CN102272039A - Process gas generation by means of heat recovery from low-temperature waste heat - Google Patents
Process gas generation by means of heat recovery from low-temperature waste heat Download PDFInfo
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- CN102272039A CN102272039A CN2009801541295A CN200980154129A CN102272039A CN 102272039 A CN102272039 A CN 102272039A CN 2009801541295 A CN2009801541295 A CN 2009801541295A CN 200980154129 A CN200980154129 A CN 200980154129A CN 102272039 A CN102272039 A CN 102272039A
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- 238000000034 method Methods 0.000 title claims abstract description 216
- 239000007789 gas Substances 0.000 title claims description 165
- 238000011084 recovery Methods 0.000 title description 7
- 239000002918 waste heat Substances 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 192
- 238000001816 cooling Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000012545 processing Methods 0.000 claims abstract description 21
- 238000000629 steam reforming Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000012546 transfer Methods 0.000 claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000003570 air Substances 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 239000012080 ambient air Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 230000001595 contractor effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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- C01B2203/14—Details of the flowsheet
- C01B2203/146—At least two purification steps in series
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
- F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- General Health & Medical Sciences (AREA)
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Abstract
Process for heat utilization in steam reforming, comprising a high-temperature conversion unit, a first heat exchanger, and hereinafter boiler feed water preheater, product condensate heat exchanger, and low-pressure evaporator, a cooling section, in which the process gas is further cooled and a condensate stream is generated and the resultant process gas is passed through at least one unit for further processing. In addition, a deionized water stream, a water treatment unit, wherein a first part of the boiler feed water stream is passed into the low-pressure evaporator, and the low-pressure steam generated is divided and a first substream of the low-pressure steam is conducted into the water treatment unit for heat transfer and a second substream of the low-pressure steam is passed to at least one consumer. A second part of the boiler feed water stream is passed via a heat exchanger and one or more boiler feed water preheaters and finally passed for steam generation. The condensate stream from the cooling section is passed into the product condensate heat exchanger via a unit for pressure elevation.
Description
The invention relates to a method for steam reforming (Dampf-reformulating) a hydrocarbon-containing feedstock (Ausgangsstoff), in particular by means of low-temperature waste heat
In the recovery of heat
To generate a process gas (Prozessgas-erzeugung). The invention is concerned with a better utilization of the energy in the hydrogen and water vapour comprising the process gas generated in the steam reforming process. Furthermore, the object of the invention is also a device (vorticichung) for carrying out the method according to the invention.
In the steam reforming process, a reaction mixture consisting of steam and a hydrocarbon-containing feedstock is converted into a hydrogen-rich process gas. The process gas leaves the steam reforming process at a temperature above 100 ℃. In most cases, the temperature is in the range of 700 to 1000 ℃.
For the purpose of further processing of the process gas, the process gas which is produced, for example, by purification and/or enhancement of the hydrogen content by means of pressure swing adsorption or semipermeable membrane processes must be cooled. The temperatures required for continued processing are in most cases in the range from 20 ℃ to 50 ℃. Other reaction steps can also be included between each cooling step, such as the reaction of carbon monoxide with water to form carbon dioxide and hydrogen.
Various methods are known from the patent literature
To utilize the heat contained in the process gas for heating the materials needed for the reaction process itself and/or other materials in the process. In particular, the contained heat is often used to exchange heat by means of heat
Boiler feed water (kesselspeeisewasser) is used to preheat the steam reforming process.
In typical conventional heat recovery processes integrated on synthesis gas plants, the heat in the process gas is generally used in such a way that it is first of all in a waste heat boiler
High pressure steam (Hochdruckdampf) is generated and the process gas is converted to carbon dioxide and hydrogen in a carbon monoxide conversion unit (CO-Konversionseinheit). It is then typically passed through various heat exchangers, for example to heat the hydrocarbon-containing feedstock, boiler feed water and/or Make-up water (Make-Upwasser). The remaining heat contained in the process gas is then largely dissipated to the surroundings via a cooling line (kuhlstrecke). The condensate falling in the cooling section will be sent to a water treatment unit (Wasseraufbereitungseinheit) where it is mixed with make-up water, immediately led to the boiler feed water preheater, and the heated water stream is led to the steam generating system.
A disadvantage of the conventional method of heat recovery is that a large part of the heat of the process gas leaving the carbon monoxide conversion unit is the heat generated when the humid gas condenses. The condensate is subjected to a contraction effect (Pinch-effect) by further cooling, whereby it becomes very difficult to recover the contained heat and a considerable part of the heat is discharged to the surroundings through the cooling section. Furthermore, the pinch effect is defined by an approximation of the temperature of the two parts of the fluid, so that temperature differences between the two parts of the fluid are avoided and the driving force for the heat exchange is minimized. Whereby a very large amount of energy in the process gas is lost to the white because it is not utilized.
US 2006/0231463 a1 discloses a solution to avoid this problem. Wherein the water is heated and fed to the water treatment unit. A first stream of water from the unit is sent to a low pressure steam generator and a second stream of water is sent to a first boiler feed water preheater. The process gas to be heat exchanged flows through both apparatus sections. The water stream emerging from the first boiler feed water preheater and generated therein is divided into two water streams and fed to two further boiler feed water preheaters, the first of which is designated below by the boiler feed water preheater 1, through which the process gases to be heat-exchanged likewise flow, and the second of which is designated below by the boiler feed water preheater 2, through which the exhaust gases to be heat-exchanged flow. The water streams generated in the last-mentioned two boiler feed water heat exchangers are subsequently directed towards the steam generator.
The disadvantage of this system is that the heat exchange in the boiler feed water preheater 1 through which the process gases flow is subject to a contraction effect, so that the desired heat transfer takes place only to a very limited extent. It is generally believed that the greater the amount of boiler feed water flowing through the unit, the greater the heat gain that can be utilized. However, the water flow is split into a limited amount of boiler feed water before flowing through the boiler feed water preheater 1, which flows through the unit and therefore a considerable part of the heat contained in the process gas is discharged to the surroundings through the cooling section, which is typically realized by an air cooler, and is therefore not utilized and lost. In addition, a portion of the heat in the exhaust gas is used to heat the boiler feed water. The heat fraction in the exhaust gas is no longer used for the original steam production.
A further disadvantage of interconnecting the individual pieces of equipment in US 2006/0231463 a1 is that the water to be heated, which is then sent to the water treatment unit, should be heated by the heat contained in the process gas. The water treatment unit is usually constituted by a retort. Most of them operate in a near atmospheric environment or in a slightly overpressure, typically less than 5bar (absolute), so that as much oxygen and other gases as possible are separated from the water. In the concept, the temperature of the water input stream (Wasser-Zulaufstrom) to the water treatment unit is typically limited to 80 ℃ to 95 ℃. Technically, the input water stream can be heated to a temperature greater than 100 ℃ by the heat contained in the process gas. It is therefore necessary to provide a control means for keeping the temperature of the inlet stream to the water treatment unit below the 95 c limit. In this way, the heat of the process gas cannot be used to its full extent, and the remaining heat contained is finally discharged to the surroundings without being used.
The invention is further developed in the context of the above-mentioned technology, wherein the task of the invention is to propose a method for producing a process gas in which the above-mentioned problems encountered in the recovery of the heat contained in the process gas no longer occur and in which the heat recovery is designed to be more efficient. In addition, an apparatus for carrying out the method according to the invention is also to be disclosed within the scope of the invention.
The object of the invention is achieved by using a method for utilizing heat in the steam reforming of a hydrocarbon-containing feedstock by means of steam, wherein a process gas having a first heat and an offgas having a second heat are generated in a steam reformer, comprising at least six heat exchangers, a water treatment unit, a cooling stage, a high-temperature conversion unit, at least two units for pressure increase, at least one load and at least one unit for further processing the resulting process gas. The process gas produced, containing the first heat, is first passed through a high-temperature conversion unit, in which the majority is converted to carbon dioxide and hydrogen, after which the process gas produced, containing heat, is conducted for further heat transfer into a first heat exchanger and then through at least two further heat exchangers, these heat exchangers operate as boiler feed water preheaters, product condensing heat exchangers or low pressure evaporators, and they are connected to each other in any order, wherein the resulting process gas from the low pressure evaporator is first directed into the other boiler feed water preheater by transferring heat energy from the water treatment unit to a portion of the boiler feed water stream, after which the resulting process gas is passed through a cooling section, where the process gas is further cooled and a condensate stream is formed which is finally led to at least one unit for further processing of the resulting process gas.
Subsequently, the stream of deionized water is directed into a second heat exchanger for heating. The deionized water stream from the second heat exchanger is directed to a water treatment unit for exhaust, a boiler feedwater stream from the water treatment unit is passed through a unit for raising pressure and is split, wherein a first portion of the boiler feedwater stream is directed to a low pressure evaporator, wherein low pressure steam is generated, and the resulting low pressure steam is split, a first portion of the low pressure steam is transferred to the water treatment unit for heat transfer, and a second portion of the low pressure steam is directed to at least one load. The second part of the low pressure steam can also be used to preheat other application media, such as liquid feed, or be supplied to applications outside the plant. A second part of the boiler feed water flow is conducted through a second heat exchanger for the purpose of energy transfer, then through one or more boiler feed water preheaters for heating by means of the heat contained in the process gas, and finally into the steam generator.
The water treatment unit removes a substantial portion of the oxygen in the deionized water primarily in a deaerator. Subsequently, other metering agents (Dosierungsmittel) can also be added, for example ammonia for pH adjustment. The product obtained in this process is called boiler feed water.
The condensate stream obtained from the cooling section is conducted to a product condensate heat exchanger for heating by means of the heat contained in the process gas via a unit for pressure increase, after which further heating of the condensate stream is effected.
Preferably, the process gas from the first heat exchanger first flows through the first boiler feed water preheater, in which heat energy is transferred to the boiler feed water stream, and then through the product condensing heat exchanger, in which heat energy is transferred to the condensate stream, and from there the resulting process gas is conducted to the low-pressure evaporator, in which low-pressure steam is generated from the boiler feed water stream by means of the heat contained therein, in order to continue flowing from there through the defined process train.
In a further embodiment of the invention, the process gas from the first heat exchanger is first passed through a first boiler feed water preheater, in which heat energy is transferred to the boiler feed water stream, before being conducted to a low-pressure evaporator, in which low-pressure steam is generated from the boiler feed water stream by means of the heat contained therein, and the resulting process gas flows out therefrom and through a product condensation heat exchanger, in which heat energy is transferred to the condensate stream in order to continue flowing through the defined process train from here on.
It is advantageous for the process gas from the first heat exchanger to first flow through a product condensing heat exchanger, in which heat energy is transferred to the condensate stream, from which the process gas flows out, and through a first boiler feedwater preheater, in which heat energy is transferred to the boiler feedwater stream, after which the process gas is conducted to a low-pressure evaporator, in which low-pressure steam is generated from the boiler feedwater stream by means of the heat contained therein, after which the resulting process gas continues to flow through the defined process train, as described above. In a further embodiment of the invention, the process gas from the product condensing heat exchanger is first passed through a first boiler feed water preheater, in which heat energy is transferred to the boiler feed water stream, and after that, the process gas is passed through a further product condensing heat exchanger before it is introduced into the low-pressure evaporator, after which the process gas flows further through the defined process train after it has exited the low-pressure evaporator.
Another possibility in the design of the invention is that the process gas from the first heat exchanger first flows through a product condensing heat exchanger, in which thermal energy is transferred to a partial flow of the condensate stream and the boiler feedwater stream, and from there out to a low-pressure evaporator, in which low-pressure steam is generated from the boiler feedwater stream by means of the heat contained therein, and the resulting process gas then continues to flow through the defined process train.
Optionally, the process gas leaving the first heat exchanger is conducted for further heat transfer to another boiler feed water preheater supplied by another part of the stream resulting from the continued splitting of the second part of the boiler feed water stream flowing through the water treatment unit, the pressure boosting unit and the second boiler feed water preheater and being heated further.
Preferably, the process gas leaving the first heat exchanger and/or the other boiler feed water preheater is led to a low temperature conversion unit, where carbon dioxide and hydrogen are formed, which carbon dioxide and hydrogen flow out of the low temperature conversion unit and into one of the other heat exchangers of the defined process train.
In a further embodiment of the invention, the process gas flowing through the heat exchanger is subsequently conducted through a Separator (Separator) and the resulting liquid stream is separated from the heat-containing process gas and collected with condensate streams from the cooling section and from further separators, these mixtures being conducted through a unit for pressure increase and finally through a product condensation heat exchanger for heating by means of the heat contained in the process gas.
Optionally, for further heat transfer, the process gas is conducted in a targeted manner through further additional heat exchangers which are included in the process before and after flowing through the low-pressure evaporator, respectively.
A corresponding plant for the steam reforming of hydrocarbon-containing materials by means of steam, which is suitable for carrying out the method according to claim 1, has a series of plants (apparatus) through which a process gas flows, comprising a high-temperature reforming unit, at least four heat exchangers, a cooling section and at least one unit for further processing of the resulting process gas, wherein for conducting the process gas, conducting means are provided which connect the individual plants to one another via a gas outlet and a gas inlet.
Furthermore, the device for gas conversion comprises a further heat exchanger, a water treatment unit, at least two pressure raising units, at least one load, a device for conducting a flow of deionized water into the further heat exchanger, a device for conveying a flow of deionized water from the further heat exchanger to the water treatment unit, a device for conveying a flow of boiler feed water leaving the water treatment unit to the pressure raising units, and a device for diverting a flow of boiler feed water leaving the pressure raising units, wherein a first feed line (Zuleitung) is provided for feeding a first part of the flow of boiler feed water to the low-pressure evaporator, and a discharge line (Ableitung) for discharging the low-pressure steam generated from the low-pressure evaporator comprises a device for conveying a first part of the low-pressure steam generated to the water treatment unit and a further device for conveying a second part of the low-pressure steam generated to the further load, and for conveying a second part of the boiler feed water flow to the further heat exchanger a second conveying line is provided, and a conveying line leading to the second boiler feed water preheater is drawn off there, and a discharge line leading to the first boiler feed water preheater or to the product condensation heat exchanger and/or directly to the further evaporator is provided there, and means are provided for conveying the condensate flow flowing out of the cooling stage to the product condensation heat exchanger or exchangers by means of a pressure raising unit.
For the circulation of the process gas, the series of devices advantageously comprises a series of connections: a high temperature conversion unit, a first heat exchanger, a first boiler feed water preheater, a product condensing heat exchanger, a low pressure evaporator, a second boiler feed water preheater, a cooling section and at least one unit for further processing the resulting process gas, which are connected in the above-mentioned order.
In a further advantageous embodiment of the apparatus, the series of apparatuses comprises, for the passage of the process gas, a series of successive connections: a high temperature conversion unit, a first heat exchanger, a first boiler feed water preheater, a low pressure evaporator, a product condensation preheater, a second boiler feed water preheater, a cooling section and at least one unit for further processing of the resulting process gas, which are connected in the above-mentioned order.
For the circulation of the process gas, the series of apparatuses preferably comprises, connected in series: a high temperature conversion unit, a first heat exchanger, a product condensing heat exchanger, a first boiler feed water preheater, a low pressure evaporator, a second boiler feed water preheater, a cooling section and at least one unit for further processing the resulting process gas, which are connected in the above-mentioned order.
Preferably, for the circulation of the process gas, the series of devices comprises, connected in series: a high temperature conversion unit, a first heat exchanger, a product condensing heat exchanger, a low pressure evaporator, a second boiler feed water preheater, a cooling section and at least one unit for further processing the resulting process gas, the devices being connected in the order mentioned, wherein a device is provided for conveying a first part of the boiler feed water stream from the second boiler feed water preheater to the product condensing heat exchanger and another device is provided for conveying a second part of the boiler feed water stream from the second boiler feed water preheater directly to other steam generators.
Another possibility of the design according to the invention is that, for the circulation of the process gas, a further third boiler feed water preheater is provided in the series of plants, the inlet of which is connected to the outlet of the first heat exchanger and the outlet of which is connected to the inlet of the optional low-temperature shift unit or the subsequent heat exchanger, and into which further third boiler feed water preheater means for transporting a further part of the fluid of the boiler feed water originate from the water treatment unit and the second boiler feed water preheater.
In a further embodiment of the plant, for the circulation of the process gas, a low-temperature conversion unit is provided in the series of plants, the inlet of which is connected to the outlet of the first heat exchanger or of the further third boiler feed water preheater and the outlet of which is connected to the subsequent heat exchanger.
For the passage of the process gas, further separators are advantageously provided in the series of plants, whose gas inlets are connected to the gas outlet of each previously connected heat exchanger and whose gas outlets are connected to the respective subsequent heat exchanger in the process chain and which each have a discharge conduit for the liquid produced, and the liquid flows into the plant for conveying the condensate stream from the cooling section to the product condensate heat exchanger and is guided through the pressure-raising unit.
In another embodiment of the invention, the second boiler feedwater preheater is integrated in a separator, which is optionally equipped with further equipment and/or packaging, and is provided with a discharge conduit which conveys the generated process condensate to the equipment for conveying the condensate stream from the cooling section to the product condensing heat exchanger.
A further possible embodiment of the plant according to the invention provides that, for the passage of the process gas, a further additional heat exchanger is provided in the series of plants.
Advantageously, the unit for air preheating is used as a load for preheating ambient air, which load is provided for the circulation of low-pressure steam.
In addition, it is also possible to provide a pressure swing adsorption unit or a cooling tank as a unit for processing the process gas obtained in a targeted manner.
Alternatively, other devices for diverting a second partial flow of the low-pressure steam are provided, so that a supply line for air preheating and a supply line to other consumers are provided.
The invention is subsequently further elucidated, by way of example, with reference to seven drawings, in which:
FIG. 1: is a schematic illustration of the method according to the invention of a process for utilizing heat in the steam reforming of a hydrocarbon-containing feedstock by means of steam.
FIG. 2: is an alternative connection of the heat exchanger in the process for utilizing heat in the steam reforming of a hydrocarbon-containing feed by means of steam, as shown in fig. 1.
FIG. 3: a further advantageous method variant for utilizing heat in the steam reforming of hydrocarbon-containing raw materials by means of steam is provided, in which a process gas is passed through a product condensing heat exchanger upstream of a first boiler feed water preheater.
FIG. 4: is a further embodiment of the connection of the heat exchangers used to each other. The main difference with respect to fig. 1 to 3 is, among other things, that the use of a first boiler feed water preheater is dispensed with.
FIG. 5: is a supplementary description of fig. 1, in which for example a third boiler feed water preheater, a low temperature conversion unit, an additional optional separator, and a heat exchanger are connected.
FIG. 6: is an additional integration of other product condensing heat exchangers in the process chain according to figure 1.
Fig. 7A to D: the process gas cooling is illustrated (dashed lines) and the heating behavior of the heat exchangers connected by the inventive method (transverse lines) for the respective medium.
Fig. 1 shows a schematic diagram of a method for utilizing heat in the steam reforming of a hydrocarbon-containing feedstock by means of steam, wherein the generated heat-containing process gas 1a first flows through a high-temperature conversion unit 2, in which a part of the carbon monoxide is converted into carbon dioxide and hydrogen. The generated process gas 1b containing heat is introduced into the first heat exchanger 3 for subsequent further heat transfer. The process gas 1c containing heat then flows through the first boiler feed water preheater 4, wherein the heat contained in the process gas is transferred to the already preheated boiler feed water 14e, which originates from the water treatment unit 13 and has passed through the pressure boosting unit 25, the heat exchanger 16 and the boiler feed water preheater 8. The deionized water 12a is heated in the heat exchanger 16, and the heated deionized water 12b is introduced into the water treatment unit 3 for gas removal. The advantage of preheating the di water is that one side of the heat exchanger is only subjected to low pressure and that parts of the product made of low alloy steel are sufficient, thus saving costs. From which is derived boiler feed water 14a, which is preheated accordingly in the manner described above. The resulting boiler feedwater 14f is then directed to a steam generator for further processing.
The heat-containing process gas 1d obtained from the boiler feed water preheater 4 is then conducted to the product condensate heat exchanger 5, in which heat is given to the process condensate 15a, which passes through the pressure raising unit 27 and exits from the cooling stage 10. The preheated process condensate 15b is then used for further heating.
The process condensate 15a is obtained in a separator (Abscheider) of a cooling stage 10, which consists for example of an air cooler and a water cooler together and is reheated in the product condensate heat exchanger 5. This process can be carried out in a contactor (Kontaktapparat) which is impinged with water, wherein at least a part of the water vapour separated from the process gas is condensed by direct cooling, which part is subsequently separated from the water used for cooling. By using such a device, the process condensate will be further preheated, which has the advantage that the higher the preheating temperature of the process condensate, the more heat can be utilized in the exhaust gas by the other media and the evaporator.
The heat-containing process gas 1e obtained from the product condensate heat exchanger 5 is then conducted to the low-pressure evaporator 6, where the heat is transferred to a portion of the pressure-boosted boiler feedwater stream 14c generated in the water treatment unit 13. The low-pressure steam 19a thus obtained is returned to the water treatment unit 13 in the form of a first portion 19b, while at the same time a second portion of the heated boiler feed water 19c is supplied to a load, here an air preheater 18, which heats ambient air 17 which is then used further as combustion gas 20.
The heat-containing process gas 1f obtained from the low-pressure evaporator 6 is then fed to the boiler feed water preheater 8, in which a portion 14d of the boiler feed water produced in the water treatment unit 13 is further preheated before being fed to the boiler feed water preheater 4. The process gas 1g obtained from the boiler feed water preheater 8 then flows into the cooling section 10 where it is further cooled and a condensate stream is generated, the condensate stream 15a being conducted to the product condensing heat exchanger 5. Finally, the condensed heat-containing process gas 1h flows through a unit for further processing of the resulting process gas 11, which is, for example, a pressure swing adsorption unit, in which the hydrogen formed is separated off from the process gas.
Fig. 2 presents a variant of the method shown in fig. 1. Fig. 1 differs from fig. 2 in that the heat-containing process gas 1d leaving the boiler feed water preheater 4 first flows through the low-pressure evaporator 6 and then through the product condensation heat exchanger 5. Other ways of interconnecting the devices are not affected. However, it is desirable to have a better energy utilization by the variant shown in fig. 1.
Fig. 3 shows another embodiment. The difference to fig. 1 is that the heat-containing process gas 1c obtained from the heat exchanger 3 first flows through the product condensate heat exchanger 5 and is then conducted through the boiler feed water preheater 4. Other interconnections of the various devices are not affected and correspond to the series of devices shown in fig. 1.
In fig. 4, the use of the boiler feed water preheater 4 is completely dispensed with. Here, the heat-laden process gas 1c from the heat exchanger 3 is conducted to a product condensing heat exchanger 5, from which the resulting heat-laden process gas 1d flows through a low-pressure evaporator 6 followed by a boiler feed water preheater 8. The preheated boiler feed water 14e generated in the boiler feed water preheater 8 is in this case branched off, and a partial stream 14f is fed together with the process condensate 15a through the product condensate heat exchanger 5 in order to be subjected to further preheating. A second portion 14g of the preheated boiler feed water is given for the production of steam.
Fig. 5 uses alternative equipment in the connection, which has a positive effect on the process. This is illustrated and described by the differences from fig. 1. Here, the heat-containing process gas 3 from the heat exchanger 3 is conducted to an additional boiler feed water preheater 21, which is supplied with a further part 14g of the boiler feed water stream, which is preheated in the boiler feed water preheater 8. The resulting heated boiler feed water 14h is also directed to the steam generator and utilized thereby. In the embodiment shown in the figure, the resulting process gas is directed to the low temperature shift unit 22 after exiting the boiler feed water preheater 21 and forming carbon dioxide and hydrogen therein. The process gas 1e containing heat obtained therein then flows through a boiler feed water preheater 4 and a product condensation preheater 5 as shown in fig. 1. The process gas 1g obtained from the product condensate preheater 5 next enters a separator 23, in which the process condensate 15c formed is separated from the process gas and is conducted together with the other process condensate streams as process condensate 15d to the product condensate heat exchanger 5 via a unit 27 for pressure increase. In addition, the process gas 1h containing heat obtained in the low-pressure evaporator 6 and the separator 7 flows through. The condensate stream 15e from the separator 7 is likewise led to the product condensate heat exchanger 5 together with other condensate streams 15d obtained from the overall process. The low-pressure steam 19a obtained from the low-pressure evaporator 6 is branched into three portions. In this case, a partial flow 19b of the low-pressure steam is conducted to the water treatment unit 13, 19c to the air preheater 18, 19d to the further load 26. After the separator 7, a further heat exchanger 24 is connected for further energy transfer. Thus, the process train depicted in fig. 1 comprises a boiler feed water preheater 8, a cooling section 10 and a pressure swing adsorption unit 11. In this embodiment, a further heat exchanger 9 is provided between the boiler feed water preheater 8 and the cooling stage 10.
Fig. 6 shows another variant of fig. 1. Wherein the process condensate stream 15a from the condensing section 10 is passed through a unit for pressure increase 27 and through further additional product condensing heat exchangers 28 before flowing through the product condensing heat exchanger 5. This has the advantage that the product condensation receives more heat, which can be applied to the heating of other media.
The additional devices in fig. 5 can be combined in the manner shown in fig. 5, but can also be integrated in the individual process chains as separate components. In addition, not only is the basis for device integration in fig. 1, but also the basis for integration in all the drawings. It can thus be seen that the process offers a number of options, namely the option of adapting the individual methods to each requirement of the plant operator and embedding the corresponding plant accessories in the existing plant. In addition, it is also possible to implement the conversion of method variants in the new device.
In the case of suitable dimensioning, the low-pressure evaporator can be equipped with a safety reversing device (sicheritsreverse), the process gas being cooled by the generation and venting of low-pressure steam once a power failure has occurred. The low-pressure steam generated can additionally be used for air preheating and water treatment, as described above, and for example can also be used for CO2CO in process gas cleaning2Decocting (Auskochung). Here, the temperature of the generated low-pressure steam is 200 ℃ at maximum.
The improved energy utilization should then be demonstrated in connection with the calculation example, which is shown as the sum of the low pressure steam, boiler feed water and condensate stream. Starting from the typical connection in the background art, this connection works with a minimum of equipment set-up and occurs in the conventional method in the background art. In this case, the use of the low-pressure evaporator 6 and the boiler feed water preheater 8 is dispensed with from fig. 1, so that the boiler feed water stream 14d is conducted directly into the boiler feed water preheater 4. As is evident, the invention has a very positive effect on the energy utilization compared to such a typical connection, which is shown in the following table. Some of the previously described figures are used here as the basis for the calculations. The starting point here is that for the circulation of the process gas, a separator is connected downstream of the first four heat exchangers connected in series. This is for example a plant capacity of 33455Nm3Hydrogen/h as starting point.
It can be seen that the connection according to the invention is reflected in fig. 3 and 6, which has a very high energy utilization compared to the connection typical in the prior art. The sum of the energy utilization is raised in this case by approximately 3270kW, which is not utilized and is wasted in the typical connection of the background art.
Calculation of the base conditions allows a graphical function as temperature and energy utilization to be seen in fig. 7A to 7D. Wherein the dashed lines indicate the temperature drop of the process gas as a function of the energy involved, while the continuous lines indicate the heating behavior of the respective medium in the process. The individual steps are represented again in the figures and are reflected by the reference numerals introduced, which are likewise applied in the remaining fig. 1 to 6.
The advantages obtained according to the invention are:
improving the energy utilization of the heat of the process gas
Further preheating of the process condensate in a product condensing heat exchanger, more energy from the off-gas can be used to heat other media and to produce steam
According to the background art, the process condensate in the exhaust gas line is preheated to boiling. The preheating of the process condensate by the integrated process gas according to the invention makes it possible to dispense with the conventional heating in the waste gas line, which simplifies the process concept
The advantage of the method according to the invention is that it can be integrated in existing plants which do not have an inlet for low-pressure steam and which produce low-pressure steam from valuable high-pressure steam.
The temperature and pressure conditions in the heat exchanger 16 reduce the risk of steam impingement, thereby increasing the safety of operation.
Reference numerals
1a, 1b, 1c, 1d, 1e, 1f, 1g, process gas containing heat 1h, 1i, 1j, 1k, 1l, 1m, 1n
2 high temperature conversion unit
3 Heat exchanger
Feed water preheater for 4 boilers
5 product condensing heat exchanger
6 low pressure evaporator
7 separator
8 boiler feed water preheater
9 heat exchanger
10 cooling section
11 pressure alternating adsorption unit
12a, 12b deionized water
13 Water treatment unit
14a, 14b, 14c, 14d, 14e, boiler feedwater streams 14f, 14g, 14h, 14i
15a, 15b, 15c, 15d, 15e process condensate
16 heat exchanger
17 ambient gas
18 air preheater
19a, 19b, 19c, 19d low pressure steam
20 combustion gas
21 boiler feed water preheater
22 low temperature conversion unit
23 separator
24 heat exchanger
25 pressure raising unit
26 other loads
27 Unit for pressure raising
28 product condensing heat exchanger
Claims (22)
1. A method for utilizing heat in the steam reforming of a hydrocarbon-containing feedstock by means of steam, wherein a process gas having a first heat and an exhaust gas having a second heat are generated in a steam reformer, comprising:
at least six heat exchangers, a water treatment unit, a cooling section, a high-temperature conversion unit, at least two units for pressure increase, at least one load, and at least one unit for further processing of the resulting process gas, wherein,
the process gas produced, containing a first amount of heat, is first passed through the high-temperature conversion unit, where the majority is converted to carbon dioxide and hydrogen, after which the resulting process gas, containing heat, is conducted for further heat transfer into a first heat exchanger and subsequently through at least two further heat exchangers, which heat exchangers operate as boiler feed water preheaters, product condensate heat exchangers or low-pressure evaporators, and which heat exchangers are connected in any sequence one after the other, wherein the process gas obtained by the low-pressure evaporators is first conducted to another boiler feed water preheater by transferring heat energy from the water treatment unit to a portion of the boiler feed water stream, after which the resulting process gas is passed through a cooling stage, where the process gas is further cooled and a condensate stream is produced, and finally conducted to at least one unit for further processing the resulting process gas,
for heating, a flow of deionized water is conducted into a second heat exchanger, the flow of deionized water from the second heat exchanger is conducted into the water treatment unit for degassing, the flow of boiler feedwater from the water treatment unit is passed through a unit for pressure increase and is split, wherein,
a first part of the boiler feedwater stream is conducted to the low-pressure evaporator, in which low-pressure steam is generated and the generated low-pressure steam is branched off, a second part of the low-pressure steam is conducted to at least one load for heat transfer of a first part of the low-pressure steam to the water treatment unit, and
a second part of the boiler feedwater stream is conducted through the second heat exchanger for the purpose of transferring energy, then through one or more boiler feedwater preheaters for heating by means of the heat contained in the process gas, and finally is conducted to a steam generator,
the condensate stream obtained from the cooling section is conducted into the product condensate heat exchanger for heating by means of the heat contained in the process gas via a unit for pressure increase, after which further heating is effected.
2. The method of claim 1, wherein the process gas from the first heat exchanger first flows through a first boiler feedwater preheater, wherein thermal energy is transferred to the boiler feedwater stream, and thereafter flows through a product condensing heat exchanger, wherein thermal energy is transferred to the condensate stream, and thereby begins to direct the resulting process gas into the low pressure evaporator, wherein the low pressure steam is generated from the boiler feedwater stream with the contained heat, so as to continue to flow through the defined process train from the low pressure evaporator.
3. The method of claim 1, wherein the process gas from the first heat exchanger first flows through the first boiler feedwater preheater, where heat energy is transferred to the boiler feedwater stream, before being directed into the low-pressure evaporator, where low-pressure steam is generated from the boiler feedwater stream with the contained heat, and the resulting process gas flows out of the low-pressure evaporator and through the product condensing heat exchanger, where heat energy is transferred to the condensate stream to continue flowing from the low-pressure evaporator through the defined process train.
4. The method of claim 1, wherein the process gas from the first heat exchanger first flows through the product condensing heat exchanger, in which heat energy is transferred to the condensate stream, the process gas flows out of the product condensing heat exchanger and flows through the first boiler feed water preheater, in which heat is transferred to the boiler feed water stream, after which the process gas is conducted to a low pressure evaporator, in which low pressure steam is generated from the boiler feed water stream by means of the contained heat, the resulting process gas then continuing to flow through the defined process train.
5. The method of claim 4, wherein the process gas from the product condensing heat exchanger first flows through the first boiler feedwater preheater, where heat energy is transferred to the boiler feedwater stream, and then continues to flow through the defined process train after exiting the low pressure evaporator through another product condensing heat exchanger before being directed into the low pressure evaporator.
6. The method of claim 1, wherein the process gas from the first heat exchanger first flows through the product condensing heat exchanger, where heat energy is transferred to a condensate stream and to a portion of the boiler feedwater stream, and exits the product condensing heat exchanger and is directed into the low pressure evaporator, where low pressure steam is generated from the boiler feedwater stream with the contained heat, the resulting process gas then continuing to flow through the defined process train.
7. The method of any one of claims 1 to 6, wherein the process gas exiting the first heat exchanger is directed for further heat transfer into another boiler feedwater preheater supplied by another portion of the fluid from which the second portion of the boiler feedwater stream continues to be diverted and heated, the boiler feedwater stream passing through the water treatment unit, the pressure boosting unit, and the second boiler feedwater preheater.
8. The method according to any one of claims 1 to 7, wherein the process gas leaving the first heat exchanger and/or the other boiler feed water preheaters is led to a low-temperature conversion unit, where carbon dioxide and hydrogen are formed, which flow out of the low-temperature conversion unit and into one of the other heat exchangers of the defined process train.
9. Process according to any one of claims 1 to 8, characterized in that the process gas flowing through the heat exchanger is subsequently conducted through a separator and the liquid fluid produced is separated by the process gas containing heat and is collected with the condensate stream from the cooling section and from the further separator, the mixture being conducted through a unit for pressure increase and finally through a product condensation heat exchanger for heating by means of the heat contained in the process gas.
10. Method according to any one of claims 1 to 9, characterized in that the process gas is conducted through further additional heat exchangers for further heat transfer, which heat exchangers are included in the method before and after flowing through the low-pressure evaporator, respectively.
11. A plant for the steam reforming of a hydrocarbon-containing feedstock by means of steam, suitable for being carried out according to the method of claim 1, having a series of plants through which a process gas flows, including
A high-temperature reforming unit, which is,
at least four heat exchangers, which are arranged in parallel,
a cooling section, and
at least one unit for further processing the resulting process gas,
wherein, in order to conduct the process gas, a conducting device is also provided for connecting each device with each other through the gas outlet and the gas inlet;
in addition, it also includes
The other heat exchangers are arranged in parallel with each other,
a water treatment unit for treating the water in the water tank,
at least two pressure-raising units, which,
at least one load, which is connected to the load,
means for introducing a stream of deionized water into the further heat exchanger,
means for passing the stream of deionized water from the further heat exchanger to the water treatment unit,
means for conveying a boiler feedwater stream exiting the water treatment unit to the pressure boost unit,
means for splitting the boiler feedwater stream exiting the pressure boosting unit,
wherein,
a first feed line for feeding a first portion of the boiler feedwater stream to the low-pressure evaporator, and a discharge line for discharging the low-pressure steam generated from the low-pressure evaporator, comprising means for conveying a first portion of the low-pressure steam generated to the water treatment unit, and further means for conveying a second portion of the low-pressure steam generated to a further load,
and for conveying a second part of the boiler feedwater stream to the further heat exchanger a second conveying line is provided, and a conveying line leading to the second boiler feedwater preheater is drawn off there, and a discharge line leading to the first boiler feedwater preheater or to a product condensation heat exchanger and/or directly to a further evaporator is provided here,
and means are provided for conveying the condensate stream emerging from the cooling section to one or more product condensing heat exchangers via a pressure-rising unit.
12. The plant according to claim 11, characterized in that for the circulation of the process gas, the series of plants comprises, connected in series: a high temperature conversion unit, a first heat exchanger, a first boiler feed water preheater, a product condensing heat exchanger, a low pressure evaporator, a second boiler feed water preheater, a cooling section and at least one unit for further processing the resulting process gas, which are connected in the above-mentioned order.
13. The plant according to claim 11, characterized in that for the circulation of the process gas, the series of plants comprises, connected in series: a high temperature conversion unit, a first heat exchanger, a first boiler feed water preheater, a low pressure evaporator, a product condensation preheater, a second boiler feed water preheater, a cooling section and at least one unit for further processing of the resulting process gas, which are connected in the above-mentioned order.
14. The plant according to claim 11, characterized in that for the circulation of the process gas, the series of plants comprises, connected in series: a high temperature conversion unit, a first heat exchanger, a product condensing heat exchanger, a first boiler feed water preheater, a low pressure evaporator, a second boiler feed water preheater, a cooling section and at least one unit for further processing the resulting process gas, which are connected in the above-mentioned order.
15. The plant according to claim 11, characterized in that for the circulation of the process gas, the series of plants comprises, connected in series: a high temperature conversion unit, a first heat exchanger, a product condensing heat exchanger, a low pressure evaporator, a second boiler feed water preheater, a second heat exchanger, a cooling section and at least one unit for further processing the resulting process gas, which devices are connected in the above-mentioned order, wherein a device is provided for conveying a first part of the boiler feed water stream from the second boiler feed water preheater to the product condensing heat exchanger and a further device is provided for conveying a second part of the boiler feed water stream from the second boiler feed water preheater directly to a further steam generator.
16. An apparatus according to any one of claims 11 to 15, characterized in that for the circulation of the process gas, there is provided in the series an additional third boiler feed water preheater, the inlet of which is connected to the outlet of the first heat exchanger, the outlet of which is connected to the inlet of the optional low temperature shift unit or the subsequent heat exchanger, and in that the means for transporting an additional part of the flow of boiler feed water originating from the water treatment unit and the second boiler feed water preheater is passed to the additional third boiler feed water preheater.
17. The plant according to any of claims 11 to 16, characterized in that for the circulation of the process gas, a low-temperature conversion unit is provided in the series of plants, the inlet of which is connected to the outlet of the first heat exchanger or the outlet of the further third boiler feed water preheater and the outlet of which is connected to the subsequent heat exchanger.
18. Apparatus according to any one of claims 11 to 17, characterized in that for the passage of the process gas, further separators are provided in the series of apparatuses, whose gas inlets are connected to the gas outlet of each previously connected heat exchanger and whose gas outlets are connected to the heat exchangers following each other in the process chain, and that the separators each have a discharge conduit for the liquid produced, and that the liquid flows into the apparatus for conveying the condensate stream from the cooling section to the product condensation heat exchanger and is guided through the pressure-raising unit.
19. The plant according to any one of claims 11 to 18, characterized in that the second boiler feed water preheater is integrated in the separator, which is optionally equipped with further equipment and/or packaging and is provided with a discharge conduit which conveys the generated process condensate to the equipment for conveying the condensate stream from the cooling section to the product condensing heat exchanger.
20. The plant as claimed in any of claims 11 to 19, characterized in that for the circulation of the process gas, further additional heat exchangers are provided in the series of plants.
21. The apparatus according to any one of claims 11 to 20, characterized in that the unit for air preheating is used as a load for preheating ambient air, which load is provided for the circulation of low-pressure steam.
22. The plant as claimed in any of claims 11 to 21, characterized in that a pressure swing adsorption unit or a cooling tank is provided as a unit for processing the resulting process gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008056538.5 | 2008-11-10 | ||
| DE102008056538A DE102008056538A1 (en) | 2008-11-10 | 2008-11-10 | Process gas production by means of heat recovery from low-temperature waste heat |
| PCT/EP2009/007368 WO2010051900A1 (en) | 2008-11-10 | 2009-10-14 | Process gas generation by means of heat recovery from low-temperature waste heat |
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| CN102272039A true CN102272039A (en) | 2011-12-07 |
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| CN2009801541295A Pending CN102272039A (en) | 2008-11-10 | 2009-10-14 | Process gas generation by means of heat recovery from low-temperature waste heat |
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| US (1) | US20110277962A1 (en) |
| EP (1) | EP2349922A1 (en) |
| CN (1) | CN102272039A (en) |
| BR (1) | BRPI0916065A2 (en) |
| CA (1) | CA2743089A1 (en) |
| CO (1) | CO6361983A2 (en) |
| DE (1) | DE102008056538A1 (en) |
| EA (1) | EA201190010A1 (en) |
| MX (1) | MX2011004916A (en) |
| SG (1) | SG171719A1 (en) |
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| CN103805290A (en) * | 2012-11-01 | 2014-05-21 | 通用电气公司 | System and method for using boiler feedwater |
| CN110986649A (en) * | 2019-12-20 | 2020-04-10 | 乔治洛德方法研究和开发液化空气有限公司 | Synthetic gas heat recovery system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102010044939C5 (en) | 2010-09-10 | 2015-11-19 | Thyssenkrupp Industrial Solutions Ag | Process and device for generating process steam and boiler feed water vapor in a heatable reforming reactor for the production of synthesis gas |
| EP3124433B1 (en) * | 2015-07-27 | 2021-09-01 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Method for cooling synthesis gas |
| EP3138810B1 (en) | 2015-09-03 | 2018-04-25 | Air Products And Chemicals, Inc. | Hydrogen production process for cold climates |
| US9556026B1 (en) | 2015-09-03 | 2017-01-31 | Air Products And Chemicals, Inc. | Hydrogen production process for cold climates |
| DE102016218438A1 (en) * | 2016-09-26 | 2018-03-29 | Thyssenkrupp Ag | Process and arrangement for heat energy recovery in plants comprising at least one reformer |
| CN114735657B (en) * | 2022-04-22 | 2024-06-07 | 瑞切尔石化工程(上海)有限公司 | Condenser for sulfur production device, sulfur production device based on Claus method and sulfur production process |
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- 2009-10-14 CN CN2009801541295A patent/CN102272039A/en active Pending
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- 2009-10-14 BR BRPI0916065A patent/BRPI0916065A2/en not_active IP Right Cessation
- 2009-10-14 SG SG2011032463A patent/SG171719A1/en unknown
- 2009-10-14 CA CA2743089A patent/CA2743089A1/en not_active Abandoned
- 2009-10-14 EP EP09748703A patent/EP2349922A1/en not_active Withdrawn
- 2009-10-14 US US13/128,565 patent/US20110277962A1/en not_active Abandoned
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Also Published As
| Publication number | Publication date |
|---|---|
| SG171719A1 (en) | 2011-07-28 |
| DE102008056538A1 (en) | 2010-05-12 |
| EP2349922A1 (en) | 2011-08-03 |
| US20110277962A1 (en) | 2011-11-17 |
| EA201190010A1 (en) | 2012-02-28 |
| CO6361983A2 (en) | 2012-01-20 |
| ZA201104320B (en) | 2012-02-29 |
| CA2743089A1 (en) | 2010-05-14 |
| WO2010051900A1 (en) | 2010-05-14 |
| MX2011004916A (en) | 2011-10-28 |
| BRPI0916065A2 (en) | 2015-11-10 |
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