Classifications

• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

Definitions

• the invention relates to a method for the treatment of
• Waters in particular for pH stabilization, pH increase and / or neutralization of waters, wherein a feedstock is introduced into a body of water to be treated. Furthermore, the invention relates to the use of an unburned lime product for the treatment of waters. Finally, the invention comprises an aqueous suspension containing the starting material and a vessel for introducing the feed into a body of water to be treated.
• Open-pit mining technology results in cavities in the utilized landscape that fill with groundwater and surface water.
• the rising groundwater and the associated geological and chemical conditions in the newly created overburden form a lake landscape characterized by very acidic waters.
• Another problem is the persistent supply of acidity into such waters with the inflowing groundwater.
• a method for improving the water quality of acidic waters wherein in a first treatment stage, at a low pH, a calcium or calcium / magnesium-containing feed and in a second stage, at a higher pH, sodium hydroxide is used. On the one hand, this process is high overall
• the concentration of the feedstock suspension should be kept lower than in the low pH range of ⁇ 4.5.
• burned reactive products such as quicklime or hydrated lime
• unburned inert products such as limestone powder are used.
• the disadvantage of this method is that due to the efficiency when using unburned lime products in pH ranges of> 4 large product quantities are to bring with high entry costs.
• a high time requirement is required, the short-term reaction times required
• the starting material is that its production involves a high level of logistics and equipment.
• the calcined lime particles are covered by a plaster layer.
• the gypsum layer can cause the particles to become coarser, sink faster and accumulate at the bottom of the water, where they undesirably increase the pH.
• a disadvantage of the gravel is further that less reaction surface is available for neutralization of the water. As a result, this may result in the resulting
• unburned lime products such as commercial calcium carbonate, which is marketed as limestone flour with D-50 values of> 12] i, it comes in the pH range of> 6 due to the low solubility and the low Reactivity to low process efficiencies with high sedimentation levels of unreacted feed. Therefore, such unburned lime products are considered, if at all, only at lower pH and more reactive for complete neutralization
• an object of the invention was to provide a cost-effective method with which it is possible in a simple and economically effective manner to treat acidic waters and also over a longer
• a feedstock is introduced into a body of water to be treated in accordance with the above-mentioned prior art.
• a feedstock which contains an unfired lime product, in particular a fine-grained unbaked lime product, wherein the unfired lime product has a grain size with a fraction ⁇ about 10 m of 50%.
• Lime products lie in the fact that, before it can ever come to a reaction with the less reactive feedstock, this sinks to the bottom of the water and can no longer be available for the reaction. That's how it is Use of commercially available CaC0 3 (eg limestone flour, D-50 value> 12 ⁇ ) in the pH range of> 6 due to the low solubility and low reactivity to low
• Feedstock contained unfired lime product by its fine grain size floatable or Schwebecolor and a
• the inventive method provides an ecologically safe, economical solution for the inlake treatment of acidic waters, with a sustainable adjustment of the pH to ⁇ 6 at a sufficiently high efficiency of
• feedstock even when acidity is supplied via groundwater or other sources, over periods of up to several months.
• waters are understood to mean all types of waters, in particular surface waters.
• the inventive method is particularly suitable for the treatment of surface waters, in particular of natural lakes and / or mining or opencast mining lakes.
• the invention is particularly for the treatment of open acidic waters, in particular of
• Such waters are often characterized by re-acidification by a prolonged supply of acidity with the inflowing groundwater or other acidic sources.
• fine graininess of the starting material or of the lime product is mentioned here, then in particular a grain size with at least a fraction ⁇ about 10 ⁇ m of 50%, an average particle size of less than about 40 ⁇ m and / or particle sizes of about 0.01 to about> 60 ⁇ ⁇ meant.
• a preferred embodiment of the invention provides that the starting material contains an unfired lime product which has a particle size of ⁇ about 10 pm of> 50%. Optimal results are obtained when the unfired lime product has a grain size with a proportion ⁇ about 4 ⁇ of ⁇ 50%, in particular a proportion ⁇ about 3 microns of ⁇ 50%.
• unburned lime products with coarser grain size does not come to the long-lasting neutralization according to the invention and a cyclic aftertreatment is necessary. This is probably due to the fact that feedstocks, in particular the unfired lime products contained therein with a coarser Grain are not hoverable and therefore fall to the bottom of the lake, which means that they are not for a longer period of time for a neutralization reaction
• Range specified in ⁇ the particle diameter corresponds to the particle size distribution in the form of the D-50 value which is widespread in lime products. Under a D-50 value of 10 ⁇ the skilled person understands that 50% or more of the particles have a particle diameter smaller than 10 ⁇ . There is a volumetric evaluation of the measurement results. Standard methods for determining the grain size of lime products are known to the person skilled in the art. The determination of the particle sizes, their distribution and the mean particle size has proven to be particularly practical
• Laser diffraction which is also called laser granulometry or laser diffraction proven (see ISO standard 13320-1). Unless indicated otherwise, the degrees of granulation and particle sizes given here are values determined by means of volumetric laser diffractometry. In this case, the particle size x ( ⁇ ) at the volume passage (D) of 50% is indicated as D-50 value.
• the unfired lime product has a grain size with an average particle size of about 0.05 to about 40 ⁇ m, in particular an average particle size of about 0.05 to about 20 ⁇ m.
• the unburned lime product may also have the aforementioned particle size distributions (D-50 values).
• the starting material contains an unfired lime product having the aforementioned D-50 values and / or a grain size having an average particle size of about 0.05 to about 40 pm, in particular an average particle size of has about 0.05 to about 20 ⁇ .
• fine-grained unbaked lime product to a re-acidification by inflow of acidic groundwater, which can not be buffered come. This is probably because feedstocks, in particular
• Embodiment of the invention are also realized in that the starting material contains an unfired lime product, which has a grain size of about 0.01 to about 60 ⁇ ⁇ , in particular from about 0.01 to about 40 ⁇ has.
• the unfired lime product has a grain size of about 0.01 to about 20 ⁇ or a grain size selected from the group consisting of less than about 60 ⁇ , less than about 40 ⁇ , less than about 30 ⁇ and less than about 20 ⁇
• Unburned lime products with a coarser grain size do not show the inventive, long-lasting
• unburned lime product also have one of the previously described particle size distributions (D-50 values) and / or one of the previously described mean particle sizes.
• Water is introduced, characterized in that for pH stabilization of weakly acidic surface waters in the pH range of 5 to 7.5 as the feedstock an unbaked fine-grained lime product is used with a share of CaC0 3 of> 85%, the feedstock thereby a grain size from 0 to 40 ⁇ and by means of entry systems in a
• Embodiment of the invention are also realized by the fact that the feedstock for pH stabilization of weak acidic surface waters in a suspension with water is introduced into the waters to be treated, characterized in that for the pH stabilization of weakly acidic surface waters in the pH range of 5.0 to 7.5, the feedstock of a fine microcrystalline
• Sedimentary rock which consists of> 85% photosensitized carbonic acid precipitated calcium carbonate and has a total age of 50 to 140 million years, is an unbaked fine-grained lime product and the
• Feedstock has a grain size of 0.1 to 40 ⁇ i and the proportion ⁇ 4 pm while ⁇ 50%.
• the feedstock may have a grain size of 0.1 to 20 ⁇ while the proportion ⁇ 3 ⁇ preferably ⁇ 50%.
• lime product is understood to mean all products obtained from carbonate rocks.
• lime product used here should also include dolomitic limestone and dolomite.
• Limestone based lime products have delivered optimal results in practical trials.
• the starting material used is preferably an unbaked lime product.
• the feed consists essentially of unbaked lime products.
• the starting material in addition to unbaked lime product and fractions of burned
• a natural substance which fulfills this requirement and is also present in the fine granularity provided according to the invention is, for example, fine chalk.
• Fine chalk is a fine one
• Microcrystalline sedimentary rock which consists of> about 85% by weight of precipitated by photosynthetic carbonic acid withdrawal calcium carbonate.
• Fine chalk usually has an approximate age of about 50 to about 140 million years. Since chalk is ready to use commercially available, it represents a particularly suitable for use in the method according to the invention fine-grained lime product.
• microcrystalline sedimentary rock such as fine chalk without elaborate grinding a very finely divided feedstock can be provided.
• Optimal results in this case provides a microcrystalline sedimentary rock such as fine chalk, which preferably has a mean grain size of about 0.01 to about 20 ⁇ for use as feedstock or feedstock.
• the proportion ⁇ about 4 ⁇ is preferably ⁇ 50%.
• the sedimentary rock preferably has an approximate age of about 50 to about 140 million years. Also mixtures of fine chalk and other sedimentary rocks are possible.
• the process according to the invention can in particular Stabilization, the pH increase and / or the neutralization of waters serve.
• the feed according to the invention is used for the pH stabilization of acidic waters.
• Sauer here means a pH of the body of less than about 7.5, in particular between about 2 and about 7.5.
• the feedstock according to the invention is also suitable for pH stabilization of weakly acidic waters, that is
• a strongly acidified body of water can first be subjected to a start neutralization in a first step or at least the pH can be raised to the weakly acidic pH range. This can be done both by incorporation of an unburned lime product with commercial grain size, such as limestone, as well as with others, the
• the body of water is treated with the starting material according to the invention, in particular one containing an unfired fine-grained lime product with a particle size of ⁇ about 10 ⁇ m of> 50%.
• feedstock even when acidity is supplied via groundwater or other sources, over periods of up to several months.
• unburned lime product or feed can also be used only for the installation of a buffer cloud in a body of water, which has previously been neutralized by other methods and / or already had a suitable pH of its own accord.
• Feedstock is introduced in a suspension with water in the water to be treated or applied to the water to be treated.
• the present invention provides an aqueous suspension containing at least one unburned lime product according to the invention, in particular one having a particle size of less than about 10 ⁇ m of 50%, for the treatment of waters.
• the suspension according to the invention can be mixed shortly before entry into the body of water to be treated. However, they are also ready to use, storable
• Suitable concentration ranges for the aqueous feedstock suspension used in the process according to the invention are, in particular, concentrations of about 0.1 to about 40% by weight. For many applications, a suspension concentration of about 1 to about 15% by weight is particularly practical. For economic and procedural reasons, it has proved to be advantageous if the starting material
• Treating waters batchwise the batch entry can be done for example by means of remediation vessels and / or by means of one or more piping distribution systems. This can the refurbishment ship and the
• Pipe distribution system also work in an alternating operation for the feed intake.
• the entry can be made by means of a refurbishment vessel and at night the entry can be made by means of a
• Alkaline substances are known, for example, from WO 2009/037194 A2, whose disclosure content is hereby incorporated by reference.
• refurbishment vessel it refers to all vessels that are capable of handling alkaline feedstocks
• Feedstock according to the invention by means of watercraft proved to be particularly advantageous.
• the invention further provides a watercraft for introducing a feedstock according to the invention, in particular a green lime product with a
• a further preferred embodiment of the invention provides for the introduction of the feedstock according to the invention by means of pipeline distribution systems.
• Pipe distribution systems which are suitable for introducing alkaline feedstocks into the treatment of acidic waters are described, for example, in DE 102009049739 A1. The disclosure of this document is hereby expressly incorporated by reference.
• the piping distribution system operates in an alternating operation for the feedstock supply.
• Pipe distribution system with feed entry is set from a wind speed of ⁇ about 1 m / s. At a lower wind speed that remains
• Pipeline distribution system with feedstock entry out of service In this case, the pipeline distribution system can continue to be operated and rinsed with seawater without adding material.
• Feed input such as amount
• the entry of the input material can be done both by overwater and underwater distribution.
• Feedstock distribution takes place via water, while at Shore area underwater distribution of the feedstock takes place.
• the feedstock according to the invention also provides optimal results in areas of water that are difficult to access with a watercraft or pipe laying. It has been shown that the buffer cloud formed by the fine-grained feedstock in the water also in
• Inlet entry takes place at a natural confluence or at an influx into the water to be treated. This is due to flow-induced spread of
• Feed cloud in the water an optimal distribution of the feed.
• Feedstock according to the invention can be used in suitable Local conditions are observed by aerial photographs over the treated waters.
• the buffer cloud can be formed with the process according to the invention for periods of up to 3 months, without a complete reduction of feed to the riverbed. This is especially true in the case where the acidity input via groundwater or other sources is less than the alkalinity potential of the buffer cloud.
• the advantage of the formation of buffer clouds is that consuming short-term successive aftertreatments avoided and longer periods such as winter periods with
• the input material is a fine chalk containing 90% by weight of CaC0 3 .
• the grain size of the starting material is determined using a laser diffraction sensor (Helos, Sympatec).
• the D-50 value of the starting material is between 2 and 4 ⁇ .
• the starting material has a grain size of ⁇ 20 ⁇ .
• the order of the feedstock suspension takes place in another area of the sea surface.
• the application of the feed suspension to the same takes place only once a day
• the total amount of feed is entered into the water in a period of about 2 weeks.
• the pH is about 7.0 and the
• Treatment according to the invention can be achieved.
• Fine chalk of approx. 220 t in the water body is only required after approx. 9 months if the acidity of the body of water remains the same.
• An open pit residual sea had a weakly acidic pH.
• unfired limestone flour with a D50-value of> 12 ⁇ ⁇ was used.
• the feed was introduced into the water by a watercraft. Much of the feed sank to the bottom of the lake without reacting.

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• Life Sciences & Earth Sciences (AREA)
• Hydrology & Water Resources (AREA)
• Engineering & Computer Science (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Processing Of Solid Wastes (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Removal Of Specific Substances (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)

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• 2011
  • 2011-12-19 CN CN201180065225XA patent/CN103354804A/zh active Pending
  • 2011-12-19 WO PCT/EP2011/073269 patent/WO2012080514A1/de active Application Filing
  • 2011-12-19 EA EA201300718A patent/EA024888B1/ru unknown
  • 2011-12-19 DE DE202011110411U patent/DE202011110411U1/de not_active Expired - Lifetime
  • 2011-12-19 EP EP11801735.9A patent/EP2651832A1/de not_active Ceased
  • 2011-12-19 CA CA2821853A patent/CA2821853A1/en not_active Abandoned
  • 2011-12-19 BR BR112013015226A patent/BR112013015226A2/pt not_active IP Right Cessation
  • 2011-12-19 US US13/994,490 patent/US9290395B2/en not_active Expired - Fee Related

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