New Feedstock Approaches For The Chemical Industry

Tecnon OrbiChem Marketing Seminar at APIC 2019

Shaking the Tree – Alternative, Disruptive, Sustainable Solutions
Taipei, 16 May 2019

Dr. Charles Fryer

APIC 2019
REFINERIES ↔ CHEMICAL COMPANIES
If future production of base chemicals like ethylene and benzene will become
increasingly the province of refineries, chemical companies may need to seek new
feedstock approaches. Technologies such as:
• Use of synthesis gas as the raw material
• Carbon dioxide capture and utilisation (CCU)
• Electrolytic generation of hydrogen
• Use of biomaterials
• Metabolic conversion of biomass
• Regeneration of monomers or chemical feedstocks from plastics waste
will have to be examined and developed to maintain independence.

Source: Tecnon OrbiChem

APIC 2019
USE OF SYNGAS TO MAKE CHEMICALS
Make ammonia, and then fertilisers (urea, ammonium nitrate)
Make methanol, and then:
• Methanol-to-olefins (MTO)
• Methanol-to-propylene (MTP)
• To acetic acid
• To dimethyl ether
Make liquid fuels, plus olefins and alcohols, via Fischer-Tropsch
Separate out carbon monoxide, used to make, for example:
• Oxo alcohols
• Dimethyl carbonate
• Nickel tetracarbonyl
• Phosgene

Source: Tecnon OrbiChem

APIC 2019
SYNTHESIS GAS PRODUCTION
Natural gas consists mostly of methane, which is very un-reactive chemically. To make it
chemically useful, it is converted or ‘reformed’ to synthesis gas, a mixture of carbon
monoxide and hydrogen:
CH4 + ½O2 → CO + 2H2
Biomass or coal or plastics waste can be converted to synthesis gas for chemical use.
This is done by partial oxidation in a gasifier in the presence of steam:
2CH (biomass) + ½O2 + H2O → 2CO + 2H2
Biomass, coal or plastics waste can give rise to a synthesis gas of low hydrogen content,
in which case it can be subjected to a shift reaction to raise the proportion of hydrogen:
CO + H2O → CO2 + H2
Use of the shift reaction is the main method to produce hydrogen on-
purpose.
The CO2 from the last reaction is isolated and must be disposed of. In future this will
increasingly require sequestration and storage of this greenhouse gas. However, the shift
reaction can be operated in reverse:
CO2 + H2 → CO + H2O
This offers an opportunity for usage of carbon dioxide [CCU] rather than
storage [CCS], provided there are abundant supplies of hydrogen.
Source: Tecnon OrbiChem
APIC 2019
METHANOL PRODUCTION CAN BE A SINK FOR CO2

Natural
Gas

H2 Rich
Steam Syngas Methanol
De-sulphuriser Methanol
Reformer Synthesis

Steam CO2

This is the shift reaction in reverse.

It can be used to absorb CO2 from
other operations on site.

Source: Tecnon OrbiChem

APIC 2019
METHANOL: A TRANSPORT MEDIUM FOR CH4 & CO2
Natural gas, consisting mostly of methane, is often produced in remote locations. Such
‘stranded gas’ can be sourced from shale gas and tight oil, associated gas from oil
fields, and gas fields. To move it to market, it must be liquefied to LNG, and transported
in specialised vessels at minus 165 ºC. The logistics and storage costs are high.
An alternative is to convert the methane to methanol, via production of syngas. Since
methanol is a liquid at ambient temperature (b.p. 65 ºC), logistics costs are much lower.
At destination, methanol can be used as a transport fuel, or converted into chemicals:
• Formaldehyde
• Dimethyl Ether
• MTBE
• Acetic Acid
• Methanol-to-Propylene (MTP)
• Methanol-to-Olefins (MTO)
Note It may be possible to produce methanol directly from methane. Preheated methane is reacted
with oxygen to produce a mixture of methanol and formaldehyde. [See US Patent
8293186B2; US Patent 9180426B2

There is much debate and experimentation on using methanol production as a sink for
carbon dioxide where it is produced (for example at a steel works), taking electrolytic
hydrogen made from renewable electricity and using the reverse shift reaction. The
methanol can then be shipped to destinations for use as fuel or as a chemical feedstock.
Source: Tecnon OrbiChem
APIC 2019
METHANE TO METHANOL TO ACETIC ACID

Oxygen Acetic
Acid
Hydrogen

Carbon
Monoxide
Hydrocarbon Unit
Methane

Distillation Column
CO

Crude
Syngas Methanol Carbonylation
Unit Synthesis Reactor Acetic
Acid

Steam
Remote Site Industrial Park Rejects

China imported 7.4 million tons of methanol in 2018, mostly for chemical use.

Source: Tecnon OrbiChem

APIC 2019
CAN HYDROGEN BECOME A TRANSPORT MEDIUM
FOR ENERGY AND CHEMICALS USE?
Hydrogen is widely used in refineries and chemical plants. World sources of hydrogen are:
A. 48% from steam reforming of methane (SMR)
B. 30% from light hydrocarbon cracking and reforming
C. 18% from coal (mostly in China)
D. >4% from electrolysis, mostly in production of caustic soda.
E.and C. involve direct production of large volumes of carbon dioxide.
B. and D. involve production of carbon dioxide in steam generators/power plants.
Production of carbon-neutral hydrogen requires the use of either:
• SMR together with Carbon Capture & Usage or Storage (CCUS)
• Electrolysis using electricity from renewable sources
Trials are starting using electrolysis with “green” electricity.
Example: Nouryon and Gasunie project to use sustainable electricity in a 20 MW water
electrolysis unit at Delfzijl to make hydrogen, supplied to methanol producer BioMCN which
combines it with CO2.

Source: Tecnon OrbiChem

APIC 2019
WHY SHOULD TRANSPORT OF HYDROGEN BE
NECESSARY?
Renewable electrical energy has a vital role in replacing power generated from
fossil fuels, so as to reduce carbon emissions.
The problem with renewable power is that it can fail to be generated at times
when needed (when the wind does not blow and the sun does not shine), and
conversely it can be over-produced at other times. It is necessary to accompany
renewable power plants with storage facilities. Possibilities are:
A. Storage batteries -- practical but very expensive at present, though costs will
surely decrease in future
B. Water reservoirs -- have long been in use, but using land for water storage is
becoming increasingly controversial
C. Generate hydrogen electrolytically -- it can be stored, used when required to
generate power, and transported, allowing use in remote locations. But costs
of compression or liquefaction are high.

Source: Tecnon OrbiChem

APIC 2019
WORLD ELECTRICAL POWER GENERATION BY SOURCE
FUEL SHARES IN POWER GENERATION (%) RENEWABLES SHARE OF POWER
50 GENERATION BY SOURCE (%)
40
Coal

40
30

30 20

Gas 10
20

0
10 2000 2010 2020 2030 2040

Geothermal & Biomass

0 Solar Wind
2000 2010 2020 2030 2040

Source: BP Energy Outlook 2019

APIC 2019
HYDROGEN PRODUCTION COST – SCENARIO 2040
$ per Kg H2 $ per Kg H2 (2017 $)

4 4

3 3
CCS

2 2

1 1

0 0
SMR SMR + CCS Electrolyser off-grid Liquid H2 via MCH via Ammonia

Shipping Cost Deep Sea

Capital cost Fuel Conversion

Operating cost Electricity Shipping Dehydrogenation

Source: International Energy Agency

APIC 2019
MOVING HYDROGEN TO MARKET
Transport

Electrolysis Liquefaction Regasification

Fuel cells
using e.g. in
renewable automobiles
electricity
Dehydrogenation
hydrogen Hydrogenation of Chemical
of methyl
toluene to MCH feedstock
cyclohexane MCH

Power
Reforming of generation
methane or Dehydrogenation
other fossil Ammonia
fuel production via
Haber- Bosch
Use Directly Fuel cell

CO2 Chemical
feedstock

Combustion

CCUS

Source: Tecnon OrbiChem

APIC 2019
WHAT CAN HYDROGEN IN BULK BE USED FOR?

To make chemicals, such as:

• 1,4 - Butanediol
• Caprolactam
• Cyclohexane
• Hydrogen peroxide
• Hydroxylamine
• Tetrahydrofuran

Extensive use in refineries, for desulphurisation, hydrotreating, hydrocracking

As an energy carrier
For decarbonisation
For automobiles and other transport via on-board fuel cells
For addition to natural gas distribution networks
For storage of surplus power generation

Source: Tecnon OrbiChem

APIC 2019
HYDROGEN AND CARBON DIOXIDE

Carbon Capture and Usage (CCU) is a process that is one of the hopes for
reducing climate change. There are many schemes for capturing and using
carbon dioxide, with hydrogen involved in two possible ways:
1. The reverse shift reaction:
CO2 + H2 → CO + H2O
Carbon monoxide (CO) can then be used in various chemical processes.
2. The Sabatier process:
CO2 + 4H2 → CH4 + 2H2O
This produces methane (so is the reverse of SMR process), which can then be
introduced into the natural gas distribution grid.

Source: Tecnon OrbiChem

APIC 2019
THE HYDROGEN ECONOMY

There has been much talk of ‘the hydrogen economy’, in which many of our
energy sources, like the gas in our kitchens and the gasoline in our cars, will be
replaced with hydrogen. This would certainly make a massive contribution to
combatting climate change, provided the hydrogen has been made without
generation of carbon dioxide.
Some of this future gazing has been over-blown. Storage of hydrogen is not easy
(especially in cars) and transport and distribution are expensive. But use in
transport may be viable where pollution reduction is critical.
By end 2017 there were 328 hydrogen fuel stations in the world, of which 139
in Europe, 118 in Asia and 68 in North America.
Hydrogen fuel cell buses were introduced in Shanghai in September 2018 and it
is planned to have 3,000 in operation by 2020.
This is an opportunity for the chemical industry to be a provider of carbon-neutral
hydrogen supplies, and also a creator of carbon-negative products and fuels.

Source: Tecnon OrbiChem

www.orbichem.com