material and to provide said high entrained flow cross-sectional throughput through said reaction zone, and (c) insulating means for maintaining said heated hydrogen thermally separated from said carbonaceous material prior to said mixing to prevent agglomeration of said carbonaceous material; and quenching means located adjacent the other end of said reaction chamber for rapidly quenching the reaction products exiting said reaction chamber to arrest said hydrogenation reaction.
a source of hydrogen;
heating means for heating said hydrogen to a temperature several hundred degrees Fahrenheit above that of the carbonaceous material and that of the desired hydrogenation reaction temperature;
an unimpeded flow-through single reaction chamber defining a single reaction zone, said reaction zone providing for the unimpeded high-velocity entrained flow therethrough of said hot hydrogen and carbonaceous material and reaction products formed therefrom, said chamber having opposite ends and having a length sufficient to provide for a residence time of said hot hydrogen and pulverized carbonaceous material in said reaction zone substantially equal to a reaction time of up to about 500 milliseconds and having a cross-sectional area sufficient to provide a high entrained flow cross-sectional throughput through said reaction zone of pulverized carbonaceous material in said hot hydrogen;
injector means adjacent one end of said reaction chamber, said injector means including (a) means for introducing said pulverized carbonaceous material into said reaction zone, (b) means for introducing said heated hydrogen into said reaction zone in an amount sufficient to rapidly heat said carbonaceous material to the desired hydrogenation reaction temperature in said reaction zone and at a high velocity of at least several hundred feet per second in excess of that of said carbonaceous material to ensure rapid and uniform mixing with said carbonaceous material and to provide said high entrained flow cross-sectional throughput through said reaction zone, and (c) insulating means for maintaining said heated hydrogen thermally separated from said carbonaceous material prior to said mixing to prevent agglomeration of said carbonaceous material; and quenching means located adjacent the other end of said reaction chamber for rapidly quenching the reaction products exiting said reaction chamber to arrest said hydrogenation reaction.
10. The process of Claim 1 wherein the high entrained flow cross-sectional throughput through said reaction zone is not less than about 33,000 lbs./hr. ft.2 of pulverized carbonaceous material in said hydrogen stream.
11. The process of Claim 1 wherein the relative velocities of the hot hydrogen stream and of the carbonaceous material stream being introduced into the reaction zone are of the order of about 1000 ft. per second to about 7 ft. per second.
12. The apparatus of Claim 9 wherein said cross-sectional area is sufficient to provide a high entrained flow cross-sectional throughput through said reaction zone of not less than about 33,000 lbs./hr. ft.2 of pulverized carbonaceous material in said hot hydrogen.
13. The apparatus of Claim 9 wherein said means (a) and (b) of said injector means consist of a concentric tube injector wherein the inner tube thereof is the coal flow injecting tube and the outer tube thereof is the heated high velocity hydrogen injecting tube.
14. The apparatus of Claim 9 wherein said means (a) and (b) of said injector means consist of a four-on-one injector, said injector having a center orifice therein to flow said coal therethrough, said injector further having four orifices therein equidistantly spaced around said center orifice at an angle with respect to said center orifice to flow hot hydrogen therethrough and impinge said hot hydrogen at a high velocity on said coal downstream of said injector in said reaction chamber.
15. The apparatus of Claim 9 wherein said quenching means has associated therewith expansion means for expanding the flow cross-section of reaction products exiting said reaction chamber to substantially reduce the flow velocity of said reaction products.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68900276A | 1976-05-24 | 1976-05-24 | |
| US689,002 | 1991-04-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100068A true CA1100068A (en) | 1981-04-28 |
Family
ID=24766666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,052A Expired CA1100068A (en) | 1976-05-24 | 1977-04-26 | Coal conversion using rocket engine type injector device |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS6019349B2 (en) |
| AU (1) | AU506536B2 (en) |
| CA (1) | CA1100068A (en) |
| DE (1) | DE2723457A1 (en) |
| FR (1) | FR2352769A1 (en) |
| GB (1) | GB1582547A (en) |
| ZA (1) | ZA772537B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4206032A (en) * | 1978-03-17 | 1980-06-03 | Rockwell International Corporation | Hydrogenation of carbonaceous materials |
| JPS55128924U (en) * | 1979-03-09 | 1980-09-11 | ||
| DE2943537A1 (en) * | 1979-10-27 | 1981-05-07 | Hermann Berstorff Maschinenbau Gmbh, 3000 Hannover | METHOD AND SYSTEM FOR CONVERTING COAL WITH HYDROGEN INTO HYDROCARBON |
| GB2121426A (en) * | 1982-05-24 | 1983-12-21 | British Gas Corp | Hydrogenated carbonaceous solids |
| JPS5936191A (en) * | 1982-08-24 | 1984-02-28 | Asahi Chem Ind Co Ltd | Method for treating carbonaceous material |
| GB2180464A (en) * | 1985-09-18 | 1987-04-01 | British Gas Corp | Gas-solid phase reactions and apparatus therefor |
| GB2182344A (en) * | 1985-11-04 | 1987-05-13 | British Gas Corp | Gasification of solid carbonaceous material |
| FR2614751B1 (en) * | 1987-04-29 | 1991-10-04 | Aerospatiale | METHOD AND DEVICE FOR THE INJECTION OF A MATERIAL IN A FLUID FORM INTO A HOT GAS FLOW AND APPARATUS USING THE SAME |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3030297A (en) * | 1958-03-11 | 1962-04-17 | Fossil Fuels Inc | Hydrogenation of coal |
| GB1089092A (en) * | 1963-08-27 | 1967-11-01 | Coal Industry Patents Ltd | Process for treating coal |
| US3960700A (en) * | 1975-01-13 | 1976-06-01 | Cities Service Company | Coal hydrogenation to produce liquids |
| FR2352048A1 (en) * | 1976-05-21 | 1977-12-16 | Cities Service Co | Coal hydrogenation with extremely brief reaction times - minimising gas prodn and polymerisation of liquid components |
-
1977
- 1977-04-20 AU AU24448/77A patent/AU506536B2/en not_active Expired
- 1977-04-26 CA CA277,052A patent/CA1100068A/en not_active Expired
- 1977-04-27 ZA ZA00772537A patent/ZA772537B/en unknown
- 1977-04-29 GB GB18085/77A patent/GB1582547A/en not_active Expired
- 1977-05-18 JP JP52056499A patent/JPS6019349B2/en not_active Expired
- 1977-05-24 DE DE19772723457 patent/DE2723457A1/en active Granted
- 1977-05-24 FR FR7715850A patent/FR2352769A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6019349B2 (en) | 1985-05-15 |
| AU506536B2 (en) | 1980-01-10 |
| DE2723457A1 (en) | 1977-12-15 |
| FR2352769A1 (en) | 1977-12-23 |
| ZA772537B (en) | 1978-03-29 |
| DE2723457C2 (en) | 1988-03-10 |
| FR2352769B1 (en) | 1983-04-29 |
| AU2444877A (en) | 1978-10-26 |
| GB1582547A (en) | 1981-01-07 |
| JPS52142703A (en) | 1977-11-28 |
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