CA1288949C - Annular nozzle and process for its use - Google Patents
Annular nozzle and process for its useInfo
- Publication number
- CA1288949C CA1288949C CA000506684A CA506684A CA1288949C CA 1288949 C CA1288949 C CA 1288949C CA 000506684 A CA000506684 A CA 000506684A CA 506684 A CA506684 A CA 506684A CA 1288949 C CA1288949 C CA 1288949C
- Authority
- CA
- Canada
- Prior art keywords
- segment
- slurry
- gas
- stream
- central
- 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 - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/50—Fuel charging devices
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/50—Fuel charging devices
- C10J3/506—Fuel charging devices for entrained flow gasifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
- C10J2200/152—Nozzles or lances for introducing gas, liquids or suspensions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Nozzles (AREA)
Abstract
ABSTRACT
The present invention provides an improved burner nozzle and process for making a synthetic or fuel gas mixture containing hydrogen and carbon monoxide by the partial oxidation in a free-flowing hollow reactor of a slurry of solid carbonaceous fuel in a liquid carrier admixed with a gas containing free oxygen. The nozzle and process include the enveloping of an annular slurry stream between a central and annular layer of high velocity gas, where a zone of high shear forces and impinging the annular slurry stream on a downstream nozzle diffuser, produce a uniform atomized admixture of solids, liquids and gases, and then transporting the admixture through an exit orifice at an accelerated velocity to further atomize the admixture.
The present invention provides an improved burner nozzle and process for making a synthetic or fuel gas mixture containing hydrogen and carbon monoxide by the partial oxidation in a free-flowing hollow reactor of a slurry of solid carbonaceous fuel in a liquid carrier admixed with a gas containing free oxygen. The nozzle and process include the enveloping of an annular slurry stream between a central and annular layer of high velocity gas, where a zone of high shear forces and impinging the annular slurry stream on a downstream nozzle diffuser, produce a uniform atomized admixture of solids, liquids and gases, and then transporting the admixture through an exit orifice at an accelerated velocity to further atomize the admixture.
Description
12~ 49 ~1--ANNULAR NOZZLE AND PROCESS
FOR ITS USE
The present invention concerns the production of synthetic gas or fuel gas containing hydrogen and carbon monoxide which is formed by partially oxidizing a slurry of solid carbonaceous fuel and a carrier liquid admixed with a gas containing free oxygen in a hollow free-flowing reactor. More particularly, this invention concerns an improved burner nozzle for admix-ing the slurry and oxygen-containing gas, and then introducing the admixture into a reactor.
Three basic processes have been developed for the gasification of carbonaceous materials. They are the fixed bed process, fluidized bed process, and the suspen-sion or entrained process. The efficiency of the entrained process, with which the present invention is concerned, is significantly affected by the degree of mixing of reac-tants prior to carrying out the partial oxidation reaction leading to gasification. In the case where a slurry of a finely divided carbonaceous fuel in a carrier liquid 2~,382-F -1-~288949 is admixed with an oxygen containing gas, it is very important that the reactants are uniformly mixed and atomized into very fine droplets at the time they are vaporized and then iynited to form a gaseous product.
Annular-type burner nozzles have been employed for introducing an admixture of slurry and oxygen-containing gas into a reactor. For example, annular-type burners are shown in U.S. Patents 4,364,744 and 4,443,230.
Problems that have been addressed with such burner nozzles include mixing to provide proper distribution of the fuel and oxygen in the admixture, atomization of the admixture, stability of burner nozzle operation, reduction of localized overheating in the reactor and burner nozzle, and reduction of mechanical wear of the burner nozzle. In addition to these problems, slurries containing a high concentration of divided solids also tend to plug or partially plug annular passageways as they are transported through the burner nozzles.
In general, the present invention provides an improved burner nozzle and process for making a syn-thesis gas or fuel gas mixture containing hydrogen and carbon monoxide by the partial oxidation of a slurry of solid carbonaceous fuel in a liquid carrier admixed with a gas containing free oxygen, the partial oxidation occuring in a free-flowing hollow reactor. By means of the burner nozzle, the slurry and oxygen-containing gas are admixed, atomized and introduced into the reactor.
The gas is produced in the reactor at a temperature of from about 1700 (927C) to about 3500 (1927C) and a pressure from about atmospheric to about 3500 pounds per square inch (0.1 to 2~ MPa). Processes and reactors for producing such a gas are generally illustrated and 29,382-F -2-i28~9~
described in U.S. Patents 2,716,598; 3,607,156; and 3,607,157. The raw gas produced also contains addi-tional by-product gases such as nitrogen, carbon dioxide and hydrogen sulfide, as well as particulate matter, which usually requires additional processing to remove the same before final use of the product gas. An inorganic slag by-product may also be produced in the reaetor along with the product gas.
One embodiment of the present invention provides an improved process for making a gas mixture eontaining hydrogen and earbon monoxide by the partial oxidation of a slurry of solid earbonaceous fuel in a liquid earrier admixed with a gas containing free oxygen, the partial oxidation oceuring in a free-flowing hollow reactor, the improvement which comprises:
(a) passing a first gas stream containing free oxygen through a first passageway formed by a central conduit of a burner with an exit discharge velocity from about 75 feet per second (23 m/s) to about sonic velocity, the burner nozzle including a spaced coaxial second and third conduits surrounding the central conduit forming a second annular passageway between the central and second conduits and a third passageway between the seeond and third eonduits, the first, seeond and third passageways being elosed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream diseharge ports;
29,382-F -3-~ 2889a~9 (b) simultaneously passing a second gas stream containing free oxygen through the third annular passageway with an exit discharge velocity from about 75 feet per second (23 m/s) to about sonic velocity and a stream of the slurry through the second annular passage-way with an exit discharge velocity from about 1 to about 50 feet per second (0.3 to 15 m/s) (c) impinging the stream of slurry on a converg-ing surface of a nozzle diffuser, whereby the stream of slurry and first and second gas streams are mixed by the impact of the slurry on the converging surface and by the shearing action of the first and second gas streams to produce a uniformly dispersed atomized admix-ture of finely divided solid carbonaceous fuel, liquid carrier and gas containing free oxygen;
(d) passing the admixture through an elongated exit orifice at an accelerated velocity of from about 100 feet per second (30 m/s) to about sonic velocity to further atomize the admixture before it enters the reactor; and (e) reacting the admixture in the reactor to form the partially oxidized gas rnixture containing hydrogen and carbon monoxide.
A further embodiment of the present inventon provides a burner nozzle for a free flowing hollow reactor used to make a gas mixture containing hydrogen and carbon monoxide by a process of partially oxidizing 29,382-F -4-128~39~9 a slurry of solid carbonaceous fuel in a liquid carrier admixed with a gas containing free oxygen comprising, a central conduit forming a central passageway for trans-porting a gas stream containing free oxygen; a second spaced coaxial conduit forming a second annular pas-sageway between the central and second conduits for transporting a stream of slurry; a third spaced coaxial conduit forming a third annular passageway between the second and third conduits for transporting a gas stream containing free oxygen; the first, second, and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream discnarge ports formed by the termination of the central, second, and third conduits; a nozzle diffuser interconnecting with and disposed near the end of the third conduit, and in a juxtaposed position downstream from the discharge ports of the central and second passageways, the dif-fuser having a converging surface on which the slurry stream impinges; and an elongated exit orifice inter-connected with the diffuser through which the admixture of slurry and gas containing free oxygen is transported at an accelerated velocity into the reactor; the second passageway formed by the central and second conduits including a first elongated segment and a second elongated sement, the first segment extending from the slurry feed inlet and converging into the second segment which in turn extends to its discharge port formed by the termination of the central and second conduits, the cross-sectional area of the first segment being substan-tially larger than the cross-sectional area of the second segment thereby providing a pressure of the slurry stream in the first segment which is substantially uniform throughout the annular area of the first segment 29,382-F -5-~28~g~9 at the point where it converges and interconnects with the second segment.
The present invention also provides an improved plug resistant nozzle which can be used in other appli-cations such as their use as spray nozzles duringaireation of waste slug in waste disposed plants. The nozzle has been designed to provide an efficient and uniform admixture of a slurry having a high concentra-tion of finely divided solids with a gas while, at the same time, reducing the tendency of such a concentrated slurry to partially or completely plug annular passage-ways in the nozzle An additional embodiment of the present invention provides an improved plug resistant nozzle for admixing a slurry having a high concentration of a finely divided solid in a carrier liquid with a gas stream comprising, a central conduit for transporting a gas stream; a second spaced coaxial conduit forming a second annular passageway between the central and second conduits for transporting a stream of slurry;
and a third spaced coaxial conduit forming a third annular passageway between the second and third con-duits for transporting a gas stream; the first, second and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream discharge ports formed by the termination of the central, second and third conduits; the second passageway formed by the central and second conduits including a first elongated segment and a second annular segment, the first segment extending from the slurry feed inlet and converging 29,382-F -6-~X8~949 into the second segment which in turn extends to its discharge port formed by the termination of the central and second conduits, the cross-sectional area of the first segment being substantially larger than the cross-sectional area of the second segment thereby proYiding a pressure of the slurry stream in the first segment which is substantially uniform throughout the annular area of the first segment at the point where it converges and interconnects with the second segment.
The nozzle of the present invention may also be used in other applications where nozzles are required to handle slurries having a high concentration of finely divided solids that must be uniformly admixed with a gas, as for example, in the aireation or inciner-ation processes of a waste disposal plant. In a pre-ferred embodiment of this invention, means are provided to reduce plugging by the separation of solids in the slurry passageways and providing uniform flow over the entire passageway cross-section, which means include maintainig a uniform annular pressure in the annular slurry passageways. This characteristic makes the nozzle not only useful as a gasification burner nozzle, but also for other nozzle applications as well.
The present burner nozzle comprises a central conduit with coaxial second and third conduits sur-rounding the central conduit which form a central passageway and two annular passageways. The central and annular passageways are closed at their upstream ends wherein inlets are provided for gas and slurry feedstreams, and are open at their downstream discharge 29,382-F -7-~288949 ports formed by the termination of the central and annular conduits. The burner nozzle includes a nozzle diffuser interconnecting with and disposed near the end of the third conduit which is in a juxtaposed position downstream from the discharge ports of the central and first annular passageway. The burner nozzle also includes an elongated exit orifice interconnected with the diffuser.
During operation of the burner nozzle a gas feedstream and slurry feedstream are introduced into upstream inlets. The gas feedstream is split and passes through the central axial passageway and through the outer annular passageway while the slurry feedstream simultaneously passes through the middle annular pas-sageway between the central passageway and outer annularpassageway, thereby enveloping the annular slurry stream between a central axial stream of oxygen-con-taining gas and an outer annular stream of the same gas. The slurry stream and gas streams are discharged through the discharge parts of their respective pas-sageways and the slurry stream is then impinged on a converging surface of the nozzle diffuser, whereby the slurry stream and gas streams are mixed by the impact of the slurry on the converging surface of the diffuser and by the shearing action of the gas streams to produce a uniformly dispersed atomized admixture of finely divided solid carbonaceous fuel, liquid carrier and gas containing free oxygen. This admixture is then passed through an elongated exit orifice at an accelerated velocity to further atomize the admixture before it enters the reactor.
29,382-F -8-~28~394~3 g These and other aspects of the invention will be apparent to those skilled in the art from the fore-going description and from the more detailed description which follows, including the following description of the drawings.
FIGURE l is a partial longitudinal cross-sec-tion illustrating a burner nozzle made in accordance with the principles of the present invention;
FIGURE 2 is a transverse cross-section taken at line A-A of FIGU~E 1 illustrating an embodiment of the burner nozzle;
FIGURE 3 is a partial longitudinal cross-sec-tion illustrating another preferred burner nozzle made in accordance with the principles of the present inven-tion; and FIGURE 4 is a transverse cross-section taken at line B-B of FIGURE 3 illustrating an embodiment of the burner nozzle.
The following description, by reference to the drawings, illustrates the manner in which the principles of the present invention are applied, but it is not to be construed as in any sense limiting the scope of the invention.
More specifically, referring to Figures 1-4, burner nozzle 10 and 30 are illustrated. Burner nozzle 10 includes a central conduit 1 forming a passageway 4;
a second coaxial annular conduit 2 forming an annular 29,382-F -9-~288949 passageway 5; and a third coaxial annular conduit 3 forming an annular passageway 6. The passageway 5 is held in a spaced relationship with passageways 4 and 6 by spacers 17. Spacers 17 should be kept to a minimum to avoid unnecessary disruption of the slurry stream flow in passageway 5. The passageways 4, 5 and 6 are closed at their upstream ends by walls 7a, 7b and 7c wherein inlets 15 and 16 are provided for slurry and gas feedstreams. A distribution chamber 18 is provided to uniformly transport the slurry feedstream into the annular passageway 5. The passageways 4, 5 and 6 have discharge ports 8a, 8b, and 8c at their downstream ends formed by the termination of conduits 1, 2 and 3. A
tube 19 is used to provide open communication between passageways 4 and 6 for the transport of the gas feed-stream.
The burner nozzle 10 also includes a nozzle diffuser 9 having a converging surface 9a for impinging the slurry passing through passageway 5, and an elongated exit orifice 11 to transport the admixture of slurry and oxygen-containing gas into the reactor at an accel-erated velocity. In this embodiment the diffuser 9 is a continuing extension of conduit 3. As a result of the harsh environment to which the diffuser 9 is sub-jected, i.e., high temperatures, chemical attack, andmechanical wear, it is an advantage, if not a necessity, to construct the diffuser 9 from a material, for example, which has high corrosion resistance, toughness, and wear characteristics, such as tungsen carbide or silicon carbide, whereas the remainder of the nozæle 10 can be constructed of a metal such as stainless steel. It is also an advantage to provide a water jacket 12 having a 29,382-F -10-~X88949 water inlet 13 and outlet 14 to cool the diffuser 9 and walls lla of the orifice 11. The orifice 11 of nozzle lO has a cylindrical design, but may also have diverging or converging walls lla. Also, although not a critical design requirement, the length of the orifice 11 is beneficially longer than its diameter to provide for additional time in a zone of high shear for the slurry/-gas mixture, and for a high degree of atomization of the admixture transported into the reactor.
Referring to Figures 3 and 4, another embodi-ment of the present invention is illustrated. Elements of burner nozzle 30 shown in Figures 3 and 4 which are like characters of reference as those shown in Figures 1 and 2 for burner nozzle 10 have the same reference numerals. Burner nozzle 30 includes modification of both the central and second annular conduit, thus changing the central gas passageway and the slurry passageway, as well as including changes in the nozzle diffuser and exit orifice. Thus, burner nozzle 30 includes annular conduit sections 31a and 31b which form an annular passageway with a first segment 32a and a second segment 32b. The cross-sectional area of segment 32a is substantially larger than the cross-sec-tion of segment 32b. The slurry feedstream from the inlet 15 is fed dixectly into segment 32a, thereby eliminating the need for the gas tube 19 of nozzle 10 and allowing direct flow of the gas feedstream into passageways 4 and 6. This provides much less disrup-tion of the slurry flow in passageway segments 32a and 32b. If necessary, fasteners 34 may be included to overcome any structure weakness.
29,382-F -11-12~9~
Burner nozzle 30 also includes a ceramic nozzle diffuser 33 having a converging surface 9a for impinging the slurry stream from passageway segment 32b which diffuser 33 is held in place by conduit 3. There are many well known ceramic materials that can be used to make the diffuser 33, for exampie, a dense-phase alumina refractory. Use of a ceramic diffuser not only provides the diffusion surface 9a, but also insulates the nozzle from the heat produced in the reactor.
As previously noted, handling highly concen-trated slurries of finely divided solids in annular nozzles such as burner nozzles 10 and 30 may result in a problem of the finely divided solids separating from the liquid carrier and plugging slurry passageways. To overcome the possibility of this occuring, and to provide uniform flow across the entire cross-section of the annular flow passageway, nozzle 10 includes the distribution chamber 18 and nozzle 30 includes the combined segments 32a and 32b that form the slurry passageway. In both nozzles 10 and 30, the upstream chamber or segment of the passageway for the slurry stream has a substantially larger cross-sectional area than the downstream segment. As a specific example, a nozzle designed like nozzle 30 was constructed of metal pipe wherein the central gas stream passageway had about a three inch (7.6 cm) diameter and 16 inch (40.6 cm) length, and the first segment of the slurry passage-way had an annular cross-sectional thickness of about one and one-half inches (3.8 cm) around the central passageway and a 4 inch (10 cm) length, and the second segment of the slurry passageway had an annular cross--sectional thickness of about one quarter of an inch (0.6 cm) and a 12 inch (30.5 cm) length.
29,382-F -12-~Z~3139~9 The slurry stream in the larger upstream chamber or segment provides a substantially uniform pressure throughout the annular area of the upstream segment at the point where the upstream segment inter-connects with the downstream annular portion of thepassageway, thus substantially reducing flow variations around the annular flowpath of the slurry stream. It has been also found that this uniform annular pressure at the point of interconnection can be substantially maintained by designing the upstream portion of the slurry passageway from the inlet downstream to the point of interconnection with the annular portion of the passageway so that the pressure drop is about 20 percent or less of the pressure drop that occurs in the annular portion of the slurry passageway downstream to its discharge port.
In order to produce the desired uniformity of dispersion and atomization of the admixture of slurry and gas, it has been determined that the preferred velocities of the gas and slurry streams through the various passageways should be maintained within the following ranges. The gas stream passing through the central axial passages should have an exit discharge velocity from about 75 feet per second (23 m/s) to about sonic velocity. The gas stream passing through the outer annular passageway should have an exit dis-charge velocity of from about 75 feet per second (23 m/s) to about sonic velocity. The slurry stream passing through the second or middle annular passageway should have an exit discharge velocity from about 1 to about 50 feet per second (0.3 to 15 m/s). The velocity of the combined admixture of slurry and gas through the 29,382-F -13-~'~813~
exit orifice of the nozzle into the reactor should be from about 100 feet per second (30 m/s) to about sonic velocity.
29,382-F -14-
FOR ITS USE
The present invention concerns the production of synthetic gas or fuel gas containing hydrogen and carbon monoxide which is formed by partially oxidizing a slurry of solid carbonaceous fuel and a carrier liquid admixed with a gas containing free oxygen in a hollow free-flowing reactor. More particularly, this invention concerns an improved burner nozzle for admix-ing the slurry and oxygen-containing gas, and then introducing the admixture into a reactor.
Three basic processes have been developed for the gasification of carbonaceous materials. They are the fixed bed process, fluidized bed process, and the suspen-sion or entrained process. The efficiency of the entrained process, with which the present invention is concerned, is significantly affected by the degree of mixing of reac-tants prior to carrying out the partial oxidation reaction leading to gasification. In the case where a slurry of a finely divided carbonaceous fuel in a carrier liquid 2~,382-F -1-~288949 is admixed with an oxygen containing gas, it is very important that the reactants are uniformly mixed and atomized into very fine droplets at the time they are vaporized and then iynited to form a gaseous product.
Annular-type burner nozzles have been employed for introducing an admixture of slurry and oxygen-containing gas into a reactor. For example, annular-type burners are shown in U.S. Patents 4,364,744 and 4,443,230.
Problems that have been addressed with such burner nozzles include mixing to provide proper distribution of the fuel and oxygen in the admixture, atomization of the admixture, stability of burner nozzle operation, reduction of localized overheating in the reactor and burner nozzle, and reduction of mechanical wear of the burner nozzle. In addition to these problems, slurries containing a high concentration of divided solids also tend to plug or partially plug annular passageways as they are transported through the burner nozzles.
In general, the present invention provides an improved burner nozzle and process for making a syn-thesis gas or fuel gas mixture containing hydrogen and carbon monoxide by the partial oxidation of a slurry of solid carbonaceous fuel in a liquid carrier admixed with a gas containing free oxygen, the partial oxidation occuring in a free-flowing hollow reactor. By means of the burner nozzle, the slurry and oxygen-containing gas are admixed, atomized and introduced into the reactor.
The gas is produced in the reactor at a temperature of from about 1700 (927C) to about 3500 (1927C) and a pressure from about atmospheric to about 3500 pounds per square inch (0.1 to 2~ MPa). Processes and reactors for producing such a gas are generally illustrated and 29,382-F -2-i28~9~
described in U.S. Patents 2,716,598; 3,607,156; and 3,607,157. The raw gas produced also contains addi-tional by-product gases such as nitrogen, carbon dioxide and hydrogen sulfide, as well as particulate matter, which usually requires additional processing to remove the same before final use of the product gas. An inorganic slag by-product may also be produced in the reaetor along with the product gas.
One embodiment of the present invention provides an improved process for making a gas mixture eontaining hydrogen and earbon monoxide by the partial oxidation of a slurry of solid earbonaceous fuel in a liquid earrier admixed with a gas containing free oxygen, the partial oxidation oceuring in a free-flowing hollow reactor, the improvement which comprises:
(a) passing a first gas stream containing free oxygen through a first passageway formed by a central conduit of a burner with an exit discharge velocity from about 75 feet per second (23 m/s) to about sonic velocity, the burner nozzle including a spaced coaxial second and third conduits surrounding the central conduit forming a second annular passageway between the central and second conduits and a third passageway between the seeond and third eonduits, the first, seeond and third passageways being elosed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream diseharge ports;
29,382-F -3-~ 2889a~9 (b) simultaneously passing a second gas stream containing free oxygen through the third annular passageway with an exit discharge velocity from about 75 feet per second (23 m/s) to about sonic velocity and a stream of the slurry through the second annular passage-way with an exit discharge velocity from about 1 to about 50 feet per second (0.3 to 15 m/s) (c) impinging the stream of slurry on a converg-ing surface of a nozzle diffuser, whereby the stream of slurry and first and second gas streams are mixed by the impact of the slurry on the converging surface and by the shearing action of the first and second gas streams to produce a uniformly dispersed atomized admix-ture of finely divided solid carbonaceous fuel, liquid carrier and gas containing free oxygen;
(d) passing the admixture through an elongated exit orifice at an accelerated velocity of from about 100 feet per second (30 m/s) to about sonic velocity to further atomize the admixture before it enters the reactor; and (e) reacting the admixture in the reactor to form the partially oxidized gas rnixture containing hydrogen and carbon monoxide.
A further embodiment of the present inventon provides a burner nozzle for a free flowing hollow reactor used to make a gas mixture containing hydrogen and carbon monoxide by a process of partially oxidizing 29,382-F -4-128~39~9 a slurry of solid carbonaceous fuel in a liquid carrier admixed with a gas containing free oxygen comprising, a central conduit forming a central passageway for trans-porting a gas stream containing free oxygen; a second spaced coaxial conduit forming a second annular pas-sageway between the central and second conduits for transporting a stream of slurry; a third spaced coaxial conduit forming a third annular passageway between the second and third conduits for transporting a gas stream containing free oxygen; the first, second, and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream discnarge ports formed by the termination of the central, second, and third conduits; a nozzle diffuser interconnecting with and disposed near the end of the third conduit, and in a juxtaposed position downstream from the discharge ports of the central and second passageways, the dif-fuser having a converging surface on which the slurry stream impinges; and an elongated exit orifice inter-connected with the diffuser through which the admixture of slurry and gas containing free oxygen is transported at an accelerated velocity into the reactor; the second passageway formed by the central and second conduits including a first elongated segment and a second elongated sement, the first segment extending from the slurry feed inlet and converging into the second segment which in turn extends to its discharge port formed by the termination of the central and second conduits, the cross-sectional area of the first segment being substan-tially larger than the cross-sectional area of the second segment thereby providing a pressure of the slurry stream in the first segment which is substantially uniform throughout the annular area of the first segment 29,382-F -5-~28~g~9 at the point where it converges and interconnects with the second segment.
The present invention also provides an improved plug resistant nozzle which can be used in other appli-cations such as their use as spray nozzles duringaireation of waste slug in waste disposed plants. The nozzle has been designed to provide an efficient and uniform admixture of a slurry having a high concentra-tion of finely divided solids with a gas while, at the same time, reducing the tendency of such a concentrated slurry to partially or completely plug annular passage-ways in the nozzle An additional embodiment of the present invention provides an improved plug resistant nozzle for admixing a slurry having a high concentration of a finely divided solid in a carrier liquid with a gas stream comprising, a central conduit for transporting a gas stream; a second spaced coaxial conduit forming a second annular passageway between the central and second conduits for transporting a stream of slurry;
and a third spaced coaxial conduit forming a third annular passageway between the second and third con-duits for transporting a gas stream; the first, second and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream discharge ports formed by the termination of the central, second and third conduits; the second passageway formed by the central and second conduits including a first elongated segment and a second annular segment, the first segment extending from the slurry feed inlet and converging 29,382-F -6-~X8~949 into the second segment which in turn extends to its discharge port formed by the termination of the central and second conduits, the cross-sectional area of the first segment being substantially larger than the cross-sectional area of the second segment thereby proYiding a pressure of the slurry stream in the first segment which is substantially uniform throughout the annular area of the first segment at the point where it converges and interconnects with the second segment.
The nozzle of the present invention may also be used in other applications where nozzles are required to handle slurries having a high concentration of finely divided solids that must be uniformly admixed with a gas, as for example, in the aireation or inciner-ation processes of a waste disposal plant. In a pre-ferred embodiment of this invention, means are provided to reduce plugging by the separation of solids in the slurry passageways and providing uniform flow over the entire passageway cross-section, which means include maintainig a uniform annular pressure in the annular slurry passageways. This characteristic makes the nozzle not only useful as a gasification burner nozzle, but also for other nozzle applications as well.
The present burner nozzle comprises a central conduit with coaxial second and third conduits sur-rounding the central conduit which form a central passageway and two annular passageways. The central and annular passageways are closed at their upstream ends wherein inlets are provided for gas and slurry feedstreams, and are open at their downstream discharge 29,382-F -7-~288949 ports formed by the termination of the central and annular conduits. The burner nozzle includes a nozzle diffuser interconnecting with and disposed near the end of the third conduit which is in a juxtaposed position downstream from the discharge ports of the central and first annular passageway. The burner nozzle also includes an elongated exit orifice interconnected with the diffuser.
During operation of the burner nozzle a gas feedstream and slurry feedstream are introduced into upstream inlets. The gas feedstream is split and passes through the central axial passageway and through the outer annular passageway while the slurry feedstream simultaneously passes through the middle annular pas-sageway between the central passageway and outer annularpassageway, thereby enveloping the annular slurry stream between a central axial stream of oxygen-con-taining gas and an outer annular stream of the same gas. The slurry stream and gas streams are discharged through the discharge parts of their respective pas-sageways and the slurry stream is then impinged on a converging surface of the nozzle diffuser, whereby the slurry stream and gas streams are mixed by the impact of the slurry on the converging surface of the diffuser and by the shearing action of the gas streams to produce a uniformly dispersed atomized admixture of finely divided solid carbonaceous fuel, liquid carrier and gas containing free oxygen. This admixture is then passed through an elongated exit orifice at an accelerated velocity to further atomize the admixture before it enters the reactor.
29,382-F -8-~28~394~3 g These and other aspects of the invention will be apparent to those skilled in the art from the fore-going description and from the more detailed description which follows, including the following description of the drawings.
FIGURE l is a partial longitudinal cross-sec-tion illustrating a burner nozzle made in accordance with the principles of the present invention;
FIGURE 2 is a transverse cross-section taken at line A-A of FIGU~E 1 illustrating an embodiment of the burner nozzle;
FIGURE 3 is a partial longitudinal cross-sec-tion illustrating another preferred burner nozzle made in accordance with the principles of the present inven-tion; and FIGURE 4 is a transverse cross-section taken at line B-B of FIGURE 3 illustrating an embodiment of the burner nozzle.
The following description, by reference to the drawings, illustrates the manner in which the principles of the present invention are applied, but it is not to be construed as in any sense limiting the scope of the invention.
More specifically, referring to Figures 1-4, burner nozzle 10 and 30 are illustrated. Burner nozzle 10 includes a central conduit 1 forming a passageway 4;
a second coaxial annular conduit 2 forming an annular 29,382-F -9-~288949 passageway 5; and a third coaxial annular conduit 3 forming an annular passageway 6. The passageway 5 is held in a spaced relationship with passageways 4 and 6 by spacers 17. Spacers 17 should be kept to a minimum to avoid unnecessary disruption of the slurry stream flow in passageway 5. The passageways 4, 5 and 6 are closed at their upstream ends by walls 7a, 7b and 7c wherein inlets 15 and 16 are provided for slurry and gas feedstreams. A distribution chamber 18 is provided to uniformly transport the slurry feedstream into the annular passageway 5. The passageways 4, 5 and 6 have discharge ports 8a, 8b, and 8c at their downstream ends formed by the termination of conduits 1, 2 and 3. A
tube 19 is used to provide open communication between passageways 4 and 6 for the transport of the gas feed-stream.
The burner nozzle 10 also includes a nozzle diffuser 9 having a converging surface 9a for impinging the slurry passing through passageway 5, and an elongated exit orifice 11 to transport the admixture of slurry and oxygen-containing gas into the reactor at an accel-erated velocity. In this embodiment the diffuser 9 is a continuing extension of conduit 3. As a result of the harsh environment to which the diffuser 9 is sub-jected, i.e., high temperatures, chemical attack, andmechanical wear, it is an advantage, if not a necessity, to construct the diffuser 9 from a material, for example, which has high corrosion resistance, toughness, and wear characteristics, such as tungsen carbide or silicon carbide, whereas the remainder of the nozæle 10 can be constructed of a metal such as stainless steel. It is also an advantage to provide a water jacket 12 having a 29,382-F -10-~X88949 water inlet 13 and outlet 14 to cool the diffuser 9 and walls lla of the orifice 11. The orifice 11 of nozzle lO has a cylindrical design, but may also have diverging or converging walls lla. Also, although not a critical design requirement, the length of the orifice 11 is beneficially longer than its diameter to provide for additional time in a zone of high shear for the slurry/-gas mixture, and for a high degree of atomization of the admixture transported into the reactor.
Referring to Figures 3 and 4, another embodi-ment of the present invention is illustrated. Elements of burner nozzle 30 shown in Figures 3 and 4 which are like characters of reference as those shown in Figures 1 and 2 for burner nozzle 10 have the same reference numerals. Burner nozzle 30 includes modification of both the central and second annular conduit, thus changing the central gas passageway and the slurry passageway, as well as including changes in the nozzle diffuser and exit orifice. Thus, burner nozzle 30 includes annular conduit sections 31a and 31b which form an annular passageway with a first segment 32a and a second segment 32b. The cross-sectional area of segment 32a is substantially larger than the cross-sec-tion of segment 32b. The slurry feedstream from the inlet 15 is fed dixectly into segment 32a, thereby eliminating the need for the gas tube 19 of nozzle 10 and allowing direct flow of the gas feedstream into passageways 4 and 6. This provides much less disrup-tion of the slurry flow in passageway segments 32a and 32b. If necessary, fasteners 34 may be included to overcome any structure weakness.
29,382-F -11-12~9~
Burner nozzle 30 also includes a ceramic nozzle diffuser 33 having a converging surface 9a for impinging the slurry stream from passageway segment 32b which diffuser 33 is held in place by conduit 3. There are many well known ceramic materials that can be used to make the diffuser 33, for exampie, a dense-phase alumina refractory. Use of a ceramic diffuser not only provides the diffusion surface 9a, but also insulates the nozzle from the heat produced in the reactor.
As previously noted, handling highly concen-trated slurries of finely divided solids in annular nozzles such as burner nozzles 10 and 30 may result in a problem of the finely divided solids separating from the liquid carrier and plugging slurry passageways. To overcome the possibility of this occuring, and to provide uniform flow across the entire cross-section of the annular flow passageway, nozzle 10 includes the distribution chamber 18 and nozzle 30 includes the combined segments 32a and 32b that form the slurry passageway. In both nozzles 10 and 30, the upstream chamber or segment of the passageway for the slurry stream has a substantially larger cross-sectional area than the downstream segment. As a specific example, a nozzle designed like nozzle 30 was constructed of metal pipe wherein the central gas stream passageway had about a three inch (7.6 cm) diameter and 16 inch (40.6 cm) length, and the first segment of the slurry passage-way had an annular cross-sectional thickness of about one and one-half inches (3.8 cm) around the central passageway and a 4 inch (10 cm) length, and the second segment of the slurry passageway had an annular cross--sectional thickness of about one quarter of an inch (0.6 cm) and a 12 inch (30.5 cm) length.
29,382-F -12-~Z~3139~9 The slurry stream in the larger upstream chamber or segment provides a substantially uniform pressure throughout the annular area of the upstream segment at the point where the upstream segment inter-connects with the downstream annular portion of thepassageway, thus substantially reducing flow variations around the annular flowpath of the slurry stream. It has been also found that this uniform annular pressure at the point of interconnection can be substantially maintained by designing the upstream portion of the slurry passageway from the inlet downstream to the point of interconnection with the annular portion of the passageway so that the pressure drop is about 20 percent or less of the pressure drop that occurs in the annular portion of the slurry passageway downstream to its discharge port.
In order to produce the desired uniformity of dispersion and atomization of the admixture of slurry and gas, it has been determined that the preferred velocities of the gas and slurry streams through the various passageways should be maintained within the following ranges. The gas stream passing through the central axial passages should have an exit discharge velocity from about 75 feet per second (23 m/s) to about sonic velocity. The gas stream passing through the outer annular passageway should have an exit dis-charge velocity of from about 75 feet per second (23 m/s) to about sonic velocity. The slurry stream passing through the second or middle annular passageway should have an exit discharge velocity from about 1 to about 50 feet per second (0.3 to 15 m/s). The velocity of the combined admixture of slurry and gas through the 29,382-F -13-~'~813~
exit orifice of the nozzle into the reactor should be from about 100 feet per second (30 m/s) to about sonic velocity.
29,382-F -14-
Claims (10)
1. In a process for making a gas mixture containing hydrogen and carbon monoxide by the partial oxidation of a slurry of solid carbonaceous fuel in a liquid carrier admixed with a gas containing free oxygen, the partial oxidation occuring in a free-flowing hollow reactor, the improvement which comprises:
(a) passing a first gas stream containing free oxygen through a first passageway formed by a central conduit of a burner with an exit discharge velocity from about 75 feet per second (23 m/s) to about sonic velocity, the burner nozzle including a spaced coaxial second and third conduits surrounding the central conduit forming a second annular passageway between the central and second conduits and a third passageway between the second and third conduits, the first, second and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream discharge ports;
(b) simultaneously passing a second gas stream containing free oxygen through the third annular passageway with an exit discharge 29,382-F -15-velocity from about 75 feet per second (23 m/s) to about sonic velocity and a stream of the slurry through the second annular pas-sageway with an exit discharge velocity from about 1 to about 50 feet per second (0.3 to 15 m/s);
(c) impinging the stream of slurry on a converg-ing surface of a nozzle diffuser, whereby the stream of slurry and first and second gas streams are mixed by the impact of the slurry on the converging surface and by the shearing action of the first and second gas streams to produce a uniformly dispersed atomized admix-ture of finely divided solid carbonaceous fuel, liquid carrier and gas containing free oxygen;
(d) passing the admixture through an elongated exit orifice at an accelerated velocity of from about 100 feet per second (30 m/s) to about sonic velocity to further atomize the admixture before it enters the reactor; and (e) reacting the admixture in the reactor to form the partially oxidized gas mixture containing hydrogen and carbon monoxide.
(a) passing a first gas stream containing free oxygen through a first passageway formed by a central conduit of a burner with an exit discharge velocity from about 75 feet per second (23 m/s) to about sonic velocity, the burner nozzle including a spaced coaxial second and third conduits surrounding the central conduit forming a second annular passageway between the central and second conduits and a third passageway between the second and third conduits, the first, second and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream discharge ports;
(b) simultaneously passing a second gas stream containing free oxygen through the third annular passageway with an exit discharge 29,382-F -15-velocity from about 75 feet per second (23 m/s) to about sonic velocity and a stream of the slurry through the second annular pas-sageway with an exit discharge velocity from about 1 to about 50 feet per second (0.3 to 15 m/s);
(c) impinging the stream of slurry on a converg-ing surface of a nozzle diffuser, whereby the stream of slurry and first and second gas streams are mixed by the impact of the slurry on the converging surface and by the shearing action of the first and second gas streams to produce a uniformly dispersed atomized admix-ture of finely divided solid carbonaceous fuel, liquid carrier and gas containing free oxygen;
(d) passing the admixture through an elongated exit orifice at an accelerated velocity of from about 100 feet per second (30 m/s) to about sonic velocity to further atomize the admixture before it enters the reactor; and (e) reacting the admixture in the reactor to form the partially oxidized gas mixture containing hydrogen and carbon monoxide.
2. The process of Claim 1, wherein the diffuser is a continuous converging section of the third conduit connected to the exit orifice.
29,382-F -16-
29,382-F -16-
3. The process of Claim 1, wherein the diffuser is a separate plug held in place by the third conduit with the exit orifice extending through the plug.
4. The process of Claim 1, wherein the second passageway comprises a first elongated segment and a second annular elongated segment, the first elongated segment extending from the slurry feed inlet and converging into the second segment which in turn extends to its discharge port, the cross-sectional area of the first segment being substantially larger than the cross-sectional area of the second segment thereby providing a pressure of the slurry stream in the first segment which is substantially uniform throughout the annular area of the first segment at the point where it converges and interconnects with the second segment.
5. The process of Claim 2, 3 or 4, wherein the pressure drop for the slurry stream from the slurry feed inlet to the point where the first segment inter-connects with the second segment is about twenty percent or less of the pressure drop for the slurry stream from the point of interconnection to the discharge port of the second segment.
6. A burner nozzle for a free flowing hollow reactor used to make a gas mixture containing hydrogen and carbon monoxide by a process of partially oxidizing a slurry of solid carbonaceous fuel in a liquid carrier admixed with a gas containing free oxygen comprising, a central conduit forming a central passageway for trans-porting a gas stream containing free oxygen; a second 29,382-F -17-spaced coaxial conduit forming a second annular pas-sageway between the central and second conduits for transporting a stream of slurry; a third spaced coaxial conduit forming a third annular passageway between the second and third conduits for transporting a gas stream containing free oxygen; the first, second, and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream discharge ports formed by the termination of the central, second, and third conduits; a nozzle diffuser interconnecting with and disposed near the end of the third conduit, and in a juxtaposed position downstream from the discharge ports of the central and second passageways, the dif-fuser having a converging surface on which the slurry stream impinges; and an elongated exit orifice inter-connected with the diffuser through which the admixture of slurry and gas containing free oxygen is transported at an accelerated velocity into the reactor; the second passageway formed by the central and second conduits including a first elongated segment and a second elongated sement, the first segment extending from the slurry feed inlet and converging into the second segment which in turn extends to its discharge port formed by the termination of the central and second conduits, the cross-sectional area of the first segment being sub-stantially larger than the cross-sectional area of the second segment thereby providing a pressure of the slurry stream in the first segment which is substan-tially uniform throughout the annular area of the first segment at the point where it converges and inter-connects with the second segment.
29,382-F -18-
29,382-F -18-
7. The burner nozzle of Claim 6, wherein the diffuser is a continuous converging section of the third conduit connected to the exit orifice.
8. The burner nozzle of Claim 6, wherein the diffuser is a separate plug held in place by the third conduit with the exit orifice extending through the plug.
9. An improved plug resistant nozzle for admixing a slurry having a high concentration of a finely divided solid in a carrier liquid with a gas stream comprising, a central conduit for transporting a gas stream; a second spaced coaxial conduit forming a second annular passageway between the central and second conduits for transporting a stream of slurry;
and a third spaced coaxial conduit forming a third annular passageway between the second and third con-duits for transporting a gas stream; the first, second and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream dis-charge ports formed by the termination of the central, second and third conduits; the second passageway formed by the central and second conduits including a first elongated segment and a second annular segment, the first segment extending from the slurry feed inlet and converging into the second segment which in turn extends to its discharge port formed by the termination of the central and second conduits, the cross sectional area of the first segment being substantially larger than the cross-sectional area of the second segment thereby providing a pressure of the slurry stream in the first 29,382-F -19-segment which is substantially uniform throughout the annular area of the first segment at the point where it converges and interconnects with the second segment.
and a third spaced coaxial conduit forming a third annular passageway between the second and third con-duits for transporting a gas stream; the first, second and third passageways being closed at their upstream ends wherein inlets are provided for a gas feedstream and a slurry feedstream and open at downstream dis-charge ports formed by the termination of the central, second and third conduits; the second passageway formed by the central and second conduits including a first elongated segment and a second annular segment, the first segment extending from the slurry feed inlet and converging into the second segment which in turn extends to its discharge port formed by the termination of the central and second conduits, the cross sectional area of the first segment being substantially larger than the cross-sectional area of the second segment thereby providing a pressure of the slurry stream in the first 29,382-F -19-segment which is substantially uniform throughout the annular area of the first segment at the point where it converges and interconnects with the second segment.
10. The burner nozzle of Claim 6, 7 or 9, wherein the cross-sectional areas of the first and second segments are proportioned to provide a pressure drop for the slurry stream from the slurry feed inlet to the point where the first segment interconnects with the second segment which is about twenty percent or less of the pressure drop for the slurry stream from the point of interconnection to the discharge port of the second segment.
29,382-F -20-
29,382-F -20-
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72376785A | 1985-04-16 | 1985-04-16 | |
| US723,767 | 1985-04-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1288949C true CA1288949C (en) | 1991-09-17 |
Family
ID=24907585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000506684A Expired - Lifetime CA1288949C (en) | 1985-04-16 | 1986-04-15 | Annular nozzle and process for its use |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0198700B1 (en) |
| JP (1) | JPH0735887B2 (en) |
| KR (1) | KR930011069B1 (en) |
| CN (1) | CN1007881B (en) |
| AU (1) | AU583370B2 (en) |
| CA (1) | CA1288949C (en) |
| DE (1) | DE3680375D1 (en) |
| IN (1) | IN167217B (en) |
| NZ (1) | NZ215762A (en) |
| TR (1) | TR22939A (en) |
| ZA (1) | ZA862842B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN167311B (en) * | 1985-04-16 | 1990-10-06 | Dow Chemical Co | |
| JP2627552B2 (en) * | 1988-02-17 | 1997-07-09 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Partial burner with spiral flow cooling surface |
| US4887962A (en) * | 1988-02-17 | 1989-12-19 | Shell Oil Company | Partial combustion burner with spiral-flow cooled face |
| US5261602A (en) * | 1991-12-23 | 1993-11-16 | Texaco Inc. | Partial oxidation process and burner with porous tip |
| CN1298816C (en) * | 2005-03-08 | 2007-02-07 | 北京航天动力研究所 | Environmental-protection combustible powder clean gasifying apparatus |
| SE534818C2 (en) * | 2010-05-06 | 2012-01-10 | Cortus Ab | Method and apparatus for introducing powdered material into a gasification reactor, the apparatus comprising a laval nozzle |
| US8974557B2 (en) * | 2011-06-09 | 2015-03-10 | Good Earth Power Corporation | Tunable catalytic gasifiers and related methods |
| CN103438447B (en) * | 2013-08-16 | 2016-05-18 | 武汉华尔顺冶金工程技术有限公司 | Water-cooled petroleum coke power combustor |
| PL3161109T3 (en) | 2014-06-27 | 2019-04-30 | Tubitak | A coal feeding system |
| CN104327881B (en) * | 2014-10-16 | 2017-01-11 | 煤炭科学技术研究院有限公司 | Liquid continuous slag-removal fixed bed gasification furnace and gasification method thereof |
| CN113917068A (en) * | 2021-09-27 | 2022-01-11 | 聚光科技(杭州)股份有限公司 | System and method for detecting carbon in water |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2199850A5 (en) * | 1972-09-20 | 1974-04-12 | Lillers Indle | |
| US4364744A (en) * | 1979-12-26 | 1982-12-21 | Texaco Inc. | Burner for the partial oxidation of slurries of solid carbonaceous fuels |
| US4338099A (en) * | 1979-12-26 | 1982-07-06 | Texaco Inc. | Process for the partial oxidation of slurries of solid carbonaceous fuels |
| GB2099843B (en) * | 1981-06-10 | 1985-01-30 | Texaco Development Corp | Partial oxidation process |
| US4443230A (en) * | 1983-05-31 | 1984-04-17 | Texaco Inc. | Partial oxidation process for slurries of solid fuel |
| GB8318195D0 (en) * | 1983-07-05 | 1983-08-03 | Shell Int Research | Burner |
-
1986
- 1986-04-07 IN IN253/MAS/86A patent/IN167217B/en unknown
- 1986-04-09 NZ NZ215762A patent/NZ215762A/en unknown
- 1986-04-14 DE DE8686302759T patent/DE3680375D1/en not_active Expired - Lifetime
- 1986-04-14 EP EP86302759A patent/EP0198700B1/en not_active Expired - Lifetime
- 1986-04-14 AU AU56068/86A patent/AU583370B2/en not_active Expired
- 1986-04-15 CA CA000506684A patent/CA1288949C/en not_active Expired - Lifetime
- 1986-04-16 ZA ZA862842A patent/ZA862842B/en unknown
- 1986-04-16 TR TR200/86A patent/TR22939A/en unknown
- 1986-04-16 JP JP61087877A patent/JPH0735887B2/en not_active Expired - Lifetime
- 1986-04-16 CN CN86102614A patent/CN1007881B/en not_active Expired
- 1986-04-16 KR KR1019860002915A patent/KR930011069B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TR22939A (en) | 1988-12-08 |
| JPH0735887B2 (en) | 1995-04-19 |
| JPS61259016A (en) | 1986-11-17 |
| EP0198700B1 (en) | 1991-07-24 |
| KR860008257A (en) | 1986-11-14 |
| AU583370B2 (en) | 1989-04-27 |
| DE3680375D1 (en) | 1991-08-29 |
| CN86102614A (en) | 1987-01-28 |
| AU5606886A (en) | 1986-10-23 |
| ZA862842B (en) | 1987-12-30 |
| CN1007881B (en) | 1990-05-09 |
| NZ215762A (en) | 1989-03-29 |
| KR930011069B1 (en) | 1993-11-20 |
| IN167217B (en) | 1990-09-22 |
| EP0198700A3 (en) | 1987-06-03 |
| EP0198700A2 (en) | 1986-10-22 |
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| MKEX | Expiry |