Phosphorite resources Shimonoseki Mitsui Chemicals, Inc.

Onoda Chemicals, Inc.

Phosphorous Recycling as Green

Industry

Phosphorus is an essential constitute for all living organisms.

NO LIFE CAN EXIST WITHOUT PHOSPHORUS

Phosphorus is used in a wide

variety of manufacturing industries.

Flame-retardants Etching agent

Food additives

Surface treatment chemicals

PHOSPHORUS FOR GREEN GROWTH

Without phosphorus, there will be no biomass, no biofuel, no agriculture, nor life.

PHOSPHORUS FOR GREEN GROWTH

Today, phosphorus is mostly obtained from mined rock phosphate which is a non-renewable resource.

From Prof. D. A. Vaccari

D. Cordell et al., Global Environ. Change, 19：292-305 (2009).

1900 1920 1940 1960 1980 2000 2020 2040 2060 2080 2100

30

25

20

15

10

5

0

Around 2040

Although the demand of phosphorus fertilizer is predicted to increase more than 50% by 2050, the global peak in phosphorus production is expected around 2040 .

Ph

osp

ho

rus

pro

du

ctio

n (

MT

P/Yr

)

Year

Global production

Global demand

PEAK PHOSPHORUS

Rock phosphate is a nonrenewable resource.

No alternative to phosphorus is available for agriculture and biomass production.

The price of P fertilizer must be kept low to make foods as inexpensive as possible.

From Prof. D. A. Vaccari

LOOMING CRISIS OF PHOSPHORUS DEPLETION

(103 ton/year)

Natural

Waters

Other

Industry

Phosphate

rock

Steelmaking

Industry

Products/

By-products Other mineral

resources

Livestock

Domestic

products

Wastewater

Wastes

Soils

Agricultural

lands

River/Coastal water

Farm/Ranch

Slag

Steel

Food & Feed

Humans

Steelmaking

Industry

Food & Feed

Livestock

Humans

Fertilizer

Wastes

Fertilizer

Chemical

Industry

141.3

110.6

155.9

157.2

395.2

103.6

Chemical

Industry

63.9 10.5

356.1

111.6

145.2

129.3

96.4

88.2

54.5

173.4

224.9

Food &Feed Livestock

Fertilizer

Domestic and

municipal wastes

Waste sludges

55.4

54.5

4.3 10.6

0.1

14.2

110.6

0.2

2.1

0.2

3.1

22.9 0.2

4.7

24.5

14.2

32.9

42.0 0.4

Crop

17.5 75.1

2.6 Wastes

3.2 4.3

2.1

Wastes

18.7

Fertilizer 10.6

0.1

14.5

6.6

32.9

17.4

18.7

3.2

14.2

Chemical

Industry

Fertilizer

Farm/

Ranch

42.8

Humans

Waste sludges

Yokoyama, et al., ISIJ International, 47: 1541-1548 (2007)

Total inflow of phosphorus to Japan is approximately 750 kt/Y. The import of rock phosphate accounts for 15%.

NATIONAL P METABOLISM IN JAPAN

P Recycling for Industry

High-tech

Industry Sewage Wastewater

treatment

Food and Feed

Biosludge

P

recovered

As

h

Yellow P

manufacturin

g

P-

free

ash

Yellow P Phosphoric

acid

manufacturing

High-quality

phosphate

Iron ore

Coke Steel

Industry

Steel-making

slag

P-free

slug P-free slag can be returned

to a steel manufacturing

process.

P

slag

Phosphoric

acid

manufacturing

Phosphat

e

Phosphate

production by a wet

process

Water

reclamation

Steel-making

Industry

Chemical Industry

Recycle Industry

Cement

Industry The P content of clinker

needs to be lower than

0.5%.

Automobile

Semiconduct

or Liquid crystal

Agriculture Food

Consume

r Fertilizer

Industry P

fertilizer

Manure Ash Farmland

P recovered

Eutrophication

control

P recycle through

yellow phosphorus

regeneration

Vegetable oil

refinery

process

Food Industry

P RECYCLING AS GREEN INDUSTRY

Microcystis aeruginosa cyanobacterium

Eutrophication

INCENTIVE TO EUTROPHICATION CONTROL

PPK

PPX

GppA

Ppa

PhoB

Pta

PhoRR

PhoRA PhoB＊

BAP

CreB

PhoE＊

PhoU＊

Organic Pi

polyP PPi

Inorganic Pi

Pi

Pit Km=0.4mM, Ka=1mM Vmax=15.9nmol /min mg

G3P

Ugp＊(ugpBAECQ)

GlpT

Pst＊ (pstSCAB)

H6P G1P

Phosphonates

Phosphonates

PhnG~M＊ Degradation of Phosphonates

Organic Pi

Organic Pi

[Pi]>4mM

[Pi]<4mM

phosphorylation

PhoB-P dephosphorylation

Pho regulon promoter

Succinyl-CoA

ATP PhoB

Phosphorylation Transcriptional factor ?

efficiency Activation

Cross regulation

Activation

Cross Regulation （C and energy metabolism）

Phosphorylation or

Detection by censor

Leader peptidase１ Amino peptidase

471amino acids

Arg-22 S-S Bond forming

Dimer（BAP activity）

330 amino acids Tertial structure

trimer

Hydrolysis

ADP

Acetyl-CoA + Pi

Acetyl phosphate

CoA

ATP+Acetate

A E

C

Phn＊ CDE

TCA Cycle

NADH

ATP, GTP, NTP

Pi

RNA,DNA + PPi

PolyPn+1

PolyPn+Pi

PolyPn

Pi

NTP (Trinucleotides)

Ca2+

Mg2+etc.

Pi Inhibition Pi

UhpT

Glycerophosphoryl diester

(Hydrolysis ） Q

E

M H G P

N

CreC

Pi

Central metabolic pathway

PEP

ATP

BPG GAP

Pi ATP

Glycolysis

Succinic

acid

GDP+Pi GTP

ADP

GDP

Electron transport H+

ADP+Pi

ATP

H+

Organic Pi

Pi

PhoQ PhoP

Unknown target

Most favorable

＊Pi regulon genes

Pi-starvatopm inducible but

not involved in Pi regulon

genes

Pi Pi

(pitA)

（constitutive）

Bap＊

AppA●

CpdB

Agp UshA

H6P (pH4~6)

(pH7.5)

(pH2.5)

(pH8~10)

C source

C source

polyP

cAMP+CAP Control Inhibition of UDP-G

degradation

?

Pi starvation

1000-fold increase

Pi-starvation 10-fold increase

Periplasmic region

Enzymes and proteins

ATPase activity

Outer

membrane

Km=1.5mM Vmax=3nmol/min mg

cAMP+CAP Control

s70 Pho Box

OmPF

OmPC

＊

1 channel/monomer

Amino ester phosphonate etc.

Methyl phosphonate

Ortho phosphonate etc.

K I J

L

C-Plyase Pathway

Accesary

F O Control

AckA

[0.5mM]

PPi

Glucose

ATP

[0.2mM]

A C

Pi [10mM]

Pgc

Gapa

sucCD Pyruvate kinase

FADH2

Fumaric acid a-ketogluttaric acid

Isocitric acid

L-Malic acid

Oxalacetic acid

PsiF

PhoH

PsiE

Unknown function

AtpLBEAGDC

PhoA

Amino acid starvation

Lon protease

ribosomal protein degradation

PolyP-PHB

complex

Ca++

+

-

RelA ppGpp ATP

GTP

+

Km=38.2mM Vmax=55nmol /min mg

＊

(pitB)

PhoB control

Polyphosphates

H-P-OH

OH

-

=O

R-P-OH

OH

-

=O

HO-P-OH

OH

-

=O

-O-P-O-P-O-P-OH

=O

=O

=O

OH

-

OH

-

OH

-

[polyP]

HO-P-OH

OH

-

=O

RO-P-OH

OH

-

=O

[Pi] [Pt]

H-P-OH

OH

-

=O

[Pt]

[Pn]

Polyphosphate

PhnCDE PhnG-M

PhnG-M

PhnCDE

[ATP]

PPK

PPX

PST PIT

BAP

Inducible under Pi limitation

[Pi] [Org-Pi]

K. Imazu et a., Appl. Environ. Microbiol., 64: 3754-3758 (1998).

Phosphate Inorganic Transport

Polyphosphate kinase

exopolyphosphatase

Phosphate-specific Transport

Polyphosphate

GENETIC ENGINEERING OF POLYP ACCUMULATION

MICROBIAL CONSORTIA FOR PHOSPHORUS REMOVAL

Enhanced biological phosphorus removal primarily relies on the ability of sludge microorganisms to accumulate polyphosphate.

INNOVATION FOR P RECOVERY FROM SEWAGE SLUDGE

A range of issues impede further advancement in P recovery from sewage sludge, relevant to the quality control, capital and operating costs, and the immature market for recovered P.

Phosphate can be released from polyphosphate-accumulating sludge by anaerobic sludge digestion.

SLUDGE MANAGEMENT

Heating tank

Phosphate can also be released from polyphosphate-accumulating sludge by heating at 70

oC, if inexpensive heat is available. Kuroda et al. Biotechnol. Bioeng., 78:333-338 (2002).

SLUDGE MANAGEMENT

Struvite crystallization reactor

PHOSPHORUS RECOVERY AS STRUVITE

Struvite often causes difficult incrustation problems in pipelines. The hard crystalline incrustations have to be removed by means of mechanical cleaning techniques.

From Mr. K. Goto, Gifu City Office

PHOSPHORUS RECOVERY FROM INCINERATION ASH

From Mr. K. Goto, Gifu City Office

Recovered phosphorus

QUALITY, COST, AND MARKET BARRIERS

Calcium Silicate Hydrate (CSH) Patent publication number: JPA_2009285635

Before use

Ca/P＝2 Ca/P＝1.5 Ca/P＝1

N 0.13 0.12 0.19

P2O5 15.6 18.3 22.0

N and P content after P adsorption

After P adsorption

Onoda Chemical Industry Co., Ltd.

Phosphate can be recovered from the sludge digestion liquor using calcium silicate hydrate as an inexpensive adsorbent.

Onoda Chemical Industry Co., Ltd.

P Recycling for Industry

High-tech

Industry Sewage Wastewater

treatment

Food and Feed

Biosludge

P

recovered

As

h

Yellow P

manufacturin

g

P-

free

ash

Yellow P Phosphoric

acid

manufacturing

High-quality

phosphate

Iron ore

Coke Steel

Industry

Steel-making

slag

P-free

slug P-free slag can be returned

to a steel manufacturing

process.

P

slag

Phosphoric

acid

manufacturing

Phosphat

e

Phosphate

production by a wet

process

Water

reclamation

Steel-making

Industry

Chemical Industry

Recycle Industry

Cement

Industry The P content of clinker

needs to be lower than

0.5%.

Automobile

Semiconduct

or Liquid crystal

Agriculture Food

Consume

r Fertilizer

Industry P

fertilizer

Manure Ash Farmland

P recovered

Eutrophication

control

P recycle through

yellow phosphorus

regeneration

Vegetable oil

refinery

process

Food Industry

Business

model 1

Business model

2

Business

model 3

BUSINESS MODELS FOR P RECYCLING

Model area in P recycling

Ashidagawa WWTP Biophosphorites

P recycling center

Sales Fertilizer Industry

Waste water treatment plants (WWTP)

Recovered P

・Hotels ・Superstores ・Food manufacturers

Biogas Electricity

Heat energy

P industry

Night soil treatment plant

P recovery （Heatphos）

Industrial Wastes Industrial Wastes

P recovery （Heatphos）

P recovery （Heatphos）

Recovered P

The Phosphorus Recycling Promotion Council of Japan

Industry Academia Government

BEYOND GAPS BETWEEN SECTORS

THE PHOSPHORUS RECYCLING PROMOTION COUNCIL OF JAPAN

Phosphate rock

P recycle technology

Yellow phosphate

International cooperation for P recycling in Asia

Yellow phosphate

China

Vietnam

Others

Transfer of P recycle technology

Stable supply of P from Asia

Japan

P fertilizer

Food and Feed

Industrial P

Efficiency of P use

P recycling

Technology improvement

P depletion is a common challenge in Asia. The P recycling technology of Japan can make a great contribution to the crisis prevention.

INTERNATIONAL COLLABORATION