HIGH QUALITY FERTILIZERS BASED ON BIOMASS PYROLYSIS BIO-OIL AND CHAR A.R. Fernandez-Akarregi*1, J. Makibar1, F. Cueva1, J. Branas2, P. del Campo2, J.Piskorz3, J. Miranda-Apodaca4, A. Robredo4, U. Pérez-López4, M. Lacuesta4, A. Muñoz-Rueda4, A.Mena-Petite4 1

IKERLAN-IK4, Juan de la Cierva 1, Arabako Parke Teknologikoa, E-01510 Minao, Araba, Spain: [email protected] Tel: +34 943 71 24 00 Fax: +34 945 29 69 26 2 Dep. I+D+i, FERTIBERIA S.A., Huelva. Spain 3 RTI, Resource Transforms International. Canada 4 Dep. Plant Biology and Ecology, University of the Basque Country/EHU, Leioa. Spain

ABSTRACT: This work is focus on describing the composition, lixiviability and effects on the plants of a novel NPK-C slow release organic fertilizer and soil improver based on biomass pyrolysis bio-oil fraction and char. A dual product-component, charcoal and oligomeric lignin, can be considered as a flexible matrix in the formulation of fertilizers, where a range of nutrients and additives could be included. Thus, a unique and valuable fertilizer for agricultural and horticultural applications can simply be specified and then formulated, which also can also return bio-carbon to the soil (carbon sequestration in form of solid organic carbon). The aim is to enhance the economic viability of the fast pyrolysis process, producing high value chemicals from part of the liquid and solid products, in this case high quality organic fertilizers. First plant growing test showed promising results. The treatments with novel fertilizers based on pyrolysis products compared to the control treatment showed better results in: germination percentage, biometric parameters (stem height, leaves´ number, etc) and physiological responses (chlorophyll level and fluorescence). Based on the first measurements, the NPK 8-16-8 had better results as a fertilizer. Nevertheless, different parameters evolution indicate that the slow release treatments based on the novel fertilizer need more time to achieve the plant growth but it reached higher values than the commercial one with the time. Leaching test results will evaluate this novel fertilizer slow release effect. The next step will be to design a longer duration plant growing test phase to study slow release effects on plants and over consecutive plantings without any extra fertilizer addition. More factors could be considered, such as different treatment concentration and composition, plant species, plant growing phases, etc.

Keywords: biochar, fertilization, pyrolysis, soil fertility,

1

INTRODUCTION

Products from fast pyrolysis process can be used for different purposes, enhancing the economic viability. Bio oil and char can used as bio-fuels or also for another applications such as fine chemicals, additives, resins, fertilizers, etc. Slow release fertilizer applications are being under study by different companies and universities. Thus, they are working in the production of nitrogenous fertilizer from biomass within some projects. Supergen Bioenergy II project continued with the work carried in the early 2000s, which confirmed the feasibility of nitrogenolysis of biomass in terms of fertilizer and environmental performance [1]. This project is aimed to improve the processing conditions and testing of the fertilizers on plants and soils. Charcoal is considered due to its fertilizing effect (alkali metals from biomass) and the soil conditioning effect [2]. Mistra project [3] aim is to develop a mobile pyrolysis unit for biochar production from waste organic material, with the aim to use the char as a fertilizer and soil improver, as well as carbon sequestration effect [4]. Besides, other companies have products as Biopirol, used as fertilizer, based on biomass extract diluted in water. And also others have demonstrated in plant trials the beneficial effect of humic acids or humates supplemented with water soluble minerals as soil conditioners and supplements [5, 6]. The originality of the proposed work is the fertilizer production method and its effects in plants compared to a

control and a commercial NPK treatment. The main advantages of this work are: - Waste biomass valorization producing high quality organic fertilizers from its products, enhancing fast pyrolysis economical viability. - Soil improver effect of the biochar. It is also considered a potential carbon sequestration strategy. - The new slow release organic fertilizer will avoid ground water pollution, so its effect could be very positive if its use and production is extended to the agricultural field.

2

DESCRIPTION OF NOVEL FERTILIZER

2.1 Method of producing Novel Fertilizers The early methodology to produce fertilizers based on biomass pyrolysis products, bio-oil and char, is described in the patent EP 0716056B1 [7]. This invention is based on the discovery that the liquids produced by flash or fast pyrolysis of biomass react readily with ammonia, urea and related compounds to form organic nitrogen compounds and, furthermore, these compounds polymerize and solidify on heating to give stable products. These products therefore function as organic slow-release nitrogen fertilizers. So, it will enhance the economic viability of biomass fast pyrolysis processes, especially as an integral part of a "bio-refinery", by providing a method for utilization of different parts of

liquid and solid products. 3

PLANT GROWING TEST

3.1 Experimental methodology One species, barley (Hordeum vulgare L., var. Iranis) has been chosen as a model to analyze the effect of the new fertilizer on its growth. The experimental design was based on six fertilizing procedures: control test without fertilizers, tests for comparison with a commercial fertilizer and, finally, tests with the new fertilizer based on biomass pyrolysis products. Table II: Treatments composition Treatment Botton fertilizing NPK T1 NPK T2 66,6% NPK, 33,3% T3 lignin 63,3% NPK, 31,7% lignin, 5% biochar Biochar -

T4 T5 T6-control

2.2 Biomass Fast Pyrolysis products Biomass fast pyrolysis products, bio-oil and biochar are the base for the Novel Fertilizer “NPK-C”. The fast pyrolysis of the biomass takes place in a reactor at 450-500ºC, at ambient pressure and in absence of oxygen. Main characteristics of pyrolysis products used as fertilizer are given below: Table I: Biomass Pyrolysis Product Analysis Analysis %C %H Others

Oligomeric Lignin 55 6

Biochar 70 3 5% Minerals*

*silica, carbonates, calcium, sodium, potassium

Urea 50% Urea+50%lignin Urea Urea Urea -

0,1

0,03 T1 T2 T3 T4 T5

0,08

0,025

T1 T2 T3 T4 T5

T2

0,07

0,02

0,06 T5

0,05 0,04

T1

0,015

T1 T2

T3 T4

0,01

T3 T4 T1 T2

0,02

T3

0,01

g/pot

0,09

0,03

Aproximately, 20 to 50% of biomass could be converted to a novel oligomeric lignin and char composite wherein the lignin and the char are physically combined. Such composite could be utilized as a novel soil enhancer, rich in SOC (soil organic carbon). Such composite can be utilized also (by adopting known-art) to formulate a variety of fertilizers with specified nitrogen, phosphorous, and potassium content. In particular, oligomeric lignin melt is suitable to be used as a coating of commercially available solid NPK fertilizers converting them into a slow or controllable release type. A novel fertilizer formulae, this time, including an element carbon is described by the 4-letters “NPK-C”.

Upper fertilizing

All the treatments were equalized in nitrogen (Figure 1). Usually, the fertilizer used for cereals is the NPK 816-8. In the bottom the recommended dose is 400-500 kg fertilizers /Ha, while in the upper is 180-220 kg urea/Ha.

g/pot

The pyrolysis liquids contain high concentrations of carbonyl, carboxyl and phenolic functional groups and it is likely that these groups are largely responsible for the reactions with ammonia. The pyrolysates also contain a substantial amount of lignin degradation products and are therefore likely to be good sources of humic material and hence to have useful soil conditioning properties. The pyrolysis products are preferably chemically combined with a suitable nitrogen compound containing the -NH 2 group by forming a mixture between both of them. The mixture is then mixed and heated to form organic nitrogen compounds. Preferably, the mixing and heating is carried out in a temperature range of approximately 150° C to 180° C. Lignin thermal degradation product – oligomeric lignin- and its utilization in fertilizer formulation is described in patent US 2009/0126433A1 [8]. New fertilizer formulae “NPK-C” slow release fertilizers basically will consist on: Oligomeric lignin: the most abundant aromatic polymer in nature, lignin, under fast pyrolysis conditions, breaks down to oligomeric molecular fragments -“oligomeric lignin” containing circa 2-20 aromatic rings of molecular weight in the range of 400-2500 Daltons. This chemical fraction is water insoluble, odorless and little volatile. There is a strong analogy/similarity between oligomeric lignin and humic acids. Humic acids are arguably the most important part of the soil. Both, oligomeric lignin and humic acids are products of lignin-polymer degradation. The exact chemical structures of both substances have not been established. Pyrolytic char: by-product of the pyrolysis process with soil conditioning effect [9].

T5

0,005 T4

T5

0

0 Bottom Fert.

Upper Fert.

N

P

K

Figure 1: Seeds sowing, 30 pots for each treatment. Fitotron chamber for plant growing As a first step, previous to field study, the tests were carried out in climatic chambers (Fitotron, edificio FEDER UPV-EHU) where light, temperature and humidity were under control, so all the samples had almost the same conditions with the fertilizer as principal analysis factor. The watering was done with tap water. Table III: Fitotron conditions Temperature Humidity Lighting

Day 24ºC 60% 14 h light 600 micromol*m-2*s-1

Night 18ºC 80% 10 h dark

For each treatment, 30 pots were used and four seeds of barley were sowed in each 0.35 l pot (figure 2). The susbtrate used is a mixture 1:1 v/v of soil (cereal field, Ciriano, Alava) and medium grain sand. Before being mixed, the soil was grinded and sieved and the sand was washed. The bottom substrate of each treatment was composed by soil and sand mixture with a fertilizer.

Table IV: Substrate composition 1:1 v/v Soil Sand 0.535 %N 0.225 %N 8.559 %C 1.138 %C 0.692 %H < 0.06%H < 0.2% S < 0.2% S Different treatments defined in Table II were characterized, thus density, pH, and water retention were measured. Table V: Treatments characterization Bulk density pH Water retention % (kg/m3) T1 688 7.52 45.8 T3 585 6.48 45.5 T4 568 6.50 45.6 T5 200 8.26 46.4 Urea 448 7.99 42.7

Figure 2: Seeds sowing, 30 pots for each treatment. Fitotron chamber for plant growing In 10 days, a thin out was performed to avoid shadows between the plants, and only 15 plants by treatment continued the test (figure 3). At that time, germination and other biometric parameters (stem height, root and aerial biomass, leaf´s number by plant, etc) were measured.

4

Figure 3: Left: 8th day and right: 14th day of plant growing test The upper fertilizer application for each treatment was done when 50% of the plants show any tillering (figure 4), in the 30thday. Biometric parameters were measured.

Figure 4: Six treatments growing stage in 28th day In 49th day, the biometric parameters and some physiological parameters such as Fv/Fm (Fluorlen FP100, Photon Systems Instruments) and relative chlorophyl quantity (CCM-200 OptiSciences, Inc. NH USA) were measured. The studies determined for the different fertilizing procedures, a quantification of the percentage of seed germination and the response of the plants after vegetative growing period.

3.2 Soil and treatments characterization The substrate used for the test was characterized with an elemental analysis.

NITROGEN RELEASE INTO SOIL TEST

4.1 Nitrogen cycle The nitrogen fixed in the soil has to be transformed prior to be absorb by the plant roots. The proteins are degraded into nitrates. Nitrogen wastes are mainly due to plant absorption, erosion, leaching and its volatility [10]. Basically, organic fertilizers are mainly slow release fertilizers, because the organic nitrogen has to be transformed into inorganic by the soil bacteria, before being absorbed by the plant roots. Urea is one of the most common organic fertilizer around the world. It has a very high nitrogen concentration (%N 46) and high solubility in the soil. Urea pH is around 9 to 10 in a 10% water solution. It is generally used in the upper fertilizing procedure and it is recommended to be buried to avoid ammonia exhaust 4.2 Experimental methodology The objective of the leaching test is to evaluate the different nitrogen release of different fertilizing treatments. Test will carried out for three months, so the results will be available on June 2010. Three different treatments have been considered: one with a 100% of urea as commercial fertilizer and other two with different lignin and urea percentages. It is also control pots without any fertilizer. During the whole time test were carried out in field capacity conditions. Table VI: Nitrogen release test Treatment Composition T1 75% lignin, 25% urea T2 25% lignin, 75% urea T3 100% urea Control Without any fertilizer Each treatment was carried out in 4 pots, 4 l/pot (figure 5). There are 3 extra pots for control use. Each pot bottom was covered with double mesh, and 1 kg of gravels to avoid soil dragging. Over the gravels 2 different layers were defined: lower layer of 7 cm with 1.5 kg soil, medium layer of 5 cm with 1kg of soil mixed

with the fertilizer and higher layer of 1 cm with 0.45 kg of soil.

Figure 5: Leaching test: procedure and samples

The leaf´s number per plants (figure 8) was clearly better for NPK fertilizer case. All treatments slopes showed that treatments T1, T3, T4 and T5 have better growth attending their leaves than the other two. 25

100%

90%

75% 70% 65%

T1 T2 T3 T4

T3

10

T4

5

T5 T6

0 0

10

20

30

40

50

60

Time (days)

Figure 8: Leaves´ number per plant Leaves´number is somehow related to the biomass per plant (figure 9). Thus, NPK fertilizer showed higher biomass values in the root and leafs. Nevertheless, T4 and T5 treatments had very close values to the NPK fertilizer and obviously higher than the control results. This means that T4 and T5 treatments fertilizing ability has to be considered for further studies.

T5 T6

2

60%

PS shoot

1,5

-2

T1

T2

T3

T4

10th day

49th day

49th day

10th day

49th day

-1 -1,5

10th day

0

-0,5

49th day

Other parameter measured is the stem height (figure 7). The height of the stem for NPK fertilizer reached was maximum at 30th day, while other treatments were still increasing at 49th day (last measure available at this time). It means that slow release fertilizers needed more time to achieve the same plant growth, but in some treatments it is clear that stem height goes higher than with the commercial NPK fertilizer. Once again all the treatments have better results than the control.

0,5

10th day

Figure 6: Germination percentage

PS root

1

10t h day

50%

Biomass (g·plant -1)

55%

T5

10th day

80%

T2

49th day

85%

15

49th day

Germination percentage

95%

T1

Upper fertilizing

5

20

Thin-out

FIRST RESULTS First results on plant growing test are given. However, longer test results will be needed for a proper evaluation. Leaching test results, available from June 2010 will contribute for a better understanding of novel slow release fertilizers. Germination percentage achieved values between 92% (T4) and 98% (T2), except for the control (89%). In this case NPK and biomass pyrolysis products based slow release fertilizers showed similar results. So, its effect on germination could be considered similar to the commercial NPK fertilizer.

Figure 7: Stem height evolution

Leaves´ number/plant

Every 5 days the pots are watered with a fixed amount of water to restablish its field capacity. There is a very small quantity of drain-water (small drops), that is included in the next watering of the same pot. Samples from medium and lower layer of each pot are taken in 1st, 5th, 15th, 30th, 60th and 90th days of the test. Thus, nitrogen release in the medium layer could be studied. Sample analysis is mainly based on ammonia nitrogen, nitric nitrogen and pH.

T6

Figure 9: Biomass g/plant: shoot and root values The chlorophyll levels indicate that treatments T4 and T5 and also control have the highest values. Nevertheless, other treatments level is enough to maintain a suitable photosynthesis.

7 T1 6

Chlorophyll level

5

T2 T3 T4

4 3

T5 T6

2 1

0

Figure 10: Chlorophyll level Finally, Fv/Fm values were almost the same for all the treatments (0.75), attending the optimum value in 0.84. This value indicate, in general, the good condition of the system responsible of light capture to carbohydrates production in the plants. 6

CONCLUSION It has been proved that the use of bio-oil and char from biomass fast pyrolysis to produce organic fertilizers is technically viable. During the test no toxicity effects were observed in the different treatments, so the concentration used for the test seems to be healthy for the plants growth. Plant growing test showed promising results. The treatments with novel fertilizers based on pyrolysis products compared with the control treatment showed better results in: germination percentage, biometric parameters (stem height, leaves´ number, etc) and physiological responses (chlorophyll level and fluorescence). Based on the first measurements, the NPK 8-16-8 has better results as a fertilizer. Nevertheless, the stem height reached was maximum at 30th day while other treatments continued increasing their height. The different parameters´ evolution indicate that the slow release treatments based on the novel fertilizer need more time to achieve the plant growth. This is easy to explain due to the lower release of organic fertilizers compared to inorganic fertilizers such as NPK 8-16-8. So, when leaching test is finished and its results available, organic novel slow release fertilizers will be evaluated from this point of view. Comparison with other commercial fertilizer will be possible because the leaching methodology included urea commercial fertilizer. The next step will be to design another longer duration plant growing test phase to study slow release effects on plants and over consecutive plantings without any extra fertilizer addition. More factors could be considered, such as different treatments concentration and composition, plant species, plant growing phases, etc. This will be a long term test.

7 REFERENCES [1] A.B. Harms, T.Bridgwater “Pyrolysis and Nitrogenolysis of unusual feedstocks”. Bioenergy Research Group. [2] T. Bridgwater, A. Harms, “Sustainable Fertilisers”, Pyne issue 26 [3]http://www.mistra.org/mistraenglish/research/ideasupp ortgrant/ideasupportgrants/amobilepyrolysisunitforcar bonsequestrationandfertilizerproduction.4.87749a811c bd4c4fb4800036256.html

[4] A. Gathorne-Hardy, J. Mercier, “The use of biochar to reduce GHG emissions from UK arable crops” 17th European Biomass Conf. 2009. Hamburg,Germany. [5] K.Magrini-Bair, S. Czernik,, H.M. Pilath, R.J.Evans, P.C.Maness and J.Leventhal “Biomass Derived, carbon Sequestering, Designer Fertilizers” , Annals of Environmental Science (2009), Vol3, 217-225 [6]http:www.humates.co.nz/VEGELI_Technology_and_ Seed_Enhancement.pdf Vegeli Technology, “Newly developed technology provides the best for the growers of organic seed”. Canada, (2006). [7] D.Radlein, J. Piskorz and P. Majerski, Patent EP 07160565B1, Method of producing slow-release nitrogenous organic fertilizer from biomass. 1995. [8] J. Piskorz and P. Majerski, Patent US2009/0126433A1, Method of producing Hodge carbonyls and oligomeric lignin, 2009. [9] J. Lehmann, S. Joseph. Biochar for Environmental Management. Ed. Earthscan, 2009. [10] Navarro, G. 2003. Química Agrícola: El suelo y los elementos químicos esenciales para la vida vegetal. Ediciones Mundi-Prensa, 2ª Edición, Madrid.

8 ACKNOWLEDGEMENTS The authors wish to express their acknowledgement to the Basque Government and the Provincial Council of Gipuzkoa. This work has been funded by them as part of ETORTEK Strategic Program and also with the cofunding of the European funds. 9

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