Yara BPO Presentation - Ver 2 0 (4x3)

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Introduction to Yara Biogas Production Optimizer

Yara International Application & Product Development, Nitrates

Yara Biogas Production Optimizer (BPO) Introduction and background information

Background of Anaerobic Digestion Process • Anaerobic digestion to reduce organic matter and to produce useful methane • Conversion to electricity and heat • Upgrading to bio-methane and input into gas grid • Substrates of anaerobic plants • Agricultural goods (“energy plants”) • Manure, slurry • Co-fermentation: Food waste and fat trap disposals • Waste water treatment plants: Primary / secondary sludge

Application & Product Development

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September 2018

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Background of Anaerobic Digestion Process

Organic waste

Input

Manure tank

Storage

Conversion

Dry fermenter

WWTP sludge

Energy crops

Manure

Silo

Wet fermenter Percolate

Electricity

WWTP digester

Heat

Biogas

Biogas storage

Output Power grid

Slurry

Digestate storage Biogas

Power converter (CHP)

Gas grid

Application & Product Development

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September 2018

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Lab Tests – Various Kinds of Sludge Yara BPO Addition to AD • Initial Laboratory Tests: • Fermentation tests with / without dosage of BPO (2x Master thesis at HSN, Norway) • Easy degradable substrate: Primary sludge (waste water treatment plant) • 15% increased COD degradation • 20% more biogas formation • 30% higher methane concentration • Hard degradable substrate: Pig and cattle manure Result dependent on specific dosage • More biogas • Less H2S • Even during „over-dosage“ (less biogas formation) no long-term breakdown of the anaerobic fermentation process

Application & Product Development

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September 2018

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Scientific Verification Yara BPO Addition to AD • Lab tests at Fraunhofer Research Institutes, Germany • Batch tests Fraunhofer UMSICHT (DE, Oberhausen) • Corn & cattle manure: + 2.6 - 6.3% CH4 • Food waste:

+ 10.2% CH4 - 31.3% H2S

• Batch test Fraunhofer UMSICHT (DE, Sulzbach) • Effect on fermentation of pre-treated substrate (thermal pressure hydrolysis): + 36% more biogas • Nitrogen behaviour: Physico-chemical analysis at Fraunhofer UMSICHT (DE, Oberhausen) • > 96% in gas phase determined via abundance ratio of isotope 15N

Application & Product Development

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September 2018

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Biological Research Activities Yara BPO Addition to AD

+ BPO

• Kaiserslautern University (DE) 2015-08-18

• Quantitative analysis: FISH (Genetic markers & epi-fluorescence technology) • Verification of changed bacterial metabolism (agricultural biogas plants, digesters) • Shift of total bacteria community towards methanogenic species • Increased diversity of bacteria  more robust and resilient plant operation • Qualitative analysis: RNA analysis • Verification of bacterial enzyme formation (agricultural biogas plants, digesters) • More efficient bacterial metabolism in ALL anaerobic process steps • Increased enzyme activity for methane production and degradation of cellulose • Reduced enzyme activity for H2S formation

Application & Product Development

2015-11-19 Methanogenic bacteria (agri plant)

t with BPO dosage

30% growth of methanogenic bacterium Methanoculleus sp. (sample analysis agri plant)

The relative expression of the methane formation gene is 107 times higher on 2015-11-19 compared to 2015-08-18.

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September 2018

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Dosage Control Yara’s IDA Controller Series • IDA = Information, Documentation and Archive • Dosing profile is individually adapted to the certain dosing site (signals from customer side requested) • Free programmable dosing script: • Total dosage can be adapted by customer • Dosing algorithm can be adjusted by Yara technician according to customer’s demand • Automatic stop according to limit definition • Control by additional analogue and digital inputs • Access via Yara web-service • Tank monitoring included • Colour graphics display with touchpad gives access to basic functions and values

Application & Product Development

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September 2018

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Shifting to Higher Redox Potential Yara BPO addition to AD

Application & Product Development

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September 2018

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Intellectual Property and Commercialization BPO is Yara’s Biogas Production Optimizer, an industrial grade calcium nitrate solution

Patent granted in Europe

Roll out under the brand “BPO” in Europe

Application & Product Development

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September 2018

10

Results Yara BPO – Full Scale

Results from Full-Scale Yara BPO Installations (commercial biogas plants) Biogas • In addition: 1 dosage at landfill site Country Capacity plant

Substrate

Target of dosage

1

DE

700 kWel plus 1.800 kWth

corn silage, liquid manure (div.)

less substrate demand, H2S reduction

2

DE

600 kWel

corn and grass silage, manure (div.)

more biogas

3

DE

2.000 kWel plus direct input

mainly corn silage, manure (div.)

more biogas, less substrate demand

4*

DE

1.200 kWel

bio-waste

more biogas

5

DE

290 kWel plus 280 kWth

corn silage, manure

H2S reduction (more biogas)

6

DE

750 kWel

grass and corn silage, manure

more biogas

7

IT

150 kWel

mainly cattle manure, corn silage

H2S reduction, more biogas

8

IT

360 kWel

mainly cattle manure, corn silage

H2S reduction, more biogas

9

IT

250 kWel

mainly cattle manure, corn silage

H2S reduction, more biogas

10

IT

250 kWel

pig / cattle manure corn silage,

H2S reduction, more biogas

* thermophilic fermentation Application & Product Development

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September 2018

12

Methane Concentration increases 56,5

without Yara BPO

with Yara BPO

56,0

55,5

%

55,0

54,5

54,0

53,5

53,0 Jan Feb Mar Apr May Jun 15 15 15 15 15 15

Jul 15

Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun 15 15 15 15 15 16 16 16 16 16 16

Application & Product Development

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Jul 16

Aug Sep Oct Nov Dec 16 16 16 16 16

September 2018

13

Bio-Methane-Difference: Yield minus Potential without Yara BPO

with Yara BPO

Nov 16 Sep 16 Jul 16 May 16 Mar 16 Jan 16 Nov 15 Sep 15 Jul 15 May 15 Mar 15 Jan 15 -2.000

-1.500

-1.000

-500

0 m³/d

500

Application & Product Development

1.000

PUBLIC

1.500

September 2018

2.000

14

Bio-Methane - Specific Yield increase by 10% (fresh-mass) 120

without Yara BPO

with Yara BPO

m³ per ton fresh-mass

110

100

90

80

70

60 Jan Feb Mar Apr May Jun 15 15 15 15 15 15

Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun 15 15 15 15 15 15 16 16 16 16 16 16

Application & Product Development

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Jul Aug Sep Oct Nov Dec 16 16 16 16 16 16

September 2018

15

Bio-Methane - Specific Yield increase by 20% (org. DM) 390

without Yara BPO

with Yara BPO

m³ per ton organic dry matter

370

350

330

310

290

270

250 Jan Feb Mar Apr May Jun 15 15 15 15 15 15

Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun 15 15 15 15 15 15 16 16 16 16 16 16

Application & Product Development

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Jul Aug Sep Oct Nov Dec 16 16 16 16 16 16

September 2018

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Substrate use is less without Yara BPO

with Yara BPO

Nov 16

January 2015 = 100%

Sep 16 Jul 16 May 16 Mar 16 Jan 16 Nov 15 Sep 15 Jul 15 May 15 Mar 15 Jan 15 60

65

70

75

80

85

90

95

100

105

110

115

%

Application & Product Development

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September 2018

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Substrate use is less Maize

Grass

Potatoes

Sugar-Beets

Chicken-Dung

Cow-Dung

Liquid Manure

Corn

Nov 16 Sep 16

Jul 16 May 16 Mar 16 Jan 16 Nov 15 Sep 15 Jul 15 May 15

start dosing Yara BPO

Mar 15 Jan 15

0

20

40

60

80

100

120

140

160

to/d Application & Product Development

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September 2018

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Substrate-Feeding - % of the Different Substrates Maize

Grass

Potatoes

Sugar-Beets

Chicken-Dung

Cow-Dung

Liquid Manure

Corn

Nov 16 Sep 16 Jul 16 May 16 Mar 16 Jan 16 Nov 15 Sep 15 Jul 15

start dosing Yara BPO

May 15 Mar 15 Jan 15 0%

10%

20%

30%

40%

50%

60%

Application & Product Development

70%

PUBLIC

80%

90%

September 2018

100%

19

Substrate Costs are lower 5.000

without Yara BPO

with Yara BPO

4.800

4.600

4.400

€/d

4.200

4.000

3.800

3.600

3.400

3.200

3.000 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec 15 15 15 15 15 15 15 15 15 15 15 15 16 16 16 16 16 16 16 16 16 16 16 16

Application & Product Development

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September 2018

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Specific Substrate Costs are lower 0,46

without Yara BPO

with Yara BPO

0,44

0,42

0,40

€/m³ bio-methane

0,38

0,36

0,34

0,32

0,30

0,28

0,26 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec 15 15 15 15 15 15 15 15 15 15 15 15 16 16 16 16 16 16 16 16 16 16 16 16

Application & Product Development

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September 2018

21

H2S - with 30% less ferric-hydroxide similar results 450

without Yara BPO

with Yara BPO

400

350

ppm

300

250

200

150

100

50

0 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec 15 15 15 15 15 15 15 15 15 15 15 15 16 16 16 16 16 16 16 16 16 16 16 16

Application & Product Development

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September 2018

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Dosage Yara BPO 220 200 180 160 140

l/d

120 100 80 60 40 20 0

Application & Product Development

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Summary of Signature Site Data Dosage up to 120 litres a day Less substrate required – at least 10% Increase in bio-methane – up to 20% Why? • Prof. Dr. Stoeck, Kaiserslautern University: “First the structure of the community changes, afterwards abundances explode” Quantification of bacterial cells per DAPI staining Bacteria density [106 cells ml-1]

• • • •

5,0 4,5 4,0 3,5 3,0 2,5 2,0 1,5 1,0 0,5 0,0 15.04.2015 (without BPO)

02.06.2015 (with BPO)

01.07.2015 (with BPO)

13.08.2015 (with BPO)

Application & Product Development

30.09.2015 (with BPO)

PUBLIC

15.10.2015 (with BPO)

September 2018

24

BPO Dosage Effect on Microbial Communities in AD • Aim of study: • Verification of biological effects due to calcium nitrate dosage • Methods: • Genetic determination of microbial community structures and metabolic activities in control and treated fermenters of operating plants

† patented application

• Empirical measurements and observations during calcium nitrate dosage to anaerobic digesters: • Increased yield of methane • Reduced hydrogen sulfide concentration • Substrate savings • Improved viscosity • More robust plant operation

Application & Product Development

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Bacteria Community Structure

• Significant differences between treated and non-treated control digester: • Increase of denitrifying bacteria (DNB; N-metabolism) • Increase of methanogens (MET; methane production) • Decrease of sulfate-reducing bacteria (SRB; species involved in Smetabolism

Ref: Stoeck et al. (Genetic analyses of microbial communities in anaerobic digesters reveal enhanced methanogenesis during calcium nitrate dosage)

Application & Product Development

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September 2018

26

Gene Activity

• Increased gene activity involved in nitrate reduction

• Increased gene activity involved in methanogenesis

Ref: Stoeck et al. (Genetic analyses of microbial communities in anaerobic digesters reveal enhanced methanogenesis during calcium nitrate dosage)

Application & Product Development

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Proposal of Mechanistic Model

• Possible mode of actions of calcium nitrate (BPO*) as additional energy source in anaerobic digesters: • De-nitrifiers outcompete SRBs in metabolizing organic substrates • Nitrite additionally inhibits the ATP Sulfurylase (inhibited conversion of sulfate into sulfide) • Results: • Enhanced methanogenesis • Enhanced denitrification • Decreased sulfide production

Ref: Stoeck et al. (Genetic analyses of microbial communities in anaerobic digesters reveal enhanced methanogenesis during calcium nitrate dosage)

Application & Product Development

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September 2018

28

with Yara BPO (2015, 2016)

75,0 70,0 65,0

60,0 Sep

Polymer kg per ton dry matter

• BPO effect: • Higher methane concentration • Lower H2S concentration (verified in WWTP lab) • Strong impact of other parameters: e.g. additional sludge, industrial wastewater • improved degradation of organics • Less polymer demand for sludge dewatering (to be verified in 2nd winter season)

Methane %

BPO Concept in Digester of WWTPs 80,0 Field Test (Germany) without Yara BPO (2014, 2015)

Oct

Nov Dec

Jan

Feb Mar

without Yara BPO (2014, 2015)

01/12/15

H2S ppm

Aug

with Yara BPO (2015, 2016)

16 14 12 10 Apr May Jun

without BPO

01/10/15

Jul

18

Sep Oct Nov Dec Jan Feb Mar

70 60 50 40 30 20 10 0 01/08/15

Apr May Jun

01/02/16

01/04/16

Application & Product Development

01/06/16

PUBLIC

Jul

Aug

with BPO

01/08/16

September 2018

29

BPO Concept in Digester of WWTPs Field Test (Germany) • BPO effect (genetic analyses): • Higher density of eubacteria and methanogens Eubacteria

Archaea

Application & Product Development

PUBLIC

September 2018

30

BPO Concept in Digester of WWTPs Field Test (Germany) • BPO effect (genetic analyses): • Change in bacterial community • Diversity, enzymes (to be evaluated)

3

2,5

Bacteria density [108 cells ml-1]

2

1,5

BPO start

1

0,5

0

Application & Product Development

PUBLIC

September 2018

31

BPO – Installation and Equipment

Yara BPO Application Pictures of an Installation in Germany

Application & Product Development

PUBLIC

September 2018

33

Installation of a Yara BPO Test Dosage System

Application & Product Development

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September 2018

34

Yara BPO Test Containers and Dosage System

Application & Product Development

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September 2018

35

Dosage of Yara BPO into the Substrate Feed System

Application & Product Development

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September 2018

36

Dosage of BPO into the Substrate Feed System

Application & Product Development

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September 2018

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Dosage of Yara BPO into Sludge Pipeline

Application & Product Development

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September 2018

38

Summary • By using Yara BPO: • Increased biogas yield • Improved biogas quality • increasing the methane concentration • Reduce amount of substrate needed • Improve the quality of digestate • To be used as fertilizer • Reduce the overall cost for hydrogen sulfide removal • More stabilized biogas plant performance • Less fluctuation in process and more stable biogas production

Development partners along the value chain helped to create this innovative solution

Application & Product Development

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September 2018

39

IMPORTANT NOTICE • Yara disclaims all responsibility and liability for any expenses, losses, damages and costs incurred as a result of relying on or using the information contained in this document. Yara reserves the right to adjust and revise this document at any time. • Any forward-looking statement made by Yara in this document is based only on information currently available to Yara and speaks only as of the date on which it is made. Yara undertakes no obligation to publicly update any forward-looking statement. • No rights, including, but not limited to, intellectual property rights, in respect of this document are granted to any recipient unless specifically stated. • ©Yara International ASA. All rights reserved.

Application & Product Development

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September 2018

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