Environment-Enhancing Energy Paradigm -- Integrated ... Cover page Slides.pdfEnvironment-Enhancing Energy Paradigm --Integrated Approach for BioEnergy, Water and Carbon Capture Yuanhui

UNIVERSITY OF ILLINOIS

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Environment-Enhancing Energy Paradigm

-- Integrated Approach for BioEnergy, Water and Carbon

Capture

Yuanhui Zhang, PhD, PE

Innoventor Professor in Engineering

Dept. Agricultural and Biological EngineeringUniversity of Illinois at Urbana-Champaign


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Biocrude oil

Clean water

Multi-cycle nutrient and water reuse

CO2Sun light

Algae production

Hydrothermal liquefaction (HTL)

Wastewater and nutrients from Post HTL to algae

Biomass from algae

to HTL

Liquid

Solids

Biowaste

Environment-Enhancing Energy Road-Map

http://www.google.com/imgres?imgurl=http://news.cnet.com/i/bto/20080620/Seambiotic_Ponds_540x354.jpg&imgrefurl=http://news.cnet.com/8301-11128_3-9973649-54.html&h=354&w=540&sz=48&tbnid=Uyn7TEnnK8HLQM:&tbnh=90&tbnw=137&zoom=1&usg=__NG95Py5oBYkD5bjEv7oBEMauif4=&docid=MzPDlNqo6NTD2M&hl=en&sa=X&ei=wYN0UP3lN4TWyQHOo4G4CQ&sqi=2&ved=0CCcQ9QEwAQ&dur=6843





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Alternative EnergyGenerate electricity and heat:

Generate transportation fuel:

Biofuel

Renewable resourcesConversion

Solar energy Wind farm Geothermal energy Hydroelectric power


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Why Low-Lipid Microalgae?

5

(Williams & Laurens, 2010)(Rodolfi et al., 2009)

Energy intensive

(~75% of total)

Harvest

Drying

Oil

Extraction

Transesterification

Current approach: high-lipid microalgae for biodiesel.



青岛

太湖滇池

巢湖

The naturally

occurring algal

bloom s are all

Low-lipid, fast –

grow species.Low-lipid

Slow-grow

Lipid Content (%）

Bio

ma

ss

High-lipid

Fast-grow

(Extraction)

High-lipid

Slow-grow

（Pharmceuticals）

High

High

Low

Low Lipid

Fast-grow

（HTL）

7



Based on the biogenic hypothesis

All fossil fuels found on earth – petroleum (including oil

shale and tar sand), natural gas and coal, are formed

through processes of ThermoChemical Conversion*

from biomass buried beneath the ground and

subjected to millions of years of high temperature and

pressure.

*ThermoChemical Conversion processes include pyrolysis,

hydrothermasl liquefaction and gasification



Hydrothermal Liquefaction (HTL)

Mimicking Mother Nature’s millions-of-years

process of turning deceased living matters buried

beneath the ground into petroleum, swine manure and

other bio-waste, have been converted into crude oil in

minutes using hydrothermal liquefaction (HTL)

technology in 10 – 40 minutes.



Source: Hunt, John. 1996

Petroleum Geochemistry and Geology

HTL

1.8 min

1 billion yr

CHG



Algae to Biocrude Conversion Efficiency

Initial lipid content and HTL oil conversion efficiency for different

feedstocks. Energy recovery ratio is 3~11 to 1. Note that the HTL

can convert the very low-lipid algae into crude oil – a paradigm

shift from ‘extracting’ to ‘converting’. (Yu et al., 2011)

0%

5%

10%

15%

20%

25%

30%

35%

40%C

hlo

rella

Sp

iru

lina

Ch

lam

ydo

mo

nas

Alg

ae S

WP

Alg

ae G

OM

Dia

tom

Alg

ae U

CS

D

RT

Alg

ae

KE

LP

Re

d A

lgae

Sea

wee

d

Sew

age

slu

dg

e

Sw

ine

man

ure

Pe

rce

nta

ge

(w

t%) Bio-crude oil Yield

Lipid Content

Microalgae Macroalgae Biowastes



1996 1999 2005 2015201320112007

Hydro-thermal?

He et al., 2000,

2001PFR pilot/commercial

system (12 bbl/d)

Licensed from UIUC

PFR reactor system

(2 gallon/d)

Minarick et al.

CSTR system

(1 gallon/d)

Ochemia et al., 2005,

CSTR Commercial

system (160 bbl/d)

Licensed from UIUC

CSTR Pilot system

(10 bbl/d)

Licensed from UIUC


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HTL Feedstock and Biocrude

14

Food- Slaughter- Swine MWWprocessing house manure Algae

Feedstook Properties:

Ash Content (dry based) 1.5 8.38 16.3 47.5

Lipid content 52.3 23.8 20.3 1.7

C 60.7 59.5 41.1 27.9

H 8.49 8.77 5.42 3.01

N 3.33 5.44 3.36 3.9

O 27.5 26.3 50.1 65.2

Biocrude oil yield (% dw TS) 62.4 72.1 39 46.8**

High Heating Value (MJ/kg) 40.6 36.5 38.8 32.5

C 75.4 69.7 76.6 59.4

H 12 11.1 10.3 7.79

N 1.79 2.32 3.76 2.5

O 10.8 16.8 9.4 30.3

Energy Recovery (%)* 91.2 96.7 83.8 84.2**

* ER not include 5-10% HTL process energy; ** For volatile solids


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Distillation of HTL Biocrude

15



Fuel specification analysis and engine test of BD10-20

Fuel Spec Property Upgraded BD-10

(FPW)

Upgraded BD-20

(FPW)

Diesel

Viscosity @20 °C (mm2/s)a 3.737 3.050i 3.746

Acidity (mg KOH/g)b 0.08-0.23 0.26-0.33 0.3 e

Existent Gum (mg/100ml)f 0.17 wt.% 0.21 wt.% 0.21 wt.%

Net Heat of Combustion (MJ/kg)e 44.7 44.2 46.1

Cetane Number (min) f 44.2 43.6 40> e

Lubricity (μm) f 364 324 <520 e

Oxidation Stability (hrs) f 48> 48> 6> e

Engine Test

Power Generated (ft-lb) 7.4 -13.5 6.0-13.7 7.3-13.5

EGT (°C) h 326.3- 569.6 303.7-554.1 334.9 -574.4

Thermal Efficiencies j TBAi TBAi TBAi

CO emission (ppm) 0.04-1.82 0.05-1.66 0.05-2.12

CO2 emission (ppm) 7.06-11.4 6.22-11.7 7.12-11.6

NOx emission (ppm) 606-1576 551-1456 540-1549

Unburnt hydrocarbons (ppm) 14-26 18-29 14-32

Particulate matter emission (Soot) TBD TBD TBDaMeasured by Cannon-Fenske Viscometer (ASTM D7566-14a); bMeasured by ASTM D664; cMeasured by ASTM D93; d According to ASTM D7566-14a;e ASTM D7467-13; f Modified ASTM D381, heat the sample in the furnace from room temperature to 240 °C for 30 minutes; g Not applied; h Exhaust Gas

Temperature; Through the cooperation with Prof. Chia-Fon Lee; i To be analyzed; j check the reference papers on Biomass & Bioenergy


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Synergy of Algae and Wastewater Treatment

17

National Algal Biofuels Technology Roadmap:

(DOE, 2010, pg. 83)

“Inevitably, wastewater treatment and recycling must be

incorporated with algae biofuel production.” WHY?

“Nutrient recycling would be needed since wastewater

flows in the United States are insufficient to support

large-scale algae production on the basis of a single use

of nutrients.”


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Nitrogen Balance of the HTL Process

As temperature increased, more nitrogen was recovered by aqueous product.

NR of bio-crude oil increased mainly due to the increase of its yield.

About 75% of nitrogen remained in the aqueous phase after HTL.

Chlorella Chlorella

Yu et al., 2011


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Destruction of Bio-active Compounds and

Antibiotic Resistance Gene via HTL Process

14 C-BPA/Estradiol

+ Swine Manure

Flofernicol

Certiofur

Estrone

HTL Treatment

Temperature:250 – 300oC

Reaction Time: 15, 30, 60 min HPLC Analysis

Liquid Scintillation

Counter

BPA Estradiol

Distribution of 14C from BPA and Estradiol in the HTL final products (3000C, 60 min RT)


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Destruction of Bisphenol A

a) 3000C-60 min

b) 3000C-45 min

c) 3000C-15 min

60 min 45 min 15 min0

20

40

60

80

100

Feedstock

% C

14 in

pos

t HT

L w

aste

wat

er

Figure 3: Percentage of 14C in HTL

wastewater.

Detection of BPA and its breakdown products before and after HTL treatment at 300oC

and three different reaction times: a) 60 min, b) 45 min, and c) 15 min. (Pham et al.,

2013)

300 C


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Left: DNA concentration pre- and post HTL treatment;

Right: Agarose gel of plasmid DNA extracts from pure E. Coli

culture before HTL treatment (Well 1) and after various HTL

treatments (Well 2-7) versus size standards (Well 8).

0 15 30 45 60 750.1

1

10

100

1000

E.Coli-250oC

E.Coli-300oC

Swine manure+E.Coli-250oC

DN

A c

oncentr

ation (

ng/m

L)

Retention time (min)

Destruction of Plasmid DNA via HTL Treatment



Aq

ueo

us

Solids

Gases

Bio

cru

de

→Ⅰ: 3, 2+4(2-, 3-)

→Ⅱ: 4(6)+(5, 2)

→Ⅲ: 3(1, 2)

Ⅰ

Ⅱ

Ⅲ

HTL Pathway Analysis (Outputs Distribution)



Pathway Analysis -- Effect of FS Composition


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STELLA Widely used in biological, ecological, and environmental sciences

(Hannon and Ruth 1999, Ouyang 2008)

24

Model Construction

1 2 3 4 5


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Evaluate process improvements

25

Dilute Liquid

Concentrated

Biosolids

Hydrothermal

Liquefaction

Algal-

bacterial

Cultivation

Waste

PretreatmentHarvested Biomass

PHWW

Biocrude Oil

Residue

CO2

Waste

Stream

Q 1000

TSS 210

C 132

N 40

Q 999TSS 63

C 75N 37

Q 0.7

TSS 147

C 57

N 4

Q 9.0

C 226

N 121

CO2 C 31

TSS 942

C 472

N 147

Q 1008TSS 20

C 38N 9

Oil 990

C 657

N 23

Residue 379

C 123

N 7

Improved Scenario:

10 Times Biosolids Amplification

Treated

Wastewater

C 314

Solids 210C 132

C 686

Solids 1959

C 992

= 10_________+

TSS 147

1 2 3 4 5Zhou, 2014


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The combination system diagram

Raw

materials

Biogas Membrane

The condensed effluent was used

for water soluble fertilizer

The diluted

Microalgae

cultivation

N, P absorption and

wastewater treatment

Biocrude

oil

production

Microalgae used as co-

digestion to produce CH4

Fig. The diagram of anaerobic digestion and microalgae

cultivation

CO2

E2-Energy Demonstration Unit on Campus

Pilot HTL Reactor (2 ton/day Biocrude Capacity)

Feedstock Supply System



Clean water

Multi-cycle nutrient and water reuse

CO2Sun light


Wastewater and nutrients from Post HTL to algae

Biomass from algae

to HTL

Liquid

Solids

Manure

Q = 1000

TSS = 4.0C = 3.6

N = 0.725

Carbon capture

C = 9.1 ton

Biomass = 37.9C captured = 18.9

N recycled = 2.61

Biocrude

= 14.5 ton

A Case Study: 1,000 t/d Wastewater Treatment Plant(Equivalent to a 6,000 hog farm based on TSS, N&C)



Let’s think big … E2-Energy Potential

Collected per year:

54 Billion m3 wastewater

200 million tons

nutrient-rich solids

http://news.cnet.com/i/bto/20080620/Seambio

tic_Ponds_540x354.jpg

0.6~1.2 Billion tons

Biocrude equivalent!

US consumed

1.1 billion tons of

crude oil in 2013




Thank you

Documents

Environment-Enhancing Energy Paradigm -- Integrated ... Cover page Slides.pdfEnvironment-Enhancing Energy Paradigm --Integrated Approach for BioEnergy, Water and Carbon Capture Yuanhui