Introduction of company and product "Porous Alpha" (English Version)

Tottori Resource Recycling, Inc.
Company & Technology overview
1
October 2015

第I部：会社・商品説明編
– Company Overview
– Core Technology
– Applications
第II部：事業戦略編
2
Company Overview

We, Tottori Resource Recycling Inc. is a venture
company focused on foamed glass as core technology
 Name: Tottori Resource Recycling Inc.
 President: Yoshiaki Takeuchi (Mr.)
 Establishment: December, 2001
 Capital: 40 million JPY
 Location:583 Toen, Hokuei-cho, Tohaku-gun,
Tottori, 689-2202, Japan
 Number of employees: 9
 Business area
– Producing foam glass by clean recycling process（patented technology）
– Inventing and selling the following solutions based on foam glass
• Microbial Deodorizing
• Water treatment: Adsorption and recovery of fluorine (Patent-pending)
• Water treatment: Adsorption and recovery of Phosphorus ion (Patented)
• Water treatment: Microbial decomposition
• Soil conditioning: improving water retention & aeration capacity
• Land improvement for salinity control...and other applications under development
3
Company Overview

We carry the global environment to the next
generation by improving it
 The global warming associated with water shortage affects agriculture,
farming, food insecurity and its skyrocketing price for 7+ billion
population over the world part of which conflicts and lootings take place
 We are specialized in the application of safe and multifunctional porous
material “Porous Alpha” by foaming used glass with patent technology
 Based on the glass foaming technology to create safe porous material,
which was difficult before, we contribute to realize the comfortable
global environment and reduce the environmental burden at the same
time
 We carry the beautiful earth to the next generation by improving the
global environment
4
Company Overview

We research and develop the core technology of foaming
glass with Univ. of Tottori, selling and developing
applications with partner companies
University of
Tottori
Collaborative
R&D
Customers
Partners with market
focused technology
Sell
Collaborative
R&D
Provision of
Porous α
Sell
e.g.
 Home center
 Engineering company
 Distributors
5
Cities around
factory
Raw material
（Used glass bottle)
Partner
manufacturer
Sell
Sell production plant &
technology
Our Company
Company Overview
Public research
institutes in
Tottori

Japanese govt. agency and local govt. appreciate our
technology, providing various financial support
Timing Agency Awards
2004 Pref. Tottori Certificate as Green Product by the governor of prefecture of Tottori
July 2005 Pref. Tottori Award of collaborative R&D for recycling technology of prefecture of Tottori
Aug. 2008 Pref. Tottori Award of incubation for next generation & local resource based industry (R&D for water
saving vegetable growing with recycled material)
Dec. 2009 Org. for SME
and Regional
Innovation,
JAPAN
Award of R&D support for SME manufacturer (Evaluation for water saving vegetable
growing in sandy soil with recycled material)
Aug. 2010 Pref. Tottori Award of employment program of important sector
Sep. 2010 Pref. Tottori Award of commercialization of recycle technology and products (R&D of adsorption of
Phosphorus ion with recycled glass)
May 2011 Pref. Tottori Award of grant for strategic economy growth of prefecture of Tottori
Apr. 2013 JICA Award of feasibility study to introduce private technology for African development
(Senegal)
Dec. 2014 Pref. Tottori Award of incubation of next generation and local resource based industry
Jun. 2015 JICA Award for the verification study with the private sector for disseminating Japanese
Technologies for Water –Saving Agriculture in arid area
6
Company Overview

– Core Technology
– Applications
7
Company Overview

Our technology is centered at foamed porous glass “Porous
Alpha” from glass and shell as core technology, developing
its application
8
Electron microscope image
Porous AlphaGlass
Shell
Air treatment as biofilter media
Water treatment: Adsorption
and recovery of Phosphorus ion
Water treatment: Microbial
decomposition
Soil conditioning: improving water
retention capacity and aeration
capacity
Land improvement for salinity
control
…etc.
Application
Transformed
for each
application
Core Technology
Water treatment: Adsorption and
recovery of fluorine
Core Technology

Core technology and some of applications are
patented in Japan
9
Name of invention Patent
Number
Applicants
Inorganic foam product and its
production method
3898116 Tottori Resource Recycling,
Inc.
Production process of formed glass and
foamed glass (Production methodology
for safe foamed glass)
4088930 Prefecture of Tottori
(Right to use patent is held
by Tottori Resource
Recycling, Inc.)
Production methodology of adsorption
agent of Phosphorus ion, Phosphorus
acid fertilizer and adsorption agent of
Phosphorus ion
5382657 University of Tottori
Prefecture of Tottori
Tottori Resource Recycling,
Inc.
Irrigation equipment, irrigation system
and irrigation method
5731791 University of Tottori
Inc.
Fluorine adsorption agent and fluorine-
containing water treatment (patent
pending)
2012-023795
(Pending)
University of Tottori
Prefecture of Tottori
Inc.
Core technology
Adsorption & desorption of
Phosphorus ion
Soil conditioning: improving
water retention & aeration
capacity
Adsorption & desorption of
fluorine (Patent-pending)
Application Core Technology

Porous Alpha is made by burning of mixture of
pulverized glass and shells
①Crush ②Pulverize
④Burning
③mixture of
foam agent
①Crushed glass ②Pulverized
glass
④Foamed glass
Pulverize
Shell
Burning
Used glass bottles
10
Core Technology

Porous Alpha is a soda-lime glass composed mainly of
silicon dioxide (silica), calcium oxide and sodium oxide
11
Composition of Porous Alpha
Material Safety Data Sheet of Porous Alpha , Oct., 2011
*Ti, Cr, Mn, Ni and Ｓare included as minor elements.
62.00%24.70%
8.60%
2.00%
1.70%
1.00% 0.00%
SiO2CaO
Na2O
K2O
Al2O3
Fe2O3 Others*
Core Technology

Physical characteristics is as follows;
Visual appearance: Achroma or light green etc.
Odor: Odorless
True density: ca 2.5 g/c ㎥
Size density: 0.9～1.2 g/c ㎥
Grain size: 50～2,000 μm ( Median 700μm)
Grain shape: Abrasive infinite shape
pH: Max. pH 10.3 or pH 7(after water washing)
Solubility: Not identified
Softening temperature: 720～730℃(unresolved)
Volatile: not identified
12
Based on Material Safety Data Sheet of Porous Alpha , Oct., 2011
Core Technology

Porous Alpha has three uniqueness which are the
base for our diversified applications
13
Competitors’
products
Heavy metal
elution is not
avoidable
 Range of acceptable raw material (glass) is wider
than competitors’ products
 Widen range of application by safety nature
- Usable for agriculture as soil conditioner
- Not contaminating the treated water when used
as water treatment agent
Uniqueness
Non-elution of
heavy metal
Merit by the uniqueness
１
Coexistence of
Interconnected and
closed pore
２
Only closed
pores
 Possible to contain diversified matter and
microbes
- Diversified microbes for deodorizing
- Water and air for soil conditioner
 Air and water are permeable
- Perform as water treatment agent by
sinking in water
Adjustable specific
gravity and pore
size
３ Constant specific
gravity
 Adjustable to the requirement by application
and environment
Core Technology

（Ref.）Leaching test result of Porous Alpha
14
No. Item Result
1 Alkyl mercury Undetectable
2 Total mercury < 0.0005 mg/l
3 Cadmium < 0.001 mg/l
4 Lead 0.001 mg/l
5 Organophosphorus Undetectable
6 Hexavalent chromium 0.014mg/l
7 Arsenic < 0.001mg/l
8 Total cyanogen Undetectable
9 PCB Undetectable
10 Trichloroethylene < 0.03 mg/l
11 Tetrachloroethylene < 0.01 mg/l
12 Dichloromethane < 0.02 mg/l
13 Carbon tetrachloride < 0.002mg/l
14 1,2 – Dichloroethane < 0.004 mg/l
15 1,1 – Dichloroethane < 0.02mg/l
16 Cis1,2 – Dichloroethylene < 0.04 mg/l
No. 項目結果
17 1,1,1 – Trichloroethane < 0.3 mg/l
18 1,1,2 – Trichloroethane < 0.006 mg/l
19 1,3 –Dichloropropene < 0.002 mg/l
20 Thiuram < 0.006 mg/l
21 Simazine < 0.003 mg/l
22 Thiobencarb < 0.02 mg/l
23 Benzene < 0.01 mg/l
24 Selenium < 0.001 mg/l
25 Fluorine < 0.08 mg/l
26 Boron < 0.1 mg/l
27 Carbon < 0.5 mg/kg
Result of leaching test based on “Environmental regulation on soil contamination,
23 Aug. 1991, Ministry of Environment)
Analyzed by Tottori health association, Jan. 2008
Core Technology

– Core Technology
– Applications
• Water treatment: Adsorption & desorption of fluorine
• Water treatment: Adsorption & desorption of Phosphorus ion
15
Applications

We develop various applications out of the uniqueness
of Porous Alpha
16
Uniqueness of
Porous Alpha
Non-elution of
heavy metal
１
Coexistence of
Interconnected and
closed pore
２
Adjustable specific
gravity and pore
size
３
High
safety
Various
sizes of
pores
Water & air
permeable
Microbial
Deodorizing
Adsorption
& recovery
of fluorine
Microbial
water
purification
Soil
conditioning
✓ ✓ ✓ ✓ ✓
✓ ✓ ✓
✓ ✓
✓
✓ ✓ ✓ ✓
✓
✓ ✓ ✓ ✓ ✓
Applications
Adjustable for
applications
Reusable as input
of agri.
No heavy metal in
treated water
Capable of retaining
various microbes
Longer contact
time with air &
water
Capable of
retaining various
matters
Sinkable in
water
Needs, Mechanism, Case Studies and Specifications of each
application follow
Applications
Adsorption &
desorption of
phosphorus ion

– Core Technology
– Applications
17
Applications

Deodorizing of livestock barn, food processing factory,
composting facility is required for their business
 Deodorizing is one of the important
business issue for livestock business
 Deodorizing is required in other
industries
– Food-processing facilities
– Hotels・restaurants
– Kitchen waste disposal facilities
– Composting facilities
– Feed manufacturing
18
Needs Mechanism Competition Case Study Specs.
56%25%
7%
12%
Complaint to livestock farmers (2012)*
*Livestock Department, Ministry of Agriculture, Forestry and Fisheries
Odor
Vermination
Others
Water
pollution
Porous Alpha enables the low cost deodorizing solution
Microbial Deodorizing

Layered Porous Alpha with microbe deodorizes the
odorous gas when the gas passes through
19
watering
Closed unit to prevent the
odor emission
Blower
Odor-free air
Microbe
deodorizing unit
Odor source
(Manure,
Compost, etc.)
Odorous Gas
Water circulation
Submersible
Pump
Layered Porous
Alpha with microbe
Conceptual figure of deodorizing system with Porous Alpha
Needs Mechanism Competition Case Study Specs.Microbial Deodorizing

Microbes derived from manure, contained in Porous
Alpha, digest gases in the interconnected pores
20
Concept image of deodorizing process
Odorous Air: mixture of
100+ gases
Odorous
gas
Odor-free air
Microbes
digesting specific
gas
Porous Alpha
Pore
Odor-free air Layered Porous Alpha
Diversified & interconnected pores in Porous Alpha is the source of
high performance of deodorizing

Deodorizing by Porous Alpha is suitable for aerobic
fermentation
 Our deodorizing solution is realized through digestion by microbe, i.e. aerobic fermentation
 Aerobic fermentation requires five principal requirements which are suitably met in the
application of Porous Alpha
21
Microbe
１
Nutrition
2
Air
3
Water
4
Requirements for aerobic
fermentation
How to realize
Source of odor is taken and put to the layer of Porous
Alpha where microbe inhabit
The odorous air is the nutrition for microbe
Watering by sprinkler is installed
The odorous gas has the air also
Temperature
5
Digestion of nutrition by microbe generates heat

Compared to the competing solution based on rock
wool, we have advantages in durability & cost
22
Comparison of deodorizing solution between rock wool-base
solution and Porous Alpha for livestock farmers
Mechanism
Cost
Durability
Rock wool Porous Alpha
Large scale system needs
high initial investment
Expensive Rockwool
(120～150 K JPY/ m3)
Simple system with low
initial investment
Less expensive Porous
Alpha
More than 15 years8～13 years
Microbial
Deodorizing
Model case
（30 000 pigs）
169 mil. JPY＋55k
JPY / month
Initial invest
Running
22.8mil. JPY＋
16k JPY/month
Microbial
Deodorizing

We have various experience in deodorizing
23
No. Customer Scale of
odor
source
Density of source
odorous air
Quantity of
Porous Alpha
Rate of deodorizing
(output density)
Cost of Porous
Alpha system
(JPY)
Cost of rock
wool based
system (JPY)
1 Poultry
house
30K birds Ammonium
100～800ppm
1.82m3 99%（0.1 ppm） 200K＋
5K/month
700K＋
15K/month
2 Poultry
abattoir
3t/day Ammonium
2.81ppm
Methylmercaptan
0.33ppm
Hydrogen sulfide
0.32ppm
7m3 Ammonium
99.7%（0.01ppm）
Methylmercaptan 98.9%（0.004ppm）
hydrogen sulfide 100%（0.00ppm）
2mil.＋
10K/month
10mil.＋
30K/month
3 Pig
house
15 pigs Ammonium
11.3ppm
5ｍ3 Ammonium
100% (0ppm)
200K＋
5K/month
700K＋
15K/month
4 Poultry
house
300K
birds
Ammonium
2091ppm
Methylmercaptan
6.7ppm
70m3 Ammonium98.2%（37.9ppm）
Methylmercaptan 100%
（0ppm）
3.5mil.＋
30K/month
23mil＋
55K/month
5 Poultry
abattoir
50t/day Trimethylamine
250ppm
1m3 Trimethylamine
100%（0ppm）
150K＋
30K/month
220K+
90 K/month
6 Pig
house
30K pigs Ammonium
2000ppm
Methylmercaptan
4ppm
135m3 Ammonium95% (100ppm)
Methylmercaptan 100% (0ppm)
(Less than 1month after installation)
22.80mil＋
16K/month
169mil＋
55K/month
Summary of case studies for microbial deodorizing
Case No.1 is explained in the following pages in detail

Case 1：Our system deodorizes 100-800 ppm of
ammonium at poultry house of 30K birds
24
Composting unit Blowing the
odorous gas
Deodorizing unit
(Porous Alpha)
Odor-
free air
 30K birds
 Odorous gas
- Ammonium100
-800ppm
 2 m3/min.  Deodorizing unit
size 2m3, incl.
1.8m3 of Porous
Alpha
 Watering
50L/hr
 Contact time
54 sec.
 Rate of deodorizing
more than 99%
（50 days after the
installation ）
Case1: Poultry house (30K birds)
Porous Alpha Rock wool
Initial investment 200K JPY 700K JPY
Running cost 5K JPY/month 15 K JPY/month

Case 1：Deodorizing performance increases as time
proceeds, more than 99% after 50 days of installation
25
97
97.5
98
98.5
99
99.5
100
0
100
200
300
400
500
600
700
800
900 0
10
20
30
40
56
76
95
117
137
156
186
216
249
279
334
379
Density of ammonium and rate of deodorizing
Density of
ammonium
(ppm)
Rate of
deodorizing
(%)
Rate of
deodorizing (%)
Density of inflow
ammonium (ppm)
Density of output
ammonium (ppm)

Case1: Odorous gas emission in manure fermenter
26
Composting unit
Odorous gas
Composting unit
Blowing the
odorous gas
Deodorizing
Odor-free
air

Case 1: Vacuuming odorous gas in by blower at
composting unit
27
Suctioning pipe
Suctioning odorous gas from upper side of composting unit
Odorous gas
Composting unit
Blowing the
odorous gas
Deodorizing
Odor-free
air

Case1: Blower and deodorizing unit
28
Porous Alpha
Sprinkler
Deodorizing
unit
Blower
Water
tank
Pump
Interior of deodorizing unitExterior of deodorizing unit
Odorous
gas Odor-free
air
Composting unit
Blowing the
odorous gas
Deodorizing
Odor-free
air

Case2: Exterior view of deodorizing plant with Porous
Alpha for poultry abattoir
29
Odor-free
air
Deodorizing
unit
PumpBlower
Odorous
gas

Specification and applied conditions for deodorizing by
Porous Alpha
 Watering
– Moisture of support (Porous Alpha) should be more than 50%
• In summer season, Porous Alpha becomes dried. Watering should be more frequent than other seasons.
Water for watering should be maintained
– If there is risk of frost, measures to prevent it is required
– Salt concentration of water should be less than 5,000 ppm
 Blower and its power source is required to transfer the odorous gas
 Source of odor should be enclosed so that the blower can suction the gas
 A filter at the end of the pipe for blower should be installed and changed periodically
 Required period of habituation for microbe: About 1 month
 Temperature for active performance of microbe: 10 – 40 ℃
(There is experience of working less than 10℃)
 Track record of odorous gas source
– Pig house compost
– Poultry house compost
– Food waste compost
– Hotel restaurant compost
 Track record of odorous gas
– Ammonium
– Methylmercaptan
– Hydrogen sulphide
– Trimethylamine
30

– Core Technology
– Applications
31
Applications

Water treatment for industries using fluorine is
serious issue
 Various industries use and discharge fluoric fluid
– Semiconductor manufacturer uses fluoric fluid to clean silicon
wafers
– Glass manufacturer and processor uses fluoric fluid as material for
etching
– Liquid crystal display manufacturer use fluoric fluid for etching glass
– Metal processing company use fluoric fluid for pickling
– Coal thermal power plant discharge waters with fluorine from
desulfurization system
 Water treatment is serious issue
– Regulation of discharge of fluorine (8mg/l) must be followed
– Existing solution requires a lot of cost
• Large quantity of sludge, which is industrial waste, is generated
• Resin solution, discharging small amount of waste, is expensive
32
Porous Alpha can reduce the cost of fluoric water treatment
Needs Mechanism Competition Case Study Specs.Fluorine Adsorption

The hydrothermally-processed Porous Alpha has
increased specific surface area which adsorbs fluorine
 Hydrothermal process to Porous Alpha increase the specific surface
area
33
Specific surface area：83 m2 g-1 Specific surface area : 278 m2 g-1
Before Hydrothermal process
After Hydrothermal process
Fluorine Adsorption

Fluorine is removed from its solution as a result of
precipitation of fluorine ion as sodium fluorosilicate
34
SiF6
2- + 2Na+ → Na2SiF6
SiO2 + 6HF → SiF6
2- + 2H+ + 2H2O (pH < 3.2)
SiO2 + 4H+ + 6F- → SiF6
2- + 2H2O (pH > 3.2)
NaF → Na+ + F-
F- + H+ ⇆ HF （ pKa = 3.2）
ヘキサフルオロケイ酸ナトリウム
（ケイフッ化ナトリウム)
Sodium fluorosilicate
Sodium fluorosilicate
is valuable as a raw
material for hydrofluoric
acid
Chemical mechanism of precipitation of fluorine
Fluorine Adsorption

Fluorine is adsorbed by contacting for 1-2 hours with
Porous Alpha
35
初濃度：CF, 1000 mg L -1
初濃度：CF, 100 mg L -1
0
400
800
1200
0 2 4 6
CF/mgL-1
時間 / h
0
40
80
120
0 2 4 6
CF/mgL-1
時間 / ｈ
Hydrothermally-
processed Porous
Alpha 0.2g,
Sodium fluoride
solution:20mL, 25℃
Historical trend of the density of fluorine for different initial density*
Initial concentration：CF, 1000 mg L -1
Initial concentration：CF, 100 mg L -1
*Based on ionic electrometry method
Contact time (Hour)
Hydrothermally-
processed Porous
Alpha 0.2g,
Sodium fluoride
solution:20mL, 25℃
Fluorine Adsorption

The fluorine adsorbed in Porous Alpha can be
desorbed with nitric acid (> 0.5mol/L）
36
0
40
80
120
0 0.5 1 1.5 2
WF/mgg-1
CHNO3 / mol L-1
Fluorine desorption
weight per Porous Alpha
with adsorbed fluorine
(mg/g)
Fluorine desorption from Porous Alpha with adsorbed fluorine
Hydrothermally-processed Porous Alpha 0.2g,
Nitric acid solution 10ml, Contact time 4hours
Concentration of nitric acid mol/L

Volume of desorption strongly depends on
concentration of nitric acid, not on contact time
37
0
40
80
120
0 2 4 6
WF/mgg-1
時間 / hContact time
CHNO3
（molL-1) =
0.5
CHNO3
（molL-1) =
0.1
Fluorine desorption
weight per Porous Alpha
with adsorbed fluorine
(mg/g)
Fluorine desorption from Porous Alpha with adsorbed fluorine
Hydrothermally-processed Porous Alpha 0.2g, Nitric acid solution 10ml
Fluorine Adsorption

Fluorine adsorption and desorption process could be
implemented in a simple manner with Porous Alpha
38
NaOH
Discharged
fluid with highly
concentrated
hydrofluoric acid
pH
adjustment
unit
H2SiF6
Generation
unit
Glass powder
Fluorine
adsorption unit
NaOH
pH adjustment
unit
Na2SiF6
precipitation
Concentr
ation of
fluorine
Very high
(> 70000ppm）
pH
High
(50000ppm～10ppm）
Hydrothermally-processed
Porous Alpha
Discharge
Low
(< 8ppm)
Strong acidity
(pH0.5～1）
Acidity
（pH4～5）
Strong acidity
(≦ pH0.5）
Mild acidity～Mild alkaline
（pH5～8）
Process flow of fluorine water treatment with Porous Alpha
In case of high initial concentration of fluorine, this step should be
multiplied to gradually reduce the concentration

39
（Ref.）Competitor’s plant (F-Free) is more
complicated than ours
Original
fluid
Ca
Original fluid unit
Polymer
Reactor I
Fluorine removal
agent
Precipitation
unit I
Precipitation
unit II
Acid
Reactor II
Slurry receiver
Discharge
Filter press

Porous Alpha’s capacity of adsorption of fluorine is
drastically higher than other agents
40
Agent for adsorption of fluorine Adsorbed fluorine capacity
(mg g-1)
Contact
time(Hr)
Hydrothermally-processed Porous Alpha
800 (Initial concentration 100,000mg/L) 72
393 (Initial concentration 5,460mg/L) 4
Schwertmannite (Fe8O8(OH)6(SO4)·nH2O) 55 24
Nano-geothite 59 2
Glutaraldehyde/Calcium alginate 74 1.5 - 2
Al(OH)3 /Lime stone 84 5
Fe3O4/Al(OH) 3 nanoparticles 88 4
Al-Ce hybrid adsorbent 91 24
Fe-Al mixed hydroxide 92 2
Tunisian clay mineral 93 72 - 96
CaO/ Activated alumina 101 48
CaO nanoparticles 163 0.5
Fe-Al-Ce trimetal oxide 178 24
Calcined Mg-Al-CO3 lyered double hydroxides 213 5
Nanomagnesia 268 1.5 - 2
A. Bhatnagar, E. Kumara, M. Sillanpaa, Chem. Engineering J., 171 (2011) 811.
Adsorption capacity and contact time for different agent for adsorption of fluorine

Fluoric water treatment with Porous Alpha has wider range
of use and/or is more cost effective than others
41
In addition to above, simple plant structure can realize small
size of initial investment
Competito
rs
Precipitation method
using calcium
Precipitation method
using aluminium
Adsorption method Crystallization method
Nature an
issues
 Generate precipitation of
calcium fluoride (CaF2)
by adding calcium
hydroxide or calcium
chloride
 Difficult to decrease the
concentration of fluorine
to regulated level (8mgL-
1)
 Lots of sludge generated
 Generate precipitation by
adding aluminum sulfate or
poly-aluminum chloride
 Capable only for low
concentration fluoric
water
 Possible to decrease the
to less than 5 mgL-1, but
input volume of aluminum
salt and sludge are
increased
 Remove fluorine
with adsorption
agent such as
activated alumina,
layered double
hydroxide, rare earth
compound and
chelate resin
supporting aluminum
 Difficulties in highly
concentrated fluoric
fluid
 High running cost
 Remove fluorine by
crystallization with
additive agent such as
calcium fluoride and
fluorapatite
 Control of reactive
condition such as
volume of additive
agent is required
 Each additive agent has
limited range of
concentration of
fluorine for
crystallization
Advantage
of Porous
Alpha
 Possible to decrease the
under regulation
 Limited generation of
sludge
 Possible to use high
concentration fluoric
water
 Limited generation of
sludge
 Possible to adsorb
highly concentrated
fluoric fluid
 Low running cost
 Control of reactive
condition is easy
 Wide range of fluoric
concentration is
covered

Our solution for fluoric water treatment is under
verification in liquid crystal manufacturer
Customer：Manufacturer of liquid crystal related
product
Concentration of fluorine before treatment：Hundreds
of thousand ppm
Currently they’re using the combination of precipitation
method with calcium and aluminum to remove fluorine
They have intention to use our technology to reduce
the discharging cost of industrial waste (sludge)
42

Specification and applied conditions for fluorine
adsorption and desorption by Porous Alpha
 Minimum contact time: 1hour
 Fluorine adsorption capacity per 1g of Porous Alpha: 400mg
– In case of high concentration of fluorine, the adsorption process should be repeated
 Required quantity of Porous Alpha per 1 step: 5% of quantity of fluid
 Concentration of fluorine after adsorption process: less than 8ppm
– Not guaranteeing to decrease the concentration to 0.8 ppm (for potable water)
 The purity of precipitation on sodium fluorosilicate is decreased according to the
concentration of Fe (III) and Al(III)
 Technical issues to be solved
– The fluoric water discharged from glass etching contains boron. As a water treatment
solution, the removal of BF4 is also required. Now we are developing to remove the boron
alongside with fluorine.
– To provide as a system for water treatment of fluoric discharging water, it is required to
remove boron at the same time
– Methodology to remove boron is now under investigation.
43

– Core Technology
– Applications
44
Applications

Phosphorus is a rare resource but, on the other hand, one
of factors of water pollution. Discharge is regulated
 Though phosphorus is a rare resource...
– One of main materials of fertilizer (NPK fertilizer)
– Uneven distribution over the world
• The top 3 producing countries(China, Morocco and USA) account
for 71%
• 74% of global reserve is in one country (Morocco)
• Japan imports the 39% and 26% from China and Jordan, respectively
– Fertilizer consumption is expected to be increased due to higher
food demand and decreased arable area
 ...its discharge is regulated as one of the factors of water
pollution
– Factor of eutrophication in rivers and lakes
– Factor of Water pollution in fish ponds
– Discharge regulated （16mg/L（8mg/L in average of 24h）*）
45
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
*The standard emission of phosphorus is applied to only wastewater discharged, to lakes specified that phosphorus could cause significant
phytoplankton multiplication by Minister of the Environment , to a sea area specified that phosphorus could cause significant marine
phytoplankton multiplication by Minister of the Environment or to public water flowing in them.

International price of a phosphate rock surged during the
food crisis in 2007～2008 is now stabilized but more than
double of before-crisis level
0
50
100
150
200
250
300
350
400
450
500
2000-01
2001-01
2002-01
2003-01
2004-01
2005-01
2006-01
2007-01
2008-01
2009-01
2010-01
2011-01
2012-01
2013-01
2014-01
2015-01
46
115USD/t
430USD/t
(2014/8)
* ：World Bank（Phosphorus rock (Morocco), 70% BPL, contract, f.a.s. Casablanca Phosphorus rock Price, $/mt）
44USD/t
USD/t
International price trend of phosphate rock*
Phosphorus adsorption & recovery decrease environmental
burden and utilize rare resource

Increased specific surface area of Porous Alpha by
hydrothermal process realizes phosphorus ion adsorption
47
Specific surface area：83 m2 g-1 Specific surface area : 278 m2 g-1
Before Hydrothermal process After Hydrothermal process

（Ref.）X‐ray diffraction
48
0
200
400
600
800
1000
1200
1400
0 20 40 60 80 100
0
200
400
600
800
1000
0 20 40 60 80 100
0
200
400
600
800
1000
0 20 40 60 80 100 2θ / deg
2θ / deg
2θ / deg
Hydrothermally-processed
Porous Alpha
Porous Alpha
Soda-lime glass

Soda-lime glass has the elements with which
phosphorous ion is adsorbed or precipitated
49
Ion-exchange reaction
≡ Si-OH + H2PO4
- → ≡ Si-H2PO4
- + OH-
2(≡ Si-OH) + H2PO4
- → （≡ Si)2HPO4
- + OH- + H2O
Hydrogen bond OH …O- OH
=Si(OH) 2 + H2PO4
- → = Si P
OH…O- OH
V. V. Murashov, et al., J. Phys. Chem. A, 103, 1228 (1999)
Composition of Soda-lime
glass
Precipitation reaction
Ca2+ + PO4
3- → Ca3(PO4)2
Ca2+ + HPO4
2- → Ca HPO4
Al3+ + PO4
3- → AlPO4
Fe3+ + PO4
3- → FePO4
Adsorption & precipitation of phosphorous ion
Elements

50
0
200
400
600
800
1000
1200
0 1 2 3 4 5 6 7 8
PO4濃度/mgL-1
Time/h
Initial concentration 1065 mg L-1
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8
PO4濃度/mgL-1
Time/h
0.0
0.2
0.4
0.6
0.8
1.0
0 1 2 3 4 5 6 7 8
PO4濃度/mgL-1
Time / h
0.0
2.0
4.0
6.0
8.0
10.0
0 1 2 3 4 5 6 7 8
PO4濃度/mgL-1
Time / h
Regardless of the initial concentration, phosphorous
ion is adsorbed to Porous Alpha in 1hour
Initial concentration 9 mg L-1
Initial concentration 79.4 mg L-1
Initial concentration 0.8 mg L-1
ConcentrationofPO4
mgL-1ConcentrationofPO4
mgL-1
ConcentrationofPO4
mgL-1
ConcentrationofPO4
mgL-1

The best pH for adsorption performance is around 7
51
0
20
40
60
80
100
1 4 7 10
pH
Rateofadsorption(%)
Rate of adsorption for different pHs
Concentration of PO4: 2000mg mL-1; contact time 24hrs

The adsorbed phosphorous can be recovered in high
purity form with nitric acid and citric acid
52
0
20
40
60
80
100
0.001 0.01 0.1 1 10
CHNO3
/ mol L-1
0
20
40
60
80
100
0 2 4 6 8 10
クエン酸濃度/10-2
mol L-1
Needs Mechanism Competition Case Study Specs.Phosphorus ion AdsorptionRateofrecovery(%)
Rateofrecovery(%)
Concentration of HNO3 mol L-1 Concentration of citric acid mol L-1

Porous Alpha with adsorbed phosphorus can be used
as delayed release fertilizer
53
Dry weight of harvested tomato with different type of phosphorus fertilizer*
Dryweightofharvested
tomato(gplant-1)
*: Master graduation thesis, University of
Tottori, 2013
Nophosphorus
fertilizer
Yourin(store-bought
phosphorusfertilizer)
PorousAlpha
+Yourin
PorousAlpha
withadsorbed
phosphorus

Existing technology to recycle phosphorus as fertilizer has
issues such as limited recoverable form of phosphorus and
high running cost
54
Technology ＨＡＰＭＡＰ Ash alkali extraction Reducing smelting
Principle Crystallization of
hydroxyapatite
Ca10(OH)2(PO4)6)
Crystallization of
magnesium ammonium
phosphate (MgNH4PO4)
Alkali extraction of
phosphorus in sludge
incineration ash and
adsorb calcium
phosphate
Add calcium and
magnesium, reducing
smelting and recovery
the sludge with
phosphorus
Source of
Phosphorus
Recycle flow,
Filtered water
Filtered water, Digestive
juice
Sludge incineration ash Sludge incineration ash
Concentration of
phosphorus
PO4 - P: 10～50 mg
Ｌ-1
PO4-P : 100～150 mg Ｌ
-1
P2O5 : more than 25％ P2O5 : more than 20％
Recovery rate 80% 50～90% More than 55% More than 80%
Influential factor Ca, pH,
Temperature,
HCO3
-
Mg, NH4
+, pH,
Temperature
Ca, Al Al
Problems Impossible to
recover from
suspended solid
phosphorus
Ｍg is expensive.
Impossible to adsorb
organic phosphorus
Reaction temperature
is 50～70℃.
Generation of residual
ash
Measure to exhaust gas
required
Registration as
fertilizer
Phosphate fertilizer Compound fertilizer Phosphate fertilizer Compound fertilizer
OPEX/yr 7 mil. JPY 4.1～6.5mil. JPY 80 mil. JPY 815 mil. JPY
Source: Method for recycling of phosphoric resource in waste water, Ministry of Land, Infrastructure, Transport and Tourism,
Japan, 2010

Adsorption capacity of phosphorus with Porus Alpha
is drastically higher than others
55
a) Etsuro Kobayashi etc., Nikka, 1981，1319. b) Shinya Tange, Patent2007-38203.
c) Shinobu Inenaga etc., 「Ninngen to kannkyo」, 31(2005)11.
Adsorbents Capacity of adsorption /mg g-1
Hydro thermal treated foam glass 111
Calcium silicatea)
50
Zirconium hydroxidea)
48.5
Metatitanic acida)
44.2
Hydrotalciteb)
33.2
Y-ferrous hydroxide(III)a)
24.7
Activated aluminaa)
22.5
Kanuma pumicea)
17.5
Acid clay, Coralitea)
2
Foam glassc)
0.049
Activated carbon, Natural zeolitea)
0

We are now testing phosphorus application to the water
flowing into public sewage plant
Pilot project site: Public sewage plant
Contents of pilot project
– Adsorption of phosphorus from water flowing into
sewage plant
– Desorption of phosphorus
– Evaluation of the Porous Alpha with phosphorus as
fertilizer
56

Specification and applied conditions for phosphorus
adsorption, recovery and usage as fertiliser
 Phosphorus adsorption
– Adsorption ability is the highest approximately pH 7.0
– Necessary contact time is approximately 1 hour
– Applicable initial concentration is higher than 0.8 ppm
– Phosphate concentration in treated solution is lower than 0.2 ppm
– It’s required to prevent the suspended solids adsorbed to Porous
Alpha
• SS should be removed in pre-treatment; or
• Put filter to protect Porous Alpha from SS
 Phosphorus recover
– With nitric acid higher than 0.5mol/L
– Phosphorus recovery rate: more than 80%
– Nitric acid (more than 0.1mol/L） or citric acid (more than
0.05mol/L)
57

– Core Technology
– Applications
58
Applications

There are demands for lake and aquaculture farm to
purify the water by microbial decomposition
Water pollution takes place in lake, reservoir and
aquaculture farm by eutrophication
Especially for aquaculture, water contamination directly
impact on the productivity. Diseases from water
contamination can critically damage the business
In addition to phosphorus, many organic matter in the water
are the cause for eutrophication
Porous Alpha with microbe which decompose organic
matter can offer the water quality improvement
59
Needs Mechanism Competition Case Study Specs.Microbial decomposition

Microbe living in water is inhabited in Porous Alpha. They
decompose the organic matter when it passes through the
interconnected cell
60
Conceptual image of decomposition of organic matter in the water
Organic
matter
Purified water
Microbe
digesting
specific
organic
matter
Porous Alpha
Pore
Purified
water
Porous Alpha Layer
Water containing various kinds
of organic matters
Microbial decomposition

Pilot project in Chinese small pond realize the reduction of
COD by 85.4% and BOD by 83.0% in one month
61
Needs Mechanism Competition Case Study Specs.Microbial decomposition
Location：Nanming District, Guizhou, China
Period：Jan. 15, 2012 ～ Feb. 15, 2012
Volume of pond water
– 80 m3 (10m*10m*0.8m)
• 200 m3 in maximum (10m*10m*2m)
– No inflow, no outflow
Quantity of Porous Alpha：2.5m3
Subject Before installation 1month later Reduction(％)
COD (mg L-1) 7.35 1.07 85.4
BOD (mg L-1) 2.53 0.43 83.0

– Core Technology
– Applications
62
Applications

Mixing Porous Alpha for sandy soil or argillaceous soil
realize improved yield with less water consumption
 Water saving is critical issue for agriculture in arid zone mainly in Middle
East and Africa where
– Morocco, no.4 biggest exporter of tomato, has their production base in
arid zone close to Sahara desert
– Without effective water utilization, agriculture cannot be sustainable
 Water scarce can be the direct cause of conflict
 Drip irrigation is great solution for water saving. However further water
saving is now required
– Most of export tomato farmers in Morocco use drip irrigation in the
– Nevertheless, groundwater level is getting deeper every year. Currently
many farmers pump up the water from 100 – 150 m below surface.
– Water related cost for agriculture is now 10 – 15%, which has been
increasing
 Utilization of Porous Alpha as soil conditioner can realize water saving
with increased yield
63
Needs Mechanism Competition Case Study Specs.Soil conditioning

Pores in Porous Alpha provide moisture and air for
soil, realizing further water saving for drip irrigation
64
Irrigation
Evaporation  Water is retained in Porous Alpha
 Air is also retained
Porous Alpha
With Porous AlphaWithout Porous Alpha
Permeation
Irrigation tube
water
air
Irrigation tube
 Soil mixed with Porous Alpha retains
proper moisture and air which realize
improved yield with less consumption
of water

Porous Alpha has the advantage mainly in duration
65
Competitors Superabsorbent polymer Expanded vermiculite Diatomite Peat moss
Characteristic  High absorbing capacity
 Degradable
 After degradation, it’s
required to remove
from the soil because
it’s petrochemical
product. However, it’s
not easy to remove it
because it’s mixed
with soil
 Expensive
 Produced by burning
hydro-mica in 600-
1000℃
 Porosity is more than
90%, which is suitable
to improve water
permeation
 20% of the soil is
required
 Vermiculite product
can contain asbestos
as the mining site is
close
 Unstable
quality
 Expensive
 Strong acidity
 Depending on
the raw material,
water retention
capacity get lost
once dried up
 Fragmented peat
moss has quite
limited capacity
of permeation
Advantage of
Porous Alpha
 Usable more than 10yrs,
not degradable
 Porous Alpha is not
required to remove
from soil as it’s
harmless to the soil
and the composition is
very close to the soil
itself.
 Less quantity; Porous
Alphas is used for 10%
of soil
 It takes time for
extended vermiculite to
retain the water. No
such characteristics
for Porous Alpha
 Less
expensive
than
diatomite
 No need to
adjust pH
 Porous Alpha
keep the
capacity of
retention of
water and
aeration
 Larger aeration

Installation is quite simple: mixing Porous Alpha with
soil by tractor
66
Lay the Porous Alpha on the field and mix them by tractor
No special skills required
Installation in Senegal

In the test in Mauritania, Porous Alpha set as layer in the
soil almost doubled the yield with higher moisture in the soil
67
Case in Mauritania
Feb. 2009 Harvesting
With Porous Alpha Without Porous Alpha
Comparison of harvest Historical trend of soil moisture
(15cm below surface)
Nov. 2008 Plantation of tomato
With
Porous
Alpha
Without
Porous
Alpha
Harvest
(kg/m2)
With
Porous
Alpha
Without
Porous
Alpha

In the test in Senegal, Porous Alpha mixed with the
soil improved the yield of green beans by 70%+
68
Harvest of green beans in the field of 10m*10m
* 3rd harvest is only calculated
for one of the six ridges for
each condition
Condition
1st
harvest
6/1/2014
2nd
harvest
12/1/2014
3rd
harvest(*)
21/1/2014
With Porous Alpha
73 kg 57 kg 4kg
Without Porous
Alpha
58 kg 24 kg 2kg
x 1,26 x 2,38 x 2,0
x 1.88
(In average)
Comparison: Two months after seeding
With Porous Alpha Without Porous Alpha

Specification and applied conditions as soil
conditioner
Required quantity of Porous Alpha : 10% of the soil of
root zone is the base. But it can change depending on
the soil nature
Durability of Porous Alpha: More than 10 years
Water retention capacity: 50% of volume of Porous
Alpha
69

Introduction of company and product "Porous Alpha" (English Version)

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