COMBINED BIOLOGICAL TREATMENT OF SINTER PLANT WASTE WATER, BLAST FURNACE GAS SCRUBBER WATER POLLUTED GROUNDWATER AND

COKE PLANT EFFLUENT By Antoine van Hoorn Environmental Management Corus Staal This paper was presented at a COMA Meeting in March 2005 held at the Corus Conference Centre, Scunthorpe 1. The History of Treating Coke Plant Waste Water The second coke plant at the Corus location IJmuiden was taken into operation in 1972. At a production rate of approximately 2 million tons of coke a year for both plants, about 65 m3/h of wastewater had to be treated. From start up on the wastewater was handled according to the traditional and well known activated sludge process. So air was put in by very inefficient surface aerators and the sludge was recycled over a settling basin for reuse. The biomass concentration in the aeration basin was controlled at a constant level of 3 5 grams/litre. The activated sludge plant was designed on the basis of experiences with treating domestic wastewater. Already some months after commissioning the plant it became clear that coke plant effluent is very different from domestic sewage. Overall the removal efficiency was very poor. Most of the times only phenols, one of the major components of coke plant wastewater, were removed and not the rest of the COD and thiocyanate. Nitrification, converting ammonia or TKN into nitrate via specialised bacteria which are usually part of the biomass, never occurred during that time. In the eighties it became clear that phenol removal only was not sufficient anymore. The Dutch water authorities demanded that that the part of the COD that can be degraded by biomass should be removed almost completely before it is permitted to discharge the treated wastewater into the sea. Due to the fact that there was no room available at coke plant #2 another less room consuming treatment system had to be developed. After extensive research including long term pilot plant testing it was decided in 1988 to build a so called Oxitron fluidised bed system. By dissolving pure oxygen in a circulating water flow and keeping the water velocity in the reactors at a level that sand grains stayed in a kind of fluidised state it was possible to grow biomass on these sand grains and to remove almost all the COD from the wastewater. Under these conditions it also seemed to be possible to grow nitrifying bacteria at the same time. Biomass concentrations in this system went up to as high as 20 25 grams per litre. So the same amount of biomass or sludge as in the traditional activated sludge plant could be achieved in a much smaller volume.

Figure 1: The fluidised bed installation at Coke Plant Treating coke plant wastewater means that all the problems known from sewage works have to be solved. From several coke plants all over the world was reported that bulking or floating sludge, pin point flocks causing settling problems and high suspended solids in the treated effluent are frequently observed. Probably due to the fact that coke plant effluent contains toxic components the sludge is constantly under stress. One of the components that cause these toxic effects is probably cyanide, but also other so far unknown substances can be responsible for these phenomena. Anyway, several plants in the world have the same problems and need a lot off attention from plant personnel and often the results as for example in removal efficiency are still not satisfying. At the end of the nineties the water authorities concluded that some other waste water flows from the Corus plant in IJmuiden did contain more COD and TKN than allowed. The quality of the canal and the sea where the Corus wastewaters are discharged to is still not satisfying and not in accordance with European standards. At the same time it was also found out that the problems at the fluidised bed plant could only be solved by investing a considerable amount of money. The problems basically concerned the sand biomass separation, a part of the process that during design was underestimated. In reality this part of the installation became a major problem to control the process and a bottle neck to continue. The fluidised bed problems and the pressure from the water authorities directly led to the decision to reconsider the way Corus IJmuiden was treating the different waste water flows. 2. Different Waste Water Flows In 1997 an inventory was made of the different waste water flows and it was concluded that the waste water coming from the gas scrubbers from the blast furnaces, the water coming from the flue gas scrubbers from the Sinter Plant end the polluted groundwater from Coke Plant #1could be very well treated in combination with coke plant effluent. 2.1 Sinter Plant Waste Water To prevent emissions to the air from SO2, heavy metals and other harmful components, the flue gases from the Sinter Plant are cleaned with a patented process based on high pressure scrubbing. The process has been developed by Voest Alpine in Austria and is called Airfine.

In the first scrubber SO2 is removed by spraying water in a recycle loop. The pH is regulated by caustic soda addition. In the second step of the scrubber system very fine water droplets are sprayed causing the fine particles to be wetted. These particles are together with the bottom flow of both scrubbers sent to the separate water treatment plant.
Demister

Stack

Quench

Fine scrubber Flue gas

NaOH

Settler

Heavy metal precipitation Settler Neutralization

Filter press

Filter press

Gravel bed filter Recycling Recycling/immobilization Sewer

Figure 2: The high-pressure gas scrubber system at the Sinter Plant In this plant through pH-variations and the addition of different chemicals the heavy metals are batch wise separated in two steps. In the first step the more harmful components like mercury and cadmium are removed. The destination of the sludge from this step was originally storage and possibly controlled dumping as chemical waste material. The rest of the heavy metals in the water coming from the first step is treated in a second batch process. The sludge containing the more harmless metals is used again in the Sinter Plant. Up till now the separation in harmful and harmless waste material has not been a success. All the produced sludge is for the time being put back into the Sinter Plant. For dewatering of the sludge two filter presses are available. Table 1 shows the average composition of water produced by the Airfine installation. The COD and TKN concentrations are higher than is permitted by the water authorities. Metals in general and lead in specific, make a direct discharge to surface water impossible. 2.2 Blast Furnace Gas Scrubber Water The gas coming from the two blast furnaces is used for energy production. It has to be cleaned before it is transported to the external power station. The gas is washed in so called venturi or Bischoff scrubbers. Both furnaces have their own water circulation system (650 and 850 m3/h respectively for BK#6 and BF#7). Solids are removed from the water in a shared water treatment plant. To prevent built up of salts and scaling that can cause precipitation on several critical places in the installation some water has to be extracted from the circulation loops. Before the discharge of this water is permitted a separate treatment has to take place to remove all the solids and the heavy metals present is this blow down.

explosion valves

Dust bag gas

BF gas expansion turbine gas

production of electricity for iron production in BF

G

gas
G

Bisschof gas scrubbers

Energy production

untreated water treated water course BF-dust BF-dust Sinter plant Zn-poor Water treatment BF-dust Zn-rich

temporary storage

BIO 2000

Figure 3: Gas treatment at the Blast Furnaces

The settled sludge from the basins in the re-circulating flows and from the basin where the extra treatment takes place is separated through a 3 step hydro cyclone system. The fraction with the smallest particles contains the most Zn. It is dewatered by a filter press and is stored for future processing. Nowadays the Zn-concentration is still to low to extract it from the sludge. The Zn-poor fraction of the sludge, this is the fraction with the more coarse particles, is dewatered in a decanter centrifuge and is transported back to the Sinter Plant for reuse. The recycle of scrubber water takes place via the basins 11 en 12. From this recycle about 140 m3/h is withdrawn to keep the risk of precipitation in the installation at a minimum. This blow down is led to basin 13. Here are the particles separated that are left in the wastewater. To keep the discharge of Zn as low as possible an addition of sodium sulphide takes place in basin 13. Any dissolved Zn will in this way precipitate as insoluble Zn-sulphide. The overflow from basin 13 contains normally not more than 1 mg/l Zn.

from BF#7 make-up water (WRK) and gascondensate from BF#6

cooling tower

MASH-water and/or Na2S

basin 11

basin 12

basin 13

sludge to hydrocyclones

sludge to hydrocyclones

sludge to hydrocyclones

effluent to Bio2000

clean water basin 11

clean water basin 12

clean water basin 13

to BF#7

to BF#6

Figure 4: Waste water treatment at the blast furnace department Table 1 (see below) shows the average composition of blow down water of the blast furnaces gas scrubbers. Again COD and TKN concentrations are higher than permitted by the water authorities. Metals in general and zinc in specific, make a direct discharge to surface water impossible. Despite the fact that a by-pass cooling tower is used in the circulation flow the temperature of the blow down is fairly high. A separate small cooling tower is used to get the temperature at levels acceptable for a biological treatment process.

2.3 Polluted Groundwater At the end of World War 2 a RAF-pilot dropped a bomb by accident on the BTX-recovery of Coke Plant #1. As a result of this action the ground water at this plant is highly polluted. BTX concentrations of 5 10 mg/l were found. Local authorities demanded treatment of this water. After pilot plant testing it was concluded that biological treatment could clean this water. For the next 25 years we have to pump up about 40 m3/h to neutralise the pollution. The average composition is shown in the table below. 2.4 Coke Plant Wastewater Coke oven gas is cleaned at coke plant #2 in a very traditional way. After cooling and tar separation ammonia, H2S and BTX are removed from the gas. BTX is prepared for reuse in an installation at coke plant #1. Ammonia liquor coming from the scrubbers is treated in 2 stripper columns, a combination of a so called de-acidifier and an ammonia stripper where free and fixed ammonia are removed at elevated pH-levels. For pH control caustic soda is dosed. The H2S-gas is converted to hydrogen sulphuric acid. The ammonia gas is oxidised in this acid plant at the same time. The gas treatment at coke plant #1 is a little different. Here ammonia sulphate is produced. The ammonia liquor from coke plant #1 is transported by pipeline to coke plant #2 for further treatment. The steam consumption of the combined stripper and acidifier is 11 t/h; the amount of ammonia liquor is app. 60 m3/h and the amount of water coming from the H2S-scrubber app 20 m3/h. NaOH addition is 9 11 l/m3 waste water.

After stripping the average composition of the wastewater is as shown in the table below. The main constituents are the high COD, TKN and cyanide concentrations where TKN stands for Total Kjeldahl Nitrogen (see table 1). This is the total of ammonia nitrogen and possibly present organic nitrogen compounds. TSS stands for total suspended solids and is in majority responsible for the PAH that normally will be found in coke plant effluent. 3. Developing a Combined Treatment Plant Because all the above mentioned waste water flows contain COD and TKN that can be removed biologically after extensive pilot plant testing it was decided to develop a combined biological treatment system. An extra advantage of the bio treatment is that a main part of the remaining heavy metals will be absorbed by the bio sludge and the discharge will be even smaller then it is already. After the pre-treatment at the blast furnaces and at the Sinter Plant the waste water is transported to a new biological treatment plant at Coke Plant 2. Together with the wastewater from both coke plants and the groundwater from coke plant #1 a total amount of approximately 320 m3/h has to be handled in the new installation. The resulting cyanide concentration in the mixture of wastewater is about 15 mg/l. For a biologically treatment this level can be harmful under certain process conditions. Table 1: Composition of the different waste water flows
Flow m3/h BF SP CP GW Total 140150 50-55 80-90 35-40 320 Temp C 40-44 35-40 30-35 10-12 33 COD mg/l 65-120 250-450 3.0003.500 150-350 1.100 TKN mg/l 130150 200300 200300 100200 180 CNtotal mg/l 5-20 20-60 10-20 15 TSS mg/l 25-35 10-25 20-50 <10 25 Zn mg/l 2-4 metals mg/l 1-3 0,3-0,5 Phenols mg/l 500-750 -

CNS mg/l 200250 -

BF = Blast Furnace scrubber water blow down SP = Sinter Plant scrubber water CP = Coke Plant effluent GW = Polluted groundwater form CP#1 Besides the connections with the water treatment plants of the Blast Furnaces and the Sinter Plant in the beginning also the effluent from the Pellet Plant was considered to be part of the influent of the new bio treatment plant. However the problems over there were especially caused by high amounts of heavy metals in particular arsenic. Biodegradable components were relatively low. August 2004 a specially developed Arsenic Removal Plant was installed at the Pellet Plant. Nowadays the arsenic concentrations are decreased through chemical processes in this installation from about 1500 g/l to less than 50 g/l. The combined treatment of these four waste water flows was studied for more than a year. Pilot plant testing showed the possibilities of the so called pre DN/N concept where pre DN/N stands for pre-denitrification-nitrification.

Nitrification and COD removal can take place simultaneously in the aerobic part of the installation. The end products from this conversion are CO2, water and nitrate, NO3-. Denitrification is the biological process where nitrate is converted by bacteria into nitrogen gas. This process has to take place under anaerobic or anoxic conditions. So there should be a special part of the installation where dissolved oxygen concentrations are more or less equal to zero. Denitrifying bacteria however need some COD as feed also. By putting in (part of) the influent in the anoxic part of the installation and recycling nitrified wastewater, COD and nitrate come together in this part. Because the denitrification takes place in the first part of the installation this is called predenitrification. The denitrifying part of the biomass is the most sensitive to changes in process parameters like temperature and pH. Also a lot of components that are biodegradable under aerobic conditions are toxic for denitrifying bacteria.

4. The New Biological Treatment Plant The heart of the new water treatment configuration is the biological treatment plant the so called Bio 2000. This Carrousel type of installation was built in 1999 2000 and is quite famous in Western Europe where it is applied quite often for the treatment of domestic wastewater. The large basins with surface aerators and the relatively high velocities make the installation more a complete mix reactor than a plug flow. The aerators are controlled by measuring dissolved oxygen continuously and comparing it with a set point of 1,5 to 2 mg/l. Also pH is controlled by adding caustic soda when the pH is lower than 6,8 or by adding sulphuric acid when the pH in the basin is higher than 7.4. One of the major problems during the first years of operation was keeping the temperature in the aeration basin low enough, that means lower than 33 C. Through extra cooling of the water coming from the blast furnaces via a cooling tower and sometimes putting in some cold river water this maximum temperature level was not exceeded since the summer of 2003. Behind the BET-plant continuous backwashing sand filters were installed. Despite the fact that the combination of wastewaters can easily be treated sometimes very fine biological flocks are present in

Figure 5: Floor-plan of the new Biological Treatment Plant At the picture below you see the carrousel with the surface aerators installed in the blue boxes. These boxes are isolated to prevent troubles with noise in the direct neighbourhood of the installation. The light blue columns in front are the six sand filters; in the back you will see the blast furnaces nr 6 and 7. Excess sludge is pumped to a thickener first. After that the sludge is dewatered and mixed with the coal that goes into the ovens.

Figure 6: The new Biological Treatment Plant Some dimensions: the aeration volume is 15.000 m3, this means a hydraulic retention time of 33 hours. The settling volume is 1500 m3. The diameter of the settling basin is 29 m. The surface load is 5 m3/m2/h.

The sludge thickener is a basin with a diameter of 9,5 m and a volume of 250 m3. Average sludge waste is 45 m3/day with 3 % dry solids. The sludge recirculation flow is max 640 m3/h (twice the amount of influent). Dosage of phosphoric acid is based on 2 mg/l phosphate in effluent. That means app. 5 l/h 75% phosphoric acid has to be added.

5. Performance of the New Biological Treatment Plant Commissioning the new treatment plant took about 10 weeks. In that period the influent flows were gradually increased. To start up the biological processes sludge was transported by truck from a sewage treatment works to introduce nitrifying bacteria and from the industrial wastewater treatment plant from the company that is distilling the tar coming from the coke plants. The latter sludge should be adapted more or less to the composition of our wastewater. COD concentrations from the different waste water flows seemed to be very constant as can be concluded from figure 7. When this concentration is changing this will only happen gradually and over a longer period. Especially changes in coal mixture can influence COD concentrations in coke plant effluent. But also changes in process can have this effect. For example changes in coking time. At present for coke plant #1 it is minimal 17 h and for coke plant #2 19 hours. TKN-concentrations on the other hand are fluctuating considerably (see figure 8). The highest variations are observed in coke plant effluent. Roughly TKN concentrations are in the range of 100 300 mg/l. It seems like the ammonia strippers are not working as constant as always was thought.

4.500 4.000 3.500 3.000 2.500 m g /l 2.000 1.500 1.000 500 0 21-ju n-01 20-ju l-00 4-jan-01 31-au g-00 23-n o v-00 12-o kt-00 15-feb -01 2-au g-01 25-o kt-01 10-m ei-01 13-sep -01 29-m rt-01 6-d ec-01
6-d ec-01

COD from BF COD from BF COD from CP1+2 COD influent Bio 2000

Figure 7: COD-concentrations incoming waste water

500 from Blast Furnace from Sinter Plant from Coke Plant 1+2

400

300
m g /l

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0
20-ju l-00 4-jan -01 31-au g -00 23-n o v-00 21-ju n -01 12-okt-00 15-feb -01 2-au g -01 10-m ei-01 13-sep-01 29-m rt-01 25-okt-01

Figure 8: TKN-concentrations incoming waste water Dutch laws and regulations are in majority based on the European legislation. However, every country in the European Community has the right to make their local laws and regulations stricter than necessary according to these European directives. For a long time this was the policy of our government. Since last year our government is taking into account the big changes that will be caused by the new Water Framework Directive. This new directive can have a considerable impact on industry the coming years. As a direct consequence the discharge permit for the bio treatment at coke plant 2 probably is not more than temporarily. On the longer term, probably within a few years, the limits on discharging wastewater will change. Especially the limited concentrations for COD, TKN, suspended solids and the heavy metals that are linked with the suspended solids, will most likely become stricter. It is possible that under these circumstances a third treatment step like activated carbon adsorption or a completely new treatment process will be necessary. Nowadays the limits for the bio plant are as in table 2. Table 2: waste water discharge limits
Maximum Flow TSS COD TKN Phosphate Cyanide Thiocyanate Cd Hg As Cr+Cu+Pb+Ni+Zn PAH m3/h mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l 400 60 100 30 10 10 4 0.01 0.005 0.025 0.8 0.005 Average 340 30 150 15 5 6 2

The performance of the installation is excellent. COD removal efficiency is almost always over 85 % and TKN removal or nitrification is nearly 100 %. Concentrations are most of the time within the limits set by the authorities (see figure 9). Thiocyanate is together with phenols responsible for the high COD concentrations in coke plant effluent. However phenols are very easily to degrade. Nowadays no samples are taken anymore for analysing the phenol concentration because it is always lower than the detection limit. From thiocyanate always a small fraction will not be removed. In the treated effluent most of the times 1 3 mg/l of thiocyanate will be present. Cyanide itself is probably only for a small part degradable. It is also possible that removal of cyanide takes place by adsorption on the bio sludge. However a small portion of the cyanide can not be biodegradable also.

350

flow mg/l COD TSS

300

250

200 m3/h 150 100 50 0 4-nov 18-nov 7-okt 11-mrt 25-mrt 17-jun 23-sep 21-okt 3-jun 15-jul 29-jul 9-sep 1-jul 2-dec 16-dec 12-aug 26-aug 20-mei 30-dec 1-jan 15-jan 29-jan 12-feb 26-feb 8-apr 22-apr 6-mei

Figure 9: Flow, COD- and TSS-concentrations in treated waste water Long term BOD tests proved that about 70 100 mg/l cannot be degraded biologically. For coke plant effluents only these values are as high as 370 mg/l. This part of the COD consists of very persistent components. So far these components are not identified. The COD concentrations in the treated effluent are about 100 mg/l. This means that almost all the biodegradable COD is removed. The average suspended solids concentration is 30 mg/l. Some water waste water coming from the sulphuric acid plant is after neutralisation also transported to the discharge point of the bio treatment plant. It is possible that variations in suspended solids concentrations are a direct consequence of this extra water because Ca-sulphate can be formed. So possible gypsum particles are part of the suspended solids. Up till now we did not succeed in keeping denitrifying bacteria in such a state that stable denitrification over longer period occurred. The possible reason for that is the presence of toxic components in the incoming coke plant wastewater. From time to time the nitrification process becomes unstable. This happened frequently especially in the first two years of operating the bio treatment plant. These instabilities results firstly in higher nitrite levels and in a later stage in higher ammonia concentrations. When the conditions are not changed finally nitrification will come to a complete stop. In the years 2001 and 2002 three major failures in nitrification efficiency occurred. No explicit explanation could be found for these failures. There only are made a few suggestions and possible causes afterwards. Toxification of the biomass resulting in inhibiting the nitrification process could have been caused by one or more toxic compounds in one of the influent flows. Most likely this has been a cyanide complex that can be present in coke plant effluent or blast furnace scrubber blow down. Other reasons are more common like a biomass that was under stress and in that situation overloaded. Too high food over micro organism levels can have a killing effect on bacteria. A too high sludge load is often the reason for unhealthy sludge. Sludge in a stressed condition also can be the result of amongst others higher temperatures and large variations in wastewater composition.

It can take several weeks before the installation is working well again. In the IJmuiden situation it is possible to discharge part of the waste water directly without treatment during the time the biomass is recovering. This situation occurred once so far and was followed by extensive discussions with the water board resulting in a much higher pollution tax that had to be paid. TKN concentrations in the treated effluent are around 8,5 mg/l. The variation is about 6 mg/l. This means that nitrification is complete (over 95 %). This is confirmed by the NH3 concentrations that normally are not exceeding the level of 2,4 mg/l (see figure 10). The difference between ammonia and TKN probably are non biodegradable organic nitrogen compounds.

40

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15 20 10 10 5

0 jun-04 jul-04 aug-04 mei-04 nov-04 sep-04 mrt-04 feb-04 jan-04 jan-04 apr-04 okt-04 dec-04 dec-04

Figure 10: TKN- and NH3-concentrations in treated waste water The nitrogen removal rate is high. The nitrate concentrations are around 480 mg/l. Sometimes a little nitrite is found in the effluent but under normal circumstances not more than 0,2 0,4 mg/l. Comparing the actual effluent data of 2004 with the limits from the discharge permit learns that COD and TKN are well below these limits. Also heavy metals are lower than allowed in our permit. CN and suspended solids are the only components that are not always in compliance. Suspended solids concentrations can be influenced by the small wastewater flow from the sulphuric acid plant as mentioned before. An investigation is on its way how to handle this problem. CN is frequently too high. Suggestion is to find a way to remove CN from coke oven effluent separately and before biological treatment. All the alternatives found so far are too complex or produce high amounts hard to settle sludge. Alternative methods consist of oxidation in combination with Fe-addition.

6. Controlling the Process One of the most important things in treating wastewater biologically is controlling the process. There are several ways to do so.

mg/l Total Kjeldahl Nitrogen TKN

35

TKN NH3

mg/l Ammonia NH 3

1. By regular analyses of influent and influent. Shift personnel are taking samples of the influent every day. With so called test kits COD en NH3 are analysed immediately. These test kits are not accurate, but the results are satisfying enough to see any essential changes. From the effluent samples are taken on a continuous base using special sampling devices. These devices are connected to the flow meter so that is it is possible to take volume proportional samples. Every three days a sample collected during from 24 hours, is analysed by the chemical department. Besides COD and TKN also the other components are analysed. 2. pH, temperature, Dissolved Oxygen and NH3 are analysed continuously. pH is controlled between 6,8 and 7.2, DO set-point is 1,5 2,0 mg/l, temperature in the aeration basin should be not higher than 32 C. The ammonia monitor is the most important one. If ammonia is increasing actions have to be taken. Departments that are delivering wastewater are contacted to see if nothing has changed in there processes and for example the oxygen input has to be increased. All monitoring is done by the central control room. 3. The sludge concentration is kept on a level of 4,5 to 5 grams/l. Every other day the sludge concentration is analysed and excess sludge is wasted based on the results of these analyses. 4. Every couple of months, app. 4 times a year the sludge is examined by an experienced microbiologist from an external company. From the microscopic view and the changes that are observed information gets available about the health of the sludge. 5. By measuring the respiration rate of the sludge. Tests are done with an instrument from Strathkelvin in Glasgow. The primary goal is controlling sludge health by measuring respiration every day. A secondary goal is recognizing toxic components in influent and inhibition of the biological processes. The tests done in the second half of 2004 did result in purchasing the Strathtoxmodel in Feb 2005. At the moment implementation in day-to-day-operation is taken place. Regular tests are done by shift personnel.