A Commercial Demonstration on Biorefinery of lipids:

Co-production of biodiesel and 1,3-propanediol

Dehua Liu
China-Latin America Joint Laboratory for Clean Energy
and Climate Change, Tsinghua University, China
 Outline
A novel enzymatic process for
biodiesel production
Integrated production of 1,3-PDO from
by-product glycerol
Biodiesel : defined as “a substitute for, or an additive to
diesel fuel that is derived from oils and fats of plants, animals
and microbes”
CH2-OOC-R1 R1-COOR' CH2-OH
Catalyst
CH-OH
CH-OOC-R2 + 3R’OH R2-COOR'
+
R3-COOR' CH2OH
CH2-OOC-R3
Glyceride Biodiesel Glycerol

Catalyst
R-COOH + R’OH R-COOR’ + H 2O

Chemical approaches (alkali, acid)

Transesterification at supercritical condition
Enzymatic approaches (lipase)
 Acid/alkali Waste water containing acid or alkaline requires extra
Chemical ways treatment; it has high requirements for oil feedstocks’
quality especially with alkali as the catalyst.

High temperature
and pressure
Supercritical It is energy and capital intensive with reaction carried
fluid systems out at high temperature and high pressure conditions.

lipase The transesterification can be performed under mild

reaction conditions and the whole production process
Enzymatic ways
is environmentally friendly. Reducing the lipase cost is
the key for lipase-mediated biodiesel production.
 Negative effect

lipase
oil + methanol Biodiesel + glycerol

Poor stability and activity of the lipase should be due to the negative effect of
methanol and glycerol. With TU’s novel technology, the negative effect of both
methanol and glycerol on enzyme activity could be greatly eliminated

100

MEyield(%)
80
60
40
20
0
0 50 100 150 200 250 300
cycle number
 Demonstration from lab scale to commercial scale

Industrialization (50,000 tons/y)

Pilot plant

Lab scale
40m3 bioreactor for lipase 1
25m3 bioreactor for Lipase 2
Evaporation Centrifugation

Storage tank
Technology demonstration in Brazil

2011.04 2012.06

2012.06 2012.08
 Various oil sources were tested:
Soybean oil
Rapeseed oil
Palm oil
Jatropha oil
Cotton seed oil
Rice husk oil
Animal oil
Waste oils
Oils from algae, yeast
……

The above oils can be transformed into biodiesel

effectively using TU novel technology.
 Stability and activity of lipase have been
improved significantly
Some cheap oil sources could be used for
biodiesel production

How to deal with the by-product glycerol ?

 Biodiesel Production Glycerol Price Trend
4
6,000
Million Gallons

5,000
3

Price (cents/lb)
4,000

3,000 2

2,000
1
1,000

0 0

Year
Time

Vegetable Oil + Methanol 

Catalyst
 Biodiesel + Glycerol
10 1
www.biodiesel.org
 Integrated production of
Biodiesel and 1,3-PDO

Tsinghua University has proposed a novel flexible process

for 1,3-PDO production from glycerol or glucose.
Yeast bacteria
glucose glycerol 1,3-PDO

vegetable oil biodiesel PTT

More than 50 patents were filed, among which more than 30 have been granted.
 PTT- A Novel Polyester
What is PTT ? Made from PDO
 Glycerol fermentation Seed culture C. krusei

k. pneumoniae glucose
Seed culture fermentation flocculation filtration

distillation concentration desalting

PDO

two-phases fermentation process for 1,3-PDO production

The industrial scale production of PDO with capacity of 20,000
tons /year is running in Jiangsu province, China .
 "Schircks, Markus" <markus.schircks@thyssenkrupp.com>

2008/09/25 17:58
To: "'koichi.yamashita@mitsubishicorp.com'"
<koichi.yamashita@mitsubishicorp.com>

Subject:
PDO von Mitsubishi

Dear Mr. Yamashita

With your PDO we have done some polymerization tests in
the laboratory. We also have done the same tests with a
reference PDO from MERCK. Our main focus was to confirm
that your PDO will polymerize
Mitsubishi PDO
The color of your PDO is more yellow (APHA 32) then the
reference PDO from MERCK (AHPA 0).
The gas chromatography didn't any other peaks then PDO.

I will carry some sample polymer with me.

Best regards
Markus Schircks
发件人: koichi.yamashita@mitsubishicorp.com
[mailto: koichi.yamashita@mitsubishicorp.com ]
发送时间: 2011年2月22日 11:57
收件人: dhliu@tsinghua.edu.cn
抄送: liujianbo@warivers.com ; fuji@yifengenergy.com ;
tetsuya.matsuura@mitsubishicorp.com ; hiroki.igarashi@mitsubishicorp.com ;
shuo-heng.huang@mitsubishicorp.com ; koichi.yamashita@mitsubishicorp.com
主题: PTT meeting

Dear Dr. Liu

I'm afraid that it is a little bit late, but I wish you happy new year!

We would like to discuss with you about future program.

Please let me know your schedule whether you are available on

March/10th(THU) or March/11th(FRI) in Beijing.

Now that NPC and TFJ(Teijin Fiber Japan) acknowledged and confirmed that your monomer
can be used as raw material of PTT polymer which is equal to Dupont's.

On the other hand, they duly understand that we cannot supply monomer immediately after they
decide to start polymer production.

So we have to consider practical counter measure in order to go forward.

Detailed agenda will be sent later.

Looking forward to hearing from you soon.

K.Yamashita
Mitsubishi Corp.
 Summary

Enzyme technology Chemical method

(Tsinghua University) ( alkali)
Requirements on oil Applied to Oils with varied
feedstock quality Only refined oil feedstocks
(0-100% FFA)
Content of water and No requirement
FFA (FFA can also be converted to Strict requirements
biodiesel simultaneously)
Methanol or ethanol Hydrous anhydrous
By-product glycerol High quality; Easier
Containing metals
purification and utilization
Waste water containing
Waste emission Almost zero emission
acid, metals, etc
Conversion of by-product glycerol to 1,3-PDO significantly
improves the comprehensive economic benefit of the whole project.
 Acknowledgements
Ministry of Science and Technology
National Development and Reform Commission
Ministry of Education
National Natural Science Foundation of China (NSFC)
My colleagues and students

……………
 Website：www.wbsrio.com

11th World Bioenergy Symposium (WBS)

August 6th – 9th , 2018Fortaleza, Brazil
 Tsinghua University, China
 Federal university of Ceara (UFC), Brazil
 Federal University of Rio de Janeiro (COPPE/UFRJ), Brazil
Organizers
 China Brazil Center for Climate Change and Energy
Technology Innovation
 China-Latin America Joint Laboratory for Clean Energy and
Climate Change
 Bio-oil
 Fuel Ethanol
 Jet fuel Ms. Zeng Jing:
 Biodiesel ceng-j03@mails.tsinghua.edu.cn
 Flexi-fuel
Topics  Biobutanol Ms. Rejane Rocha:
cars Contacts rejane@peq.coppe.ufrj.br
 Biogas
 Feedstock Prof. Diana Cristina Azevedo:
 Biohydrogen diana@gpsa.ufc.br
 Policy
Thanks!

Contacting:
Tel: +86-10-62772130
Fax: +86-10-62792128
dhliu@tsinghua.edu.cn