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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&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
6
Company Overview
第I部:会社・商品説明編
– Company Overview
– Core Technology
– Applications
第II部:事業戦略編
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
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
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
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
第I部:会社・商品説明編
– Company Overview
– 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
第II部:事業戦略編
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
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
第I部:会社・商品説明編
– Company Overview
– 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
第II部:事業戦略編
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
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
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
Needs Mechanism Competition Case Study Specs.Microbial 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
Needs Mechanism Competition Case Study Specs.Microbial Deodorizing
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 investmentExpensive Rockwool(120~150 K JPY/ m3)
Simple system with low initial investmentLess expensive Porous Alpha
More than 15 years8~13 years
Microbial Deodorizing
Model case(30 000 pigs)
169 mil. JPY+55k JPY / month
Initial invest
Running22.8mil. JPY+16k JPY/month
Needs Mechanism Competition Case Study Specs.
Microbial Deodorizing
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 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
Needs Mechanism Competition Case Study Specs.
Summary of case studies for microbial deodorizing
Case No.1 is explained in the following pages in detail
Microbial Deodorizing
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
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
Needs Mechanism Competition Case Study Specs.Microbial Deodorizing
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
9000
10
20
30
40
56
76
95
117
137
156
186
216
249
279
334
379
Needs Mechanism Competition Case Study Specs.
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)
Microbial Deodorizing
Case1: Odorous gas emission in manure fermenter
26
Composting unit
Odorous gas
Composting unitBlowing the odorous gas
DeodorizingOdor-free
air
Case1: Poultry house (30K birds)
Needs Mechanism Competition Case Study Specs.Microbial Deodorizing
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 unitBlowing the odorous gas
DeodorizingOdor-free
air
Case1: Poultry house (30K birds)
Needs Mechanism Competition Case Study Specs.Microbial Deodorizing
Case1: Blower and deodorizing unit
28
Porous Alpha
Sprinkler
Deodorizing unit
Blower
Water tank
Pump
Interior of deodorizing unitExterior of deodorizing unitOdorous
gas Odor-free air
Needs Mechanism Competition Case Study Specs.
Composting unitBlowing the odorous gas
DeodorizingOdor-free
air
Case1: Poultry house (30K birds)
Microbial Deodorizing
Case2: Exterior view of deodorizing plant with Porous Alpha for poultry abattoir
29
Needs Mechanism Competition Case Study Specs.Microbial Deodorizing
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
Needs Mechanism Competition Case Study Specs.Microbial Deodorizing
第I部:会社・商品説明編
– Company Overview
– 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
第II部:事業戦略編
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
Needs Mechanism Competition Case Study Specs.
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)
Needs Mechanism Competition Case Study Specs.
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
35
初濃度:CF, 1000 mg L -1
初濃度:CF, 100 mg L -1
Needs Mechanism Competition Case Study Specs.
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)
36
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
Needs Mechanism Competition Case Study Specs.Fluorine Adsorption
Volume of desorption strongly depends on concentration of nitric acid, not on contact time
37
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
Needs Mechanism Competition Case Study Specs.
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
38
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
Needs Mechanism Competition Case Study Specs.Fluorine Adsorption
39
(Ref.)Competitor’s plant (F-Free) is more
complicated than ours
Needs Mechanism Competition Case Study Specs.Fluorine Adsorption
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
Needs Mechanism Competition Case Study Specs.Fluorine Adsorption
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
Needs Mechanism Competition Case Study Specs.Fluorine Adsorption
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
Needs Mechanism Competition Case Study Specs.Fluorine Adsorption
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
Needs Mechanism Competition Case Study Specs.Fluorine Adsorption
第I部:会社・商品説明編
– Company Overview
– 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
第II部:事業戦略編
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
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
Increased specific surface area of Porous Alpha by hydrothermal process realizes phosphorus ion adsorption
47
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
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
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
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
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
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
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
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
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
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
53
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
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
54
Technology HAP MAP 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
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
Adsorption capacity of phosphorus with Porus Alpha is drastically higher than others
55
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
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
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
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
Needs Mechanism Competition Case Study Specs.Phosphorus ion Adsorption
第I部:会社・商品説明編
– Company Overview
– 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
第II部:事業戦略編
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
Needs Mechanism Competition Case Study Specs.
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
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
第I部:会社・商品説明編
– Company Overview
– 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
第II部:事業戦略編
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
Needs Mechanism Competition Case Study Specs.Soil conditioning
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
Needs Mechanism Competition Case Study Specs.Soil conditioning
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
Needs Mechanism Competition Case Study Specs.Soil conditioning
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
67
Needs Mechanism Competition Case Study Specs.Soil conditioning
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
Without Porous Alpha
In the test in Senegal, Porous Alpha mixed with the soil improved the yield of green beans by 70%+
68
Needs Mechanism Competition Case Study Specs.Soil conditioning
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
Without Porous Alpha
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
69
Needs Mechanism Competition Case Study Specs.Soil conditioning