EP0801262A1 - Dispositif avec récipient sans pression contenant de l'ammoniac - Google Patents

Dispositif avec récipient sans pression contenant de l'ammoniac Download PDF

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Publication number
EP0801262A1
EP0801262A1 EP96810246A EP96810246A EP0801262A1 EP 0801262 A1 EP0801262 A1 EP 0801262A1 EP 96810246 A EP96810246 A EP 96810246A EP 96810246 A EP96810246 A EP 96810246A EP 0801262 A1 EP0801262 A1 EP 0801262A1
Authority
EP
European Patent Office
Prior art keywords
ammonia
stream
catalyst
water
heat exchanger
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.)
Withdrawn
Application number
EP96810246A
Other languages
German (de)
English (en)
Inventor
Martin Roland Dr. Bierer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sulzer Escher Wyss GmbH
Original Assignee
Sulzer Escher Wyss GmbH
Escher Wyss GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sulzer Escher Wyss GmbH, Escher Wyss GmbH filed Critical Sulzer Escher Wyss GmbH
Priority to EP96810246A priority Critical patent/EP0801262A1/fr
Publication of EP0801262A1 publication Critical patent/EP0801262A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C13/00—Details of vessels or of the filling or discharging of vessels
    • F17C13/12—Arrangements or mounting of devices for preventing or minimising the effect of explosion ; Other safety measures
    • F17C13/126—Arrangements or mounting of devices for preventing or minimising the effect of explosion ; Other safety measures for large storage containers for liquefied gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • F17C2250/0439—Temperature
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2250/00—Accessories; Control means; Indicating, measuring or monitoring of parameters
    • F17C2250/04—Indicating or measuring of parameters as input values
    • F17C2250/0404—Parameters indicated or measured
    • F17C2250/0447—Composition; Humidity
    • F17C2250/0452—Concentration of a product
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/03—Dealing with losses
    • F17C2260/035—Dealing with losses of fluid
    • F17C2260/037—Handling leaked fluid
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2260/00—Purposes of gas storage and gas handling
    • F17C2260/03—Dealing with losses
    • F17C2260/035—Dealing with losses of fluid
    • F17C2260/038—Detecting leaked fluid

Definitions

  • the invention relates to a device with an ammonia pressure container which has a filling pressure above atmospheric pressure and which is surrounded by a further shell, the space between the shell and the ammonia container having an inlet opening and an outlet opening so that it can be used to discharge ammonia leaks by a fan with a flushing flow is flushable from normal outside air.
  • ammonia systems - be it as a pressure tank for chemical uses or as refrigeration systems or heat pumps operated with ammonia - have so far managed to dilute ammonia leaks as much as possible in order to bring them to a concentration below the odor limit, i.e. around 5 ppm Surrender environment.
  • Another option is to surround the ammonia system with a second shell and to flush the resulting space with fresh air. Especially if the space in between has to be accessible, this is a possibility of a planned dilution of the ammonia leaks.
  • an absorption device with dilute sulfuric acid can be used as an absorption device with dilute sulfuric acid.
  • the ammonia is not dissolved in such a safety device, but is bound.
  • the reaction product is ammonium sulfate (artificial fertilizer) in dissolved form. This solution must then be disposed of in a flat manner.
  • Ammonia does not form any chemical bond with water, so it is not firmly bound in water, but only dissolved. In principle, a very large amount of ammonia can be taken up in water. However, note the high vapor pressure of the ammonia, i.e. the strong desire to steam out of the water again.
  • the mixture of liquid ammonia and water creates highly concentrated water-ammonia mixtures (ammonia spirit).
  • ammonia spirit When stored in a closed container, the leakage of ammonia must be prevented by gas-tight sealing of the container.
  • the object of the invention is to provide a device which prevents the disadvantages listed above. This is achieved in accordance with independent claim 1 in that for the disposal of ammonia leakage, an apparatus is connected downstream of an escaping flushing stream, which apparatus has a large-area, for example metallic catalyst, a heating device, at least one temperature sensor, at least one sensor for ammonia in the intermediate space and a controller and which heats the rinsing stream when a given ammonia concentration K 1 is exceeded to given temperatures for a catalytic oxidation in order to catalytically decompose ammonia leaks into nitrogen and water from the rinsing stream with the help of oxygen taken from the rinsing stream and to discharge the latter to the environment outside the envelope.
  • the advantage of such a device is that, knowing the amount of air passed through in the flushing flow, the operator can determine from which concentration K 1 the ammonia, which corresponds to an absolute amount, is determined by a wants to decompose catalytic oxidation into water and nitrogen, the nitrogen mixed with the flushing stream reaching the atmosphere, while the precipitated water can be fed to an industrial sewage treatment plant.
  • Advantageous developments of the invention are listed in the dependent claims 2 to 10. So it is advantageous, after the process has been ignited by the heating device upstream of the catalytic converter, to recover the heat escaping with the purge flow, which is done by a control flap which redirects the purge flow entering the apparatus via a heat exchanger at the outlet.
  • the heating power can be regulated back by the temperature detected between the heating device and the catalytic converter, so that no unnecessary amounts of nitrogen oxides are generated by exceeding a predetermined temperature and so that the material is not overheated by the catalytic converter.
  • a reversing device which is designed, for example, as a control flap, takes over the temperature control by only passing a partial flow through the heat exchanger, to which a non-preheated residual current is mixed before the catalytic converter. This has the advantage that even large amounts of ammonia leakage can be broken down for as long as the oxygen content in the purge stream is sufficient.
  • a further possibility in order to be able to reduce large leaks of ammonia that occur at short notice without overdimensioning the apparatus is to pre-purge the purge flow in such a case, which is detected, for example, as an impermissible concentration K 2 via an ammonia sensor at the outlet of the apparatus to change the entry into the apparatus through a control flap via a washing system.
  • this washing system is always connected to the inlet to the catalytic converter and can Therefore, slowly release the briefly dissolved ammonia as a buffer to a later flushing stream that is not diverted by the control valve.
  • a further passive safety is obtained if the inlet opening to the intermediate space has a non-return flap which, even in the event of a fan failure, forces an additional volume flow through the apparatus caused by leakage and a possibly upstream washing system. Even if it is no longer possible to enter the space due to excessive ammonia concentrations, a redundant replacement fan can be put into operation without large amounts of ammonia getting into the environment.
  • Platinum and platinum alloys are suitable as catalyst material at temperatures between 150 ° C and 250 ° C in order to keep the proportion of nitrogen oxides low.
  • the material can be processed into a large reaction surface in the form of fine-meshed wire nets processed into a package or in the form of layers which are applied to a large-area substrate, such as an open-pore ceramic body.
  • Mixed oxide catalysts can also be used.
  • the energy control of the heating device or the flap control for the energy consumption of the partial flow can also be controlled in accordance with the deviation from a predetermined outlet temperature from the catalyst in order to prevent overheating and formation of nitrogen oxides.
  • the figures show a device for ammonia plants 1 which have an internal pressure greater than atmospheric pressure and which are surrounded by a further shell 2 which has an inlet and an outlet opening 19, 20 for purging the intermediate space 3 with a purging stream 10 of outside air.
  • an ammonia leakage which is inadvertently mixed with the flushing stream 10 can be catalytically oxidized with oxygen from the flushing stream and broken down into nitrogen and water, the apparatus comprising a large-area catalyst 7, a heating device 11, at least one temperature sensor 16, at least one sensor 13 for Ammonia in the space 3 and a controller 14 to carry out the catalytic oxidation at a predetermined temperature.
  • FIG. 1 shows an ammonia pressure container 1 in the form of a closed refrigeration circuit 9 of a closed shell 2, for example in the form of a walk-in one Machine hall surrounded.
  • a fan 6 promotes a flushing stream 10 emerging from the shell 2, which is composed of a flushing stream 4 of ambient air 8 entering through an inlet opening 19 and any leaks within the shell 2.
  • the position of the fan 6 at the outlet from the casing 2 has the advantage that a negative pressure is created in the casing 2 via the flow resistance of the inlet opening, which prevents loss of ammonia due to unwanted leaks in the casing.
  • the inlet opening is provided with a non-return flap in order to generate a flow in the direction of the outlet from the casing even if the fan fails with a volume increase due to ammonia leakage in the casing 2.
  • the fan 6 could also be attached to an outlet opening 20 of the apparatus 5 in order to prevent leakage to the outside in the event of leaks in the apparatus 5.
  • the fan drives the rinsing flow 10 against the flow resistance of the subsequent components, the rinsing flow 10 being divided according to the resistances by a heat exchanger 12 connected in parallel with a flap 21 into a partial flow 10a and a remaining rinsing flow 10b, which subsequently mix.
  • a temperature sensor 16 monitors the mixing temperature and reports it to the controller 14.
  • the mixed stream flows through a heating device 11, for example an electric heater with a limited surface temperature, which, if necessary, supplies the mixed stream with heat in order to maintain a predetermined temperature, which is reported back via a temperature sensor 17, in the controller 14 with a heating control when entering a catalytic converter 7.
  • a catalytic reaction takes place in the catalytic converter, in which, with the help of the oxygen present in the purge stream, a decomposition of Ammonia in nitrogen and water is made partly in vapor form. At the same time, heat is released.
  • the sub-stream 10a Since heat is released with the decomposition and oxidation in the catalytic converter, depending on the dimensioning of the purge stream 10 and catalytic converter area, the sub-stream 10a must be regulated back by an overarching regulation as a function of an impermissibly increased outlet temperature 18 at the outlet of the catalyst 7.
  • a first portion of condensed water 23 is already formed, which is precipitated from the flushing stream, while a further portion is formed in the downstream heat exchanger 12 and is likewise collected in a sump 30.
  • the sump 30 releases its water via a siphon from a water outlet 24.
  • the nitrogen released in the catalytic converter reaches the flushing stream via an outlet opening 20 The atmosphere.
  • An ammonia sensor 15 is mounted in the outlet opening, which measures the remaining ammonia content and, if necessary, triggers an alarm via the control.
  • Another ammonia sensor 13 measures the ammonia portion in the intermediate space 3.
  • a predetermined limit value at the sensor 13 is exceeded, the ignition of the process is initiated by heating the flushing stream 10 to a predetermined value dependent on the catalyst material.
  • the flap 21 is practically closed and the entire purge stream 10 passes through the heat exchanger 12.
  • additional heat is released in the catalytic converter, which is partially released in the heat exchanger 12 to the purge stream 10.
  • the heating output must now be reduced in accordance with the specified permissible temperatures 16, 17, 18.
  • the flap 21 takes over the temperature control in that the partial flow 10a through the heat exchanger is reduced accordingly and the remaining purge flow 10b through the flap 21 is increased.
  • the components which are exposed to high temperatures are provided with thermal insulation 25.
  • the actual "ignition" of the system takes place via the control 14 by the ammonia sensor 13 in the intermediate space 3.
  • the response value for ignition can, for example, be lower than the MAK Value (50 ppm) can be set when the space is accessible and a second, lower value can be specified in order to prevent the supply of heat in the heating device 11 and thus the process.
  • the size of the flushing flow 10 therefore determines the maximum installed heating power by the predetermined one To reach ignition temperature in the catalytic converter. For example, to break down and oxidize 50 kg of ammonia according to the above equation, the oxygen of 140 m 3 of normal air is necessary.
  • a large flushing stream 10 allows the volume in the intermediate space to be converted relatively often and more leakage to be removed with the same outlet concentration, but it also costs correspondingly more heating energy in order to keep the larger flushing stream at the ignition temperature. For this reason, it is possible, starting from a minimum purge flow 10, to design the controller 14 in such a way that, in combination with a multi-stage fan 6, the purge flow 10 is increased and additional heating registers are switched on if the concentration measured with the ammonia sensor 13 in the interspace is not returns within a reasonable period. In this way, a multi-stage fan can be used to achieve a flushing flow that is tailored to the needs and disposal. When the second, lower concentration value is reached, it is possible to switch from a higher flushing current to a lower flushing current in order to save heating power.
  • FIG. 2 shows how, by interposing a washing system, a buffer 27 of ammonia dissolved in water is created, which enables a later slow degradation if the solution equilibrium is disturbed by a reduced ammonia concentration above the liquid level.
  • the flushing flow 10 is reversed via a flap 26a and brought in counterflow to a spray device 26c via a pipe 28.
  • the spray device 26c is activated by drawing water out of a water basin below the spray device 26c with a pump 26b and supplying it to the spray device 26c.
  • the ammonia is delivered to spray drops in the spray device, which collect in the water basin and form a buffer 27 with dissolved ammonia there.
  • the flushing stream 10d thus reduced in its ammonia content is further treated as described in relation to FIG. 1. In the example of FIG.
  • a reversing flap 26a was dispensed with and instead a second fan 6a was installed which leads directly to a pipe 28 and the characteristics of which can be adapted to the additional resistance in the washing system. It should be noted that when passing through pipe 28 and by blowing holes 29 into the water bath, an additional resistance arises, which should be able to be compensated for by the delivery characteristics of fan 6a.
  • the fan 6 conveys a flow 10, while the second fan 6a generates an additional flow 10e, which - reduced in the ammonia concentration - combines as a flow 10d with that of the fan 6 in order to be fed to the catalyst 7.
  • the controller 14 can switch the second Switch on the fan 6a and thus ensure a substantially greater air throughput and briefly reduce the concentration in the combined flow of the fans 6, 6a with the buffer 27.
  • An additional non-return valve 31 in the flow 10 ensures that the system is effective even if the fan 6 fails.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Treating Waste Gases (AREA)
EP96810246A 1996-04-18 1996-04-18 Dispositif avec récipient sans pression contenant de l'ammoniac Withdrawn EP0801262A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96810246A EP0801262A1 (fr) 1996-04-18 1996-04-18 Dispositif avec récipient sans pression contenant de l'ammoniac

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96810246A EP0801262A1 (fr) 1996-04-18 1996-04-18 Dispositif avec récipient sans pression contenant de l'ammoniac

Publications (1)

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EP0801262A1 true EP0801262A1 (fr) 1997-10-15

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EP96810246A Withdrawn EP0801262A1 (fr) 1996-04-18 1996-04-18 Dispositif avec récipient sans pression contenant de l'ammoniac

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109163216A (zh) * 2018-09-26 2019-01-08 苏州市创优净化科技有限公司 一种安全智能型液氨汽化系统

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926854A (en) * 1970-12-17 1975-12-16 Univ Southern California Oxidation catalyst
JPS63283752A (ja) * 1987-05-18 1988-11-21 Japan Pionics Co Ltd 有害ガスの除去触媒
EP0496228A1 (fr) * 1991-01-24 1992-07-29 ILKA MASCHINENFABRIK HALLE GmbH Dispositif de sécurité pour un réfrigérateur utilisant l'ammoniac comme réfrigérant
DE4223497A1 (de) * 1992-07-17 1994-01-20 Ilka Luft Und Kaeltetechnik Gm Luftgekühlte NH¶3¶-Kälteanlage
WO1995016110A1 (fr) * 1993-12-09 1995-06-15 W.R. Grace & Co.-Conn. Convertisseur combine ameliore avec section a chauffage electrique et section passive

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926854A (en) * 1970-12-17 1975-12-16 Univ Southern California Oxidation catalyst
JPS63283752A (ja) * 1987-05-18 1988-11-21 Japan Pionics Co Ltd 有害ガスの除去触媒
EP0496228A1 (fr) * 1991-01-24 1992-07-29 ILKA MASCHINENFABRIK HALLE GmbH Dispositif de sécurité pour un réfrigérateur utilisant l'ammoniac comme réfrigérant
DE4223497A1 (de) * 1992-07-17 1994-01-20 Ilka Luft Und Kaeltetechnik Gm Luftgekühlte NH¶3¶-Kälteanlage
WO1995016110A1 (fr) * 1993-12-09 1995-06-15 W.R. Grace & Co.-Conn. Convertisseur combine ameliore avec section a chauffage electrique et section passive

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 013, no. 107 (C - 576) 14 March 1989 (1989-03-14) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109163216A (zh) * 2018-09-26 2019-01-08 苏州市创优净化科技有限公司 一种安全智能型液氨汽化系统
CN109163216B (zh) * 2018-09-26 2024-02-09 苏州市创优净化科技有限公司 一种安全智能型液氨汽化系统

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