PHOSPHATE INDUSTRY IN THE BALANCE OF SUSTAINABLE

DEVELOPMENT AND CIRCULAR ECONOMY

Katarzyna GorazdaB.Tarko, H.Kominko, Z. Wzorek, A.K.Nowak

7TH INTERNATIONAL CONFERENCE ON SUSTAINABLE SOLID WASTE MANAGEMENT26­29 June 2019, Heraklion, Crete Island, Greece

Cracow University of Technology, Poland

CIRCULAR ECONOMY

Pawłowski, A., How many dimensions does sustainable development have?, Sustainable Development  2008, 16, 81­90.

2

Circular economy (CE) is sustainable development strategy

Is characterized in closed loop flows of materials in production, distribution and consumption.

(Su et al., 2013; Ghisellini et al., 2016)

CIRCULAR ECONOMYClosing the loop

BOOSTING THE ECONOMY & CREATING J OBS

A number of crucial raw materials are fini te, and can be difficu l t or expensive to acquire in Europe. The circular economy will retain the value of the resources we use in products, returning them into the product cycle at the end of their use. New jobs will be created in innovative design and business models, research, recycling, re-manufacturing and product development.

REDUCING OUR ENVIRONMENTAL FOOTPRINT

The less products we discard, the less materials we extract, the better for our environment. Long-term targets and measures to optimise waste management will boost recycling and reduce landfil

l

.

The Circular Economy, a win-win situation:

Savings of €600 billion for EU businesses, equivalent to 8% of their annual turnover Creation of 580,000 jobs Reduction of EU carbon emissions by 450 million tonnes by 2030

The European Commission is supporting the EU’s transition to a Circular Economy with a broad set of measures to maintain

the value of products, materials and resources for as long as possible, while minimising the gen-eration of waste. The aim of today’s package is to give clear signals to economic operators and society on the way forward. Action at EU level can drive investments, create a level playing fie

ld, and remo ve obstacles in the single market.

The EU currently loses a significa nt amount of materials that are discarded instead of being reused or recycled. The circular economy pack-age includes specific proposals to amend the EU’s waste legislation and turn waste into valu-able resources.

WHAT IS THE CIRCULAR ECONOMY?

€ Production

Fro

m w

aste

to res

ources

C o n s u m

p t io n

Wa

s t e m

a n a g e m e n t

AN AMBITIOUS EU CIRCULAR ECONOMY PACKAGE

CLEANER INNOVATIONS - implement the concept of sustainable development, which combines activities in a number of areas

THE TECHNICAL AREA

is considered to be the most significant one due to the minimization of environmental destruction through the interference into the technological process thanks to the achievements of technical sciences

TECHNICALTECHNICALECOLOGICALECOLOGICALECONOMICECONOMICSOCIAL SOCIAL POLITICALPOLITICAL

CLEANER INNOVATIONS

assume three levels of activity, which may be chosen individually in order to improve the production process:

Misra K. B. (Ed.) Clean Production Environmental and Economic Perspectives, Springer

3

OPTIMIZATION of the existing

technological process

MODIFICATION of the

technological process,

The first stage in the implementation of cleaner technologies, thus allowing the control and generation of savings in the stream flows of matter, energy and raw materials.

The basic process remains unchanged, significant modifications are carried out before and, above all, after the main process

This is a solution which conditions the best effects. requires considerable accessibility of workforce, techniques, finances, and it must be accompanied by an increase in the profitability of a given company

G.M. Filippelli / Chemosphere 84 (2011) 759–766 761 4

82,00%

7,00% 5,00%

3,00% 2,00% 1,00%

fertilizers

feed additives

detergents

technical phosphorus for other technologies

food additives

other

TOTAL PRODUCTION 24.87 Mln t Pfrom 191 Mln t phosphate rocks

R.W. Scholz et al. / Science of the Total Environment 461–462 (2013) 799–803

PHOSPHATE INDUSTRY Assesment of the phosphate industry:

• significant feedstock problems• negative environmental impact.• excessive energy-consumption

biosphere, animals obtain phosphorus from food (plants or lower trophic-level animals)

plants, in turn, obtain phosphorus from soils

Mineral sources of soil phosphorus originally come from rock, that has

taken around 10–15 million years to form

Study on the review of the list of critical raw materials, EU Commission, 2017 5

P

Biogenic element

Energy carrier in

cells

Nucleic acids component

Bone component

P Firearms, grenades, napalm

component

Chemical weapons, war gases (tabun, sarin, soman,

VX)

Pestycidies

Drugs (Dezomorphine,

the so-called crocodile,

methamphetamine)

PHOSPHORUS – CRITICAL ELEMENT

Import to EU 2010­2014

D. A. Vaccari, M. Mew, R. W. Scholz, i F.-W. Wellmer, „Exploration: What reserves and resources?”, Springer, 2014, p. 129–151

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PHOSPHATE INDUSTRY - Non-renewable resources as an input material

Static resource lifetime

ores with a lower concentration of the main component, a higher level of impurities,in places requiring the use of more advanced technologies

reserves/production

„early warning indicator”

7

National Statistical Office, 2014.Waste catalog, 29.12.2014, Dz. U. poz 1923.

PHOSPHATE INDUSTRY – POLISH CASE

technical (phosphoric) acid

fertilizer ammonium phosphate (MAP, DAP)

  forage calcium phosphate,

  sodium phosphates,triple superphosphate,

phosphorus oxide technical,

technical phosphorus sulphide,

phosphorus chloride technical

PHOSPHATE ROCK949 000 tons

308 000 tons P2O5

from Algiers , Egypt and Syria

ELEMENTAL PHOSPHORUS

25 000 tons from  Kazachstan

WASTEGroup 06: 2 149.7 thousand tons total mass on landfills till 2013:

112 806.4 thousand tons

WASTE06 09 - waste from the production, preparation, marketing and use of

phosphorous chemicals with chemical processes of phosphorus

processing1 533.4 thousand tons Recovery rate<20%

Ch. W. Police S.A.,

19.07 mln tons

wasteduring 2004-2010

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Environmentally friendly solutions includes:

Improvement of the phosphorus balance in

waste streams

Feedstock flow release and replacement

application of waste raw materials available on a

domestic market

Change of the production technology

single-stage production method

of sodium tripolyphosphate

Hemihydrate technology for phosphoric acid production

PHOSPHATE INDUSTRY – SUSTAINABLE SOLUTIONS

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STRATEGIES FOR RAW MATERIALS

the limitation of feedstock flow (decreased exploitation),

feedstock flow release (quality, longer exploitation),

feedstock flow recycling (re-use)

feedstock flow replacement (renewable materials)

Environmental technologies introduce a constant improvement on processes, products and services through the protection of raw materials.

PHOSPHATE INDUSTRY – SUSTAINABLE SOLUTIONS

CLEANER INNOVATIONS IN THE PRODUCTION OF PHOSPHATE SALTS

10

11

K. Gorazda, B. Tarko, Z. Wzorek , H. Kominko, A.K. Nowak, J. Kulczycka, A. Henclik, M. Smol, „Fertilisers production from ashes after sewage sludge combustion -strategy towards sustainable development“, Environmental Research, 2017, 154(2017), s.171-180.

comparable P source

comparable P source

Lower Ca content

Lower Ca content

preferred particle

size:84-99% below 0,25

mm

preferred particle

size:84-99% below 0,25

mm

micronutrientsFe, Cu, Zn, Mn,

micronutrientsFe, Cu, Zn, Mn,

SEWAGE SLUDGE ASH VS PHOSPHATE ROCK

feedstock flow replacement (renewable materials)

P2O5

CaO

SiO2

Fe2O3

Al2O3

MgO

Na2O

K2O

0,0 5,0 10,0 15,0 20,0 25,0 30,0 35,0 40,0 45,0

22,5

17,5

39,3

9,9

8,0

3,7

0,5

1,1

28,1

33,3

22,0

5,5

4,2

2,0

0,5

0,8

Polish SSA average

% wt

produkcji fosforowych soli nawozowych

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M. Smol, J. Kulczycka, A. Henclik, K. Gorazda, Z. Wzorek, “The possible use of Sewage sludge Ash in the construction industry as a way towards a circular economy”, Journal of Cleaner Production, 2015, 95, s.45-54, K. Gorazda, Z. Wzorek, A.K. Nowak, B. Tarko,“ Odzysk fosforu z popiołów ze spalenia osadów ściekowych- analiza potencjału surowcowego“, Gospodarka odpadami komunalnymi, Tom IX, Komitet Chemii Analitycznej PAN, 2013, Wydawnictwo Politechniki Łódzkiej,

Evaluation of the raw material potential of ashes after the combustion of sewage sludge generated in Poland

Selected industrial objects have been characterizedTechnological sequences and the amount of ashes generated have been followed.

• total annual capacity of existing installations

170 620 Mg d.s of

sewage sludge

170 620 Mg d.s of

sewage sludge

• the actual annual potential of mono-combustion100 000

Mg d.s of sewage

sludge

100 000 Mg

d.s of sewage sludge

• The amount of ash produced in Poland

43 000 Mg43 000 Mg

The technology of combustion in a fluidized bed furnace, grate furnaceProcess residues are transferred to external companies, solidified or stored,in accordance with processes D5, R5

feedstock flow replacement (renewable materials)

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K. Gorazda, Z. Wzorek, A. K. Nowak, B. Tarko, J. Kulczycka, A. Henclik, Phosphorus cycle- possibilities for its rebuilding, 2013, Acta Biochimica Polonica , 60(4), s.725-730.

Technological challenges:• In thermochemical methods, low iron content in

ashes is required• Extraction of ash using hydrochloric and sulfuric

acid (VI) involves the generation of additional waste in the form of calcium chloride or phosphogypsum

• high recovery efficiency• process flexibility

feedstock flow replacement (renewable materials)

EXTRACTION

METHODS

EXTRACTION

METHODS

THERMAL METHODSTHERMAL METHODS

SSA

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important factors:

- the origin of sewage sludge - methods applied in sewage treatment plant - combustion technology

TRL 5 Extraction Neutralisation Filtration Granulation

feedstock flow replacement (renewable materials)

Gorazda, K., Jodko, M., Kowalski, Z., Wzorek, Z. (2010) PL Patent No. 207630 B1,

Gorazda, K., Jodko, M., Kowalski, Z., Wzorek, Z. (2012) PL Patent No. 210459 B1

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K. Gorazda, Z. Wzorek, A.K. Nowak, B. Tarko, J. Kulczycka, A. Henclik, „Phosphorus recovery from sewage sludge ash“, Proceedings 5th International Conference on Engineering for Waste and Biomas Valorisation, 25-28.08.2014, Rio De Janerio, Brazylia

The application of a grate furnace for the incineration of sewage sludge reduces the utilization of ash in extraction processes

SSA A

Fluidal furnace

SSA BGrate furnace

x5000

x500

x500

x1500

x2500

x5000

component SSA B SSA A

P [%] 9.92 10.83Fe [%] 6.01 8.69Ca [%] 11.2 11.7Mg [%] 2.67 1.17Al [%] 4.67 2.26K [%] 1.25 1.30

Zn [mg/kg] 605 2681Pb [mg/kg] 3.47 78.8Cu [mg/kg] 1015 849Ni [mg/kg] 120 95Cr [mg/kg] 148 165Cd [mg/kg] 13 20Co [mg/kg] 10.7 14.6Sr [mg/kg] 552 319

BET: 5.1767 [m2/g]

BET: 1,7516 [m2/g]

feedstock flow replacement (renewable materials)

ASHLeaching

agentP recovery rate

[%]

SSA A H3PO4 93.66

SSA B H3PO4 29.60

SSA A HNO3 90.14

SSA B HNO3 62.03

Plant Location

Combusted Sewage sludge [t d.s./d]

Combustion Technology

Temperature

Kielce 19 fluidal 850-900°C

Szczecin

40 grate

850-1000°C

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K. Gorazda, B. Tarko, Z. Wzorek, A.K. Nowak, J. Kulczycka, A. Henclik, “Characteristic of wet method of phosphorus recovery from polish sewage sludge ash with nitric acid”, 2016, Open Chemistry, 14, s.37-45.K. Gorazda, B. Tarko, Z. Wzorek , H. Kominko, A.K. Nowak, J. Kulczycka, A. Henclik, M. Smol, „Fertilisers production from ashes after sewage sludge combustion -strategy towards sustainable development“, Environmental Research, 2017, 154(2017), s.171-180.

high content of Al in ash reduces its utilization in extraction processes

The mass ratio of Al/P in ash applied as feedstock not higher than 0.7 was accepted as the limit value

high content of Ca in ash reduces its utilization in extraction processesMass ratio of Ca/P in ash applied as feedstock, which is not higher than 1.4, was accepted as the limit value

1 2 3 4 5 6 7 80

10

20

30

40

50

60

70

80

90

100

0,0

0,1

1,0

10,0

100,0

P extraction efficiency [%]P/Al. ratio in SSA [g/g]P/Ca ratio in SSA [g/g]

P R

eco

very

rate

[%

]

Mass

rati

o [

g/g

]

feedstock flow replacement (renewable materials)

It was confirmed that differences in the composition of ashes obtained at different periods of sewage treatment plant operation remain without a significant impact on the extraction parameters

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PHOSPHORUS EXTRACTIONPHOSPHORUS EXTRACTION

NUTRIENTS

RECYCLING

NUTRIENTS

RECOVERY

NEUTRALISATIONNEUTRALISATION

FLUID FERTILISERSSUSPENSION FERTILISERS

NP, NPK SOLID FERTILISERS

FLUID FERTILISERSSUSPENSION FERTILISERS

NP, NPK SOLID FERTILISERS

extracts

SSA

HNO3

H3PO

4

CaO, NH3

MBM ashBiomas

ash   

Gorazda, K., Jodko, M., Kowalski, Z., Wzorek, Z. (2010) PL Patent No. 207630 B1, Gorazda, K., Jodko, M., Kowalski, Z., Wzorek, Z. (2012) PL Patent No. 210459 B1

feedstock flow replacement (renewable materials)

CONCLUSIONS

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Developed cleaner innovations ensure:

- using renewable phosphorus raw materials, i.e. ash after

combustion of sewage sludge from Thermal Stations of Sewage

Sludge Utilization for the production of mineral fertilizers

- recovery of the critical element - phosphorus from waste with a

yield above 80%,

- recirculation to the environment of approx. 4 000 tones of P in

Polish case;

being the equivalent of 31 thousand Mg of imported

phosphorus ore

3.3% of the imported phosphate

rock

CONCLUSIONS

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Wastewaters

Sewage sludgeASH

Animal by product

Agri-waste

Food waste

Industrial streams

Consumption of nutrients like N, P and K ( world: 170 mln Mg, EU: 12 mln Mg)

recovery from concentrated renewable sources:

animal by-product, sewage sludge, nutrient-rich biomass after thermal treatment

salts precipitated form nutrient-rich streams

present potential of phosphorus substitution by renewable concentrated

inorganic sources is only 17-38%

Huygens;, D., Saveyn;, H., D.Tonini;, ;, P.E., Sancho, L.D.: Pre-final STRUBIAS Report, DRAFT STRUBIAS recovery rules and market study for precipitated phosphate salts & derivates, thermal, oxidation materials & derivates and pyrolysis & gasification materials in view of their possible inclusion as Component Material Categories in the Revised Fertiliser Regulation. In. Circular Economy and Industrial Leadership Unit, Directorate B - Growth and Innovation, Joint Research Centre - European Commission, (2018)