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         Production of Magnesia (Wet-process)
         Description  of the proces of producing  magnesia by the    so called “wet route”.
         1  Magnesia plant   in Veendam
         The magnesia plant in Veendam, the Netherlands (an example plant for the wet process applied in the
         EU (BREF —LVIC-SO (2007)) produces synthetic dead-burned magnesia (DBM), caustic calcined magnesia,
         magnesium chloride, magnesium hydroxide and calcium chloride. The           raw materials used  are MgCl,
         brine and dolomite, which are very pure.
         The data used for the BREF LVIC-SO (2007) is updated to current process data. The       production capacity
         of the magnesia plant in the Netherlands in (DBM-+caustic) is aproximately 150 KT
         It should be noted, however, that for the total capacity of dead burned magnesia (DBM)        in the EU,
         amounting   to 1080   kt/year, the wet process route   is currently applied only in two Member States (the
         Netherlands: 150   kt/year, and Ireland: 90 kt/year),  and  covers approximately 22 % of the total EU DBM
         capacity.
         Whilst the wet process route used by the Dutch plant in Veendam, starting from pure raw materials, i.e.
         MgCl, brine and dolomite (Ca0.MgO0), is fully addressed in this document.The dry process route for the
         production of dead-burned magnesia (MgO), starting from mined natural magnesite (MgCOs),            is not
         covered in this document.
         Therefore, it should be also stressed that  BAT conclusions on    magnesium compounds based on data and
         information relevant to the wet process route, cannot be considered illustrative for the     dry process
         route.
         1.1 Industrial processes used
         As stated above the wet process described in this section is that of the     magnesia plant inVeendam,    in the
         Netherlands. This   plant produces dead-burned magnesia as an end-product from two raw materials,
         calcium magnesium lime (dolime) and magnesium chloride brine. The dolime is imported, while the
         company mines the      magnesium chloride itself. The overall process contains three sections: Mining,    wet
         proces and  dry proces. The last two are descripted below
         2 Wet section:
         2.1 Production of DBM and other      Mg compounds
         2.1.1 Boron/sulphate     reduction
         Crude magnesium chloride brine for the production of MgO is treated in an ion exchanger for
         boron removal. Hydrochloric acid regenerates the boron selective resin. Spent hydrochloric acid
         is gathered and used for neutralising the effluent.
         To reduce the  sulphate in the magnesium chloride brine, calcium chloride brine is subsequently
         used. A vacuum belt filter thickens and dewaters the gypsum precipitate (CaS04.2H,0) formed.
         The overflow from the thickener is purified brine ready for use in the magnesium hydroxide
         precipitation stage. The gypsum precipitate is transported to the mining location and pumped
         into the caverns.
         The chemical reaction of brine    desulphurisation is:
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            MgSOs   + CaCl,   >   MgClz  + CaS0a.2 H.0
         Boron is reduced in order to      improve the chemical purity of the magnesium hydroxide and the
         refractoriness of sintered magnesium oxide respectively. The sulphate content in the raw
         magnesium chloride brine must be decreased to reduce SO, emissions from sintering at a later
         process stage. High sintering temperatures can even cause emissions of elementary sulphur
         when present.
         2.1.2 Purification
         Some     applications require additional purification of the magnesium chloride brine. Filtration
         removes     undissolved iron. Further purification is achieved by oxidation of the dissolved iron
         into   Fe(II) precipitate followed by membrane filtration.
         2.1.3   Slaking of dolomite
         The other    raw  material, solid dolime (calcium oxide/magnesium oxide) has      to be slaked before
         it  can  be used in the process.
         During slaking, the calcium oxide component hydrates completely while only part of the
         magnesium oxide hydrates. The chemical reaction is:
         Ca0.MgO + 2H,0 => Ca(OH), + Mg(OH),
         2.1.4   Magnesium hydroxide precipitation
         The slaked dolime is mixed with the      pretreated magnesium chloride brine (MgCl,). The     net
         chemical reaction is:
         Ca(OH)z + Mg(OH)2 + MgCl, = 2 Mg(OH). + CaCl: (aq)
         During the washing process, magnesium oxide hydrates further to form magnesium hydroxide.
         The magnesium hydroxide precipitate is washed, filtered and fed into the calciners. The calcium
         chloride is partly re-used for brine desulphurisation. The other part is used for the production of
         concentrated and prilled calcium chloride (see BREF LVIC-SO).
         2.1.5   Washing and thickening
         The   slurry containing magnesium hydroxide solids and dissolved calcium chloride, is washed
         countercurrently to remove all chlorides. During this process a flocculant is added to improve the settling
         and compaction behaviour of the magnesium hydroxide suspension. In three vacuum rotary drum filters,
         the magnesium suspension is dewatered to form a filter cake with approximately 54 wt-% solids. The
         spent brine is partly recycled to the desulphation step, while the other part together with wash-water is
         the effluent, which is neutralised to prevent it from silting up.
         3 Dry section:
         3.1 The    production of magnesium compounds
         Dry processes applied in the production of magnesium compounds include: calcining, briqueting, and
         sintering.
         3.1.2   Calcining
         A   part of the magnesium hydroxide filter cake is directly fed into the top of the   two  multistage
         Herreshoff calciner furnaces (F3101 and F3201). The material dries further and calcines to form caustic
         magnesium oxide.
         The other part of the filter cake is fed to the  pre-dryer. Thereto  it is mixed with the already dried
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         Mg(OH)2 and is dosed with the hot off-gases to the pre-dryer. This pre-dried magnesium hydroxide filter
         cake is fed  halfway into the calcining furnace. This calcination process is carried out at controlled
         temperatures of up to 1100 eC, using natural gas/air burners. The chemical reaction of calcining is:
         Mg(OH)2 = MgO + H.0
         The caustic powder produced is transported to the briquetting section or sold as caustic MgO
         powder.
         3.1.3  Briquetting
         In two  stages, the caustic magnesium oxide powder is compacted into almond shaped briquettes.
         During pre-compression, caustic MgO mixes with sieved material from the second step. This pre-
         compressed material is further compressed in the second step. Subsequently these so called ‘green’
         briquettes are sieved. The fine material is returned to the pre-compression step, while the coarse
         fraction is fed into the shaft kilns for sintering or supplied to the market and sold as it is.
         3.1.4  Sintering
         The green briquettes are sintered (dead-burned) in two shaft kilns (F3102 and F3202). The shaftkilns
         have an oval shaped crosssection and a packed bed.
         The shaft kiln is gas-fired. A mixture of natural gas and primary air is burned with preheated secondary
         air. The green briquettes are fed continuously to the shaft kiln (packed bed). The briquettes sag slowly in
         the kiln during which they are compressed because of the high temperature. In the bottom section of
         the kiln, the hot briquettes are cooled by secondary air. This preheated secondary air is responsible for
         the complete combustion of the natural gas. The residence time in the shaft kiln is controlled by a drag
         bar, which is a moving beam on a table, that removes the product from the kiln. A temperature of up to
         2200 °C is reached, to produce dense high purity dead-burned magnesia. After leaving the shaft kiln, the
         product is cooled and stored in bunkers. The hot off-gases from the product cooler are dedusted and are
         mixed with the off-gases from the kiln.
         4 Present   consumption and emission levels
         The main environmental issues associated with the        production of magnesium compounds      are air
         pollutants, the  use of water and energy and waste      production.
         4.1 Use of raw material and energy      consumption
         For the  production of one   tonne of dead-burned     magnesia 1.2 tonnes of dolime as well as 1.2 tonnes of
         MgCI2 brine is needed. Energy used for mining is mainly for compressing and pumping. The main energy
         consumption for the production of magnesium compounds is for the calcining and sintering processes.
         The energy intake is both electricity and natural gas. The overall energy use for the production of
         magnesium oxide is about 10.5 GJ/tonne MgO
         4.2 Emissions to air
         The emissions to air   are mainly off-gases from calcining and sintering containing NOx, CO, CO», SO and
         magnesia containing dust (MgO). Also small amounts of chlorides and fluorides are emitted due to the
         decomposition of salts caused by the high sintering temperature.
         4.2.1 Dust
         The total dust emission of the magnesia plant in the Netherlands is about 0.2 kg dust/tonne of magnesia
         (as MgO) produced (BREF LVIC-SO (2007) <0.3 kg/ton). The overall mean dust concentration is 35
         mg/Nm?3, mainly    due to the  new  ESPs  (electrostatic precipitator).
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         The main     sources of dust emissions are the off-gas emissions from calcining and sintering. At the
         briquetting section, air is collected to prevent MgO dust emissions. The filtered air is emitted separately
         from the chimney stack. The dolime intake and the loading of the end DBM product result in minor dust
         emissions compared with the off-gases. The air here is also collected from the belt conveyor as well as
         the loading equipment to prevent dust emissions. After dust filtering, this air is released at roof level to
         the atmosphere.
         4.2.2 NOx, CO and CO,
         Due to the combustion processes of natural gas and air, in both         calcining and sintering, there are
         emissions of    nitrogen oxides as well as carbon oxides. The carbon      content of natural gas, about
         2 kg  CO2/Nm?    also contributes to the CO, emissions.
         4.2.350,, Cl-and     F
         Because of the very     high sintering temperature, even salts of remaining chlorides, sulphates and
         fluorides evaporate or decompose to volatile constituents. A part of these volatile constituents
         condenses in the top of the shaft kiln or in the off-gas channel before the scrubber.
         Emission of HCl and Fluor in the off gasses is <30 and       < 1 mg/Nm?
         5 Calcining and sintering
         The indicative emissions from the magnesia plant in the Netherlands in the year 2017 from the
         calcining furnaces and the sintering kilns are given separately, because they each emit through          a
         separate chimney     stack
         Calcining furnaces off-gas emissions (kg/tonne MgO production):
              eo
                   SO, n.a. (not available)
              e    CO       0.2-2
              e    NOx 0.1-0.5
         Sintering kilns off-gas emissions (kg/tonne MgO production):
         The SO, emission of the shaftkiln of gasses     are reduced by a two stage scrubber system
              e
                   SO;      0.05-0.10
              e    CO       1.2-3
              eo
                   NO       2-3
         The total indicative NOx emission for     calcining and sintering  is 2.1- 3.5 kg NOx (as NO)/t
         MgO.
         The total indicative CO emission for     calcining and sintering is about 1.4 5 kg CO/t MgO.
                                                                                         -
         The total indicative CO, emission     for calcining and sintering is about 570 kg CO2/t MgO.
         6 Abatement      techniques
         6.1 Abatement      techniques for the   emissions of dust
         Description
         Abatement      techniques for calcining, briquetting and sintering    are described below.
         6.1.1   Calcining
         The hot    off-gas from the calcining furnace, including MgO dust, is used in the magnesium hydroxide pre-
         dryer to evaporate the water from the filter cake. After the pre-dryer, a cyclone separates the solid dust
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         particles from the off-gases, which are sent back to the calcining furnace. Subsequently, the fine dust is
         caught in an electrostatic precipitator (ESP). The cleaned off-gas is released to the atmosphere by the
         chimney stack. The separated dust is transported to the bag filter and fed back halfway into the calcining
         furnace. The electrostatic precipitators were replaced by new ones, and hence they now remove about
         99 % of the dust from the offgases of the calcining furnace.
         6.1.2 Briquetting
         In several  places of the briquetting section, air is collected to prevent dust from being released into the
         production area. This exhaust air is cleaned by a bag filter. The separated dust is returned to the
         briquetting section while the cleaned air is emitted separately from the chimney stack.
         6.1.3 Sintering
         The combustion gases leave the shaft kiln at the top by the off-gas channel. The hot off-gases         are treated
         in three steps. First, the larger dust particles are separated in a drop-out box. Subsequently, a      cyclone
         separates the smaller particles. This so-called ‘shaft kiln dust’    can either be fed back to the process or
         gathered and sold.    For the second step  cleaning  a venturi scrubber is installed, which ,along with HCl and
         SO, also   removes   volatile substances and dust. In the third    cleaningstep, magnesiumhydroxide
         suspension is injected into a spraying gasses scrubber with reciculated liquid to reduce the SO,. The
         treated off-gasses saturated with water vapour is led through a demister and mixed with the hot ait of
         the product cooler. The combined stream is released to atmoshpere through the chimney stack of the
         shaftkilns.
         6.1.4 Achieved environmental benefits
         Abatement     techniques used for the   emission of dust in the   production of magnesium compounds
         allow for the reduction of MgO dust and SO, released to the atmosphere.
         Emission concentrations of SO, < 180 mg/Nm? can be achiefed.
         6.1.5 Cross-media effects
         No side effects  or disadvantages   are  caused  by the implementation of this technique.
         6.1.6 Operational data
         In the calcination section average dust concentration of <35        mg/Nm?   is reached. In the sintering section,
         dust emissions   are  reduced to about 115   mg/Nm?3.
         The protection of the environment.
         Example plants: The dead-burned magnesia plant         in Veendam, the Netherlands (BREF —LVIC-SO).
         Applicability
         Applicable to the plants producing dead-burned magnesia by the           so called “wet proces”.
         Driving force for implementation: The protection of the environment.
         6.2 Abatement     techniques for the   emissions of NOx and CO
         Description
         Abatement     techniques for calcining and sintering are described below.
         6.2.1 Calcining
         For the  calcining ovens, burner   regulation is standard   procedure. The   CO emission of the
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         calciners is  high due to non-optimal burning conditions. With new equipment, regulating the
         air/gas  ratio by flow, the burning efficiency is going to be increased and the CO emission will
         be lower [56, InfoMil, 2004].
         6.2.2 Sintering
         The shaftkiln is  a packedbed    kiln full of MgO briquetees,   so  low NOx-burners   can not  be used because of
         the mechanical stress.
         From   an  evaluation  study in the late 1990s, it appeared that SCR (selective catalytic reduction) used as
         the deNOX     technique for the combustion gases from the sintering kilns is very uncertain technically as
         well as economically. This is mainly due to the uncertainty in the life-time of the catalyst and the strong
         pollutive nature of the off-gases [56, InfoMil, 2004]. The emissions of NOx and CO from the shaft kilns for
         sintering have, therefore, been reduced by processintegrated measures. The quantity of secondary
         excess air is reduced to achieve stoichiometric burning conditions. Secondary excess air is used for
         cooling the hot product from the kiln.
         Therefore, the decrease of temperature must be compensated with extra water injection. So due to
         proces optimalisations the NO, emission has been reduced by about 50%.
         The accompanying CO emission can be decreased by changing the depth of the burners [56, InfoMil,
         2004].
         6.2.3 Achieved environmental benefits
         Substantial reduction of NOx and CO emissions to the          atmosphere.
         6.2.4 Cross-media effects
         No information submitted.
         6.2.5 Operational data
         In the  sintering section, the  CO emission is in the range of 1.2    -
                                                                                 3  kg/tonne MgO produced    and the NOx
         emission is in the range of 2    —
                                             3 kg/tonne MgO produced.
         The total indicative NOx emission for       calcining and sintering is 2.1- 3.5 kg NOx (as NO2)/t
         MgO. The total indicative CO      emission for calcining and sintering is 1.4 5 kg CO/t MgO.
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