IMPLEMENTATION OF GREEN CHEMISTRY

PRINCIPLES IN THE PETROCHEMICAL INDUSTRY (PI)

FOR CIRCULAR ECONOMY

31th-August 2018

National Taiwan University

Dr. Kinjal J. Shah, Post-doctoral Fellow

Carbon Cycle Research Center, National Taiwan University

Kinjal J. Shah, Ziyang Guo, Shuting Wang, Pen-Chi Chiang*

Outline:

1. Introduction

2. Barriers and Strategies

3. Green Chemistry

4. Circular Economy for Pl

5. Case Study

6. Recent Activities and Future Directions

1. Introduction - Development Status of the Petrochemical Industry

1. Introduction - History of Petrochemical IndustryYear Process Purpose Notes

1860batch distillation to separate kerosene and

heating oil from other crude fractions

Generated Kerosene and heating oil Cost of $15000.

1862 Atmospheric distillation Produce kerosine By product: Naphtha, tar

1870Vacuum distillation, cracking feedstork Lubricant (original) By product:Asphalt, residual coker feedstork

1912 Catalytic cracking The first widely recognized continuous refinery plants

1913 Thermal cracking Increasing Gasoline By product: Residual, bunker fuel

1916 Sweetening Reduce sulfur and odor

1930 Thermal reforming Hydrocarbon with improved octane number By product: Residual

1932 Hydrogenation Produce gasoline base stocks By product: Sulfur

1932Coking Produce gasoline base stocks By product: Coke

1933 Solvent extraction Improve lubricant viscosity index By product:Aromatics

1935 Solvent extraction Improve pour point By product:Waxes

1935 Catalytic polymerization Improve gasoline yield and octane number By product: Petrochemical feedstocks

1937 Catalytic cracking Higher octane gasoline By product: Petrochemical feedstocks

1939 Visbreaking Reduce viscosity By product: Increased distillate, tar

1940 Alkylation Increase gasoline yield and octane By product: High-octane aviation gasoline

1940 Isomerization Produce alkylation feedstock By product: Naphtha

1942 Fluid catalytic cracking Increase gasoline yield and octane By product: Petrochemical feedstocks

1950 DeasphaIting Increase cracking feedstock By product:Asphalt

1952 Catalytic reforming Convert low-quality naphtha high-octane number By product:Aromatics

1954 Hydrodcsulfurization Remove sulfur By product: Sulfur

1956 Inhibitor sweetening Remove mercaptans By product: Disulfides

1957 Catalytic isomerization Convert to molecules with high-octane number By product:Alkylation feedstocks

1960 Hydrocracking High quality and reduce sulfur By product:Alkylation feedstocks,Wax

1974 Catalytic dewaxing Increased pour point By product:Wax

1975 Residual hydrocracking Increase gasoline yield from residual By product: Heavy residuals

1. Introduction - World’s Petrochemical industry

Company2016 chemical sales

($ million)

1. BASF (Germany) 60,654

2. Dow Chemical (U.S.) 48,158

3. Sinopec (China) 42,815

4. SABIC (Saudi Arabia) 30,986

5. Formosa Plastic (Taiwan) 27,141

6. ExxonMobil (U.S.) 26,058

7. LyondellBasell (Netherlands) 24.624

8. Ineos (Switzerland) 23,530

9. Mitsubishi Chemical (Japan) 23,358

10. DuPont (U.S.) 19,679

• Petrochemical are the chemicalsproduced form natural gas or therefinery product derived fromcrude oil.

• Petrochemical industry havefueled rapid economic growthover the past 50 years but havealso been the source ofenvironmental problems.

1. Introduction – Environmental Issues for the Petrochemical Industry

Air pollution Water pollution

Land pollution Accident

Categories Barriers Strategies

Institu

tion

al

1. Lack of resources sustainability and

availability

2. Petroleum administrative monopoly

3. Resistance on information transfer

4. Lack of knowledge for product design

5. Geographical issues between companies

among the supply chain

Develop Integrated Management

1. Strengthen oil research for resource efficiency and

sustainable development.

2. Introduce antitrust law and encourage private

investment.

3. Establish information sharing system

4. Consider refer success experience from international

and encourage international cooperation

5. Establish industrial park to near up-streams

2. Barriers and Strategies

Categories Barriers Strategies

Reg

ula

tory

1. Lack of penalty policy for environmental

pollution.

2. Lack of reward system for green and

innovation technology

3. Lack of statistical supervision for pollution

and waste.

4. Lack of regulation industry for small

companies

5. Restriction from environmental protection

laws to the oil industry

Establish Reasonable and Fair Regulations

1. Establish environmental law like carbon trading

system or carbon tax

2. Set up certification system for innovation

technique

3. Construction of comprehensive supervision

platform

4. Establish pollution discharge permission system

and response system.

5. Encourage cleaner production and design for

degradation

2. Barriers and Strategies

Categories Barriers Strategies

Tec

hn

olo

gica

l

1. Lack of innovation technology.

2. High energy consumption.

3. Large amount of waste generated during

production.

4. Lack of assurance for chemical and

process safety.

5. Lack of real-time pollution monitoring and

analysis technology.

Implement Green Chemistry Principle

1. Encourage innovation technology by industry-

university cooperation.

2. Develop energy efficiency equipment and process

rather than cost efficient. Application of catalyst to

reduce energy consumption.

3. Reduce derivatives in the process, and calculate

atom economy for waste prevention.

4. Use safer chemical or solvent for accident

prevention, design for less hazardous chemical

production.

5. Implementation of IOT technology for monitoring.

2. Barriers and Strategies

2. Barriers and Strategies

Categories Barriers Strategies

Fin

an

cial

1. High tax for oil trading.

2. The increased cost of oil exploration and

production is increasing.

3. The decline of oil price in the market.

4. Lack of investment on innovation process and

new equipment

5. High cost on waste treatment

Provide Economic instrument

1. Bonder the adjustment of tax

2. Develop oil exploration and drilling technology

for more efficient operation

3. Focus on the high value chemical production.

4. Design more profitable product and Policy to

attract investment such as preferential treatment

for reduction or exemption of tax.

5. Develop innovation technology or recycling

system for waste treatment.

Categories Barriers Strategies

Pu

blic

1. Consumer preference toward low prices

product rather than green product.

2. Lack of innovative and technical talents.

3. Resistance from resident for the establishment

of petrochemical plant.

4. Lack of awareness and employment security

cause health issue and accident.

5. The risk of regional instability bring

uncertainty to international company

Promote Sustainable Educational Program

1. Increase publicity and popularize of green

products

2. Set up research center and educational program

for training talent

3. Enhance the satisfaction and credibility

4. Carry out safety training to employee.

5. Perform preliminary investigation

2. Barriers and Strategies

3. Green Chemistry –

Twelve Green Chemistry Principles

GLOBAL GREEN CHEMICALS MARKET

BY REGION: 2011–2020

3. Green Chemistry – Twelve Green Chemistry Principles

Heat

Exchanger

Cooling

TowerStorage

Eth

ylbenze

ne

Distillatio

n to

wer

Pump

Heater

Distillatio

n

Tow

er

Dehydrogenation

Reaction

Cooling Water

Low pressure steam

147 ºC

70 ºC, 27 ton/h

35 ºC

70 ºC

Heat

Exchanger

Cooling

TowerStorage

Eth

ylbenze

ne

Distillatio

n to

wer

Pump

Heater

Distillatio

n

Tow

er

Dehydrogenation

Reaction

Cooling Water

Low pressure steam

147 ºC

35 ºC

70 ºC

Before improvement

After improvement

70 ºC, 20 ton/h

GreenTechnology - Styrene Production in Formosa

Low pressure steam

Low pressure steam

Boiler water

Boiler water

Green technology of Styrene Production in Formosa

Heat

Exchanger

Cooling

TowerStorage

Eth

ylbenze

ne

Distillatio

n to

wer

Pump

Heater

Distillatio

n

Tow

er

Dehydrogenation

Reactor

Cooling Water

Low pressure steam

147 ºC

35 ºC

70 ºCAfter improvement

70 ºC, 20 ton/h

• By introduce the red stream, the material flow could go straight to the dehydrogenation reactor.

• This eliminate the intermediate storage and transfer step, which reduce the burden of heat exchanger and pump

• It will save 0.4 tons/hour of steam, 9.4 tons/day of water and 17.7 KWH of electricity.

Low pressure steam

Boiler water

1) Prevention

2) Design for energy efficiency;

1) Prevention;

2) Atom Economy;

3) Use of renewable feedstock;

4) Reduce derivatives;

5) Catalyst;

Green technology of Acetic Acid Production

4. Circular Economy for Pl

Green Chemistry Principles I. Upstream: Oil refinery

Technology

Principles toward circular economy:

1. Prevention;

2. Atom Economy;

6. Design for energy efficiency;

7. Use of renewable feedstock;

8. Reduce derivatives;

9. Catalyst;

• Application vacuum distillation to further distillate residual from atmospheric

distillation

• Gas processing to treat waste gas

• Solvent treatment process to prevent corrosion

• Rearranging Process (isomerization, catalytic reforming) to convert hydrocarbon

molecule to produce product

• Coking process convert residual into useful product

• Hydrogen production from byproduct

Gas processing for propane recovered

• Fluid Catalytic Cracking/ Hydrocracking to replace thermal cracking

• Steam generation which produced from heat exchanger and cooler

• Fluid Catalytic Cracking include use of catalyst

Hydrotreating processing with presence of catalyst

3. Green chemistry as technological strategies for petrochemical industry: Upstream process

Green Chemistry Principles II. Midstream: Petrochemical Processing

Technology

Pollution and Accident Prevention:

1. Prevention;

2. Atom Economy;

6. Design for energy efficiency;

7. Use of renewable feedstock;

8. Reduce derivatives;

9. Catalyst;

• Hydrogen purification to prevent waste gas formation

• Biomass based production to increase biodegradability

• Use biomass as renewable feedstock

• Implementation of catalyst in Ziegler-Natta in polymerization, deep

catalytic cracking, ammoxidation process and hydroformylation

3. Green chemistry as technological strategies for petrochemical industry: Midstream process

Green Chemistry Principles III. Downstream: Product Application

Technology

Pollution and Accident Prevention:

1. Prevention;

2. Atom Economy;

6. Design for energy efficiency;

7. Use of renewable feedstock;

8. Reduce derivatives;

9. Catalyst;

• Electronics Recycling to prevent metal pollution

• Deign of bio-modified polymer (like poly alkyl glucosides) to

introduce biodegradability

• Electronics Recycling for metal reuse

• Carbon capture and storage/utilization

3. Green chemistry as technological strategies for petrochemical industry: Downstream process

A ‘circular economy’ would

turn goods that are at the end

of their service life into

resources for others, closing

loops in industrial ecosystems

and minimizing waste.

There are three kinds of

industrial economy:

1. Linear

2. Circular

3. Performance

4. Circular Economy for Petrochemical Industry

• To replace conventional "take, make and dispose” industrial model.

• The circular economy is restorative and regenerative by design. The resource input and

waste, emission, and energy leakage are minimised by closing energy and material loops

• Green cycle include material, water and energy recycling.

Raw material

Oil refineryChemical processing

Product Manufacture

End of use

Product reuse

Chemical recycling

Water, energy and carbon utilization

Renewable

Biodegradation and biomass balance

4. Circular Economy for Petrochemical Industry

N-butanol Plant

CO2

12.8 k tons/year

Syngas

Unit

CO2

CO2

8.7 k tons/year

Propylene

160 k tons/year

Light Oil

61.5 k tons/year

12.8 k tons/year

(Supply Reduction)

Isooctane &

Ethylene

glycol plant

Isooctane

plant &

Ethylene

glycol plant

Oil

Department

Alkali

plant

Hydrogen

6.4 k tons/year

Hydrofor

-mylation

Unit

Hydrogena

-tion

Unit

Butyraldehyde

N-butanol

Incinerator

Vinyl ester

plant & Sale

Syngas

Atomsphere0.3 k

tons/year

32 k tons/year

32 k tons

5. Case Study of N-butanol Plant in Formosa--- Raw Material Circulation

Waste oil & gas

10.7 k tons/year

Waste oil & gas

10 k tons/yearInter plant

Intra plant

Cross

Company218 k tons/year

5. Case Study of N-butanol Plant in Formosa--- Carbon Circulation

Isooctane plant &

Ethylene glycol plant

Isooctane plant &

Ethylene glycol plant

Atomsphere

CO2

8.7 k tons/year

Light Oil

61.5 k tons/year

12.8 k tons/year

(Supply Reduction)

Atomsphere

N-butanol

CO2

12.8 k tons/year

Syngas

CO+H2N-butanol processing

CO2

CO2

Steam

O2 H2

Ethylene

CO

2

Separatio

n to

wer

CO

2

Syngas

Reactor

• Before improvement: Carbon dioxide emissions is 21.5 k tons/year, light oil usage is 61.5 k tons/year

• After improvement: Carbon dioxide emissions reduce to zero, light oil usage reduce to is 48.7 k tons/year (20.8%)

Syngas reaction:

Transfer reaction:

Inter plant

Intra plant

Cross

Company

Inter plant

Intra plant

Cross

Company

Cooling water

96 tons/day

Rain water

120 tons/day

Wastewater

Discharge

250 tons/day

Wastewater

Wastewater

120 tons/day

Water recycling

168 k tons/day

Water recycling

46.6 k tons/day

Rain water

134 tons/day

Supplement water

1226 tons/day 876

350

Supply Reduction

Water

Discharge

96

tons/day

5. Case Study of N-butanol Plant in Formosa--- Water Circulation

Process

water use

250

tons/day

Cooling

Tower

880

tons/day

Inter-plant rain

water recycling

Other plants

or companies

rain water

recycling

Absorbent resin

plant

Formosa

petrochemical

plantFormosa

wastewater

plant

Tower

Discharge

Steam lose 856 tons/day

Absorbent

resin plant

Washing

tower

A circular

economy

development

level

6. Recent Activities and Future Directions

Principle Description Performance Indicator Reference

1. Prevention

It is better to prevent waste

than to treat or clean up waste

after it has been formed.

Environmental (E)

factor *E-factor = total waste / product Sheldon et al., 2007

2. Atom Economy

Synthetic methods should be

designed to maximize the

incorporation of all materials

used in the process into the

final product.

Atom economy * Trost et al., 1995

6. Design for Energy

Efficiency

Energy requirements of

chemical processes should be

recognized for their

environmental and economic

impacts and should be

minimized. If possible,

synthetic methods should be

conducted at ambient

temperature and pressure.

Energy Efficiency

△Patterson et al., 1996

𝐴𝐸 =𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠x 100 %

Yield = 𝑘𝑔 𝑜𝑓 𝑟𝑒𝑛𝑒𝑤𝑎𝑏𝑙𝑒 𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘

𝑘𝑔 𝑜𝑓 𝑇𝑜𝑡𝑎𝑙 𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘

Green Chemistry Principles and performance indicator

Principle Description Performance Indicator Reference

7. Use of Renewable

Feedstocks

A raw material or feedstock

should be renewable rather

than depleting whenever

technically and economically

practicable.

Yield □

8. Reduce Derivatives

Unnecessary derivatization

(use of blocking groups,

protection/ deprotection,

temporary modification of

physical/chemical processes)

should be minimized or

avoided if possible, because

such steps require additional

reagents and can generate

waste.

Reaction Mass

Efficiency

(RME) *

Dicks et al., 2015

9. Catalysis

Catalytic reagents (as

selective as possible) are

superior to stoichiometric

reagents.

Turn over number

(TON) △

For homogeneous catalyst:

For heterogeneous catalyst: Kozuch et al., 2012

Yield = 𝑘𝑔 𝑜𝑓 𝑟𝑒𝑛𝑒𝑤𝑎𝑏𝑙𝑒 𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘

𝑘𝑔 𝑜𝑓 𝑇𝑜𝑡𝑎𝑙 𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘

RME=𝑀𝑎𝑠𝑠 𝑜𝑓 𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠× 100%

TON=Moles of desired product formed

moles of catalyst

TON=Moles of desired product formed

number of active centers or surface area

Green Chemistry Principles and performance indicator

FUTURE DIRECTIONS AND RECOMMENDATIONS

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1. Developing the diversified investment policy for promoting GreenChemistry technology in PI.

2. Strengthening the waste to resource system for building SustainableMaterials Management plans in PI.

3. Integrating Green Chemistry supply-chain and commercial council forestablishing Circular Economy system in all streams of PI.

4. To formulate an international alliance in PI to promote green productsthrough awards in the category of product manufacturer, purchaseand distributer, retailer, supporters and innovators in green supplychain to increase public participation.

BIBLIOGRAPHY

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[7] US-EPA, Presidential Green Chemistry Challenge Winners, https://www.epa.gov/greenchemistry/presidential-green-chemistry-challenge-winners.

[8] K.J. Shah, T. Imae, Photoinduced enzymatic conversion of CO2 gas to solar fuel on functional cellulose nanofiber films, J. Mater. Chem. A. 5 (2017) 9691–9701.

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[10] S.-Y. Pan, K.J. Shah, Y.-H. Chen, M.-H. Wang, P.-C. Chiang, Deployment of Accelerated Carbonation Using Alkaline Solid Wastes for Carbon Mineralization and Utilization Toward a Circular Economy, ACS Sustain. Chem. Eng. 5 (2017) 6429-6437.

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