FLOCCULATION AND SOLID-LIQUID SEPARATION OF ANIMAL SLURRY; FUNDAMENTALS, CONTROL AND APPLICATION

PH.D. THESIS BY MAIBRITT HJORTH

FLOCCULATION AND SOLID-LIQUID SEPARATION OF ANIMAL SLURRY; FUNDAMENTALS, CONTROL AND APPLICATION

PH.D. THESIS BY MAIBRITT HJORTH, JUNE 2009

SUPERVISOR: PROFESSOR SVEN GEDDE SOMMER, UNIVERSITY OF SOUTHERN DENMARK, INSTITUTE OF CHEMICAL ENGINEERING, BIOTECHNOLOGY AND ENVIRONMENTAL TECHNOLOGY EDUCATIONAL RESPONSIBLE: FACULTY OF ENGINEERING, UNIVERSITY OF SOUTHERN DENMARK EMPLOYING COMPANY: FACULTY OF AGRICULTURAL SCIENCES, AARHUS UNIVERSITY FUNDING: MINISTRY OF FOOD, AGRICULTURE AND FISHERIES AND MINISTRY OF ENVIRONMENT, ACTION PLAN FOR THE AQUATIC ENVIRONMENT III

Separated [] animal slurry is more environmentally friendly than untreated slurry, as it replaces mineral fertilizers better and leaches to a lesser extend. (Danish Government, 2009)

PREFACE
This thesis is the termination of the ph.d. study at The Institute of Chemical Engineering, Biotechnology and Environmental Technology at The Faculty of Engineering on Southern Danish University. The employing company has been The Department of Agricultural Engineering at The Faculty of Agricultural Sciences on Aarhus University, which in the beginning though was a research institute of the Ministry Food, Agriculture and Fisheries and named The Danish Institute of Agricultural Sciences. The presented study was carried out at Research Centre Bygholm and Research Centre Foulum between September 2005 and June 2009. In addition, a part of the work was carried out during a five months stay late 2006 at the Section of Chemistry at The Faculty of Engineering on Aalborg University. The study is a part of the research project Separation of Animal Slurry Optimizing Harmony in Plant Nutrient Cycling and Reducing Odour and Ammonia Emission funded by The Ministry of Food, Agriculture and Fisheries and The Ministry of Environment as part of the Action Plan for the Aquatic Environment III. The partners of the research project are Aalborg University, Copenhagen University, The Danish Pig Production, The Danish Agricultural Advisory Service, Novozymes A/S and Kemira Milj A/S. The study has resulted in six peer reviewed publications and five international conference papers, of which most may be found in the manuscript appendix of the thesis and/or listed in bold in the thesis references. A broad range of people and institutions has made this work possible. The largest thank you and respect goes to Sven G. Sommer, who gave me so many possibilities and was so good at helping me to understand and value the realities of the researching world. I am much grateful of Morten L. Christensen, who made my stay at Aalborg University so very rewarding and was an invaluable partner in discussions. Theres a surprisingly long list of scientist working with animal faces that includes people like Martin N. Hansen, Tavs Nyord, Henrik Mller, Alistair Ward, Ryoh Nakakubo, Anders M. Nielsen, Karin Jrgensen and Anders Peter S. Adamsen; talking with you develops me. Micael Stckler, Karl Martin Schelde and colleages at CBMI, Torkild Birkmose and colleages at The Danish Agricultural Advisory Service, Torkild Frandsen and colleagues at Agrotech, you are invaluable guides to the missing knowledge in the real world. Preben Nissen at AL-2 Teknik A/S and Kemira Milj A/S, Lene Venke Kofoed at Novozymes A/S, Anders Larsen at Q-interline, youve all been priceless coaches. Sren Brams at SB Engineering and Martin Rishj at GEA Mechanical Equipment thank you so much for your highly competent help. A large thank you goes to Gitte Hastrup Andersen, Tina Christensen, Lisbeth Wybrandt, Claudia Nagy and Heidi G. Christiansen for magnificent help and for making time so enjoyable in the lab. The remaining previous and present staff at The Department of Agricultural Engineering on Aarhus University I additionally owe a lot; despite the tough times, you made the days pleasant and managed to drag me back to the world during the breaks. And last but certainly not at least, a very large thank goes to my dear husband and the best son in the world the leave with you was a treat - and additionally our friends and extremely helpful family, who surely supported me in all the ways possible.

RESUME
Det meget intensive landbrug er den vigtigste rsag i Danmark for at udfre separere gylle, fordi den nuvrende praksis udfordrer landmnd og miljet. Landmndene har kun f nrliggende landbrugsomrder til at gde med gylle, hvilket begrnser mulighederne for udvidelse og produktionsoptimering. Miljet er blevet eutrofieret p grund af tab af gyllens nringsstoffer, som har resulteret i sers dd og ndringer i biodiversiteten. Hertil kommer, at energi fra ikkevedvarende energikilder forrsager omfattende udledning af drivhusgasser. Separering af gyllen i en lille nringsstofkoncentreret fast fraktion og en stor flydende fraktion med get kvlstof-til-fosfor forhold kan mindske disse problemer. Mens trykfiltrering er den mindst effektive af de mekaniske fast-vske separeringsteknikker, er centrifugering den overlegne af teknikkerne med hensyn til trstof og fosfor separering. Flokkulering forud for mekanisk fast-vske separering ger fosfor og trstofindholdet af den faste fraktion yderligere, men mindsker volumen separeringen. Hvorvidt et flokkuleringstrin skal inkluderes er derfor et sprgsml om de specifikke separerings- og produktkrav. Flokkulering medfrer aggregering af oplste partikler i strre flokke, som i sidste ende flder ud af oplsningen. To flokkulering metoder er koagulering og polymer flokkulering. Gylle partikler kan koaguleres og fosfat udfldes ved at tilstte FeCl3 eller Al2(SO4)3. Omtrent halvdelen af det tilsatte jern flder fosfor og koagulerer partikler. Bagefter skal gyllen flokkuleres med en stor, kationisk, liner polymer med stor ladningsdensitet. Polymeren neutraliserer en fjerdedel af partiklernes overfladeladning og inducerer polymer bridging. Polymeroplsningen skal tilfres langsomt under nje overvejet omrring, som tillader homogenisering og effektiv aggregering. Gyllen kan fastvske separeres ved drning. Gyllens ionstyrke, partiklernes zeta-potentiale, partiklernes overfladeladning, totale og specifikke trstofindhold, indholdet af multivalente metaller og specieringen af nringsstoffer er gylleegenskaber, der afgrer flokkuleringens effektivitet. Gyllens karakteristika afgres af dyret der udskiller gyllen og behandlingen af gyllen mellem udskillelse og separering. Flokkulering af det konstant skiftende gylle input kan automatiseres. Syv analyser har indikeret potentiale til at monitere gylleseparering i laboratorie skala forsg eller online p fuldskalaseparatorer. Efterflgende reguleres processens parametre i henhold til input gyllen. Disse er den faste fraktions trstofindhold, den flydende fraktions turbiditet og viskositet, den flokkulerede prves flok strrelse, afvandelighed og kapillre sugetid, og mlinger med nr infrard (NIR) spektroskopi. Opbevaring i tanke, anvendelse p marker, anaerob udrdning, membranfiltrering og afbrnding er potentielle nutids behandlinger af gyllesepareringsprodukter for at forbedre praktiske landbrug forhold, gdskning og /eller energiproduktion. Fast-vske separering og flokkulering forbedrer de fleste af de typiske gyllebehandlinger eller kan endda vre en forudstning. Opmrksomhed er ndvendigt, for at der ikke skal vre nogen eller kun positiv pvirkning p gylleprodukternes samlede emission af ammoniak, drivhusgasser og lugt og deres effektivitet som et plantesubstrat. Selvom forskning stadig mangler, er meget allerede kendt om grundlggende mekanismer, kontrol og anvendelse af flokkulering og fast-vske separation af husdyrgdning, hvilket har resulteret i at 3% af Danmarks gylle i 2007 blev separeret.

ABSTRACT
The highly intensive farming is the main reason in Denmark for performing animal slurry separation, because current practice challenges the farmers and the environment. The farmers have only little agricultural fields nearby to fertilize with the animal slurry. This creates a limit to expansion and optimization of the production. The environment has become eutrophicated by losses of slurry nutrients. This has resulted in lakes dying and biodiversity changes. In addition, energy from non-renewable sources causes e.g. extensive greenhouse gas emissions. Separating the slurry into a small nutrient concentrated solid fraction, and a large liquid fraction of increased nitrogen-tophosphorus ratio may alleviate these challenges. While pressurized filtration is the poorest of the mechanical solid-liquid separation techniques, centrifugation is the superior one of the techniques with respect to dry matter and phosphorus separation. Flocculation prior to the mechanical solid-liquid increases the phosphorus and dry matter content of the solid fraction further, but lessen the volume separation. Thus inclusion of flocculation is a matter of the specific separation and product requirements. Flocculation results in aggregation of suspended particles into larger flocs, which eventually settle out of suspension. Two flocculation methods are coagulation and polymer flocculation. Slurry particles may be coagulated and phosphate precipitated by adding FeCl3 or Al2(SO4)3. Roughly half of added Fe precipitate phosphorus and coagulate particles. Afterwards, the slurry may be flocculated with a large, cationic, linear polymer with large charge density. The polymer neutralizes one fourth of the particle charges and induces polymer bridging. The polymer solution must be added slowly under carefully considered stirring allowing homogenisation and proper aggregation. The manure could be solid-liquid separated by drainage. The slurrys ionic strength, particle zeta-potential, particle surface charge, total and specific dry matter content, content of multivalent metals and speciation of nutrients are slurry characteristics in control of flocculation efficiency. The characteristics are determined by the animal excreting the slurry and the handling of the slurry between excretion and separation. The flocculation of the continuously changing slurry may be automated. Seven analyses have indicated potential to monitor slurry separation in bench scale experiments or on-line at full scale separators. The aim is to regulate the process parameters subsequently, according to the changing input manure. These are the solid fractions dry matter content, the liquid fractions turbidity and viscosity, the flocculated samples floc size, dewaterability and capillary suction time, and near infrared (NIR) spectroscopic measurements. Storage in tanks, application on fields, anaerobic digestion, membrane filtration and thermal conversion are potentially present-day handlings of slurry separation product. These improve practical farming aspects, fertilization and/or energy production. Solid-liquid separation and flocculation improve most of the typical handlings of manure or it may even be a pre-requisite. Consideration is necessary if the there should be no effect or there should be a positive effect on the slurry products overall emission of ammonia, greenhouse gases and odour, and the products efficiency as a substrate for plants. Though research is still lacking, much is known concerning fundamentals, control and application of flocculation and solid-liquid separation of animal manure, which has resulted in the fact that 3% of Denmarks animal slurry in 2007 were separated.

PREFACE RESUME ABSTRACT 1

1.1 1.2 1.3

3 4 5 9
9 9 9

WHY SHOULD SLURRY BE SOLID-LIQUID SEPARATED?

Legislation Ocurrence Motivation

2
2.1 2.2

HOW SHOULD SLURRY BE SOLID-LIQUID SEPARATED?

Efficiency of solid-liquid separation Efficiency of flocculation and solid-liquid separation

11
11 13

3
3.1 3.2 3.3 3.4

HOW SHOULD SLURRY BE FLOCCULATED?

Polymer flocculation Coagulation and precipitation Addition procedure Solid-liquid separation

14
14 17 19 19

4
4.1 4.2

WHAT AFFECTS FLOCCULATION?

Physical and chemical characteristics of slurry Slurry origin and pre-treatment

21
21 22

5
5.1 5.2 5.3

HOW SHOULD FLOCCULATION BE CONTROLLED?

At-line direct analytical methods At-line indirect analytical methods On-line indirect analytical methods

24
24 25 25

6
6.1 6.2 6.3 6.4 6.5

HOW SHOULD SEPARATION PRODUCTS BE APPLIED?

Storage Field application Membrane filtration Biogas Thermal conversion

28
28 28 29 29 30

7
7.1

WHAT LIMITS SOLID-LIQUID SEPARATION AND FLOCCULATION?

Future studies

31
31

REFERENCES

32

WHY SHOULD SLURRY BE SOLID-LIQUID SEPARATED?

Danish legislation encourages the application solid-liquid separation of animal slurry, because large environmental profits make separation advantages for the society. Additionally, slurry separation may be practically and economically advantages for the farmer. To enhance the motivation, questions must necessarily be answered concerning the fundamental understanding, control techniques and application potentials. Definition: Solid-liquid separation The plan Grn Vkst was published by The Danish Production of a solid and a liquid Government in April 2009. Three of the 11 intends are fraction by sedimentation, potentially related to solid-liquid separation of animal slurry: centrifugation, drainage or An aquatic system of good quality through reduction in pressurized filtration. May include a nitrogen and phosphorus leaching. flocculation pre-treatment. Input Create frames for using up to 40% of Danish animal material is the slurry collected slurry for green energy in 2020. In the long term, all outside the livestock housing. animal slurry should be used for energy production Investments in new green technologies The means to achieve the goals include increasing the permitted fertilization distance to aquatic systems, improving the payment and sale of green energy, and through grants for joint biogas plants and solid-liquid separators for slurry treatment (Danish Government, 2009). Framed by the European Water Framework Directive (2001), the Danish regulations have also previously encouraged the application of solid-liquid separation of animal slurry. A reduction in the required area of agricultural fields for slurry application per animal could be obtained by separating the slurry. Thereby the nitrogen can be exported from the farm in the form of the solid fraction. Thus, high investments in agricultural fields were not as necessary when expanding the production (Arealkravsbekendtgrelsen, 2006; Danish Environmental Protection Agency, 2006). In addition, Danish grants for solid-liquid separators were offered in 2006.

1.1 Legislation

1.2 Ocurrence
Mainly caused by these previous Danish initiatives, 1 million tons or 3% of Denmarks animal slurry were separated in 2007 by 51 solid-liquid separators (Birkmose, 2007). In contrast, while no separators were operating in 2001. By 2007, half the separators include a flocculation treatment prior to the mechanical solid-liquid separation. In comparison, slurry separation was not yet commonly applied in other countries (Burton, 2007). Because 3 of the 11 goals of the new Danish plan Grn Vkst is potentially related to solid-liquid separation of animal slurry, the future application of slurry separators in Denmark is expected to increase further.

1.3 Motivation
The highly intensive farming is the main reason in Denmark for performing animal slurry separation, because current practice challenges the farmers and the environment. The farmers have only little agricultural fields nearby to fertilize with the animal slurry. This creates a limit to expansion and optimization of the production. The environment has turned eutrophicated by losses of slurry nutrients. This has resulted in e.g. lakes dying and biodiversity changes. In addition, energy from non-renewable sources causes e.g. extensive green house gas emissions. Slurry separation may alleviate these challenges. 9 Definition: Manure and slurry Manure is a mixture of fecal and urinary excretions by livestock, bedding material and water. Manure with a water content of more than 96% is defined as liquid. Manure with a moisture content between 90 and 96% is referred to as slurry, while manure with a moisture content of less than 90% is considered solid.

Slurry separation produces a large liquid fraction with a reduced nitrogen and phosphorus content compared to the raw slurry. Thus the liquid slurry may be spread on a smaller field area, and in consequence closer to slurry source. The nitrogen-to-phosphorus ratio is increased. This matches the plants requirements better, and it result in reduced phosphorus loss to the environment. In addition, the ammonium-to-total nitrogen ratio may be higher, thus the nitrogen becomes initially more available to the plants. The liquid fraction may alternatively to the field application, be further refined. For instance by membrane filtration, evaporation, struvite crystallization and stripping. This will generate fertilizer concentrates for plant production, and a water-ish product for water deficient fields or washing on the farm. A small, highly concentrated solid fraction is also produced by the slurry separation. In particular the phosphorus, dry matter and organic matter contents are high and liquid content is low. The fraction may be used, or because of the small and concentrated character it may even be essential, on distant phosphorus deficient fields. Alternatively, the fraction may be used for green energy production through biogas production and thermal conversion, or as input material to production of mineral fertilizer. Questions remain to be answered to motivate increased application of slurry separation, and ensure that both farmers, environment and society gain further advantages from the technology:

How should slurry be solid-liquid separated? The answer includes comparisons of efficiencies of the four types of solid-liquid separators. These are also compared with the efficiency of including a pre-flocculation. How should slurry be flocculated? The answer includes identification of what is chemically occurring. Based on that and experimental comparisons, optimum chemical and physical treatment are determined. What affects flocculation? The answer includes considerations on the physical and chemical slurry characteristics. In addition, slurry origin and slurry pre-treatment effects are discussed. This is related to what is chemically occurring upon flocculation. How should flocculation be controlled? The answer includes evaluations of chemical analytical methods for monitoring the slurry separation. What should separation be combined with? The answer includes considerations on the effect of potentially present-day handlings of separation products on emissions and nutrient plant availability. What limits solid-liquid separation and flocculation? The answer includes discussions on further questions necessary to examine.

10

HOW SHOULD SLURRY BE SOLID-LIQUID SEPARATED?

Pressurized filtration is the poorest of the mechanical solid-liquid separation techniques with respect to dry matter and phosphorus separation. In contrast, centrifugation is the superior one of the mechanical techniques. Flocculation increases the phosphorus and dry matter content of the solid fraction further, but reduces the volume separation. Thus centrifugation versus flocculation is a matter of the specific product requirements.

2.1 Efficiency of solid-liquid separation

Solid-liquid separation produces a solid and a liquid fraction of the input slurry. It may be sedimentation, centrifugation, drainage and pressurized filtration. A flocculation cause aggregation of the slurry particles, and it may be carried out before the solid-liquid separation. Separation methods may be compared on the basis of the different separation goals; the volume of the fractions, the dry matter separation, the phosphorus separation, the nitrogen separation and the separation of the ammoniacal nitrogen may be of interest. For comparisons, the separation index or the reduced separation index may be applied. The calculation of the separation index (Et): m( x) solid 100% m( x) slurry (1) where m(x)slurry and m(x)solid are the mass (g) of x in consideration in, respectively, the slurry being treated by the separator and of the solid fraction being produced (Svarovsky, 1985). The range of the separation index is 0-100%, with e.g. Et(P) = 80% indicating that 80% of phosphorus is present in the solid fraction. Et ( x) = Concentration is one of the main purposes of separation, i.e. to obtain the largest amount of compounds in the smallest solid fraction. In contrast to the separation index (Et), the reduced separation index (Et) takes this into account:
Et ( x) Et ' ( x) = 1 msolid mslurry

(2)

msolid mslurry

where mslurry and msolid are the total mass (g) of slurry being treated and the total mass of solids being produced (Svarovsky, 1985). A reduced separation index at 0 corresponds to no increase in concentration in either solid of liquid fraction. If 90% of compound x is present in the solid and the mass of solid is 10% of the total input slurry, the reduced separation index equals 0.89. Though rarely desired, an increasing concentration in the liquid fraction may occur. This results in a negative reduced separation index. E.g. the reduced separation index equals -0.5, if 10% of compound x is present in the solid and the mass of solid is 40% of the total input slurry. For the calculations, the masses of the liquid and solid fractions are necessary. However on continuous separators, this may be difficult to measure. It has proved useful to apply cobber as reference element, because of the non-volatile nature. From the concentrations in the input slurry and the solid and liquid fractions, the volume separation can be calculated (Petersen and Sorensen, 2008). An experiment has been performed (Jrgensen and Hjorth, 2009): Half litre subsamples of one swine slurry and one cow slurry were allowed to settle for 24 hours. Additionally, they have been centrifuged at 3.000 g for 35 sec, and have been filtered through a static 1 mm filter with 6 bars pressure applied by a piston. Drainage was not performed, as filtration through a static 200 mm filter produced a filtrate being 5% of the total volume. The reduced separation indexes of the swine and 11

Table 2.1 Efficiency for separation by five separation methods applied to swine and cow manure (Jrgensen and Hjorth, 2009). The effect of the different separation methods has been compared for each slurry type (swine, cow) (n=3) and slurry characteristic (DM, N, P) by Turkeys test (P = 0.05) (SAS Institute Inc., 2000); statistically equal results are indicated by equal letters. Separation method Dry matter Swine Cow 0,13 (0,05)a 0,17 (0,02)a 0,10 (0,01)a 0,14 (0,03)a 0,14 (0,03)a 0,29 (0,01)b 0,25 (0,05)b 0,34 (0,03)b 0,20 (0,01)ab Reduced separation index, Et Nitrogen Swine Cow 0,10 (0,02)a 0,13 (0,02)a 0,07 (0,09)a 0,03 (0,01)a 0,08 (0,02)a 0,40 (0,06)b 0,39 (0,02)b 0,37 (0,06)b 0,40 (0,02)b Phosphorus Swine Cow 0,77 (0,02)c 0,70 (0,02)b 0,70 (0,03)b 0,15 (0,02)a 0,37 (0,02)a 0,90 (0,02)d 0,91 (0,01)c 0,98 (0,01)e 0,93 (0,01)c

Sedimentation Centrifugation Pressurized filtration Polymer flocculation and drainage Coagulation, polymer flocculation and drainage

cow slurries were similar (12 of 16 were statistically equal). With respect to phosphorus, centrifugation is generally superior to pressurized filtration and equal to sedimentation (Table 2.1). The three mechanical techniques are equal for nitrogen and dry matter. Numerous solid-liquid separations have been performed and presented in the scientific literature. One in six articles presents data sufficient to calculate the reduced separation index (Et). One in four contains information to determine the separation index (Et). Despite the lower information level, the separation index is therefore a better option than the reduced separation index, for comparing the studies presented in the literature. It is essential to keep in mind when comparing the separation indexes, though, that the studies has been performed on slurries of a range of characteristics, thus it is necessary to be cautious with the conclusions. Further specification on the individual studies may be found in Hjorth et al (2010) and the cited references. In general, the literature indicates that sedimentation and drainage provide similar separations (Table 2.2). Centrifugation is superior with respect to phosphorus separation, and pressurized filtration is less efficient with respect to phosphorus separation. The differences between the solid-liquid separation techniques are primarily a matter of the distribution of the colloids (10nm-1m particles) between the two fractions, with the phosphorus content being large in this fraction (Christensen et al., 2009; Masse et al., 2005). According to Stokes law, settling, i.e. both by gravity and forced as in centrifugation, depends on the size and weight of the particles (Henriksen et al., 1998). Brownian movements are substantial for the light colloids, which causes settling to be slow. However, the colloids will settle by allowing long time for settling and/or by applying sufficient force. Sedimentation may therefore be as efficient as centrifugation. When filtering with or without applying pressure, the colloids are detained in the solid fraction if the filter or the filter cake detains it. Filtering slurry, the pore size of the filter needs to be relatively
Table 2.2 Efficiency for separation of five parameters by five separation methods applied to swine and cow manure (Hjorth et al., 2010). The effect of the different separation methods has been compared for each slurry characteristic (volume, DM, N, TAN, P) by Turkeys t-test (P = 0.05) (R development core team, 2008); statistically equal results are indicated by equal letters. Separation method Volume 22 (4)ab 14 (7)ab 23 (16)b 11 (15)a 22 (16)ab Separation index, Et (%) Dry matter Nitrogen Total ammoniacal nitrogen 56 (10)ac 33 ( 2)b 28 ( 2)a bc ab 61 (16) 28 (10) 16 ( 8)a ab ab 44 (27) 27 (17) 23 (19)a a a 37 (18) 15 (17) - ( -) 70 (13)c 43 (24)b 20 (14)a # Experiments

Phosphorus 52 (21)bc 71 (14)c 34 (21)b 17 (14)a 79 (21)c

Sedimentation Centrifugation Drainage Pressurized filtration Flocculation and solid-liquid separation

3-6 5-16 4-14 13-17 10-28

12

large for any filtration to occur at all. In drainage, the necessarily large pore openings cause large loss of the colloids to the filtrate. In pressurized filtration, smaller pore sizes may be utilized. However, because of the applied force, the colloids may penetrate the filter and thus lost to the filtrate. In addition, the force destroys the filter cake causing a more compact structure. The cake may therefore have fewer sites for colloids. Smaller amounts of the colloids are therefore detained by the cake compared to upon drainage. For further discussion on the differences between solidliquid separation techniques, see Hjorth et al. (2010).

Definition: Flocculation To clump together (aggregate) suspended particles into larger masses (flocs), which eventually settle out of suspension. Flocculation is caused by polyelectrolytes. Two flocculation methods are coagulation by multivalent ions and polymer flocculation.

2.2 Efficiency of flocculation and solid-liquid separation

A flocculation may be carried out before the solid-liquid separation. The efficiency of flocculating slurry before the solid-liquid separation may be determined by comparing the efficiency of the solidliquid separations without a pre-flocculation to the efficiency of the solid-liquid separations with pre-flocculation. An experiment has been performed (Jrgensen and Hjorth, 2009): Subsamples of one swine slurry and one cow slurry were flocculated and drained 30 min through a 200 mm filter. Per litre swine and cow slurry was added 0.7 L, respectively, 1.0 L 0.20% Superfloc c-2260 in small dosages; a large, linear cationic polyacrylamide (PAM) with 40 mol% charge density. The swine and cow slurries were also coagulated and flocculated before drainage for 30 min through a 200 mm filter. Per litre swine and cow slurry was added 10 mM FeCl3 and subsequently 0.7 L, respectively, 0.80 L 0.20% Superfloc c-2260. The reduced separation indexes of the two slurries proved an increased efficiency of the solid-liquid separation due to the flocculation pre-treatment (Table 2.1). The coagulation did not improve the solid-liquid separation flocculation significantly. Only the phosphorus separation was more efficient for swine slurry, if the coagulation step was included. Comparisons of literature separation efficiencies indicate flocculation, with and without a coagulation step included, to improve the dry matter separation (Table 2.2). The phosphorus separation is, however, not indicated to be significantly improved by the flocculation. This is in opposition to the results of the previously mentioned study. One experiment provided exceptionally low phosphorus separation indexes (Powers and Flatow, 2002); more than 60% of the phosphorus was reported particle-bound, but the sedimentation without flocculation caused only 17% of the phosphorus to end in the solid fraction, which may be caused by the low sedimentation time (20 min). Excluding this experiment from the calculations of the average separation efficiency, causes the phosphorus separation index calculated from the studies presented in the literature to be significantly improved at flocculation.

13

HOW SHOULD SLURRY BE FLOCCULATED?

Slurry particles may be coagulated and phosphate precipitated by adding FeCl3 or Al2(SO4)3. Roughly half of added Fe precipitates phosphorus and coagulate particles. Afterwards, the slurry should be flocculated with a large, cationic, linear polymer with large charge density. The polymer neutralizes one fourth of the particle surface charges and induces polymer bridging. The polymer solution must be added slowly under carefully considered stirring allowing homogenisation and proper aggregation. The manure could be solid-liquid separated by drainage.

3.1 Polymer flocculation

If flocculation is carried out before solid-liquid separation, the separation of dry matter and phosphorus is improved. Flocculation clumps together (aggregate) hundreds of suspended particles into larger masses (flocs), which eventually settle out of suspension (Gregory, 1989). In a stable solution, particles are dispersed evenly because of an electrostatic barrier, i.e. the particles are negative and repel one another. Upon addition of cationic polyelectrolytes, the solution becomes destabilized, because the positive polyelectrolytes react with the negative particles and the particles are therefore coupled. The mechanisms behind the reaction between a cationic polyelectrolyte and a suspended anionic particle are charge neutralisation, polymer bridging and patch flocculation (Gregory, 1989). Polymer bridging occurs when long-chained polymers adsorb onto the surface of more than one particle, causing the formation of large flocs (Fig. 3.1c) (Gregory, 1989). When a cationic polymer is added to anionic particles, the interaction is a very strong ionic adsorption. Deflocculation occurs at high doses of added polymer or at high ionic strength of the slurry, because polymer loops and tails are formed (Gregory, 1973). At high polymer concentration, the many polymers compete for the particle charges, which cause the polymers to be more randomly attached. If e.g. two neighbour charges on a particle are matched by two charged monomers on a linear polymer that are separated by 3 charged monomers, the part of the polymer string consisting of the three unattached charged monomer and the four related neutral monomers becomes a loop (Fig. 3.1c). At increasing ionic strength, the charged polymer becomes more coiled because of the attraction and repelling by the increasing amount of charges within the solution. This causes a more erratic reaction with the particles, and loops and tails are formed. Due to steric hindrance between the particles, the loop and tail formation leads to deflocculation at large polymer amounts (Gregory, 1973). The maximum adsorbed mass of polymers increases with increasing ionic strength (Eriksson et al., 1993). This is because of an increasingly more coiled structure of the polymer, which result in
Figure 3.1 Principle of interactions between suspended particles and multivalent ions/polymers. a: charge neutralisation, b: patch flocculation and c: polymer bridging (Hjorth et al., 2008)

14

fewer of the polymer charges to be available for reaction with the particles. Polymer characteristics of importance to polymer bridging are molecular weight and the molecular structure (Bouyer et al., 2001; Larsson et al., 1999). This is because large molecules with long tails are capable of catching by-passing particles relatively easily and thus bridge to them. Charge density is also important, as this affects the number of loops and tails that are formed and the interaction between polymer and particles (Ashmore and Hearn, 2000).

Patch flocculation is the adsorption to particles of oppositely charged polyelectrolytes with a charge density higher than the charge density of the particles. Thus, local positively and negatively charged areas are formed on the surface of the particles (Fig. 3.1b) (Gregory, 1973). This results in a strong positive-negative electrical attraction between the particles, especially when the electrical attraction extends far into the solution, i.e. at low ionic strength (Gregory, 1973). This mechanism may be considered as a combination of polymer bridging and charge neutralisation (Fig. 3.1). Deflocculation will occur when the particle surface charges have been reversed. Greater tendencies to patch flocculation are expected for branched polymers compared with linear polymers (Bouyer et al., 2001). This is because branched polymers are more rigid and cannot stretch out and match the charges on the particle. This will thus create more local surface charge reversal than the flexible linear polymers. Additionally, patch flocculation has been not been observed for low-molecular-weight polymers, because a relative large area of the particle surface has to be covered by the polymer (Bratskaya et al., 2005). The actual significance of the different mechanisms may be studied by considering the charge neutralisation degree prior to deflocculation. The analysis assumes a simple one charge-to-one charge reaction. The charge neutralisation mechanism (Fig. 3.1a) may be speculated to neutralize up to 100% of the charges for high efficiency. Patch flocculation may be speculated to require close to 100% of the charges for highest efficiency, as this causes 50% of the negative charges to become positive. The polymer bridging may result in 1-100% charge neutralisation (Stoll and Buffle, 1996). However, the polymer needs to catch every particle, thus a minimum of cationic polymer charges is required. On the other hand, deflocculation due to difficulties with finding available particle sites and steric repulsion needs to be avoided, thus there is also an upper limit for the cationic polymer charges added. Hence it may be speculated that 20-80% of the surface charges need to be neutralized (Gregory, 1989). Two very different polyacrylamides both proved optimum flocculation at a charge neutralisation degree of one fourth (Hjorth et al., 2008). Thus it appears to be reasonable to assume, that polymer bridging is the main mechanism. For cationic polymer and anionic particles, polymer bridging has previously proved less significant. This was explained by the fact that the polymer adopt a rather flat configuration on the negative particle, and thus reduces the opportunity of bridging contacts (Gregory, 1973). High ionic strength reduces the significance of electrical attractions. Thus in contrast to this previous study, the high ionic strength of slurry (Christensen et al., 2009) may cause the increased significance of polymer bridging.

Definition: Polymer A large molecule consisting of a series of monomers covalently linked. Variations include: o Charge: Positive, neutral or negative, which is controlled by the monomers charges. o Charge density: 0-100 mol%, which is adjusted by the neutral-to-charged monomer ratio. o Structure: Linear or branched, which is adjusted by sites available for polymer chain reaction on monomers. o Molecular weight/size: Small, medium, large or very large, i.e. no specific sizes, as the polymerization reaction is difficult to control.

15

The efficiency of the slurry flocculation depends on the polymer characteristics, i.e. charge, charge density, molecular size and structure (Hjorth et al., 2010), with efficiency being one or several of the motivators discussed in section 1.3. In the literature (Hjorth et al., 2010) most studies indicate that a cationic polyacrylamide polymer is superior to anionic and neutral polymers, which correlates well with the fact that the particles in animal slurry are mainly negatively charged (Christensen et al., 2009). Polymers of medium charge density (2040 mol%) have been shown to be most efficient in most studies. This confirms that polymer bridging is the main mechanism behind flocculation in slurry (Hjorth et al., 2008; Vanotti and Hunt, 1999). That is, a polymer of medium charge density has a large number of charged sites. Hence it has the ability to catch particles efficiently as required in polymer bridging. However, a polymer of medium charge density also has many non-charged sites. It will therefore not neutralize the particular area of the particle surface completely. It will leave charges available on the particle surface for another polymer. Hence charge neutralisation (Fig. 3.1a) is not pronounced, and neither must patch flocculation be significant. Further indications on the optimum polymer characteristics are that polymers of large molecular weight are preferable to those of smaller molecular weight (Hjorth et al., 2010). The reason may be the very efficient capture of smaller particles by the large flocs. Additionally, the resulting large size shape of the flocs may be an advantage in the solidliquid separators used to treat the flocculated slurry, especially when using separators, where liquid is drained off the solids. An experiment has been performed (Hjorth et al., 2008): Subsamples of a swine slurry sample were flocculated with different amounts of two cationic polyacrylamides: a linear, large polymer with a charge density of 40 mol% and a branched, medium sized polymer with a charge density of 80 mol%. The samples were separated by centrifugation, drainage and pressurized filtration. Small differences were observed between the polymer types, which were mainly because of the different shapes of the flocs. Small and compact flocs was formed by the smaller, branched, large-chargedensity polymer. This caused the observed slightly larger dry matter content of the solid and slightly lower resistance to drainage, as the liquid more easily passed by the small and dense flocs. The large, linear, low-charge-density polymer created large and loose flocs. This resulted in efficient catching of the small particles. Thus a slightly lower liquid turbidity and liquid phosphorus content following drainage was observed. If the polymer was under dosed, the linear polymer caused fewer difficulties with the Figure 3.2 Average specific filter-cake resistance at pressurized filtration of flocculated resistance to filtration. slurry (Hjorth et al., 2008) If the polymer was 1e+16 overdosed, the branched polymer branched polymer Fe and branched polymer caused the largest linear polymer 1e+15 liquid turbidity, but the Fe and linear polymer lowest resistance to 1e+14 filtration. The high filtration resistance induced by overdosing 1e+13 the linear polymer (Fig. 3.2) is because of the increased steric 1e+12 hindrance at a smaller polymer amount above 1e+11 optimum. This results in deflocculation and destruction of floc 1e+10 structure. The higher 0 1 2 3 4 5 6 Polymer charge (meq/kg slurry) liquid turbidity caused
Specific filter-cake resistance (m/kg)

16

by the branched polymer, is that despite the less pronounced deflocculation, the compact flocs are less efficient at adsorbing the small particles. Selecting between the two polymers are thus a matter of the individual application. However, the linear, large, low-charge-density polymer appears to be the appropriate polymer in many applications.

Definition: Polyacrylamide (PAM) Consists of n times the monomer acrylamide and m times a charged monomer, e.g. the cationic N,N-dimethylaminoethylacrylate methylchloride:
CH CH2 C O (CH2) 2 O m CH CH2 C O NH2 n

The polymer applied for slurry flocculation + N in the literature is primarily polyacrylamide Cl CH3 CH3 (Hjorth et al., 2010). The separation products CH3 are often destined to be applied to cultivated (Cytec Indutries Inc., 2006) fields. Thus the environmental and health consequences of the applied polymer must be considered. The solid fraction will contain the majority of the polymer. Therefore, if e.g. this fraction is to be anaerobically digested or thermally converted, the environmental and health consequences may be expected to be less. Although polyacrylamide has proved nontoxic, the monomers of polyacrylamide are toxic and e.g. a nerve toxin (Caulfield et al., 2002). A study on separated slurry products, however, showed the risk of polyacrylamide to be minimal (Schechter et al., 1995). In the USA, these additives are considered to be generally recognized as safe (GRAS) when added to the slurry below a specific application rate related to the end use (Vanotti et al., 2002). However, there is a need for further studies on the efficiency of alternative polymer types for slurry separation, with the objective of replacing polyacrylamide with potentially less toxic polymers. Furthermore, when considering new polymers, it is necessary to consider the toxicity of the organic components produced during degradation of the polymers. Alternative flocculants include the synthetic polymer polyethylene imine and polydiallyldimethylammonium chloride and the natural polymer chitosan, as well as the natural flocculants guar gym, sodium alginate, starches, seed extracts and microbial extracellular polymers (Garcia et al., 2009; Gregory, 1989; Salehizadeh and Shojaosadati, 2001; Sievers et al., 1994). Recently, the effect of polyacrylamide and chitosan flocculation has been compared with respect to the separation of dry matter, volatile solids, nitrogen and phosphorus. The cationic chitosan was proved potential as a replacement of polyacrylamide in slurry separation (Garcia et al., 2009).

3.2 Coagulation and precipitation

Flocculation may include a coagulation step before the polymer flocculation. Through addition of multivalent cations (coagulants) it is possible to neutralise the particles surface charge by oppositely charged counterions. Aggregation is induced because of the reduced electrostatic repulsion; a process termed charge neutralisation (Fig 3.1a). Overdosing occurs if the adsorbed ions reverse the surface charge, as the positive particle surfaces will cause increased repulsion between two particles (Gregory, 1989). According to the modified double layer theory, a negative particle is surrounded by the rather stationary Stern layer of positive counterions electrostatically attracted to the particle. The Stern layer is surrounded by diffusive layer of positive counterions distributed more broadly in the dispersion medium (Gregory, 1989). In addition, the Van der Waahls forces induce attraction between particles. The sum of these interaction contributions has been assumed to result in the attraction and repulsion between particles; the DLVO approach. The result is two interaction energy minima and thus two particle-particle interaction distances. The secondary electrical minimum and longest interaction distance predominantly is related to polymer flocculation. The primary electrical minimum is related to the coagulation interaction with a multivalent cation. In addition to charge neutralisation, the multivalent positive ions may precipitate the dissolved orthophosphorus, i.e. PO43-/HPO42-/H2PO4-. The reactions between iron and orthophosphate include 17

precipitation of ironphosphates such as FePO4, co-precipitation with ferric hydroxides which could be Fe(OH)3(s), and adsorption of phosphate ions onto ferric hydroxide ions which could be Fe(OH)3+(aq) (Pierri et al., 2000; Takacs et al., 2006). An experiment has been performed (Hjorth et al., 2008): A swine slurry characterized by 0.3 g total phosphorus and 0.05 g phosphate per L and a particle surface charge of -9.81 meq L-1 slurry was used. The slurry samples were added 0 and 10ml 1M FeCl3 per L slurry, and after polymer flocculation and drainage, 87% respectively 92% of the total phosphorus was retained in the solid fraction. Based on this, an estimate may be obtained on how much of the added multivalent ions coagulate and how much precipitate phosphorus. The slurry contained 1.5 mmol phosphate per L and the 10mmol Fe added caused the precipitation of 0.5 mmol phosphorus (0.3gP / 31g mol-1 * (92%-87%)). Under the specific experimental conditions and assuming that the phosphate was not retained as dissolved in water within the flocs upon polymer flocculation, the reaction ratio in slurry was therefore roughly estimated 0.05 phosphate ion per added Fe atom (0.5mmol phosphate/10mmol Fe). The essential iron-phosphate precipitate is FePO4 (Takacs et al., 2006). Thus the iron-phosphate precipitate has a 1:1 molar ratio in P:Fe. The phosphate precipitation will therefore require approx. 0.5 mmol Fe L-1 slurry (0.5mmol PO43- * 1meq P / 1meqFe). It was evident from the appearance of the floc formation in the slurry solution that 100% charge neutralisation did not occur. However, if 100% charge neutralisation of the slurry particle surface actually had occurred, it would require 5 mmol Fe L-1 slurry (9.81meq / 2meqFe/mmolFe). Thus, approximately 50% of the added Fe ((5 mmolFe for coagulation + 0.5 mmolFe for precipitation) / 10mmolFe added) is precipitating or coagulating. The rough estimate that half the added Fe precipitate phosphorus and coagulate particles indicate that the Fe is also involved in other reactions. Additionally, despite the apparent Fe and P excess (1.5mmol phosphate available but 0.05mmol precipitated), the calculated ratio of 0.05 phosphate ion precipitating per added iron atom are very low compared to in municipal waste water, in which a reaction ratio of 0.3-1.2 has been measured (Smith et al., 2008; Takacs et al., 2006). The efficiency of Fe appears to be low in slurry under the higher conductivity conditions of slurry. This may be because e.g. of formation of non-P containing Fe hydroxides, ion exchange on existing slurry molecules and precipitation of other slurry components. The improved phosphorus separation by the multivalent ion addition is a result of phosphate precipitation and/or agglomeration of small particles. However, the particle agglomeration in slurry is only slightly significant, which is expressed e.g. by the absence or only low reduction in polymer requirement and dewatering (Hjorth et al., 2008; Hjorth et al., 2009; Jrgensen and Hjorth, 2009). Aggregation of the small particles may alternatively be performed by a small polymer instead of or in addition to the coagulation by the multivalent ion (Odegaard et al., 1999). Unlike the multivalent ion addition, this will not result in the dissolved phosphate to be precipitated. However because of the relatively high phosphorus content in the small particles (Christensen et al., 2009; Masse et al., 2005), which may be more effectively coagulated, a rather efficient phosphorus removal may still result. A broad range of multivalent cations have been tested for slurry treatment. This provides the opportunity to compare the efficiency of additives, and to assess which multivalent ions provide the best slurry separation (Hjorth et al., 2010), with efficiency being one or several of the motivators discussed in section 1.3. If the multivalent cation added to the slurry is calcium, the efficiency is ranked as CaO > Ca(OH)2. If the multivalent ion is iron, the efficiency is ranked as FeCl3 > Fe2(SO4)3 > FeSO4. While, if the multivalent ion is aluminium, the efficiency is ranked as Al2(SO4)3 > AlCl3. When comparing the most efficient molecule of the three mentioned multivalent ions, the efficiency order is: Al2(SO4)3 FeCl3 > CaO.

18

The higher the cationic valence, the more efficient, which is explained by the increasing efficiency for reducing a particles surface charge (Gregory, 1989). In addition, the atomic size is also slightly relevant. That is, decreasing the radius of a particle without changing the charge, the hydration layer thickens, the particle approaching velocity decreases, and the efficiency for reducing the particle repulsion decreases. Iron is slightly larger than aluminium, but though added as Fe3+ it may under the typically anaerobic conditions of slurry be present as Fe2+. Aluminium may be only trivalent: This is one explanation to the absence of a straightforward efficiency comparison. The ultimate use of the separation products should, in addition, be considered when selecting the multivalent ion. For example, a decrease in pH is observed upon addition of FeCl3 and Al2(SO4)3 (Hjorth et al., 2009). This could be an advantage as this will reduce NH3 emissions. CaO causes pH to increase. This may be preferable when nitrification/denitrification or NH3 stripping is to follow the separation (Szgi et al., 2006). Aluminium, iron and calcium are naturally present in soils. However, the significance of the amount added with slurry relative to the natural content should also be considered, as e.g. aluminium is toxic to organisms living in water (Nahm, 2005).

3.3 Addition procedure

The addition procedure is essential for the reactions to be efficient. That is, for the coagulation and phosphorus precipitation induced by the multivalent ion, and additionally for the polymers flocculation of slurry particles, coagulated slurry particles and orthophosphate precipitates. If both additive types are used, the multivalent ion is initially added to the slurry to collect the dissolved phosphorus and small particles in larger agglomerates. Upon addition in batch experiments, an initial vigorous mixing causes a homogeneous distribution. A secondary longer and slower stirring is performed with the aim of allowing time for reactions ensures efficient reactions (Szabo et al., 2008). Next, the polymer is added to collect the larger particles and the agglomerates formed by the multivalent ion. Under continuous operation, the polymer should be added continuously and gradually, and the applied shearing velocity should be carefully selected. In batch experiments, the polymer should be added slowly in small doses during a short vigorous stirring (e.g. 30 sec). This should be followed by a longer lasting slow stirring (e.g. 2 min). This is necessary for polymer bridging and patch flocculation to occur. The shear applied, which depends on the time and stirring velocity of the impeller, has a large impact on the formation of the aggregates. In addition, the design of the stirring chamber has an effect on the flocculation kinetics. The flocculation kinetics are controlled by the actual particle collision mechanism, which depends on the specific sample and shear conditions. The possible mechanisms are perikinetic flocculation (brownian motion/diffusion which occurs at low shear), orthokinetic flocculation (fluid motion which occur at large shear) or differential settling (different particle density/sizes causing different settling velocities and thus collisions which occur at lower shear). Too low a shear causes primarily perikinetic flocculation and differential settling. This causes the aggregates to be non-uniform and unstable. Additionally, the particle catchment will be inefficient, and polymer droplets may even act as nuclei for floc formation. On the other hand, too large a shear causes primarily orthokinetic flocculation, and cause the aggregates to be destroyed, or even the polymer chains to be broken (Gregory, 1989; Mikkelsen, 1999).

3.4 Solid-liquid separation

After the careful multivalent ions and polymer additions and flocculation, the slurry may be transferred to ordinary solidliquid separators. In laboratory this is e.g. 0.1-1 L samples drained by using a cylinder covered by a filter cloth in the bottom (Hjorth and Christensen, 2008), and on farms being continuous separation of e.g. 5 tons per hour on a belt separator (Hjorth et al., 2010). An experiment has been performed (Hjorth et al., 2008): Swine slurry was flocculated with four flocculent combinations and centrifugation, drainage and pressurized filtration was performed. The 19

effect on the dry matter separation, phosphorus separation and liquid turbidity by the three solidliquid separations techniques were insignificantly different. Comparing the studies in the literature the indication is the following efficiency ranking for separation phosphorus: drainage > centrifugation > sedimentation, while for separation dry matter and nitrogen: sedimentation > drainage > centrifugation. The previous studies indicate that sedimentation removes dry matter and nitrogen but not phosphorus efficiently from the liquid. The largest particles generally settle the quickest. Hence the settling time in the experiments may not have been sufficient for settling of the smallest particles, which has a high amount of phosphorus. Very little shear is applied to the flocs upon drainage, and therefore are drainage an efficient solidliquid separation following flocculation. The relative efficiency of solid-liquid separation techniques may depend on the flocculation, with small compact flocs preferential upon settling and fluffy easily-drained-by flocs preferential upon drainage. Alternative solid-liquid separation techniques are being developed for flocculated slurry that take into account the fragile nature of the slurry flocs. Examples are the Filter tower, i.e. drainage though a filter sock and gentle squeezing sideways by balloons (Timmerman, 2008). Another example is the solid-liquid separator draining along a pipe, and gentle squeezing along the pipe by multiple rings slowly, sequentially expanding and contracting the diameter (Christophersen, 2008).

20

WHAT AFFECTS FLOCCULATION?

The slurry ionic strength, particle zeta-potential, particle surface charge, total and specific dry matter content, content of multivalent metals and speciation of nutrients are slurry characteristics in control of flocculation efficiency. The characteristics are determined by the animal excreting the slurry, and the handling of the slurry between excretion and separation

4.1 Physical and chemical characteristics of slurry

Polymer flocculation, coagulation and phosphorus precipitation are modifications of the slurrys chemical and physical characteristics. The chemical and physical characteristics of the input slurry are therefore of significance to these processes. The slurrys physical and chemical characteristics differ significantly from other media commonly flocculated, such as municipal wastewater. This causes the mechanisms of polymer flocculation, coagulation and phosphorus precipitation to differ. The ionic strength expresses the ionic content of the liquid. The conductivity is typically applied to express this (Sommer and Husted, 1995). For slurry of young pigs, finishing pigs and gestating sows, the conductivity has been observed to be 17-21 mS/cm (Christensen et al., 2009), Relative to e.g. municipal wastewater, this ionic strength is high. Increasing the conductivity affects flocculation, because it reduces the spatial extent of particles electrostatic attraction and repulsion. Thus it affects the potential range of interaction. This is according to the DLVO theory, because as the concentration of counterions in the Stern layer and diffusive layer increases, the thinner the ion layers is required to balance the particle charges (Gregory, 1989). The chance of coagulation is increased due to the reduction in layer thickness and thus reduced electrostatic repulsion. More charges in the liquid are available for reaction at high conductivity. Thus the chance is larger for reaction between the cationic polymer and a nearby ion. Therefore the polymer flocculation may be less efficient as e.g. the polymer becomes curled. The high ionic strength will also reduce the molecules activities/effective concentrations, which may be expected to result in reduced phosphate precipitation by the multivalent ion. A particles zeta-potential is the electrical potential at the plane of shear, i.e. between a particle and a fluid when there is relative motion between them (Gregory, 1989). The zeta-potential is assumed an adequate substitute of the Stern-potential between the Stern and diffusive layer. The particle zetapotential is approximately -35 mV in swine slurry (Christensen et al., 2009). Thus, the overall slurry particle charge is negative, and the flocculating agents need to be cationic. Additionally, the size of the zeta-potential indicates the slurry solution to be moderately stabile, thus it does not flocculate spontaneously (Gregory, 1989). A solution with a zeta-potential of 0 mV is an unstable solution, which spontaneously flocculate. When increasing the amount of flocculating agent, the zetapotential will increase. The charge density will therefore decrease, and the slurry solution will become instable and flocculate. A particles free surface charge may be measured at the plane of shear. That is plane of shear is the actual surface charge partially neutralised by the Stern layer counterions. It is reasonable to apply this as a measure of a particles surface charge, as the interaction between charged particles is governed predominantly by the overlap of diffusive layers (Gregory, 1989). The surface charge originates from ionization of surface groups and specific adsorption of ions. It may be measured by quantifying the amount of a small well-defined polymer required to reach a zeta-potential of 0 mV (Mikkelsen, 2003). The average surface charge of one swine slurry was assessed to -10 meq/kg (Christensen et al., 2009). Hence, if 100% charge neutralization is to be obtained, 10 * 10-3 equivalent positive charges need to be added per kg slurry. Slurry particles consists of 10-15% proteins, 15-20% humic substances/lignin, 10-30% carbohydrates/cellulose, 10-25% hemi cellulose, 5% fat, and in addition 15-25% inorganic 21

compounds such as struvite (Christensen et al., 2009; Liao et al., 2004; Rico et al., 2007). The relative amount of free charges on these compounds varies. E.g. fat have fewer free charges than the humic substances, as humic substances is a mixture of partially degraded organic compounds. By increasing the relative content of the high charge compounds such as the humic substances, the slurry particles free surface charge density increases. The protein content appear to hold the main responsibility for the different surface charge of different particle size groups. The argument is that the charged organic compound primarily changing in content between particle size groups are the protein (Christensen et al., 2009). The total dry matter content of slurry is 4-7% under Danish conditions (Sommer and Husted, 1995). The polymer bridges between the particles, thus by lowering the concentration of dry matter, while keeping the particles being the same, an equally efficient polymer flocculation will require lower polymer amount. The relationship between the slurrys dry matter content and the polymer requirement may, however, not be linear (Stoll and Buffle, 1996). At high particle concentrations, steric hindrance and thus deflocculation may more likely occur. This causes a smaller polymer volume range to result in optimum flocculation. This is supported by experiments on polymer flocculation of slurry, showing that slurry with low dry matter content requires a very high polymer dosage for deflocculation (unpublished data). At very low particle concentration, the polymer bridging may not be as efficient due to difficulties with catching the particles. Thus, this results in an increased polymer demand. This is indicated by experiments performed on polymer flocculation of slurry (Vanotti et al., 2002; Zhang and Lei, 1998). In addition, the required shear for optimum floc formation may depend on the dry matter content. The most significant multivalent ions naturally occurring in slurry is Ca, Mg and Fe (Masse et al., 2005). The dissolved content is 200-300 mg/kg, 5-20 mg/kg and 2-3 mg/kg, respectively (Christensen et al., 2009). This is 5-20% of the total content of the specific multivalent ion. In a flocculation experiment with efficient phosphorus separation, 0.5 mgFe/L was added (Hjorth et al., 2009). Hence the naturally occurring multivalent ions play a significant in the phosphorus precipitation and coagulation, and the additionally added multivalent ions may merely push the chemical equilibrations. Approximately 30% and 70% of swine slurry nitrogen and phosphorus, respectively, is contained in particles (Christensen et al., 2009). Approx. 70% of the phosphorus and particle-bound-nitrogen is contained in or adsorbed to the 0.45-10 m particles (Masse et al., 2005). Nitrogen and phosphorus separation is of large importance to farmers. The most essential nutrient in the small particles is thus phosphorus. Coagulation is the primary mean of flocculating the small particles of slurry. Thus increasing the phosphorus content in the small particles will raise the need for a coagulating agent. In addition, the particle size distribution has an effect on the surface area available for reactions and the particle sizes present for polymer catching. Other characteristics that may have an effect of slurry flocculation include the particle shapes, slurry particle rigidness, pH and viscosity, see e.g. further in Hjorth et al. (2010) and Christensen et al. (2009) and cited references.

4.2 Slurry origin and pre-treatment

The slurrys physical and chemical properties are determined by the animal origin and pretreatments of the slurry. Cattle and swine manure have different chemical compositions (Hjorth et al., 2010). There is, however, no general trend on the flocculation efficiency between the slurry types (Hjorth et al., 2010; Jrgensen and Hjorth, 2009). The chemical composition of swine manure differs between young pigs, sows and finishing pigs (Christensen et al., 2009; Hjorth et al., 2010). E.g. the particle surface charge is the highest for sows. The dissolved multivalent cation content is highest for the finishing pigs. This may be expected to have an effect on the flocculation efficiency. The feeding strategy of swine has proved an effect on the separation (Daumer et al., 2004; Powers and Flatow, 22

2002; Sommer et al., 2008). Phytase addition has resulted in increased separation efficiency of phosphorus upon screw press separation and reduced separation efficiency of phosphorus upon flocculation and drainage. This may be explained by the phytases effect on the particle size distribution (Sommer et al., 2008). Storage of slurry has in practice been observed to increase the polymer demand (Nissen, 2006). During storage of three pig slurries for 35 days at 12 C, the free surface charge, the total content of humic substances and total content of dry matter remained unchanged, while the content of phosphate increased (Christensen et al., 2009). The phosphate increase may result in a reduced phosphorus separation index. However, the absence of change in total content of dry matter and humic substances and the free particle surface charge does not support the findings in practice of the increased polymer demand. The absence of effect on the expected polymer demand, may however be ascribed to the low storage temperature, and thus the low microbial metabolism. Previously, e.g. storage for 8 days at 18 C has proved to reduce the particle sizes, while storage at 20 C for 5 months has proved to decrease the dry matter content by 25% (Kunz et al., 2009; Moller et al., 2000). If assuming unchanged composition of the dry matter, the decrease in the dry matter content would result in a decreased polymer demand. The observed dry matter decrease must, though, be a result of slow dry matter degradation. Thus e.g. the content of smaller particles of partially degraded organic matter (humic substances) may increase, and therefore increase the free particle surface charge density. Storage may thus result in an increased polymer demand and/or e.g. a changed charge density of the polymer to be applied. An experiment has been performed (Hjorth et al., 2009): Swine manure was fermented in a thermophilic reactor with a retention time of 15 days to produce biogas. Three FeCl3 dosages were applied to the unfermented and the fermented slurry, and for polymer flocculation, the optimum charge density of a cationic, linear, very large polymer was determined, as was the optimum polymer amount. In addition, the phosphorus separation was determined, and showed a decrease after fermentation. The optimum charge density of the polymer for the unfermented slurry was 40%, as has also been observed in several experiments previously (Hjorth et al., 2010). The optimum charge density of fermented slurry was 10%. The required polymer dosage was 1/3 larger than the unfermented slurry. The approx. 30% reduction in the required polymer amount may be explained by the 40% reduction in DM and VS content upon fermentation. The decrease in required charge density may be explained by the fermentations extensive degradation of e.g. large, high charged humic substances into smaller, lower charged substances such as volatile fatty acids. This degradation may also have caused the reduced phosphorus separation, as phosphorus containing compounds may have been entirely degraded. Thus the particle bound phosphorus would have turned into dissolved phosphorus. In addition, a reduced amount of surface charges on the particles, causes fewer phosphate ions to be adsorbed as a counterion on the particles. Additionally, e.g. addition of acids for reducing NH3 emission and ozonation for reducing H2S emissions may result in a change in the physical and chemical characteristics of the slurry and therefore affect the flocculation.

23

HOW SHOULD FLOCCULATION BE CONTROLLED?

The flocculation of the continuously changing slurry may be automated. Seven analyses have indicated potential to monitor slurry separation in bench scale experiments or on-line at full scale separators, with the aim of subsequently regulating the process parameters according to the input manure. These are the solid fractions dry matter content, the liquid fractions turbidity and viscosity, the flocculated samples floc size, dewaterability and capillary suction time, and near infrared spectroscopic measurements.

5.1 At-line direct analytical methods

Because the slurry origin and pre-treatments have such effect on the physical and chemical characteristics of slurry, the polymer amount required to achieve the optimum flocculation of slurries varies considerably. The slurry origin varies rapidly on farms, e.g. because the sty with animals of different ages and feedings are emptied randomly into the manure pre-tank to handle. In addition, deflocculation occurs if the polymer dosage becomes too high (e.g. fig. 3.2). This makes it impossible to merely add a large polymer amount to ensure proper flocculation. Thus, control of the flocculation is necessary to ensure optimum flocculation, which may be done by monitoring the flocculation using an analytical method. In practise today, the polymer dosage is determined in laboratory scale by multiple, manual tests in 1L beakers by trained personal (Nissen, 2006). This is done initially for assessing the required polymer volume and on a regular basis on continuously running separators. A simple, cheap and quick analytical method would thus be preferred for assessing the optimum polymer volume. When performing slurry flocculation, five aspects are essential (Table 5.1)
Table 5.1 Separation performance criteria, the aim and the connected direct analytical method (Hjorth and Christensen, 2008) Connected direct No. Separation criterion Aim analytical method 1 Low P content of liquid fraction Reduce P loss after field-spreading of manure P content of liquid fraction 2 High DM content of solid fraction Minimize long-distance transportation of nutrients DM content of solid fraction 3 High VS content of solid fraction Increase the energy concentration VS content of solid fraction 4 High throughput of separator (L/hr) Reduce cost Dewaterability 5 High floc strength Avoid reduction in dewatering and Surface erosion in separation efficiency

Five direct analytical methods are therefore of interest for monitoring the flocculation, with the term direct referring to the fact that an analytical method is directly linked to a separation criterion. Because the separation criterions may be achieved at similar polymer amounts (Hjorth and Christensen, 2008), an analytical method may also be useful for monitoring the fulfilment of a nonconnected separation criterion. Thereby the analytical method may be termed indirect. Two of the analytical methods have proved the largest potential, i.e. the dry matter content of the solid fraction, which is determined by heating the sample to 105 C for 24 hours, and the dewatering measure, which is calculated from the continuously monitored weight of the filtrate (Hjorth and Christensen, 2008). The two analytical methods may be applied to monitor the connected separation criterion as well as the other four separation criteria. The reason for the relation between the dry matter and the volatile solid content are that the dry matter and volatile solids mass ratio is not significantly affected by small extra loss of organic matter upon separation, which is lost because the colloids are mainly organic and colloids may be lost to the filtrate. Dewatering and dry matter content of retentate are related (Fig 5.1), because an efficient and time-limited dead-end drainage causes the largest volume of filtrate. Phosphorus is primarily contained in the particles, thus increasing the dry matter content of the solid fraction 24

increases the phosphorus content Figure 5.1 Correlation between gravity dewatering of flocculated slurry and of the solid fraction, which dry matter content of the obtained solid fraction. Samples were flocculated with different volumes of the indicated additives (Hjorth and Christensen, explains the correlation between 2008). the solid fraction dry matter content and liquid fraction 15% phosphorus content and the dewatering. In addition, the dry matter content of the solid 10% fraction may be used to monitor the flocs surface erosion. By improving the polymer 5% flocculation, the particle becomes Branched polymer Branched polymer + FeCl3 more entangled by the polymer Linear polymer Linear polymer + FeCl3 causing less erosion on the floc 0% surface. Additionally, when 0 1 10 100 improving the polymer 1/2 Dewatering (L/s ) flocculation, more particles becomes entangled by the polymer, thus improving the dewatering and increasing the solid content of the solid fraction. See further on the relationship between the methods in (Hjorth and Christensen, 2008).

5.2 At-line indirect analytical methods

Dry matter determination of the solid fraction is time consuming. Dewatering measurement requires specific equipment and calculations. In addition, the actual flocculation needs to be performed. Alternative analytical methods measure other flocculation characteristics than the ones measuring the separation criteria directly (Table 5.1) and therefore termed indirect analyses, but are correlated to the direct measurements of the criteria. Sludge volume index (SVI), capillary suction time (CST) and floc size have previously proved valuable as indirect methods for the laboratory determinations of the optimum polymer volume of other media (Bache and Zhao, 2001; Baskerville and Gale, 1968; Zhao, 2003). Of the three, floc size and CST determination have proved large potential in slurry (Hjorth and Christensen, 2008). Floc size is a relative visual determination with 1 being practically no floc visible and 5 for the largest flocs. CST is determined by pouring a flocculated sample into a cylinder positioned centrally on a filtration paper, and measuring the duration for saturation of the paper. Capillary suction time expresses the velocity of drainage through the sample, therefore the relation to the dewatering despite different sample height-to-filter area of the two techniques. Large flocs cause minimum surface erosion, thus evidently, the large flocs has the particles firmly attached to the polymer. See further on the relationship between the methods in (Hjorth and Christensen, 2008). Ionic strength, particle zeta-potential, particle surface charge, total and specific dry matter content, content of multivalent metals, particle size distribution and speciation of nutrients are slurry characteristics that affect the flocculation. Thus measuring one or a combination of these characteristics of unflocculated slurry may also have potential for indirectly determination the polymer demand.

5.3 On-line indirect analytical methods

In continuous operation on farms, correct polymer addition needs to be monitored continuously as the input slurry varies, such as when emptying a slurry tank. For continuous operation, a quick and on-line analytical method is preferred for the process monitoring. Turbidity of the liquid fraction, viscosity of the liquid fraction and particle dispersion analysis (PDA) have previously proved valuable as indirect methods for the laboratory determinations of the 25

DM (%), solid

optimum polymer volume of other media (Dentel et al., 2000; Eriksson et al., 1992; Huang and Chen, 1996). All are methods that may be applied on-line. Of the three, liquid turbidity and viscosity determination have proved large potential in slurry (Garcia et al., 2009; Hjorth and Christensen, 2008). Liquid turbidity is measured as the light scattering at 600 nm with a spectrophotometer. Liquid viscosity is measured with a devoted apparatus as the resistance exhibited by the liquid on a rotating object. Turbidity estimates the particle size distribution and amount in the liquid, which relates to the amount of small particle in the flocculated sample. These clog the filter and formed filter cake. This causes filtration resistance, and therefore the relationship between dewatering and liquid turbidity. Liquid viscosity increases with particle content, and is therefore related to the liquid turbidity. See further on the relationship between the methods in (Hjorth and Christensen, 2008). Near infrared (NIR) spectroscopy is a method that may have potential to be applied on-line. In contrast to the previously mentioned methods, NIR may be applied without flocculating the slurry. The NIR region of the electromagnetic spectrum is 800-2500 nm. The energy is absorbed by overtones and combination bands of a molecular vibrations and rotations. These molecular movements are executed by covalent bondings. An NIR spectrum, therefore, primarily displays band of O-H, C-C, C-H, C-O, C-N bondings one or more places in the spectrum (Benito et al., 2008). Slurry contains multiple organic components and 90% water, thus the resulting slurry spectrum becomes a disturbed water spectrum (Fig. 5.2). That is impossible to interpret directly. Multivariate analysis is therefore required such as PLS1 with a validation set. To obtain a calibration curve of one slurry characteristic, thus, 100-200 samples needs to be analyzed for the actual characteristic, and NIR spectra needs to be obtained (Malley et al., 2005). Sampling is essential to obtain the optimum NIR spectra. Due to the dark colour and high particle content of slurry, reflection measurements have previously been used (Malley et al., 2005; Saeys et al., 2004; Sorensen et al., 2007). However, transmission has proved advantages over reflection measures e.g. for determining slurry pH and ammonia content (unpublished data). Slurry particles settles rapidly (Hjorth et al., 2010), thus to obtain the optimum number of scans to average for a spectrum, the slurry needs to be in motion. A flow cell has been developed (Holm-Nielsen et al., 2007). However, transmission is not possible, and an alternative sampling apparatus has therefore been developed (unpublished data, Fig. 5.2). An experiment has been performed (Hjorth and Larsen, 2007): Swine slurry was flocculated with forty different flocculant combinations and drained. The phosphorus, dry matter and volatile solid separation as well as the dewaterability were determined. Of the flocculated samples and liquid fractions transmission NIR spectra was obtained: The FT-NIR QFAflex600 from Qinterline/Bohmem was used, an InGaAs detector Figure 5.2 Near infrared spectra of one cow, one pig slurry and water (2, was applied, the 10 respectively 1 replicate measures of 1L samples), measured as transmission resolution was 32 cm-1, in through a polyethylene hose with 4 mm path length containing slurry in movement. Absorbance 10 sec 50 scans was obtained and averaged to obtain a spectrum, vials with a 3 mm path length were applied, and calibration was done with PLS1 on spectra pretreated by mean centering and validated using cross validation. Comparisons of the r2, standard error of cross validation (SECV), ratio of NIR standard error prediction to sample standard error prediction
Wave number (cm-1)

26

(RPD), and ratio of the sample value range to standard error of NIR prediction (RER) were performed. Because of the low sample amount in the calibration, the precision should be improved before the calibration may be applied, as RER = 8-12 which is equal to a moderately successful/useful calibration (Malley et al., 2005). However, the near infrared spectrum of the liquid fraction provided excellent/moderately successful predictions, and the liquid fractions were superior to the flocculated sample (r2 = 0.97, 0.88 respectively 0.87 versus 0.77, 0.81 respectively 0.79) to control the phosphorus, dry matter and organic dry matter separation. Thus, NIR may additionally be a potential technique for determining the optimum slurry flocculation.

27

HOW SHOULD SEPARATION PRODUCTS BE APPLIED?

Storage in tanks, application on fields, anaerobic digestion, membrane filtration and thermal conversion are potentially present-day handlings of slurry separation product. These improve practical farming aspects, fertilization and/or energy production. Solid-liquid separation and flocculation improve most of the typical handlings of manure or may even be a pre-requisite. Attention is necessary if the overall result should be no effect or there should be positive effect on the slurry products emission of ammonia, greenhouse gases and odour and the efficiency as a substrate for plants.

6.1 Storage
A well-controlled flocculation and solid-liquid separation produce products useful for many purposes, which involves one or several additional treatments (Fig. 6.1). Depending on the posttreatment, different practical and environmental goals may be achieved. Storage of the raw slurry and of solid and liquid fraction should, according to Danish legislation, occur in a covered storage tank with dimensions sufficient to contain 9 months production of slurry (Husdyrgdningsbekendtgrelsen, 2006). Storage is performed until further treatment, and is a passive but essential treatment. During the storage and upon filling and emptying the storage, the slurry becomes aerobically/anaerobically digested and emission of ammonia, odour and greenhouse gasses occur. The actual degradation of the slurry and the emissions depends on the specific separation performed. Mechanical separation increases the emission of ammonia and CO2, and decreases methane emission during storage from the solid and the liquid fraction compared to the raw slurry (Amon et al., 2006; Dinuccio et al., 2008; Fangueiro et al., 2008; Petersen and Sorensen, 2008). Flocculation causes a decrease in the ammonia, methane and CO2 emission from the liquid fraction with e.g. increasing the addition of FeCl3 causing further reduction in the ammonia emission (Fangueiro et al., 2008; Hjorth et al., 2009). Mechanical separations have no effect on the odour emission (Zhu et al., 2001). A tendency toward odour reduction has been observed following the polymer and FeCl3 addition (Hjorth et al., 2009). Flocculations reduction of emissions from the liquid fractions may, when observed, be caused by pH reduction by the multivalent ion, lower nitrogen content, and minor amount of small particles.

6.2 Field application

Raw slurry, solid and liquid fraction and fractions further refined may be applied onto agricultural fields. It may be applied by a tractor with slurry reservoir using a broad spreader, trailing hoses or injected, with injection proving Figure 6.1 One of many combinations of slurry treatments superior for the liquid fraction (Nyord et al., 2008). Field application is performed to re-cycle the nutrients and replace mineral fertilizers. Raw slurry application according to the nitrogen requirements of the crops results in excessive phosphorus application, and thus leaching into the environment. However, the liquid fraction produced at separation contains less phosphorus, and thus result in reduced leaching to the environment. The solid fraction 28

contains a large amount of phosphorus. It may therefore be applied as a phosphorus source on phosphorus deficient fields. The changed distribution of the nutrients in the slurry may cause reduced slurry transportation. Fractions of both mechanically and polymer flocculated slurry has been observed to increase the plant yield (Chantigny et al., 2007; Ebeling et al., 2003; Fanguelro et al., 2007). In the liquid fraction, it may be explained by an increased availability of nitrogen. On the other hand, a negative impact on plant yield could be expected by flocculation upon multivalent ion addition as a result of reduced plant availability of the phosphorus (Romer, 2006), and because of possible toxicity of the multivalent ion and monomer of polyacrylamide (Caulfield et al., 2002; Nahm, 2005). Emission of ammonia is reduced from the solid and liquid fraction relative to raw slurry application (Amon et al., 2006; Balsari et al., 2008; Chantigny et al., 2007; Fanguelro et al., 2007; Gordon and Schuepp, 1994; Hjorth et al., 2009). The methane and nitrous oxide emissions have been indicated to increase. And e.g. application of the liquid fraction with increasing FeCl3 amount result in decreasing ammonia emission.

6.3 Membrane filtration

The liquid fraction may be divided into a water-ish liquid and fertilizer concentrate(s) by membrane filtration. Depending on the required products ultrafiltration, microfiltration, nanofiltration and reverse osmosis may be applied. Ultrafiltration screens away particles larger than 0.1-5 m. Reverse osmosis removes NH4+ and particles larger than 100 Da including virus and bacteria (Masse et al., 2007). With reverse osmosis, 90% reduction in dry matter, potassium concentration and ammonium concentration have been measured (Thorneby et al., 1999; Zhang et al., 2004). Additionally, retention of Ca and Mg has been observed. Fouling is a substantial problem, thus an efficient particle removal from the input slurry liquid by solid-liquid separation is essential (Masse et al., 2007). Previously applied pre-treatments include filtrations two times through screens of reducing mesh, and another applied pre-separation is flocculation followed by solid-liquid separation (Bilstad et al., 1992; Norddahl and Rohold, 2000; Pieters et al., 1999; Thorneby et al., 1999). Whether the considerable removal of the small and fouling particles at flocculation is advantages, yet remains uncertain as the polymer itself may create other fouling troubles (Masse et al., 2007). The liquid fraction may be used for watering nearby fields. If ensured that no disease transport will occur, the liquid fraction may alternatively be applied for washing of barns, and thus returned to the animal slurry instead of drinking water. A concentrated nitrogen fertilizer could be produced that may be applied for plant fertilization by farmers or exported to other industries, and thus may have an economical value. The emission of ammonia, odour and greenhouse gases may be affected by the high infiltration rates, the very high concentrations of the chemical substances as ammonium in the water-ish fraction and additionally the possibly high pH of the concentrate.

6.4 Biogas
Anaerobic digestion of slurry produces methane and carbon dioxide that can be used for heating and electricity. Raw animal slurry and/or the solid fraction combined with other substrates are widely applied for biogas production. The liquid fraction may be applied to low retention timereactors (Faculty of Agricultural Sciences, 2009; Wen et al., 2007). A large amount of the easily converted carbon is collected as methane and carbon dioxide, thus the potential for greenhouse gas emissions of the slurry is reduced. Applying the slurry to agricultural fields, the reduced amount of organic matter is a disadvantage. On the other hand, it is an initial advantage that the ammonium content-to-total nitrogen content is increased under the digestion of nitrogen containing compounds such as proteins. The digestion of the slurry molecules causes the profile of odorous compounds to change and the odour to reduce (Hjorth et al., 2009). The ammonia emission increases due to the pH 29

increase and the increased ammonium content. A particulate removal at separation following the digestion reduces the emissions from the liquid fraction. Slurry transport to and from a biogas plant will be optimized by combining the operation with separation. A separation before the transport will reduce the required transportation. As biogas is degraded organic matter, the optimal separation prior to anaerobic digestion of the solid fraction separates the largest amount of organic matter into the solid fraction, which is a separation including a flocculation (Jorgensen and Jensen, 2009; Moller et al., 2007a). An experiment has been performed (Hjorth et al., 2009): A swine slurry was anaerobically digested for 15 days in a thermophilic reactor, the raw and digested slurry were each separated with three flocculant combinations, and the raw slurry and the six solid fractions were anaerobically digested. The biogas production per slurry volume was superior from the solid fractions of raw slurry over the raw slurry. In terms of volatile solids, the productions were similar. Fermenting the slurry after the separation produced a biogas yield equal to fermenting the slurry before and after the separation. In terms of additives, minimizing the FeCl3 amount and increasing the polyacrylamide amount added to raw slurry, causes the largest biogas production.

6.5 Thermal conversion

Upon thermal conversion of solid fractions together with other substrates, heat and ash is produced (Sweeten et al., 2003). Depending on the oxygen availability and temperature, the thermal conversion may be termed incineration, pyrolysis or gasification. Emission of greenhouse gases as carbon dioxide and nitrous oxide occurs during the thermal conversion. Thus the emissions must be controlled and possibly collected. In consequence, the emission from the ash is minimal. In contrast to the anaerobic digestion, all of the organic matter is lost and is not a value on fields (Thygersen et al., 2009). Because gaseous compounds containing phosphorus is uncommon, the phosphorus ends in the ash. Thus, the ash has a large nutrient value on agricultural fields, especially following degradation of stable phosphorus compounds by an acid treatment (Moller et al., 2007b). Because water inhibits the thermal conversion, separation of slurry is a pre-requisite. Especially a high organic matter content of the solid fraction is an important parameter. In addition, if the ash is to be used as a phosphorus source for plants, a highly efficient phosphorus separation may be advantages, such as performing an initial flocculation. This flocculation could include addition of a multivalent ion such as CaO, as calcium-phosphorus minerals will be formed, which in contrast to ironphosphorus minerals are largely available to the plants (Romer, 2006).

30

WHAT LIMITS SOLID-LIQUID SEPARATION AND FLOCCULATION?

Flocculation conditions may be improved further, control apparatus should be identified, and the superior separation following or prior to other slurry treatments should be clarified.

7.1 Future studies

The slurrys massive contribution eutrophication and the farmers substantial transportation of slurry may be reduced by performing solid-liquid separation and flocculation of the slurry. It may be combined with other attractive slurry technologies. In Denmark, slurry separation is beginning to be established, because through numerous investigations, many questions have been answered. How raw animal slurry should be solid-liquid separated and flocculated has been determined. A range of slurry parameters responsible for slurry flocculation has been located. Analytical methods useful for controlling flocculation have been identified, and the slurry technologies to combine with separation have been determined. However, several aspects still need to be investigated. Aspects of the flocculation mechanism remain unclear. This includes the optimum charge neutralisation degree and the primary flocculation mechanism for different samples and flocculants. In addition the relative responsibilities of the slurry properties for the flocculation requirements need clarification. The optimum flocculants to apply may be further investigated. This includes addition of a small polymer between the addition of the multivalent ion and the large polymer, or omitting the multivalent ion and only adding the small and the large polymer. Neutral and anionic polymers may together with e.g. addition of a cationic multivalent ion also be applicable, and improve the collection of the present anionic particles. Alternative polymers to the potentially toxic polyacrylamide flocculant should also be identified. The effect of addition procedure, i.e. the mean of addition and mixing, need further exploration, as do the optimum solid-liquid separation technique depending on the specific flocculation. To identify promising simply, cheap and quick methods for controlling and automate flocculation and/or solid-liquid separation further research is needed. Studies to carry out include full-scale experiments applying the already identified analytical techniques. Examination on whether the raw slurrys average free surface charge is useful to calculate the required polymer amount must be performed. Investigation on other raw slurry characteristic, such as the humic content, is useful to determine the flocculant amount required should be carried out. Additionally, whether NIR spectra of the raw slurry may be applicable must be examined. Questions additionally arise on which separation technique to apply to slurry post or pre-treated by specific technologies. These answers must necessarily include the elements of a life cycle analysis. The superior separation technique and possibly the flocculation method should be identified if the slurry has been pre-treated e.g. by ozonation or acidified. And equivalently, if the separation products are to be used for membrane filtration, biogas production, thermal conversion or phosphorus fertilizer production. Much is known concerning fundamentals, control and application of flocculation and solid-liquid separation of animal manure, but much research is also still ahead.

31

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