JPS5889678A - Absorption of fluctuation in heat load in batch type operation - Google Patents

Abstract

PURPOSE:To reduce heat loss extremely, by carrying out load leveling using both endothermic heat during hydrogen release of alloy for occluding hydrogen and exothermic heat during hydrogen occlusion of the alloy. CONSTITUTION:Hydrogen is released from the alloy A for occluding hydrogen in the regeneative tank 6 using excess heat when the heat is in excess state in a batch operation. A regenerative device which is used in the operation is obtained by providing the regenerative thak 6 packed with the alloy A for occluding hydrogen with the tank 7 for storing hydrogen packed with the alloy B for occluding hydrogen through the hyrogen pipe 8. The operation system is cooled by the endothermic heat during the operation, the evolved hydrogen is sent through the hydrogen pipe 8 to the tank 7, for storing hydrogen, and hydrogen is occluded in the alloy B for occluding hydrogen. While, when a heating medium in the heating medium pipe L is in a heat demanding state, hydrogen occluded in the alloy B for occluding hydrogen is released, transferred through the hydrogen pipe 8 to the regenerative tank 6, and hydrogen is occluded in the alloy A for occluding hydrogen in the regenerative tank 6. The heating medium in the pipe L is heated by the heat generated during this operation.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention aims to reduce heat load fluctuations in batch operations to heat absorption during hydrogen release and heat generation during hydrogen absorption of the hydrogen storage alloy.
It relates to a method of absorbing and performing .

In batch-type operations such as tool-type reactions, heat demand (state II requiring heating) and heat surplus (state requiring cooling) often occur periodically. There is a demand for heat to raise the temperature, while there is a surplus of heat to remove the stirring heat and lower the temperature during the latter stages of polymerization and during removal. In addition, in the dyeing process, there is heat demand for heating the dye, material to be dyed, and dyeing medium at the initial stage, and there is a surplus of heat for cooling the temperature after dyeing.Even in batch operations in food processing and fermentation industries, Similarly, heat demand and heat surplus often occur with a time lag.

For example, FIG. 1 is a flow V-) schematically showing the process of producing a polymeric substance by polymerization. First, an initial polymer is obtained in an initial polymerization tank 1, and then sent to a late polymerization tank 3 through a pipe 2. The polymerization reaction is carried out while being heated by a heating medium at ℃. 6 in the figure indicates a boiler.1 As the polymerization reaction progresses, the viscosity increases, and the temperature of the reaction liquid gradually increases due to the heat of stirring that accompanies it. If the temperature rises too high, decomposition, coloring, side reactions, etc. will occur, so at the end of the polymerization, the heating medium is passed through a broken line fin cooler 4 to lower the temperature to, for example, 100°C to prevent the reaction liquid from rising excessively.・Furthermore, when taking out the reactant, it is cooled to bring the temperature down to around normal gourd temperature, but the cooling water used for cooling as in c is mostly discharged, and the thermal energy is The loss was quite large.The inventors focused on the above circumstances,
We conducted intensive research with the idea that thermal energy loss could be reduced by accumulating thermal energy when there is surplus heat and releasing it when heat is needed.

Generally, the sensible heat storage method and the latent heat storage method are known as heat storage methods that can be used for such purposes, but each of these methods has the following disadvantages, and it is difficult to find a top-satisfactory method.

Sensible heat storage: Sensible heat t Part 11 T by the method of heat retention and heat storage
OP, heat dissipation loss is large and heat storage density is small, and heat is stored at high temperatures and can only be used at lower temperatures.

Latent heat storage: Phase transition CM unique to heat storage materials! This method stores heat as energy, and the heat storage density is high, but the above phase transition fllJI! Heat can be stored and reused only at one point. On the other hand, there is a relatively new heat storage method that uses metal hydride. This takes advantage of the property of hydrogen storage alloys to generate heat when storing hydrogen and absorb heat when releasing hydrogen.The amount of heat stored is extremely large, and by adjusting the pressure of hydrogen gas, the heat storage and heat release temperatures can be adjusted freely. For example, Table 1 shows the amount of heat storage of typical heat storage media, ToD, and the characteristics of hydrogen storage alloys as heat storage media can also be learned from this table.

According to the present invention, the above-mentioned hydrogen storage alloy has (b) excellent heat storage properties (a).
(As a result of extensive research, the Kabuto IEii Taremo 0'c School is made of a hydrogen storage alloy. It is used on a heat storage device equipped with a heat storage tank filled with hydrogen, a hydrogen storage tank, and hydrogen piping connecting both tanks, and when there is a surplus of heat in batch operation, hydrogen is released from the O metal hydride in the heat storage tank to control the operation system. At the same time as cooling, the generated torpedo is sent to the hydrogen storage tank for storage, and when there is a lack of heat, hydrogen is transferred from the hydrogen storage tank to the heat storage tank and stored in the hydrogen storage alloy in the heat storage tank. The gist of this invention is to repeat the process of absorbing hydrogen and heating the operating system with the generated heat.In the present invention, the process of absorbing hydrogen and heating the operating system with the generated heat is clearly carried out. It uses a hydrogen storage alloy.
Each alloy releases hydrogen and absorbs heat under the conditions below the equilibrium decomposition pressure curve, and absorbs hydrogen and generates heat under the conditions above. For tS, the released hydrogen is stored as heat by using the heat when there is surplus heat, and when heat is needed, the released hydrogen is stored and the heat generated at that time is supplied to the operating system. are doing.

The configuration and effects of the present invention will be explained below based on drawings showing examples, but the following are representative examples and do not limit the present invention, and specific configurations of the heat storage device, piping, etc. can be arbitrarily designed as long as it is applicable to the purpose of IaO and IaO.

Figure-8 is a conceptual diagram illustrating the heat storage method according to the present invention, showing a heat storage tank 6 filled with hydrogen storage alloy A and hydrogen storage alloy Bt.
The filled water storage rosewood 7 is connected by a hydrogen pipe 8, and a flow rate control valve 9 is attached to the hydrogen pipe 8. In the heat storage tank 6, a heat medium pipe Lt connecting the boiler 6 and the late polymerization reaction tank 8t in the polymerization reaction apparatus shown in FIG. 1 is passed through, for example, and heat exchange is performed in this part. The heat exchange piping M installed in 7 is connected to cooling water C and process hot water H
heat recovered from exhaust gas, high-temperature dyeing wastewater in the dyeing process, etc.) is controlled by flow control valves 10' and 11, and a temperature sensor is installed downstream of the heat medium piping. 12, and the detector l! is the flow control valve 9
, 10.11 in a control system.

When the heating medium in the heating medium piping has a surplus of heat, the excess heat is used to release hydrogen from the hydrogen storage alloy A in the heat storage tank 6, and the heat absorbed at that time causes the heat in the piping to be released. While the temperature of the medium is lowered, the released hydrogen is sent to the water storage rosewood 7 through the bulk water pipe 8 and the flow rate regulating valve 9, and is stored in the hydrogen storage alloy B in the hydrogen pipe.

At this time, cooling water Ci flows through the pipe M to cool the water storage rosewood 7, thereby promoting the hydrogen storage reaction.

On the other hand, when the heating medium in the heating medium piping is in a heat demand state, the flow rate control valve 1lt is opened to flow the process heated waste water H into the piping M, and the hydrogen storage alloy B is heated by heating the water storage rosewood 7. The stored hydrogen is released and returned to the heat storage tank 6 through the hydrogen pipe 8 and the flow control valve 9. As a result, nuclear hydrogen is stored in the hydrogen storage alloy A, and the heat generated at this time can heat the heat medium in the piping. Opening and closing of the flow rate control valve 9 and switching of the flow rate control valves to and tt are as follows:
This can be done automatically using the temperature sensor 111 (or an automatic control device, not shown).

The above heat storage control method tA will be explained in relation to the specific hydrogen storage alloy as follows. That is, Ml-101N1. When La Nis is used as Oka B, if the temperature of the heating medium at the time of heat surplus is 880°C and the temperature difference between the heating medium and hydrogen storage alloy A in the heat storage tank 6 is 110"0, the temperature of the hydrogen storage alloy is is 320°C, and the equilibrium dissociation pressure at this time is 8.48 to 9/wound.On the other hand, assume that the water storage rosewood 7 filled with taN1s is cooled with cooling water at !6°C, and the cooling water and LaNI, The 0 temperature difference between t1゜℃ and ゜ and x-a x l s (hydrogen storage alloy II) is 8s℃, and its equilibrium dissociation pressure is equal to 〈198%l/♂.Therefore, Hydrogen flows from the heat storage tank 6 to the water storage rosewood 7 at the above-mentioned differential pressure of 0.6 KYaa.
” (m14g-198) K!tsu’t”1K11 people
L, Ml-111Ni.

The heat absorption inside the piping is cooled by the heat absorption that accompanies the increase in the degree of dehydrogenation.

Also, during heat demand, the temperature difference between Ml-1011LNl and heating medium O is t-10°C, and the temperature of Mll-1011N16 is 1140°C, and the equilibrium dissociation pressure at this time is 6.961 [9/cIM. Water storage rosewood 7 inside 0LaN1. When heated with t110″00 heated waste water H, La
N1. () The temperature is 70℃ (temperature difference 10℃) 9
The SO equilibrium dissociation pressure is 6.46&V'aIP tonal.

Therefore, due to the differential pressure o, 8 KG□, hydrogen moves to the heat storage tank 6 due to the water storage rosewood T, and the heating medium is heated by the heat generated by the hydrogen storage reaction of MI-10SN1. In other words, by adjusting the temperature of the heated wastewater introduced into the piping in the water storage tank 7, the heat medium in the piping can be adjusted to a predetermined value so that a hydrogen pressure difference can be obtained according to the amount of heat required at the time of heat demand. It can be heated in a temperature chamber. Moreover, the heating source at this time is, as mentioned above, the stored heat that is released in the 7 directions of the stored water rosewood and generated by the return of 9 hydrogen when there is a surplus of heat, so in the end, the heat during the surplus heat is temporarily stored and used when there is a demand for heat. As a result,
Heat loss can be reduced as much as possible.

In the above example, Ml is used as a hydrogen storage alloy in the case of a polymerization reaction.
-10 NI, L-N amount, t-Explained using an example,
This combination is not limited to this combination, and may be applied to an alloy having an equilibrium dissociation pressure of o, s NFIQ atm at the temperature level of the target process and 0.0 at the temperature level of the heating heat source and cooling source.
64I! Any combination of alloys having an equilibrium dissociation pressure of @mtlIO is sufficient (if the hydrogen pressure is below QJatm or above l@atm, there are many problems in practical use).

For example, polyester, polyamide, dimethyl terephthalate V acid, ethylene glycol-V, asphalt.

Inter-1 construction Z*V and Vn, melamine resin, putty fin,
Alkyd resin, acrylic A'll metallurgical annealing.

480℃~i! of heating furnaces, etc. Alloys, Mg-based, Mg-Mg-based, Ml- that have an equilibrium dissociation pressure of 0.6-6 mtm at the operating temperature level for Dase XK operated at a temperature of 50 °C.
C1l type, PD type, etc. and the above alloys are made into nine-element type, drying oven 1, food processing and sterilization.

For processes operating at temperatures between 260°C and 70°C, such as dyeing, rubber, tobacco, and leather products, the operating temperature is 0.
．． Alloy with equilibrium dissociation pressure of 6 to 59 atm, T I −
C (I system, Zr-M, system, tS-C/system 9-1-F/-
For use with Ni-based, (a-)(-based, etc.) and multi-component systems based on the above alloys, alloys with an equilibrium dissociation pressure of 0.5 to 59 atm at the temperature level of the heating heat source and cooling source, Mm
-Ni system, CI-M, -Ni system, MHI-NI-F@ system, T I-M, system, ye-TI system, Ll-81 system, T
1・-) Ii system, F・-T I -M n system @M
Combinations with multi-component systems based on the ta-Nl-A I system, Ll-111-Al system, etc. and the above alloys are conceivable.

FIG. 4 is another embodiment of the present invention, which is a schematic diagram showing a control method suitable for batch operation with short switching cycles between heat demand and heat surplus. That is, in the example shown in FIG. 8, the storage and release of hydrogen O in the water storage rosewood T is performed by switching the flow rate control valve 1G for cooling water and the flow rate control valve 11) for hot water discharge,
Since cooling and heating of hydrogen storage alloy B requires a considerable amount of time,
It may not be possible to keep up with batch operations where heat demand and heat surplus are repeated in short cycles. However, in the example shown in Fig. 4, two water storage rosewood tanks 7a*7bt are installed in parallel, and one water storage battery tank 7
1 is the cooling water pipe M. 1 and filled with an alloy that has a small amount of hydrogen storage (remaining a large amount of hydrogen storage capacity), and a heated drainage pipe MHI is installed in the water storage battery tank 7b, and an alloy that stores a large amount of urea (has a high hydrogen release activity). Filled with water storage rosewood 7m, 71*Fi! The water pipe 111ia is connected to the water pipe 8KIIi via the diverter valve 11. When the O heat medium in the reckless piping is in a heat surplus state, the three-way valve 18 connects the hydrogen piping 8 to the water storage rosewood 7maro, and the released hydrogen is guided to the water storage battery tank 7a and stored there, thereby reducing the heat demand. At this time, the three-way valve 18 is switched to connect the hydrogen pipe 8t to the water storage battery tank yb, and the hydrogen in the water storage rosewood 7b is supplied to the heat storage tank 6. In other words, the water storage battery tank 7m acts exclusively as a hydrogen storage unit, so it is always cold.
On the other hand, since the water storage rosewood b is constantly heated to function exclusively as a hydrogen release section, it can be immediately followed by simply switching the three-way valve II. In this example, as the operating time passes, the amount of hydrogen stored in the water storage battery tank 7a increases and the amount of released hydrogen in the water storage rosewood 7b decreases. However, as shown in the figure, switching piping 14.18 with a valve connecting the cooling water supply pipe and the heated wastewater supply pipe
If the supply direction of the cooling water C and the heated waste water H is changed periodically, the alloy O in the water storage battery tank 7-
1! By switching the water storage rosewood yat hydrogen release WIAK at the time when the hydrogen storage amount reaches the saturated level or just before that!
(At this point, the amount of hydrogen stored in the water storage rosewood 7b is almost gone, so it is switched to the hydrogen storage section.) By repeating this operation, the hydrogen balance can be maintained at the same level.

Fig. 3 shows still another embodiment of the present invention, in which a simple high-pressure hydrogen tank 16- and a low-pressure hydrogen tank 16b are conveniently used as water storage batteries, and the water is released in the heat storage tank 6 when there is excess heat. The hydrogen is sent to the low-pressure hydrogen tank 16b through the hydrogen pipe 8, the flow control valve 9, and the three-way valve St. When heat is required, the hydrogen is transferred from the high-pressure hydrogen tank 16 to the heat storage tank through the three-way valve 13, the solenoid valve 9, and the hydrogen pipe St. Supply hydrogen into 6. The hydrogen fed into the low-pressure hydrogen tank 16b for one meal is intermittently (or continuously) pressurized by the compressor 17 and returned to the high-pressure hydrogen tank 16 for circulation. , , P indicate a pressure indicating regulator. In this way, the water storage battery tank may be filled with a hydrogen storage alloy, or it may be a simple hydrogen tank.

The present invention is configured, for example, as described above, but the key point is to utilize the heat absorbed by the hydrogen storage alloy when releasing hydrogen and the heat generated when it absorbs hydrogen, to accumulate heat during surplus heat during batch operation, and to store heat during heat demand. By using this as a heat source, it was possible to significantly reduce heat loss in the entire operating system.

[Brief explanation of the drawing]

FIG. 1 is a process diagram showing a polymer polymerization process as a specific example of batch operation to which the present invention is applied, FIG. 2 is a graph showing the temperature dependence of equilibrium pressure of various metal hydrides, and FIG. Figures 1 to 6 are schematic diagrams showing the rush side of the present invention. 6-・Heat storage tank 7.71, 7-・・Water storage rosewood 8・-Hydrogen piping 9.10.11-・Solenoid valve A,
B--Hydrogen storage alloy L...Reckless piping M--Piping C-Cooling water H--Heat drainage applicant Industrial Technology Director 2nd R! ! To J 10007T) Figure 3

Claims (1)

[Claims] (1) Conveniently use a heat storage device in which a water storage battery tank is connected to a heat storage tank filled with a hydrogen storage alloy via hydrogen piping, and when there is surplus heat in batch operation, hydrogen is extracted from the metal hydride in the heat storage tank. At the same time, the generated hydrogen is sent to the water storage battery tank for storage, and when there is insufficient heat, the hydrogen is transferred from the water storage battery tank to the heat storage tank to cool the operation system. A method for absorbing heat load fluctuations in batch operation, which is characterized by repeating the steps of storing hydrogen in a hydrogen storage shell in a tank and heating an operating system with the generated heat.