Perspective utilisation of digestate with a modification of conventional technology of biogas production

Perspective utilisation of digestate is connected with envisaged modifications of the technology of biogas production in agricultural biogas plants. These plants have digesters for the solid phase only or the most frequent are liquid (suspension) digesters. These are digesters without partition wall where the biomass of microorganisms is carried by the processed substrate. In reactor systems for the technological processing of waste from chemical and food technologies and from the technology of municipal and industrial waste water treatment those digesters are preferred where the biomass of functional microorganisms is fixed onto a solid carrier or onto partition walls of apparatuses. It is often granulated and is maintained in the digester as a suspended sludge cloud. These reactors may be affected by short-circuiting and therefore they are sensitive to the particle size of the processed substrate but they withstand a much higher organic load than the digesters without partition wall. Of course, the reactor is smaller, cheaper and more efficient.

Hence a perspective modification of the biogas production technology in agricultural biogas plants is gradual transition to the procedures of anaerobic digestion that are currently used in industrial plants for the treatment of organic waste water. The promising utilisation of digestate from such digesters is mainly the manufacture of solid fuels in the form of pellets that are prepared from the solid phase of agricultural waste before the proper aerobic digestion of the material for a biogas plant. The first proposal of this type is the IFBB procedure, the principle of which was explained in Chapter 1.4. The liquid phase from the preparation of processed material, which is destined for anaerobic fermentation in digesters with partition wall, could be used as a liquid or suspension fertiliser but researchers would have to solve the cheap method of nutrient concentration in this waste. The current price of Diesel fuel, machinery and human labour and low purchase prices of agricultural products do not allow the application of highly diluted fertilisers and in fact handling of water.

The problem is that a small biogas plant is only scarcely profitable. Hence economic reasons favour large-capacity plants with the volume of digesters 5 000 — 10 000 m3. In such large plants the reactors with partition wall would be unjustifiably expensive and therefore in these large-capacity facilities for biogas production it is necessary to use reactors without partition wall. The utilisation of their digestate should be based on this scheme: separation of digestate — concentration of fugate and its utilisation as a liquid mineral nitrogenous fertiliser. The solid phase of digestate should be used as an inert aeration component in compost production and as a material for the improvement and aeration of heavy-textured soils.

In any case, researchers must resolve a cheap method of nutrient concentration in fugate.

A number of different reactors are available for small to medium-sized biogas plants with the treatment of material according to IFBB that were developed on a research basis mainly in the sixties to the nineties of the twentieth century. At first, these were reactors with suspension biomass, e. g. mixing contact anaerobic reactor (ACR — AG), its innovation was a membrane anaerobic reactor system (MARS) and sequencing batch reactors (SBR). Then reactors with immobilised biomass were developed that are divided into reactors with biomass on the surface of inert material and reactors with aggregated (granulated) biomass. The former group is divided into upflow reactors and downflow reactors. Reactors with a mobile filling are the third variant.

The latter group is divided into reactors with the internal separator of biogas and biomass, reactors with the external separator of biomass and reactors with partitions.

Further development brought about biofilm reactors where the biomass of microorganisms is fixed onto a solid carrier. These reactors are considered as facilities with the highest operating stability, very resistant to the fluctuation of operating conditions. But they do not usually allow for such a high load as reactors with suspension biomass. The oldest reactor of this series was an upflow anaerobic filter (UAF) reactor from 1967, then a downflow stationary fixed film reactor (DSFF) and downflow reactor with filling in bulk followed. Great progress was made by designing an anaerobic rotating biological contactor (ARBC) and fluidized bed reactor (FBR) in the eighties of the last century. A similar type of reactor, expanded bed reactor (EBR), also designated by AAFEB (anaerobic attached film expanded bed), is suitable to be operated at low temperatures. The detention time is only several hours and the portion of residual organic impurities is practically the same as in modern aerobic systems for the treatment of organically contaminated waters.

Further advance was the development of reactors with aggregated biomass. The most important representative of this group of digesters is an upflow anaerobic sludge blanket (UASB) reactor. It is a reactor with sludge bed and internal separator of microorganism biomass. The biggest reactor of this type (5 000 m3) processes waste water from the manufacture of starch in the Netherlands, it withstands the load of 12.7 kg chemical oxygen demand (COD) per 1 m3/day, 74% of organic matter is degraded and the detention time is 33 hours only. Besides the UASB reactor these reactors belong to this group: hybrid upflow bed filter (UBF) reactor, anaerobic baffled reactor (ABR), expanded granular sludge bed (EGSB) reactor, internal circulation (IC) reactor and upflow staged sludge bed reactor (USBB), often also called biogas tower reactor (BTR), and other design models of the UASB reactor.

At the end of this chapter it is to note that modern anaerobic reactors have almost amazing outputs — unfortunately, the more perfect the reactor, the more expensive, and also their advantage over huge digesters without partition wall we have got accustomed to in biogas plants is gradually disappearing. The selection of modern anaerobic reactors is also more difficult than the selection of conventional technology of reactors without partition wall, because they are mostly rather specific to the substrate to be processed. They also have higher demands on processing, attendance and checks.

The perspective possibility of using modern anaerobic reactors for biogas production in smaller plants and the simultaneous solution to the use of the digestate solid phase as a raw material for the production of solid pelleted biofuels initiated our study of the IFBB procedure (Chap. 1.4.) for the substrate commonly used in biogas plants in the CR. The results of our experimental work are presented below:

The IFBB technological procedure is based on a high degree of cell wall maceration as a result of the axial pressure and abrasion induced with a screw press. Reulein et al. (2007) used this procedure for dehydration of various field crops; it is also known from the technologies of processing rapeseed, sugar beet and leguminous crops for the production of protein concentrates (Telek and Graham 1983, Rass 2001) and in biorefineries for the extraction of lactic acid and amino acids (Mandl et al. 2006).

The basic substrate contained 37.5% by weight of cattle slurry and 62.5% by weight of solid substrates, i. e. a mixture of chopped maize silage and grass haylage of particle size max. 40 mm mixed at a 4.75 : 1 ratio, i. e. 51.6% of silage and 10% of haylage. In total, the substrate accounted for 19.3% of dry matter. This substrate at 15°C is designated by A. A portion of this substrate was mixed with water at a weight ratio of 1 : 5, put into a thermostat with a propeller stirrer at 15°C and intensively stirred for 15 minutes. Analogically, the other portion was also mixed with water at a substrate to water ratio of 1: 5 and put into a thermostat at a temperature of 60°C with 15-minute intensive stirring again. The sample of the substrate with water 15°C was designated by B, the sample with water 60°C was designated by C. The liquid phase from substrate A was separated by centrifugation while the liquid phases from substrate B and C were separated in a laboratory screw press for the pressing of fruits and vegetables. The separated liquid phases of substrates A, B and C were diluted with water to obtain a unit volume and the analytical results were recalculated to a transfer ratio in the liquid phase in relation to the content of particular nutrients in dry matter of the original substrate mixture.

The experiments conducted in an experimental unit of anaerobic digestion and in an equipment for IFBB made it possible to determine the content of mineral nutrients in substrate A after 42-day anaerobic digestion in mesophilic conditions (40°C), in the liquid phase of substrate A after anaerobic digestion, in the liquid phase of substrate B and C after recalculation to the dry matter content and concentration corresponding to substrate A, also after the process of anaerobic digestion under the same conditions (42 days, 40°C).

The above recalculations enable to clearly show the advantages of the IFBB process in nutrient transfer from solid to liquid phase when substrate A and 5 times diluted substrates B and C are compared, but they may unfortunately evoke a distorted idea about the real

concentration of nutrients in liquid phases. It is to recall that IFBB increases the mass flow and transfer to the liquid phase but with regard to the 5-fold dilution the nutrient concentration in liquid waste for fertilization continues to decrease. This is the reason why the table below shows the original, not recalculated concentrations in the fugate of fermented substrate A and in the fermented liquid phases of the same substrate in IFBB conditions designated by B and C, which document considerable dilution of these potential mineral fertilizers.

The solid phases of substrates A, B and C after anaerobic digestion were subjected to determination of organic matter hydrolysability in sulphur acid solutions according to Rovira and Vallejo (2000, 2002) as modified by Shirata and Yokozawa (2006); we already used this method to evaluate the degradability of a substrate composed of pig slurry and sludge from a municipal waste water treatment plant (Kolar et al. 2008).

Cattle

slurry

Maize

silage

Grass

haylage

Substrate

Transfer ratio to liquid phase

A

B

C

Dry matter

6.4

28.9

18.7

19.3

0.06 + 0.01

0.18 + 0.04

0.20 + 0.03

N-compounds (N x 6.25)

25.6

11.5

7.4

16.3

0.05 + 0.01

0.20 + 0.04

0.26 + 0.05

Digestible

nitrogen

compounds

6.2

3.8

7.3

Nitrogen-free

extract

52.8

48.6

49.9

0.30 + 0.03

0.45 + 0.05

0.48 + 0.05

Crude fibre

25.7

29.8

18.0

0.01 + 0.00

0.10 + 0.00

0.10 + 0.00

Fat

4.8

1.5

2.8

Organic

substances

76.4

94.8

87.3

87.0

Mineral N (N — NH4+, NO3-)

2.4

< 0.1

> 0.1

1.0

0.74 + 0.05

0.89 + 0.06

0.95 + 0.06

P

1.3

0.2

0.3

0.6

0.40 + 0.05

0.52 + 0.07

0.65 + 0.08

K

5.3

1.4

1.7

2.9

0.57 + 0.04

0.60 + 0.04

0.79 + 0.05

Ca

1.3

0.4

0.6

0.8

0.31 + 0.06

0.38 + 0.08

0.46 + 0.08

Mg

0.5

0.2

0.3

0.3

0.38 + 0.07

0.43 + 0.08

0.55 + 0.07

Na

0.1

< 0.1

<< 0.1

< 0.1

0.70 + 0.08

0.77 + 0.04

0.80 + 0.08

Cl

0.3

0.2

0.2

0.2

0.77 + 0.06

0.85 + 0.05

0.85 + 0.06

Table 8. Dry matter content in the fresh mass of used materials and their chemical composition in % dry matter. The transfer ratio of mass flow to the liquid phase from the fresh mass of substrate not diluted with water at 15°C (A), diluted with water at a 1:5 ratio at 15°C (B) and diluted with water at a 1:5 ratio at 60°C (C). Liquid phase A was separated by centrifugation, liquid phases B and C with a screw press.

(Sample size n = 5, reliability interval of the mean for a significance level a = 0.05)

Table 8 documents that the IFBB procedure proposed by German authors for grass haylage is applicable to the typical substrate of Czech biogas plants, to a mixture of cattle slurry, maize silage and grass haylage. In agreement with German experience the observed transfer ratios are markedly higher at 60°C compared to 15°C of hydrothermal conditions but the value of transfer ratios to the liquid phase is generally lower in our experiments. We ascribe this fact to the properties of the material and also to the achieved axial force of the used press that was apparently lower even though the same perforation size of the conical part of the press (1.5 mm) and slope of the body (1 : 7.5) were used.

The results in Table 8 illustrate that the separation of the liquid and solid phase of the substrate that has not been subjected to anaerobic digestion yet by means of centrifugation only is rather imperfect from the aspect of the mass flow of components. The IFBB system (water dilution, intensive stirring at a temperature of 60°C and subsequent separation of the liquid and solid phase with a screw press) increases the transfer of organic and mineral substances into the liquid phase by about 15 — 20%, and it is also true of the saccharidic nitrogen-free extract and organic nitrogen compounds. This fact documents that the liquid phase has a higher amount of active, well-degradable organic material for anaerobic digestion, and so it is possible to expect not only the higher production of biogas but also more mineral nitrogen in the liquid after anaerobic digestion.

The high mass flow of alkaline metals and chlorine into the liquid phase, and on the contrary, the low transfer of calcium confirm the opinion of German researchers (Wachendorf et al. 2007, 2009) that the IFBB procedure largely increases the quality of biomass solid phase as a material for the production of solid fuels: the production of polychlorinated dioxins and dibenzofurans is reduced, waste gases will be less corrosive and the temperature of ash fusion will be higher.

Nitrogen compounds of the substrate dry matter account for 16.3%, i. e. these nitrogen organic compounds contain 2.6% of nitrogen in dry matter (Table 8). The content of mineral nitrogen in the substrate before anaerobic digestion was 1%. If the digestate contains 2.26% of mineral nitrogen in the same dry matter after anaerobic digestion, it is to state that during anaerobic digestion about a half of organic nitrogen mineralized and enriched the original 1% content of the substrate before the fermentation process. But the dry matter content decreased in the course of fermentation, and therefore the concentration of all nutrients in digestate apparently increased contrary to the original substrate. In our experiment the concentration of substrate dry matter decreased from 19.3% to 13.3% by weight during anaerobic digestion. The content of mineral nitrogen amounting to 3.28% at this dry matter content corresponds to 2.26% of min. N at the original dry matter content of 19.3% by weight (Table 9). The contents of the nutrients P, K, Ca and Mg in digestate dry matter after anaerobic digestion (Table 9) are apparently substantially higher than before fermentation. However, anaerobic digestion did not actually bring about any increase in the content of these nutrients, and the increased concentrations completely correspond to a reduction in dry matter content, 19.3 : 13.3 = 1.45.

It is not a new fact, but Table 9 shows how this mineral nitrogen is transferred to the liquid phase of substrates B and C compared to substrate A. Obviously, the liquid phase of substrate B has a higher amount of mineral nitrogen than that of substrate A, and so the effects of the screw press, which already before anaerobic digestion enriched the liquid substrate B with colloidal solutions (sols) of nitrogen organic compounds from the crushed cell walls of the plant material that provided further mineral nitrogen during fermentation, were significantly positive at the same temperature. It was still more evident in the liquid phase of substrate C while a conclusion can be drawn that a higher temperature contributes to a higher extraction of insoluble or partly soluble nitrogen organic compounds from which further mineral nitrogen is released after subsequent fermentation.

Substrate A

Liquid phase of substrate A

Liquid phase of substrate after recalculation to dry matter content and concentration of substrate A

B

C

N

3.28

2.43

2.92

3.11

P

0.87

0.35

0.45

0.56

K

4.20

2.39

2.52

3.32

Ca

1.16

0.25

0.30

0.36

____ Mg___

0.43

0.11

0.13

0.16

Table 9. Contents of mineral nutrients after anaerobic digestion (42 days, 40°C) in digestate (substrate A), in its liquid phase and in fermented liquids from IFBB in % dry matter by weight

Table 10 documents the original (before their recalculation) concentrations of mineral nutrients in the liquid phase of substrates A, B and C. These results indicate that liquid phase A can be considered as a highly diluted mineral fertilizer. Even though the IFBB process increases the concentration of nutrients (nitrogen) in the liquid phase before and after fermentation (liquid phase B and C), the dilution is very high. The recommended dilution with water, used by Wachendorf et al. (2009) and also in our experiments, produces liquid wastes diluted to such an extent after anaerobic digestion that they are practically hardly utilizable as a solution of mineral nutrients. Fugates are still rather problematic as mineral fertilizers, especially for applications in humid years and to soils with low microbial activity and consequently slow immobilization of mineral nitrogen, and naturally they are hardly applicable to pervious soils.

Liquid phase

A

B

C

N

0.32 + 0.03

0.09 + 0.01

0.10 + 0.01

P

0.05 + 0.00

0.01 + 0.00

0.02 + 0.10

K

0.31 + 0.04

0.08 + 0.01

0.11 + 0.15

Ca

0.03 + 0.00

0.01 + 0.00

0.01 + 0.00

____ Mg____

0.01 + 0.00

0.00 + 0.00

0.00 + 0.00

Note: Statistical evaluation of this recalculation table is based on original data in Table 10.

Table 10. Contents of mineral nutrients after anaerobic digestion (42 days, 40°C) in the liquid phase of digestate A and in liquid phases B, C with the application of IFBB in % by weight of solutions that should be used for mineral fertilization

(Sample size n = 4, reliability interval of the mean for a significance level a = 0.05)

Table 11 shows the results of hydrolytic experiments with solid phases of substrates A, B and

C. They confirm the previously observed fact in the work with the substrate consisting of a mixture of pig slurry and primary sludge from a municipal waste water treatment plant that the solid phases of wastes from anaerobic digestion cannot be efficient as mineral fertilizers because of their very low degradability (Kolar et al. 2008). The IFBB process, which enriches the liquid phases with organic, easily degradable substances and improves biogas yields during the anaerobic degradation of only liquid phases, further depletes of these substances the solid phases of substrates and impairs their quality as organic fertilizers, even though it is not the case of an increase in the resistant component but only in worse hydrolysable LP II.

Solid phase of substrate

Proportion

LP I

LP II

RP

A1

43 + 8

41 + 7

16 + 2

A2

22 + 4

20 + 3

58 + 8

B

39 + 6

44 + 6

17 + 3

C

31 + 6

47 + 8

16 + 2

Note: Description of fractions according to the method of Rovira, Vallejo 2002:

LP I = (labile pool I) = the reserve of very labile, easily hydrolysable organic substances expressed as % of the total amount of organic matter in a sample

LP II = (labile pool II) = the reserve of intermediately labile, less easily hydrolysable organic substances in %

RP = (recalcitrant pool) = the reserve of hydrolysis resistant, very hardly degradable organic substances in %

Table 11. Proportions of the three pools of carbon in the solid phase of substrate A before anaerobic digestion (A1), after anaerobic digestion (A2) and in the solid phase of substrate A1 after IFBB procedure before anaerobic digestion at 15°C (B) and at 60°C (C) as determined by the acid hydrolysis method of Rovira and Vallejo (2002).

(Sample size n = 4, reliability interval of the mean for a significance level a = 0.05).

Hence it is to state:

We tested the Integrated Generation of Solid Fuel and Biogas from Biomass (IFBB) procedure proposed for ensiled grass matter from the aspect of suitability of its use for a typical substrate of new Czech biogas plants, a mixture of cattle slurry, maize silage and grass haylage. The agrochemical value of the liquid phase from a biodigester was also evaluated. We concluded that this procedure is suitable for the tested substrate and improves the agrochemical value of a fugate from biogas production. By chlorine transfer to the liquid phase it makes it possible to use the solid phase as a material for the production of solid biofuels with a reduced threat of the generation of polychlorinated dioxins and dibenzofurans during combustion. However, the concentration of mineral nutrients in the liquid phase during IFBB procedure is extremely low after anaerobic digestion as a result of dilution with water, and so its volume value is negligible.

Here research must go on.