Contribution to the achievement of SDGs
by Furukawa Electric Group

Technology for Producing Green LPG With Ramune Catalyst
Yuichiro Bamba*1, Junya Hirano*1, Hirokazu Sasaki *2,Masayuki Fukushima*1, Takao Masuda*3

A cooperative study with Hokkaido University is in progress to reduce greenhouse gas emissions, which is a global social issue. A technology to convert
biogas into Liquefied Petroleum Gas (LPG) has been successfully developed by applying thedeveloped metal catalyst fixing technology. LPG produced, by using this technology, from carbon dioxide and methane obtained from livestock manure is easy to store and transport, and canbe used as energy in ordinary households and in industrial sites such as dairy farming, as well as
in the event of a disaster. We believe that this technology not only contributes to a decarbonizedsociety but also to the formation of a circular and ecological economy by promoting local consumption of local production on energy assisting the new social infrastructure of the region.

ABSTRACTINTRODUCTION
1.1.INTRODUCTION
Furukawa Electric Group has formulated “Furukawa
Electric Group Vision 2030 (the Vision 2030): In order tobuild a sustainable world and make people’s life safe,
peaceful and rewarding, Furukawa Electric Group will create solutions for the new generation of global infrastructure combining information, energy and mobility.” andpromoting initiatives for the Vision 2030.
We have identified the “creation of social issue-solvingbusinesses” as a part of materiality for exploiting revenue
opportunities toward achieving Vision 2030.
While there are many social issues before us, one of thebiggest challenges for our Group is the realization of adecarbonized society, namely, the initiatives aimed at carbon neutrality1).
From the initiatives of Furukawa Electric (FEC) regarding the carbon neutrality, an activity of the Sustainable
Technology laboratory is introduced in this paper. Our
mission is to create new business seeds through the“search for budding technologies” which anticipate
advanced technology in order to build a new social infrastructure that converts social issues into value. The
research and development on “Green LPG synthesis
technology using greenhouse gases as raw materials” isproceeding as one of the “seeds for new businesses”.
With this theme, we have been working closely withsocial issues from its setting to its research and developFrontier Research Department,
Sustainable Technology laboratory, R&D Division*2Analysis Technology Center,Sustainable Technology laboratory, R&D Division*3
Professor (Specially-appointed) Faculty of Engineering,
Hokkaido University*1ment. The latest progress of the research and development will be introduced.

2.

THEME SETTING BASED ON
OUTSIDE-IN APPROACH

The fundamental idea of the Group in the carbon neutrality is “1 Eliminate or reduce direct CO 2 emissions”,“2 Eliminate or reduce CO2 emissions by customers andsociety”, and “3 Capture or transform the CO2 that isemitted”. We have been selected as a CDP Climate
Change A-listed company for the second consecutive
year, based on the evaluation of our goal-setting andactions in efforts to address climat change, and transparancy. For further growth of the initiative, also for achievement of the Vision 2030, we are considering developing
products and services that make effective use of CO2.
We focused on the carbon recycling technology. On
developing the carbon recycling technology, the important thing is “What shall be created from CO2”. By hearing
opinions directly from various people, we extracted twokeywords, “dairy farming / livestock industry”, and “natural disasters”.
“Dairy farming / Livestock industry”
At COP26 held in 2021, the attention was focused onmethane gas which accounts for approximately 30% of
the greenhouse gas effect. More than half of the world’s
methane generation sources come from fossil fuels,
waste, and agriculture / dairy farming, of which the largest amount of methane is said to be in the agriculture /dairy farming 2). Methane gas generated from agriculture /dairy farming and wastes is the greenhouse gas if it isreleased into the atmosphere, but it can be effectively
used as energy when it is retrieved actively in sufficient
Furukawa Electric Review, No. 53 20222

Technology for Producing Green LPG With Ramune Catalyst

LPGElectricity
City gas
LPG: Full recovery on April 21.
City gas: Full recovery on May 3.
Electricity:
Full recovery on June 18.
６\\\

６５\

13 20 27

６ ３\５\\５４\

15 22 29

５ ６\４\\４\４ ８\３

11 18 25

４ １\３\500
450
400
350
300
250
200
150
100500３

The number of unsupplyable units
for each infrastructure / 10 k units

amount. For example, a biogas power generation using
methane fermentation of livestock manure is one of theutilization methods, and it is playing an active role as aregional energy supply source. On the other hand, wecould confirm the followings: surplus electricity has generated at some of regions where livestock manure can becollected. In addition, another problem is, even thoughwishing to supply to other regions, the electricity cannot
be transmitted due to lack of power system capacity,
especially lack of transmission capacity. Therefore, weconsidered to provide a method that can utilize biogas asalternative energy by avoiding limitation described above.
“Natural disaster”
When considering about energy, we focused on “rapidly increasing natural disaster”. Recently, heavy rainfalls
once every 100 years occur almost every year causing agreat damage in each case. In such of us, LPG, which
has been rooted in our lives for a long time, is evaluatedfor its high resilience again. As shown in Figure 1, after
the Great East Japan Earthquake, recovery of LPG was
faster than other energy as it is easy storability / transportability and availability in distributed independence 3).
Therefore, we considered that when LPG could be generated from livestock manure, at the same time of thereduction of greenhouse gases, energy can be supplied
to the region simultaneously with the disaster countermeasure implementation, and the self-reliance of theregion would be established.

10 173.

– DEVELOPMENT OF GREEN LPG
SYNTHESIS TECHNOLOGY –CONVERTING CO2 (GREENHOUSE GAS)TO A USEFUL COMMODITY

We proceeded with the development in a two-step process. First, syngas was produced from biogas* (dryreforming reaction). From there, LPG was synthesizedfrom syngas (LPG synthesis reaction). The details areshown in Figure 2. In order to achieve this process, anissue for the catalyst technology was required to besolved.
* Biogas is a mixed gas consists of methane (CH4) andcarbon dioxide (CO2) obtained by methane fermentationof organic waste (livestock manure, paper waste, foodresidue, etc.) (CH 4 approx. 60%, CO 2 approx. 40%).
Since electricity can be generated by using CH4 in thecomponents as fuel, it is positioned as one of the renewable energy. And, CO2 in biogas is not utilized, as it is a
nonflammable gas, and released into the atmosphere.
3.1 Issues Regarding the Catalyst
The issues differ depending on the type of reaction, theissues regarding catalysts can be divided into (1) the catalytic activity and (2) the catalyst life. In general catalysts,in order to improve the activity, a method to ensure aneffective surface area is taken by supporting metal particles having catalytic activity on supports in highly dispersed state. However, in a catalyst having such a structure, sintering of metal particles tend to occur on the supports during the reaction. In addition, in reactions that usehydrocarbons as a raw material, coking is caused at thesame time as sintering. Coking is a phenomenon ofdeposit of carbon on the catalyst, and it is thought that amass of carbon is formed by polymerizing hydrocarbons
on the catalyst.
When such sintering and coking occur, the effective
area as a catalyst decreases, then the catalytic activity
decreases. As a result, problems such as the need toreplace and regenerate the catalyst in a short period oftime occur (Figure 3).

Figure 1 Changes in the number of unsupplyable units foreach infrastructure in the three disaster prefectures3)(including estimates) .

New technology under development
Livestock manure

Methanefermentation

Biogas*
CH4

CO2

Dry reforming
reaction

LPG synthesis
reaction
Easy storage / transportation

Figure 2 Green LPG production process from manure (outline).

Furukawa Electric Review, No. 53 2022

3

Technology for Producing Green LPG With Ramune Catalyst(a) The Structure of(b) The Sintering ofa metal supported
metal particles.
catalyst.
Metalparticle

Supports(c) The Coking.
Coke(carbon component)

Supports

Supports

Figure 3 Image of supported catalyst structure, metal particle
sintering and coking.

3.2

New Structural Catalyst, Features andEvaluation Results of Ramune Catalyst
To solve sintering and coking of the catalyst, we proceeded with the creation of ideas, through the collaboration
with Professor (Specially-appointed) Takao Masuda ofFaculty of Engineering, Hokkaido University (currentlyEmeritus Professor, Hokkaido University), who has been
active in the field of catalytic reaction engineering over a
period of time. As a result, we developed an idea to suppress sintering and coking by encapsulating metal nanoparticles in a porous material (Figure 4). The collaborated
idea has the following two features. The first feature of
the collaborated idea is the encapsulation of metal nanoparticles in a porous material with small pores. The second feature is to prevent sintering and coking by fixing
metal nano particles in the porous material.
Several nm

NiPorous material
Figure 4 Structure of our novel catalyst (Ramune catalyst).

3.2.1 Ramune catalyst structure analysis
We made a prototype of the developed catalyst and its
structure was analyzed. The cross section of the prototype catalyst was cut out, and the cross-sectional elemental analysis was performed with a Scanning Electron
Microscope (SEM) (SU8020 from Hitachi High-TechCorporation) and with an Energy Dispersive X-ray spectroscopy) (EDX) (X-Max by HORIBA, Ltd.) also the crosssection was observed with a Transmission Electron
Microscope (TEM) TITAN G2 from FEI Company JapanLtd.).
As a result of the cross-sectional elemental analysis,the Nickel element (Ni) was detected inside the catalyst.
Furthermore, by using the photographed cross-sectional
TEM image, 100 or more Ni particles were arbitrarily
selected, and the most frequent particle diameter wascalculated by measuring each particle diameter. As aresult, we confirmed that mode diameter of nickel particle
contained in the prototype catalyst was approximately
4 nm.(Table 1) However, in principle, TEM can obtain only
local information in the prototype catalyst. Then, in orderto obtain the average information of the Ni particle contained in the entire prototype catalyst, an observation
with a Small-Angle X-ray Scattering (SAXS) was performed. For the SAXS measurement, SPring-8 beam line
BL19B2 was used. From the obtained SAXS data, withassumption that the electron density of the particles wasuniform, the particle diameter was calculated using
Guinier approximation. The result is shown in Table 1.
Table 1

Observation result on the Nickel particle size of theRamune Catalyst.

Measuring method

Cross-sectional TEM

SAXS

Ni particles size

4 nm

2-3 nmFrom the cross-sectional elemental analysis, the crosssectional TEM and the SAXS analysis, we confirmed thatthe prototype catalyst had a structure in which several
nm of Ni particles were encapsulated inside the porous
material as shown in Figure 4 which is our design. This
new catalyst structure (the structure in which the catalysts are fixed inside the porous material) is named
Ramune Catalyst as it resembles a bottle of Ramune inwhich a glass ball is fixed.
3.2.2 Catalyst performance of Ramune Catalyst
On producing LPG from the biogas, the dry reforming isnecessary. Dry reforming (CO2 + CH4 → 2CO + 2H2) is oneof the focused reactions in the field of carbon recycling,for its opportunity to utilize greenhouse gases. Ni has
been reported to be active as a catalyst, but this reaction
has the problem of deactivation of the catalyst due tocoking on Ni particles.
We evaluated Ramune catalyst for dry reforming performance. The result is shown in Figure 5, and the evaluation result for the catalyst after the reaction is shown in
Table 2. As shown in Figure 5 and Table 2, the conventional Ni-based catalyst was deactivated in a few hours
and a large amount of coke was detected in the catalyst
after the reaction. On the other hand, Ramune Catalyst
maintained stable activity for 100 days or more, and theamount of coke formation was below the lower limit of
the analysis. From these results, we confirmed that
Ramune catalyst has an excellent tolerance of sinteringand prevention of coke formation, and these characteristics achieve good catalytic activity and stability required
as practical catalysts.
In this paper, only the results of the first-stage dry
reforming reaction are introduced, but we have confirmedthat our catalyst under development also exhibited good
performances for the LPG synthesis catalsyt.

Furukawa Electric Review, No. 53 2022

4Technology for Producing Green LPG With Ramune Catalyst

Ramune catalyst

Catalytic activity(CO2 conversion / %)10080

conventional LPG, CO2 can be reduced by the amount ofthe replacement. Based on the above consideration, CO2
reduction amount is calculated by the formula shownbelow.
The Green LPG amount obtained from the manure of
one cattle is 86 kg/year. Here, since LPG emits threetimes as much CO2 when burned, the amount of CO2
reduction of the Green LPG is approximately 260 kg/year
from a cattle. Furthermore, the CO2 reduction amount inJapan and in the world are calculated by multiplying thenumber of cattle in Japan and the number of cattle in theworld.

Ni

6040

Porous material

20* Conventional Ni-based catalyst wascompletely deactivated in 5 hours

00

10

20

30

40

50

60

70

8090 100 110

Reaction time / day
Figure 5 Performance of the dry reforming on the Ramune
Catalyst in the test result.
Table 2Results of the analysis on the catalytic activity andamount of coke of Ramune Catalyst.

Analysis
resultRamune Catalyst

ConventionalNi-based catalyst

Reaction time

107 days

5 hours

Catalystactivity(Initial activity)
Over 90%(After 100 days)
Over 90%(Initial activity)
Over 90%(After 5 hours)
Over 0%Coke amountafter thereaction*<0.3wt%30wt%･Ni particle maintained
nano-size･Coke wasn’t detectedfrom ramune catalyst

Large amount coke
was formatted onconventional catalyst

Catalyst structure after
dry reforming(Image diagram)CO2 reduction amountCO2 emission factor of petroleum

5.

NiSupports* Carbon sulfur analysis result.

CO2 REDUCTION AMOUNTWe decided to calculate the LPG amount produced
based on the laboratory evaluation results with the catalyst under development in the Company. LPG amountobtained from one cattle and CO2 reduction amount werecalculated. The result is shown in Figure 6.
LPG currently used is from fossil fuels, but if Green LPG
derived from livestock manure can be replaced with theManure
Manure for one cattle

IMPACT OF THIS TECHNOLOGY ON
SOCIETY AND SOCIAL
IMPLEMENTATION SCHEDULE

This technology uses CO2 and CH4 as raw materials, andthe greenhouse gas reduction can be expected. In addition, since the Green LPG can be easily stored and transported like existing LPG, then it can contribute to use as
an energy in the event of disasters and to solve a problemof lack of capacity in power grids.
In Japan, the LPG supply is heavily depending onimports. Against this fact, our technology enables us togenerate LPG domestically, then “local consumption oflocal production regarding the Green LPG” will beenabled. Thus we believe that this technology will contributes to job creation and regional revitalization. We areaiming for “local production, a wealth for local future generations* ” regarding the Green LPG by inheriting thisindustry to the next generation (Figure 7) (Table 3).
* “Local production, a wealth for local future generations” is topass on (or inherit, succeed) natural resources, facilities, traditions,culture, etc. existing in a community to the next generation4).

Marketscale

Approx.
230 thousand yen / year
(LPG 86 kg / year)

Manure from all cattle in Japan(For 1.3 million cattle)

LPG consumption derived
from livestock manure× derived LPG (3 kg-CO2/kg)

Porous material

4.

=Approx.

30.7 billion yen / year

CO2 reduction
amountApprox.

260 kg / year
Approx.

360 thousand ton/ year

(LPG 120 thousand ton / year)

Manure from all cattle in the world(For 140 million cattle)

Approx.
3.3 trillion yen / year
(LPG 12 million ton / year)

Approx.
36 million ton / year
* Compared to using
fossil fuel-derived LPG

Figure 6 Market scale and amount of CO2 emission reduction.

Furukawa Electric Review, No. 53 2022

5

Technology for Producing Green LPG With Ramune Catalyst

An assistance for local self-reliance
Community

Utilizing greenhouse gases

Community(CO2 and CH4)

Clean
energyLivestockmanure

Energy for
general household(LPG)

LPGASCommunity

Energyfor farm

Energy foremergency* Only CH4 is used for the biogas power generation.

Community

Current issues

Green energy (LPG)

Community to aim for- Japan aims for zero greenhousegas emissions (in 2050)- Utilize livestock manure asa raw material- A big step for greenhouse gases reduction- Development in the primary industry- Rapidly increasing natural disaster- Lack of capacity in power grid

- Storage and transportation
available- Energy useful for disaster prevention andmitigation- Solution for lack of capacity in power grids- Import fossil fuels from overseas- Local consumption of local
production available- Local production, a wealth for local next
generations, job creation and regional
revitalization- Energy self-sufficiency

Figure 7 New community created by our Green LPG.
Table 32020

Social implementation schedule.
2021

2022

2023

2024

2025

2026

2027

2028

2029

2030

2050

Practicaluse

Globalexpansion

Demonstration bysmall test machine★

Field demonstration test★

6.

CONCLUSIONThe CO2 generation amount is directly related to the primary energy production amount. The net amount of CO2
generation can be reduced by producing a primary energy using renewable bio-derived resources as an alternative resource to fossil resources. Also, instead of transferring primary energies over a wide area as secondary
energy such as electricity, if the primary energy can be
stored in a simple and stable manner for a long period, it
will be a Business Continuity Plan (BCP) against disasters. From this point of view, producing LPG, which iseasily accepted by the general public, from the biogas
and supplying it is considered to be an extremely
advanced and rare technology which is closely serving
the general public. We are convinced that this technology
is a Japanese-launched type that can be applied to mostregion of the world where natural gas supply facilities are

not well equipped, and its practical realization is muchneeded.
Therefore, the Company will continue to promote thedevelopment of this technology to produce LPG from thebiogas, toward its practical application.

REFERENCES
1) Furukawa Electric Group Integrated Report 2021
2) Japan International Research Center for Agricultural Sciences(JIRCAS), 292. Benefits and Costs of Mitigating Methane
Emissions to Prevent Global Warming (Referred on May 17, 2022)		https://www.jircas.go.jp/en/program/proc/blog/20210513
3) Ministry of Economy, Trade and Industry: “Survey on the ideal
way of the future of stable supply of LPG based on the Great East
Japan Earthquake”, Feb. 2012. (In Japanese)
4) Nikkei BP, The process to “Roppo-yoshi management” is initiatedby cross-border learnings. (Referred on May 17, 2013)		https://business.nikkei.com/atcl/seminar/19nv/120500136/072
900528/?P=4 (in Japanese)

Furukawa Electric Review, No. 53 2022

6