I n d i a n I n s t i t u t e o f Te c h n o l o g y D e l h i

CHL 112 - Term Report

Petrochemicals from Shale Gas
Bhanu Mittal, Nimit Jain, Kartik Saraf
Keywords: ABSTRACT
Shale This report emphasizes the use of non-conventional source of natural gas, shale, to
Hydraulic Fracking produce a variety of petrochemicals. Shale gas is extracted using horizontal drilling
Cryogenic techniques called hydraulic fracturing (or fracking). The major contaminants H2S,
Natural Gas Liquids RSH, CO2 and water are removed using amine solution as a solvent. Different
(NGLs) petrochemicals like Methanol and Natural Gas Liquids(NGL) can be extracted from
shale gas using different processes. To extract NGL, four technologies, Lean Oil
Absorption Process, Mechanical Refrigeration, Cryogenic Turbo-expander and Iso-
Pressure Open Refrigeration Process (IPOR), are being analyzed. IPOR process is
found to be the best as typical gas recovery levels are highest. IPOR is also economical
than the Turbo-expander process which involves rotary machines and thus increasing
power consumption enormously.

INTRODUCTION Extraction of Shale Gas

In petroleum and petrochemical industry, more
than 2500 useful petroleum products are produced
from crude oil [1] and the annual worldwide
consumption of petroleum hydrocarbons is estimated
to be approximately 1012 US gallons [2]. But since the
availability of conventional fossil fuels is limited and
the demand of petrochemicals rise there is a need to
look at non-conventional sources for petrochemicals.
Shale gas is found trapped within shale formations
deep underground in earths crust (7000 ft. approx.).
Horizontal drilling techniques like hydraulic fracking
are used for extraction of shale gas.
Shale Gas primarily has methane as its major
component along with it also contains higher degree
hydrocarbons. It also contains acid gas impurities
namely H2S and CO2 along with COS and mercaptans
(RSH) which are removed by adsorption [3]. One of
the main chemicals that is produced from shale gas
is methanol. In this report conversion of methanol to
olefins is also explained, this technique will help to
cater the demands of the petrochemical industry as it
primarily produces propylene and ethylene.
As the shale gas also contains natural gas liquids
(NGLs) or higher degree hydrocarbons we can extract
these for further use. NGL extraction is mainly done
throgh cryogenic process.
The location of shale gas reservoirs renders the
conventional extraction techniques useless. We
therefore need to use a technique called Hydraulic
fracturing (or fracking) to extract the shale gas. In
hydraulic fracturing, a mixture of hydraulic fluid
with propping agents and additives is pumped at high
pressure into the well bore. The fracturing fluid is
90% water, 9% propping agent, and less than 1% of
functional additives containing pH adjusting agent,
biocides, clay stabilizer, scale and corrosion inhibitors,
gelling agent, friction reducer, surfactants etc.
This pressurized mixture causes the rock layer to
crack, pushing the earth apart so a fracture forms
and propagates to unlock the natural gas trapped in
the rocks allowing it to flow from the shale into the
well. Hydraulic fluid pressure creates fractures in the
reservoir and causes the fractures to grow. The fracking
operations utilizes between 2 to 4 million gallons of
water depending on the type of shale formation. After
drilling and fracturing of the well are completed, water
is produced along with the natural gas.
When the supply of fracking fluid is stopped the
cracks try to close again. This is prevented by propping
agents (generally sand) which do not allow the cracks
to close. [3]
Source: ProPublica http://www.propublica.org/special/hydraulicfracturingnational

Shale Gas Processing and Purification

The infrastructure requirement in the development the shale gas, it is sent to the NGL extraction unit that
of shale gas is generally similar to the conventional separates different hydrocarbons from the shale gas.
gas gathering and processing infrastructure. The The different products that are obtained are natural
main difference is in the type of gas contaminants, gas that can be used as fuel or to produce electricity.
constituents and substantial quantity of produced It can also be used for production of chemicals like
water returned back from the wells because of large methanol, ammonia or urea. The NGLs that are
quantity of water utilized in the hydraulic fracturing. recovered include ethane, propane, butane and light
The shale gas processing facility is generally a naphtha.
dedicated processing and separation facility that A detailed block diagram describing the processing
begins with the gas purification or removal of acid of shale gas is given on the next page.
gases (CO2, H2S and other organic sulfur compounds
such as COS, CS2 etc.) contained in the natural gas. If
large amount of sulfur contaminants are present, the
facility may require a sulfur recovery unit to recover
elemental sulfur from the off gas stream of this process.
Where the amount of sulfur is small, the off gases can
be either incinerated or vented from the process to the
atmosphere. [3]
The natural gas is processed further to remove
water and mercury from the gas prior to any heavier
hydrocarbon. Once the impurities are removed from
Purification of Shale Gas
This process removes H2S, CO2 and organic sulfurs
(such as mercaptan and COS) in the raw feed gas so
as to make it suitable for use in further downstream
processes. In the scrubber amine counter-currently
contacts the source gas inside the absorber column,
and the hazardous acid gas substances are absorbed
by amine for treatment. Since this is a wet process, the
dehydration process by molecular sieve is necessary at
a later stage [4].
The choice of amine concentration in the circulating
aqueous solution depends upon a number of factors
and may be quite arbitrary. It is usually made simply
on the basis of experience. The factors involved
include whether the amine unit is treating raw
natural gas or petroleum refinery by-product gases
PFD for Amine solvent based acid gas removal process
that contain relatively low concentrations of both
H2S and CO2 or whether the unit is treating gases
with a high percentage of CO2 such as the off gas
from the steam reforming process used in ammonia
production process. Both H2S and CO2 are acid gases
and hence corrosive to carbon steel. However, in an
amine treating unit, CO2 is the stronger acid of the
two. H2S forms a film of iron sulfide on the surface of
the steel that acts to protect the steel. When treating
gases with a high percentage of CO2, corrosion
inhibitors are often used and that permits the use
of higher concentrations of amine in the circulating
solution. Another factor involved in choosing an
amine concentration is the relative solubility of H2S
and CO2 in the selected amine. [3]
Petrochemicals from Shale Gas
1.Methanol
The annual production of methanol exceeds 40
million tons [5] and continues to grow by 4% per
year. Methanol has traditionally been used as feed for
production of a range of chemicals including acetic
acid and formaldehyde. In recent years methanol has
also been used for other markets such as production of
DME (Di-methyl-ether) and olefins by methanol-to-
olefins process (MTO) which will be discussed later.
The production of methanol from coal is increasing
in locations where natural gas is not available or
expensive such as in China. However, most methanol
is produced from natural gas. Several new plants have
been constructed in areas where natural gas is available
and cheap such as in the Middle East. Cheap natural
gas will remain the predominant feed for methanol
production for many years to come.
Oxygen and Shale gas enter a Partial Oxidation
Reactor and are converted to CO and H2 with H2 to
CO ratio around 1.8. Then they enter a VLE Separator
which removes any water present and bring the H2
to CO ratio around 2. Then a stream of steam is
introduced which reacts in a water-gas shift reactor
and fixes the ratio to exactly 2. Some CO2 is also
produced in this step. Then a gases again pass through
a VLE Separator which removes the unreacted steam.
Then a CO2 separator removes the CO2 present. The
feed now essentially consists of 2H2 + CO. Then these
gases are compressed and converted to methanol in a
MeOH reactor according to:
CO + 2H2 CH3OH
PFD for Methanol Production
The methanol and unreacted feed are separated in a
flash tank and are piped as required. A detailed PFD
[6] of the process is provided at the bottom.
2. Methanol to olefins
Worldwide, ethylene and propylene are mainly
produced by steam cracking of hydrocarbons such as
ethane, LPG or naphtha. Methanol to olefins (MTO)
is a new and innovative technology fro producing
olefins.
The MTO process utilizes a fluidized reactor and
regenerator system to convert methanol to olefins
using silicoaluminium phosphates (SAPO-34) as
catalyst. A fluidized bed reactor and regenerator
system is best suited for the process because it allows
for heat removal and continuous catalyst regeneration.
A detailed PFD is given on the next page. [7]
The methanol feed is preheated and then introduced
into the reactor. The reactor operates between 620 to
820 K and at pressures between 15 psig and 45 psig. The
reaction is exothermic so heat can be recovered from
the reaction. Coke accumulates on the catalyst and is
removed by combustion with air in the regenerator.
The reactor effluent is cooled to separate water, then
the product stream is compressed and unconverted
oxygenates are recycled back. Then the stream is
further processed in the fractionation and purification
section to separate key products namely ethylene and
propylene.
 PFD for MTO Process

3.NGL Extraction entering the absorber. The lean absorber oil trickles
The NGL extraction development has evolved over down over trays or packing while the gas flows upward
the last century from the lean oil absorption process counter current to the absorber oil. The gas leaves the
developed to extract butanes and heavier components top of the absorber while the absorber oil, now rich in
from the gas to mechanical refrigeration processes to light hydrocarbons from the gas, leaves the bottom of
extract propane and heavier components and finally the absorber. Rich oil flows to the rich oil de-ethanizer
the modern day cryogenic turbo-expander processes (or de-methanizer) to reject the methane and ethane
to extract ethane and heavier components from the (or the methane alone) as flash gas. Absorber oil then
natural gas. Then, there is the latest Iso-Pressure Open flows to a still where it is heated to a high enough
Refrigeration (IPOR) process which not only extracts temperature to drive the propanes, butanes, pentanes
hydrocarbons efficiently but also consumes lesser and other natural gas liquid components to the
energy than the turbo-expander. overhead.
This method was discontinued as it was very difficult
3.1 Lean Oil Absorption process to operate, difficult to predict its efficiency at removing
In this process, the inlet gas is cooled by a heat liquids from the gas as the lean oil deteriorates with
exchanger with the outlet gas and a cooler before time. Typical liquid recovery levels are: C3 = 80%, C4
= 90%, C5 = 98%. [8]
Methane Product
and Ethane Condenser Out
to fuel &
compression

Adsorber Rich oil

De-ethanizer Reflux
Pump

Still

Inlet
Gas

Cooler
Reboiler
Residue Gas

Cooler
Lean oil pump
PFD for Lean Oil Absorption Process
 Residue Gas
Gas-refrigerant
Exchanger
Cooler

Re-compressor

225 psig

-10 F Stabilizer

Feed Gas 975 psig

Gas Gas Cold
Gas chiller
Exchanger seperator
Reboiler

PFD for Mechanical Refrigeration C3 + product

3.2 Mechanical Refrigeration
In this process, Propane was used as the refrigerant,
with glycol injection used for hydrate inhibition and
dehydration. Feed gas for the refrigeration unit was
taken downstream of the feed-gas compression, with
residue gas sent directly to the sales gas pipeline.
Typical liquid recovery levels are: C3 = 33.1%, C4 =
60%, C5+ = 83.4%. [8]
Straight refrigeration units are economical, easy to
construct and reliable. However, with their operating
temperature typically limited to about 35 F, their
capability for NGL extraction is limited.
as low as 200 F, NGL product recoveries are quite
high. Typical liquid recovery levels are: C3 = 33.1%,
C4 = 60%, C5+ = 100%. This process is quite similar
to mechanical refrigeration except that it involves
the usage of a Turbo-expander. Turbo-expander is a
centrifugal or axial flow turbine through which a high
pressure gas is expanded to produce work that is often
used to drive a compressor. Because work is extracted
from the expanding high pressure gas, the expansion
is approximated by an isentropic process and the low
pressure exhaust gas from the turbine is at a very low
temperature, 150 C or less. [9]

3.3 Turbo expander process

For higher NGL recovery, Cryogenic Turbo-
expanders are used. With operating temperatures

PFD for Turbo expander Process

3.4 IsoPressure Open Refrigeration Process
The unique feature of IPOR process is its open-loop
ethane-rich mixed refrigeration cycle. The refrigerant
is extracted from the feed and is a mixture of ethane
with lower concentrations of methane, propane.
This refrigeration cycle serves a dual purpose:
Producing cryogenic temperatures to enable lower
temperature while at the same time providing a reflux
which produces high product extraction.
Feed gas, at a pressure typically 300-550 psig, is
initially cooled and partially condensed in the gas-gas
heat exchanger by cross exchange with cold residue
gas and propane refrigerant. The cooled and partially
condensed feed-gas stream is then fed to the middle
section of the de-ethanizer. Heat for the separation
is provided by the de-ethanizer reboiler stripping
section removes the lighter fractions 2-5% ethane in
the recovered propane. Reflux provides additional
cooling for the feed-gas stream and also selectively
absorbs the propane and heavier components from
the gas, thereby providing high product recovery
efficiencies. The cooled and partially condensed gas
stream flows to the de-ethanizer overhead separator.
The liquid from this separation, a mixture of methane,
Feed Sales
365 psig
-10 F
Gas-gas
exchanger
-42 F
De-ethanizer
reboiler
NGL
PFD for IPOR Process
ethane, and propane, is used as the refrigerant for the
open-loop mixed refrigerant cycle. The de-ethanizer
overhead separator therefore has a twofold function: It
acts as a conventional two-phase gas-liquid separator,
and it provides surge capacity for the liquid mixed
refrigerant system.
From the de-ethanizer overhead separator, the
pressure of the liquid mixed refrigerant is reduced,
100-200 psig. The mixed refrigerant stream is heated
further as it flows through the mixed refrigerant gas-
gas exchanger to the mixed refrigerant compressor.
The compressed ethane-rich, mixed refrigerant
stream is then cooled and partially condensed in
the mixed refrigerant gas-gas exchanger. Cooling
for this exchanger is provided by low-temperature
mixed refrigerant and propane. The two-phase stream
flows to the de-ethanizer reflux drum, a conventional
two-phase gas liquid separator. This liquid is used to
provide reflux to the de-ethanizer column, thereby
completing the open cycle of the mixed refrigerant
loop.
For the LPG-recovery configuration above, product
extraction efficiencies are excellent, with C3 recovery
in the range of 95-99%+, with essentially 100%
recovery of the C4+ fraction. [10]
Propane refrigerant 120 psig Mixed refrigerant
compressor compressor
410 psig
Mixed refrigerant
Gas-gas exchanger
Fuel
De-ethanizer
Overhead
condenser
De-ethanizer
Reflux drum
-75 F
De-ethanizer
Overhead
seperator
20 MMscfd IPOR process Refrigeration 100 MMscfd IPOR process Turbo-expander
Product recovery, %: Product recovery, %:
C3 99.0 33.1 C3 99.0 33.1
C4 100.0 60.0 C4+ 100.0 60.0
C5+ 100.0 83.4 Power (BHP)
Power (BHP) Inlet Compression 9,780 10,460
Inlet Compression 810 1,830 Residue Compression 7,060 11,930
Residue Compression 975 Refrigeration 4,730 1,910
Refrigeration 915 270 Pumps, air coolers 490 560
Total 2,700 2,100 Total 22,020 24,860
Table 1 Table 2
*MMscfd : Million standard cubic feet per day

Comparative Analysis (Energy and Output) hydrocarbon/cryogenic pumps, no stainless steel de-
Table 1 has a comparison between IPOR process methanizer column and less alloy material for the
and Mechanical Refrigeration process for a 20 construction of reactors.[8]
MMscfd feed. Although the total power consumption
of the IPOR process is more than Refrigeration 3.Conclusion
process (mainly due to compression power), but NGL Taking into consideration all the factors like ease of
production with the IPOR unit is more than double extraction, product recovery rate, power consumption
that of the refrigeration plant. and the criticality of the processes involved in NGL
Table 2 has a comparison between IPOR process and extraction we concluded that IPOR process is the best
Cryogenic Turbo-expander process for a 100 MMscfd available method. The main reasons being:-
feed. Here, both the factors, power consumption and 1. Achieves higher NGL recovery.
NGL recovery are better for the IPOR process. Power 2. Requires about 32% less process compression
consumption in Turbo-expander is more due to the power.
extensive involvement of rotary machinery in the 3. Requires about 20% less major equipment.
process. 4. Requires less rotating equipment.
5. Less Maintenance Cost
6. High reliability
Economic Analysis
1.Operating Costs References
The operating cost of the IPOR process estimates to 1. Y. Yavuz, A.S. Koparal, U .B. O gu tveren,
be about $150,000/year more than the refrigeration Treatment of petroleum refinery wastewater by
process. However, NGL production with the IPOR electrochemical methods, Desalination 258 (13)
unit is more than double that of the refrigeration (2010) 201205.
plant. The value of this additional NGL revenue 2. S.O. Rastegar, S.M. Mousavi, S.A. Shojaosadati,
was estimated at $5.1 million/year which more than S. Sheibani, Optimization of petroleum refinery
compensates the additional operating costs involved. effluent treatment in a UASB reactor using
The IPOR process was estimated to consume response surface methodology, Journal of
about $700,000/year less than the Turbo-expander Hazardous Materials 197 (2011) 2632.
in utilities, the savings resulting mainly from lower 3. SHAH, Kamal* IHI E & C International
compression power requirements, and hence lower Corporation, Houston, USA, Transformation of
fuel gas consumption. Energy, Technologies in Purification and End Use
of Shale Gas, Journal of the Combustion Society
2.Installation Costs of Japan Vol.55 No.171 (2013) 13-20
Estimated capital cost of the IPOR process 4. https://www.chiyoda-corp.com/technology/en/
design is $11 million less than that of the turbo- upstream_gasprocessing/acid_gas_removal_agr.
expander plant, the savings being the result of less html
installed compression, no turbo-expander, no light 5. Kim Aasberg-Petersen, Charlotte Stub Nielsen,
 Ib Dybkjr and Jens Perregaard, Large Scale 8. Robert R. Huebel, Michael G. Malsam, New NGL-
Methanol Production from Natural Gas, Haldor recovery process provides viable alternative, Oil &
Topsoe Gas Journal, September 2012
6. Victoria M. Ehlinger, Kerron J. Gabriel, Mohamed 9. Gas Processing with Cryogenic Turboexpander
M. B. Noureldin, and Mahmoud M. El-Halwagi, Technology, Randall Gas Technologies, Houston;
Process Design and Integration of Shale Gas to January 2011 Edition.
Methanol, ACS Sustainable Chem. Eng. 2014, 2, 10. Malsam, Michael G, IPOR TechnologyA
3037 new means of LPG recovery, Gas Processors
7. Gregory A. Funk, David Myers, and Bioin Vora, Association Annual Convention, High Definition
UOP, USA, Discuss New Technologhy for the at 90Advancing the Midstream Vision, March
Production of Ethylene and Propylene from 2011.
Methanol, Hydrocarbon Engineering, December
2013