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EP3431859A1 - Method for leak-proof storage of liquefied chlorine - Google Patents

Method for leak-proof storage of liquefied chlorine Download PDF

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Publication number
EP3431859A1
EP3431859A1 EP17182482.4A EP17182482A EP3431859A1 EP 3431859 A1 EP3431859 A1 EP 3431859A1 EP 17182482 A EP17182482 A EP 17182482A EP 3431859 A1 EP3431859 A1 EP 3431859A1
Authority
EP
European Patent Office
Prior art keywords
chlorine
pressure
pvc
cpvc
leak
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Withdrawn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
EP17182482.4A
Other languages
German (de)
French (fr)
Inventor
Daniel Gordon Duff
Verena Haverkamp
Giulio Lolli
Jose FONSECA
Stefanie Eiden
Thomas König
Rainer Weber
Jürgen KINTRUP
Andreas Bulan
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.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
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 Covestro Deutschland AG filed Critical Covestro Deutschland AG
Priority to EP17182482.4A priority Critical patent/EP3431859A1/en
Priority to EP18740227.6A priority patent/EP3655693A1/en
Priority to PCT/EP2018/069202 priority patent/WO2019016116A1/en
Priority to CN201880048179.4A priority patent/CN110945276A/en
Priority to US16/632,017 priority patent/US20200141540A1/en
Publication of EP3431859A1 publication Critical patent/EP3431859A1/en
Withdrawn legal-status Critical Current

Links

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
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • 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
    • F17C5/00—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures
    • F17C5/02—Methods or apparatus for filling containers with liquefied, solidified, or compressed gases under pressures for filling with liquefied gases
    • 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
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/052—Size large (>1000 m3)
    • 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
    • F17C2201/00—Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05—Size
    • F17C2201/054—Size medium (>1 m3)
    • 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
    • F17C2221/00—Handled fluid, in particular type of fluid
    • F17C2221/03—Mixtures
    • 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
    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
    • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
    • F17C2223/0146—Two-phase
    • F17C2223/0153—Liquefied gas, e.g. LPG, GPL
    • 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
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/03—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the pressure level
    • F17C2225/033—Small pressure, e.g. 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
    • F17C2225/00—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel
    • F17C2225/03—Handled fluid after transfer, i.e. state of fluid after transfer from the vessel characterised by the pressure level
    • F17C2225/035—High pressure, i.e. between 10 and 80 bars
    • 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
    • F17C2260/036—Avoiding leaks
    • 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
    • F17C2260/04—Reducing risks and environmental impact
    • F17C2260/044—Avoiding pollution or contamination

Definitions

  • the invention relates to the leak-proof storage of liquefied chlorine in pressure tanks under elevated pressure, which is intended to prevent or reduce the escape of chlorine in the event of leaks in the pressure tank.
  • Part B Polymer Physics 38 (2000) 3201-3209 describe, among other things, the diffusion of chlorine in cPVC.
  • MOF metal-organic frameworks
  • POPs porous organic polymers
  • a chlorine functionalized POP shows a highly selective sorptive interaction with CO 2 compared to CH 4 ( J. Mater Chem. 2012, 22,13524 ) - a possible interaction of the POP with chlorine gas (or even liquid Cl 2 ) is not discussed in the article.
  • Chlorine is stored in the prior art either at low pressures and low temperatures, in the range of -34 ° C, or at high pressures, in the range of 4-10 bar, and ambient temperatures.
  • chlorine For pressure storage, chlorine must be liquefied by compression and then filled into storage tanks.
  • the object of the invention is to enable a safe storage of chlorine, which avoids or reduces in particular the leakage of chlorine tanks and the escape of chlorine from the pressure tank.
  • the object is achieved in that the pressure tank is filled with PVC or cPVC of the filling with liquefied chlorine, which can seal leakage in a pressure tank.
  • the invention relates to a method for the leak-proof storage of liquefied chlorine under elevated pressure in pressure vessels, characterized in that up to 20 wt .-% of polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (cPVC) prior to filling the pressure vessel with liquefied chlorine be submitted in the pressure vessel.
  • PVC polyvinyl chloride
  • cPVC chlorinated polyvinyl chloride
  • the pressure in the pressure vessel after the application of chlorine is 2 to 15 bar (2,000 to 15,000 hPa).
  • the measurements were carried out in a system for measuring phase equilibria.
  • the system includes a high-pressure view cell, pumps for filling the viewing cell with chlorine and a vacuum tank.
  • the high-pressure view cell consists of a sapphire glass cylinder and stainless steel flanges (material 316 stainless steel, volume 325 cm 3 , maximum pressure: 10 Mpa).
  • the temperature is measured by a calibrated Pt-100 platinum resistance thermometer and the pressure is measured by means of a calibrated precision pressure transducer (Keller PA-25 HTC), which is directly coupled to the cell.
  • Compressed chlorine is added by means of a screw pump (Sitec).
  • Sitec The upper flange of the viewing cell is provided with openings, which can be simulated by switching a valve, a sudden pressure drop in the container.
  • the high-pressure view cell is connected via the valve with a vacuum container (volume 20 l), in which the escaping gas is collected.
  • liquid chlorine (Fimra Linde, 99.999%) was added to the cell until the level of liquid chlorine was about 2 centimeters.
  • the pressure in the cell was equal to the vapor pressure of chlorine, 7.1 bar at 22 ° C. Subsequently, the pressure in the cell was suddenly released by opening a valve against vacuum. The valve was closed when a pressure of 1 bar abs in the vacuum vessel. The time to reach this pressure was 69 s.
  • Example 2 Chlorine release from a mixture of chlorine and cPVC (13% by weight)
  • a first step 48 g of polyvinyl chloride, PVC (Aldrich Chemistry, product number 189588-1kg with a mean, number-average, molecular weight of Mn 35,000.) was introduced into the high-pressure view cell. Liquid chlorine (company Linde, 99.990%) was added to a pressure of 7.1 bar abs and a temperature of 22 ° C, so that a liquid PVC / chlorine solution has formed this resulted in a ratio of 13 wt. % PVC in solution. After addition of the chlorine, the PVC is first converted to cPVC with elimination of HCl. Therefore, it was waited for a period of 2 h and evolved HCl discharged from the cell.
  • PVC Polyvinyl chloride
  • the time to reach the pressure of 1 bar abs in the vacuum vessel was 145 s.
  • Example 3 Chlorine release from a mixture of chlorine and cPVC (16% by weight)
  • the time to reach the pressure of 1 bar abs in the vacuum container was 179 s.
  • Examples 2 and 3 show, compared to Example 1, a slowing of the chlorine release by a factor of 2 - 2.5.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

Es wird ein Verfahren zur leckage-sicheren Speicherung von verflüssigtem Chlor unter erhöhtem Druck in Druckbehältern beschrieben, bei dem bis zu 20 Gew.-% von Polyvinylchlorid (PVC) oder chloriertes Polyvinylchlorid (cPVC) vor der Befüllung des Druckbehälters mit verflüssigtem Chlor im Druckbehälter vorgelegt werden.The invention relates to a process for the leak-proof storage of liquefied chlorine under elevated pressure in pressure vessels in which up to 20% by weight of polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (cPVC) is introduced into the pressure vessel prior to filling the pressure vessel with liquefied chlorine become.

Description

Die Erfindung betrifft die leckagesichere Speicherung von verflüssigtem Chlor in Drucktanks unter erhöhtem Druck, die einen Austritt von Chlor bei Undichtigkeiten des Drucktanks vermeidet oder vermindern soll.The invention relates to the leak-proof storage of liquefied chlorine in pressure tanks under elevated pressure, which is intended to prevent or reduce the escape of chlorine in the event of leaks in the pressure tank.

Zum Stand der Technik beschreibt US5788743A1 u.a. einige Lösemittel für Chlor, aber keine makromolekülaren Lösemittel. Polymerlösungen in flüssigem Chlor sind schon bekannt. Zum Beispiel wird in US4459387 ein Prozess zur Photochlorierung von Polyvinylchlorid (PVC) beschrieben, bei dem verflüssigtes Chlor das PVC-Granulat quillt und damit ein Gel bildet. Dabei reagiert das Chlor mit dem PVC und bildet CPVC (chloriertes PVC). Jedoch wird die somit gebildete Lösung (ob PVC in Chlor oder CPVC in Chlor) nicht als potenzielle Speicherungsform für Chlor beschrieben. AIChE-Journal 34 (1988) 1683-1690 sowie J. Polym. Sci. Part B: Polymer Physics 38 (2000) 3201-3209 beschreiben zudem u.a. die Diffusion von Chlor in cPVC. In US8343261 wird die Lagerung von Methan in metallorganischen Gerüstverbindungen (metal-organic frameworks, MOF) beschrieben, und in US5518528 die Anwendung von Sorbentien zur verbesserten Sicherheit beim Transport und bei der Lagerung von gefährlichen Gasen. Bei den beiden Anwendungen geht es jeweils um eine sorptive Wechselwirkung und nicht um gegenseitige molekulare Lösung der Komponenten ineinander. Als Alternative zu MOFs gibt es die sogenannten POPs (poröse organische Polymere). Ein mit Chlor funktionalisiertes POP zeigt eine stark selektive, sorptive Wechselwirkung mit CO2, verglichen mit CH4 ( J. Mater Chem. 2012, 22,13524 ) - über eine mögliche Wechselwirkung des POP mit Chlor-Gas (oder gar flüssigem Cl2) wird im Artikel gar nicht eingegangen.The prior art describes US5788743A1 Some solvents for chlorine, but no macromolecular solvents. Polymer solutions in liquid chlorine are already known. For example, in US4459387 a process for the photochlorination of polyvinyl chloride (PVC) is described in which liquefied chlorine swells the PVC granules and thus forms a gel. The chlorine reacts with the PVC and forms CPVC (chlorinated PVC). However, the solution thus formed (whether PVC in chlorine or CPVC in chlorine) is not described as a potential storage form for chlorine. AICHE-Journal 34 (1988) 1683-1690 such as J. Polym. Sci. Part B: Polymer Physics 38 (2000) 3201-3209 describe, among other things, the diffusion of chlorine in cPVC. In US8343261 describes the storage of methane in metal-organic frameworks (MOF), and in US5518528 the use of sorbents for improved safety during transport and storage of hazardous gases. The two applications each involve a sorptive interaction and not a mutual molecular solution of the components. As an alternative to MOFs, there are the so-called POPs (porous organic polymers). A chlorine functionalized POP shows a highly selective sorptive interaction with CO 2 compared to CH 4 ( J. Mater Chem. 2012, 22,13524 ) - a possible interaction of the POP with chlorine gas (or even liquid Cl 2 ) is not discussed in the article.

Chlor wird nach Stand der Technik entweder bei niedrigen Drücken und tiefen Temperaturen, im Bereich von -34°C, oder bei hohen Drücken, im Bereich von 4-10 bar, und Umgebungstemperaturen gelagert. [ Euro Chlor (2002), Guideline "Technical and safety aspects for chlorine producers and users" GEST 73/17 6th Edition, November 2002, "Low Pressure Storage of Liquid Chlorine "; Euro Chlor (2002), Guideline "Technical and safety aspects for chlorine producers and users" GEST 72/10, 9th Edition, September 2002, "Pressure Storage of Liquid Chlorine "]Chlorine is stored in the prior art either at low pressures and low temperatures, in the range of -34 ° C, or at high pressures, in the range of 4-10 bar, and ambient temperatures. [ Euro Chlor (2002), Guideline "Technical and Safety Considerations for Chlorine Producers and Users" GEST 73/17 6th Edition, November 2002, "Low Pressure Storage of Liquid Chlorine "; Euro Chlor (2002), Guideline "Technical and Safety Considerations for Chlorine Producers and Users" GEST 72/10, 9th Edition, September 2002, "Pressure Storage of Liquid Chlorine "]

Für die Niederdruck-Lagerung muss Chlor tiefgekühlt und dann als Flüssigchlor in Lagertanks gefüllt werden.For low-pressure storage, chlorine must be frozen and then filled into storage tanks as liquid chlorine.

Für die Druck-Lagerung muss Chlor über Kompression verflüssigt und dann in Lagertanks gefüllt werden.For pressure storage, chlorine must be liquefied by compression and then filled into storage tanks.

Euro Chlor empfiehlt als maximale Lagerkapazität eines einzelnen Tanks 300 - 400 t, das entspricht bei Drucklagerung etwa 200 - 270 m3.[ Ullmann's Encyclopedia of Industrial Chemistry (2011), 7th Edition, "Chlorine", 8 (12), S. 604 ]Euro Chlor recommends 300 - 400 t as the maximum storage capacity of a single tank, which corresponds to approximately 200 - 270 m 3 when pressurized. [ Ullmann's Encyclopedia of Industrial Chemistry (2011), 7th Edition, "Chlorine", 8 (12), p. 604 ]

Nachteil beider Lagerarten ist, dass bei Verlust der Lagerbehälterintegrität schnell größere Mengen Chlor in die Umgebung entweichen könnten und daher aufwendige Sicherheitsmaßnahmen notwendig sind, um dies zu vermeiden. Daher wird von Seiten der Chlorhersteller auch die Lagermenge an Chlor möglichst gering gehalten, was wiederum dazu führt, dass keine größeren Puffer an Chlor zur Verfügung stehen.Disadvantage of both types of storage is that when loss of storage container integrity quickly larger amounts of chlorine could escape into the environment and therefore expensive security measures are necessary to avoid this. Therefore, the amount of chlorine stored on the part of the chlorine manufacturer is kept as low as possible, which in turn means that no larger buffers of chlorine are available.

Aufgabe der Erfindung ist es eine sichere Lagerung von Chlor zu ermöglichen, die insbesondere die Leckage von Chlortanks und den Austritt von Chlor aus dem Drucktank vermeidet oder vermindert.The object of the invention is to enable a safe storage of chlorine, which avoids or reduces in particular the leakage of chlorine tanks and the escape of chlorine from the pressure tank.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, dass der Drucktank mit PVC oder cPVC von dem Befüllen mit verflüssigtem Chlor befüllt wird, die bei einer Leckage des Drucktanks dass Leck abdichten können.The object is achieved in that the pressure tank is filled with PVC or cPVC of the filling with liquefied chlorine, which can seal leakage in a pressure tank.

Gegenstand der Erfindung ist ein Verfahren zur leckage-sicheren Speicherung von verflüssigtem Chlor unter erhöhtem Druck in Druckbehältern, dadurch gekennzeichnet, dass bis zu 20 Gew.-% von Polyvinylchlorid (PVC) oder chloriertem Polyvinylchlorid (cPVC) vor der Befüllung des Druckbehälters mit verflüssigtem Chlor im Druckbehälter vorgelegt werden.The invention relates to a method for the leak-proof storage of liquefied chlorine under elevated pressure in pressure vessels, characterized in that up to 20 wt .-% of polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (cPVC) prior to filling the pressure vessel with liquefied chlorine be submitted in the pressure vessel.

Bevorzugt es eine Ausführung des erfindungsgemäßen Verfahrens, die dadurch gekennzeichnet ist, dass 1 bis 20 Gew.-% PVC oder cPVC, bevorzugt von 2 bis 18 Gew.-% PVC im Druckbehälter vorgelegt werden.It prefers an embodiment of the method according to the invention, which is characterized in that 1 to 20 wt .-% PVC or cPVC, preferably from 2 to 18 wt .-% PVC are placed in the pressure vessel.

Bevorzugt ist eine Ausführung des Verfahrens, die dadurch gekennzeichnet ist, dass das Molekulargewicht Mn des PVCs oder cPVCs von 20.000 bis 250.000, bevorzugt von 25.000 bis 200.000 beträgt.Preferred is an embodiment of the method, which is characterized in that the molecular weight M n of the PVC or cPVCs from 20,000 to 250,000, preferably from 25,000 to 200,000.

In einer weiteren bevorzugten Ausführung des neuen Verfahrens beträgt der Druck im Druckbehälter nach der Beaufschlagung mit Chlor 2 bis 15 bar (2000 bis 15.000 hPa).In a further preferred embodiment of the new method, the pressure in the pressure vessel after the application of chlorine is 2 to 15 bar (2,000 to 15,000 hPa).

Beispiel PVC/cPVCExample PVC / cPVC

Die Messungen wurden in einer Anlage zur Messung von Phasengleichgewichten durchgeführt, Die Anlage beinhaltet eine Hochdrucksichtzelle, Pumpen zum Befüllen der Sichtzelle mit Chlor und einen Vakuumbehälter. Die Hochdrucksichtzelle besteht aus einem Saphirglaszylinder und Edelstahlflanschen (Material Edelstahl 316, Volumen 325 cm3, maximaler Druck: 10 Mpa).The measurements were carried out in a system for measuring phase equilibria. The system includes a high-pressure view cell, pumps for filling the viewing cell with chlorine and a vacuum tank. The high-pressure view cell consists of a sapphire glass cylinder and stainless steel flanges (material 316 stainless steel, volume 325 cm 3 , maximum pressure: 10 Mpa).

Die Temperatur wird durch ein kalibriertes Pt-100 Platin Widerstandsthermometer und der Druck mittels eines kalibrierten Präzisions-Druckaufnehmers (Keller PA-25 HTC) gemessen, welcher direkt an die Zelle gekoppelt ist. Komprimiertes Chlor wird mittels einer Schraubenpumpen (Sitec) zugegeben. Der obere Flansch der Sichtzelle ist mit Öffnungen versehen, über die mittels Schaltung eines Ventils ein plötzlicher Druckabfall im Behälter simuliert werden kann.The temperature is measured by a calibrated Pt-100 platinum resistance thermometer and the pressure is measured by means of a calibrated precision pressure transducer (Keller PA-25 HTC), which is directly coupled to the cell. Compressed chlorine is added by means of a screw pump (Sitec). The upper flange of the viewing cell is provided with openings, which can be simulated by switching a valve, a sudden pressure drop in the container.

Hierzu ist die Hochdrucksichtzelle über das Ventil mit einem Vakuumbehälter (Volumen 20 I) verbunden, in dem das entweichende Gas aufgefangen wird.For this purpose, the high-pressure view cell is connected via the valve with a vacuum container (volume 20 l), in which the escaping gas is collected.

Während jedes Experiments wurde der Druck und die Temperatur im Vakuumbehälter, der Druck und die Temperatur in der Hochdrucksichtzelle und die Zeit bis zu Erreichen eines von 1 bar abs Druck im Vakuumbehälter gemessen.During each experiment, the pressure and temperature in the vacuum vessel, the pressure and temperature in the high pressure gauge cell, and the time to reach a pressure of 1 bar abs in the vacuum vessel were measured.

Beispiel 1: Chlorfreisetzung von flüssigem ChlorExample 1: Chlorine release of liquid chlorine

Für dieses Beispiel wurde flüssiges Chlor (Fimra Linde, 99,999%) in die Zelle gegeben, bis das Niveau des flüssigen Chlors etwa 2 Zentimetern betrug. Der Druck in der Zelle war gleich dem Dampfdruck von Chlor, 7,1 bar bei 22°C. Im Anschluss wurde der Druck in der Zelle über das Öffnen eines Ventils plötzlich gegen Vakuum entspannt. Das Ventil wurde bei Erreichen eines Druckes von 1 bar abs im Vakuumbehälter geschlossen. Die Zeit bis zum Erreichen dieses Druckes betrug 69 s.For this example, liquid chlorine (Fimra Linde, 99.999%) was added to the cell until the level of liquid chlorine was about 2 centimeters. The pressure in the cell was equal to the vapor pressure of chlorine, 7.1 bar at 22 ° C. Subsequently, the pressure in the cell was suddenly released by opening a valve against vacuum. The valve was closed when a pressure of 1 bar abs in the vacuum vessel. The time to reach this pressure was 69 s.

Beispiel 2: Chlorfreisetzung aus einer Mischung von Chlor und cPVC (13 Gew.-%)Example 2: Chlorine release from a mixture of chlorine and cPVC (13% by weight)

In einem ersten Schritt wurde in die Hochdrucksichtzelle, 48 g Polyvinylchlorid, PVC (Firma Aldrich Chemistry, product number 189588-1kg mit einem mittleren, number-average, Molekulargewicht von Mn 35.000.), vorgelegt. Flüssiges Chlor (Firma Linde, 99,990%) wurde bis zu einem Druck von 7,1 bar abs und einer Temperatur von 22°C zugegeben, so dass sich eine flüssige PVC/Chlor Lösung gebildet hat Hierbei stellte sich ein Verhältnis von 13 Gew.-% PVC in Lösung ein. Nach Zugabe des Chlors setzt sich das PVC zunächst unter Abspaltung von HCl zu cPVC um. Daher wurde über einen Zeitraum von 2 h abgewartet und entstandenes HCl aus der Zelle abgelassen.In a first step, 48 g of polyvinyl chloride, PVC (Aldrich Chemistry, product number 189588-1kg with a mean, number-average, molecular weight of Mn 35,000.) Was introduced into the high-pressure view cell. Liquid chlorine (company Linde, 99.990%) was added to a pressure of 7.1 bar abs and a temperature of 22 ° C, so that a liquid PVC / chlorine solution has formed this resulted in a ratio of 13 wt. % PVC in solution. After addition of the chlorine, the PVC is first converted to cPVC with elimination of HCl. Therefore, it was waited for a period of 2 h and evolved HCl discharged from the cell.

Anschließend wurde der Druck in dem Behälter durch Öffnen eines Ventils plötzlich gegen Vakuum entspannt. Hierbei wurde Chlor freigesetzt bis auf einen Enddruck im Vakuumbehälter von 1 bar abs. Nach Öffnen bildete sich ein Schaum aus, welcher mehrere Zentimeter hoch stieg und auch nach Schliessen des Ventils bestehen blieb.Subsequently, the pressure in the container was suddenly released by opening a valve against vacuum. This chlorine was released to a final pressure in the vacuum vessel of 1 bar abs. After opening, a foam formed, which rose several centimeters high and persisted even after closing the valve.

Die Zeit bis zum Erreichen des Druckes von 1 bar abs im Vakuumbehälter betrug 145 s.The time to reach the pressure of 1 bar abs in the vacuum vessel was 145 s.

Beispiel 3: Chlorfreisetzung aus einer Mischung von Chlor und cPVC (16 Gew.-%)Example 3: Chlorine release from a mixture of chlorine and cPVC (16% by weight)

Es wurde wiederum Polyvinylchlorid vorgelegt und Chlor zugegeben bis zu einem Verhältnis von 16 Gew.-% PVC in Lösung. Nach Zugabe des Chlors setzt sich das PVC zunächst unter Abspaltung von HCl zu cPVC um. Daher wurde über einen Zeitraum von 2 h abgewartet und entstandenes HCl aus der Zelle abgelassen.It was again submitted to polyvinyl chloride and chlorine was added up to a ratio of 16 wt .-% PVC in solution. After addition of the chlorine, the PVC is first converted to cPVC with elimination of HCl. Therefore, it was waited for a period of 2 h and evolved HCl discharged from the cell.

Anschließend wurde der Druck in dem Behälter durch Öffnen eines Ventils plötzlich gegen Vakuum entspannt. Hierbei wurde Chlor freigesetzt bis auf einen Enddruck im Vakuumbehälter von 1 bar abs.Subsequently, the pressure in the container was suddenly released by opening a valve against vacuum. This chlorine was released to a final pressure in the vacuum vessel of 1 bar abs.

Nach Öffnen bildete sich ein Schaum aus, welcher mehrere Zentimeter hoch stieg und auch nach Schliessen des Ventils bestehen blieb.After opening, a foam formed, which rose several centimeters high and persisted even after closing the valve.

Die Zeit bis zum Erreichen des Druckes von 1 bar abs im Vakuumbehälter betrug 179 s.The time to reach the pressure of 1 bar abs in the vacuum container was 179 s.

Die Beispiele 2 und 3 zeigen im Vergleich zu Beispiel 1 eine Verlangsamung der Chlorfreisetzung um den Faktor 2 - 2,5.Examples 2 and 3 show, compared to Example 1, a slowing of the chlorine release by a factor of 2 - 2.5.

Claims (4)

Verfahren zur leckage-sicheren Speicherung von verflüssigtem Chlor unter erhöhtem Druck in Druckbehältern, dadurch gekennzeichnet, dass bis zu 20 Gew.-% von Polyvinylchlorid (PVC) oder chloriertes Polyvinylchlorid (cPVC) vor der Befüllung des Druckbehälters mit verflüssigtem Chlor im Druckbehälter vorgelegt werden.A method for the leak-proof storage of liquefied chlorine under elevated pressure in pressure vessels, characterized in that up to 20 wt .-% of polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (cPVC) are presented before filling the pressure vessel with liquefied chlorine in the pressure vessel. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass 1 bis 20 Gew.-% PVC oder cPVC, bevorzugt von 2 bis 18 Gew.-% PVC im Druckbehälter vorgelegt werden.A method according to claim 1, characterized in that 1 to 20 wt .-% PVC or cPVC, preferably from 2 to 18 wt .-% PVC are placed in the pressure vessel. Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Molekulargewicht Mn des PVCs oder cPVCs von 20.000 bis 250.000, bevorzugt von 25.000 bis 200.000 beträgt.Process according to Claim 1 or 2, characterized in that the molecular weight M n of the PVC or cPVC is from 20,000 to 250,000, preferably from 25,000 to 200,000. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Druck im Druckbehälter nach der Beaufschlagung mit Chlor 2 bis 15 bar (2000 bis 15.000 hPa) beträgt.Method according to one of claims 1 to 3, characterized in that the pressure in the pressure vessel after the application of chlorine is 2 to 15 bar (2000 to 15,000 hPa).
EP17182482.4A 2017-07-21 2017-07-21 Method for leak-proof storage of liquefied chlorine Withdrawn EP3431859A1 (en)

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EP17182482.4A EP3431859A1 (en) 2017-07-21 2017-07-21 Method for leak-proof storage of liquefied chlorine
EP18740227.6A EP3655693A1 (en) 2017-07-21 2018-07-16 Method for leakage-proof storage of liquefied chlorine
PCT/EP2018/069202 WO2019016116A1 (en) 2017-07-21 2018-07-16 Method for leakage-proof storage of liquefied chlorine
CN201880048179.4A CN110945276A (en) 2017-07-21 2018-07-16 Leakage-proof storage method for liquid chlorine
US16/632,017 US20200141540A1 (en) 2017-07-21 2018-07-16 Method for leakage-proof storage of liquefied chlorine

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