Design of an industrial process for the production of

aniline by direct amination

R.T. Driessen, P. Kamphuis, L. Mathijssen, R. Zhang, A.G.J. van der Ham, H. van den
Berg, A.J. Zeeuw
University of Twente, Faculty of Science and Technology, Enschede, The Netherlands,
(r.t.driessen@student.utwente.nl); Huntsman Belgium BVBA, Everberg, Belgium

1
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Aniline is a frequently used bulk chemical

 Precursor for MDA production

 MDA is used for MDI production

4,4-methylenedianiline (MDA)

Aniline

methylene diphenyl di-isocyanate (MDI)

2
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

The current aniline production needs to be improved,

due to major drawbacks

Conventional chemistry:

Drawbacks:
• Low atomic efficiency
• Formation of acids
• Expensive raw materials

T. Kahl et al., Ullmann’s Encycl. Ind. Chem., (2000)

B. Saha et al., Rev. Environ. Sci. Technol., 43, 840-120 (2011) 3
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

The aim of the project is to design a process of direct

amination of benzene to aniline

benzene Protonated
Aniline production by aniline (75 wt%) MDI
N-compound MDI production
direct amination 250
kton/year

Project boundary

Requirements:
• Location: Rotterdam
• Direct amination of benzene
• 250 kt/year
• 75 wt% protonated aniline

4
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

All design alternatives are kept, until sufficient basis for

rejection

 Douglas’ method:
Functions  unit operations
 Development of alternatives

J. M. Douglas, Conceptual design of chemical processes. McGraw-Hill (1988)

Van den Berg et al., Direct amination of benzene for aniline production,
CHISA 2014
5
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

All design alternatives are kept, until sufficient basis for

rejection
Start

 Douglas’ method:
Background

Functions  unit operations

information

 Development of alternatives Feasible?

No
Alternative
designs

Yes

No
Blackbox Feasible?

Yes
No
Data
complete? Detailed
design
Yes
Preliminary
economic
analysis Economics

No
Feasible?
No
Feasible?
J. M. Douglas, Conceptual design of chemical processes. McGraw-Hill (1988) Yes
Van den Berg et al., Direct amination of benzene for aniline production, Yes
Conceptual
CHISA 2014
Design
Finalization 5
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

All design alternatives are kept, until sufficient basis for

rejection
Start

 Douglas’ method:
Background

Functions  unit operations

information

 Development of alternatives Feasible?

No
Alternative
designs

Yes

No
Blackbox Feasible?

Main choice
Yes
No
Direct amination with … Data
Detailed
complete?
design
1. Hydroxylamine (NH2OH) Yes
Preliminary
2. Ammonia (NH3) economic
analysis Economics

 Adverse equilibrium No
Feasible?
No
Feasible?
J. M. Douglas, Conceptual design of chemical processes. McGraw-Hill (1988) Yes
Van den Berg et al., Direct amination of benzene for aniline production, Yes
Conceptual
CHISA 2014
Design
Finalization 5
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

The focus of this project is on hydroxylamine

Reaction conditions:
• T = 70 ˚C, P = 1 bar
• good conversion (68.5%), high selectivity (>99.9%)
•Mn-MCM-41 catalyst

K.M. Parida et al., Appl. Catal., A., 351, 59-67 (2008)

6
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

The focus of this project is on hydroxylamine

Reaction conditions:
• T = 70 ˚C, P = 1 bar
• good conversion (68.5%), high selectivity (>99.9%)
•Mn-MCM-41 catalyst

•Hydroxylamine is however expensive

 Hydroxylamine production included in scope

Protonated aniline
N-compound NH2OH (75 wt%)
Hydroxylamine Aniline production by direct
production amination 250 kton/year

Project boundary Benzene

K.M. Parida et al., Appl. Catal., A., 351, 59-67 (2008)

6
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Chemical reduction of nitric oxide is the most promising

route to produce hydroxylamine

Protonated aniline
N-compound Hydroxylamine NH2OH Aniline production by (75 wt%)
production direct amination 250
kton/year

Project boundary Benzene

• Electrochemical reduction:
• T = 27 ˚C, P = 1 bar, ζ = 17.6% , σ = 93%
• Chemical reduction:
• T = 25 ˚C, P = 1 bar, ζ = 77% , σ > 85%
• Proven technology
• Platinum catalyst

K. Otsuka et al., J. Electrochem. Soc., 143, 3491, (1996)

R.E. Benson, et al. J. Am. Chem. Soc., 78, 4202–4205, (1956)
7
T. Hara et al., Appl. Catal. A Gen., 320, 144-151 (2007)
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Due to low availability of nitric oxide, the production of

nitric oxide is incorporated in the project boundary
Protonated aniline
N-compound NO Hydroxylamine NH2OH Aniline production by (75 wt%)
Nitric oxide
production production direct amination 250
kton/year
Project boundary Benzene

NO:
• Greenhouse gas
• Only low quantities commercially available

Reaction conditions:
• T = 70 ˚C, P = 1 bar
• η = 99%
• Proven technology in nitric acid production
• 5%-Rh-Pt catalyst

M. Thiemann et al., Ullmann’s Encycl. Ind. Chem., 24, 177-223 (2012) 8

 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Proposed process

9
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Proposed flowsheet
Hydroxylamine production

H2 H2 NH3, NO, N2, N2O

20 °C, 11.6 bar 35 °C, 10.1 bar 33 °C, 1.5 bar

S3
(pressure swing
adsorption)

NH3, NO, N2,

Nitric oxide production N2O, H2
35 °C, 10.3 bar

Air
Air R1 N2O, NO, N2, N2O, NO, N2,
R2 H2O, H+,
20 °C, 1 bar N2O, NO, N2, N2O, NO, N2, N2O, NO, H2O, NH3, H+, H2O, NH3, H+,
H2O, NH3 H2O, NH3 N2, NH3 Cl-, H2, NH3OH+ Cl-, NH3OH+
407 °C, 12 bar Cl-, H2, NH3OH+
S1 S2
NH3 850 °C, 11.8 bar 35 °C, 11.6 bar 28 °C, 11.6 bar 163 °C, 10.5 bar 350 °C, 10.3 bar
35 °C, 10.3 bar
20 °C, 12 bar

H2O H2O, H+,

H2O
188 °C, 12 bar Cl-, NH3OH+
35 °C, 11.6 bar
70 °C, 10.3 bar Aniline production
H2O
H+, Cl-, H2, H2O
20 °C, 11.6 bar
35 °C, 12 bar

H2
35 °C, 9.9 bar

Purge
H+, H2O, Cl-, H+, H2O, Cl-,
R3 C6H6, C6H5NH3+,
C6H6, C6H5NH3+,
C12H10, H2 C12H10, H2 H2O, Cl-, H+, C6H5NH3+
S4
165 °C, 10.1 bar 35 °C, 9.9 bar 35 °C, 9.9 bar

C6H6, C12H10
70 °C, 10.3 bar
C6H6, C12H10
35 °C, 9.9 bar
Modeled with UniSim R410 (NRTL-PR) C6H6, C12H10

35 °C, 9.9 bar

Purge

C6H6, C12H10

35 °C, 10.3 bar

C6H6
20 °C, 10.3 bar
10
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Proposed flowsheet
Hydroxylamine production

H2 H2 NH3, NO, N2, N2O

20 °C, 11.6 bar 35 °C, 10.1 bar 33 °C, 1.5 bar

S3
(pressure swing
adsorption)

NH3, NO, N2,

Nitric oxide production N2O, H2
35 °C, 10.3 bar

Air
Air R1 N2O, NO, N2, N2O, NO, N2,
R2 H2O, H+,
20 °C, 1 bar N2O, NO, N2, N2O, NO, N2, N2O, NO, H2O, NH3, H+, H2O, NH3, H+,
H2O, NH3 H2O, NH3 N2, NH3 Cl-, H2, NH3OH+ Cl-, NH3OH+
407 °C, 12 bar Cl-, H2, NH3OH+
S1 S2
NH3 850 °C, 11.8 bar 35 °C, 11.6 bar 28 °C, 11.6 bar 163 °C, 10.5 bar 350 °C, 10.3 bar
35 °C, 10.3 bar
20 °C, 12 bar

H2O H2O, H+,

H2O
188 °C, 12 bar Cl-, NH3OH+
35 °C, 11.6 bar
70 °C, 10.3 bar Aniline production
H2O
H+, Cl-, H2, H2O
20 °C, 11.6 bar
35 °C, 12 bar

H2
35 °C, 9.9 bar

Purge
H+, H2O, Cl-, H+, H2O, Cl-,
R3 C6H6, C6H5NH3+,
C6H6, C6H5NH3+,
C12H10, H2 C12H10, H2 H2O, Cl-, H+, C6H5NH3+
S4
165 °C, 10.1 bar 35 °C, 9.9 bar 35 °C, 9.9 bar

C6H6, C12H10
70 °C, 10.3 bar
C6H6, C12H10
35 °C, 9.9 bar
Modeled with UniSim R410 (NRTL-PR) C6H6, C12H10

35 °C, 9.9 bar

Purge

C6H6, C12H10

35 °C, 10.3 bar

C6H6
20 °C, 10.3 bar
10
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Proposed flowsheet
Hydroxylamine production

H2 H2 NH3, NO, N2, N2O

20 °C, 11.6 bar 35 °C, 10.1 bar 33 °C, 1.5 bar

S3
(pressure swing
adsorption)

NH3, NO, N2,

Nitric oxide production N2O, H2
35 °C, 10.3 bar

Air
Air R1 N2O, NO, N2, N2O, NO, N2,
R2 H2O, H+,
20 °C, 1 bar N2O, NO, N2, N2O, NO, N2, N2O, NO, H2O, NH3, H+, H2O, NH3, H+,
H2O, NH3 H2O, NH3 N2, NH3 Cl-, H2, NH3OH+ Cl-, NH3OH+
407 °C, 12 bar Cl-, H2, NH3OH+
S1 S2
NH3 850 °C, 11.8 bar 35 °C, 11.6 bar 28 °C, 11.6 bar 163 °C, 10.5 bar 350 °C, 10.3 bar
35 °C, 10.3 bar
20 °C, 12 bar

H2O H2O, H+,

H2O
188 °C, 12 bar Cl-, NH3OH+
35 °C, 11.6 bar
70 °C, 10.3 bar Aniline production
H2O
H+, Cl-, H2, H2O
20 °C, 11.6 bar
35 °C, 12 bar

H2
35 °C, 9.9 bar

Purge
H+, H2O, Cl-, H+, H2O, Cl-,
R3 C6H6, C6H5NH3+,
C6H6, C6H5NH3+,
C12H10, H2 C12H10, H2 H2O, Cl-, H+, C6H5NH3+
S4
165 °C, 10.1 bar 35 °C, 9.9 bar 35 °C, 9.9 bar

C6H6, C12H10
70 °C, 10.3 bar
C6H6, C12H10
35 °C, 9.9 bar
Modeled with UniSim R410 (NRTL-PR) C6H6, C12H10

35 °C, 9.9 bar

Purge

C6H6, C12H10

35 °C, 10.3 bar

C6H6
20 °C, 10.3 bar
10
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Proposed flowsheet
Hydroxylamine production

H2 H2 NH3, NO, N2, N2O

20 °C, 11.6 bar 35 °C, 10.1 bar 33 °C, 1.5 bar

S3
(pressure swing
adsorption)

NH3, NO, N2,

Nitric oxide production N2O, H2
35 °C, 10.3 bar

Air
Air R1 N2O, NO, N2, N2O, NO, N2,
R2 H2O, H+,
20 °C, 1 bar N2O, NO, N2, N2O, NO, N2, N2O, NO, H2O, NH3, H+, H2O, NH3, H+,
H2O, NH3 H2O, NH3 N2, NH3 Cl-, H2, NH3OH+ Cl-, NH3OH+
407 °C, 12 bar Cl-, H2, NH3OH+
S1 S2
NH3 850 °C, 11.8 bar 35 °C, 11.6 bar 28 °C, 11.6 bar 163 °C, 10.5 bar 350 °C, 10.3 bar
35 °C, 10.3 bar
20 °C, 12 bar

H2O H2O, H+,

H2O
188 °C, 12 bar Cl-, NH3OH+
35 °C, 11.6 bar
70 °C, 10.3 bar Aniline production
H2O
H+, Cl-, H2, H2O
20 °C, 11.6 bar
35 °C, 12 bar

H2
35 °C, 9.9 bar

Purge
H+, H2O, Cl-, H+, H2O, Cl-,
R3 C6H6, C6H5NH3+,
C6H6, C6H5NH3+,
C12H10, H2 C12H10, H2 H2O, Cl-, H+, C6H5NH3+
S4
165 °C, 10.1 bar 35 °C, 9.9 bar 35 °C, 9.9 bar

C6H6, C12H10
70 °C, 10.3 bar
C6H6, C12H10
35 °C, 9.9 bar
Modeled with UniSim R410 (NRTL-PR) C6H6, C12H10

35 °C, 9.9 bar

Purge

C6H6, C12H10

35 °C, 10.3 bar

C6H6
20 °C, 10.3 bar
10
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Proposed flowsheet
Hydroxylamine production

H2 H2 NH3, NO, N2, N2O

20 °C, 11.6 bar 35 °C, 10.1 bar 33 °C, 1.5 bar

S3
(pressure swing
adsorption)

NH3, NO, N2,

Nitric oxide production N2O, H2
35 °C, 10.3 bar

Air
Air R1 N2O, NO, N2, N2O, NO, N2,
R2 H2O, H+,
20 °C, 1 bar N2O, NO, N2, N2O, NO, N2, N2O, NO, H2O, NH3, H+, H2O, NH3, H+,
H2O, NH3 H2O, NH3 N2, NH3 Cl-, H2, NH3OH+ Cl-, NH3OH+
407 °C, 12 bar Cl-, H2, NH3OH+
S1 S2
NH3 850 °C, 11.8 bar 35 °C, 11.6 bar 28 °C, 11.6 bar 163 °C, 10.5 bar 350 °C, 10.3 bar
35 °C, 10.3 bar
20 °C, 12 bar

H2O H2O, H+,

H2O
188 °C, 12 bar Cl-, NH3OH+
35 °C, 11.6 bar
70 °C, 10.3 bar Aniline production
H2O
H+, Cl-, H2, H2O
20 °C, 11.6 bar
35 °C, 12 bar

H2
35 °C, 9.9 bar

Purge
H+, H2O, Cl-, H+, H2O, Cl-,
R3 C6H6, C6H5NH3+,
C6H6, C6H5NH3+,
C12H10, H2 C12H10, H2 H2O, Cl-, H+, C6H5NH3+
S4
165 °C, 10.1 bar 35 °C, 9.9 bar 35 °C, 9.9 bar

C6H6, C12H10
70 °C, 10.3 bar
C6H6, C12H10
35 °C, 9.9 bar
Modeled with UniSim R410 (NRTL-PR) C6H6, C12H10

35 °C, 9.9 bar

Purge

C6H6, C12H10

35 °C, 10.3 bar

C6H6
20 °C, 10.3 bar
10
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Due to the PSA purge 27% of the atomic nitrogen is lost

11
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

No atomic carbon is lost in the process

12
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Due to the water purge, 14.1% of atomic hydrogen is lost

13
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Due to an excess of energy it is possible to produce a

considerable amount of steam

Reactor ΔTad (°C)

R1 749
R2 505
R3 84

Steam Q F
(MW) (ton/h)
High pressure (40 bar) 40.4 84.7
Medium pressure (10 bar) 22.5
Low pressure (3.5 bar) 1.4

14
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

An overview of the costs and revenues shows that the

process is profitable
Total revenue = 418 M$/year
Based on:
6% 2%
4% • Material cost factor
5%
• Hand factor, e.g. piping
11%
• Location

72%

CAPEX (M$) 460

Variable Production Cost Return on investment (ROI) (%) 5.5
Fixed Production Cost
Payback period (PBP) (years) 8
General Expenses
Depreciation Profit (M$/year) 26
Profit Profit margin (%) 6
Profit taxes

15
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Improving the separation efficiency or conversion in

hydroxylamine reactor can reduce the nitric oxide loss

 Selectively separate hydrogen and nitric oxide from separator (S2) outlet
 Selectively separate nitric oxide from the purge
 Choose a different catalyst
 Increase conversion
H2 H2 NH3, NO, N2, N2O

20 °C, 11.6 bar 35 °C, 10.1 bar 33 °C, 1.5 bar

S3
(pressure swing
adsorption)

NH3, NO, N2,

N2O, H2
35 °C, 10.3 bar

N2O, NO, N2, N2O, NO, N2,

R2 H2O, H+,
N2O, NO, H2O, NH3, H+, H2O, NH3, H+,
N2, NH3 Cl-, H2, NH3OH+ Cl-, NH3OH+
from nitric oxide Cl-, H2, NH3OH+
S2 to aniline production
production 28 °C, 11.6 bar 163 °C, 10.5 bar 35 °C, 10.3 bar
350 °C, 10.3 bar

16
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Burning ammonia to obtain nitric oxide is not

energetically efficient, instead an alternative
production route should be investigated

 Energetically not favorable

o >28 GJ per tonne NH3 (via Haber-Bosch)

 T = 2727 - 3227 ˚C, P = 20 - 30 bars

 η = 1.5%

N. Cherkasov et al. Chem. Eng. Process, 90, 24-33 (2015)

M. Appl, Ullmann’s Encycl. Ind. Chem., (2011) 17
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

The process design still has an information gap

 Investigate kinetics for reactors for sound reactor design

 Detailed engineering of separation steps
 More effort on process modelling (e.g. electrolytic thermodynamic model)

18
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Conclusion

The designed process is technologically feasible, but economically it does not meet
industry guidelines.
Economically:
 ROI<20%
 Capex: 460 M$
 Revenue: 420 M$/year
Technically:
 Atomic efficiency (C=100%, N = 72%, H = 86%)
 Formation of high quality steam
 Proven technologies
 Integration with MDI production
 Raw materials remain expensive
19
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Conclusion

The designed process is technologically feasible, but economically it does not meet
industry guidelines.
Economically:
 ROI<20%
 Capex: 460 M$
 Revenue: 420 M$/year
Technically:
 Atomic efficiency (C=100%, N = 72%, H = 86%)
 Formation of high quality steam
 Proven technologies
 Integration with MDI production
 Raw materials remain expensive
19
 Background – Project boundary – Design – Technical – Economics – Recommendations - Conclusion

Conclusion

The designed process is technologically feasible, but economically it does not meet
industry guidelines.
Economically:
 ROI<20%
 Capex: 460 M$
 Revenue: 420 M$/year
Technically:
 Atomic efficiency (C=100%, N = 72%, H = 86%)
 Formation of high quality steam
 Proven technologies
 Integration with MDI production
 Raw materials remain expensive
19
20