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

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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&DProvision 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 JapaneseTechnologies for Water –Saving Agriculture in arid area

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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 PatentNumber

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 TottoriPrefecture of TottoriTottori Resource Recycling,Inc.

Irrigation equipment, irrigation system and irrigation method

5731791 University of TottoriTottori Resource Recycling, Inc.

Fluorine adsorption agent and fluorine-containing water treatment (patent pending)

2012-023795 (Pending)

University of TottoriPrefecture of TottoriTottori Resource Recycling,Inc.

Core technology

Adsorption & desorption of Phosphorus ion

Soil conditioning: improving water retention & aeration

capacity

Adsorption & desorption of fluorine (Patent-pending)

Applic

atio

nCore Technology

Porous Alpha is made by burning of mixture of pulverized glass and shells

①Crush ②Pulverize④Burning

③mixture of foam agent

①Crushed glass ②Pulverizedglass

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 AlphaMaterial 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

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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

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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

２Only 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

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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

• Microbial Deodorizing

• Water treatment: Adsorption & desorption of fluorine

• Water treatment: Adsorption & desorption of Phosphorus ion

• Water treatment: Microbial decomposition

• Soil conditioning: improving water retention & aeration capacity


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Applications

We develop various applications out of the uniqueness of Porous Alpha

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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

MicrobialDeodorizing

Adsorption& recoveryof fluorine

Microbialwater

purification

Soilconditioning

✓ ✓ ✓ ✓ ✓

✓ ✓ ✓

✓ ✓

✓

✓ ✓ ✓ ✓

✓

✓ ✓ ✓ ✓ ✓

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

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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

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watering

Closed unit to prevent the odor emission

Blower

Odor-free air

Microbe deodorizing unit

Odor source(Manure, Compost, etc.)

Odorous Gas

Water circulation

SubmersiblePump

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

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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

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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

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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 investmentExpensive Rockwool(120～150 K JPY/ m3)

Simple system with low initial investmentLess expensive Porous Alpha

More than 15 years8～13 years


Model case（30 000 pigs）

169 mil. JPY＋55k JPY / month

Initial invest

Running22.8mil. JPY＋16k JPY/month




We have various experience in deodorizing

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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 Poultryhouse

30K birds Ammonium100～800ppm

1.82m3 99%（0.1 ppm） 200K＋5K/month

700K＋15K/month

2 Poultryabattoir

3t/day Ammonium2.81ppmMethylmercaptan0.33ppmHydrogen sulfide0.32ppm

7m3 Ammonium99.7%（0.01ppm）Methylmercaptan 98.9%（0.004ppm）hydrogen sulfide 100%（0.00ppm）

2mil.＋10K/month

10mil.＋30K/month

3 Pig house

15 pigs Ammonium11.3ppm

5ｍ3 Ammonium100% (0ppm)

200K＋5K/month

700K＋15K/month

4 Poultryhouse

300K birds

Ammonium2091ppmMethylmercaptan6.7ppm

70m3 Ammonium98.2%（37.9ppm）Methylmercaptan 100%（0ppm）

3.5mil.＋30K/month

23mil＋55K/month

5 Poultryabattoir

50t/day Trimethylamine250ppm

1m3 Trimethylamine100%（0ppm）

150K＋30K/month

220K+90 K/month

6 Pighouse

30K pigs Ammonium2000ppmMethylmercaptan4ppm

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

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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

Watering50L/hr

Contact time54 sec.

Rate of deodorizingmore 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

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97

97.5

98

98.5

99

99.5

100

0

100

200

300

400

500

600

700

800

9000

10

20

30

40

56

76

95

117

137

156

186

216

249

279

334

379


Density of ammonium and rate of deodorizingDensity 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

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Composting unit

Odorous gas

Composting unitBlowing the odorous gas

DeodorizingOdor-free

air



Case 1: Vacuuming odorous gas in by blower at composting unit

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Suctioning pipe

Suctioning odorous gas from upper side of composting unit

Odorous gas



air



Case1: Blower and deodorizing unit

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Porous Alpha

Sprinkler

Deodorizing unit

Blower

Water tank

Pump

Interior of deodorizing unitExterior of deodorizing unitOdorous

gas Odor-free air




air



Case2: Exterior view of deodorizing plant with Porous Alpha for poultry abattoir

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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

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– 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

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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

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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

SiF62- + 2Na+ → Na2SiF6

SiO2 + 6HF → SiF62- + 2H+ + 2H2O (pH < 3.2)

SiO2 + 4H+ + 6F- → SiF62- + 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 fluorosilicateis 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

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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

/ m

g L-1

時間 / h

0

40

80

120

0 2 4 6

CF

/ m

g L-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）

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0

40

80

120

0 0.5 1 1.5 2

WF /

mg

g-1

CHNO3 / mol L-1

Fluorine desorption weight per Porous Alpha with adsorbed fluorine(mg/g)

Fluorine desorption from Porous Alpha with adsorbed fluorineHydrothermally-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

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0

40

80

120

0 2 4 6

WF

/ m

g g-

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 fluorineHydrothermally-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

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NaOH

Discharged

fluid with highly concentrated

hydrofluoric acid

pHadjustment

unit

H2SiF6

Generationunit

Glass powder

Fluorine adsorption unit

NaOH

pH adjustment unit

Na2SiF6

precipitation

Concentration of fluorine

Very high(> 70000ppm）

pH

High(50000ppm～10ppm）

Hydrothermally-processedPorous 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


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（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) 72393 (Initial concentration 5,460mg/L) 4

Schwertmannite (Fe8O8(OH)6(SO4)·nH2O) 55 24Nano-geothite 59 2Glutaraldehyde/Calcium alginate 74 1.5 - 2Al(OH)3 /Lime stone 84 5Fe3O4/Al(OH) 3 nanoparticles 88 4Al-Ce hybrid adsorbent 91 24Fe-Al mixed hydroxide 92 2Tunisian clay mineral 93 72 - 96CaO/ Activated alumina 101 48CaO nanoparticles 163 0.5Fe-Al-Ce trimetal oxide 178 24Calcined Mg-Al-CO3 lyered double hydroxides 213 5Nanomagnesia 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

Competitors

Precipitation methodusing calcium

Precipitation methodusing 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 concentration of fluorine to less than 5 mgL-1, but input volume of aluminum salt and sludge are increased

Remove fluorinewith 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 concentration of fluorineunder 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 fluoricconcentration 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

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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 whichphosphorous ion is adsorbed or precipitated

49

Ion-exchange reaction≡ Si-OH + H2PO4

- → ≡ Si-H2PO4- + OH-

2(≡ Si-OH) + H2PO4- → （≡ Si)2HPO4

- + OH- + H2OHydrogen bond OH …O- OH=Si(OH) 2 + H2PO4

- → = Si POH…O- OH

V. V. Murashov, et al., J. Phys. Chem. A, 103, 1228 (1999)

Composition of Soda-lime glass

Precipitation reactionCa2+ + PO4

3- → Ca3(PO4)2Ca2+ + HPO4

2- → Ca HPO4

Al3+ + PO43- → AlPO4

Fe3+ + PO43- → 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/m

g L-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/m

g L-1

Time/h0.0

0.2

0.4

0.6

0.8

1.0

0 1 2 3 4 5 6 7 8

PO4濃

度/m

g L-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/m

g L-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-1Initial concentration 0.8 mg L-1

Concen

trat

ion o

f P

O4

mgL

-1

Concen

trat

ion o

f P

O4

mgL

-1

Concen

trat

ion o

f P

O4

mgL

-1

Concen

trat

ion o

f P

O4

mgL

-1

The best pH for adsorption performance is around 7

51

0

20

40

60

80

100

1 4 7 10pH


Rat

e o

f ad

sorp

tion

(%)

Rate of adsorption for different pHsConcentration 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 10CHNO3 / 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 AdsorptionR

ate o

f re

cove

ry(%

)

Rat

e o

f re

cove

ry (%)

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

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Dry weight of harvested tomato with different type of phosphorus fertilizer*

Dry

weig

ht

of

har

vest

ed

tom

ato (

g pl

ant-

1)

*: Master graduation thesis, University of Tottori, 2013

No p

hosp

horu

s fe

rtili

zer

Yourin (

store

-bo

ugh

t ph

osp

horu

s fe

rtili

zer)

Poro

us

Alp

ha

+ Y

ourin

Poro

us

Alp

ha

with a

dsorb

ed

phosp

horu

s

Existing technology to recycle phosphorus as fertilizer has issues such as limited recoverable form of phosphorus and high running cost

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Technology ＨＡＰＭＡＰ Ash alkali extraction Reducing smelting

Principle Crystallization of hydroxyapatiteCa10(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,

TemperatureCa, Al Al

Problems Impossible to recover from suspended solidphosphorus

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

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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)

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– 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 waterMicrobe 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

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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

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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

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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

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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 burninghydro-mica in 600-1000℃

Porosity is more than 90%, which is suitable to improve water permeation

20% of the soil is required

Vermiculite productcan contain asbestosas the mining site isclose

Unstable quality

Expensive

Strong acidity Depending on

the raw material, water retention capacity get lost once dried up

Fragmented peatmoss 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 tractorNo 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

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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

Har

vest

(k

g/m

2)

With Porous Alpha


In the test in Senegal, Porous Alpha mixed with the soil improved the yield of green beans by 70%+

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Harvest of green beans in the field of 10m*10m

* 3rd harvest is only calculated for one of the six ridges for each condition

Condition1st harvest6/1/2014

2nd harvest12/1/2014

3rd harvest(*)21/1/2014

With Porous Alpha73 kg 57 kg 4kg


58 kg 24 kg 2kg

x 1,26 x 2,38 x 2,0x 1.88

(In average)

Comparison: Two months after seedingWith 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

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

Environment

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