US 20120114546A1

(19) United States

(12) Patent Application Publication

(10) Pub. No.: US 2012/0114546 A1

Chee et al.
(54)

HYBRID TCS-SIEMENS PROCESS EQUIPPED

WITH TURBO CHARGER FBR; METHOD

(51) Int Cl

0F SAVING ELECTRICITY AND

(22)

Filed:

(57)

vided to save electricity and initial investment cost from TCS

synthesizing process and silicon tetrachloride to TCS con

verting process in a TCS-Siemens polysilicon plant, Whose
siZe is over 10,000 MT/Y R of polysilicon. The hybrid TCS
Siemens process of the current application is equipped With
one direct chlorination FBR (FluidiZed Bed Reactor) and one
hydro-chlorination FBR. Three different TCS-Siemens pro
hybrid TCS-Siemens process saves at least 78,000,000KWhr/
year of electricity from TCS generation only from a 10,000

MT/Y R polysilicon plant When compared With a Closed

Loop TCS-Siemens Process, Which is equipped With only
high-pressure, high-temperature operating hydro-chlorina

Division of application No. 12/ 802,320, ?led on Jun. 4,

2010.

ABSTRACT

A hybrid TCS (Trichlorosilane)-Siemens process is pro

cesses are compared based on mass balance calculation. The

Oct. 6, 2011

Related US. Application Data

(62)

(200601)

(52) US. Cl. ....................................... .. 423/349; 422/141

Yong Chee, Beverly Hills, CA

(US); Tetsunori Kunimune,
LaCanada, CA (US)

Appl. No.: 13/200,989

(200601)

B01] 8/26

PROCESS POLYSILICON PLANTS 0F

CAPACITY OVER 10 000 MT/YR

(21)

Publication Classi?cation

C023 3/027

EQUIPMENT COST FROM TCS-SIEMENS

(76) Inventors:

May 10, 2012

(43) Pub. Date:

tion FBRs.

TCS= so

TCS= 47 I

4-6

MGSi=11

Si = 1

4-2
TCS = 420

HCL=42

'

STC

= 2.6

TCS=294

TCS=126
TCS

TCS =294
STC = 94.5

STC=166

43

4-1

1 STC =e3.5
FOR SILICA

STC

Patent Application Publication

May 10, 2012 Sheet 1 0f 10

US 2012/0114546 A1

1507,
7-503, 75-12,
7711261
4, 775268

TE-09

TE-IU

430
TIE
26C

250

260
320

TE-26D

371]

270

280
330

380

290
340
3

300
350

310
360

420

Minutes

Fig
. 1

Patent Application Publication

May 10, 2012 Sheet 2 0f 10

US 2012/0114546 A1
TE26B,
7526
C)
TE26D

72429

330

320

310

300

290

300

7212

270

20:35.31

350

20:36:14 20:36:58 20:37:41

20:38.24 203907
340

\775427,
15418,
TIE-26A,

20.13%50

Fig. 2

Patent Application Publication

May 10, 2012 Sheet 3 0f 10

US 2012/0114546 A1
25

20

Deg C
15
HCI. CUT\

MGSI

HCLCUT\

250.11)

35

30 I

MQIICHARGER;

L
27000

290.00

310.00

330.00
Minulm

Fig.
3

350.00

37000

39000

Patent Application Publication

May 10, 2012 Sheet 4 0f 10

US 2012/0114546 A1

STC = 29

TCS=294

TCS=132

TCS

1-4

STC

TCS=44 A

TCS= 44

CS= 470

Si = 1

STC = 29

1-6

1-2
TCS = 426

Fig.4

TCS =294 STC=166

STC = 166

1-3

Patent Application Publication

May 10, 2012 Sheet 5 0f 10

US 2012/0114546 A1
20-U

28

Fig.
5

Patent Application Publication

May 10, 2012 Sheet 6 0f 10

US 2012/0114546 A1

000o000

000

0000 0000

0O
O
O
O

0
0
0
0

0000.1Q

000000

000000000

000

00004

0000000000o

00000000000000000000000

0000000

00000000

000000 000000

00000

000 000

Fi
g.
6

Patent Application Publication

May 10, 2012 Sheet 7 0f 10

US 2012/0114546 A1

ST; = 2.3
TCS=132
TCS
=294 $TC=166

TCS

2-5

TCS= 44TCS= 47 Si

2-6

STC = 166

23

24

= 1

2-2

TCS = 416

Fig. 7

TCS=294

Patent Application Publication

May 10, 2012 Sheet 8 0f 10

US 2012/0114546 A1
STC = 767

TCS=294
STC=166
TCS
=
294

Si=11

TCS=176
3-1

STC = 624

TCS=176

TCS=47

3-5
TCS
=
294

Fig
. 8

Patent Application Publication

May 10, 2012 Sheet 9 0f 10

US 2012/0114546 A1

STC = 2.6

TCS=

STC=

TCS=126
TCS

TCS =294
sTg = 94.5

4-1

4-4

1 s

TCS= 5o

TCS= 47

'

Si

STC

= 1

4-6

42
TCS = 420

Fig. 9

Patent Application Publication

TCS = 50

TCS= 50

CS= 470

May 10, 2012 Sheet 10 0f 10

Si = 1

STC = 33.3

5-6

5-2

TCS = 420

*--~ STC = 33.3

TCS=126

TCS

51

TC$=294

TCS =294 STC=166

STC = 94.5

56

5-1
STC = 63.5

FOR SILICA
STC

Fig. 10

US 2012/0114546 A1

Ma
y
10
,
20
12

US 2012/0114546 A1
MT/YR

DESCRIPTION
OF PRIOR
ARTS

HYBRID TCS-SIEMENS PROCESS EQUIPPED

WITH TURBO CHARGER FBR; METHOD

[0004] US. Pat. No. 2,943,918

OF SAVING ELECTRICITY AND

to G. Paul, et al. illustrates

EQUIPMENT COST FROM TC S-SIEMENS

a laboratory scale method of

PROCESS POLYSILICON PLANTS OF

CAPACITY OVER 10,000 MT/YR

producing

TCS

lane)

by

contacting

(Trichlorosi

directly

HCL

With

MGSI

(Metallurgical

[0001] Current application is a divisional application of the US.

Grade

patent application Ser. No. 12/802,320 ?led on Jun. 4,

2010.

FBR

Reactor)

from

and

Bed

depositing

polysilicon

quartZ

FIELD OF THE INVENTION

Silicon)

(FluidiZed
tube

after

in

separating

TCS

[0002] Current application relates to a method of and STC (Silicon

saving electricity and equipment investment from a Tetra Chloride).
polysilicon plants, especially relates to plants [0005] US. Pat. No. 3,148,035

Which produce polysilicon using TCS in Siemensto E. Enk,

method of
type CVD (Chemical Vapor Deposi tion) reactors.

et al. illustrates a
generating

TCS

by

direct chlorination of HCl in a

BACKGROUNDS OF THE INVENTION

[0003]

Traditional

TCS-Siemens

process

is

heat of reaction. They

also found that as the
reaction tempera ture
goes up, the amount of
TCS generated decreases
and the amount of STC
increases.

[0006]
US.
Pat.
No.
3,704,104 to M. S. BaWa,
et al. illus trates an
operation condition of FBR
for maximum produc tion

of
TCS
by
direct
chlorination
of
MGSI.
Dilution of HCl gas With

nitrogen is suggested.
[0007]

US.

4,044,109

Pat.
to

KotZsch,

No.

H.

J.

et

illustrates

increasing

TCS

al.

method

of

production

by direct chlorination of

polysilicon

MGSI

in

continuously

producing process Which is equipped With thermal con verter

operating FBR. They co-fed

direct

iron chloride to control the

to

convert

STC

from

the

CVD

reactors

into

TCS

and

chlorination FBR for TCS generation. Later, a closed loop

exothermal

hydro chlorination TCS-Siemens process is introduced.

reaction.

heat

of

the

That process is equipped With a huge hydro chlorination FBR

[0008]

(FluidiZed Bed Reactor) for TCS generation and STC con version

4,213,937

in the same reactor. Hybrid TCS-Siemens process,

al. illustrates a commercial

Which is suggested in the current application, is equipped

scale polysilicon plant design.

With a small direct chlorination FBR for TCS generation and a

TCS Was pro duced from a FBR by

small hydro chlorination reactor for converting STC from

direct

CVD reactors to TCS. The traditional TCS-Siemens process has been

TCS Was introduced a FBR for

proved

granular

as

successful

commercial

polysilicon

pro

cess

for

decades. HoWever, since 2007, it is knoWn to the industry that it

US.

Pat.

No.

to

Padovani,

et

chlorination

of

MGSI.

deposition

of

polysilicon.

consumes huge amount of electricity to con vert STC to TCS. After

[0009]

that, hydro chlorination FBR, in

4,585,643 to T. H Baker Jr.

US.

Pat.

Which STC is converted to TCS by hydrogenation in the presence

illustrates

of

maximizing TCS production by

MGSI

(Metallurgical

Grade

Silicon),

is

asked

by

many

customers Who Want plant siZe smaller than 5,000

MT/YR

polisilicon.

But,

after

2011

many

bigAsian

chemical

No.

method

direct

chlorina

MGSI

from

tion
FBR

of

of
by

companies announced to build polysilicon plants of produc tion

intermediately

capacity over 10,000 MT/YR to take advantage of scale merit of the

oxygen gas to the FBR during

polysilicon plant. HoWever, the closed loop hydro chlorination

continuous operation.

process

has

limit

in

scale

up

due

to

its

inherent

problem

of

generating tWo times of STC than TCS at the same time. For, 10,000
MT/Y

polysilicon

plant,

the

amount

of

STC

recycling

in

the

[0010] US.
Application
No.

injecting

Patent
Publication

process is 800,000 MT/Y R.

20100264362

Recycling the huge amount of STC costs more operation cost and

al.

by

equipment investment. It is purpose of the current appli cation to

of

provide an economical process to save electricity and equipment cost in

bed temperature in a FBR,

a polysilicon plant of siZe over 10,000

Wherein

illustrates
control

CHEE,
a

ling
direct

et

method

?uidized
chlo

rination occurs, Within a temperature deviation of 11 C. at [0016]

ment.

reaction temperature of 350 C.

tWo stage process Which com

US.
Pat.
No.
4,676,967 to William C.
[0011] Investor Relation Book issued by Hankook Silicon Breneman
illustrates
disclosed that their commercial FBR built by the applica process
of
generating
tions description, under contract, produces crude TCSTCS plus STC from FBR

The equipment

bines
silicon

the

is for

reaction

of

tetrachloride

and

hydrogen

silicon

With

loWer

illus trates hydrogenation of STC in the presence of chlorosilane products are

It generates much more TCS

MGSI at reaction temperature of 310 to 350 C.

changed

into

[0014] US. Pat. No. 2,499,009 to G. H. Wagner illustratesintroduced

into

silane
a

FBR

portion

of

in

operating at temperature
[0012] US. Pat. No. 2,406,605 to Schenectady illustrates range of 400 to 600 C.
hydrogenation of STC in the presence aluminum granules at
and pressure range of 300
to 600 psi.
400 C.
All
the
[0013] US. Pat. No. 2,458,703 to David B. Hatcher [0017]

from the FBR of 95% purity at 5 bar and 300 C.

equipment.

Reaction

hydro

chloride

gen

the
of
With

silicon occurs in the upper

portion

of

the

equipment.

and

than single hydro genation

for

of STC.

hydrogenation of STC in the presence of MGSI at reaction

granular deposition of poly

[0019] Masahito Sugiura, et al.

temperature of 310 to 350 C. catalyZed by copper com

silicon. It does not need to

illustrates

pounds.

convert STC.

tion that changes STC into TCS

US.
[0015] US. Pat. No. 2,595,620 to G. H. Wagner, et al. [0018]
4,526,769
to
illustrates hydrogenation of STC in the presence of MGSI at

Pat.
William

bench scale FBR and the method of

controlling

trichloro-silane

exothermal

and

actual

reac

No.

is not a single step reaction

M.

suggested by Breneman in the

various temperatures, pressure and retention time of STC inIngle, et al. illustrates a
for
producing
the reactor. Yield of TCS is less than 20% and the yield process
increased as the retention time increases.

that

equip

US. Pat. No. 4,676,967.

Instead, it is series/parallel
reaction of gas phase hydrogena

tion of STC combined With direct

chlorination of MGSI.

Ma
y
10
,
20
12

US 2012/0114546 A1
KWhr

per

year

from

TCS

generation only in a 10,000

MTA

polysilicon

compared

Union Carbide has commercialized a bubbling bed mode

FBR

for

producing

polyethylene

and

polyole?ns

of

polypropylene

high

and

capacity

density built

With

plant
a

polysilicon

same
plant

by Closed Loop TCS-

the Siemens Process. Com pared

licensed

With traditional TCS-Siemens

technology through out the World since 1980.

[0020] GT Solar, a US. company, announced a feasibility study Process, the Hybrid

TCS-Siemens

report comparing old direct chlorination TCS-Siemens

Process

and

their

Closed

Loop

Process

chlorination saves 220,000,000 KWhr

Hydro

from 10,000
R polysilicon
of the plant Which can be MT/Y
7,000 MTA. But, even that plant.

process Working at high temperature, high pres sure. In per year

the article, the maximum siZe
built by their tech nology is

number is for simulation, not a designed capacity.

BRIEF
DESCRIPTION
OF DRAWINGS

[0021] HoWever, none of the prior arts illustrates a hybrid TCSSiemens

process

to

reduce

energy

consumption

equipment

and

investment for a polysilicon plant built by TCS

Siemens process of annual production

[0023]
capacity over 10,000 metric tons.

FIG. 1 is a
temperature pro?le inside
of a FBR

SUMMARY OF THE INVENTION

[0022] The traditional TCS-Siemens process has been proved as

(FluidiZed Bed Reactor)

operating direct
chlorination of

MGSI only With MGSI and

successful
commercial
polysilicon
process
for
decades. HCl along the reaction
HoWever, since 2007, it is knoWn to the industry that it time.
consumes huge amount of electricity to convert STC to

TCS. After that, hydro chlorination FBR, in Which STC is

converted to TCS by hydrogenation in the presence of MGSI

(Metallurgical Grade Silicon), is asked by many customers

Who Want plant siZe smaller than 5,000 MT/Y R polisilicon.
But, after 2011 many big Asian chemical companies announced to

build polysilicon plants of production capacity over 10,000 MT/Y

R

to

take

advantage

of

scale

merit

of

the

polysilicon

plant.

[0024] FIG. 2 is a temperature

pro?le

inside

of

operating

FBR

direct

chlorination

of

MGSI

With

turbo charger,
Which is inert charging
material, along the reaction
time.
[0025]

FIG.

average
deviations
uidiZing

is

mean

temperature
inside

bed

for

of
the

?
MGSI

only direct chlorination and

in

the

presence

of

turbo

charger along the reaction

time.
[0026] FIG. 4 is a schematic
block diagram of old direct

chlorination

FBR

equipped

TCS-Siemens

process

shoWing

TCS and STC mass

How in case of
10,000 MT/YR
polysili con plant.
[0027] FIG. 5 is a FBR
for
direct
chlorination of MGSI
in the presence of

turbo charger.
[0028] FIG. 6 is an elevated
vieW of a gas distributorused
in

the

FBR

in scale up due to its inherent problem of generating tWo times of STC

presence of

than TCS at the same time.

turbo charger.

10,000

MT/Y

polysilicon

plant,

the

amount

of

STC

recycling in the process is 800,000 MT/YR. Recycling the huge

amount of STC costs more operation cost and equip ment investment.
It is purpose of the current application to provide an economical
process to save electricity and equip ment cost in a polysilicon
plant of siZe over 10,000 MT/Y R.

method

of

saving

electricity

and

investment

cost

from

processes for TCS (Trichlorosilane) synthesis and regenera

tion of STC (Silicon Tetra Chloride) of a TCS-Siemens pro cess for
polysilicon

plants

siZe

over

10,000

MT/YR

is

pro

vided.

Three

different TCS-Siemens processes of 1) a traditional TCS-Siemens

Process, 2) a closed loop hydro chlorination Siemens Process,

and 3) a hybrid TCS-Siemens process are compared based on mass balance
calculation.

hybrid

TCS-Siemens

equipped

With

direct

chlorination FBR (FluidiZed Bed Reactor), Which is disclosed in the

US.

Patent

Application

Publication

No.

20100264362

of

applicants of current invention, saves at least 78,000,000

the

MGSI

direct

chlorination

For,

of

for

HoWever, the closed loop hydro chlorina tion process has limit

in

the

[0029] FIG. 7 is a
schematic block diagram of
Turbo
Charger direct
chlorination FBR equipped
TCS-Siemens
process shoWing TCS and
STC mass How in a 10,000
MT/Y R

polysilicon
plant.

[0030] FIG. 8 is a
schematic block diagram of
Closed
Loop Hydro chlorination
FBR equipped TCS-Siemens
pro
cess shoWing TCS and STC
mass How in a 10,000 MT/Y
R

polysilicon

direct

plant.

[0031] FIG. 9 is a schematic block diagram of Turbo

Charger direct chlorination FBR equipped Hybrid TCS
Siemens process shoWing TCS and STC mass in a 10,000

MT/Y R polysilicon plant.

[0032] FIG. 10 is a schematic block diagram of old direct

chlorination FBR equipped Hybrid TCS-Siemens process

shoWing TCS and STC mass in a 10,000 MT/YR polysilicon

plant.

chlorination

running

With

old

should

TE-26A

indicate

doWn

to

at

continuous

to

TE-26D

temperature
corners

readings

of

plate,

gas

Which

four

distribution

placed

at

the

bottom of the FBR. From Lines

TE-07

to

TE-11,

the

number

means temperature reading from

locates

ver

tically aWay from the bottom of

the

FBR

With

interval

of

distance equivalent to internal

[0033] In spite of many technologies of direct chlorination diameter

of MGSI to generate TCS, none of them Was reported as

FBR

chlorination

thermocouples

DETAILED DESCRIPTION OF PREFERRED

EMBODIMENT

method,

along the reaction time. Lines

of

loWer

section

of

stable enough to the FBR. FIG. 1 clearly shoWs

every

2
TCS

direct

be

shut

months.

For

production,

at

least

tWo FBRs of the old types

are recommended for
continuous

operation.
[0035] FIG. 2 is a temperature
pro?le

inside

of

operating
chlorination

FBR

direct
of

MGSI

With

turbo charger,
Which is inert charging
material, along the reaction
time. The

produce high purity crude TCS from the

that temperature pro?les in old

FBR used. The applicant has disclosed the reason of such

direct chlorination method are

turbo charger is a material that

very irregular, unstable. Most

does not react With HCl and other

instability in a previous US. patent application

of
Ser. No. 12/802,320, Which is noW published as
application publica tion NO. 20100264362.

of

all,
the

temperature
?uidiZing

[0034] FIG. 1 is a temperature pro?le inside of a FBR operating steadily

increased.

direct chlorination of MGSI only With MGSI and HCl, like an old of

steady

such

increase the,

inside

chlorosilanes, Which are produced

bed

at the reaction con dition. The

Because

temperature

turbo

charger

is,

but not limited to,

including

Ma
y
10
,
20
12

US 2012/0114546 A1

uidiZing bed is hotter than the

other points. If that point is
much

hotter

than

the

average

bed temperature, it is called

hot spot. In this hot spot

non-porous silica powder or porous silica powder, such as

Grace

Davison

952,

quartz

powder,

glass

Zirconium the reaction is different from

beads,

powder, sand, diamond powder, ruby powder, gold powder,

silver

powder,

sapphire

powder,

garnet

powder,

opal

powder, any kind of gemstone powder, and powder of salt of metal,

including but not limited to oxide and halides of metals, except
iron

compound.

The

turbo

charger

should

have

contents at least 0.1 wt %. Particle siZe, true

elemental

SiO2

density, and bulk

density of the turbo charger material is equivalent to that of

the metallurgical silicon as shown in the

Table 1.

the

such

100~150

Bulk Density (gcc)

0.98~1.02

True Density (g/cc)

1.98~2.01

S102 content (wt %)

[0038] But, the temperature

of

the

at

the

chlorina

tion

of

plug

the

turbo charger is very uniform

viscous

and
of

holes

of

reside

FBR
gas

to

distribution

number

means

distance

>0.1

temperature

equivalent

to

reading

from

internal

diameter

of

and

do

not

temperature

thermo
lower

change along the

Turbo Charger direct chlorination method, stable produc

average temperature deviations inside of ?uidiZing bed for
the MGSI only direct chlorination and in the presence of
turbo charger along the reaction time. Two different curves
deviations,

from

six

different

locations, inside of ?uidiZing bed of the FBR along the reac

11 C. at about 350 C., the

target

temperature.

and

the

bed

[0039]

built

applicants,
produces
built

marked

at

each

location, among six locations, inside of the ?uidiZing bed and

the average of the temperature at the six locations. As shown in
the FIG. 3, the temperature inside of the ?uidiZing bed of the old
direct chlorination method, packed the FBR with MGSI only, is very
unstable and not uniform. This means that some point in the ?

the

U.S.

patent

Before

the

of

the

applicants

turbo

charger

direct

chlorination FBR, all the

direct
FBR
the

addition

temperature

in

[0040]

charger.
between

design

the

development

every

deviations

to

crude

Ser. No. 12/802,320,

at
much
lower
pressure
and
temperature compared
to other methods.

reaction

the

reported

application

when MGSI reacts with HCl in the presence of the turbo

averaging

is

with

purity

applicants

line shows the temperature deviation

[0037] The mean average temperature deviation was calcu lated by

is

95%
by

control

CHARGER

contract

disclosed

direct

MGSI/

direct

which

TCS from the FBR, which is

rination

the

FBR,

under

previous

and

According

commercial

chlorination

temperature deviation when MGSI and HCl react accord ing to old

method

is

controlled within

tion time laps are recorded. The MGSI marked line shows the

chlorination

bed.

TCS from the FBR

reaches over 95%.

happens

tion of high purity crude TCS is possible. FIG. 3 is mean

temperature

?uidiZing

temperature

3,148,035, selectivity of crude

reaction time. Due to such advantages of the

average

gas,

un-plugged

the

and channeling of the bed

the gas distribution plate and two points inside of the ?uidiZing
temperature

reactant
to

is

of
the

gas enters to the bed increases

method, as shown in FIG. 2, the temperature ridings of 4 points on

same

the

shifts

plate

And

with

to FIG. 1 of the Us. Pat. No.

section of the FBR. In the Turbo Charger direct chlo rination

almost

distribution

inside

direct
MGSI

holes and the velocity of the

couples locates vertically away from the bottom of the FBR with

mean

molecules

bottom

the bottom of the FBR. From Lines TE-07 to

of

products.

pro?le

readings at four corners of gas distribution plate, which placed at

are

silicone

the product is known

as STC, that is not
desirable result.

are

[0036] In FIG. 2, lines TE-26A to TE-26D indicate tem perature

bed

molecular

silicone

HCl,

Particle size (micro meter)

of

high

These high molecular weight

plugged,

Properties

interval

and

products,

plate. Once some holes of the

TABLE 1

the

reaction

unwanted

as

weight

gas

TE-11,

desired

generates

increases
steadily
to reach over 5000
C.
At
this
temperature most of

and
to
to

chlo

could

hot
must
4
that

not

exothermic
shut

down

months.

In

there

is

limit of siZe of the FBR due

to the poor heat control of
the reaction.

TCS and STC Mass Flows

in Various TCS-Siemens
Pro cesses Over 10,000

MT/Y R Capacity
[0041]

For the following calculations, the CVD (Chemical

Vapor Deposition) reactors, Siemens reactors, are regarded as

the same commercial reactors. Therefore, the inlet rate of
TCS in to the CVD reactor is ?xed as 470,000 MT/Y R and the outlet

gas rate and compositions are regarded all the same in every
different process. Typically, one commercial CVD reactor produces
200 to 500 MT/Y R of polysilicon. For con venience, all the CVD

rest is reported as STC.

CVD

[0043]

As

Meanwhile,

470,000

MT/Y

assumedbefore
R

of

TCS

is

1. TCS-Siemens Process with Old Direct

Chlorination Meth ods.
FRS

(1-1)

equipped

TCS-Siemens

(1

-2)

to

produce

(1-4)

genation.

10,000

MT/Y

polysilicon.

the

be

STC

of

of

166,000 MT/Y R is converted

294,000

into 132,000 of MT/YR of TCS

Then

All

to

and joined with the 294,000

and

MT/Y R of TCS to reach 426,000

166,000 MT/Y R of STC comes out of

MT/Y R of TCS recycle stream.

the CVD reactors (1-2) as a gas

Once

mixture.

thermal

reactors

as

These

un-reacted

mixture

gases

are transferred to OGR (off gas

process also

includes

separator

TCS and STC mass ?ow in case of 10,000 MT/Y R system (not shown in the
polysilicon plant. Due to the heat transfer limit shown in drawing) to separate TCS and
the previous section, at least four small FBR are needed to STC. TCS, after separated from
pro duce enough TCS for 10,000 MT/YR polysilicon plant as STC, is recovered and returned
shown in the FIG. 4. In addition to the often shut down, the into the

the

STC

goes

converter

into

(1-4)

the
about

20% of STC is converted into

TCS

at

one

pass.

Then,

the

converted TCS and un-converted

STC

mixture

is

intro

duce

another separator system (15). Then, un-reacted STC

selectivity of crude TCS from the FBR is 60% and most of the
bed temperature
returns to the

is

thermal

converted into STC by hydro

reactors

showing

becomes more unstable. Most of all, the

into

converters

CVD

[0042] FIG. 4 is a schematic block diagram of old direct recovery) system (1-3) that

chlorination

transferred

STC

of

CVD

MT/Y R.

(1-2).

the

intro duced into pluralities

reactors are presented as one block diagram. Unit of the numbers MT/Y R of TCS comes out of the

in the Figures are 1,000

reactors

thermal converter converted TCS

(1 -4) and the

Ma
y
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US 2012/0114546 A1

feeding rate range of 1 kg/hr to

10,000 Kg/hr.

[0050] The turbo charger

is

chosen

goes to the TCS recycle stream. Finally, all the 166,000

material,

MT/YR of STC converted into 132,000 MT/Y R of TCS.

compounds,

Another separator system (1-5) may roles as the separator react

from

solid

except

iron

that

With

system of the OGS system (1-3). Since 470,000 MT/Y R of TCS is chemicals

does

any

kind

of

than

20

degrees.

(20)

via

(32).

the

The

MGS1

MGSI

feeder

feeder

(32)

supposed

may be the same type as the

needed to produce 10,000 MT/Y R, additional 44,000 MT/YR of TCS to be generated during the

turbo charger feeder (31-

is

generated

from

direct

chlorination.

But,

for

old

direct hydro

Which

not

smaller

MGSI (43) is fed to the PER

chlorination

chlorination reactor the selectivity of TCS is 60% and the rest of silicon

at

40%

up

of

1).

reaction

[0052]

6000

C.

connected to the PER (20) via

generated. This STC can be converted to TCS after separated from and reaction pressure of 30

an exit gas line (38) from the top

third separator system (1-6). The third separator system (1-6) bar.

of

may roles as another separator system (1-5) and the separator [0051] Another poWder feeder,

recycling

is

STC.

Therefore,

29,000

MT/YR

of

unWanted

extra

STC

is temperature

to

the

cyclone

PER

(20)

(37)

and

is

via

line

(39)

that

point

(40),

just

system of the OGS system

MGSI feeder (32), is con nected

reaches

(1-3).

to the PER (20) via a feeding line

beloW the upper end (35) of the

[0044] But, if this extra TCS is returned into the recycle (33) that reaches a point (34)

loWer reactor section (21), With

stream, the TCS balance is broken. Therefore, the extra STC can be just beloW the upper end (35)
sold to other customer or converted into TCS for emergency TCS
of the loWer reactor section
supply or sold to customers Who need TCS.

an angle

HoWever, the poWer consumption rate of the thermal con

verter, 25 KWhr/Kg Si, should be kept in mind.

2. TCS-Siemens Process Equipped With Turbo Charger

from

(21) With an angle (3 6) from a

(27)

vertical

line

degrees.

extended

from

(27),
the

Which

Wall

loWer reactor section (21),

Direct Chlorination FBR.

(41)

of

is
the

vertical

smaller
Plu

thermocouples

line

than

20

ralities

(51),

of

to

36,

are installed along the brim of

the

gas

distribution

plate

[0045] FBR (?uidized bed reactor) (20) for TCS production by

(24),

direct chlorination of MGSI in the presence of turbo charger is

couples are installed along

shoWn in the FIG. 5. The key features of the PER

the height of the PER (20).

(20) are as folloWs;

[0046] In the loWer reactor section (21) of the PER (20), the ratio
of the height of the straight Zone (H') over internal diameter (D1)
is ?xed betWeen one to eleven. Cooling jacket

(22) surrounds the outer surface (23) of

the loWer reactor section (21).
[0047]

gas

distributionplate

(24),

Which

has

pluralities of small holes (6) and chevron type hole caps (4-1)
as shoWn in the FIG. 6, is installed at the bottom of the loWer
reactor

section

(21).

An

expanding

Zone

(25)

maintains

an

angle (26) from a vertical line (27), Which is extended from the
Wall

of

the

loWer

reactor

section,

smaller

than

degree

and

and

to

36

thermo

The temperature reading tells

real-time information inside of
the

PER (20).

[0053] FIG. 7 is a
schematic block diagram of
Turbo

Charger
direct
chlorination FBR (2-1)
equipped
TCS-Si
emens
process shoWing TCS
mass How in a 10,000

MT/Y

(28) reaches over tWo times of the inner diameter (D1) of the loWer

Due

reactor section (21).

transfer

inside

[0048] An internal cooler (29) may be installed inside of the

uidiZing

bed,

upper reactor section (28) via a ?ange (30) for easy replace

charger direct chlorination

ment of cooler (29). HoWever, the loWer end of the internal

produces

uidiZing bed to avoid severe erosion. In another embodi ment, there

is no internal cooler.

[0049] A turbo charger hopper (31) is installed at the top

of the upper reactor section to dump in the turbo charger at the
start up of the PER (20). A poWder feeder-1, named as

turbo charger feeder, (31-1), installed betWeen the turbo

charger hopper (31) and the top dome section (20-U), intro
duces the turbo charger to the PER (20) to maintain the content

polysilicon

STC

expands until the inner diameter (D2) of the upper reactor section

cooler (29) locates at least 6 m above the upper surface of the ?

and

to

plant.

ef?cient

heat

of

the

the

crude

turbo

TCS

With

minimum selectivity of 95%,

STC

is

5%.

reactors

(2-2)

470,000

MT/Y

introduced

Since
are
R

into

the
the

of
CVD

CVD
same,

TCS

is

reactors

(2-2) to produce 10,000 MT/Y

of

polysilicon.

Then

294,000

of the turbo charger material in the ?uidiZing bed (20-1). The

MT/Y R of TCS comes out of

turbo charger feeder (31-1) shoWs 15% accu racy of feeding the

the CVD reactors (2-2) as

turbo charger Within the pressure range up to 10 bar and Within the

un-reacted

and

166,000

MT/Y R of STC comes out of the

CVD reactors (2-2) as a gas mixture. These mixture gases are transferred

to OGR system (2-3) that also includes a separator system (not

shoWn in the draWing) for separation of TCS and

STC. TCS, after separated from STC, is recovered and

returned into the CVD reactors (2-2). Meanwhile, the STC is
transferred into thermal converters (2-4) to be converted into

STC by hydrogenation. All the STC of 166,000 MT/Y R is

converted into 132,000 of MT/YR of TCS and joined With the

294,000

[0054] MT/YR of TCS to reach 426,000 MT/YR of TCS recycle

stream. Once the STC goes into the thermal converter (2-4) about
20% of STC is converted into TCS at one pass.
Then, the converted TCS and un-converted STC mixture is introduce

another separator system (2-5). Then, un-reacted

STC returns to the thermal converter (2-4) and the converted
TCS goes to the TCS recycle stream. Finally, all the 166,000

MT/Y R of STC converted into 132,000 MT/YR of

TCS. Another separator system (2-5) may roles as a
separator sys tem in the OGR system (2-3).
[0055] Since 470,000 MT/YR of TCS is needed to produce 10,000 MT/Y
R,

additional

54,000

MT/Y

of

TCS

is

gener

ated

from

direct

chlorination. Since the turbo charger direct chlorination FBR (21) shoWs 95% TCS selectivity, about

3,000 MT/YR of STC is generated. This amount is less than

10% of the amount of STC generated from old direct chlori
nation FBR. It can be sold to customer after separated from TCS in
third separator system (2-6) or can be converted to
TCS

and

saved

electricity

as

emergency

consumption

by

TCS

source.

the

HoWever,

thermal

still

the

converters

is

major concern for operation cost. The third separator system

(2-6) may roles as another separator system (2-5) and the
separator system in the OGR system (2-3).

3. TCS-Siemens Process Equipped With Closed Loop

Hydro Chlorination FBR Operating at High Temperature and

High Pressure.
[0056]

FIG. 8 is a schematic block diagram of Closed

Loop Hydro chlorination FBR (3-1), Which operates at about

550 C. and 25 bar, equipped TCS-Siemens process shoWing

TCS and STC mass How in a 10,000 MT/Y R polysilicon

plant.

Ma
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US 2012/0114546 A1

produce 10,000 MT/Y R of

polysilicon.

Then

294,000

MT/YR of TCS comes out of

the

CVD

reactors

as

un-

[0057] As shown in the many prior arts, the hydro chlorireacted and 166,000 MT/YR of
STC comes out of the CVD
nation reaction as equation (1) has very poor selectivity of

TCS in the products. It is knoWn as around 20 to 25%. reactors

22% selectivity of TCS in the crude product Was used.

(4-2)

as

gas

mixture. These mixture gases

are transferred to off OGR

system

(4-3)

that

also

a
separator
[0058] In the closed loop hydro chlorination TCS-Si emens includes
process, one hydro chlorination reactor, Which oper ates around 500 C. system for sepa ration of
to 600 C. and 20 to 30 bar, generates TCS and consumes STC at the TCS and STC. 294,000 MT/YR
same time. So all the STC generated from the CVD reactors (3-2) are ofTCS,

after

sepa

rated

sent to hydrogenation FBR after puri?cation in the OGR system (3- from STC, is recovered and
3) and separated in a separator system (3-4). Amount of TCS returned

into

the

CVD

reactors (4-2).

directly returned to
CVD reactors are the same as the tWo previous processes,

[0063] For STC, some technical

294,000 MT/Y R. Same as the tWo previous TCS-Siemens

modi?cation

processes, 470,000 MT/Y R of TCS is needed to produce

10,000 MT/YR. Therefore, 176,000 MT/Y R of additional
TCS is generated from the hydro chlorination FBR (3-1).

is

needed

to

resolve problems of inherent

hydro-chlorination.

If

all

the

STC from OGR system (4-3) is

put into the
of the hydro chlorination reaction, 22% TCS selectiv ity in crude hydrochlorination
Until noW, it is not a big problem. But, due to the inherent nature

product from the hydro chlorination FBR (3-1),

FBR

(4-1),

it

generates

more

615,000 MT/YR of STC is generated at the same time. Then moles of TCS than STC accord
total amount of chlorosilane produced is about 800,000
MT/YR. It is not easy to generate such huge amount of chlorosilane

ing to the equation (1 ). Then

from one single FBR. Moreover, another huge separator system (3- We have excess TCS that breaks

5) is necessary to separate the huge amount of STC from TCS.

The

huge separator

system (3-5)

roles

as

the

steady

balance

state

of

process.

To

undesirable

mass

the

entire

avoid

such

situation,

part

of STC is removed from the

process to meet the TCS overall
balance.

The

amount

of

STC

removed is 38% of STC from

OGR system (4-3). The removed
STC is reacted With pure Water
to recycle HCl and make SiO2
for

sales

or

use

in

the

process. Or, the total STC is

converted to TCS and the extra
TCS is reserved for emer gency
or

sell

at

other

chemical

industry after puri?cation in

?rst separator system (4-4).

The

?rst

separator

system

(4-4) may role as the separator

system included in the OGR system

(4-3)

[0064]

Then,

94,500

MT/Y R

converted

the

rest

of STC

into

is

126,000

MT/Y R of TCS. Therefore,

total 420,000

separator

MT/Y R of TCS is recovered from

system (3-4) folloWing the OGR system (3 -3). In addition to this,

the CVD Off gas. To meet the

as shoWn in the FIG. 8, about

assumption of 470,000 MT/Y R of

772,000 MT/YR of STC is returned to the hydro chlorination

TCS

FBR (3-1). In other Words, about 800,000 MT/Y

R of chlo rosilane is repeatedly heat up,

polysilicon, only 50,000 MT/Y R

compresses and condensed

may

the

again and again.

[0059] As disclosed in the many previous articles, the

hydro chlorination reactor, as disclosed in the Us. Pat. No.
4,676,967, shouldbe built With especially expensive material,
Inconel 800 H, because of the high reaction temperature, over

500 C., and reaction pressure, over 25 bar.

10,000

TCS

should

MT/Y

of

generated

be

from turbo charger direct

chlorination FBR (4-5).
[0065]

As

proven

by

the

customer and the previous tem

perature

pro?le

turbo

charger

data,

the

direct

chlorination

4. Hybrid TCS-Siemens Process

[0060]

of

for

FBR

4-A; Hybrid TCS-Siemens Process With Turbo

Charger Direct Chlorination FBR.

(4-5)

shoWs

selectivity

crude

over

TCS
95%.

Therefore, only 2,500 MT/Y R

sumption by

of STC is generated. The STC is

thermal converters, relatively small hydro chlo rination FBR

intro duced into small STC to

[0061] To reduce the enormous amount of electricity con

(4-1), Which operates at about 5500 C. and 25 bar, is suggested for

TCS

converter

(4-1),

after

separated

from

second

Process. The process block diagram of the Hybrid TCS-Siemens Process

separator

system

(4-6).

is illustrated in

The ?rst separator sys tem

FIG. 9.

(4-4), the second separator

converting STC to TCS. The process is named as Hybrid TCS-Siemens

[0062] As assumed before 470,000 MT/Y R of TCS is

(4-6)

intro duced into pluralities of CVD reactors (4-2) to

system in the OGR system (4-3)

and

the

separator

may be one separator system.

4-B; Hybrid TCS-Siemens Process With

Old Direct Chlori nation FBR.

it generates more moles of TCS

?rst separator system (5-4).

than

The

STC

[0066] FIG. 10 is schematic block diagrams of old equation

direct

chlorination

FBR

equipped

Hybrid

TCS-

Siemens process shoWing TCS and STC mass in a 10,000

MT/YR polysilicon plant. As assumed before 470,000 MT/Y
R of TCS is intro duced into pluralities of CVD reactors
(5-2)

to

produce

10,000

MT/Y

of

polysilicon.

and

166,000

MT/Y

of

STC

comes

reactors (5-2) as a gas mixture.

out

of

the

(1).

excess

TCS

steady

state

the

entire

such

to

Then

that

We

the
have

breaks

mass

the

balance

process.

To

undesirable

of

Then process
CVD STC

to

meet

the

is

separator

(5-3)

Then,

situation,

94,500

MT/Y R

TCS

overall

38%

of

STC

from OGR system (5-3). The

converted

MT/Y R of TCS is recovered

polysilicon,

TCS

and

the

is

126,000

total 420,000

returned into the CVD reactors (5-2).

to

rest

MT/Y R of TCS. Therefore,

[0067] These mixture gases are transferred to off removed STC is reacted With
OGR system (5-3) that also includes a separator pure Water to recycle HCl and
system for sepa ration ofTCS and STC. 294,000 MT/YR make SiO2 for sales or use in
ofTCS, after sepa rated from STC, is recovered and the process. Or, the total STC
converted

the

of STC

into

from

is

system

system included in the OGR system

[0069]

The amount of

removed

?rst

(5-4) may role as the separator

avoid

part of STC is removed from the

294,000 MT/Y R of TCS comes out of the CVD reactors as un- balance.
reacted

according

the

meet

CVD

the

470,000
10,000

Off

MT/Y

of

MT/Y
R

gas.

assumption

of

TCS
R

only
TCS

To
of
for
of

50,000

[0068] For STC, some technical modi?cation is needed to resolveextra TCS is reserved for emer
problems of inherent hydro-chlorination. If all the STC from gency or sell at other chemical

MT/Y

should

OGR system (5-3) is put into the hydro chlorina tion FBR (5-1),industry after puri?cation in

chlorination FBR (5-5).

be

generated from old direct

Ma
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US 2012/0114546 A1

[0070] However, as proven by many existing TCS-Siemens

sumes about 40% of energy compared to the traditional pro

cess. The Hybrid TCS-Siemens Process consumes less than

polysilicon plants, pluralities of small old direct chlorination

FBR (5-5) s, each of them generating feW thousand MT/Y R

TCS, are installed in a plant to compensate for the scale up
limit of the old direct chlorination FBR due to dif?cult reac
tion heat control. In addition to that the purity of crude TCS
out of the old direct chlorination FBR is about 60% due to

poor reaction temperature control. Therefore, 33,000 MT/Y R

of STC is produced as un-Wanted by product to produce

10% of energy compared to the traditional TCS-Siemens

Process. Here, the FBR used for direct chlorination is the neW

Turbo Charger FBR. Therefore, the hybrid TCS-Siemens

process equipped With turbo charger FBR is the most eco
nomical process to generate TCS in large scale polysilicon

plant of siZe over

MT/YR.

50,000 MT/YR of TCS. This amount of 33,000 MT/YR of 10,000

STC is about 20% of STC generated from the CVD reactors

(5-2).

[0075] As shoWn in the

Table 2, The Hybrid TCS[0071] In the previous step of 4-A; Hybrid TCS-Siemens Siemens
process With turbo charger direct chlorination FBR, 30% of Process using turbo charger

the old

traditional TCS-Siemens
process that uses thermal
con
verters, the Hybrid TCSSiemens process, saves
218,201,

STC from the CVD reactors (5-2) are not converted into TCS bydirect chlorination FBR saves

139 KWhr per year from a

the hydro-chlorination FBR (5-1) to keep the overall TCS78,211,145 KWhr per year

10,000 MT/Y R polysilicon

mass How in balance. Instead the un-converted STC is planned than the Closed Loop

plant. These are equivalent

to

TCS

to 7.8 KWhr/kg Si and 21.9

Siemens that has a FBR

KWhr/kg Si

by product STC to compensate for the effect of draW out of STC

25 bar

from the process.

from a 10,000 MT/Y R

polysilicon plant. Compared to

electricity
savings.

sale

for

economical

use.

HoWever,

the

old

direct

chlorination FBRs (5-5) produce enough amount of un-Wanted operates at about 550 C. and

TABLE 2
Energy consumption related With
STC conversion and TCS
generation in

three different Siemens

Processes for 10 000 MTA Polysilicon

Plant *

Mass to Converter

Converter

Energy

MT/Y R
(A); Closed Loop

TCS-Siemens
TCS-Siemens

(B); Hybrid
TCS-Siemens
(A) (B)

800,000
166,000

94,500
705,500

KWhr/kg Si ** Toatal (KWhr)

10 (Hydro-

10 x 10,000,000 =

20 for TC

24 x 10,000,000 =

Chlorination) 100,000,000

4 for DC
240,000,000
1.18 I for HC 2.18 x 10,000,000 =
l for DC
21,800,000
7.818

1*

Energy
consumption
in
Distillation,
Siemens Reactor, and Off Gas Recycle steps are not
considered because they are common steps for all the three
processes.

1*

Energy consumption from commercial

heater, cooler and compressor power consumption.

plants.

Includes

1 10 X (94,500/800,000); Reduction ofH.C. reactor

size reduces energy consumption.

is calculated
by adding the
[0072]

As

Hybrid
equipped
direct

conclusion,

TCS-Siemens
With

processconvert

pluralities

chlorination

theenergy

FBRs

of
are

old
much

less economical compared to the other

Hybrid TCS

STC

to
TCS
and
separation.
The

numbers

are collected

Siemens
process from
equipped With a single
turbo charger direct commercial
[0074]

Table

5. Total Energy Consumption for 2 clearly

shoWs that the
TCS Production in Each
traditional
TCS

Process

[0073] Total energy consumption Siemens

related With TCS genera tion and Process
STC

conversion

for

the

above

mentioned Closed

using

Loop TCS-Siemens Process, the Thermal

above

mentioned

TCS-Siemens

tradi

Process,

tional Converter
and

the

above mentioned

Reactor SiZes
and Initial
Capital
Investment

high
temperature of

temperature

550

C.,

betWeen

high

pressure

300~350o C. and
about

pressure
5
FBR

conversion and TCS can

be

the manufactured

above
that
be

25

bar,
must

constructed

With

the

expensive
Incoloy

various
constructio
n materials
Siemens
process
as
in terms of reactor such
siZes due to its carbon
steel,
inherent
less
disadvantage
of stain
and
the
hydro steel,
Inconel.
chlorination.

or

Process has another

advantage over the
Closed Loop TCS

The

Turbo

in

direct

Charger

parison.
The
total
energy Loop
consumption related With TCS Siemens

process

FBR,

chlori
Hybrid
Process,

nation
of

material
safety
In

for

addition

this,

due

internal
structure,
cult

dif?
level

excess

since

prod

and
side

uct,

chlorination

is

FBR

impossible

reactor
US.

Pat.

4,676,967
oper operates
at

to
to

complex

control,

the of

reason.

[0078]

TCS-Siemens No.
is

800

equivalent

MeanWhile,
hydro

and

FBR

Hybrid TCS-Siemens With

adopted

gen eration and STC conversion

The

energy
most.
Hybrid
TCS-Siemens
Process
Closed
are listed in Table 2 for com The
TCS

at

controlled

consumption in STC bar.

[0077]

consumes

ated

[0076] In addition at a
to
loWer
energy range

generation,

plants.

chlorination FBR.

Process con

it

almost
to

build a single
large hydro

Ma
y
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,
20
12

US 2012/0114546 A1

simulation, not a designed

capacity.
[0086]

Due

to

the

[0083] The result of such

limitations of the previous

chlorination FBR, Which has a capacity to produce 10,000

effective

TCS-Siemens processes discussed

MT/YR of TCS. This size is equivalent to produce TCS for

control

6,000 MT/Y R polysilicon plant built by the Closed Loop

FIG.

TCS-Siemens Process.
[0079] On the other hand, the Turbo Charger FBR for direct

chlorination, developed by the applicants genuine in

house technology, has totally different from the old FBR for direct

heat
is

transfer

shoWn

as

in

the

the

uniform

temperature pro?le inside of

the

?uidizing

bed,

the

reaction zone.
Charger FBR has no internal

turbo charger direct chlorination FBR is to control the reac structure,

it

is

easy

to

tion in stoichiometrically equivalent, Which is impossible scale-up. For example, Union

for the other tWo FBRs. The other key feature is operating the

commercialized

Carbide

?uidizing bed in Bubbling Bed Mode that similar

Mode
maximize mixing of the bed material.

Bubbling

scale reactor of a laboratory state reactor. They just pile up

unnecessarily

excess

amount

of

MGSI

in

FBR

Without

considering

Uniopl

for

Polyole?n

movement of the bed material. Therefore, the

?uidizing bed, Where the reaction occurs is in an extended

?xed

bed

or

slugging

bed

mode,

is

unstable

and

the

reactant gas feeding rate is limited. Due to the limitation,

the

heat

of

the

reaction

is

controlled

by

only

conductional heat transfer and as a result temperature pro?

le in the reaction zone is unstable and not uniform.

production.
about

Bed

FBR,

[0080] Meanwhile, the other tWo type FBRs are just large Reactor,

Since

100

1980

reactor

of

100,000 MTA are commercially

in

operation

single

With

out

accident.

any

Maximum

size of the reactor is 500,

000 MTA from single reactor.
[0085]

GT

company,

Solar,

US.

announced

[0081] The neW FBR for direct chlorination utilize an inert feasibility

study

report

medium named as turbo charger inside the ?uidizing bed comparing

old
direct
to dilute heat generated per vole of the bed and at the same chlorination TCS-Siemens
time transfer the heat generated to the reactor Wall by Process and their Closed
Convec tional Heat transfer due to the Bubbling Bed Mode Loop Hydro chlorination
process
move ment of the bed material.
[0082] Features of the turbo charger FBR for direct chlo
rination is listed in Table 3 and compared With other tWo

at

high

temperature,
pressure.

FBRs.

large

polysilicon

scale

plant

over

10,000 MT/Y R to save

Opex

and

CaPex.

of

Size

and

for

TCS

FBRs

produc tion for 10,000 MT/Y

R

and

20,000

polysilicon
to

three

are

MT/Y

plant

different

summarized

according
processes

in

Table

4.

Speci?c cost is not estimated

because

material

cost

and

fabrication cost are different

for each plant site. Sizes of

each reactor are based

on commercial reactors.
[0087] As shoWn in the Table
4, at least 4 to 8 FBRs are
needed to comprise a Hybrid
TCS-Siemens
old
FBR.

direct
In

Process

using

chlorination

this

case,

TCS

due

to

frequent shut-doWn of the FBR,

additional
poWer

is

possibility

maintenance

needed
of

and

man

the

malfunction

of the FBR is very

high.

high
In

the

article, the maximum size

of the plant Which can be

TABLE 3

built by their tech nology

Features of different FBRs for TCS Production

is

7,000

that

MTA.

number

But,
is

even
for

Old Direct

Cooler
Turbo Charger
Direct

Chlorination FBR

Chlorination FBR

Bed Level Control Semi-Auto

Non-Stoichiometric
Incoloy
Gas Velocity <20 cm/sec
Internal Speci?c
Cooling Coil
Crude TCS Selectivity 60~90%
*Bed Mode; Bubbling bed

300~350 Medium

gases

Reaction

Temperature (0 C.) 300~400

Inside Bed Cooling STC, N2,Up-Time

H2 and 02

4~5

Bed Mode

Extended ~Slugging Bubbling*

>110O C.

mode shows maximum mixing

~40%

**High SGV enables the bed

Scale-up limit, 15,000
convects. So, convectional

MT/Y
R TCS
Thermal Conductivity 0.1~0.2
W/(mK)
transfer is possible.
Reason
of limit Hot
Spot,
Poor
<11O C. Internals
Cooling Coil,
Bubble
***For
96,000
MTA

Pressure (bar)

A T across bed

Working

build

number

chlorination and the FBR for hydro chlorination dis closed in the [0084] Since this neW Turbo
US. Pat. No. 4,676,967. One key feature ofthe

above a neW process is needed to

Breaker

material
heat

TCS at least

288,000
MTA STC is generated
heat
transfer

from steel,
the same
FBR
Construction Material Cabon
SUS,

Incoloy

M
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,
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2

US 2012/0114546 A1

[0088] Meanwhile, With applicants new turbo charger

[0096] In addition to this, Hybrid TCS-Siemens Process

FBR automatically produces enough TCS through a Whole

equipped With applicants Turbo Charger direct chlorination

investment for TCS production is reduced doWn.

TCS generation related equipment.

FBR saves huge amount of initial capital investment from

year Without shut-doWn of the FBR. Therefore, initial capital

TABLE 4
Size and number ofFBRs for TCS production for 10,000 MTA and 20,000
MTA Polvsilicon plant according to three different processes.
TCS
FBR:

No. of

MT/Y R

FBR

Hybrid
83,000
With Old
(166,000)
D.C. FBR
Hybrid With
53,000
Turbo
(106,000)
D.C. FBR
H.C. Closed
0

Dimension

H.C. FBR
MT/YR

No. ofH.C.

STC Only

FBR

4
8

01.5 m, H 25 m
01.5 m, H 25 m

95,000
190,000

01.5 m, H 25 m
G 2.2 m, H 25 m

95,000
190,000

Loop FBR

Dimension
01.4 m, H 25 m
02.1 m, H 25 m

01.4 m, H 25 m
$2.1m, H 25 m

STC +

No. ofFBR

TCS

400,000
MT/YR

800,000
1,600,000

2
03.0 m, H 25 m
4
03.0 m, H 25 m
mandatory
supplementary
equipment

to

the

FBR,

[0089] On the other hand, Closed Loop TCS-Siemens Pro-cess should also be increased.
does not need separate FBR for TCS production only. HoWever, TCS is As We knoW Well, lnconl 800
H

generated from one hydrochlorination FBR

hard

With un-necessarily huge amount of STC at the same time.

Therefore, the size and number

hydro chlorination FBR increases.

very
to

Charger FBR, one small Turbo Charger FBR for TCS pro
duction and one small REC type hydrochlorination FBR for

STC converter is enough.

[0091] MeanWhile, at least 2 or 4 large hydro chlorination
reactors, Which has tWice larger diameter than the Hybrid
process case, are needed to build a 10,000 MTA or 20,000

MTA polysilicon plant by Hydrochlorination Closed Loop

expen

fabricate.

sive

and

And

the

Wall thickness of a pressure

of vessel

[0090] To build one polysilicon plant of 10,000 MTA or

20,000 MTA by Hybrid TCS-Siemens Process using Turbo

TCS-Siemens Process.

is

increases With square

of the diameter ratio of the

ves

sels.

Therefore,

the

price of FBR also increases

With

square

of

diameter

ratio.

[0093]

As

conclusion,

initial capital investment

for

TCS

production

Hybrid
Process
than

for

TCS-Siemens
is

Closed

much
Loop

[0092] In addition to this, the FBR for this process should Siemens Process.
be built With the expensive lnconel 800H to secure the opera [0094]
Hybrid

smaller
TCS-

TCS-

tion conditions of high temperature and high pressure. And at Siemens Process equipped
the same time size of super heater and settler, Which are With
applicants
Turbo

Charger

direct

chlorination

FBR saves at least 78,000,000

KWhr

per

year

from

TCS

generation only in a 10,000

M/YR.

polysilicon

plant

compared With a same capacity

polysilicon

plant

by

Loop

Closed

emens
MT/Y

Process.
R

plant

the

For

built
TCS-Si
20,000

amount

is

156,

000,000 KWh.
[0095] Compared With
traditional
TCSSiemens Process, the
Hybrid
TCS-Siemens
Process
saves
220,000,000
KWhr
per
year from 10,000 MT/YR
plant.

[0097] As a conclusion, Hybrid TCS-Siemens Process equipped With

applicants Turbo Charger direct chlorination

FBR is the most economical process for

process over 10,000 MT/Y R capacities.

a polysilicon

What is claimed is:

1. A hybrid TCS-Siemens process for building a polysili

con plant of scale larger than 10,000 MT/Y R economically
and save more electricity is comprised of;
a direct chlorination FBR (Fluidized bed reactor) that uses

turbo charger and is comprised of;

a loWer reactor section of the ?uidized bed, in Which the
ratio of the height of the straight zone (H') over
inter nal diameter (D1) is ?xed as six,

and

a cooling jacket surrounding the outer

surface of the loWer reactor section,

and
a

gas

distribution

plate,

Whose

brim

is

rounded

con

cavely to form a smooth round inner surface betWeen

the

vertical

section and

inner

surface

of

the

loWer

reactor

the gas distribution plate Which is

installed at the bottom of the loWer reactor section

and Which is equipped With pluralities of gas holes

of diameter 2 mm and pluralities of chevron shape

gas hole caps that cover the holes,

and

a
n

and maintains an angle

from a vertical line

of

u
p
p
e
r

degree

and

until

the

diameter

(D2)

expands
inner

of the upper reactor

section
times

r
e
a
c
t
o
r

reaches
of

the

tWo
inner

diameter (D1) of the

loWer

reactor

section,

and
an

internal

cooler

that

is installed inside of

s
e
c
t
i
o
n
,

the

upper

section

via

reactor
a

?ange

for easy replacement,

and
an

initially

charging

material hopper that is

installed at the top of

a
n
d

the

upper

reactor

section to dump in the

an expanding zone locates
betWeen

the

loWer

reactor section and the

upper

reactor

section

seed bed material at the

start up of the ?uidized
bed reactor,

Ma
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US 2012/0114546 A1

cavely
to
form
a
smooth
round
inner
surface betWeen the
vertical
inner
surface of the loWer

and

reactor

an MGSI feeder that controls feeding rate of the silicon at a

and is connected to the ?uidized bed reactor via a feeding
loWer reactor section With an angle from a vertical line

loWer reactor section

and
Which
is

smaller than 20 degrees,

and

equipped
pluralities

an initial charging material feeder that controls feeding

rate of the initial charging material at a range of 100
Kg/hr With +5% deviation at a pressure of 150 Pisa and is

and

exit gas line from the top of the ?uidized bed reactor and

upper end of the loWer reactor section

degrees,

pluralities of thermocouples; four of them are installed along

the brim of the gas distribution plate and tWelve of them
are installed along the height ofthe FBR to get real-time
temperature information inside of the FBR,

and

a hydro chlorination FBR for converting STC (Silicon

Tetra Chloride) to TCS (Tri Chloro Silane),

and

pluralities of CVD (Chemical Vapor Deposition) reactors

for depositing silicon from TCS introduced,

and
system for separating TCS and STC comes from the

CVDs and returns TCS into the CVD reactors,

and
a ?rst separator system that separates the STC and
TCS from the hydro chlorination FBR,

and
produced from the direct chlorination FBR that uses

hybrid

TCS-Siemens

for

building

an

inter nal diameter (D1) is ?xed as six,

MGSI

feeder

controls
of

that

feeding

the

rate

silicon

at

range of 100 Kg/hr With

+5%

deviation

pressure

r
e
a
c
t
o
r

of

at

150

Pisa

and is connected to the

?uidized

bed

reactor

via a feeding line that

reaches

point

just

beloW the upper end of

the

loWer

reactor

section

With

from

vertical

smaller

an

angle
line

than

20

degrees,

and

an

initial

charging

material feeder that

controls feeding rate
of the initial charging

betWeen

the

material at a range of

reactor

100

loWer

of

section

from a vertical line

of

expands

degree

and

Kg/hr

With

+5%

deviation at a pressure
150

connected

and maintains an angle

ratio of the height of the straight zone (H') over

Pisa

and

to

is

the

uidized bed reactor,

and
a

cyclone
connected

that
to

is

the

uidized bed reactor via

and

a cooling jacket surrounding the outer

surface of the loWer reactor section,

seed bed material at the

u
p
p
e
r

upper

turbo charger and is comprised of;

reactor

bed reactor,

reactor section and the

a loWer reactor section of the ?uidized bed, in Which the

upper

section to dump in the

and

economically and save more electricity is comprised of;

and

the

start up of the ?uidized

polysili con plant of scale larger than 10,000 MT/YR

a direct chlorination FBR (Fluidized bed reactor) that uses

charging

installed at the top of

an expanding zone locates

process

initially

material hopper that is

a
n
d

a second separator system that separates TCS and STC

an

and

s
e
c
t
i
o
n
,

a off gas recovery system that also includes a separator

and

cover the holes,

a
n

With an angle from a vertical line smaller than 20

turbo charger.

With
gas

of
chevron
shape
gas hole caps that

a cyclone that is connected to the ?uidized bed reactor via an

via a recycling line that reaches a point just beloW the

of

holes of diameter 2
mm
andpluralities

connected to the ?uidized bed reactor,

2.

and

gas
plate

Which is installed
at the bottom of the

line that reaches a point just below the upper end of the

and

section

the
distribution

range of 100 Kg/hr With +5% deviation at a pressure of 150 Pisa

until
the
inner
diameter
(D2)
of
the upper reactor
section reaches tWo
times of the inner
diameter
(D1)
of
the loWer reactor
section,

gas

distribution

plate,

Whose

brim

is

rounded

con

an exit gas line from

the top of the ?uidized
bed reactor and via a
recycling

line

that

reaches a point just beloW the upper end of the loWer

TCS from the hydro

separates the STC and TCS

reactor section

chlorination FBR,

from

With an angle from a vertical line smaller than 20

and

degrees,

pluralities of thermocouples; four of them are installed along

a second separator
system that separates
TCS and STC produced

are

installed

along

the

height

of

the

FBR

to

get

real-time

temperature information inside of the FBR,

and
a hydro chlorination FBR for converting STC (Silicon

Tetra Chloride) to TCS (Tri Chloro Silane),

and

3.

hybrid

process
polysili

in

and
a off gas recovery system that also includes a separator
system for separating TCS and STC comes from the

CVDs and returns TCS into the CVD reactors,

and
a ?rst separator system that separates the STC and

pro

duced

4.

process

TCS-Siemens

for
con

separator

system

from

the

direct

FBR

that

uses

charger

are

one

separator system.
hybrid

larger

economically

Wherein the separator system

building

polysili con plant of scale

scale

of

TCS-Siemens

for

producing

pluralities of CVD (Chemical Vapor Deposition) reactors 10,000 MT/YR of claims 1 and 2,
for depositing silicon from TCS introduced,

hydro

that separates TCS and STC

turbo

turbo
charger.
A

second

chlorination

from the direct

chlorination FBR that
uses

the brim of the gas distribution plate and tWelve of them

the

chlorination FBR, and the

and

than

10,000
and

MT/Y

save

more

electricity of claims 1 and 2,

the

hybrid

TCS-Siemens

included in the OGR system

Process saves 21.9 KWhr/kg Si

for separating

compared

to

Process

that

TCS and STC come from the

CVDs and returns TCS into
the

CVD

reactors,

separator

the

system

?rst
that

old

TCS-Siemens

uses

thermal

converters for

STC conversion to
TCS.