EP3156507A1 - Method and device for generation and treatment of protection and/or reaction gases especially for heat treatment of metals - Google Patents
Method and device for generation and treatment of protection and/or reaction gases especially for heat treatment of metals Download PDFInfo
- Publication number
- EP3156507A1 EP3156507A1 EP16187277.5A EP16187277A EP3156507A1 EP 3156507 A1 EP3156507 A1 EP 3156507A1 EP 16187277 A EP16187277 A EP 16187277A EP 3156507 A1 EP3156507 A1 EP 3156507A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- heat treatment
- protective
- cleavage
- reaction gases
- 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.)
- Granted
Links
- 239000007789 gas Substances 0.000 title claims abstract description 244
- 238000010438 heat treatment Methods 0.000 title claims abstract description 85
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 150000002739 metals Chemical class 0.000 title claims abstract description 17
- 230000001681 protective effect Effects 0.000 claims abstract description 60
- 230000004992 fission Effects 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000003134 recirculating effect Effects 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- 238000003776 cleavage reaction Methods 0.000 claims description 23
- 230000007017 scission Effects 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 230000008014 freezing Effects 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 10
- 239000002918 waste heat Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005255 carburizing Methods 0.000 claims description 7
- 238000005261 decarburization Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000005336 cracking Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000012159 carrier gas Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/767—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material with forced gas circulation; Reheating thereof
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/76—Adjusting the composition of the atmosphere
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
Definitions
- the invention relates to a process for the production and / or treatment of protective and / or reaction gases for the heat treatment of metals, in particular for carburizing and / or for preventing the decarburization of metal components.
- the invention further relates to a device for generating and / or treating protective and / or reactive gases.
- a heat treatment plant or a heat treatment furnace is gassed with reducing protective and / or reactive gases.
- These protective and / or reaction gases usually consist essentially of carbon monoxide, hydrogen, nitrogen, water vapor and carbon dioxide.
- Gas components of these protective and / or reaction gases can be obtained in particular by thermal decomposition of hydrocarbon-containing substances, for example by thermal decomposition of methanol.
- the resulting gas components are also called fission gas (s) or fission gas mixture.
- protective and / or reaction gases are used in a discontinuous batchwise operated chamber furnace system. Within this heat treatment plant, the protective and / or reaction gases are generated at the high heat treatment temperatures of natural gas and air. The protective and / or reaction gases are recirculated in the heat treatment plant via a high-temperature catalyst and treated with hydrocarbon gas. This procedure is - not least due to the use of high-temperature catalyst - associated with a disadvantageously high energy consumption. The recirculating protective and / or reaction gases also accumulate in this process with a disadvantageously high carbon dioxide and water vapor content. To compensate for this enrichment, additional feed gas must be added while increasing the input gas flow rate. This in turn means that excess protective and / or reaction gases must be burned or flared. This involves the disadvantages already described above.
- the invention the technical problem of providing a method of the type mentioned, in which the disadvantages described above can be avoided, which is simple and inexpensive to carry out and which is optimized in energy technology and environmental terms.
- the invention is further based on the technical problem of specifying a corresponding device for carrying out the method.
- the invention teaches a method for generating and / or treatment of protective and / or reaction gases for heat treatment of metals, in particular for carburizing and / or preventing the decarburization of metal components, which by a - preferably continuously operated - heat treatment plant Guided gases between at least one gas outlet of the system and at least one gas inlet of the system are circulated or recirculated and wherein the recirculating gases generated outside the heat treatment plant fission gas or fission gas mixture for renewal or replacement of gas components is mixed.
- the protective and / or reaction gases are passed through the heat treatment plant and then discharged from the at least one gas outlet of the system and then returned to the gas inlet of the system and in turn introduced into the system, so that the circulation of the protective and / or reaction gases results.
- the protective and / or reaction gases are first passed through the heat treatment plant and then discharged from the at least one gas outlet of the system and then returned within the furnace chamber of the heat treatment plant via a gas line from the furnace side separate line to the gas inlet of the system and again introduced into the plant.
- gas components of the protective and / or reaction gases in the form of a fission gas or fission gas mixture are metered.
- the content of gas components of the protective and / or reaction gases are measured or measured automatically and, depending on the determined need, fission gas or specifically fission gas is added.
- the invention is based on the finding that due to the recycling of the protective and / or reaction gases according to the invention a method can be operated with little effort and low cost, in which the material use and energy use advantageously limits and targeted in the energy or heat can be used or recycled.
- the method according to the invention meets all environmental requirements. This will be explained in more detail below.
- the heat treatment of the metals is carried out by a continuous procedure. It is thus in the heat treatment system used preferably a continuously operated heat treatment plant for the heat treatment of metals.
- At least one gas generating substance is introduced into the heat treatment plant when starting up the process or the method. Furthermore, it is within the scope of the invention that within the heat treatment plant - in situ - from this at least one gas generating substance protection and / or reaction gases are formed.
- the gas generant is methanol.
- methanol is introduced as a gas generating substance together with at least one carrier gas, preferably with nitrogen as a carrier gas in the heat treatment plant.
- the generation of the fission gas or the fission gas mixture takes place outside the plant or outside of the furnace under heat and the heat required for this purpose is taken from the exhaust gas from the heating of the heat treatment plant.
- the waste heat of the heat treatment plant is utilized to generate the fission gas. It is within the scope of the invention that the generation of the cracked gas is carried out via an indirect heating by means of the waste heat from the heat treatment plant.
- a particularly recommended embodiment of the method according to the invention is characterized in that the cleavage gas is generated by cleavage of at least one alcohol, preferably by cleavage of methanol.
- the alcohol or preferably the methanol by means of a carrier gas, recommended added with nitrogen as the carrier gas.
- Particularly preferred in the context of the method according to the invention is the Recovery of the fission gas by catalytic low-temperature cracking.
- Empfohlene the low temperature cleavage at a temperature of 200 to 400 ° C, preferably at a temperature of 240 to 370 ° C is performed.
- a temperature of 250 to 360 ° C for the low temperature cracking is particularly preferred.
- the temperature of the catalytic low-temperature cracking is significantly lower than the temperature in the heat treatment plant (about 800 to 1000 ° C, in particular 850 to 950 ° C). It is within the scope of the invention that in the catalytic low-temperature cracking, the conditions of the cleavage are set precisely, so that as little carbon dioxide and as little water vapor as possible. Furthermore, it is within the scope of the invention that only the necessary supply of gas components for a replacement or renewal of the gas components of the protective and / or reaction gases is supplied by the catalytic low-temperature cracking. In that regard, the gas supply from the catalytic low-temperature cracking is expediently only a fraction of the volume flow of the recirculating protective and / or reaction gases.
- a highly recommended embodiment of the method according to the invention is characterized in that the fission gas generated outside the heat treatment plant is passed through at least one cleaning device in order to at least reduce the content of at least one gas component.
- This at least one gas component is in particular carbon dioxide and / or water or water vapor. This avoids that a disadvantageous accumulation of the protective and / or reaction gases of carbon dioxide and / or water or water vapor takes place.
- the cracked gas is passed only partially and / or only when needed by the at least one cleaning device and to that extent an expedient embodiment variant is characterized in that the at least one cleaning device is accommodated in a bypass guide of the split gas.
- an analysis or an automatic analysis of the cracking gas takes place on its carbon dioxide content and / or on its water content.
- the cracked gas is then passed, if necessary, partially or completely through the at least one cleaning device.
- care is taken that the carbon dioxide content and / or the water content in the protective and / or reaction gases does not exceed a certain desired value.
- At least one freezing device is present as a cleaning device, with this freezing device expediently carbon dioxide being frozen out of the cleavage gas.
- a particularly preferred embodiment of the invention in this context is characterized in that the cold generated during the nitrogen supply during the starting process is used for freezing in the freezing device. If nitrogen is used as the carrier gas during the starting process, expediently a relaxation of the frozen or frozen nitrogen takes place and the resulting cold is expediently used for freezing in the freezing device.
- the Ausfrier can be used for the Ausfrier worn also the cold, which arises during relaxation of the frozen nitrogen for the purpose of generating the carrier gas nitrogen for the supply of alcohol or methanol in the formation of the fission gas.
- At least one gas scrubber and / or at least one gas absorber is used as a cleaning device for scrubbing or removing a gas component, preferably for scrubbing out water vapor, from the cleavage gas.
- a gas component preferably for scrubbing out water vapor.
- One especially proven embodiment of the invention is characterized in that at least one Ausfrier adopted for freezing of carbon dioxide and at least one gas scrubber for washing water vapor are used as cleaning devices.
- the recirculating protective and / or reaction gases are heated prior to their introduction through the gas inlet into the heat treatment plant and are preferably heated by the hot exhaust gases from the heating of the system.
- the heating of the protective and / or reaction gases takes place via at least one heat exchanger.
- the protective and / or reaction gases are brought to a temperature during the heating, which is at least close to the heat treatment temperature in the heat treatment plant.
- the recirculating protective and / or reactive gases are passed through a high temperature line within the heat treatment plant during their recirculation over part of their way or over at least a large part of their way. They can not cool down and do not need to be heated additionally.
- the invention further teaches a device for the production and treatment of protective and / or reaction gases for heat treatment of metals, in particular for carburizing and / or preventing the decarburization of metal components, wherein a heat treatment plant for heat treatment of the metals is provided the heat treatment plant at least one gas inlet and at least one gas outlet for recycling the protective and / or reaction gases and wherein outside of the heat treatment system, at least one split gas generating means for generating cracked gas or for generating a cracking gas mixture is arranged, wherein cracking gas is the protective and / or reaction gases can be mixed or metered. It is within the scope of the invention that the heat treatment plant is a continuous heat treatment plant.
- At least one starting device is provided for introducing at least one gas generating substance into the heat treatment system.
- this starting device is only when starting the process or the method in operation.
- Empfohlene junk is supplied to the starting device at least one hydrocarbon-containing gas generating substance, preferably at least one alcohol, preferably methanol as a gas generating substance.
- the at least one gas-generating substance - preferably methanol - together with at least one carrier gas - preferably together with nitrogen - is introduced into the heat treatment plant.
- the operation of the starting device is set again after the starting process.
- the starting process is switched on when introducing heat treatment material into the system and when discharging heat treatment material from the system and preferably the recirculation of the protective and / or reaction gases is interrupted during this time.
- This switching on the starting process during the entry and / or removal of heat treatment material serves to maintain pressure during the Schleusungsvorganges in the system.
- the recirculation circuit for example, short-circuited become.
- process-damaging contaminations of the re-cursing protective and / or reaction gases are reduced by lock flushing of the system.
- At least one pressure relief chamber is provided at the gas inlet and at the gas outlet of the heat treatment plant.
- each pressure relief chamber is assigned a gas delivery device.
- at least one pressure sensor is arranged in each pressure relief chamber. In principle, temperature sensors can also be provided here.
- the recirculated protective and / or reaction gases are conducted via a recirculation line from the gas outlet of the heat treatment plant to the gas inlet of the heat treatment plant and in this way the circulation of the recirculating gas is realized.
- the cracked gas from the split gas generating device is supplied via a supply line of the recirculation line and fed to a feed point in the recirculation line.
- at least one cleaning device for the cracking gas formed in the split gas generating device is arranged in a bypass line of the feed line.
- this bypass line begins in the flow direction behind the split gas generating device at a branch point in the supply line and preferably opens in front of the feed point for the recirculation line in the supply line.
- Empfohlenelik a volumetric flow controller is provided at the branch point of the supply line. In this way, the volumetric flow of the cracked gas passed via the bypass line and thus through the at least one cleaning device can be adjusted. ever if necessary, the cracked gas is passed partly or completely through the bypass line through the at least one cleaning device.
- a recommended embodiment of the device according to the invention is characterized in that at least one cleaning device for removing at least one gas component from the cracking gas is present.
- the removal of the gas component or the gas components has already been explained in more detail above. It is preferably the removal of carbon dioxide and / or water or water vapor.
- At least one sensor for detecting the carbon dioxide content and / or water content of the split gas is preferably arranged in the flow direction behind the split gas generating device and expediently before the branch point of the feed line for the cracked gas. It is further recommended that at least one sensor for detecting the carbon dioxide content and / or water content in the recirculation line is arranged and preferably in the flow direction behind the feed point of the cracked gas. With the aid of this sensor or with the aid of these sensors, the extent or the volume flow of the cracked gas can be determined, which is to be guided through the bypass line and through the at least one cleaning device. Appropriately, this scheme is done automatically.
- the invention is based on the finding that with the method according to the invention and with the device according to the invention, a relatively simple and inexpensive, in particular less expensive, heat treatment of the metals for carburizing the metals is possible.
- the protective gases and / or the reaction gases can be very completely recirculated or recycled and therefore can be largely dispensed within the scope of the invention on the combustion or flaring of excess protective and / or reaction gases. This is in comparison to the known methods in environmental terms of particular advantage.
- the resulting heat / energy or waste heat in the context of the method according to the invention can be exploited very largely and effectively, so that the invention is characterized by particular advantages in terms of energy technology.
- a device according to the invention for carrying out the method is constructed relatively compact and with little complexity. The realization of such a device is associated with relatively low costs.
- FIGURE shows a very simplified block diagram relating to the method steps according to the invention.
- the device according to the invention has a continuously operated heat treatment plant 1 with a gas inlet 3 and a gas outlet 2 for the circulating or for the recirculating protective and / or reaction gases.
- a pressure relief chamber 9, 10 is preferably arranged at the gas inlet 3 and at the gas outlet 2 and in the exemplary embodiment.
- At least one gas-generating substance for producing gas components of the protective and / or reaction gases is introduced into the heat treatment plant 1 by means of the starting device 8, which is shown only schematically.
- methanol is introduced as a gas-generating substance and nitrogen as a carrier gas by means of the starting device 8 via the gas inlet 3 in the system 1.
- the starting device 8 is shown only schematically.
- methanol is introduced as a gas-generating substance and nitrogen as a carrier gas by means of the starting device 8 via the gas inlet 3 in the system 1.
- the starting device 8 is shown only schematically.
- methanol is introduced as a gas-generating substance and nitrogen as a carrier gas by means of the starting device 8 via the gas inlet 3 in the system 1.
- Appropriately, and in the embodiment are within the Annex 1 - as it were in situ - produces gas components for the protective and / or reaction gases from the methanol.
- the protective and / or reaction gases are then guided in the direction of the arrow from the gas inlet 3 through the system 1 to the gas outlet 2 and then in turn returned via the recirculation line 11 to the gas inlet 3 and recycled in this way.
- the starting device 8 is again put out of operation and the protective and / or reaction gases are recirculated without supplying further gas generating substances in the system.
- a fission gas generating device 7 for the replenishment or for the renewal of the gas components of the protective and / or reaction gases, a fission gas generating device 7 is provided in which fission gas or a fission gas mixture is generated which can be added to the recirculating in the recirculation line 11 protective and / or reaction gases.
- the cracking gas is generated by catalytic cleavage of methanol.
- the fission gas generating means 7 is provided for a catalytic low temperature cracking of methanol at a temperature between 250 and 360 ° C.
- a cracked gas or fission gas mixture is formed, which consists essentially of carbon monoxide, hydrogen, carbon dioxide and water vapor.
- the cracked gas is introduced via a feed line 18 at a feed point 14 in the recirculation line 11.
- the cracking gas is passed as required via a bypass line 12 through cleaning devices 4, in which the carbon dioxide content and the water content of the cracking gas is reduced.
- a branch point 19 for the bypass line 12 is provided in the supply line 18.
- the quantity or the volume flow of the cracked gas can be adjusted via the volumetric flow controller 15, which is to be guided via the bypass line 12 and the cleaning devices 4.
- a cleaning device 4 is designed as a freezing device 5 for carbon dioxide and a cleaning device 4 is designed as a gas scrubber 6 for the removal of water vapor.
- at least one sensor 13 for detecting the carbon dioxide content and / or water content of the quenching gas is arranged after the split gas generating device 7 and before the bypass line 12.
- a sensor 13 is also provided behind the feed point 14 of the fission gas / fission gas mixture in the recirculation line 11.
- carbon dioxide and water contents can be adjusted or regulated with the arranged behind the split gas generating means 7 and at the branch point 19 volume flow regulator 15, the volume flow of the guided over the bypass line 12 fission gas.
- the cracked gas emerging from the cleaning devices 4 is heated or reheated with the aid of a first heat exchanger 16.
- the heat for this first heat exchanger 16 is recommended and in the exemplary embodiment of the exhaust gas or waste heat from the heating of the heat treatment plant 1.
- a second heat exchanger 17 in the recirculation line 11 for heating the recirculating protection and / or Be provided reaction gases is expediently taken from the exhaust gas or the waste heat from the heating of the heat treatment plant 1.
- a highly recommended embodiment of the invention is further characterized in that - as not shown in detail in the figure - the heat for the split gas generating device 7 and for the catalytic low-temperature cracking of the methanol exhaust gas or waste heat of heating Heat treatment plant is removed. In this way, a particularly advantageous in terms of energy technology method can be performed.
- each pressure relief chamber 10 such a pressure sensor can be assigned as well as the recirculation line 11 in front of and behind the feed point 14 for the cracked gas.
- a pressure sensor can also be provided immediately after the fission gas generating device 7 or at the gas outlet of the fission gas generating device 7 and in the bypass line 12 with the cleaning devices 4.
- feed devices for an inert gas for the protective and / or reaction gases leading lines can also be arranged at different locations of the device.
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- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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Abstract
Verfahren zur Erzeugung und/oder Behandlung von Schutz- und/oder Reaktionsgasen zur Wärmebehandlung von Metallen, wobei die durch eine Wärmebehandlungsanlage geführten Gase zwischen zumindest einem Gasauslass und zumindest einem Gaseinlass der Anlage im Kreislauf geführt werden. Den rezirkulierenden Gasen wird ein außerhalb der Anlage erzeugtes Spaltgas bzw. Spaltgasgemisch zur Erneuerung bzw. zum Ersatz von Gaskomponenten zugemischt.Process for the production and / or treatment of protective and / or reaction gases for the heat treatment of metals, wherein the gases guided through a heat treatment plant are circulated between at least one gas outlet and at least one gas inlet of the plant. The recirculating gases are admixed with a split gas or fission gas mixture produced outside the plant for renewal or replacement of gas components.
Description
Die Erfindung betrifft ein Verfahren zur Erzeugung und/oder Behandlung von Schutz- und/oder Reaktionsgasen zur Wärmebehandlung von Metallen, insbesondere zur Aufkohlung und/oder zur Verhinderung der Entkohlung von Metallkomponenten. Die Erfindung betrifft fernerhin eine Vorrichtung zur Erzeugung und/oder Behandlung von Schutz- und/oder Reaktionsgasen. - Bei der Wärmebehandlung von Metallen zur Aufkohlung der Metalle bzw. der Metallkomponenten wird eine Wärmebehandlungsanlage bzw. ein Wärmebehandlungsofen mit reduzierenden Schutz- und/oder Reaktionsgasen begast. Diese Schutz- und/oder Reaktionsgase bestehen normalerweise im Wesentlichen aus Kohlenmonoxid, Wasserstoff, Stickstoff, Wasserdampf und Kohlendioxid. Gaskomponenten dieser Schutz- und/oder Reaktionsgase können insbesondere durch thermische Spaltung von kohlenwasserstoffhaltigen Substanzen, beispielweise durch thermische Spaltung von Methanol erhalten werden. Die dabei entstehenden Gaskomponenten nennt man auch Spaltgas(e) bzw. Spaltgasgemisch.The invention relates to a process for the production and / or treatment of protective and / or reaction gases for the heat treatment of metals, in particular for carburizing and / or for preventing the decarburization of metal components. The invention further relates to a device for generating and / or treating protective and / or reactive gases. - In the heat treatment of metals for carburizing the metals or metal components, a heat treatment plant or a heat treatment furnace is gassed with reducing protective and / or reactive gases. These protective and / or reaction gases usually consist essentially of carbon monoxide, hydrogen, nitrogen, water vapor and carbon dioxide. Gas components of these protective and / or reaction gases can be obtained in particular by thermal decomposition of hydrocarbon-containing substances, for example by thermal decomposition of methanol. The resulting gas components are also called fission gas (s) or fission gas mixture.
Aus der Praxis sind unterschiedliche Verfahren der eingangs genannten Art bekannt. So ist es bereits bekannt ein Gemisch von Stickstoff und Methanol in eine Wärmebehandlungsanlage einzudüsen, so dass bei den hohen Wärmebehandlungstemperaturen von beispielsweise 850 bis 950° C in der Wärmebehandlungsanlage Schutz- und/oder Reaktionsgase mit den oben genannten Gaskomponenten gebildet werden. Nachdem die Schutz-und/oder Reaktionsgase die Wärmebehandlungsanlage durchströmt haben, werden sie aus der Anlage abgelassen und aus Sicherheitsgründen verbrannt bzw. abgefackelt. Damit verbunden ist ein nicht unerheblicher Aufwand bzw. Kostenaufwand bei der Schutz- und/oder Reaktionsgas-Herstellung und -Versorgung. Außerdem ist die Verfahrensweise in umwelttechnischer Hinsicht bedenklich.From practice different methods of the type mentioned are known. So it is already known to inject a mixture of nitrogen and methanol in a heat treatment plant, so that at the high heat treatment temperatures of, for example, 850 to 950 ° C in the heat treatment plant protection and / or reaction gases are formed with the above-mentioned gas components. After the protective and / or reaction gases have flowed through the heat treatment plant, they are discharged from the plant and burned or flared for safety reasons. This is associated with a significant effort and cost the protection and / or reaction gas production and supply. In addition, the procedure is of environmental concern.
Aus
Demgegenüber liegt der Erfindung das technische Problem zugrunde, ein Verfahren der eingangs genannten Art anzugeben, bei dem die vorstehend beschriebenen Nachteile vermieden werden können, das einfach und wenig aufwendig durchführbar ist und das in energietechnischer und umwelttechnischer Hinsicht optimiert ist. Der Erfindung liegt weiterhin das technische Problem zugrunde, eine entsprechende Vorrichtung zur Durchführung des Verfahrens anzugeben.In contrast, the invention, the technical problem of providing a method of the type mentioned, in which the disadvantages described above can be avoided, which is simple and inexpensive to carry out and which is optimized in energy technology and environmental terms. The invention is further based on the technical problem of specifying a corresponding device for carrying out the method.
Zur Lösung des technischen Problems lehrt die Erfindung ein Verfahren zur Erzeugung und/oder Behandlung von Schutz- und/oder Reaktionsgasen zur Wärmebehandlung von Metallen, insbesondere zur Aufkohlung und/oder Verhinderung der Entkohlung von Metallkomponenten, wobei die durch eine - vorzugsweise kontinuierlich betriebene - Wärmebehandlungsanlage geführten Gase zwischen zumindest einem Gasauslass der Anlage und zumindest einem Gaseinlass der Anlage im Kreislauf geführt werden bzw. rezirkuliert werden und wobei den rezirkulierenden Gasen ein außerhalb der Wärmebehandlungsanlage erzeugtes Spaltgas bzw. Spaltgasgemisch zur Erneuerung bzw. zum Ersatz von Gaskomponenten zugemischt wird.To solve the technical problem, the invention teaches a method for generating and / or treatment of protective and / or reaction gases for heat treatment of metals, in particular for carburizing and / or preventing the decarburization of metal components, which by a - preferably continuously operated - heat treatment plant Guided gases between at least one gas outlet of the system and at least one gas inlet of the system are circulated or recirculated and wherein the recirculating gases generated outside the heat treatment plant fission gas or fission gas mixture for renewal or replacement of gas components is mixed.
Nachfolgend wird anstelle des Begriffes Wärmebehandlungsanlage auch kurz der Begriff Anlage verwendet und anstelle des Begriffes Schutz- und/oder Reaktionsgase auch kurz der Begriff Gase verwendet. - Erfindungsgemäß werden die Schutz- und/oder Reaktionsgase durch die Wärmebehandlungsanlage geführt und anschließend aus dem zumindest einen Gasauslass der Anlage ausgeschleust und daraufhin zu dem Gaseinlass der Anlage zurückgeführt und wiederum in die Anlage eingeführt, so dass die Kreislaufführung der Schutz- und/oder Reaktionsgase resultiert. Nach einer bevorzugten Ausführungsform der Erfindung werden die Schutz- und/oder Reaktionsgase zunächst durch die Wärmebehandlungsanlage geführt und anschließend aus dem zumindest einen Gasauslass der Anlage ausgeschleust und daraufhin innerhalb des Ofenraumes der Wärmebehandlungsanlage über eine vom Ofenraum gasseitig getrennte Leitung zu dem Gaseinlass der Anlage zurückgeführt und wiederum in die Anlage eingeführt. - Außerhalb der Anlage werden gezielt zu erneuernde bzw. zu ersetzende Gaskomponenten der Schutz- und/oder Reaktionsgase in Form eines Spaltgases bzw. Spaltgasgemisches zudosiert. Zweckmäßigerweise wird der Gehalt von Gaskomponenten der Schutz- und/oder Reaktionsgase gemessen bzw. automatisch gemessen und je nach dem ermittelten Bedarf wird Spaltgas bzw. gezielt Spaltgas hinzugeführt.Hereinafter, instead of the term heat treatment plant and the term plant briefly used and instead of the term protective and / or reaction gases also briefly the term gases used. - According to the invention the protective and / or reaction gases are passed through the heat treatment plant and then discharged from the at least one gas outlet of the system and then returned to the gas inlet of the system and in turn introduced into the system, so that the circulation of the protective and / or reaction gases results. According to a preferred embodiment of the invention, the protective and / or reaction gases are first passed through the heat treatment plant and then discharged from the at least one gas outlet of the system and then returned within the furnace chamber of the heat treatment plant via a gas line from the furnace side separate line to the gas inlet of the system and again introduced into the plant. - Outside the plant to be renewed or replaced gas components of the protective and / or reaction gases in the form of a fission gas or fission gas mixture are metered. Conveniently, the content of gas components of the protective and / or reaction gases are measured or measured automatically and, depending on the determined need, fission gas or specifically fission gas is added.
Der Erfindung liegt die Erkenntnis zugrunde, dass aufgrund des erfindungsgemäßen Recycling der Schutz- und/oder Reaktionsgase ein Verfahren mit geringem Aufwand und geringen Kosten betrieben werden kann, bei dem sich der Materialeinsatz und Energieeinsatz vorteilhaft in Grenzen hält und bei dem Energie bzw. Wärme gezielt genutzt bzw. verwertet werden kann. Außerdem genügt das erfindungsgemäße Verfahren in umwelttechnischer Hinsicht allen Anforderungen. Das wird nachfolgend noch näher erläutert.The invention is based on the finding that due to the recycling of the protective and / or reaction gases according to the invention a method can be operated with little effort and low cost, in which the material use and energy use advantageously limits and targeted in the energy or heat can be used or recycled. In addition, the method according to the invention meets all environmental requirements. This will be explained in more detail below.
Gemäß besonders empfohlener Ausführungsform der Erfindung erfolgt die Wärmebehandlung der Metalle durch kontinuierliche Verfahrensweise. Es handelt sich somit bei der eingesetzten Wärmebehandlungsanlage bevorzugt um eine kontinuierlich betriebene Wärmebehandlungsanlage zur Wärmebehandlung von Metallen.According to a particularly recommended embodiment of the invention, the heat treatment of the metals is carried out by a continuous procedure. It is thus in the heat treatment system used preferably a continuously operated heat treatment plant for the heat treatment of metals.
Es liegt im Rahmen der Erfindung, dass beim Anfahren des Prozesses bzw. des Verfahrens zumindest eine Gaserzeugungssubstanz in die Wärmebehandlungsanlage eingeführt wird. Fernerhin liegt es im Rahmen der Erfindung, dass innerhalb der Wärmebehandlungsanlage - in situ - aus dieser zumindest einen Gaserzeugungssubstanz Schutz- und/oder Reaktionsgase gebildet werden. Nach empfohlener Ausführungsform handelt es sich bei der Gaserzeugungssubstanz um Methanol. Vorzugsweise wird Methanol als Gaserzeugungssubstanz zusammen mit zumindest einem Trägergas, bevorzugt mit Stickstoff als Trägergas in die Wärmebehandlungsanlage eingeführt. Diese Einführung der Gaserzeugungssubstanz bzw. des Methanol - vorzugsweise in Kombination mit Stickstoff - erfolgt zweckmäßigerweise lediglich beim Anfahren des Prozesses und nach dem Anfahrprozess wird diese Begasung wieder eingestellt und erfindungsgemäß werden dann die Schutz- und/oder Reaktionsgase im Kreislauf geführt bzw. rezirkuliert. Es empfiehlt sich, dass gegen Ende des Anfahrprozesses die genannte Begasung in dem Maße reduziert wird, wie die Rezirkulation des Schutz- und/oder Reaktionsgase hochgefahren werden kann. - Im Rahmen des erfindungsgemäßen Verfahrens finden nach bevorzugter Ausführungsform also zwei Zuführungsprozesse für die Gaskomponenten der Schutz- und/oder Reaktionsgase statt, nämlich zum einen beim Anfahren des Prozesses die Zufuhr und Zersetzung der zumindest einen Gaserzeugungssubstanz und zum anderen während des Kreislaufbetriebs der Schutz- und/oder Reaktionsgase die gezielte bzw. dosierte Spaltgaszuführung. Die Spaltgaszuführung dient insbesondere der Aufrechterhaltung eines ausreichenden Kohlenstoffpotentials in den Schutz- und/oder Reaktionsgasen.It is within the scope of the invention that at least one gas generating substance is introduced into the heat treatment plant when starting up the process or the method. Furthermore, it is within the scope of the invention that within the heat treatment plant - in situ - from this at least one gas generating substance protection and / or reaction gases are formed. In the recommended embodiment, the gas generant is methanol. Preferably, methanol is introduced as a gas generating substance together with at least one carrier gas, preferably with nitrogen as a carrier gas in the heat treatment plant. This introduction of the gas generating substance or the methanol - preferably in combination with nitrogen - is expediently only when starting the process and after the startup process, this fumigation is set again and according to the invention then the protective and / or reaction gases are circulated or recirculated. It is recommended that towards the end of the start-up process, said gassing is reduced to the extent that the recirculation of the protective and / or reaction gases can be started up. In the context of the process according to the invention, therefore, two feed processes for the gas components of the protective and / or reaction gases take place according to the preferred embodiment, namely the supply and decomposition of the at least one gas generating substance and the other during the cycle operation of the protective and / or reaction gases, the targeted or metered split gas supply. In particular, the cracked gas feed serves to maintain a sufficient carbon potential in the protective and / or reaction gases.
Nach besonders bewährter Ausführungsform des erfindungsgemäßen Verfahrens findet die Erzeugung des Spaltgases bzw. des Spaltgasgemisches außerhalb der Anlage bzw. außerhalb des Ofens unter Wärmezufuhr statt und die hierzu erforderliche Wärme wird dem Abgas aus der Beheizung der Wärmebehandlungsanlage entnommen. Insoweit wird also die Abwärme der Wärmebehandlungsanlage zur Generierung des Spaltgases ausgenutzt. Es liegt im Rahmen der Erfindung, dass die Erzeugung des Spaltgases über eine indirekte Beheizung mittels der Abwärme aus der Wärmebehandlungsanlage durchgeführt wird.According to a particularly well-proven embodiment of the method according to the invention, the generation of the fission gas or the fission gas mixture takes place outside the plant or outside of the furnace under heat and the heat required for this purpose is taken from the exhaust gas from the heating of the heat treatment plant. In that regard, therefore, the waste heat of the heat treatment plant is utilized to generate the fission gas. It is within the scope of the invention that the generation of the cracked gas is carried out via an indirect heating by means of the waste heat from the heat treatment plant.
Eine besonders empfohlene Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, dass das Spaltgas durch Spaltung zumindest eines Alkohols, vorzugsweise durch Spaltung von Methanol erzeugt wird. Vorzugsweise wird dabei der Alkohol bzw. bevorzugt das Methanol mittels eines Trägergases, empfohlenermaßen mit Stickstoff als Trägergas zugefügt. Besonders bevorzugt ist im Rahmen des erfindungsgemäßen Verfahrens die Gewinnung des Spaltgases durch katalytische Niedertemperaturspaltung. Zweckmäßigerweise wird ein Alkohol - bevorzugt Methanol - einer solchen katalytischen Niedertemperaturspaltung unterworfen. Empfohlenermaßen wird die Niedertemperaturspaltung bei einer Temperatur von 200 bis 400° C, bevorzugt bei einer Temperatur von 240 bis 370° C durchgeführt. Besonders bevorzugt ist eine Temperatur von 250 bis 360° C für die Niedertemperaturspaltung. Die Temperatur der katalytischen Niedertemperaturspaltung liegt deutlich niedriger als die Temperatur in der Wärmebehandlungsanlage (ca. 800 bis 1000° C, insbesondere 850 bis 950° C). Es liegt im Rahmen der Erfindung, dass bei der katalytischen Niedertemperaturspaltung die Bedingungen der Spaltung präzise eingestellt werden, damit dabei möglichst wenig Kohlendioxid und möglichst wenig Wasserdampf entsteht. Fernerhin liegt es im Rahmen der Erfindung, dass durch die katalytische Niedertemperaturspaltung nur der notwendige Nachschub an Gaskomponenten für einen Ersatz bzw. eine Erneuerung der Gaskomponenten der Schutz- und/oder Reaktionsgase geliefert wird. Insoweit beträgt die Gaszufuhr aus der katalytischen Niedertemperaturspaltung zweckmäßigerweise nur einen Bruchteil des Volumenstromes der rezirkulierenden Schutz- und/oder Reaktionsgase.A particularly recommended embodiment of the method according to the invention is characterized in that the cleavage gas is generated by cleavage of at least one alcohol, preferably by cleavage of methanol. Preferably, the alcohol or preferably the methanol by means of a carrier gas, recommended added with nitrogen as the carrier gas. Particularly preferred in the context of the method according to the invention is the Recovery of the fission gas by catalytic low-temperature cracking. Conveniently, an alcohol - preferably methanol - subjected to such a catalytic low temperature cracking. Empfohlenermaßen the low temperature cleavage at a temperature of 200 to 400 ° C, preferably at a temperature of 240 to 370 ° C is performed. Particularly preferred is a temperature of 250 to 360 ° C for the low temperature cracking. The temperature of the catalytic low-temperature cracking is significantly lower than the temperature in the heat treatment plant (about 800 to 1000 ° C, in particular 850 to 950 ° C). It is within the scope of the invention that in the catalytic low-temperature cracking, the conditions of the cleavage are set precisely, so that as little carbon dioxide and as little water vapor as possible. Furthermore, it is within the scope of the invention that only the necessary supply of gas components for a replacement or renewal of the gas components of the protective and / or reaction gases is supplied by the catalytic low-temperature cracking. In that regard, the gas supply from the catalytic low-temperature cracking is expediently only a fraction of the volume flow of the recirculating protective and / or reaction gases.
Eine sehr empfohlene Ausführungsform des erfindungsgemäßen Verfahrens ist dadurch gekennzeichnet, dass das außerhalb der Wärmebehandlungsanlage erzeugte Spaltgas durch zumindest eine Reinigungseinrichtung geleitet wird um den Gehalt von zumindest einer Gaskomponente zumindest zu reduzieren. Bei dieser zumindest einen Gaskomponente handelt es sich insbesondere um Kohlendioxid und/oder Wasser bzw. Wasserdampf. Dadurch wird vermieden, dass eine nachteilhafte Anreicherung der Schutz- und/oder Reaktionsgase an Kohlendioxid und/oder Wasser bzw. Wasserdampf stattfindet. Gemäß einer bewährten Ausführungsform der Erfindung wird das Spaltgas nur zum Teil und/oder nur bei Bedarf durch die zumindest eine Reinigungseinrichtung geleitet und insoweit ist eine zweckmäßige Ausführungsvariante dadurch gekennzeichnet, dass die zumindest eine Reinigungseinrichtung in einer Bypass-Führung des Spaltgases untergebracht ist. Vorzugsweise findet eine Analyse bzw. eine automatische Analyse des Spaltgases auf seinen Kohlendioxidgehalt und/oder auf seinen Wassergehalt statt. Je nach Ergebnis dieser Analyse bzw. Messung wird dann das Spaltgas bei Bedarf teilweise oder vollständig durch die zumindest eine Reinigungseinrichtung geleitet. Zweckmäßigerweise wird dafür Sorge getragen, dass der Kohlendioxid-Gehalt und/oder der Wasser-Gehalt in den Schutz- und/oder Reaktionsgasen einen bestimmten Sollwert nicht übersteigt.A highly recommended embodiment of the method according to the invention is characterized in that the fission gas generated outside the heat treatment plant is passed through at least one cleaning device in order to at least reduce the content of at least one gas component. This at least one gas component is in particular carbon dioxide and / or water or water vapor. This avoids that a disadvantageous accumulation of the protective and / or reaction gases of carbon dioxide and / or water or water vapor takes place. According to a proven embodiment of the invention, the cracked gas is passed only partially and / or only when needed by the at least one cleaning device and to that extent an expedient embodiment variant is characterized in that the at least one cleaning device is accommodated in a bypass guide of the split gas. Preferably, an analysis or an automatic analysis of the cracking gas takes place on its carbon dioxide content and / or on its water content. Depending on the result of this analysis or measurement, the cracked gas is then passed, if necessary, partially or completely through the at least one cleaning device. Appropriately, care is taken that the carbon dioxide content and / or the water content in the protective and / or reaction gases does not exceed a certain desired value.
Nach empfohlener Ausführungsform der Erfindung ist zumindest eine Ausfriereinrichtung als Reinigungseinrichtung vorhanden, wobei mit dieser Ausfriereinrichtung zweckmäßigerweise Kohlendioxid aus dem Spaltgas ausgefroren wird. Eine besonders bevorzugte Ausführungsform der Erfindung ist in diesem Zusammenhang dadurch gekennzeichnet, dass die bei der Stickstoffzufuhr beim Anfahrvorgang entstehende Kälte für das Ausfrieren in der Ausfriereinrichtung genutzt wird. Wenn beim Anfahrvorgang Stickstoff als Trägergas eingesetzt wird, findet zweckmäßigerweise eine Entspannung des gefrorenen bzw. tiefgefrorenen Stickstoffs statt und die dabei entstehende Kälte wird zweckmäßigerweise zum Ausfrieren in der Ausfriereinrichtung eingesetzt. Nach empfohlener Variante der Erfindung kann für die Ausfriereinrichtung auch die Kälte genutzt werden, die bei Entspannung des gefrorenen Stickstoffs zwecks Erzeugung des Trägergases Stickstoff für die Zuführung des Alkohols bzw. des Methanols bei der Bildung des Spaltgases entsteht. - Gemäß einer zusätzlichen oder alternativen Ausführungsform der Erfindung wird zumindest ein Gaswäscher und/oder zumindest ein Gasabsorber als Reinigungseinrichtung zum Auswaschen bzw. Entfernen einer Gaskomponente - bevorzugt zum Auswaschen von Wasserdampf - aus dem Spaltgas eingesetzt. - Eine besonders bewährte Ausführungsform der Erfindung ist dadurch gekennzeichnet, dass zumindest eine Ausfriereinrichtung zum Ausfrieren von Kohlendioxid und zumindest ein Gaswäscher zum Auswaschen von Wasserdampf als Reinigungseinrichtungen eingesetzt werden.According to the recommended embodiment of the invention, at least one freezing device is present as a cleaning device, with this freezing device expediently carbon dioxide being frozen out of the cleavage gas. A particularly preferred embodiment of the invention in this context is characterized in that the cold generated during the nitrogen supply during the starting process is used for freezing in the freezing device. If nitrogen is used as the carrier gas during the starting process, expediently a relaxation of the frozen or frozen nitrogen takes place and the resulting cold is expediently used for freezing in the freezing device. According to the recommended variant of the invention can be used for the Ausfriereinrichtung also the cold, which arises during relaxation of the frozen nitrogen for the purpose of generating the carrier gas nitrogen for the supply of alcohol or methanol in the formation of the fission gas. According to an additional or alternative embodiment of the invention, at least one gas scrubber and / or at least one gas absorber is used as a cleaning device for scrubbing or removing a gas component, preferably for scrubbing out water vapor, from the cleavage gas. - One especially proven embodiment of the invention is characterized in that at least one Ausfriereinrichtung for freezing of carbon dioxide and at least one gas scrubber for washing water vapor are used as cleaning devices.
Es liegt im Rahmen der Erfindung, dass die rezirkulierenden Schutz- und/oder Reaktionsgase vor ihrer Einführung durch den Gaseinlass in die Wärmebehandlungsanlage erwärmt werden und zwar vorzugsweise mittels der heißen Abgase aus der Beheizung der Anlage erwärmt werden. Zur Erwärmung der Schutz- und/oder Reaktionsgase vor ihrer Wiedereinführung in die Wärmebehandlungsanlage wird also die Abwärme aus der Beheizung der Wärmebehandlungsanlage ausgenutzt. Zweckmäßigerweise findet die Erwärmung der Schutz- und/oder Reaktionsgase dabei über zumindest einen Wärmetauscher statt. Vorzugsweise werden die Schutz- und/oder Reaktionsgase bei der Erwärmung auf eine Temperatur gebracht, die zumindest nahe bei der Wärmebehandlungstemperatur in der Wärmebehandlungsanlage liegt. Gemäß einer sehr bevorzugten Ausführungsform der Erfindung werden die rezirkulierenden Schutz- und/oder Reaktionsgase bei ihrer Rezirkulation über einen Teil ihres Weges bzw. über zumindest einen großen Teil ihres Weges durch eine Hochtemperaturleitung innerhalb der Wärmebehandlungsanlage geführt. Dabei können sie nicht abkühlen und müssen nicht zusätzlich erwärmt werden.It is within the scope of the invention that the recirculating protective and / or reaction gases are heated prior to their introduction through the gas inlet into the heat treatment plant and are preferably heated by the hot exhaust gases from the heating of the system. To heat the protective and / or reaction gases prior to their reintroduction into the heat treatment plant so the waste heat from the heating of the heat treatment plant is utilized. Expediently, the heating of the protective and / or reaction gases takes place via at least one heat exchanger. Preferably, the protective and / or reaction gases are brought to a temperature during the heating, which is at least close to the heat treatment temperature in the heat treatment plant. According to a very preferred embodiment of the invention, the recirculating protective and / or reactive gases are passed through a high temperature line within the heat treatment plant during their recirculation over part of their way or over at least a large part of their way. They can not cool down and do not need to be heated additionally.
Zur Lösung des technischen Problems lehrt die Erfindung weiterhin eine Vorrichtung zur Erzeugung und Behandlung von Schutz- und/oder Reaktionsgasen zur Wärmebehandlung von Metallen, insbesondere zur Aufkohlung und/oder Verhinderung der Entkohlung von Metallkomponenten, wobei eine Wärmebehandlungsanlage zur Wärmebehandlung der Metalle vorgesehen ist, wobei die Wärmebehandlungsanlage zumindest einen Gaseinlass und zumindest einen Gasauslass zur Kreislaufführung der Schutz- und/oder Reaktionsgase aufweist und wobei außerhalb der Wärmebehandlungsanlage zumindest eine Spaltgaserzeugungseinrichtung zur Erzeugung von Spaltgas bzw. zur Erzeugung eines Spaltgasgemisches angeordnet ist, wobei Spaltgas den Schutz- und/oder Reaktionsgasen zumischbar bzw. zudosierbar ist. Es liegt im Rahmen der Erfindung, dass die Wärmebehandlungsanlage eine kontinuierliche Wärmebehandlungsanlage ist.To solve the technical problem, the invention further teaches a device for the production and treatment of protective and / or reaction gases for heat treatment of metals, in particular for carburizing and / or preventing the decarburization of metal components, wherein a heat treatment plant for heat treatment of the metals is provided the heat treatment plant at least one gas inlet and at least one gas outlet for recycling the protective and / or reaction gases and wherein outside of the heat treatment system, at least one split gas generating means for generating cracked gas or for generating a cracking gas mixture is arranged, wherein cracking gas is the protective and / or reaction gases can be mixed or metered. It is within the scope of the invention that the heat treatment plant is a continuous heat treatment plant.
Weiterhin liegt es im Rahmen der Erfindung, dass zumindest eine Anfahrvorrichtung zur Einführung zumindest einer Gaserzeugungssubstanz in die Wärmebehandlungsanlage vorgesehen ist. Zweckmäßigerweise ist diese Anfahrvorrichtung nur beim Anfahren des Prozesses bzw. des Verfahrens in Betrieb. Empfohlenermaßen wird mit der Anfahrvorrichtung zumindest eine kohlenwasserstoffhaltige Gaserzeugungssubstanz zugeführt und zwar vorzugsweise zumindest ein Alkohol, bevorzugt Methanol als Gaserzeugungssubstanz. Es hat sich als zweckmäßig erwiesen, dass die zumindest eine Gaserzeugungssubstanz - bevorzugt Methanol - zusammen mit zumindest einem Trägergas - bevorzugt zusammen mit Stickstoff - in die Wärmebehandlungsanlage eingeführt wird. Es liegt im Rahmen der Erfindung, dass der Betrieb der Anfahrvorrichtung nach dem Anfahrprozess wieder eingestellt wird.Furthermore, it is within the scope of the invention that at least one starting device is provided for introducing at least one gas generating substance into the heat treatment system. Appropriately, this starting device is only when starting the process or the method in operation. Empfohlenermaßen is supplied to the starting device at least one hydrocarbon-containing gas generating substance, preferably at least one alcohol, preferably methanol as a gas generating substance. It has proved to be expedient that the at least one gas-generating substance - preferably methanol - together with at least one carrier gas - preferably together with nitrogen - is introduced into the heat treatment plant. It is within the scope of the invention that the operation of the starting device is set again after the starting process.
Nach einer bevorzugten Ausführungsform der Erfindung wird der Anfahrprozess beim Einschleusen von Wärmebehandlungsgut in die Anlage und beim Ausschleusen von Wärmebehandlungsgut aus der Anlage eingeschaltet und bevorzugt wird während dieser Zeit das Rezirkulieren der Schutz- und/oder Reaktionsgase unterbrochen. Dieses Einschalten des Anfahrprozesses während des Ein- und/oder Ausschleusens von Wärmebehandlungsgut dient der Druckhaltung während des Schleusungsvorganges in der Anlage. Zur Unterbrechung der Rezirkulation der Reaktions- und/oder Schutzgase während eines solchen Schleusungsvorganges kann der Rezirkulationskreislauf beispielsweise kurzgeschlossen werden. - Durch Schleusenspülungen der Anlage werden im Übrigen prozessschädliche Kontaminierungen der rezikulierenden Schutz- und/oder Reaktionsgase vermindert.According to a preferred embodiment of the invention, the starting process is switched on when introducing heat treatment material into the system and when discharging heat treatment material from the system and preferably the recirculation of the protective and / or reaction gases is interrupted during this time. This switching on the starting process during the entry and / or removal of heat treatment material serves to maintain pressure during the Schleusungsvorganges in the system. To interrupt the recirculation of the reaction and / or protective gases during such Schleusungsvorganges the recirculation circuit, for example, short-circuited become. In addition, process-damaging contaminations of the re-cursing protective and / or reaction gases are reduced by lock flushing of the system.
Zweckmäßigerweise ist an dem Gaseinlass und an dem Gasauslass der Wärmebehandlungsanlage jeweils zumindest eine Druckentlastungskammer vorgesehen. Nach einer Ausführungsvariante ist jeder Druckentlastungskammer eine Gasfördereinrichtung zugeordnet. Im Übrigen liegt es im Rahmen der Erfindung, dass in jeder Druckentlastungskammer zumindest ein Drucksensor angeordnet ist. Grundsätzlich können hier auch Temperatursensoren vorgesehen sein.Expediently, at least one pressure relief chamber is provided at the gas inlet and at the gas outlet of the heat treatment plant. According to one embodiment variant, each pressure relief chamber is assigned a gas delivery device. Incidentally, it is within the scope of the invention that at least one pressure sensor is arranged in each pressure relief chamber. In principle, temperature sensors can also be provided here.
Es liegt im Rahmen der Erfindung, dass die im Kreislauf geführten Schutz- und/oder Reaktionsgase über eine Rezirkulationsleitung vom Gasauslass der Wärmebehandlungsanlage zum Gaseinlass der Wärmebehandlungsanlage geführt werden und auf diese Weise der Kreislauf des rezirkulierenden Gases realisiert ist. - Zweckmäßigerweise wird das Spaltgas aus der Spaltgaserzeugungseinrichtung über eine Zuführungsleitung der Rezirkulationsleitung zugeführt und an einer Einspeisestelle in die Rezirkulationsleitung eingespeist. Gemäß besonders bevorzugter Ausführungsform der Erfindung ist zumindest eine Reinigungseinrichtung für das in der Spaltgaserzeugungseinrichtung gebildete Spaltgas in einer Bypass-Leitung der Zuführungsleitung angeordnet. Zweckmäßigerweise beginnt diese Bypass-Leitung in Strömungsrichtung hinter der Spaltgaserzeugungseinrichtung an einer Abzweigungsstelle in der Zuführungsleitung und mündet bevorzugt vor der Einspeisestelle für die Rezirkulationsleitung in die Zuführungsleitung. Empfohlenermaßen ist an der Abzweigungsstelle der Zuführungsleitung ein Volumenstromregler vorgesehen. Damit kann der über die Bypass-Leitung und somit durch die zumindest eine Reinigungseinrichtung geführte Volumenstrom des Spaltgases eingestellt werden. Je nach Bedarf wird das Spaltgas zum Teil oder auch vollständig über die Bypass-Leitung durch die zumindest eine Reinigungseinrichtung geführt.It is within the scope of the invention that the recirculated protective and / or reaction gases are conducted via a recirculation line from the gas outlet of the heat treatment plant to the gas inlet of the heat treatment plant and in this way the circulation of the recirculating gas is realized. - Advantageously, the cracked gas from the split gas generating device is supplied via a supply line of the recirculation line and fed to a feed point in the recirculation line. According to a particularly preferred embodiment of the invention, at least one cleaning device for the cracking gas formed in the split gas generating device is arranged in a bypass line of the feed line. Conveniently, this bypass line begins in the flow direction behind the split gas generating device at a branch point in the supply line and preferably opens in front of the feed point for the recirculation line in the supply line. Empfohlenermaßen a volumetric flow controller is provided at the branch point of the supply line. In this way, the volumetric flow of the cracked gas passed via the bypass line and thus through the at least one cleaning device can be adjusted. ever if necessary, the cracked gas is passed partly or completely through the bypass line through the at least one cleaning device.
Eine empfohlene Ausführungsform der erfindungsgemäßen Vorrichtung ist dadurch gekennzeichnet, dass zumindest eine Reinigungseinrichtung zur Entfernung zumindest einer Gaskomponente aus dem Spaltgas vorhanden ist. Die Entfernung der Gaskomponente bzw. der Gaskomponenten wurde weiter oben schon näher erläutert. Es handelt sich dabei vorzugsweise um die Entfernung von Kohlendioxid und/oder von Wasser bzw. von Wasserdampf. Vorzugsweise ist in Strömungsrichtung hinter der Spaltgaserzeugungseinrichtung und zweckmäßigerweise vor der Abzweigungsstelle der Zuführungsleitung für das Spaltgas zumindest ein Sensor zur Erfassung des Kohlendioxid-Anteiles und/oder Wasser-Anteiles des Spaltgases angeordnet. Es empfiehlt sich fernerhin, dass zumindest ein Sensor zur Erfassung des Kohlendioxid-Gehaltes und/oder Wasser-Gehaltes in der Rezirkulationsleitung angeordnet ist und zwar bevorzugt in Strömungsrichtung hinter der Einspeisestelle des Spaltgases. Mit Hilfe dieses Sensors bzw. mit Hilfe dieser Sensoren kann das Ausmaß bzw. der Volumenstrom des Spaltgases bestimmt werden, das/der durch die Bypass-Leitung und durch die zumindest eine Reinigungseinrichtung geführt werden soll. Zweckmäßigerweise erfolgt diese Regelung automatisch.A recommended embodiment of the device according to the invention is characterized in that at least one cleaning device for removing at least one gas component from the cracking gas is present. The removal of the gas component or the gas components has already been explained in more detail above. It is preferably the removal of carbon dioxide and / or water or water vapor. At least one sensor for detecting the carbon dioxide content and / or water content of the split gas is preferably arranged in the flow direction behind the split gas generating device and expediently before the branch point of the feed line for the cracked gas. It is further recommended that at least one sensor for detecting the carbon dioxide content and / or water content in the recirculation line is arranged and preferably in the flow direction behind the feed point of the cracked gas. With the aid of this sensor or with the aid of these sensors, the extent or the volume flow of the cracked gas can be determined, which is to be guided through the bypass line and through the at least one cleaning device. Appropriately, this scheme is done automatically.
Der Erfindung liegt die Erkenntnis zugrunde, dass mit dem erfindungsgemäßen Verfahren und mit der erfindungsgemäßen Vorrichtung eine relativ einfache und wenig aufwendige, insbesondere wenig kostenaufwendige Wärmebehandlung der Metalle zur Aufkohlung der Metalle möglich ist. Die Schutz- und/der Reaktionsgase könne sehr vollständig rezirkuliert bzw. recycelt werden und deshalb kann im Rahmen der Erfindung auf die Verbrennung bzw. Abfackelung überschüssiger Schutz- und/oder Reaktionsgase weitgehend verzichtet werden. Das ist im Vergleich zu den bekannten Verfahren in umwelttechnischer Hinsicht von besonderem Vorteil. Im Übrigen kann die entstehende Wärme/Energie bzw. die Abwärme im Rahmen des erfindungsgemäßen Verfahrens sehr weitgehend und effektiv ausgenutzt werden, so dass sich die Erfindung auch in energietechnischer Hinsicht durch besondere Vorteile auszeichnet. Eine erfindungsgemäße Vorrichtung zur Durchführung des Verfahrens ist relativ kompakt und wenig komplex aufgebaut. Die Realisierung einer solchen Vorrichtung ist mit verhältnismäßig geringen Kosten verbunden.The invention is based on the finding that with the method according to the invention and with the device according to the invention, a relatively simple and inexpensive, in particular less expensive, heat treatment of the metals for carburizing the metals is possible. The protective gases and / or the reaction gases can be very completely recirculated or recycled and therefore can be largely dispensed within the scope of the invention on the combustion or flaring of excess protective and / or reaction gases. This is in comparison to the known methods in environmental terms of particular advantage. Incidentally, the resulting heat / energy or waste heat in the context of the method according to the invention can be exploited very largely and effectively, so that the invention is characterized by particular advantages in terms of energy technology. A device according to the invention for carrying out the method is constructed relatively compact and with little complexity. The realization of such a device is associated with relatively low costs.
Nachfolgend wird die Erfindung anhand einer lediglich ein Ausführungsbeispiel darstellenden Zeichnung näher erläutert. Die einzige Figur zeigt ein sehr vereinfachtes Blockschaltbild bezüglich der erfindungsgemäßen Verfahrensschritte.The invention will be explained in more detail with reference to a drawing showing only one exemplary embodiment. The single FIGURE shows a very simplified block diagram relating to the method steps according to the invention.
In der Figur ist eine Vorrichtung zur Durchführung des erfindungsgemäßen Verfahrens zur Erzeugung und/oder Behandlung von Schutz- und/oder Reaktionsgasen zur Wärmebehandlung von Metallen und zur Aufkohlung von Metallkomponenten dargestellt. Die erfindungsgemäße Vorrichtung weist eine kontinuierlich betriebene Wärmebehandlungsanlage 1 mit einem Gaseinlass 3 und einem Gasauslass 2 für die im Kreislauf geführten bzw. für die rezirkulierenden Schutz- und/oder Reaktionsgase auf. Dabei ist an dem Gaseinlass 3 und an dem Gasauslass 2 bevorzugt und im Ausführungsbeispiel jeweils eine Druckentlastungskammer 9, 10 angeordnet.In the figure, an apparatus for carrying out the method according to the invention for the production and / or treatment of protective and / or reaction gases for the heat treatment of metals and for the carburization of metal components is shown. The device according to the invention has a continuously operated heat treatment plant 1 with a
Beim Anfahren des Prozesses wird mittels der lediglich ganz schematisch dargestellten Anfahrvorrichtung 8 zumindest eine Gaserzeugungssubstanz zur Erzeugung von Gaskomponenten der Schutz- und/oder Reaktionsgase in die Wärmebehandlungsanlage 1 eingeführt. Bevorzugt und im Ausführungsbeispiel wird Methanol als Gaserzeugungssubstanz sowie Stickstoff als Trägergas mittels der Anfahrvorrichtung 8 über den Gaseinlass 3 in die Anlage 1 eingeführt. Zweckmäßigerweise und im Ausführungsbeispiel werden innerhalb der Anlage 1 - gleichsam in situ - Gaskomponenten für die Schutz- und/oder Reaktionsgase aus dem Methanol erzeugt. Die Schutz- und/oder Reaktionsgase werden dann in Richtung des Pfeiles vom Gaseinlass 3 durch die Anlage 1 zum Gasauslass 2 geführt und anschließend wiederum über die Rezirkulationsleitung 11 zum Gaseinlass 3 zurückgeführt und auf diese Weise im Kreislauf geführt. Nach dem Anfahren des Prozesses wird die Anfahrvorrichtung 8 wieder außer Betrieb gesetzt und die Schutz- und/oder Reaktionsgase werden ohne Zufuhr weiterer Gaserzeugungssubstanzen in der Anlage rezirkuliert.When the process is started, at least one gas-generating substance for producing gas components of the protective and / or reaction gases is introduced into the heat treatment plant 1 by means of the starting
Für den Nachschub bzw. für die Erneuerung der Gaskomponenten der Schutz- und/oder Reaktionsgase ist eine Spaltgaserzeugungseinrichtung 7 vorgesehen, in der Spaltgas bzw. ein Spaltgasgemisch erzeugt wird, das den in der Rezirkulationsleitung 11 rezirkulierenden Schutz- und/oder Reaktionsgasen zudosierbar ist. Vorzugsweise wird das Spaltgas durch katalytische Spaltung von Methanol erzeugt. Empfohlenermaßen und im Ausführungsbeispiel ist die Spaltgaserzeugungseinrichtung 7 für eine katalytische Niedertemperaturspaltung von Methanol bei einer Temperatur zwischen 250 und 360° C vorgesehen. Bei dieser katalytischen Niedertemperaturspaltung von Methanol entsteht ein Spaltgas bzw. Spaltgasgemisch, das im Wesentlichen aus Kohlenmonoxid, Wasserstoff, Kohlendioxid und Wasserdampf besteht. Das Spaltgas wird über eine Zuführungsleitung 18 an einer Einspeisestelle 14 in die Rezirkulationsleitung 11 eingeführt. Empfohlenermaßen und im Ausführungsbeispiel wird das Spaltgas bei Bedarf über eine Bypass-Leitung 12 durch Reinigungseinrichtungen 4 geführt, in denen der Kohlendioxidgehalt und der Wassergehalt des Spaltgases reduziert wird. Dazu ist in der Zuführungsleitung 18 eine Abzweigstelle 19 für die Bypass-Leitung 12 vorgesehen. Hier kann über den Volumenstromregler 15 die Menge bzw. der Volumenstrom des Spaltgases eingestellt werden, der über die Bypass-Leitung 12 und die Reinigungseinrichtungen 4 geführt werden soll.For the replenishment or for the renewal of the gas components of the protective and / or reaction gases, a fission gas generating device 7 is provided in which fission gas or a fission gas mixture is generated which can be added to the recirculating in the
Im Ausführungsbeispiel ist eine Reinigungseinrichtung 4 als Ausfriereinrichtung 5 für Kohlendioxid ausgebildet und eine Reinigungseinrichtung 4 als Gaswäscher 6 zur Entfernung von Wasserdampf ausgebildet. Vorzugsweise und im Ausführungsbeispiel ist nach der Spaltgaserzeugungseinrichtung 7 und vor der Bypass-Leitung 12 zumindest ein Sensor 13 zur Erfassung des Kohlendioxid-Anteils und/oder Wasser-Anteiles des Spaltgases angeordnet. Zweckmäßigerweise und im Ausführungsbeispiel ist ein solcher Sensor 13 auch hinter der Einspeisestelle 14 des Spaltgases/Spaltgasgemisches in der Rezirkulationsleitung 11 vorgesehen. In Abhängigkeit von mit diesen Sensoren 13 gemessenen Kohlendioxid- und Wassergehalten kann mit dem hinter der Spaltgaserzeugungseinrichtung 7 und an der Abzweigungsstelle 19 angeordneten Volumenstromregler 15 der Volumenstrom des über die Bypass-Leitung 12 geführten Spaltgases eingestellt bzw. geregelt werden.In the exemplary embodiment, a
Vorzugsweise und im Ausführungsbeispiel wird das aus den Reinigungseinrichtungen 4 austretende Spaltgas mit Hilfe eines ersten Wärmetauschers 16 erwärmt bzw. wiedererwärmt. Die Wärme für diesen ersten Wärmetauscher 16 stammt empfohlenermaßen und im Ausführungsbeispiel aus dem Abgas bzw. aus der Abwärme der Beheizung der Wärmebehandlungsanlage 1. Bevorzugt und im Ausführungsbeispiel kann fernerhin ein zweiter Wärmetauscher 17 in der Rezirkulationsleitung 11 für die Erwärmung der rezirkulierenden Schutz- und/oder Reaktionsgase vorgesehen sein. Auch die Wärme dieses zweiten Wärmetauschers 17 wird zweckmäßigerweise dem Abgas bzw. der Abwärme aus der Beheizung der Wärmebehandlungsanlage 1 entnommen. - Eine sehr empfohlene Ausführungsform der Erfindung ist weiterhin dadurch gekennzeichnet, dass - wie in der Figur nicht näher dargestellt - die Wärme für die Spaltgaserzeugungseinrichtung 7 bzw. für die katalytische Niedertemperaturspaltung des Methanols dem Abgas bzw. der Abwärme der Beheizung der Wärmebehandlungsanlage entnommen wird. Auf diese Weise kann ein in energietechnischer Hinsicht besonders vorteilhaftes Verfahren durchgeführt werden.Preferably and in the exemplary embodiment, the cracked gas emerging from the
Es liegt noch im Rahmen der Erfindung, dass an verschiedenen Stellen der erfindungsgemäßen Vorrichtung in der Figur nicht dargestellte Drucksensoren zur Erfassung des Gasdruckes angeordnet sind. So kann jeder Druckentlastungskammer 10 ein solcher Drucksensor zugeordnet werden sowie auch der Rezirkulationsleitung 11 vor und hinter der Einspeisestelle 14 für das Spaltgas. Ein Drucksensor kann auch unmittelbar nach der Spaltgaserzeugungseinrichtung 7 bzw. am Gasaustritt der Spaltgaserzeugungseinrichtung 7 vorgesehen werden sowie in der Bypass-Leitung 12 mit den Reinigungseinrichtungen 4. Fernerhin ist es im Rahmen der Erfindung möglich, Einspeisevorrichtungen für ein Inertgas für die die Schutz- und/oder Reaktionsgase führenden Leitungen zur Inertisierung dieser Leitungen vorzusehen. Weiterhin können auch Temperatursensoren an verschiedenen Stellen der Vorrichtung angeordnet werden.It is still within the scope of the invention that are arranged at different points of the device according to the invention in the figure, not shown, pressure sensors for detecting the gas pressure. Thus, each
Claims (15)
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3403987A1 (en) * | 1984-02-04 | 1985-10-10 | Nicolai, Stephan Peter, 4230 Wesel | METHOD FOR THE PRODUCTION OF SEMI-SYNTHETIC PROTECTIVE AND REACTION GAS, ESPECIALLY FOR THE HEAT TREATMENT OF STEEL AND METAL MATERIALS, CONSISTING OF A MIXTURE OF DIFFERENTLY SELECTABLE QUANTITIES OF NITROGEN, OXYXIDE, WATER |
DE4110361A1 (en) * | 1991-03-28 | 1992-10-01 | Linde Ag | Carburising iron@ workpieces in gas phase process - with carbon mon:oxide to hydrogen@ ratio increased during specific phases of process to optimise carbon transfer to iron@ surface |
DE4318400C1 (en) * | 1993-06-03 | 1994-06-23 | Loi Ind Ofenanlagen | Method and device for heat treating workpieces |
US5591274A (en) * | 1994-08-18 | 1997-01-07 | Kanto Yakin Kogyo K.K. | Heat treatment method for metals |
DE102008029001B3 (en) | 2008-06-20 | 2009-09-17 | Ipsen International Gmbh | Method and device for the heat treatment of metallic materials |
DE202011105262U1 (en) * | 2011-06-03 | 2012-09-05 | Carbon-Clean Technologies Ag | Plant for low-carbon dioxide, preferably carbon dioxide-free production of a liquid hydrocarbon-containing energy carrier and / or for the direct reduction of metal oxides |
-
2015
- 2015-10-16 DE DE102015117683.1A patent/DE102015117683B3/en active Active
-
2016
- 2016-09-05 HU HUE16187277A patent/HUE041563T2/en unknown
- 2016-09-05 EP EP16187277.5A patent/EP3156507B1/en active Active
- 2016-09-05 PL PL16187277T patent/PL3156507T3/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3403987A1 (en) * | 1984-02-04 | 1985-10-10 | Nicolai, Stephan Peter, 4230 Wesel | METHOD FOR THE PRODUCTION OF SEMI-SYNTHETIC PROTECTIVE AND REACTION GAS, ESPECIALLY FOR THE HEAT TREATMENT OF STEEL AND METAL MATERIALS, CONSISTING OF A MIXTURE OF DIFFERENTLY SELECTABLE QUANTITIES OF NITROGEN, OXYXIDE, WATER |
DE4110361A1 (en) * | 1991-03-28 | 1992-10-01 | Linde Ag | Carburising iron@ workpieces in gas phase process - with carbon mon:oxide to hydrogen@ ratio increased during specific phases of process to optimise carbon transfer to iron@ surface |
DE4318400C1 (en) * | 1993-06-03 | 1994-06-23 | Loi Ind Ofenanlagen | Method and device for heat treating workpieces |
US5591274A (en) * | 1994-08-18 | 1997-01-07 | Kanto Yakin Kogyo K.K. | Heat treatment method for metals |
DE102008029001B3 (en) | 2008-06-20 | 2009-09-17 | Ipsen International Gmbh | Method and device for the heat treatment of metallic materials |
DE202011105262U1 (en) * | 2011-06-03 | 2012-09-05 | Carbon-Clean Technologies Ag | Plant for low-carbon dioxide, preferably carbon dioxide-free production of a liquid hydrocarbon-containing energy carrier and / or for the direct reduction of metal oxides |
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DE102015117683B3 (en) | 2016-09-29 |
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