Acrylamide free polymer for dewatering applications

The present application is directed to an acrylamide-free polymer for dewatering of sludge water streams, a water-in-oil emulsion comprising the polymer, a process and the use of the polymer for dewatering of sludge water streams.

Global rate of sedimentation and total volume of sediments has increased dramatically within the recent years. Dealing with these sediments responsibly has become an important issue to minimize the impact on the environment. Sediments collect not only in staggering volumes in our rivers, waterways and harbors but are also generated as a consequence of industrial activity in numerous economic sectors. At present, hundreds of millions of tons of these sediments require effective dewatering in order to be disposed or re-used. Furthermore, competition for water for industrial, agricultural and human consumption increases, making water re-use an increasingly relevant topic.

A very efficient way to dewater sediments is by use of flocculation technology. This technology involves the use of chemical aids, including polymers, which aggregate smaller silt particles to form larger composites ("floes") to facilitate separation from the water.

As all sediments are different, effective dewatering presents a technical and economic challenge, especially where very fine sediments are concerned. In addition, silt materials are often contaminated, e.g. by heavy metals. The prevention of leach of heavy metals from the dewatered sediment is therefore mandatory. Further, re-use of the remaining water strongly depends on the use of non-toxic and environmentally friendly chemicals.

Within the state of the art, polyacrylamide-containing polymer compositions are known to be effective flocculants and mostly used in industrial-scale applications. Within the WO

2002/083258 such polyacrylamide-containing polymers are described as suitable for the flocculation of sediments with a high solid content.

Such compositions often still contain a certain amount of acrylamide. Acrylamide is known as a potential occupational carcinogen by U.S. government agencies and classified as a Group 2A carcinogen by the IARC. The European Chemical Agency added acrylamide to the list of substances of very high concern in March 2010. In animal models, exposure to acrylamide caused tumors and was found to be genotoxic (EFSA, 4. Juni 2015). The WHO recommends a guideline value of 0.5 g/l, with the additional proviso that exposure should be reduced to as low a level as technically achievable.

According to the WHO, the most important source of drinking-water contamination by acrylamide is the use of polyacrylamide flocculants that contain residual acrylamide monomer. Every effort should be made to limit free acrylamide monomer in polyacrylamide used for water treatment, and water suppliers should also make every effort to ensure that residual acrylamide in drinking-water is kept as low as is technically feasible. In particular, if acrylamide is controlled by limiting the amount dosed, overdosing should always be avoided (Report of a Joint FAO/WHO Consultation, WHO Headquarters, Geneva, Switzerland 25-27 June 2002 Issued).

Thus, there is a high need for new, environmentally friendly and safe chemicals which further guarantee efficient flocculation of sediments.

The inventors of the present invention have met this need by developing an acrylamide-free polymer for dewatering of sludge water streams characterized by a sedimentation capacity Csed Of more than 70 1 /min.

The polymer according to the present invention has been found to be particularly

advantageous as it guarantees a speedy flocculation of all common sediments / sludge water types. Further, the polymer according to the present invention enables the retention of rare earth minerals and/or metals, which can be recovered from the flocculated sediments for further applications. Therefore, economic benefits are not only due to a higher speed of flocculation compared to state of the art material but also due to the possible recovery of valuable sludge components. In addition, the polymer according to the present invention will retain toxic compounds such as toxic heavy metals (for examples mercury, cadmium, tin and/or zinc) or their organometallic species within the floes.

Acrylamide (or acrylic amide) is a chemical compound with the chemical formula C3H5NO (lUPAC prop-2-enamide), which polymerizes readily to polyacrylamides. Acrylamide is derived through hydrolysis of acrylonitrile as a white odorless crystalline solid, soluble in water, ethanol, ether, and chloroform. Acrylamide decomposes in the presence of acids, bases, oxidizing agents, iron, and iron salts. It decomposes non-thermally to form ammonia. Thermal decomposition produces carbon monoxide, carbon dioxide and oxides of nitrogen.

Within the present application, the term "polymer" refers to a molecule whose structure is composed of multiple repeating units, from which originates a characteristic of high relative molecular mass and attendant properties. The units composing polymers derive from molecules of low relative molecular mass, so called "monomers". Polymers may be of synthetic or natural origin. Within the present application, the term "polymer" refers to polymers of synthetic origin.

Within the present application, the term "acrylamide-free" is referring to any polymer, which has not been generated/polymerized by the use of the monomer acrylamide. Within a particularly preferred embodiment, the "acrylamide-free polymer" has been generated by radical polymerization. The term "sedimentation capacity" is a parameter, which depicts the volume of water, which can be separated (dewatered from the sludge) within a certain amount of time also depending of the concentration of polymer (within the present invention the acrylamide free polymer functions as the flocculant) used and the turbidity of the supernatant after the flocculation. The "sedimentation capacity" is therefore a parameter which shows the performance quality of a certain flocculant (also referred to as flocculation agent or in case of the present invention the acrylamide free polymer or in case of the comparative examples the e.g. acrylamide polymers)

The sedimentation capacity is calculated as follows:

Vt 1000

Csed =— *—

V0 * ts _ln( Tsup^ _cpol

Wherein V ₀ represents the total volume of the sludge sample before addition of the flocculant (within the present invention the acrylamide free polymer) (ml_), V _t represents the volume of the supernatant (dewatered water from the sludge sample at the time t _s ) (ml), t _s represents the sedimentation time (min), T1 represents the turbidity of the sludge sample diluted to 1 mg/kg solids (FNU), ln(T _sup /T1 ) represents the natural logarithm of the ratio of turbidity of the supernatant (FNU) and T1 measured after 30 min and c _p0 i represents the concentration of the polymer (within the present invention the acrylamide free polymer which functions as the flocculant) compared to the solids present in the sludge sample (kg/1000kg solids).

Within the present invention, the sedimentation capacity is preferably higher than 70 1/min, further preferred higher than 1 10 1/min in particular preferred higher than 200 1 /min and most preferred higher than 300 1/min. Within another preferred embodiment, the

sedimentation capacity is selected within the range of from 70 to 2000 1/min, further preferred of from 100 to 1000 1 /min and most preferred of from 200 to 700 1/min.

Within the present invention the ratio of volume V _t and sedimentation time t _s is preferably selected from the range of from 6 to 100 mL/min, preferred of from 10 to 70 mL/min, further preferred of from 14 to 60 mL/min, in particular preferred of from 20 to 55 mL/min and most preferred of from 25 to 55 mL/min.

Within the present invention, the term "sedimentation time" is to be understood as referring to the time of dewatering of the sediment or sludge through flocculation (formation of floes) and subsequent deposition of the floes, forming a supernatant on top of the deposited floes. The sedimentation time is measured by a 30% volume change of the volume of the supernatant e.g. how long it takes to dewater 30 ml_ supernatant from a 100 ml_ sludge sample. The measurement method of the sedimentation time is also described within the examples.

Within the present invention the turbidity of the filtrate is preferably less than 730 FNU, preferably less than 650 FNU also preferred less than 600 FNU, in particular preferred less than 410 FNU and most preferred less than 300 FNU. It is further preferred to select the turbidity within the range of from from 1 to 730 FNU, preferably of from 5 to 650 FNU, further preferred of from 9 to 600 FNU, in particular preferred of from 10 to 410 FNU and most preferred of from 1 1 to 300 FNU. According to the present invention, the turbidity of the filtrate is measured photometrically by a HACH 2100Qis portable turbimeter calibrated with 4 standards (10, 20, 100 and 800 FNU) according to ISO 7027.

Within the present invention the concentration of the polymer c _p0 i is preferably selected within the range of from 0.01 to 2.5 kg/1000kg solids, preferably of from 0.05 to 2.0 kg/1000kg solids, further preferred of from 0.1 to 1 .0 kg/1000kg solids and most preferred of from 0.15 to 0.7 kg/1000kg solids.

Within the present invention the temperature of the filtrate is preferably selected from the range of from 1 to 50 °C, further preferred of from 4 to 40 °C, in particularly preferred of from 8 to 35 °C and most preferred of from 10 to 22 °C.

Within the present invention the term "sludge water" is to be understood as referring to any liquid composition comprising at least 60 wt.-% H20 and at least 5 wt.-% of solids of any kind. Within the present invention, the term "solids" preferably refers to silt particles of a granular material of a size between 0.002 mm and 0.063 mm (ISO 14688). Further, "solids" also refers to clay particles of a grain size of less than 0.002 mm. "Sludge water" may further comprise rare earth minerals and metals, salts but also toxic substances such as heavy metals (for examples mercury, cadmium, lead, chromium, nickel, copper, tin and/or zinc), organometallic compounds (such as tetrabutyltin) and toxic organic compounds (polycyclic aromatic substances and/or halogenated organic compounds). Sludge water may originate from marine waters or freshwaters but also from mining, dredging, civil engineering or oil production sites.

"Sludge water" according to the present invention may also comprise any kind of waste water known to a person skilled in the art. The term "waste water" as used within the present application particularly refers to any liquid comprising at least 60 wt.-% of H20, which has been adversely affected in quality by anthropogenic influence. Waste water may also contain a certain amount of solids but is further characterized by its origin from a combination of domestic, industrial, commercial or agricultural activities, surface runoff or stormwater, and from sewer inflow or infiltration. The "dewatering" according to the present invention is carried out by contacting the polymer according to the present invention with the sludge water, a subsequent flocculation and final filtration of the flocculated solids. Dewatering is preferably carried out by use of a dewatering unit such as geobags, sewn bags of various sizes constructed from woven or nonwoven geotextile material of various specifications, which is characterized by retaining the flocculated solids but releasing the liquid contained in the sludge water. However, within the scope of the present invention any kind of dewatering known to a person skilled in the art as suitable for the inventive purpose can be applied (further exemplary dewatering units are filter or belt presses).

Within another preferred embodiment of the present invention, the acrylamide-free polymer has an overall anionic charge. The term "overall anionic charge" as used within the present invention is to be understood as comprising any acrylamide-free polymer with more than 50 mol-% anionic charges, preferably more than 55 mol-% anionic charges, more preferred more than 60 mol-% anionic charges and most preferred more than 65 mol-% anionic charges. Particularly preferred are acrylamide-free polymers with from 55 to 100 mol-% anionic charges, more preferred from 65 to 95 mol-% anionic charges and most preferred from 70 to 90 mol-% anionic charges.

Within another preferred embodiment of the present invention, the acrylamide-free polymer has an average molecular weight (Mw) of more than 500,000 Da, more preferred of more than 700,000 Da, further preferred of more than 800,000 Da and most preferred of more than 1 ,000,000 Da. Particularly preferred are acrylamide-free polymers with from 500,001 Da to 20,000,000 Da, preferably from 650,000 to 10,000,000 Da and most preferred from 750,000 to 5,000,000 Da. Within the present invention, the weight-average molecular weight (Mw) is to be measured by gel permeation chromatography against polyacrylate standards using PSS NOVEMA MAX Guard columns (size 1 x30 A and 2x1000 A; 10 μηι, 300 mm x 8 mm).

Within another preferred embodiment of the present invention, the acrylamide-free polymer comprises from 50.1 to 100 mol-% polyacrylic acid and/or polymethacrylic acid and/or salts of polyacrylic and/or polymethacrylic acid, preferably from 55 to 98.0 mol-%, further preferred of from 60 to 90 mol-%, particularly preferred of from 65 to 85 mol-% and most preferred of from 68 to 82 mol-% polyacrylic acid and/or polymethacrylic acid and/or salts of polyacrylic and/or polymethacrylic acid. Salts of polyacrylic acids and/or polymethacrylic acids are preferably selected from the group consisting of Na ⁺ , K ⁺ , Mg ²⁺ , Al ³⁺ , NRV (FT = hydrogen, C1 -C4-alkyl or C1 -C4-hydroxylalkyl) and Ca ²⁺ containing salts.

Within another preferred embodiment of the present invention, the acrylamide-free polymer comprises from 0.001 to 49.9 mol-%, preferably of from 5.0 to 49 mol-%, further preferred of from 10.0 to 35 mol-% and most preferred of from 15.0 to 25.0 mol-% of a repeating unit consisting of the following structure according to formula I:

wherein R1 is hydrogen, methyl or ethyl, carboxymethyl

wherein Y is OR2 or NR2R3,

wherein R2 is hydrogen, a linear alkyl group having 1 to 50 carbon atoms, a branched alkyl group having 1 to 50 carbon atoms, a linear monohydroxyalkyi group having 2 to 6 carbon atoms, a branched monohydroxyalkyi group having 2 to 6 carbon atoms, a linear

dihydroxyalkyl group having 2 to 6 carbon atoms, a branched dihydroxyalkyl group having 2 to 6 carbon atoms, a linear primary, secondary, tertiary or quarternary aminoalkyi group having 2 to 6 carbon atoms, a branched primary, secondary, tertiary or quarternary aminoalkyi group having 2 to 6 carbon atoms , an ethylenically unsaturated free radical polymerizable group capable of polymerization, a linear sulphonic acid alkyl group having 2 to 6 carbon atoms or its salts or a branched sulphonic acid alkyl group having 2 to 6 carbon atoms or its salts, wherein R3 is a linear alkyl group having 1 to 50 carbon atoms, a branched alkyl group having 1 to 50 carbon atoms, a linear monohydroxyalkyi group having 2 to 6 carbon atoms, a branched monohydroxyalkyi group having 2 to 6 carbon atoms, a linear dihydroxyalkyl group having 2 to 6 carbon atoms, a branched dihydroxyalkyl group having 2 to 6 carbon atoms, a linear primary, secondary, tertiary or quarternary aminoalkyi group having 2 to 6 carbon atoms, a branched primary, secondary, tertiary or quarternary aminoalkyi group having 2 to 6 carbon atoms , an ethylenically unsaturated free radical polymerizable group capable of polymerization, a linear sulphonic acid alkyl group having 2 to 6 carbon atoms or its salts, a branched sulphonic acid alkyl group having 2 to 6 carbon atoms or its salts or morpholine.

Acrylamide-free polymers comprising from 15 to 30 mol-%, with a general structure according to formula I as defined above have been found to show particularly rapid formation of floes with t _s < 1 min.

Within another preferred embodiment of the present invention, the acrylamide-free polymer comprising a co-monomer wherein the co-monomer is selected from the group consisting of 2-methyl-2-(1 -oxo-2-propenyl)amino-1 -propanesulfonic acid and its salts, 4- acryloylmorpholine, N,N'-dimethyl-2-propenamide, N,N'-diethyl-2-propenamide, N-isopropyl- 2-propenamide, hydroxyethyl-2-propenamide, Ν,Ν'-dimethylaminoethyl methacrylate, Ν,Ν'- dimethylaminoethyl acrylate , 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, maleic anhydride, itaconic acid, 2-carboxyethyl acrylate and N,N'-methylene-bis-2-propenamide and combinations thereof. Particularly preferred combinations of co-monomers are selected from the group consisting of 2-methyl-2-(1 -oxo-2-propenyl)amino-1 -propanesulfonic acid and its salts, N,N'-dimethyl-2-propenamide and 2-hydroxylethyl methacrylate. According to the present invention the term "co-monomer" is to be understood as a second monomer which is present in an amount of less than 50.0 mol-%.

According to the present invention the term "co-monomer" is to be understood as a second monomer which is present in an amount of less than 50.0 mol-%.

Acrylamide-free polymers comprising from 0.001 to 49.9 mol-%, preferably of from 1 to 40 mol-%, further preferred of from 4 to 35 mol.-% and most preferred of from 5 to 30 mol.-% of a co-monomer to as defined above have been found to lead further significantly shortening the sedimentation time.

Within another preferred embodiment, the acrylamide-free polymer is selected from the group consisting of poly(acrylic acid-co-2-methyl-2-(1 -oxo-2-propenyl)amino-1 - propanesulfonic acid) and its salts, poly(acrylic acid-co-4-acryloylmorpholine) and its salts, poly(acrylic acid-co-N,N'-dimethyl-2-propenamide) and its salts, poly(acrylic acid-co-N,N'- diethyl-2-propenamide) and its salts, poly(acrylic acid-co-N-isopropyl-2-propenamide) and its salts, poly(acrylic acid-co-hydroxyethyl-2-propenamide) and its salts, poly(acrylic acid-co- Ν,Ν'-dimethylaminoethyl methacrylate) and its salts, poly(acrylic acid-co-N,N'- dimethylaminoethyl acrylate) and poly(acrylic acid-co-2-hydroxylethyl acrylate) and its salts, poly(acrylic acid-co-2-hydroxylethyl methacrylate) and its salts, poly(acrylic acid-co-maleic anhydride) and its salts, poly(acrylic acid-co-itaconic acid) and its salts, poly(acrylic acid-co- 2-carboxyethyl acrylate) and its salts and poly(acrylic acid-co-N,N'-methylene-bis-2- propenamide) and its salts.

Within another preferred embodiment the present invention relates to a water in oil emulsion comprising

(a) 10 to 65 wt.-% acrylamide-free polymer as defined before;

(b) 10 to 65 wt.-% water;

(c) 20 to 45 wt.-% oil;

(d) 2 to 6 wt.-% emulsifier. The water in oil emulsion according to the present invention has the advantage that the polymer dissolves faster than dry polymer granules or powders or can even be directly dispensed into the dewatering-unit. Time consuming pre-dissolving of a dry preparation by a further device (as within the state of the art) is not necessary. The preparation of the water- in-oil emulsion of the present invention is described within the examples.

The term "oil" as used within the present invention is to be understood as comprising any oil known to a person skilled in the art as suitable for the inventive purpose. Within a preferred embodiment, the oil is selected from the group consisting of oils of plant or animal origin and synthetic oils, wherein synthetic oils (e.g. paraffinic and/or isoparaffinic oils, or organic solvents (e.g. cyclohexane) with low aromatic content (<1 % aromatics) and natural oils (e.g. rapeseed oils including canola, palm oils, beeswax, jojoba wax, sunflower oil, soya oil, and peanut oil and mixtures thereof are particularly preferred.

The term "emulsifier" as used within the present invention is to be understood as comprising any emulsifier known to a person skilled in the art as suitable for the inventive purpose.

Within a preferred embodiment, the emulsifier is selected from the group consisting of non- ionic emulsifiers with a preferred low hydrophilic/lipophilic balance (HLB value) preferably selected from the group consisting of sorbitan fatty acid esters and mixtures thereof.

Within preferred embodiments of the present invention, the HLB is selected within the range of from 1 .5 to 7.5, preferably of from 2 to 6. Suitable low HLB emulsifiers include sorbitan fatty acid esters, specifically mono, sesqui, and/or tri-fatty acid esters, particularly C^ to C ₂ o mono-unsaturated fatty acid, especially oleic acid, esters and in particular sorbitan mono- oleate; glycerol mono and/or di-fatty acid esters, particularly C^ to C ₂ o mono-unsaturated fatty acid, especially oleic acid, esters; and fatty acid alkanolamides, particularly

ethanolamides, especially diethanolamides, particularly those based on C^ to C ₂ o mono- unsaturated fatty acids, especially oleic acid. The oleic acid in such compounds may be provided by mixed fatty acid feedstocks e.g. rape seed fatty acids, including C^ to C ₂ o mono- unsaturated fatty acid, particularly oleic acid, as a main constituent.

Within a particularly preferred embodiment, the water in oil emulsion according to the present invention comprises

(a) 30 to 65 wt.-% acrylamide-free polymer as defined before;

(b) 30 to 65 wt.-% water;

(c) 25 to 35 wt.-% oil; (d) 2 to 4 wt.-% emulsifier.

Within another preferred embodiment the inventive water in oil emulsion shows a viscosity of from 10 to 2000 mPas, preferably of from 20 to 1800 mPas, further preferred of from 50 to 1700 mPas and most preferred of from 80 to 1500 mPas. The viscosity is measured as described within the examples.

Within another preferred embodiment, the present invention relates to a process for dewatering of sludge water streams comprising the following steps:

(i) Contacting the sludge water stream with from 0.01 to 2.5 kg of the

acrylamide-free polymer as defined before per 1000 kg solids of the sludge water stream for a time period of from 1 second to 1 hour;

(ii) Separation of the sediment.

Within the present invention, the "contacting" can be carried out by any method and/or any means known to a person skilled in the art as suitable for the inventive purpose. Within a preferred embodiment, the contacting is carried out by injecting an aqueous dispersion of acrylamide-free polymer directly into the sludge water stream immediately prior to a point of high turbulence, using injection nozzles into the pipe carrying the material or by diverting the flow of sludge-water stream through a conditioning unit specifically designed to create the optimal dispersion of the acrylamide-free polymer within the sludge water. An example of such a conditioning unit is disclosed within DE 10 2016 101 417A1 .

Within the present invention, the "separation" can be carried out by any method and/or any means known to a person skilled in the art as suitable for the inventive purpose. Within a preferred embodiment the separation is carried out by transferring the sediment into geobags which retain the flocked sediment particles but release the purified water. Within another preferred embodiment the separation is carried out by transferring the conditioned/treated sediment into membrane filter presses, where the flocked sediment particles are pressed between membranes attached to filter plates which press out clear water but retain the flocked sediment particles until the produced filter-cake is dry enough to be recovered. Within another preferred embodiment the separation is carried out by transferring the sediment into belt filter presses, where the flocked sediment particles are pressed between two moving porous fabrics in order to press out clear water but where the flocked sediment particles remain on the belts until the produced filter-cake is dry enough to be recovered. Within another preferred embodiment the separation is carried out by transferring the

conditioned/treated sediment into gravity tables, where the flocked sediment particles are deposited onto a moving porous fabric to allow clear water to drain from the fabric but which retains the flocked sediment particles until the produced filter-cake is dry enough to be recovered. Within another preferred embodiment the separation is carried out by transferring the conditioned/treated sediment into a tailings pond or lagoon, where the flocked sediment particles rapidly precipitate and consolidate at the bottom of the lagoon, leaving a clear supernatant and the formation of a compact sediment base material.

Within a preferred embodiment of the inventive process, the the sludge water stream with is contacted with from 0.01 to 2.5 kg of the acrylamide-free polymer as defined before per 1000 kg solids, preferably of from 0.05 to 2.0 kg, further preferred of from 0.1 to 1 .0 kg and most preferred of from 0.15 to 0.7 kg per 1000 kg solids.

Within another preferred embodiment of the inventive process, the contacting is carried out for a time period of from 5 seconds to 55 minutes, preferably of from 10 seconds to 45 minutes, further preferred of from 25 seconds to 40 minutes and most preferred of from 30 seconds to 30 minutes.

Within another preferred embodiment the inventive process further comprises the step:

(x) Contacting the sludge water stream with from 0.001 % to 2.0 wt.-% (weight mineral per dry weight sediment) of at least one mineral.

The term "dry weight" refers to the total weight of all sediment particles with zero moisture.

The contacting may be carried out by any method and/or means known to a person skilled in the art as suitable for the inventive purpose.

Within a preferred embodiment, the mineral may be added in an amount of from 0.005% to 1 .8 wt.-% (weight mineral per dry weight sediment), preferably from 0.01 to 1 .5 wt.-%, further preferred from 0.1 to 1 .5 wt.-% and most preferred from 0.5 to 1 wt.-%.

The at least one mineral is preferably a clay mineral and within a more preferred embodiment the at least one mineral is selected from inorganic minerals and within a particularly preferred embodiment the at least one mineral is selected from the group consisting of MgC0 ₃ , hydromagnesite, diatomaceous earth, bentonite, saponite, sepiolite, zeolite, hydrotalcite, quartz, kaolinite, talcum, alginite, smectite group minerals such as montmorillonite, saponite, hectorite and palygorskite, and mixtures thereof.

Within a preferred embodiment, the at least one mineral is coated with an cationic, anionic or neutral polymer ("coating polymer"), preferably cationic starch, anionic starch, guar gum, xanthan, fatty acids or the acrylamide-free polymer according to the invention.

Within a further preferred embodiment, the at least one mineral is coated with from 0.1 to 5 wt.-% (weight coating material/weight mineral), preferably from 0.2 to 4 wt.-%, particularly preferred from 0.3 to 3 wt.-% and most preferred from 0.5 to 2.5 wt.-% of the coating polymer.

Within the present invention step (x) may be carried out before, after or concurrently with step (i) of the inventive process. Within a preferred embodiment, step (x) is carried out before step (i) of the inventive process.

Within a particularly preferred embodiment of the inventive process, the sludge water stream contains from 0.1 to 5 wt.-% of a salt, preferably NaCI.

Within a further aspect, the present invention relates to the use of the inventive, acrylamide- free polymer for dewatering of sludge water streams.

In the following particularly preferred embodiments of the inventive process are described which are not to be understood as limiting the invention in any respect. It is to be understood that irrespective of the following particularly preferred embodiments any combination of the features as defined before is within the scope of the present invention.

Particularly preferred embodiment 1

Acrylamide-free polymer for dewatering of sludge water streams with a sedimentation capacity C _se d selected from the range of from 200 to 700, an average molecular weight of from 750,000 to 5,000,000 Da and comprising from 68 to 82 mol-% polyacrylic acid and/or polymethacrylic acid and/or salts of polyacrylic and/or polymeth acrylic acid.

Particularly preferred embodiment 2

Acrylamide-free polymer for dewatering of sludge water streams as described within particularly preferred embodiment 1 , further comprising of from 5 to 30 mol.-% of a co- monomer selected from the group consisting of 2-methyl-2-(1 -oxo-2-propenyl)amino-1 - propanesulfonic acid and its salts, 4-acryloylmorpholine, N,N'-dimethyl-2-propenamide, 2- hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, maleic anhydride, itaconic acid and its salts, and combinations thereof.

Particularly preferred embodiment 3

Acrylamide-free polymer for dewatering of sludge water streams as described within particularly preferred embodiment 1 or 2, further comprising of from 15.0 to 25.0 mol-% of a repeating unit consisting of the following structure according to formula I: wherein R1 is hydrogen, methyl or ethyl, carboxymethyl

wherein Y is OR2 or NR2R3,

wherein R2 is hydrogen, a linear alkyl group having 1 to 50 carbon atoms, a branched alkyl group having 1 to 50 carbon atoms, a linear monohydroxyalkyi group having 2 to 6 carbon atoms, a branched monohydroxyalkyi group having 2 to 6 carbon atoms, a linear

dihydroxyalkyi group having 2 to 6 carbon atoms, a branched dihydroxyalkyi group having 2 to 6 carbon atoms, a linear primary, secondary, tertiary or quarternary aminoalkyi group having 2 to 6 carbon atoms, a branched primary, secondary, tertiary or quarternary aminoalkyi group having 2 to 6 carbon atoms , an ethylenically unsaturated free radical polymerizable group capable of polymerization, a linear sulphonic acid alkyl group having 2 to 6 carbon atoms or its salts or a branched sulphonic acid alkyl group having 2 to 6 carbon atoms or its salts,

wherein R3 is a linear alkyl group having 1 to 50 carbon atoms, a branched alkyl group having 1 to 50 carbon atoms, a linear monohydroxyalkyi group having 2 to 6 carbon atoms, a branched monohydroxyalkyi group having 2 to 6 carbon atoms, a linear dihydroxyalkyi group having 2 to 6 carbon atoms, a branched dihydroxyalkyi group having 2 to 6 carbon atoms, a linear primary, secondary, tertiary or quarternary aminoalkyi group having 2 to 6 carbon atoms, a branched primary, secondary, tertiary or quarternary aminoalkyi group having 2 to 6 carbon atoms , an ethylenically unsaturated free radical polymerizable group capable of polymerization, a linear sulphonic acid alkyl group having 2 to 6 carbon atoms, a branched sulphonic acid alkyl group having 2 to 6 carbon atoms or morpholine.

Particularly preferred embodiment 4 Water in oil emulsion comprising

(a) 30 to 65 wt.-% acrylamide-free polymer as described within any of particularly

preferred embodiments 1 to 3;

(b) 30 to 65 wt.-% water;

(c) 25 to 35 wt.-% oil;

(d) 2 to 4 wt.-% emulsifier. Particularly preferred embodiment 5

Process for dewatering of sludge water streams comprising the following steps:

(i) Contacting the sludge water stream with from 0.01 to 2.5 kg of the acrylamide- free polymer as described in any of particularly preferred embodiments 1 to 3 per 1000 kg solids of the sludge water stream for a time period of from 1 second to 1 hour;

(ii) Separation of the sediment; wherein the sludge water stream contains from 0.1 to 5 wt.-% of a salt.

Particularly preferred embodiment 6

Process for dewatering of sludge water streams as described within particularly preferred embodiment 5, further comprising step (x) contacting the sludge water stream with from 0.001 to 2.0 wt.-%

(weight mineral per dry weight sediment), at least one mineral, wherein step (x) is carried out before step (i).

Particularly preferred embodiment 7

Process for dewatering of sludge water streams as described within particularly preferred embodiment 6, wherein the at least one mineral is coated with from 0.1 to 5 wt.-% of cationic starch, anionic starch, guar gum, xanthan, fatty acids or the acrylamide-free polymer according to the invention.

Particularly preferred embodiment 8

Use of the acrylamide-free polymer as defined in any of particularly preferred embodiments 1 to 3 for dewatering of sludge water streams with a salt content of from 0.1 to 5 wt.-%. Examples

The present invention is now described by the following examples and figures. The examples and figures are for illustrative purposes only and are not to be understood as limiting the invention.

Fig. 1 shows the particle size distribution of Hamburg Harbour water used within the

examples.

Fig. 2 shows a graphical illustration of the particle size distribution of Hamburg Harbour water used within the examples.

Example 1 : Sedimentation of sludge from Hamburg harbour and determination of sedimentation capacity of invented polymer emulsions

1 . Preparing the acrylic acid ammonium salt solution

In a 4-neck round-bottom flask, equipped with a KPG stirrer, a pH electrode (Knick

Portamess 913), an internal thermometer and a dropping funnel, 500 g of acrylic acid (Sigma-Aldrich) were cooled with an ice bath. By drop-wise addition of 363 g of 33% ammonium hydroxide solution (Sigma-Aldrich), the pH was adjusted to 6.5. The resulting solution had a concentration of 72.4%.

2. Preparing the 2-acrylamido-2-methyl-1 -propanesulfonic acid ammonium salt solution

In a 4-neck round-bottom flask, equipped with a KPG stirrer, a pH electrode (Knick

Portamess 913), an internal thermometer and a dropping funnel, 500 g of a 50% aqueous solution of 2-acrylamido-2-methyl-1 -propanesulfonic acid (Sigma-Aldrich) were cooled with an ice bath. By passing ammonia gas through the solution, the pH was adjusted to 6.8. The resulting solution had a concentration of 52.3%.

3. Emulsion polymerization (exemplary description polymer No. 7)

In a 4-neck round-bottom flask, equipped with a KPG stirrer, a distillation bridge with removal vessel and vacuum connection, an internal thermometer and a dropping funnel, 99.7 g of the ammonium acrylate solution described under 1 ., 18.1 g of dimethylacrylamide (Sigma- Aldrich), 1 .2 g of sodium diethylenetriaminepentaacetate (40%, Sigma-Aldrich) were dissolved in 93.4 g of water. In a glass beaker, 6.3 g of Tween 85 (Sigma-Aldrich), 3.1 g of Genapol O080 (Clariant) and 0.04 g of 2.2'-azobis(2.4-dimethylvaleronitrile) (V-65, Wako) were dissolved in 78.2 g of Total EDC 99 (Total) and this solution was added with steady stirring to the aqueous reaction mixture. This produced a white W/O emulsion having a viscosity of 24 cP (spindle 4). N2 was blown through the reaction mixture for 15 minutes, followed by treatment with a three-fold vacuum/N2 filling cycle. After the preparations were concluded, the polymerization was initiated by an increase in internal temperature to 60°C, with the vacuum being set at 120 - 140 mbar and being maintained for 20 minutes. After the polymerization has subsided, the reaction mixture was heated to an internal temperature of 80°C and stirring was continued for 60 minutes. To destroy the residual monomer, the reaction mixture was cooled to an internal temperature of 30°C and 0.3 g of sodium persulfate and 0.3 g of sodium disulfite in solution each in 2 g of water were added, followed by stirring for 30 minutes more. The water/oil mixture (30.8 g) removed by distillation was discarded, to give as the product an emulsion having a solids content of 32.2%, a Brookfield viscosity of 175 cP (spindle 3) and a weight-average molecular weight of Mw = 2,250,000 Da with a dispersity of D = 7.9.

4. Preparation of polymers No. 4 to 6 and 8 to 16

Polymer emulsions no. 4 to 6 and 8 to 16 were prepared in the same way as No. 7, with the composition described in Table 1 .

List of abbreviations

W/O water-in-oil

KPG Kerngezogenes Prazisions-Glasgerat (core-drawn precision glass

apparatus - mechanical stirrer)

D Dispersity determined by GPC

Mw Weight-average molecular weight determined by GPC

Dl water deionized water

AmAA Acrylic acid ammonium salt solution (72,4 wt.-% in water)

AMPSAA 2-Acrylamido-2-methyl-1 -propanesulfonic acid ammonium salt solution

(52,3 wt.-% in water)

DMA N.N -Dimethyl acrylamide (Sigma-Aldrich)

HEA 2-Hydroxyethyl acrylate (Sigma-Aldrich)

HEMA 2-Hydroxyethyl methacrylate (Sigma-Aldrich)

DMAEMA 2-(Dimethylamino)ethyl methacrylate (Sigma-Aldrich) MAH Maleic anhydride (Sigma-Aldrich)

MBA N.N'-Methylenbis(acrylamide) (Sigma-Aldrich)

IA Itaconic acid (Sigma-Aldrich)

ACM 4-Acryloylmorpholine (Sigma-Aldrich)

DMAPAA N-[3-(Dimethylamino)propyl]acrylamide (Kohjin)

O080 Genapol O080 (Clariant)

T85 Tween 85 (Sigma-Aldrich)

EDC99 Total EDO 99 (Total)

NaS208 Sodium persulfate (Sigma-Aldrich)

NaS205 Sodium metabisulfite (Sigma-Aldrich)

V65 2,2'-Azobis-(2 _< 4-dimethylvaleronitrile) (Wako)

NaSDTPA Diethylenetriamine-pentaacetic acid pentasodium salt solution (Sigma- Aldrich, 40 wt.-% in water)

Table 1 Composition of the inventive polymers

5. Production of an aqueous polymer solution

Table 2 Dissolving times for producing a 0.1 % solution of polymer in Dl water, ready for use in the application

^a Nerolan Wassertechnik GmbH Krefeld

These results show that the inventive emulsion solutions of the flocculation polymers were able to reduce very sharply the long preparation times of the flocculation polymers typically employed in this application.

6. Determination of sedimentation capacity

In this example, the flocculation capacity of the polymer emulsions used in the present invention was investigated using a sample of water from Hamburg harbour. The solids content was measured according to DIN 38414 Part 2 at 105 °C and was 6.2%.

Experimental procedure: To a 100 ml measuring cylinder containing 50 ml of harbour water (6.2% solids content) were added 0.3 g/kg of the anionic polymer solutions No.s 4 to 16 (diluted as a 0.1 % aqueous solution). The mixture was shaken for three times by turning the covered cylinder up-side-down and left for phase separation. The sedimentation time (ts) was measured for the formation of supernatant forming above the depositing floes between a volume of 45 mL and 30 ml_. That means the stop clock was started when the deposit passed 45 mL and stopped when it passed the 30 mL mark. The quantity figures are based on the dry mass of the sludge sample for dewatering. For instance, 0.3 g/kg stands for 0.3 g of component per kg of dry mass of the sludge to be dewatered (1 kg of harbour sludge contained 62 g solids); for a batch size of 50 ml of sludge to be dewatered, 0.3 g/kg corresponds to 0.00093 g of polymer or 0.93 g of a 0.1 wt.-% polymer solution.

The sedimentation behaviour of the fiocculation polymers used in this example can be seen in Table 3, with a shorter sedimentation times and higher ratio of V _t /t _s representing more effective dewatering. Furthermore, a lower turbidity number is an expression of improved sedimentation and therefore of greater purity of the water removed.

Table 3. Sedimentation behaviour of the fiocculation polymers

^a) Sedimentation time (t _s ), obtained from sludge water sample with a volume V ₀ = 50 mL, referring to the time for the formation of a supernatant with a volume of V _t = 15 mL ^b) Polymer concentration (c _p0 i) compared to the solids present in the sludge sample

(kg/1000kg solids ^c) Turbidity, measured photometrically according to ISO 7027 using HACH 2100Qis Portable Turbimeter. calibrated with 4 standards (10, 20, 100 and 800 FNU). ^d) Sedimentation capacity C _se d = V,*V ₀ ¹ V *(ln(T _sup /T1 )) ¹ *CpoT ¹ *1000, wherein V ₀ represents the total volume of the sludge sample before addition of the flocculant (mL), V _t represents the volume of the supernatant (dewatered water from the sludge sample at the time t _s ) (ml), t _s represents the sedimentation time (min), T1 represents the turbidity of the sludge sample diluted to 1 mg/kg solids (FNU), ln(T _SU p/T1 ) represents the natural logarithm of the ratio of turbidity of the supernatant (FNU) and T1 measured after 30 min and c _p0 i represents the concentration of the polymer compared to the solids present in the sludge sample

(kg/1000kg solids). ^e) Nerolan Wassertechnik GmbH Krefeld; Nerolan AG570 contains polyacrylamide-containing polymer ^f > BASF

7. Sedimentation of sludge from Hamburg harbour

In this example, the flocculation capacity of the polymer emulsions used in the present invention was investigated using a sample of sludge from Hamburg harbour. The solids content was measured according to DIN 38414 Part 2 at 105°C and was 6.2%. The particle size distribution of Hamburg harbour sludge as used within the examples is shown in figures 1 and 2.

Analysis of sludge from port of Hamburg s.c. 6.2 %

pH-value 7.3

conductivity 1530 με/οηι

charge -412,5 mV charge density 15,64 μeq/g

T1 = 1 FNU

Analysis of metals of sludge from port of Hamburg by ICP-MS and ICP-OES aluminum: 15000 μg/g

arsenic: 14 μg/g

barium: 130 μg/g

lead: 33 μg/g

boron: 18 μg/g

chromium: 31 μg/g

ferrum: 13000 μg/g

copper: 48 μg/g

manganese: 990 μg/g

nickel: 14 μg/g

phosphorous: 870 μg/g

rubidium: 33 μg/g

strontium: 65 μg/g

titanium: 130 μg/g

vanadium: 26 μg/g

zinc: 250 μg/g

Instrumentation:

Weight-average molecular weights were obtained by gel permation chromatography (GPC), measured against polyacrylate standards using PSS NOVEMA MAX Guard columns (size 1 x30A and 2x1 ΟΟθΑ; 10 μηι, 300 mm x 8 mm). The viscosity was measured on a Brookf ield DV-I viscometer. The conductivity was measured by a ProfiLine Cond 197i, turbidity was measured photometrically according to ISO 7027 using HACH 2100Qis Portable Turbimeter, calibrated with 4 standards (10, 20, 100 and 800 FNU). The charge and the charge density were measured by Mutek PCD-04 equipped with a titrator PCD-T3 using a 5 min stabilization time and polydiallyldimethylammonium chloride (Poly(DADMAC)®) as titrant. The solid content was measured gravimetrically b drying a representative sludge sample in vacuum oven at 105 °C until constant weight. Inductively coupled plasma mass spectrometry (ICP- MS) was measured on a Varian 820-MS and inductively coupled plasma optical emission spectrometry (ICP-OES) was measured on an Agilent 5100. To a 100 ml measuring cylinder containing 50 ml of harbour sludge (6.2% solids content) were added 3 g/kg of a surface-treated calcium carbonate (MCC R 450 ME (Omya AG)). The mixture was shaken for three times by turning the covered cylinder up-side-down.

Afterwards, 0.3 g/kg of the anionic polymer solutions (polymers No 4 to 8; diluted as a 0.1 % aqueous solution) were added to the mixture and shaken again for three times by turning the covered cylinder up-side-down and left for phase separation. The sedimentation time (ts) was measured for the formation of supernatant forming above the depositing floes between a volume of 45 mL and 30 mL. That means the stop clock was started when the deposit passed 45 mL and stopped when it passed the 30 mL mark. The quantity figures are based on the dry mass of the sludge sample for dewatering. For instance, 0.3 g/kg stands for 0.3 g of component per kg of dry mass of the sludge to be dewatered (1 kg of harbour sludge contained 62 g solids); for a batch size of 50 ml of sludge to be dewatered, 0.3 g/kg corresponds to 0.00093 g of polymer or 0.93 g of a 0.1 wt.-% polymer solution. The surface- treated calcium carbonate (MCC R 450 ME) was applied as 10 wt.-% solution.

The sedimentation behaviour of the flocculation polymers used in this example can be seen in Table 4, with shorter sedimentation times and higher ratio of Wt _s representing more effective dewatering. Furthermore, a lower turbidity number is an expression of improved sedimentation and therefore of greater purity of the water removed.

Table 4. Sedimentation behaviour of the flocculation polymers

Polymer ts ^a) Cpo! ^b > T i sup ^c > Csed ^d) V,/ts

(min) (kg/1000kg) (FNU) (1/min) (mL/min)

Nerolan AG570 2.55 0.3 44 104 5.9

(comparison, not

acrylamide-free)"

Nerolan AG580 8.67 0.3 47 30 1 .7

(comparison, acrylamide- free) ^e)

Sokalan 1 10S 1 1 .28 0.3 34 25 1 .3

(comparison, acrylamide- free)"

Polymer no. 4 (invention) 1 .57 0.3 77 147 9.6

Polymer no. 5 (invention) 0.98 0.3 45 268 17.7

Polymer no. 6 (invention) 0.55 0.3 76 420 27.3

Polymer no. 7 (invention) 0.78 0.3 47 334 19.2

Polymer no. 8 (invention) 0.28 0.3 179 688 53.6 ^a) Sedimentation time (ts), obtained from sludge water sample with a volume V ₀ = 50 mL, referring to the time for the formation of a supernatant with a volume of \A = 15 mL ^b) Polymer concentration (c _p0 i) compared to the solids present in the sludge sample

(kg/1000kg solids) ^c) Turbidity, measured photometrically according to ISO 7027 using HACH 2100Qis Portable Turbimeter, calibrated with 4 standards (10, 20, 100 and 800 FNU). ^d) Sedimentation capacity C _se d = V, ^* V ₀ ^~1 V ^* (ln(T _S up T1 *Cpd ^{1 *} 1000, wherein V ₀ represents the total volume of the sludge sample before addition of the flocculant (mL), V _t represents the volume of the supernatant (dewatered water from the sludge sample at the time t _s ) (ml), t _s represents the sedimentation time (min), T1 represents the turbidity of the sludge sample diluted to 1 mg/kg solids (FNU), ln(T _SU p/T1 ) represents the natural logarithm of the ratio of turbidity of the supernatant (FNU) and T1 measured after 30 min and c _p0 i represents the concentration of the polymer compared to the solids present in the sludge sample

(kg/1000kg solids). ^e) Nerolan Wassertechnik GmbH Krefeld; Nerolan AG570 contains polyacrylamide-containing polymer ^f > BASF

These results show that the inventive flocculation polymers achieve the best results, particularly in the context of dewatering. Furthermore, the inventive examples afford outstanding results in relation to the other parameters.

Example 2: Sedimentation of sludge from Hamburg harbour by direct use of the concentrated emulsion

In this example, the flocculation capacity of the polymer emulsions prepare and used in the present invention was investigated, as under points 1 . to 7. of example 1 , on the same sample of sludge from Hamburg harbour. In this case the concentrated polymer emulsion was used directly as a flocculant and was compared with the 0.1 % solutions of the comparative polymers and of the inventive polymers. The experimental procedure took place in the same way as in the method described under point 7, with the difference that polymer no. 5 was used, in one case as a dilute 0. 1 % solution and in one case directly as a concentrated polymer emulsion. When the polymer was used as concentrated solution, the sludge was shaken for 1 0 times instead of 3. Table 4 shows the results of the investigation and the comparison with known polymers, all of which can be used only as 0. 1 % solutions.

Table 5

^a) Sedimentation time (ts), obtained from sludge sample with a volume V ₀ = 50 mL, referring to the time for the formation of a supernatant with a volume of V _t = 15 mL ^b) Polymer concentration (c _p0 i) compared to the solids present in the sludge sample

(kg/1000kg solids) ^c) Turbidity, measured photometrically according to ISO 7027 using HACH 2100Qis Portable Turbimeter, calibrated with 4 standards (10, 20, 100 and 800 FNU). ^d) Sedimentation capacity C _se d = V, ^* V ₀ ^~1 V ^* (Ιη(Τ _8ϋρ /Τ1 )) ¹ *Cpd ^{~1 *} 1000, wherein V ₀ represents the total volume of the sludge sample before addition of the flocculant (mL), V _t represents the volume of the supernatant (dewatered water from the sludge sample at the time t _s ) (ml), t _s represents the sedimentation time (min), T1 represents the turbidity of the sludge sample diluted to 1 mg/kg solids (FNU), ln(T _SU p/T1 ) represents the natural logarithm of the ratio of turbidity of the supernatant (FNU) and T1 measured after 30 min and c _p0 i represents the concentration of the polymer compared to the solids present in the sludge sample

(kg/1000kg solids). ^e) Nerolan Wassertechnik GmbH Krefeld; Nerolan AG570 contains acrylamide-containing polymer ^f > BASF

These results show that the inventive fiocculation components can also be used directly as a concentrated emulsion in the context of sediment dewatering and that the best outcome is obtained in relation to the short preparation time. Furthermore, the inventive examples yield outstanding results in terms of turbidity.

Example 3

Sediment from the Eti Maden Emit Site

In this example, the fiocculation capacity of the polymer emulsions used in the present invention was investigated using a sample of water from Eti Maden Emit Site. The solids content was measured according to DIN 38414 Part 2 at 105 °C and was 24 wt.-%, which was diluted to 5.0 wt.-% with destilled water and 0.3 wt.-% of sodium chloride (NaCI) were added.

Analysis of sample from the Eti Maden Emit Site

s.c. 5.3 wt.-%

pH-value 3.9

conductivity 7400 8/ατι

Charge (1 wt.-% solution) -291 .3 mV

charge density (1 wt.-% solution) 4.07 ^eq/g

T1 = 1 FNU

Analysis of chemical elements of sample from the Eti Maden Emit Site by ICP-MS and ICP-

OES

Table 6

values in solid matter

Al %

As mg/kg 2600 Experimental procedure: To a 100 ml measuring cylinder containing 50 ml of Eti Maden Emid site water (5.3 wt.-% solids content) were added 0.15 g/kg of the anionic polymer solutions No.s 4 to 7 (diluted as a 0.1 wt.-% aqueous solution). The mixture was shaken three times by turning the covered cylinder up-side-down and left for phase separation. The sedimentation time (ts) was measured for the formation of supernatant forming above the depositing floes between a volume of 45 mL and 30 mL. That means the stop clock was started when the deposit passed 45 mL and stopped when it passed the 30 mL mark. The quantity figures are based on the dry mass of the sludge sample for dewatering. For instance, 0.15 g/kg stands for 0.15 g of component per kg of dry mass of the sludge to be dewatered (1 kg of harbour sludge contained 53 g solids); for a batch size of 50 ml of sludge to be dewatered, 0.15 g/kg corresponds to 0.0004 g of polymer or 0.4 g of a 0.1 wt.-% polymer solution.

The sedimentation behaviour of the flocculation polymers used in this example can be seen in Table 7, with a shorter sedimentation times and higher ratio of V _t /t _s representing more effective dewatering. Furthermore, a lower turbidity number is an expression of improved sedimentation and therefore of greater purity of the water removed.

Table 7 Sedimentation behaviour of the flocculation polymers

^a) Sedimentation time (t _s ), obtained from sludge water sample with a volume V ₀ = 50 referring to the time for the formation of a supernatant with a volume of V _t = 15 mL ^b) Polymer concentration (c _p0 i) compared to the solids present in the sludge sample

(kg/1000kg solids ^c) Turbidity, measured photometrically according to ISO 7027 using HACH 2100Qis Portable Turbimeter, calibrated with 4 standards (10, 20, 100 and 800 FNU). ^d) Sedimentation capacity C _se d = V,*V ₀ ¹ V *(ln(T _SLip T1 )) ¹ *Cpd ^"1 *1000, wherein V ₀ represents the total volume of the sludge sample before addition of the flocculant (mL), V _t represents the volume of the supernatant (dewatered water from the sludge sample at the time t _s ) (ml), t _s represents the sedimentation time (min), T1 represents the turbidity of the sludge sample diluted to i mg/kg solids (FNU), ln(T _SU p/T1 ) represents the natural logarithm of the ratio of turbidity of the supernatant (FNU) and T1 measured after 30 min and c _p0 i represents the concentration of the polymer compared to the solids present in the sludge sample

(kg/1000kg solids). ^e) Nero!an W assert echnik GmbH Krefeld; ^f) BASF

Example 4

Sediment from the Golden Horn in Istanbul

In this example, the flocculation capacity of the polymer emulsions used in the present invention was investigated using a sample of harbour water from the Golden Horn in

Istanbul. The solids content was measured according to DIN 38414 Part 2 at 105 °C and was 27.5 wt.-%, which was diluted to 5.0 wt.-% with destilled water and 0.7 wt.-% of sodium chloride (NaCI) were added.

Analysis of sample from the Golden Horn in Istanbul

s.c. 5.7 wt.-%

pH-value 7.8

conductivity 19200 μ8/οιτι

Charge (1 wt.-% solution) -830.8 mV

charge density (1 wt.-% solution) 1 .09 μβς,¾

T1 = 1 FNU

Analysis of chemical elements of sample from the Golden Horn in Istanbul by ICP-MS and ICP-OES

Table 8

Experimental procedure: To a 100 ml measuring cylinder containing 50 ml of Golden Horn harbour water (5.7 wt.-% solids content) were added 0.3 g/kg of the anionic polymer solutions No.s 4 to 7 (diluted as a 0.1 wt.-% aqueous solution). The mixture was shaken for three times by turning the covered cylinder up-side-down and left for phase separation. The sedimentation time (ts) was measured for the formation of supernatant forming above the depositing floes between a volume of 45 mL and 30 mL. That means the stop clock was started when the deposit passed 45 mL and stopped when it passed the 30 mL mark. The quantity figures are based on the dry mass of the sludge sample for dewatering. For instance, 0.3 g/kg stands for 0.3 g of component per kg of dry mass of the sludge to be dewatered (1 kg of harbour sludge contained 57 g solids); for a batch size of 50 ml of sludge to be dewatered, 0.3 g/kg corresponds to 0.00086 g of polymer or 0.86 g of a 0.1 wt.-% polymer solution.

The sedimentation behaviour of the fiocculation polymers used in this example can be seen in Table 9, with a shorter sedimentation times and higher ratio of V _t /t _s representing more effective dewatering. Furthermore, a lower turbidity number is an expression of improved sedimentation and therefore of greater purity of the water removed.

Table 9. Sedimentation behaviour of the fiocculation polymers

^a) Sedimentation time (t _s ), obtained from sludge water sample with a volume V ₀ = 50 mL, referring to the time for the formation of a supernatant with a volume of V· = 1 5 mL ^b) Polymer concentration (c _p0 i) compared to the solids present in the sludge sample

(kg/1000kg solids ^c> Turbidity, measured photometrically according to ISO 7027 using HACH 2100Qis Portable Turbimeter, calibrated with 4 standards (10, 20, 100 and 800 FNU). ^d) Sedimentation capacity C _se d = V _t *V ₀ ^~1 V *(Ιη(Τ _8υρ /Τ1 )) ^~1 *Cpd ¹ *1000, wherein V ₀ represents the total volume of the sludge sample before addition of the flocculant (mL), V _t represents the volume of the supernatant (dewatered water from the sludge sample at the time t _s ) (ml), t _s represents the sedimentation time (min), T1 represents the turbidity of the sludge sample diluted to 1 mg/kg solids (FNU), ln(T _sup T1 ) represents the natural logarithm of the ratio of turbidit of the supernatant (FNU) and T1 measured after 30 min and c _p0 i represents the concentration of the polymer compared to the solids present in the sludge sample

(kg/1000kg solids). ^e) Nerolan Wassertechnik GmbH Krefeld; ^f > BASF