B-13E

Moonshot Goal 4 Annual Report 2023

Innovative Circular Technologies for Harmful Nitrogen
Compounds/
To Solve Planetary Boundary Issues

PM：Dr. Tohru KAWAMOTO, Prime Senior Researcher, AIST
Implementing organizations :AIST, The University of Tokyo, Waseda University,
Tokyo University of Agriculture and Technology, Kobe University,
Osaka University, Yamaguchi University,Kyowa,Hakko Bio Co., Ltd., ASTOM Corporation, Toyobo Co., Ltd.,FUSO Corporation, Ube Industries, Ltd,
Subcontracting：Tokyo Institute of Technology, Kyoto University,
Hiroshima University, Nagoya University, Seibu Giken

Dr. Tohru Kawamoto1

Environmental pollution problems to be solvedNonAnthropogenic
220M

2010

(b)Current status and target foranthropogenic nitrogen compoundemissions
180M
260M

BAU scenario
2050(a)Target of Nitrogencompounds emission(t-N/year)
NaturalDecomposition
300M
Stock in environment,
Balanced with
Anthropogenic=80M

Anthropogenic
Target 80M
2050 forecast
260M

Galloway, Biogeochem. (2004),
Fowler, Philos.Trans. R. Soc. B Biol. Sci. (2013)de Vries, Curr. Op. Env. Sus. (2013)

With measure for
agriculture and foodTarget 80M
010,000

180M-100Mt-N/year

20,00030,000

Anthropogenic emission(10,000t-N/year)

Tsunemi et al., Sustainability
2024.01.31MS Annual Report2

Target: Establishment of Novel Nitrogen
Circulation System

2024.01.31MS Annual Report3Image of Implementation
NOx in exhaust is converted to NH3, and utilized as an industrial raw material.
Nitrogen compounds in wastewater are recovered as NH3, and reused as fuel and raw material.

2024.01.31MS Annual Report4Outline of this projectProf. Ogura, Tokyo Univ.
【1. NOx to ammonia】①concentration of NOx NH3 in gas phase②catalyst for NOx→NH3 at low temperature③catalyst even with O2 coexistenceProf.
【2-2. ammonia recovery in water】
Matsuyama,(1) membrane/adsorption separation Kobe Univ.

(2) Construction of ultra energy-saving
separation and concentration processNH4+濃縮液 浸透圧駆動(自発的な水透過)Exhaustgas

NOx

NTA

50％FuelNOx NOxreductant(HC, CO)

DS

H2O

N2

NH4+

DSDS

H2O

正浸透膜駆動溶液(DS)

廃水

低浸透圧

50% conversion forcomplete purification ofNOx , and use excess NH3
as a resource【2-1. conversion to NH3 in wastewater】 Dr. Hori
AIST
Efficient NH4+ conversion bioprocess
for various conditions●microaerobic conversion to NH4+・Low NH4+ loss
・Use excess sludge
as nitrogen source

高浸透圧membranes

アンモニアdistillation(conventional)

廃水

adsorption<1/100 of theenergy consumptionof conventional
methods

Prof. Matsumoto,【3. Process and evaluation】
1)Design of actual equipment and Tokyo Inst. Tech.
pilot-scale process 2) Techno-economic
analysis and environmental impact assessment.
Process simulation●anaerobic membrane bioreactor (AnMBR) for high-NH4+
・Work at high NH4+
concentration
・High energy efficiency
and compact size

EconomyEnvironment

LCA

Risk assessment 52024.01.31MS Annual Report

Development scheduleBench demonstration in 2024, pilot demonstration in 2029
2020
overallR&D for Basictechnology
deNOx
・R&Ds for highperformance NTA
catalysts andadsorbents

Ammonium recovery
from aqueous phase
・Development of
separation membranes
and adsorbents
Process design,
Environmental impact
assessment
・Modeling, Constructing
inventory database2025

Conversion toNH4+ andAmmonium
recovery・Bench-scaledemonstration
・Evaluation
using real
wastewater
Process
evaluation
・Energysaving, Risk,
LCA

2027

2028

Establishment oftechnologies forpilot test

BenchscaledeNOx・NTA catalyst
system design(1step, 2step,strorage)

2026

reNOx
・Evaluation of NTA
catalyst and adsorbent
using bench scaleequipment
・Identification of issues

Conversion to NH4+
・ Management
method and design ofpilot-scale system
Ammonium recovery
from aqueous phase
・Pilot plant development
・Modules preparation
Design of nitrogen
circular systems
・Pilot plant performance,
Local environmental
impact

2029

2039

2050

implementation

Pilotscale
Pilot
demonstration(Hundreds
Nm3/h)

Pilot-scaledemonstration(5-15m3/d)

Final evaluation

Conversion to NH4+・ Construction ofnitrogen convertingmicrobial community

2024

Interim evaluation and review

Establishme
nt of Ncircularsystem

2023

Interim evaluation and review

Nitrogencompoundto ammonia
inwastewater

2022

Interim evaluation and review

NOx toammonia ingas phase2021

Practical
application
andprevailing N
recyclingtechnologies
to solve thePlanetary
boundaries
problems

Design ofglobal
nitrogencircularsystem
2024.01.31MS Annual Report6

Item 1.deNOx and reNOx - overview
First of all “deNOx” to transform half to NH3. Local production for local
comsumption. Then, ”reNOx”.

NTA system
implant targetDust combustion
High temp exhaust,
impurities

Ships posttreatment
Urgently required

Power plant
Large volume of out gas,
ultra low conc. NOx
2024.01.31MS Annual Report

7

ITEM 1: A Single Stage NTA in O2 and H2O (Waseda University)
Development of efficient single-stage NTA catalysts to realize ultra-dilute NO
detoxification and NH3-SCR systems without NH3 supply
1. Development of a single-stage NTA catalyst,
WSD-02, applicable to 100 ppm NO, paving the way
to realize ultra-dilute NO detoxification

2. A hydrocarbon-based NTA catalyst, WSD-03, wasdeveloped to provide a temporary solution until therealization of a hydrogen society

The developed NTA catalyst was effective for thereaction of ultra-dilute NO below the current
environmental standards. Promote further
improvement of the atmospheric environment.

If a hydrogen supply network is not available, the NTA
reaction can be carried out using a hydrocarbon-based
reducing agent. Compatible with current internal
combustion engines.

A single step NTA for 100 ppm NO

2nd Component in cat. / wt%
5.0(violet), 2.0(blue),1.5(green), 1.0(red),0.7(brown)

Catal. Sci. Technol.
(2023), Front Cover2024.01.31MS Annual Report8

THEME 1.Results of deNOx and reNOx (Univ.Tokyo, AIST)
Seamless continuous reaction of 2step catalytic reactions with far different conditions
2029 model：
1. NOx selective adsorption from combustion exhaust (treatment zone)
2. Supply conc. NOx in O2-free stream to AIST-NTA catalyst(regeneration zone)

2029 model of 2step NTA
catalyst systemusing honeycomb rotor

NTA bench reactor＠AIST FREA

Cat.: 0.15g; flow rate: 250
mL/min (SV 40,000 h-1) ;composition: NO 1000ppm,
H2 3000ppm

Catalyst bed at most 100 cc
5 ThermoCouples to measureheat of reaction and for heatmanagement

Test piece honeycomb

2024.01.31MS Annual Report

9THEME 1. A successful example of gas-phase NOx purification/recycling (AIST)
Achieving over 90% selectivity to NH3 by a gas-switching NOx storage reduction

1000<Reaction conditions>1000 ppm NO + 10% O2 ⇆ 1~5% H2
100 mL min-1
Reduction
H2 (Recycling)
Storage

800
600
400
2000Switching the inlet gas
at constant reaction temp.

-50510 15 20

Reaction time (min)NOOxidation

O2NH3

Reductive gas(H2, etc.)Concentration of NH3 (ppm)

Combustion gas
NO+O2・・・
Storage
1200of NOx

Selective synthesis of NH312001000

Recoveryof NH3800600
4002000-50510 15 20Reaction time (min)NO3NO2-Nanocomposite NSR catalyst

NH3100

Selectivity to NH3 (%)

Concentration of NOx (ppm)

Effective recovery of NOx★Influencesof coexisting gases

8060
4020A. Tomita, R. Wakabayashi, T. Kimura*, released on our web site on 31 Jan 2023.
*STD
A nanocomposite catalyst for the recycling of NOx in combustion gas~ A proposal of a new method to synthesize NH3 for nitrogen resource circulation ~0*3rd cycle+10% CO2+10 ppm SO2

A. Tomita, R. Wakabayashi, T. Kimura*, Catal. Sci. Technol., 2023, 13, 2927-2936. (Front Cover)2024.01.31MS Annual Report

10THEME 1. deNOx and reNOx (AIST)
Adsorption and recovery of NH3 to produce ammonium carbonate solid

Precipitate

Desorption

Adsorption

NH4HCO3 aq
NH3coolingrepeated

NH4HCO3NH3 adsorbent(Prussian blue analog)

CO2•••Converts to ammonium bicarbonate solids without heating and with low energy consumption
Ammonium Bicarbonate is not toxic or deleterious substance. It is also a solid, which isadvantageous for storage, etc.
Ammonium Bicarbonate decomposes at low temperatures (~70°C) and is immediately
converted to a gas mixture of NH3:H2O:CO2 = 1:1:1
Usuda, ACS Sustain. Chem. Eng., accepted
2024.01.31MS Annual Report

11

THEME 2. Recycling nitrogen compounds
in wastewater to ammonia resource
Systems connecting “conversion to NH4+” and “separation and concentration of NH4+”
Ammonia resource(fuel, material)● Current state
N compounds in wastewater
were converted to N2 gas,accompanied with N2Oemission
Required massive energy
Residual N discharge

NH3

Resource recovery plant

NH4+
Organic N

Theme２−１ Theme２−２
NH3
resourceDischarge
to riverIndustrial
wastewater

Effectiveand fast
conversion

Ultra energy
savingseparation● Future image in 2050
Conversion to NH4+ andsubsequent separation andconcentration of NH4+
→ Utilization as ammonia
resource

2024.01.31MS Annual Report12

THEME 2-1. R&D on microbial conversion ofnitrogen compounds to ammonia
Constructing multi-bioconversion processes for various wastewater types and situations● Microaerobic conversion process● Anaerobic membrane bioreactor（AnMBR）

2024.01.31MS Annual Report

13

THEME 2-1. R&D on microbial conversion ofnitrogen compounds to ammonia (Output 1)
Microaerobic process: Optimization using lab-scale reactors towards bench-scale test
● Lab-scale reactor mass balance: >90% of carbon removal and >80% of NH4+ recovery
Nitrogen>80% conversion

Carbon>90% removal

N2O-N

CO2-C

Discharged
sludge (DS)
余剰汚泥等

余剰汚泥等
DS

Other NIC

NO3-N, NO2-N等

TOC

Org-NCNH4-NN

Zhou et al., Water Research, 247,120780, 2023.

● Preparation for bench-scale demonstration＜Location＞＜Material flow＞
NH4

Wastew ater pit

N2O

pHDO
ORPpHLevel

pHDO
ORP

pH adjuster
pH
DO
ORP

YT-1A

YT- 1B

FI

FI

FI

P-2

Recycle

FI

YP-1B

T-2

T- 3

T-4

Wastew ater
supplyFeed

1 st tank

2 nd tank

3 rd tank

Treatedw astew aterdischarge

I nstallation site

Wastewaterpit

Reactiontank

T-5

T-6A

Settlingt ank

Coagulation
settling tank

T- 8
AirP-3
Aeration

P-6

Supplytank

Aeration tank（ conversion ）SSrem o va lta n k

・Tr e a te dw a ste w a te r ta n k
・Co a g u l a ti o nse ttl in g ta n k

T- 3

T-6B
Level

OverflowT- 7

Tr eated
W astew atertank

P-5

T- 6 AT- 2
Anaerobic tank（ conversion ）ExcesssludgeFI

ExcesssludgeAirP-1 AirP-2A
AirP-2B

Su p p ly
ta n k

YP- 3

YP-2

P- 4

ReturnsludgeT- 8

YT- 3（ PAC）

pH

P-3A
P-3B

Overflow

T-1

SS rem oval
YT-2

（ N aOH ） （ Sulfate ） （ Methanol）

YP-1A

P-1＜Design chart＞

T- 7A

T- 7B

Cont ainer

Container

T- 6 B
Settling tank

T- 4

T- 7
T- 5

2024.01.31MS Annual Report

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THEME 2-2. Ammonium recovery from aqueous phase (Concentration)
Combining several membrane technologies to treat various wastewater
FO membrane: Ultra low-energy, 40~400 mg/L→0.4％

FOプロセス

Waste
廃水
water
Sea
海水
water

NH4+

H2O

Na＋

MD: Membrane distraction

BC: Brine concentration

NH4+

membrane
FO膜

BC & MD：High concentration, 0.4%→ >25%

NH4+

Cl-Concentrated
濃縮廃水
wastewater

NH3vapor
蒸気Discharge
放流水
Diluted Sol.
希釈水

• Diluted seawater generated by FO can be returned to the sea• Only required energy is pump power

Ion exchange membrane: Ca removal, <400mg/L→4%

RefluxConc.多孔膜Conc.
NH3
廃水
凝縮液
wastewater

4% → >25%

Adsorbent: Na removal, ~1000 mg/L → ~2%
Othersubstances+Conc. NH4
recovery②Desorption
by heat etc.

①NH4adsorption
Open

NH4+ adsorbent
Concentrated Desalinated side
(Raw water)
side

冷媒

Coolant

NH3

n段目
0.4%→ 4%

DC current－NH
3蒸気凝縮液PorousMembrane

ConcentratedFeed sol. 圧力ΔP
濃縮水
⊿Psol.

NH4+othersubstances(gas・liquid)

ClosedHeat ordesorvant
etc.

2024.01.31MS Annual Report

15THEME 2-2. Ammonium recovery from aqueous phase(Kobe Univ., Toyobo MC Corp., Waseda Univ.)
FO membrane process to concentrate wastewater with very low energy consumption
Forward osmosis (FO) process
FO processprocess
FO

Waste
Waste
waterwater

FO membraneFOmembrane

Sea
Sea
water
water+Na＋
Na

H2O
Cl−Cl

NH4+150

Concentrated
Concentrated
waste water
waste
water
Discharged
Discharged
waterwater

Using seawater as the draw solution allows
to concentrate sewage at a low cost

Development of polymer membrane

BNH4/Aw (-)

100
10[1]X. Bao et al., J. Membr. Sci., 573 (2019) 135

Excellent selective
permeation performance

Membrane area : 180 m3

Urban sewage was concentrated more than 100 times byvolume at FS flow rate of 2
L/min (=2.88 m3/day)

Concentration ratio (-)

NH4+

NH4+

Concentration test in bench scale

100100 times

500050 100 150 200 250 300
Operation time (min)Development of zeolite membrane
Zeolite: Crystalline aluminosilicate materials

10.10.010.001

Succeeded in developing a highperformance FO membrane• Size sieving separation• High thermal andchemical stability• Hydrophilic zeolites without
cation exchange sites• Apply positive charge

Succeed in developing zeolite membranes toconcentrate NH4+
2024.01.31MS Annual Report

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THEME 2-2. Ammonium recovery from aqueous phase (Kobe Univ.)
Membrane process to highly concentrate and recover NH3 as high conc. NH3 solution

MD membrane process

BC + RO membrane process

Condensed
NH3 vapor
NH3蒸気凝縮液

BC
Concentrated
solution

NH3 vapor
NH3蒸気 Cooling

冷媒mediumNH3ROWaste waterPorous 凝縮液
Condensate
廃水 多孔膜membrane(NH3 aq.)

MembraneDistillation (MD)Development of brine concentration (BC) - reverse
osmosis (RO) hybrid process for simultaneous
NH4+ high-concentration and water recovery

Pretreatment process
was constructed toremove scale components,
and its effectiveness wasconfirmed with actual
wastewater(patent pending).

【Real wastewater】
Target T-N 41,000ppm

50,00040,000Temperature = 48 oC
Swep gas flow rate = 4.5 L/min

35%
30%

48 oC
3.2 L/minConcentration
Optimization of membrane/Recovery
Targetmodule configurations and25%

30,00020,000Ini. conc.
400ppm00200
Time [min]40015%
80%

38 oC
4.5 L/min

operating conditions

42 oC
4.5 L/min Target concentration and20%

10,000Condensate
NH3 aq.

One-pass NH3 recovery systemwith multiple membrane modules

NH3 conc. in permeate (wt%)

T-N [ppm]

BC-RO Hybrid membraneprocess was established,achieving 41,000 ppm T-Nfrom FO concentrate ofactual wastewater

NH3 aq. (4wt%)

recovery ratio was achieved.
・NH3 recovery ratio > 90%
・NH3 concentration > 20 wt%
85%

90%

95% 100%

Recovery ratio (%)
2024.01.31MS Annual Report17

TMEME 2-2. Ammonium recovery from aqueous phase(Yamaguchi Univ., Astom Corp.)

Recovery and concentration of NH4+ from wastewater containing foulingcomponents without pretreatment using ion exchange membranes
Anion exchange membrane

NH4+ selective cation exchange membrane

−

NH4+

NH4+

NH4+

Pretreatment

−

Na+

Ca2+

Wastewater

Concentrate

Na+

Fouling component

+
NH4+

Ca2+

−

Ca2+
Water

Na+

NH4+

NH4+

Clear NH4+
concentrate

DiluteElectrodialysis

No need to pretreat wastewater

Real wastewater concentration test (<400ppm→4000ppm T-N)

6000

0.5 M NaCl solutionReal wastewater(dilute)Donnan dialysis(CDD)

Tap water
Energy generation

Total N, ppm

Ion exchange membranes

Concentrate

4000

10 times
Real wastewater

2000400

Concentrate
Recovery and concentration

Dilute0051015
Operationtime[h][h]
濃縮時間

80%
recoveryConcentrate
2024.01.31MS Annual Report18

THEME 2-2. Ammonium recovery from aqueous phase(AIST, Fuso Corp., Univ. Tokyo)
Recovery of NH4+ ions in wastewater as NH4+ concentrate by optimizing adsorbent andadsorption/desorption process
NH4+ recovery by adsorbent

Multi-Column Continuous Adsorp./Desorp. SystemAdsorp.
Desorp.
DryingKZnHCF granules (made by Fuso Corp.)（K2Zn3[Fe(CN)6]2・3H2O）
KZnHCF granules can beused to adsorb anddesorb (concentrate)
ammonium ions.

Low-conc. platingwaste liquid(NH₄Cl)Treated liquid(KCl)High-conc.
NH₄Cl

KZnHCF

Desorp.
Solution(KCl)

NH₄ZnHCF

NH4 recovery treatment
Dried ->
is continuously
desorption
performed by operatingprocess
the adsorption anddesorption columns incirculation (byreconnecting the tubes).
Adsorbed column -> drying process
Desorbed ->adsorption
processLaboratory test equipment(simulated effluent)On-site Test Equipment(actual waste liquid)

NH4 conc.(mmol/L)

Adsorp.：500 cycles

8060
4020001,000
2,000
Flow volume(mL)NH4 conc.(mmol/L)

Column adsorp./desor. cycle test (single column)
Desorp.：500 cycles
2,000
1,500
1,000
500
00 40 80 120160200
Flow volume(mL)No hinderance of performance is observed until the 500th cycle.

150 mL/column Reflected
in on-site
Optimization of NH4test
outlet concentration,
NH4 concentration
rate, etc. in labo tests

350 mL/column

Development of electrochemical recovery systems that do
not require K+ for desorption is being accelerated.
2024.01.31MS Annual Report

19TMEHE 3. Process and evaluation(Tokyo Inst. Tech, Nagoya Univ., AIST)
Basic design and multidimensional evaluation of process systems for nitrogen cycle
Examining the ideal structure of thenitrogen circular process system
Model / Data

Basic design ofprocess systems

Data

R&D of elementary
process technologies

・Calculation of mass balance for NOx in
gas and nitrogen compounds in wastewater・Calculation of energy balance
・Calculation of CO2 emissions , etc.

■Life cycle assessment of nitrogen
circular technologies
Nitrogen inventory data and input-output tables
mainly for chemical industrial products■Risk assessment of nitrogen

Flow analysis of NH3, reactive
nitrogen and other harmfulsubstances

compound cycle

Benefits of nitrogen circular technologies tohuman health and the ecosystems

2024.01.31MS Annual Report20

TMEHE 3. Process and evaluation(Tokyo Inst.Tech)
Synthesis, dynamic analysis and evaluation of NTA process systems
Comparison of the amount of CO2 emissions
required to achieve zero NOx emissions

Adsorprion equipment of NO

CO2 emissions[ton-CO2/ton-N]

Dynamic analysis Calculation of mass andof NO desorptionenergy balance using
process using R&D steady-state simulationmaterials

NTA reactor
Build dynamicmodels by extending
the steady models

NTA

NTA
(Heat recoveryand utilization)

NH3-SCR(benchmark)Influence of unsteady operation of NO adsorption
process to the behavior of NTA reactor

Develop reaction
rate equation
modelsCatalyst activity test data for NTA

Dynamic simulation
2024.01.31MS Annual Report

21

TMEHE 3. Process and evaluation(Nagoya Univ)

Investigation of combinationsof various elemental processtechnologies

Calculation ofmass andenergybalance using
steady-state
simulation

From a steady model toa dynamic model

Energy consumption [kW]

Synthesis, dynamic analysis and evaluation of liquid phase concentration process systems
Comparison of energy input required forNH3 concentration

MSN

Stripping with
heat-pump

Stripping(benchmark)Dynamicsimulation
Investigation of interactions among elemental
processes with different throughputs, residence
times, materials and energies
2024.01.31MS Annual Report22TMEHE 3. Process and evaluation(AIST)
Environmental impact assessment of introduction of nitrogen circular technologies
Examining the ideal structure of thenitrogen circular process system

Construction of databasefor assessment of nitrogen
circular technologies

・Calculation of mass balance for NOx in
gas and nitrogen compounds in wastewater・Calculation of energy balance
・Calculation of CO2 emissions , etc.

Visualization of domestic nitrogen flow byadapting annual production based on nitrogen
input and output amount of each productConstructing nitrogeninventory data ofapproximately 700
products

Development of application methods for
simulation based on air quality modelsConsidering the effect of reducing reactive
nitrogen, the impact of climate change, etc.
Ship

Multidimensional evaluation of effectsof nitrogen circular technologies (NRT)
through integration with processsystem design

On-roadvehicle
Stationary

Estimated NOx emissions in2050

O3 concentration in 2015 and 2050

●LCA visualizes energy wellbeing,environmental improvement after
installation of NRT.
●Suggesting benefits of NRT tohuman health and the ecosystem.
2024.01.31MS Annual Report23Summary◆Background◆• Environmental release of nitrogen compounds is one of the biggest challenges in theplanetary boundary.
• The United Nations Environment Program adopted a resolution recommending
significant reduction of nitrogen waste and sharing of national action plans.
Ministry of the Environment also started to consider.
◆Research and Development◆• Conversion of NOx in exhaust gas to ammonia for detoxification and recycling.
• Conversion of nitrogen compounds in wastewater to ammonia for recycling.
• Evaluation of the effectiveness of the developed ammonia recycling technology.
→Shifted to the overall design of the process, and the solution of problems
in actual gas and liquid utilization for the social implementation.
◆Summary of Achievements◆
255 external publications, including 39 academic papers and 21 patent applications

2024.01.31MS Annual Report24