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Syngas to Chemicals and Fuel - JM Technologies and Catalysts
2
syngas
DME
oxo
Gasoline / Diesel
methane
ammonia
methanol
polyolefins
2EH/butanol
2PH
MEG
FT
SNG
NH3
MTOBy others
MEG
C3=
C4=
formaldehyde
methanol
oxo
methylamines
Global Methanol Demand and Uses
3Source: MMSA Methanol and Derivatives Analysis (MDA)
Fuel, additives
Plastics
Wood resin
boards
Paints
Coal to Methanol
Entrained flow gasifiers preferred
• High exit temperature
• Low CH4 in syngas
Shift converts CO + H2O to H2 + CO2
Acid Gas Removal (AGR) removes excess CO2 and H2S
Most recent methanol projects in China use syngas produced from
low/medium ash coal
AGR MeOH
Unit
ShiftGasifierCoal
Oxygen CO2 & H2S Purge(Steam)
SMR
Optional
Natural
gas
Methanol
4
Typical syngas compositions
Syngas technology R ratio CO/CO2 % CH4
Steam Methane Reformer (SMR) 2.9 2 3
SMR+CO2 2.1 2 3
SMR+ Auto Thermal Reformer 2.1 3 1
SMR+ Gas Heated Reformer 2.1 2 1
Gasifier – coal1 2.05 10 0.5
Gasifier - biomass 2.05 5 5
• R ratio – Excess H2 R = ([H2]-[CO2])/([CO]+[CO2])
• CO/CO2 – Heat of reaction/ reactivity
• CH4 – Loop efficiency
1 Entrained flow gasifier
5
Tube Cooled
Converter (TCC)
Radial Steam Raising
Converter(R-SRC)
Axial Steam Raising Converter(A-SRC)
Methanol Synthesis – Reactor options
• Three Converter Types used for different applications• Reactor configuration is optimised for feedstock and plant capacity• Single reactor can produce 2000tpd (A-SRC) to 3000tpd (R-SRC)• Plant capacity >6500tpd in commercial operation
6
steam methane reforming
distillationmethanol synthesis methanolsynthesis
gas
JM Global Methanol Experience
JM’s technology and catalyst provides the world’s premier
process for production of methanol from syngas
• JM have for > 60 years supplied the methanol industry with leading technology and catalysts.
• Licensed into 92 Plants in 35 countries.
• 32% of all global methanol capacity is JM technology
• 66% of all plants >2000 MTPD operating or being built in P.R. China are JM technology
• >15 coal based projects ranging from 600kta to >2,000 kta since 2006
Shenhua Baotou: Coal to Chemical complex
• China’s drive into self sufficiency, utilise domestic feedstock and reduce dependency on imported oil for petrochemicals production
• First large scale coal to chemicals complex in China, produces polyethylene, polypropylene and oxo alcohol
• 3 million tons of coal converted to ~700kta chemical products
• JM designed 5500 tpd Methanol to Olefin (MTO) grade methanol
• Successful start-up in 2010 has led to >20 CTC complexes
8
FORMOX™
9
formaldehyde oxide process
formaldehyde reaction
methanol
formaldehydesystem
oxidation
• Used in over 160 plants in 36 countries
• Total sold capacity is >20MMTPA
• FORMOX is the world’s largest supplier of molybdenum oxide catalyst, used in ~70% of all oxide plants.
air
10
Monoethylene Glycol (MEG)
• MEG is the most widely used industrial diol with global consumption >26 million tpa
• MEG + PTA PET (polyester)
air MEG productformaldehyde
plantmethanol formaldehyde DEG co-product
MEG plant
CO H2
Methylamines and derivatives
11
ChClChCl
synthesis
HClethylene
oxide
NMPNMP
synthesis
GBL
ammonia
lights purge
amination
wastewater
MMA
DMA
TMA
recycle methanol, MMA, TMA
methanol
distillation DMFNMP
synthesis
Carbon
Monoxide
Downstream of the Methanol to Olefin (MTO) unit
The MTO unit produces a mixture of:
• Ethylene, used mainly for polyethylene
• Propylene, used mainly for polypropylene
• Mixed Butenes, recycled to increase conversion to propylene or used
as fuel
However higher value can be generated by converting the propylene
and/or the mixed butenes to alcohols via the LP OxoSM Alcohols process.
oxo
methanolpolyethylene & polypropylene
2EH/butanol
2PH
MTOBy others
C3=
C4=
oxo
Oxo Alcohols
13
n-butyraldehyde
iso + n-butyraldehyde
2-ethylhexanol
iso-butanol
n-butanol
propylene
syngasLP Oxo
SM
hydroformylation
hydrogen
hydrogen
hydrogenationaldolisation refining
refininghydrogenation
• LP Oxo Technology is a low pressure oxo process utilizing rhodium catalyst systems
• Licensed into 53 projects, at 41 plants in 15 countries.
2-Propylheptanol (2PH) – Value Creation
14
C4 streamraffinate III
syngas
2PH2PH plant
butene-1
CC4=
TC4=
IC4=
MTBE butene-1
MTBE & butene-1 unit
methanol
CC4=
TC4=
hydrogen
• 2PH is produced from essentially fuel value feedstock
• Above scheme operates on an integrated Coal to Chemical
facility in China
Dimethyl ether (DME)
Process
• Dehydration of methanol
Uses
• Fuel as LPG blend stock
• Aerosol as an alternative to
propane and butane
Global Market
• Fuel grade ~6 million tpa
• Aerosol grade ~500,000 tpa
Substitute Natural Gas (SNG)
16
Coal to syngas to SNG
• Large plants producing gas for pipeline export to major cities
• Mostly in China to meet environmental and energy security needs
SNG Plant in Inner Mongolia, 1.33 Billion Nm³/y
By others
Substitute Natural Gas (SNG)
17
JM licensed SNG plants produce >50% of global SNG production
JM has >100 years’ experience in methanation research and CRGTM
methanation catalyst is the world’s most widely-used for this application
LNGproduct
coal
COG
coke
SNGcokeoven
COGpurification
methanationliquefaction (optional )
Coke Oven Gas to LNG• Smaller plants extracting value from by-product gas streams
Petcoke to Refinery Fuel Gas• Upgrade low value coke via gasification and methanation• Large project for Reliance at Jamnagar under implementation
Gas-to-Liquids
18
naturalgas
naphtha
diesel
upgradingFischer Tropsch
conversion
or
reforming (compact reformer)
or
biomass
petcoke
coal
or
or
other syngas generation
Fixed-bed FT technology reforming (ATR, SMR, GHR)
• Fixed bed technology proven at commercial scale producing 300 bbl/day of synthetic crude
• Recent development has focused on new catalyst and reactor technology to improve performance and economics
Gas-to-Liquids - Reactor Improvement
Gas flows from CAN above passingdown a porous central channel.
Flows radially through the catalyst bed where reaction occurs and heats up by absorbing reaction heat
Gas exits via porous outer wall and flows to the top of the inner side of the CAN Body
Gas flows down a narrow annulus between the CAN Body and the inside wall of the tube where it cools by transferring heat to boiling water on the shellside
A seal prevents the gas bypassing the next CAN and the gas enters the CAN below to repeat the process.
Catalyst Carrier or “CAN” – How it works
19
Multiple CANS in tubes
Commercial Demonstration of Reactor Improvement
20
• Radial flow through each of multiple CANS in a large diameter tube delivers very low pressure drop even with small catalyst particles
• Allows the use of 300 - 500 micron catalyst particles in a fixed bed tube giving high productivity and improved selectivity
• Commercial scale demonstrated in a JM Mini Plant with Commercial size CAN’s and tube
• CAN unit operation sees same flows and conditions as in a commercial reactor
CANs Mini Plant
Together, adding value to chemical processes
22
Feedstock
Ammonia
GTL
Hydrogen
SNG
Formaldehyde
Fertilizers
Clean fuels
Adhesives
Construction
Shampoo
Natural gas
Syn
gas
Building blocks Intermediates End use products
Edible oils and other oleochemicals
Biorenewables
Detergents and soaps
Food
Biochemicals
Biomass and natural oils
Ole
o /
bio
Propylene
Butanediol
Films, fibres and bottles
Packaging
Films and cables
Engineering polymers
Natural gasliquids
Petroleum
Petr
och
em
icals
Mono ethylene glycol
Ethylene
Aromatics
Butane
Methanol
Natural detergent alcohols
PTA
Catalyst Licensing JM covered technology / products / service
Coal Vinyl chloride monomer
Oxo alcohols
Speciality
Agrochemicals & solvents
Methylamines
Nylon
Ethyl acetate
Hexanediol
Solvent
Acrylics
Nitric acid
UFC
MTO
Cu
sto
m c
ata
lyst
so
luti
on
s
Plastics