Specalist Process Report For Purification of Chorosilanes
Specalist Process Report For Purification of Chorosilanes
Specalist Process Report For Purification of Chorosilanes
7093018090
15-08-2018
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Content
1. Abstract. 3
1. Natural Process.
2. Actual Process.
3. Specialist process.
4. CVD Reactors. 7
6. STC Converter. 7
9. Conclusion. 8
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A. Natural Process.
B. Actual Process.
C. Specialist process.
A. Natural Process: The purification train consists of fixed columns size, generally 1.5
meter diameter and 60 sieve tray columns arranged in order of TCS purification. The purity
will be in the range of solar grade i.e. 99.9999%(6N). All the condenser and reboiler sizes
will be same for all columns in the process. Critical task is to "Tune" columns, condensers
and reboilers to desire optimum purity, conditions and productivity. Process modelling
simulation software's like Aspen, Hysys, will be more helpful in tuning the process.
B. Actual Process: The purity will be in the range of electronic grade i.e. 99.9999999%(9N).
All the condenser and reboiler sizes will be vary depend on duty necessary to achieve desire
results(purity and yield). Simulation software "Aspen plus" is needed to get estimates of
Dimensions for columns, condensers and reboilers.
C. Specialist process: The purity will be in the range of electronic grade i.e.
99.99999999999%(13N). The purification train consists of variable columns size. All the
condenser and reboiler sizes will be vary depend on duty necessary to achieve desire results
(purity and yield). estimates of dimensions for columns, condensers and reboilers were scaled
up on previous process results.
The main benefit of Specialist process is that "It keeps the whole plant in running and
in single run it will try to flush the impurities out of the process without multiplication of
impurities and loss of major chlorosilanes. The utility will be running from minimum to
maximum condition". The main technique is you collect or Add trays in single column for
specific task (ex.TCS LB imp separation column) and develop the short roots to the column.
the column is called "Split column" it will have single condenser and reboiler (shown in the
excel file attached), it will have room for more trays and can handle "whole" process crude to
"minimum" crude.
In Natural and Actual process, the MG-Si is converted and purified and then added to
CVD and STC converter feed (from storage tank) as make up. so there is a possibility of
multiplying of impurities in the storage tank, purification trains or in the CVD & STC off-gas
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recovery units (Batch process). In specialist process, the Basics of designing the process is
that it "should collect all the hot gaseous product streams from FBR's,CVDs and STC
converters and should be capable of purifying the chlorosilanes to high purity without
accumulation in a continuous process. so you keep the whole process in a loop (prevent the
accumulation of impurities) and let the impurities exit from the process to quench.
optimization of process plays key role.
The purpose of valves is to direct the CVD & STC converter out let streams to off-gas
recovery units (using valve V2) or to main process where separation goes along with FBR
reactor exit (product) streams (using V3). Valve V4 is used to re-circulate DCS,TCS and STC
in case of process start-up or stop.
In specialist process, all the process operation parameters are controlled using control
systems. intermediate valves were used to direct chlorosilane flow to respective columns
based on the final TCS purity. design pressure, dimensions will be different for each
chlorosilane column. so we have to design all chlorosilane columns, condensers and
reboilers. the design can be based on mainly purity, Sylterm XLT for condensers and
Syltherm 800 for reboilers ( recommended). Optimization of process should be done in order
to reduce the cost of equipment and reduce operation cost. in order to increase residence time
and purity , more trays were added in chlorosilane columns (more than tray number in Actual
case), special type of tray design (like Bubble cap trays) were also considered and used in the
column. special type separation columns like spilt columns, packed columns were used in
purification of chlorosilane at downstream. utility management is crucial, because circulation
of Sylterm XLT for condensers and Syltherm 800 for reboilers should be in close loop no
makeup is required for a period of time. Close loop mass balance for DCS, TCS, STC should
be considered, so that concentration of DCS, TCS, STC in quench stream should be in the
range of 0.01%. Simulation of specialist process require more understanding, knowledge and
techniques to achieve desire target. the life time of Syltherm XLT & Syltherm 800 process is
bigger than that of actual process. Accumulation of impurities will be less than that of actual
process. In this process Purity, Efficiency, Yield and Performance is more than that of Actual
and Natural process. complete recovery of H2,HCl from vent steams will be observed.
Specialist process with Hydro-Chlorination FBR and CVD reactor study is under process
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Conversion of Metallic grade Silicon (MG-Silicon) to Solar grade polysilicon is carried out
by Chlorinating the MG-silicon to produce crude chlorosilane. the crude chlorosilane, which
contains DCS (SiH2Cl2), TCS (SiHCl3) ,STC (SiCl4) and chlorides and Hydrides of Metallic
impurities like Boron, Phosphorous, aluminium, iron, carbon is send to purification trains
where impurities are separated from DCS, TCS and STC. Highly pure TCS is send to CVD
reactor to decompose to from High purity Polysilicon. the by-product from the CVD reactor
is send to CVD Off Gas recovery unit, which separates H2, HCl and Chlorosilanes. By
products of TCS are DCS which is converted to TCS in Re-Distribution Reactor and STC
which is send to STC Converter along with H2. the unreacted by products is send to STC Off
Gas recovery Units, which separates H2, HCl and Chlorosilanes.
The fluid bed reactor (FBR) is designed to accommodate a reaction between milled MG-Si
and anhydrous HCl gas. This reaction produces TCS and H2. The products of the reaction are
fed directly into a cyclone to allow small solid particles to be recycled back to the FBR, while
the FBR reaction products are carried out of the top of the cyclone as vapours and fed to the
polysilanes column, after passing through a bag house filter to remove fine dust particulates.
The reactor bed is initially heated to 324oC using hot oil flowing through tubes contained in
the reactor. Once reactants are introduced, the reaction produces TCS and co-products
releasing heat generated by the highly exothermic chemical reaction. The temperature ranges
needed for optimum rates of reaction are between 304oC and 324oC. This optimum
temperature range is maintained within the reactor in a very precisely controlled manner. The
expected yield of the TCS reaction will be 82-89 % depending on how precisely the
temperature of the reaction is controlled. Also the yield is dependent on the degree of
uniformity of the milled MG-Si being fed to the FBR.
The purpose of the AlCl3 removal system is to remove a key proton acceptor, aluminium as
AlCl3. The purpose for the polysilanes column associated with each FBR is to remove
carbon, chlorinated trace metals, and polysilane impurities present after the reaction of the
raw MG-Si with HCl gas. The polysilanes and other metallic impurities are removed from the
column bottom as a liquid sludge and sent to the Quench Operation Unit .valve V3 will direct
the CVD & STC converter product streams to the AlCl3 removal column and mixed with
FBR out let feed stream.
The undistilled TCS product stream and hydrogen gas (H2) are removed as vapour from the
top of the polysilanes columns and sent to crude separation trains present. Hydrogen gas (H2),
HCl, formed as a result of the TCS reaction from FBR , CVD'S and STC converter, is
removed from the distilled vapour effluent coming from the top of the chlorosilane recovery
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column in each crude separation train. This H2 gas along with a small amount of HCl vapour
is sent either to the Chemical Recovery System.
Col-3 I-II: Col-3 is a split column ,receives impure chlorosilanes from pre-distillation column
,Col-2 A&B and also product from SiH2Cl2/SiCl4 Redistribution reactor , Off-Gas recovery
systems (Valve V2 is open) . Col-3 Separates STC from STC low boiling. the bottom of the
column is send to Col-8 I-II. and the distillate which contains DCS, TCS, STC Low boiling
impurities is send to Col-4 I-II.
Col-4 I-II: Col-4 receives DCS, TCS, STC Low boiling. The column separates DCS from
DCS high boiling. the bottom of the column is send to Col-5 I-II-III. the distillate is send to
Col-7,I-II.
Col-5 I-II-III: Col-5 receives TCS,TCS high & low boiling impurities from Col-4.The bottom
TCS high boiling impurities is send to quench. The distillate of the column which contains
TCS, TCS low boiling impurities is send to Col-6 I-II-III.
Col-6 I-II-III: Col-6 receives TCS, TCS low boiling impurities from Col-5. the distillate of
the column which contains TCS low boiling impurities is send to Quench. the bottom which
contains high purity TCS is send to column 9 packed column for further purification.
Col-7 I-II: Col-7 receives DCS, DCS low boiling impurities from Col-6.The distillate DCS
low boiling impurities is send to quench. The bottom of the column which contains DCS, is
send to DCS storage tank and used as feed to DCS/STC Re-distribution reactor.
Col-8 I-II: Col-8 receives STC, STC high boiling impurities from Col-3. the bottom of the
column which contains STC high boiling impurities is send to Quench. the distillate which
contains High Purity STC is send to storage tank and used as feed to DCS/STC Re-
distribution reactor and STC converter.
Col-9: Col-9 is a packed column which purifies TCS to maximum extent. The column
recycles 55% of TCS back to Col 5 to exit TCS LB and HB impurities.
Col-10: Col-10 is a packed column which receives H2,HCl feed from pre-distillation column
2 A & B. The column separates H2 from HCl. the Distillate H2 is send back to H2 storage and
bottom HCl is send back to HCl Tank.
DCS from DCS surge tank ,and STC from STC surge tank are being fed to DCS/STC
conversion reactors. In order to maximize the TCS conversion process a molar ratio of 4:1
(STC: DCS) is used to feed the reactors. The reaction is a couple reaction between DCS &
STC whereby,
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The conversion reaction is exothermic and the process uses DOWEX-M43 catalyst to
promote the reaction. The product from these reactors consists mainly of TCS. A small
amount of DCS along with unreacted STC and other impurities are also contained in the
stream, which is recycled back to chlorosilanes purification.
4.CVD Reactors:
The CVD Reactor is where the polysilicon rods are produced. The reactor is also referred to
as a Siemens type or Siemens Reactor. This is a specially designed vender provided reactor
which runs at high temperatures and pressures. It is a batch operation requiring several
reactors depending on the capacity of the plant. The reaction is a reduction process whereby
high purity TCS mixed with H2 gas is reduced to silicon and HCl. The silicon deposits onto
the electrically heated polysilicon seed or filament rods assembled inside the reactor. The
rods are grown while a program controls TCS / H2 flow rates and current flow rates through
the polysilicon rods. The batch continues for a specified period of time to produce the
required size rods. Reaction by-products include STC, DCS, and various chlorosilane
polymers. Unreacted TCS also vents off as a vapour stream from the reactor. The CVD
Reactor consists of a bell jar cylinder top, a base plate with inlet /outlet nozzles, rod holders,
and a power supply to send current to the rod holders for heating the polysilicon rods. The
bell jar and base plate are water cooled. Demineralised water is used to cool the rod holders
that are connected to the power supply to send current through the rods. The reactor vent gas
containing H2, unreacted TCS, DCS, STC, and HCl is vented to the water cooled CVD
Reactor Off Gas Cooler to cool the stream prior to sending vent gas to the CVD Reactor
Vent Gas Recovery System.
The purpose of this unit is to supply high purity hydrogen to the CVDs and to process the
reactor’s exhaust gas. The exhaust gas from the reactors mainly consist of H2, TCS, and HCl.
The vent gas also contains STC, DCS various chlorosilane polymers, silicon dust and
impurities. The STC, DCS and TCS, will be referred collectively as recovered TCS or simply
TCS for this unit. The unit includes processes to separate and recover the TCS and HCl. In
the last step of the process, impurities are removed from the H2 and the purified H2 is
recycled back to the CVDs. H2 compressors maintain the circulation loop.
6.STC Converter:
The overall process involves hydrogenating or converting STC with H2 gas at high
temperature and pressure to produce TCS and the by-product HCl. The conversion rate is
approximately 15% to 20% using a mole ratio of H2 to STC of ~3.3 at 750 oC and 5 bar(g).
The STC converter is similar to the CVD reactor in that it consists of a bell jar cylinder case
top, base plate, and is electrically heated. While the converter does contain graphite heater
rods that are heated, it does not contain the polysilicon seed rods as in the CVD reactors. The
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top cylinder and base plate are constructed of stainless steel and are water jacketed. The
cooling water temperatures are approximately 80 to 85°C. The vaporized STC and H2 gas are
mixed together at a specific ratio and rate. Then the STC is fed into the outer jacket of the
inlet nozzle at the bottom of the base plate. The reactor does require scheduled shutdowns for
heater rod replacement and inspections. A controlled flow of liquid STC is fed to the
vaporizer system, where it is converted to a gas by heating it with hot oil. The flow of the H2
gas is also controlled through a manifold in order to control the H2 to STC mole ratio in the
feed to the reactor. The H2 and STC gases are brought together in a mixing tube prior to the
reactor inlet nozzle. Both the STC and the H2 flows are fully automated and carefully
controlled using control valves and mass flow measurement. The electrodes are jacketed and
welded into the base plate. Demineralised water is used for cooling the electrodes. Water
temperature is approximately 30 to 40°C for inlet and outlet. The graphite heaters are
attached to the electrode heads. The hot gas mixture of H2, STC and TCS, leaves the reactor
through the centre of the jacketed bottom nozzle in the base plate. The gas then passes
through the STC Converter Off Gas Cooler, which uses cooling water to cool the gas stream,
prior to entering the STC Converter Reactor Vent Gas Recovery system, Cooling water
temperature is approximately 80 to 95°C.
The purpose of this unit is to supply H2 to the STC converters and to process the converter’s
exhaust gas. The exhaust gas from the converters, mainly consist of H2, STC, TCS, and HCl.
The vent gas also contains DCS and impurities. The TCS, STC and DCS will be referred
collectively as recovered STC or simply STC for this unit. The unit includes processes to
separate and recover the STC and HCl. The remaining stream containing mostly H2 is
recycled back to the converters. H2 compressors maintain the circulation loop.
8. Plant Vent Gas Recovery System: The purpose of the Plant Off-Gas Recovery System is
to collect all of the various process vents from the TCS production and purification. Vent
streams containing N2, H2, HCl and chlorosilanes are collected ,separated and send to storage
tanks.