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Synthetic fluid V1101 P1101 NaOH solution Cl2 Absorber V1103 Mixer H1101 Synthesis Reactor E1107 V1102 P1102 Synthetic fluid E1105 Synthetic fluid

E1106 Crystallizer

buffer tank

E1108 Crystallizer

V1104

Fig. 12. Flow chart of the synthesis reaction system.

V1304 Vapor-solid separator Hydrazine hydrate and water P1304 Flowmeter E1301 Evaporator T1301 Fractionator E1303 Condenser

Distillate

V1302

Fig. 13. Flow chart of the evaporation fractionation system.

1# Condenser

2# Condenser

Semiproduct tank

1# Reboiler

Prefractionator

2# Reboiler

Product column

Distillate tank

Fig. 14. Flow chart of the fractionation concentration system.

From Fig. 15 it can be seen that the minimum hot utility is 21,293 kW and the minimum cold utility is 10,168 kW. The current heat exchange network consumes 44,195 kW hot utility and 33,070 kW cold utility. Therefore, the potential energy saving is 22,902 kW, which accounts for 51.8% of the current hot utility. The existing heat exchanger network of the hydrazine hydrate plant is shown in Fig. 16. According to the principles of pinch technology, we can see from Fig. 16 that heat is transferred across the pinch. These pinch violations are listed in Table 9. In the existing network conguration, ten coolers, two exchangers and three heaters are pinch violators because they are inappropriately placed.

The heat loads of streams C3 and C5 are quite small, so they are not considered for recovery in order to reduce capital cost. The retrot scheme devised for the continuous streams is described below. For the coolers above the pinch, the following measures are adopted.  Addition of a new heat exchanger (E11) with a heat load of 1666.67 kW for heat exchange between H5 (8555 C) and C3 (4475 C).  Addition of a new heat exchanger (E12) with a heat load of 2666.67 kW for heat exchange between H6 (8555 C) and C5 (4475 C).  Addition of a new heat exchanger (E13) with a heat load of 4500.00 kW for heat exchange between H7 (8555 C) and C7 (4568.4 C).  Addition of a new heat exchanger (E14) with a heat load of 4500.00 kW for heat exchange between H8 (8555 C) and C9 (4568.4 C).  Addition of a new heat exchanger (E15) with a heat load of 4500.00 kW for heat exchange between H9(10083.6 C) and C11(7090 C). The rest part of H9 is cooled by cooling water through the existing E1122.

6.5. Retrot of the heat exchanger network (1) Retrot scheme for continuous streams: It is necessary to retrot the network to eliminate heat transfer across the pinch. Firstly, a retrot scheme is proposed for the continuous streams involved in the pinch violations. These continuous streams are shown in Table 10, in which the temperature range between the inlet and outlet temperatures is that of the heat transferred across the pinch for each stream.

40 Table 7 Stream data for the hydrazine hydrate plant. No. H1 H2 H3 Stream Hypochlorite Synthesis uid Synthesis uid

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Supply temperature (C) 20 100 80 65 45 80 67 50 30 85 85 85 85 100 113 113 12 5 30 44 95 44 95 45 95 45 95 70 60 60

Target temperature (C) 10 80 65 45 2 67 50 30 2 30 30 30 30 70 70 70 108 30 44 110 105 110 105 95 105 95 105 110 123 123

Heat load (kW) 555.56 1388.89 471.06 636.57 135.42 444.44 597.22 694.44 57.87 3055.56 4888.89 8250.00 8250.00 2361.11 1362.85 1753.47 2527.78 1388.89 444.44 6042.50 611.11 5694.44 972.22 9611.11 1638.89 9611.11 1638.89 2583.33 1423.61 1840.28

H4

Synthesis uid

H5 H6 H7 H8 H9 H10 H11 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13

Overhead product of fractionator Overhead product of fractionator Overhead product of fractionator Overhead product of fractionator Semi-nished product Distillate from product column Distillate from product column Mixture of hypochlorite and urea Synthesis uid Synthesis uid Mixture of hydrazine hydrate Synthesis uid Mixture of hydrazine hydrate Synthesis uid Mixture of hydrazine hydrate Synthesis uid Mixture of hydrazine hydrate Mixture of hydrazine hydrate Semi-nished product Semi-nished product

and water and water and water and water and water

Table 8 Batch stream data. No. H3 H4 H10 H11 C12 C13 Stream Synthesis uid Synthesis uid Distillate from product column Distillate from product column Semi-nished product Semi-nished product Supply temperature (C) 80 80 113 113 60 60 Target temperature (C) 2 2 70 70 123 123 Start time (h) 0:00 11:30 3:00 9:00 3:00 9:00 End time (h) 11:00 23:30 18:00 24:00 18:00 24:00 Heat load (kW) 2712.11 3587.94 2180.56 2805.55 2277.78 2944.45

For the heater below the pinch, because stream C1 contains NaClO, which is unstable and easily decomposable, the heater is left as it is. The above retrot saves 16,014 kW of heating and cooling utilities. (2) Retrot schemes for batch streams: From Tables 8 and 9, we get the batch streams involved in the heat transfer across the pinch situation and they are shown in Fig. 17. In this gure the heat load for each stream is given in parentheses and placed beside the vertical axis. Numbers placed next to the arc arrows indicate inappropriately exchanged heat. The batch process is cyclic with a batch period of 24 h. Two retrot schemes are considered: matches between batch streams and matches between batch and continuous streams. Matches between batch streams: To recover more energy, indirect heat integration is adopted for this retrot scheme. The procedures for indirect heat integration are as follows. (a) Determination of potential streams for indirect heat integration: The potential heat sources are all the hot streams involved in the inappropriate heat exchange matches

Fig. 15. Temperatureenthalpy diagram based on the stream data of the case study.

 For the exchangers across the pinch, the following measures are implemented.  Addition of a new heat exchanger (E16) with a heat load of 1388.89 kW for heat exchange between H2 (10080 C) and C9 (68.475.6 C).  H2 (5546 C) is cooled by C2 (530 C) through the existing E1104 with a heat load of 1388.89 kW.

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Fig. 16. Existing heat exchanger network of the case study.

Table 9 The heat transfer across the pinch situation in the hydrazine hydrate plant. Heat exchanger E1105a E1105b E1107b E1111abc E1114abc E1117abcde E1120abcde E1122 E1124 E1126 E1104 E1107a E1102abc E1109 E1112 Stream Synthesis uid Synthesis uid Synthesis uid Overhead product of fractionator Overhead product of fractionator Overhead product of fractionator Overhead product of fractionator Semi-nished product Distillate from product column Distillate from product column Synthesis uid Synthesis uid Mixture of hypochlorite and urea Synthesis uid Synthesis uid Heat transfer across the pinch/kW 471.06 318.29 421.57 1666.67 2666.67 4500.00 4500.00 2361.11 1362.85 1753.47 1388.89 444.44 868.92 91.56 86.28 Total = 22901.80 Type of inappropriate match Use of cold utility above the pinch

Heat transfer across the pinch Use of hot utility below the pinch

depicted in Fig. 17, and the potential heat sinks are the cold streams that can cool the sources. The results are shown in Table 11.

(b) Transformation into media streams: The temperature of each source is lowered by DTmin (10 C) to form a media hot stream (h) and that of each sink remains unchanged to

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Table 10 Continuous streams involved in the heat transfer across the pinch situation. No. H2 H5 H6 H7 H8 H9 C1 C3 C5 Stream Synthesis uid Overhead product of fractionator Overhead product of fractionator Overhead product of fractionator Overhead product of fractionator Semi-nished product Mixture of hypochlorite and urea Synthesis uid Synthesis uid Heat exchanger E1104 E1111abc E1114abc E1117abcde E1120abcde E1122 E1102abc E1109 E1112 Inlet temperature (C) 100 85 85 85 85 100 12 44 44 Outlet temperature (C) 80 55 55 55 55 70 45 45 45 Heat load (kW) 1388.89 1666.67 2666.67 4500.00 4500.00 2361.11 868.92 91.56 86.28

Fig. 17. Batch streams involved in the heat transfer across the pinch situation.

Table 11 Potential heat sources and heat sinks for the case study. Type HR11 HR10 HR4 HR3 HS13 HS12 Time interval (h) 9:0024:00 3:0018:00 11:3023:30 0:0011:00 9:0024:00 3:0018:00 Host stream H11 H10 H4 H3 C13 C12 Temperature interval (C) 11370 11370 8055 8055 60123 60123 Heat load (kW) 2805.55 2180.56 1093.88 826.86 2944.45 2277.78

Table 12 Media hot and cold streams for the case study. Original name HR11 HR10 HR4 HR3 HS13 HS12 Name after transformation h11 h10 h4 h3 c13 c12 Supply temperature (C) 103 103 70 70 60 60 Target temperature (C) 60 60 45 45 123 123 Start time (h) 9:00 3:00 11:30 0:00 9:00 3:00 End time (h) 24:00 18:00 23:30 11:00 24:00 18:00 Heat load (kW) 2805.55 2180.56 1093.88 826.86 2944.45 2277.78

form a media cold stream (c). The sources and sinks in Table 11 are transformed into the corresponding media hot and cold streams in Table 12. (c) The Qt diagram for media streams: All the media streams in Table 12 are plotted on the Qt diagram, as shown in Fig. 18. The streams can be matched without time sequence constraints.

(d) Direct heat integration of media streams: As before, a DTmin of 10 C is used. According to the stream temperatures and heat loads, h11 and h10 can be matched with c13 and c12. Because the original streams of c13 and h11 are C13 and H11, which appear in the same column (the product column), such matching of streams belonging to the same column should have rst priority. This is also true for streams

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Fig. 18. Qt diagram for media streams of the case study.

Table 13 Batch streams involved in inappropriate heat exchange matches. No. H11 H10 H4 H3 Name Distillate from product column Distillate from product column Synthesis uid Synthesis uid Heat exchanger E1126 E1124 E1107a E1107b E1105a E1105b Supply temperature (C) 113 113 80 80 Target temperature (C) 70 70 55 55 Start time (h) 9:00 3:00 11:30 0:00 End time (h) 24:00 18:00 23:30 11:00 Heat load (kW h) 2805.55 2180.56 1093.88 826.86

H1 H2 H3 H4 H5 H6 H7 H8 H9 H10 H11 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13

E1101abc E16 E1107a E1107bc E1104 E1105ab E1108 E11 E12 E13 E14 E15 E1122 E18 E17 E1102abc E1107a E1109 E1110 E1112 E1113 E1115 E1116 E1118 E1119 E1121 E1123 E1125 E17
Fig. 19. Retroted heat exchanger network of the case study.

E1111abc E1114abc E1117 E1120 E1122 E1124 E1126

E1104

E11

E12 E13

E16

E14

E15 E18

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c12 and h10. Accordingly, h11 is used to heat c13 and h10 is used to heat c12. In this way, 2735 kW (15 h/24 h) utilities or 1710 kW (24 h) can be saved. Matches between batch and continuous streams: When a batch stream matches with a continuous stream, they can only exchange heat during the time interval in which the batch stream exists. The continuous stream will have to exchange heat with utilities in other time intervals. Because continuous streams exist in all time intervals, direct heat integration can be used. The hot batch streams involved in the inappropriate heat exchange matches are listed in Table 13, in which the supply and target temperatures only cover the inappropriate heat exchange. A DTmin of 10 C is again used. According to the temperatures of the batch streams in Table 13, continuous streams C7 and C9 are the suitable ones for matching with the batch streams. Because the temperature and heat load of C7 and C9 are identical (4595 C, 9611.11 kW), and the heat load of either stream is sufcient to cool all the four batch streams in Table 13, only one continuous stream can be selected. The retrot scheme is developed using C7 as example stream. C7 is split into ve sub-streams. The one with a heat load of 2805.55 kW, i.e. C71, cools H11 through the existing E1126 and the one with a heat load of 2180.56 kW, i.e. C72, cools H10 through the existing E1124. C73 (4570 C, 1093.88 kW) cools H4 through the existing E1107a and E1107b, C74 (4570 C, 826.86 kW) cools H3 through the existing E1105a and E1105b, and the last one, i.e. C75, together with the remaining heat load of the other four sub-streams, will have to be heated by hot utility through the existing E1115. In summary, a saving of 4094 kW of hot and cold utilities is achieved. (3) Choice of retrot schemes: Three retrot schemes have been devised for the heat exchanger network of the hydrazine hydrate plant. From the energy saving standpoint, the retrot scheme for continuous streams is a good choice because it gives signicant energy savings. The two retrot schemes for batch streams provide additional heat recovery opportunities. Of the two schemes, the one based on matches between batch and continuous streams is more attractive as it gives a bigger energy saving. The energy saving from this retrot scheme is about 25% of that from the retrot scheme for continuous streams. It is evident that integration of this heat exchanger network without considering its batch streams can limit the total energy saving. Fig. 19 shows the network structure after retrot. The dished lines and exchangers indicate the indirect heat integration. The structure consider the retrot scheme for continuous streams and the indirect heat integration schemes. From the gure, the network is much more integrated than the original one. 7. Conclusions In this paper, heat integration of continuous processes featuring batch streams has been studied. A list of major ndings is given below. (1) The proposed heat dutytime (Qt) diagram can intuitively and fully express the time and thermal features of batch streams and provide a graphical basis for heat integration of continuous processes featuring batch streams.

(2) The energy targets for a batch process example identied by the Qt diagram method are identical to those obtained from the cascade analysis method. The Qt diagram method has the further advantage that the structure of the initial heat exchanger network can be easily obtained. (3) By considering heat degradation in the intermediate heat storage, the concept of media streams is used to transform indirect heat integration of batch streams into direct heat integration of media streams. This transformation allows indirect heat integration analysis to be carried out on the Qt diagram. (4) The heat exchanger network of a hydrazine hydrate plant has been analyzed and optimized using the proposed method. This network has 18 continuous and six batch streams. The following three retrot schemes have been considered: (a) scheme based on matches between continuous streams, (b) scheme based on matches between batch streams, and (c) scheme based on matches between batch and continuous streams. The retrot analysis reveals that the third scheme can give substantial heat recovery. As such, heat integration of this network without considering its batch streams can limit the total energy saving.

Acknowledgements Financial support from the National Basic Research Program of China (973 Program: 2012CB720500) and the National Natural Science Foundation of China under Grant No. 20936004 is gratefully acknowledged. References
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