Phosphorous Recycling as Green
IndustryPhosphorite resources Shimonoseki Mitsui Chemicals, Inc.
Onoda Chemicals, Inc. NO LIFE CAN EXIST WITHOUT PHOSPHORUS
Phosphorus is an essential constitute for all living organisms. PHOSPHORUS FOR GREEN GROWTH
Surface treatment chemicals Etching agent Flame-retardants
Phosphorus is used in a wide variety of manufacturing industries.
Food additives PHOSPHORUS FOR GREEN GROWTH
Without phosphorus, there will be no biomass, no biofuel, no agriculture, nor life. Today, phosphorus is mostly obtained from mined rock phosphate which is a non-renewable resource.
From Prof. D. A. Vaccari PEAK PHOSPHORUS
Around 2040
Global production 30
25
20
15
10
5
Phosphorus production (MT P/Yr) (MT production Phosphorus Global demand 0 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080 2100 Year
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 .
D. Cordell et al., Global Environ. Change, 19：292-305 (2009). LOOMING CRISIS OF PHOSPHORUS DEPLETION
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 NATIONAL P METABOLISM IN JAPAN
3 173.4 2.6 (10 ton/year) Food &Feed Livestock Wastes Crop 3.2 Fertilizer 4.3 River/Coastal water 141.3 10.6 42.0 4.3 Food & Feed Chemical Fertilizer 395.2 0.4 Industry Domestic and 32.9 municipal wastes 0.1 111.6 2.1 54.5 Waste sludges 14.2 224.9 Farm/ Ranch 17.5 75.1 Humans Wastes 110.6 Phosphate 129.3 0.2 10.6 55.4 rock Humans Livestock Fertilizer 110.6 2.1 145.2 0.1 356.1 18.7 Wastewater Fertilizer 155.9 Wastes Chemical Industry Agricultural 0.2 14.2 lands 24.5 Steelmaking 3.1 42.8 14.5 Industry Other 88.2 10.5 6.6 Natural 63.9 Products/ Waste sludges Industry Waters 157.2 Other mineral By-products 14.2 resources Fertilizer Soils 32.9 103.6 4.7 Steel Farm/Ranch 17.4 Humans 22.9 Steelmaking 0.2 96.4 54.5 Domestic Livestock 18.7 Chemical Industry products Slag Industry Food & Feed 3.2 Wastes
Total inflow of phosphorus to Japan is approximately 750 kt/Y. The import of rock phosphate accounts for 15%.
Yokoyama, et al., ISIJ International, 47: 1541-1548 (2007) P RECYCLING AS GREEN INDUSTRY
Food Industry Food Food and Feed Agriculture Vegetable oil refinery Consume process r Fertilizer P Farmland Ash Manure Water Industry fertilizer reclamation P Eutrophication recovered control Recycle Industry
High-tech Sewage Wastewater Biosludge P- Cement Industry treatment free Industry ash The P content of clinker Automobile needs to be lower than As 0.5%. Semiconduct h or Yellow P Phosphoric High-quality Liquid crystal P Recycling for Industry Yellow P manufacturin acid phosphate g manufacturing P slag Phosphate production by a wet Iron ore Steel Steel-making process Coke Industry slag Phosphoric P-free Phosphat Chemical Industry slug acid e P-free slag can be returned manufacturing to a steel manufacturing process. P recovered Steel-making P recycle through Industry yellow phosphorus regeneration INCENTIVE TO EUTROPHICATION CONTROL
Eutrophication
Microcystis aeruginosa cyanobacterium Inorganic Pi Organic Pi ＊Pi regulon genes Pi-starvatopm inducible but Most favorable 1000-fold increase not involved in Pi regulon Pi polyP PPi Organic Pi G1P H6P G3P genes Pi starvation Enzymes and proteins Bap＊ (pH8~10) Hydrolysis ATPase activity Ca2+ Pi Inhibition Pi ● (pH2.5) Mg2+etc. BAP AppA polyP PhoA Pi Periplasmic region C source H6P (pH4~6) CpdB （constitutive） C source ＊Pi-starvation Agp UshA (pH7.5) cAMP+CAP Pst 10-fold increase Control ? (pstSCAB) Dimer（BAP activity） Pit ＊(ugpBAECQ) Km=0.4mM, Ka=1mM cAMP+CAP Ugp Km=38.2mM (pitA) (pitB) Control Inhibition of UDP-G Arg-22 Km=1.5mM Vmax=15.9nmol /min mg ++ degradation S-S UhpTGlpT Vmax=3nmol/min mg Vmax=55nmol /min mg Ca Bond forming Outer Leader peptidase１ membrane Amino peptidase PhoB control C A PolyP-PHB A E Q (Hydrolysis ） complex C 471amino acids NTP RNA,DNA + PPi [0.5mM] Pi Pi Glycerophosphoryl Amino acid starvation (Trinucleotides) [Pi]<4mM + Ppa diester + ＊ PolyPn+Pi PPi PhoB phosphorylation A Pi PhoR Pi [10mM] ATP s70 Pho Box ＊ RelA PPX Pho regulon promoter ATP ppGpp GppA PPK Polyphosphates GTP - ＊ PolyP PolyP Central metabolic pathway PhoB-P dephosphorylation R ribosomal protein n+1 n PhoR [0.2mM] degradation PhoU＊ [Pi]>4mM Lon protease ATP, GTP, NTP H+ Electron transport NADH Acetyl-CoA 330 amino acids ADP+Pi Tertial structure FADH Oxalacetic acid + Cross Regulation 2 Isocitric acid Pi （C and energy metabolism） ＊ H+ Pta Phosphorylation PhoE CoA or trimer AtpLBEAGDC L-Malic acid Detection by censor 1 channel/monomer OmPF Fumaric acid TCA a-ketogluttaric acid Acetyl phosphate Activation ATP Glycolysis PhoB Cycle Gapa AckA ADP F O OmPC GAP BPG PEP C-Plyase ＊ Control sucCD PhnG~M Succinic Organic Pi Pathway Degradation of Pi Pgc Pyruvate kinase Succinyl-CoA Acetate E ＊ acid ATP+ Phosphonates Phn Cross regulation Pi Organic Pi Glucose Pi ATP ATP CDE GDP GDP+Pi Phosphorylation K I GTP ? J ATP Activation PhoB CreB Transcriptional factor P G Phosphonates efficiency M H ADP N PhoP L Amino ester phosphonate etc. Unknown target Accesary PhoQ Methyl phosphonate CreC Ortho phosphonate etc. PsiE PhoH Unknown function PsiF Phosphonates
GENETIC ENGINEERING OF POLYP ACCUMULATION
=O
=O BAP
RO-- P-OH [Org-Pi] [P ] HO-- P-OH i OH OH
Phosphate-specific Transport Phosphate Inorganic Transport
PST PIT
Polyphosphate kinase
=O
=O =O =O
PhnCDE PhnG-M PPK =O =O
H-- P-OH
- - -
H-P-OH [ATP] -O-P- -O-P-O-P-OH
HO-- P-OH
OH OH OH OH OH OH PPX [Pt] [P ] [Pi] [polyP] t exopolyphosphatase
PhnG-M Polyphosphate
PhnCDE
=O
R-- P-OH Inducible under Pi limitation OH
[Pn] Polyphosphate
K. Imazu et a., Appl. Environ. Microbiol., 64: 3754-3758 (1998). 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. SLUDGE MANAGEMENT
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 70oC, if inexpensive heat is available. Kuroda et al. Biotechnol. Bioeng., 78:333-338 (2002). PHOSPHORUS RECOVERY AS STRUVITE
Struvite crystallization reactor Struvite often causes difficult incrustation problems in pipelines. The hard crystalline incrustations have to be removed by means of mechanical cleaning techniques. PHOSPHORUS RECOVERY FROM INCINERATION ASH
From Mr. K. Goto, Gifu City Office QUALITY, COST, AND MARKET BARRIERS
Recovered phosphorus
From Mr. K. Goto, Gifu City Office Calcium Silicate Hydrate (CSH) Onoda Chemical Industry Co., Ltd. Patent publication number: JPA_2009285635
After P adsorption Before use
N and P content after P adsorption Ca/P＝2 Ca/P＝1.5 Ca/P＝1 N 0.13 0.12 0.19
P2O5 15.6 18.3 22.0 Phosphate can be recovered from the sludge digestion liquor using calcium silicate hydrate as an inexpensive adsorbent.
Onoda Chemical Industry Co., Ltd. BUSINESS MODELS FOR P RECYCLING
BusinessFood Industry model Food Food and Feed Agriculture 2 Vegetable oil refinery Consume process Fertilizer Businessr P Farmland Ash Manure Water Industry model 3 fertilizer reclamation P Eutrophication recovered control Recycle Industry
Business High-tech Sewage Wastewater Biosludgemodel 1 P- Cement Industry treatment free Industry ash The P content of clinker Automobile needs to be lower than As 0.5%. Semiconduct h or Yellow P Phosphoric High-quality Liquid crystal P Recycling for Industry Yellow P manufacturin acid phosphate g manufacturing P slag Phosphate production by a wet Iron ore Steel Steel-making process Coke Industry slag Phosphoric P-free Phosphat Chemical Industry slug acid e P-free slag can be returned manufacturing to a steel manufacturing process. P recovered Steel-making P recycle through Industry yellow phosphorus regeneration BEYOND GAPS BETWEEN SECTORS Waste water treatment Night soil treatment plant ・Hotels plants (WWTP) ・Superstores
・Food manufacturers P recovery P recovery （Heatphos） （Heatphos）
Recovered P Industrial Wastes Industrial Wastes
P recycling center Biogas Electricity Ashidagawa Heat energy WWTP Biophosphorites P industry Sales P recovery Fertilizer （Heatphos） Recovered P Industry
Model area in P recycling
The Phosphorus Recycling Promotion Council of Japan
Industry Academia Government THE PHOSPHORUS RECYCLING PROMOTION COUNCIL OF JAPAN INTERNATIONAL COLLABORATION
Phosphate rock P depletion is a common challenge in Asia. The P recycling technology of P recycle technology Japan can make a great Yellow phosphate contribution to the crisis prevention.
Yellow phosphate
Transfer of P recycle technology Efficiency of P use China P fertilizer P recycling Vietnam Japan Food and Feed Technology improvement Others Industrial P Stable supply of P from Asia
International cooperation for P recycling in Asia