EVALUATION METHOD ON WASTE HEAT RECOVERY FROM BURNING

ELEMENTAL PHOSPHORUS
ZAN Cheng, SHI Lin, SONG Yaozu*, ZHU Mingshan
Key Laboratory of Thermal Science and Power Engineering, Dept. of Thermal Engineering,
Tsinghua University, China
*Dept. of Engineering Mechanics, Tsinghua University, China

In China, thermal phosphoric acid is widely made by conventional two-step method.

This conventional method causes enormous energy dissipation and serious
environmental pollution, especially has a bad economic performance. To solve these
problems, a two-step method with waste heat recovery, containing a phosphorus
burning boiler, has been developed by us.
With the aim to guide this energy-saving retrofit, an evaluation method was presented
by means of modeling and exergy analysis, which considered the new indicators about
process driving force and the energy-saving potential and their calculating
methods of thermal process of phosphoric acid. The feasibility of energy-saving retrofit
should be evaluated from three aspects: energy utilization ratio, economic performance
and environment effects.
The evaluation method has been successfully used to analyses the retrofit of waste
heat recovery for thermal process of phosphoric acid. It was found that all the
evaluating indicators of the evaluation method were effective. Further more, the waste
heat recovery project has been practically applied. It has proved that considering the
process driving force and the energy-saving potential are practical and effective for
evaluation of performance of other production processes.

Introduction
In China manufacture of thermal phosphoric acid by conventional two-step method has caused
serious energy dissipation and environmental pollution. In the conventional method, a great
deal of heat energy, generated during burning elemental phosphorus, is discharged to
environment by heat exchanger. In order to reduce the production costs and protect the
environment, a two-step method with waste heat recovery, containing a phosphorus burning
boiler, has been developed by us. The special boiler could generate saturated steam of 8bar
through recovering the waste heat.
The feasibility of this kind of energy-saving retrofits needs to be evaluated rationally. Zhang et
al. made a feasibility analysis by means of thermoeconomics [1]. The results of exergy analysis
showed that a considerable energy loss still existed after energy-saving retrofit, which seemed
that the recovery of waste heat was ineffective.
It was found, that the misunderstanding was caused mainly by without considering the
irreversibility in the production process. In other words, the unavoidable exergy losses were
neglected in the conventional exergy analysis. With the aim to solve the problem, a new

evaluation method was presented by means of modeling and exergy analysis in this paper,
which specially considered the new indicators about process driving force and the
energy-saving potential and their calculating methods of thermal process of phosphoric acid.
Furthermore, the new evaluation method was used to evaluate the feasibility of energy-saving
retrofit of production of thermal phosphoric acid in china.

Thermal process
In the manufacture of thermal phosphoric acid, the condensed elemental phosphorus is burned
in air. The phosphorus oxide vapor (P4O10) formed reacts with water to produce phosphoric
acid [2]:
Air ( O2 )
(1)
P4O10 + 6 H 2O 4 H 3 PO4
(2)
P4
P4O10
The conventional two-step method
In China all conventional thermal-process plants use the two-step method involving separation
of phosphorus with subsequent combustion to the oxide and absorption in water. The main
variation in the phosphorus oxidation-hydration step is the number of vessels used. In some
plants the phosphorus is burned in one chamber and the oxide absorbed in another. In others
combustion and hydration are carried out in the same vessel (Fig.1).
Fig 1 shows that the most of heat resulting from phosphorus combustion and oxide hydration is
carried off by indirect cooling of the circulating phosphoric acid with water in the plate heat
exchanger. Else heat is carried off by direct cooling with water which flows along outer surface
of the combustion-hydration tower. The equivalent coal burning boiler is supposed as the boiler
which could generate equivalent vapor with the phosphorus burning boiler.

Figure 1: Combustion and hydration in a single vessel (a process flow of conventional two-step
method). The equivalent coal burning boiler provides vapor to melt phosphorus.
The two-step method with waste heat recovery
Fig 2 shows that phosphorus is burned in a special boiler, named phosphorus burning boiler.
The heat resulting from phosphorus oxidization is carried off by feedwater which flows along
outer surface and inner water wall of the boil. The special boil could generate saturated steam
of 8bar which is an available borderline product both in this process flow and other fields. The
oxide is hydrated in another vessel. The heat resulting from oxide hydration, which is much less
than the former, is carried off by indirect cooling of the circulating water with air.

Figure 2: Combustion and hydration in separate vessels (a process flow of two-step method
with waste heat recovery). The coal burning boiler is replaced by phosphorus burning boiler.

Evaluation Method with Process Driving Force

Evaluation System
Fig.3 shows the frame of the evaluation system presented by us. The evaluation system is built
based on thermal process, GB/T 14909-2004 [3], Engineering economics, Thermoeconomics
[4] and environmental impact analysis. Software has been made by C++ and Excel, which
could calculate the thermal physical properties of reactants and products, and gain the
evaluating indicators conveniently.
Technical

Conventional

New

parameters

method

method

Burning phosphorus

500

500

280
24
85

280
24
85

70

70

12491

12491

2876

2876

0.345

233

50

rate (t/h)
Workday (day/year)
Work hour(hour/day)
Concentration of
output acid (%)
Temperature of
output acid ( )
Flux of
output acid (t/a)
pressure of output
saturated vapor (bar)
Flux of output
saturated vapor(kg/h)
Burning standard
coal rate (t/h)
Power consumption
(kW)

Figure 3: The frame of evaluation system

Table 1 Details of technical parameters of

conventional and new process flows

Process Driving Force ( I d ) and Energy-saving potential ( )

In order to evaluate the performance of energy utilization rationally, two indicators named
process driving force and energy-saving potential were presented in the evaluation system.
The process driving force ( I d ) is defined as exergy loss of the process flow with the most
reasonable energy utilization in the same period. The process flow with the most reasonable
energy utilization has to meet high energy efficiency and good economical efficiency
synchronously, which always represent the highest production-level in a period.
The energy-saving potential is defined based on process driving force, which is expressed as
I
(3)
= 1 d
I
where I is the practical exergy loss of a process flow which includes internal and external
exergy loss. Energy-saving potential indicates the necessity of a process flow retrofit.
The process driving force is considered as a constant toward a given process flow in a given
period. The larger practical exergy loss is, the larger energy-saving potential is. If =0 (when
I=Id), the process flow is just with the most reasonable energy utilization in the period.
It is emphasized that the process driving force is a variable in the whole period. The process
driving force of a process flow will be decreased with technological change.

Case study
The evaluation system has been used to study the retrofit of waste heat recovery in
conventional two-step method. The Fig. 1 and Fig. 2 show the process flows before and after
retrofit. The technical parameters of conventional and new process flows are in the table 1.
Process Driving Force of Thermal process
Thermal process consists of three essential processes: phosphorus oxidization, gaseous
product cooling and phosphorus oxide vapor (P4O10) hydration. The models of process driving
force ( I d ) of these three processes have been built in the following.
In the process of phosphorus oxidization, I d is defined as exergy loss of constant temperature
combustion (2000K) of phosphorus.
T
kJ/h
(4)
I d 1 = nP4 G 0
T
where nP4 is phosphorus burning rate (kmol/h); G is Gibbs free energy change in the process
of constant temperature oxidation (kJ/mol);T is reaction temperature;T0 is ambient temperature;
is the rate of exergy loss by heat dissipation and -G in irreversible reaction (here =1).
In the process of gaseous product cooling, the phosphorus burning boiler represents the
highest cooling level. Therefore, the thermodynamic model of Td is built based on phosphorus
burning boiler.

I d 2 = nP4 ( Ein Eout ) kJ/h

(5)

where Ein is the sum of inlet exergy; Eout is the sum of outlet exergy.
In the process of hydration, the thermodynamic model of I d is built based on hydrator of
two-step method with waste heat recovery. The inlet temperature of hydrator is supposed to be
500 which is the lowest allowable temperature for normal reaction (the practical inlet
temperature is 600 ).

I d 3 = nP4 ( Ein Eout ) kJ/h

(6)

An evaluating indicator named internal residual exergy loss is defined as

I int, r = I int I d kJ/h
(7)
where I int is internal exergy loss.
Energy Evaluation
With the same production capacity, the phosphorus burning boiler could recover 54.1% of the
total inlet heat. The exergy analysis considering process driving force (PDF) has been done
carefully (Tab 2). The exergy flow charts have been made (Fig. 4 and Fig.5). Because the I d
of thermal process has been separated from internal exergy loss, the correct energy evaluating
indicators could be obtained [5]. It was found, that the energy-saving potential has a sharply
decrease due to retrofit of waste heat recovery.
Energy evaluating

Before

After

Change

indicators

retrofit

retrofit

rate

Process driving

7.976

7.976

13.442

2.174

-83.83%

Payoff exergy (GJ/h)

25.734

14.118

-45.14%

Income exergy (GJ/h)

3.853

3.853

External exergy loss

0.462

0.114

-75.26%

14.97%

27.29%

force (GJ/h)
Internal residual
exergy loss (GJ/h)

(kJ/h)
Object exergy
efficiency
Vapor payoff exergy

3762.62

2501.33

-33.52%

8023.97

3725.78

-53.57%

0.635

0.223

Fig.4 Exergy flow chart of conventional

two-step method

(kJ/kg)
Acid payoff exergy
(kJ/kg)
Energy-saving
potential ()

Tab.2 Results of exergy analysis before and

after retrofit (The exergy loss by heat
dissipation is regarded as internal exergy
loss)

Fig.5 Exergy flow chart of two-step method

with waste heat recovery

Economic Evaluation
The economic evaluation has been done by incremental analysis (Tab.3) and thermoeconomic
analysis. The output vapor is supposed as valuable borderline product. The results of financial
analysis show that the retrofit is favorable. The exergy cost of output vapor is equal to the
exergy cost of vapor generated by low-pressure coal burning boiler. By the thermoeconomic
analysis, the unit cost of exergy of phosphoric acid decreases 31.9 Yuan/t due to
energy-saving retrofit.
Environmental Evaluation

The environmental effects of the thermal process are considered as three aspects:
consumption of fossil fuel (coal), heat pollution of atmosphere and consumption of water (Tab.
4). The evaluating indicators show that the retrofit is friendly with environment.
Economic evaluating indicators

Results

First cost of retrofit (Ten-Thousand-Yuan)

420

Length of life (Year)

Incremental static pay back period (Year)

4.9

Incremental dynamic pay back period (Year)

6.6

Incremental net present value (Ten-Thousand-Yuan)

135.6

Referenced rate of return (%)

12

Incremental internal rate of return (%)

20.6

Tab.3 Results of economic evaluation. First cost is equity fund. The price of every
component is average price in China.
Environmental evaluating indicators
Coal consumption for vapor t /a

Before

After

Change

retrofit

retrofit

rate

2378

-100%

Coal consumption for power t /a

581

125

-78.5%

Heat dissipation GJ/h

17.28

6.14

-64.5%

Flux of circulating cooling water t/h

218

87

-60.0%

Tab.4 Results of environmental impact analysis before and after retrofit.

Rate of coal consumption is 371g (standard coal)/kW.

Conclusions
1. A systemic evaluation method, which considered the new indicators about process driving
force and energy-saving potential, was presented. It is suggested that the feasibility of an
energy-saving retrofit should be evaluated from energy utilization ratio, economic performance
and environment effects synchronously by the method.
2. The energy-saving retrofit of production of thermal phosphoric acid in china was evaluated.
The evaluating results prove that the retrofit of waste heat recovery is feasible.
3. The conventional exergy analysis neglects irreversibility in a production process, which
could be corrected by considering process driving force. The evaluation method presented in
this paper is applicable to feasibility analysis of other energy-saving retrofits.
Acknowledgements. The author acknowledges financial support provided by the National
Basic Science Research Program 973 project (China G2000026307).

References
[1] ZHANG Xinhui, SHI Lin, SONG Yaozu, ZHANG Guanzhong, Thermal economical analysis and waste heat
reclamation in two-step phosphorous acid production process, Journal of Tsinghua University (Sci & Tech) 43(6):
(2003) 798-801
[2] JIANG Shanxiang, Phosphoric Acid Phosphate and Complex Fertilize, Beijing:Chemical Industry Press 1999.
[3] China GB/T 14909-2004, Technical guides for exergy analysis.
[4] ZHU Mingshan, Exergy Analysis of Energy System, Beijing: Tsinghua University Press 1988.
[5] ZAN Cheng, SHI Lin, SONG Yaozu, ZHU Mingshan, Process Driving Force and Energy Analysis in
Phosphorous Acid Production. Journal of Engineering Thermophysics 25 Suppl. :( 2005) (accepted).