phosphorous recycling as green industry
TRANSCRIPT
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Phosphorite resources Shimonoseki Mitsui Chemicals, Inc.
Onoda Chemicals, Inc.
Phosphorous Recycling as Green
Industry
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Phosphorus is an essential constitute for all living organisms.
NO LIFE CAN EXIST WITHOUT PHOSPHORUS
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Phosphorus is used in a wide
variety of manufacturing industries.
Flame-retardants Etching agent
Food additives
Surface treatment chemicals
PHOSPHORUS FOR GREEN GROWTH
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Without phosphorus, there will be no biomass, no biofuel, no agriculture, nor life.
PHOSPHORUS FOR GREEN GROWTH
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Today, phosphorus is mostly obtained from mined rock phosphate which is a non-renewable resource.
From Prof. D. A. Vaccari
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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
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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
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(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
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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
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Microcystis aeruginosa cyanobacterium
Eutrophication
INCENTIVE TO EUTROPHICATION CONTROL
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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
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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
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MICROBIAL CONSORTIA FOR PHOSPHORUS REMOVAL
Enhanced biological phosphorus removal primarily relies on the ability of sludge microorganisms to accumulate polyphosphate.
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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.
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Phosphate can be released from polyphosphate-accumulating sludge by anaerobic sludge digestion.
SLUDGE MANAGEMENT
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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
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Struvite crystallization reactor
PHOSPHORUS RECOVERY AS STRUVITE
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Struvite often causes difficult incrustation problems in pipelines. The hard crystalline incrustations have to be removed by means of mechanical cleaning techniques.
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From Mr. K. Goto, Gifu City Office
PHOSPHORUS RECOVERY FROM INCINERATION ASH
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From Mr. K. Goto, Gifu City Office
Recovered phosphorus
QUALITY, COST, AND MARKET BARRIERS
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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.
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Phosphate can be recovered from the sludge digestion liquor using calcium silicate hydrate as an inexpensive adsorbent.
Onoda Chemical Industry Co., Ltd.
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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
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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
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THE PHOSPHORUS RECYCLING PROMOTION COUNCIL OF JAPAN
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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