DE102011005523B3 - Method for treatment of refrigerant e.g. chlorofluorocarbon used in refrigerator, involves supplying exhaust from one scrubber to another scrubber arranged in combustion chamber - Google Patents

Abstract

The refrigerant and/or blowing agent exhibiting gas is supplied into a combustion chamber, and the exhaust gas in the combustion chamber is quenched by using cooling liquid. The quenching process is performed from the top to bottom of the exhaust gas in the combustion chamber. The exhaust from one scrubber is supplied to another scrubber. The scrubbers are arranged from bottom to top of the combustion chamber, and the exhaust gas is traversed from top to bottom of chamber in countercurrent to the cooling liquid. The refrigerant and/or blowing agent exhibiting gas is supplied into combustion chamber, and the exhaust gas in the combustion chamber is quenched by using cooling liquid/washing liquid. The quenching process is performed from the top to bottom of the exhaust gas in the combustion chamber. The exhaust from one scrubber is supplied to another scrubber. The scrubbers are arranged from bottom to top of the combustion chamber, and the exhaust gas is traversed from top to bottom of chamber in countercurrent to the cooling liquid. The reactions are occurred in the combustion chamber include reaction of trichlorofluoromethane (CFCl 3) with water (2H 2O) to give carbon dioxide (CO 2), hydrochloric acid (3HCl) and hydrogen fluoride (3HF), reaction of dichlorodifluoromethane (CF 2Cl 2) with water (2H 2O) to give carbon dioxide (CO 2), hydrochloric acid (2HCl) and hydrogen fluoride (2HF), reaction of tetrafluoroethane (C 2H 2F 4) with water (2H 2O) and oxygen (3/2O 2) to give carbon dioxide (2CO 2), hydrogen fluoride (4HF) and water and/or reaction of dichlorofluoroethane (C 2H 3FCl 2) with oxygen (2O 2) to give carbon dioxide (2CO 2), hydrochloric acid (2HCl) and hydrogen fluoride (HF). An independent claim is included for plant for treatment of refrigerant and/or blowing agent exhibiting gas.

Description

The invention relates to a method and a system for the treatment of refrigerant gas having according to the features of claim 1 and 9.

The DE 101 39 236 A1 discloses a method and apparatus for separating refrigerant from a refrigerant-oil mixture. First, the refrigerant is separated from the oil. The oil is collected in a collecting container. The separated oil from the oil can be fed to a combustion with backup firing.

The DE 42 44 966 B4 describes a system for recovering a thermal insulation material in the disposal of refrigerators.

By the DE 42 23 663 A1 is a method for the thermal recycling of waste PVC with admixed chlorinated hydrocarbons known, wherein a burner is a quencher downstream.

From the booklet "Climate Protection through Recycling", SCPI, November 2009, a process for the recycling of refrigerators is known, whereby CFCs are extracted from a cooling circuit and an insulation. This extracted CFC is completely burned in a high-temperature furnace. The emission reductions achieved by incineration are verified as climate protection certificates and can be traded as CO ₂ equivalents.

The EP 1 306 769 A2 refers to the determination of CO ₂ equivalents by measuring and converting gases.

The DE 10 2009 036 649 A1 discloses a method and apparatus for disposing of refrigerated appliances. In this case, refrigerant and release agent is fed to a pore burner. An exhaust gas of the pore burner is treated by means of a lye scrubber, wherein hydrochloric acid or hydrofluoric acid is formed.

From the DE 42 04 603 A1 and the US 2006/0141414 A1 It is well known to burn ammonia-containing gas with a fuel while supplying air.

From the company publication "incineration plants" of the company. Currenta, as of March 2010, it is known in the case of hazardous waste incinerators downstream of a flowed through from top to bottom quench two downstream through scrubber.

The DE 10 2007 039 926 A1 describes a method for exhaust gas purification, in which a quench and a second purification stage are provided. In the washing liquids of the quencher and the second cleaning stage, a ph value of the washing liquid is regulated.

By the DE 198 21 470 A1 is a method for the treatment of waste refrigeration equipment known, wherein a concentration of combustible blowing agent of the insulating layer in the exhaust air of chambers is measured. This exhaust air can be treated by means of thermal afterburning.

The DE 101 31 464 B4 discloses a method for burning highly halogenated liquid wastes in a waste incinerator. In this case, a halide concentration in the waste water of the flue gas scrubbing is determined and a hydrogen halide measurement is carried out in the flue gas.

The invention has for its object to provide a method and a system for the treatment of refrigerant gas having.

The object is achieved by the features of claims 1 and 9. Advantageous developments to this are mentioned in the dependent claims.

The achievable with the present invention consist in particular that an efficient, environmentally sound treatment of refrigerant and / or propellant gas having is possible. It is possible to simultaneously treat a plurality of different refrigerants and / or propellant-containing fluids and disposed of environmentally friendly and / or to recycle.

In particular, the invention is suitable for the disposal and / or recycling of refrigeration appliances, in particular refrigerators.

It is advantageous that fluids containing different refrigerants and / or propellants (eg, refrigerant, oil of a compressor, means for foaming a plastic / insulating material) can be treated together in the disposal of refrigeration appliances.

Also, the combustion of external refrigerants and / or propellants is possible, in particular, a metering is done automatically via a CFC and / or HFC measurement at the entrance of a combustion chamber.

Advantageously, water condensates (contaminated with refrigerant and / or propellant) in the process of cooling appliance disposal can likewise be incinerated.

Advantageously, refrigerant and / or propellant can be passed directly from the detection point to the combustion, in particular, no intermediate condensation is necessary. In particular, the oil of the compressor no longer needs to be degassed.

The treatment of the fluids is very economical, as the consumption of fuel can be reduced by the combustion of oil of a compressor and / or combustible refrigerant and / or propellant.

The non-obstructing free combustion chambers, in particular pore burners occurring disadvantages, such as deposition of dust and / or soot do not occur with the present, preferably obstacle free and / or packing free and / or working with an open flame combustion chamber.

Advantageously, in one embodiment of the invention, gas produced in the treatment of these fluids is processed into a further-processed dilute acid and pollutant-free clean gas.

The acid concentration of the Dünnsäuregemischs (especially Fußsäure- and / or hydrochloric acid mixture) can be selected in a range and can thus be tailored to the recovery.

With at least one of a quench after proper scrubber the quality of the plant is improved. In particular, a surface is increased with a packed bed in the at least one further scrubber, so that the effect for cooling and / or cleaning is increased.

With controllable and / or controllable fans, the flow of a combustion air and / or a clean gas is kept substantially constant, so that the system can be operated in the range of optimum efficiency.

Embodiments of the invention are illustrated in the drawings and will be described in more detail below.

Show it:

1 A schematic representation of a plant for recycling and / or treating and / or disposing of articles and / or materials containing at least one CFC (fluorochlorohydrocarbon) and / or HFC (hydrofluorocarbon) and / or HC (pentanes and / or propanes and / or butanes ) having fluid;

2 a schematic representation of a system with a combustion chamber.

The designations in the figures largely correspond to DIN 19227.

In a method and a plant at least one hydrocarbon (in particular halogenated hydrocarbons and / or pentanes) containing fluid is treated.

This is a fluid, in particular CFC (fluorochlorohydrocarbon) and / or HFC (hydrofluorocarbon) and / or HC (pentanes and / or propanes and / or butanes).

In particular, the following hydrocarbons are provided for treatment individually and / or in combination and are part of the fluids to be treated: R11 CFCl3 trichlorofluoromethane CFC R12 CF2Cl2 Dichlorodifluoromethane CFC R134a C2H2F4 1,1,1,2-tetrafluoroethane HFCs R141b C2H3FCl2 1,1-dichloro-1-fluoroethane HCFCs R290 C3H8 propane KW R600 C4H10 butane KW R600a methylpropane KW R601 C5H12 n-pentane KW R601a C5H12 isopentane KW R601b C5H12 neopentane KW C5H10 cyclopentane KW

This o. G. Hydrocarbons are referred to as refrigerants. These refrigerants are also used as blowing agents (in particular C5H10 cyclopentane), in particular foams of, for example, porous plastic, in particular polyurethane (PUR).

This fluid is referred to below as the raw gas. In this raw gas refrigerant and / or blowing agent, in particular foaming agent is included.

A plant 01 for recycling and / or treating and / or disposing of articles and / or materials which have at least one CFC (fluorochlorohydrocarbon) and / or HFC (hydrofluorocarbon) and / or HC (pentane, propane, butane) containing fluid. These items are in particular refrigerators.

This plant 01 in particular has at least one comminuting device 02 on, This shredder 02 become the objects to be treated by means of a transport device 03 fed and crushed. In the case of refrigerators at least one compressor has been removed from the refrigerators by means of at least one station, not shown. The comminuted components of the articles become individual groups of components by means of at least one sorting device 04 separated. Such groups of constituents are, for example, plastics KST and / or ferrous metals FE and / or non-ferrous metals NE. In the case of plastics, a distinction is made in particular between polyurethane (PUR) and other plastics. The comminution device is preferably a pellet press 06 downstream. The polyurethane (PUR) parts (fractals) become the pellet press 06 led to and pressed into pellets, in particular raw gas is produced. When cooling the at the pellet press 06 Liberated raw gas can produce hydrous and blowing agent-containing condensate. In particular, the crushing device 02 and / or the pellet press 06 and / or the transport device 03 and / or the sorting device 04 are each with at least one lead 07 connected to the transport of raw gas. This line 07 leads the raw gas in the present embodiment preferably to a plant 11 for the treatment of raw gas.

In the present embodiment, preferably at least the crushing device 02 and the pellet press 06 twice in the area. From both crushers 02 and both pellet presses 06 becomes raw gas of the plant 11 supplied for the treatment of raw gas.

The attachment 11 for the treatment of at least one hydrocarbon (in particular halogenated hydrocarbons and / or pentanes, propanes, butanes) having fluid has at least one combustion chamber 12 on.

This combustion chamber 12 has a horizontal section 13 and an adjoining the horizontal portion in particular vertical Ausbrandteil 14 on. The example designed as a gas-tight welded construction combustion chamber 12 is at least partially, preferably completely provided with a refractory lining, in particular for a max. Operating temperature of 1250 ° C is designed. In addition, preferably, the inner circumferential surface of the existing example of steel substantially combustion chamber 12 provided with a heat-resistant coating to prevent corrosion. This coating and / or the lining have a proportion of at least 90%, in particular 98% Alumina (eg Al ₂ O ₃ ). The combustion chamber 12 Preferably obstacle is free and / or filler free and / or works in operation with an open flame.

At a first end, preferably at an end face of the horizontal portion of the combustion chamber 12 is at least a first feeder 16 In the exemplary embodiment, two first feeders 16 for introducing raw gas and at least one second feed 17 provided for introducing a second fluid. In particular, oil is provided as the second fluid. This oil preferably has refrigerant (in particular CFC (fluorochlorohydrocarbon) and / or HFC (fluorohydrocarbon) and / or HC (pentane)) and has been discharged, for example, from a compressor of a refrigerating machine. This second feeder 17 is preferably connected to the station for removing compressors from refrigerators. The second, preferably a nozzle having feed 17 additionally has at least one supply line 18 for pressure medium, in particular compressed air and / or at least one supply line 19 for oxygen-containing combustion gas, in particular combustion air. In the present embodiment is optional on the second feed 17 yet another supply line 21 for a further fluid, in particular condensate from a collecting container (in particular during cooling on the pellet press 06 incurred water condensate) provided. This condensate preferably has refrigerants (in particular CFC (fluorochlorohydrocarbon) and / or HFC (fluorohydrocarbon) and / or HC (pentanes, propanes, butanes)).

In addition, at the first end, preferably at the front side of the combustion chamber 12 another burner 22 (In particular support heating) for a further fluid, in particular for a preferably gaseous fuel, preferably liquid gas ("LPG", propane and / or butane and / or isobutane), for preheating and / or holding the combustion chamber 12 to an operating temperature (preferably 1,000 ° C-1,200 ° C) provided.

At a second end, in particular at the upper end of the vertical Ausbrandteiles 14 , the combustion chamber 12 is a derivative 23 for the removal of waste gas and, preferably, an emergency chimney 24 arranged.

The at least one first feeder 16 , In the embodiment, the two first feeders 16 for introducing raw gas are preferably via a line with at least one sensor 26 for measuring the concentration of the at least one refrigerant of the raw gas and preferably with at least one sensor 27 for measuring the amount of the at least one refrigerant of the raw gas and preferably with at least one flame filter 28 connected, which is a possible backfire from the combustion chamber 12 from Z. B. should prevent pentane in the crude gas. This the flame filter 28 containing line is in turn connected via at least one (in the embodiment via two) line with at least one source supplying the raw gas, in the embodiment with two sources. In each of these two lines is preferably a fan 29 included to increase the pressure. In the embodiment, the at least one source with the at least one crushing device 02 and / or the at least one pellet press 06 connected. At least one of these sources (in the exemplary embodiment, preferably both sources) has at least one exhaust device for raw gas and is (are) arranged in particular in a refrigerator recycling plant.

In addition to the raw gas coming from the respective source, it is possible for at least one further, in particular at least one storage container to be used 31 (Preferably, a variety of storage containers 31 , in particular pressure bottles) having source refrigerant and / or propellant fluid by means of at least one further line 32 be supplied. This fluid, which originates in particular from an external method not coupled to the present system and / or process, is placed, for example, in front of the respective fan 29 (on the suction side) in the delivery of the respective raw gas source line 07 fed. For this purpose, that of the at least one reservoir 31 outgoing line 32 two sub-branches with the outgoing from the two sources lines 07 with interposition of a shut-off valve 33 connected. These two shut-off valves 33 are preferably to the operation of the respective source of the raw gas, for example to the respective associated fan 29 coupled, so that an additional introduction of further fluid only at raw gas-supplying source, such as running fan 29 can be done.

In the present example, the supply of oxygen-containing combustion gas, in particular combustion air, takes place for the second feed 19 and the additional burner 22 the combustion chamber 12 by means of a common fan 34 , In a line after the fan 34 is preferably a pressure sensor 36 arranged, the signal preferably via a frequency converter, the electric motor of the fan 34 regulates. This variable speed fan 34 is in particular pressure-controlled, ie the speed of the fan 34 is dependent on the pressure in which preferably directly to the fan 34 subsequent line. This line branches into two sub-lines, the first sub-line via a gas flap 37 with the second feeder 19 and the second sub-line via a gas flap 38 with the additional burner 22 connected is. Due to the pressure-controlled fan 34 prevails in front of the two gas valves 37 . 38 a constant form. An opening of the additional burner 22 associated gas damper 38 depends on a temperature of the combustion chamber 12 , To determine the temperature of the combustion chamber 12 is preferably in the vertical Ausbrandteil at least one sensor 39 For example, a sensor for controlling the temperature and an additional sensor 41 arranged for monitoring a limit temperature. An opening of the second feeder 19 associated gas damper 37 depends on a temperature at the end of the system 11 , To determine the temperature is preferably at the end of the system 11 a sensor 42 arranged. In the present embodiment, no preheating of the combustion air is arranged, which, however, may be provided as needed.

In a preheating phase, the combustion chamber 12 first with the additional burner 22 with, for example, liquefied petroleum gas as fuel, preferably preheated to the predetermined operating temperature (preferably 1,000 ° C-1,250 ° C) via a temperature ramp. After reaching the predetermined temperature, the release for the operating phase, ie for the operation with raw gas. In the operating phase, at least one fluid containing at least one refrigerant and / or propellant, preferably two different fluids (for example, gas and oil containing CFCs and / or propellants) are burnt together. Preferably, additional still a third, in particular refrigerant and / or blowing agent exhibiting fluid (for example condensate) is burned together with the first fluid and second fluid. In particular, second fluid and third fluid are atomized together, in particular by means of a nozzle, and the combustion chamber 12 fed.

In the operating phase, the flow of raw gas from a source (in particular from a recycling line) of the two sources (in particular from the two recycling lines) or the two sources by means of the respective fan 29 conveyed separately, in particular aspirated. The raw gas from the respective source can be supplied from the further, external raw gas-producing source further raw gas. It is also possible to supply raw gas only from the further, external raw gas-producing source and / or from at least one of the other two sources of raw gas to the further treatment. For measuring the concentration of the at least one refrigerant and / or blowing agent of the raw gas, at least one representative part of the raw gas supplied to the at least one sensor 26 for measuring the concentration. After that, the raw gas passes the flame filter 28 to subsequently with a form of z. B. 25 mbar over the two feeders 16 into the combustion chamber 12 blown. To achieve and / or maintain the required reaction temperature (substantially equal to the operating temperature) is via the second, having a nozzle feeder 17 the second fluid of the combustion chamber 12 fed. At the same time, the combustion chamber 17 the third condensate fluid is supplied together with the second fluid via the nozzle.

By means of compressed air (about 4 bar) this nozzle atomizes the second formed as an oil fluid, possibly the third fluid (for example, condensate) and sprays the (the) fluid (s) in the combustion chamber 12 , This nozzle produces a very fine droplet spectrum with good distribution in the flame area. The required for the oil and / or condensate combustion air is also via the second feed 17 supplied, wherein the amount of combustion air in particular can be additionally adapted via an oxygen control to the actual combustion air requirement. The second feeder 17 is designed for a constant combustion chamber pressure of, for example, minus 2 mbar, ie negative pressure and is modulated by a temperature control, in particular with a fixed gas / air ratio. By means of the sensor 39 at the end of the combustion chamber 12 becomes the temperature of the combustion chamber 12 determined and preferably regulated. Depending on the temperature of the combustion chamber 12 For example, the supplied amount of the combustion air is changed by means of a gas flap. In the present embodiment, this is the additional burner 22 associated gas flap 38 used.

The dimensioning of the combustion chamber 12 and thus the residence time of the raw gas in the combustion chamber 12 are designed so that the emission limit values can be significantly undercut.

Overall, run above the respective reaction temperature (ie, at about 900-1000 ° C) at low oxygen content and presence of water vapor simplified and without consideration of the burner exhaust one or more of the following reactions: R11 CFCl ₃ + 2H ₂ O → CO ₂ + 3HCl + HF and or R12 CF ₂ Cl ₂ + 2H ₂ O → CO ₂ + 2HCl + 2HF and or R134a C ₂ H ₂ F ₄ + 2H ₂ O + 3 / 2O ₂ → 2CO ₂ + 4HF + _H2O and or R141b C ₂ H ₃ FCl ₂ + 2O ₂ → 2CO ₂ + 2HCl + HF and or pentane C ₅ H ₁₂ + 8O ₂ → 5 CO ₂ + 6H ₂ O

In essence, therefore, CO ₂ (carbon dioxide), HCl (hydrogen chloride) and HF (hydrogen fluoride) is generated.

Since the pentane fraction can change rapidly due to different input concentrations, the oxygen value in the combustion chamber is controlled.

Elemental chlorine reacts to HCl due to the presence of water vapor and low excess oxygen.

The optimum mode of operation is therefore about 900-1000 ° C, preferably 950 ° C combustion temperature, with the lowest possible oxygen content of, for example, 2-6%, preferably 3-5%, with a residence time of 1-3 s and a water content of over 10-15%.

At least one first scrubber 46 is the derivative 23 the combustion chamber 12 connected to the discharge of generated exhaust gas. Preferably, the combustion chamber 12 and the first scrubber 46 arranged directly behind one another, in particular without the interposition of further heat exchangers. This scrubber 46 is preferably as quench 46 executed, with the derivative 23 into an upper end of the quenche 46 empties. This upper, the entry zone of the quenches 46 exhibiting end of the quench is performed in a high heat and corrosion resistant material. In this upper end is also at least one nozzle 47 (In particular, a nozzle lance) arranged for spraying a cooling liquid and / or washing liquid. At least the upper part (in particular the quench zone) of the quenches 46 is provided with a cooling jacket, which is flowed through by the cooling liquid. This cooling jacket is connected by means of openings with an interior of the quencher, so that a partial flow of the cooling liquid on the inner circumferential surface, in particular in the quench zone of the quenches 46 creates a film flow.

The quench 46 is from top to bottom of the exhaust gas of the combustion chamber 12 and the cooling liquid / washing liquid flows through in direct current, wherein a longitudinal axis of the nozzle lance and / or a flow direction of the exhaust gas and / or a flow direction of the cooling liquid on the cooling jacket in the interior of the quench 46 parallel to a vertical longitudinal axis of the quenches 46 and / or are arranged facing each other and from top to bottom.

A lower end of the quench 46 is as a collection container 48 (Quench template) formed for the cooling liquid. To this collection container 48 is preferably a circulatory system 49 for the circulation of the cooling liquid to the nozzle 47 and connected to the cooling jacket. To this circulatory system 49 is a derivative 51 and / or withdrawal facility 52 connected to the removal of designed as dilute acid coolant and for transport to a tank. In addition, a supply system can be attached to the cooling jacket 53 be connected for fresh water that supplies fresh water to the cooling jacket in an emergency operation. The emergency operation occurs, for example, pump failure or power failure when a temperature of an exhaust gas after the quench 46 exceeds a predetermined limit. For emergency operation, an emergency power supply can be provided, for example, at least one pump of the supply system 53 operates for fresh water.

The quench 46 cools the exhaust gas of the combustion chamber 12 quickly preferably to a saturation temperature of the exhaust gas. By this shock-like cooling (ie quenching), the recombination of the separated by the combustion z. As chlorine and / or fluoroorganic compounds avoided. The nozzle 47 The cooling liquid generates a very fine droplet spectrum, which causes a short evaporation time and thus cooling time. At the end of the quench zone, the exhaust has approximately reached its saturation temperature of about 75 ° -80 ° C. The quench 46 cools the exhaust gas of the combustion chamber 12 at least 700 ° C from.

Within the quenche 12 Due to the high concentration of HCL and / or HF, a reduction takes place, a dilute acid (hydrochloric acid and / or hydrofluoric acid, especially in aqueous form) being produced from the cooling liquid in conjunction with the exhaust gas on the basis of a physical absorption.

At the end of the quench zone, the quencher points 46 a transition piece with capacitor on. At the bottom of the quenche 46 and for example at the top of the collection container 48 the quenche 46 is another line 54 for the transfer of the exhaust gas in, for example, at least one other scrubber 56 , preferably in at least two other scrubbers 56 . 57 , The quench 46 , the second scrubber 56 and the third scrubber 57 are via lines for transporting the exhaust gas with respect to a flow direction of the exhaust gas of the combustion chamber 12 serial downstream. Each of the two scrubbers 56 . 57 has at least one nozzle in its upper end 58 for spraying coolant, in the middle a packed bed 59 and at its lower end a collection container 61 for coolant on. The exhaust gas is in each case above the collecting container 61 and preferably below the packed bed 59 in the respective scrubber 56 . 57 introduced and from below on the packed bed 59 up to an upper end of the respective scrubber 56 . 57 directed. The coolant is from the top of the nozzles 58 over the packed bed 59 down into the collection container 61 guided. The two scrubbers 56 . 57 therefore work in countercurrent, ie countercurrent scrubber. The first washer 46 is preferably a DC scrubber.

To these respective collection container 61 the second scrubber 56 and third scrubber 57 is preferably a circulatory system 62 for circulation of the cooling liquid / washing liquid to the nozzle 58 connected. All three scrubbers 46 . 56 . 57 are equipped with separate circulation systems for cooling liquid / washing liquid and preferably with own monitoring means for the level of the cooling liquid / washing liquid.

The concentration of pollutants (in particular halogenated hydrocarbon) in the exhaust gas and the concentration of acid from the first scrubber decrease due to the multistage scrubbing 46 starting in the direction of the last scrubber 57 from. By means of a preferably a conductivity of the washing liquid sensor detects the concentration of acid in the circulatory system 49 the first scrubber 46 detected. When a preselected, in particular variably adjustable limit value of the concentration of acid is reached, a partial flow of the washing liquid is, for example, at the location of the highest concentration, in particular by the extraction device which can be actuated as a function of the determined concentration 51 . 52 ausgeschleusst. This partial flow and possibly occurring evaporation losses are preferably detected by the monitoring device for the level of the cooling liquid / washing liquid and by washing liquid of the subsequent, second scrubber 56 replaced. Accordingly, the missing washing liquid of the second scrubber 56 by washing liquid of the third scrubber 57 replaced. The missing washing liquid of the last, third scrubber 57 is replaced by fresh water.

Also in the second scrubber 56 and third scrubber 57 takes place as already in the quench 46 due to HCL and / or HF, a reduction wherein a dilute acid is generated from the washing liquid in connection with the exhaust gas on the basis of a physical absorption.

It will be transferred HCl (gas) → HCl (water) + heat HF (gas) → HF (water)

From the last scrubber 57 starting is via another line and a mist eliminator 63 the purified exhaust gas (clean gas) by means of a fan 64 supplied for transporting the exhaust gas of a clean gas line with measuring section. The measuring section is preferably with at least one sensor 66 for measuring the concentration of the at least one refrigerant and / or propellant of the purified exhaust gas, and preferably with at least one sensor 67 for measuring the amount of at least one refrigerant and / or blowing agent of the purified exhaust gas provided. From the measuring section, the cleaned exhaust gas reaches a chimney 68 ,

The ventilator 64 is in particular speed-controlled, preferably as a function of a pressure in the system 11 , With this fan 64 is under different load conditions in the plant 11 maintained a constant negative pressure and the purified exhaust gas of the plant 11 over the fireplace 68 to derive into the atmosphere.

At least part (preferably all) of the exhaust gas contacting parts are at least from the quench zone up to and including the last scrubber 57 at least partially (preferably completely), preferably made of GRP (glass fiber reinforced plastic), wherein a lining of PVDF in particular (polyvinylidene fluoride) may be provided.

In one embodiment, the measurement of the concentration of the hydrocarbon-containing fluid, in particular of the refrigerant and / or propellant by means of at least one photometric device (photometer). For example, in the photometric device at least one preferably broadband infrared radiation generating radiation source, at least one in particular designed as a cuvette sample cell and at least one detector.

The sample cell is charged by means of openings and / or lines with at least one sample gas (raw gas or clean gas). For example, at least one filter is arranged between sample cell and detector (s). Instead of at least one filter, it is also possible to arrange a modulation device, for example in the form of a prism or a grating arrangement.

A radiation emanating from the radiation source is guided through the sample gas located in the sample cell. This radiation is absorbed by the sample gas in a wave-selective manner in accordance with its substance composition. A degree of absorption of a specific wavelength range is a measure of the concentration of a specific substance content.

If several different substances and / or substance fractions of the sample gas are to be evaluated, the absorption of a specific wavelength range and / or a specific wavelength assigned to the substance proportion must be measured for this substance fraction.

Therefore, in the present embodiment, multiple combinations of filters and detectors are used.

The proportions of the refrigerants R11 and / or R12 and / or R134a and / or R141b in the raw gas and / or clean gas are preferably determined.

For this purpose, for example, with a first photometer with a triple detector, the coolant R134a and R141b and R12 of a sample gas in the cuvette are measured simultaneously and / or directly one after the other. The three detectors are arranged on a common board. With a second photometer R11 and R12 are detected, whereby the measured value for R12 serves only for a compensation. R11 is evaluated and processed. The following cross-sensitivities exist between the individual substances and / or substance fractions: R141b -> R12 17.1% R134a -> R12 0.2% R11 -> R12 1.5% R141b -> R11 0.4% R134a -> R11 3.7% R12 -> R11 1.6% R134a -> R141b 59.8% R12 -> R141b 186.1% R11 -> R141b 6.6% R141b -> R134a 2.9% R12 -> 134a 2.5% R11 -> R134a 0,0%

The optimization of these cross-sensitivities z. B. in a software by correction values. In particular, the correction is carried out by means of a third-order equation system and / or non-linear corrections. Preferably, a cross sensitivity existing between the at least two refrigerants and / or propellants, in particular between R11 and / or R12 and / or R134a and / or 141b, is corrected and / or optimized by means of at least one correction value.

The following residual errors exist after the optimization:

System R11 (including R12 cross-sensitivity correction)
for clean gas = 2 mg / m ³ -2 g / m ³ / detection limit 2 mg
for crude gas = 2 g / m ³ -100 g / m ³ / detection limit 2 g

System R12, R134a, R141b (including cross-sensitivity correction)
for clean gas = 2 mg / m ³ -2 g / m ³ / detection limit 2 mg for R12 a. R134a
for clean gas = 5 mg / m ³ -2 g / m ³ / detection limit 5 mg for R141b
crude gas = 2 g / m ³ -100 g / m ³ / detection limit of 2 g for R12, R134a, R141b

With these values defining the concentration of the individual refrigerants and / or propellants, ie the concentration values of R11, R12, R134a and R141b and the associated amount of fluid, preferably of the raw gas and / or clean gas, the associated amount of R11, R12, R134a and R141b determined per unit time. From the difference in the plant 11 introduced quantities and the plant 11 leaving amounts of the refrigerant and / or blowing agent is a value for the amount of in the plant 11 reconditioned coolant for each refrigerant and / or propellant individually and / or calculated jointly for all refrigerants and / or propellants. From this value and / or these values, equivalents of environmentally hazardous substances, in particular CO ₂ equivalents, are formed and / or certified. This value and / or these values and / or these CO ₂ equivalents are linked to a unique, in particular plant-specific identification and passed on, if necessary, online to a certification authority and / or commercial agency. The amount of in the plant 11 Reclaimed refrigerant and / or propellant and / or at least one corresponding CO ₂ equivalent are provided with a plant-specific identification and / or certified.

In the present embodiment are preferably in front of the combustion chamber 12 each a concentration of at least R11, R12, R134a and R141b in the refrigerant and / or propellant having gas and after the combustion chamber 12 in each case a concentration of at least R11, R12, R134a and R141b in the exhaust gas of the combustion chamber ( 12 ).

LIST OF REFERENCE NUMBERS

01

investment

02

comminution device

03

transport device

04

sorter

05

06

pellet Press

07

management

08

09

10

11

investment

12

combustion chamber

13

Section ( 12 ), horizontal

14

Burnout part ( 12 )

15

16

Feeder ( 12 ), Raw gas

17

Feeder ( 12 ), Oil

18

Supply line ( 12 ), Compressed air

19

Supply line ( 12 ), Combustion air

20

21

Supply line ( 12 ), Condensate

22

Burner ( 12 )

23

Derivation ( 12 )

24

Emergency chimney ( 12 )

25

26

Sensor, concentration raw gas

27

Sensor, amount of raw gas

28

Flammenfilter

29

fan

30

31

reservoir

32

management

33

shut-off valve

34

Fan ( 19 ; 22 )

35

36

Pressure sensor ( 34 )

37

Throttle valve ( 19 )

38

Throttle valve ( 22 )

39

sensor

40

41

sensor

42

Sensor; temperature

43

44

45

46

Scrubber, quenches

47

Jet ( 46 )

48

Collecting container ( 46 )

49

Circulatory system ( 46 )

50

51

Derivation ( 49 )

52

removal device

53

supply system

54

management

55

56

Scrubber, second

57

Scrubber, third

58

Jet ( 56 ; 57 )

59

Packed bed ( 56 ; 57 )

60

61

Collecting container ( 56 ; 57 )

62

Circulatory system

63

Droplet

64

fan

65

66

Sensor, concentration exhaust

67

Sensor; Amount of exhaust gas

68

fireplace

69

70

71

heaters

72

pellet cooler

73

filter

74

Dust recycling

75

76

BigBag

77

pellets

78

dust

79

Pelletaustrag

80

81

Raw gas cooler (pelleting)

82

water

83

Air, clean

84

water collection

85

86

Raw gas entry line

87

Crude gas entrance line II

88

refrigeration unit

Claims (16)

Method for treating gas containing refrigerant and / or propellant by means of at least one combustion chamber ( 12 ), wherein the combustion chamber ( 12 ) the gas containing refrigerant and / or propellant is supplied from a refrigerator recycling plant, wherein in the combustion chamber ( 12 ) one or more of the reactions R11 CFCl3 + 2H ₂ O in CO ₂ + 3HCl + HF and or R12 CF ₂ Cl ₂ + 2H ₂ O in CO ₂ + 2HCl + 2HF and or R134a C ₂ H ₂ F ₄ + 2H ₂ O + 3 / 2O ₂ in 2CO ₂ + 4HF + H ₂ O and or R141b C ₂ H ₃ FCl ₂ + 2O ₂ in 2CO ₂ + 2HCl + HF take place and at least in a first scrubber ( 46 ) is formed from a HF and / or HCl-containing exhaust gas hydrochloric acid and / or hydrofluoric acid, wherein the exhaust gas of the combustion chamber ( 12 ) by means of Coolant / scrubbing liquid in the quencher first scrubber ( 46 ) is quenched from top to bottom of the exhaust gas of the combustion chamber ( 12 ) and the cooling liquid / washing liquid is flowed through in the DC, wherein the from the first scrubber ( 46 ) exiting exhaust gas at least one other scrubber ( 56 ), wherein the at least one further scrubber ( 56 ) is flowed through from bottom to top of the exhaust gas and from top to bottom of the cooling liquid / washing liquid in countercurrent, wherein in each of the scrubbers ( 46 . 56 ) by means of a respective one the respective scrubber ( 46 . 56 ) associated circulatory system ( 49 . 62 ) the cooling liquid / washing liquid is circulated, whereby from the circulatory system ( 49 ) of the first scrubber ( 46 ) is at least temporarily removed a subset of acid-comprising cooling liquid / washing liquid, wherein in the circulatory system ( 49 ) of the first scrubber ( 46 ) a concentration of acid is detected at least in part and when a limit value is reached, the subset of acid-comprising cooling liquid / washing liquid is removed and removed by washing liquid from the second scrubber ( 56 ) is replaced. A method according to claim 1, characterized in that in the at least one further scrubber ( 56 ) the exhaust gas and the cooling liquid / washing liquid are passed over a packed bed. A method according to claim 1, characterized in that the from the further, second scrubber ( 56 ) exiting exhaust gas to a third scrubber ( 57 ) is supplied. Process according to claim 3, characterized in that in the third scrubber ( 57 ) by means of a third scrubber ( 57 ) associated circulatory system ( 62 ) the cooling liquid / washing liquid is circulated. Method according to claim 4, characterized in that in each of the circulatory systems ( 49 . 62 ) the level of the cooling liquid / washing liquid is detected by means of a separate monitoring device. Method according to claim 1, characterized in that the products from the circulatory system ( 49 ) of the first scrubber ( 46 ) removed subset of acid-containing cooling liquid / washing liquid and possibly occurring losses are replaced by supply of fresh water. Method according to claim 4 or 5, characterized in that the circulatory systems ( 49 . 62 ) the scrubber ( 46 . 56 . 57 ) are at least temporarily connected to each other and that missing washing liquid of the second scrubber ( 56 ) by washing liquid of the third scrubber ( 57 ) is replaced. A method according to claim 7, characterized in that missing washing liquid of the third scrubber ( 57 ) by supplying fresh water into the circulatory system ( 62 ) of the third scrubber ( 57 ) is replaced. Plant for the treatment of refrigerant and / or propellant gas having at least one combustion chamber ( 12 ), wherein the refrigerant and / or propellant R11 and / or R12 and / or R134a and / or R141b and / or R290 and / or R600 and / or R601 and / or R601a and / or R601b and / or C5H10 (cyclopentane) , where at the combustion chamber ( 12 ) at least a first, the refrigerant and / or propellant having gas supplying feed ( 16 ), wherein the at least one first feeder ( 16 ) is connected to a refrigerator recycling plant, wherein the combustion chamber ( 12 ) a quencher-trained first scrubber ( 46 ), the derivation of the combustion chamber ( 12 ) opens into an upper end of the quench, wherein in this upper end at least one nozzle ( 47 ) is arranged for spraying a cooling liquid and / or washing liquid that at the first scrubber ( 46 ) a line for the transfer of the exhaust gas in at least one other scrubber ( 56 ), wherein the at least one further scrubber ( 56 ) in its upper end at least one nozzle ( 58 ) for spraying coolant / washing liquid, in the middle of a packed bed ( 59 ) and at its lower end a collecting container ( 61 ) for cooling liquid / washing liquid, wherein the line for transferring the exhaust gas in the at least one further scrubber ( 56 ) above the collecting container ( 61 ), each of the scrubbers ( 46 . 56 ) each one the respective scrubber ( 46 . 56 ), the cooling liquid / washing liquid circulating circulatory system ( 49 . 62 ), wherein the circulatory system ( 49 ) of the first scrubber ( 46 ) at least a second time a concentration of acid-detecting sensor is assigned and wherein depending on the determined concentration, in particular as a function of a variably adjustable limit concentration, a removal device for acid is actuated and by washing liquid from the second scrubber ( 56 ) is replaced. Plant according to claim 9, characterized in that on the further, second scrubber ( 66 ) a line for the transfer of the exhaust gas in a third scrubber ( 57 ) is arranged. Plant according to claim 10, characterized in that the third scrubber ( 57 ) a third scrubber ( 57 ), the cooling liquid / washing liquid circulating circulatory system ( 62 ) having. Plant according to claim 11, characterized in that the circulatory systems ( 49 . 62 ) the scrubber ( 46 . 56 . 57 ) are at least temporarily connected to each other and that a supply of fresh water the circulatory system ( 62 ) of a third scrubber ( 57 ) assigned. Plant according to claim 9, characterized in that one of the combustion chamber ( 12 ) Combustion air supplying, variable speed, pressure controlled fan ( 32 ) is arranged upstream. Plant according to claim 10, characterized in that the third scrubber ( 57 ) a clean gas transporting, variable-speed, pressure-controlled fan ( 64 ) is subordinate. Plant according to claim 10, characterized in that each of the scrubbers ( 46 . 56 . 57 ) each with a respective scrubber ( 46 . 56 . 57 ), the level of the cooling liquid / washing liquid monitoring monitoring device is equipped. Installation according to claim 9, characterized in that at one at the upper end of the combustion chamber ( 12 ) a chimney which is active in the event of a fault ( 68 ) is arranged.

Images