NEW TECHNICAL POSSIBILITIES FOR REDUCTION OF COKE OVEN EMISSIONS Michael HEIN, Friedrich HUHN, Frank ROSSA, Deutsche

Montan Technologie GmbH, Essen, Germany Heinz OPDENWINKEL, Joachim STRUNK, Deutsche Steinkohle AG, Herne, Germany This paper was first presented at the 5th European Iron & Cokemaking Conference Stockholm 2005 Abstract A research and development program was initiated to reduce the emissions from coke ovens. Main targets were the improvement of the charging process with particular consideration of the levelling procedure and the reduction of door emissions. For reduction of the charging emissions a new levelling system was developed and is since 2000 in operation at the Prosper coke plant. A new kind of door sealing system was developed to reduce the effective raw gas pressure, and hence the emissions at the door seal. This is achieved by means of a pressure equalisation duct arranged around the door concerned and connected with the gas collection chamber. Furthermore the flexibility of the oven door membrane was improved by means of a new multilayer-membrane. A test door was built and applied for 2 years at the Prosper coke plant. After the successful test operation 20 door sealing systems of the new design were installed in 2004 at the Prosper coke plant. After a description of the design principles the paper will mainly describe the practical experience using the 2 new emission reduction systems at the Prosper Coking Plant, Bottrop. Introduction BaP Emissions in Coke Plant Operation Fugitive emissions from the operation of a coke battery cannot be avoided completely. These emissions contain small concentrations of polycyclic aromatic hydrocarbons (PAH). Because most of the PAHs are carcinogen, these compounds are in the focus of public discussions; as a guiding reference compound for PAH the Benzo(a)pyrene (BaP) is usually considered [1]. Depending on the terms and conditions of coke oven operation, coke oven age, technical standard and maintenance status of the overall plant, the product-specific BaP emissions of the coke plants currently operated in Europe range between 10 and 100 mg/tcoke [2]. Generally, from health protection reasons the demands by the public for a further reduction of industrial emissions were markedly strengthened in the past decade; in the EU the fourth daughter directive [3] was recently fixed in which a target value for the Benzo(a)pyrene (BaP) ambient air concentration of 1 ng/m is set effective from 2013. Member states must transpose it into national law by 15 February 2007. The European Commission will report on its implementation by 31 December 2010. It is a great challenge for the coke making industry to cope with the BaP ambient air concentration target value, at least concerning the concentration in the direct vicinity. It is questionable whether state-of-the-art emission reduction technologies are sufficient to prevent leakages to the necessary extent. This situation was the starting point for DMT to derive more advanced possibilities for additional emissions reductions. Special consideration was laid on the realisation of primary solutions for emission control, to which a higher potential for improvement may be attributed than to only an abatement of the effects. Primary solutions mean process technical measures to reduce the relevant pressure gradient that is the driving force for any emission. Meanwhile the developed solutions have found its way into industrial practice. Reduction of door emissions

State of the art In the 80s at most German coke plants the technological transition from rigid doors to systems equipped with flexible diaphragms was carried out [4-8]. Several different solutions were invented: Efficient insulations reduce the heating-up and deflection of the door body. Gas channels with large cross-sections behind the door body reduce the pressure gradient between the inside and outside of the sealing edge. Flexible sealing elements allow to a certain extent a movement of jamb and door throughout the coking cycle.

Despite of all the improvements made leakages can be observed quite frequently in the first hour after charging. The gaps causing leakages in the beginning of the coking time have to be sealed off by the workmen; to this end additional measures e.g. manual sealing with fibrous materials or slurries or readjustment of the sealing edges have to be undertaken. To facilitate this work several modern coke plants have installed so-called service cars allowing an easy access to the whole outer door area. In every case all this means that despite of a very high status of development of the doors a sufficient tightness can be achieved not without this additional regular work. Further cleaning work is necessary by means of the cleaning machinery to remove the condensates that are deposited at the seal and the jamb and would give rise also to the formation of gaps. However, every mechanical work at the door seal is a curious combination of heavy work and precision mechanics with tolerances of tenth of a mm; this combination bears a high risk of damaging the sealing elements. To improve the situation any need for further maintenance handling should be lowered. These problems that are typical for more or less all oven doors could also be observed at the light weight doors which are installed at the Prosper coke plant of DSK (Deutsche Steinkohle AG). This door type has been in use on DSK coking facilities for a longer period of time for testing purposes and has proved its worth (Figure 1). The door body itself comprises of several segments of steel that can be adjusted to the relevant door jamb contour by means of eccentrically adjustable wedges. The pre-adjustment of the segmented door body of a 7 m door alone allows for a certain compensation of the jamb deformation. The sealing effect is brought about by a diaphragm. A multitude of elements similar to plate springs are distributed over the entire frame and act on the diaphragm. The seal itself consists of a material that easily withstands the high temperatures and corrosive conditions. The weight of the door body is 15 % lower than of a conventional cast iron body. The doors were equipped with a ceramic heat shield which enabled the raw gas to pass between door body and coke cake. In this way, the gas pressures prevailing in the entire oven quoin area could be distinctly reduced. Furthermore the door weight is lowered considerably because of the missing door plug.

Figure 1 Coke oven door installed at the Prosper coke plant

Improved door sealing To lower the leakage risk causally it was the target to further decrease the pressure gradient behind the sealing in combination with the avoidance of any gap from thermal distortion. To reduce simultaneously the deposition of tarry condensates the direct contact of the seal with raw gas should be reduced. To this end DMT developed a new sealing type and implemented it into the existing door body at the Prosper coke plant. One door was installed in May 2002 and tested over a time of 2 years in continuous operation [9-11]. Reduction of the driving force for door emissions. To reduce the driving force for emissions, i.e. the pressure gradient, a double sealing was developed that is arranged around the door and forms a duct (Figure 2); by an opening in the upper part this duct is connected with the free space of the coke oven [12]. This provides the possibility of a pressure equalization over the height without originating an undesirable pressure increase: At the beginning of the coking time the pressure behind the inner sealing (in the oven) is quite high because of the strong gas formation. If there would be any leakage at the inner seal the gas would penetrate through the gap and expand into the gas channel. Here the driving force for emissions, the pressure behind the outer sealing is very low such that the gas could not penetrate through the outer seal.

At the end of the coking time the pressure in the oven behind the inner sealing may be lower than the ambient air pressure. However, because of the possibility of a gas exchange the pressure behind the outer door seal is increased, such that no air can be sucked into the oven. The lower temperature in the gas duct (approx. 160C) is of additional advantage. If there is a gap at the inner seal only a small amount of gas in the gas duct can flow into the oven; no detrimental effect by air flowing into the oven can take place. The gas duct works like a gas lock. Because of the connection to the free gas space only the pressure level present there is effective. Improvement of flexibility of the sealing system The amount and the transmission of the forces onto the sealing is an important precondition to get a good seat of the sealing. The effect of the forces onto the sealing must not be deteriorated by a too high stiffness of the diaphragm and the springs; this would lead to the formation of gaps because of thermal distortion. To this end the flexibility in combination with the distribution of the bearing pressure was improved using a multi-layer diaphragm [12] as shown in Figure 3.

Compared to a single diaphragm of similar total thickness this design has the advantage that the flexibility is enhanced by more than 300% because the individual layers can slide over each other - and this without any irreversible deformation. The multi-layer concept also has the advantage that any corrosion of one of the sheets will not lead to any leakage, because the other sheets in combination with the deposition of condensate assure the tightness. The force transmission is applied by leaf springs to realize a contact pressure uniform over the length.

Figure 2 Oven door area - principle of the new sealing system

Figure 3 Design of the sealing system Figure 4 shows the conventional and the practical realization of the improved door. The springs are also executed in a multi-layer manner; the force is transmitted near the outer sealing. This allows for an ability of tilting of the gas channel and thus for an additional adaptability. Corner area of the sealing system A particular problem of most door constructions is the corner area. These areas usually have a much higher inherent stiffness and often give rise to leakage. Furthermore because of the missing flexibility thermal stresses occur resulting in the creation of fissures. In this area a construction based on the application of cup springs provides for a very high flexibility and a sufficient bearing pressure (Figure 4, center). The leveller door at many plants frequently is a source of leakages. This results in particular on the higher temperature level in this area leading to thermal distortions and thus to the formation of gaps. The flexibility of the existing door was only a tenth of a millimetre at the given contact force. For improvement the double sealing and multi-layer diaphragm concepts were also applied to the leveller door construction (Figure 4, right). Thereby its flexibility was enhanced drastically to a level of some millimetres. To prevent any stiffening by the corner construction and to maintain the flexibility also a special cup spring construction was used. The 4 side pieces of the sealing are not directly connected or welded and can be pressed with the cup spring construction each individually onto the jamb.

Figure 4 Prosper coke oven door; left: conventional; center: equipped with the DMT-sealing system and the advanced corner construction; right: new leveller door Leveller door sealing system

Practical experience Because of the positive results using the new sealing system at the test door over more than 2 years DSK decided to apply the new system at 20 coke side doors. After engineering of the changes necessary to adapt the sealing system to the coke side conditions the sealings were pre-manufactured; then the system was installed at existing door bodies in the door shop of the Prosper coke plant. Simultaneously the regular maintenance was applied to the door bodies. Week by week one or two doors were modified. Each modified door was inserted after a heating up in the preheat box. By means of the existing bolt mechanism the door was pre-adapted to the door jamb contour. After one coking time the door has accommodated to operating temperature and a second adjustment was made, in most cases the final one. In December 2004 the modification of the doors 51-70 (battery no. 2) was completed (Figure 5); since then the doors are in regular operation.

Figure 5 Coke side oven doors of the Prosper coke oven battery no. 2 equipped with the new sealing

Emission reduction The pressure development behind the door seals reflects a considerable lowering of the driving force for emissions [9-11]: Behind the sealing of the conventional Prosper door the gas pressure reaches max. values of approximately 1.8 mbar in the first hour of the coking time. In contrast to this the corresponding pressure at the outer sealing of the DMT door amounts only to 1.2 mbar. At the end of the coking time the pressure at the conventional sealing is near suction at 0 mbar whereas the pressure level at the outer DMT sealing remains at a save level of 0.2 mbar. Thus the new system lowers the driving force for emissions drastically and simultaneously prevents any risk of wall damage by air penetration into the oven at the end of the coking time. The positive pressure at the end of the coking time gives the operator the opportunity to lower the collecting main pressure with the effect of an additional emission reduction. Corresponding to the pressure development the emission reduction is considerable. Really no leakages are visible right from the beginning of the coking time. To assess the emission reduction using the new sealing type more detailed measurements were performed. To quantify the emissions the door area was completely enclosed by a polyester foil (Figure 6); subsequently the concentration and the mass flow of Benzo(a)pyrene and organic carbon compounds was determined. To exclude any fortuity the measurements were performed 2 or 3 times at each door.

Figure 6 Measurement of door emission by enclosing the door area The results are shown in Figure 7. Whereas the specific BaP-emission of the conventional door attains values up to approx. 5 mg/tcoke, the corresponding value for the DMT-type sealing amounts only to 0.3 mg/tcoke. This considerable reduction was achieved without any manual sealing off. In contrast to this the conventional doors were sealed off by the workmen manually using fibrous materials or slurries to seal the remaining leakages after charging. It has also to be noted that there is a considerable spread of the values concerning the conventional door, but quite consistent values for the new sealing system.

Figure 7 Specific BaP-emission from CS-doors with the DMT sealing system compared with the emissions from the conventional door. Door cleaning The existing mechanical door cleaner of the Prosper coke plant cannot be applied for the modified doors. However, as it was established already during the operation of the test door, the doors needed only a reduced cleaning work. At time only an occasional manual cleaning mainly at the bottom gas channel is performed. During the remaining time the door is operated without cleaning. In combination with the lack of the necessity to perform manual sealing it can be stated that cleaning and maintenance can be reduced considerably. However, to ensure a safe operation even in the long-term an appropriate cleaning device will be indispensable. At time DSK and DMT are jointly developing an equipment suitable for cleaning of the gas channel sealing. Low Emission Levelling System To achieve an even and flat coke oven charge in top-charging processes, wet coking coal is charged through 4 or 5 coal charging holes into the coke ovens. The charging cones developing under the individual charging holes are levelled-off by means of the leveller bar. During the charging special care is to be taken because substantial charging gas volumes evolve already at the start of coal charging, the exhausting of which into the collecting main, is further prevented through the coal still to be charged. However, to allow charging gases to escape from the coke oven, a sufficient suction is necessary which is generated typically by means of high-pressure liquor in the ascension pipe. The coke oven batteries equipped with the PROven process [13,14] have the system inherent advantage of the collecting main being

operated under negative pressure. This suction is used very effectively for charge gas transfer without a need for a high pressure liquor system. However, as long as the leveller flap is still closed, the charging gases are discharged due to the adequately effective suction. Usually it is sufficient as long as the gas discharge routes are not blocked by too high a formation of charging cones in the oven. However, to enable levelling, the leveller door must be opened, causing the negative pressure to collapse. On account of the growing gas pressure in the oven, charging gases or even flames might escape from the open leveller flap, the charging holes and the coal charging telescopes. An additional problem is the fact that during the levelling period the cross section of the gas space is more or less blocked by the leveller bar construction itself. Thus a free gas flow is obstructed. To prevent the occurrence of charging emissions the gas exhausting system the suction losses in the levelling system have to be minimized. This was achieved by means of a combination of improvements at the leveller sleeve and the leveller bar [15,16].

Features of the DMT levelling system Leveller bar To avoid the blocking of the gas space during levelling a completely new construction of the leveller bar was designed: As a main feature, the height of the cross-bars was reduced and the tip of the bar was constructed as an open structure, too [17]. From this measure the formation of an integrated gas duct results (Figure 8), which is located above the cross-bars and which extends from the tip over the entire length of the leveller bar. The statics layout was calculated in such a way that despite of the open structure of the bar and the lower weight the stability could be increased and the bending be reduced. Detailed temperature measurements at leveller bars in operation serve as a basis for realistic assumptions.

The coal in front of the open leveller tip is transported and distributed by means of the cross bars instead of being compressed in front of the tip. By way of a tighter arrangement of the cross-bars the distribution capacity of the leveller bar was improved. In addition frameworkconstruction openings were implemented into the side walls of the leveller bar; thus, the charging gases are afforded access to the integrated gas duct also from the sides. At the same time, the coal instead of building-up between chamber walls and leveller bar, as mentioned before, can fall laterally between the cross-bars and is also distributed.

Figure 8 Integrated gas duct framework construction of the new leveller bar (left) compared to a conventional bar (right)

Leveller sleeve The second main feature is a special sealing and a counter-suction at the leveller sleeve [17] to avoid a breakdown of the suction in the oven during levelling as occurring usually.

Figure 9 Scheme of the sealing and counter suction at the leveller sleeve sleeve The sealing encloses the bar in such a manner that a box type profile closed all around, also in the inner free gas duct results (Figure 9). The inner sealing consists of several loop-shaped stripes of stainless steel sheets. In combination with the cross bars of the leveller, an undesired intake of air into the oven during coal levelling is reduced. The practical realisation at the Prosper plant can be taken from Figure 10.

Figure 10 Leveller bar with integrated gas channel, side openings and the inner sealing

system at the sleeve The counter-suction is realized by means of an exhauster at the leveller sleeve. This exhauster sucks air from the front opening of the sleeve in; hereby a dead space in terms of flow is created in front of the opened leveller flap. Thus the same effect as with a closed leveller flap is achieved. By means of the sealing and the additional counter suction system the suction in the coke oven during charging is made more effective. The system, that was first tested at the Hassel coke plant of DSK, is in operation at one pushing machine of the Prosper coke plant since January 2000 and since 2003 also at the second machine. Results Levelling uniformity Because of the improved mechanical construction and the higher stability the bending of the new bar during operation is considerably lower than that of the conventional bar. This is valid in cold as well as in hot condition of the bar. In combination with the higher distribution capacity of the bar the charging heights are on a high level leading to higher charge weights than with the conventional bar (Fig.11).

Figure 11 Charging heights using the conventional (left) and the DMT-type (right) levelling system

Figure 11 Charging heights using the conventional (left) and the DMT - type (right) levelling system Emission reduction The improved pressure conditions caused by the new levelling system leads to a considerable emission reduction compared to the conventional system. To assess the emission reduction by the new system the dust load and B(a)P (Benzo(a)pyrene)-concentration in during a series of charging procedures using air samplers. The samplers were placed in a distance of 3 m from each charging telescope in the wind direction. Sampling was performed from the beginning to the end of each charging procedure. The improvement concerning B(a)P and dust is considerable as shown in Figure 12.

Figure 12 Dust and BaP concentrations near the charging car during charging procedure

Conclusions With view to the new EU regulations concerning BaP in ambient air primary measures for a causal reduction of the driving force for emissions at oven doors and during levelling were developed. A new door sealing concept has shown its potential for an important emission reduction even compared to state-of-the-art doors. Meanwhile, for a customer the sealing system was also adapted to a hammer-type door. Two correspondingly modified doors will be tested in industrial operation shortly. The modification of a leveller door with the DMT sealing system is recently under development for another customer. Also, the new levelling system is an effective solution for emission reduction during charging and simultaneously to improve the throughput of the battery, i.e. the economic situation. In next future the system will be implemented at 2 other coke plants.

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