Allyl chloride [107-05-1]

CONTENTS OF FACTORY GATE TO FACTORY GATE

LIFE CYCLE INVENTORY SUMMARY

Chemistry
Process Summary
Summary of LCI Information
Process Diagram Interpretation Sheet
Process Diagram or Boundary of LCI
Mass Balance of Chemicals in each Process Stream (Highlighting Chemicals that are Waste and the
Physical State when Lost)
Graph of Cumulative Chemical Losses through Manufacturing Process
Graph of Cumulative Contaminated Water Use/Emission through Manufacturing Process
Graph of Cumulative Non-Contaminated Water Use/Emission through Manufacturing Process
Energy Input for each Unit Process, Cumulative Energy Requirements, Cooling Requirements
(exotherms), and Assumed Heat Recovery from Hot Streams Receiving Cooling
Graph of Cumulative Energy Requirements

Authors Students, E. Griffing, and Y. Li

Peer reviews, name (date) MR Overcash (9-1-1999); MR Overcash (9-5-2007)
Gtg report last modified on 10-4-2010
Additional notes

Checked for database consistency on 10-4-2010

First gtg version finalized on 9-1-1999
Modification history, Author (date) EMG (9-5-2007), EMG (10-4-2010), YL (9-1-2005), and Stu (9-
1-1999)

Products Allyl Chloride, Hydrogen chloride

Standard inputs Propylene, Chlorine

Methodology: Environmental Clarity gtg lci reports are based on industrial practice information, standard
methods of engineering process design, and technical reviews. These reports are intended to be
representative of industrial production based on the stated route.
Terms of use: Environmental Clarity does not assume any liability due to use of these lci data. Integration
of these data with lci data based on other methodologies is the responsibility of the user. Each report may
be updated to improve model accuracy or representativeness.
Users of this report should cite: E. Griffing and M. Overcash, Chemical Life Cycle Database,
www.environmentalclarity.com, 1999 - present.

updated on 10/3/2010 1
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
CHEMISTRY:

Net Reaction

CH2=CH-CH3 + Cl2 CH2=CH-CH2Cl + HCl

Propylene Chlorine Allyl Chloride Hydrogen Chloride

Side Reactions

CH2=CH-CH3 + Cl2 CH2=CCl-CH3 + HCl

Propylene Chlorine 2-Chloropropene Hydrogen Chloride

CH2=CH-CH3 + HCl CH3-CHCl-CH3

Propylene Hydrogen Chloride Isopropyl Chloride

CH2=CH-CH3 + 2Cl2 CHCl=CH-CH2Cl + 2HCl

Propylene Chlorine 1,3 Dichloropropene Hydrogen Chloride

CH2=CH-CH3 + 2Cl2 CH2=CCl-CH2Cl + 2HCl

Propylene Chlorine 2,3 Dichloropropene Hydrogen Chloride

CH2=CH-CH3 + Cl2 CH2Cl-CHCl-CH3

Propylene Chlorine 1,2 Dichloropropane

For the purpose of the energy balance the Heavy Ends were assumed to be 1- Decene

updated on 10/3/2010 1
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
Process Summary:

In this process, allyl chloride is produced by reacting gaseous propylene and

chlorine at 510oC. Propylene enters the process at 25oC and 1 Atm where it is

compressed to 2 Atm (55.4oC) and mixed with a stream containing recycled propylene

and trace amounts of water. This mixture then enters a dryer where any residual water is

removed. The dry propylene is preheated to 200 OC before it enters the reactor. Chlorine

enters the production loop at 25 O C and is compressed to 3 Atm and 107.1 OC. All of the

Chlorine entering into the reactor is reacted to yield allyl chloride, HCl, and small

amounts of other chloronated hydrocarbons. Black carbon accumulates on the walls of

the reactor and must be periodically removed.

The reaction product mixture proceeds through a series of purification operations.

The effluent from the reactor is first passes through a heat exchanger where it is cooled to

25oC. The cooled mixture then passes through a prefractionator, where gaseous

propylene and hydrogen chloride is separated from the halogenated organics. The gas

leaving the prefractionator is preheated to 25oC before entering into a absorbtion column.

The absorbtion column produces viable 36% by wt. HCl (aq). The remaining HCl of the

propylene recycle stream is removed by a scrubber, and then passes to a mixing tank

where it is mixed with the incoming pure propylene supply.

The halogenated organics from the heel of the prefractionator enter into

distillation column one, where the top cut contains 2-chloropropene, isopropyl chloride,

and a small fraction of allyl chloride. This stream is leaves the process as a waste. The

bottoms of distillation column one contains allyl chloride, 1,2 dichloropropane, 1,3

dichloropropene, 2,3 dichloropropene, and heavy ends. This stream is pumped into

updated on 10/3/2010 1
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
distillation column two were the top cut is composed of 100 % allyl chloride. The allyl

chloride product stream passes through a cooler where it is cooled to 25oC and 1 Atm.

The bottoms of distillation column two are considered a waste stream, which is cooled to

25oC and 1 Atm before leaving the production system.

Summary of LCI Information:

Product: Allyl Chloride

Basis: 1000 kg/hr allyl chloride

Reference: Commercial Scale Manufacture of Allyl Chloride
and Allyl Alcohol From Propylene, A.W. Fairburn
et al, Chemical Engineering Progress, Vol. 43, No.
6., June 1947, pp. 280-290
Plant Location: Shell Chemical Corp., Houston TX
Comments: All mass and energy units per hour are equivalent to
1000 kg of allyl chloride

Standard inputs
UID Name Flow Purity Units Comments
115-07-1 Propylene 682 - [kg/hr] includes
3.4kg/hr
fugitive loss
replacement
7782-50-5 Chlorine 1195 - [kg/hr] includes 5.9
kg/hr fugitive
loss
replacement
Total 1877 [kg/hr]
Non-reacting inputs
UID Name Flow Purity Units Comments
7732-18-5 Water 1085 - [kg/hr]
Total 1085 [kg/hr]
Ancillary inputs
UID Name Flow Purity Units Comments
Total 0 [kg/hr]
Products
UID Name Flow Purity Units Comments
107-05-1 Allyl Chloride 1000 100 [kg/hr]
7647-01-0 Hydrogen 600 100 [kg/hr] 1666kg of 36%
chloride HCl
Total 1600 [kg/hr]
Benign outflows
UID Name Flow Purity Units Comments
7732-18-5 Water 1085 100 [kg/hr] 1066 kg/hr in
HCl stream
Total 1085 [kg/hr]

updated on 10/3/2010 2
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
Process emissions
UID Name Gas Liquid Solid Solvent Units Comments
115-07-1 Propylene 19.8 0 0 0 [kg/hr]
7647-01- Hydrogen 5.71 0 0 0 [kg/hr]
0 chloride
107-05-1 Allyl Chloride 0 20.9 0 0 [kg/hr]
75-29-6 2- 0 27.6 0 0 [kg/hr]
chloropropane
7782-50- Chlorine 5.94 0 0 0 [kg/hr]
5
563-54-2 1,2- 0 113 0 0 [kg/hr]
dichloropropene
872-05-9 1-decene 0 17.4 0 0 [kg/hr]
78-88-6 2,3 0 13.9 0 0 [kg/hr]
dichloropropene
78-87-5 1,2- 0 46.0 0 0 [kg/hr]
dichloropropane
Total 31.4 239 0 0

Mass balance
Total inputs 2962
Total outflows 2955
Net input 7.39

Energy use
Energy type Amount Units Comments
electricity 458 [MJ/hr] Net electricity use at
plant
heating steam 2222 [MJ/hr] heating by steam (0.85
efficiency included)
Net input requirement 2680 [MJ/hr] Net of energies input to
system
cooling water -3932 [MJ/hr] net cooling by cooling
water
potential recovery -994 [MJ/hr] potential energy
recovery (negative)
Net energy 1686 [MJ/hr] Net input requirement -
potential recovery

Process Diagram:

Shown on the following pages.

updated on 10/3/2010 3
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
Phase II Group 11 Allyl Chloride Process 6(g) 25oC
679.13 Kg/hr Propylene

C3

7 (g) 52.7o C
P=2 Atm
22c (l,g) 52.80C
C33 (l) 50oC 22 (l,g) 250C
Mixer P=2 Atm
Entire process runs at 1 Atm 1(g) 250C
C1
4.20 Kg/hr H2O
52.77 oC
C6
B
unless otherwise specified 1188.87
7a (l,g) 52.77oC
Kg/hr
Chlorine 9b (l) 25o C P=2 Atm
2.68 Kg/hr H20
C4

Cooler 5
0C
2(g) 117
8 (l,g) 62.2oC

Packed Bed Dryer

P=3 Atm
C32 (l) 20oC P= 2.5 Atm
S3 (g) 207oC
245.52 Kg/hr Steam
S5 (g) 207oC
S4 (l) 207oC
5.59 Kg/hr Steam
245.52 Kg/hr H2O
C31 (l) P25
20oC 9a (l) 65o C
4.20 Kg/hr S6 (l) 207oC
H2O 2.68 Kg/hr H20 65oC 5.59 Kg/hr H2O

9 (g) 65o C
C5 Heater 2
C26 20oC P=2.3 Atm P=3 Atm
Reactor
o
10 (g) 76.7 C

C25 20oC
4264.64 Kg/hr H2O 11 (g) 200oC
P= 3 Atm
P21

510oC
C27 50oC 11a (s) 510oC
4264.64 Kg/hr H2O 1.88 Kg/hr Black Carbon
Periodically Cleaned Out A
12 (g) 510oC 13 (l,g) 25oC
Cooler 1
P= 3 Atm P=3 Atm

C2 (l)

8162.87 Kg/hr
C3(l) 50oC
20oC

H 2O
C1 (l) 20oC
11-16

8162.87 Kg/hr H O
updated on 10/3/2010 2
8
P3
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
 1071.78 Kg/hr H2O

P6
18 (l) 25oC
S13 (g) S14 (l)
207oC 207oC
5.20 Kg/hr 5.20 Kg/hr H2O
Steam

C8 (l) 20oC

C7 (l) 20oC
15a (g) 22oC 15b (g) 25oC 9158.94 Kg/hr H2O
Heater 3 A
P=3 Atm bs
or P7
Pr
efr be C9 (l) 50oC
A act
io
19 (l) 25oC
r
25oC
9158.94 Kg/hr H2O

13 (l,g) 25oC
na
P=3 Atm
tor
599.86 Kg/hr HCl 20 (l,g) 25oC
22oC 1066.42 Kg/hr H2O 22 (l,g) 25oC
P= 3 Atm C28 20oC
899.89 Kg/hr H2O B
C7
P24
C29 20oC
21 (l,g) 52.8oC C30 50oC
15 (l) 22oC P= 2 Atm Sc
P=3 Atm ru 899.89 Kg/hr H2O
bb
er

21a 25oC 21b 25oC 22d (l,g) 25oC

T1 13.15 Kg/hr H2O 25oC 19.78 Kg/hr Propylene
5.71 Kg/hr HCl
C21 (l) 50oC P23 15.83 Kg/hr H2O
C12 (l) 50oC 5.24 Kg/hr H2O
276.25 Kg/hr H2O 22a (l,g)
C10 (l) 20oC 25o C
o
C11 (l) 20 C C15 (l) 50oC
276.25 Kg/hr H20 P8
8193.76 Kg/hr H2O
C13 (l) 20oC
25 (l) 36oC 8193.76 Kg/hr H2O
25a (l) 25oC
24 (l) 36oC C14 (l) 20oC C18 (l) 50oC
Distilla Cooler 3 Light Ends
P12 tion o
306.56 Kg/hr H2O
27.58 Kg/hr 2-Chloropropene 28 (l) 45 C 30 (l)
Colum 45oC
23 (l) 22oC n1 2.46 Kg/hr Isopropyl Chloride 32 (l) 25oC
o P13 C20 (l) 20 C o Distilla Cooler 2
C19 (l) 20 C 10.79 Kg/hr Allyl Chloride P15 1000 Kg/hr
tion
36oC 5.24 Kg/hr H2O C16 (l) 20oC Allyl Chloride
Colum
306.56 Kg/hr H2O P16
n2
P19 C17 (l) 20oC C24 (l) 50oC
45oC 54.67 Kg/hr H2O
26 (l) 36oC
27 (l) 36oC P17
33 (l) 25 oC
29 (l) 45oC Cooler 4
S9 (g) 207oC P14 31 (l)
S10 (l) 207oC S11 (g) 207oC 45oC
27.46 Kg/hr Steam
27.46 Kg/hr H2O 616.25 Kg/hr Steam S12 (l) 207 Co
P18 C23
616.25 Kg/hr H2O (l)
20oC
C22 (l) 20oC
54.67 Kg/hr H2O P20

updated on 10/3/2010 9
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
Mass Balance Table

Gas
Liquid
Solid

dichloropropa
Allyl Chloride
Chloropropen

dichloroprope

Black Carbon

Black Carbon
2,3dichloropr

Heavy Ends
Total Flow

Propylene

Saturated

Saturated
Isopropyl
Chlorine

Chloride
Pressure
Stream

Water

Water
Steam
Temp

(Atm)

opene
Rate

HCl
(C)

1,2

1,3
ne

ne
2

e
1 25 1 1188.87 1188.87
2 117 3 1188.87 1188.87
6 25 1 679.13 679.13
7 52 2 679.13 679.13
7a 52.7 2 2679.65 2676.97 2.68
8 62.2 2.5 2679.65 2676.97 2.68
9 65 2.3 2676.97 2676.97
9a 65 1 2.68 2.68
9b 25 1 -2.68 -2.68
10 76.7 3 2676.97 2676.97
11 200 3 2676.97 2676.97
11a 510 1 -1.88 -1.88 -1.88
12 510 3 3863.96 2017.62 605.57 2.46 27.58 1020.34 46.03 113.02 13.91 17.43
13 25 3 3863.96 2017.62 605.57 2.46 27.58 1020.34 46.03 113.02 13.91 17.43
15 22 3 1240.77 2.46 27.58 1020.34 46.03 113.02 13.91 17.43
15a 22 3 2623.19 2017.62 605.57
15b 25 1 2623.19 2017.62 605.57
17 25 1 1071.78 1071.78
18 25 1 1071.78 1071.78
19 25 1 -1666.28 -599.86 -1066.42
20 25 1 2028.69 2017.62 5.71 5.36
21 52.8 2 2028.69 2017.62 5.71 5.36
21a 25 1 13.15 13.15
21b 25 1 13.15 13.15
22 25 1 2000.52 1997.84 2.68
22a 25 1 41.32 19.78 5.71 15.83
22c 52.8 2 2000.52 1997.84 2.68
22d 25 1 -41.32 -19.78 -5.71 -15.83
23 22 1 1240.77 2.46 27.58 1020.34 46.03 113.02 13.91 17.43

updated on 10/3/2010 10
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
 dichloropropa
Allyl Chloride
Chloropropen

dichloroprope

Black Carbon

Black Carbon
2,3dichloropr

Heavy Ends
Total Flow

Propylene

Saturated

Saturated
Isopropyl
Chlorine

Chloride
Pressure
Stream

Water

Water
Steam
Temp

(Atm)

opene
Rate

HCl
(C)

1,2

1,3
ne

ne
2

e
24 36 1 40.83 2.46 27.58 10.79
25 36 1 40.83 2.46 27.58 10.79
25a 25 1 -40.83 -2.46 -27.58 -10.79
26 36 1 1199.94 1009.55 46.03 113.02 13.91 17.43
27 36 1 1199.94 1009.55 46.03 113.02 13.91 17.43
28 45 1 1000 1000
29 45 1 200.49 10.1 46.03 113.02 13.91 17.43
30 45 1 1000 1000
31 45 1 200.49 10.1 46.03 113.02 13.91 17.43
32 25 1 -1000 -1000
33 25 1 -200.49 -10.1 -46.03 -113.02 -13.91 -17.43
Fugitive Losses 3.40 5.94 3.03 0.05 2.04
S3 207 1 245.52 245.52
S4 207 1 -245.52 -245.52
S5 207 1 5.59 5.59
S6 207 1 -5.59 -5.59
S9 207 1 27.46 27.46
S10 207 1 -27.46 -27.46
S11 207 1 616.25 616.25
S12 207 1 -616.25 -616.25
S13 207 1 5.2 5.2
S14 207 1 -5.2 -5.2
C1 20 1 8162.87 8162.87
C2 20 1 8162.87 8162.87
C3 50 1 -8162.87 -8162.87
C7 20 1 9158.94 9158.94
C8 20 1 9158.94 9158.94
C9 50 1 -9158.94 -9158.94
C10 20 1 276.25 276.25
C11 20 1 276.25 276.25
C12 50 1 -276.25 -276.25
C13 20 1 8193.76 8193.76
C14 20 1 8193.76 8193.76
C15 50 1 -8193.76 -8193.76
C16 20 1 306.56 306.56
C17 20 1 306.56 306.56

updated on 10/3/2010 11
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
 dichloropropa
Allyl Chloride
Chloropropen

dichloroprope

Black Carbon

Black Carbon
2,3dichloropr

Heavy Ends
Total Flow

Propylene

Saturated

Saturated
Isopropyl
Chlorine

Chloride
Pressure
Stream

Water

Water
Steam
Temp

(Atm)

opene
Rate

HCl
(C)

1,2

1,3
ne

ne
2

e
C18 50 1 -306.56 -306.56
C19 20 1 5.24 5.24
C20 20 1 5.24 5.24
C21 50 1 -5.24 -5.24
C22 20 1 54.67 54.67
C23 20 1 54.67 54.67
C24 50 1 -54.67 -54.67
C25 20 1 4264.64 4264.64
C26 20 1 4264.64 4264.64
C27 50 1 -4264.64 -4264.64
C28 20 1 899.89 899.89
C29 20 1 899.89 899.89
C30 50 1 -899.89 -899.89
C31 20 1 4.2 4.2
C32 20 1 4.2 4.2
C33 50 1 -4.2 -4.2

updated on 10/3/2010 12
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
 Cumulative Chemical Waste
350

300

250
kg Waste/1000kg Product

200

150

100

50

Fugitive Losses
0
15a

22d

S10

S13
10

12

18

21

22

25

27

30

33

S5

C11

C14

C17

C20

C23

C26

C29

C32
1

C2

C8

Stream Number

updated on 10/3/2010 13
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
 Cumulative Contaminated Water Waste

20

18

16
kg Contaminated Water/1000kg Product

14

12

10

0
15a

22d

S10

S13
10

12

18

21

22

25

27

30

33

S5

C11

C14

C17

C20

C23

C26

C29

C32
1

C2
Stream Number C8

updated on 10/3/2010 14
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
 Cumulative Non-Contaminated Water

35000

30000

25000
kg Water/1000kg Product

20000

15000

10000

5000

0
15a

22d

S10

S13
10

12

18

21

22

25

27

30

33

S5

C11

C14

C17

C20

C23

C26

C29

C32
1

C2

C8

Stream Number

updated on 10/3/2010 15
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
 Energy Input and Recovery Summary
Energy Input (MJ/hr) Energy Loss (MJ/hr)
Index
Temp.
of
Stream Potential
Cooled Energy
o
Unit Energy Input Cumulative Unit Energy Loss Cumulative ( C) Recovery
Compressor 1 69.81649838 69.8164984 Cooler 5 -0.45 -0.4484176 30 0
Pump 21 0.498674269 70.3151727 Reactor -454.89 -455.342352 510 -341.1705
Compressor 3 38.64913819 108.964311 Cooler 1 -870.70534 -1326.04769 510 -653.029
Compressor 6 113.8866053 222.850916 Absorber -976.95 -2302.99856 25 0
Compressor 4 52.12732694 274.978243 Scrubber -95.99 -2398.98649 25 0
Dryer 11.57448387 286.552727 Turbine 1 -0.009936 -2398.99643 22 0
Distillation Column
Pump 25 0.000350345 286.553077 1 Condenser -29.45 -2428.44243 36 0
Compressor 5 64.42750537 350.980583 Cooler 3 -0.55925001 -2429.00168 36 0
Distillation Column
Heater 2 508.1999899 859.180573 2 Condenser -874.00 -3303.00168 45 0
Pump 3 0.69 859.868095 Cooler 2 -32.7 -3335.70168 45 0
Prefractionator 25.5 885.368095 Cooler 4 -5.83156093 -3341.53324 45 0
Heater 3 10.77295569 896.14105 Total: -994.1995
Pump 6 0.365400362 896.506451
Pump 7 0.773532388 897.279983
Compressor 7 115.9378309 1013.21781
Pump 24 0.075816548 1013.29363
Pump 23 1.06077E-07 1013.29363
Pump 8 0.065035856 1013.35867
Pump 12 0.023207655 1013.38187
Distillation Column
1 Reboiler 56.83 1070.21401
Pump 13 0.003830526 1070.21784
Pump 19 0.000436943 1070.21828
Pump 14 0.01 1070.22814
Pump 15 0.69 1070.92033
Distillation Column
2 Reboiler 1275.47 2346.38947
Pump 16 0.100586371 2346.49006
Pump 17 0.025802577 2346.51586
Pump 18 0.016651537 2346.53251
Pump 20 0.004558964 2346.53707

Heat Recovered -994.199456

Total Energy
Recovered 1352.33761

updated on 10/3/2010 9
Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.
 MJ/ 1000 Kg Allyl Chloride

500
1000
1500
2000
2500

0
Compressor 1

Pump 21

updated on 10/3/2010
Compressor 3

Compressor 6

Compressor 4

Dryer

Pump 25

Compressor 5

Heater 2

Pump 3

Prefractionator

Heater 3

Pump 6

Pump 7

Compressor 7

Pump 24

Process Unit
Pump 23
Cumulative Energy Input

Pump 8

Pump 12

Distillation Column 1 Reboiler

Pump 13

Griffing and Overcash, Chemical Life Cycle Database, www.environmentalclarity.com, 1999-present.

Pump 19

8
Pump 14

Pump 15

Distillation Column 2 Reboiler

Pump 16

Pump 17

Pump 18

Pump 20

Total Energy Recovered