NL9001697A - Process for regenerating an adsorption filter DAT (HALOGEN) HYDROCARBONS PRESENT METHOD FOR REMOVING (HALOGEN) HYDROCARBONS FROM GAS AND METHOD FOR REGENERATION OF AN (HALOGEN) HYDROCARBONS CONTAINING adsorbent AND FOR CONCENTRATED PROCESSING (HALOGEN) HYDROCARBONS IN LIQUID FORM. - Google Patents

Description

Method for regenerating an adsorption filter containing (halogen) hydrocarbons, method for removing (halogen) hydrocarbons from gases, and method for regenerating an adsorbent containing (halogen) hydrocarbons, and for processing concentrated (halogen) hydrocarbons in liquid form.

The invention relates to a method for regenerating an adsorption filter containing (halogen) hydrocarbons.

In order to remove (halogen) hydrocarbons from gases, it is generally customary to pass them over an adsorption filter, which usually consists of activated carbon, whereby these (halogen) hydrocarbons are adsorbed. So far, the spent activated carbon has subsequently been burned. The disadvantage of this is that the contaminated activated carbon must be dumped or burned and then replaced. In addition, undesired compounds such as dioxins, nitrogen oxides and other undesired by-products can be formed during combustion.

Halogenated hydrocarbons (HKW) in particular chlorinated hydrocarbons are widely used. They are used intensively in agriculture to control weeds and micro-organisms. They find many applications in the chemical industry, for example as raw materials for the production of polymers and pesticides, among others. Furthermore, they are widely used as a degreasing agent in the surface treatment of metals, as a solvent in adhesives, as a diluent in paints and inks, as an extraction agent in chemical processes and in cleaning clothes.

HKWs are always somewhat toxic. Some HKW compounds are many times more toxic than, for example, potassium cyanide. Unlike other environmentally unfriendly substances such as N0X, S02 and NH3, HKWs are not included in the ecological cycle. They are microbiologically non-degradable or very difficult to degrade and they are also chemically unreactive under normal conditions.

As far as HQs are released into the air, they can be converted in the higher air layers into other environmentally unfriendly substances; the damage to the ozone layer is a consequence of this. If they end up in the soil, they accumulate in soil and water and threaten the drinking water supply, among other things. The number of soil and groundwater remediation projects is increasing rapidly, and this mainly concerns HQ pollution. In all these cases, the HQS are irresponsible for the environment.

Remediation of soil and water is technically possible. Usually the HQs are included in activated carbon, which is then presented and processed as chemical waste. A number of problems arise here. For example, the current processing capacity is insufficient to process the ever-growing stream of chemical waste. The chemical industry already offers many thousands of tons of heavily chlorinated waste, at the AVR alone 2,200 tons of waste containing HWH is incinerated annually and even greater processing takes place at sea.

If soil remediation is to be applied on a scale foreseen in the national environmental policy plan, taking into account the almost daily new notifications of soil contamination, the current processing capacity is only a fraction of what is required.

Another drawback of the combustion method is that this approach is by no means attractive from a financial point of view. Finally, incineration of HKW has the major drawback that, with the current state of technology, it is a burden on the environment; there is significant CO 2 and NO 2 emissions, while dioxin emissions still cannot be avoided.

It has now been found that one can regenerate a used adsorption filter containing (halogen) hydrocarbons by placing the adsorption filter in a desorber, passing steam through it in such a ratio that the steam / carbon molar ratio is greater than 1, the resulting the mixture into a catalytic reactor and contact it with a catalyst consisting of one or more transition metals and reacting thereon. In particular, a molar ratio of steam to carbon of 1: (2-4) is preferably used here: 1: (2.5-4). For the dichloroethane (DCE) model fabric, it is preferably 5 to 7. The catalyst used is preferably applied to a porous ceramic support. The catalyst is expediently composed on the basis of Pt, Rh, Ir, Pd, Ru, Ni, Fe and / or Co.

The invention also provides a method for removing (halogen) hydrocarbons from gases, characterized in that a) a physical separation is applied at the remediation site, using an adsorption filter b) the adsorption filter in which the (halogen) hydrocarbons to be removed are taken to a destruction plant and c) in such a plant desorbs the adsorbed hydrocarbons and converts the collected (halogen) hydrocarbons into harmless components and the easily separable hydrogen chloride.

In the process according to the invention, by suitable selection of the steam to carbon ratio, the products obtained in the desorption can then be directly destroyed, i.e. converted into substances which are considerably less harmful to the environment or can be reused.

In the process according to the invention, the added steam is not only used for the desorption but also for the conversion reaction, which leads to a considerable saving in energy and costs. Process control is also excellent and recycling saves on raw materials (activated carbon) and there is no waste flow, while a fully automated business form is possible and contaminants can be removed to extremely low levels.

By using this reductive waste gas cleaning method in the method according to the invention, any form of environmental burden is avoided. In a reductive environment, the only products that are formed are hydrogen halides, harmless hydrocarbons, hydrogen and carbon monoxide and carbon dioxide.

Steam reforming is the heating of organic material with water vapor and a suitable catalyst in a closed system without oxygen (air). When nickel or platinum catalysts are used, a number of reactions occur simultaneously, the most important of which are: i) Steam reforming: C «Hm + h20 -> n CO + (m + n) / 2 H2 ii) Water-gas shift reaction: CO + H20 <===> C02 + H2 iii) Methanization: CO + 3 H2 <===> CH4 + H20

The first equation represents a reaction considered kinetic and the other two are equilibria. Reaction i) is endotherm and the other two are exothermic. If the conditions are chosen correctly, the process can proceed autothermally. This system can be applied to HKW's which are then converted into, for example, hydrogen, carbon dioxide, methane and hydrogen halide.

The method according to the invention has the advantage that large air flows can be processed without having to heat them up. Due to the central regeneration of the adsorber, the heat to be supplied is therefore used much more efficiently. High efficiency is obtained by processing using steam reforming.

By using adsorption filters, which can be collected, it is possible to efficiently build a large regeneration device at a central location and it becomes possible to use cheaper standard adsorption exchange. The used and regenerated adsorber can go back for reuse after regeneration.

Particularly suitable absorbent materials in the adsorption exchange in the method according to the invention are activated carbon, coconut coal and aluminum oxide. However, other absorbent materials can also be used.

In practice, depending on the exact application, an adsorber can be regenerated at least 100 times without the adsorption decreasing too much. Naturally, this depends on the type of contamination on the active absorbent. Obviously, if poisoning of the absorbent material occurs, fewer regeneration cycles will be possible. This is, however, known to the expert.

The amount of steam used in steam reforming also serves to prevent carbon deposition on the catalyst. The steam that has a dual function. On the one hand, the steam serves as a sorbent, and the steam also serves as a means to form the reaction mixture with halohydrocarbons to be passed over the catalyst.

The method according to the invention is suitable for cleaning waste gases from, for example, paint shops, paint factories, for cleaning stripper air in groundwater remediation and for destroying or converting substances from the residue of oils, paints, processing chemical waste, processing raw materials into the chemical industry and the like.

The applicability of the cleaning method according to the invention is illustrated by a number of simple experiments with dichloroethane (DCE) and the nickel and platinum catalysts. Both are mounted on an aluminum oxide support. Most tests were done at low temperature, on the one hand to keep energy consumption as low as possible, on the other hand to avoid problems with the possible poisoning of the catalyst by hydrogen halide. The tests were carried out in a flow-through tube reactor at short contacts and at long contact times in a batch reactor, which was also suitable for high pressure tests.

In the batch tests, calcium hydroxide (slaked lime) was added to bind acids released in the reaction. In this way possible poisoning of the catalyst by hydrogen halide is prevented and the total of chemical reactions is forced to a situation where (halogen) hydrocarbons no longer occur. Furthermore, this addition of lime also leads to a favorable influence of the pressure increase because the reaction equation now contains fewer molecules in the products than in the reactants. In practice, two further limitations arise, namely the following 1) The batch reactor tests used an autoclave with an unheated stirrer housing and an unheated tube with a manometer and a sample valve. During the tests, probably a part of the vapor phase condensed in these cold parts, after which some of this dripped back later. As a result, only a small portion of the dichloroethane was found in the vapor phase. However, it was found that there was always only a trace of dichloroethane in the vapor phase and a rapidly growing amount of products. This indicates that as soon as dichloroethane enters the vapor phase it is immediately converted. Due to this phenomenon, it is not possible to monitor the conversion as a decreasing dichloroethane concentration.

2) Flow controllers (ie flow control and flow rate regulators) could not be used in the flow-through reactor reactor with the result that the flow rate and thus the dichloroethane concentration fluctuated. However, with an improved implementation this must be able to be overcome. The following parameters were used in the tests:

Gas conversion:

This was calculated from the DCE partial pressure as measured, and the converted DCE partial partial pressure calculated from the product concentrations found. The gas conversion is expressed as the percentage of DCE converted.

In the batch reactor experiments, the calculated percentage of converted DCE can be monitored over time in this way. This percentage is defined as the product concentration, which is expressed as the percentage of DCE converted.

Because of the experimental limitations, four concepts have been introduced that together give an impression of the total DCE conversion during the experiment.

Total DCE converted: via GLC analysis from the product spectrum obtained via the GLC analysis the content of converted DCE is calculated, which together with the total reaction time gives a measure of the reaction rate and the amount of DCE converted.

Total converted DCE from Cl analysis of the lime: this is the amount of converted DCE as calculated by the amount of HCl released, since probably an amount of HCl still remains in the vapor phase, the actual conversion is much higher.

Total converted DCE from lime weighting: when hydrochloric acid is formed, it is chemically bound by the quicklime. Here, hydroxyl groups are replaced by chloride, which is considerably heavier. From the weighting it can be calculated how much chloride was present and ultimately how much DCE was converted. Total converted DCE from the N2 content reduction; when DCE is converted into a number of products, the nitrogen content decreases proportionally and an impression of the conversion is obtained. This method only makes sense if the DCE content in the vapor phase remains constant due to reflux.

Examples I-IV Batch tests.

10 g of Catalyst was placed in a 1 L three neck flask with 1.5 g DCE and 1.6 g water. The flask was equipped with a reflux condenser, the outlet of which was connected to a wash bottle with water. A glass capillary was also passed through one of the necks which was connected to a nitrogen cylinder with a pressure relief valve to operate in an inert nitrogen environment and to cause turbulent gas flow through the capillary so that the vapor could contact the catalyst. 50 ml gas samples were passed through the cooler from the center of the flask through a plastic hose. In the wash bottle was 250 ml of demineralized water in which the hydrochloric acid formed was collected. The flask could be heated by an applied heating jacket.

The results are reported in Table A.

Table A

Examples I-IV

Batch tests with the Pt catalyst

Reactor Batchwise

Catalyst Pt

Reactor charge 1.5 g DCE + 1.6 g H 2 O + 10 g catalyst

Example I II II III IV IV IV

Sample 2 3 4 7 11 12 13

Temperature (C) 500 472 465 425 400 425 425

Pressure (Bar) 1 111111

Time at temp. (min) 80 10 70 30 40 30 70

Response time (min) 80 10 70 30 40 70 110

Gas composition (volume%) H2 - CO _______ CO2 0.23 9.44 0.02 0.01 0.09 0.09 0.09 CH4 0.00 4.26 0.00 0.00 0.00 0.00 0.00 C2H * 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C2H6 0.00 1.00 0.00 0.00 0.00 0.00 0.00 C3Hs 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C3Ha 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C4 0.00 0.00 0 0.00 0.00 0.00 0.00 0.00

Cs 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Ce 0.00 0.00 0.00 0.00 0.00 0.00 0.00 DCE 0.62 3.39 4.50 7.89 3.99 5.19 3.94

Gas conversion \% DCE 16 70 0.3 0.1 1.1 0.8 1.0

Examples V-VII

In addition to atmospheric pressure tests described in Examples I-IV, tests were also carried out under elevated pressure in an autoclave. The catalyst was mixed with slaked lime and placed in a 250 ml autoclave with DCE and water in a glass insert. The vapor was circulated through a vertical stirrer mechanism to allow good contact with the catalyst. The autoclave was flushed with nitrogen at the start of the experiment by successively placing the autoclave under a pressure of 10 bar nitrogen and then releasing the pressure again. The autoclave was then heated to the desired temperature with a pre-pressure of 2 bar and finally brought to the desired working pressure with nitrogen. Gas samples were collected via a sample tap in 50 ml Teflon gas syringes and subsequently analyzed by gas chromatography.

In the first experiments in the three-necked flask, only a small conversion was observed with the Pt catalyst. Perception may be biased because light product gases could escape through the cooler and the DCE reflux through the cooler so that it remained at a constant equilibrium concentration. Also, contact with the catalyst has probably been very poor. At these low conversions, CO2 was virtually the only observed product.

In the experiment with Ni at 60 bar (example VII), a large amount of a substance which was possibly propane was initially produced. The respective gas chromatograms show the presence of a component that could not be defined but, on the basis of retention time data, may have been methanol but more likely to be propane. For these experiments, it was not important to elaborate on the identity of this substance and it was provisionally assumed to be propane. Products, such as, for example, monochloroethene, were not present. In addition to propane, ethylene was shown as the second product, while ethane CO2 and higher hydrocarbons were also shown later.

Initially, when the DCE conversion was not yet complete, the tests with Pt at 30 bar (Example V) showed mainly ethane and some ethylene and CO2. Methane and higher hydrocarbons were also observed later. At higher pressure, 130 bar (Example VII), the initial product was not ethane but CO 2 and ethylene were found in a 2: 1 ratio. This means that as much DCE has been converted to CO2 as to ethylene. In addition, as in the experiment with Ni, a large amount of undefined substance, possibly propane, was present. There is no clear explanation for this. At a temperature of 440 ° C, at both pressures (Examples V and VI), methane and higher hydrocarbons are also immediately formed, while ethane is by far the most important product.

DCE was converted quickly and completely under elevated pressure.

Both at 30 and 130 bar this already happened at 300 ° C, a temperature at which no conversion was yet expected and which was chosen to determine the initial concentration of DCE. Pt seems slightly more active than Ni, although this cannot be said with certainty. Both catalysts seem to be stable, the product concentration increases strongly with the reaction time.

In all cases, no to very little co was observed. Elemental analyzes of the catalyst at the end of the experiment showed that only little organic material was deposited on the catalyst. 0.49% C and 2.28% H were found on the Pt catalyst and 1.12% C and 0.95% H on the Ni catalyst.

Example V

Reactor Batchwise

Catalyst Pt

Reactor charge 1.5g DCE + 1.6g H2O + 10g catalyst + 2.0 Og Ca (OH) 2

Sample 57 58 59 60 61 62 + 63

Temperature (C) 300 300 442 442 442 442

Pressure (Bar) 30 28 34 32 30 28

Time at temp. (min) 5 7 3 33 63 93

Response time (min) 5 7 44 63 93 123

Gas composition (volume%) H2 - - 0.13 CO _____ 0.05 CO2 0.05 0.14 0.81 0.73 0.75 0.87 CH4 0.00 0.19 4.44 4.82 5. 38 5.64 C2H4 0.02 0.34 0.47 0.28 0.21 0.17 C2H6 0.29 0.86 3.47 4.01 4.17 4.08 C3H6 0.02 0.04 0 .07 0.30 0.13 0.64 C3Ha 0.04 0.08 0.13 0.09 0.06 0.06 C4 0.01 0.02 0.06 0.20 0.31 0.33

Cs 0.00 0.00 0.01 0.06 0.06 0.09 C6 0.00 0.00 0.00 0.02 0.03 0.03 DCE 0.29 0.01 0.12 0, 01 0.01 0.01

Gas conversion \% DCE 79.28 99.98 98.00 99.99 99.99 99.99

Product concentration \% 0.55 1.90 6.20 6.78 6.93 9.54

Total converted DCE - Cl analysis in lime: z 0.8 g DCE; GLC: 1.5 g DCE; various methods N2 content reduction: 2.0 g DCE;

calcification: 1.4 g DCE

Example VI

Reactor Batchwise

Catalyst Pt

Reactor charge 32g DCE + 13g H2O + 10g catalyst + 3.2g Ca (OH) 2

Sample 67 68 69 70 + 71 72 73 + 74 75

Temperature (C) 300 300 440 440 440 440 440

Pressure (Bar) 100 97 130 127 124 121 118

Time at temp. (Min) 57 0 30 60 90 225

Response time (min) 5 7 30 60 90 120 255

Gas composition (volume%) H2 - 0.00 - 0.12 - CO - - - 1.73 - 2.18 - CO2 0.53 0.72 2.95 3.51 3.58 5.33 4.06 CH4 0.00 0.00 1.99 3.73 4.49 4.68 5.43 C2H4 0.24 0.63 3.92 3.26 2.13 2.58 0.79 C2He 0.08 0.20 21.81 10.95 7.80 9.40 10.47 C3HS 0.02 0.01 0.21 0.89 0.98 0.52 1.23 C3He 1.43 1.64 2.44 1.81 1.46 1.17 0.29 C4 0.06 0.13 1.95 3.11 2.58 2.33 1.38 C = 0.08 0.16 0.08 0.32 0.29 0, 27 0.35 C6 0.00 0.00 0.00 0.01 0.06 0.87 0.10 DCE 0.15 0.02 0.02 0.01 0.01 0.01 0.01 0.01

Gas conversion \% DCE 95.26 99.70 99.94 99.98 99.97 99.98 99.98

Product concentration% 3.08 5.09 32.50 29.90 23.70 28.50 22.20

Total converted DCE - Cl analysis in lime: z 4.1 grams DCE; GLC: 18 g DCE.

- various methods N2 content reduction: 17 g DCE; calcification: 14 g DCE.

C content catalyst: 0.49%, 0.05 g C

H content catalyst: 2.28%, 0.23 g H

Example VII

Reactor Batchwise

Catalyst Reduced and passivated Ni

Reactor charge 10g DCE + 11g H2O + 10g catalyst + 1Og Ca (OH) 2

Sample 76 77 78 80 + 81 82 83 + 84 85

Temperature (C) 200 200 300 350 400 440 440

Pressure (Bar) 30 30 60 57 54 51 48

Time at temp. 12 10 10 10 20 80 (min)

Response time 1 2 55 85 105 120 180 (min)

Gas composition (volume%) H2 - 0.00 - 0.00 CO - 0.25 - 0.09 CO2 0.00 0.00 0.05 0.17 0.07 3.28 9.79 CH4 0.00 0 0.00 0.00 0.84 0.00 0.12 0.00 C2H4 0.00 0.10 4.98 2.77 0.12 0.37 0.14 C2H6 0.00 0.00 2.05 1 .40 0.23 0.31 0.19 C3H6 0.00 0.00 0.25 0.19 0.04 0.03 0.01 C3He 0.00 0.86 11.87 8.38 1.00 0 .92 0.01 C4 0.00 0.00 0.20 0.09 0.03 0.03 0.01 C5 0.00 0.00 0.00 0.06 0.05 0.05 0.00 C6 0.00 0.00 0.00 0.01 0.10 0.10 0.00 DCE 0.02 0.07 0.02 0.34 0.23 0.41 0.41

Gas conversion \% 0 96 99 98 96 91 93

DCE

Product concentration \% 0.00 1.38 25.61 18.00 2.40 4.30 5.37

Total converted DCE - Cl analysis in lime: & 5 g DCE; GLC: 1.8 g DCE; - various methods N2 content reduction: 0.5 g DCE; calcification:> 5 g DCE.

C content catalyst: 1.14%, 0.11 gC

H content catalyst: 0.95%, 0.10 g H

Examples VIII-X Flow-through tube reactor Method:

The experiments were performed in a quartz tube reactor with a concentric preheater. The reactant stream consisted of nitrogen mixed with water vapor and DCS. The partial voltage of these components was in the ratio 6: 1 to meet the condition S / C (molar steam to carbon ratio) = 3. For this, nitrogen was passed in two parallel flows through a flow management rotameter and then through a wash bottle filled with water or DCE, respectively, after which the two streams were combined in a non-return vessel. The combined stream was then passed to the preheater and the reactor, after which the waste gas was vented to the ambient air through a wash bottle containing 250 ml demineralized water. The latter vial serves as a visible indication of the gas flow rate through the reactor, as a water seal to prevent oxygen from flowing back to the reactor, and also as a scavenger of acidic product components.

At the start of an experiment, the reactor was first purged with the reaction mixture at room temperature for at least an hour, after which time a sample of the reaction mixture was taken from the vent of the water seal. The analysis of this sample was used to calculate the composition of the reaction mixture, which is necessary for conversion calculations.

Results:

Significant conversion of DCE was found in both Pt (Example VIII) and Ni (Examples IX and X). The main products initially were ethylene and CO2 with Pt (Example VIII) and reduced Ni (Example X), while with untreated Ni propane and CO2 are seen (Example IX); later also other products are created. The Ni catalyst appears to be more active and stable in a reduced form than in an untreated form. To see if the presence of hydrocarbons has an effect, cyclohexane was added to the reactant mixture in example IX, but no major differences were observed with the results of comparative example IX where no cyclohexane was used. Therefore, only samples 42 and 45 (see appendix) were calculated. In all cases, no to very little CO was observed.

Example VIII

Reactor Flow-through tube

Catalyst Pt (0.7 g, 0.6 ml)

Gas flow rate (ml / min) 23 (Contact time = 0.3 s, linear speed = 0.03 m / s, 2-4% DCE in N2)

Sample 47 48 49 50 51 52A + b

Temperature (C) 417 417 417 417 442 442

Pressure (Bar) 1 1111 1

Time at temp. (Min) 10 40 85 129 35 100

Operating time (min) 10 40 85 129 164 229

Gas composition (volume%) H2 _____ 0.004 CO _____ 0.004 CO2 0.00 0.05 0.06 0.06 0.12 0.09 CH4 0.00 0.00 0.00 0.00 0.00 0, 03 C2H4 0.18 0.74 0.48 0.54 0.63 0.42 C2HS 0.00 0.06 0.02 0.01 0.03 0.01 C3H6 0.00 0.09 0.04 0 .09 0.09 0.04 C3Ha 0.00 0.22 1.02 1.02 0.47 0.30 CΛ 0.00 0.00 0.00 0.00 0.00 0.00 C = 0, 00 0.00 0.00 0.00 0.00 0.00

Ce 0.00 0.00 0.00 0.00 0.00 0.00 DCE 1.39 1.53 1.68 1.58 1.44 0.56

Gas conversion \% DCE 12 45 49 59 52 63

Example VIII (continued)

Sample 53 54 55A + B 56 65 66

Temperature (C) 442 442 442 442 442 442

Pressure (Bar) 11 111 1

Time at temp. 142 259 319 627 656 955 (min)

Operating time 271 388 448 756 685 984 (min)

Gas composition (volume%) H2 - - 0.00 - - CO - 0.12 - - CO2 0.12 0.15 0.09 0.09 0.15 0.02 CH4 0.02 0.01 0.00 0 0.00 0.00 0.00 C2H4 0.66 0.18 0.27 0.48 0.36 0.58 C2H6 0.01 0.02 0.02 0.01 0.00 0.01 C3H6 0.05 0.02 0.04 0.04 0.05 0.04 C3He 0.39 0.00 0.03 0.06 0.05 0.04 C4 0.00 0.00 0.00 0.00 0.00 0.00

Cs 0.00 0.00 0.00 0.00 0.00 0.00

Cs 0.00 0.00 0.00 0.00 0.00 0.00 DCE 0.77 0.76 0.51 0.23 0.31 0.33

Gas conversion \% DCE 64 28 55 75 66 69

Acidity of washing water: average conversion is approx. 70%.

Example IX

Reactor Flow-through tube

Catalyst Ni (not pretreated CRG, 0.10 g, 1.3 ml)

Gas flow rate (ml / min) Contact time = 8 s, linear speed = 0.0013 m / s, approx. 2-4% DCE in N2)

Sample 29 30 31 32 33 34 35 36

Temperature (C) 231 429 430 456 456 500 540 426

Pressure (Bar) 111 11 111

Time at temp. 30 12 42 40 80 60 40 80 (min)

Response time 30 42 72 112 155 215 255 285 (min)

Gas composition (volume%) H2 ________ co _____ CO2 0.35 0.38 0.29 0.29 0.23 0.29 0.03 0.21 CH4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C2H4 0.00 1.16 1.05 0.93 0.70 0.35 0.02 0.52 C2Hs 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C3h6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

CsHa 0.34 0.17 0.17 0.08 0.03 0.00 0.00 0.00

Approx 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C = 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0, 00 C6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 DCE 1.92 2.00 1.60 1.70 1.80 2.22 1.82 1, 59

Gas conversion 26 45 75 41 32 37 2 28% DCE Washing water acidity: average conversion is approx. 39%

Total DCE converted (H *): approx.0.12 g CDE

Example X.

Reactor Flow-through tube

Catalyst Ni (not pretreated CRG, 0.10 g, 1.3 ml)

Gas flow rate (ml / min) 18 (Contact time = 0.4 s, linear speed = 0.02 m / s, approx. 2-4% DCE and 10% cyclohexane in nitrogen)

Sample 37 38 39 40 41 42 43 44 45

Temperature 100 299 299 344 344 400 400 400 400 (C)

Pressure (Bar) 111111111

Time at temp. - - - -27- -163 (min)

Response time - - - - -153 - - 289 (min)

Gas composition (volume%) H2 ________ CO ________ CO2 0.00 0.00 0.00 0.00 0.00 0.09 0.00 0.00 0.05 CH4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C2H4 0.00 0.00 0.00 0.00 0.00 0.29 0.00 0.00 0.18 C2H6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C3He 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 C3Hs 0.00 0.00 0.00 0.00 0.00 0.30 0.00 0.00 0.24 C4 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0 0.00 0.00

Cs 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Cs 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 DCE 0.00 0.00 0.00 0.00 0.00 0.98 0.00 0.00 0.82

Gas conversion (% DCE) 00 0 0 0 45 0 0 41

Acidity of washing water: average conversion is approx. 40%

Total DCE converted (H *): approx.0.12 g CDE

Note: About the same product as in Example IX

Cyclohexane does not or hardly appear to be converted. Only two samples were calculated, the other analyzes are available.

Example XI

Reactor Flow-through tube

Catalyst Ni (reduced and passivated CRG, 0.09 g, 0.17 ml)

Gas flow 23 (Contact time = 0.4 s, linear speed = 0.04 m / s, 4% DCE in N2

Sample 87 88 89 90 91

Temperature 450 450 450 501 501 (C)

Pressure (Bar) 11111

Time at temp. 30 75 130 5 68 (min)

Response time 30 75 130 135 198 (min)

Gas composition (volume%) H2 - CO _____ CO2 0.16 0.21 0.23 0.85 0.50 CH4 0.00 0.00 0.00 0.00 0.00 C2H4 1.49 1.60 1, 31 0.24 0.52 C2H6 0.00 0.00 0.00 0.00 0.00 C3H6 0.00 0.00 0.00 0.00 0.00 C3He 0.00 0.09 0.03 0 0.00 0.00 C4 0.00 0.00 0.00 0.00 0.00 C = 0.00 0.00 0.00 0.00 0.00

Ce 0.00 0.00 0.00 0.00 0.00 DCE 1.35 0.89 1.12 0.69 0.15

Gas conversion (% DCE) 54 65 59 49 83

Example XI (Continued)

Sample 92 93 94 + 95 95 97

Temperature 501 501 544 544 544 (C)

Pressure (Bar) 11111

Time at temp. 121 191 55 126 191 (min)

Response time 251 330 387 458 523 (min)

Gas composition (volume%) H2 0.14 CO - - 0.88 CO2 0.15 0.10 0.10 0.46 0.24 CH * 0.00 0.00 1.85 2.43 2.15

CzH.4 0.65 0.02 0.00 0.00 0.00

CzHe 0.02 0.02 0.01 0.00 0.00 C3He 0.00 0.00 0.00 0.00 0.00

CaHs 0.00 0.00 0.00 0.00 0.00 C4 0.00 0.00 0.00 0.00 0.00

Cs 0.00 0.00 0.00 0.00 0.00

Ce 0.00 0.00 0.00 0.00 0.00 DCE 0.17 0.15 0.08 0.06 0.06

Gas conversion (% DCE) 81 35 95 96 95

Acidity of wash water: average conversion is high, but a pressure drop built up over the catalyst bed, reducing the flow and no average conversion can be calculated.

Claims (8)

A process for regenerating an adsorption flute containing carbon, characterized in that the adsorption filter is introduced into a desorption apparatus, steam is passed therethrough in such a ratio that the steam / carbon molar ratio is at least 1, the resulting mixture into a catalytic reactor and contact with a catalyst consisting of one or more transition metals and reacting thereon. 2. Process according to claim 1, characterized in that a steam to carbon ratio of 1: (2-4) is used. 3. Process according to claim 1, characterized in that a steam to carbon ratio of 1: (2.5-4) is used. 4. Process according to claims 1-3, characterized in that a catalyst on a porous ceramic support is used. 5. Process according to claims 1-5, characterized in that a catalyst based on Pt, Rh, Ir, Pd, Ru, Ni, Fe and / or Co is used. 6. Method for removing (halogen) hydrocarbons from gases, characterized in that a) a physical separation is applied at the remediation site, using an adsorption filter, b) the adsorption filter in which the (halogen) hydrocarbons to be removed are included , to a destruction device and c) in such a device desorbs the adsorbed (halogen) hydrocarbons and converts the mixture of steam with the collected (halogen) hydrocarbons into harmless components and the easily separated hydrogen chloride. 7. Process according to claim 6, characterized in that step c is carried out according to the process of claims 1-5. 8. Process according to claim 6 or 7, characterized in that an adsorption filter based on activated carbon, coconut coal or aluminum oxide is used.